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  • Chemistry  (15,117)
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  • 2020-2023
  • 1985-1989  (11,112)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 27 (1988), S. 311-320 
    ISSN: 1432-1432
    Keywords: Genome composition ; Coding sequences ; Isochores ; Humans ; Murids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The compositional distributions of coding sequences and DNA molecules (in the 50-100-kb range) are remarkably narrower in murids (rat and mouse) compared to humans (as well as to all other mammals explored so far). In murids, both distributions begin at higher and end at lower GC values. A comparison of homologous coding sequences from murids and humans revealed that their different compositional distributions are due to differences in GC levels in all three codon positions, particularly of genes located at both ends of the distribution. In turn, these differences are responsible for differences in both codon usage and amino acids. When GC levels at first+second codon positions and third codon positions, respectively, of murid genes are plotted against corresponding GC levels of homologous human genes, linear relationships (with very high correlation coefficients and slopes of about 0.78 and 0.60, respectively) are found. This indicates a conservation of the order of GC levels in homologous genes from humans and murids. (The same comparison for mouse and rat genes indicates a conservation of GC levels of homologous genes.) A similar linear relationship was observed when plotting GC levels of corresponding DNA fractions (as obtained by density gradient centrifugation in the presence of a sequence-specific ligand) from mouse and human. These findings indicate that orderly compositional changes affecting not only coding sequences but also noncoding sequences took place since the divergence of murids. Such directional fixations of mutations point to the existence of selective pressures affecting the genome as a whole.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 10 (1988), S. 93-95 
    ISSN: 1573-739X
    Keywords: Anthracyclines ; Chemistry ; Drug stability ; Mitomycins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 10 (1988), S. 101-116 
    ISSN: 1573-739X
    Keywords: Chemistry ; Chromatography ; Etoposide ; Immunoassay ; Metabolism ; Podophyllotoxin ; Pharmacokinetics ; Teniposide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Etoposide (VP 16-213) and teniposide (VM 26) are semisynthetic epipodophyllotoxin derivatives active against a variety of tumours. The clinical efficacy has led to an increasing interest in these compounds. This review presents information on the mechanism of action, biochemical pharmacology, bioanalysis, metabolism and pharmacokinetics of etoposide and teniposide.
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of the nature of the polyols used in polyurethane (PUR) synthesis on the structural transformations after ageing by UV irradiation has been studied. The investigations were performed on PUR prepared from polyester and polyether diol oligomers.The characterization of the samples before and after ageing in view of the structural changes, which influence the course of the photooxidative degradation and photocrosslinking as well as in view of changes of mechanical properties has been done. Comparative investigations were performed by spectroscopic and viscometric measurements.The results show pronounced heterogeneity of the degradative reactions, including the existence of crosslinking processes and producing thus very inhomogeneous polymeric material. The course and the intensity of photooxidative degradation of PUR differ together with changes of mechanical properties depending whether polyester or polyether polyol have been used. The processes of photooxidative degradation is less expressed in polyesterurethane then in polyurethane based on polyether, under the same conditions of experiments. Different structures of polyester diols caused the various ageing behaviour of PUR too.
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  • 5
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: QUALIFICATION OF HALS COMPOUNDSA complex method of examination has been developed suitable for the qualification of light stabilizers; by this method, according to experience, the efficacy of HALS compounds can be extensively and expediently characterized.Several light stabilizers of the HALS-type were examined and qualified, used alone or together with a UV-absorber.It has been found that, when selecting the appropriate structure for a given polymer, the weatherability of polyolefine foils is effectively increase to six-eightfold; the increase is even tenfold when the stabilizer is combined with a benzophenone-type compound.As a utilization of these experiences, a contract with the industry, led to the production of an LDPE based agricultural foil with a life-time of several years.
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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Natural hail impact tests are scarcely available because hailstorms are limited to a small area and cannot be predicted regarding time, place and intensity. Therefore we relied on laboratory tests simulating natural hailstones by polyamide balls (5-50 mm dia.) whose final velocity could be varied according to meteorological data. So the influence of diameter (weight) and velocity of the artificial hailstones could be taken into consideration independently.The energy of damage or equivalent natural hailstone diameter were determined for 16 mm double skin sheet from PMMA as 0.2 J (14 mm dia.) for star shaped cracks and 2 J (26 mm dia.) for holes. These values do not significantly decrease after 10 years weathering. 10 mm double skin sheets from PC show an extremly high energy of damage of abt. 10 J (38 mm dia.) which decreases to a medium level of 2 J (26 mm dia.) after several years weathering. This decrease is remarkably reduced by weather resistant protective coating.As hailstorms consist to more than 80% of hailstones below 10 mm dia. (0.04 J) the mentioned sheet materials are quite hail resistant also after long weathering periods, but they cannot withstand an extreme hail catastrophe as in Munich July 12, 1984.
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  • 7
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the specimen temperature on many ageing processes is well known. Two aspects is dealt with: -Measurements of the specimen temperature on several positions of a specimen in commercial weathering devices at different exposure conditions. Technical measures to achieve to uniform ageing at all positions of a planar and homogeneous specimen. Examples from practical use.-Changing specimen temperatures (+60°C to -20°C) during the course of accelerated weathering, i.e. a combination of conventional accelerated weathering with a temperature cycle test.
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  • 8
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An Folien (Dicke 100 pm) aus isotaktischem Polypropylen mit verschiedenen Antioxidansgehalten (0,0% bis 0,1%) wird die thermooxidative Alterunq mit der isothermen Langzeit-Differential-Thermo-Analyse (ILDTA) bis zu Temperaturen weit unter dem Kristallitschmelzbereich verfolqt und die Messwerte mit Ergebnissen aus dem Zeitstand-Zugversuch korreliert. Dabei zeigt sich, daß aus Messunqen mit der ILDTA bereits vor Einsetzen der autokatalytischen Zersetzunq sreaktion Ruckschlüsse auf die thermische Vorqeschichte der Proben und Aussagen auf das rnit einem Abfall der mechanischen Eigenschaften verbundene Ende der thermo-oxidativen Stabilität des Polymeren getroffen werden können.Weiters bietet die ILDTA die Moglichkeit, durch den direkten Zusamenhang zwischen Oxidationszeit und Antioxidansögehalt die örtliche Stabilisatorverteilung in Platten und in Folien zu bestimmen und damit Diffusionsvorqange zu verfolgen.
    Notes: Thermo-oxidative ageing processes were investigated in films (100 μm thick) made from isotactic polypropylene with different antioxidant concentrations between 0% and 0.1% using isothermal long-term differential thermal analysis (ILDTA). The end of the oven life of polypropylene coincided with the loss of mechanical properties which was confirmed by tensile tests at temperatures far below the crystallite melting range. Already prior to the beginning of autocatalytic decomposition, ILDTA experiments permits conclusions to be drawn on the thermal history of the specimens and statements made regarding the end of thermo-oxidative stability of the polymer, which is accompanied by a deterioration in the mechanical properties.In consequence of the correlation between oxidation time and antioxidant concentration the local antioxidant concentration in sheets or films can be measured by ILDTA. Thus, investigating the diffusion of an antioxidant in polypropylene using ILDTA is possible.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Größenverteilungsfunktion von Dispersionen mit extrem breiter Verteilung (Durchmesserbereich 20 〈 D 〈 2000 nm) kann in der analytischen Ultrazentrifuge (AUC) nicht durch eine Standardmethode, z. B. durch Messung der Trübung τ bei einer einzigen Konzentration, bestimmt werden, weil sich die spezifische Trübung τ/c von sehr kleinen und sehr großen Teilchen zu stark unterscheidet. Um dieses Problem zu lösen, haben wir eine neue AUC-Technik, die sogenannte Coupling-PSD-Technik entwickelt. Dabei werden zwei unterschiedliche Konzentrationen derselben Dispersion gleichzeitig in einem einzigen AUC-Lauf vermessen und zwei korrespondierende Lichtintensitiit-Zeit-Kurven aufgezeichnet. Bei einer niedrigen Standardkonzentration cs werden hauptsachlich die größeren Teilchen erfaßt während bei einer 5 bis 30 mal heheren Konzentration ch vor allem die kleineren Teilchen registriert werden. Die beiden I(t)-Kurven werden mathematisch verkniipft und unter Verwendung des Stokeschen Gesetzes und der Streutheorie von Mie für homogene isotrope Kugeln in die gesuchte breite Verteilungsfunktion umgerechnet. Wir benutzen eine mit einem 8-Zellen-Rotor und einem Multiplexer ausgestattete AUC. Da sehr groBe und sehr kleine Teilchen gleichzeitig in einem einzigen Zentrifugenlauf bestimmt werden, kennen wir nicht mehr wie zuvor eine konstante Rotorgeschwindigkeit N anwenden, sondern miissen diese mit Hilfe eines Geschwindigkeitsprogramms N(t) innerhalb einer Stunde von 0 auf 40000 U/min erhehen.
    Notes: The particle size distribution (PSD) of extremely broad distributed dispersions (diameter range 20 〈 D 〈 2000 nm) is not possible to be measured by analytical ultracentrifuge (AUC) using the standard technique, i.e. measuring turbidity τ at a single concentration c, because the specific turbidity τ/c varies too much between very small and very large particles. To solve this problem we have developed a new AUC technique, the so-called Coupling-PSD-Technique. Here two different concentrations of the same dispersion are measured simultaneously by one single AUC run with two corresponding curves of light intensity I vs. time t being registered. At a low standard concentration cs, mainly the larger particles are detected, while at a concentration ch 5 to 30 times higher mainly the smaller particles are registered. Both I(t)-curves are coupled mathematically and transformed into the requested broad distribution curve employing Stokes' law and Mie's light scattering theory for homogeneous isotropic spheres.We use an AUC together with an 8-cells-rotor and a multiplexer. Because very large and very small particles are to be measured simultaneously in one single run, we can no more apply a constant rotor speed N as before, but by means of a time program N(t) we always have to increase the rotor speed from 0 to 40000 rpm within one hour.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 135-148 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die chemische Modifizierung von Polyvinylchlorid (PVC) durch ein Amin verleiht dem Polymeren höhere Reaktivität gegenüber der Pfropfcopolymerisation mit einem Vinylmonomeren. Die Pfropfcopolymerisation von Methylmethacrylat auf mit n-Butylamin modifiziertes PVC wurde thermisch mit Benzoylperoxid (Bz2O2) als Initiator oder photoaktiviert mit Benzophenon (BP) als Photosensibilisator gestartet. Das aus bestimmten Experimenten erhaltene rohe Polymerprodukt wurde durch fraktionierte Fällung in die verschiedenen Bestandteile wie Polymethylmethacrylat (PMMA, Homopolymeres), PVC-g-PMMA (Pfropfcopolymeres) und unverändertes (aminiertes) PVC aufgespalten. Die getrennten Fraktionen wurden mit Hilfe der IR-Spektroskopie und der Thermogravimetrie charakterisiert. Der Mechanismus der Pfropfcopolymerisation von den beiden verschiedenen Systemen wurde erörtert. In beiden Fällen wurden Pfropfausbeuten um 30 - 70%* und Pfropfcopolymerzusammensetzungen, PMMA/PVC (w/w) zwischen 2 und 3 erhalten.
    Notes: Chemical modification of poly(vinyl chloride), PVC, by an amine renders the polymer more reactive towards graft copolymerization with a vinyl monomer. The graft copolymerization of methyl methacrylate (MMA) on PVC modified by treatment with n-butylamine (n-BA) was started thermally at 30° using benzoyl peroxide (Bz2O2) as initiator and under photoactivation at 40° using benzophenone (BP) as photo sensitizer. The gross polymer products from selected experiments were fractionally separated into the constituent polymeric entities viz., poly(methyl methacrylate), PMMA (homopolymer), PVC-g-PMMA (graft copolymer), and unreacted (aminated) PVC following a method of fractional precipitation. The separated fractions were characterized by IR spectroscopy and thermogravimetry. The mechanisms of graft copolymerization for the two different systems have been discussed. In each case, grafting efficiencies of the order of 30-70% and graft copolymers having compositions given as PMMA/PVC (w/w) equal to 2-3 were readily obtained.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 193-201 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe oberflächensulfonierter, makroporöser Styrol-Divinylbenzol-Copolymerer mit unterschiedlichen Gehalten an SO3H-Gruppen wurden hergestellt. Sowohl von diesen Copolymeren als auch vom nichtsulfonierten Copolymeren wurden Porenstruktur, Oberflächenhydrophilie und -polarität sowie das Sorptionsverhalten gegenüber einigen in Blut vorkommenden Substanzen bestimmt. Der Sorptionsgrad wird umso kleiner, je größer die Oberflächenpolarität ist. Die teilsulfonierten Polymeren könnten eine Anwendung in der Hämoperfusion finden.
    Notes: A series of surface sulphonated macroporous styrene-divinylbenzene (S-DVB) copolymers containing various amounts of  - SO3H groups was obtained. Porous structure, surface hydrophilicity and polarity, and sorption properties of these copolymers as well as those of starting S-DVB resin towards some substances which are present in blood were determined. The sorption degree becomes the smaller the higher is the surface polarity. The partially sulphonated copolymers may find an application in hemoperfusion.
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  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer chemischen Behandlung von dünnen Filmen einer Composit-Membran aus sulfoniertem Polyphenylenoxid wurde untersucht. Über den Einfluß der Konzentration von wáßrigen Lösungen von Formaldehyd, Schwefelsäure, Salzsäure, Phosporsäure, Natriumhydroxid sowie der Behandlungsdauer auf die Trenncharakteristik der inversen Osmose der Composit-Membranen mit einer Ionenaus-tauschkapazität von 2,14 und 2,50 meq/g in verschiedenen Kombinationen wird ausführlich berichtet. Die Ergebnisse zeigen, daß unter den besten chemischen Behandlungsbedingungen eine Erhöhung der Trenncharakteristik der inversen Osmose der sulfonierten Polyphenylenoxid/Polysulfon-Composit-Membran erreicht wird.
    Notes: The effect of chemical treatment on the reverse osmosis (RO) separation characteristics of sulfonated poly(phenylene oxide) (SPPO) thin film composite membranes was investigated. The effects of the concentrations of aqueous solutions of formaldehyde, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, and treatment time on the RO separation characteristics of the composite membranes with ion exchange capacity (IEC) of 2.14 and 2.50 meq/g in various combinations are reported in detail. The results indicate some enhancement in RO separation characteristics of the SPPO/polysulfone (PS) composite membrane under the best conditions of the chemical treatment.
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  • 13
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bei der Herstellung dünner Filme von sulfonierten Polyphenylenoxid/Polysulfon (SPPO/PS)-Composit-Membranen wurde untersucht, daß ein Zusatz von Nitromethan zu einer Lösung von sulfoniertem Polyphenylenoxidnatrium erhöhte Wirkung auf die Trenncharakteristik der inversen Osmose besitzt. Der Einfluß von gamma-Strahlung auf dünne Filme der Composit-Membran unter nassen und trockenen Bedingungen wurde ebenfalls untersucht. Um die maximal mögliche Verbesserung zu erreichen, wurden die Composit-Membranen einer kombinierten chemischen und Gammastrahlen-Behandlung unter nassen und trockenen Bedingungen unterworfen.Die experimentellen Ergebnisse dieser kombinierten Behandlung zeigen, dalß die SPPO/PS Composit-Membran dabei abgebaut wird.
    Notes: The enhancement effect of the addition of nitromethane into the coating solution of sulfonated sodium poly(phenylene oxide) (SPPONa) polymer for the synthesis of sulfonated poly(phenylene oxide)/polysulfone (SPPO/PS) thin film composite membranes on reverse osmosis (RO) separation characteristic was studied. The effect of gamma-ray irradiation on the SPPO/PS thin film composite membranes was also evaluated when the membrane samples were in the wet and dry conditions. The composite membranes were also subjected to a chemical treatment combined with gamma-ray irradiation in both wet and dry conditions in the hope of obtaining the maximum possible enhancement under each treatment. However, the experimental data of this combined treatment indicated the possibility of some degradation of the SPPO/PS composite membranes.
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  • 14
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 37-45 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mischungen aus Poly(styrol-co-butadien)/Polybutadien, Naturkautschuk/Poly-(ethylen-co-propylen-co-dien und Naturkautschuk/Poly(butadien-co-acrylnitril)) wurden nach drei unterschiedlichen Verfahren compoundiert und Härtungsverhalten sowie Zugfestigkeit und Bruchdehnung der Vulkanisate wurden verglichen.
    Notes: Compounding of styrene-butadiene copolymer/polybutadiene, natural rubber/ethylene-propylene-diene terpolymer and natural rubber/butadiene-acrylonitrile copolymer blends was done in three different ways and their curing behaviour and the tensile properties of the vulcanizates are compared.
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  • 15
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Methylmethacrylat (MMA) wurde mit Hilfe von Cerammoniumnitrat als Initiator auf Stärke gepfropft. Die Pfropfcopolymeren wurden durch selektive Lösungsextraktion in einem Soxhlet-Extraktor isoliert. Der Einfluß von Reaktionszeit, Initiatorkonzentration, Temperatur sowie der Monomer- und Särekonzentration auf die Pfropfausbeute wurde untersucht. Eine erste Studie der Kinetik dieser Pfropfcopolymerisationsreaktion zeigt, daß sie dem üblichen kinetischen Verhalten einer Radikalpolymerisation folgt.
    Notes: Methyl methacrylate (MMA) was grafted onto starch using ceric ammonium nitrate as initiator. The graft copolymers were isolated by selective solvent extraction in a Soxhlet apparatus. The effects of reaction time, initiator concentration, temperature, monomer, and acid concentrations on the graft yields were investigated. A preliminary kinetic study of the graft copolymerisation reactions shows that they follow the conventional kinetic behaviour of free radical polymerisation.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 47-61 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Verwendung von Phenol-Formaldehyd-Harz mit gepreßten Olivenkenen im Gewichtsverháltnis 20/80 wurden kleine zylindrische Formkörper durch Härtung hergestellt. Diese wurden pyrolysiert und einige Proben mit Wasserdampf aktiviert. Für diese Formkörper und für zwei kommerzielle Aktivkohlen für Laboratoriumsbzw. Industrie-Anwendungen wurden folgende Eigenschaften bestimmt: die spezifische Oberfláche, die Struktur, die Adsorptionseigenschaften sowie die Adsorptionskapazität. Die Ergebnisse zeigen, daß die hergestellten kohlenstoffhaltigen Materialien durch Aktivierung höhere Werte für die untersuchten Eigenschaften ergeben als die nur pyrolysierten Proben und die zwei kommerziellen Aktivkohlen. Es wurde festgestellt, daß die Adsorption des 4-Nitrophenols für alle untersuchten kohlenstoffhaltigen Materialien gemäß der Freundlich-Gleichung stattfindet. Die Raster-Elektronenmikroskopie zeigt, daß die hergestellten kohlenstoffhaltigen Materialien andere Porenarten aufweisen als die kommerziellen Aktivkohlen. Die experimentellen Ergebnisse werden durch die molekularen Dimensionen der zur Adsorption verwendeten Substanzen und den Polarisationseffekt der Substituenten am Benzolring erklärt.
    Notes: Mixtures of phenol-formaldehyde-resin and pressed olive stones in a weight ratio of 20/80 were cured as small cylinders and then pyrolyzed. Some samples were also activated by steam. For these specimens and for two commercial activated carbons of laboratory or industrial uses the specific surface area, the structure, the adsorption properties, and the adsorption capacity were determined. The results indicate that the carbonaceous material produced by activation has greater values for the examined properties in comparison to the only pyrolyzed and the two commercial activated carbons, respectively. It was found that the Freundlich-equation is valid for the adsorption of 4-nitrophenol on all carbonaceous materials examined. The produced carbonaceous materials have different kinds of pores than the commercial activated carbons. The experimental results are explained with regard to the molecular dimensions of the adsorptive substances and the polarization effect of the substituents of the benzene ring.
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  • 17
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 101-114 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Anwendung der nichtlinearen Programmiermethode basierend auf der mittleren harmonischen Näherung wurden aus den Kontaktwinkeldaten die freie Dispersions- und polare, freie Oberflächenenergie, γSVd und γSVp, sowie die kritische, freie Oberflächenenergie, γc, von Polymeren bestimmt. Die Komponenten der freien Oberflächenergie der zu untersuchenden Flüssigkeiten, γLVd und γLVp, die die Bedingungen für den maximalen Wechselwirkungsparameter, Φ, wiedergeben, wurden ebenfalls mit Hilfe dieser Methode bestimmt.
    Notes: The dispersion and polar surface free energy components, γSVd and γSVp, and the critical surface free energy, γc, of polymers were determined from contact angle data by the application of a nonlinear programming method using harmonic mean approximation.The surface free energy components of the probe liquids, γLVd and γLVp, which reflect the conditions of the maximized interaction parameter, Φ, were also simultaneously determined by this method.
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  • 18
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 169-193 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The condensation reaction of bisphenol A, melamine, and formaldehyde was investigated by gel permeation chromatography, 13C-NMR-spectroscopy, IR-spectroscopy and elemental analysis. Because of the high reaction rates the condensation could be investigated only in the range of pH 6-10. At pH 6 and 7 the reaction of melamine with formaldehyde is dominating.With increasing pH-value the condensation of bisphenol A with formaldehyde is observed preferably. At pH 10 the condensation results in high molecular products. Cocondensation of melamine and bisphenol A through methylene bridges does not take place. But as a separation of the bisphenol A-formaldehyde condensates from the other condensation products was not possible, the three components may be connected through methylene-ether groups and/or intermolecular hydrogen bridges.
    Notes: Die gemeinsame Kondensation von Bisphenol A, Melamin und Formaldehyd wurde mit Hilfe der Gelpermeationschromatographie, der 13C-NMR-Spektroskopie, IR-Spektroskopie und Elementaranalyse untersucht. Wegen der hohen Kondensationsgeschwindigkeit verläuft die Reaktion in Gegenwart der drei Komponenten nur im Bereich von pH 6-10 kontrollierbar. Bei pH 6 und 7 überwigt die Kondensation zwischen Melamin und Formaldehyd. Mit steigendem pH-Wert tritt die Reaktion von Bisphenol A mit Formaldehyd in den Vordergrund und führt bei pH 10 zu hochmolekularen Kondensationsprodukten.Auf direkte Cokondensation hinweisende Methylenverknüpfungen zwischen der phenolischen Komponente und Melamin konnten nicht nachgewiesen werden. Die Kondensationsprodukte des Melamins bzw. des Bisphenol A mit Formaldehyd lassen sich aber nicht mehr vollständig aus den Reaktionsgemischen der Vorkondensation abtrennen, was dafür spricht, daß die Komponenten über Methylenetherbrücken und/oder intermolekularen Wasserstoffbrücken miteinander verknüpft sind.
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  • 19
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 205-207 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclodextrin membrane-modified electrodes as sensor materials have been prepared by dipping platinum electrodes in the water suspensions of an oriented cyclodextrin polymer, followed by drying the polymer layers on the electrodes. The polymer is obtained by the solid-liquid reaction between the crystal of cyclodextrin inclusion complex and hexamethylene diisocyanate in anisole. The thickness (2 - 80 μm) of the cyclodextrin membrane is satisfactorily controlled by changing the concentration of the water suspension of the polymer. The cyclodextrin membranemodified electrodes show a significant response to p-nitrophenolate in water which is highly in contrast with no measurable response to o- and m-nitrophenolates.
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  • 20
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Zusammenhang mit dem Studium des Wirkungsmechanismus von industriell hergestellten Antidegradantien vom Typus der N-Phenyl-N′-sek-alkyl-1,Cphenylendiamine wurde die Reaktion von N-Phenyl-1,4-benzochinonimin (I) und 4-Hydroxydiphenylamin (II) mit dem Kohlenstoff-Radikal 1-Cyano-l-methylethyl (R·) studiert. Das Gemisch von I und II reagiert mit R· sehr leicht unter Bildung der Verbindungen III, VI und VIII. I allein reagiert wesentlich langsamer, und das Reaktionsgemisch enthält mehrere Produkte. Neben der Verbindung III wurden auch die Verbindungen IV und VII identifiziert. II allein reagiert bei denselben Bedingungen nicht. Die Verbindung IV bildet die zwei isomeren Strukturen syn und anti. Die Verbindung VIII ist ziemlich unbeständig; aus ihren Umwandlungsprodukten wurde XI isoliert. Bei der Reduktion von IV entsteht die Verbindung V, die ähnlich wie VIII unbeständig ist.
    Notes: The reaction of N-phenyl-1,4-benzoquinoneimine (I)Decoding of abbreviations see p. 103/104. and 4-hydroxydiphenylamine (II) with the carbon centred 1-cyano-1-methylethyl radical (R·) was studied in connection with an investigation of the action mechanism of industrial antidegradants, such as N-phenyl-N′-sec-alkyl-1,4-phenylenediamines. The mixture of I and II reacts very readily with R·, giving rise to III, VI, and VIII. I alone reacts much slowlier, and the reaction mixture contains more products. IV and VII were identified along with III. Under the conditions used, II alone does not react at all. IV exists in two isomeric forms, syn and anti. VIII is very labile; XI was isolated from its transformation products. Reduction of IV gives V, which is labile, similarly to VIII.
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  • 21
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 123-137 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Samples of polyoxymethylene (unstabilized and stabilized with the antiozonants N-isopropyl-N′-phenyl-p-phenylenediamin (IPPD) and bis-(1,2,3,6-tetrahydrobenzaldehyd)pentaerithritylacetal (Vulkazon AFS)) were ozonized under mechanical load in a special climate chamber. Surface damages were determined by IR-spectroscopy and scanning electron microscopy. During the ozonolysis a damaged layer is formed, the thickness of which increases with increasing time of ozonization. During this damaging reaction acetal groups are attacked and oligomers are formed.
    Notes: Proben von unstabilisiertem und mit den Antiozonantien N-Isopropyl-N′-phenyl-p-phenylendiamin (IPPD) und Bis-(1,2,3,6-tetrahydrobenzaldehyd)-pentaerithrityl-acetal (Vulkazon AFS) stabilisiertem Polyoxymethylen wurden unter mechanischer Belastung in einer Klimakammer ozonisiert. Die Schädigungen auf der Oberfläche wurden IR-spektroskopisch und rasterelektronenmikroskopisch untersucht. Während der Ozonisierung von POM bildet sich eine geschädigte Schicht, deren Dicke mit zunehmender Ozonisierungszeit wächst. Hierbei wird das Polymere an den Acetalbindungen angegriffen, wodurch Ketten gespalten werden und Oligomere entstehen.
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  • 22
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 105-121 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mit Hilfe verschiedener Methoden wurde der Einfluß der Entfernung unterschiedlicher porenbildender Verdünner aus porösen Styrol-Ethylstyrol-Acrylnitril-Divinylbenzol-Copolymeren auf die Netzwerkstruktur untersucht. Der günstigste Weg, den ursprünglichen strukturellen Bau des porösen Netzwerkes zu bewahren, welches in Gegenwart von solvatisierenden Verdünnern erhalten wurde, ist das Entfernen des inerten Mediums mit Methanol. Wenn die Wasserdampfmethode angewendet wird, fin det der sog. Kollapseffekt statt, und die aus solchen Harzen hergestellten Anionenaustauscher adsorbieren weniger Farbstoff im Vergleich zu jenen, die aus Perlen hergestellt worden sind, die mit Methanol behandelt wurden; Grund hierfür ist die durch den Kollaps veränderte Porengröße. Es wurde ebenfalls festgestellt, daß die in Anwesenheit von solvatisierenden Verdünnern (Mischungen aus Quellungs- und Fällmitteln) hergestellten Copolymeren in Methanol sehr gut quellen, obwohl dieses ein Fällungsmittel für Polystyrol ist.
    Notes: The influence of the removal of various diluents, pore forming agents from the porous styrene-ethylstyrene-acrylonitrile-divinylbenzene copolymers on the structure of the matrix was investigated by several methods. The most advantageous pathway to preserve the initial structural edifice of the porous networks performed in the presence of solvating diluents consisted in the removal of the inert media with methanol as it was noticed from the experimental data. If the steam treatment is applied, the collapse effect takes place and the anion exchangers prepared from such matrices exchange/adsorb less dye stuff by comparison with ones formed from beads treated with methanol, because the pore size was changed. It was also noticed that the porous copolymers performed in the presence of the solvating diluents (mixtures of solvatings and precipitants) swell very well in methanol though it is a precipitating medium for the polystyrenic macromolecular chains.
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  • 23
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 139-149 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An Styrol-Zinkacrylat-Copolymeren wurde die Abhängigkeit der Glasübergangstemperatur von der Aufheizgeschwindigkeit und der Zusammensetzung mit Hilfe der Differential-Scanning-Calorimetrie untersucht. Die Thermogravimetrie wurde benutzt, um die Pyrolyse dieser Copolymeren an Luft bei drei verschiedenen Aufheizge-schwindigkeiten zu untersuchen. Die thermische Zersetzung von Ionomeren ist ein 3-Stufen-Prozeß. Die Reaktionsordnung und Aktivierungsenergie wurde für jede Stufe der Zersetzung bestimmt unter Verwendung eines Computerprogramms, das auf den Methoden von Kissinger, Freeman-Carrol und Ozawa basiert. Es zeigte sich, daß die thermische Stabilität durch die ionischen Gruppen abnimmt.
    Notes: The dependence of glass temperature on the heating rate and the composition for styrene-zinc acrylate copolymers has been investigated by differential scanning calorimetry. Thermogravimetry was used in order to examine these copolymers undergoing pyrolysis in an atmosphere of air at three different heating rates. Thermal decomposition of ionomers is a three-stage process. The orders and activation energies have been determined for each stage of decomposition using the computer programs based on the methods of Kissinger, Freeman-Carrol, and Ozawa. It was found that the heat stability is lowered by the ionic groups.
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  • 24
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 151-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Pfropfung der hydrophilen Monomeren N-Vinylpyrrolidon, 2-Hydroxyethyl-methacrylat und Acrylamid auf ungesättigte segmentierte Polyurethane in N,N-Dimethylformamid mit 2,2′-Azobisisobutyronitril als Initiator wurde untersucht. Die Pfropfcopolymeren wurden von den Homopolymeren durch selektive Extraktion in Soxhlet-Apparaturen abgetrennt. Die kinetische Untersuchung der Pfropfcopolymerisation zeigte, daß die Reaktionen dem gewöhnlichen kinetischen Verhalten radikalischer Polymerisationen folgen. Die Abhängigkeiten der Pfropfungsgeschwindigkeit von der Initiator- und N-Vinylpyrrolidonkonzentration waren von 0,5 bzw. 1,0 Ordnung. Für 2-Hydroxyethylmethacrylat wurden sie zu jeweils 0,5 und 2,0 gefunden. Die Gesamtaktivierungsenergie der Pfropfcopolymerisation des 2-Hydroxyethylmethacrylats und des N-Vinylpyrrolidons betragen jeweilig 21,81 und 16,28 kJ/mol.
    Notes: Grafting of unsaturated segmented polyurethanes with some hydrophilic monomers such as N-vinyl pyrrolidone, 2-hydroxyethylmethacrylate and acrylamide in N,N-dimethylformamide have been studied using 2,2′-azobisisobutyronitrile (AIBN) as initiator. Graft copolymers were isolated from homopolymers by selected solvent extraction using a Soxhlet apparatus. A kinetic study of graft copolymerization reactions showed that the reactions follow the conventional kinetic behaviour of free radical polymerization. The dependencies of the grafting rate on initiator and N-vinyl pyrrolidone concentrations were of 0.5 and 1.00 order, respectively. However, for the 2-hydroxyethylmethacrylate, the dependencies of the grafting rate on initiator and monomer concentrations were found to be of 0.5 and 2.00 order, respectively. The overall activation energy for the graft copolymerization of the 2-hydroxyethylmethacrylate and N-vinyl pyrrolidone were 21.81 kJ/mol and 16.28 kJ/mol, respectively.
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  • 25
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    Angewandte Makromolekulare Chemie 156 (1988), S. 179-185 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultra fine particles were impregnated by using a finely porous cellulose gel membrane. The impregnated gel membrane is a green transparent one and looks like a solid solution. Highly dispersed Ni catalysts on carbon were obtained from thermal decomposition of these gel membranes. The particle size is in the range of several nm to a few ten nm. They show interesting catalytic properties for hydrogenation of olefins such as cyclooctadiene.
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  • 26
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermo-oxidation resistance and weatherability of LDPE and HDPE compositions, containing up to 45 wt.% calcium carbonate, are investigated. The thermo-oxidation resistance is investigated by dynamic DTA and natural ageing is carried out in an exposure station in a seaside climate. The change in strength and colour after ageing is determined. The behaviours of filled and unfilled polymers are compared. Empirical equations are given, describing the change in the investigated parameters during natural ageing.
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  • 27
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An Proben aus Polypropylen, die bei sehr unterschiedlichen Einstellungen von Spritzgußmaschinen und Extrudern hergestellt wurden, stellten sich deutliche Abhängigkeiten des Alterungsverhaltens von den thermischen und mechanischen Produktionsparametern ein, die nicht durch unterschiedliche Schmelzetemperaturen bedingt sind. Insbesondere kann ausgesagt werden, daß bei Spritzguß eine hähere Scherbelastung und damit stärkere Orientierungen -eine stärkere Veränderung der Eigenspannungen hervorrufen-einen früheren Glanzabfall und-eine geringere Initialzeit bis zur Rißbildung bewirken.Bei Extrusion fiihrt eine geringere Abkühlgeschwindigkeit und damit ein gröberes Gefüge zu -einer stärkeren Veränderung der Eigenspannungen-einem friiheren und ausgeprägteren Glanzverlust-sowie zu einem früheren Abfall der Reißdehnungen.Unbekannt ist, -ob diese Wirkungen auch bei anderen Thermoplasten als PP auftreten-ob sie auch bei stabilisierten Systemen in relativ gleichem Umfange auftreten-und ob es sich lohnt, die beobachteten Effekte ggf. durch ge zielte Maschineneinstellungen auszunutzen.Auf jeden Fall sollten auf diesem Gebiet weitere Arbeiten durchge-führt werden.
    Notes: Specimens of unmodified polypropylene have been manufactured using extreme adjustings of injection moulding machines and extruders. After artificial weathering, distinct relations of ageing processes to thermal and mechanical production parameters were found, which are not influenced by different melting temperatures. It can be started in particular, that during injection moulding a larger shear stress (resulting in more distinct orientation) results in -a greater change in residual stresses-an earlier gloss reduction-a shorter initial period before cracking.During extrusion a lower cooling rate (resulting in a coarser structure) leads to -a greater change in residual stresses-an earlier and more distinct gloss reduction-an earlier loss of ultimate strain.It remains unknown, whether -these relationships will be similar with other thermoplastic materials than PP-these relationships appear to the same relative extend with stabilized systems-it may be advantageous, to use the observed effects by adjusting the injection moulding and extrusion machines in a special way.It seems to be significant to do more research work in this field.
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  • 28
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 1-15 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(tetramethylenadipat)diol mit einer Molmasse von 2000 wurde bei Temperaturen von 60 und 80°C in Gegenwart von Wasser bzw. 1,4-Butandiol sowie den gebräuchlichsten PUR-Katalysatoren (Dabco und Dibutylzinndilaurat) gelagert und die Solvolyse untersucht. Die Geschwindigkeit der Solvolyse nimmt mit steigender Temperatur deutlich zu. Die Alkoholyse wird durch Dibutylzinndilaurat weitaus stärker katalysiert als durch 1,4-Diazabicyclo[2.2.2]oktan. Die Hydrolyse verläuft langsamer, da vermutlich die Katalysatoren bei diesem Prozeß desaktiviert werden. Die mechanischen Eigenschaften von Polyurethanen, die mit den partiell abgebauten Diolen hergestellt wurden, korrelieren gut mit der Abnahme der Molmasse.
    Notes: Poly(tetramethylene adipate)diol having a molar mass of 2000 was stored at temperatures of 60 and 80°C in the presence of water or 1,4-butanediol and a common PUR-catalyst like 1,4-diazabicyclo [2.2.2]octane (DABCO) or dibutyltindilaurate (DBTL) and the solvolysis was investigated. The rate of solvolysis is low at 60°C except for DBTL and shows a drastic increase at 80°C. In the alcoholysis reaction DBTL is a much more active catalyst than DABCO. The rate of hydrolysis is slower probably because the catalysts are deactivated by the acidic products formed in this process. The mechanical properties of polyurethanes made from the degraded polyols are in good correlation with the decrease in molar mass.
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  • 29
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 17-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß der Zugabe von Bis(allylphenyl) Typ (TM 120)-Monomeren auf die Eigenschaften von unidirektional mit Carbonfasern verstärkten 4,4′-Bismaleimidodiphenylmethan (BM) - 2,4-Tolylendiamin (A) (1:0,3 Molverhältnis) (BM-A)-Verbundkörpern wird vorgestellt. Das Aushärteverhalten sowie das thermische Verhalten in Luft wurde mit Hilfe der Differentialkalorimetrie (DSC) und der Thermogravimetrie (TGA) untersucht. Die thermische Stabilität nimmt mit ansteigenden Konzentrationen von TM 120 deutlich zu. Demgegenüber steht ein Anstieg der Biegefesigkeit, der interlaminaren Scherfestigkeit sowie der Schlagzähigkeit mit zunehmender Monomerkonzentration. Optimale mechanische Eigenschaften wurden bei etwa 20 Tle./100 Tle. TM 120 erreicht.
    Notes: The paper deals with the effect of addition of bis(allylphenyl) type (TM 120) monomer on the properties of unidirectionally carbon fibre reinforced 4,4′ bismaleimidodi-phenyl methane (BM) - 2,4-tolylene diamine (A) (1:0.3 molar ratio) (BM-A) composites. The curing and thermal behaviour of the blends was investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) in air atmosphere. A marginal decrease in thermal stability was observed with increasing concentration of TM 120. Flexural, interlaminar, and impact strength of the laminates increased in the presence of this monomer. Optimum mechanical properties were observed at ∼ 20 phr of TM 120.
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  • 30
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In dieser Arbeit wurden Veränderungen des verschweisßten Rohr- und Fittingmaterials (isotaktisches Polypropylen Homo- bzw. Copolymer PP-R grau pigmentiert) wührend der für die Praxis relevanten Innendruckversuche untersucht.Bei der technischen Verschweißung von Polyolefinen entstehen charakteristische Gefüigezonen im Schweißnahtbereich, welche vom Fßgematerial und den Fngebedingungen beeinflußt werden. In der vorliegenden Untersuchung wurden sowohl die Materialcbergange im Fiigebereich (mit den Methoden - schichtenweise Differentialkalorimetrie, Polarisations- bzw. Elektronenmikroskopie sowie Fluoreszenzspektroskopie mit extrem hoher Ortsauflösung) als auch die Eigenspannungen hinsichtlich ihrer Verlnderung bei Langzeitpriifung im Innendruckzeitstandversuch bei 95°C bis zu einer Prüfzeit von 18.100h untersucht.Die Abbauvorgänge der Makromoleküle bei der Langzeitprüfung der 364 untersuchten Schweißmuster werden in einer gesonderten Arbeit behandelt (1).Durch die Innendruckversuche bei 950 C findet eine Nachkristallisation und eine Gefügevergrijberung sowohl in der Schweißnaht als auch im Gefüge der Schweißpartner statt. Dabei werden die beim Schweißvorgang eingebrachten Orientierungen und Eigenspannungen unter dem Einfluß von Wärme beim Innendruckversuch weitgehend abgebaut. Durch die unter Druckeinwirkung einsetzenden Flieävorgange jedoch werden neue Eigenspannungen eingebracht.Es konnte gezeigt werden, daß bei guter Verschweißung von PP mit PPCO ein kontinuierlicher Übergang (Mischungsbereich) vom Homopolymeren zum Copolymeren auftritt, der auch beim Langzeiteinsatz im Innendruckversuch erhalten bleibt.
    Notes: The present study deals with changes of welded material of pipes and fittings (isotactic polypropylene homo and copolymer PP-R grey pigmented) during the standardized internal pressure tests, which are commonly used for these products.Technical welding of polyolefines causes characteristic structures, which depend on the natural of the welded material and the welding conditions.In this investigation both the transition of material in the welding seam and the changes of internal stresses during internal pressure tests at 95°C until 18.100h test time were examined. The methods we used were Differential calorimetry of think layers, Polarization- and Electron microscopy, Fluorescence spectroscopy with extreme high local resolution.The effects of decomposition of the macromolecules in the welded samples during the internal pressure tests will be described in a separate paper (1).The internal pressure tests at 95O C cause a recrystallization and an increase of the particle size in the structure of the welding seam and in the structure of the welded parts themselves. Under the above described testing conditions the orientations and internal stresses initiated by the welding procedure will relaxe influenced by heat. However the creep effects that occur in the material when exposed to pressure introduce new internal stresses. It could be shown that in perfectly welded parts a continuous transition from PP to PPCO occurs, which did not change after long time application of internal pressure tests.
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  • 31
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    Angewandte Makromolekulare Chemie 160 (1988), S. 67-81 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden neue Coordinationspolymere mit Schiffschen Basen aus Terephthalal dehyd und S-Benzyldithiocarbazol als Liganden in DMF-Lösung hergestellt. Die erhaltenen Coordinationspolymeren wurden durch Elementaranalyse, magnetische Suszeptibilität, elektronische und IR-Spektroskopie charakterisiert. Die durch Thermogravimetrie bestimmte thermische Stabilität der Coordinationspolymeren nahm in der folgenden Reihenfolge ab: \documentclass{article}\pagestyle{empty}\begin{document}${\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere haben eine Oktaederstruktur mit der Koordinationszahl6, während bei den Cu(II)- und Zn(II)-Coordinationspolymeren eine 4-fach koordinierte quadratisch-planare bzw. eine tetraedrische Struktur gefunden wurde. Ligandenfeld- und nephelawetische Parameter wurden aus den Spektren errechnet. Dam wurde die Ligandenfeldtheorie spin-erlaubter Übergänge angewandt, die sich als konsistent mit einer 6-fach koordinierten Struktur für Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere erwies. Die Elementaranalysen ergaben bei allen Coordinationspolymeren ein Ligand: Metall-Verhältnis von 1 : 1 und deuteten bei den Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymeren auf am Zentralatom assoziierte Wassermoleküle hin.
    Notes: New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements.The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.
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  • 32
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    Angewandte Makromolekulare Chemie 160 (1988), S. 91-106 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Emulsionen von aromatischen Polyamidsären (PMPE and PBPPM) in DMF und Methanol wurden benutzt, um gleichmäßige Filme auf Leiteroberflächen durch Elektrophorese abzuscheiden. Die Ausbeute und Qualität der abgeschiedenen Filme hängen von der Art der Polyamidsäre, dem Lösemittel, dem Fällungsmittel, dem oberflächenaktiven Mittel, dem pH-Wert und dem Polymergehalt ab. Die Bedingungen zum Erreichen der höchsten Abscheidungsausbeuten wurden bestimmt.
    Notes: The emulsions of aromatic polyamic acids (PMPE and PBPPM) in DMF and methanol were used to coat uniform films on conductor surfaces by electrodeposition. The deposition yield and quality of the deposited films are dependent on sort of polyamic acid, solvent (DMF), precipitant (MeOH), surfactant (TEA), pH value and solid content. To get maximum deposition yields from PMPE and PBPPM, the best conditions of electrodeposition were required as follows: pH value 5.7 and 5.58, MeOH/DMF weight ratio 3.0 and 2.8, solid content 3.5 and 2.4 wt.-%. Deposition yield was found to obey Faraday's law of electrolysis, and the higher the equivalent weight of the polyamic acid, the higher the coulombic yield.
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  • 33
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    Angewandte Makromolekulare Chemie 160 (1988), S. 107-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein einfaches Modell von Doppelassoziaten wurde verwendet, um die Doppelschichtsorption von binären Gasgemischen an flexiblen linearen Polymerketten zu beschreiben. Die Isothermengleichung nach diesem Modell ist ein einfaches Produkt der isothermen Gleichung, die die Doppelschichtadsorption von binären Gasgemischen an einer homogenen festen Oberfläche beschreibt und einer Funktion, die die spezifischen Merkmale der Sorption an Polymeren widerspiegelt.
    Notes: A simple model of double associates is used to represent bilayer sorption of binary gas mixtures on a flexible linear chain of a polymer. The isotherm equation derived in terms of this model is a simple product of the isotherm equation describing bilayer adsorption of binary gas mixtures on a homogeneous solid surface and a function reflecting specific features of sorption on polymers.
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  • 34
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 131-140 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: For a polymer system sulfur-styrene containing 10 wt.-% styrene the morphologie depending on the polymerization temperature and time is described. Besides the characteristical orthorhombic phase a monoclinic and a pseudoorthorhombic phase were detected. Moreover amorphous material exists, depending on the polymerisation parameters.
    Notes: Für ein Polymersystem Schwefel-Styrol mit 10% Styrol wird die Abhängigkeit der Morphologie von der Polymerisationstemperatur und -zeit beschrieben. Neben der charakteristischen orthorhombischen Phase wurden röntgenographisch eine monokline und eine pseudoorthorhombische Phase nachgewiesen. Außerdem liegt, abhängig von den Polymerisationsparametern, ein amorpher Anteil vor.
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  • 35
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    Angewandte Makromolekulare Chemie 160 (1988), S. 117-129 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Für eine anionische Polymerisation mit langsamer Start- und schneller Wachstumsreaktion wurde ein analytischer Ausdruck entwickelt, der es erlaubt, mittlere Molekulargewichte und Molekulargewichtsverteilungen von Polymeren vorauszuberechnen, die in einem halbkontinuierlichen Polymerisationsverfahren bei Zulauf einer verunreinigten Monomerlösung zu einer vorgelegten Initiatolösung entstehen. Die Gültig keit des Modells wurde an der Polymerisation von Isopren mit n-Butyllithium in n-Heptan überprüft. Die beobachteten Unterschiede zwischen theoretischen und experimentellen Werten werden auf die Änderungen in den Geschwindigkeitskonstanten von Start- und Wachstumsreaktion zurückgeführt, die dadurch hervorgerufen werden, daß sich die Polarität der Lösung durch die Anreicherung mit polaren Verbindungen ändert. Weiterhin wird gezeigt, daß bimodale Molekulargewichtsverteilungen entstehen, wenn sich an die halbkontinuierliche Verfahrensweise eine diskontinuierliche zur Erhöhung des Monomerumsatzes anschließt.
    Notes: For anionic polymerization with slow initiation and rapid propagation step analytical expressions are presented to calculate average molecular weights and molecular weight distributions for a semi-batch process, in which a monomer solution contaminated by impurities is fed to an initiator solution in the reactor. The validity of the model was checked for the case of the polymerization of isoprene by n-butyllithium in n-heptane. The differences observed between theoretical and experimental values are explained by the changes in the rate constants of the initiation and the propagation step caused by the change in the polarity of the reaction solution by the continuously fed impurities. Furthermore it is shown that polymers with bimodal molecular weight distributions are formed if the semi-batch procedure is followed by a batch one to increase the monomer conversion.
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  • 36
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    Angewandte Makromolekulare Chemie 160 (1988), S. 141-154 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Wärmehärtungsmechanismus von zu Anstrichen verwendeten Polyethersulfonen wurde unter Verwendung von FTIR/PAS und ESCA untersucht. Als Ergebnis wurde bestätigt, daß der Luftsauerstoff Einfluß auf den Wärmehärtungsmechanismus hat. Das heißt, die Härtung des Polyethersulfonfilms beginnt an der Oberfläche und verläuft entsprechend Reaktion (4) weiter.
    Notes: Thermosetting mechanism of paint-use polyethersulfones was studied by utilizing FTIR/PAS and ESCA. As a result, it was confirmed that the oxygen in the air has an effect on the thermosetting mechanism. That is, the polyethersulfone film were baked from the surface, and proceeded according to reaction (4).
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  • 37
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    Angewandte Makromolekulare Chemie 160 (1988), S. 155-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde der Mechanismus der Reaktion von 4-Ethylphenol mit Zimtaldehyd mittels HET 2DJ 13C-NMR Spektroskopie, 1H-NMR Spektroskopie und GPC untersucht. In der ersten Stufe findet die Addition des 4-Ethylphenols an die Carbonylgruppe und an die Doppelbindung des Zimtaldehyds statt. In der zweiten Stufe reagiert die —CH(OH)-Gruppe mit 4-Ethylphenol und bildet verzweigte Produkte in rötlich gefärbten Harzen mit einem Durchschnittsmolekulargewicht on 600. Die Reaktion verläuft bei Temperaturen über 100°C in stark saurem Medium.
    Notes: The mechanisms of the reaction between 4-ethylphenol and cinnamaldehyde were studied by means of HET 2DJ 13C-NMR spectroscopy, 1H-NMR spectroscopy and GPC. In the first step of the reaction the addition of 4-ethylphenol to carbonyl group and to double bond of cinnamaldehyde takes place. In the second step of the reaction the —CH(OH)-group reacts with 4-ethylphenol to form branched products of red coloured resins with an average molecular weight of 600. The reaction takes place at temperatures above 100°C in strong acid medium.
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  • 38
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    Angewandte Makromolekulare Chemie 160 (1988), S. 163-173 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die elektrischen und paramagnetischen Eigenschaften des durch eine direkte Methode aus Benzol und Schwefel synthetisierten Poly(phenylensulfid)s wurden untersucht. Die Geichstromdunkelleitfähigkeit dieses Polymeren im nativen Zustand ist 10-10 S/m. Sie nimmt während des Dotierens mit Jod um 8 Größenordnungen zu. Es wurde für undotierte Proben n-Typ- und für die mit Jod dotierten Proben p-Typ-Leitfähigketi beobachtet. Anhand der ESR-Messungen wurden die Zahl der paramagnetischen Zentren und der g-Faktor bestimmt, die entsprechend gleich 0.80 · 1017 Spins/g und 2.0037 für das undotierte Polymere bei Raumtemperatur betragen. Änderungen der Spinkonzentration sowohl für die mit Jod dotierten als auch für die im Temperaturbereich von 513 - 903 K getemperten Proben werden dargestellt. Es wird versucht, die Form der ESR-Linien auf eine quantitative Weise zu diskutieren.
    Notes: Electrical and paramagnetic properties of poly(phenylene sulphide) synthesized by a direct method from benzene and sulphur were investigated. In darkness dc conductivity of the polymer in its pristine state is of the order 10-10 S/m. Upon doping with iodine it increases by 8 orders of magnitude. For undoped samples the n-type conductivity and for those doped with iodine the p-type conductivity was observed. On the basis of ESR experiments the number of spins and g-value were determined, which for undoped polymer at room temperature are equal to 0.80 · 1017 spins/g and 2.0037, respectively. Next, the changes in spin concentration both for the iodine doped samples and these annealed within the temperature range 513 - 903 K were described. An attempt to discuss the ESR lineshape in a quantitative way was also made.
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  • 39
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    Angewandte Makromolekulare Chemie 160 (1988), S. 175-186 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 3-Carboxy-4-hydroxyacetophenon (CHAP) wurde in verschiedenen Mengenverhältnissen mit Formaldehyd unter Verwendung von Alkali als Katalysator polykondensiert. Die erhaltenen Polykondensate (CHAP-F) wurden durch Elementaranalyse, IR-Spektroskopie, Bestimmung des Zahlenmittels der Molmasse (M̄n), Thermogravimetrie und Bestimmung der Grenzviskosität charakterisiert. Es wurden polymere Metallchelate mit Cu2+ -, Fe3+ -, Co2+ -, Ni2+ - und UO2+2 -Ionen hergestellt und charakterisiert. Mit Hilfe der Batch-Austauschmethode wurden Ionenaustauschereigenschaften eines CHAP-F Harzes gegen Fe3+ - Cu2+ - und Ni2+ -Ionen bestimmt.
    Notes: 3-Carboxy-4-hydroxyacetophenone (CHAP) was polycondensed with various proportions of formaldehyde using alcoholic alkali as catalyst. The resin samples, designated as CHAP-F, have been characterized by elemental analyses and IR spectroscopy, by estimation of their number average molecular weights (M̄n), by measurement of intrinsic viscosity, and by TGA. Polymeric metal chelates of one CHAP-F sample with Cu2+, Fe3+, Co2+, Ni2+, and UO22+ ions have been prepared and characterized.Ion-exchanging properties of one CHAP-F resin sample for Fe3+, Cu2+, and Ni2+ metal ions are studied by the application of the batch-equilibration method.
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  • 40
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    Angewandte Makromolekulare Chemie 160 (1988), S. 187-192 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktionsenthalpien für die Addition von Hydroxidanion an substituierte Phenylisocyanate wurden mit MNDO berechnet. Die erhaltenen Werte stimmen sehr gut mit den Reaktionsgeschwindigkeiten der Addition von 2-Ethylhexanol an Phenylisocyanate überein. Dies ermöglicht eine Abschätzung der Reaktionsgeschwindigkeiten für nucleophile Additionen innerhalb vernünftiger Grenzen, ohne daß experimentelle Arbeiten durchgeführt werden müssen.
    Notes: The enthalpies for the addition of hydroxide anion to substituted phenylisocyanates have been calculated with MNDO. The results obtained correlate well with the rates of addition of 2-ethylhexanol to phenylisocyanates. This allows us to estimate the rates for nucleophilic addition within reasonable limits without the need for experiments.
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  • 41
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    Angewandte Makromolekulare Chemie 160 (1988), S. 211-211 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 42
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    Angewandte Makromolekulare Chemie 163 (1988), S. 63-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Copolymerisation von Butylacrylat (BA) mit Vinylbenzylglycidylether (VBGE) wurden neue Acrylkautschuke mit Epoxyseitengruppen hergestellt. Um die Zähigkeit eines gehärteten Epoxidharzes (Bisphenol A/Diglycidylether/p,p′-Diaminodiphenylsulfon) zu erhöhen, wurde dieses mit den erhaltenen Acrylkautschuken modifiziert. Eine Zugabe von 20 Gew.-% eines Copolymeren mit 74% BA und 26% VBGE-Einheiten führte zu einer 30proz. Zunahme der Bruchzähigkeit (KIC) des gehärteten Harzes bei einer minimalen Einbuße an Festigkeit und Steifigkeit. Die modifizierten Harze wiesen eine Zwei-Phasen-Morphologie auf, bei der Kautschukteilchen mit einer mittleren Größe von 2 μm in eine Epoxymatrix eingebettet sind. Das Copolymere ohne Epoxyseitengruppen, das aus BA und Vinylbenzylmethoxyethylether hergestellt wurde, war als Modifier unwirksam, was darauf hindeutet, daß die seitenstándigen Epoxidgruppen zu einer guten Zwischenphasenadhäsion zwischen Kautschukteilchen und Matrix, und damit zu erhöhter Zähigkeit führen. Kautschuke, die 55 oder 86% BA-Einheiten enthielten, waren ebenfalls ungenügende Modifier. Zugabe des ersteren ergab Harze mit einer homogenen Phasenstruktur, während die Zugabe des letzteren zu einer Phasentrennung zwischen Kautschuk und Epoxidharz führte.
    Notes: New acrylic rubbers with a pendant epoxy group were prepared by copolymerization of butyl acrylate (BA) with vinylbenzyl glycidyl ether (VBGE). The modification of an epoxy system (bisphenol-A diglycidyl ether/p,p′-diaminodiphenyl sulfone) with the acrylic rubbers was carried out in order to increase the toughness of the cured epoxy resin. The addition of 20 wt.-% of the copolymer containing 74% of BA and 26% of VBGE units resulted in a 30% increase in the fracture toughness (KIC) of the cured resin at minimal expenses of strength and modulus of the resin. The modified epoxy resin had two-phase morphology in which the rubber particles with average diameter of 2 μm are dispersed in the epoxy matrix. The copolymer without the pendant epoxy group, prepared from BA and vinylbenzyl methoxyethyl ether, was ineffective as a modifier, indicating that the reaction of the pendant epoxide with the epoxy matrix resulted in good interfacial adhesion between the rubber particles and the matrix, and in the increased toughness. The epoxide-containing copolymers with 55 or 86% of BA units were also insufficient modifiers. The addition of the former yielded cured resins with homogeneous structure, whereas that of the latter resulted in macroscopic phase separation between the rubber and the epoxy resin.
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  • 43
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    Angewandte Makromolekulare Chemie 163 (1988), S. 77-91 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Lösungen von Polyether/Polyurethan-Kationomeren, die auf Toluoldiisocyanaten basieren, wurden hergestellt und durch Zugabe von Wasser emulgiert. Die Eigenschaften von aus diesen Lösungen und Emulsionen gegossenen Filmen werden mit Hilfe der Infrarot-Spektroskopie, dynamisch-mechanischer Messungen, der Differentialkalorimetrie, der Weitwinkel-Röntgendiffraktometrie und von Zug-Dehnungsmessungen untersucht. Der Einbau eines asymmetrischen, kettenverlängernden Bausteins, wie N-Methyldiethanolamin, führt zu einem Polyurethan (PU), das, ßhnlich wie das mit symmetrischem, kettenverlängerndem 1,4-Butandiol aufgebaute Polyurethan, eine meßbare Ordnung innerhalb der Hartsegmente aufweist. Nach der Quarternisierung mit Glykolsaure haben die PU-Kationomeren erhöhte Werte für Reißdehnung, Zugmodul und -festigkeit. Dies kann auf die Coulomb-Wechselwirkung zwischen benachbarten Hartsegmenten zurückgefiihrt werden. Das Emulgieren der PU-Ionomer-Lösung führt zu einer verstärkten Mischung der Weich-und Hartsegmente, wodurch die ursprünglichen Hartsegmentbereiche mit asymmetrischen 2,4-Urethanisomeren eine höhere Konzentration an 2,6-Isomeren enthalten. Die Hartsegmentbereiche erreichen dadurch höhere Ordnung. Diese erhähte Ordnung und Phasenmischung führt zu einer Verbesserung der mechanischen Eigenschaften. Die Veränderung der Leitfähigkeit und Viskosität wahrend dem Emulgieren zeigt, daß das Wasser zuerst auf der Oberfäche des Mikroionengitters der Hartsegmente adsorbiert wird und dann in die ungeordneten und geordneten Hartsegmentbereiche eindringt.
    Notes: Toluene diisocyanate based polyether polyurethane cationomer solutions are prepared and then emulsified by adding water. Properties of films cast from the solutions and emulsions are studied using infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, wide-angle X-ray diffraction, and tensileelongation testing. It is found that the use of the asymmetric chain extender, N-methyl-diethanolamine, also leads to a polyurethane (PU) with detectable order in the hard domains as in the PU with symmetric chain extender such as 1,4-butandiol. After quaternization with glycolic acid, the PU cationomers have increased elongation and tensile strength and modulus. These can be attributed to the proper Coulomb interaction between two neighboring hard segments. The emulsification of the PU ionomer solution results in an increased mixing between the soft segments and the hard segments with asymmetric 2,4-urethane isomers originally located in the hard domains, and therefore make the hard domains containing a higher concentration of symmetric 2,6-isomer. The hard domains then become more ordered. Such increased order and phase mixing leads to an increase of the three tensile properties. During the emulsification conductivity and viscosity variations show that water is firstly adsorbed on the surface of the hard segment microionic lattices and then enters into the disordered and ordered hard domains successively.
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  • 44
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    Biopolymers 18 (1979), S. 35-45 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric measurements have been carried out on partially hydrated collagen in the frequency ranges 100 kHz-5 MHz, 100 MHz-1 GHz, and 8-23 GHz. In the low-frequency range, a dispersion was observed around 100 kHz which results from inhomogeneous conductivity of the samples. A dielectric relaxation was observed aroud 0.3 GHz using time-domain-spectroscopy techniques. This relaxation can be considered to originate from mobile side chains. Microwave measurements indicate that the water relaxation may extend into the 10-GHz region. An apparent discrepancy between the main water relaxation time and the average rotational correlation time of water as measured by nmr line widths was resolved by the assumption that a fraction of the water molecules is bound to the collagen with residence times on the order of 10-6 sec, whereas the remainder of the water is only weakly bound and exhibits rotational rates on the order of 10-10 sec.
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  • 45
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    Biopolymers 18 (1979), S. 83-100 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model for the time dependence of DNA conformational state probabilities is formulated in the form of first-order differential equations. This model is applied to investigate the renaturation and denaturation rates for T2 and T7 DNA as reported in the series of experiments by Record and Zimm. Qualitative agreement is found in denaturation and for series of renaturation experiments with the same initial condition. However, partial agreement with series of renaturation experiments having the same final condition is obtained only by including an initial bimolecular step with properly matched pairs of strands. Comparison of all experiments with the calculated rates yields 5 × 104 min-1 as the step rate for melting a single base pair.
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  • 46
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conventionally protected oligopeptides of the two homologous series Boc-(L-Ile)n-OMe and Boc-(D-aIle)n-OMe (n = 2-6) were synthesized in a standard stepwise fashion and their uv and CD spectra in 2,2,2-trifluoroethanol, and solid-state ir spectra were investigated. In addition, two oligomeric products derived from the NCAs of L-isoleucine and of D-allo-isoleucine and having a DP of 20 and 12, respectively, were studied in the solid state by x-ray and ir. No substantial differences between the properties of the diastereomeric oligomers in the solid state were noticed, a β-structure being very likely at least for the Boc-protected hexapeptides and the higher oligomers. In contrast, differences were observed between the spectroscopic properties of the diastereomeric oligopeptides, and especially of the hexapeptides, in trifluoroethanol solution. The different properties of the hexapeptides in solution were related to the existence, in the case of Boc-(L-Ile)6-OMe, of soluble molecular aggregates in which the peptide chains assume the β-conformation. These results provide an additional example of the influence of the configuration of asymmetric carbon atoms of the side chains on the conformational properties of peptide molecules in solution.
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  • 47
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    Biopolymers 18 (1979), S. 285-297 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1H-nmr chemical shifts and the spin-spin coupling constants of the common amino acid residues were measured in solutions of the linear tetrapeptides H-Gly-Gly-X-L-Ala-OH in D2O and H2O, the influence of X on the nmr parameters of the neighboring residues Gly 2 and Ala 4 was investigated. The titration parameters for the side chains of Asp, Glu, Lys, Tyr, and His were determined. The pKa values obtained in D2O, with the use of pH-meter readings with a combination glass electrode uncorrected for istope effects, were 0.06 pH units higher in the acidic range and 0.10 pH units higher in the basic range than the corresponding pKa values in H2O. This suggests that the present data are suitable “random-coil” 1H-nmr parameters for conformational studies of polypeptide chains in D2O and H2O solutions.
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  • 48
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    Biopolymers 18 (1979), S. 299-311 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper shows that backbone amide proton titration shifts in polypeptide chains are a very sensitive manifestation of intramolecular hydrogen bonding between carboxylate groups and backbone amide protons. The population of specific hydrogen-bonded structures in the ensemble of species that constitutes the conformation of a flexible nonglobular linear peptide can be determined from the extent of the titration shifts. As an illustration, an investigation of the molecular conformation of the linear peptide H-Gly-Gly-L-Glu-L-Ala-OH is described. The proposed use of amide proton titration shifts for investigating polypeptide conformation is based on 360-MHz 1H-nmr studies of selected linear oligopeptides in H2O solutions. It was found that only a very limited number of amide protons in a polypeptide chain show sizable intrinsic intration shifts arising from through-bond interactions with ionizable groups. These are the amide proton of the C-terminal amino acid residue, the amide protons of Asp and the residues following Asp, and possibly the amide proton of the residue next to the N-terminus. Since the intrinsic titration shifts are upfield, the downfield titration shifts arising from conformation-dependent through-space interactions, in particular hydrogen bonding between the amide protons and carboxylate groups, can readily be identified.
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  • 49
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    Biopolymers 18 (1979), S. 359-372 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a method that can reduce conformational energy calculations for an arbitrary peptide consisting of n residues (n-peptide) to the complexity of a computation for (Gly)n. This reduction, and the concomitant savings in computer time, is accomplished by replacing all side chains, as well as the backbone CαHα and CαH2α groups, by “interaction centers.” The backbone CONH group is left intact in order to preserve its directional character. The interaction centers “see” each other, and the atoms of the CONH group via Boltzmann and space-averaged effective center-center and center-atom potentials, respectively. This averaged-interaction method is tested on the repeat tetra-, penta-, and hexapeptides of elastin, Val-Pro-Gly-Gly (VPGG), Val-Pro-Gly-Val-Gly (VPGVP), and Ala-Pro-Gly-Val-Gly-Val (APGVGV), using the stereoalphabet strategy for the energy calculations. The excellent qualitative and quantitative agreement we obtain with both full atom-atom calculations and extensive nmr data, coupled with the order-of-magnitude reduction in computer time, augurs well for the potential usefulness of the method.
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  • 50
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    Biopolymers 18 (1979), S. 393-409 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear response theory in the decorrelation or random-phase approximation is used to calculate the absorption and CD spectra of model helical polymers, including single-stranded polyadenylic acid. The method, which makes use of infinite polymer selection rules for the linear response tensor, has the advantages that (1) only a few three-dimensional matrices need be inverted; (2) spectral band shapes of the polymer arise naturally from those of the monomer, as well as from the geometry-dependent interactions in the helix; and (3) the spectral dependence on geometrical factors of the helix is made transparent. It is found that the structure of the polymer CD spectrum depends critically on monomer bandshape. An asymmetric CD spectrum, similar to some experimental spectra, arises from either a Gaussian or a composite monomer band. Single-stranded polyadenylic acid spectra are sensitive to helix geometry in the region 200-240 nm, in reasonable agreement with experimental spectra. This sensitivity arises from the 207-nm monomer transition, and the results suggest that this region of the spectrum should be more fully exploited as a tool for helix geometry studies.
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  • 51
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C24H34N2O9, orthorhombic, P212121; a = 39.432 (10), b = 14.061 (5), c = 4.850 (2) Å, M = 494 a.m.u., Z = 4, Dm = 1.22 g cm-3, Dx = 1.22 g cm-3, R = 0.13 for 1205 observed reflections after refinement with isotropic thermal factors. The urethane and amide bonds are in the trans configuration, as well as all the ester groups. The ϕ and ψ angles of the L-glutamyl residues fall in the β-structure region of the Ramachandran's plot; the molecule is rather flat with the amide plane almost parallel to the c axis along which two hydrogen bonds hold the molecules together to form long rows in a “parallel pleated-sheet” fashion.
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  • 52
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The far-ir absorption spectrum of lysozyme was measured at room and liquid-nitrogen temperatures. Dried layers of single crystals of tetragonal lysozyme chloride with a diameter of 100-300 μm were grown on a silicon plate. Such single-crystalline samples were considered to have the following advantages in obtaining far-ir spectra: (1) surface scattering is reduced, (2) the protein molecules are closely packed, and (3) air-drying of the crystals reduces the number of water molecules without considerably changing the original configuration. The spectrum obtained consisted of a strong background absorption and a number of absorption peaks that were not clearly observed with the sample in the form of lyophilized powder. The peaks were ascribed to various delocalized vibrations of the main and side chains in the molecule. The peaks were also compared with the positions of Raman lines. The uniform background was assigned to the water molecules remaining in the crystals.
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  • 53
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    Biopolymers 18 (1979), S. 553-569 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The duplex-to-strand transition of the self-complementary sequence dG-dC-dG-dC has been probed at the exchangeable and nonexchangeable protons and backbone phosphates by high-resolution nmr spectroscopy. The Watson-Crick imino and amino hydrogen-bonded protons, as well as the exposed amino protons, could be followed through the duplex-to-strand transition and provide information on base-pair stability at the tetranucleotide duplex level. The magnitudes of the experimental upfield nonexchangeable base-proton chemical shifts on duplex formation are consistent with calculations based on base-pair overlap geometries of the B-DNA type. The variation of the 31P chemical shifts in dG-dC-dG-dC with temperature appear to monitor changes in the ω,ω′ rotation angles about the O—P bonds in the postmelting transition temperature region. The complex formed between the antitumor anthracycline antibiotic daunomycin and the dG-dC-dG-dC duplex was probed at the nucleic acid and the antibiotic resonances as a function of temperature. The experimental complexation shifts of the observable daunomycin resonances have put constraints on possible overlap geometries between the intercalating anthracycline ring and adjacent base pairs.
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  • 54
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Conformational analyses of cyclic tetrapeptides consisting of alternating cis and trans peptide units have been made using contact criteria and energy calculations. This study has been restricted to those structures having a symmetry element in the backbone ring, such as a twofold axis (d) or a center of inversion (i). There are five main results. (1) There are two distinct types of conformations, which are stereochemically favorable corresponding to each of twofold and inversion-symmetrical structures, designated as d1, d2 (for twofold symmetrical) and i1, i2 (for inversion-symmetrical). Among these, the i1 type has the lowest energy when glycyl residues occur at all four α-carbon atoms. (2) With the glycyl residue at all four α-carbon atoms, methyl substitution at the cis peptide nitrogen atoms is possible in all the four types, whereas the substitution at trans peptide nitrogen atoms is possible only for the i1 type. Thus only in the i1 type can all the nitrogen atoms be methylated simultaneously. The conformation of the molecule in the crystal structure of cyclotetrasarcosyl belongs to the i1 type. (3) When alanyl residues occur at all four α-carbon atoms, the possible symmetrical type is dependent on the enantiomorphic form and the actual sequence of the alanyl residues. (4) The methyl substitution at peptide nitrogen atoms for cyclic tetrapeptides having alanyl residues causes more stereochemical restriction in the allowed conformations than with glycyl residues. (5) The prolyl residue can be incorporated favorably at the cis-trans junction of both d and i types of structures. The results of the present study are compared with the data on cyclic tetrapeptides available from the crystal structure and nmr studies. The results show an overall agreement both regarding the type of symmetry and the conformational parameters.
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  • 55
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    Topics: Chemistry and Pharmacology
    Notes: Based on equilibrium binding studies, as well as on kinetic investigations, two types of interactions of Cu2+ ions with native DNA at low ionic strength could be characterized, namely, a nondenaturing and a denaturing complex formation. During a fast nondenaturing complex formation at low relative ligand concentrations and at low temperatures, different binding sites at the DNA bases become occupied by the metal ions. This type of interaction includes chelate formation of Cu2+ ions with atoms N(7) of purine bases and the oxygens of the corresponding phosphate groups, chelation between atoms N(7) and O of C(6) of the guanine bases, as well as the formation of specific intestrand crosslink complexes at adjacent G°C pairs of the sequence dGpC. CD spectra of the resulting nondenatured complex (DNA-Cu2+)nat may be interpreted in terms of a conformational change of DNA from the B-form to a C-like form on ligand binding. A slow cooperative denaturing complex formation occurs at increased copper concentrations and/or at increased temperatures. The uv absorption and CD spectra of the resulting complex, (DNA-Cu2+)denat, indicate DNA denaturation during this type of interaction. Such a conclusion is confirmed by microcalorimetric measurements, which show that the reaction consumes nearly the same amount of heat as acid denaturation of DNA.From these and the kinetic results, the following mechanism for the denaturing action of the ligands is suggested: binding of Cu2+ ions to atoms N(3) of the cytosine bases takes place when the cytosines come to the outside of the double helix as a result of statistical fluctuations. After the completion of the binding process, the bases cannot return to their initial positions, and thus local denaturation at the G·C pairs is brought about. The probability of the necessary fluctuations occurring is increased by chelation of Cu2+ ions between atoms N(7) and O of C(6) of the guanine bases during nondenaturing complex formation, which loosens one of the hydrogen bonds within the G·C pairs, as well as by raising the temperature. The implications of the new binding model, which comprises both the sequence-specific interstand crosslinks and the described mechanism of denaturing complex formation, are discussed and some predictions are made. The model is also used to explain the different renaturation properties of the denatured complexes of Cu2+, Cd2+, and Zn2+ ions with DNA.In temperature-jump experiments with the nondenatured complex (DNA-Cu2+)nat, a specific kinetic effect is observed, namely, the appearance of a lag in the response to the perturbation. The resulting sigmoidal shape of the kinetic curves is considered to be a consequence of the necessity of disrupting a certain number of the crosslinks existing in the nondenatured complex before the local unwinding of the binding regions (a main step of denaturing complex formation) may proceed.
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    Biopolymers 18 (1979), S. 931-938 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new analysis has been made on studies of the influence of imino acid content on the changes of collagen thermal stability (tm). It is shown that, for the interstitial vertebrate collagens, there is a strict regularity in the changes of tm depending on hydroxyproline content. No correlation is observed between tm and proline content. Also, no correlation between tm and hydroxyproline content is observed for invertebrate and basement membrane collagens. On the basis of the reported data, the dependence of tm on hydroxyproline content is considered to be not a correlation between tm and the total content of hydroxyproline, but only as the correlation between tm and the content of hydroxyproline occurring at the third position in the sequence (Gly-R2-R3)n. The results agree with the idea that the influence exerted by proline and hydroxyproline on the stabilization of the triple helix of collagen is different.
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  • 57
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    Topics: Chemistry and Pharmacology
    Notes: The conformation and conformational transitions of poly(His-Ala-Glu) have been investigated by ir, nmr, and CD measurements. The results obtained - as well as the results of our previous investigations by potentiometric titration and hydrodynamic techniques [Goren et al., Biopolymers (1977) 16, 1541-1555] - indicate that when dissolved in water, the co-polymer assumes a disordered conformation. On changing the pH of the solution, the states of ionization of the side-chain imidazole and carboxyl groups change in the same manner as in low-molecular-weight model compounds. Concomitantly, the overall shape of the macromolecule is altered, while the conformation of the polypeptide backbone changes from one disordered state to another but never assumes a regular form. In water/methanol and water/trifluoroethanol mixtures, transitions from a disordered state to the α-helix conformation were observed on increasing the alcohol content of the system. The conformational transitions followed pathways which differ from one another according to the experimental conditions employed. Conformational landmarks (intermediates) have been identified along these pathways.
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    Biopolymers 18 (1979), S. 1023-1026 
    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 18 (1979), S. 1821-1828 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decrease in the limiting viscosity number [η] with temperature T for hyaluronic acid in nonalkaline solution and chondroitin 4-sulfate in neutral and alkaline solutions may be expressed in terms of the temperature coefficient of the Kratky-Porod persistence length a: d ln a/dT = -0.0040 (±0.0005). The result, while numerically somewhat smaller, resembles qualitatively that of cellulose derivatives. As in the latter case, standard conformational calculations underestimate the coefficient, which may be due to neglect of random occurrence of local conformational features of higher energy. In alkaline solution, large decreases in [η] of hyaluronic acid are accompanied by a positive temperature coefficient of [η]. This temperature effect is interpreted as an endothermal shift from the alkaline, low [η] form of the polymer to the neutral, high [η] form with increasing temperature.
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    Biopolymers 18 (1979), S. 1809-1820 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have considered whether or not the tertiary structure of a biomolecule is the same in a crystal (or an oriented film) as it is in solution. A methodology has been developed for comparing polarized absorption spectra obtained from a solid-state sample with those obtained from an oriented solute to further resolve this question. An electric dichroism instrument built in our laboratory was used to measure the solution dichroism signal which, along with the ordinary solution uv absorption spectra, yields polarized absorption spectra in the directions parallel and perpendicular to the applied electric field. These were then compared to polarized absorption data from oriented films of nucleic acids to determine whether the two sets of data could be rotated into coincidence. This rotation was accomplished using a computer program based on a nonlinear programming method. Four nucleic acids were studied and the film and solution data for three of these were found to be equivalent, requiring rotation through an angle of 3°-20°, depending on film humidity, to bring them into coincidence. For the fourth sample we were unable, perhaps because of signal-to-noise ratio limitations, to find a correlation. Flow dichroism and electric dichroism data were also found to be quite similar. Thus it is clear that the induced dipole moment is along the helical axis and that the physical, hydrodynamical, and electrical axes of the nucleic acid molecules are equivalent.
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  • 61
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    Topics: Chemistry and Pharmacology
    Notes: The effect of enzyme-inhibitor complex formation on the hydration properties of the macromolecular moiety was investigated on the model system of α-chymotrypsin and its Ser-195 tosyl derivative. The primary (A-shell) hydration of the native and modified enzyme was compared by sorption measurements. The secondary (B-shell) hydration water was investigated by differential scanning calorimetry. Tosylation is known to induce pronounced conformational changes in the chymotrypsin molecule. These structural modifications have the following effects on the hydration of the native enzyme.The water binding capacity of the protein surface is significantly increased, as shown by both the calorimetric and the sorption results. The amount of unfreezable water of primary hydration is increased by 50 mol H2O/mol chymotrypsin.The heats (ΔH) and entropies (ΔS) of the interaction of water with chymotrypsin are strongly reduced in the modified enzyme. This effect is interpretable by a reduction of the H bonding potential of the protein surface. Parallel to this decrease in δH, the heats of fusion of the secondary hydration water (Qfus) are significantly increased by tosylation (Qfus = 256.2 ± 7.8 and 294.2 ± 4.8 J g-1 H2O for the native and the tosylated enzyme, respectively). This increase in Qfus reflects an increase in the extent of H bonding in the B-shell hydration sphere.These changes in the hydration of the native enzyme, associated with the reaction: native chymotrypsin → tosylchymotrypsin, are interpreted by cooperative phase transitions of water molecules in the primary and secondary hydration water. One of these transitions was found to exhibit a significant, linear enthalpy-entropy compensation effect. The compensation temperature \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} is 290.7 ± 2.8°K. This \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} value agrees well with compensation temperatures reported in the literature for a series of biochemical reactions in aqueous solution (250-320° K). This agreement in \documentclass{article}\pagestyle{empty}\begin{document}$ \hat{\beta} $\end{document} may point to a common source of both compensation phenomena.
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    Biopolymers 18 (1979), S. 1829-1830 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 18 (1979), S. 1831-1833 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 18 (1979) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 18 (1979), S. 1835-1848 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformations of melanostatin have been studied experimentally using CD spectroscopy and via calculations. In aqueous solution and 2,2,2-trifluoroethanol (TFE) there is no evidence that monomers of the tripeptide exist in an ordered (β-bend) structure. In water and TFE solutions (3-6 × 10-4M) the neutral molecules aggregate very slowly, taking about 3 days to attain equilibrium at room temperature. At equivalent concentrations in TFE, although not in water, the cationic molecules also slowly aggregate, although to a lesser extent. Calculations using rotational isomeric state theory give the most probable unperturbed end-to-end distance of the molecule at 9.3 ± 0.1 Å and indicate that a vast majority of the molecules exist in some extended conformation, end-to-end distance ≥6 Å. Only 0.4% of the molecules are calculated to have O…H separations compatible with a β-bend structure. An intramolecular hydrogen bond must have an energy at least 2 kcal/mol lower than that of an intermolecular hydrogen bond to solvent if a β-bend is to be experimentally observable.
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  • 66
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    Topics: Chemistry and Pharmacology
    Notes: Nps-[Glu(OBzl)]6-NHEt has been prepared by coupling Nps-[Glu(OBzl)]2-OH with HCl,H-[Glu(OBzl)]4-NHEt by means of dicyclohexylcarbodiimide. The ir spectra of its nujol mull show that the hexapeptide has the β-structure of antiparallel chains. When it is dissolved in dioxane or ethylene dichloride, the hexapeptide consists of a mixture of the β-form and the solvated σ-form, but the β-form can exist only above a certain critical concentration. The critical concentration is about 0.4g dl-1 in dioxane and 0.08g dl-1 in ethylene dichloride, and the content of β-form increases with increasing concentration above it. The CD of the dioxane and ethylene dichloride solutions shows concentration dependence in visible and uv regions.
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    Biopolymers 18 (1979), S. 2115-2126 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light scattering from the solutions of Nps-[Glu(OBzl)]6-NHEt in dioxane or ethylene dichloride has been measured at different concentrations, and a critical concentration of intermolecular association is found to exist, which is equal to the critical concentration of β-form formation. The Debye plot of light scattering leads to the molecular weight of aggregates at the critical concentration, which corresponds to an aggregation number 15 in dioxane and 53 in ethylene dichloride. In the latter solvent the aggregates further associate into a larger aggregate consisting of 330 molecules when the concentration is increased beyond the critical concentration. The content of β-form, which is a measure of number of hydrogen bonds, is derived from the ir data previously obtained. The results on the modes of intermolecular association and hydrogen bonding lead to possible structures of aggregates formed by both hydrogen bonds and other nonbonding side-chain interactions.
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  • 68
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    Topics: Chemistry and Pharmacology
    Notes: Low shear viscosities have been determined for a 1 mg/ml poly(L-lysine) solution as a function of added salt concentration in the region of the previously reported ordinary-extraordinary phase transition. The measured viscosities indicate that the polyions are far from completely extended at the transition. Estimates of the longest internal relaxation time for an equivalent free-draining Rouse-Zimm chain give τ ≃ 10-5 sec, similar to that of the rapid, angle-independent component previously observed in the dynamic light-scattering correlation function at the transition. An unusual peak and valley are observed in the curve of [η]0 versus [NaBr] in the transition region. Possible interpretations of these features, and their bearing on the nature of the extraordinary phase, are discussed.
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  • 69
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    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of the valinomycin analog, cyclo-[(-D-Val-Hyi-Val-D-Hyi-)3-] (meso-valinomycin, C60H102N6O18) has been determined by direct x-ray diffraction procedures. The crystals are triclinic, space group P1, number of molecules per unit cell Z = 1, and cell parameters a = 11.831, b = 13.815, c = 14.889 Å, α = 109.54°, β = 116.10°, γ = 98.89°. The atomic coordinates for the C,N,O atoms were refined in the anisotropic thermal motion approximation and for the H atoms in the isotropic approximation to R = 0.07.The structure is centrosymmetric and has a threefold axis of pseudosymmetry. The depsipeptide chain is in the form of a bracelet stabilized by six identical intramolecular 4 → 1 hydrogen bonds between the amide C=O and NH groups. The ester carbonyls are oriented towards the symmetry axis, their O atoms forming an ellipsoidal molecular cavity. The isopropyl side chains are located on the molecular periphery. The structure found differs considerably from the conformation of the crystalline naturally occurring antibiotic, valinomycin, but completely resembles that of valinomycin and meso-valinomycin in nonpolar solvents. In the crystal, meso-valinomycin molecules form stacks. The molecular cavities situated in the stacks one above the other along the pseudo-C3 axis form a continuous channel, the internal surface of which is lined by O atoms. The possible conformations of depsipeptides of the valinomycin series and their mode of action in membranes are discussed in the light of the data obtained.
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    Biopolymers 18 (1979), S. 2353-2356 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Large molecular weight bacteriophage G DNA, about five times larger than T2 DNA, was used to test Zimm's theory [(1974) Biophys. Chem. 1, 279-291] for the effect of rotor speed on the sedimentation of large linear monodisperse DNA. Sedimentation profiles from neutral sucrose gradinets at low and high rotor speeds show G DNA sedimenting from 1.8 to 0.7 times as fast as T2 DNA. Experimental measurements indicate that the sedimentation coefficient of G DNA decreases with increasing rotor speed about as fast as predicted by theory.
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  • 71
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined the NH stretching frequencies of N-acetyl-N′-methyl-L-alanineamide (blocked Ala), N-acetyl-N′-methylglycineamide (block Gly), and N-acetyl-N′-methyl-L-leucineamide (blocked Leu) in chloroform using irspectroscopy. Their spectrum of blocked Leu in carbon tetrachloride was also obtained. A major absorption band at 3450 cm-1 is attributed to the unperturbed NH stretching frequency. Another major band at 3437 cm-1 (for Ala) or 3432 cm-1 (for Leu) is attributed to conformations in which the NH stretching frequency is perturbed by the spatial proximity of the Cβ atom. An absorption band between 3300 and 3370 cm-1, which has in the past been assigned to the intramolecular hydrogen-bonded NH in the C7eq conformation, was found to be concentration dependent and could not be observed below 5 × 10-4M in chloroform; thus we find no evidence for a strongly hydrogen-bonded NH in the C7eq conformation in chloroform. An absorption band at 3416 cm-1 was observed in chloroform solutions of blocked Gly, and a similar absorption appeared as a shoulder on the 3437- and 3432-cm-1 bands of blocked Ala and blocked Leu, respectively, in the same solvent. These bands, occurring near 3416 cm-1, may be assigned to extended (C5) conformations [Avignon et al., Biopolymers 8, 69 (1969)]. In CCl4 the spectrum of blocked Leu remained concentration dependent below 2.8 × 10-4M, with the 3300-3370-cm-1 band progressively weakening and shifting to higher frequencies on dilution from higher concentrations. Analysis of the spectra indicates that there is considerable flexibility in the blocked single residues, in agreement with the results of conformational energy calculations.
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    Biopolymers 18 (1979), S. 2523-2535 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Type I collagen fibrillogenesis in vitro has been studied by laser light scattering, and the results indicate that initiation of aggregation involves at least two steps. Step I of aggregation involves no change in the intensity of scattered light at an angle of 90° and is accompanied by a decrease in the diffusion coefficient. Step II is characterized by an increased intensity of scattered light and decreased diffusion coefficients. Theoretical calculations using the Stokes-Einstein equation for the translational diffusion coefficient and the Perrin equation for the frictional coefficient of a prolate ellipsoid indicate that the step I aggregates are 4D staggered linear dimers and trimers 570 and 845 nm long, whereas step II aggregates are greater than 950 nm in length. These dimensions are similar to those previously reported based on physicochemical measurements and electron microscopy. It is proposed that the rate and extent of fibrillogenesis in vitro is controlled by the concentration of the linear aggregates and that the effects of temperature and collagen concentration on fibrillogenesis previously observed are qualitatively explained in terms of their effects on the concentration of these aggregates.
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    Biopolymers 18 (1979), S. 2537-2547 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method hitherto used for estimating the electrostatic term in empirical intramolecular calculations of stable conformations of biologically important molecules and macromolecules and intermolecular calculations of molecular associations or packing energy in molecular crystals had been analyzed. It has been shown that the contribution of atomic hybridization moments is omitted in the calculation of electrostatic interactions from net atomic charges localized on nuclei which have been determined by standard quantum-chemical methods. This contribution plays an important part in determining electrostatic interactions, mainly in molecules containing atoms with lone pairs. Simultaneously, a modified method for calculating the electrostatic term comprising the interaction of the lone pairs, which are represented by atomic hybridization moments, has been proposed. The relationship between the atomic hybridization moment and the bond angle has been expressed for some typical configurations occurring in biologically important molecules. Finally, this new approach is illustrated by results of the conformational analysis of some model compounds for biomolecules and compared with the approach used so far for the estimation of the electrostatic interaction in empirical methods of calculation of the intra- and intermolecular energy.
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    Biopolymers 18 (1979), S. 2549-2567 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intensity fluctuations of laser light scattered from filamentous viruses Pf1 [length L (Å) × diameter d (Å) = 20,000 × 90], M13 (9000 × 90), potato virus X (5150 × 130), and tobacco mosaic virus (3000 × 180) in sucrose density gradients were measured with a photon correlation spectrometer over a range of scattering angles from 15° to 120°. The experimental data can be approximated by two exponential decays, “slow” and “fast.” The slow decay rate constant ts-1 corresponds to the translational diffusion D of the virus, i.e., ts-1 = K2D, where K is the magnitude of the scattering vector. The amplitude of the slow component, i.e., translational diffusion, remains greater than that of the fast component, even at high KL. The fast decay rate constant tf-1 is also proportional to K2 for viruses such as Pf1, M13, and even potato virus X. In the companion paper, we shall attribute the amplitude enhancement of the translational diffusion to the coupling of its anisotropy to the rotational diffusion modes. In order to explain the excessive decay rates in the fast component, we need to consider the bending mode of rodlike viruses, especially in the longer viruses such as M13 and Pf1, in addition to the usually expected rotational diffusion modes.
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    Biopolymers 18 (1979), S. 2569-2588 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have compared four theoretical effects of rodlike macromolecules with the fast components, i.e., components other than translational diffusion, of our experimental data, which are presented as amplitude autocorrelation functions of electric field scattered from dilute solutions of monodisperse rodlike viruses with lengths from 3300 Å for tobacco mosaic virus to 20,000 Å for Pf1. The four effects are (1) the optic anisotropy treated by Aragón and Pecora, (2) coupled translational-rotational diffusion due to anisotropy in translational mobility recently reformulated by Gierke, (3) anisotropic rotational diffusion with respect to the direction of translational displacement first discussed by Berne and Pecora, and (4) the bending mode of a rod by Fujime and Maruyama. We show that both the first and second effects are required to explain the enhancement of amplitude of the translational diffusion at the expense of fast components. The experimental decay rates of the fast component exceed that of the rotational diffusions. In order to explain the excessive decay rate in the fast component, we need to include a minute amount (∼1%) of bending mode of rodlike viruses, especially in longer viruses such as M13 and Pf1.
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  • 76
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    Biopolymers 18 (1979), S. 2607-2623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The previous report that poly(L-glutamic acid) exhibits doubled resonances in the helix-coil transition region by either proton or carbon-13 nmr resolves the question of whether or not this behavior is limited to uncharged polypeptides in organic solvents, as had been previously thought. In the present work, we show that the underlying principle causing this anomalous double-peak behavior is due to molecular-weight polydispersity of the sample. The molecular-weight range in which this phenomenon is observed is largely dependent on the values of σ, the nucleation or cooperativity factor. The principles developed are shown to encompass all classes of polypeptides in a very natural way and to explain the key experimental data in the literature.
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  • 77
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    Biopolymers 18 (1979), S. 2589-2606 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Empirical conformational energy calculations with the use of ECEPP energy functions have been carried out for linear dipeptides H-X-L-Pro-OH, with X = Gly, L-Ala, D-Ala, L-Leu, D-Leu, L-Phe, and D-Phe, in different states of protonation of the end groups. The results of these calculations are compared with the previously reported experimental equilibrium populations for the cis and trans isomers of the X-Pro bond in the different species. For all the protonation states of the seven dipeptides, the calculated nonbonded interactions and the conformational entropy term lead to a preference of the trans forms over the cis isomers by at least 1 kcal/mol. The electrostatic interactions stabilize the cis conformations in all species except the cationic forms of the D,L-peptides, and it could further be shown that only the carbonyl group of X and the two end groups contribute significantly to the total electrostatic energy. One of the principal results of the experimental studies, i.e., the occurrence of 5-15% cis-proline in all the peptides with an uncharged C-terminus, was corroborated by our investigation of the cationic species. A detailed assessment of the electrostatic contribution to the total energy of the different conformations of H-Gly-L-Pro-OH indicates that the standard ECEPP parameters tend to overestimate the electrostatic interactions in aqueous solutions of the X-Pro dipeptides.
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  • 78
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    Biopolymers 18 (1979) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 79
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    Biopolymers 18 (1979), S. 2625-2643 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The secondary structure of the lac repressor protein proposed by Chou et al. has been modified to include the recent revisions in sequence. In addition to the Chou and Fasman method, five other methods were used; they include those of (1) Lim, (2) Ptitsyn and Finkelstein, (3) Burgess et al., (4) Bunting et al., and (5) Wu and Kabat. Any two individual methods gave results differing sharply from one another. Three or more methods were in agreement for 91, 39, and 126 residues in helix, in β, and in combined coil plus turn conformations, respectively; there were such agreements for a total of 256 of the 360 residues. Agreements in the amino-terminal third of the molecule were found for 68% of the residues, whereas in the remainder of the molecule only 53% of the residues showed such agreements. Only two helix-breaking and two β-breaking tripeptides were inconsistent with the composite predictions by three or more methods. The large number of disagreements among the results for different methods indicates that only very limited information is provided by each method and that the basis on which they operate is not clear. There is no a priori reason for a composite prediction to be more reliable than any individual prediction, and such a procedure does not permit the determination of an unambiguous secondary structure. Since these methods were applied to lac repressor before any three-dimensional crystallographic structure was known, the methods may ultimately be evaluated should such a structure become available.
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  • 80
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    Biopolymers 18 (1979), S. 2645-2657 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational changes and binding behavior of tetranactin on complexation with sodium, potassium, rubidium, cesium, and ammonium ions were investigated by the measurements of proton magnetic resonance, ir, and Raman spectra. It has been clearly shown that alkali cations coordinate to the oxygen atoms of both the carbonyl group and the tetra-hydrofuran ring, but the ammonium ion coordinates only to the oxygen atom of the tetrahydrofuran. Among the alkali cations the potassium ion most strongly coordinates to the tetrahydrofuran oxygen atoms. The complexation with larger cations induces an expansion of the cavity of the macrocyclic ring of tetranactin and smaller cations contract the cavity. The evidence is revealed by the coupling constants of the methylene protons and the frequency separation between the carbonyl stretching vibrations of the ir- and Raman-active modes. The conformations of the cation complexes in the solid are maintained in solution but that of the cation free form is not.
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  • 81
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intercalation-site geometries are generated for a tetramer duplex extracted from B-DNA. Glycosidic angles and puckers of the deoxyribose sugar groups bonded to base pairs BP1 and BP4, namely, those at either end of the tetramer duplex, are assumed to be those of B-DNA to insure continuity. All possible geometrical conformations for combinations of C(2′)-endo, C(3′)-endo, C(2′)-exo, and C(3′)-exo sugar puckers are determined for the tetranucleotide backbone. Those with minimum energy are selected as candidates for intercalation sites. Calculations reveal two pairs of physically meaningful families of intercalation sites which occur in two distinct regions, I and II, of helical angles which orient BP2 relative to BP3 and with the helical axis disjointed between these base pairs. For each site I and II within BP2 and BP3, there are two distinct backbone conformations, A and B, connecting BP3 to BP4 or BP1 to BP2 which do not disrupt backbone conformations connecting BP2 to BP3. Hence two pairs, IA and IB, and IIA and IIB, of intercalation sites exist in which the sugar puckers along the backbone of the tetramer alternate from C(2′)-endo to C(3′)-endo on the backbone (5′p3′) connecting BP2 to BP3. The glycosidic angles of the C(3′)-endo sugar χ3γ are, coincidentally, 80° ± 2° for both conformations γ = A and B connecting BP3 to BP4 along the phosphate backbone (5′p3′). Consistent with the theoretical results, the experimental unwinding angles can be grouped into two categories with absolute values of 18° and 26°. The theoretical unwinding angles for sites IA and IB of 16° and for sites IIA and IIB of 20° occur for a displacement of -0.8 Å in the helical axes of BP2 and BP3 and for a 100% G·C composition, with a decrease depending on the amount of A·T base pairs present. Ratios of theoretical unwinding angles of sites I and II, which range from 0.75 to 0.84 for the two principal sites, compare well with the experimental value of 0.71. The theoretical results, in agreement with experimental observation, provide a new interpretation of the nature and conformation of the possible binding sites. Conformations obtained from these studies of intercalation sites in a tetramer duplex are used to rationalize the well-known neighbor-exclusion principle. The possibility of violation of this principle is demonstrated by the existence of two families of physically meaningful conformations. Conformations of unconstrained dimer duplexes are also obtained, one of which corresponds to the experimental crystal structure of ethidium-dinucleoside complexes, but these cannot be joined to the B-DNA structure. Backbone conformations of the tetramer duplex can be constructed until the base-pair separation reaches 8.25 Å, which may limit the molecules that can intercalate.
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  • 82
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As a continuation of previous papers [Biopolymers (1976) 15, 879; (1978) 17, 1508], the low-frequency dielectric relaxation of DNA solutions was studied with a four-electrode cell and the simultaneous two-frequency measurement. Below a critical concentration, the dielectric relaxation time agrees with the rotational relaxation time estimated from the reduced viscosity and is almost independent of DNA concentration Cp, and the dielectric increment is proportional to Cp. The critical concentration is approximately 0.02% of DNA for molecular weight Mr 2 × 106 and 0.2% for Mr 4.5 × 105 in 1 mM NaCl. Dielectric relaxations are compared for samples before and after deproteinization, and the protein contamination is found to have a minor effect on the dipole moment of DNA. The effect of a mixed solvent of water and ethanol on the dielectric relaxation of DNA is well interpreted in terms of changes in viscosity and the dielectric constant of the solvent, assuming that the relaxation arises from rotation of the molecule with a quasi-permanent dipole due to counterion fluctuation.
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  • 83
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    Biopolymers 18 (1979) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 84
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    Biopolymers 18 (1979), S. 2911-2911 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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  • 85
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energies of α- and β-D-glucopyranoses were computed by varying all the ring bond angles and torsional angles using semiempirical potential functions. Solvent accessibility calculations were also performed to obtain a measure of solvent interaction.The results indicate that the 4C1 (D) chair is the most favored conformation, both by potential energy and solvent accessibility criteria. The 4C1 (D) chair conformation is also found to be somewhat flexible, being able to accommodate variations up to 10° in the ring torsional angles without appreciable change in energy. Observed solid-state conformations of these sugars and their derivatives lie in the minimum-energy region, suggesting that the substituents and crystal field forces play a minor role in influencing the pyranose ring conformation. Theory also predicts the variations in the ring torsional angles, i.e., CCCC 〈 CCCO 〈 CCOC, in agreement with the experimental results. The boat and twist-boat conformations are found to be at least 5 kcal mol-1 higher in energy compared to the 4C1 (D) chair, suggesting that these forms are unlikely to be present in a polysaccharide chain. The 1C4 (D) chair has energy intermediate between that of the 4C1 (D) chair and that of the twist-boat conformation. The calculated energy barrier between 4C1 (D) and 1C4 (D) conformations is high - about 11 kcal mol-1.
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  • 86
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    Biopolymers 18 (1979), S. 3043-3065 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Earlier determinations of density gradient proportionality constants β0, density distributions ρ(r), and the effect of pressure on density gradients in the analytical ultracentrifuge have been of limited precision and usefulness in the study of proteins and polypeptides. Reasons for these difficulties are that numerous intermediate relationships were required in the calculations, and the density ranges studied were generally above 1.2 g/ml. Relations are derived in the present paper to directly compute β0(ρ) values and β0′(ρ) values from the original data without any intermediate expansions or approximations. Data are presented for CsCl, CsBr, and Cs2SO4 and compared with literature values. Density distributions are computed for all three salts under a wide variety of experimental conditions of density, column length, and angular velocity. These values of ρ(r) and re are obtained by a numerical iterative technique. Values obtained by this new method are compared with values obtained using closed-form expressions. The effects of pressure on the composition density gradient for the three salts given above are calculated and found to be significant for Cs2SO4 solutions.
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  • 87
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    Biopolymers 18 (1979), S. 3077-3087 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present evidence for structures of two ordered forms of polyxanthylic acid based on ir spectroscopy, pH titrations, and thermal transitions. Over the pH range ∼6-9.5, the structure is a four-stranded helix with alkali metal ions specifically complexed in the central channel. These internal counterions stabilize the structure by complexing with carbonyl oxygens and by partial screening of electrostatic repulsion caused by ionization of the xanthine residues in this pH range. Below pH 5, the structure is quite different and much more stable. Our data are consistent with a six-stranded helix in which both carbonyl oxygens and both NH protons are hydrogen bonded.
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  • 88
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational energetics of the tetranucleoside triphosphates d(ApApApA), d(GpGpGpG), d(CpCpCpC), d(TpTpTpT), ApApApA, GpGpGpG, CpCpCpC, and UpUpUpU are thoroughly examined using a classical potential energy function. The sugar modeling method and multiple correlation functions derived in previous papers of this series are utilized in these examinations. The data are analyzed and compared in terms of the energy profiles for rotation about the conformation-determining torsion angles in the tetramers. Overall, the predictions are in reasonable qualitative agreement with the existing experimental data. It is found that the base type does not greatly affect the locations of the important minima in these profiles, but rather exerts a large influence on the relative depths of the minima and the barriers to conversion between them. Conformational sequence dependence is manifest to a greater extent by the DNA tetramers than the RNA tetramers. Of the DNA tetramers, d(CpCpCpC) appears, from the results presented herein, to have the greatest potential for polymorphism. This and other findings are analyzed in terms of the preferences of particular DNA sequences for either the A-, B-, or Z-conformation.
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  • 89
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple graphical method for calculating stoichiometric and site binding constants for systems with two initially equivalent interacting sites is derived from a modified Scatchard equation. The binding constants can be calculated from Scatchard plots (r/[A] as a function of r) using the values of r/[A] (r is the molar ratio of bound ligands to total protein and [A] is the equilibrium concentration of free ligand) when r = 0 and r = 1 (half-saturation). The applicability of the method to the adsorption of bilirubin by peptide pendants immobilized on a polyacrylamide support is demonstrated.
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  • 90
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The statistical mechanical theory for the helix-to-random-coil transition in two-chain coiled coils is applied to extant data for two synthetic coiled-coil polypeptides. These peptides have the primary structure K(LEALEGK)n, in which n = 4, 5. This repeating heptet sequence mimics the pattern of hydrophobic, acidic, and basic residues characteristic of the 284-residue tropomyosin molecule, the prototypical coiled-coil protein. Theoretical calculations for single chains show that such model peptides cannot be directly compared to proteins like tropomyosin because of differences in chain length (29 and 36 residues vs 284) and in intrachain interactions, the latter caused by the differences in amino acid composition and seqeunce between protein and model. Application of the theory to extant data on the two synthetic peptides provides a semiquantitative fit and results in an assessment of the interhelix interaction in the model peptides. The value obtained, ∼ 2000 cal · (mol of turn pairs)-1, is four to five times larger than has been obtained for tropomyosin. This probably is a result of greater regularity in the structure of the synthetics and of the exclusive presence of leucine in the hydrophobic interface. The theory employed here insists that this powerful interhelix interaction in the synthetic is the principal reason that such short chains can be so highly helical at moderate and low temperatures. Theory predicts, indeed, that a tropomyosin-length chain with a sequence homologous to these synthetics would be completely thermally stable in the entire temperature range accessible in aqueous solutions. Theory also predicts a much more pronounced effect of concentration on the 29- and 36-residue synthetic polymers than is predicted or observed in the case of tropomyosin, and it also predicts a pronounced stabilizing effect of pH-reduction on the thermal curves. On the last two points, sufficient data are not yet available with which to test the theory.
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  • 91
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    Biopolymers 27 (1988), S. 165-169 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
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    Biopolymers 27 (1988) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 93
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A cyclic peptide analogue of somatostatin, including the o-aminomethylphenylacetic acid spacer, was studied by the combined use of two-dimensional nmr spectroscopy, distance geometry, and restrained molecular dynamics. Analysis of distances determined from nuclear Overhauser effect (NOE) buildup rates revealed that these were inconsistent with a unique backbone conformation near the spacer. Assuming that the conformational heterogeneity is localized to the spacer, the NOE distances measured for the remaining part of the molecule were used to generate a large number of structures with the distance geometry algorithm, which were then refined by restrained energy minimization. Four classes of structures emerged, which together account for all observed NOEs. A representative structure of each class was further refined with the restrained molecular dynamics technique, and shown to be stable on a 20-ps time scale. The flexibility of the spacer was examined by simulating interconversions induced by an appropriate restraining potential. As a result, the explanation for the lack of somatostatin activity of the analogue studied was reconsidered.
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    Biopolymers 27 (1988) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 95
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    Biopolymers 27 (1988), S. 415-421 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A semiempirical theory of saccharide optical activity indicates that the dominant source of NaD rotation is a vacuum-uv CD band near 150 nm, a band observed experimentally in polysaccharide film CD spectra. The model is a modification of polarizability theory in which high-energy electronic excitations are coupled by degenerate perturbation theory, giving rise to “molecular excitons.” The existence of an excitation mode well separated in energy from even higher energy modes arises from the local symmetry of tetrahedral carbon atoms in a puckered ring structure. Calculated NaD rotations correlate well with experimental values.
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  • 96
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    Biopolymers 27 (1988), S. 451-477 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is demonstrated that protein α-helix content can be predicted from an autocorrelation analysis of the protein hydrophobicity sequence. The Fourier transform of the autocorrelation function yields the spectral densities or weights of the various frequencies contributing to the autocorrelation function. Using sequence and secondary structure data from more than 160 proteins and domains, a linear relationship was found between spectral density at periodicity 3.7 and protein α-helix content (r = 0.83). This relation permits prediction of the helix content (x) of proteins of known sequence to within ± 15%, i.e., as (x ± 15)%. Predictions based on the autocorrelation procedure are compared with values obtained by other methods.
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    Biopolymers 27 (1988), S. 479-491 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Evidence for a helical contribution to the conformation of methylcellulose in dilute solution is given by CD measurements. Congo red binds to methylcellulose in dilute aqueous solution and becomes optically active. The shape of the induced CD spectra is as predicted by exciton coupling for a helical arrangement of chromophores. The magnitude of the induced CD changes reversibly with temperature, decreasing upon heating. The dimer analogue of the polymer, prepared by acid methanolysis, does not show this effect. These observations suggest that the induced optical activity reflects the conformational dissymmetry of the polymer. Analogous experiments with the cellulose oligomers (cellotriose through cellohexaose) show that five anhydroglucose units are necessary before asymmetry is induced upon dye binding.
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  • 98
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    Biopolymers 27 (1988), S. 493-507 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polarized Raman spectra have been obtained from single microcrystals of the duplex of the decamer d(A5T5)2 using a Raman microscope. This is the first report of Raman spectra from a crystal of a deoxyoligomer that contains only long, nonalternating sequences of adenine and thymine. Sequences containing d(A)n and d(T)n are of interest in view of recent suggestions that they induce bends in DNA and that they might exist in a nonstandard B-conformation. Polarized Raman spectra of a crystal of d(pTpT) have also been obtained. Both crystals display Raman bands whose intensities are very sensitive to the orientation of the crystal with respect to the direction of polarization of the incident laser beam. These spectra indicate that the helical axes of the oligonucleotides are parallel to the long axes of the crystals and that the d(A5T5)2 is not appreciably bent in the crystal. The Raman spectrum from the d(pTpT) crystal indicates that all of the furanose ring puckers are in a C2′-endo configuration since only the C2′-endo marker band at 835 ± 5 cm-1 is present. Crystals of d(A5T5)2 show measurable Raman intensities in both the 838- and 816-cm-1 bands. This indicates the presence of both the C2′-endo and C3′-endo, or possibly other non-C2′-endo, furanose conformations. The 816-cm-1 band is weak so that only a small fraction of the residues are estimated to be in the non-C2′-endo conformation. In both the d(pTpT) and d(A5T5)2 crystals the intensity of the bands due to vibrations of the backbone show only a small dependence on orientation of the crystals. This result is explained by the low symmetry of the puckered sugar rings. It is concluded that Raman spectra obtained from oligonucleotide crystals in which the orientation of the crystal axes to the laser polarization is not carefully controlled may contain intensity artifacts that are due to polarization effects.
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  • 99
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: On the basis of a harmonic dynamics calculation, it is shown that in the 800-500-cm-1 spectral region of DNA vibrational spectra, the characteristic Raman peaks and ir bands do not arise from the same nucleosidic motions. The Raman spectra involve mainly the ring-breathing modes of nucleic bases while the ir spectra reveal essentially their out-of-plane vibrations. Moreover, the calculated results show the splitting of the guanine- and adenine-residue breathing modes upon their coupling with the sugar-pucker motions. This fact is in agreement with the poly[d(G-C)] and poly[d(A-T)] Raman spectra.
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  • 100
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional 1H-nmr spectra of the α-mating factor [in dimethyl sulfoxide-d6 (DMSO) and in water] and several dodecapeptide analogues (in DMSO) were obtained. Homonuclear correlated spectroscopy resulted in the complete and unequivocal assignment of all backbone and side-chain resonances of the peptides. The solution conformation of the pheromones was probed using two-dimensional (2D) nuclear Overhauser effect spectroscopy (NOESY) and rotating frame nuclear Overhauer effect spectroscopy (ROESY). The 2D NOE results, and results of complementary one-dimensional experiments, suggest that a type II β-turn is assumed by the central portion of active pheromones in both DMSO and water. Inactive analogues of the α-factor do not exhibit this structural feature. Except for this one β-turn, the nmr parameters for α-factor are indicative of a conformationally flexible molecule in both solvents. This conclusion is in contrast to that of other researchers who have proposed a highly structured conformation of α-factor in aqueous solution.
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