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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 7 (1971), S. 232-240 
    ISSN: 1432-0827
    Keywords: Calculus ; Infrared ; Spectroscopy ; Calcium ; Oxalate ; Phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les noyaux centraux de 500 calculs urinaires, comportant 421 calculs des voies urinaires supérieures, 64 calculs des voies urinaires inférieures et 15 calculs de la prostate ont été analysés au Japon par spectroscopie infrarouge. Les résultats de cette analyse indiquent que 50,8% des calculs sont composés d'un mélange d'oxalate de calcium et phosphate de calcium: 17,4% d'oxalate de calcium simple; 17,4% de phosphate de magnésium ammoniaqué, mélangé au phosphate de calcium et probablement aussi au carbonate de calcium: 4,4% d'acide urique et d'urate avec ou sans phosphate de calcium ou d'oxalate de calcium: 3,2% de phosphate de calcium: 1,0% de cystine et 0,2% (un cas) constitué de protéine. Sur 119 calculs, constitués d'oxalate-phosphate, les rapports de l'oxalate de calcium et du phosphate de calcium sont mesurés á l'aide des spectres infra-rouges et les rapports de 53 régions corticales de ces calculs ont été déterminés et comparés è ceux des régions nucléaires centrales. Il apparait ainsi que le noyau des calculs d'oxalate phosphate contient de plus grandes quantités de phosphate de calcium.
    Abstract: Zusammenfassung In Japan wurden die zentralen Nuclei von 500 Nierensteinen mittels Infrarotspektroskopie untersucht. Es handelte sich dabei um 421 Steine aus den oberen Harnwegen, 64 Steine aus den unteren harnwegen und 15 Prostatasteine. Die Analysen ergaben folgende Resultate: 50,8% der Steine setzten sich aus einem Gemisch von Calciumoxalat und Calciumphosphat usammen; 17,4% enthielten nur Calciumoxalate; 17,4% bestanden aus einem Gemisch von Magnesiumammoniumphosphat mit Calciumphosphat und vermutlich auch Calciumcarbonat; 4,4% enthielten Harnsäure und Urate mit oder ohne Calciumphosphat oder Calciumoxalat; 3,2% bestanden aus Calciumphosphat; 1,0% aus Cystin und 0,2% (ein Fall) aus Protein. Bei 119 Phosphatoxalatsteinen wurde das Verhältnis von Calciumoxalat zu Calciumphosphat aus den Kurven der erhaltenen Infrarotspektra bestimmt. Dieses Verhältnis wurde ebenfalls für die äußere Schicht von 53 solcher Steine berechnet und mit dem Wert der zugehörigen zentralen Nuclei verglichen. Aus diesen Resultaten geht hervor, daß die Nuclei der Phosphatoxalatsteine größere Mengen von Calciumphosphat enthalten.
    Notes: Abstract The central nuclei of 500 urinary calculi in Japan, including 421 calculi of upper urinary tracts, 64 calculi of lower urinary tracts and 15 prostatic calculi, were analysed by infrared spectroscopy. The results of analysis revealed that 50.8% of calculi were composed of mixed calcium oxalate-calcium phosphate; 17.4%, simple calcium oxalate; 17.4%, magnesium ammonium phosphate mixed with calcium phosphate, and probably also with calcium carbonate; 4.4%, uric acid and urate with or without calcium phosphate or calcium oxalate; 3.2%, calcium phosphate; 1.0%, cystine; and 0.2% (one case) were composed of protein. Of 119 oxalate-phosphate calculi the ratios of calcium oxalate to calcium phosphate were measured on the chart of infrared spectra, and also the ratios of 53 cortices taken from these calculi were measured and compared to the ratios of these central nuclei. The results showed that the nuclei of oxalate-phosphate calculi contained greater amounts of calcium phosphate.
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  • 2
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    Calcified tissue international 8 (1971), S. 320-333 
    ISSN: 1432-0827
    Keywords: Osteoporosis ; Calcium ; Deficiency ; Osteocytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé De jeunes rats sont soumis à un régime pauvre en calcium pour provoquer de l'ostéoporose. Les métatarses sont étudiés histologiquement, histochimiquement et radiologiquement. Les premiers signes d'ostéoporose sont visibles sept jours après le début du régime. Une résorption osseuse plus avancée se manifeste par amincissement de l'os compact, sous l'action de cellules hypertrophiées et par formation de cavités de résorption, autour d'ostéocytes hypertrophiés. La résorption osseuse s'effectue en deux stades. Au cours du premier, le calcium disparait de la matrice osseuse périlacunaire ainsi que de la matrice adjacente aux cavités de résorption et de la zone située sous l'endoste. La matrice organique résiduelle de ces régions se colore métachromatiquement et est PAS positive; elle est éliminée dans un second stage. Après deux mois, lorsque les animaux se sont habitués au régime pauvre en calcium, l'épaisseur de l'os compact reste stationnaire et les cavités de résorption disparaissent. Les animaux, soumis à nouveau, après cinq mois, à un régime normal, présentent une augmentation de l'épaisseur de l'os compact. Les diverses fonctions des cellules ainsi que leurs modifications sont décrites.
    Abstract: Zusammenfassung Um eine Osteoporose zu erzeugen, erhielten junge Ratten eine Calcium-arme Diät. In verschiedenen Zeitabständen wurden die Metatarsalknochen histologisch, histochemisch und radiologisch untersucht. Eine Osteoporose wurde erstmals 7 Tage nach Beginn der Calcium-armen Diät beobachtet. Das Dünnerwerden der Compacta durch das Einwirken von hypertrophierenden Zellen sowie die Bildung von Resorptionshöhlungen in der Compacta durch hypertrophierende Osteocyten wiesen auf eine verstärkte Knochenresorption hin. Die Knochenresorption spielte sich in 2 Stufen ab. Während der ersten Stufe verschwand Calcium aus der perilakunären Knochenmatrix, aus der an die Resorptionshöhlungen angrenzenden Matrix und aus dem subendostalen Bereich. Die an diesen Stellen verbleibende organische Matrix ließ sich metachromatisch anfärben und war PAS-positiv; sie verschwand in der zweiten Resorptionsstufe. 2 Monate später hatten sich die Tiere der Calcium-armen Diät scheinbar soweit angepaßt, daß die Dicke der Compacta stationär blieb und die Resorptionshöhlungen verschwanden. Tiere, die nach 5 Monaten wieder auf die normale Diät zurückversetzt wurden, zeigten ein Dickerwerden ihrer Compacta. Die während der Zellumwandlung sich verändernde Rolle der verschiedenen Zellen wird besprochen.
    Notes: Abstract Young rats were fed with a calcium-deficient diet in order to produce osteoporosis. Metatarsals were examined histologically, histochemically, and radiologically, at intervals. Osteoporosis was first observed seven days after initiation of the diet. Increased bone resorption was manifested by thinning of the compacta through the action of hypertrophied cells, and by the formation in the compacta of resorption cavities by hypertrophied osteocytes. Bone resorption took place in two stages. In the first stage calcium disappeared from the perilacunar bone matrix, from the matrix adjacent to the resorption cavities, and from the subendosteal area. The residual organic matrix in these locations stained metachromatically and was PAS positive; it was removed in the second stage. After two months, when the animals apparently adapted to the calcium-deficient diet, the width of the compacta remained stationary, and the resorption cavities disappeared. Animals returned to a normal diet after five months showed an increase in the thickness of their compacta. The changing role of the various cells together with cell transformation is discussed.
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  • 3
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    Calcified tissue international 7 (1971), S. 93-102 
    ISSN: 1432-0827
    Keywords: Strontium ; Vitamin D3 ; Calcium ; Absorption ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des poulets, âgés de 2 semaines, après a voir été soumis pendant 7 jours à un régime pauvre en calcium (0,1%), riche en vitamine D3, à contenu stable en strontium à une concentration équimolaire à 1,2% de calcium, reçoivent à nouveau une alimentation normale. Les graves lésions osseuses, provoquées par le régime au strontium, disparaissent au bout de 3 jours d'alimentation normale. L'inhibition du mécanisme d'absorption intestinal du calcium et l'action inhibitrice initiale du strontium alimentaire sont totalement abolies. Cependant les troubles de la minéralisation ne disparaissent que partiellement.
    Abstract: Zusammenfassung Nachdem normale, 2-wöchige Kücken während 7 Tagen eine calciumarme (0,1%), Vitamin D3-reiche und 2,62% kaltes Strontium (molaraequivalent mit 1,2% Calcium) enthaltende Nahrung erhielten, wurden sie wieder auf normales Futter gesetzt. Die schwere Knochenläsion, die sich durch die Strontiumfütterung entwickelt hatte, bildete sich zu einem großen Teil schon nach 3 Tagen normaler Nahrung wieder zurück. Die Hemmung der Calciumabsorption im Darm, die anfängliche inhibierende Wirkung des Strontiums aus der Nahrung, wurde vollständig aufgehoben; dagegen besserte sich der Mineralisationsdefekt nur teilweise.
    Notes: Abstract Two week old normal chicks, after having been fed a low-calcium (0.1%), vitamin D3-replete diet containing stable strontium at a level equimolar to 1.2% calcium for 7 days, were transferred back to a normal diet. The severe bone lesion that developed with strontium feeding was, to a large extent, reversed after only 3 days on the normal diet. The inhibition of the intestinal calcium absorptive mechanism, the initial inhibitory action of dietary strontium, was fully reversed whereas the recovery from the defect in mineralization was only partially reversed.
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  • 4
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    Calcified tissue international 7 (1971), S. 150-162 
    ISSN: 1432-0827
    Keywords: Uranium ; Bone ; Distribution ; Fission ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une concentration moyenne de 2.4×10−8 g U/g de cendre a été obtenue à partir de l'os humain normal. La microdistribution de l'uranium dans l'os indique que cet élément est surtout limité à surface de l'endoste et, en particulier, aux surfaces de l'os lamellaire et aux parois des canaux de Havers, ouverts dans l'os corticol. Cette répartition suggère que l'uranium se présente sous une forme chimique impropre à son incorporation dans l'apatite osseux: il ne semble donc pas exister une distribution diffuse significative de l'uranium dans l'os.
    Abstract: Zusammenfassung Eine mittlere Konzentration von 2,4×10−8 g Uran/g Asche wurde in normalen menschlichen Knochen gefunden. Die Feinverteilung von Uran im Knochen zeigt, daß dieses Element hauptsächlich an der endostalen Oberfläche vorkommt, insbesondere an der Oberfläche des trabeculären Knochens und an den Wänden der offenen Haversschen Kanäle im kortikalen Knochen. Diese Verteilung läßt vermuten, daß Uran in einer chemischen Form vorliegt, welche sich für den Einbau in das Knochenapatit nicht eignet. Daraus folgt, daß keine signifikante diffuse Verteilung des Urans innerhalb des Knochens vorliegt.
    Notes: Abstract A mean concentration of 2.4×10−8 g U/g ash has been obtained for normal human bone The microdistribution of uranium in bone indicates that this element is mainly restricted to endosteal surfaces; in particular the surfaces of trabecular bone and the walls of open Haversian canals in cortical bone. This distribution suggests that uranium is present in a chemical form that is not acceptable for incorporation into bone apatite and consequently there does not appear to be a significant diffuse distribution of uranium throughout bone.
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  • 5
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    Calcified tissue international 8 (1971), S. 24-35 
    ISSN: 1432-0827
    Keywords: Bone ; Cartilage ; Epiphysis ; Calcium ; Phosphorus ; Vitamin D
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les électrolytes ont été analysés dans le sérum et dans les tissues en voie de minéralisation, à des stades variables de calcification, chez des poulets et des pores normaux et rachitiques. L'humidité, les cendres et les matières organiques et déssèchées ont été analysées. Il apparait que d'autres électrolytes sériques, en plus du Ca, sont modifiés au cours du rachitisme. Le Mg et le P inorganique sont modifiés de façon variable au cours de l'avitaminose D. Des changements plus importants en contenu minéral des tissus sont observés dans les stades précoces de calcification que ceux que l'on a pu constater dans le sérum à des stades similaires, ce qui suggère un effet direct de l'avitaminose sur le tissu en voie de calcification. Quant au contenu du sérum, le dépôt de Ca est plus élevé dans les tissus d'animaux rachitiques par rapport aux témoins. Ceci n'est pourtant pas le cas du Mg ou du P inorganique, indiquant une affinité préférentielle du Ca pour le tissue rachitique. L'analyse gravimétrique de matières organiques et déssèchées des zones épiphysaires montre que les quantités de cartilage hypertrophique et en voie de dévelopment augmentent dans le cas de rachitisme, alors que le cartilage calcifié diminue, confirmant les observations histologiques antérieures. De manière inattendue, la proportion de cartilage au repos augmente au cours du rachitisme.
    Abstract: Zusammenfassung Die Elektrolyte im Serum und in mineralisierenden Geweben wurden zu verschiedenen Zeitpunkten der Verkalkung bei normalen Hühnern und Schweinen und bei solchen mit Vitamin D-Mangel analysiert. Wassergehalt, Asche, trockene und organische Substanz wurden ebenfalls gemessen. Die Ergebnisse zeigten, daß außer Ca auch andere Elektrolyte bei Rachitis verändert wurden. Mg und anorganischer P wurden durch den Vitaminmangel bei den beiden Gattungen verschiedenartig beeinflußt. In den Geweben wurde in den frühen Phasen der Verkalkung eine größere Änderung des Mineral-Spiegels gefunden, als dies zu übereinstimmenden Zeiten im Serum der Fall war, was auf eine direkte Wirkung des Vitaminmangels auf das verkalkende Gewebe schließen läßt. Im Verhältnis zum Serumspiegel wurde Ca in den Geweben der rachitischen Tiere zu einem größeren Grade als normal abgeschieden. Dies war nicht der Fall bei Mg oder anorganischem P, was einen Vorzug für Ca in den rachitischen Geweben anzeigt. Gravimetrische Analysen von organischer und trockener Substanz in epiphysischen Schichten zeigten, daß die Menge des proliferierenden und hypertrophischen Knorpels zunahm und daß verkalkter Knorpel bei Rachitis abnahm, gemäß klassischen histologischen Beobachtungen. achtungen. Ganz unerwartet war bei Rachitis eine verhältnismäßige Zunahme des ruhenden Knorpels festzustellen.
    Notes: Abstract Electrolytes were analyzed in serum, and in mineralizing tissues at varying stages of calcification, in normal and vitamin D-deficient chickens and pigs. Moisture, ash, and organic matter were also measured. Results revealed that in addition to Ca, other serum electrolytes were altered in rickets. Mg and inorganic P were diversely affected by the vitamin deficiency. Larger changes in mineral level were seen in the tissues in the early stages of calcification than were seen at corresponding times in the serum, suggesting a direct effect of the vitamin deficiency on the calcifying tissue itself. Relative to the serum level, Ca was deposited in the tissues of rachitic animals to a greater extent than in normal animals. This was not true for Mg or inorganic P, indicating a preferential affinity for Ca in the rachitic tissue. Gravimetric analyses of organic and dry matter in epiphyseal zones revealed that the amounts of proliferating and hypertrophic cartilage were increased, and calcified cartilage decreased, in rickets, in accord with previous histological observations. Unexpectedly, the proportion of resting cartilage was also increased.
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  • 6
    ISSN: 1432-0827
    Keywords: Morphology ; Glycosaminoglycans ; Cartilage ; Chemistry ; Audioradiography ; Healing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une perte de substance ostéo-cartilagineuse, de taille limitée et identique, est réalisée chez le lapin adulte et la cicatrisation est étudiée histologiquement et par autoradiographie après marquagein vitro au35S-sulfate. Une analyse microchimique est pratiquée pour le contenu et la composition en glycosaminoglycanes. 1. Entre la première semaine et la 4ème et 8ème semaine, un tissu conjonctif non-métachromatique se différencie en un cartilage métachromatique et la quantité de sulfate de chondroitine augmente de façon significative aux dépens des glycoprotéines. 2. Jusqu'à la 4ème semaine, la perte de substance est surtout comblée par de l'os néoformé: après cette période, la région est comblée au delà de la limite de la surface articulaire. 3. Le cartilage hyalin, ressemblant morphologiquement, autoradiographiquement et chimiquement au cartilage articulaire, en ce qui concerne la distribution en glycosaminoglycanes, constitute la surface articulaire de la perte de substance comblée dans un tiers des cas après 8 semaines. Le cartilage hyalin s'observe surtout dans les régions où de l'os néoformé a comblé la cavité médullaire. 4. Dans les deux tiers des cas, après 8 semaines, les surfaces articulaires des zones comblées comportent, non seulement du cartilage, mais aussi du tissu fibreux se formant essentiellement sur les parties latérales et dans les régions, où la cavité médullaire, fliant face, à la surface articulaire, n'a pas été comblée par du tissue osseux. La fraction glycoprotéique augmente par rapport à la fraction chondroitine sulfate. 5. Dans la majorité des cas, après 20 semaines, le cartilage néoformé subit des phénomènes dégénératifs, qui se traduisent par une diminution en chondroitine sulfate.
    Abstract: Zusammenfassung Bei ausgewachsenen Kaninchen wurde ein begrenzter, standardisierter, osteochondraler Defekt hervorgerufen, und das regenerierte Gewebe wurde histologisch und autoradiographisch durch Markierung in vitro mit35S-Sulfat und durch mikrochemische Bestimmung des Gehaltes und der Zusammensetzung der Glykosaminglykane untersucht. Die wichtigsten Befunde waren: 1. Zwischen 1 und 4–8 Wochen veränderte sich nichtmetachromatisches Bindegewebe zu metachromatisch gefärbtem Knorpel, und der Anteil an Chondroitin-Sulfat nahm auf Kosten der Glykoproteine signifikant zu. 2. Bis zu 4 Wochen war der Hauptteil des defekten Gebietes mit neugebildetem Knochen gefüllt; nach dieser Zeit lag dieser Bezirk oberhalb der Verknöcherungsgrenze in Richtung der Gelenkoberfläche. 3. Nach 8 Wochen bestand die Gelenkoberfläche des defekten Gebietes in einem Drittel der Fälle aus hyalinem Knorpel, der morphologisch, autoradiographisch und chemisch dem Gelenkknorpel in Bezug auf die Verteilung von Glykosaminoglykanen glich. Hyaliner Knorpel wurde hauptsächlich an Stellen beobachtet, wo neugebildeter Knochen die Markhöhle geschlossen hatte. 3. Nach 8 Wochen bestand die Gelenkoberfläche des defekten Gebietes in einem Drittel der Fälle aus hyalinem Knorpel, der morphologisch, autoradiographisch und chemisch dem Gelenkknorpel in Bezug auf die Verteilung von Glykosaminoglykanen glich. Hyaliner Knorpel wurde hauptsächlich an Stellen beobachtet, wo neugebildeter Knochen die Markhöhle geschlossen hatte. 4. Nach 8 Wochen bestanden Teile der Gelenkoberfläche des Defektes in zwei Dritteln der Fälle nicht nur aus Knorpel, sondern auch aus fibrösem Gewebe, welches vor allem in den seitlichen Teilen des Defektes und an Stellen vorlag, wo die Markhöhle gegenüber der Gelenkoberfläche nicht mit Knochengewebe verschlossen worden war. Die Glykoproteinfraktion nahm im Vergleich zur Chondroitin-Sulfatfraktion zu. 5. Nach 20 Wochen zeigten sich in den meisten Fällen bei neugebildetem Knorpel degenerative Veränderungen, welche durch eine gewisse Abnahme des Chondroitin-Sulfats wiedergegeben wurden.
    Notes: Abstract A limited, standardized osteochondral defect was created in adult rabbits and the regenerated tissue was examined histologically and autoradiographically after labellingin vitro with35S-sulphate, and microchemically for its content and composition of glycosaminoglycans. The principal findings were: 1. Between 1 week and 4 to 8 weeks, non-metachromatic connective tissue differentiated to metachromatically stained cartilage, and the proportion of the chondroitin sulphate increased significantly at the expense of the glycoproteins. 2. Up to 4 weeks, the major part of the defect area was filled with newly formed bone; after this time, the area lay above the level of the “tidemark”, towards the articular surface. 3. Hyaline cartilage with morphological, autoradiographic and chemical resemblance to the articular cartilage in terms of the distribution of glycosaminoglycans constituted the articular surface of the defect area in one-third of the cases at observation times after 8 weeks. Hyaline cartilage was observed mainly in areas where newly formed bone had closed the medullary cavity. 4. In two-thirds of the cases, after 8 weeks, parts of the articular surface of the defect consisted not only of cartilage but also of fibrous tissue, occurring mainly in the lateral parts of the defect and in areas where the medullary cavity facing the articular surface had not been sealed by bone tissue. The glycoprotein fraction increased relative to the chondroitin sulphate fraction. 5. In most cases after 20 weeks, newly-formed cartilage underwent degenerative changes, which were reflected in some reduction of the chondroitin sulphate.
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  • 7
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    Calcified tissue international 8 (1971), S. 121-132 
    ISSN: 1432-0827
    Keywords: Calcium ; Skeleton ; Autoradiography ; Isotope ; Deposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Le taux de formation osseuse d'un chien adulte a été déterminé en divers endroits, en utilisant deux marqueurs à la tétracycline. Les valeurs obtenues ont été comparées avec des mesures similaires de dépôts calciques, obtenues par45Ca. Les mesures du ≪marquage diffus≫ de45Ca ont également été réalisées en utilisant l'autoradiographie quantitative. Les résultats ont été comparés avec les études similaires de Leeet coll. (J. Bone Joint Surg.47B, 157, 1965), effectuées à l'aide d'un chien nouveau-né et d'un chien adolescent. Il apparait ainsi que les études au45Ca permettent de mesurer la formation osseuse chez les chiens d'âges différents. Cependant, il est probable que le ≪marquage diffus≫ de calcium marqué chez l'Homme rend difficile la mesure du dépôt de calcium.
    Abstract: Zusammenfassung Die Geschwindigkeit der Knochenbildung bei einem ausgewachsenen Hund wurde mittels 2 Tetracyclinmarkierungen an verschiedenen Stellen des Knochens gemessen. Durch Messungen der Calciumzuwachsrate mittels45Ca-Tracer konnten die Werte beider Methoden verglichen werden. Die „diffuse Markierung” von45Ca wurde anhand von quantitativer Autoradiographie ebenfalls gemessen. Die Resultate wurden mit denjenigen ähnlicher Studien ausgewachsener Hund verwendet wurden. Es wird daraus geschlossen, daß die Knochenbildungsgeschwindigkeit von Hunden aller Altersstufen anhand von45Ca-Tracer-Studien gemessen werden kann. Es ist jedoch wahrscheinlich, daß die „diffuse Makierung” mit Tracer-Calcium beim Menschen zu einer schwierigen Interpretation der Messung der Calciumzuwachsrate führt.
    Notes: Abstract The bone formation rate of an adult dog has been found at several bone sites using two tetracycline markers. The values found have been compared with similar measurements of calcium accretion rate using45Ca as a tracer. Measurements of the “diffuse label” of45Ca were also made using quantitative autoradiography. The results have been compared with similar studies by Leeet al. (J. Bone Joint Surg.47 B, 157, 1965) using a puppy and an adolescent dog. It is concluded that45Ca tracer studies can measure the bone formation rate of dogs at any age. However, it is probable that the “diffuse label” uptake of tracer calcium in humans makes the calcium accretion rate measurement difficult to interpret.
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  • 8
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    Calcified tissue international 8 (1971), S. 142-153 
    ISSN: 1432-0827
    Keywords: Calcium ; Phosphate ; Precipitate ; Electrolyte ; Physiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La précipitation de phosphates de calcium, peu solubles, à partir de solutions de chlorure de calcium (3×10−4M à 1×10−1M) et de phosphate de sodium (Ptot. 1×10−3M à 6×10−2M, [NaOH]/[H3PO4]∼1.75, pH 7.4), est étudiée à 25° et à 37°. Les précipités, obtenus 24 heures après mélange, sont identifiés par microscopie optique et électronique, par diffraction électronique et aux rayons X, par analyses chimiques et par leurs indices de réfraction. Dans un large éventail de concentrations des réactifs à 25°, c'est surtout du phosphate octocalcique qui se forme, alors qu'à 37°, on obtient des apatites déficients en calcium. A cette dernière température, l'OCP se différencie seulement à des concentrations faibles, à la limite de précipitation. A des concentrations relativement élevées (Catot.×Ptot.〉10−4)et aux deux températures, des mélanges de dihydrate de phosphate dicalcique (DCPD) et d'apatites sont obtenus, la zone de concentration diminuant avec l'augmentation de la température.
    Abstract: Zusammenfassung Die Ausfällung von schwer löslichen Calciumphosphaten aus wäßrigen Calciumchloridlösungen (3×10−4M bis 1×10−1M) und Natriumphosphatlösungen (Ptot. 1×10−3M bis 6×10−2M, [NaOH]/H3PO4]∼1,75, pH 7,4) wurde bei 25° und bei 37° untersucht. Niederschläge, welche 24 Stunden nach dem Mischen isoliert wurden, konnten mittels Licht- und Elektronenmikroskopie, Röntgenstrahlen und Elektronendiffraktion, chemischen Analysen und Refraktions-Indices identifiziert werden. Über den weitesten Konzentrationsbereich der Versuchssubstanzen wurde bei 25° hauptsächlich Octocalciumphosphat gebildet, während bei 37° calciumarme Apatite entstanden. Bei der letztgenannten Temperatur fiel das OCP nur bei niedrigen Konzentrationsprodukten aus, d.h. an der Ausfällungsgrenze. Bei relativ hohen Konzentrationsprodukten (Catot.×Ptot.〉10−4) und bei beiden Versuchstemperaturen wurden Gemische von Dicalciumphosphatdihydrat (DCPD) und Apatiten erhalten, indem der Konzentrationsbereich bei zunehmender Temperatur abnimmt.
    Notes: Abstract Precipitation of slightly soluble calcium phosphates from aqueous solutions of calcium chloride (3×10−4M to 1×10−1M) and sodium phosphate (Ptot. 1×10−3M to 6×10−2M, [NaOH]/[H3PO4]∼1.75, pH 7.4) was studied at 25° and 37°. Precipitates isolated 24 hours after mixing were identified by means of light and electron microscopy, X-ray and electron diffraction, chemical analyses and refractive indices. Over the widest range of reactant concentrations at 25°, octacalcium phosphate was predominantly formed, while at 37°, calcium deficient apatites were obtained. At the latter temperature OCP separated at very low concentration products only, i.e. at the precipitation boundary. At relatively high concentration products (Catot.×Ptot.〉10−4) and at both temperatures, mixtures of dicalcium phosphate dihydrate (DCPD) and apatites were obtained, the concentration region decreasing with increasing temperature.
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  • 9
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    Calcified tissue international 8 (1971), S. 228-236 
    ISSN: 1432-0827
    Keywords: Skin ; Calcinosis ; Keratin ; Chemistry ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des études histologiques antérieures ont montré que le follicle pileux est particulièrement susceptible de se calcifier, lorsque la peau de rats hypercalcémiques est lésée. Des analyses chimiques et par diffraction aux rayons X du follicule ont confirmé ce résultat. — En se basant sur l'augmentation du calcium et du phosphore, les calcifications débutent dans le tissue folliculaire 6–12 h après une blessure d'intensité moyenne de la peau de rats, ayant reçu du dihydrotachysterol (DHT), et 24–48 h après une blessure similaire chez des rats non injectés. Les diagrammes de diffraction aux rayons X sont diffus. Trois heures après la blessure, on note une augmentation du calcium du tissu folliculaire qui ne semble pas en rapport avec le DHT qui traduit probablement une liaison de calcium plutôt qu'un dépot minéral.
    Abstract: Zusammenfassung Frühere histologische Untersuchungen haben gezeigt, daß der Haarfollikel besonders anfällig für Verkalkungen ist, wenn die Haut von hypercalcämischen Ratten verletzt wird. Dieses Resultat wurde nun durch direkte chemische Bestimmungen und Röntgendiffraktions-analysen von Follikelgewebe bestätigt. Aufgrund der erhöhten Calcium- und Phosphatwerte kann gesagt werden, daß nach einer leichten Quetschung der Haut von Ratten, die mit Dihydrotachysterol (DHT) behandelt wurden, im Haarfollikelgewebe nach 6–12 Std Mineral-ablagerungen stattfanden, wogegen Kontrollratten mit der gleichen leichten Hautverletzung diese Ablagerungen erst nach 24–48 Std zeigten. Röntgendiffraktionsanalysen ergaben ein diffuses Apatit-Muster. Innerhalb 3 Std nach der Verletzung wurde ein Anstieg des Calcium-gehaltes im Follikelgewebe beobachtet, der nicht im Zusammenhang mit der DHT-Behandlung stand, also nicht eine Mineralablagerung, sondern eher eine Bindung von Calcium widerspiegelte.
    Notes: Abstract Previous histological investigations have shown that the hair follicle is particularly susceptible to mineralization when the skin of hypercalcaemic rats is injured. Direct chemical and X-ray diffraction analyses of follicle tissue have now confirmed this finding. As judged by increases in both calcium and phosphorus, mineral deposits began to form in hair follicle tissue 6–12 h after a mild crush injury to the skin of rats dosed with dihydrotachysterol (DHT), and 24–48 h after a similar injury to the skin of non-dosed rats. X-ray diffraction gave a diffuse apatite pattern. Within 3 h of injury there was a rise in the calcium content of follicle tissue which was not related to DHT-dosing and which was probably a reflection of calcium binding rather than mineral deposition.
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  • 10
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    Calcified tissue international 8 (1971), S. 304-319 
    ISSN: 1432-0827
    Keywords: Chemistry ; Calcium ; Phosphate ; Solubility ; Computer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Un programme d'ordinateur a été mis au point pour calculer les activités ioniques du calcium et l'orthophosphate dans un grand nombre de solutions. Dans le cas de solutions synthétiques, les calculs sont vérifiés en comparant les valeurs de pH, obtenues par ordinateur, avec celles observées expérimentalement. Des essais de ce type, avec des solutions possèdant des concentrations de calcium et d'orthophosphate trouvées dans les liquides biologiques et à des valeurs de pH variant de 3.00 à 10.00, indiquent que le programme est adapté pour des applications biologiques. Le programme n'est pas effectif pour des solutions, dans les lesquelles l'ion bromure est la source principale de la force ionique, sans doute, par manque d'équation étendue de Debye-Hückel dans ces circonstances. Aucune formation de complexe de phosphate de sodium n'a été notée à des concentrations biologiques normales.
    Abstract: Zusammenfassung Es wurde ein Computer-Programm ausgearbeitet, um die Ionenaktivitäten von Calcium und Orthophosphat in einer breiten Varietät von Lösungen zu berechnen. Die Berechnungen wurden bei synthetischen Lösungen durch Vergleiche zwischen den auf diese Weise errechneten pH-Werten und den experimentell gefundenen kontrolliert. Diese Art Kontrollen mit Calcium-und Orthophosphatkonzentrationen, wie sie in biologischen Flüssigkeiten gefunden werden, und mit pH-Werten zwischen 3,0 und 10,0 wies darauf hin, daß das Programm für biologische Anwendungen geeignet war. Das Programm konnte nicht benützt werden für solche Lösungen, bei welchen hauptsächlich das Bromidion zur Einstellung der Ionenstärke verwendet wurde, vermutlich weil die erweiterte Debye-Hückel-Gleichung unter diesen Umständen nicht anwendbar ist. Die Bildung eines Natriumphosphat-Komplexes unter normalen biologischen Konzentrationen konnte nicht nachgewiesen werden.
    Notes: Abstract A computer program has been designed to calculate the ionic activities of calcium and orthophosphate in a wide variety of solutions. In the case of synthetic solutions the calculations were checked by comparing the computed pH values with those observed experimentally. Tests of this type with solutions having the concentrations of calcium and orthophosphate found in biological fluids and with pH values ranging from pH 3.0–10.0 indicated that the program was suitable for biological applications. The program was not effective for solutions in which the bromide ion was a principal source of ionic strength probably because of the failure of the extended Debye-Hückel equation under those circumstances. No evidence for the formation of any sodium phosphate complex at normal biological concentrations could be found.
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  • 11
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    Calcified tissue international 7 (1971), S. 81-92 
    ISSN: 1432-0827
    Keywords: Strontium ; Vitamin D3 ; Calcium ; Absorption ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des poulets normaux, âgés de 2 semaines, présentent une condition voisine d'une rachitisme grave, lorsqu'on les soumet pendant 7 jours à un régime pauvre en calcium (0,1%), riche en vitamine D3, et contenant une quantité stable de strontium, équimolaire à 1,2% de calcium. Alors que l'on pensait que le rachitisme induit par le strontium était lié à une inhibition directe de la calcification, il apparait qu'avant toute modification osseuse apparente, le strontium inhibe la production du CaPB induit par la vitamine D3, ainsi que le mécanisme d'absorption intestinale du calcium. Il semble que cet effet du strontium soit lié à sa participation dans le mécanisme normal de la régulation du calcium au cours de la synthèse de CaBP.
    Abstract: Zusammenfassung Normale, 2wöchige Kücken gerieten innerhalb von 7 Tagen in einen schweren, rachitisänhlichen Zustand, wenn sie eine calciumarme (0,1%0 und Vitamin D3-reiche Nahrung erhielten, welcher kaltes Strontium in einer Konzentration von 2,62% (molaraequivalent mit 1,2% Calcium) zugesetzt wurde. Während man früher vermutete, daß die “Strontium-Rachitis” nur durch eine direkte Inhibition der Verkalkung entstehe, konnte nun gezeigt werden, daß — bevor eine sichtbare Knochenveränderung eintritt — die Vitamin D3-gesteuerte Bildung von CaBP (calciumbindendes Protein) und gleichzeitig der Mechanismus der Calciumabsorption im Darm durch Strontium gehemmt wird. Die gefundenen Resultate weisen auf die Möglichkeit hin, daß dieser Strontiumeffekt auf dessen Interferenz mit dem normalen Mechanismus der Calciumregulation durch die CaBP-Syntheses zurückgeführt werden kann.
    Notes: Abstract Normal 2-week-old chicks, when fed a low-calcium (0.1%), vitamin D3-replete diet containig stable strontium at a level equimolar to 1.2% calcium, developed a severe rachiticlike condition within 7 days. Whereas formerly it was suspected that “strontium rickets” resulted from direct inhibition of calcification only, it was shown that, preceding any detectable bone change, strontium inhibited vitamin D3-induced CaBP production and, simultaneously, the intestinal calcium absorptive mechanism. The results suggest the possibility that this effect of strontium may be due to its interference with the normal mechanism of calcium regulation of CaBP synthesis.
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  • 12
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    Calcified tissue international 7 (1971), S. 133-138 
    ISSN: 1432-0827
    Keywords: Hydroxyapatite ; Magnesium ; Crystals ; Isotopes ; Calcium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des cristaux d'apatite sont synthétisés dans des conditions physiological approximatives et en présence d'ions de magnésium. Après vieillissement de 4 à 21 jours, les cristaux sont analysés et l'échange du magnésium incorporé est étudié à l'aide de28Mg. A la fois, l'étude cinétique et l'ampleur des échanges indiquent que les ions de magnésium sont nettement rejetés de la maille de l'apatite. Au niveau de vieux cristaux, près de 90% du magnésium est situé dans des positions (de surface) échangeables. Ces résultats confirment la théorie qui admet que le magnésium de l'apatite est surtout un ion de surface. Ils expliquent la grande labilité du magnésium squelettique chez des animaux soumis à des régimes pauvres en magnésium.
    Abstract: Zusammenfassung Apatitkristalle wurden unter annähernd physiologischen Bedingungen und in Anwesenheit von Magnesiumionen synthetisiert. Nach einer Ausreifungszeit von 4–21 Tagen wurden die Kristalle und der Austausch des eingebauten Magnesiums mittels28Mg untersucht. Sowohl die Kinetik als auch das Ausmaß des Austausches zeigten, daß die Magnesiumionen vom Apatitgitter heftig abgestoßen werden. bie ausgereiften Kristallen waren nahezu 90% des Magnesiums leicht austauschbar an der Oberfläche gelagert. Durch diese Befunde wird ein Konzept unterstützt, wonach das im Apatit vorkommende Magnesium hauptsächlich ein oberflächengebundenes Ion ist. Ferner läßt sich dadurch erklären, weshalb bei magnesiumarm ernährten Tieren so leicht Magnesium aus dem Skelet verfügbar ist.
    Notes: Abstract Apatite crystals were synthesized under approximately physiological conditions and in the presence of magnesium ions. After ageing from 4 to 21 days, the crystals were analyzed and their exchange of incorporated magnesium studied with the use of28Mg. Both the kinetics and the extent of the exchange showed that magnesium ions were strongly rejected by the apatite lattice. In aged crystals, nearly 90% of the magnesium was located in readily exchangeable (surface) positions. These findings support one concept that apatitic magnesium is essentially a surface-limited ion and help to explain the ready availability of skeletal magnesium in animals on magnesium deficient diets.
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    Calcified tissue international 8 (1971), S. 83-86 
    ISSN: 1432-0827
    Keywords: Bone ; Strontium ; Calcium ; Vitamin D ; Calcification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des poulets sont nourris avec une alimentation contenant 0,5% de Ca et 0,5% de Sr, plus diverses concentrations de vitamine D3. La moitié des besoins en calcium pour la croisance corporelle chez le poulet est assurée par le Sr, tant que la concentration en Vitamine D3 est maintenue entre 500 et 1000 ICU/kg de nourriture. Les besoins totaux en calcium pour la croissance ne sont pas couverts par le Sr. Bien que Sr soit incorporé dans l'os lorsque l'alimentation renferme de faibles doses de vitamine D3, le contenu total en cendre, ainsi que le contenu en calcium, sont diminués.
    Abstract: Zusammenfassung Eine Untersuchung an Hühnern, welche Futter mit 0,5% Ca und 0,5% Sr und verschieden hohen Vitamin D3-Zusätzen erhielten, läßt vermuten, daß die Hälfte des für das Körperwachstum des Huhnes benötigent Ca durch Sr ersetzt werden kann, solange das Vitamin D3 in der Höhe von 500–1000 IE/kg Futter gehalten wurde. Die Gesamtmenge des für das Knochenwachstum benötigten Ca konnte jedoch nicht durch Sr ersetzt werden. Obschon Sr bei niederem Vitamin D3-Gehalt der Nahrung im Knochen eingebaut wurde, waren sowohl der totale Aschegehalt als auch der Calciumgehalt vermindert.
    Notes: Abstract An investigation involving chicks fed diets with 0.5% Ca and 0.5% Sr supplemented with various levels of vitamin D3 suggests that one-half of the Ca requirement of body growth in the chick is met by Sr as long as the vitamin D3 level was maintained at 500 to 1000 ICU/kg foodstuff. The entire Ca requirement for bone growth could not, however, be met by Sr. Even though Sr was incorporated into the bone when low levels of vitamin D3 were fed in the diet, the total ash content, as well as Ca content, was reduced.
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  • 14
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    Calcified tissue international 8 (1971), S. 197-210 
    ISSN: 1432-0827
    Keywords: Fluorescence ; Calcium ; Collagen ; Chemistry ; Bone ; Dentine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Des composants fluorescents de l'os et la dentine sont séparés des hydrolysats alcalins de leur marice sur des colonnes Sephadex C25 CM d'échange cationique. Les concentrations en fluorescence et le spectre d'excitation (λ max 330 nm) et d'émission (λ max 395 nm) sont les mêmes que ceux observés au niveau des matrices intactes et gélatinisées. Les paramètres de fluorescence ne sont pas altérés par hydrolyse. La filtration sur gel à l'aide de colonnes Sephadex G 10 perment de différencier le matériel isolé en deux composants, ayant la même fluorescence et la même absorption UV. La fluorescence est indépendante de pH de 3.5–9.5. Des études de dialyse et de filtration sur gel de matrices gélatinisées indiquent une association étroite du matériel fluorescent avec les chaines polypeptidiques de collagène.
    Abstract: Zusammenfassung Fluorescierende Bestandteile aus Knochen und Dentin wurden in Sephadex C25 CM Kationen-Austauschersäulen von alkalischen Hydrolysaten ihrer Matrices getrennt. Die Fluorescenzintensitäten sowie die Erregungs- (λ max 330 nm) und Emissions- (λ max 395 nm) Spektren waren dieselben wie bei intakten und gelatinisierten Matrices. Die Fluorescenzparameter wurden durch die Hydrolyse nicht verändert. Eine Gelfiltration über Sephadex-G10-Säulen trennte das isolierte Material in 2 Komponenten auf, welche gleiche Fluorescenz- und UV-Absorptionseigenschaften zeigten. Im pH-Bereich zwischen 3,5 und 9,5 war die Fluorescenz unabhängig vom pH. Dialysierversuche sowie Gelfiltrationsexperimente mitden gelatinisierten Matrices zeigten eine starkgefügte Bindung des fluorescierenden Materials mit den Polypeptidketten des Kollagens.
    Notes: Abstract Fluorescent components in bone and dentine were separated from alkaline hydrolysates of their matrices on Sephadex C25 CM cationic exchange columns. The fluorescence levels, and the excitation (λ max 330 nm) and emission (λ max 395 nm) spectra, were the same as those observed in the intact and gelatinised matrices. The fluorescence parameters were unaltered by the hydrolysis procedure. Gel filtration on Sephadex G. 10 columns further resolved the isolated material into two components with the same fluorescence and UV absorption properties. The fluorescence was independent of pH over the range 3.5–9.5. Dialysis and gel filtration studies on the gelatinised matrices indicated a firmly-bonded association of the fluorescent material with the collagen polypeptide chains.
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    Calcified tissue international 8 (1971), S. 154-164 
    ISSN: 1432-0827
    Keywords: Calcium ; Phosphate ; Fluoride ; Calcification ; Tooth Enamel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Les dépôts simultanés en calcium, phosphate et fluorure et le taux de formation en ion hydrogène, pendant la minéralisation, de surfaces d'émail, attaquées par des acides, sont mesurés du point de vue cinétique dans un système fermé. Le taux de dépôt en calcium et phosphate, à partir de la solution, dépend des concentrations en fluorure et du pH. Les proportions de calcium par rapport au phosphate et de calcium par rapport au fluor suggère la formation de fluoroapatite ou de fluorohydroxyleapatite sur l'émail. L'adjonction d'ions hydroxyles pour maintenir un pH constant au moment du dépôt minéral, dépasse les ions phosphates totaux qui se déposent. Ce fait semble indiquer la possibilité d'une hydrolyse de phosphate acide pendant le dépôt minéral.
    Abstract: Zusammenfassung In einem geschlossenen System wurden die gleichzeitigen Ablagerungen von Calcium, Phosphat und Fluorid sowie die Geschwindigkeit der Wasserstoffionenproduktion während der Mineralbildung an säureverätzten Zahnschmelz-Oberflächen kinetisch gemessen. Die Ablagerungsgeschwindigkeiten von Calcium und Phosphat aus der Lösung hingen von den Fluoridkonzentrationen und dem pH ab. Das Verhältnis von Calcium zu Phosphat und von Calcium zu Fluorid zeigte die Bildung von Fluorapatit oder Fluorhydroxyapatit auf dem Zahnschmelz an. Die Hydroxylionenzugaben, welche nötig waren, um das pH während der Mineralablagerung konstant zu halten, überschritten die totalen, aus der Lösung ausgeschiedenen Phosphationen. Dies weist auf die Möglichkeit hin, daß während der Mineralablagerung eine saure Phosphat-Hydrolyse stattfindet.
    Notes: Abstract Concurrent calcium, phosphate and fluoride depositions, and the rate of hydrogen ion production, during formation on acid etched enamel surfaces were kinetically measured in a closed system. The deposition rate of calcium and phosphate from solution was dependent on the fluoride concentrations and pH. The proportions of calcium to phosphate and calcium to fluoride indicated fluorapatite or fluorhydroxyapatite formation on the enamel. The hydroxyl ion additions to maintain constant pH, concurrent with mineral deposition, exceeded the total phosphate ions deposited from solution. This indicates the possibility that acid phosphate hydrolysis occurs during mineral deposition.
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  • 16
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    Calcified tissue international 8 (1971), S. 172-176 
    ISSN: 1432-0827
    Keywords: Sodium ; Calcium ; Strontium ; Bone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Une colonne faite de poudre d'os dégraissé peut discriminer le22Na et le85Sr ou le47Ca. Le sodium est absorbé et élué par une telle colonne à une vitesse plus rapide que les deux autres isotopes. Ces observations rendent inutiles d'admettre l'existence d'un processus actif comme explication principale du comportement différentiel du Na et de ces cations multivalents d'osin vivo.
    Abstract: Zusammenfassung Eine Säule bestehend aus entfettetem Knochenpulver erlaubt die Unterscheidung zwischen22Na und85Sr oder47Ca. Natrium wird von einer solchen Säule schneller aufgenommen und eluiert als die beiden anderen Isotopen. Die Annahme eines aktiven Prozesses als hauptsächliche Erklärung für das differenzierte Verhalten von Na und diesen multivalenten Kationen im Knochenin vivo wird auf Grund dieser Beobachtung überflüssig.
    Notes: Abstract A column constructed of defatted bone powder can discriminate between22Na and58Sr or47Ca. Sodium is taken up, and eluted, from such a column at a more rapid rate than the other two isotopes. These observations make it unnecessary to assume the existence of an active process as a major explanation for the differential behaviour of Na and these multivalent cations in bonein vivo.
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  • 17
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    Calcified tissue international 7 (1971), S. 201-211 
    ISSN: 1432-0827
    Keywords: Autoradiography ; Calcium ; Oviduct ; Shell-gland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé La localisation cellulaire du calcium de la muqueuse de l'oviducte d'oiseaux a été étudiée par autoradiographie au45Ca, à partir de tissus préparés soit par incubation dans le45Ca, soit par injection intraveneuse du45Ca. La congélation — substitution est utilisée pour retenir le calcium aisément diffusible dans le tissu. L'épithelium cylindrique de la glande de la coquille s'enrichit significativement plus en45Cain vitro, en fonction de l'augmentation du temps d'incubation, de une à dix minutes et/ou en élevant la température de 0° à 42°. Ces effets sont diminués par l'adjonction de dinitrophenol au milieu d'incubation. Les glandes tubulaires de ce tissu réagissent à peine. Généralement, après injection intravenieuse de45Ca, la glande de la coquille retient plus de radionuclide que les autres régions de l'oviducte. Lorsqu'une coquille d'œuf est en voie de calcification, l'épithelium cylindrique de cette glande contient plus de grains que les glandes tubulaires, mais, en cas d'absence de formation d'œuf, le nombre de grains est identique dans les 2 types cellulaires. Il semble que l'épithélium cylindrique de la glande de la coquille a une affinité plus grande et plus variable pour le45Ca que la glande de la coquille les glandes tutulaires ou les cellules muqueuses d'autres régions de l'oviducte. Ces résultats indiquent sans le prouver, que l'épithélium cylindrique est plus actif dans le transfert du calcium des vaisseaux sanguins vers la lumière de la glande de la coquille.
    Abstract: Zusammenfassung Die celluläre Verteilung von Calcium in der Eileitermucosa von Hühnern wurde anhand von45Ca-Autoradiographien in Gewebe studiert, welches entweder durch Inkubation mit45Ca oder durch intravenöse Injektion von45Ca präpariert wurde. Gefriersubstitution wurde verwendet, um leicht diffundierbares Calcium im Gewebe zurückzuhalten.In vitro nahm das Cylinderepithel der Schalendrüse auffallend mehr45Ca auf, wenn die Inkubationszeit von einer auf zehn Minuten verlängert wurde und/oder wenn die Temperatur von 0° auf 42° erhöht wurde. Diese Wirkungen wurden durch die Zugabe von Dinitrophenol zum Inkubations-medium vermindert. Die Tubulärdrüsen dieses Gewebes reagierten kaum. Im allgemeinen schlossen die Schalendrüsen nach intravenöser Injektion von45Ca mehr Radionuklid ein als andere Teile des Eileiters. Wenn eine Eierschale calcifizierte, zeigte das Cylinderepithel der Schalendrüse bei der Autoradiographie eine höhere Anzahl von Silberkörnern als die Tubulärdrüsen, aber wenn keine Schale gebildet wurde, war sie bei beiden Zelltypen ähnlich. Die Resultate zeigen, daß das Cylinderepithel der Schalendrüse, eine größere und unterschiedlichere Affinität für45Ca hat als Schalendrüse Tubulärdrüsen oder Schleimhautzellen aus anderen Gebieten des Eileiters. Die Befunde deuten darauf hin, aber beweisen es nicht, daß das Cylinderepithel beim Transport von Calcium aus den Blutgefäßen in die Schalendrüse das aktivste ist.
    Notes: Abstract The cellular location of calcium in the mucosa of the avian oviduct has been studied by45Ca autoradiography in tissue prepared either by incubation with45Ca or by intravenous injection of45Ca. Freeze-substitution was used to retain easily diffusible calcium in the tissue.In vitro, columnar epithelium of the shell gland acquired significantly more45Ca as the length of incubation time was increased from one to ten minutes and/or when the temperature was raised from 0° to 42°. These effects were diminished by the addition of dinitrophenol to the incubation medium. The tubular glands of this tissue responded minimally. Genrally, after intravenous injection of45Ca, the shell gland sequestered, more radionuclide than the other regions of the oviduct. When an egg shell was being calcified, the columnar epithelium of the shell gland revealed a higher grain count than the tubular glands, but when a shell was not forming, grain counts were similar over the two types of cells. The results show that the columnar epithelium of the shell gland has a greater and more variable affinity for45Ca than have the shell gland tubular glands or mucosal cells from other regions of the oviduct. The data suggest, but do not prove, that the columnar epithelium is the most active in translocation of calcium from the blood vessels to the lumen of the shell gland.
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    Calcified tissue international 7 (1971), S. 299-306 
    ISSN: 1432-0827
    Keywords: Kinetics ; Calcium ; Metabolism ; Lactation ; Strontium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Le taux de dépôt du calcium et l'ampleur du calcium total échangeable sont déterminés chez le rat entre le 12ème et 17ème jour de lactation, après une injection intrapéritonéale unique de47Ca et85Sr. L'activité spécifique du sérum et la rétention des deux isotopes radioactifs dans l'organisme entier et le tibia (diaphyse et épiphyses) sont déterminées. L'analyse des résultats est réalisée à l'aide du modèle cinétique de Bauer à un compartiment unique. C'est ainsi qu'on observe une diminution du taux de dépôt et une augmentation du calcium total échangeable pendant la lactation.
    Abstract: Zusammenfassung Die Geschwindigkeit der Calciumzunahme und die Größe des austauschbaren Calciumpools wurde bei Ratten zwischen dem 12. und 17. Tag der Lactation nach einer einmaligen intraperitonealen Injektion von47Ca und85Sr bestimmt. Die spezifische Aktivität beider radioaktiven Isotopen im Serum und ihre Retention im ganzen Körper und in der Tibia (Schaft und Epiphysen) wurden bestimmt. Das kinetische Modell von Bauer für ein Kompartiment wurde für die Datenanalyse verwendet. Die Resultate zeigen eine Verminderung der Zunahmegeschwindigkeit und eine Erhöhung des austauschbaren Calciumpools bei laktierenden Tieren, verglichen mit unbegatteten Ratten.
    Notes: Abstract The calcium accretion rate and the size of the exchangeable calcium pool was determined in rats between the 12th and 17th day of lactation after a single intraperitoneal injection of47Ca and85Sr. The serum specific activity and the retention of both radioactive isotopes in the whole body and tibia (shaft and ends) was determined. The single compartment kinetic model by Bauer was used for the analysis of data. The results show a decrease in the accretion rate and an increase in the exchangeable calcium pool in lactating rats as compared to unmated animals.
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    Calcified tissue international 8 (1971), S. 73-82 
    ISSN: 1432-0827
    Keywords: Bone ; Calcium ; Phosphorus ; Sodium ; Magnesium ; Electron probe
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé L'analyse par microsonde électronique, technique récente, a été peu utilisée pour l'étude du tissu osseux. Le rapport molaire Ca/P a été mesuré pour l'os normal et certains os pathologiques. Les résultats sont en accord avec ceux obtenus par les autres méthodes, en particulier la microradiographie. La microsonde électronique permet le dosage du sodium et du magnésium, constituants secondaires de l'os, à l'échelle microscopique. Nos observations mettent en évidence l'hétérogénéité de la distribution de ces éléments: concentration élevée dans l'os jeune (ostéone), moindre dans l'os interhaversien. Ces résultats sont en accord avec l'hypothèse de Neuman de l'absorption des ions sodium et magnésium à la surface du crystal d'apatite.
    Abstract: Zusammenfassung Die Mikroanalyse mittels Elektronensonde ist eine neue Technik für die Untersuchung von Knochen; die Bedingungen für eine richtige Interpretation der Resultate werden beschrieben. Das molare Ca/P-Verhältnis wurde in normalen und in drei pathologischen Knochen gemessen. Diese Messungen wurden in verschiedenen Regionen des corticalen Knochens durch-geführt. Die Resultate stimmen mit den durch Mikroradiographie erhaltenen überein. Mikroanalysen mittels der Elektronensonde ermöglichten es, die Verteilung von Na und Mg in den zwischenhaversschen und haversschen Geweben von corticalem Knochen Erwachsener zu untersuchen. Unsere Beobachtungen zeigen die heterogene Verteilung dieser Elemente. In Übereinstimmung mit der Hypothese der Ionen-Absorption an der Oberfläche des Apatitkristalles sind die Konzentrationen in jungen Knochen (Oesteonen) höher.
    Notes: Abstract Electron probe microanalysis is a recent technique for the study of bone and the conditions for the correct interpretation of the results are described. The Ca/P molar ratio was measured in normal and in three pathological bones. These measurements were carried out in different regions of cortical bone. The results are in agreement with the results obtained by microradiography. Microprobe analysis, however, allows the measurement of elements at the microscopic level. Electron probe microanalysis was used to study the distribution of sodium and magnesium in the interhaversian and haversian tissues of adult cortical bone. Observations show the heterogeneity of distribution of these elements. Concentrations are higher in young bone (osteons), in agreement with the hypothesis of ion absorption on the surface of the apatite crystal.
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    Calcified tissue international 8 (1971), S. 265-275 
    ISSN: 1432-0827
    Keywords: Calcium ; Vitamin D ; Zinc ; Bone ; Teeth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Description / Table of Contents: Résumé Deux groupes de rats sevrés sont soumis à une alimentation contenant un excès de zinc, une faible quantité de calcium avec ou sans vitamine D. Deux tiers des animaux dans les deux groupes sont sacrifiés respectivement après cinq et dix semaines, alors que les animaux restants sont soumis à ce régime pendant cinq semaines, puis, pendant les cinq semaines suivantes, reçoivent les régimes correspondants, avex une concentration normale de zinc. Des études histologiques et microradiographiques sont réalisées sur l'humérus et les incisives. L'effet porotique connu des régimes pauvres en calcium et normaux en vitamine D est notablement augmenté avec un excès de zinc. Après avoir ramené le zinc à la normale, la gravité de l'ostéoporose est réduite à celle recontrée au cours de concentration faible en calcium, avec peu d'effet sur la dentine. L'absence de vitamine D, dans les régimes à contenu élevé en zinc et faible en calcium, provoque des changements porotiques et ostéomalaciques des os, alors que le ratrait consécutif de l'excès de zinc provoque une ostéomalacie typique. La dentine est nettement atteinte et des bandes alternantes de tissus bien mal minéralisés sont observées. En ajustant le zinc ingéré à une concentration normale, de larges couches de dentine non minéralisée sont observées avec une bande étroite de tissu minéralisée. En l'absence de vitamine D, l'excès de zinc semble exercer un effet porotique sur l'os et un effet de minéralisation sur la dentine, alors qu'il augmente l'effet porotique au niveau de l'os lorsque la vitamine est présente.
    Abstract: Zusammenfassung Zwei Gruppen entwöhnter Ratten wurden mit Calcium-armen Futter mit oder ohne Vitamin D-Zusatz und einem Zinküberschuß ernährt. Zwei Drittel der Tiere in beiden Gruppen wurden nach 5, beziehungsweise nach 10 Wochen getötet, während die übrigen Tiere dieses Futter während 5 Wochen erhielten und anschließend für weitere 5 Wochen die entsprechende Nahrung mit einem normalen Zinkgehalt bekamen. Die Humeri und die Schneidezähne wurden dann histologisch und mikroradiographisch untersucht. Der bekannte porotische Effekt der Calcium-armen, normal Vitamin D-haltigen Nahrung war bei Zinküberschuß deutlich erhöht. Wurde die Zinkaufnahme zur Norm gebracht, so reduzierte sich der Grad der Porose auf denjenigen, der typisch für niedrige Calcium-Einnahmen ist, mit wenig Wirkung auf das Dentin. Fehlte das Vitamin D in der Zink-reichen und Calcium-armen Nahrung, so entstanden in den Knochen sowohl porotische als auch osteomalazische Veränderungen; nach Absetzen des Zinküberschusses jedoch entstanden typische Anzeichen einer Osteomalacie. Das Dentin wurde stark angegriffen, und es wurden abwechslungsweise Banden von normal und schlecht mineralisiertem Gewebe beobachtet. Wenn die Zinkeinnahme zur Norm gebracht wurde, so entstanden breite Säume von unverkalktem Dentin mit einer schmalen Bande von mineralisiertem Gewebe. Bei Fehlen von Vitamin D scheint der Zinküberschuß eine porotische Wirkung auf den Knochen und eine verkalkende Wirkung auf das Dentin zu haben; dieser Überschuß erhöht den Grad der Knochenporose auch in Anwesenheit des Vitamins.
    Notes: Abstract Two groups of weanling rats were maintained on diets containing an excess of zinc, with low calcium intake and with, or without, added vitamin D. Two thirds of the animals in the two groups were killed after five and ten weeks respectively while the remainder received these diets for five weeks and were then maintained for a further five weeks on the corresponding diets with a normal level of zinc. Histological and microradiographical observations of the humeri and incisors were then carried out. The known porotic effect of low calcium-normal vitamin D diets was markedly increased in zine excess. After adjusting the intake of zinc to normal, the degree of porosis was reduced to that typical of low calcium conditions, with little effect on the dentine. Absence of vitamin D from the zinc-low calcium diet resulted in both porotic and osteomalacic changes in the bones, while subsequent removal of the zinc excess resulted in a condition typical of osteomalacia. Dentine was drastically affected and, alternating bands of poorly and adequately-mineralized tissue were observed. Adjusting the zinc intake to normal resulted in wide seams of unmineralized dentine with a narrow band of mineralized tissue. In the absence of vitamin D, zinc excess appears to exert a porotic effect in bone and a mineralizing effect in dentine, while it also increases the degree of porosis found in bone when the vitamin is present.
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    Cell & tissue research 121 (1971), S. 181-198 
    ISSN: 1432-0878
    Keywords: Heart muscle cells ; Calcium ; Mitochondria ; Intercalated discs ; Excitation-contraction coupling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary To investigate calcium distribution in cardiac muscle cells, two methods, one using oxalate and another using lead acetate, were used concomitantly to determine the subcellular localization of calcium. Particular attention was paid to the specificity of the methods employed. Chemical and physical analyses of the electron-opaque deposits of the reaction end-products was performed by chelation with EGTA or X-ray and electron diffraction. Results obtained show that the distribution of the calcium deposits in the cardiac muscle cells is more complex than that described for striated muscle fibers. The implications of these findings are discussed and an original viewpoint on the calcium distribution and movement in cardiac muscle cells is presented.
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    Biopolymers 10 (1971), S. 1049-1057 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultrastructural morphology and x-ray and electron diffraction of poly (Gly-Gly-Ala) have been studied. The polymer has two forms; the first, form I possesses a super-folded cross-β structure, long fibers of which show some twisting and intertwining. Form II precipitates in a less distinct fibrous form from aqueous solution. The x-ray diffraction and oriented electron diffraction data suggest that form II is a polyglycine II helix situated in a monoclinic cell with dimensions a = 8.86 Å, b = 22.0 Å, c = 9.42 Å, and β = 90°. Combined with the morphological evidence it appears likely that form II is also in an antiparallel superfolded array.
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    Biopolymers 10 (1971), S. 1099-1101 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A statistical mechanical model was developed for use in connection with the problem of preferential binding of solvent components to proteins and of conformational transition in water-organic solvent systems. The model is a statistical one for the conformational transition of globular proteins induced by the adsorption of solutes in the solution, considered as a nearest-neighbor problem in statistical mechanics. Although a few illustrative examples are given, the actual interpretations of the experimental data using this theory are reserved for a later paper.
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    Biopolymers 10 (1971), S. 1103-1103 
    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 10 (1971), S. 1121-1138 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concept and representation of a logical tree as defined in computer science is applied to obtain a suitable representation of protein molecules in computer programs which handle or calculate atomic coordinates of protein molecules. On the basis of this analysis and of the analysis of the calculation and modification of the structure of a protein from bond lengths, bond angles, and dihedral angles, which is reproduced in an appendix, program modules which accomplish the various required computations are described. Three such modules are given in Iverson notation; in fact, it is hoped that this article will serve as a reasonably complete basis for the preparation of machine programs by moderately proficient programmers.
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    Biopolymers 10 (1971), S. 1207-1212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism spectrum obtained from a dilute aqueous solution of poly (ala-gly-gly) resembles that described for charged polypeptides such as the salt form of poly glutamic acid. A similar spectrum is found for films cast from aqueous solution where x-ray studies reported elsewhere have indicated a poly-glycinc II conformation. Evidence is presented for a heat induced poly-glycine II to unordered state transition similar to that described for collagen. The interpretation of this, the first observation of the optical properties of a poly-amino acid in the poly glycine II conformation, is further rationalized on the basis of spectra obtained from a number of polypeptides whose conformation approaches that of a 31 helix.
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    Biopolymers 10 (1971), S. 1229-1242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of cupric ion on the emission of tryptophan, tyrosine, and serum albumins is studied by emission spectroscopy and lifetime measurements. It is found that whenever cupric ion is bound to tryptophan or tyrosine, their emissions are quenched completely. The quenching may be due to an electron transfer mechanism. The fluorescence of complexes of cupric ions with serum albumins is partially quenched; this is because energy is transferred from tryptophan to the complexed cupric ions by a dipolar energy transfer mechanism. It is deduced from the present study that the tryptophan in the human serum albumin molecule is between 11 and 16 Å from the nearest eupric ion binding sites (assumed to be at the surface of the protein) and that one of the tryptophan in the bovine serum albumin molecule is very close to the cupric ion binding sites and the other is near the center of the bovine serum albumin molecule. It is also found that the deuterium solvent effect on serum albumin fluorescence is very small, and that the quenching of bovine serum albumin fluorescence at the N-F transition is the result of quenching of the fluorescence of both tryptophans. The phosphorescence lifetime apparatus, capable of measuring decay times of signals with intensities changing over a few orders of magnitude, and the ratio spectrofluorometer, both of which were constructed in this laboratory, are also described.
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    Biopolymers 10 (1971), S. 1253-1260 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The measurements were made for the volume and the sound velocity changes (ΔV and ΔU) on titrating the sodium salt of poly (S-carboxymethyl L-cysteine) with dilute HCl. For the reaction, —COO- + H+ → —COOH, ΔV per mole of H+ bound was + 12. 7 ml and +11. 4 ml in salt-free and 0. 2 M NaCl solutions, respectively. Corresponding ΔU was about -13 cm/sec in salt-free polymer solution where 11.5 mM carboxylate ion reacts with equimolar hydrogen ion. ΔV associated with the coil-to-β transition was found to be +2. 35 ml in H2O and +1. 90 ml in 0. 2 M NaCl per mole of amino acid residue, respectively. These values are larger than those obtained for the coil-to-helix transition of poly (L-glutamic acid). ΔU for the transition was about -30 cm/sec in salt-free solution of polymer concentration 0.0115 mole/liter. Possible sources of ΔV and ΔU for reaction; coil → β, are (1) the formation of void volume and (2) the changes in the extent of solvation in amide linkage and in side chain.
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    Biopolymers 10 (1971), S. 1317-1329 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of three aromatic molecules to apomyoglobin has been investigated. In each case equilibrium dialysis studies and tryptophan fluorescence quenching studies indicate that a one to one complex has been formed. The fluorescence quenching studies further suggest that the binding of the aromatic molecules is at the heme site with possible involvement of the arginine CD3. Xenon, which is known to quench the fluorescence of aromatic hydrocarbons, is found to be bound to apomyoglobin-aromatic molecule complexes and quenches the emission of the aromatic molecule in the complexes. Oxygen quenches pyrene fluorescence in water solution but does not quench the pyrene fluorescence from the apomyoglobin-pyrene complex. This is explained by a slower rate of diffusion of oxygen to pyrene in the apomyoglobin-pyrene complex.
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    Biopolymers 10 (1971), S. 1365-1369 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotor speed-dependent aggregation of T4 DNA in the analytical ultracentrifuge is studied in the presence of high pressure generated by compressed nitrogen gas in the cell. The extents of aggregation at various speeds are found to be practically the same in the presence and absence of pressure.
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    Biopolymers 10 (1971), S. 1331-1349 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-dependent theory developed in Part I is specialized to treat tetrameric hemoglobin, and the results of the theory for dimeric-and tetrameric hemoglobin are compared with data on the kinetics of the reactions of hemoglobin with carbon monoxide and oxygen at various salt concentrations for the case of large concentration of ligand relative to that of hemoglobin. The fit of the theoretical results to the data suggests that hemoglobin at a 2 M salt concentration is predominantly dimeric and that the tetramer should be taken as the functional unit to explain the kinetics of the reactions of normal hemoglobin. A relationship is established between the time-dependent theory arid Adair's Intermediate Compound Hypothesis (I.C.H.) for hemoglobin, as brought to its present state by Gibson and Roughton. A generalization (G.I.C.H.) of the I.C.H. is presented and is shown to be equivalent to the time-dependent theory in the limit of infinite ligand concentration. The I.C.H. is shown to be an excellent approximation to the centralized theory (G.I.C.H.) in this limit.
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    Biopolymers 10 (1971), S. 1421-1425 
    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 10 (1971), S. 1427-1428 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 1429-1454 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of oligodesoxyribonucleotides of various chain lengths to form complexes has been compared with that of oligoribonucleotides. Four series of oligonucleotidcs were prepared and investigated, i.e., dCn at acid pH versus rCn, dAn and dTn versus. rAn and rUn at neutral pH. The results indicate that in dilute solution, the formation of complexes is greatly facilitated in the case of desoxyoligomers and occurs for shorter oligomere than in the corresponding ribooligomers. The spectrophotometric titration of deoxyribooligo C indicates the appearance of two pK values in the 4-5 pH region characteristic of the double-stranded form, which occurs for much shorter dCn than rCn. The circular dichroism (CD.) spectra of deoxycytidylies in dilute solution starting from the trimer are conservative, characteristic of the double-stranded helical form of poly C at acid pH. In contrast, the CD spectra of a series of corresponding ribo Cn, under identical conditions is of nonconservative character similar to that of the single-stranded form of poly C at neutral pH, but differs in the band position. This spectrum is called intermediate. Only at higher concentrations of oligonucleotidcs (i.e., 10-3Minstead of 10-4M) does the circular dichroism spectrum of longer ribocytidylics assume conservative character. Thermal denaturation of deoxycytidylces at acid pH are strongly dependent on chain length and concentration, its one would expect for a cooperative helix-coil transition. The circular dichroism spectra measured at different temperatures shows one isosbestic point. In dilute solution, the standard-state enthalpy change found was 5-6 kcal/mole for higher oligomers (dC7). These properties are all in agreement with a structural transition from the d-Cn double-stranded form to a coil for n 〉 3. Studies of dAn and dTn in solutions of high ionic strength at low temperature indicate that complex formation occurs already at the level of trimer and for high oligomers. Under identical conditions a complex between rAn and rUn is detected only for oligomers longer than the hexamer. The nature of the “intermediate” form of oligoribo C at acid pH and low temperature was investigated by sedimentation and circular dichroism. A model of rCn is proposed of linear molecules which are partially double-stranded and partially single-stranded, which probably are slowly rearranged by “slippage” into a regular-double-stranded helical form.
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The number average molecular weight, Mn, of low molecular weight dextran was determined through endgroup analysis, and the intrinsic, viscosities of these materials in aqueous solution were determined at 25°C. The ultrasonic velocities in their aqueous solutions were also measured at 25 and 45°C. As concerns the molecular weight dependence of the intrinsic viscosity, partial specific compressibility of solute and the hound water around the solute, the following results were obtained. (1) log [η]-log Mn and [η]/Mn0.5 - Mn0.5 plots were in accord with the Mark-Houwink and Stockmayer-Fix-man equations respectively for Mn 〉 2, 000, but these plots deviated from the equations for Mn 〈 2, 000. (2)The partial specific compressibility, β1°, of dextran is expressed by following equation for Mn 〈 2,000: β1° = 10-12 × (13.6 log Mn - 51.7) (cm2/dyne). In contrast, it, becomes the constant value, -- 7.3 × 10-12 cm2/dyne, for Mn 〉 2,000. (3) The amount of bound water of dextran calculated from the sound velocity measurement lakes constant value of 0.17 ml g for Mn 〉 2, 000, but the amount of hydration increase with decreasing molecular weight for Mn 〈 2,000. From these results, a dextran molecule in aqueous solution is expected to change its conformation from random coiling to uncoiling stretched form at the molecular weight of around 2, 000 or about 12 glucose units.
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    Biopolymers 10 (1971), S. 1559-1581 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical rotation studies were performed on five compounds containing two peptide groups. Four of the molecules were confined to restricted regions of conformational space by the presence of closed rings. Solvent and temperature were varied, and theoretical calculations were done for each compound covering the appropriate conformational space. The interpretation which results is qualitatively successful over the conformational regions covered by the compounds. Quantitative correlation between theory and experiment will require compounds of high rigidity.
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    Biopolymers 10 (1971), S. 1617-1623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy maps have been calculated for α-D-mannuronic acid (1-4) α-L-guluronic acid and for α-L-guluronic acid (1-4) β-D-mannuronic acid. These have been used, together with maps previously calculated for the homomonomeric dimers, to estimate the characteristic ratios and Kuhn lengths of the alternating copolymer and of a stochastic copolymer similar in composition to that extracted from L. digitata.The results show that the alternating copolymer is less extended than either homopolymer. Kuhn lengths calculated for the stochastic copolymer agree well with experimental results on high ionic strength solutions of alginate isolated from L digitata.
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    Biopolymers 10 (1971), S. 1635-1648 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-S-carboxyethyl-L-cysteine, a higher side-chain homolog of poly-S-carboxymethyl-L-cysteine, has been prepared from poly-S-carbobenzoxyethyl-L-cysteine with hydrogen bromide in chloroform or acetic acid. The polymer is found to be in the β-conformation of an antiparallel arrangement of polypeptide chains in solid films, both in acid and salt forms, when examined by infrared spectra. Aqueous solutions of t he polymer have been investigated by measurements of rotatory dispersion and circular dichroism as well as by infrared spectra in D2O. These properties show sharp changes around pH 5.5, as the pH of solution is varied. At higher ionization the polymer is randomly coiled, but at lower ionization it is in the β-conformation. Dependence of the rotatory properties upon polymer concentration as well as on ionic strength has been observed even at the lowest degree of ionization attained, and this has been attributed to the formation of intermolecular β-conformation in solutions. The β-structure is characterized by a negative circular dichroic band at 223 mμ and a positive dichroic band at a wavelength lower than 200 mμ, and furt her by a negative bo value, -140°. The pH-induced coil-β transition of the polymer is compared with that of poly-S-carboxymethl-L-cysteine.
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    Biopolymers 10 (1971), S. 1681-1699 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific heat, of rat tail tendon at various water contents was measured as a function of temperature. The resulting graphs showed peaks arising from the melting, near 50°C, of helical material in the collagen, and from the melting of absorbed water in the range -40°C to 0°C. The heat of melting of helical material was 11.7 cal per gram of dry tendon. Determination of the heat and temperature of fusion of the absorbed water allowed resolution of the water into four states in the case of tendon before denaturation, and three states after denaturation. The four states are (1) water not freezable on cooling to - 70°C, (2) freezable water with-both heat and temperature of fusion different from the values for ordinary water, (3) freezable water with the heat of fusion of ordinary water, but a different temperature of fusion, and (4) water not distinguished from ordinary water. The fourth state was absent in denatured tendon. The results are discussed in terms of increasing size of clusters of absorbed water molecules.
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 1743-1757 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption and rotatory properties of acridine orange-poly-S-carboxymethyl-L-cysteine system in water and in 0.2 M NaCl have been measured at different pH and polymer-to-dye mixing ratios. The absorption spectra indicate that the dyes are bound to the polymer in dimeric or highly aggregated forms. At neutral pH where the polymer is randomly coiled, no optical activity is induced on the absorption bands of bound acridine orange. At acid pH where the polymer has the β-conformation, a pair of positive and negative circular dichroic bands occur at each of the absorption bands, centered around 458 and 261 mμ. The signs of those bands are opposite to those found for α-helical poly-L-glutamic acid. A model for the binding of dye to the β-form polymer is presented, in which dimeric dyes are attached to ionized carboxyl groups and slack one another to form linear arrays on both sides of an extended polypeptide chain. The observed circular dichroism spectra can be explained by the Tinoco's exciton mechanism, based on this model. Low molecular weight poly-S-carboxymethyl-L-cysteine induces quite a different circular dichroism on bound acridine orange.
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    Biopolymers 10 (1971), S. 1853-1863 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dicrosim (CD) spectra of complexes of DNA with ethidiun bromnide, profiavine, 9-aminoacridine and 4-etliyl-9-amino-acridine have been determined between 220 and 450 nm, the range lieing extended to 600 nm for ethidiufm bromide. The variation of the magnitude of the visible and near - ultraviolet CD spectra of ethidium bromide - DNA complexes with the amount of ligand bound (r) suggests a common binding position with profiavine. On the other hand, 4-ethyl-9-aminoacndine complexed to DNA shows CD spectra not distinguishable from those of 9-aminnoacnidmc in both the visible and ultraviolet. The interpretation of these results with respect to the stereochemistry of the DNA-ligand complexes is discussed.
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    Biopolymers 10 (1971), S. 1901-1924 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The various treatments of sedimentation equilibrium are compared on a theoretical and an experimental basis. Particular attention is paid to the polyelectrolyte nature of the problem and the choice of a neutral component. The effective density gradients of several cesium salts for DNA are measured. Two previous theories for the effective density gradient are shown to be equivalent, and the experimental values are interpreted with respect to these theories. It is clear t hat sedimentation equilibrium in a density gradient may be used for the determination of unambiguous molecular weights.
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    Biopolymers 10 (1971), S. 1949-1972 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The theory of friction-limited DNA unwinding is developed explicitly for moderate tind large perturbations. This extension of the earlier theory of the relaxation kinetics is necessary because of the complex nature of the rate limitation for small perturbations. The assumption of the theory that is violated under relaxation conditions is that base pairing reactions occurring at a constant local degree of twist of the strands are fast compared to the net unwinding of the molecule. However, these reactions that are slow for small perturbations have a large activation energy, and become faster than friction-limited un winding for large enough temperature jumps and sufficiently large DXA molecules. Thus only the rate for moderate and large perturbations is clearly limited by frictional resistance to turning the molecule in solution. The model used is a diffusional unwinding of the two strands, driven by the accompanying decrease in free energy. For large perturbations a numerical solution of the diffusion equation is required, since the diffusion coefficient is not constant. Two new parameters must be introduced into the equilibrium statistical theory to describe friction-limited unwinding kinetics. These are the force constant b, for winding up coil regions and the frictional coefficient per base pair βcfor rotating coil regions in solution. We find by fitting the theory to experiment that b = 1.8 × 10-13 ergs/ rad2- and βc = 3.5 × 10-21 erg see/base pair, both for DNA melted in alkali at 0.4.M Na + and ∼30 °C. The latter value is in agreement with predictions based on the viscosity of single stranded DNA in alkali. The quoted value of bcan be interpreted to mean that the number of conformational states of a nucleolide is reduced by an average factor of 1.55 when it is wound around another strand to the degree of twist in a double helix, but without forming a base pair.
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    Topics: Chemistry and Pharmacology
    Notes: The properties of oligonucleotide helices of adeuylic- and uridylic acid oligomers have been investigated by measurements of hypo-and hyperchromieity. High ionic strengths favor the formation of triple helices. Thus, the double helix-coil transition can be studied (without interference by triple helices) only at low ionic-strength. A “phase diagram” is given representing the Tm-values of the various transitions at different ionic strengths for the system A(pA)17 + U(pU)17. Oligonucleolides of chain lengths 〈8 always form both double and triple helices at the nucleotide concentrations required for base pairing. For this reason the double helix-coil transition without coupling of the triple helix equilibrium can only be measured for chain lengths higher than 7. Melting curves corresponding to this transition have been determined for chain lengths 8, 9, 10, 11, 14 and 18 at different concentrations. An increase in nucleotide concentration leads to an increase in melting temperature. The shorter the chain length the lower the Tm-value and the broader the helix-coil transition. The experimental transition curves have been analysed according to a staggering zipper model with consideration of the stacking of the adeuylic acid single strands and the electrostatic repulsion of tlip phosphate charges on opposite strands. The temperature dependence of the nucleation parameter has been accounted for by a slacking factor x. The stacking factor expresses the magnitude of the stacking enthalpy. By curve fitting xwas computed to be 0.7, corresponding to a stacking enthalpy of about S kcal/mole. The model described allows the reproduction of the experimental transition curves with relatively high accuracy. In an appendix the thermodynamic parameters of the stacking equilibrium of poly A and of the helix-coil equilibria of poly A + poly U at neutral pH are calculated (ΔHA = -7.9 kcal/mole for the poly A stacking and ΔH12 = -10.9 kcal/mole for the formation of the double helix from the randomly coiled single strands). A formula for the configurational entropy of polymers derived by Flory on the basis of a liquid lattice model is adapted to calculate the stacking entropies of adenylic oligomers.
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    Biopolymers 10 (1971), S. 2049-2049 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 2071-2077 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The data on the band widths and band shapes of several DNA's at various concentrations in sedimentation equilibrium in a CsCl density gradient have recently become available. In the present report, these literature data are treated in the following manner: (1) based on a theory of isotope-substitution, calculations are made of the molecular weights at infinite dilution, and (2) to explain the concentration dependence of band widths and band shapes, a theory of charge and hydration is put forth, and it is shown that by retaining the terms involving the charge of the macromolecules, it is possible to account for most of the concentration dependence.
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    Biopolymers 10 (1971), S. 2083-2094 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the unique and specific association of a given amino acid to its t-RNA is investigated by theoretical methods. Several possible schemes are proposed to explain specificity. The physical forces which act within these mechanisms are illustrated by the computer simulation of probable interactions between glycine and nucleotide bases and base pairs. It is demonstrated that glycine has direct and selective affinities for the nucleotide bases and that these interactions are principally determined by the polar groups. Energies have been calculated for the interaction of glycine with several base pairs. From these, the possibility that specificity arises through direct complexing of an amino acid with its anticodon is evaluated.
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    Biopolymers 10 (1971), S. 2147-2160 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Equations are developed to describe the shift in the temperature of the helix-coil transition when small molecules bind to nucleic acids. Included are high polymers, oligonucleotides, and oligomer-polymer interactions. The equations prescribe simple ways of plotting experimental data to evaluate transition and binding parameters.
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    Biopolymers 10 (1971), S. 2181-2197 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transitions for poly-L-lysine (PL) were investigated by the methods of spectropolarimetry, viscometry and potentiometric titration in 0.2M NaCl at different temperatures as well as in 0.2MNaBr, 1MKCl, and in mixtures of 0.2MNaCl or NaBr with methanol at room temperature. The enthalpy and entropy differences between the helical and coillike states of uncharged PL molecules in 0.2.M NaCl were determined from the potentiometric titration curves. The cooperativity parameters σ for PL in different solvents were determined by two methods (from the sharpness of the transition and from the dependence of the intrinsic viscosity on the helical content in the transition region). In 0.2MNaCl σ has a value of (2.3 ± 0.5) × 10-4 and does not depend on temperature, i.e., the cooperativity of the helix-coil transition, as for PGA, is mainly of an entropy origin (the initiating of the helical region is accompanied by the entropy decrease ΔSi = -12 eu/mole of helical regions). A comparison of the obtained results for PGA and PL with the molecular theories of the helix-coil transitions shows that the role of dipole-dipole interactions of nonneighboring peptide groups is greatly overestimated in these theories, leading to a considerable enthalpy contribution to the free energy of initiating helical regions which is not observed in the experiment.
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    Biopolymers 10 (1971), S. 2029-2037 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The variation of the polarized components of fluorescence of a rodlike particle bearing a fluorescent label upon partial orientation is calculated for some special geometry of the dye macromolecules complexes. Explicit expressions are given for the case where the energy of the molecule in the field depends only on one angle θ, showing that the result is a function of both 〈sin2θ〉 and 〈sin4θ〉. For the case of orientation in an electric field through an anisotropic induced moment, the expressions allow the calculation of this anisotropy of polarizability. The method is applied to the measurement of the polarizability of rodlike fragments of DNA labeled by intercalated molecules of Acridine Orange.
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    Biopolymers 10 (1971), S. 2039-2048 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: As the temperature of solid poly(β-benzyl-L-aspartate) (PBLA), (CO.NH.CH.-CH2COOCH2C6H5)n, in the α-helieal form is raised from -150 °C, tlie line width and second moment of the proton magnetic resonance (PMR) signal decrease in stages until the conformational transition to the ω-helix occurs at about 90 °C. A similar temperature dependence of the PMR parameters is observed as the transformed polymer is cooled. Below -100°C (where the lattice is presumed to be rigid), the measured second moments are 9.5 Oe2 and 10.7 Oe2 for the α and ω forms, respectively. Second moments, calculated from the Van Vleck formula for the rigid lattice and also estimated for possible motional cases in which the polymer is taken to be in the ω form, are compared with the PMH data. By combination with the results of X-ray diffraction and infrared spectroscopic measurements, a tentative explanation can be made of the types of motion occurring in PBLA.
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    Biopolymers 10 (1971), S. 2133-2145 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have performed potentiometric titrations of poly-L-lysine. From these data we have calculated the free energy and enthalpy changes for the folding of the random coil to the α-helix in 10% ethanol (-120 and -120 cal/mole) and from the random coil to the β-structure in water (-140 and 870 cal/mole) and in 10% ethanol (-180 and 980 cal mole). Comparison of these values with each other and with values for the coil → α- helix transition in water (-78 and -880 cal/mole) led to the following conclusions. The stabilization by ethanol of ethanol of the α-helix with respect to the coil is that predicted from the known free energy of transfer of the peptide group from water to 10% ethanol. Similar data to explain the enthalpy difference are not available. The thermodynamic functions for the transition from α-helix to β-structure, obtained by subtracting those for the coil → α-helix and coil → β-structure transitions, are explained from a consideration of the structural differences: non bonded interactions of the polypeptide backbone are less favorable in the β-structure than in the α-helix, causing an increase in the energy, while hydrophobic contacts between side chains raise the entropy of the β-structure as compared with the α-helix, so that the free energy difference between the two structures is small, but enthalpy and entropy differences are large. The observation of only small differences in the free energy and enthalpy changes for the transition from coil β-structure upon going from water to 10% ethanol is expected by considering both the free energy of transfer of the peptide group (as for the α-helix) and the free energy and enthalpy of transfer of the apolar part of the side chain involved in hydrophobic bond formation.
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    Biopolymers 10 (1971), S. 2209-2221 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Valine specific transfer RNA (tRNAVal) was isolated from Bacillus stearothermophilus and Escherichia coli by chromatography on benzoylated DEAE-cellulose (BD-cellulose). Likewise isoleucine specific transfer RNA (tRNAIle) was isolated from B. stearothermophilus and from Mycoplasma sp. Kid. The thermal denaturation profiles (melting curves) of the two tRNAVal species in the presence of Mg+ + were nearly identical. However, the Tm for the Kid tRNAIle was about 10°C lower than that for the B. stearothermophilus tRNAIle. A nuclease and tRNA-free aminoacyl-tRNA synthetase (AA-tRNA synthetase) preparation from B. stearothermophilus was able to function efficiently at temperatures up to 80°C in the aminoacylation of all four tRNA species. Determination of the amino acid-acceptor activity of each tRNA species as a function of temperature of the aminoacylation reaction showed in each case a strong correlation between the loss of acceptor activity and the thermal denaturation profile of the tRNA. Evidence is presented that the loss in acceptor activity is most likely due to a change in structure of the tRNA as opposed to denaturation of the enzyme. These results further support the idea that correct secondary and/or tertiary structure must be maintained for tRNA to be active as a substrate for the AA-tRNA synthetase.
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    Biopolymers 10 (1971), S. 2275-2281 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The Cotton effects of N-acetoacetyl amino acids and derivatives were examined by a circular dichroism technique. A correlation has been established between the sign of the Cotton effect and the absolute configuration of the asymmetric center. The L derivatives show, in dioxane, negative circular dichroism curves, whereas the D antipodes present positive curves. The effect of solvent and pH and influence of alkylation at the amide nitrogen are also discussed.
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    Biopolymers 10 (1971), S. 2345-2358 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anisotropy of electrical polarizability of rodlike fragments of DNA has been studied by a number of electro-optical methods: Kerr effect (combined with flow birefringence), light scattering, diehroism, and fluorescence in an electric field. The most sensitive technique (Kerr effect) has been used to study the variation of the polarizability with the nature and concentration of counteroins. DNA fragments constitute a truly rigid polyelectrolyte of known structure. The value obtained can then be quantitatively compared to the predictions of those of the theories of the longitudinal polarizability of rigid polyelectrolytes which are based on true molecular parameters. The comparison emphasizes the role of the counterion-counterion repulsion. Oosawa's theory seems to represent the best approach but fails to explain the differences observed between monovalent and divalent ions.
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    Biopolymers 10 (1971) 
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    Biopolymers 10 (1971), S. 2537-2553 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The MCD (magnetic circular dichroism) spectra of Ap, ApA, ApApA, poly A, Up, UpU, poly U and double-stranded poly A:U alternating copoly A-U and alternating deoxyribopoly A-T were measured with a Cary 61 spectropolarimeter fitted with a Varian superconducting magnet at a field strength of 50 Kgauss. The MCD spectra of T2 and T5 DNA at various stages of heal denaturation were measured as a function of hyperchromicity of the sample. MCD spectra of the intact and degraded T2 and T5 phages were used to study the degree of alteration of the DNA inside the phages versus the DNA in vitro. The results for the adenine polymers show that the main MCD bands, B2u(271 nm), B1u(252 nm), and E1u(212 nm), show a decrease in specific magnitude as the length of the polymer is increased, reflecting the degree of stacking of the polymer. In contrast, the uridine series of polymers shows little change of the MCD bands, indicating that there is little interaction between the bases regardless of the length of the polymers. The MCD spectra of poly A:U, alternating poly r(A-U): (A-U), and alternating poly d(A-T):(A-T) show significant differences among themselves in the magnitude of the B2u band and when compared with the sum of the spectrum for the poly A plus poly U. This may indicate the selective effect of hydrogen bonding on the B2u band. Alternatively, the difference may be due to the absence of an n → π* transition in the double-stranded polymer. Measurements of denatured T2 and To DNA's show increases in all MCD bands. The T2 DNA internally packed in phage shows an increase of the B2u and E1ubands, the B2u remaining unchanged. The internal T5 DNA shows an increase of the B1u band only. Thus, the internal DNA structure is altered in a manner quite different from a simple denaturation caused by hydrogen bond breaking. Furthermore, different MCD bands indicate that different modes of DNA packing exist for T2 and T5 phages.
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    Biopolymers 10 (1971), S. 2591-2596 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The infrared absorption of poly-L-proline in concentrated aqueous salt solutions was measured in the fundamental region. Of primary interest were the carbonyl absorption of the peptide linkage and the methylene C-H bending absorption of the pyrrolidine ring. These spectral regions each show an additional component in the concentrated salt solutions. Using the position of the absorptions of poly-L-proline I (cis) and II (trans) as models, we conclude that both cis-trans linkages are present in the peptide in salt solutions. Increasing the temperature shifts the equilibrium slightly in favor of cis.
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    Biopolymers 10 (1971), S. 2619-2621 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 2635-2638 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971), S. 221-224 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 10 (1971) 
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    Notes: The base-stacking patterns in over 70 published crystal structures of nucleic acid constituents and polynucleotides were examined. Several recurring stacking patterns were found. Base stacking in the solid state apparently is very specific, with particular modes of interaction persisting in various crystalline environments. The vertical stacking of purities and pyrimidines in polynucleotides is similar to that observed in crystals of nucleic acid constituents. Only partial base overlap was found in the majority of the structures examined. Usually, the base overlap is accomplished by positioning polar substituents over the ring system of an adjacent base. The stacking interactions are similar to those found in the crystal structures of other polar aromatic compounds, but are considerably different from the ring-ring interactions in nonpolar aromatic compounds. Apparently, dipole-induced dipole forces are largely responsible for solid-state base stacking. It is found that halogen substituents affect base-stacking patterns. In general, the presence of a halogen substituent results in a stacking pattern which permits intimate contact between the halogen atom and adjacent purine or pyrimidine rings. Considering differences in the stacking patterns found for halogenated and nonhalogenated pyrimidines, a model is proposed to account for the mutagenic effects of halogenated pyrimidines.
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    Biopolymers 10 (1971), S. 225-242 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The desorption and melting with temperature of proflavine-DNA complexes has been studied by spectrophotometry and spectrofluorometry. Two methods are described to determine at each temperature the concentration of free and bound dye. The first one is based on the quenching of fluorescence of the free dye by the iodine ion, the second on fluorescence polarization measurements. It is shown that the sites where the bound dye fluoresces are thermally less stable than those where it is quenched, in such a way that a redistribution of the dye between the two types of sites occurs at intermediate temperatures, leading to a drop in the total fluorescence. This confirms the nature of the “emitting” sites which correspond to AT-rich region, while “quenched” sites correspond to GC-rich region. The first have a larger binding constant at room temperature, but only the latter are stabilized by dye intercalation. The desorption and melting have also been followed through the relative changes of absorption. The curves obtained at different wavelengths are not superimposed which is at variance with what is observed with complexes of proflavine with poly dAT and poly dG.dC. The beginning of the desorption process corresponds to minor variations at 445 nm, the maximum of absorption of the free dye, but large changes occur at 460 nm, the maximum of the difference spectrum of the complexes proflavine-poly dAT and proflavine-poly dG.dC. The spreading of the melting curves for different wave lengths must therefore reflect the dependence of the absorption spectra of the dye on the nature of the neighboring bases. However, the action spectrum of the fluorescence, which gives the absorption spectrum of the “emitting” sites only, is identical with the total absorption spectrum of the bound dye.
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  • 68
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    Biopolymers 10 (1971), S. 337-355 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical and hydrodynamic properties of T2 bacteriophage DNA have been determined by steady-state flow birefringence and viscosity in glycerol-aqueous buffer solvents at 25°C. Flow birefringence and extinction angle data were obtained over a velocity gradient range of 0.1 to 5 sec-1 and at concentrations from 3 to 55 μg/ml in solvents containing approximately 30, 42, and 48 vol-% glycerol. Large optical backgrounds were observed in the mixed solvent flow birefringence studies which presented special experimental difficulties; these are described and their effect upon the flow birefringence data are discussed. The data on extinction angle provide no evidence for an internal viscosity effect on the stationary-state hydrodynamic properties of high molecular weight DNA over a range of solvent viscosity from 0.9 to 4.6 cP. Both the optical and hydrodynamic properties under present conditions of measurement appear to be self-consistent in terms of the values for these quantities in neutral aqueous buffer solution. Interpretation of the birefringence is complicated by uncertainties inherent in calculating the form anisotropy of DNA in non-aqueous solvents, but the data imply no large changes in helical structure with increasing glycerol concentration. Both intact and slightly degraded DNA samples were investigated, and no significant polydispersity effects were observed under the experimental conditions described.
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  • 69
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    Biopolymers 10 (1971), S. 379-389 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper extends a previous study in which a discontinuity in the specific rotation of open chain α-l,4-linked glucopyranosides in the water-dimethyl sulfoxide (H2O-DMSO) system was attributed to a symmetry change about a polymer chain segment. Optical rotation of amylose, cyclohexamylose, methyl β-maltoside, and dextran was measured in the following mixed solvent systems: formamide-dimethyl sulfoxide (F-DMSO), ethylenediamine-dimethyl sulfoxide (E-DMSO), and hexamethylphosphoramide-dimethyl sulfoxide (HMPA-DMSO). Refractive index measurements were used in an attempt to detect hydrogen bonding between solvent components. The specific rotation of amylose corrected for variation in refractive index (CSR), as a function of solvent composition, showed a discontinuity at solvent compositions corresponding to about 1 mole F to 2 moles DMSO and to 1 mole E to at least 8 moles DMSO. A discontinuity in the CSR function of amylose in the H2O-DMSO mixed solvent that occurs at 25°C is not observed at 70°C. The CSR function of methyl-β-maltoside exhibits a discontinuity in solvent composition corresponding to mole ratios between 2F-DMSO and 3F-DMSO. Present results indicate that an amylose chain segment may undergo a symmetry change in solvent compositions corresponding to mole ratios between F-DMSO and F-2DMSO. Our CSR measurements of amylose and model compounds in E-DMSO and HMPA-DMSO do not permit us to distinguish between possible changes in amylose chain segment symmetry and solvent interactions that could affect symmetry properties of the glucopyranose ring.
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  • 70
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    Biopolymers 10 (1971), S. 547-564 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the effect of polypeptide concentration on the helix-coil transition of poly(γ-benzyl L-glutamate) (PBLG) in both dichloroacetic acid (DCA) and DCA-chloroform (CHF) mixtures. In agreement with other reports, we find the van't Hoff transition enthalpy to be strongly dependent on PBLG concentration. Also, an apparent effect of polypeptide concentration was noted on the transition temperature; however, corrections for finite PBLG concentration on the mole fraction of DCA seem to remove this effect. In order to explain our data, as well as some calorimetric data in the literature, we consider the transition free energy and enthalpy as a sum of three partial terms. These represent the thermodynamic parameters associated with: (1) conformational changes of the polypeptide, e.g. formation or disruption of intramolecular hydrogen bonds; (2) binding by the strong acid to the nonhelical segments of the polypeptide; (3) an overall (weak) interaction of the polypeptide with the nonbound solvent giving rise to dilution parameters that are dependent on the polypeptide conformation. The latter effect is generally ignored, since it is assumed that solvent interactions, other than specific binding, are similar for both the helical and the nonhelical conformation. Striking effects of water (small amounts) and solution aging on the formation of PBLG helices was observed. Water, as expected, acts as a helicogenic solvent when combined with DCA. The processes occurring during solution aging are not known, although the net effect is to stabilize the helical conformation. Finally, we present some rather unique thermally induced transitions of concentrated PBLG (about 200 mg/ml) in DCA. At low temperatures the soluble randomly coiled conformation is present. Heating produces first an isotropic gel, followed at higher temperatures by an isotropic solution consisting of about 70% α-helicity.
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  • 71
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    Topics: Chemistry and Pharmacology
    Notes: Potential energies of conformation of a dipeptide unit with butyl, seryl, threonyl, eysteinyl, and valyl side groups have been computed by using classical energy expressions. The presence of a γ-atom introduces characteristic restrictions on the backbone rotational angles φ and ψ the γ-atom itself is restricted to three staggered positions about the Cα - Cβ bond. The important results are that a γ-carbon in position I (χ1 ≃ 60°) cannot be accommodated in the standard right-and left-handed α-helices, whereas a γ-oxygen or sulfur could easily be accommodated in the right-handed α-helix. Further, a γ-carbon or a heteroatom in position II (χ1 ≃ 180°) does not favor a conformation ψ ≃ 180°, compared to two other positions. The valyl side group significantly reduces the allowed φ and ψ values and energetically prefers a β-conformation compared to right-or left-handed α-helical conformations. The less favorable α-helical conformation is possible only for γ (III, II) combination of the valyl residue. The observed φ, ψ, and χ1 values of all the amino acid residues in the three protein molecules, lysozyme, myoglobin, and chymotrypsin are compared with the theoretical predictions and the agreement is excellent. The results bring out the important fact that even in large molecules, the conformation of local segments are predominantly governed by the short-range intramolecular interactions.
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    Biopolymers 10 (1971), S. 593-599 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three methods are described for the preparation of oriented samples of DNA molecules in films. The methods involve simple equipment and produce films of good optical qualities, suitable for the determinations of dichroic spectra, for example. To illustrate the quality of the films the dichroism of DNA and of acridine orange-DNA complex are described. Evidence is given that native DNA structure is stabilized by poly-(vinyl alcohol).
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    Biopolymers 10 (1971), S. 699-710 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A molecular conformation of Gramicidin S was derived on the basis of conformational calculations taking into account the available experimental data.The conformation is characterized by a dyad axis which relates the two chemically equivalent halves of the molecule and contains four hydrogen bonds; other structural features agree with experimental results. X Ray Crystallographic evidences for the relative position of the Ornithine residues is also reported which supports an important feature of the structure of Gramicidin S.
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    Biopolymers 10 (1971), S. 657-680 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heat ΔH° for converting an uncharged lysine residue from a coil to an α-helical state in poly-L-lysine in 0.1N KCl has been determined calorimetrically to be -1200 cal/mole at both 15°C and 25°C. Essentially the same value has been obtained for the conversion of an uncharged residue from a coil to a β-pleated sheet state. Titration data provided information about the state of charge of the polymer in the calorimetric experiments, and optical rotatory dispersion data about its conformation. In order to compute ΔH°, the observed Calorimetric heat was corrected for the heat of breaking the sample cell, the heal of dilution of HCl, the heat of neutralization of OH- ion, and the heat of ionization of the ε-amino group in the random coil. The latter was obtained from similar Calorimetric measurements on poly-D,L-lysine, which was shown to be a good model for the random coil form of poly-L-lysine. The measured transition heat was ∼0.7 cal., which is only 7% of the total heat liberated when a 40 ml solution of 0.25% w/v poly-L-lysine is brought, from pH 11 to pH 7; nevertheless it could be determined with a precision of ±8%. The conformation of poly-L-lysine at pH 11 appears to be completely helical at 15°C, but a mixture of 90% α-helix, 5% β form, and 5% coil at 25°C. Since ΔH° ∼ 0 for the α ⇌ β conversion, the polymer behaves like one of 95% α-helix and 5% coil in the calorimeter at 25°C. At neutral pH, poly-L-lysine is an extended coil, like poly-D,L-lysine.
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  • 75
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    Topics: Chemistry and Pharmacology
    Notes: Four fragments (named K, L, M, and N) of Escherichia coli formylmethionine transfer RNA have been prepared by a partial digestion with ribonuclease T1 followed by a chromatographic separation with a DEAE-Sphadex (A-25) column and then a DEAE-cellulose column. The fragment K is the anticodon fragment with 19 nucleotides (previously reported). L is a fragment with 57 nucleotides involving the 3′-terminal (CCA). M is a fragment with 51 nucleotides which is equal to L except that M lacks 6 nucleotides at the 3′-terminal. N is a fragment with 20 nucleotides which involved the 5′-terminal and corresponds to the complementary half to L. The infrared absorption spectrum has been observed of each of these fragments and two equimolar mixtures L + N and M + N in D2O solutions at several temperatures. The results indicate that at 37°C, K has about 4 hydrogen-bonded base-pairs, L about 11, and M about 13. On the other hand, fragment N is found to have only three weak G-C pairs. For both L + N and M + N, 15-17 strong base pairs are found. The observations give direct support to the clover-leaf structure and at the same time provide information on the stability of each of the four arms in the structure.
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  • 76
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 77
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    Biopolymers 10 (1971), S. 767-775 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The matrix method is used for calculating the grand partition function for the reaction: 2 polymer + solute = complex. The homogeneous polymers are assumed to have two types of sites within each nucleotide unit: sites for the polymer-polymer association, i.e., (p-p) sites; sites for polymer-solute association i.e., (p-s) sites. The respective binding parameters, P and F, and nearest-neighbor interaction parameters, W and S, are assumed independent. Complications due to ring entropy are avoided by rest riding the model to one-solute-stack systems, which are physically realizable when the reciprocal of the solute cooperativity parameter is much larger than the number of nucleotides in the polymer. The 4 × 4 generating matrix is shown to be a tensor product of two 2 × 2 matrices, each the generating matrix of a particular type of site. The scalar product of the 4 × 4 matrix is shown to be equivalent to the scalar product of a 2 × 2 matrix in the weak interaction limit, W ≈ 0. Calculations are presented for the general case which restricts the (p-s) association to occur only with (p-p) associated nucleotide units. The nature of the binding curve in relation to partitioning the total interaction energy (F + P + S + W) among the parameters is discussed. Also presented is a criterion for neglecting possible states in the calculation of the grand partition function.
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    Biopolymers 10 (1971), S. 777-788 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The x-ray scattering method has been used to investigate the structure in two amorphous crosslinked polymers which are regarded as test systems to establish the power of the method as applied to amorphous biologically significant polymer associations. It is shown that structural information can be determined about the rigid regions within the polymer systems, i.e., those regions held in particular configuration by stereochemical effects. Models of such regions extending over distances with dimensions of ca 18 Å are proposed for an Araldite polymer and for crosslinked poly (methyl/butyl methacrylate). The results allow some general statements about the usefulness and limitations of the amorphous x-ray method.
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    Biopolymers 10 (1971), S. 789-794 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spectra of proton and deuteron magnetic resonance of water molecules in oriented biopolymer samples (collagen, DNA, cellulose) are interpreted on the basis of a model of molecular Schottki-type diffusion. The presence of narrow splittings are shown to be the result of slight distortions of “ideal” symmetry of orientations of p-p and O-D vectors, corresponding to the point symmetry group of a tetrahedron, one of whose C3-axes is oriented along the fiber axis.
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    Biopolymers 10 (1971), S. 795-808 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transitions of aqueous solutions of poly-α-L-lysine (PLL), poly-α-L-ornithine (PLO), and poly(α,γ-L-diaminobutyric acid) (PLDBA) have been investigated as functions of pH at 25°C and of temperature at pH 11.75, where these polymers are uncharged; in the cases of the latter two polyamino acids, the transitions have also been studied as functions of apparent pH in methanol-water solution (50/50 by volume). The helix stability of the polypeptides is shown to be a direct function of the number of methylene groups on the side chain. From an analysis of potentiometric titration data, we find that the difference between the helix stability of PLL and that of PLO is due to a difference of about 1 e.u. in the ΔS° of the transition. Combining the “melting curves” obtained from optical rotatory dispersion studies with the potentiometric titration data permits evaluation of the initiation parameter Z (or 1/σ½) of the statistical mechanical theories for these transitions. The value obtained for Z in the case of uncharged aqueous PLO is ca. 35.
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    Biopolymers 10 (1971), S. 809-820 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the first time ORD measurements in the near-infrared region from 0.7 to 2.0 μ for well-known polypeptides, namely, poly(γ-benzyl L-glutamate), poly(L-glutamic acid), poly-L-lysine·HCl, poly-S-carbobenzoxymethyl-L-cysteine, and Bombyx mori silk fibroin, were carried out. It was found that the value of the optical activity infrared term, which is proportional to the sum of rotational strengths of vibrational transitions, depends on polypeptide conformation. The optical activity infrared term value is equal to zero for the random-coil conformation, it is small but exceeds the measurement error for the α-helical state, and finally, for the β conformation it is an order of magnitude higher than for the α-helical state. The obtained results permit one to hope that on the basis of ORD measurement in the near-infrared region it will be possible to suggest a method of determining the β-form content in polypeptides and proteins
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    Biopolymers 10 (1971), S. 821-826 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 95% ethanol solution of the prolamin zein and of the synthetic polymer polyvinyl-pyrrolidone (PVP) can be successfully electrosprayed and a molecular beam, containing ions of these substances in nitrogen carrier gas, formed. Similarly to polystyrene in benzene-acetone solvent, negative beams of zein and PVP have more substructure than beams containing positive ions. The results indicate considerable aggregation in the beam, possibly of six molecular units per aggregate, in addition to the singly charged single molecules.
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  • 83
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    Topics: Chemistry and Pharmacology
    Notes: Sedimentation experiments have been performed on a polydisperse bacterial DNA sample over a wide range of ionic strength (8 × 10-4M to 2M Na+), at very low DNA concentrations (5-30 μg ml). True sedimentation constant distributions were obtained by careful analysis of experimental data and extrapolation to infinite dilution. In order to give a quantitative description of macromolecular shape, the changes of the exponent as in the general equation, s0 = ksMas, have been determined by comparing sedimentation constant distributions obtained at different ionic strengths. as has been found to vary from 0.419 at 2M Na+ to 0.200 at 8 × 10-4M Na+. As well as the decrease of the mean sedimentation constant, this result indicates a pronounced expansion of DNA molecules with decreasing ionic strength. A discussion of the distinct mechanism responsible for the expansion behavior of DNA is given. Furthermore, the dependence of the Mandelkern-Flory parameter β on ionic strength has been calculated by combining the s0 data with the corresponding [η] values of the sample.
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  • 84
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have determined the ultraviolet optical rotatory properties of the cyanogen bromide peptides of myoglobin and reduced, S-carboxymethylated α-lactalbumin in both aqueous and aqueous alcohol solutions. Similar measurements were also made on the tryptic digests of apomyoglobin. In aqueous solutions the α-helicity of the various peptides was between 5 and 15%, while in concentrated ethanol solutions the helicity could be increased significantly, but never to more than about 55%. The maximum helicity attained by the various peptides at high ethanol concentrations, as well as the cooperativity of the coil-to-helix transition (reflected in the slope at the steep portion of the helicity-alcohol concentration curves), does not depend on the number of residues in the peptide in the manner expected. We have used a model which treats proline residues as absolute helix breakers, thus introducing the concept of effective chain length. By applying available theories of helix-coil transitions of short-chain polypeptides to this model, one can satisfactorily describe most of the data on the myoglobin peptides. Significantly, it was possible to predict the helicity of acid-denatured apomyoglobin from the behavior of the shorter fragments. By using the model, the peptides were found to have an equal intrinsic helix-forming tendency which, with only two exceptions, was not raised by the formation of tertiary structure. The exceptions were apomyoglobin and peptide 56-131, which show, respectively, a considerable and a very small helicity attributable to tertiary structure formation in water at neutral pH. These results agree with the demonstrated absence of stable intermediates in protein unfolding equilibria. The results offer a further correlation between helical structure in the native molecule and the tendency to helix formation in isolated peptides. The results do not support the hypothesis that small folded regions are responsible for initiating the folding of the molecule, and an alternate description is proposed which envisages approximately half-folded structures at the rate limiting step in the folding reaction. Helix formation in the 33-residue C-terminal peptide of α-lactalbumin was found to be as easy as in the myoglobin peptides. If the proposed structural analogy between lysozyme and α-lactalbumin is correct, then this is a case where helix formation occurs in a peptide which is not helical in the native protein. On the other hand, an α-lactalbumin peptide corresponding to a region which has β-structure in lysozyme did not lend to form α-helices.
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    Biopolymers 10 (1971), S. 945-960 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of Mg++ to poly A and poly U has been measured quantitatively by using the metallochromic indicator calmagite. The method is described in detail. It is shown that there is electrostatic interaction between the binding sites, viz., the phosphate groups, and the intrinsic association constant, for the specific binding can be determined. After extrapolation to zero ionic strength we find that, for the binding of Mg++ to poly A, kint = 4 × 104 and for that, to poly U, kint = 3 × 104. The intrinsic enthalpy of association is negative. The effect of Mg++ on the secondary structure of poly A and poly U has been studied by measuring the ultraviolet absorbance, optical rotatory dispersion and viscosity as a function of the amount of added Mg++ ions. It was found that Mg++ promotes the formation of a more ordered secondary structure by neutralizing or screening the negative charges. It is concluded from the absorbance measurements that for poly A at pH ≥ 7 and for poly U at pH 〉xs 9 this ordering involves stacking of the bases. Likewise, in solutions of UDP with a pH around 10, base stacking occurs on addition of Mg++.
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    Biopolymers 10 (1971), S. 961-972 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previous equilibrium model is generalized to study time-dependent behavior of hemoglobin and allosteric enzymes. An exact solution for two interacting subunits (e.g., diheme) is given, and a general method for solving the resulting set of differential equations is outlined. At half saturation (equilibrium) concentration, the model takes a particularly simple form which suggests an experiment to determine the number of subunits of an allosteric enzyme, or in particular to distinguish diheme from ordinary hemoglobin. The relation between the present model and other kinetic models is also discussed.
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    Biopolymers 10 (1971), S. 973-989 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper a microscopic model is developed which considers conformational changes in polypeptides. The model applied here to diglycine involves calculation of torques due to pairwise interatomic forces acting about the two single bonds (N—C and C—C′) of the peptide unit. Account is taken of Brownian motion and rotational frictional resistance in addition to a van der Waals 6-12 potential, a classical electrostatic potential and a torsional potential. The rates of the conformational transition from an initial α-helical position are computed. The mechanism of Conformational change is a random walk within the minimum well followed by a jump out of the minimum into another portion of the energy surface. The latter process occurs when a fluctuation carries the dipeptide into a high energy region of the potential surface. Correlation times for the process are computed. Estimates are made for the relaxation times for the process. A first passage-time treatment is developed and used to compute internal diffusion coefficients for the relaxation process.
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    Biopolymers 10 (1971), S. 991-1001 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation coefficient of calf thymus and of T7 DNA was determined at several concentrations up to saturation in solutions of each of the following salts: MgCl2, MgBr2, and MgSO4. Under certain conditions, a plot of the product of the relative viscosity and sedimentation coefficient against the density of the solution has been found to be linear and to extrapolate to zero at a density corresponding to that of the solvated molecule. This behavior was realized in MgSO4 solutions, the zero intercept occurring at a density of 1.41 g/cc, corresponding to a wafer activity of 0.89. The preferential solvation of DNA in MgSO4 solutions calculated for this value is 10.5 moles water/mole of nucleotide, in good agreement with published values of solvation of DNA at the same water activity in univalent salt solutions. Since linear plots were not obtained in MgCl2 and MgBr2 solutions, buoyant densities could not be determined in these cases. The nonlinear behavior observed in MgCl2 and MgBr2 solutions may be due to a change in shape of the DNA molecule at the lower water activities reached in these solutions. The possibility of increased DNA-solute interactions in MgBr2 and MgCl2 solutions is also considered as an explanation for the difference in behavior between MgSO4 and the two magnesium halides.
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between acridine orange (AO) and deoxyribonucleic acid (DNA) was studied by the stopped-flow method. The spectral change of AO due to interaction with DNA was followed over the wavelength range 350-600 nm at various concentration ratios of DNA phosphate to dye. The spectral change observed by the stopped-flow method was found distinctly different from that, during the dead-time, leading to a conclusion that the binding of AO to the outside of DNA occurs much faster than the intercalation into base pairs of DNA. The dependence of the rate of reaction on the reactant concentration and on the salt, concentration of the solution was also studied. The results are consistent with the mechanism that the intercalation proceeds via the outside bound state.
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    Biopolymers 10 (1971), S. 1013-1019 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A strong magnetic field has been utilized to orient the liquid crystalline phase of concentrated polypeptide solutions enabeling the preparation of nematic solid films. The uniaxially oriented nematic films are suitable for x-ray studies of the polypeptide backbone chain conformation. A distorted α-helix with 3.5 residues per turn is observed in nematic films of the L-isomer of poly (benzyl glutamate) when the film is cast from chloroform. The normal α-helix (3.6 residues per turn) is found in similarly prepared films cast from dichloromethane.
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  • 91
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared spectra of homo- and co-oligopeptides containing glutamate residues were studied in both solution and solid state. Conformational analyses of these oligomers were carried out by using amide I and II band frequencies. Trimethyl phosphate supports the folded structure of oligomers above the heptamer. In chloroform solution, these oligomers assume the β-extended structures above the pentamer.
    Additional Material: 5 Ill.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ultraviolet absorption and circular dichroism spectra of azlactones derived from N-acetoacetyl amino acids are examined. A number of model compounds of the isomeric forms possibly present in the equilibrium mixtures of these azlactones have also been prepared and their spectral properties compared. The reported data permit, structural and stereochemical assignments on these amide compounds.
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  • 93
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    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2377-2386 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The far-infrared absorption spectrum (40-400 cm-1) of solid pellets and films of several globular proteins (lysozyme, myoglobin, hemoglobin, serum albumin, ribonuclease, chymotrypsinogen, subtilisin) and of some representative polypeptides [nylon 66, poly (γ-benzyl L-glutamate)] have been investigated by using a Michelson interferometer. While polypeptides are known to present several peaks which can be assigned mostly to hydrogen-bond modes, all the investigated globular proteins display only one broad, intense baud in the 100-200 cm-1 region. The origin of this band, which persists even after denaturation or partial digestion, is discussed.
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  • 94
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    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2435-2443 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of rotation of the peptide (amide) bond in dimethylacetamide, glycine dimethylamide, N-acetylsarcosine, and glycylsarcosine have been studied in basic, neutral, and acidic aqueous solutions by proton magnetic resonance spectroscopy. The data indicate that the presence of nearby negative or positive charges do not greatly perturb the energetics of conformational equilibration about the amide carbon-nitrogen bond. In N-acetylsarcosine and glycylsarcosine two distinguishabe conformers are present; their relative abundance is essentially 50%/50% except at low pH. It is suggested that intramolecular hydrogen bonding is responsible for deviations from this population ratio. The activation enthalpies (ΔH
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  • 95
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971) 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 96
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971), S. 9-18 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Bedeutung der Abgase aus Verbrennungsmotoren wie auch aus Düsenstrahltriebwerken spielt mit wachsender Motorisierung eine immer größere Rolle für die Luflverunreinigung. In den USA beträgt der Anteil auf diese Art entstandener Schadstoffe an der Gesamtbelastung heute schon mehr als 60%, in der Bundesrepublik liegt er über 40%.
    Additional Material: 10 Ill.
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  • 97
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971), S. 27-28 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 98
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971), S. 33-40 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 8 Ill.
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  • 99
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971), S. 43-49 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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  • 100
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 5 (1971), S. 63-64 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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