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  • Reimer
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  • 1
    Publication Date: 2024-04-25
    Description: Die Toskana ist die stärkste geothermische Anomalie auf dem europäischen Kontinent. In dieser Anomalie finden sich zahlreiche lokale geothermische Felder mit hoher Enthalpie, wie z.B. das Feld von Travale. In diesem geothermischen Feld, das im Era-Graben liegt, wurden in den Jahren 1980/81 elektromagnetische Messungen durchgeführt. Es war das Ziel der Untersuchungen, die Quelle und die Ursache dieser teilweise bekannten Anomalie zu finden. Hierzu sollte die Verteilung der elektrischen Leitfähigkeit in der Erdkruste bis in Tiefen der Kruste-Mantel-Grenze mit den Methoden der Magnetotellurik und Erdmagnetischen Tiefensondierung untersucht werden. Parallel dazu wurde die geothermische Anomalie von Travale mit einer Vielzahl weiterer elektromagnetischer, seismischer und geochemischer Methoden untersucht. Das Ziel, die geothermische Anomalie in der Erdkruste zu lokalisieren, war nicht einfach zu erreichen. Deshalb war es notwendig, ein Modell der Anomalie zu erarbeiten, aus dem die Lokalität folgen sollte. Vor angegangene elektromagnetische Untersuchungen (HAAK & SCHWARZ 1981) hatten gezeigt, daß nahezu das gesamte Gebiet der Toskana als eine Anomalie der elektrischen Leitfähigkeit anzusehen ist: Gutleitende Deckschichten, mit bis zu 10 km Mächtigkeit, werden von einem hochohmigen Basement unterlagert. An einigen Meßorten deutet sich der Übergangsbereich Kruste / Mantel - in einer Tiefe zwischen 20 und 30 km - durch eine Zone hoher Leitfähigkeit an. Dieser Bereich zeichnet sich durch Lamellen hoher und extrem niedriger seismischer Wellengeschwindigkeiten aus. Petrologisch kann dieses durch eine Wechsellagerung von basischem und saurem Material gedeutet werden. Die zeitlichen Variationen des elektrischen und magnetischen Feldes wurden im geothermischen Feld von Travale in einem breiten Periodenbereich von 6 - 10.000 s registriert. Die Meßorte liegen überwiegend auf zwei Profilen, eines verläuft parallel zum Era-Graben aus der Anomalie heraus nach NW, das zweite schneidet die Anomalie senkrecht zum Graben. Der Meßpunktabstand war mit einigen hundert Metern bis zu mehreren Kilometern sehr dicht, um möglichst alle lateralen Variationen der scheinbaren spezifischen Widerstände beobachten zu können. Es zeigte sich, daß die lateralen Variationen der spezifischen Widerstände im Gebiet von Travale sehr groß waren. Bis zu Perioden von 50-100 s ist der Era-Graben die dominierende zweidimensionale Leitfähigkeitsstruktur. Die gemessenen scheinbaren spezifischen Widerstände sind bei längeren Perioden durch dreidimensionale Leitfähigkeitsstrukturen verzerrt. Die scheinbaren elektrischen Widerstände sind innerhalb der geothermischen Anomalie mit Werten bis zu 50 Qm äußerst klein, während sie nördlich des geothermischen Feldes auf 100-300 Qm ansteigen, um dann etwa 7 km NW der Anomalie wieder deutlich abzufallen. Selbst in der tieferen Kruste werden keine höheren Widerstände angetroffen. Die integrierte Leitfähigkeit weist das geothermische Feld ebenso als eine Anomalie der elektrischen Leitfähigkeit aus, während nördlich davon die "hochohmige Barriere" bestätigt wurde. Aus den Ergebnissen der Seismik und Magnetotellurik wurde ein Modell für die geothermische Anomalie von Travale und die Toskana abgeleitet, das sich in drei Stockwerke gliedert: - Das unterste Stockwerk, die Übergangszone zwischen Oberem Mantel und Unterkruste in 20-30 km Tiefe ist die Quelle auf steigender heißer Gase und Flüssigkeiten. Die Temperatur beträgt etwa 700° C. - Das mittlere Stockwerk ist von tief reichenden, vertikalen Störungen durchsetzt, die einen konvektiven Wärmetransport durch die hydrothermalen Phasen in das oberste Stockwerk erlauben. Im Gebiet von Travale hat sich durch längs- und zum Era-Graben querstreichende Störungen eine ausgeprägte Schwächezone in der Kruste gebildet, die einen besonders intensiven Wärmetransport zuläßt. Der Temperaturgradient wird mit 15° C/km angenommen. - Das oberste Stockwerk besteht aus Sedimenten und kristallinen Formationen, die im wesentlichen von horizontalen Abscherungs- und Störungsflächen durchzogen sind, in denen hydrothermale Phasen zirkulieren. Innerhalb der Basements hat sich so ein zweites Reservoir ausgebildet, welches das bekannte geothermische Reservoir in den Karbonaten in Tiefen von 1-2 km durch ein ausgeprägtes Bruchsystem speist. Die Temperatur ist in 4 km Tiefe mit 400° C sehr hoch. Die augenblicklich geförderten heißen Gase und Wässer sind meteorologischen Ursprungs und werden an der Oberkante des toskanischen Basements aufgeheizt. Aus tektonischer Sicht besteht das oberste Stockwerk aus allochthonen Decken, die während der Orogenese über die Toskana hinweggeschoben wurden. Dieser tektonischen Kompressionsphase folgte eine Phase starker lateraler Dehnungen, die bis heute andauern. Das System von Grabenbrüchen und tiefgreifenden Verwerfungen ist Ausdruck dieser Dehnungstektonik. Die damit verbundenen Störungszonen tragen zu einer Entwässerung und Entgasung der tiefen Erdkruste bei und lassen die hydrothermalen Phasen in das oberste Stockwerk aufs teigen. In ausgeprägte Schwächezonen, die die gesamte Kruste durchziehen und die durch undurchlässige Schichten nach oben abgeschlossen werden, kann sich so ein geothermisches Reservoir ausbilden.
    Description: Tuscany is the strongest geothermal anomaly in continental Europe. Numerous local high enthalpy geothermal fields are to be found within this anomaly, e.g. the Travale field. Electromagnetic soundings have been carried out in this geothermal field, which lies in the Era-Graben, in the years 1980 and 1981. The aim of this study was to find the origin as well as the cause of this partly known anomaly, using the methods of magnetotelluric- and geomagnetic depth soundings to study the distribution of electrical conductivity in the earth's crust downwards to the crust/mantle boundary, at least. Parallel to this study the geothermel anomaly of Travale has been studied with the help of various other methods, including electromagnetic, seismic and geochemical surveys. To localize the geothermal anomaly in the earth's crust was not an easy task. Therefore it seemed to be necessary to develop a model of the anomaly, first, and then to localize it. Earlier electromagnetic investigations (HAAK & SCHWARZ 1981) have shown, that nearly the whole area of Tuscany corresponds to an electrical conductivity anomaly: A well conducting cover, reaching down to 10 km depth is underlain by a high resistive basement. At some places within the geothermal anomaly a zone of high conductivity has been found at the depth of the crust/mantle-boundary (between 20 and 30 km) . Seismic refraction measurements are indicating a wide transition zone between the crust und upper mantle, displayed by alternating high- und extreme low-velocity layers. The time-varying electric- and magnetic fields have been recorded in the Travale area in a broad period range from 6-10.000 s, mainly on two profiles, the one parallel, the other perpendicular to the Era-Graben. The stations have been very close to each other, spacings varied between some hundreds of meters and a few kilometers, to study lateral variations of apparent resistivities within the Graben. In deed, lateral variations of apparent resistivities have been very large in the Travale area. Up to 50-100 s the Era-Graben is the dominating 2D-structure, but for longer periods of investigation the three-dimensionality of the electrical conductivity structure has to be considered. The apparent resistivities inside the geothermal anomaly are extremely low, reaching not more than 50 Gm, even in the lower crust, whereas going up to 100-300 firn north of the geothermal field. Further to NW apparent resistivities are coming down again to 5-5o Gm. Total conductance as well indicates the geothermal field as a local conductivity anomaly, whereas more to the north the poorly conducting "barrier" has been confirmed. Based on the results of the magnetotelluic soundings and those of the seismic survey a geothermal model for the anomaly of Travale as well as for Tuscany has been developed. The crust is built up by 3 stories: - The lowermost story of the transition from the mantle to the crust at 20-30 km depth has to be regarded as the origin of hot gases and fluids. Temperature amounts to 700° C. - The central story is more or less fractured vertically so that pathways allow convective transport of heat by means of hydrothermal fluids to the upper story. In the Travale area a weak crustal zone of faults crossing over has developed, allowing the transport of heat to be very intensive. The temperature gradient is assumed to reach not more than 15° C/km. - The uppermost story consists of sediments and more or less horizontally fractured crystalline formations, filled with hot, circulating fluids. Within the basement a second reservoir has evolved, which feeds the known geothermal reservoir in the carbonate series at 1-2 km depth through fractures and cracks in the top of the basement. The temperature of about 400° C in 4 km depth is extremely high. The actually exploited hot gases and fluids are of meterological origin and heated up at the top of the basement. From the tectonic point of view, the uppermost story consists of allochthonous nappes shifted across Tuscany during orogenesis. This compressive tectonic deformation was followed by strong dilatational forces, which are still active in the whole crust, expressed by the features of graben structures and deep reaching faults. This process gives volatiles and water generated by dehydration in the deep crust the chance to rise to the uppermost story. A basement fractured at the top and an impermeable cover in the uppermost layer will then favour the development of a geothermal reservoir.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:550 ; Geophysik ; Geothermie ; Magnetotellurik
    Language: German
    Type: doc-type:book
    Format: 103
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  • 2
    Publication Date: 2024-04-08
    Description: Die regional-geologische Aufnahme im Maßstab 1:100.000 der chilenischen Hauptkordillere zwischen 34° und 34°30' südlicher Breite ließ eine etwa 10.000 m mächtige und verschiedenartig deformierte stratigrapnisehe Abfolge erkennen, die teilweise von Intrusivkörpern durchschlagen ist.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.7 ; ddc:551.8 ; ddc:558 ; Paläogeografie ; Magmatismus ; Tektonik ; Geologie
    Language: German
    Type: doc-type:book
    Format: 280
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  • 3
    Publication Date: 2024-04-08
    Description: Der Einsatz des LANDSAT-Satellitensystems zur Abbildung nahezu der gesamten Erdoberfläche (Maßstab 1 : 1 000 000) hat den Geowissenschaften, nicht zuletzt der Geologie, neues Datenmaterial erschlossen, das als zusätzliche Information bei der Bearbeitung großer Gebiete herangezogen werden kann. Der multispektrale Ansatz des Satellitensystems, d. h. die Abbildung der Erdoberfläche in verschiedenen Spektralbereichen vom Grün bis zum nahen Infrarot, macht neue Arbeitsmethoden zur Datenanalyse notwendig.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.8 ; ddc:550.285 ; Satellitenbildauswertung ; Gesteinsoberfläche ; Gestein ; Klassifikation ; Luftbild
    Language: German
    Type: doc-type:book
    Format: 108
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  • 4
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-04-08
    Description: Die Insel Elba nimmt im Zusammenhang mit der alpinen und apenninen Gebirgskette eine strukturell überaus bedeutende Lage ein. So befindet sich diese größte Insel des toskanischen Archipels auf einer überleitenden Position zwischen dem nordostvergenten Nordapennin und dem westvergenten alpinen Teil Korsikas. Das Gesamtbild Elbas wird von ophiol ithischen Gesteinen mit ihrem sedimentären Auflager bestimmt. Im Ost- und Mittelteil der Insel sind weitgehend Nordapenninverhältnisse gegeben. Die Deformation der toskanischen und ligurischen Einheiten ist streng ostvergent, wobei in den eugeosynkl in〈* len Liguriden, welche klar mit der Bracco-Einheit korreliert werden können, Erscheinungen einer Thermodynamometamorphose fehlen. Dagegen werden auf West-Elba in den Ophiol ithserien enorme Abweichungen schon im Aufschlußbild deutlich, da diese intensiv isoklinal verfaltet und kräftig geschiefert sind.
    Description: Elba, the greatest Island of the Tuscan Archipelago» has an important position within the Alpine and Apenninie chains: It is situated in the transitional zone between the NE-vergent Northern Apennines and the Alpine part of Corsica with Western vergencies. Elba shows a widespread distribution of ophiolitic rocks and their sedimentary cover. In Eastern and Middle Elba there are conditions which are largely similar to those of the Northern Apennines. The tectonic trend of the Tuscan and Ligurian units is clearly eastward. The eugeosyncl inal Ligurides, which can be correllated with the Bracco unit of the Apennines, are not affected by thermodynamometamorphism. In this respect this area differs from the Western part of Elba, where also ophiolitiferous series occur. These however show tight isoclinal folding and strong cleavage.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:554 ; Elba ; Ophiolith ; Tektonik ; Stratigraphie
    Language: German
    Type: doc-type:book
    Format: 169
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  • 5
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-04-08
    Description: Seit gut 20 Jahren wird die Grundwassernutzung im Rahmen des "New Valley Project" stark vorangetri eben . Um eine langfristige Funktionsfähigkeit der Entwicklungsprojekte zu gewährleisten, mußte die Frage der Grundwasserbildung und -herkunft geklärt werden. Radiokarbon-Altersbestimmungen, Isotopenuntersuchungen und hydrochemische Analysen zeigen, daß das Grundwasser des Dakhl a-Beckens fossil ist; eine rezente Grundwasserneubildung ist nicht nachzuweisen. Grundwasserbildung fand letztmals während des letzten Hauptpluvials (〉20.000 Jahre B.P. ) statt, postpluviale Grundwässer wurden nicht nachgewiesen. Das Grundwasser wurde aus Niederschlägen atlantischer Feuchtmassen gebildet, die über eine Westwinddrift in die östliche Sahara gelangten. Die Grundwasserbildung war weitgehend lokal, großräumige Grundwasserbewegung findet nicht statt. Die Möglichkeit von Überläufen fossiler Grundwässer aus Nachbarbecken, wie Nordsudan-Becken und Kufra -Becken , konnte nicht geklärt werden. Aufgrund der analytischen Untersuchungen ist der Aquifer des Dakhl a-Beckens weder regional noch vertikal gliederbar; seine Ausbildung ist bei großräumiger Betrachtung sehr homogen. Wegen der ungleichen Verteilung der Informationen im Dakhla-Becken wurde zur Grundwassermassenberechnung ein dreidimensionales Computermodell entwickelt, das über Regressionen mit Polynomen höherer Ordnung die Volumina des Aquifers errechnete. Soweit überprüfbar, erbrachte das Modell gute Ergebnisse, so daß es künftig auch in Becken angewandt werden kann, von denen noch weniger Informationen vorliegen. Es wurde ein Zeit-Volumen-Modell erstellt, das zum einen den Absenkungsverlauf des Grundwasserspiegels beschreibt, zum anderen die zur Klärung der Grundwassersituation verwendeten Parameter stützt und sie als weitgehend richtig ausweist.
    Description: For about twenty years the use of the groundwater has been increased closely within the frame of the "New Valley Project". The questions of the formation and origin of the groundwater had to be elucidated in order to insure the long time function of the project. The investigations of isotopes, radiocarbon age dating and the hydrochemical analyses indicate the groundwater of the Dakhla Basin to be fossil; a recent formation of groundwater may safely be excluded. The last time groundwater formation occurred was during the last main pluvial (〉20,000 B.P.); there are no indications of postpluvial formation. The groundwater was formed by the precipitation of Atlantic humid air masses which reached the eastern Sahara by western drift. The groundwater formation was mainly local, regional groundwater movement does not occur. The possible overfl ow of fossil groundwater from the neighbouring basins as the North Sudan Basin and the Kufra Basin could not be clarified. Analytical investigations show the aquifer of the Dakhla Basin neither regionally nor vertically divisible; the shape is very nomogeneous over large regions. Since informations about the Dakhla Basin are distributed unevenly for the calculation of the groundwater masses the volumes of the aquifer were calculated using a three dimensional Computer model working with polynomal regressions of higher order. As far as possible the model shows good results; therefore it can be used in the future in basins with even less informations. A model of time and volume was made describing the decrease of the waterhead; the same model supports the Parameters used for the analysis of the groundwater Situation indicating that the Parameters are correct.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.4 ; ddc:556 ; Grundwasser ; Ägypten
    Language: German
    Type: doc-type:book
    Format: 150
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  • 6
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    Reimer
    In:  SUB Göttingen | ZB 45198:39
    Publication Date: 2024-04-08
    Description: Mit der Abu Bal las Formation sind erstmals unterkretazische marine Ablagerungen innerhalb der Kubischen Gruppe Südwest-Ägyptens nachgewiesen worden. Transgression und Regression erfolgten wahrscheinlich während des Apt. Die Ablagerungen der Formation treten in der Region zwischen dem Gilf Kebir und dem Abu Tartur Plateau zutage, wo sie die fluviatilen Sandsteine der Six Hills Formation (Basal Clastics) im Liegenden von den ebenfalls fluviatilen Sandsteinen der Sabaya Formation (Desert Rose Beds) im Hangenden trennen. Die Abu Bal las Formation besteht lithologisch überwiegend aus roten und grünen Tonsteinen, untergeordnet kommen auch Silt- und Feinsandsteine vor. Die Mächtigkeit beträgt durchschnittlich 20 bis 30 m, örtlich kann sie 45 m erreichen. Nach Westen, Süden und Osten keilt die Formation aus. Die Ablagerungen der Formation lieferten neben etlichen Pflanzenresten eine unerwartet arten- und individuenreiche marine Fauna. Im einzelnen wurden gefunden: Pflanzen: Vier bisher unbekannte Fruktifikationen sowie acht weitere bisher zum Teil unbekannte Pflanzenreste. Foraminiferida: Drei agglutinierende Arten. Scleraciinia: Eine ahermatype Art. Brachiopoda: Eine inarticulate Art. Scaphopoda: Eine Art. Gastropoda: Acht Arten. Bivalvia: 33 Arten. Die Bivalven stellen die umfangreichste Fossilgruppe innerhalb der Fauna dar. Annelida: Eine Art. Arthropoda: Zwölf Arten. Echinoidea: Eine Art. Vertebrata: 14 Arten. Spurenfossilien: 23 Arten. Koprolithen: Vier Formen. Folgende zwei Taxa sind neu aufgestellt worden: Palaeosabellaxda aegyptiaca gen. nov., sp. nov.; Anomoeodus parvulus sp. Nov.. Die Abu Ballas Formation ist in einem sehr flachen Epikontinentalmeer abgelagert worden. Die Wassertiefe betrug in dem Gebiet, in dem die Formation zutage tritt, höchstens etwa 20 m, größtenteils war sie wahrscheinlich bedeutend geringer. Die Salinität des Meereswassers war fast während der gesamten Zeit vermindert, in Küstennähe kam es aber zu starken Schwankungen und kurzfristig auch zu euhalinen Verhältnissen. Es lassen sich mehrere Faziesräume des oberen und mittleren Sublittorals unterscheiden, die durch unterschiedliche Sedimente und durch verschiedene Faunengemeinschaften gekennzeichnet sind. Im Übergangsbereich zwischen mariner und fluviatiler Sedimentation kam es Örtlich zu Deltaschüttungen und zur Ausbildung einer Marsch. Die Apt-Transgression überflutete weite Teile Ägyptens. Lediglich der äußerste Südwesten und der Südosten des Landes sowie große Teile der Eastern Desert und der südliche Sinai blieben Festland.
    Description: The Abu Ballas Formation is the first known Lower Cretaceous marine transgression within the Nubia Group of southwestern Egypt. Transgression and Regression probably happened at Aptian times. The depositions of the formation crop out in the area between the Gilf Kebir and the Abu Tartur Plateau. They are underlain by fluvial deposits of the Six Hills Formation (Basal Clastics) and overlain by fluvial deposits of the Sabaya Formation (Desert Rose Beds). Lithologically the Abu Ballas Formation mainly consists of red and green claystones, siltstones and finegrained sandstones are more rarely. The thickness averages 20 to 30 ms, reaching 45 ms locally. To the west, south, and east the formation wedges out. Aside from several plant remains the formation yields a marine fauna, which is unexpectedly rieh in species and individuals. There were found the following flora and fauna: Plants: Four fructifications unknown till now and eight other partly unknown plant remains. Foraminiferida: Three agglutinated species. Scleractinia: One ahermatypic coral . Brachiopoda: One inarticulate species. Scaphopoda: One species. Gastropoda: Eight species. Bivalvia: 33 species. The Bivalvia represent the most extensive group within the fauna. Annelida: One species. Arthropoda: Twelve species. Echinoidea: One species. Vertebrata: 14 species. Trace fossil s; 23 species. Coprolites: Four forms. The following two new taxa have been established: Palaeosabellaria aegyptiaea gen. nov., sp. nov. (Annelida: Hermell idae) and Anomoeodus parvulus sp. nov. (Hol ostei: Pycnodontidae) .The Abu Ballas Formation has been deposited in a very shallow epi Continental sea. In the area, where the formation crops out, the depth of the water was probably ca. 20 ms at most, usually it was considerably shallower. The salinity was reduced to some degree, near the coast however, it varied in a high extent. For a short time the conditions were euhaline. Several facies of the upper and middle sublittoral can be distinguished, characterised by different Sediments and different faunal associations. In the transitional zone between the marine and the fluviatile facies deltaic and marsh deposits were found locally. This transgression had flooded large areas of Egypt. Only the extreme southwestern part and the southeastern part of the country, probably wide areas of the Eastern Desert too, and the Southern half of the Sinai remained Continental.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.77 ; Paläontologie ; Ägypten ; Afrika
    Language: German
    Type: doc-type:book
    Format: 187
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  • 7
    Publication Date: 2024-04-08
    Description: Aus feinstratigraphisch aufgenommenen Profilen im kontinentalen Neogen (Jungpliozän-Altpleistozän) der Insel Kos (Dodekanes) werden horizontiert gesammelte Populationen der limnischen Gastropoden-Gattung Viviparus biometrisch untersucht und aufgrund dessen die bestehende taxonomische Aufteilung revidiert. Die Höhe und Breite der allometrischen Gehäuse werden an jeder Windung ermittelt und dargestellt. Diese Daten werden auf signifikante Unterschiede zwischen Populationen geprüft und die verallgemeinerten Trennwerte nach der Häufigkeit aufgetragen. Sie sind meist nahezu normal verteilt. Daraus wird auf ähnliche Variabilität der Populationen geschlossen. Durch die Cluster-Analyse wird die Ähnlichkeit der Individuen jeder Probe hierarchisch geordnet und gezeichnet (Dendrogramme) . Vermuteter Sexual-Dimorphismus der Gehäuse ist wahrscheinlich, kann aber nicht mit Sicherheit bestätigt werden. Im Laufe der Zeit verändern sich glattschalige kontinuierlich zu drei gekielten Formen trotz mehrfachen und deutlichen Milieuwechsels. Damit ist genetisch bedingte evolutive Umgestaltung der Gehäuse wahrscheinlich zu machen. Die Einordnung der Individuen aller Populationen in verschiedene Formklassen verdeutlicht diesen evolutiven Trend. Gleichzeitig treten fünf distinkte Häufigkeitsmaxima übereinander auf. Dadurch ist eine gegenüber anderen Methoden erheblich verfeinerte biostratigraphische Gliederung der ca. 250 m mächtigen nv:- parus- führenden Neogenfolge von Ost-Kos möglich.
    Description: On Kos Island, populations of the limnic gastropod genus Viviparus taken from defined horizons from Neogene (Late Pliocene to Early Pleistocene) sequences have been analyzed biometrically and have been revised paleontologically. Height and width of all coils of the allometric Shells have been measured and plotted. These data are examined with respect to significant differences between the populations. The discriminant scores of the samples show approximately Gaussian distributions. From this, a similar variability of the populations is deduced. The similarity of individuals within populations is hierarchically clustered in dendrograms. A supposed sexual dimorphism of the analyzed Shells is probable but has not been confirmed. In spite of several remarkable environmental changes, strongly sculptured forms conti nually develop from smooth Shells in the course of approximately 2 m.y. This proves a genetically controlled development of the various forms, i.e. evolution. By the arrangement of all the individuals in different morphological classes this evolutionary trend is illustrated. Moreover, five distinct maxima of frequency distributions are found. Accordingly, a refined biostratigraphic subdivision of the Neogene sequence bearing Viviparus in eastern Kos (approx. 250 m thick) has been rendered possible.
    Description: A l'Est de l’Tle de Kos (Dodecanese, Grece), des populations d’horizons determines du genre de gasteropodes limniques de Viviparus, provenant d’une sequence ininterrompue du Neogene Continental (Pliocene superieur au Pleistocene inferieur) ont ete etudiees par des methodes statistiques multivariees. Grace ä leurs resultats, une revision du groupement taxonomique existant est effectuee. La hauteur et la largueur de chaque circonvolution des coquilles allometriques sont mesurees et presentees graphiquement. Ces dates morphometriques sont examinees quant aux differences significatives dont leurs distances general isees sont tracees en distributions de frequence. Celles-ci sont pour la plupart normalement distribuees. De lä est deduite une variabilite ressemblante des populations. La ressemblance des individus de chaque faune est evaluee par l'analyse des similarites et tracees hierarchiquement en forme de dendrogrammes . II en res ulte la vraisemblance d'un dimorphisme sexuel de ces coquilles du genre Viviparus. Au cours de 2 millions d'annees environ, des formes lisses se sont developpees conti nuellement en forme multicarenees malgre plusieurs changements ecologiques prononces. Ainsi, le developpement de la forme de coquilles, genetiquement controllee, donc son evolution, peut etre constate. Le classement des individus de chaque population en dix types morphologiques differents precise cette tendance evolutive. En plus, cinq maxima de distributions de frequence sont nettement ä distinguer. De ce fait resulte, en comparaison avec d'autres methodes appliquees jusqu'ä present, une subdivision biostratigraphique plus detaillee de la sequence neogene de 1'Tie de Kos, epaisse de 250 m environ.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:564.3 ; Gastropoda ; Paläontologie ; Kos
    Language: German
    Type: doc-type:book
    Format: 138
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  • 8
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-04-08
    Description: Unter der Bezeichnung "Scaglia" wird im Südalpin und im Nordapennin eine Folge überwiegend pelagischer, kreide- und tertiärzeitlicher Sedimente zusammengefaßt, die aus bunten Tonschiefern, Mergeln und Kalken besteht. Zusätzlich können detritische Kalke, Breccien und Konglomerate auf treten. Die in der vorliegenden Arbeit behandelten Scaglia-Sedimente der Toskanischen Decke ("Scaglia Toscana“) konnten nach ihrer Lithofazies sechs Formationen zugeordnet werden. Mit Hilfe mikropaläontologischer Untersuchungen an pelagischen Foraminiferen wurden die Ablagerungen biostrati graphisch datiert; sie repräsentieren den Zeitraum Alb – Oligozän. Zahlreiche im Gelände auf genommene Schichtfolgen wurden lithofaziell und biostrati graphisch bearbeitet. Die Profile wurden korreliert und in einem standardisierten Normal profil zusammengefaßt. Es zeigte sich, daß die Verbreitung der Fazies typen sowie ihre Mächtigkeit von einer Beckenkonfi guration abhängt, die bereits seit dem Lias erkennbar ist. Eine generelle Umgestaltung des Ablagerungsraumes an der Wende Unter-/Oberkreide, wie sie als Folge der paläoapenninen Phase von verschiedenen Autoren angenommen wurde, konnte nicht nachgewiesen werden. Aus der Abfolge der mesozoischen bis alttertiären Ablagerungen läßt sich vielmehr im Zentrum des Sedimentationsraumes ein Hochgebiet mit lückenhafter und geringmächtiger Sedimentation rekonstruieren, welches vom älteren Jura bis in das Eozän hinein Bestand hatte und beiderseits von Becken mit mächtigeren und vollständigeren Schichtfolgen gesäumt wurde. Diese Schwellenregion wird als "Zentral toskanisches Hochgebiet" bezeichnet und entspricht teilweise der von BOCCALETTI & BORTOLOTTI (1965) rekonstruierten "Dorsale costiera". Im Oligozän - ?Miozän wurden diese morphologischen Strukturen entland der Linie Livorno-Sillaro in zwei gegeneinander versetzte Blöcke zerlegt. Die paläoapennine Phase (Wende Unter-/Oberkreide) sowie auch die ligurische Phase (Eozän), die in den internen Bereichen des Nordapennins (Ligurikum) zu einer bedeutenden Umgestaltung der Sedimentationsraume führten, dokumentieren sich in der Schichtfolge der Toskanischen Decke lediglich im vermehrten Auftreten von Breccien, Konglomeraten und ersten ganz lokal vorkommenden Grauwackenschüttungen. Im Neokom und verstärkt mit Beginn der Scaglia-Sedimentation im Alb und damit auch zeitgleich mit der palaoapenninen Phase, setzt im toskanischen Abi agerungs raum außerdem von NE her die Schüttung detritischer Kalke ein. Diese füllen zunächst das Becken östlich des Zentral toskanischen Hochgebietes ; vom Eozän ab greifen sie auch auf die westlichen Gebiete über. Diese detritischen Kalke der Scaglia Toscana zeigen Sedimentstrukturen wie sie für Turbiditablagerungen typisch sind. Sie müssen als Kalkflysch angesprechen werden, der sich mit normal sedimentierten Ablagerungen verzahnt. Die Scaglia Toscana kann deshalb nicht mehr als rein pelagische Schichtfolge der Präflyschphase angesehen werden, sondern repräsentiert, wenigstens in Teilen, schon das volle Flyschstadium des Drögens.
    Description: In the Southern Alps and in the Northern Apennines the name "Scaglia" is used for a mainly pelagic, cretaceous to tertiary sedimentary sequence which is composed of variegated clayey shales, marls and limestones. In this succession detrital limestones, breccias and conglomerates may occur as well. The Scaglia Sediments of the Tuscan Nappe ("Scaglia Toscana") examinated in the present study were subordinated to six forma tions according to their lithofacies. The Sediments were dated biostratigraphically by means of micropaleontological studies on pelagic foraminiers; they represent the period between Albian and Oligocene. Detailed field investigations and biostratigraphical datings of numerous strati graphical sequences allowed a correlation of serial sec tions and a summari za tion to a Standard! zed columnar section. It was evident that the distribution of the different facies types as well as their thickness depends on a bas in topography which is recognizable since Liassic times. A general transformation of the deposition area at the boundary of Lower and Upper Cretaceous as a consequence of the "Paleoapenninic Phase", postulated by several authors, could not be proved. From the sequence of the Mesozoic to Paleogene sediments one could rather reconstruct a ridge characterized by thin Sedimentation and Stratigraphie gaps in the centre of the deposition area. This rise existed from the Juras sic up to the Eocene and was accompanied on both sides by bas ins with thicker and more complete strati graphical sequences. This ridge is called "Central Tuscan Ridge" ("Zentral toskanisches Hochgebiet") and corresponds partly to the "Dorsale costiera" reconstructed by BOCCALETTI & BORTOLOTTI (1965). In the Oligocene - (?)Miocene these morphological structures were divided into two blocks which were displaced versus each other along the Livorno-Sillaro-Structure. The "Paleoapenninic Phase" (Lower/Upper Cretaceous) as well as the "Ligurian Phase" (Eocene) which initiated significant translocations in the inner areas of the Northern Apennines (Ligurids), are documented within the sequence of the Tuscan Nappe only by an increasing occurrence of breccias, conglomerates and a first local accumulation of graywackes. In the Neocomian and even more intensive with the beginn! ng of Scaglia-sedimentation and therefore contemporaneous with the "Paleoapenninic Phase", in the Tuscan area the accretion of detrital limestones begins from NE. At first these limestones fill up the bas in east of the Central Tuscan Ridge and from the Eocene on they also start spreading out towards Western areas. These detrital Times tones of the Scaglia Toscana show sedimentary fabrics typical of turbidites. They represent a carbonate facies which interfingers with normal sedimentated depositions. Thus the Scaglia Toscana can no longer considered a pure pelagic sequence of the pre-flysch period but represents, at least in parts, the flysch stage of the orogene.
    Description: Nel Sudalpino e nel Appennino settentrionale con il nome di "Scaglia" viene intesa una sequenza di sedimenti per lo piü pelagici, di etä Cretaceo-Terziaria, ehe e costituita da scisti argillosi policromi, marne e calcari; possono essere presenti anche calcari detritici, brecce e conglomerati. I sedimenti della Scaglia della Falda Toscana (Scaglia Toscana) trattati nel presente lavoro, potrebbero venire attribuiti, in base al la loro litofacies, a sei formazioni. Con l'aiuto di ricerche micropaleontologiche su foraminiferi pelagici le fasi di sedimentazione sono state datate in un periodo tra l'Albiano e l’Oligocene. Numerose sequenze di strati osservate in campagna sono state esaminate sia dal punto di vista della litofacies ehe da quello biostratigrafico. Le sezioni strati graf i ehe sono state correlate e vengono rappresentate da una sezione Standard. Si e notato ehe la diffusione dei tipi di facies come pure il loro spessore sia dipeso dal la presenza di un bacino esistente giä dal Lias. Contrariamente a quanto e stato affermato da vari autori , non si e potuto di mostrare un cambiamento dei bacini di sedimentazione nel periodo tra il Cretaceo inferiore e quello superiore, come conseguenza della fase paleoappeninica. Dalle sequenze sedimentarie dal Mesozoico al Paleogene si lascia ricostruire nel centro del bacino di sedimentazione una regione elevata con sedimentazione incompleta e scarsa, ehe e esistita dal Giurassico inferiore fino all'Eocene ed era circondata dall'una e dall’altra parte da bacini con sequenze sedimentarie complete e di grande spessore. Questa regione montuosa e ondulata e indicata con il nome di "Dorsale Toscana centrale” ( "Zentral toskanisches Hochgebiet") e corrisponde in parte al la "Dorsale costiera" ricostruita da BOCCALETTI & BORTOLOTTI (1965). Nell ‘Oligocene - (?)Miocene queste strutture morfologiche sono state divise in due blocchi rivolti l’uno contro l'altro. La fase paleoappeninica (tra Cretaceo inf. e sup.) e la fase ligure (Eocene), ehe nelle zone interne del Nord Appenino (Ligurico) hanno portato ad un notevole cambiamento dei bacini di sedimentazione, sono documentate nel la sequenza sedimentaria della Falda Toscana tramite la presenza di brecce, conglomerati e le prime deposizioni di grovacke. Nel Neocomiano e ancor piü con 1‘inizio della sedimentazione della Scaglia nell ’Albiano, contemporaneamente alla fase paleoappeninica, comincia nel bacino toscano la sedimentazione di calcari detritici da NE. Questi riempiono dapprima il bacino posto al lato orientale della "Dorsale Toscana centrale"; dall'Eocene in poi si diffondono anche nella zona occidentale. Questi calcari detritici della Scaglia Toscana mostrano strutture sedimentarie tipiche delle turbiditi. Essi devono venire considerati flysch cal carei i quali si intercalano alla sedimentazione normale. Per questo motivo la Scaglia Toscana non puo piü essere considerata una pura sequenza pelagica della fase preorogenica ma rappresenta, almeno in parte, giä il pieno stadio del flysch, durante l'orogenesi.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551 ; Sediment ; Geologie ; Oligozän
    Language: German
    Type: doc-type:book
    Format: 134
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  • 9
    Publication Date: 2024-04-08
    Description: Die Untersuchungen der Grundwasserbeschaffenheit und der hydrogeologischen Zusammenhänge erstrecken sich auf das nördliche Stadtgebiet von Berlin (West), das ein Teil des Einzugsgebietes der oberen Havel ist. Das betrachtete Grundwassersystem erfaßt die im Hangenden des mittel oligozänen Septarientons in normaler stratigraphischer Abfolge ausgebildeten Ablagerungen des Oberoligozäns, Miozäns und Pleistozäns Die Mächtigkeiten der auftretenden Schichtfolgen sind abhängig von einer durch Salzbewegungen verursachten Aufwölbung im NE und einer im W gelegenen Salz-Emigrationszone. Folglich treten die größten Mächtigkeiten (ca. 380 m) im W des Untersuchungsgebietes auf. Die pleistozänen Ablagerungen erreichen ihre größten Mächtigkeiten im Bereich einer Erosionsrinne, die im mittleren Teil des Untersuchungsgebietes bis in den Septarienton eingeschnitten ist. Die Betrachtung der Druck- und Fließverhältnisse zeigt sowohl für das tiefere, gespannte Grundwasser der tertiären Schichtfolgen als auch für den oberen Grundwasserleiter einen hauptsächlich nach SW gerichteten Grundwasserabstrom. Für die Potentialdifferenzen zwischen dem oberen und dem gespannten Grundwasser kann in den Bereichen großer Grundwasserentnahmen ein relatives Ansteigen der Druckfläche des tieferen Grundwassers erkannt werden. Die höhere Druckfläche des tieferen Grundwassers weist, in Abhängigkeit von der Durchlässigkeit der stauenden Schichten, auf ein Aufsteigen tieferer Grundwässer hin. Dies wird bekräftigt durch die Ergebnisse der geothermischen Untersuchungen, die für die entsprechenden Bereiche eine großflächige positive geothermische Anomalie erkennen lassen. Der Chemismus der untersuchten Grundwässer läßt im allgemeinen mit zunehmender Tiefe eine Abnahme der Gesamtmineralisation erkennen. Die durchschnittliche Gesamtmineralisation der tieferen Grundwässer liegt mit 15.07 mval/1 unter der des Grundwassers der pleistozänen Schichten (17.38 mval/1). Die räumliehe Betrachtung der Mineralisationsverteilung läßt für die tieferen Grundwässer im NE- und SE-Teil des Untersuchungsgebietes eine erhöhte Mineralisation erkennen, die hauptsächlich auf höhere Kalziumsulfatgehalte zurückzuführen ist. In westlicher Richtung kommt es, durch Reduktionsvorgänge, zu einer Abnahme der Mineralisation. Im tieferen Bereich der Rinne und in den oberoligozänen Schichtfolgen läßt sich das Auftreten von alkalihydrogenkarbonathaltigen Wässern erkennen, deren Entstehung auf Ionenaustauschvorgänge zurückzuführen ist. Die Spurenmetallgehalte zeigen im Grundwasser der tertiären Schichtfolgen, bedingt durch die auftretenden Gesteine, für die Elemente Aluminium, Kupfer und Zink deutlich höhere mittlere Gehalte. Die gegenüber dem Grundwasser der oberoligozänen Schichtfolgen höheren mittleren Bor-, Kupfer- und Nickelgehalte im Grundwasser der miozänen Schichten stehen in Verbindung mit der primären Anreicherung dieser Elemente in den organischen Ablagerungen des Miozäns. Für das Auftreten der Elemente Chrom (III), Strontium und Eisen lassen sich keine Unterschiede zwischen dem tiefen und dem oberflächennahen Grundwasserleiter erkennen.
    Description: The quality of groundwater and hydrogeological relationships of the northern part of the town of Berlin (West), a catchment area of the upper part of the river Havel, were investigated. The observed groundwater System belongs to the stratas above the middle oligocene "Septarienton", in the normal sequence of upper oligocene, miocene and pleistocene. The thicknesses of the occuring layers are influenced by a salt dorne in the NE and a rim syncline in the W, caused by salt tectonics. Consequently the greatest thickness (~380m) is found in the Western part of the investigated area. The pleistocene deposits obtain their greatest thickness in the area of an erosion channel which is in the middle of the investigated area, incised into the middle oligocene Septarienton. The investigations of the relations between artesian head and groundwater flow of the deeper confi ned groundwater in the tertiary strata and of the upper aquifer proved a groundwater flow mainly in southwestern direction. The potential differences between the upper and the confined groundwater shows in the areas of ground-water lowering a relative rising of the hydrostatic pressure of the deeper groundwater. The higher artesian head of the deeper groundwater points to a rise of deeper groundwater, dependent on the permeability of the less permeable layers. This is confi rmed by the results of the geothermical investigations, which show a great positiv geothermal anomal y for these areas. The Chemical composition of the investigated groundwater shows a decreasing total mineral isation with increasing depth. The average total -mineral isation of the deeper groundwater of 15.07 mval/1 lies beneath the level of the groundwater of pleistocene layers (17.38 mval/1). Spacial observations of the mineral isation-distribution show a higher mineral isation for the deeper groundwater in the NE- and SE-part of the investigated area, which is mainly based on a higher calcium-sulfat-content. In the W a decrease of mineral isation, caused by reduction processes, can be observed. In the deeper part of the channel and in the upper oligocene layers an occurrence of alkali-hydrogencarbonat-water, caused by ion-exchange reactions, is recognizable. Trace-metalls contents in the groundwater of the tertiary layers have a definite higher average content of the elements Al, Cu and Zn, caused by the occuring Sediments. The concentration of B, Cu and Ni is higher in the groundwater of the miocene layers than in the groundwater of the upper oligocene layers, this is caused by the primary enrichment of these elements in the organic deposits of the miocene. There are no differences recognicable between the upper and the lower aquifers concerning the occurrence of the elements Co(III), Sr and Fe.
    Description: Les recherches concernant la composition de l'eau souterraine et les relations hydro-geologiques Interessent la partie nord de la ville de Berlin (Ouest), qui fait partie de l'aire d'al imentation de la Havel superieure. Le Systeme de l'eau souterraine considere englobe les Sediments de l'oligocene superieur, du miocene et du pleistocene, surmontant strati graphiquement les couches de l'oligocene moyen (Septarienton). Les puissances des differentes series strati graphiques sont influencees par un bombement au Nord-Est, du ä une tectonique salifere, et par une zone d'emigration salifere situee a' l’ouest. En consfequence les puissances maximales (environ 380m) apparaissent dans la partie ouest du terrain analyse. Les formations du pleistocene atteignent leur plus grande epaisseur au niveau d'une gouttiere d'erosion pentue, encaissee dans la partie moyenne du terrain analyse jusqu'au Septarienton. L'observation des conditions de pression et d'ecoulement montre, tant pour l'eau souterraine profonde et captive des suites de couches tertiaires, tant pour les aquiferes superieurs, un ecoulement principalement vers le Sud-Ouest. Pour les differences de pression entre les eaux souterraines superieures et captives on note dans les terrains, desquels on preleve beaucoup d'eau, un soulevement relatif de la surface de pression de l'eau souterraine profonde. Le plus haut plan de pression de celle-ci indique donc que les eaux souterraines profondes montent en fonction de la permeabilite des couches accumulees. Ceci est renforce par les resultats des analyses geothermiques, qui montrent une anomal ie geothermique positive sur une grande surface des terrains en question. Les caracteri stiques hydrogeochimiques des eaux souterraines analysees font apparaTtre en general une diminution de la mineral isation totale en fonction de 1 ’augmentation de la profondeur. La mineral isation totale moyenne des eaux profondes souterraines est avec 15.07 mval/1 inferieure ä celle des eaux profondes des couches pleistocenes(17. 38 mval/1). La repartition horizontale de la mineral isation laisse apparaTtre pour les eaux profondes de la partie Nord-Est et Sud-Est du terrain analyse une mineral isation surelevee, qui est due principalement a une haute teneur en Sulfate de calcium. Vers 1 'ouest, la mineral isation diminue par l'effet de processus de rfeduction. Dans les terrains du fond de la gouttiere et dans les series de couches de l'oligocene superieur on remarque l'apparition d'eaux contenant du NaHCOp provenant du processus de changements des ions. Les teneurs de metaux traces dans les eaux souterraines des series tertiaires montrent nettement-conditionne par les roches y apparaissant- des valeurs moyennes elevees pour l’aluminium, le cuivre et le zinc. Les teneurs moyennes en bore, cuivre et nickel des eaux souterraines des couches du miocene, surelevees par rapport aux eaux souterraines des couches de l'oligocene superieur, sont en relation avec l'enrichissement primaire de ces elements dans les gisements organiques du miocene. En ce qui concerne la repartition des eie ments chrome( III), Strontium et fer aucune difference est notable entre les aquiferes profonds et ceux pres de la surface.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:553.79 ; Grundwasser
    Language: German
    Type: doc-type:book
    Format: 98
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  • 10
    Publication Date: 2024-04-18
    Description: Das Untersuchungsgebiet der vorliegenden Arbeit ist der westliche und nordwestliche Rand der Adriaplatte bis in den Bereich der Vortiefen nördlich und östlich des Apennins sowie der Kontaktbereich der Adriaplatte zur europäischen Platte im Westalpenbogen und im Gebiet des Ligurischen Meeres. Für dieses Areal werden Aufbau und Struktur der Erdkruste beschrieben.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.13 ; Geophysik ; Erdkruste ; Geothermische Anomalie
    Language: German
    Type: doc-type:book
    Format: 122
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  • 11
    facet.materialart.
    Unknown
    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-04-18
    Description: Die Erdkruste und der obere Erdmantel Westeuropas sind in den letzten 30 Jahren intensiv durch refraktionsseismische Messungen erforscht worden. Die Daten und Ergebnisse sind in zahlreichen Arbeiten veröffentlicht worden. Abgesehen von einigen regionalen Zusammenfassungen fehlt bislang jedoch eine überregionale Gesamtdarstellung dieses umfangreichen Materials. Es ist das Ziel dieser Arbeit, die in zahlreichen Publikationen verstreuten Einzeldaten und Ergebnisse zu sammeln, unter einheitlichen Gesichtspunkten auszuwerten und die Ergebnisse in einer Reihe von Karten darzustellen. Aus verschiedenen Publikationen, Forschungsberichten und den Archiven des geophysikalischen Institutes der Freien Universität Berlin wurden insgesamt 360 Sei smogrammon tagen in reduzierter Form (V = 6 km/s) gesammelt.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:554 ; Seismic refraction method
    Language: German
    Type: doc-type:book
    Format: 142
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  • 12
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-04-18
    Description: In der vorliegenden Arbeit wurde ein numerisches Verfahren für die zweidimensionale Simulation stationärer Strömung in porösen Medien entwickelt. Dabei können Modelle mit anisotroper Permeabilität und Wärmeleitfähigkeit ebenso berechnet werden wie Modelle in geneigten und gekrümmten Gebieten. Das Verfahren basiert auf einer Finite-Differenzen-Methode mit einem Schema 2. Ordnung (Il'in-Schema). Für das nichtlineare Gleichungssystem wird ein Iterationsansatz mit einer Art Mehrgittermethode verwendet. Um den großen Anwendungsbereich des entwickelten Verfahrens zu demonstrieren, wird es auf zwei unterschiedliche Fragestellungen aus der Hydrothermik und der Schneemetamorphose angewendet.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:550 ; Wärmeübertragung ; Schnee ; Porosität
    Language: German
    Type: doc-type:book
    Format: 118
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  • 13
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-07-02
    Description: Über den paläozoischen Sedimenten im Dakhla-Becken folgen überwiegend fluvio-kontinentale Sedimente des Mesozoikums, die sich aufgrund ihrer gleichartigen Ausbildung innerhalb des Beckens in Ost-West-Erstreckung verfolgen lassen. Die pauschal als "Nubischer Sandstein" bezeichneten klastischen Sedimente konnten in sechs Formationen gegliedert und ihre strati graphische Stellung weitgehend gesichert werden. Die Einheiten der Nubischen Gruppe heißen von unten nach oben: Six Hills Formation (Basal Clastics), Abu Ballas Formation (Lingula Shale), Sabaya Formation (Desert Rose Beds), Maghrabi Formation (Plant Beds), Taref Formation (Taref Sandstein) und Mut Formation (Variegated Shales). Sie sind fast ausschließlich der Kreide bis zum Maastricht zugehörig. Der Sedimentationsraum gehört zu einem sich nach Nordwesten vertiefenden Becken zwischen der Calanscio-Uweinat-Schwelle im Westen und dem Kharga-Upl ift im Osten. Die Sandstein-Formationen bestehen in der Körnerfraktion ausschließlich aus Quarz, Zirkon, Turmalin, Rutil und Leukoxen und zeigen bei den Tonmineralen eine absolute Kaolinitvormacht. Die überwiegend tonigen Formationen, mit unterschiedlichen Tonmineral-Vergesellschaffungen, deuten auf eine Sedimentation in einem flachen Epikontinentalmeer hin. Die Sedimente der Nubischen Gruppe entstammen Gebieten mit lateritischer Verwitterung. Die Resedimentation erfolgte unter gleichen Klimabedingungen, wie synsedimentäre Bodenbildung und Sesquioxid-Krusten zeigen. Die Faktoren-Analyse ergab folgende Elementgruppen: Ti, Nb, Zr und Cr: Elemente, die überwiegend in Schwermineralen auftreten ; Mn, Co, Ni und Cu: adsorptiv an Mn gebunden und in manganreichen Krusten angereichert ; Y, SE; an Tonminerale angelagerte Elemente ; Ca, Sr, Rb und Pb: an Tonminerale gebundene Elemente. Eisen konnte keiner dieser Gruppen zugeordnet werden. Da die fünf Elementgruppen in den Formationen der Nubischen Gruppe charakteristisch verteilt sind, ist eine Unterscheidung der Formationen aufgrund der Elementverteilung möglich.
    Description: The Paleozoic sediments within the Dakhla Basin are overlain by fluvio-continental sediments of Mesozoic age which can be traced in the. basin in east-west extension caused by their similar development. The clastic sediments, generally called "Nubian Sandstone", could be subdivided into six formations and their: stratigraphic position could be more or less assured. The units of the Nubia Group are named from the bottom towards the top as follows: Six Hills Formation (Basal Clastic Unit), Abu Ballas Formation (Lingula Shale Unit), Sabaya Formation (Desert Rose Unit), Maghrabi Formation (Plant Bed Unit), Taref Formation (Taref Sandstone Unit), and Mut Formation (Variegated Shale Unit). Stratigraphically they are nearly exclusively of Cretaceous up to Maastrichtian age. The area of sedimentation is a basin between the Calanscio-Uweinat Uplift in the west and the Kharga Uplift in the east. The bottom of the basin dips towards the northwest. The more sandy units contain as grains exclusively quartz, zircone, turmaline, rutile and leocoxene. The same units show as a clay-mineral an absolute predominance of kaolinite. The chiefly clayey units with a different association of clayminerals point at a sedimentation in a shallow epicontinental sea. The sediments of the Nubia Group are descended from regions with a lateritic weathering. The resedimentation took place under the same climatic conditions as it is shown by syn sedimentary development of soil horizons and sesquioxide crusts. The factor analysis caused the following groups of elements: Ti, Nb, Zr and Cr: elements which occur mainly in heavy minerals ; Mn, Co, Ni and Cu: elements which are bound adsorptively at Mn and are concentrated in crusts with a high content of manganese ; Y and R.E.E.: elements which are attached to clayminerals ; Ca, Sr, Rb and Pb: elements which are bound at clayminerals. Iron could not be associated with one of these groups. As the five groups of elements are distributed characteristically in the units of the Nubia Group, a differentiation of the units is possible based on the dissamination of the elements.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551 ; Nubischer Sandstein ; Stratigraphie ; Geochemie ; Sedimentologie
    Language: German
    Type: doc-type:book
    Format: 93
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  • 14
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    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-07-02
    Description: Das Sebkha-Gourine-System am Golf von Gabes in Süd-Tunesien wird in der vorliegenden Arbeit sedimentologisch, hydrogeologisch und geobotanisch beschrieben. Der für das Mittelmeer ungewöhnlich hohe Tidenhub bewirkt hier die Ausbildung eines sehr breiten Gezeitenbereiches. Das gemäßigt-aride Klima des Hinterlandes führt zur Bildung evaporitischer Minerale: in dem Sebkha-Bereich kommt es zur Ausscheidung von Gips-Lagen oberhalb des Grundwasserspiegels und zur Entstehung von temporären Halit- und Gipskrusten an der Sedimentoberf lache. Die gleichmäßig feinkörnigen, karbonatischen und silikatischen Sedimente sind marinen, fluviatilen und äolischen Ursprungs. Mit Hilfe der halophytischen Vegetationszonierung war eine flächenhafte Kartierung der Grundwasser-Salinitäten möglich. Anhand der Kalium-Gehalte konnten bei der chemischen Analyse der Sebkha-Grundwässer Lösungen marinen und kontinentalen Ursprungs voneinander unterschieden werden. Mit dem Trockenfallen während der grimaldischen Regression vor ca. 8000 Jahren entstand in einem ehemaligen Ästuar ein breiter Gezeitenbereich, dessen Faziesräume sich mit der zurückweichenden Küstenlinie stetig meerwärts verlagerten. Die in pleistozäne und mio-pliozäne Sedimente erodierte Hohlform wurde vom Kontinent her mit feinkörnigen Wadi-Sedimenten und vom Meer her mit Strandsand karbonatischer und silikatischer Zusammensetzung aufgefüllt. In Lagunen und im Oberen Gezeitenbereich kam es immer wieder zum Absatz feinkörniger Sedimente (Verlandung). Der heutige Zustand wird charakterisiert durch eine flache Küstenlagune, die insgesamt noch im Gezeitenbereich liegt und täglich trocken fällt. Dadurch ist eine Voranreicherung des Meerwassers durch Eindunstung und reduzierte Zirkulation (wie z. B. in der Laguna Madre, Texas) nicht möglich. Das max. 1000 m breite Intertidal ist durch massenhaftes Pflanzenwachstum ( Salicovnla fruticosa und Halocnenwn strobilaeeum ), dichte, lederartige Grünalgen -Matten und sil tig-tonige Sedimente gekennzeichnet. Die Salinität liegt im Bereich der Meerwasser-Konzentration. Der eigentliche Sebkha-Bereich mit nur gelegentlichen Überflutungen bei Sturmfluten reicht noch etwa 3000 m weit ins Landesinnere. Die Sedimente bestehen aus einer Wechsellagerung von dünnen Ton- und Algenschichten und Feinsand-Lagen aus umgelagertem Flugsand. Überflutungsdauer und -häufigkeiten reichen für eine effektive Infiltration des eindringenden Meerwassers in die porösen Sedimente. Die hohen sommerlichen Temperaturen und die starken, trockenen Winde erzeugen eine Verdunstungsrate von ca. 2000 mm/ Jahr, die einen überwiegend aufwärts gerichteten Grundwasserstrom bedingt. Durch die Evaporation werden im Grundwasser Salinitäten bis zu 30 % erreicht, so daß oberhalb des Grundwasserspiegels eine lagenweise Kristallisation von Gips ("Wüstenrosen") zu beobachten ist. Bei dem weiteren kapillaren Aufstieg entsteht eine oberflächennahe Mineralisation der unverfestigten, sandigen Sedimente in Form von feinen, unverwachsenen Gips-Plättchen ("disks"), die auf organische Substanzen und alkalische Verhältnisse hinweisen. An der Oberfläche kommt es zu dünnen Halit-Krusten und -Imprägnationen. Bei den meist im Winter auftretenden Sturmfluten und verstärkt durch die oberirdisch ablaufenden Niederschläge werden nur die Halit-Krusten wieder quantitativ aufgelöst und in das Meer zurücktransportiert. So kommt es ohne unterirdischen Abfluß einer angereicherten Lauge ("reflux") zur Entstehung einer geringmächtigen Gips-Lage in karbonatischen und silikatischen Sanden. Eine Dolomitisierung ist nicht zu beobachten. Die im Sebkha-Gourine-System beobachteten Sebkha-Prozesse folgen weitgehend dem von BUTLER (1969) für die Sebkhas am Persischen Golf aufgestellten "flood water recharge"-Modell , in dem die Salz-Bilanz durch die winterlichen Überflutungen geprägt wird. Das "evaporative pumping"-Modell nach HSÜ & SIEGENTHALER (1969) kann für das Untersuchungebiet ausgeschlossen werden.
    Description: This study describes the sedimentological, hydrogeological and geobotanical features of the Sebkha Gourine in the Gulf of Gabes, Southern Tunisia. The tidal spring range is exceptionally high for Mediterranean conditions and creates a very wide intertidal zone. Formation of evaporite minerals like gypsum and halite is due to the attenuated arid climate. Gypsum cristals are found in layers above the groundwater table. Crusts of halite and gypsum occur temporarily on the sebkha surface. The fine-grained carbonate and quartzose sediments are of marine, fluviatile and eolian origin. Zonation of halophytic vegetation was used as a tool for mapping groundwater salinities. Sebkha groundwaters of marine and continental origin were distinguished by their potassium content. An ancient estuary, carved into Pleistocene and Mio-Pliocene sediments, was filled after the "Grimaldic" regression (8000 BP). Continental fine-grained wadi sediments interlock with carbonate and quartzose beach sands. Minor lagoons and the upper intertidal zone were constantly being silted up. Even today a shallow coastal lagoon is still flooded daily. Therefore the effects of evaporation within the lagoon cannot be accumulated and only a slight increase can be observed in the salinity of sea water entering the sebkha. The intertidal zone extends well over 1000 m and is occupied by a living algal mat and in its upper parts by a dense halophytic vegetation (mainly Salicornia fruticosa and Haloenemum strobilaceun ). The salinities are within the range of sea water concentration. The sebkha itself extends well over 3000 m and is flooded only during spring tides. Sediments consist of gray and brown carbonate sands interlaminated with fine algal mats. These sediments are sufficiently porous to allow for effective infiltration of flood waters. Evaporation is high due to high summer temperatures and strong dry winds and creates an upward groundwater flow. Salinities rise to 30 % leading to massive gypsum cristallization ("desert roses"). Gypsum "disks" are found in unconsolidated surface sediments at shallow depths. Their untwinned habit is related to the presence of organic matter and alcaline conditions. The sediment surface is temporarily impregnated by a thin halite crust, which is removed by winter storm flooding and transported back into the sea. No underground backflow of enriched brine ("reflux") and associated dolomitization could be observed. The "flood water recharge "-model by BUTLER (1969) thus is applicable to the Sebkha Gourine area. The salinity balance is controlled by winter flooding and summer evaporation. The "evaporative pumping" -model by HSÜ & SIEGENTHALER (1969) on the other hand can be rejected for the area in consideration.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551 ; ddc:580 ; ddc:551.48 ; Sedimentologie ; Hydrologie ; Geobotanik
    Language: German
    Type: doc-type:book
    Format: 114
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  • 15
    facet.materialart.
    Unknown
    Reimer
    In:  Herausgeberexemplar
    Publication Date: 2024-07-02
    Description: Die Arbeit behandelt die in vielen Küstengebieten auf tretende Erscheinung des Eindringens von Meerwasser in den Untergrund des Binnenlandes und die daraus resultierende Grundwasserversalzung (Küstenversalzung). Zur Klärung dieser Frage wurden im ostfriesischen Küstengebiet seewärts und landwärts der Süßwasser-/Salzwassergrenze mittels spezieller Bohrungen aus Tiefen zwischen 5 und 300 m u.G. insgesamt 46 Grundwasserproben entnommen, der Stoffbestand analysiert, die Sauerstoff- und Schwefel -Isotopenverhältnisse ermittelt und die Radiokohlenstoffkonzentration bestimmt. Ergänzende Untersuchungen betrafen die Dynamik der Versalzungsvorgänge. Ein hydrochemisches Profil durch die Versalzungsfront zeigt, daß im Untersuchungsgebiet eine durch intrudiertes Meerwasser verursachte Versalzung bis zu 16 km landeinwärts der heutigen Küstenlinie und bis in einer Tiefe von 250 m u.G. nachzuweisen ist. Unterhalb dieser Tiefe ist eine zunehmende GrundwasserVersalzung durch hochmineralisierte Tiefengrundwässer zu beobachten. Der intrudierte Meerwasserkörper ist sowohl hinsichtlich Art und Konzentration der gelösten Salze als auch altersmäßig heterogen. Die Versalzung erfaßt gutdurchlässige quartäre wie geringdurchlässige tertiäre Ablagerungen. Die Form der Süßwasser-/Salzwassergrenze ist keine mehr oder weniger flach einfallende Fläche, sondern eine Verzahnung zwischen süßwasser- und salzwassererfüllten Schichten, so daß hochversalzte Wässer von Süßwässern unterlagert werden können. Die Versalzung des Grundwassers im Untersuchungsgebiet ist nicht das Ergebnis eines einheitlichen Vorgangs; auf Grund der hydrochemischen Untersuchungen und Radiokohlenstoffdatierungen sind innerhalb des durch intrudierte Meerwässer versalzten Bereichs mindestens 3 Salzwasserkörper zu unterscheiden, die zu verschiedenen Zeiten in den Untergrund eingedrungen sind. Zwischen dem Altersaufbau der Versalzungsfront und dem großklimatischen Geschehen der letzten 7000 Jahre scheinen Zusammenhänge zu bestehen.
    Description: This work deals with the intrusion of sea water into the underground of binnen lands and with the resulting groundwater salinization, which is a common phenomenon of many coastal areas. For the solution of this problem in the coastal areas of East Frisia in all 46 groundwater samples have been taken from special boreholes (depth between 5 and 300 m below surface) located seaward and landward of the fresh water-/salt water boundary. The mineral contents of the ground-water samples have been analysed, the isotope relations of oxygen and sulphur have been determined and the concentrations of radiocarbon have been assessed. Further investigations dealt with the dynamics of salinization processes. A hydrochemical section crossing the salinization front shows, that within the area of investigation salinization caused by sea water intrusion can be demonstrated up to 16 km landwards from the recent coast line and down to a depth of 250 m below surface. Below this depth an increasing salinization of highly mineralized deep groundwater can be observed. The intruded sea water body is very heterogenous regarding the kind and concentration of soluted salts as well as regarding its age. The salinization incorporates both the well permeable Quaternary layers and the less permeable Tertiary sediments. The form of the fresh-water/salt-water interface is no more or less slightly dipping plane, but an interfingering of layers with salt water and layers with fresh water; thus highly mineralized waters can be underlain by fresh waters. The salinization of the groundwater in the investigated area is not the result of a uniform process. On the base of the hydrochemical investigations and the radiocarbon datings within the area affected by sea-water intrusion at least three different salt water bodies can be distinguished which intruded at different times into the underground. Apparently a correlation exists between the age relations within the salinization front and the large scale climatic history of the last 7000 years.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:551.48 ; Versalzung ; Hydrochemie ; Grundwasser ; Küste
    Language: German
    Type: doc-type:book
    Format: 94
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  • 16
    Publication Date: 2024-07-02
    Description: Kernproben aus dem Bereich der Abu-Ballas-Formation (Lingula Shale, früher Teil des "Nubischen Sandsteins") in der Bohrung Mawhoub West 2 (Teufe 596 - 634 m) lieferten zwei praktisch ausschließlich kontinentale Palynomorphen-Assoziationen (vgl. Tab. 1). Beide Assoziationen sind charakterisiert durch einen hohen Anteil an Pollen von Ephedripites- (in der älteren Mikroflora ca. 22 %, in der jüngeren ca. 24 %) und Retimonocolpites-Arten (in der älteren Mikroflora ca. 24 %, in der jüngeren ca. 17 %). Unter den Sporen ist die Deltoidospora/Cyathidites- ruppz mit ca. 8 % vom Gesamtbestand der Mikrofloren am häufigsten. Die verschiedenen Retimonocolpites-Arten repräsentieren die aus Ägypten noch kaum dokumentierte frühe monosulcate, reticulate Phase der Angiospermen-Pollen-Evolution. Nach einem Vergleich mit der palynologischen Zonierung für die algerisch/tunesische Sahara (REYRE 1973) sowie unter Berücksichtigung des ebenfalls vorhandenen "Reticulatasporites" jardinus, der in S-Amerika und in Afrika auf das Intervall Apt/Cenoman beschränkt ist, können die Mawhoub-West-Mikrofloren ins Apt (bis unteres Alb?) gestellt werden.
    Description: Core samples from the borehole Mawhoub West 2 (depth 596 - 634 m) probably belonging to the Abu Ballas Formation (Lingula Shale, a part of the former "Nubian Sandstone") have yielded two nearly exclusively continental associations of palynomorphs (see Table 1). Both associations are characterized by a high percentage of Ephedripites (ca. 22 % in the lower microflora, ca. 24 % in the upper microflora) and Retimonocolpites (ca. 24 % in the lower microflora, ca. 17 % in the upper microflora). The Deltoidospora/Cythidites group is most frequent among the spores. It represents ca. 8 % of all spore/pollen grains found. The different species of Retimonocolpites represent the early monosulcate, reticulate phase of angiosperm pollen evolution hitherto hardly recorded from Egypt. After a comparison with the palynological zonation of the Algerian/Tunesi an Sahara (REYRE 1973) and taking into consideration the also occurring "Reticulatasporites" jardinus, which is restricted in South America and in Africa to the Aptian/Cenomani an , the Mawhoub West pollen and spores may be placed in the Aptian (until Lower Albian?).
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:561.13 ; Sporomorphae ; Kreide ; Nubischer Sandstein ; Palynologie
    Language: German
    Type: doc-type:book
    Format: 40
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  • 17
    Publication Date: 2024-07-01
    Description: Die Magmatite des Indosinia-Orogens in NE-Thailand wurden auf Grund von petrographischen und petrochemischen Untersuchungen durch die Einführung geochemischer Indizes nach folgenden Gesteinstypen und Sippen klassifiziert, sowie den entsprechenden magmatischen Phasen im orogenen Zyklus zugerechnet. - Alkali-Rhyolithe, die als Ignimbrite und Tuffe auftreten, sowie Dacite, die der Kalk-Alkali-Reihe angehören (frühe Phase des finalen Magmatismus) im Pak Chom-Si Chiang Mai Gebiet und im Loei-Chum Phae Gebiet. Letztere zeigen auch eine Tendenz zu einer höheren Alkalini tat (finaler Magmatismus) im Saraburi -Gebiet bzw. Loei-Tha Li Gebiet. - Andesite, die als Tuffe und Agglomerate vorliegen und der Kalk-Alkali-Reihe mit einem mittelstark pazifischen Charakter angehören (früher subsequenter Magmatismus) im Chum Phae-Lom Sak Gebiet. - Lenco-Basalte mit einem ophitischen Gefüge, die sowohl der Kalk- Alkali -Reihe (früher subsequenter Magnetismus) im Chiang Khan Gebiet, als auch einer Obergangsphase zur Alkali-Reihe (finaler Magnetismus) im Petchabun und Saraburi Gebiet zuzurechnen sind. - Granite-Monzonite, die der Kalk-Alkali-Reihe angehören (synorogener Magnetismus) im Loei-Chiang Khan Gebiet. Petrographische und geochemische Untersuchungsergebnisse, sowie paläogeographische und quantitative Voraussetzungen zeichnen die alkali-rhyolithischen Ignimbrite und Tuffe des Pak Chom-Si Chiang Mai Gebietes als potentielle Uran-Lieferanten aus. Folgende Untersuchungsergebnisse können als Begründung herangezogen werden: - Die ober-triassischen bis unter-jurassischen Ignimbrite und Tuffe des Pak Chom-Si Chiang Mai Gebietes sind dicht verschweißt und ihre Grundmasse liegt zu einem großen Teil in einem vollständig devitrifizierten Zustand vor, im Gegensatz zu den der Saraburi und Loei-Tha Li Gebiete, in denen die holohyalinen Anteile in der Grundmasse z.T. überwiegen. -Die Alkali-Rhyol ithe des Pak Chom-Si Chiang Mai Gebietes sind am höchsten differenziert, wie dem numerischen +Differentiationsindex (bis 16,65) zu entnehmen ist. - Sie zeigen die größten Gehalte an lithophilen Spurenelementen (Ba: 415 - 969 ppm; Rb: 109 - 213 ppm; Sr: 35 - 124 ppm; Zr: 77 - 209 ppm;) innerhalb vergleichbarer Differentiationsgrade der Alkali-Rhyolithe des Loei-Tha Li und Saraburi Gebietes. - Die Uran- und Lithium-Gehalte sind dagegen ungewöhnlich niedrig und liegen im Bereich von 2,09 - 3,6 ppm U bei einem Th/U-Verhältnis von 2,2 - 8,5 und 2,5 - 61,3 ppm Li (mit einem Mittelwert von 15,60 ppm Li), im Gegensatz zu den U- und Li-Gehalten des Loei-Tha Li Gebietes (U = 3,1 - 7 ppm; Th/U = 1 - 2; Li = 6,0 - 210,0 ppm, mit einem Mittelwert von 79 ppm Li) und des Saraburi Gebietes (U = 3,6 - 5 ppm; Th/U = 3,2 - 4,0; Li = 10,90 - 43,00 ppm, mit einem Mittelwert von 27,9 ppm Li). - Der xOxidationsgrad (0x0 = 0,51 - 0,99) ist mit dem U-Gehalt negativ korrelierbar im Gegensatz zu dem der Alkali-Rhyolithe in den anderen Gebieten. Zu ähnlichen, sich scheinbar widersprechenden, Untersuchungsergebnissen in Ignimbriten und Tuffen gelangten ROSHOLT et al. (1969), SCHATKOV et al. (1970) und ZIELINSKI (1978). Die geringen U-Gehalte werden auf die größere Mobilationsbereitschaft der leichtflüchtigen Elemente (Uran, Lithium, Fluor und Chlor) und deren Verbindungen während des Devitrifikationsprozesses im Zuge der langen Abkühlungszeit mächtiger Ignimbrit- und Tuffdecken zurückgeführt. Das in mobiler Phase vorliegende Uran (U6+) kann entweder supergene Anreicherungen innerhalb der Ignimbrit-Tuff-Decken bilden, die bei einer einsetzenden Erosion in Form von Uran-angereichertem Detritus weiter transportiert werden, oder direkt in migrierende Grundwässer gelangen. Der so eingetretene Verlust von Uran kann bei den Pak Chom-Si Chiang Mai alkali-rhyolitischen Ignimbriten und Tuffen mit einer Größenordnung von 46 - 52 % angegeben werden. Zu den von SCHATKOV (1970) ermittelten prospektionssignifikanten Faktoren (Devitrifikationsgrad, Th/U und 0x0 in Abhängigkeit vom U-Gehalt) kann als ergänzende Prospektionshilfe für supergene U-Anreicherungen in Ignimbriten bzw. Tuffen die geochemische Inkongruenz des U-Li-Gehaltes und des Differentiationsindex erwähnt werden. Im Gegensatz zur normalerweise positiven Korrelation von Oxidationsgrad, Thorium-Uran-Lithium-Gehalt und Differentiationsindex nimmt bei den Pak Chom-Si Chiang Mai Ignimbriten und Tuffen der U-Li -Gehalt bei den höchsten Differentiationsgraden ab. +Differentiationsindex: 1/3 Si + K - Ca - Mg xOxidationsgrad (0x0) : Fe3+ / Fe2+ + Fe3+ + Mn
    Description: According to the results of petrographic and petrochemical investigations using geochemical indices, the magmatites of the Indos inia-orogeny in NE-Thailand have been classified in the following rock types and associations as well as attributed to the corresponding magmatic phases of the orogenic cycles. - alkalirhyolithic ignimbrites and tuffs as well as dacites belonging to the calc-alkaline series (early phase of the final magmatism) in the Pak Chom-Si Chiang Mai and Loei-Chum Phae area. Both rock types tend toward alkalinity (final magmatism) in the Saraburi, that is Loei-Tha Li area. - andesitic tuff and agglomerates »belonging to the calc-alkaline series with a medium to strong Pacific character (early subsequent magmatism) in the Chum Phae-Lom Sak area. - leuco-basalts with an ophitic texture, belonging partly to the calc-alkaline series (early subsequent magmatism) in the Chiang Khan area and partly to a transitions phase of the alkaline series (final magmatism) in the Pete ha bun and Saraburi province. - granite-monzonites, belonging to the calc-alkaline series (synorogenic magmatism) in the Loei-Chiang Khan area. The petrographic and goechemical investigations, as well as the palaeographic and quantitative conditions suggest that the alkalirhyol ithic ignimbrites and tuffs of the Pak Chom-Si Chiang Mai area are the potential uranium source-rocks in the area under investigation. The following results support this assuption: - the Upper Triassic - Lower Jurassic alkalirhyolithes of the Pak Chom-Si Chiang Mai area consist of densely welded and nearly completely devitrified ignimbrites and tuffs, in contrast to those of the Saraburi and Loei-Tha Li areas, which show a high amount of holohyaline groundmass. - the alkalirhyolithes of the Pak Chom-Si Chiang Mai area are the most differentiated of all those investigated, as shown by the high numerical differentiationindex+ (16,65). - the content of lithophile trace elements (Ba: 415 - 969 ppm; Rb: 109 - 213 ppm; Sr: 35 - 124 ppm; Zr: 77 - 209 ppm;) is higher than that of the alkalirhyolithes exhibiting the same degree of the differentiation
    Description: thesis
    Description: DFG, SUB Göttingen
    Language: German
    Type: doc-type:book
    Format: 107
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  • 18
    Publication Date: 2024-07-03
    Description: Bei der Auswertung von' Fernerkundungsdaten wurde bisher davon ausgegangen, daß die untersuchten Objekte angenähert LAMBERT'sch reflektieren. Daß diese Annahme für Pflanzen falsch ist, wurde schon vor über 10 Jahren erkannt und seitdem mehrfach systematisch untersucht. In der vorliegenden Arbeit wurde in grundlegender Weise das Reflexions verhalten von natürlichen Gesteinsoberflächen untersucht. Besonderes Augenmerk wurde dabei auf die Richtungsverteilung der reflektierten Strahlung unter verschiedenen geometrischen Bedingungen gerichtet. So wurde als Simulation der natürlichen Geländebedingungen, wie sie etwa in den Alpen vorliegen, der Beleuchtungswinkel, die Probenneigung und der Detektorstand systematisch variiert und der Einfluß dieser Veränderungen auf das Reflexionsverhalten der Gesteine registriert. Die meisten Messungen erfolgten im Labor mit Hilfe eines speziell für diesen Zweck konstruierten Meßtisches, Als Proben dienten natürliche Gesteinsproben, die vorher unter Geländebedingungen gemessen worden waren. Bei den meisten Proben handelte es sich um Karbonatgesteine; wenige Ausnahmen, wie z,B. Sandsteine, wurden als Sonderfälle studiert. Bei zahlreichen Vergleichs- und Kontrollmessungen wurde versucht, den Zusammenhang zwischen Labor- und Geländemessungen herzustellen, Als wichtigstes Ergebnis wurde nachgewiesen, daß die Reflexion bei keiner der untersuchten Proben dem LAMBERT‘schen Reflexionsgesetz folgt: Der Reflexionsfaktor hängt also von den geometrischen Bedingungen ab, bei denen die Messung erfolgte, Sonnenstand, Hangneigung und Detektorstand sind als zusätzliche Parameter zu berücksichtigen. Die Ursachen für diese Richtungsabhängigkeit der Reflexion sind einerseits die innere Struktur − also die Ausbildung von primären Reflexionsflächen, die sich auf die Gesteinsoberfläche durchprägen − und andererseits die Rauhigkeit oder Relieftiefe der Oberfläche. Die größten Abweichungen vom LAMBERT'schen Reflexionsverhalten wurden bei größeren Zenitdistanzen, besonders bei schrägem bis streifendem Lichteinfall beobachtet. Die Konsequenzen für die Bildverarbeitung sind eindeutig: Bei der Klassifizierung und Identifizierung von Gesteinen aus Fernerkundungsdaten muß das Geländerelief und die Beleuchtungssituation mit berücksichtigt werden. Schon die unterschiedliche Beleuchtung auf verschieden geneigte Flächen gleicher Oberfläche erzeugt unterschiedliche Grauwerte für die einzelnen Flächen. Das gilt für jede Oberfläche, unabhängig von ihrem Reflexionsverhalten. Das richtungsabhängige oberflächenspezifische Reflexionsverhalten bewirkt (je nach der Winkel Konfiguration) eine weitere Veränderung der Grauwerte. In dieser Arbeit wurde gezeigt, wie die Korrektur der Beleuchtungsverhältnisse mit Hilfe eines digitalen Geländemodells erfolgen könnte. Die aus einer topographischen Karte entnommenen Höhendaten bilden die Grundlage für eine radiometrische Reliefkorrektur, bei der die durch schräge Beleuchtung verfälschten Grauwerte so korrigiert werden, daß die Ergebnisse einer Aufnahme ohne Relief entsprechen. Somit sind alle korrigierten Aufnahmen, unabhängig vom Sonnenstand, untereinander vergleichbar. Die Wirkung der Korrektur wurde an einem Modellgelände demonstriert. Eine Korrektur von vollständigen Aufnahmen, wie z.B, ganzen LANDSAT-Szenen, war bis zur Fertigstellung der Arbeit wegen der begrenzten Rechnerkapazität noch nicht möglich. Mit einer erweiterten Rechenanlage wird es aber in Zukunft möglich sein, eine ganze Szene in Hinblick auf ihre Beleuchtungsverhältnisse zu korrigieren. Der nächste Schritt, die gesteinsspezifische Korrektur mit Hilfe der ermittelten Labordaten, kann dann ebenfalls mit Hilfe des digitalen Geländemodells erfolgen.
    Description: During the evaluation of Remote Sensing Data it has been assumed up to now that the examined objects reflect approximately with LAMBERT'S law. In the case of plants it has been recognized over ten years ago that this assumption is wrong and this has led to numerous systematic examinations. In the present thesis the basics of the reflective behavior of natural rock surfaces was studied. Special emphasis was placed on the directional distribution of the reflected radiation under various geometric conditions, Natural terrain conditions, as found for instance in the Alps, were simulated by systematic variation of the angle of illumination, the sample inclination and the position of the detector. The influence of these variations on the reflective behavior of rocks was registered. Most of the measurements were done in the laboratory with the help of an apparatus which was constructed for this specific purpose. Samples of natural rocks were used; these were measured previously in the terrain. Most of these samples were carbonates; a few exceptions, such as sandstone, were also studied. During numerous comparitive and verifying measurements it was attempted to establish the correlation between laboratory and terrain measurements. As prime result, it was shown that none of the examined samples followed LAMBERT’S law of reflection. The reflection factor, therefore, depends on the geometric conditions at the time of measurement. Additional parameters that have to be accounted for are: position of the sun, terrain inclination and position of the detector. The reasons for this directional dependency of the reflection are on one hand the inner structure, i.e. the formation of primary reflection surfaces, which are imprinted on the rock surface, and on the other hand the roughness or depth of relief of the surface. The largest deviations from LAMBERT'S reflective law were noticed at larger zenith angles, particularly for sloping to glancing illumination. The consequences for the image analysis are clear-cut: during the classification and identification of rocks using remote sensing data the terrain relief and the illumination conditions have to be taken into account. Even a varying illumination of tilted areas of identical surfaces results in different gray values for the individual areas. This is true for any surface, regardless of its reflective behavior. The surface-specific directional reflectance gives rise to a further change in the gray values (depending on the angle configuration). In this thesis it has been shown how a correction of the illumination can be achieved with the help of a digital terrain model. The elevation data extracted from a topographic map give the basis for a radiometric relief correction. The gray values falsified by sloping illumination are corrected, such that the result is an image without relief. Therefore all corrected images, independent of the position of the sun, are comparable. The effect of this correction was demonstrated using a terrain model. Complete images such as LANDSAT scenes could not be corrected in this manner at the time of completing this thesis due to limited computer capacity. With a larger computer it will be possible in future to correct complete scenes in regard to the illumination conditions. The next step, a rock-specific correction with the help of data established in the laboratory, can also be achieved with the help of the digital terrain model.
    Description: thesis
    Description: DFG, SUB Göttingen
    Keywords: ddc:550 ; Gesteinsoberfläche ; Reflektometrie
    Language: German
    Type: doc-type:book
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  • 19
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    Biopolymers 19 (1980), S. 823-831 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the DNA-binding oligopeptide distamycin A on the B to A transition of DNA in ethanol/water solutions has been studied by means of CD. (The overbars indicate that it does not matter which particular form of the corresponding families is considered.) The results show that increasing the concentration of distamycin A reverses the A conformation (in 82% ethanol) to the B conformation due to its strong binding and stabilization of the latter. In accordance with previous data for pure aqueous solutions, a site size of 3.5 base pairs is obtained from the studies in water/ethanolic solutions. From the data on the B to A transition in the presence of distamycin A, we estimated the length of the cooperativity ν0 = 10 base pairs.The results demonstrate that the oligopeptide systems of distamycin, as well as those of netropsin, are effective stabilizers of the DNA B-conformation.
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  • 20
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrapeptides with proline in position 2, asparagine or leucine in position 3, and glycine in positions 1 and 4, with end groups free or blocked on the N-terminal side, were studied in their various ionic states in 2H2O and in Me2SO-d6 by 1H- and 13C-nmr. In order to clarify or refine some details, successive substitutions of the residues in these peptides with amino acids enriched to 85% in 13C, or to 85% 13C plus 97% 2H were carried out. The 1H and 13C chemical shifts as well as the 1H-1H, 13C-13C, and 13C-1H coupling constants and the signal intensities show strong similarity of behavior between the tetrapeptides of asparagine and leucine. The main conformational characteristics are (1) the almost total stabilization of the trans conformer in the type I β-turn structure when the peptide is in the zwitterion state dissolved in Me2SO. This is deduced from the 3JC3αH-N3H and the 3JC2′-H3α coupling constants, which both furnish a dihedral angle of φ3 = -90°, and from the positive value of the temperature coefficient of the glycine-4 amide protons, which suggests a type 4 → 1 hydrogen bond; (2) the evolution of cis and trans isomer fractions which change with the ionic state of the peptides in Me2SO, whereas they remain constant in aqueous solution; and (3) the conformation of the pyrrolidine ring as it follows the variations in cis:trans isomer populations together with the side-chain rotamer fractions of the residue in position 3. In the β-turn conformation the isomer cis is less abundant and the pyrrolidine ring is more flexible; this explains the perfect accommodation of the proline residue in position 2 of a bend. The interdependence of these phenomena where interactive forces play a predominant role underlines the importance of cooperative effects in the molecule. The results also suggest that the cis isomer of proline can adapt itself just as well as the trans isomer to position 2 of a type I β-turn.
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  • 21
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An algorithm is presented for the Monte Carlo simulation of the decay of fluorescence polarization from segmentally flexible molecules. Based on the random walk model of Brownian motion, the treatment explicitly follows the stochastic changes in the diffusion coefficients as the molecule bends. It includes the effects of a linear restoring force opposing the bending and the effects of hydrodynamic coupling between the translational, rotational, and bending motions. One application is presented: the simulation of anisotropy decay curves for hinged rods. A variety of decay curves are obtained, including single- and multiexponential behavior, and the following conclusions are reached: (1) increasing the flexibility is usually, but not always, accompanied by a more rapid rate of depolarization; (2) reducing the size of the fluorescent subunit will usually, but not always, increase the rate of depolarization; and (3) the complex interplay between the effects of molecular shape, relative sizes of the subunits, restoring force, and orientation of the transition dipoles renders it unlikely that any simple method can be used to interpret anisotrophy data without simulation. In particular, it is not possible to determine the extent of bending by fitting the data with the two-exponential approximation used by some investigators in the past.
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  • 22
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    Biopolymers 19 (1980), S. 977-990 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-nmr spectra of red seaweed galactans, belonging to the agar and carrageenan groups or having the “intermediate” type of structure, were interpreted on the basis of 13C-nmr spectra of model compounds. Signal assignments have been made for most of the known extreme structures of such galactans. 13C-nmr spectroscopy was shown to be a rapid and convenient method of structural analysis, which permits one to determine the type of galactan structure, the absolute configurations of its constituents (galactose and 3,6-anhydrogalactose), and the positions of the sulfate and O-methyl groups in a polysaccharide molecule.
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  • 23
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dielectric response of human umbilical cord hyaluronic acid in various environments has been studied at microwave frquencies using a resonant microwave cavity as a probe. Both the real and imaginary parts of complex dielectric constant and the loss tangent for hyaluronate solutions are obtained by utilizing equations for perturbation of a resonant cavity. Dielectric changes at room temperature have been observed in aqueous solutions of hyaluronic acid as a function of concentration ranging from 0 to 350 mg/ml. The data indicate the existence of ordered phases in hyaluronate solutions at selective concentrations, that is, exhibiting lyotropic-type transitions. Hyaluronate solutions at 1.5 and 3 mg/ml concentrations have been studied at various pH in the range of 6-8 and at constant ionic strength 0.1. A temperature-dependent transition in hyaluronate solution of 120 mg/ml concentration has been observed at physiological temperature. It is shown that this temperature-dependent behavior can be related to the orientational polarizability term in the Debye theory of polar molecules in liquids.
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  • 24
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    Biopolymers 19 (1980), S. 945-964 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1974, Zimm described a theory which predicts that the sedimentation coefficient of high-molecular-weight DNA will decrease as the rotor speed of measurement increases. In 1979, this theory was revised, and the new formula predicts speed-dependence effects that are substantially smaller than the predictions of the original version. This report describes the results of subjecting both the original and the revised versions of the theory to quantitative tests using a well-defined sucrose-gradient system and a DNA of known molecular weight (T4c DNA). T4c bacteriophage is a mutant, whose DNA contains the unmodified base cytosine, instead of the glucosylated hydroxymethylcytosine characteristic of the T-even bacteriophages, and has a molecular weight of 115 ± 3 × 106. The DNA of the wild-type phage (T4D+) was also used in some experiments.In addition to the quantitative tests, the experiments test for an effect first observed by Rubenstein and Leighton, which showed that the sedimentation coefficient measured for T2 DNA depended on the composition of the centrifuge tube used for the measurement (tube composition effect). It can be inferred from this observation that an interaction occurs between particle and tube wall during sedimentation, and this leads to a reduction in sedimentation velocity independent of the reduction in S described by Zimm's theory.The results show that in the range of 25,000-50,000 rpm, the original but theoretically incorrect form of the theory quite accurately describes the sedimentation behavior of both T4c and T4D+ DNA, although T4D+ was a special case in some respects. The revised (corrected) form of the theory predicts much less of a speed-dependence effect than that actually observed. The discrepancy between corrected theory and observation suggests that other factors (perhaps arising from the use of the swinging bucket rotor geometry) are causing the additional observed reduction in S20,w. However, the experiments show that the tube composition effect does not seem to be one of these.
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  • 25
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fixation of cis (NH3)2Cl2Pt(II) to poly(I)·poly(C) leads to the formation of two complexed species. One involves coordination to a single base (accounting for about 70% of the total platinum bound over the rb range 0.07-0.25) and the other to two bases which are not adjacent to each other but may be on the same strand and separated by a loop. Reaction of the platinum compound with poly(I) gives in addition to the above two species a minor one (about 15%, independent of rb over the range 0.05-0.30) in which the platinum is bound to two adjacent bases. The availability of such coordination reduces the dominance of the 1:1 species, which, however, remains the major one (ca. 55%).
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  • 26
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    Biopolymers 19 (1980), S. 1329-1344 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complex of CH3Hg(II) with the accessible cysteines of glyceraldehyde-3-phosphate dehydrogenase (GAPD, EC 1.2.1.12) from rabbit muscle has been studied by phosphorescence and optically detected magnetic resonance (ODMR) spectroscopy. The wavelength dependence of the phosphorescence decay kinetics has also been measured. Comparison of CH3Hg(II)-GAPD with GAPD by these methods shows that a specific optically resolved tryptophan site of GAPD is perturbed by the interaction with a nearby mercury atom. The perturbation on the luminescence and ODMR properties is typical of an external heavy-atom effect. Based on the x-ray diffraction structure of the lobster enzyme, it is proposed that the heavy-atom effect results from the interaction of tryptophan-310 with CH3Hg(II) bound to cysteine-281 in the rabbit muscle enzyme.
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  • 27
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    Biopolymers 19 (1980), S. 1415-1434 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The energy of interaction of a spermine molecule with the A- and B-forms of DNA has been calculated, assuming that the molecule of spermine is fixed in the narrow groove of the DNA helix with the formation of hydrogen bonds between the amino groups of spermine and the phosphate groups of DNA. The atom-atom potentials method was used. Optimal structures for the A-DNA-spermine and B-DNA-spermine complexes are suggested. It is shown that, in agreement with the experimental data, the interaction of the spermine molecule with the A-DNA is energetically more favorable than that with the B-DNA. Two main factors are responsible for this: (1) the distance between neighboring phosphates of the chain in A-DNA (which is about 1 Å less than that in B-DNA) corresponds better to the distance between the amino groups of the propyl part of spermine; and (2) the orientation of phosphate groups in A-DNA inside the groove is preferable for complex formation with spermine to the outside groove arrangement of the phosphates in B-DNA. These conclusions are further confirmed by the calculations for DNA-propane diamine complexes.
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  • 28
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of a synthetic analog of valinomycin, cyclo[-(D-Ile-Lac-Ile-D-Hyi)3-] (C60H102N6O18), has been determined by x-ray diffraction procedures. The crystals are orthorhombic, space group P212121, with cell parameters a = 11.516, b = 15.705, c = 39.310 Å, and Z = 4. The atomic coordinates for the C, N, O atoms were refined in the anisotropic thermal motion approximation and for the H atoms in the isotropic approximation. Values of standard (R) and weighted (Rw) reliability factors after refinement are 0.073 and 0.056, respectively. The structure is completely asymmetric. The cyclic molecular backbone is stabilized by six intramolecular hydrogen bonds N—H…O=C, five bonds being of the 4→1 type and one being of the 5→1 type. The side chains are located on the molecular periphery. The conformational state of isoleucinomycin in the crystal is intermediate between the corresponding crystalline states of valinomycin and meso-valinomycin. The observed conformation suggests that complexation could proceed via entry of the ion at the face possessing the L-Lac residues, the less crowded face.
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  • 29
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    Biopolymers 19 (1980), S. 1555-1566 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Possible conformations of lacto-N-tetraose, lacto-N-neotetraose, related disaccharides, and other milk oligosaccharides have been studied by an energy-minimization procedure using empirical potential functions. Lacto-N-tetraose favors a “curved” conformation, while lacto-N-neotetraose favors an approximately “straight” conformation. These two conformations differ mainly in the position of the terminal galactose residue with respect to the rest of the molecule. This difference explains the greater strength of lacto-N-neotetraose compared with lacto-N-tetraose in its ability to inhibit the cross-reaction of blood group P1 fractions with Type XIV pneumococcal antipolysaccharide. Although the favored conformation of lacto-N-tetraose (inactive) agrees with the model proposed by the earlier workers, that for lacto-N-neotetraose (active) differs. The favored conformations for the disaccharides galactose-β(1-4)-N-acetylglucosamine, galactose-β(1-3)-N-acetylglucosamine, and lactose are similar in overall shape, differing only in the nature and orientation of the side groups. This explains their nearly equal inhibitory activity. These theoretical models also explain the increased activity of lacto-N-fucopentaose I over that of lacto-N-tetraose and the relative activities of the substituted lactoses. The present studies suggest that it is the overall shape of the molecule which is important for activity, rather than the terminal β(1-4)-linked galactose residue alone.
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  • 30
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    Biopolymers 19 (1980), S. 1571-1585 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C spin-lattice relaxation times of poly(L-lysine) have been obtained at 67.9 MHz in aqueous solution and in a mixed solvent (40% methanol/60% water). A concomitant determination of the conformation by CD permits the correlation of conformation and rotational diffusion of the polymer. The dependence on pH of the spin-lattice relaxation times of the 13Cα and the side-chain carbon resonances reflects the diffusional motion in the random-coil conformation, in the helix-coil transition, and in the conformation of the α-helix. In the mixed solvent the reorientational correlation time of the Cα-Hα vector increases from τ = 0.37 nsec (random coil) to τ = 12.0 nsec (α-helix). In aqueous solution the correlation time of this vector increases from τ = 0.33 nsec (random coil) to τ ≫ 11 nsec. The reorientation rates of the side-chain methylene groups in the two solvents are markedly different. The reorientation of all methylene groups is reduced in the mixed solvent.
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  • 31
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid-state conformation of copolymers of β-benzyl-L-aspartate [L-Asp(OBzl)] with L-leucine (L-Leu), L-alanine (L-Ala), L-valine (L-Val), γ-benzyl-L-glutamate [L-Glu(OBzl)], or ∊-carbobenzoxy-L-lysine (Cbz-L-Lys) has been studied by ir spectroscopy and circular dichroism (CD). The ir spectra in the region of the amide I and II bands and in the region of 700-250 cm-1 have been determined. The results from the ir studies are in good agreement with data obtained by CD experiments. Incorporation of the amino acid residues mentioned above into poly[L-Asp(OBzl)] induces a change from the left-handed into the right-handed α-helix. This conformational change for the poly[L-Asp(OBzl)] copolymers was observed in the following composition ranges: L-Leu, 0-15 mol %; L-Ala, 0-32 mol %; L-Val, 0-8 mol %; L-Glu(OBzl), 3-10 mol %; and Cbz-L-Lys, 0-9 mol %.
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    Biopolymers 19 (1980), S. 1667-1673 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dry purified ligamentum nuchae elastin has been investigated for physical aging. The samples were quenched from a temperature (197°C) close to the softening point to a number of measuring temperatures ranging from -20 to +180°C. At each temperature, the small-strain torsional creep properties were determined at a number of elapsed intervals after the quench. Aging effects were found over the whole temperature range, and the creep and aging behavior of elastin turned out to be very similar to that of synthetic polymers.
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  • 33
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 34
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    Biopolymers 19 (1980), S. 1705-1713 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Covalently closed circular DNA can exist in different configurations known as circular, toroidal, and interwound. Changes among these forms can be made in several ways, including the insertion of dye molecules between adjacent base pairs, which tends to untwist the double-helical structure. The aim of this paper is to discuss these configurations, and the changes among them, in the context of classical elastomechanics. The concepts of twisting, linkage and writhing are explained. Simple experiments on a twisted linear-elastic rod are described, and it is shown that although the circular and interwound forms may be modeled in this way, the toroidal form does not occur, being mechanically unstable. Theoretical energy calculations by Levitt on bent and twisted DNA show that DNA exhibits a particular kind of nonlinear elasticity in which there is an unusual coupling between bending and twisting. The aim of the paper is to show qualitatively that this special kind of elasticity can stabilize the toroidal form of closed circular DNA.
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  • 35
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    Biopolymers 19 (1980), S. 1357-1374 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering, viscosity, and sedimentation experiments on aqueous solutions of k-carrageenan show that this sulfated polygalactose is an expanded flexible random coil. This expansion is due to long-range interactions that are predominantly electrostatic. Extrapolation of viscosity data to infinite ionic strength provided values for the intrinsic viscosity which were subjected to the Stockmayer-Fixman analysis, giving a value for the Mark-Houwink coefficient under theta-conditions, Kθ, of 0.27. The characteristic ratio, C∞, under these conditions is 7.8, and the conformation factor σ is 2. In a solution of 0.118 ionic strength, where a Mark-Houwink exponent aη of 0.86 is found, the radii of gyration calculated from viscosity data are lower than those found from the angular dependence of scattered light. On the other hand, the radius of gyration found from the sedimentation rate agrees well with the light-scattering radius. The relations between molecular parameters are corrected for the poly-dispersity of the sample.
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    Biopolymers 19 (1980), S. 1407-1414 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 37
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    Biopolymers 19 (1980) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 38
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    Biopolymers 19 (1980), S. 1475-1489 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An approximate analytic expression for the translational friction coefficient of a toroid modeled as a continuous shell of frictional elements is derived using the Kirkwood approximation. The accuracy of this expression was determined by comparing the friction coefficients predicted by it to those predicted by extrapolated shell-model calculations using the modified Oseen tensor. To show that these calculations do indeed yield the correct friction coefficients, actual translational friction coefficients were determined by observing settling rates of macroscopic model rings or toroids in a high-viscosity silicone fluid. Our conclusion is that the approximate expression yields friction coefficients that are about 1.5-3% low for finite rings. For thin rings, a comparison is also made with the exact result of Yamakawa and Yamaki [J. Chem. Phys. 57, 1572 (1972); 58, 2049 (1973)] for the translational friction of plane polygonal rings. This comparison shows that the approximate expression yields results which are low by 2-3% unless the rings are extremely thin, in which case the error is larger. In the limit of an infinitely thin ring the approximate expression reduces to the Kirkwood result [J. Polym. Sci. 12, 1 (1954)], which is low by 8.3%. We discuss briefly how this work may be useful in determining the structure of DNA compacted by various solvent-electrolyte systems and polyamines.
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    Biopolymers 19 (1980), S. 1451-1474 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Internal Brownian motions of clean φ29 and λ-DNAs have been studied using photon-correlation techniques at both visible (λ0 = 632.8 nm) and uv (λ0 = 363.8 nm) wavelengths. The present dynamic light scattering data, which extend to K2 = 19 × 1010 cm-2, can in every case be satisfactorily simulated by a Rouse-Zimm model polymer with an appropriate choice of the three model parameters. The effects of pH, salt concentration, single-strand breaks, and molecular weight on those model parameters have also been investigated. Intact clean DNAs exhibit surprisingly little variation with pH from 7.85 to 10.25, with salt concentration from 0.01 NaCl to 5.4M NH4Cl, or with molecular weight or GC content. The single-strand breaks have no effect at pH 9.46, but produce dramatic changes in the model parameters at pH 10.0 and 10.25, indicating the introduction of titratable joints at those pHs. The failure of either single-strand breaks or a large change in GC content to alter the model parameters in the neutral pH range is a strong indication that local denaturation is not required for those flexions and torsions that dominate the relaxation of fluctuations in the scattered light. The Langevin relaxation time for the slowest internal mode of a particular Rouse-Zimm model derived from the dynamic light scattering data is compared with pertinent literature data extrapolated to the same molecular weight. The present algorithm for determining model parameters from the light-scattering Dapp vs K2 curve actually yields a Langevin time in fairly good agreement with the literature value. For unknown reasons the light-scattering D0 values generally exceed those obtained from the molecular weight and sedimentation coefficient by about 20%.
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    Biopolymers 19 (1980), S. 1507-1515 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman spectra of polyribouridylic acid excited in the uv region, from 363 to 290 nm, are reported. The conformational changes of the polymer from random coil to ordered structure with stacked bases at high and low temperature, respectively, are reflected by important changes in the Raman line intensities; this Raman hypochromism is itself a function of the excitation wavelength - its profile has been determined and shows negative values in the region of 290 nm (near resonance), i.e., hypochromism becomes hyperchromism. Thus the knowledge of the hypochromism excitation profile is important in following order-disorder transition of a polymer using resonance Raman spectroscopy. Theoretical attempts are proposed for explanation, involving not only the relative variations of the molar extinction coefficient on the order-disorder transition of the polymer, but also the damping factors of the vibronic levels. The theoretical curve is found to fit adequately the experimental data over the excitation range, using only the frequency of the O-O transition of uracil and a vibronic linewidth of 2200 cm-1.
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    Biopolymers 19 (1980), S. 2177-2190 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preferential interaction of sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) with the solvent components in water/2-chloroethanol mixtures has been determined using density-increment measurements. The degree of preferential interaction was deduced from the density increments at constant molality of 2-chloroethanol and at constant chemical potential of 2-chloroethanol. Sodium poly(α-L-glutamate) and poly(α-L-glutamic acid) are both preferentially hydrated in the whole range of solvent composition. A dehydration process occurs during the 2-chloroethanol-induced coil-to-helix transition of sodium poly(α-L-glutamate). This dehydration process was attributed to the release of some moles of water from the neighborhood of the peptide bond during the nucleation of the helix. After the conformational transition, sodium poly(α-L-glutamate) is solvated by one 2-chloroethanol molecule. The location of water and 2-chloroethanol molecules in the different parts of the residue (more polar and less polar portions) is also discussed.
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    Biopolymers 19 (1980), S. 2223-2245 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex formation between tryptamine and mononucleotides and dinucleoside phosphates containing adenine and/or cytosine has been studied at five pD's ranging from 1.1 to 7.4 by proton magnetic resonance spectroscopy. Chemical shifts of base ring protons and the ribose anomeric proton in the nucleotides and indole ring protons in tryptamine were monitored and their changes with pD and intermolecular interactions interpreted qualitatively. Stacked complexes were found to exist at all pD's in the range studied. Complex geometries differ depending on pD. An electrostatic interaction between the tryptamine amino group and the nucleotide phosphate group contributes to complex formation above pD 4 but is not strong enough to shift the dinucleoside phosphate equilibrium towards the unstacked conformer.
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    Biopolymers 20 (1981), S. 169-185 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The IR data for the R1 CO-O-CHR2-CO-NHR3 derivatives are interpreted in terms of a H…π interaction involving the N—H bond and the π orbitals of the ester function and giving rise to a high ν(C=O) frequency and a low ν frequency. The resulting molecular conformation corresponds to the angular values φ # -90°, ψ # 0°. The H…π interaction in MeCO-L-Lac-NHMe is highly destabilized by water and aprotic solvents but is retained in methanol. Considering the high ν(C=O) ester or amide frequency of the middle function in β-folded depsipeptide or peptide sequences, it may be supposed that the residue indexed i + 2 in β turns experiences a H…π interaction which has a stabilizing effect on β turns. Some examples concerning valinomycin and some model compounds are discussed.
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  • 44
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    Biopolymers 20 (1981) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 45
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    Biopolymers 20 (1981), S. 251-268 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The difference between the theories of Manning, on the one hand, and of Odijk and Skolnick and Fixman, on the other, for the polyelectrolyte contribution to the persistence length of DNA is shown to arise entirely from a subtle geometrical error in the theory of Manning. The corrected theory of Manning predicts a negligible polyelectrolyte contribution in 1.0M NaCl and only 33 Å in 0.01M NaCl, thus giving a change in total persistence length by a factor of only 1.07 over that range, in agreement with Odijk. Pertinent data in the literature indicate that the persistence length must change by a factor of ≤ 1.6 between 1.0 and 0.01M NaCl, and very likely by less than a factor of 1.4. Evidently, the intrinsic rigidity of the uncharged double-strand filament dominates the bending rigidity at NaCl concentrations above 0.01M.
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  • 46
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of L-3,4-dehydroproline, t-butoxycarbonyl-L-3,4-dehydroproline amide, and acetyl-L-3,4-dehydroproline amide have been determined. L-3,4-Dehydroproline is orthorhombic with a = 16.756, b = 5.870, c = 5.275 Å, and Z = 4; t-butoxycarbonyl-L-3,4-dehydroproline amide is orthorhombic with a = 6.448, b = 8.602, c = 21.710 Å, and Z = 4; acetyl-L-3,4-dehydroproline amide is monoclinic with a = 4.788, b = 10.880, c = 7.785 Å, β = 105.25°, and Z = 2. The final R value for the L-3,4-dehydroproline is 0.046 based on 529 reflections; for t-butoxycarbonyl-L-3,4-dehydroproline amide, 0.050 based on 792 reflections; and for acetyl-L-3,4-dehydroproline amide, 0.058 based on 632 reflections. The structures clearly establish that the free amino acid exists in the zwitterionic form in the crystalline state. The molecular conformations of the t-Boc and acetyl derivatives consist of two planes: one involving the primary amide and the other the remaining atoms of the molecule. The acetyl-L-3,4-dehydroproline amide contains a tertiary amide bond in the cis conformation. To the best of our knowledge, this is the first example of a cis bond in an acetyl derivative of an amino acid or peptide. At variance with the previously reported proline amides, which present φ and ψ values corresponding to those of a right-handed α-helical conformation (conformation A), the t-Boc and acetyl derivatives both have φ and ψ values corresponding to a collagenlike conformation (conformation F).
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  • 47
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    Biopolymers 20 (1981), S. 359-371 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of thermally denatured Type I collagen has been studied using laser light scattering. The results indicate that the diffusion coefficients of α-chains and β- and γ-components are 1.550 ± 0.08 × 10-7, 1.000 ± 0.05 × 10-7, and 0.835 ± 0.04 × 10-7 cm2/sec, respectively, at temperatures between 20 and 40°C. It is concluded from diffusion data that these species have hydrodynamic radii of about 13.8 nm (α-chain), 21.5 nm (β-component), and 25.7 nm (γ-component), consistent with previous studies of thermal denaturation by light scattering. It is also concluded, based on volume calculations, that a large volume increase occurs when the triple helix unfolds. Homodyne correlation functions for two component mixtures of α-chains and β-and γ-components appeared to decay exponentially. In all but one case discussed the correlation function could be fitted with a single component having a translational diffusion coefficient which was an intensity weighted average of the diffusion coefficient of each component present.
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  • 48
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    Biopolymers 20 (1981), S. 387-397 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroic spectra and oscillator strengths of the π-π transition near 190 nm are calculated for helical (Gly)6 and (Ala)6 at 30° intervals of the backbone torsion angles (φ,ψ) over the range -180° ≤ φ ≤ -60°, -60° ≤ ψ ≤ 180°, using the partially dispersive normal mode treatment of the dipole interaction model. Polarizabilities of atoms and the NC′O group are those determined semiempirically in previous studies. Calculations for (Ala)6 at (φ,ψ) angles corresponding to the α-helix, the poly(Pro) II helix, a collagen single helix, a poly-(MeAla) helix, and single β-helices are found to agree well with most of the available experimental data.
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  • 49
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of the fluorinated antimalarial drug fluoroquine [7-fluoro-4-(diethyl-amino-1-methylbutylamino)quinoline] with DNA, tRNA, and poly(A) has been investigated by optical absorption, fluorescence, and 19F-nmr chemical-shift and relaxation methods. Optical absorption and fluorescence experiments indicate that fluoroquine binds to nucleic acids in a similar manner to that of its well-known analog chloroquine. At low drug-to-base pair ratios, binding of both drugs appears to be random. Fluoroquine and chloroquine also elevate the melting temperature (Tm) of DNA to a comparable extent. Binding of fluoroquine to DNA, tRNA, or poly(A) results in a downfield shift of about 1.5 ppm for the 19F-nmr resonance. The chemical shift of free fluoroquine depends on the isotopic composition of the solvent (D2O vs H2O). The solvent isotope shift is virtually eliminated by fluoroquine binding to any one of the nucleic acids. 19F-nmr relaxation experiments were carried out to measure the spin-lattice relaxation time (T1), 19F{1H} nuclear Overhauser effect (NOE), off-resonance intensity ratio (R), off-resonance rotating-frame spin-lattice relaxation time (T1ρoff), and linewidth for fluoroquine in the nucleic acid complexes. By accounting for intramolecular proton-fluorine dipolar and chemical-shift anisotropy contributions to the fluorine relaxation, all of the relaxation parameters for the fluoroquine-DNA complex can be well described by a motional model incorporating long-range DNA bending on the order of a microsecond and an internal motion of the drug on the order of a nanosecond. Selective NOE experiments indicate that the fluorine in the drug is near the ribose protons in the RNA complexes, but not in the DNA complex. Details of the binding evidently differ for the two types of nucleic acids. This study provides the foundation for an investigation of fluoroquine in intact cells.
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  • 50
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Empirical conformational energy calculations have been carried out for N-methyl derivatives of alanine and phenylalanine dipeptide models and N-methyl-substituted active analogs of three biologically active peptides, namely thyrotropin-releasing hormone (TRH), enkephalin (ENK), and luteinizing hormone-releasing hormone (LHRH). The isoenergetic contour maps and the local dipeptide minima obtained, when the peptide bond (ω) preceding the N-methylated residue is in the trans configuration show that (1) N-methylation constricts the conformational freedom of both the ith and (i + 1)th residues; (2), the lowest energy position for both residues occurs around φ = -135° ± 5° and ψ = 75° ± 5°, and (3) the αL conformational state is the second lowest energy state for the (i + 1)th residue, whereas for the ith residue the C5 (extended) conformation is second lowest in energy. When the peptide bond (ωi) is in the cis configuration the ith residue is energetically forbidden in the range φ = 0° to 180° and ψ = -180° to +180°. Conformations of low energy for ωi = 0° are found to be similar to those obtained for the trans peptide bond. In all the model systems (irrespective of cis or trans), the αR conformational state is energetically very high. Significant deviations from planarity are found for the peptide bond when the amide hydrogen is replaced by a methyl group. Two low-energy conformers are found for [(N-Me)His2]TRH. These conformers differ only in the φ and ψ values at the (N-Me)His2 residue. Among the different low-energy conformers found for each of the ENK analogs [D-Ala2,(N-Me)Phe4, Met5]ENK amide and [D-Ala2,(N-Me)Met5]ENK amide, one low-energy conformer was found to be common for both analogs with respect to the side-chain orientations. The stability of the low-energy structures is discussed in the light of the activity of other analogs. Two low-energy conformers were found for [(N-Me)Leu7]LHRH. These conformations differ in the types of bend around the positions 6 and 7 of LHRH. One bend type is eliminated when the active analog [D-Ala6,(M-Me)Leu7]LHRH is considered.
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  • 51
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on steric and electrostatic considerations, the prerequisites for binding to DNA via the intercalation mechanism are proposed. Steric contour energy curves are presented to demonstrate the region inaccessible to an intercalant. They are calculated with a 6-n (n = 14) potential. This method is a soft potential analog of an excluded-volume approach. Electrostatic contours on the steric surface illustrate the relatively positive and negative regions of the binding site. The principal intercalation sites, predicted to fit into B-DNA via a tetramer-duplex unit, and the unconstrained dimer-duplex units, obtained in crystal structures, are examined. These contours illustrate the requirements of size, conformation, and net atomic charges necessary for intercalation and optimum binding. Based on the limited space available for intercalation by the presence of the backbone and the maximum base-pair separation of 8.25 Å, an Essential Metabolite Exclusion Hypothesis is presented.
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  • 52
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    Biopolymers 20 (1981), S. 345-357 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In carbonate buffer at pH 10.5, a transparent solution of poly(L-lysine HBr) was obtained up to fairly high concentration of 3 g/dl at room temperature. The hydrodynamic behavior of the solution has been studied by sedimentation analyses and viscosity measurements. A dimer form for high concentrations and a monomer form for low concentrations were inferred. The dimer and monomer forms were assigned to a β-structure and α-helix, respectively, based on the CD and optical rotary dispersion spectra. Using CD spectroscopy, a reversible transition between α-helix and β-structure was observed as a function of either poly(L-lysine HBr) concentration or temperature. An aggregated form which was assigned to the antiparallel pleated sheet appeared at 50°C on the basis of its ir spectrum.
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  • 53
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    Biopolymers 20 (1981), S. 707-718 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Observations of induced circular dichroism (CD) bands in chloroform solution demonstrate the formation of specific, asymmetric complexes of the aromatic ligands 2-pyridone and 2,6-dichlorobenzoic acid with cyclic dipeptides of the general formula cyclo(L-Pro-X). The induced CD changes sign with the configuration of X due to subtle influences of the side chain on the geometry of the complex. Computations of interaction energies suggest that a plausible model for the complex of an aromatic ligand with the -CONH- of the cis secondary amide is a nearly planar arrangement of six heavy atoms in a ring containing two hydrogen bonds. The observed CD is matched by that computed for a tilt of the aromatic ligand toward the side chain of X. Binding constants were determined from the induced CD as a function of ligand concentration. For dichlorobenzoic acid these are about 450m-1 for the secondary amide and 50m-1 for the tertiary amide. For pyridone the binding constant is about 45m-1 for either the secondary or tertiary amide. For comparison self-dimerization constants determined by vapor-pressure osmometry in chloroform solution at 25°C are 870, 350, 50, and 20m-1 for pyridone, benzoic acid, dichlorobenzoic acid, and cyclo(L-Pro-Gly), respectively.
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    Biopolymers 20 (1981), S. 803-816 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton and phosphorus nmr have been used to investigate the double-helical structures of polyriboadenylic acid [poly(A)] formed in acidic solutions (pH 〈 6). The results obtained at low pH (∼4.5) are consistent with the model for the acid poly(A) double helix proposed by Rich [Rich, A., Davies, D. R., Crick, F. H. C. & Watson, J. D. (1961) J. Mol. Biol. 3, 71-86]. Other models that have been proposed are inconsistent with the nmr data. The nmr measurements have also been used to examine the conformation of poly(A) helix in the half-protonated state. Although the base-stacking arrangement of this state is similar to that observed in the more extensively protonated low-pH state, the phosphate backbone conformation is different from that found in either the neutral or low-pH structures.
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  • 55
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the near-uv CD spectrum of lysozyme was carried out in the presence and absence of the inhibitor tri-N-acetylglucosamine, and theoretical chiroptical calculations based on the tetragonal crystal structure of the enzyme and the enzyme-inhibitor complex were performed. The results of these calculations indicate that the near-uv CD spectrum of lysozyme can be adequately explained in terms of negative rotatory strengths arising from the tryptophan 1La (293-300 nm) and the disulfide n-σ* bands (250 rm), and positive rotatory strength contributions from the tryptophan 1Lb bands (291 nm) and the tyrosine 1Lb bands (275 nm). Contributions to the rotatory strength of each band were approximated in terms of specific interactions between chromophores. It was found that the rotatory strength of most of the near-uv transitions arises primarily from coupling interactions involving other side-chain chromophores and amide groups which are in close proximity. Changes which are observed in the lysozyme CD spectrum on binding of tri-N-acetylglucosamine may be explained in terms of changes in the rotatory strength which result from interactions of the 1La transitions of the active-site tryptophans with the acetamide groups of the inhibitor. The reasonable agreement which is found between the experimental and calculated rotatory strengths implies that the crystal conformation of lysozyme must resemble the solution conformation.
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  • 56
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    Biopolymers 20 (1981) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    Biopolymers 20 (1981), S. 39-51 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the effects of some organic cosolvents (monohydric alcohols and amides) on the reaction of hemoglobin with oxygen. We present evidence showing that our data can be analyzed within the framework of the Monod-Wyman-Changeux model and that the main effect of cosolvents is to alter the T ⇄ R conformational equilibrium of hemoglobin, without significantly affecting the intrinsic oxygen dissociation constants. Following a previously described phenomenological approach, the overall effects have been separated into effects related to the variation of the bulk dielectric constant of the solvent and effects not related to the variation of this constant.
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  • 58
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    Biopolymers 20 (1981), S. 65-88 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectroscopic properties (uv, CD, nmr) of histidine, glycylhistidine, histidylglycine, glycylhistidylglycine have been investigated in water and methanol in the temperature range 200-320 K in order to obtain information about their conformational equilibria. This analysis has been carried out for the different ionic forms of the compounds, in order to evaluate the influence of the ionization state of the carboxyl, histidyl, and amino groups on the rotamer distribution of the histidyl side chain (as evaluated from proton nmr analysis) and on the overall molecule (as judged from CD spectra). On the basis of certain approximations and from the temperature dependence of the proton nmr resonance, the thermodynamic parameters (ΔH° and ΔS°) characterizing the conformational equilibrium of the hystidyl side chain have been evaluated for the different structures and ionization states. Relatively large entropy differences between the rotamers are obtained in some cases. The data of the sidechain rotamer population, as determined by nmr, have been analytically correlated with the CD data, and in the case of hystidine and histidylglycine in basic solution, first-approximation values for the ellipticity of the single conformers have been evaluated. Finally, in the example of glycylhistidine and histidylglycine in basic solution, it is shown how the data obtained from the different experimental approaches (nmr and CD), as well as from theoretical energy calculations, converge to characterize the most stable conformation in solution.
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  • 59
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photon-correlation spectroscopy is a powerful technique for measuring the translational diffusion coefficient of particles and macromolecules in solution. In the study described here, this technique was used to analyze a specific dimerization process involving the association of two tRNA molecules through complementary anticodons. The tRNAs used in the analysis were E. coli tRNA2Glu and yeast tRNAPhe. The experimental data on the concentration dependence of the observed diffusion constants are shown to agree well with theoretical predictions. From these data, the equilibrium constant of the association reaction was determined for dimers formed over a wide range of temperatures and in several different solution conditions. In solutions of 0.1M ionic strength at 22°C, the equilibrium constants vary from 1 × 105M-1 in the absence of magnesium to 1.5 × 106M-1 in 10 mM Mg+2. The enthalpy and entropy changes for dimer formation in the absence and presence, 5 and 10 mM, of magnesium have been obtained from the temperature dependence of the equilibrium constant. The results show that both ΔH and ΔS contribute to the free energy of binding and that their relative contributions are similar for each solution condition evaluated.
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  • 60
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    Biopolymers 20 (1981), S. 231-235 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Biopolymers 20 (1981), S. 237-240 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 20 (1981), S. 243-247 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 63
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A conformational quantum-mechanical study of (Gly-Phe-Pro) and (Gly-Pro-Phe) repeating tripeptide sequences has been carried out with the PCILO method. Using appropriate molecules as a model, we investigated the conformational possibilities of each in situ residue. Computations have been done taking into account the two typical pyrrolidine ring puckering and the most favorable orientations of the phenylalanyl side chain. Major conclusions drawn from this study are that the phenylalanyl can be accommodated at both second and third positions in the sequence without preventing the formation of triple-helix conformation. However, the analogy observed between the rotational possibilities around the second residue of Gly-Pro-Pro and Gly-Phe-Pro indicates that phenylalanyl in the second position favors the triple-helix formation.
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  • 64
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    Biopolymers 20 (1981), S. 327-343 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of the nucleosome core particle in solution has been studied by neutron scattering using the full-contrast variation technique, which reduces the experimental spectra to three fundamental scatter functions holding information on shape and structure. Systematic calculations of the fundamental scatter functions expected from proposed core-particle models have been compared with the observed functions and show that the neutron-scattering criteria severely restrict the number of models which can be valid for the structure in solution. The best model for the core particle in solution has a hydrophobic histone core about which 1.7 ± 0.1 turns of DNA are wrapped at a pitch between 3.0 and 3.5 nm. This core contains most of the histone and has an average thickness of 4 nm and diameter 6.4-7.5 nm. While solution scattering is not able to specify uniquely the actual shape of the core to high resolution, all models which are possible for the shape of the core to a resolution justified by the data have been considered. It is clear that cylindrical or wedge shapes compatible with the above dimensions are valid structures. A hole probably penetrates the histone core, but the data do not allow a diameter greater than 1 nm. Available evidence suggests that about a quarter of the total histone is outside the core.
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  • 65
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relationship between published vicinal proton-proton coupling constants and the pseudorotation properties of the pyrrolidine ring in L-proline, 4-hydroxy-L-proline, 4-fluoro-L-proline, and several linear and cyclic model proline peptides is investigated. Compared to earlier studies, several important improvements are incorporated: (1) a new empirical generalization of the classical Karplus equation is utilized, which allows a valid correction for the effects of electronegativity and orientation of substitutents on 3JHH; (2) an empirical correlation between proton-proton torsion angles and the pseudorotational parameters P and τm is derived; and (3) the best fit of the conformational parameters to the experimental coupling constants is obtained by means of a computerized iterative least-squares procedure. Two pseudorotation ranges were considered, classified as type N (χ2 positive sign) and type S (χ2 negative sign). The conformational equilibrium is fully described in terms of four geometrical parameters (PN, τN, PS, τS) and the equilibrium constant K. The present results indicate that, in general, the geometrical properties found in x-ray studies of proline and hydroxyproline residues are well preserved in solution. Several novel features are encountered, however. It is demonstrated that the proline ring occurs in a practically 1:1 conformational equilibrium between well-defined N- and S-type forms. Introduction of an amide group at the C-terminal end has no observable effect on this equilibrium, but the formation of a peptide bond at the imino nitrogen site results in a pronounced, but not exclusive, preference for an S-type form which is roughly 1.1 kcal/mol more stable than its N-type counterpart. The hydroxyproline ring system in neutral or acidic medium displays a pure N-type state, but N-acetylation results in the appearance of a minor (S-type) conformation. Cyclic proline dipeptides similarly exist in a biased conformational equilibrium. The major form (77-88%) corresponds to the N-type conformer observed in the solid state; the minor S-form has not been observed before. In contrast, cyclic hydroxyproline dipeptides display complete conformational purity. Ranges of endocyclic torsion angles deduced for the various classes of pyrrolidine derivatives in solution are presented. Each torsion appears confined to a surprisingly narrow range, comprising about 4°-8° in most cases. In all, the proline ring is far less “floppy” than hitherto assumed.
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  • 66
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurement of the equilibrium distribution of persistence length fragments of DNA in high concentration in the ultracentrifuge shows that the reduced osmotic pressure rises much faster than linearly. From analysis of the data in terms of the Zimm cluster integral we infer that the net interactions between helices are purely repulsive at all distances. A theoretical equation of state derived from scaled particle theory with one adjustable parameter is in excellent agreement with the experimental data so long as the salt concentration is not excessively low. The parameter represents the hard-core radius in a simplified approximation to the potential function for the electrostatic repulsion between helices. Its value depends on the salt concentration, and it shrinks at high salt to a radius in close agreement with direct structural estimates. At a particular value of the osmotic pressure that is only slightly salt dependent, the solution undergoes a reversible transition to a denser, turbid, optically anisotropic phase. The relation between DNA volume fraction, including the electrostatic radius, at the transition point and the effective asymmetry of the molecules as a function of salt is in approximate correspondence with various theoretical treatments. However, the experimental function extrapolates to the correct limit for spherical particles. The work needed to bring DNA to a high concentration is estimated. The results suggest that the phase transition is first order.
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    Biopolymers 20 (1981), S. 2121-2136 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This report presents a quantitative test of the ability of the counterion condensation theory to describe the proton-induced lowering of DNA melting temperature. From a general approach of Record et al. [Record, M. T., Anderson, C. F. & Lohman, T. H. (1978) Q. Rev. Biophys. 11, 103-178], we have obtained an expression that may be computer-fitted to the experimental data by numerical minimization of χ2. To do this, in addition to the assumptions made by Record et al., it was necessary to suppose that the interchange between protons and sodium is independent of pH and, due to the absence of data, take the enthalpies of protonation as thermally independent over the experimental temperature range. The dependences of the enthalpy of denaturation at neutral pH on sodium concentration and on G + C content were taken from literature. In the fitting process we have used 250 melting temperatures obtained at different pH and sodium concentrations for various natural DNAs. The theoretical expression gives a good quantitative description of the G + C and sodium concentration influences on the phenomenon but is only qualitative with respect to the dependence of dT/d log[Na+] on the pH. The adjusted pK values for the bases in denatured DNA agree with those for isolated deoxynucleosides. Interchange between sodium and protons is found to be less than 1:1. Calculated protonation enthalpies are ill-defined because of their low numerical influence. In short, it appears that the theory gives a good description of most of the aspects of the phenomenon even if it has some shortcomings, perhaps due to the great number of assumptions.
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  • 68
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    Biopolymers 20 (1981), S. 2137-2142 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the kinetics of replacement of O2 by CO in hemoglobin in the presence and absence of organic cosolvents (methanol, ethanol, iso-propanol, n-propanol, formamide, acetamide, N-methyl-formamide) and at 10 and 25°C. Quantitative analysis of the results indicates that these cosolvents do not affect the intrinsic binding constants of ligands to the heme when hemoglobin is in the R conformation. The present results confirm the previously reported suggestion that the effects of the above cosolvents on the oxygen affinity of hemoglobin are related to effects on the T ⇄ R conformational equilibrium.
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  • 69
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    Biopolymers 20 (1981), S. 2195-2202 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparations have been made of acid-soluble collagens whose telopeptides have suffered different levels of proteolytic attack. The collagens with more intact telopeptides form fibrils more rapidly than those with degraded telopeptides. In addition, we have shown that a high molecular weight aggregate rich in the carboxyterminal CNBr peptide, α1CB6, can be found in cyanogen bromide digests of fibrils formed from intact collagen. A similar aggregate is found in CNBr digests of native tendons. The aggregate formed in fibrils assembled in vitro can be stabilized by reduction, and its generation is strongly dependent on the presence of intact telopeptides. The latter point is the most objective evidence that to reproduce the characteristics of native fibrils in vitro, the collagen telopeptides must be preserved from proteolysis.
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  • 70
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    Biopolymers 20 (1981), S. 2225-2241 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present an alternative to the common lattice model for nonspecific DNA-protein interactions by using ligands that translate freely along the polynucleotide instead of binding to distinct lattice sites along the polynucleotide chain. The general model we present corresponds to a one-dimensional continuum gas and is referred to as the “continuum model” to distinguish it from the general lattice model. Explicit expressions are obtained for the binding isotherm equation for two version of the continuum model, including the effects of binding-site exclusion and attractions between bound ligands. Theoretical results are compared to those obtained from the McGhee-von Hippel (1974) analysis of the lattice model with cooperative interactions between ligands occupying more than one lattice site. Practical applications of the continuum model are illustrated by analyzing (i) the noncooperative binding to single-stranded DNA by RNase (Jensen and von Hippel, 1976), and (ii) the highly cooperative binding to poly(rA) by a proteolyzed fragment of the gene 32 protein of phage T4 (Lonberg et al., 1981).
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  • 71
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    Topics: Chemistry and Pharmacology
    Notes: The structure of water and its interaction energy with a fragment of B-DNA composed of 12 base pairs and of the corresponding 24 sugar and 22 phosphate units and Na+ ions (one at each phosphate group) are analyzed using Monte Carlo simulations. The sample of water molecules, at the simulated temperature of 300 K, is composed of 447 water molecules. The results are discussed either in terms of statistical analyses over the 2,000,000 simulated conformations (after equilibration) or with reference to an “average configuration.” Comparison is made to a simulation previously presented for the same system but without counterions. Isotherm at different relative humidity, hydration, and reactivity scales for different sites, the hydration number at each site, the structure of intraphosphate and interphosphate hydrogen-bonded filaments of water are reported and discussed. The stabilization of the B-conformation induced by the solvent with counterion (“ion-induced compression effect”) is analyzed on the base of the above findings. A preliminary model to predict conformational transition in DNA is presented. The analyses reported are very detailed to allow refined interpretations of spectroscopic (infrared, Raman, and nmr) and scattering (x-ray and neutron beam) data on DNA insolution.
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  • 72
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    Topics: Chemistry and Pharmacology
    Notes: The conformational response of calf thymus DNA to solvent conditions altered by varying amounts of ethanol and NaCl has been monitored by circular dichroism (CD). These measurements, which extend over a much greater range of conditions than previously examined, reveal (above critical concentrations of ethanol and salt) a condensed form of the macro-molecule with unusually large positive ellipticity in the 250-300-nm region [the Ψ(+) state]. Mere increase in NaCl concentration at constant 35% (v/v) concentration of ethanol suffices to convert such Ψ(+) samples - via a series of intermediate forms with CD spectra resembling those of A-DNA, then B-DNA - into Ψ(-) states having anomalously large negative ellipticity similar to the well-known Ψ(-) forms produced by above-critical concentrations of poly-(ethylene oxide) and salt. These ethanol/salt-induced transitions are all completely reversible and can occur without formation of any visible precipitates. We suggest that they represent predominantly tertiary structural changes of B-form DNA molecules analogous to the changes which occur in several other systems where Ψ(+) ⇌ Ψ(-) interconversion has been reported. A “skein-of-yarn” model for the condensed tertiary (and quaternary, i.e., aggregated) state of the DNA affords one possible explanation for the inversions of ellipticity in all these cases. Such a model accords well with the accepted description of cholesteric liquid crystals.
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  • 73
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    Biopolymers 21 (1982), S. 17-24 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computer simulation shows that the time required to attain near sedimentation equilbrium is dramatically reduced by a two-step initial loading in which a macromolecular solution at low or zero concentration is layered above one at a higher concentration. To achieve the minimum time requires a good estimate of the molecular weight, but at least a 50% reduction in time can be achieved if the molecular weight of the macromolecule is known only within a factor of 2. Numerical solutions to the differential equation of the ultracentrifuge are calculated using the finite element method. An efficient Gaussian elimination algorithm can be used to minimize calculation time and computer storage requirements.
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  • 74
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    Biopolymers 21 (1982), S. 79-88 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aldehydes present in acid-soluble type I collagen react with pyrenebutyrylhydrazine to form various types of complexes under different reaction conditions. These complexes exhibit one or more of three different pyrene fluorescence bands: monomer, excimer, and aggregate fluorescence. Collagen, whose aldehydes have been reduced with NaBH4, does not react with this fluorescent hydrazine, confirming that the hydrazine reacts specifically with aldehyde groups to form hydrazones. The absence of a reaction with pepsin-treated collagen also shows that the fluorescent labels are primarily in the nonhelical terminal telopeptides. Upon dialysis, the pyrene label bound to a saturated aldehyde in an α-chain is lost; whereas that bound to an unsaturated aldehyde remains on the protein. The pyrene monomer fluorescence in the β-chain of old collagen is stronger than that of young collagen. The formation of the pyrene excimer fluorescence implies the proximity of two pyrene molecules, probably attached to two adjacent aldehydes. Upon changing from acidic to neutral pH, both excimer and aggregate fluorescence bands disappear within a few seconds, revealing a very rapid alteration at the telopeptides.
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    Biopolymers 21 (1982), S. 147-157 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe conditions which lead to complete helix formation of poly(I) in the presence of NH4+. Binding of NH4+ is shown to be specific in the presence of Li+, which does not by itself support helix formation under these conditions. The NH4+-poly(I) complex is characterized by uv, CD, and ir spectroscopy. The CD spectrum is strikingly different from those of the Na+ or K+ complexes, the first extremum being changed from negative for the metal ions to positive for NH4+. A stereospecific model is proposed for the NH4+-poly(I) helix in which the N of NH4+ is located on the axis of the four-stranded helix, midway between planar tetramers formed by the bases. The model is consistent with the tetrahedral symmetry of NH4+, the requirement for four acceptable hydrogen bonds, the observed stability of the helix, and the accepted geometry of the backbone.
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    Biopolymers 21 (1982), S. 159-167 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has recently been proven that the counterion condensate around an isolated line charge in an electrolyte, as characterized by nonlinear Poisson-Boltzmann theory, is an encapsulating δ-function. Here the identical result is shown to hold in the framework of the polyelectrolyte theory of Fuoss, Katchalsky, and Lifson. The proof fully exploits analytic solutions to the differential equation which are not available for the nonlinear, cylindrical Poisson-Boltzmann equation.
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  • 77
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    Biopolymers 21 (1982), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent and modes of binding of the divalent metal ions Mn2+ and Co2+ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA-bound Mn2+ and Co2+ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn2+ and Co2+ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn2+ and Co2+ upon binding to DNA. An average 2-3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn2+ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn2+ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.
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    Biopolymers 21 (1982), S. 265-275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dc electrical conductivity of films of the polyelectrolyte complexes of glycol chitosan (GlChi) with the sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) was measured at temperatures above and below room temperature. The maximum field strength in the thinnest film used amounted to 3 × 104 V/cm. A plot of normalized current against the reciprocal of the absolute temperature revealed two regions with different slopes, and activation energies in these two regions have been obtained for all the complexes. The activation energies in the high-temperature region vary from 0.85 to 1.18 eV and in the low-temperature region from 0 to 0.22 eV. Reasons are given to show that the conductivity is probably ionic. Near room temperature, the current-voltage relation is almost linear in the GlChi-DS complex, while in the other three complexes the current varies as a power n of the voltage with the value of n ranging from 1.7 to 2.5. A rise in temperatures causes an increase in the slope of the log I vs log V plot in GlChi-DS and GlChi-CMC complexes. The nonlinear current-voltage relation is ascribed to a space-charge-limited conductivity.
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    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
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  • 80
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The primary hydration process of native biopolymers is analyzed in a brief review of the literature, pertaining to various aspects of biopolymer-water systems. Based on this analysis, a hydration model is proposed that implies that the solution conformation of native biopolymers is stable at and above a critical degree of hydration (hp′ = 0.06-0.1 g H2O/g polymer). This water content corresponds to the fraction of strongly bound water, and amounts to ∼20% of the primary hydration sphere. In order to test this model, detailed sorption-desorption scanning experiments were performed on a globular protein (α-chymotrypsin). The results obtained are consistent with the proposed hydration model. They show that under certain experimental conditions, sorption isotherms can be obtained that do not exhibit hysteresis. These data represent equilibrium conditions and are thus accessible to thermodynamic treatment. Valid thermodynamic functions, pertinent to the interaction of water with biopolymers in their solution state, can be obtained from these sorption experiments.
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  • 81
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    Biopolymers 21 (1982), S. 451-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112, 437-452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.
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  • 82
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    Biopolymers 21 (1982), S. 475-497 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A complete analysis of all possible conformations with correct hydrogen bonds of the collagen II type was performed on the basis of developed simultaneous equations. Using a unimodal search (by varying Ψ3), the energetically favorable structure was obtained. No other energetically satisfactory structural solutions are possible. The next aim was to obtain a precise model of the molecule. The program used includes a subroutine for continual deformation of the pyrrolidine rings. The set of parameters determining the structure consists of 14 independent variables (8 dihedral and 6 bond angles). As starting points for the energy optimization, conformations produced by scanning and some structures from previous work were used. The final structures (practically the same for both polymers) have helix parameters h = 0.285 nm and t = 52°, which are in excellent agreement with the 7/2 symmetry of diffraction data. The conformations of the pyrrolidine rings are of the B type, i.e., C2-Cβ-exo-Cγ-endo. For both polypeptides, the conformations of imino acids in position 3 of the triplet are the same; in position 2, however, they are slightly different. The difference in diffraction patterns for the 7/2 and 10/3 helices is discussed.
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    Biopolymers 21 (1982), S. 547-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectrum of the enzyme adenylate kinase has been investigated. Theoretical calculations, based on the x-ray crystal structure, have been carried out by means of an origin independent matrix formalism. The entire molecule was included in the calculations in the sense that essentially all electronic transitions that occur at wavelengths longer than 185 nm were included in the basis set. A linear dielectric function was utilized to evaluate the intertransition coupling potentials. The results of the theoretical calculations were in reasonable agreement with experimental CD spectra of the molecule.
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    Biopolymers 21 (1982), S. 633-652 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mode of action of many antitumor agents entails the inhibition of nucleic acid synthesis. Because many of the drugs can intercalate, it is assumed that intercalation is an important step in the mechanism of biological activity. As intercalants contain a planar chromophore as an ingredient essential for intercalation, chromophores that should fit into DNA are desired. This is the main theme of this investigation. Binding to DNA of fundamental moieties, protonated pyridine, aniline, phenol, quinone, and 4H-thiopyran-4-one, is studied to determine their optimum placement in DNA. The optimum orientations for each moiety are superimposed to form polyaromatic systems that can intercalate in a manner in which functional groups on these chromophores are oriented as in the moieties themselves. Ideal intercalants proposed contain three and four fused ring system, have protonated ring nitrogen atoms located to maximize the electrostatic interactions with DNA, hydroxy and amino groups that can hydrogen bond to the OII and O5′ phosphate backbone atoms, and carbonyl and sulfur groups in the central position of the ring system to provide variations in the chromophore and to interact with the relatively positive region in the intercalation site. The optimum orientation occurs when the chromophore and the base pairs overlap to the maximum extent. The ideal intercalants are fundamentally of the type:
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    Biopolymers 21 (1982), S. 665-677 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA reassociation kinetics using the phenol emulsion reassociation technique (PERT) [Kohne, D. E., Levison, S. A. & Byers, M. J. (1977) Biochemistry 16, 5329-5341] has been investigated at high DNA concentrations using an endonuclease S1 assay of reaction progress. Apparent second-order rate constants fall on two intersecting straight lines when presented as a function of DNA concentrations on a log-log plot. In the low DNA concentration range, the rate constants drop about 10-fold when concentration increases 1000-fold. In the high DNA concentration range, the rate constants drop more than 10-fold when concentration increases 10-fold. The slopes of these lines are the same in different solvents and at different temperatures. The intersection between the lines occurs when the available catalytic surface is saturated. At high DNA concentrations, high-complexity heterologous denatured DNA apparently competes 2-4 times better for the surface than homologous DNA because it does not participate in a reassociation reaction. Native and partially native DNA molecules cannot compete with single-stranded DNA for a saturated surface. At high DNA concentrations, reactions using PERT become dependent on the single-strand DNA length. Increasing length lowers reassociation rates.
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  • 86
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 20 (1981), S. 2623-2633 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-Nmr was used to measure the rate of cis-trans interconversion of X-Pro bonds in linear and cyclic oligopeptides. k(cis → trans) = 2.5 × 10-3 s-1 at 25°C was found for the zwitterionic form of H-Ala-Pro-OH, in good agreement with earlier measurements. Replacement of Ala by Phe, Tyr, or Trp resulted in a 10-fold slower interconversion rate, whereas after substitution of Ala by His or Glu, the rate decreased only slightly. Independent of the residues X, the interconversion rate was increased by a factor of ca. 20 when the peptide chain was elongated by addition of Ala to the C-terminal Pro. An additional increase by a factor of 6 was observed when going from the protected linear peptide CF3CO-Gly-Gly-Pro-Ala-OCH3 to the closely related cyclic compound c[-Gly-Gly-Pro-Gly-Ala-]. These data are evaluated with regard to their possible use in future studies on the role of X-Pro cis-trans isomerization in the kinetics of protein folding.
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    Biopolymers 21 (1982), S. 859-872 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical potential functions (CPF) calculations on 3′-mononucleotides, the building blocks of nucleic acids, predict a correlation between the sugar ring pucker and the torsion angle Φ′ around the C3′—O3′ bond. In ribonucleotides, the value of Φ′ depends on the sugar pucker, viz. the C2′-endo sugar pucker is associated with Φ′ = 210° and 270°, while the C3′-endo sugar pucker favors only Φ′ = 210°. On the other hand, in deoxyribonucleotides, both sugar puckers show a preference for Φ′ = 180°. These theoretical predictions are fully corroborated by the results obtained from x-ray and nmr studies on mono-, di-, and polynucleotides.
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  • 89
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    Topics: Chemistry and Pharmacology
    Notes: The effect of several surfactants on the secondary structure of bovine β-lactoglobulin B was determined from the circular dichroism spectra. The spectra were measured at several concentrations of surfactant ranging from 1 mg/mL to the critical micelle concentration. The surfactants studied were sodium dodecyl, decyl, and octyl sulfate, sodium dodecyl sarcosinate, dodecyltrimethylammonium bromide. The data were analyzed using the method of Chen et al. [Biochemistry (1974) 13, 3350-3359] to determine the percentage of α-helix, β-sheet, and unordered form at each surfactant concentration. In every case, an increase in structured form and a 20-25% decrease in the amount of unordered form was noted when the surfactant concentration reached the critical micelle concentration. However, the relative amounts of the two structured forms present depend on the surfactant used. The profile of the secondary structure of the protein also varied from surfactant to surfactant as the protein was titrated, probably reflecting the delicate balance between ionic and nonionic forces that governs the secondary structure of β-lactoglobulin and most other globular proteins in aqueous solution.
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  • 90
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Amino acids are known to differ in their individual preferences for each of the four positions of the β-turn conformation formed by tetrapeptide segments. Proline and glycine show relatively high preferences for positions 2 and 3, respectively, of the β-turn. Using tripeptides of the type N-acetyl-Pro-Gly-X-OH, where X = Gly, Ala, Leu, Ile, and Phe, we have sought to study the influence of the 4th residue X on the stability of the β-turn conformation in these tripeptides. Our nmr and CD results show that the β-turn stability is quite significantly governed by the nature of the amino acid residue at this position in the following order: Leu 〉 Ala 〉 Ile, Gly 〉 Phe.
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    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
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  • 92
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    Biopolymers 21 (1982) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are φPro = -57.8°, ψPro = 139.3°, φAib = 61.4°, and ψAib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.
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  • 94
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    Biopolymers 21 (1982), S. 1333-1363 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The folding-unfolding process of reduced bovine pancreatic trypsin inhibitor was investigated with an idealized model employing approximate free energies. The protein is regarded to consist of only Cα and Cβ atoms. The backbone dihedral angles are the only conformational variables and are permitted to take discrete values at every 10°. Intraresidue energies consist of two terms: an empirical part taken from the observed frequency distributions of (φ,ψ) and an additional favorable energy assigned to the native conformation of each residue. Interresidue interactions are simplified by assuming that there is an attractive energy operative only between residue pairs in close contact in the native structure. A total of 230,000 molecular conformations, with no atomic overlaps, ranging from the native state to the denatured state, are randomly generated by changing the sampling bias. Each conformation is classified according to its conformational energy, F; a conformational entropy, S(F) is estimated for each value of F from the number of samples. The dependence of S(F) on energy reveals that the folding-unfolding transition for this idealized model is an “all-or-none” type; this is attributable to the specific long-range interactions. Interresidue contact probabilities, averaged over samples representing various stages of folding, serve to characterize folding intermediates. Most probable equilibrium pathways for the folding-unfolding transition are constructed by connecting conformationally similar intermediates. The specific details obtained for bovine pancreatic trypsin inhibitor are as follows: (1) Folding begins with the appearance of nativelike medium-range contacts at a β-turn and at the α-helix. (2) These grow to include the native pair of interacting β-strands. This state includes intact regular secondary conformations, as well as the interstrand sheet contacts, and corresponds to an activated state with the highest free energy on the pathway. (3) Additional native long-range contacts are completely formed either toward the amino terminus or toward the carboxyl terminus. (4) In a final step, the missing contacts appear. Although these folding pathways for this model are not consistent with experimental reports, it does indicate multiple folding pathways. The method is general and can be applied to any set of calculated conformational energies and furthermore permits investigation of gross folding features.
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  • 95
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peptide NH chemical shifts and their temperature dependences have been monitored as a function of concentration for the decapeptide, Boc-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-OMe in CDCl3 (0.001-0.06M) and (CD3)2SO (0.001-0.03M). The chemical shifts and temperature coefficients for all nine NH groups show no significant concentration dependence in (CD3)2SO. Seven NH groups yield low values of temperature coefficients over the entire range, while one yields an intermediate value. In CDCl3, the Aib(1) NH group shows a large concentration dependence of both chemical shift and temperature coefficient, in contrast to the other eight NH groups. The data suggest that in (CD3)2SO, the peptide adopts a 310 helical conformation and is monomeric over the entire concentration range. In CDCl3, the 310 helical peptide associates at a concentration of 0.01M, with the Aib(1) NH involved in an intermolecular hydrogen bond. Association does not disrupt the intramolecular hydrogen-bonding pattern in the decapeptide.
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  • 96
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    Biopolymers 21 (1982), S. 1469-1472 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 97
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    Biopolymers 21 (1982), S. 1479-1487 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.
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  • 98
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    Biopolymers 21 (1982), S. 1521-1534 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used broadline proton magnetic resonance to study molecular motion in cellulose, a sodium pectate solution, a calcium pectate gel, and isolated bean cell walls. All samples were prepared in D2O to minimize the contribution of water to the observed signals. For each sample, a free induction decay was obtained, and the second moment, spin-lattice relaxation, and dipolar relaxation were measured. Our results show that the large majority of protons in cellulose are immobile. Rigid and mobile domains were also observed in the pectate samples. We have shown that gelation induces large-scale changes in the free induction decay, the second moment, and the relaxation behavior of the pectate. As with the other samples, rigid and more mobile domains were found in bean cell walls. The fraction in the rigid domains is much larger than the fraction of cellulose in the sample, suggesting that the noncellulosic wall components are also organized into rigid and mobile domains.
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  • 99
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy computations were carried out on collagenlike triple-stranded conformations of several poly(tripeptide)s with the general structure CH3CO—(Gly—X—Y)3—NHCH3. The sequences considered had various amino acid residues in position X or Y of the central tripeptide, with either Pro or Ala as a neighbor, i.e., Gly-X-Pro, Gly-X-Ala, Gly-Pro-Y, and Gly-Ala-Y. Minimum-energy conformations were computed for the side chains, and their distributions were compared for the four sequences. The residues used were Abu (= α-aminobutyric acid), Leu, Phe, Ser, Asp, Asn, Val, Ile, and Thr. The conformational energy of a —Ch2—CH3 side chain in Abu was mapped as a function of the dihedral angle χ1. Intrastrand interactions with neighboring residues do not affect the conformations of a side chain in position Y, and they have a minor effect on it in the X-Ala sequence, but they strongly restrict the conformational freedom of the side chain in the X-Pro sequence. Conversely, interstrand interactions do not affect side chains in position X, but they strongly restrict the conformational freedom of a side chain in position Y if there is a nearby Pro residue in a neighboring strand. Hydrogen bonds with the backbone can be formed in some conformations of long polar side chains, such as Asp, Asn, or Gln. All amino acid residues can be accommodated in collagen. Because of the interactions mentioned above, steric and energetic constraints can be correlated with observed preferences of certain amino acids for positions X or Y in collagen. Hence, these preferences may be explained, in part, in terms of differences in the conformational freedom of the side chains in the triple-stranded structure.
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  • 100
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    Biopolymers 21 (1982), S. 1657-1666 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ionization constants of the tyrosyl groups of chymotrypsinogen and of nitrated-chymotrypsinogen (two tyrosyl residues nitrated) have been determined by difference spectrophotometry. In chymotrypsinogen, two of the four tyrosyl groups ionize without any time dependence. Above pH greater than ca. 12.5, time-dependent spectral changes are seen for 0.7 group equivalent. The data can be fitted to the values of pK′1 9.75 ± 0.07, pK′2 11.55 ± 0.05, pK′3 13.30 ± 0.05. In nitrated-chymotrypsinogen, the two nitrated tyrosyl residues have pK′1 6.44 and pK′2 8.30. For both proteins, these pK′ values are in agreement with those evaluated from potentiometric titration and calorimetric data using computer-assisted curve-fitting analysis.
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