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  • 1985-1989  (11,371)
  • 1989  (11,371)
  • Chemistry  (9,763)
  • Cell & Developmental Biology  (1,469)
  • Genetics  (139)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular medicine 67 (1989), S. 225-237 
    ISSN: 1432-1440
    Keywords: Atherosclerosis ; Apolipoprotein ; Gene expression ; Genetics ; Evolution ; Gene duplication ; Lipid binding ; DNA polymorphism ; Hypercholesterolemia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The plasma apolipoproteins can be classified into two subgroups: the soluble apolipoproteins including apolipoprotein (apo) A-I, A-II, A-IV, C-I, C-II, C-III, and E, and the apoBs including apoB-100 and apoB-48. The soluble apolipoproteins have very similar genomic structures, each having a total of three introns at the same locations; apoA-IV is an exception in that it has lost its first intron. Using the exon/intron junctions as reference points, we can obtain an alignment of the coding regions of all the soluble apolipoprotein genes. The mature peptide regions of the genes are almost completely made up of tandem repeats of 11 codons. The part of mature peptide region encoded by exon 3 contains a common block of 33 codons, whereas the part encoded by exon 4 contains a much more variable number of internal repeats of 11 codons. On the basis of the degree of homology of the various sequences, and the pattern of the internal repeats in these genes, an evolutionary tree has been proposed for the soluble apolipoprotein genes. ApoB-100 differs considerably from the soluble apolipoproteins. It is the largest apolipoprotein containing 4536 amino acid residues. Two types of internal repeats are identified in apoB-100: amphipathic α-helical repeats and proline-containing repeats with high β-sheet content. The apoB gene contains 29 exons and 28 introns. Its evolutionary relationship to the soluble apolipoprotein genes is unclear. The 3′ end of the apoB gene contains a region of variable number of tandem 12–16-base pair repeats. We have applied the polymerase chain reaction technique to characterize this highly polymorphic locus. The same technique can be used to accurately type other variable number of tandem repeats loci. Finally, apoB-48 was shown to be the product of an RNA editing mechanism involving an intestinal mRNA that has an in-frame UAA stop codon resulting from a C→U change in the codon CAA encoding Gln-2153 in apoB-100 mRNA. Using a molecular approach to apolipoprotein synthesis, structure and genetic analysis, we have generated information important to our understanding of lipoprotein metabolism; we also uncovered unexpected experimental results that are relevant to general cell and molecular biology and molecular evolution.
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  • 2
    ISSN: 1432-0428
    Keywords: Genetics ; insulin gene ; DQβ gene ; fibrocalculous pancreatic diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Fibrocalculous pancreatic diabetes (previously known as tropical pancreatic diabetes) is a rare cause of diabetes confined to countries within the tropical belt. The aetiology of fibrocalculous pancreatic diabetes is thought to be environmental although the agent(s) is unknown. We have investigated a possible genetic basis of this disease by looking for restriction fragment length polymorphisms of genes implicated in the aetiology of diabetes mellitus. Seventy-six Dravidian patients with fibrocalculous pancreatic diabetes were studied, and the restriction fragment length polymorphisms obtained compared to racially matched control subjects (n=94), patients with Type 2 (non-insulin-dependent) diabetes (n=87) and Type 1 (insulin-dependent) diabetes (n=58). No association of fibrocalculous pancreatic diabetes was found with restriction fragment length polymorphisms of the insulin receptor gene. Although no association of fibrocalculous pancreatic diabetes was found with polymorphism of the HLA DRα/DQα/DXα genes, an association was found with the Taq 1 restriction fragment length polymorphisms of the DQβ gene (DQβ T2/T6 present in 39% of patients with fibrocalculous pancreatic diabetes compared to 19% in control subjects; p=0.01; corrected p value=0.04) which is similar to that found in Type 1 but not Type 2 diabetes. An association of fibrocalculous pancreatic diabetes was also found with the hypervariable region in the 5-prime flanking region of the insulin gene; 40% of patients possessed the class 3 allele compared to 9.5% of control subjects p=0.0001; corrected p value=0.0008). In Type 2 diabetes, similar results were obtained with 33% subjects possessing the class 3 allele (p value compared to control subjects=0.0005; corrected p value=0.004). This study suggests that fibrocalculous pancreatic diabetes has a genetic component in its aetiology. Furthermore, its origin might be related to an individual with part of the genetic predisposition to diabetes (Type 1 or Type 2) who additionally has evidence of chronic calcific pancreatitis.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Aquatic sciences 51 (1989), S. 108-128 
    ISSN: 1420-9055
    Keywords: Chemistry ; mountain lakes ; silica ; acidity ; sediment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Alpine lakes in siliceous catchments of Tyrol and Carinthia (Austria) show signs of acidification. About 9% of the studied lakes have no alkalinity, more than 20% are below pH 6. About two thirds of all lakes have acid neutralizing capacities below 100 μeq 1−1. In spite of moderate precipitation acidity, some lakes show considerable concentrations of dissolved reactive aluminum during or shortly after snowmelt. High altitude lakes of the Alps are definitely more acidic than high mountain lakes in remote areas. Large differences in water and soil chemistry of nearby situated lakes were attributed to heterogeneities of bedrock geology. Paleolimnological investigations on former pH values of five lakes, based on diatom assemblages in the sediment, showed different developments: recent and past acidification, stable conditions, and alkalinization.
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  • 4
    ISSN: 1432-1939
    Keywords: Logging disturbance ; Land gastropods ; Ecology ; Genetics ; Population
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Ecological and genetic properties of two North American terrestrial gastropods (Mesomphix spp.) were characterized in paired control and previously logged watersheds in two North Carolina forests (Coweeta and the Great Smoky Mountains National Park) of the Southern Appalachian Biosphere Reserve Cluster. Shell growth was greater in the control sites, but density and mortality were largely independent of prior logging history and forest reserve. Based on starch gel electrophoresis data, both species showed their highest levels of genetic diversity in the Coweeta forest, the component of the reserve cluster which had the most extensive and variable history of logging disturbance. M. subplanus also exhibited higher levels of heterozygosity in logged than in control watersheds, and M. andrewsae showed over twice as many rare alleles in disturbed sites as in control sites. F-statistic analysis depicted both excess levels of homozygosity and moderate genetic differentiation among the populations, reflecting the effects of small population size and perhaps drift and inbreeding. Estimated gene flow was relatively low. These results correspond to the recent finding by Bryant et al. (1987) and others on the effects of bottlenecks, and to the contrasting history of habitat instability of the two major study forests.
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  • 5
    ISSN: 1432-2072
    Keywords: Ethanol ; Bicuculline ; Picrotoxin ; Seizures ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The convulsant potency of bicuculline, a GABA antagonist, was shown to be greater in Short-Sleep (SS) mice than in Long-Sleep (LS) mice. LS mice, selectively bred for lengthy ethanol-induced narcosis, had longer latencies to myoclonus and clonus following administration of bicuculline and picrotoxin than did ethanol-resistant SS mice. SS mice were also more susceptible to pentylenetetrazol-induced myoclonus, but not clonus. F1 hybrids showed bicuculline seizure sensitivity intermediate to the two parent lines. Ethanol weakly inhibited bicuculline-induced myoclonus in both LS and SS mice. Clonus was clearly antagonized by ethanol in both lines, but to a similar degree. These data provide evidence for a GABAergic role in geno-type-dependent sensitivity to ethanol.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 99 (1989), S. 147-150 
    ISSN: 1432-2072
    Keywords: Locomotor activity ; CNS depression ; Cocaine ; Mice ; Behavior ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cocaine produces several behavioral effects, most notably locomotor stimulation. Biochemically, cocaine is known to inhibit reuptake at the three monoamine transporter sites, and may have highest affinity at the serotonin transporter. Serotonin augmentation has been associated with decreases in behavioral activity, but cocaine has not been reported to produce behavioral depressant effects except at high doses which cause stereotypy and disruption of behavior. This study examined the effects of relatively low doses of cocaine, in the range of 0.1–10 mg/kg, on locomotor activity in C57BL/6J and DBA/2J mice. A biphasic dose-response curve was seen for both strains. At the lowest doses, activity was depressed. As the dose of cocaine increased, activity returned to baseline, and at the highest doses, increases in locomotor activity were found. DBA/2J mice were depressed at a lower dose of cocaine than were C57BL/6J mice; however, C57BL/6J mice showed locomotor depression over a broader range of doses. Activity was maximally depressed at 0.1 mg/kg for DBA/2J mice, and maximally depressed at 0.3 mg/kg for C57BL/6J mice. Thus, low doses of cocaine are shown to produce significant decreases in locomotor activity in two strains of mice. It is postulated that these low doses of cocaine which depress locomotor activity do so via inhibition of serotonin uptake, resulting in potentiation of serotonergic activity.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 98 (1989), S. 518-523 
    ISSN: 1432-2072
    Keywords: Ethanol ; GABA ; Bicuculline ; Sedation ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two lines of mice, selectively bred for differential sensitivity to the soporific effects of ethanol (ETOH), were administered GABAergic drugs in an effort to evaluate a role for GABA in ETOH sensitivity. ETOH sensitive Long-Sleep mice (LS) showed potentiated ETOH sedation when administered bicuculline, muscimol and aminooxyacetic acid (AOAA). ETOH-insensitive SS mice exhibited reduced ETOH sedation in the presence of the antagonists, bicuculline and picrotoxin, and potentiated sedation in the presence of muscimol and AOAA. These changes in narcosis duration were interpreted as central effects, since blood ethanol levels at waking from ETOH sedation varied with GABAergic drug treatment. Picrotoxin antagonized pentobarbital-induced nacrosis in both lines, but to a greater extent in SS mice. These and other experiments with a genetically heterogeneous stock suggest GABA involvement in genotype-dependent ETOH sensitivity, but do not support a simple role of GABA receptor involvement.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 98 (1989), S. 549-555 
    ISSN: 1432-2072
    Keywords: Ethanol (ETOH) ; GABA ; Bicuculline ; Sedation ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Genetic influences on the interaction between ethanol (ETOH) and gamma-aminobutyric acid (GABA) neurotransmitter systems were eveluated with a survey of responses to coadministration of ETOH and a GABA antagonist, bicuculline, in a battery of inbred mouse strains. The selectively bred ETOH-sensitive Long-Sleep (LS) mice, the relatively ETOH-resistant Short-Sleep (SS) mice, and a genetically heterogeneous stock (GHS) were also evaluated. The effect of bicuculline on ETOH-induced sedation, hypothermia, and blood ethanol content upon recovery from sedation was assessed. Inheritance of these responses was also examined using F1 hybrids. The effect of bicuculline on ETOH-produced narcosis varied widely among stocks and included antagonism, potentiation, and no effect. Changes in ETOH-induced narcosis produced by bicuculline were accompanied by changes in blood ethanol concentrations consistent with an hypothesis of altered central nervous system sensitivity to ETOH. Knowledge of a strain's seizure susceptibility to the GABA antagonist or of its sensitivity to the hypnotic effects of ETOH were of no predictive value in estimating the outcome of coadministration studies, suggesting at least partially separate genetic influences on each phenotype. In cross-breeding studies there was commonly dominance toward a profile of bicuculline antagonism of ETOH narcosis but different patterns of dominance were observed for seizure susceptibility, again inicating separate genetic control. The results suggest considerable complexity of GABAergic involvement in genotype-dependent ETOH sensitivity.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Archives of microbiology 152 (1989), S. 335-341 
    ISSN: 1432-072X
    Keywords: Carboxydotrophic bacteria ; Plasmids ; CO dehydrogenase subunits ; N-terminal sequences ; Oligonucleotides ; Hybridization ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The 17 (S), 30 (M) and 87 kDa (L) subunits of CO dehydrogenases from the CO-oxidizing bacteria Pseudomonas carboxydoflava, Pseudomonas carboxydohydrogena and Pseudomonas carboxydovorans OM5 were isolated and purified. The N-terminal sequences of same subunits from different bacteria showed distinct homologies. Dot blot hybridization employing oligonucleotide probes derived from the sequences of the S-subunit of P. carboxydovorans OM5 and the M-subunit of P. carboxydohydrogena and DNA of the plasmid-containing CO-oxidizing bacteria Alcaligenes carboxydus, Azomonas B1, P. carboxydoflava, P. carboxydovorans OM2, OM4 and OM5 indicated that all genes encoding these subunits reside on plasmids. That in P. carboxydovorans OM5 CO dehydrogenase structural genes are located entirely on plasmid pHCG3 was evident from the absence of hybridization employing DNA from the cured mutant strain OM5-12. CO dehydrogenase structural genes could be identified on the chromosome of the plasmid-free bacteria Arthrobacter 11/x, Bacillus schlegelii, P. carboxydohydrogena and P. carboxydovorans OM3. There was no example of a plasmid-harboring carboxydotrophic bacterium that did not carry CO dehydrogenase structural genes on the plasmid. The N-terminal sequences of CO dehydrogenase structural genes were found to be conserved among carboxydotrophic bacteria of distinct taxonomic position, independent of the presence of plasmids. It is discussed whether this might be the consequence of horizontal gene transfer.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    European archives of psychiatry and clinical neuroscience 239 (1989), S. 43-48 
    ISSN: 1433-8491
    Keywords: Schizophrenia ; Eye movements ; Genetics ; Twins ; Latent trait
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eye movement dysfunctions have been found in a large number of schizophrenic patients and in about half of their first-degree relatives. The distribution of these traits within the families of schizophrenic patients suggests a model of genetic transmission that fits an autosomal dominant model, which we have called the “genetic latent trait model.” The model, with seven parameters, was fitted to a U.S. population and the model was cross-validated on an independent Norwegian sample. Although the model does not invalidate other, more conventional solutions to the puzzle of schizophrenic transmission, such as multifactorial transmission, the latent trait model does more easily permit linkage studies and therefore will allow refutation or support from the use of molecular genetics techniques.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 78 (1989), S. 97-104 
    ISSN: 1432-2242
    Keywords: Beta vulgaris ; Sugar beet ; Isozymes ; Genetics ; Linkage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Five isozyme systems were genetically investigated. The different separation techniques, the developmental expression and the use as marker system in sugar beet genetics and breeding is discussed. Isocitrate dehydrogenase was controlled by two genes. The gene products form inter- as well as intralocus dimers, even with the gene products of the Icd gene in B. procumbens and B. patellaris. Adenylate kinase was controlled by one gene. Three different allelic forms were detected, which were active as monomeric proteins. Glucose phosphate isomerase showed two zones of activity. One zone was polymorphic. Three allelic variants, active as dimers, were found. Phosphoglucomutase also showed two major zones of activity. One zone was polymorphic and coded for monomeric enzymes. Two allelic forms were found in the accessions studied. The cathodal peroxidase system was controlled by two independent genes, of which only one was polymorphic. The gene products are active as monomers. Linkage was found between red hypocotyl color (R) and Icd 2. Pgm 1, Gpi 2, Ak 1 and the Icd 2-R linkage group segregated independently.
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  • 12
    ISSN: 1432-2242
    Keywords: Solanum tuberosum ; Genetics ; Breeding ; Plant appearance ; Economy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary In 1985, 1986 and 1987, 600 clones were visually assessed at harvest on plant appearance. The clones were harvested 80 days after planting in the first year, in the following years after approximately 80 days as well as after 145 days. The correlation coefficients between years and between harvest times were low to medium. Simulating different selection intensities using the performance of these 600 clones in two successive years, the relation between selection pressure in the first year and the retained proportion of well performing clones in the second year was described. Including the costs of testing, the most economic selection procedure was calculated. This procedure consisted in testing 1,579 first-year clones and 499 second-year clones for every 100 third-year clones required. The optimal period of the main evaluation in the second clonal year is at ware potato harvest time. This selection procedure also provides good selection possibilities for underwater weight and foliage maturity.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Cell & tissue research 255 (1989), S. 385-391 
    ISSN: 1432-0878
    Keywords: Myogenesis ; Muscle regeneration ; Genetics ; Autoradiography ; Tritiated thymidine ; Mouse (Swiss;BALBc)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Muscle precursor replication in Swiss mice, in which muscle regeneration is exceptionally vigorous, was compared with previous data for regeneration in BALBc mice. The tibialis anterior muscles of 23 male and 15 female inbred Swiss SJL/J mice were crush injured, and tritiated thymidine injected into mice at various times after injury to label replicating muscle precursors. Lesion samples were taken 10 days after injury, processed for autoradiography, and grain counts of myotube nuclei analysed. Muscle regeneration was more vigorous in male compared with female Swiss mice, and in both was strikingly greater than that in BALBc mice in which there was extensive fibrous connective tissue throughout the lesions. Autoradiographic analysis showed that muscle precursor replication started at 24 hours in Swiss mice, 6 hours earlier than the onset at 30 hours in BALBc mice. Muscle precursor replication appeared to be more active 96 hours after injury in female Swiss compared with male BALBc and male Swiss mice respectively, although numbers of precursor cells replicating at other times were similar. It is not known whether the slight difference in onset of muscle precursor replication can alone account for the more complete muscle regeneration seen in Swiss mice. Similar studies were carried out in 11 male and 10 female F1 hybrid (SJL/J x BALBc) mice. Analysis of labelled myotube nuclei showed that muscle precursors did not synthesise DNA prior to 30 hours after injury, and regeneration resembled that of the parental BALBc strain.
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  • 14
    ISSN: 1617-4623
    Keywords: Aspergillus ; Genetics ; Transformation ; trpC lacZ gene fusion ; Gene replacement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Aspergillus niger tryptophan auxotrophic mutants have been isolated after UV irradiation of conidiospores. The mutants belong to two different complementation groups, trpA and trpB, which complement each other in heterokaryons. Neither of the mutations could be complemented with the cloned A. niger trpC gene. To obtain A. niger trpC mutants in a direct way, gene inactivation by cotransformation was performed. For this purpose an in-frame gene fusion between the A. niger trpC and Escherichia coli lacZ genes was constructed and shown to be functionally expressed after introduction into A. niger by cotransformation with the pyrA gene as selective marker. Among the β-galactosidase expressing cotransformants, obtained with either circular or linearized vectors, no trpC mutants were detected, even after enrichment. Such mutants, however, could be obtained by cotransformation of A. niger with specific fragments of the fusion gene. Biochemical analysis of the cotransformants indicated that in nearly all cases the fusion gene had replaced the wild-type trpC gene. Genetic analysis showed that the trpC mutation is not linked to any of the A. niger loci described so far. The trpC mutants can be complemented by the cloned A. niger trpC gene as well as by the A. nidulans trpC gene.
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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: In this part properties and efficiency of the developed model1,2 are discussed. A variation of the parameters shows that vigorous effects are caused by the effective aggregation. All calculations show that at low conversion there are little temporal steps between the sequential aggregation steps. In the range of 5% to 20% conversion the velocity of aggregation decreases and the aggregative stability agrees with experiences given in the literature. It is shown that the calculated results are in agreement with the experimental results and therefore the presented model is a suitable possibility to describe the formation of some PVC-morphology properties.
    Notes: In der vorliegenden Arbeit werden die Eigenschaften des früher1,2 entwickelten Modells untersucht und diskutiert. Die Variation der Modellparameter zeigt einen großen Einfluß der Aggregationsprozesse auf die Subkornmorphologie. Bei niedrigen Monomerumsätzen ist das Zeitintervall zwischen zwei aufeinanderfolgenden Aggregationsschritten sehr klein, so daß für das Teilchenwachstum die Geschwindigkeit der Aggregation der Unterstrukturen entscheidend ist. Im Bereich zwischen 5% und 20% Monomerumsatz sinkt die Aggregationsgeschwindigkeit sehr stark, so daß für das Teilchenwachstum zunehmend die Polymerisationsreaktion an Bedeutung gewinnt. Aggregative Stabilität wird nach dem Modell für einen Teilchengrößenbereich erhalten, der sich in Übereinstimmung mit experimentellen Daten aus der Fachliteratur befindet. Die berechneten Teilchengrößen entsprechen ebenfalls den in der Literatur publizierten experimentellen Werten, so daß das Modell eine gute Grundlage für die Beschreibung einiger morphologisch bestimmter Polymereigenschaften bildet.
    Additional Material: 5 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 21-34 
    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 unidirektionale Verbundwerkstoffe aus Novolakharz mit Kohlenstoff-Fasern gemäß der Prepreg-Methode verarbeitet. Das Novolakharz wurde durch Polymerisation von Phenol mit Formaldehyd (Mol-Verhältnis 1 : 0,82) und Oxalsäure als Katalysator (1,5 Gew.-% von Phenol) hergestellt. Die Härtung des Novolakharzes wurde mit Hexamethylentetramin (Hexa) durchgeführt, während das geeignete Verhältnis durch die IR-Spektroskopie bestimmt wurde.Es wurden Proben aus Novolak/Hexa (Gew.-Verhältnis 14: 1), verstärkt mit kommerziellen Kohlenstoff-Fasern, unter verschiedenen Bedingungen (z. B. verschiedene thermische Programme und verschiedene Verhältnisse von Novolakharz : Kohlenstoff-Fasern) hergestellt. Die mechanischen Eigenschaften der hergestellten Proben (wie Biegefestigkeit, Zugfestigkeit, usw.) wurden bestimmt, und ihre Struktur wurde mit Hilfe der Elektronenmikroskopie untersucht.Mit zunehmendem Volumenverhältnis der Kohlenstoff-Fasern werden nicht nur alle mechanischen Eigenschaften des verstärkten Materials verbessert, sondern auch sein Nutzungsgrad nimmt zu, und die Herstellungsbedingungen üben einen größeren Einfluß aus. Die mit dem gleichen Verhältnis von Kohlenstoff-Fasern (z. B. 15 Vol.-%) hergestellten Proben weisen mit zunehmendem Härtungsgrad des Novolaks verbesserte mechanische Eigenschaften auf. Der Häirtungsgrad des Novolaks während der Anfangsphase (Gel-Zeit) als auch während der Endphase (Nachhärtung) kann mit Hilfe der IR-Spektren des härtenden Novolaks verfolgt werden, während der Härtungsgrad der Zwischenphase nur indirekt aus den Werten der mechanischen Eigenschaften der entsprechenden Proben bestimmt werden kann.Aus der Korrelation zwischen den Herstellungsparametern und den mechanischen Eigenschaften der Proben ergeben sich optimale Bedingungen für die Verarbeitung in der Wärmepresse zur Herstellung von mit Kohlenstoff-Fasern verstärkten Novolakharzen (1. Phase: T1 = 125-145°C, t1 = 20 min - 1 h, ohne Druck; 2. Phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN /cm2).
    Notes: Unidirectional composite materials of novolac resin with carbon fibers were fabricated according to the prepreg method. Novolac resin was prepared by polymerization of phenol with formaldehyde (mole ratio 1 : 0.82) in the presence of oxalic acid as catalyst (1.5 wt.-% to phenol). The curing of novolac resin was performed with hexamethylenetetramine (hexa), while the appropriate proportion was determined by using the IR-spectroscopy.Specimens of novolac/hexa (weight ratio 14:1) reinforced with carbon fibers commercially available were fabricated under different conditions (e.g. different thermal programs and different proportions of novolac/carbon fibers). The mechanical properties of the fabricated specimens (like flexural strength, tensile strength, etc.) were determined and their structure was examined by scanning electron microscopy.By increasing the volume proportion of carbon fibers, not only all mechanical properties of the composite material were increased, but also their degree of utilization was increased and also the production conditions had greater influence. Concerning the specimens produced by the same proportion of carbon fibers (e.g. 15 vol.-%) their mechanical properties were improved by increasing the curing of novolac. The degree of curing of novolac during the initial phase (gel time) and during the ultimate phase (post-curing) can be followed with the aid of IR-spectra of the cured resin, while the degree of curing for the intermediate phase can be obtained only indirectly from the values of the mechanical properties of the corresponding specimens.From the correlation between the production parameters and the mechanical properties of the samples the optimal conditions for processing of the thermopress for the manufacture of carbon fiber reinforced novolac were concluded (1. phase: T1 = 125-145°C, t1 = 20 min - 1 h, without pressure; 2. phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN/cm2).
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 69-78 
    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 interessieren wir uns für den Einfluß von Konzentration und Temperatur auf den elektrischen Widerstand eines Butyl-Kautschuks (IIR), der mit zwei Typen von Ruß (Hoch-Abrasion-Schmelzofen-Ruß (HAF) und Schnell-Extrusion-Hochofen-Ruß (FEF)) versetzt ist. Ergebnis war, daß die Leitfähigkeit bei niedrigem Rußgehalt hauptsächlich durch thermische Aktivierung der Ladungsträger erreicht wird. Bei mittleren Konzentrationen überwiegt der Tunnel-Mechanismus bei niedriger Temperatur, gefolgt von der thermischen Aktivierung bei relativ hoher Temperatur. Dies gilt für beide Rußarten. Das metallartige Verhalten bei Gemischen mit hoher Rußkonzentration kann sowohl der thermischen Ausdehnung der Tunnelwege zwischen Kohlenstoff-Agglomeraten als auch dem Zusammenbruch der Kohlenstoff-Agglomerate bei steigender Temperatur zugeschrieben werden.
    Notes: In this study we are interested in the effect of concentration and temperature on the electrical resistivity of butyl rubber (IIR) loaded with two types of carbon black, (namely, high abrasion furnace black (HAF), and fast extrusion furnace black (FEF)). It was found that the conductivity at low carbon black concentrations is mainly achieved by thermal activation of carriers. Tunneling mechanism at low termperature followed by thermal activation at relatively high temperature is found to be predominant for moderate concentrations for both carbon blacks. The metal-like behaviour which was observed in highly loaded compounds was attributed to both, the thermal expansion of the tunneling paths between carbon-carbon agglomerates and the breakdown of carbon agglomerates with temperature.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 79-87 
    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 Arbeit beschreibt die Synthese von Halogenderivaten des Phenylglycidylethers und die Möglichkeiten der Verwendung von diesen Komponenten als Flammverzögerer und reaktive Verdünnungsmittel für Epoxidharze.Mit Hilfe der Nelder-Mead-Simplexmethode wurden die besten Reaktionsbedingungen gefunden. Die so hergestellten Produkte zeichnen sich durch eine hohe Qualität aus und wurden mit einem niedermolekularen Epoxidharz gemischt und mit Diaminodiphenylmethan gehärtet.Die Viskosität von Harzgemischen und die Brennbarkeit der gehärteten Systeme wurden untersucht. Mit dem erhöhten Gehalt an Halogen (Chlor oder Brom) steigt die Viskosität, und die Brennbarkeit der Epoxide wird reduziert.
    Notes: This study deals with the synthesis of halogenated derivatives of phenyl glycidyl ether and with possibilities of their use as flame retardants and reactive diluents of epoxy resin.The best reaction conditions optimized by Nelder-Mead simplex method were found. The products of very high quality were prepared. They were mixed with a lowmolecular epoxy resin and cured by diamino diphenyl methane.The viscosity of the resin mixtures and limiting oxygen index of cured systems were determined. It was found that a higher content of halogen, both chlorine and bromine, causes increasing viscosity and reduced flammability of the epoxides.
    Additional Material: 2 Ill.
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  • 19
    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 Messungen von Tg, Tm und Tc (Trübungspunkt) wurden Phasendiagramme der vier verträglichen Polymermischungen von chlorierten isotaktischen Polypropylenen (Chlorgehalt 39,2 (CPP-40) und 49,8 Gew.-% (CPP-50)) mit Poly(ethylen-co-vinylacetat)en (Vinylacetatgehalt 40 (EVA-40) und 45 Gew.-% (EVA-45)) untersucht. Von den vier Mischungspaaren war die Mischung von CPP-50 mit EVA-40 am besten verträglich.
    Notes: By measuring Tg, Tm and Tc (cloud point) phase diagrams for the four miscible blends of chlorinated isotactic polypropylenes (chlorine content 39.2 (CPP-40) and 49.8 wt.-% (CP-50)) with Poly(ethylene-co-vinyl acetate)s (vinyl acetate contents 40 (EVA-40) and 45 wt.-% (EVA-45)) were investigated. The blend of CPP-50 with EVA-40 was the most compatible of the four blend pairs.
    Additional Material: 4 Ill.
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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: Die Synthese und Charakterisierung von Kationenaustauschmembranen aus PE-PS-DVB-Interpolymeren für die Elektrolyse von Borax-Lösung zur Erzeugung von Borsäure und Natronlauge wurden durchgeführt und mit den Eigenschaften von im Handel erhältlichen Membranen („Nafion 324“ und „Permaplex C-20“) verglichen.
    Notes: The synthesis and the characterization of the PE-PS-DVB interpolymer cationexchange membranes in the electrolysis of borax solutions to produce boric acid and sodium hydroxide simultaneously was carried out. The characterization of the teflon based “Nafion 324” and polystyrene-DVB based “Permaplex C-20” membranes was also performed in the same system for comparison.The DVB contents were varied between 3 - 12% (by wt. in total monomers) and the increase of the cross-links resulted in the decrease of the water contents and ionexchange capacities of the membranes. The PE present in the membrane acted as a barrier for electroosmotic water transport. The membranes with high DVB contents showed better electrolysis performance due to their low water contents and low electroosmotic water transport properties. The use of the interpolymer membrane containing 11.6% DVB resulted in high current efficiency and high sodium cation dynamic transport number and worked satisfactorily at the process conditions of borax electrolysis.
    Additional Material: 5 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 125-131 
    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: Aus Rizinusöl und difunktionellen Säuren, wie Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Suberin- und Sebacinsäure, wurden Prepolyester hergestellt. Diese Prepolyester (PPE) wurden anschließend mit Methylmethacrylat und 1% Ethylenglykoldimethacrylat als Vernetzer interpenetriert. Die Polymerisation wurde radikalisch mit Benzoylperoxid gestartet. Die neuen PPE/Polymethylmethacrylat (PMMA)-interpenetrierenden Netzwerke wurden als Pulver erhalten. Sie wurden durch ihr Löseverhalten, IR-Spektroskopie und ihr thermisches Verhalten charakterisiert.
    Notes: Prepolyesters were obtained from castor oil and dibasic acids, viz oxalic, malonic, succinic, glutaric, adipic, suberic and sebacic acid. These prepolyesters (PPE) were subsequently interpenetrated with methyl methacrylate containing 1% ethylene glycol dimethacrylate as crosslinker by radical polymerization initiated with benzoyl peroxide. The novel PPE poly(methyl methacrylate) PPE/PMMA interpenetrating polymer networks (IPNs) were obtained as powder. They were characterized by solubility behaviour, IR spectral study and thermal behaviour.
    Additional Material: 4 Tab.
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  • 22
    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: 2,4-Ionen, ein polymeres quartäres Ammoniumsalz, wurde auf einem makroporösen chlormethylierten Poly(Styrol-co-Divinylbenzol)-Harz (XAD-2) immobilisiert. Der Ionen-Gehalt des Harzes, der durch CHN-Elementaranalyse bestimmt wurde, betrug 50,2 g/kg Harz. Der wichtigste Nebeneffekt des modifizierten Harzes, das Ausbluten des Katalysators 2,4-Ionen, kann durch eine spektrophotometrische Methode, die extrem geringe Konzentraionen an freiem Ionen an der Oberfläche des Harzes messen kann, ermittelt werden.Die Aktivität der immobilisierten 2,4-Ionen/Kobalt(II)-phthalocyanin-tetranatriumsulfonat-Komplexe in bezug auf die oxidative Kupplung von Thiolen ist viel niedriger als im homogenen Fall, aber noch beträchtlich höher als im polymerfreien System. Die beobachtete Abnahme der Reaktionsgeschwindigkeit resultiert nicht aus Behinderungen des Massentransports, sondern vorzugsweise aus den Katalysatoreigenschaften wie z. B. einem sehr niedrigen N+/Co-VerhtUtnis. Die aktiven Zentren scheinen nur in der äußeren Hiille der Harzpartikel vorhanden zu sein.
    Notes: A poly(quaternary ammonium) salt, 2,4-ionene, has been immobilized on a macroporous chloromethylated poly(styrene-divinylbenzene) resin (XAD-2). The ionene content of the resin, determined by CHN elemental analysis, was 50.2 g/kg resin. The most important side effect of the modified resin, catalyst (2,4-ionene) bleeding, can be detected by a spectrophotometric method capable of determining extremely low concentrations of free ionene in the supernatant of the resin.The activity of these immobilized 2,4-ionene/cobalt(II)phthalocyanine-tetrasodiumsulfonate (CoTSPc) complexes towards the oxidative coupling of thiols is much lower than in the homogeneous case, but still considerably higher than for the polymer free system. The observed decrease in reaction rate does not originate from the considerable mass transfer resistances but predominantly from catalyst properties like a very low local N+/Co ratio. The active sites appear to be present in the outer shell of the resin particles only.
    Additional Material: 5 Ill.
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  • 23
    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: Röntgendiffraktometrische Untersuchungen und DSC-Messungen an Blend-Filmen, die aus Lösungen von PEEK und PES hergestellt wurden, zeigen eine Phasenseparation bei den Filmen, die bei 340°C hergestellt wurden. Das Kristallisationsverhalten von Filmen, die bei 340°C hergestellt, anschließend abgeschreckt und bei 180°C getempert wurden, ist identisch mit dem von PEEK. Filme, die bei 300°C hergestellt wurden, kristallisierten erst durch Tempern bei 250°C. Blockcopolymere, die aus Oligomeren von PEEK und PES erhalten wurden, unterscheiden sich in dieser Hinsicht von Blends der gleichen Zusammensetzung. Die Glastemperatur von Copolymeren mit einem PEEK-Gehalt von mehr als 50% liegt höher als die von PEEK selbst, während der Schmelzpunkt dieser Copolymeren niedriger als der von PEEK ist.
    Notes: Polymer blends of PEEK with PES were prepared by the solution blending method. Copolymers composed of PEEK and PES components were synthesized from these oligomers. The formation conditions exerted an influence over the molecular aggregation and the crystallization behaviors of the blend films and block copolymers which were examined by X-ray diffractometry and DSC analysis. As a result, phase-separation in the blend films was found when the formation temperature was high. The blend films formed at 340°C, quenched and annealed at 180°C, exhibited the same crystallization behavior as those of PEEK. In the case of the blend films formed at 300°C, the annealing of the films at 250°C was required to crystallize the blend films. The Tg of a copolymer with a PEEK component content of more than 50% tends to shift toward a higher temperature than the Tg of PEEK itself, and the Tm of the copolymer toward a lower temperature than that of PEEK ist.
    Additional Material: 16 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 129-134 
    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: Das Reaktionsprodukt eines Cyclohexanon-Formaldehyd-Harzes mit dem Säurechlorid des Radikalinitiators 4,4′-Azo-bis(4-cyanopentansäure) wurde als Initiator für die Styrolpolymerisation eingesetzt, um ein Cyclohexanon-Formaldehyd-Harz/Polystyrol-Copolymeres zu bilden. Das Copolymere zeigte ähnliche Löslichkeit wie Polystyrol.
    Notes: The reaction product of cyclohexanone-formaldehyde resin with an acid chloride of a radical initiator, 4,4′-azo-bis(4-cyano pentanoic acid) was used as initiator for styrene polymerization to form a cyclohexanone-formaldehyde resin/polystyrene copolymer. The copolymer showed similar solubility as polystyrene.
    Additional Material: 1 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 145-155 
    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: Entgegengesetzte Ladungen wurden durch tertiäre Amin- und Carboxylgruppen in Polyurethan (PU) und Polystyrol (PS) eingeführt, um durch gemeinsame Massepolymerisation ein interpenetrierendes PU/PS Polymernetzwerk (IPN) zu erhalten. Vier IPNs wurden hergestellt: ein Voll-IPN, zwei Semi-IPNs und ein lineares Blend. Die Wirkung der geladenen Gruppen auf die mechanischen Eigenschaften und die Morphologie der vier Polymermischungen wurde untersucht.Es wurde gefunden, daß PU/PS IPNs mit geladenen Gruppen keine Phasenseparation und somit homogene Verteilung aufweisen, was durch elektronenmikroskopische (SEM) Aufnahmen nachgewiesen wurde. Dynamisch-mechanische Messungen zeigen, daß die Übergangspeaks des Verlust-Moduls E″ in die Mitte zwischen den beiden Übergangspeaks der beiden Komponenten ohne geladene Gruppen liegen. Dies ist von der Zunahme des Gehaltes an geladenen Gruppen abhängig. Gleichzeitig nimmt der Speichermodul E′ in einer Stufe ab, was im Gegensatz zu der zweistufigen Abnahme bei Proben ohne Ladungsträger steht.Die Zugfestigkeit nimmt in allen vier Polymermischungen mit der Zunahme an Acrylsäure (AA) in Poly(Styrol-Acrylsäue) PSAA zu, was in dem PU/PSAA Voll-IPN besonders deutlich wird.
    Notes: Opposite charges, namely tertiary amine and carboxyl groups, were introduced into polyurethane (PU) and polystyrene (PS), respectively, to prepare PU/PS interpenetrating polymer networks (IPNs) by means of simultaneous bulk polymerization. Four IPNs were synthesized: a full-IPN, two semi-IPNs and a linear blend. The effect of charge groups on the mechanical properties and morphology of the four polymer alloys was investigated.It is found that the PU/PS IPN which was incorporated with charge groups is free of any phase-separation, and sufficiently uniformly distributed, as can be seen from the corresponding scanning electron microscopy (SEM) photographs. Dynamic mechanical analysis indicates that the transition peak of the loss modulus E″ will move towards the centre between the two transition peaks of both components in the absence of charge groups, as a function of an increase in the contents of the opposite charge groups. Meanwhile the storage modulus E′ will decrease in a single-stage way from the previous two-stage mode.The tensile strength in all the four polymer alloys increased markedly along with an increase in the contents of acrylic acid (AA) in the poly(styrene-acrylic acid) (PSAA), which clearly can be seen for the PU/PSAA full-IPN.
    Additional Material: 4 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 157-168 
    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: Pyrolysis behaviour and coke characteristics of different precursors for carbon processing: thermosetting resins (resol, novolak), hydrolytic lignin, pitch, tar as well as their blends were studied using differential thermal analysis (DTA) and X-ray diffraction techniques. The blends novolak-pitch, resol-tar and resol-hydrolytic lignin show a higher coke yield after carbonisation up to 1000°C compared to the corresponding individual substances. A good correlation between the integral procedural decomposition temperature T*A of the investigated precursors and their coke yield is found.
    Notes: Mittels Thermo- und Röntgenstrukturanalyse wird eine vergleichende Untersuchung des Pyrolysevorganges und der Mikrostruktur des aus zwei Gruppen organischer Bindemittel und deren Mischungen gewonnenen Koksrückstandes durchgeführt. Gruppe I umfaßt reine und mit Hydrolyselignin gefüllte Resol- und Novolak-Phenol-Formaldehydharze und Gruppe II Steinkohlenpech und -teer. Es wird festgestellt, daß sich die Mischungen Novolakharz-Pech, Resolharz-Teer und Resolharz-Hydrolyselignin beim Erhitzen nicht wie mechanische Gemische verhalten und eine erhöhte Ausbeute an Koksrückstand liefern. Weiterhin wird gefunden, daß die integrale Endtemperatur der Pyrolyse (T*A) dieser Substanzen als quantitatives Maß für die Ausbeute an Koksrückstand im Anschluß an die Carbonisierung der Proben dienen kann.
    Additional Material: 4 Ill.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 217-223 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper describes the successful synthesis of silicon containing bismaleimide resin 4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane. The char yield of the bismaleimide resin in N2 atmosphere was found to be 55% at 800°C. Chain extension of bismaleimide with 4,4′-diamino diphenyl sulfone reduced the char yield and thermal stability.
    Additional Material: 3 Ill.
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  • 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: As hard blocks in polyether block amides, polyamides are used whose length is intensively regulated by dicarboxylic acids. Since, with regard to melting and crystallization behaviour, this acid constitutes an interfering structural unit in the chain, and in the case of a completely converted product each chain contains one acid molecule, it is essential to know where in the chain incorporation will occur. As opposed to monofunctional chain regulators which always form a chain end, a bifunctional chain regulator can a priori also be randomly incorporated into the inner part of the chain. This leads to a far greater interference than occurs if the chain regulator molecule and the chain end, which acts as an interfering unit in any case, coincide with each other.By means of adipic acid-regulated oligoamides based on lauryl lactam, the incorporation of the chain regulator was examined by NMR spectroscopy and compared with model calculations. This resulted in a close match only if it was presupposed that the incorporation was carried out randomly with the same degree of probability at any point whatsoever between two lauryl lactam structural units or at the chain end.Further calculations illustrate the effects of the incorporation of the chain regulator on the size of the amorphous portion.
    Notes: Als Hartblöcke in Polyetherblockamiden werden durch Dicarbonsäuren stark geregelte Polyamide eingesetzt. Da die Säure in Hinblick auf das Schmelz- und Kristallisationsverhalten einen Störbaustein in der Kette darstellt und bei einem ausgeregelten Produkt jede Kette ein Säuremolekül enthält, ist es von Bedeutung zu wissen, wo in der Kette der Einbau erfolgt. Anders als bei monofunktionellen Reglern, wo der Regler stets ein Kettenende bildet, kann ein bifunktioneller Regler a priori auch statistisch im Inneren der Kette eingebaut werden. Dies führt zu einer viel stärkeren Störung, als wenn das Reglermolekül und das sowieso als Störstelle wirkende Kettenende zusammenfallen. Anhand adipinsäuregeregelter Oligoamide auf Basis von Laurinlactam wird kernresonanzspektroskopisch der Einbau des Reglers untersucht und mit Rechnungen verglichen. Es ergibt sich nur dann gute Übereinstimmung, wenn vorausgesetzt wird, daß der Einbau statistisch erfolgt und dabei mit gleicher Wahrscheinlichkeit für jede beliebige Stelle zwischen zwei Laurinlactambausteinen oder am Kettenende abläuft. Weitere Rechnungen verdeutlichen den Einfluß des Reglereinbaus auf die Größe des amorphen Anteils.
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  • 29
    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: Auf Grund von mikroskopischen Beobachtungen wurde festgestellt, daß unter dem Einfluß von UV-Strahlung die Oberfläche von PVC-Filmen einer Formveränderung unterliegt. Auf der Oberfläche erscheinen Bläschen und Löcher. Die sich absondernden Gasprodukte der Polymerfotodestruktion verursachen die Bildung dieser Bläschen und Löcher. Größere Oberflächenänderungen wurden in Filmen mit einem Zusatz von 1-5% eines MMA/MA-Copolymeren beobachtet. Das weist auf eine in diesem Modifikator stattfindende Photoabbaureaktion hin, deren Ergiebigkeit größer ist als in reinem PVC. Dieser Modifikator wird in PVC eingeführt, um die Filmoberfläche zu verbessern, beschleunigt allerdings ihre Zerstörung unter dem Einfluß von UV-Strahlung. Es wurde festgestellt, daß Cyclohexanonspuren in den Proben den Photoabbau von MMA/MA retardieren, diesen Prozeß in PVC aber beschleunigen.
    Notes: By means of microscopic observation, the deformation of the surface of PVC films caused by 253.7 nm UV radiation was investigated. Numerous blisters and holes were formed by the gaseous photodecomposition products of the polymer.More apparent deformation of the films containing MMA/MA suggests that the photodecomposition of this modifier occurs with higher efficiency than that of PVC.MMA/MA copolymer is introduced into PVC films to improve the smoothness of their surface, but this modifier accelerates the deformation of this surface under UV irradiation. It was also found that traces of cyclohexanone in samples retard the photodecomposition of MMA/MA and accelerate this process in PVC.
    Additional Material: 7 Ill.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 29-41 
    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 Anzahl von Harzen wurde durch gemeinsame Kondensation von p-Aminoacetophenon (p-AAph), substituierten Benzoesäuren wie m-Tolylsäure (m-TA), o-Tolylsäure (o-TA), Phthalsäure (PhA), p-Nitrobenzoesäure (p-NBA), p-Chlorbenzoesäure (p-CIBA) und Formaldehyd (F) in Gegenwart von verschiedenen Säuren und Basen als Katalysatoren hergestellt. Die Harze wurden IR-spektroskopisch charakterisiert. Die Löslichkeitsparameter wurden gemäß Small's Gruppenbeteiligung berechnet; sie stimmen gut mit den experimentellen Werten überein. Das thermische Verhalten und die bakteriologischen Eigenschaften der Harze wurden auch untersucht.
    Notes: A number of resins has been prepared by condensing p-amino-acetophenone (p-AAph) with substituted benzoic acid such as m-toluic acid (m-TA), o-toluic acid (o-TA), phthalic acid (PhA), p-nitrobenzoic acid (p-NBA), p-chlorobenzoic acid (p-CIBA) and formaldehyde (F) in presence of some acids and bases as catalysts. The resins were characterized by infrared spectra of the characteristic groups. The solubility parameters were calculated from Small's group contribution which agreed well with the experimental values. The thermal behaviour and the bacteriological properties of the resins have also been investigated.
    Additional Material: 3 Ill.
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  • 31
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Notwithstanding their more common beginnings, liquid crystals and molecular biology developed mainly parallel and independently during the last one hundred years.Molecule-phase relationships on the one and complex static-dynamic treatments on the other hand seem to forward mutually integrative views in our days.Biomesogen approaches will deepen our insights into the spatio-temporal coherences of biological systems. They might contribute significantly to the understanding of life processes.
    Additional Material: 23 Ill.
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  • 32
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent studies on ionic distribution in solutions and in suspensions were reviewed. Suspensions of latex particles, which were large enough to be seen under an ultramicroscope, were investigated by the 2-D Fourier transformation. The micrograph showing ordered structures gave discrete scattering spots, whereas those of disordered arrangements displayed no spots or halos. The two-state structure gave a limited number of halo, confirming our previous conclusion that the very frequently observed single, broad scattering peak was reminiscent of some kind of ordering of solute species. By using an image data analyser, the crystallization process was shown to follow the Ostwald ripening mechanism. The concurrent study by the quasi elastic light scattering method and by the Fourier analysis gave consistent scattering profiles, which indicated that the ordering phenomena took place in the entire volume of suspensions. The scattering intensity (correctly the lattice factor) was calculated for cubic systems with paracrystalline distortion. The peak intensity was lowered by enhanced distortion, while the peak position itself was not affected. This justifies our previous treatment of the single, broad peak in terms of the Bragg equation. The experimentally found scattering curve was compared with this theoretical calculation; the degree of distortion was evaluated.
    Additional Material: 14 Ill.
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  • 33
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lyotropic liquid crystalline phases of cellulose derivatives were explored as an analytical tool. Molar mass dependent measurements of the helicoidal cholesteric pitch of a cellulose tricarbanilate/solvent system may be used to determine the molar mass of this derivative by optical means. The compatibility of a ternary liquid crystalline system can be adequately investigated by a study of the supermolecular structure with spectroscopic measurements.
    Additional Material: 7 Ill.
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  • 34
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of carotenoids as natural additives in various water-based or water-compatible formulations for the pigmentation of foods and feeds is seriously hampered by their insolubility in aqueous systems.Therefore, in order to develop the full potential of colour strength and to achieve a high degree of bioavailability during gastro intestinal passage, the coarse crystalline material has to be transformed into a microdisperse state.Exemplified with β-carotene, a novel non-mechanical process is described that transforms the carotenoids into a colloidal hydrosol characterized by an average particle size of about 0.1 μm.The process is based on the preparation of a transient high temperature solute state of the carotenoid in a water-miscible solvent, coupled with succeeding rapid aqueous precipitation in the presence of a stabilizing polymer colloid. The obtained hydrosols are characterized by photon-correlation-spectroscopy(size), and microelectrophoresis(colloidal stabilization).The bioavailability was tested by monitoring plasma levels of β-carotene in veal calves.
    Additional Material: 8 Ill.
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  • 35
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer science is mature enough to allow one to think about tailor-making macromolecular compounds aimed at interacting purposely with living systems. Reasons for developing bioresorbable polymers for temporary therapeutic applications are discussed with respect to property adjustments and economical factors. The field of the applications is first described and guidelines for tailor-making multimeric macromolecules with desired properties are presented. The approach led to focuss investigations on poly(α-hydroxy acids) and functional poly(β-hydroxy acids) derived from natural hydroxy acids, namely lactic, glycolic and malic acids. Physical, mechanical and biological properties of some corresponding polymers and copolymers are presented. Last but not least, examples of applications currently investigated are recalled.
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  • 36
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When blood comes into contact with an artificial surface, a number of events occur which include protein adsorption, platelet activation and the activation of the intrinsic pathway of blood coagulation. With the increased application of blood containing artificial devices, there is a great demand to develop new biomaterials which retard thrombus formation. Our new approach to solving this problem is to mimic the non-thrombogenic surface of natural biological membranes at least in a simple form. We have developed a polymerisable phospholipid and polyesters based on the major phospholipid polar head group present on the erythrocyte outer membrane surface. The coagulation of blood exposed to these polymers was examined by the technique of Material Thrombelastography, a relatively simple test for the in vitro screening of polymer thrombogenicity. We present results which indicate that the polymerised phospholipid and polyesters show reduced thrombogenicity, and may therefore have potential for future biomaterials.
    Additional Material: 4 Ill.
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  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After implantation a stable bond between the implant and the surrounding tissue is required. Therefore a high cell adhesion of the polymer surface of the implant must be achieved. Depending on the treatment time of a polydimethylsiloxane foil with oxygen plasma, the cell adhesion can be improved. FT-IR spectroscopy and ESCA analysis were used to characterize the surface modification. The cell spreading and cell adhesion increase with increasing hydrophilic character of the polymer surface after plasma treatment. A pronounced correlation was found between the efficiency of DNA and protein content, characterizing cell growth, and the spreading of the cells.Polydimethylsiloxane, Glow-Discharge, Surface Modification, Cell Adhesion, Cell Proliferation.
    Additional Material: 6 Ill.
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  • 38
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have used synthetic polymers as tools to probe endocytosis and lysosome function. Their particular value lies in their well-defined chemical constitution and in the possibility to custom-synthesize molecules with desired characteristics. Polyvinylpyrrolidone, Percoll and polystyrene beads have been 125I-labelled and used to explore the borderland of pinocytosis and phagocytosis. Derivatized poly(aspartamide), poly(hydroxypropylmethacrylamide) and a polylysine-poly(ethylene oxide) block copolymer have been used to investigate the effects of hydrophobic moieties and sugar residues on substrate-selection in pinocytosis. The effect of cationic moieties has been studied using vinylpyrrolidone-vinylamine copolymers.Poly(hydroxypropylmethacrylamide) with certain oligopeptide side---chains have been shown to be susceptible to lysosomal peptidases. Ethylene glycol oligomers are being used to study the basal permeability of the lysosome membrane.Soluble macromolecules have considerable potential in targeted drug-delivery. Drugs attached to appropriate polymers by covalent links that are susceptible to lysosomal enzymes can deliver drug to target cells and avoid unwanted sideeffects. Synthetic macromolecules have several advantages over their natural counterparts: they are chemically more robust, less immunogenic, and easier and cheaper to prepare in bulk.
    Additional Material: 1 Ill.
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  • 39
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diagnostics are e. g. reagents or combinations of reagents or measure bloodcomponents down to concentrations of 10-15 mol/1 in reproducable form. To achieve this target diagnostics have to fullfill special requirements in purity, uniformity, producibility and reproducibility. These requirements are also valid for integrated polymers and plastics. Examples of the application of polymers and plastics in diagnostics are e. g. materials for the blood-plasma-separation, the stabilization of proteins, solid phases in immunoassays as reagent tubes, microtiterplates and latexparticles.Reciprocal actions between polymers, plastics, polymer additives, blood and bloodsubstances like proteins in diagnostic tests can be seen as indications to similar effects by the intracorporeal applications of plastics in surgery and in general for contacts of natural materials with plastics, as usual in the foodpacking.
    Additional Material: 19 Ill.
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  • 40
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using Eupergit, a synthetic resin, as an example, the necessary characteristics of a support for high performance affinity chromatography (HPAC) are demonstrated. To such a support different ligands can be immobilized and used for the separation of biopolymers.From the range of possible applications a few examples are chosen. Immunoglobulins are isolated in one step by protein A-HPAC, the purified antibodies are immobilized and applied to immunoaffinity-HPLC for the isolation of corresponding antigens. Concanavalin A-HPAC of membrane proteins was chosen to represent chromatography with immobilized lectins. Antithrombin could be isolated from human plasma by the use of immobilized heparin. HPAC has the advantage of affinity chromatography, which is above all highly specific. As the support is resistant to high pressure and has well defined microparticles with a particular pore size, it provides a much higher yield at considerable flow rates. The handling of materials like this is simpler, the separation of the sample is quicker and can be reproduced more easily.
    Additional Material: 5 Ill.
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  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 166 (1989), S. 257-272 
    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: Controlled polyelectrolyte adsorption can be used to render phospholipid bilayer membranes sensitive to physical and chemical signals. We describe in this paper the design and construction of macromolecular switches for bilayer membranes, which can be used to create lipid vesicles that release their contents rapidly and quantitatively in response to changes in pH, temperature, light intensity or glucose concentration. The kinetics and mechanisms of the molecular switching processes observed in such systems are also discussed.
    Notes: Kontrollierte Adsorption von Polyelektrolyten kann ein wirksames Werkzeug im Design von dünnen molekularen Filmen sein. Man kann erwarten, daß die Adsorption von Polyelektrolytketten das empfindliche Kräftegleichgewicht erheblich beeinflußt, das die strukturellen und funktionellen Eigenschaften von geordneten Strukturen wie Einzel-, Doppel- und Mehrfachschichten bestimmt. Andererseits ist die Adsorption von Polyelektrolyten außerordentlich sensitiv auf Umgebungsparameter, z.B. pH, Temperatur oder lonenstärke. Kontrollierte Adsorption kann daher zu Sensitivität auf bestimmte chemische oder physikalische Stimuli führen, sodaß auf diese Weise ein molekularer Schaltmechanismus entworfen werden kann. Durch Umsetzen dieser ldee in reale Systeme gelang es uns, molekulares Schalten in Mischungen von Poly(2-ethylacrylsäre) mit natürlichen oder synthetischen Phosphatidylcholinen zu bewirken. Insbesondere haben wir Phosphatidylcholinvesikel hergestellt, die ihren lnhalt nach einer Änderung von pH, Temperatur, Glukosekonzentration oder nach Bestrahlung mit Licht schnell und quantitativ freisetzen. Die Entwicklung und die Herstellung von Doppelschichtmembranen, die auf solche Änderungen reagieren, sowie die Kinetik und der Mechanismus des damit verbundenen molekularen Schaltprozesses werden im vorliegenden Artikel diskutiert.
    Additional Material: 9 Ill.
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  • 42
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enzymes can be immobilized by gel entrapment, by microencapsulation, by physical or ionic adsorption, by covalent binding to inorganic or organic carriers, or by whole cell immobilization. Of particular interest is the large number of chemical reactions developed for the covalent binding of enzymes via their nonessential functional groups to inorganic carriers such as glass, ceramics and iron, to natural polymers such as cellulose and Sepharose, and to synthetic polymers such as nylon, polyacrylamide, and other vinyl polymers and copolymers possessing reactive chemical groups. The stability of certain enzymes is markedly increased on their immobilization. It was thus possible to transform the biologically active polymer derivatives into active enzyme beads, enzyme capsules, enzyme columns and enzyme membranes and these enabled the construction of enzyme reactors such as the batch-stirred tank reactors, the continuous packed bed reactors, and fluidized bed reactors. So far mainly immobilized hydralases and isomerases are being used in industry on a large scale. It seems likely, however, that once adequate techniques become available for cofactor recycling, the use of immobilized enzymes will be extended to other organic reactions, particularly those involving stereospecific synthesis of simple or complex organic molecules. Among the industrial processes in which immobilized enzymes are being used, it is worth mentioning the industrial-scale continuous production of fructose enriched syrup from glucose by immobilized glucose-isomerase, the batch process for the production of 6-aminopenicillanic acid (6-APA) from penicillin G with the aid of immobilized penicillin amidase; the production of aspartame from aspartic acid and phenylalanine by immobilized thermoase; the large scale production of optically active amino acids with immobilized amino acid acylase; and the large scale production and application of immobilized lactase for the hydrolysis of lactose. The recently developed process for acrylamide production using immobilized nitrilase containing microbial cells should also be referred to. The successful use of an NAD-polyethylene glycol conjugate (NAD-PEG) as a nondialyzable water-soluble coenzyme derivative in the enzymic synthesis of leucine from α-ketoisocaproic acid and ammonia, in a membrane-enclosed reactor containing L-leucine dehydrogenase, NAD-PEG, formate and formate dehydrogenase, illustrates the new possibilities opened up by making use of cofactor-polymer conjugates. The use of enzyme-polymer conjugates in analytical and clinical is also illustrated.
    Additional Material: 5 Ill.
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  • 43
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The genetic make-up of living systems especially of isolated cells can be altered by a variety of methods including chemical or light-induced mutation. More modern procedures are the in vitro recombination of nucleic acids and the cell-cell fusion.The new methods are especially useful to reprogram microorganisms to produce valuable proteins or other natural products in excess quantties. In the following we will elucidate the importance of the new techniques by describing the bacterial production of glucose dehydrogenase, of the proteinase inhibitor stefin A and by outlining the methods and promisses of substractive cloning. Although the economic value of genetic engineering techniques still awaits justification, the importance of the methodology for basic biological research is well documented.
    Additional Material: 12 Ill.
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  • 44
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immobilization of whole cells has become an efficient tool for biosynthesis, biotransformation and analysis. High cell density, high operational stability, easy handling, propably in continuous systems, and multiple reuse are important advantages of immobilized cells. In comparison to other methods like adsorption, crosslinking and encapsulation, the entrapment within a polymeric network is the most widely applied technique in heterogeneous biocatalysis. For immobilizing mammalian cells nearly exclusively the adsorption onto micorcarriers is used. Requirements for the polymers to be used in such immobilized cell systems are discussed in detail.
    Additional Material: 5 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 1-8 
    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: Vier Pyridazinderivate wurden synthetisiert und als Beschleuniger für Naturkautschukmischungen entwickelt. Die rheologischen Eigenschaften wurden mit Hilfe eines Monsanto Rheometers 100 bestimmt. Die rheometrischen Daten wurden für die Berechnung der kinetischen Konstanten der Vulkanisationsreaktion in Anwesenheit der synthetisierten Verbindungen benutzt. Verglichen mit Mercaptobenzthiazol (MBT), einem Beschleuniger der häufig in der Kautschukindustrie eingesetzt wird, zeigten diese Verbindungen eine gute Beschleunigerwirksamkeit.
    Notes: Four pyridazine derivatives were synthesized and evaluated as accelerators in natural rubber (NR) mixes. The rheological characteristics were determined by a Monsanto Rheometer 100. The kinetic constants for the vulcanization reaction in the presence of the synthetic compounds were calculated using the rheometric data. The compounds showed a good accelerating efficiency compared with mercaptobenzothiazole (MBT), which is widely used in rubber industry.
    Additional Material: 1 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 173-182 
    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 Ansammlung von als inaktiv angenommenen „Dimeren“ und „Trimeren“ sowie der Verbrauch von aktiven Spezies mit der Reaktionszeit im säurekatalysierten Furfurylalkohol (FA)/Formaldehyd (F) System wurde durch GPC-Technik unter Anwendung eines Doppeldetektors bewiesen.Ein Reaktionsmechanismus wurde für den Kondensationsprozeß vorgeschlagen, der einige Widersprüche der bisherigen Untersuchungen erklären kann.
    Notes: Accumulation of “dimers” and “trimers” considered to be inactive and consumption of active ones with reaction time in furfuryl-alcohol (FA)/formaldehyde (F) acid catalyzed condensation system was proved by GPC technique using double detector.A reaction mechanism was proposed for the condensation process explaining some contradictions of investigations collected so far.
    Additional Material: 6 Ill.
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  • 47
    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: Dieser Artikel befaßt sich mit silylierten bzw. maleinisierten Polybutadienölen und ihren Effekten in Kieselsäure und Silicate bzw. Kreide enthaltenden Kautschukmischungen. Sie erweisen sich als wirksame Hilfsstoffe für die Substitution von Ruß durch mineralische Füllstoffe.
    Notes: This paper deals with silylated and maleated polybutadiene oils and their effects in rubber compounds containing silica(tes) resp. chalk as fillers. They are shown to be efficient aids in the substitution of oil-dependent carbon black by mineral fillers.
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 171 (1989), S. 79-89 
    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 isotherme und nichtisotherme Kristallisation von isotaktischem Polypropylen, das mit ausgewählten organischen Pigmenten gefärbt war, wurde mittels DSC untersucht. Es wurde gefunden, daß die Nukleierungsfähigkeit der Pigmente mit deren chemischem Aufbau und mit der Erniedrigung der freien Energie für den Keimbildungsprozeß verbunden ist. Die experimentellen Daten wurden mit Hilfe der bekannten Avrami-Gleichung analysiert.Blau-Pigment und Rot-Lack beschleunigen die Kristallisation von isotaktischem Polypropylen, während Orange-Pigment die Kristallisationsgeschwindigkeit etwas herabsetzt.
    Notes: The isothermal and non-isothermal crystallization of isotactic polypropylene coloured with selected organic pigments was examined by differential scanning calorimetry. It was found that the nucleating ability of pigments is connected with their chemical nature and with the reduction of the free energy for critical nucleus formation. The experimental data were analysed in terms of the well known Avrami equation.Blue pigment and Red lake are substances which accelerate the crystallization of isotactic polypropylene, while Orange pigment decreases the crystallization rate slightly.
    Additional Material: 5 Ill.
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  • 49
    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: Um bei Kationen-Austauschmembranen eine dauerhafte Selektivität für die Durchlässigkeit von einwertigen Kationen zu erzielen, wurde eine Polyethylenimin-Schicht auf der Membranoberfläche durch Säureamidbindung zwischen Polyethylenimin und den —SO2Cl-Gruppen einer Styrol-co-Divinylbenzol-Membran erzeugt. Nach der Reaktion wurden die im Inneren der Membran verbleibenden —SO2Cl-Gruppen durch Tauchen in wäßrige Natronlauge hydrolysiert.Die so gewonnenen Kationen-Austauschmembranen wurden mittels Elektrodialyse von Seewasser hinsichtlich ihrer Selektivität für die Durchlässigkeit von einwertigen Kationen, ihres elektrischen Widerstandes, ihrer Stromleistung und ihrer überfüh-rungszahlen für Natrium-Ionen untersucht. ATR-IR-Messungen auf der Membran-oberfläche belegen, daß die Shäureamidbindung gegenüber starker Hydrolyseeinwirkung stabil war.
    Notes: In order to give the monovalent cation permselectivity to the cation exchange membrane permanently, polyethyleneimine layer was formed on the membrane surface by acid-amide bond between polyethyleneimine and the —SO2Cl groups of a styrene-divinylbenzene copolymer membrane. After the reaction, the —SO2Cl groups remaining in the inner part of the membrane were hydrolyzed by immersing the membrane into an aqueous sodium hydroxide solution.The resultant cation exchange membranes were evaluated by electrodialysis of sea water from the point of view of the monovalent cation permselectivity, electric resistance of the membrane, current efficiency, and transport number of sodium ions calculated by membrane potential in connection with reduced viscosity of the various commercial polyethyleneimines, ATR-IR measurements on the membrane surface suggested that the acid-amide bond was stable for severe hydrolysis reaction.
    Additional Material: 10 Ill.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 171 (1989), S. 141-152 
    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 Epoxidgruppen eines Copolymeren, das man durch Pfropfung von 2,3-Epoxypropylmethacrylat auf isotaktisches Polypropylen erhält, wurden mit niedermolekularen Carbonsäuren umgesetzt. Die Reaktion verläuft in Gegenwart von organischen Lösungsmitteln heterogen und kann durch tertiäre Amine beschleunigt werden. Die Geschwindigkeitskonstanten der Reaktion werden mit der Dissoziationskonstanten der gebundenen Säure und mit der Art des verwendeten Beschleunigers korreliert. Die Reaktivität der polymergebundenen Epoxidgruppen ändert sich im Vergleich mit Reaktionen unter homogenen Bedingungen nicht.
    Notes: Epoxy groups on isotactic polypropylene, to which 2,3-epoxypropylmethacrylate was grafted, were reacted with low molecular carboxylic acids. The reaction proceeds under heterogeneous conditions in the presence of organic solvents and it may be catalysed by tertiary amines. The rate constants of this reaction are correlated with the dissociation constant of the bonded acid and with the character of the used catalyst. The reactivity of polymer-bonded epoxy groups is not changed when comparing with reactions performed under homogeneous conditions.
    Additional Material: 6 Ill.
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  • 51
    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 wird eine neue Methode zur Einführung von hydrophilen Polyetherseitenketten in segmentierte Polyurethane unter Verwendung eines Polypropylenoxid-Macromeren mit 1,3-Diol-Gruppen an einem Kettenende, die als Kettenverlängerer fungieren, beschrieben. In diesem Prozeß wird eine Seitenkette quantitativ und direkt in medizinische Polyurethanelastomere eingebaut. Diese Entwicklung ist auch für Biowerkstoffe in künstlichen Organen von Interesse.
    Notes: A new method of introducing a hydrophilic polyether side chain into segmented polyurethane using a polypropylene oxide macromer with 1,3-diol at one chain-end, which behaves as chain extender, is described. In this procedure, a molecular-designed side-chain is incorporated quantitatively and directly into polyurethane biomedical elastomer. The design is also of interest to biomaterials in artificial organs.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 172 (1989), S. 233-233 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 53
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 173 (1989), S. 85-100 
    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 Orientierungsmechanismus von kaltverstrecktem, teilkristallinem Polyoxymethylen wurde durch Messung der Intensität der Weitwinkel-Röntgenstreuung (WAXS) untersucht. Die Anisotropie der Proben wurde im einachsigen Zugversuch bei etwa 130°C im Temperaturbereich zwischen Glasübergangstemperatur und Schmelzpunkt erzeugt. Der Prozess der plastischen Deformation wurde für verschiedene Stadien der Verstreckung diskutiert. Die Orientierungsverteilung der Kristalllamellen wurde qualitativ charakterisiert durch die Berechnung von Polfiguren aus den WAXS Streuintensitätsdaten. Der Grad der Orientierung wurde durch die Berechnung des Orientierungsfaktors für den [100] Flächennormalenvektor der Einheitszelle beschrieben. Die Textur der eingeschnürten Proben mit hoher Orientierung wurde als Mischung von axialer und uniplanar-axialer Textur erkannt. Als mögliche Erklärung für diesen Orientierungstyp wird ein Einfluß der Probengeometrie angenommen.
    Notes: The orientation mechanism of cold-drawn, partially crystalline polyoxymethylene (ULTRAFORM) samples was studied by performing wide angle X-ray scattering (WAXS) measurements. The anisotropic samples were prepared in uniaxial tensile tests around 130°C, in a temperature range between the glass transition and the melting point. The process of the plastic deformation is discussed for different degrees of anisotropy. The orientation distribution of the crystalline lamellae was qualitatively characterized by performing pole figure intensity calculations from the measured WAXS intensities. The degree of orientation was quantitatively described by calculating the orientation factors for the [100] normal vector of the unit cell. The texture of the necked samples with high orientation degrees was a mixture of axial and uniplanar-axial textures. An explanation for the formation of this kind of orientation is proposed assuming an influence of the sample geometry on the orientation process.
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  • 54
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 173 (1989), S. 205-212 
    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: Herkömmliches Vernetzen von Polyethylen niedriger Dichte (LDPE) wurde mit Dicumylperoxid (DCP) als Vernetzer durchgeführt. DCP wurde in verschiedenen Konzentrationen mit LDPE-Schnitzeln in einem Extruder bei 135 - 145°C gemischt. Monofilamentfäden wurden bei 110°C auf einer Laborziehmaschine gezogen. Die Zugdehnungseigenschaften, der prozentuale Schrumpf und die Dichte wurden mit Zunahme der DCP-Konzentration und der Heizdauer verbessert, während jedoch die prozentuale Quellung abnahm.
    Notes: Conventional crosslinking of low density polyethylene (LDPE) was carried out using dicumyl peroxide (DCP) as crosslinking agent. DCP in various concentrations was mixed with LDPE chips in an extruder at 135 - 145°C. Monofilaments were drawn on a laboratory drawing machine at 110°C. It was found that tensile properties, percent shrinkage and density were improved with the increase in the concentration of DCP and in the heating period, whereas, however, the percent swelling decreased.
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  • 55
    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 Resultate von Untersuchungen über die chemische Wechselwirkung zwischen einigen monofunktionellen Modellverbindungen, die die Struktur und Reaktivität von wärmehärtbaren Phenol- und Harnstoff-Formaldehyd-Harzen simulieren, mit Holzkomponenten (Hemicellulosen, Cellulose und Lignin) werden dargelegt. Während Hemicellulosen deutlich dazu neigen, Kondensationsprodukte mit diesen Modellverbindungen zu ergeben, reagieren Lignine in manchen Fällen weniger leicht und abhängig davon, durch welchen Prozeß sie gewonnen worden sind, und abhängig von der Art der Modellverbindung. Cellulose reagierte wegen ihrer Kristallinität nicht unter den gegebenen Bedingungen.
    Notes: Results are presented on the chemical interactions occurring when some monofunctional model compounds simulating the structure and reactivity of thermosetting phenol- and urea-formaldehyde resins are mixed with wood components (hemicelluloses, cellulose, and lignins). Whereas hemicelluloses clearly show a propensity to give condensation products with these model compounds, lignins can react less readily in some instances depending on the delignification procedure used to isolate them and on the type of model compound. Cellulose did not react under the conditions chosen, mostly because of its crystalline character.
    Additional Material: 9 Ill.
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  • 56
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 173 (1989), S. 183-193 
    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: XPS-, SSIMS- und Wasserkontaktwinkelmessungen wurden verwendet, um den chemischen Einfluß von CF4/O2-Entladungen auf Polycarbonat (PC) aus Bisphenol A zu charakterisieren. Die durch Plasmabehandlung erzeugte Oberflächenmodifizierung kann auf der Basis der im Plasma vorhandenen aktiven Spezies, deren Konzentration durch Actinometrie bestimmt worden ist, erklärt werden.Bei kleinen Gehalten an O2 im Gas (1%) tritt eine umfassende Fluorierung der Oberfläche bedingt durch die Pfropfung von Fluorkohlenstoff-Radikalen ein. Es werden perfluorierte Inseln gebildet, wie der hohe Wert des zunehmenden Kontaktwinkels zeigt. Bei 20-80% O2 reagieren Fluoratome mit der Oberfläche und ätzen sie teilweise. Kleine Gehalte an Fluor, aber keine perfluorierten Inseln werden beobachtet. Sauerstoff trägt zum Ätzen bei und oxidiert die PC-Oberfläche. Die Sauerstoffkonzentration auf der Oberfläche nimmt mit Zunahme des O2-Gehalts im Gas zu, ebenso die Bildung von stark oxidierten Inselchen auf der Probenoberfläche, wie die dramatische Abnahme der Kontaktwinkel zeigt. Eine Verminderung der Aromatizität der Oberfläche, die mit Hilfe von XPS und SSIMS beobachtet wird, ist die Folge dieser Reaktionen.
    Notes: XPS, SSIMS and water contact angle measurements have been used to characterize the chemical effect of CF4/O2 discharges on polycarbonate (PC) made from bisphenol A. We found that the surface modification induced by plasma treatment can be clearly explained on the basis of the acitve species present in the plasma, whose concentration has been studied by actinometry.With very low amounts of O2 in the gas feed (1%) extensive fluorination of the surface occurs, due to grafting of the fluorocarbon radicals. Perfluorinated islands are formed, as shown by the high value of advancing contact angles. In the 20-80% O2 range, fluorine atoms react with the surface, partially inducing etching. Low amounts of fluorine are observed on the sample and no perfluorinated islands. Oxygen participates in etching and oxidizes the PC surface. We observed an increase of the surface concentration of oxygen with increasing the O2 amount in the gas feed and also the formation of strongly oxidized islets on the sample surface, as shown by the dramatic reduction of receding contact angles. A reduction of surface aromaticity, observed by XPS and SSIMS, is the consequence of these reactions.
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  • 57
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 173 (1989), S. 213-218 
    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 attempt was made to obtain cationic cellulose derivatives of highest possible degrees of substitution by treating dissolving grade pulps under homogeneous conditions with glycidyltrimethylammonium chloride in the solvent system dimethylacetamide/lithiumchloride. The influence of temperature, reaction time and molar ratio of the reagents was examined. A reaction time of 8 h and a temperature of 70°C have been found to be optimal. The cellulose content in solution and the molar ratio of the reagents have to be adapted to the used pulp.
    Notes: Es wurde der Versuch unternommen, durch Umsetzung von Zellstoffen mit Glycidyltrimethylammoniumchlorid im Lösungsmittelsystem Dimethylacetamid/Lithiumchlorid kationische Cellulosederivate mit möglichst hohen Substitutionsgraden zu erhalten. Hierzu wurden Temperaturabhängigkeit, Reaktionsdauer und Molverhältnis der Reaktanden untersucht. Als optimal erwies sich eine Reaktionsdauer von 8 h bei einer Reaktionstemperatur von 70°C. Der Cellulosegehalt in Lösung und das Molverhältnis der Reaktanden müssen dem verwendeten Zellstoff angepaßt werden.
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  • 58
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    New York : Wiley-Blackwell
    Biopolymers 28 (1989), S. 773-781 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A second example of insertion of a water molecule into the helical backbone of an apolar peptide is presented here and compared to a similar occurrence in a longer peptide with the same type of sequence of residues, i.e., Boc-Aib-(Ala-Leu-Aib)3-OMe. The backbone of the title compound assumes an approximate 310-helical form with three 4 → 1 hydrogen bonds. In the place of a fourth 4 → 1 hydrogen bond, a water molecule is inserted between O(1) and N(4), and acts as a bridge by forming hydrogen bonds N(4) … W(1) (2.95 Å) and W(1) … O(1) (2.81 Å). The water molecule participates in a third hydrogen bond with a neighboring peptide molecule, W(1) … O(4) (2.91 Å). The insertion of the water molecule causes the apolar peptide to mimic an amphiphilic helix. Crystals grown from ethyl acetate/petroleum ether (reported here) or from methanol/water solution are in space group P212121 with a = 12.024(4) Å, b = 15.714(6) Å, c = 21.411(7) Å, Z = 4 and dcalc = 1.124 g/cm3 for C32H58N6O9 · H2O. The overall agreement factor R is 6.3% for 2707 reflections observed with intensities 〉 3σ(F) and the resolution is 0.90 Å.
    Additional Material: 4 Ill.
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  • 59
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chemical shifts of base and H1′ protons of the single-stranded hexamers d(ATTACC) and d(GGTAAT), of the 1 : 1 mixtures of these complementary hexamers, and of the self-complementary dodecamer d(ATTACCGGTAAT) were measured at various temperatures in aqueous solution. Four different sample concentrations were used in the case of the dodecamer and of the mixture of the complementary hexamers; the individual hexamers were measured at two different DNA concentrations. Absorbance temperature profiles at five different NaCl concentrations were measured for the dodecamer in order to quantify the effect of the ionic strength on the duplex formation.Under suitable conditions of nucleotide concentration, temperature, and ionic strength, the dodecamer adopts either a B-DNA duplex or a hairpin-loop structure. Chemical shift vs temperature profiles, constructed for all samples, were used to obtain thermodynamic parameters either for the various stacking interactions in the single strands or for the duplex or the hairpin-loop formation. In the analysis of the duplex formation of the hexamers, a two-state approach appeared too simple, because systematic deviations were revealed. Therefore, a new three-state model (DUPSTAK) was developed. In order to investigate the magnitude of error arising from the use of the two-state approach in cases where the DUPSTAK model appears more appropriate, a series of test calculations was made. The magnitude of error in the enthalpy and in the entropy of duplex melting is found to depend linearly upon the actual melting temperature and not upon the individual ΔHOd and ΔSOd values.Thermodynamic analysis of the chemical shift vs temperature profiles in D2O solution (no added salt) yields an average Tmd value of 341 K (1M DNA) and ΔHOd of -121 kJ · mol-1 for the dimer/random-coil transition of the hexamer duplex d(ATTACC) · d(GGTAAT). For the duplex ⇄ random-coil transition of the 12-mer d(ATTACCGGTAAT) an average Tmd value of 336 K (1M DNA) and ΔHOd of -372 kJ · mol-1 are found. The hairpin/random-coil transition of d(ATTACCGGTAAT) is characterized by a rather large ΔHOh value, -130 kJ · mol-1, and an average Tmh value of 304 K.
    Additional Material: 9 Ill.
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  • 60
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational method is elaborated for studying the water environment around regular polynucleotide duplexes; it allows rigorous structural information on the hydration shell of DNA to be obtained. The crucial aspect of this Monte Carlo simulation is the use of periodical boundary conditions. The output data consists of local maxima of water density in the space near the DNA molecule and the properties of one- and two-membered water bridges as function of pairs of polar groups of DNA.In the present paper the results for poly(dG) · poly(dC) and poly(dG-dC) · poly(dG-dC) are presented. The differences in their hydration shells are of a purely structural nature and are caused by the symmetry of the polar groups of the polymers under study, the symmetry being reflected by the hydration shell.The homopolymer duplex hydration shell mirrors the mononucleotide repeat. The water molecules contacting the polynucleotide in the minor groove are located nearly in the plane midway between the planes of successive base pairs. One water molecule per base pair forms a water bridge facing two polar groups of bases from adjacent base pairs and on different strands making a “spine”-like structure. In contrast, the major groove hydration is stabilized exclusively by two-membered water bridges; the water molecules deepest in the groove are concentrated near the plane of the corresponding base pair.The alternating polymer is characterized by a marked dyad symmetry of the hydration shell corresponding to the axis between two successive base pairs. The minor groove hydration of the dCpdG step resembles the characteristic features of the homopolymer, but the bridge between the O2 oxygens of the other base-stacking type is formed by two water molecules. The major groove hydration is characterized by high probability of one-membered water bridges and by localization of a water molecule on the dyad axis of the dGpdC step.The found structural elements are discussed as reasonable invariants of a dynamic hydration shell.
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  • 61
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    New York : Wiley-Blackwell
    Biopolymers 28 (1989) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report dynamic light scattering measurements over a wide range of scattering vectors for fractionated samples of porcine submaxillary mucin (PSM) glycoproteins in two different solvents: 0.1M NaCl, and 6M GdnHCl. The relaxation spectrum has been successfully resolved into a slow mode corresponding to pure translational diffusion and a fast mode containing information on the relaxation times for intramolecular motion. Analysis of the slow mode permits a light scattering evaluation of the polydispersity of these high molecular weight mucin glycoprotein fractions. Determination of the longest intramolecular relaxation times τ1 shows that these are much longer for the PSM fractions in 0.1M NaCl compared to 6M GdnHCl. These data are consistent with earlier studies showing that the chain conformation is the same in both solvents, but that in 0.1M NaCl, the PSM glycoprotein undergoes a self-association process that is end-to-end in nature. Since the τ1 value is intimately related to the viscoelastic behavior of PSM solutions and gels, it is interesting to speculate that the end-to-end association process may be physiologically important.
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  • 63
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    New York : Wiley-Blackwell
    Biopolymers 28 (1989), S. 835-849 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical computations are performed of the intercalative binding to a model d(CpG)2 minihelix of 7-H pyrido[4.3C]carbazole, the precursor of the antitumor bisintercalating drug ditercalinium. The conformations of the intercalation site are generated by the AGNAS procedure (algorithm to generate nucleic acid structures) of Miller and co-workers. The ligand-nucleotide interactions and the nucleotide conformational energies are computed with the SIBFA procedures (sum of interactions between fragments ab intio computed), which use formulas of empirical origin that reproduce ab initio SCF (self-consistent field) computations. Among the candidate intercalation sites most favored energetically, one has a pattern of conformational angles related to the one determined crystallographically by Sobell et al. in a series of x-ray structural studies of small intercalator-dinucleotide monophosphate complexes. Optimal values of the unwinding angle, found in the range of -12° to -14°, are consistent with available experimental data on DNA.
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  • 64
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of concanavalin A (Con A) on the thermotropic behavior of positively charged, glycosyl-free lipids and their mixtures with zwitterionic lipids was investigated by differential scanning calorimetry.The gel to liquid-crystal phase transition enthalpy of pure dipalmitoylcholine (DPC) was found to be significantly increased in the presence of Con A (ΔH = 31.2 and 42.5 KJ mol-1 lipid in the presence and in absence of Con A, respectively). Addition of the lectin to DPC liposomes, furthermore, induces the appearance of a new phase transition centered at 320 K. These results are interpretable by a partial hydrophobic interdigitation of the lectin molecule into the liposomal bilayer.The effect of Con A on the phase behavior of three 2:1 mixtures of zwitterionic and of positively charged lipids was also investigated. Phase diagrams of the systems dipalmitoylphosphatidylcholine-dihydrosphingosine (DPPC-DHS), sphingomyelin-dipalmitoylcholine (SPM-DPC), and dimyristoylphosphatidylcholine-dipalmitoylcholine (DMPC-DPC) are presented. In lipid mixtures of limited miscibility (DPPC-DHS and SPM-DPC), Con A induces pronounced phase-separation effects. These effects are attributable to a direct hydrophobic interaction of the lectin with the liposomal bilayer and do not require the presence of specific receptor groups.The possible relationship between lectin-induced phase separations in the lipid matrix of biomembranes, and the observed changes in membrane permeability, membranal enzymatic activities, etc., is briefly discussed.
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  • 65
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional nuclear Overhauser enhancement (2D NOESY) data are reported for the polypentapeptide of elastin, poly(VPGVG), and the cyclopentadecapeptide, cyclo(VPGVG)3. In both, the repeating type II Pro2-Gly3 β-turn can be derived from the NOE data, providing confirmation of many previous studies. In addition, other through-space connectivities are detailed that also compare favorably with previously determined crystal and solution structures for cyclo(VPGVG)3. Also, near identical data for the cyclopentadecapeptide and the polypentapeptide demonstrate the cyclic conformation-linear (helical) conformational correlate relationship between the two molecules. The 2D NOESY experiment is seen to be an effective means of establishing the presence or absence of a conformational relationship between a cyclic repeating sequence and its higher molecular weight linear counterpart. This is an approach of substantial practical value when developing the conformation of sequential polypeptides and when attempting to identify the presence of the conformation of a repeating peptide sequence within a more complex primary structure.Having established the basic conformational relationship between a cyclic conformation and its linear helical counterpart, cross peaks present in the linear helical structure that are not present in the cyclic conformational correlate can provide information on the interactions between adjacent turns of the helix. In this connection, a ValγCH3 ↔ ProβCH2 interaction is reported that can be the basis for determining the number of pentamers per turn of helix once it is determined whether it is dominantly the Val1 or Val4γCH3 that is interacting with the Pro2βCH2.
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  • 66
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    New York : Wiley-Blackwell
    Biopolymers 28 (1989), S. 901-905 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Biopolymers 28 (1989), S. 965-973 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligo-DNAs are synthesized on a solid support using the 9-fluorenylmethyloxycarbonyl group as a 5′-OH base labile protection. The synthesis of the pure protected nucleotides, a relevant phosphoramidite-type strategy of coupling, and the optimization of the deprotection steps are described. This new synthetic method is an alternative to the standard protocol that avoids acidic conditions.
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  • 68
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have applied the formalism developed previously for the kinetics of domain-localized reaction [S. Mazur and M. T. Record, Jr. (1986) Biopolymers 25, 985-1008] to describe complex mechanisms of association of a protein with a specific site on a large DNA molecule also containing many nonspecific binding sites. These nonspecific sites participate in the mechanism of formation of the specific complex through competitive binding and the facilitating mechanisms of sliding and transfer. The effects of localizing the sites in a domain are represented by a simple algebraic expression, and the sequence of interactions within the domain are described by equations closely related to a conventional, homogeneous solution mechanism. We apply this formalism to examine the interplay between sliding and direct transfer in domain-localized interactions in general and in the lac repressor-lac operator interaction in particular. Experimental investigation of the effect of the molecular location of the specific site (e.g., end vs middle of the polymer chain) on the kinetics of association may allow the contributions of sliding and direct transfer to be resolved.
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  • 69
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    Biopolymers 28 (1989), S. 975-993 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrostatic potentials around DNA are obtained by solving the nonlinear Poisson-Boltzmann (PB) equation. The detailed charge distribution of the DNA and the different polarizabilities of the macromolecule and solvent are included explicitly in the calculations. The PB equation is solved using extensions of a finite difference approach applied previously to proteins. Electrical potentials and ion concentrations are compared to those obtained with simpler models. It is found that the shape of the dielectric boundary between the macromolecule and solvent has significant effects on the calculated potentials near the surface, particularly in the grooves. Sequence-specific patterns are found, the most surprising result being the existence of positive regions of potential near the bases in both the major and minor grooves. The effect of solvent and ionic atmosphere screening of phosphate-phosphate repulsions is studied, and an effective dielectric function, appropriate for molecular mechanics simulations, is derived.
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  • 70
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    Biopolymers 28 (1989), S. 1019-1030 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used Raman scattering to study the water O-H stretching modes at ∼ 3450 and ∼ 3220 cm-1 in DNA films as a function of relative humidity (r.h.). The intensity of the 3220-cm-1 band vanishes as the r.h. is decreased from 98% to around 80%, which indicates that the hydrogen-bond network of water is disrupted in the primary hydration shell (which therefore cannot have an “ice-like” structure). The number of water molecules in the primary hydration shell was determined from the intensity of the ∼ 3200-cm-1 band as about 30 water molecules per nucleotide pair. The ∼ 3400-cm-1 O-H stretch band was used for determining the total water content, and this band persists at 0% r.h., implying that 5-6 tightly bound water molecules per nucleotide pair remain. The frequency of the ∼ 3400-cm-1 O-H stretch mode is lower by 30 to 45 cm-1 in the primary hydration shell compared to free water. The water content as a function of r.h. obtained from these experiments agrees with gravimetric measurements. The disappearance of the ∼ 3200-cm-1 band and the shift of the ∼ 3400-cm-1 O-H stretch band provide a reliable way of measuring the hydration number of DNA.
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  • 71
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An estimation of the thermodynamic effects of a charged random coil, which is attached either to the N- or C-terminus of polyalanine, upon α-helix stability is attempted. A temperature-induced helix-coil transition of Ala20Lys20Phe and Lys20Ala20Phe was studied under various conditions of salt concentration and pH. By combining the results with previous ones for Ala20Glu20Phe and Glu20Ala20Phe, which have opposite electric charges to the present system [S. Ihara et al. (1982) Biopolymers 21, 131-145], the free energy of the coil to helix transition of the polyalanine block could be separated into two terms - one term for the electrostatic interaction of electric charges in the random-coil block with the α-helix dipole, and a second term for the intrinsic stability of the helix. The first term indicates the significance of the helix dipole-charge interactions, which affects the helix stability depending on the attaching side of the charged block and on the sign of the charges. This clearly shows the anisotropic stability of the α-helix. Furthermore, analysis of the dependence of these thermodynamic quantities on salt concentrations showed, assuming that the effect of the attached electric charges was symmetric (in other words, the absolute values of the electrostatic interaction terms were independent of the sign of electric charges), that the intrinsic stability of the α-helix was dependent on which side of the helix was attached to the random coil: a random coil attached to the N-terminus of the α-helix had little effect while that attached to a C-terminal significantly destabilized the helix.
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  • 72
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    Biopolymers 28 (1989), S. 1043-1058 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The velocity and orientation of T4 and λ DNA have been measured for the first 20 s during pulsed-field gel electrophoresis in order to clarify the DNA motions that occur. For a square pulse with field strength E = 10 V/cm, the velocity of λ DNA increases gradually to 10.5 μm/s in 1.0 s, declines to 8.6 μm/s, and then rises to a plateau value of 9.3 μm/s after 4 s. T4 DNA behaves similarly, but more slowly. Parallel measurements of fluorescence-detected linear dichroism show that the DNA becomes substantially aligned with its chain axis parallel to the electrophoretic field E after the pulse is applied. The alignment also shows an overshoot, an undershoot, and a plateau comparable to those seen for velocity. When the field strength increases, both the velocity and the alignment reach their peaks more quickly. For all field strengths and both molecular weights, the velocity peak occurs when the molecular center of mass has moved 0.3 to 0.5 L, where L is the chain contour length. A qualitative model is provided.
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  • 73
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    Biopolymers 28 (1989), S. 1059-1095 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the context of dynamic Monte Carlo simulations on a model protein confined to a tetrahedral lattice, the interplay of protein size and tertiary structure, and the requirements for an all-or-none transition to a unique native state, are investigated. Small model proteins having a primary sequence consisting of a central bend neutral region flanked by two tails having an alternating hydrophobic/hydrophilic pattern of residues are seen to undergo a continuous transition to a β-hairpin collapsed state. On increasing the length of the tails, the β-hairpin structural motif is found to be in equilibrium with a four-member β-barrel. Further increase of the tail length results in the shift of the structural equilibrium to the four-member β-barrel. The random coil to β-barrel transition is of an all-or-none character, but while the central turn is always the desired native bend, the location of the turns involving the two external strands is variable. That is, β-barrels having the external stands that are two residues out of register are also observed in the transition region. Introduction into the primary sequence of two additional regions that are at the very least neutral toward turn formation produces an all-or-none transition to the unique, native, four-member β-barrel. Various factors that can augment the stability of the native conformation are explored. Overall, these folding simulations strongly indicate that the general rules of globular protein folding are rather robust - namely, one requires a general pattern of hydrophobic/hydrophilic residues that allow the protein to have a welldefined interior and exterior and the presence of regions in the amino acid sequence that at the very least are locally indifferent to turn formation. Since no site-specific interactions between hydrophobic and hydrophilic residues are required to produce a unique four-member β-barrel, these simulations strongly suggest that site specificity is involved in structural fine-tuning.
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  • 74
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    New York : Wiley-Blackwell
    Biopolymers 28 (1989) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequence-specific photomodification of oligodeoxynucleotide pAGAGTATTGACTTA (“a target”) has been carried out with the aid of complementary fluorescent probes. Such a probe consisted of oligodeoxynucleotide pAATACTCT and a chromophore group attached to its 5′ end. Three different derivatives of ethidium bromide were used as a chromophore. The photomodification was induced by nitrogen laser radiation (337 nm, 15 MW /cm2). The irradiation induces the following photodamages: target cleavage at the specific binding site with a cutting off of the 8-mer from its 5′ end (yield up to 12%), formation of specific covalent adduct target-probe with a yield of 20-70%, and piperidine-sensitive target modifications with a 7-27% yield (for different chromophores). The total yield of specific photodamages of all kinds is 50-80%. The target cleavage and generation of piperidine-sensitive modifications are optically nonlinear processes. Piperidine treatment of the irradiated samples led to specific cleavage of the target with the yield up to 40%. All kinds of observed modifications are not influenced by high concentrations of free radical scavengers: 1.3M tBuOH and 10 mM cystamine. The pattern of cleavage indicates that the most probable position of the chromophore is between T8 and G9 of the target, i.e., the chromophore stacks on top of the last A · T base pair of the duplex. The aggregate of evidence is in agreement with the mechanism of nonlinear photomodification (the cleavage and generation of piperidine-sensitive modifications) based on the transfer of two-photon excitation energy from the chromophore to the target.
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  • 76
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    Biopolymers 28 (1989), S. 1179-1186 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The physiological importance of heparin is due to its strong interaction with bivalent counterions, especially Ca2+. A diffusional approach of this property is presented in this article: the observable is the self-diffusion coefficient of the counterions, as a function of the ratio of the polyelectrolyte over the added salt concentrations. All the results are in agreement with a simple “quasi-chemical model” in which two different states are assumed for the counterions: “free” or “bound.” The proportions of these two types of ions are calculated according to the distribution function of the counterions around the polyion. We assume that those of counterions located at a distance closer than a, the characteristic distance, are bound; the others are free. The ionic distribution function is evaluated by a numerical integration of a cell model Poisson-Boltzmann equation. Finally, this model leads to a very good agreement with the experimental results, if the radius of heparin polyion is assumed to be 6 and 10 Å.
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  • 77
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    Biopolymers 28 (1989), S. 1189-1193 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The calculated spectrum of longitudinal compressional waves on DNA polymer chains is shown to be in excellent agreement with recently performed inelastic neutron scattering measurements in hydrated, oriented DNA crystals. This opens up a previously unexplored frequency regime of DNA science and establishes the validity of the phonon extended wave description of DNA elementary excitations in this region.
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  • 78
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    Biopolymers 28 (1989), S. 1259-1269 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthetic peptide Gly-L-Ala-L-Phe (C14H19N3O4 · 2H2O; GAF) crystallizes in the monoclinic space group P21, with a = 5.879(1), b = 7.966(1), c = 17.754(2) Å, β = 95.14(2)°, Dx = 1.321 g cm-3, and Z = 2. The crystal structure was solved by direct methods using the program SHELXS-86 and refined to an R value of 0.031 for 1425 reflections (〉 3σ). The tripeptide exists as a zwitterion in the crystal and assumes a near α-helical backbone conformation with the following torsion angles: ψ1 = -147.8°; φ2, ψ2 = -71.2°, -33.4°; φ3 ψ3 = -78.3°, -43.3°. In this structure, one water molecule bridges the COO- and NH3+ terminii to complete a turn of an α-helix and another water molecule participates in head-to-tail intermolecular hydrogen bonding, so that the end result is a column of molecules that looks like an α-helix. Thus, the two water molecules of crystallization play a major role in stabilizing the near α-helical conformation of each tripeptide molecule and in elongating the helix throughout the crystal. An analysis of all protein sequences around regions containing a GAF fragment by Chou-Fasman's secondary structure prediction method showed that those regions are likely to assume an α-helical conformation with twice the probability they are likely to adopt a β-sheet conformation. It is conceivable that a GAF fragment may be a good part of the nucleation site for forming α-helical fragments in a polypeptide, with the aqueous medium playing a crucial role in maintaining such transient species.
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  • 79
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    Biopolymers 28 (1989), S. 1271-1285 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution conformation of [D-Ala2]-leucine enkephalin in its zwitterionic form in DMSO-d6 has been monitored by one- and two-dimensional proton magnetic resonance spectroscopy at 500 MHz. The resonances from the labile amide protons and the nonlabile protons have been assigned from the shift correlated spectroscopy. The chemical shift of the amide and C-α protons are found to vary with temperature but in opposite directions, except the C-α proton of the terminal tyrosine residue. This behaviour has been explained by the shifting of equilibrium between the zwitterionic and neutral forms of the [D-Ala2]-leucine enkephalin and probably conformational changes accompanying temperature variation. The low values of the temperature coefficients of leucine and glycine amide protons indicate that these protons are either intramolecularly hydrogen bonded or solvent shielded. The observation of sequential cross peaks in the nuclear Overhauser effect spectra obtained at various mixing times, τm (200-900 ms), indicate an extended backbone, which does not corroborate with the presence of a folded structure, i.e., β-bend type structure. The estimate of interproton distances in conjunction with the low values of temperature coefficients of the leucine and glycine amide protons and vicinal coupling constants 3JHN-CαH have been rationalized by the predominance of two γ-bends in the backbone conformation of [D-Ala2]-leucine enkephalin. The γ-bend around the D-Ala residue has Φ = 80° and ψ = 270°, while the one around Phe it has Φ = 285° and ψ = 90°.
    Additional Material: 9 Ill.
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  • 80
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    Biopolymers 28 (1989), S. 1287-1294 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The peptide N-Boc-L-Gly-dehydro-Phe-NHCH3 was synthesized by the combination of N-Boc-L-Gly-dehydro-Phe azlactone and methylamine. The peptide crystallizes in orthorhombic space group P212121 with a = 5.679(2) Å, b = 16.423(9) Å, c = 19.198(10) Å, V = 1791(2) Å3, Z = 4, dm = 1.212(5) Mg m-3, dc = 1.237(1) Mg m-3. The structure was determined by direct methods using SHELXS 86. The structure was refined by full-matrix least squares procedure to an R value of 0.049 for 1509 observed reflections. The molecular dimensions are, in general, in good agreement with the standard values. The bond angle Cα-Cβ-Cγ in the dehydro-Phe residue is 133.6(5)°. The peptide backbone torsion angles are θ1 = -171.4(4)°, ω0 = 178.2(4)°, φ1 = -57.2(6)°, ψ1 = 141.2(4)°, ω1 = -174.4(4)°, φ2 = 71.5(6)°, ψ2 = 7.2(6)°, and ω2 = -179.8(5)°. These values show that the backbone adopts the β-bend type II conformation. The Boc group has a trans-trans conformation. The side-chain torsion angles in dehydro-Phe are χ2 = 1.6(9)°, χ22,1 = 0.5(9)°, and χ22,2 = 179.8(6)°. The plane of C2α-C2β-C2γ is rotated with respect to the plane of the phenyl ring at 0.5(6)°, which indicates that the atoms of the side chain of the dehydro-Phe residue are essentially coplanar. As a result of the β-bend in the structure, an intramolecular hydrogen bond is formed between the oxygen of the ith residue and the NH of the (i + 3)th residue at a distance of 2.940(5) Å. The crystal structure is stabilized by a network of hydrogen bonds and van der Waals interactions.
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  • 81
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    Biopolymers 28 (1989) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 82
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    Biopolymers 28 (1989), S. 1397-1401 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Effect of glycine and NaCl on the thermal denaturation of β-lactoglobulin was examined. The results showed that the transition temperature of β-lactoglobulin is increased by the addition of glycine and NaCl at 0.5 and 1M. This observed stabilization by glycine and NaCl was interpreted in terms of their favorable interactions with the native state of β-lactoglobulin and unfavorable interactions with the denatured state.
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  • 83
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of ZI- and ZII- form RNA and DNA oligonucleotides were energy minimized in vacuum using the AMBER molecular mechanics force field. Alternating C-G sequences were studied containing either unmodified nucleotides, 8-bromoguanosine in place of all guanosine residues, 5-bromocytidine in place of all cytidine residues, or all modified residues. Some molecules were also energy minimized in the presence of H2O and cations. Free energy perturbation calculations were done in which G8 and C5 hydrogen atoms in one or two residues of Z-form RNAs and DNAs were replaced in a stepwise manner by bromines. Bromination had little effect on the structures of the energy-minimized molecules. Both the minimized molecular energies and the results of the perturbation calculations indicate that bromination of guanosine at C8 will stabilize the Z forms of RNA and DNA relative to the nonbrominated Z form, while bromination of cytidine at C5 stabilizes Z-DNA and destabilizes Z-RNA. These results are in agreement with experimental data. The destabilizing effect of br5C in Z-RNAs is apparently due to an unfavorable interaction between the negatively charged C5 bromine atom and the guanosine hydroxyl group. The vacuum-minimized energies of the ZII- form oligonucleotides are lower than those of the corresponding ZI- form molecules for both RNA and DNA. Previous x-ray diffraction, nmr, and molecular mechanics studies indicate that hydration effects may favor the ZI- conformation over the ZII- form in DNA. Molecular mechanics calculations show that the ZII-ZI energy differences for the RNAs are greater than three times those obtained for the DNAs. This is due to structurally reinforcing hydrogen-bonding interactions involving the hydroxyl groups in the ZII form, especially between the guanosine hydroxyl hydrogen atom and the 3′-adjacent phosphate oxygen. In addition, the cytidine hydroxyl oxygen forms a hydrogen bond with the 5′-adjacent guanosine amino group in the ZII- form molecule. Both of these interactions are less likely in the ZI- form molecule: the former due to the orientation of the GpC phosphate away from the guanosine ribose in the ZI form, and the latter apparently due to competitive hydrogen bonding of the cytidine 2′-hydroxyl hydrogen with the cytosine carbonyl oxygen in the ZI form. The hydrogen-bonding interaction between the cytidine hydroxyl oxygen and the 5′-adjacent guanosine amino group in Z-RNA twists the amino group out of the plane of the base. This may be responsible for differences in the CD and Raman spectra of Z-RNA and Z-DNA.
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  • 84
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    Biopolymers 28 (1989) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper reports the use of dynamic light scattering to investigate the concentration dependence of the diffusion coefficient for bovine pancreatic trypsin inhibitor (BPTI). BPTI is a small molecular weight protein (6511 Da) that has been the subject of numerous experimental studies. In addition to addressing questions that remain in the literature concerning the aggregation behavior of BPTI, we show that dynamic light scattering can be practically applied to proteins as small as BPTI, and that it can provide a useful means of parameterizing the solution behavior for proteins. We obtained values for the apparent diffusion coefficient of BPTI as a function of concentration over a range of pH values from 2.59 to 9.92 at an ionic strength of 0.3M, and over a range of ionic strength values from 0.1 to 0.5M at a pH of 7.0. The concentration dependence is linear for nearly all the conditions examined, even up to concentrations as high as 65 mg/mL. The average diffusion coefficient obtained at infinite dilution is 14.4 ± 0.2 × 10-7 cm2/s. This value agrees with that expected for a BPTI monomer hydrated with less than a monolayer of water. We used the theories of Felderhof, of Batchelor, and of Phillies, along with the DLVO theory to interpret the concentration dependence of the apparent diffusion coefficient. The variations observed with pH and ionic strength can be primarily attributed to screened coulombic interactions. In addition, there is an attractive interaction that is slightly stronger than the repulsive coulombic one, and that is essentially independent of pH and ionic strength. The attractive interactions appear to arise from nonspecific van der Waals interactions and do not lead to the formation of stable aggregates of BPTI.
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  • 86
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    Biopolymers 28 (1989), S. ii 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Biopolymers 28 (1989), S. 1-14 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preferred conformation and types of molecular folding are some of the topics that can be addressed by structure analysis using x-ray diffraction of single crystals. The conformations of small linear peptide molecules with 2-6 residues are affected by polarity of solvent, presence of water molecules, hydrogen bonding with neighboring molecules, and other packing forces. Larger peptides, both cyclic and linear, have many intramolecular hydrogen bonds, the effect of which outweighs any intermolecular attractions. Numerous polymorphs of decapeptides grown from a variety of solvents, with different cocrystallized solvents, show a constant conformation for each peptide.Large conformational changes occur, however, upon complexation with metal ions. A new form of free valinomycin grown from DMSO exhibits near three-fold symmetry with only three intramolecular hydrogen bonds. The peptide is in the form of a shallow bowl with a hydrophobic exterior. Near the bottom of the interior of the bowl are three carbonyl oxygens, spaced and directed so that they are in position to form three ligands to a K+, e.g., complexation can be completed by the three lobes containing the β-bends closing over and encapsulating the K+ ion. In another example, free antamanide and the biologically inactive perhydro analogue, in which four phenyl groups become cyclic hexyl groups, have essentially the same folding of backbone and side chains. The conformation changes drastically upon complexation with Li+ or Na+. However, the metal ion complex of natural antamanide has a hydrophobic globlar form whereas the metal ion complex of the inactive perhydro analogue has a polar band around the middle. The structure results indicate that the antamanide molecule is in a complexed form during its biological activity.Single crystal x-ray diffraction structure analyses have identified the manner in which water molecules are essential to creating minipolar areas on apolar helices. Completely apolar peptides, such as membrane-active peptides, can acquire amphiphilic character by insertion of a water molecule into the helical backbone of Boc-Aib-Ala-Leu-Aib-Ala-Leu-Aib-Ala-Leu-Aib-OMe, for example. The C-terminal half assumes an α-helix conformation, whereas the N-terminal half is distorted by an insertion of a water molecule W(1) between N(Ala5) and O(Ala2), forming and hydrogen bonds N(5)H ⃛ W(1) and W(1) ⃛ O(2). The distortion of the helix exposes C=O (Aib1) and C=O (Aib4) to the outside environment with the consequence of attracting additional water molecules. The leucyl side chains are on the other side of the molecule. Thus a helix with an apolar sequence can mimic an amphiphilic helix.
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  • 88
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Neurokinins and their receptors are a complex system consisting of at least three endogenous agents - substance P (SP), neurokinin A (NKA), and neurokinin B (NKB) - and their corresponding receptor types, respectively, NK-1, NK-2, and NK-3. Investigations on receptors have been made using sensitive and fairly selective pharmacological preparations (the dog carotid artery for the NK-1, the rabbit pulmonary artery devoid of endothelium for the NK-2, and the rat portal vein for the NK-3 receptor), and some natural peptides of mammalian and nonmammalian origin. Because of the nonselectivity of the natural peptides, analogues of the neurokinins have been found that act on one receptor only and show therefore high selectivity. The selective agonists [Sar9, Met(O2)11]SP, [Nle10]NKA (4-10), and [MePhe7]-NKB have been used successfully for (a) characterizing the three neurokinin receptors, (b) identifying isolated organs whose responses to neurokinins depend on the activation of a single (monoreceptor systems) or of more than one (multireceptor systems) receptor, and (c) elucidating some of the physiological function of the three receptor types. It is suggested that NK-1 mediate peripheral vasodilatation and exocrine secretions, NK-2 stimulate bronchial muscles and facilitate the release of catecholamines, and NK-3 promote the release of acetylcholine in peripheral organs.
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  • 89
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of replacing L-pyroglutamic acid with the cyclopropane analogue 2,3-methanopyroglutamic acid (2,3-MeGlp) on conformation and enzymatic stability have been investigated in 2,3-MeGlp-NHMe and the novel thyrotropin releasing hormone (TRH) analogue [2,3-MeGlp1]-TRH by x-ray diffraction and nmr. While 2,3-MeGlp-NHMe adopts a folded conformation (small ψ angle) in the solid state, several conformations are available to the molecule in solution. 1H-nmr of the diastereomeric mixture [(±)-2,3-MeGlp1]-TRH indicates a close orientation of the pyrrolidone and imidazole rings. The 2,3-MeGlp-His amide bond is considerably more stable to pyroglutamate aminopeptidase than the Glp-His bond in TRH.
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  • 90
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    Biopolymers 28 (1989), S. 149-160 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In view of the chemical and structural interest of cyclopeptides bearing an electron withdrawing substituent directly bonded at the amide nitrogen atom, the two N-p-toluensulfonyl (N-tosyl) derivatives cyclo[-Phe(Tos)-D-Phe-] (I) and cyclo[-Phe(Tos)-D-Pro-] (II) have been synthesized and their stereochemistry defined. The molecular structure of I, as determined by x-ray diffraction analysis, is reported together with 1H-nmr parameters indicating the preferred rotameric conformation in chloroform solution. The N-tosyl group alters the geometry of the cyclodipeptide ring by lengthening both the N—C bonds departing from the tosylated nitrogen and reducing the corresponding ring angle. The 6-membered peptide ring adopts an unusual “sofa” conformation with the Tos-Phe Cα atom deviating 0.230(3) Å out of the mean plane of the other five ring atoms. One of the two S—O bonds forms a planar system that involves the tosylated nitrogen and the corresponding amide carbonyl. In the crystal, both the benzylic side chains are folded over the heterocyclic ring, whereas in chloroform solution, the benzylic side chain of the D-Phe prefers an extended conformation.
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  • 91
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal-state molecular structures of five linear Ac3c homo-oligopeptides to the tetramer were determined by x-ray diffraction. The oligomers are H-(Ac3c)2-OMe, Fmoc-(Ac3c)2-OMe MeOH, Ac-(Ac3c)2-OMe, pBrBz-(Ac3c)3-OMe · H2O, and t-Boc-(Ac3c)4-OMe · 2H2O. The results indicate the propensity of the tri- and tetrapeptides to fold into type I β-bends and distorted 310-helices, respectively, in partial contrast to Aib, Ac5c, and Ac6c homo-peptides of comparable main-chain length, where regular type III β-bends and 310-helical structures were found. When the influence of the constraints produced by the intramolecular H bonds of the C10-type is absent, other less common structural features may be observed. The average geometry of the cyclopropyl group of the Ac3c residue is found to be asymmetric and the N—Cα—C′ bond angle significantly expanded from the regular tetrahedral value.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of Boc-(L-Val-D-Val)4-OMe has been determined by x-ray single-crystal diffraction analysis. The octapeptide crystallizes in the trigonal system, space group P3221 with a = b = 12.760 Å, c = 63.190 Å and Z = 6. The independent unit is represented by one octapeptide chain. The structure has been solved by direct methods and it was anisotropically refined by least-squares procedures to a final R value of 0.08 for the 3018 “observed” reflections. One molecule of water was also located in the unit cell. Two octapeptide chains, related by a crystallographic binary axis, wind up around each other giving rise to a double-stranded left-handed antiparallel ↑↓ β5.6-helix. The dimer, stabilized by 14 interstrand N—H⃛O=C hydrogen bonds, can be regarded as a cylinder with an hydrophilic inner core represented by the peptide units and an hydrophobic exterior of isopropyl groups. The inner diameter of the cylinder is 5.1 Å.
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  • 93
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    Biopolymers 28 (1989), S. 225-246 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The major immunodominant region of the coating protein of Plasmodium falciparum sporozoites contains multiple tandem copies of the sequence Asn-Ala-Asn-Pro (NANP). Current efforts for the development of an antisporozoite vaccine are focused on the synthesis of polypeptides reproducing part of the circumsporozoite protein repeat sequence and, in an attempt to relate conformational properties and biological response, 1H-nmr one- and two-dimensional studies of the synthetic models (NANP)2NA and (NANP)6 were carried out in water and water/methanol mixtures, at 400 and 500 MHz. In water, (NANP)6 undergoes fast conformational averaging. At variance, in water/methanol, the molecule appears to adopt an extensive structure, but detailed analysis is impaired by high spectral degeneracy. Based on the results obtained with (NANP)2NA and from preliminary expermints in water/trifluoroethanol, an interpretation is suggested for the (NANP)6 data in water/methanol in terms of a mixed sequence of βI-turns and half-turns (or/and γI-turns) around the positions Ni-1-Pi-Ni+1.
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  • 94
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    Biopolymers 28 (1989) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 95
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamics of unfolding of lysozyme cross-linked between Glu 35 and Trp 108 were studied in solutions of various concentrations of 1-propanol (1-PrOH) at pH 3.7 by means of scanning microcalorimetry. The transition temperature for the cross-linked lysozyme increases by 17-19°C due to cross-linking at every concentration of 1-PrOH. This corresponds to the increase in the unfolding Gibbs free energy of about 28 kJ · mol-1, which is independent of the concentration of 1-PrOH. It was found that the unfolding enthalpy of cross-linked lysozyme is only slightly larger than that of intact one, and the unfolding entropy of the cross-linked one is nearly equal to that of the intact one, if both are compared at the same temperature. The stabilization mechanism for the cross-linked lysozyme is discussed on the basis of these calorimetric data.
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  • 96
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    Biopolymers 28 (1989), S. 1097-1113 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of the equilibrium conformational transition from the denatured state to a four-member α-helical bundle was studied employing a dynamic Monte Carlo algorithm in which the model protein chain was confined to a tetrahedral lattice. The model chain was allowed to hunt over all phase space, the target native state was not assumed a priori, and no site-specific interactions were introduced. The exterior vs the interior part of the protein is distinguished by the pattern of hydrophilic and hydrophobic interactions encoded into the primary sequence. The importance of a statistical preference for forming bends, as a function of bend location in the primary sequence, and helical wheel type cooperative interactions were examined, and the necessary conditions for collapse of the chain to the unique native structure were investigated. It was found that an amphipathic pattern of hydrophobic/hydrophilic interactions along with a statistical preference of the central residues for bend formation are sufficient to obtain the four-helix bundle. The transition to the native state has an all-or-none character.
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  • 97
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    Biopolymers 28 (1989), S. 1115-1127 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complete assignment of resonances in the proton nmr spectrum of the 1-34 amino acid fragment of human parathyroid hormone [hPTH(1-34)], determined using a combination of one- and two-dimensional nmr techniques at 500 MHz, is described. In particular, homonuclear Hartmann-Hahn experiments, recorded in H2O and D2O, are used to resolve ambiguities in the connectivities between the highly overlapped resonances in the aliphatic region of the spectrum. One-dimensional multiple quantum filtering experiments are used to identify serine and phenylalanine spin systems. Analyses of the through-bond and through-space connectivities in the αH-NH fingerprint regions of the correlated spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) spectra lead to the assignment of resonances to specific amino acid residues in the polypeptide. Examination of the observed NOE cross peaks indicates that hPTH(1-34) has no detectable secondary structural elements in aqueous solution.
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  • 98
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    Biopolymers 28 (1989), S. 1149-1177 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional nmr data on a bulge-containing oligodeoxyribonucleotide, 5′dGATGGGCAG · dCTGACCCATC, and a regular oligomer of similar sequence, 5′dGATGGCAG · dCTGCCATC, are presented. The nonexchangeable protons are assigned from sequential nuclear Overhauser effect spectroscopy (NOESY) connectivities. The two-dimensional NOE (NOESY) and correlated (COSY) spectra of the bulge-containing oligomer are compared to those of the perfect 8-mer. Experimental proton-proton distances are determined from NOESY spectra acquired with mixing times of 100, 150, and 200 ms, using comparable distances in the B-DNA region of the molecule as a calibration. With this approach, measured distances do not depend systematically on mixing time. Energy minimization techniques are used to calculate a three-dimensional structure for the bulge-containing oligomer in agreement with the nmr data. The helix is of the B family, with the extra adenine stacked into the helix, and the helix axis is bent by 20°.
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  • 99
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    Biopolymers 28 (1989), S. 1195-1222 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A build-up technique has been devised that permits prediction of DNA structure form sequence. No experimental information is employed other than the force field parameters. This strategy for dealing with the multiple minimum problem requires a supercomputer to make the necessary global searches. The number of energy minimization trials that were made for each of the 16 deoxydinucleoside monophosphate conformational building blocks of DNA was 1944. As a test case, the minimum energy conformations of d(GpC) and d(CpG) to 5.5 kcal/mole were then combined to generate energy-minimized structures for d(CpGpC). The number of trials that were made for d(CpGpC) was 3752. Minima for this single-stranded trimer to 15 kcal/mole were then employed to search for minimum energy conformations of the duplex d(CpGpC) · d(GpCpG). The number of starting conformations that were utilized at this stage was 1514. The lowest energy duplex had a Z-II-DNA conformation, followed by a B-DNA form at 1.2 kcal/mole. The A- and Z-I-forms as well as many novel Watson-Crick base-paired structures were found at higher energy. Finally, energy-minimized structures of d(CG)6 in Z-II and B-DNA conformations were computed using torsion angles from the analogous duplex trimer minima.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 28 (1989), S. 1235-1246 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclic octapeptides having alternating Sar and hydrophobic amino acid sequences, such as cyclo[Lys(Z)-Sar-Leu-Sar-Leu-Sar-Leu-Sar] (C8KL), cyclo[Glu(OMe)-Sar-Lys(Z)-Sar-Leu-Sar-Leu-Sar] (C8KE), and cyclo[Lys(Suc)-Sar-Leu-Sar-Leu-Sar-Leu-Sar][C8K(Suc)L, Suc represents succinic acid], were synthesized. These cyclic octapeptides formed a complex selectively with Ca2+. Upon complexation, trans peptide bonds of Sar residues were isomerized to cis peptide bonds. C8KL and C8KE showed very similar characteristics of Ca2+ binding, extraction of Ca2- from an aqueous solution to a chloroform solution, and Ca2+ transport through a liquid chloroform membrane. C8KL transported Ca2+ across the lipid bilayer membrane above the phase-transition temperature, while C8KE and C8K(Suc)L did not. Therefore, the transport of Ca2+ through the lipid bilayer membrane is very sensitive to the hydrophobicity of the carrier molecule.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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