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  • 1990-1994  (9,791)
  • 1991  (9,791)
  • Chemistry  (9,599)
  • Chemical Engineering  (643)
  • Genetics  (192)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 60 (1991), S. 173-182 
    ISSN: 1570-7458
    Keywords: Genetics ; evolution ; host adaptation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract When populations are exposed to different environments, evolutionary processes can lead either to genetically differentiated strains or to the appearance of increased generalism at the individual level. For evolution to occur, genetic variability in performance in different environments is required. Here, intraspecific genetic variation across environments was estimated in the flour beetle Tribolium castaneum (Herbst) by comparing the responses of two strains of T. castaneum to different flour types. Replicated groups from each strain were allowed to develop on either the standard whole wheat medium or on one of four novel flours (wheat, rice, corn and oat). In several of the novel flours, clear differences in mean development time or population size of one or both strains were seen relative to performance in the standard medium. Moreover, the strains differed significantly in their phenotypic responses to the flours. One strain did particularly poorly on oat flour. Reduced oviposition, reduced larval survivorship and increased larval cannibalism were examined as possible causes of the low productivity on oat flour. These three factors accounted for about 70% of the reduction in population size when this strain oviposited and developed in oat flour. The difference between these two outbred strains in response to these five flours suggests that genetic variation in resource use is present within T. castaneum and may also be present within strains and natural populations in grain storage facilities. Such variation would permit an evolutionary response to selection in multiple environments (flours). This process has agricultural implications when several types of grain are stored in a single location because it could eventually lead to the evolution of highly generalized populations of T. castaneum, an important pest of stored products.
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  • 2
    ISSN: 1572-8773
    Keywords: Iron transport ; Siderophores ; Pseudomonas putida ; Genetics ; Receptors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Root-colonizingPseudomonas putida WCS358 enhances growth of potato in part by producing under iron-limiting conditions a yellow-green, fluorescent siderophore designated pseudobactin 358. This siderophore efficiently complexes iron(III) in the rhizosphere, making it less available to certain endemic microorganisms, including phytopathogens, thus inhibiting their growth. At least 15 genes distributed over five gene clusters are required for the biosynthesis of pseudobactin 358. High-affinity iron(III) transport in strain WCS358 is initiated by an 86-kDa outer membrane receptor protein (PupA) which appears to be specific for ferric pseudobactin 358. PupA shares strong similarity with TonB-dependent receptor proteins ofEscherichia coli, which suggests a TonB-like protein in strain WCS358 is required for iron(III) transport. Strain WCS358 possesses a second uptake system for ferric pseudobactin 358 and structurally diverse ferric siderophores produced by other microorganisms. A second receptor gene (pupB) responsible for iron transport from pseudobactin BN7 or pseudobactin BN8 has been identified. The production of this and certain other ferric siderophore receptor proteins requires that strain WCS358 be grown in the presence of these siderophores. An apparent regulatory gene required for the expression ofpupB is located adjacent topupB. Two positive regulatory genes have been identified which can independently activate, under low-iron(III) conditions, transcription of genes coding for the biosynthesis of pseudobactin 358.
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  • 3
    ISSN: 1437-160X
    Keywords: Immunoglobulin allotypes ; Systemic lupus erythematosus ; Genetics ; Gm ; Km ; HLA-antigens ; Autoantibodies ; Clinical symptoms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Immunoglobulin heavy chain (G1m, G2m, G3m, A2m) and kappa light chain (Km) allotype and phenotype frequencies of 323 central European Caucasian patients with systemic lupus erythematosus (SLE) were examined and correlated with various genetic, serologic and clinical markers of SLE. No significant associations were found between immunoglobulin allotypes or phenotypes and all 20 parameters tested (nephritis, vasculitis, arthralgias, photosensitivity, discoid lesions, central nervous system disease, Raynaud's phenomenon, sex, anti-Ro, anti-La, anti-nRNP, HLA-DR1-DR7, HLA phenotypes B8-DR3, B7-DR2). It could therefore be assumed that Gm, A2m and Km allotypes were not associated with HLA-antigens and had no influence on the serologic and clinical expression of SLE.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Annals of hematology 62 (1991), S. 188-189 
    ISSN: 1432-0584
    Keywords: Hemochromatosis ; Pyruvate kinase deficiency ; Hereditary anemia ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Hemochromatosis has been reported in several patients with chronic hemolytic anemia due to pyruvate kinase deficiency. We describe here a further patient with such an association and review the literature on the subject. We hypothesize that iron overload may occur in patients with pyruvate kinase deficiency who are also carriers of the hereditary hemochromatosis gene.
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  • 5
    ISSN: 1432-0428
    Keywords: Genetics ; diabetes mellitus ; restriction fragment length polymorphism ; glucose-transport ; familial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Patients with Type 2 (non-insulin-dependent) diabetes mellitus and a strong family history of the disease may represent a sub-group where genetic factors play a pree-minent role in transmission of the disease. A defect in the liver/islet cell glucose transporter (GluT 2) could explain many of the pathophysiological features of the disease. In order to test the hypothesis that genetic variation at the GluT 2 locus contributes genetic susceptibility to Type 2 diabetes, 60 unrelated Caucasian diabetic patients with at least one affected sibling were genotyped for a Taq 1 restriction fragment length polymorphism marker. Hybridisation with a cDNA GluT 2 probe identified two alleles of sizes 13 kilobase (T1) and 19 kilobase (T2). The allele frequencies in the diabetic group with a family history were significantly different from those in a racially-matched control population of 122 subjects with no personal or family history of the disease (diabetic patients T1=0.96, T2=0.04, control subjects T1=0.89, T2=0.11, p〈 0.03). However, when the study was repeated with 54 diabetic patients with indeterminate family history, statistical significance was not reached although the allele frequencies showed a similar trend. The findings of this study support the hypothesis that a genetic variant of the liver/islet cell glucose transporter may contribute to familial susceptibility in Type 2 diabetes.
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  • 6
    ISSN: 1432-0428
    Keywords: Genetics ; Type 1 (insulin-dependent) diabetes mellitus ; Type 2 (non-insulin-dependent) diabetes mellitus ; HLA ; haptoglobin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Epidemiologic data suggest that having a parent with Type 2 (non-insulin-dependent) diabetes mellitus increases the risk for Type 1 (insulin-dependent) diabetes in siblings of a Type 1 diabetes proband. This increase in risk is consistent with a shared genetic susceptibility between Type 1 diabetes and Type 2 diabetes. We contrast genetic risk factors in three sets of families, consisting of (1) a single Type 1 diabetic child (proband) and non-diabetic parents, (2) multiple Type 1 diabetic siblings and non-diabetic parents, and (3) at least one Type 1 diabetic child and at least one Type 2 diabetic parent. Previous studies have demonstrated that HLA region genes, which elevate the risk in Type 1 diabetes, have no significant effect with respect to the risk for developing Type 2 diabetes. An earlier report cited a contribution by the haptoglobin locus to genetic susceptibility for Type 2 diabetes. We provide evidence that a high risk HLA antigen (HLA-DR3) is decreased to a greater extent in Type 1 patients with a Type 2 parent than in Type 1 patients in which the parents are not diabetic. The role of HLA-DR4 is maintained in these families, with an unexpectedly significant increased rate of transmission of the HLA-DR4 allele from Type 2 parent to Type 1 offspring. The role of haptoglobin in these families does not appear to be important, either with respect to association with diabetes or with respect to linkage with a secondary susceptibility locus. These results indicate that families with a Type 2 parent and Type 1 child, heavily determined by HLA-DR4 linked factors, may represent a homogeneous subset of diabetes susceptibility.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Oecologia 86 (1991), S. 243-250 
    ISSN: 1432-1939
    Keywords: Daphnia ; Life-history ; Genetics ; Variation ; Maturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Life-history traits of 101 clones from two populations of Daphnia magna were measured under controlled environmental conditions in the laboratory. Some individuals had four juvenile instars, others had five. This depended on their length at birth and on the population they came from. Females in the group with five juvenile instars were smaller at birth but larger and older at maturity than those with four juvenile instars. Within groups of females with equal numbers of preadult instars (instar groups) age and size at maturity increased with size at birth. This relationship differed significantly among instar groups for both age and size at maturity. Significant differences in age and size at maturity between two populations became non-significant when size at birth was used as a covariable in AN-COVA. Within populations, size at birth depended on the clone and on the parity of the clutch. First-clutch offspring were considerably smaller than those from later clutches. The results suggest that variability in life-history traits is common within and between clones, but that most of this variation can be accounted for by size at birth and the number of pre-adult instars.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 104 (1991), S. 17-21 
    ISSN: 1432-2072
    Keywords: MK-801 ; Phencyclidine ; Ketamine ; CGP 39551 ; CGS 19755 ; NPC 12626 ; Locomotor activity ; Genetics ; NMDA/glutamate receptor complex ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The effects of non-competitive (MK-801, phencyclidine, and ketamine) and competitive (CGP 39551, CGS 19755, and NPC 12626) N-methyl-d-aspartate (NMDA) receptor antagonists on locomotor activity in inbred CBA and C57, and in outbred NMRI mice were examined. Administration of the non-competitive NMDA antagonists produced a dose-dependent increase in well-coordinated locomotor activity at lower doses, followed by a bizarre behavioral syndrome (head weaving, body rolling, rotations, ataxia) after higher doses. The pharmacological profile of the competitive antagonists CGP 39551, CGS 19755, and NPC 12626 was more complex. CGP 39551 dose-dependently inhibited locomotor activity, whereas CGS 19755 and NPC 12626 displayed a biphasic action, that is low doses inhibited locomotor activity, whereas higher doses produced mild behavioral stimulation. The behavioral effects of NMDA antagonists appear to be genetically determined, since CBA animals were most sensitive to both noncompetitive and competitive antagonists, followed by NMRI and C57 animals. The differential effects of NMDA antagonists in various strains of mice suggest that the observed behavioral differences may be due to genetic differences in the NMDA/glutamate receptor channel complex.
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  • 9
    ISSN: 1432-072X
    Keywords: Carboxydotrophic bacteria ; Ribulosebis-phosphate carboxylase ; Phosphoribulokinase ; Hybridization ; Plasmids ; Genetics ; CO2 fixation ; Alcaligenes eutrophus ; Pseudomonas carboxydovorans ; Rhodospirillum rubrum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Heterologous gene probes derived from cfxLp and cfxPp genes of Alcaligenes eutrophus H16 revealed the presence of structural genes encoding ribulosebisphosphate carboxylase (Rubisco) and phosphoribulokinase (PRK) on the genome of carboxydotrophic bacteria. The two genes were found to be rather conserved. In Pseudomonas carboxydovorans OM5 cfx genes reside on the plasmid pHCG3 and the chromosome as well, indicating that they are duplicated. Also in all plasmidharboring carboxydotrophic bacteria cfxL and cfxP structural genes were found to be plasmid-coded. Our results extend the list of carboxydotrophy structural genes residing on the plasmid pHCG3 and strongly support the idea that the components essential for the chemolithoautotrophic utilization of CO by Pseudomonas carboxydovorans OM5 are plasmid-coded. A cfxL gene probe from Rhodospirillum rubrum did not detectably hybridize with DNA from any of the carboxydotrophic bacteria examined.
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  • 10
    ISSN: 1432-2072
    Keywords: Habituation ; GABA ; Ethanol sensitivity ; Ethanol tolerance ; Genetics ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Habituation to a test environment following daily exposure for 5 days was examined in three genetically different strains of mice. C57 animals showed significant habituation to the new environment already on the second day. The habituation of NMRI mice was significant on the third day, whereas CBA mice showed no habituation at all during the experimental period. There was no difference between the animal strains in learning capacity in a passive avoidance test, but CBA mice displayed a significant increase in latency in their performance. When tested for sensitivity to the convulsant actions of GABAergic antagonists, picrotoxin produced seizures at lower doses in CBA as compared to NMRI and C57 mice, whereas there was no difference between the strains in the seizure activity produced by the specific GABA receptor antagonist bicuculline. When the animals were tested for sensitivity to ethanol in a horizontal wire test, ethanol (2 g/kg, IP) produced muscle relaxation in CBA mice whereas the performance of NMRI and C57 was not affected. A large dose of ethanol (4 g/kg, IP) produced a significantly longer sleeping time in CBA mice as compared to NMRI and C57 animals. Ethanol-produced hypothermia was, however, similar in all animals. Environment-dependent development of tolerance to ethanol following daily injections of ethanol for 4 days was examined. C57 mice showed the most rapid development of tolerance towards ethanol's hypnotic actions, whereas CBA mice showed no tolerance to this effect of ethanol. No difference between the strains to the development of tolerance to ethanol's hypothermic effects was observed. The present findings indicate that sensitivity to ethanol and ethanol tolerance are complex phenomena which cannot be adequately characterized by measuring only one single functional response to ethanol. The possibility that a genetically determined perturbation in the functions of the GABA receptor-coupled chloride channel, noted as variable sensitivity to picrotoxin, may be of importance for the observed disturbance in habituation to a new environment, for the different sensitivity to ethanol, and for the different rate of development of ethanol tolerance is discussed.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    European archives of psychiatry and clinical neuroscience 240 (1991), S. 188-190 
    ISSN: 1433-8491
    Keywords: Families ; Genetics ; Polydiagnostic approach ; Schizophrenia ; Swedish family complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A polydiagnostic computerized diagnostic system for psychosis was used in a Swedish family complex, and 51 patients with psychiatric symptomatology were examined with eight main diagnostic systems for schizophrenia and three systems for schizophrenic subgroups. All patients fulfilled the criteria for schizophrenia according to Taylor et al., 50 according to Carpenter, 41 according to RDC, and 31 of the 51 according to DSM-III and DSM-III-R. The hypothesis that the patients in the Swedish family complex differ from other phenotypes of schizophrenia must be refuted based on the data of the present study.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 83 (1991), S. 24-32 
    ISSN: 1432-2242
    Keywords: Genetics ; Growth curve ; Body weight ; Chickens
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Genetic improvement in growth of poultry has traditionally proceeded via selection for body weight at a fixed age. Due to increased maintenance costs and reproductive problems of adult broiler breeders, the potential for genetic manipulation of the growth curve has been receiving increased interest. Research of both male and female progeny of a three-way diallel cross was used to investigate the inheritance of growth curve parameters. The Laird form of the Gompertz equation was used to determine growth curve parameters, and was suited to the juvenile growth data frequently collected from meat-type chickens. Growth rate exhibited significant heterosis due to both autosomes and the sex chromosomes. Age at inflection point also exhibited significant average heterosis, though only among females. Growth rate was also influenced by average line effects, as was age at inflection point. Maternal effects had no influence on growth curve parameters, while additive sex linkage was observed for growth rate. Phenotypic and genetic correlations were calculated among the growth curve parameters and suggest that specific breeding programs could alter the growth trajectory of the contemporary broiler chicken. Moderate heritabilities were observed for the growth curve parameters and support the hypothesis that the growth curve could be altered via genetic manipulation of early postnatal growth, especially during the first 14 days post-hatch.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 82 (1991), S. 761-764 
    ISSN: 1432-2242
    Keywords: Rye ; Male sterility ; Genetics ; Gene location ; Trisomies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The genetics and relationships between the genes in rye located in the nucleus and cytoplasm of the male sterility of the G-type were investigated. A factor inducing male sterility was found in the cytoplasms or rye cv Schlägler alt and rye cv Norddeutscher Champagner. Monogenic inheritance was observed in linkage tests. Using primary trisomies of rye cv Esto, the nuclear gene ms1 was found to be located on chromosome 4R. Modifying genes, probably masked in normal cytoplasm but expressed in male-sterility-inducing cytoplasm together with gene ms1, were located on chromosomes 3R (ms2) and 6R (ms3). Mono-, di-, and trigenic inheritance types were found in backcross progenies of trisomies.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 81 (1991), S. 50-58 
    ISSN: 1432-2242
    Keywords: Vicia faba ; Legumin ; Vicilin ; Structure ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Legumin and vicilin were purified from seeds of Vicia faba L. var. Scuro, characterized in different electrophoretic systems, and used to produce polyclonal antibodies in rabbits. Two-dimensional electrophoretic studies showed a wide range of heterogeneity in the subunits of both legumin and vicilin. Legumin was found to be composed of 29 disulphide-linked subunit pairs with different molecular weight and/or isoelectric point. Western blot analysis of legumin of several mutants revealed molecular polymorphism based on a corresponding gene family. Three different α-major legumin patterns were found, and inheritance studies showed that the 34.3-kD legumin polypeptide is the product of one locus, Lg-1α, which is the first legumin genetic locus described in Vicia faba. Vicilin was found to be composed of as many as 59 subunits distributed in a molecular weight range of 65.7 to 42.8 kD (major polypeptides) and 37.2 to 15.2 kD (minor polypeptides), with different isoelectric points. A model is proposed that explains the possible formation of the minor subunits and the major subunits of 48.2 and 46 kD molecular weight (MW) from proteolytic cleavages and/or glycosilation of precursor polypeptides. Ten different vicilin electrophoretic patterns were observed among the analyzed accessions, which showed large molecular polymorphism that proved to be under genetic control.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 82 (1991), S. 771-776 
    ISSN: 1432-2242
    Keywords: Secale cereale ; RFLP ; α-Amylase ; Genetics ; Isozymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Rye α-Amy1, α-Amy2, and α-Amy3 genes were studied in the cross between inbred lines using wheat α-amylase cDNA probes. The α-Amy1 and α-Amy2 probes uncovered considerable restriction fragment length polymorphism, whereas the α-Amy3 region was much more conserved. The numbers of restriction fragments found and the F2 segregation data suggest that there are three α-Amy1 genes, two or three α-Amy2 genes, and three α-Amy3 genes in rye. These conclusions were supported by a simultaneous study of α-amylase isozyme polymorphism. The F2 data showed the three individual α-Amy1 genes to span a distance of 3cM at the locus on chromosome 6RL. The genes were mapped relative to other RFLP markers on 6RL. On chromosome 7RL two α-Amy2 genes were shown to be separated by 5 cM. Linkage data within α-Amy3 on 5RL were not obtained since RFLP could be detected at only one of the genes.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    European journal of epidemiology 7 (1991), S. 490-493 
    ISSN: 1573-7284
    Keywords: Creutzfeldt-Jakob diseases ; Prion disease ; Jews ; Libya ; Genetics ; Pathophysiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The focus of CJD among Jews of Libyan origin has been recognized for two decades, but the reasons underlying it were unknown. Prevailing views suggested transmission from sheep infected with scrapie. However, recent data show that in fact CJD in this ethnic group is a genetically determined disease due to a point mutation on the codon 200 of the prion protein gene. The clinical characteristics of CJD in this group, and particularly the less common periodic activity in the EEG, are reviewed. New findings include peripheral neuropathy of the demyelinating type in two cases, presumably due to involvement of Schwann cells. The pathophysiology of the disease includes, presumably, a focal post-translational modification of the prion protein, (predisposed by the mutation). Later, the disease progresses through cell-to-cell transmission.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 13 (1991), S. 109-118 
    ISSN: 1573-739X
    Keywords: Chemistry ; Consumer product safety ; Drug packaging ; Environmental pollution ; Plasticizers ; Polyvinyls
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this report the state of the art with respect to PVC as pharmaceutical packaging material is described. A general introduction into the applications of PVC is followed by a description of its production process. The metabolic effects of the monomer of PVC, vinyl chloride and of the most commonly used plasticizer diethylhexylphthalate are mentioned. Special attention is given to the pharmaceutical properties of plasticized PVC bags in comparison to other plastics and the environmental aspects of waste PVC disposal. Although there are emotional and political queries regarding the future use of PVC as a (pharmaceutical) packaging material, we conclude that there is no scientific justification for a total or partial ban of PVC. PVC will remain a fact of life as a cheap, versatile, high-performance and well-investigated plastic material for medical and pharmaceutical applications, to be replaced by newer plastics only for certain well-defined indications where the requirements of the plastic to be used are so specific that it will economically and technically be justified to use another polymer. Community and hospital pharmacists have to be prepared for a role in intake of waste plastic disposables, probably against deposit money, in order to fulfil the logistics needed for recycling.
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  • 18
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    Electronic Resource
    Springer
    Molecular genetics and genomics 228 (1991), S. 361-371 
    ISSN: 1617-4623
    Keywords: Plant ; Hormone ; Genetics ; Hypocotyl ; Development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We have isolated nine independent auxin-resistant mutants of Nicotiana plumbaginifolia by culturing M2 seedlings in the presence of indole-3-acetic acid ethyl ester or 1-naphthaleneacetic acid at concentrations which significantly inhibit hypocotyl elongation of the wild type. The mutations were induced by treating seed with ethyl methanesulphonate and were found in the course of screening 10 000 individual M2 families. Auxin resistance was in all cases the result of a mutation at a single, nuclear locus. The dominance relationships of two of the mutants could be defined as recessive or dominant; all other mutants showed partial dominance. In contrast to previously described mutants of Arabidopsis and N. plumbaginifolia, all of the present mutants were specifically resistant to auxin; the mutants were cross-resistant to several auxins, but showed no increased resistance to cytokinin, abscisic acid, ethylene or 1-amino-cyclopropane-1-carboxylic acid. The importance of the choice of the selection criterion for the isolation of specific resistance traits is discussed.
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  • 19
    ISSN: 1573-6903
    Keywords: Genetics ; catecholamine ; brain ; imprinting ; development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This study was designed to compare catecholamine concentrations among three brain areas of four pureline populations of visually isolated chicks. The purelines used were a commercial male line, a fertility selected line, an unselected fertility control line, and unselected White Jersey Giants. In general, male chicks had significantly larger brain weights than females. Six catecholamine-related compounds (norepinephrine, epinephrine,l-DOPA, dopamine, DOPAC, and MHPG) were measured via HPLC-ECD. No significant differences in neurochemical concentration were observed for any line or brain area due to sex of the chick. The hypothalamus (HT) contained the greatest concentration of catecholamines in all lines, followed by the intramedial hyperstriatum ventrale (IMHV) and optic tectum (OT). The HT exhibited consistent lateralization in all lines with the right HT containing ca. 30% more catecholamines than the left HT. While no consistent lateralization was observed among the other brain areas, the IMHV exhibited significantly different degrees of lateralization among the populations. Neuronal activity, as measured by MHPG:NE and DOPAC:DA ratio varied by line within each brain area. There were line differences for MHPG:NE in the HT, IMHV, and OT, while line differences for DOPAC:DA were observed in the HT. Since differences among purelines have been demonstrated in this study, care must be given to precisely define the genotype of chicks used in behavioral and neurochemical research.
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  • 20
    ISSN: 1573-5060
    Keywords: Brassica oleracea ; Cauliflower ; Stalk rot ; Screening ; Genetics ; Resistance ; Sclerotinia sclerotiorum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The inheritance of resistance in cauliflower to stalk rot (Sclerotinia sclerotiorum (Lib.) de Bary) was investigated in population from six generations of six crosses. Disease incidence was recorded on 4 parents, 6 Fs 1, 6 Fs 2 and 12 back-crosses in a screenhouse under artificially created epiphytotic conditions. Resistance to stalk rot in this set of parents was found to be polygenic and under the control of recessive genes and due primarily to additive gene action. A breeding strategy emphasizing recurrent selection should lead to improvement in resistance.
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  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties (squared dimensions, anisotropy, numbers of intra- and intermolecular contacts) of a single five-way cubic lattice chain embedded into an environment (matrix) of chains of the same length n = 50 were evaluated as a function of matrix volume fraction (matrix density) v and intermolecular interaction between the matrix polymer and the minority chain segments, characterized by a parameter φ. No convincing evidence was found for the occurrence of a coil-globule transition in the range of matrix densities (v ≤ 0.7) and repulsive interactions between matrix and minority chain (φ ≤ 0.2) investigated. For moderate attractive interaction (φ ≈ -0.17) a compensation of the chaincompressing action of the matrix and the chain-expanding interaction with the matrix was observed resulting in a zero-dependence of the size and shape of the minority chain on matrix density. It further turned out that there are fixed relations among the various size and shape data irrespective of the specific combination of matrix density and thermodynamic interaction by which a particular polymer dimension is produced. These interrelations are fairly the same as those evaluated for isolated chains the size of which is varied by an intramolecular energy parameter φi.
    Additional Material: 6 Ill.
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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
    Notes: New three phases composite materials made of glassbeads as filler, water as liquid dispersed phase and polystyrene as matrix were obtained by polymerization of a water in oil emulsion formed by water dispersed in styrene in which glass beads are added. For this purpose glass beads have to be modified by silanization by a coupling agent 3-(Trimethoxysilyl)propylmethacrylate (TPM) or a silane Octadecyltrichlorosilane (ODMS), in order to prevent the wetting of the glass by water. Only low coverage of the glass surface by the coupling agent (0,05% of TPM) are convenient for the preparation cellular materials having good mechanical properties. At higher coverage ratio, strong hydrophobic glass beads are obtained which destabilize the water / styrene emulsion and lead to macroporous products. Study of the rheology of the filled emulsion appears to be the more simple and more sensitive method to determine the level of wettability of the glass bead by the emulsion which is the most significant parameter for the preparation of such three phases composite materials. Composite materials made of glass beads, air and polystyrene are simply obtained by evaporation of water under vacuum.
    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
    Notes: To test the molecular parameters concerning gas sorption in polymers, the concentration of CO2, N2O, CO, N2, CH4 and the noble gases Ne, He in glassy poly(butylene terephthalate) films (PBTP) has been studied gravimetrically with a recording microbalance at 25°C. The sorption isotherms exhibit downward curvature to the pressure axis. As neither solubility nor adsorption can explain the experimental results, analysis was carried out based on the dual-sorption model: gas dissolution and microvoid filling are considered as independent sorption mechanisms. The parameters of the dual-sorption model for the mentioned penetrants are determined. The results indicate that for parameter correlation the Lennard-Jones potential parameters give a rough idea, but size exclusion of gases in small diameter microvoids is proposed and special chemical interactions must be considered.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 185 (1991), S. 283-292 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The ring opening metathesis polymerisation (ROMP) of 5-cyano-2-norbornene with tungsten hexachloride, tungesten oxytetrachloride, bis(dichloralkoxo)tungsten tetrachloride and bis(dichloralkoxo)tungsten oxydichloride as transition metal component was studied. Methylaluminoxan, diethylaluminium ethoxide, tetraisobutyldialuminoxan and tetrabutyltin served as cocatalyst. Toluene, Chlorobenzene and dichloromethane were used as solvents. The concentration of the tungsten components was in the range from 5 × 10-4 to 5 × 10-3 mol/l. Among the catalyst studied, tungsten hexachloride with diethylaluminium ethoxide proved to be the best. The polymerisation was highly selective with this system even at high monomer/tungsten ratios (e.q. 10200:1) and let to high conversions (≥82%).
    Notes: Die ringöffnende metathetische Polymerisation (ROMP) von 5-Cyano-2-norbornen wurde unter Einsatz von Wolframhexachlorid, Wolframoxidterachlorid, Bis(dichloralkoxo)wolframtetrachlorid und Bis(dichloralkoxo)wolframoxiddichlorid als Übergangsmetallkomponente untersucht. Als Cokatalysatoren dienten Methylaluminoxan, Diethylaluminiumethoxid, Tetraisobutyldialuminoxan und Tetrabutylzinn. Als Lösungsmittel wurden Toluol, Chlorbenzol und Dichlormethan verwendet. Die Konzentration der Wolframkomponente lag im Bereich 5 × 10-4 - 5 × 10-3 mol/l. Unter den geprüften Katalysatoren erwies sich Wolframhexachlorid in Verbindung mit Diethylalumiumethoxid als der geeignetste. Mit diesem System verlief die Polymerisation auch bei großen Monomer/Wolfram-Verhältnissen (10200 :1) hochselektiv und führte zu großen Umsätzen (≥82%).
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  • 25
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of dilution on the chain propagation and termination rate constants was investigated in the polymerization of ethyl acrylate in benzene solution at 50°C, with the rotating sector method. The errors of the above rate constants were determined and, by our method applied to decrease these errors, the errors of the propagation rate constant was reduced to its half value. By the application of our earlier results in polymerization kinetics, we found that in this system the chain propagation step is exclusively responsible for the solvent effects observed. Our experimental results can be quantitatively described in terms of the hot redical theory.
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  • 26
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 185 (1991), S. 329-334 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 27
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 190 (1991), S. 1-14 
    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 gemeinsame Reaktion von Benzophenontetracarbonsäuredianhydrid, Maleinsäureanhydrid und Diaminen mit 1,3,5-Triazingruppen wurden niedermolekulare Prepolymere mit Amin-Endgruppen erhalten, die sowohl 1,3,5-Triazingruppen als auch Etherbindungen enthalten. Diese reaktiven Prepolymeren sind in niedrigsiedenden Lösemitteln wie z. B. Chloroform und Tetrahydrofuran löslich. Sie wurden durch Elementaranalyse, IR- und NMR-Spektroskopie, Dampfdruckosmometrie und Viskosimetrie charakterisiert. Beim Erhitzen der Prepolymeren auf Temperaturen zwischen 180 und 190°C tritt Kettenverlängerung durch Michael-Addition auf; gleichzeitig vernetzen sie durch Reaktion der Amin- mit den Maleimid-Endgruppen. Die vernetzten Polymeren sind thermisch stabil; ihr thermisches Verhalten wurde durch TGA, DTA und isotherme Alterung untersucht. Die Biegefestigkeit und interlaminare Scherfestigkeit von aus den Prepolymeren und Carbonfasergeweben hergestellten Laminaten wurden gemessen.
    Notes: Low molecular weight amine-terminated monomaleimide prepolymers containing 1,3,5-triazine groups as well as ether linkages were synthesized by reacting benzophenone tetracarboxylic dianhydride, diamines having 1,3,5-triazine group and maleic anhydride. These reactive prepolymers are soluble in low boiling solvents such as chloroform, tetrahydrofuran etc. They were characterized by elemental analyses, IR and NMR spectroscopy, vapour pressure osmometry, and viscosity. On heating at 180-190°C these prepolymers undergo simultaneous chain extension by Michael addition reaction and crosslinking by mutual reaction between their amine-terminated and maleimide-terminated ends. The cured polymers are thermostable and the thermal behaviour was studied by TGA, DTA, and isothermal aging. Laminates fabricated using these prepolymers and carbon fiber as reinforcing agent were evaluated by their flexural strength and interlaminar shear strength.
    Additional Material: 5 Ill.
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  • 28
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 190 (1991), S. 15-32 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Epoxidharz wurde durch Reaktion mit Anilin bzw. Benzylamin in unterschiedlichen molaren Verhältnissen modifiziert. Die modifizierten Harze wurden dann mit Diethylamin und anschließend mit teilblockiertem Toluylendiisocyanat umgesetzt, wobei thermisch vernetzbare Harze mit tertiären Aminen in und am Ende der Polymerkette erhalten wurden. Die partielle Ansäuerung mit Essigsäure lieferte thermisch vernetzbare kationische Harze, aus denen durch Lösen in geeigneten Lösungsmitteln und Zugabe von entionisiertem Wasser Emulsionen hergestellt wurden. Diese wurden hinsichtlich ihrer Eignung zur elektrolytischen Abscheidung untersucht und verglichen. Die Ergebnisse zeigen, daß die Abscheidungsausbeute und das Streuvermögen der Emulsionen aus Benzylamin-modifizierten Epoxidharzen besser sind als die der Anilin-modifizierten Epoxidemulsionen. Ein hohes, vom pH-Wert der Emulsion abhängiges Streuvermögen ist für diese kationischen Harze charakteristisch.
    Notes: Aniline/benzylamine-modified epoxy resins with different molecular weights, which contain tertiary amines in the middle of the polymer chain, were synthesized by the reaction of aniline/benzylamine with epoxy resin at various molar ratios. The resulting aniline/benzylamine-modified epoxy resins were reacted with diethylamine and subsequently reacted with 2-ethylhexanol-blocked toluene diisocyanate to obtain thermally crosslinkable resins which contain tertiary amines at the end and in the middle of the polymer chain. These resins were partially neutralixed with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form various emulsions. The emulsion and electrodeposition properties of these resins were studied in some detail to compare the properties of these cationic resins. The results show that the deposition yields and throwing power of the emulsions prepared from benzylaminemodified epoxy resins are higher than those of the emulsions prepared from anilinemodified epoxy resins. The emulsion having proper pH values can give a high throwing power. High throwing power is the characteristic property of these modified cationic resins. Factors determining the throwing power and deposition yield of the emulsions were also investigated.
    Additional Material: 11 Ill.
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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: Arylacrylsäuren, wie Furylacrylsäure und Thienylacrylsäure können durch Knoevenagel-Reaktion der Arylcarbaldehyde mit Malonsäure in Pyridin dargestellt werden. Durch einfache Veresterung der Arylacrylsäuren in Methanol/Schwefelsäure werden die entsprechenden Arylacrylsäuremethylester mit guten Ausbeuten erhalten. Diese isomerisieren bei Bestrahlung mit UV-Licht (λ ≥ 280 nm) in methanolischer Lösung. Bei der Photoreaktion in Lösung wurde keine Photodimerisierung beobachtet. Die Reaktionskinetik der Photoreaktionen wurde untersucht.
    Notes: Aryl acrylic acids, e. g. furyl acrylic acid or thienyl acrylic acid are readily formed by the Knoevenagel condensation reaction of arylcarbaldehydes and malonic acid in pyridine. Esterification of these acids with methanol/sulfuric acid gives the corresponding aryl acrylic acid methyl esters in good yields. In methanolic solution these methyl esters isomerize upon irradiation (λ 280 nm). No photodimerization was observed. Kinetic data are given.
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  • 30
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 190 (1991), S. 67-80 
    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: Different composite materials, with retified or natural poplar and polyester resin were prepared by molding. The influence of the filler granulometry on certain physicochemical (density, humidity, hardness) or mechanical properties of the materials was studied. The density and the increase of mass in humid atmosphere were always found to be less when the wood was thermally treated. On the other hand, the hardness of the composites made from natural poplar was much higher. The mechanical properties were found to be weak when the wood was retified.When the wood was thermally treated, it was possible to optimise the three parameters, namely, density, water retention capacity and mechanical properties. The optimal granulometry of poplar was determined between 0.75 and 1.5 mm.The results obtained are discussed considering the physico-chemical properties of the different varieties of wood studied and the interactions which exist between the polar resin and the wood.
    Notes: Divers matériaux composites à base de peuplier rétifié ou naturel et de résine polyester insaturée ont été préparés par moulage. L'influence de la granulométrie de la charge a été étudiée sur quelques propriétés physico-chimiques (densité, reprise d'humidité, dureté) ou mécaniques des matériaux obtenus. La densité et la reprise de masse en milieu humide sont toujours plus faibles si la charge est traitée thermiquement sous atmosphère inerte. Par contre, la dureté des composites issus du peuplier naturel est plus importante. Les propriétés mécaniques sont inférieures si la charge est rétifitée.Si la charge lignocellulosique est traitée thermiquement, il est possible d'optimiser les trois paramètres: densité, reprise d'eau et propriétés mécaniques; la granulométrie optimale du peuplier est ainsi comprise entre 0,75 et 1,5 mm.Les résultats obtenus sont expliqués en tenant compte des propriétés physico-chimiques des charges et des interactions existant entre la résine polaire et le bois.
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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
    Description / Table of Contents: Die vorliegende Arbeit untersucht das Wasserdurchlässigkeitsverhalten von vier Arten verschieden modifizierter Chitosanmembranen zur Abtrennung von Wasser aus wäßrigen Ethanolmischungen. Chitosan wurde aus Chitin von Krebstierschalen durch Verseifung (Deacetylierung) gewonnen. Die in dieser Arbeit untersuchten modifizierten Chitosanmembranen enthielten Carboxymethyl-, Carboxyethyl-, Cyanethyl- und Amidoxim-Chitosan. Die Einführung hydrophiler funktioneller Gruppen in der 6-O Position des Chitosans erhöht die Selektivität der modifizierten Membranen im Vergleich zu den mit Essigsäure komplexierten Chitosanmembranen. Die Untersuchungen zeigen, daß Chitosanmembranen, die Carboxygruppen enthalten, die höchste Wasserdampfdurchlässigkeit aufweisen. Carboxymethyl-Chitosanmembranen zeigen eine maximale Quellung und den höchsten Ethanoldurchfluß bei einer Ethanolkonzentration von ca. 15 Gew.-% im Zulauf aufgrund von Bindungs- und Weichmachereffekten.
    Notes: The present study investigates the pervaporation performance of four kinds of modified chitosan membranes to separate water from aqueous ethanol solution. Chitosan was prepared from chitin abstracted from the crab shell and subsequently deacetylated with aqueous NaOH solution. Modified chitosan membranes examined in this study include carboxymethyl chitosan, carboxyethyl chitosan, cyanoethyl chitosan, and amidoxime chitosan. The incorporation of hydrophilic functional groups into the 6-O position of chitosan enhances the selectivity of modified chitosan membrane compared to the previously reported chitosan-acetic acid complex membrane. Among the modified chitosan membranes, membranes containing carboxy groups show the best pervaporation performance. Carboxymethyl chitosan membranes show the maximum swelling and ethanol flux at approx. 15 wt.-% feed ethanol concentration due to the coupling and plasticizing effect.
    Additional Material: 9 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
    Description / Table of Contents: The tensile properties of self reinforced poly(propylene)/poly(1-butene) composites, obtained by rapid extension of the melt, have been measured and correlated to morphological parameters derived from x-ray experiments. Critical fiber lengths as a function of sample composition and the elastic modulus and yield stress of the fibers could be determined. It is shown, that, applying a load to the system, the forces are fully taken up by the fibers and the system breaks by fail of the fibers. The longitudinal structure of the fibers is found to be independent of sample composition.
    Notes: Mechanische Parameter wie Elastizitätsmodul, Fliß- und Bruchspannung von aus der hochorientierten Schmelze hergestellten nadelkristallinen Mischungen aus Poly(propylen) und Poly(1-bute) wurden mit morphologischen Parametern, die aus Röntgenmessungen abgeleitet wurden, korreliert. Es wird gezeigt, daß der Elastizitätsmodul des Verbundes aus den E-Moduln der Fasern und der Matrix berechnet werden kann (Mischungsregel). Die an der Probe angreifenden Kräfte werden voll auf die Fasern übertragen; der Verbund kann daher als eigenfaserverstärktes System angesehen werden. Die Abschätzung der kritischen Faserlänge ergibt, daß die Festigkeit der FAsern voll ausgenutzt wird; der Bruch des Systems bei Belastung ist daher auf das Versagen der Fasern zurückzuführen. Das mechanische Verhalten des Verbundes wird stark beeinflußt durch die Komponentenzusammensetzung. Die longitudinale Struktur der Nadeln beider Komponenten bleibt unbeeinflußt von der jeweiligen Co-Komponente.
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  • 33
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    Angewandte Makromolekulare Chemie 192 (1991), S. 199-211 
    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: Lösliche kationische Polyelektrolyte mit quartären Stickstoffatomen in der Hauptkette wurden durch Polykondensation von Epichlorhydrin (ECH) mit Dimethylamin (DMA) und N,N-Dialkylaminoakylaminen erhalten. Die Reaktionsparameter, die die Polymereigenschaften hauptsächlich beeinflussen, sind: Molverhältnis DMA/asymmetrische Diamine, Ausgangskonzentration der Aminlösung, Molverhältnis ECH/Amine und die Struktur der asymmetrischen Diamine. Das viskosimetrische Verhalten verdünnter wäßriger Lösungen mit oder ohne Zugabe neutraler Salze veranschaulicht die flexible Natur der Polyelektrolyten.
    Notes: Water soluble cationic polyelectrolytes containing quaternary nitrogen atoms within the main chain were prepared via condensation polymerization of epichlorohydrin (ECH) with dimethylamine (DMA) and N,N-dialkylaminoalkylamines. The main parameters of the reaction that influence the polymer properties are: DMA/asymmetrical diamine molar ratio, the initial concentration of amine solution, NaOH/amine molar ratio, ECH/amine molar ratio, and asymmetrical diamine structure. The feature of flexible polyelectrolyte own to the investigated polymers was emphasized by the viscosimetric behaviour in dilute aqueous solutions with and without salt presence.
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  • 34
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    Angewandte Makromolekulare Chemie 192 (1991), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 35
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    Angewandte Makromolekulare Chemie 193 (1991), S. 1-11 
    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: Antioxidantien wurden in einer modifizierten Friedel-Crafts-Reaktion mit wasserfreiem Zinkchlorid als Katalysator an Flüssig-Naturkautschuk mit Hydroxy-Endgruppen gebunden. Die immobilisierten Antioxidantien waren weniger flüchtig und extrahierbar als konventionelle Antioxidantien. Sie wurden sowohl einem Latex als auch trockenem Kautschuk zugesetzt; die daraus hergestellten Vulkanisate zeigten eine bessere Alterungsbeständigkeit als Vulkanisate mit konventionellen Antioxidantien.
    Notes: Antioxidants were attached to hydroxy-terminated liquid natural rubber by modified Friedel-Crafts alkylation reaction using anhydrous zinc chloride as catalyst. The rubber bound antioxidants were found to be less volatile and less extractable compared to conventional antioxidants. The bound antioxidants were tried both in latex compounds and dry rubber compounds. The vulcanizates showed improved ageing resistance compared to vulcanizates based on conventional antioxidants.
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  • 36
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    Angewandte Makromolekulare Chemie 193 (1991), S. 13-20 
    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 Strom-Spannungs-Charakteristik eines Bisphenol-A-Polycarbonats im Span-nungsbereich 50-1000 V und der Einfluß von UV-Bestrahlung (λ = 225 und 300 nm) und Tempern auf die elektrische Leitfähigkeit (σ) des Polycarbonats wurden untersucht. Die Abhängigkeit von σ gegen 1/T deutet auf zwei verschiedene Leitfähigkeits-mechanismen hin. Aus den Ergebnissen wurden die Aktivierungsenergien der Leitfähigkeit und die Sprungdistanzen berechnet.
    Notes: Current-voltage characteristics of polycarbonate samples (PC) have been studied in the voltage range 50-1000 V. The effect of UV-irradiation at λ = 225 and 300 nm, and thermal annealing on the electrical conductivity (σ) of PC was studied. The σ vs. 1/T relationship shows two slopes, i.e. two possible conduction mechanisms. The obtained results made it possible to determine a complete set of conduction parameters including activation energy and jump distance.
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  • 37
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    Angewandte Makromolekulare Chemie 193 (1991), S. 21-28 
    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: Durch Suspensionspolymerisation wurden Terpolymere aus Acrylnitril (AN), Vinylacetat (VA) (7,5-30 mol-%, bezogen auf AN) und Divinylbenzol (DVB) (10 Gew.-%) hergestellt. Als Verdünner wurden Mischungen von Toluol oder Cyclohexanol (90 Vo1.-%) mit Hexadecan, Octan, Dodecan, 2-Ethylhexanol oder Benzylalkohol (jeweils 10 Vo1.-%) verwendet.Die Porosität der AN-VA-DVB-Terpolymeren ist mit 0,61-0,68 größer als die der entsprechenden AN-DVB-Copolymeren. Die übermolekulare Struktur der Terpolymeren hängt vom verwendeten Verdünner ab, obwohl sich die Porositäten nicht sehr voneinander unterscheiden. Die beim Erhitzen der Terpolymeren auf Temperaturen über 200°C auftretenden thermischen Effekte sind signifikant größer als die bei der Cyclisierung von AN-Polymeren gemessenen.
    Notes: Terpolymers of acrylonitrile (AN), vinyl acetate (VA) (7.5-30 mol-%, related to AN), and divinylbenzene (DVB) (10 wt.-%) were prepared by suspension polymerization. The diluents used were mixtures of toluene or cyclohexanol (90 vol.-%) with solvents (10 vol.-%) such as hexadecane (HD), octane (O), dodecane (D), 2-ethylhexanol (E) or benzyl alcohol (B).It has been found that AN-VA-DVB terpolymers have a higher porosity, about 0.61-0.68, than corresponding AN-DVB copolymers. The terpolymers obtained with mixtures of various diluents differ in their supermolecular structure although they had similar porosity characteristics.The thermal effects accompanying heating of the terpolymers above 200°C significantly exceed that of nitrile groups cyclization observed of the other AN polymers.
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  • 38
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    Angewandte Makromolekulare Chemie 193 (1991), S. 39-49 
    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: Die rheologischen und mechanischen Eigenschaften von Blends aus PE-HD und zwei verschiedenen PE-LLD-Typen wurden im gesamten Mischungsbereich gemessen. Die Polymeren sind im festen Zustand und in der Schmelze ausreichend verträglich, so daß ihre vorteilhaften Eigenschaften genutzt werden können.
    Notes: A high density polyethylene grade is blended with two selected grades of linear low density polyethylene and the mechanical and rheological properties of the blends are evaluated over the entire composition range. The blends show sufficient compatibility in the solid phase and in the melt and hence they can be advantageously used to capitalize on their useful properties.
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  • 39
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    Angewandte Makromolekulare Chemie 192 (1991), S. 51-55 
    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: N,N-Dimethylacrylamid (DMA) und Isopropylmethacrylat (IPM) wurden in Dimethylformamid mit Azoisobutyronitril als Initiator copolymerisiert. Die Copolymerzusammensetzung wurde 1H-NMR-spektroskopisch ermittelt. Die Copolymerisationsparameter (rDMA = 0,58, rIPM = 2,76) wurden nach Kelen-Tüdős berechnet.
    Notes: Copolymers of N,N-dimethyl acrylamide (DMA) and isopropylmethacrylate (IPM) were prepared in dimethyl formamide using azoisobutyronitrile as initiator. The composition of copolymers was determined by 1H-NMR analysis. Reactivity ratios (rDMA = 0.58, rIPM = 2.76) were calculated from these values by using the Kelen-Tüdős differential linear equation.
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  • 40
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    Angewandte Makromolekulare Chemie 192 (1991), S. 69-79 
    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 ein allgemeines numerisches Verfahren vorgestellt, um die Modifikation der Grundgleichung für hydrodynamische Schmierung, die von mit Polymeren versetzten Schmierölen mit scherabhängiger Viskosität erbracht wird, zu berechnen.Das Verfahren basiert auf dem verallgemeinerten Newtonschen Fileßmodell und erlaubt, alle Fileßregionen zwischen dem rein Newtonschen und dem Exponentialgesetzverhalten kontinuierlich zu behandeln. Die Ergebnisse zeigen, daß der Einfluß der scherspannungsabhängigen Viskosität durch eine dimensionslose Zahl vollkommen charakterisiert wird, nämlich U · τ*/h*, wobei U die relative Gleitgeschwindigkeit, h* die charakteristische Filmdicke und τ* die Relaxationszeit des Schmieröles darstellen.Als praktisches Beispiel wird die Anwendung des Verfahrens aufgezeigt, um den Einfluß des Molekulargewichts und der Konzentration der Polymerkomponente des Schmieröls auf die hydrodynamische Schmierung zu bestimmen. Dieser Einfluß ist durch die starke Beziehung zwischen Polymereigenschaften und τ* verursacht.
    Notes: A general numerical procedure is presented to calculate the modification of the basic equation for hydrodynamic lubrication brought about by the use of polymeric fluids with shear depending viscosity. The procedure is based on the generalized Newtonian fluid model and allows to treat continuously all the flow regions between the pure Newtonian and the power law behavior. The results show that the influence of the viscosity depending on shear stress is completely characterized by one dimensionless number, namely U.·τ*/h*, where U is the relative sliding velocity, h* is the characteristic film thickness, and τ* is a characteristic time of the lubricant. The procedure is exemplified by applying it for the determination of the influence of the molecular weight and concentration of the polymeric component of the lubricant on the hydrodynamic lubrication. This influence is brought about by the strong relation between the polymer properties and τ*.
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  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 57-67 
    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 Morphologien von spritzgegossenem und formgepreßtem Poly(1-buten) (PB-1) wurden im Polarisationsmikroskop und im Transmissionselektronenmikroskop untersucht. Eine dünne Oberflächenhaut und bis in den Kern der Probekörper reichende abgeplattet-sphärolithische Strukturen werden bei spritzgegossenem PB-1 beobachtet, während in formgepreßtem PB-1 typische Sphärolithe vorliegen. Das Bruchbild des spritzgegossenen PB-1 zeigt unter der Oberflächenhaut viele aufgereihte streifenartige Hohlräume, die senkrecht zur Spritzrichtung zur Mitte des Probekörpers wachsen. Aus diesen Beobachtungen kann geschlossen werden, daß eine beim Spritzgießen durch den Schmelzefluß induzierte Scherspannung nicht nur die Entstehung der Oberflächenhaut verursacht, sondern auch bis in die Mitte des Probekörpers hinein die Bildung abgeplatteter Sphärolithe bewirkt. Diese abgeplattet-sphärolithischen Strukturen sind für die beim Dehnen des spritzgegossenen PB-1 entstehenden, streifenartigen Hohlräume verantwortlich, während die Oberflächenhaut und die abgeplatteten Sphärolithe im Kern die Sprödigkeit und die im Vergleich zu formgepreßtem PB-1 geringere Bruchdehnung bewirken. Diese kann durch Tempern oberhalb des Schmelzpunktes erhöht werden.
    Notes: The injection-molded poly(1-butene) (PB-1) is found to be more brittle than the compression-molded PB-1. The morphologies of these specimens are examined by use of polarized optical microscopy and scanning electron microscopy (SEM). A skin layer and an oblate spherulitic structure extended to the core region are observed in the injection-molded PB-1, while typical spherulites exist in the compression-molded PB-1. Below the skin layer of the injection-molded PB-1, the fracture surface is found to consist of many aligned strip-like voids with ribbon edges propagating to the center of the specimen and perpendicular to the flow direction of injection-molding. Based on these observations, it can be inferred that shear stress induced by the melt flow during the injection-molding does not only cause the formation of skin layer, but also penetrates deeply into the central region of the injection-molded specimen causing the formation of oblate spherulites. The oblate spherulitic structure is responsible for the aligned voids during elongation of PB-1, while the existence of the skin layer and the oblate spherulites in core region is responsible for the brittleness of the injection-molded PB-1. The elongation of the injection-molded PB-1 is found to be lower than that of the compression-molded. This can be attributed not only to the presence of the skin layer but also to the oblate spherulites in the core region. The elongation can be improved by annealing at a temperature above the melting point of PB-1.
    Additional Material: 7 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 103-111 
    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 Kondensation von p-Xylol mit Chloracetylchloride, 1,2-Dichlorethan und Dichlormethan mit Aluminiumtrichlorid in Schwefelkohlenstoff wurden Polyketone hergestellt und IR-spektroskopisch sowie bezuglich des Molekulargewichtes charakterisiert. Die thermischen Eigenschaften wurden thermogravimetrisch und mittels DSC untersucht. Die Prüfung der Harze auf ihre biologische Aktivität gegen Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger ergab, daß deren Wachstum durch die Polyketonharze kontrolliert werden kann.
    Notes: Some polyketones were prepared from p-xylene, chloroacetylchloride, 1,2-dichloroethane and dichloromethane using anhydrous aluminiumtrichloride and carbon disulfide as solvent. The resins thus obtained have been characterized by IR spectra and number average molecular weight. The thermal properties have been studied by thermogravimetry and differential scanning calorimetry. All the resins were tested for their biological activity against Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger. The results show that the growth of the tested organisms can be controlled by the polyketone resins.
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  • 43
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 145-153 
    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 der Arbeit wurde die homogene Polyaddition von Pyromellitsäuredianhydrid und 4,4′-Diaminodiphenylmethan untersucht. Die Abhängigkeit des zahlenmittleren Molekulargewichts (M̄n) von der Zeit weist ein Maximum auf. Die Ursache der niedrigen Gleichgewichtswerte von M̄n beruht auf einer durch Wasserspuren im Lösungsmittel verursachten Dianhydridhydrolyse und damit einer gestörten Äquimolarität der funktionellen Gruppen. Im Laufe der Stabilisierung des M̄n-Gleichgewichtswertes entsteht auch die wahrscheinlichste Molmassenverteilung.
    Notes: The homogeneous polyaddition reaction of pyromellitic dianhydride with 4,4′-diaminodiphenylmethane was investigated. The dependence of the number average molecular weights on time has a maximum; low equilibrium values of M̄n are caused by a disturbed equimolarity of functional groups due to the hydrolysis of dianhydride with water present in the solvent. In the course of establishment of the equilibrium M̄n value, the molecular weight distribution changes to the most probable value.
    Additional Material: 4 Ill.
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 133-144 
    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 Phasen- und Mischbarkeitsverhalten der binären und ternären Polymermischungen von Polyarylat (PAR), Phenoxid und Poly(butylenterephthalat) (PBT) wurde untersucht. Die Mischungen wurden durch Ausfällen aus gemeinsamen Lösungen hergestellt, und die Mischbarkeit wurde durch DSC-Messungen und Transparenz der Schmelze beurteilt. Im Falle der binären Blends zeigten PAR/PBT und Phenoxid/PBT Mischbarkeit, während sich PAR/Phenoxid nicht mischen ließ. Die Mischbarkeitstendenz der unmischbaren PAR/Phenoxid-Mischungen konnte jedoch durch Zugabe von PBT erhöht werden; eine ausreichende Menge PBT machte die ternären Mischungen mischbar, so daß diese eine einzige Tg in der DSC-Kurve zeigten. Im ternären Phasendiagramm war das Maximum der Mischbarkeitsgrenze in Richtung auf die Phenoxidseite hin verschoben, was auf die bessere Mischbarkeit von PAR/PBT im Vergleich zu Phenoxid/PBT zurückgeführt wird.
    Notes: The phase and miscibility behavior of binary and ternary blends containing polyarylate (PAR), polyhydroxyether of bisphenol AIUPAC: poly[oxy(2-hydroxytrimethylene)oxy-1,4-phenylene-isopropylidene-1,4-phenylene]. (Phenoxy), and poly(butylene terephthalate) (PBT) were studied. The blends were prepared by solution-precipitation method and miscibility was examined by DSC and melt transparency. In binary blends, PAR/PBT and Phenoxy/PBT blends show miscibility, while PAR/Phenoxy appeared to be immiscible. However, the miscibility of incompatible PAR/Phenoxy blend was enhanced by addition of PBT. The addition of sufficient amount of PBT caused the ternary blend to have a single glass transition temperature. The shape of miscibility boundary of ternary blend was skewed to the apex of Phenoxy, which was attributed to the better miscibility of PAR/PBT than that of Phenoxy/PBT.
    Additional Material: 11 Ill.
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  • 45
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Festphasen-Polykondensation von amorphen, unorientierten Poly(ethylenterephthalat)-Folien (PET) (Vorstufe der Du Pont Mylar® -Polyesterfilme), die mit einem speziellen Katalysator-und Monomer-System hergestellt wurden, war Gegenstand dieser Arbeit. Der Einfluß verschiedener Reaktionsparameter, wie Reaktionstemperatur und -zeit, auf die inhärente Viskosität (ηinh) und auf die Anzahl der Carboxy-und Hydroxy-Endgruppen wurde untersucht. Aus den Messungen von ηinh wurde eine empirische Gleichung erstellt, die die Berechnung von M̄n der PET-Folien nach der Festphasen-Polykondensation bei gegebener Zeit und Temperatur erlaubt. Das Schmelzverhalten verschiedener Festphasen-Polykondensate wurde ebenfalls untersucht.
    Notes: The solid-state polycondensation of poly(ethylene terephthalate) (PET) amorphous and unoriented films from Du Pont (precursor for their Mylar® Du Pont's registered trade mark for the polyester film. polyester film) prepared from a specified catalyst and monomer system has been studied. The effect of various reaction parameters such as reaction temperature and time on inherent viscosity (ηinh) and number of carboxy and hydroxy end-groups has been investigated. From ηinh measurements an empirical equation was taken which allows the calculation of (M̄n) of PET film after solid-state polycondensation at a certain temperature and time. The melting behaviour of the solid-state polycondensated samples was also studied.
    Additional Material: 10 Ill.
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  • 46
    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: Sphärische makroporöse Partikel, die als Trägermaterialen für verschiedene Säulen-Operationen eingesetzt werden sollen, wurden mittels Suspensions- und Mikrosuspensionspolymerisation von Trimethylolpropan-trimethacrylat (TRIM) in Gegenwart verschiedener Mengen porogener Reagenzien (Toluol bzw. Mischungen von Toluol und Isooktan) hergestellt. Textur und Eigenschaften der Partikel variierten deutlich mit dem Anteil und der Zusammensetzung des porogenen Reagens und wurden zusätzlich durch die Wahl des Suspensionstabilisators beeinflußt. Die makroporösen Partikel wiesen ein Gesamtporenvolumen von 0,4 bis 3,6 cm3/g und eine spezifische Oberfläche von 7 bis 〉 450 m2/g auf. Alle Partikel enthielten Makroporen und, außer den Teilchen mit sehr niedriger spezifischer Oberfläche, einen gewissen Anteil an Mikroporen (Durchmesser 〈 60 Å). Durch Erniedrigung der Monomerkonzentration und Erhöhung des Isooktan-Gehaltes im porogenen Reagens auf 50 Gew.-% konnte das Auftreten von Mikroporen vollständig unterdrückt werden. Das Erhöhen des Isooktan-Gehaltes führte zu einem vergrößerten Gesamtporenvolumen und zu einem verringerten Quellvermögen der Polymermatrix in Toluol. Der Einfluß einer Hitzebehandlung bei 130°C und eines Aufpfropfens von Polymethylmethacrylat auf die Partikeleigenschaften wurde ebenfalls untersucht.Die Menge an nicht umgesetzten Doppelbindungen in den Partikeln konnte durch Variation der Polymerisationstemperatur verändert werden. Das Vorhandensein leicht zugänglicher Doppelbindungen ist wichtig, da sie zur Funktionalisierung der festen makroporösen Partikel verwendet werden können.
    Notes: Spherical macroporous particles, intended for use as carrier particles in various types of column operations, were prepared by suspension and microsuspension polymerization of trimethylolpropane trimethacrylate (TRIM), in the presence of various amounts of porogenic agents (toluene or mixtures of toluene and isooctane). The texture and properties of the particles varied markedly with the amount and composition of the porogenic agent, and were also affected by the choice of suspension stabilizer. Macroporous particles were prepared, ranging in total pore volume from 0.4 to 3.6 cm3/g, and in specific surface area from 7 to 〉450 m2/g. All of the particles contained macropores, and except for those with very low specific surface area, contained a certain fraction of micropores (diameter 〈60 Å). The presence of micropores could be eliminated completely by decreasing the monomer concentration and increasing the isooctane content of the porogenic agent to 50 wt.-%. Increasing the isooctane content also resulted in an increase in the total pore volume and a decrease in the tendency of the polymer matrix to swell in toluene. The effect on properties of particles by heat treatment at 130°C and by grafting poly(methyl methacrylate) onto the particles was also studied.The amount of unreacted double bonds of the particles could be varied by varying the polymerization temperature. The presence of easily accessible double bonds is important as they can be utilized for functionalization of the rigid macroporous particles.
    Additional Material: 11 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 31-38 
    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 einfache Methode für die Bestimmung der Grenzflächenhaftung in kurzfaserverstärkten Polymeren, beruhend auf der Längenverteilung von aus der Bruchfläche herausgezogenen Faserteilen, wurde entwickelt. Die Messungen mit Faserverbundwerkstoffen von isotaktischem Polypropylen mit 32 Gew.-% Kurzglasfasern bestätigen die Brauchbarkeit dieser Methode für eine empfindliche Beurteilung von Unterschieden in der Grenzflächenhaftung. Die Einflüsse von Temperatur, Polymer- und Glasfasermodifizierung sowie Faserorientierung auf die Grenzflächenhaftung wurden untersucht.
    Notes: For the evaluation of the interfacial adhesion in short-fibre composites, a simple method based on fibre pull-out length distribution was proposed. The experiments with three composites of isotactic polypropylene with 32 wt.-% of short-glass fibres confirm the potentials of the method for a sensitive determination of differences in the interfacial adhesion. The effects of temperature, crystallinity and fibre orientation angle on the interfacial adhesion were investigated.
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  • 48
    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: PE und EPDM-Kautschuk wurden durch Aufpfropfen von Dibutylmaleat (DBM) mit Dicumylperoxid (DCP) als Initiator in Substanz im Temperaturbereich von 140-220°C funktionalisiert. Der Pfropfungsgrad wurde IR-spektroskopisch und durch DSC-Messungen ermittelt. Die für die Pfropfung optimalen DBM- und DCP-Konzentrationen betragen 0,5 bzw. 0,2 Gew.-%. Die Kinetik der Pfropfreaktion ist für PE und EPDM vergleichbar; die Aktivierungsenergien betragen ca. 145 bzw. 130 kJ/mol. Die Pfropfungsgrade sind für PE höher als für EPDM; bei PE/EPDM-Blends steigt der Pfropfungsgrad mit zunehmendem PE-Anteil. Ein Pfropfungsmechanismus, der Nebenreaktionen berucksichtigt, wird vorgeschlagen.
    Notes: Functionalization of polyethylene (PE) and ethylene propylene diene terpolymer (EPDM) in the bulk through dicumyl peroxide (DCP) initiated grafting of dibutyl maleate (DBM) has been studied in the temperature range from 140 to 200°C. The degree of grafting has been determined by infrared spectrophotometry and DSC. The concentration of DBM and DCP has been optimized. 0.5 wt.-% and 0.2 wt.-% DCP for PE and EPDM, respectively, and 10% DBM for both have been found to be the optimum. The kinetics of the grafting reaction is comparable for PE and EPDM. The activation energy of grafting is ca. 145 kJ/mol for PE and ca. 130 kJ/mol for EPDM. The influence of structure of polyolefins on the degree of grafting has also been studied. A higher degree of grafting is obtained for PE than for EPDM. For PE/EPDM blends, the degree of grafting increases with increasing PE content in the blends. A through discussion and proposed mechanism for grafting and other competitive secondary reactions has been provided.
    Additional Material: 7 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 71-80 
    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 dynamisch-mechanischen Eigenschaften von gehärteten Epoxidharzen, gefüllt mit porösen Siliciumdioxid-Mikrokugeln mit unterschiedlichen spezifischen Oberflächen, Porenradien, Porenvolumina und adsorbierter Wassermenge, wurde untersucht. Die Glasubergangstemperaturten (Tg) der Composite sind 12-14°C niedriger als die des ungefullten Harzes, was auf die bevorzugte Adsorption von Härter an den porösen Mikrokugeln zurückgeführt wird. Mit zunehmender adsorbierter Wassermenge steigt die Tg der Composite an. Der Speichermodul ist mit der mit Quecksilber bestimmten spezifischen Oberfläche (Hg-Oberfläche) der Mikrokugeln, die der Summe der Oberfläche von Poren mit einem Durchmesser größer als 4 nm entspricht, korreliert.Das Verbältnis tan δc/tan δm nimmt mit zunehmender Hg-Oberfläche ab.
    Notes: Dynamic mechanical properties were studied for epoxy resin filled with porous silica microballoons with varying surface area, pore radius, pore volume and adsorbed water. The glass transition temperature (Tg) of the composites is 12-14°C lower than the Tg of the unfilled epoxy resin. This Tg depression is attributed to the preferential adsorption of curing agents on the porous silica microballoons. Tg of the composite increases with increase in the adsorbed water on fillers. The storage modulus has a distinct correlation with the Hg-surface area of silica microballoons, which corresponds to the sum of the surface area of pores with radii larger than about 4 nm.Tan δc tan δm decreases with increasing Hg-surface area.
    Additional Material: 5 Ill.
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  • 50
    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: Membranen aus Blends von Nylon 6 mit Poly(acrylsäure) (PAA) mit PAA-Gehalten zwischen 25 und 45 Gew.-% wurden durch Filmgießen hergestellt und anschließend durch Eintauchen in eine Aluminiumsalzlösung ionisch vernetzt. Die Glasübergangstemperaturen (Tg) der Membranen wurden mit der DSC-Methode bestimmt. Alle Proben zeigen eine einzige Tg oberhalb der Tg der Homopolymeren, die sich mit zunehmender Scanzeit verschiebt; dies wird auf die Eliminierung von Wasser und die Bildung von Anhydriden im nicht vernetzten PAA-Anteil zurückgeführt.Die Morphologie wurde rasterelektronenmikroskopisch untersucht; die Membranen zeigen eine dichte, porenfreie Struktur ohne Phasenseparation, was auf eine völlige Mischbarkeit der beiden Homopolymeren im untersuchten Zusammensensetzungsbereich schließen läßt. Die Festigkeit der Membranen liegt je nach PAA-Gehalt zwischen 5 und 26 MPa; Membranen mit hohem PAA-Anteil zeigen trotz höherer Vernetzungsdichte eine geringere Zugfestigkeit, was mit der geringen Festigkeit von PAA und der mit größerem PAA-Anteil zunehmenden Quellung zusammenhängt. Letztere wurde durch Messen der Wasseraufnahme trockener Membranen bestimmt; sie steigt von 23,6 Gew.-% bei einem PAA-Gehalt von 25 auf 76,3 Gew.-% bei einem PAA-Gehalt von 45 Gew.-%.
    Notes: Ionically crosslinked blended membranes were prepared from blends of nylon 6 and poly(acrylic acid) (PAA) with the proportion of PAA ranging from 25 to 45 wt.-%. The technique consists of casting a film of the blend, followed by drying and immersion in an aluminum salt crosslinking solution for a predetermined time. The glass transition temperature (Tg) of the membranes was determined by differential scanning calorimetry (DSC). All the samples exhibited a single Tg, which is higher than that of either polymer. There is also a shift in the Tg with increasing scanning time. This phenomenon is attributed to the elimination of water molecules and the formation of anhydrides in the non-crosslinked PAA portion of the membrane. The membrane morphology was studied using scanning electron microscopy (SEM) and shows a dense structure without any pores. No phase separation is observed by scanning cross-sections of the samples, indicating that nylon 6 and PAA are completely miscible in the ranges studied. The membrane material strength lies in the range of 5 to 26 MPa and varies with the amount of PAA in the membrane. Samples with higher PAA content show lower tensile strength in spite of increased crosslinking density. This is due to the inherent low strength of PAA, coupled with increasing swelling of the membrane with increasing PAA content. The latter is confirmed by the measurement of water uptake into a dry membrane which increases from 23.6% to 76.3% with the membrane PAA content increasing from 25 to 45 wt.%.
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  • 51
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 81-107 
    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: Practically no adhesion is observed at the interface poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve adhesion between these interfaces. We have also discussed the question of possible reinforcement, i.e. increase of tensile strength and a simultaneous decrease of elongation.In this first part we present some calculations demonstrating the prerequisites for reinforcement using existing theoretical models. We describe the influence of modification of the glass fiber surface by dispersion coating or by plasma polymerization.In a second part the influence of polymer surface modification and of additives will be dealt with.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff. Es wurde der Frage nachgegangen, ob es Wege zur Verbesserung der Grenzflächenhaftfestigkeit gibt und ob diese Verbesserungen ausreichen, eine Verstärkung, d. h. Anhebung der Reißfestigkeit bei gleichzeitigem Rückgang der Dehnung des Gesamtsystems zu erzielen.In diesem ersten Teil wird den theoretischen Voraussetzungen und der Modifizierung der Füllstoffoberflächen mittels Dispersionsbeschichtungen sowie Plasmaätzen und Plasmapolymerisation nachgegangen.In einem zweiten Teil werden Möglichkeiten zur Verbesserung der Grenzflächenhaftung durch Modifizierung der Polymer-Oberfläche und durch Additive untersucht.
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  • 52
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 109-126 
    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: Practically no adhesion is observed at the interphase of poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve this adhesion and discuss the influence of this improved adhesion on the mechancial properties of the multiphase system.In this paper the influence of a modified polymer surface and of additives is described.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff.Es wurde die Frage untersucht, ob es Methoden gibt, diese Grenzflächenhaftung zu erhöhen und welchen Einfluß diese Erhöhung auf die Eigenschaften des Verbundsystems hat.In dem hier vorliegenden Teil 2 wird speziell auf den Einfluß der Modifizierung der Polymeroberfläche und des Zusatzes von Additiven eingegangen.
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  • 53
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 127-144 
    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: Due to the very strong variation of the viscosity of the reaction mass with increasing monomer conversion, three stationary states for the tubes of a multitubular system with cooling vessel can be found. As a consequence, a maldistribution of the fluid arises, so that the reactor stability and the polymer quality are negatively influenced. The recycling of the reaction mass is a helpful method to increase the reactor stability. In this paper some fundamental aspects of the use of multitubular reactors for the polymerization of styrene are studied.
    Notes: Infolge der sich mit steigendem Monomerumsatz stark verändernden Viskosität der Reaktionsmasse existieren im Multirohrreaktor mit Kühlung mindestens drei stationaäre Punkte bezüglich des Einzelrohrmassenstromes gleichzeitig. Als Konsequenz ergibt sich eine Ungleichverteilung der Rohrbelastung, die sowohl die Reaktorstabilität als auch die Polymerqualität negativ beeinflußt. Das Betreiben einer Rückführung kann das Reaktorverhalten stabilisieren. In der vorgelegten Arbeit werden einige fundamentale Aspekte der Anwendung von Multirohrreaktoren für die Massepolymerisation von Styrol untersucht.
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  • 54
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 191 (1991), S. 171-176 
    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 nucleophile Substitution von verschieden substituierten Phenoxygruppen in Polyphenylacrylaten durch Ethanolamin in Dioxan wurde bei 60, 80 und 100°C untersucht. Der Umsatz wurde IR- und 1H-NMR-spektroskopisch und elementaranalytisch bestimmt; er hängt sowohl von der Temperatur als auch von der Art der Substituenten am Phenylring ab.
    Notes: The nucleophilic substitution reaction of differently substituted phenoxy groups with ethanolamine in various poly(phenyl acrylate)s was investigated in dioxane at 60, 80, and 100°C. The conversion, as determined from IR- and 1H-NMR spectroscopy and elemental analysis, depends on the temperature and the kind of substituents at the phenyl ring.
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  • 55
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 31 (1991) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 56
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heteronuclear multispin coherence proton-detected two-dimensional nmr spectroscopic experiments were used to obtain information on protonated carbons and nitrogens of the self-complementary d (G-G-T-A-T-A-C-C) and d (G-G-A-A-T-T-C-C) duplexes, with and without the drug netropsin dissolved in aqueous solution. Many correlations of protons coupled to 13C nuclei on the base and sugar rings of the octanucleotides were detected, allowing the carbon resonances to be assigned based on previous homonuclear proton two-dimensional nmr studies. Imino nitrogen assignments can also be made using the proton assignments from previous one-dimensional nuclear overhauser effect experiments. Imino nitrogen shifts may be useful indicators of changes in local hydrogen-bonding interactions to base-pair edges.
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  • 57
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyriboadenylates of alkali metals were obtained from (1) K+-poly(A) (salts I) and (2) H+-poly( A) (salts II) by the ion-exchange method. The conductivity of these salts as well as of H+-poly(A) were studied. Salts I and II of the same counterion were shown to have significantly different conductivity coefficients (f) and polyion conductances (λp0). The charge density parameter (ζ) was 1.3 and 2.5, respectively, with λp0 equal to 44 and 83 ohm-1 cm2 mole-1 for poly(A)-I and poly (A)-II salts, respectively. This is credited to the difference in the conformations of corresponding polyions. The linear dependence of equivalent conductivity on the square root of polymer concentration (Kohlrausch coordinates), earlier obtained for DNA, is also satisfied for the studied polynucleotides. A comparison of the slopes of straight lines in Kohlrausch coordinates for poly(A), simple electrolytes, and for earlier studied polyribouridylic acid salts lends credence to the concepts, developed by a number of authors, that DNA can act as a “buffer” against the ion-ion interaction in concentrated electrolyte solutions. Using the approximation that the polyion conductance is independent of the counterion nature, parameter f (agreeing in this case with Eisenberg parameter φ) has been shown to decrease as the polynucleotide concentration is increased; the decrease is caused by the relaxation effect. The transference numbers of counterions, which have negative values in poly (A)-II solutions, grow with the increase in polymer concentration; the higher the ζ, the more apparent is this increase. This is explained by the increase in the fraction of conductivity along the polyion chains (“surface” conductivity) with the growth of polyelectrolyte concentration.
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  • 58
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding of the hydrophobia fluorescent probe, 1-anilino-naphthalene-8-sulfonate (ANS), to synthetic polypeptides and proteins with a different structural organization has been studied. It has been shown that ANS has a much stronger affinity to the protein “molten globule” state, with a pronounced secondary structure and compactness, but without a tightly packed tertiary structure as compared with its affinity to the native and coil-like proteins, or to coil-like, α-helical, or β-structural hydrophilic homopolypeptides.The possibility of using ANS for the study of equilibrium and kinetic molten globule intermediates is demonstrated, with carbonic anhydrase, β-lactamase, and α-lactalbumin as examples.
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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: We employ a mean field, modified, self-consistent phonon theory to evaluate the single base-pair opening rate and the probability of a base pair in the amino proton exchangeable state for the homopolymer poly(dA) · poly(dT) at temperatures below the helix-coil transition region. Our calculated premelting single base-pair opening probabilities are in general agreement with several available experimental estimates from imino proton exchange and formaldehyde-induced DNA melting measurements. These calculated opening probabilities, however, are in disagreement with the prediction of the helix-coil transition theory. Possible reasons for the differences are discussed, especially the possible different definition of a meaningful open state in the premelting region. The premelting open state of the modified self-consistent phonon approximation theory seems to be appropriate to describe a solvent-accessible open configuration that is sufficient to facilitate important chemical reactions such as imino proton exchange and formaldehyde reaction with the bases. This can be compared with the completely unstacked open state of the helix-coil transition theory originally defined in the helix-coil transition region. We propose that the amino proton exchangeable state is different from the open state associated with melting and only involves the breaking of the amino interbase H bond. The agreement between the calculated and experimentally estimated probability of a base pair in the amino proton exchangeable state seems to support this hypothesis.
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  • 60
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    Biopolymers 31 (1991), S. 169-176 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results of free electrophoresis and free sedimentation of charged rods are introduced to allow for electrical double-layer effects in the gel electrophoresis of DNA, modeled as a Random flight sequence of rodlike Kuhn chain elements. The kinetics of DNA is shown to depend strongly on the orientation of the chain elements with respect to the external field and with respect to the direction of their velocity. The new theory gives approximate agreement between the DNA charge derived from electrophoresis of free and tethered DNA (close to 1.0e per DNA phosphate in both cases), compared with the earlier discrepancy of a factor 10 or 20 for the theory without shielding by salt. As part of a realistic force field for macromolecular dynamics simulation, the small ion effects are included in an expression for the gel forces restraining the DNA in gel electrophoresis from moving as in free electrophoresis.
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  • 61
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    New York : Wiley-Blackwell
    Biopolymers 31 (1991), S. 211-232 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of G · T mispair incorporation into a double-helical environment was examined by molecular dynamics simulation. The 60-ps simulations performed on the two hexanucleotide duplexes d (G3C3)2 and d (G3TC2)2 included 10 Na+ counterions and first hydration shell waters. The resulting backbone torsional angle trajectories were analyzed to select time spans representative of conformational domains. The average backbone angles and helical parameters of the last time span for both duplexes are reported. During the simulation the hexamers retained B-type DNA structures that differed from typical A- or B-DNA forms. The overall helical structures for the two duplexes are vary similar. The presence of G · T mispairs did not alter the overall helical structure of the oligonucleotide duplex. Large propeller twist and buckle angles were obtained for both duplexes. The purine/pyrimidine crossover step showed a large decrease in propeller twist in the normal duplex but not in the mismatch duplex. Upon the formation of wobble mispairs in the mismatched duplex, the guanines moved into the minor groove and the thymines moved into the major groove. This helped prevent purine/purine clash and created a deformation in the relative orientation of the glycosidic bonds. It also exposed the free O4 of the thymines in the major groove and N2 of the guanines in the minor groove to interactions with solvent and counterions. These factors seemed to contribute to the apparently higher rigidity of the mismatched duplex during the simulation.
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  • 62
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    Biopolymers 31 (1991), S. 253-254 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 63
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a factor analysis technique, the experimental physicochemical data on the hydration of mononucleotides, several polynucleotides, their double-helical complexes and natural DNAs were studied. The information about the factors determining the changes in physicochemical parameters vs the hydration was obtained. This work discusses a possible physical sense of the factors obtained and the expedience of using factor analysis to interpret the molecular-biophysical experiments.
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  • 64
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    Biopolymers 31 (1991), S. 319-330 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Electrostatically Driven Monte Carlo (EDMC)method was applied in a study of a decamer of glycine whose conformational behavior is described by the Empirical Conformational Energy Program for Peptides (ECEPP/2) potential energy model. When free neutral end groups were used, it was found that conformations that were not α-helical had significantly lower potential energies than fully α-helical ones. However, when the N- and C-termini were blocked by acetyl and methyl amide groups, respectively, the number of unsatisfied hydrogen-bond donors and acceptors at the helix termini was diminished from 8 to 6; in this case, the possibility of forming two additional α-helical hydrogen bonds was an important enough factor in making the α-helical conformation the one with the lowest energy. The EDMC method was used as a global energy optimizer since it does not often become trapped in high-energy local minima.
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  • 65
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of the complexes formed in aqueous solution between ditercalinium, a bisintercalating drug, and both the self-complementary tetranucleotide d(GCGC)2 and octanucleotided(CCTATAGG)2, have been investigated by 400-MHz 1H-nmr and 162-MHz 31P-nmr. All the nonexchangeable protons, as well as the exchangeable imino protons and the phosphorus signals, have been assigned. Both oligonucleotides have been shown to adopt a right-handed B-DNA type structure. The addition of ditercalinium to the oligo-nucleotides lead to the formation of complexes in slow exchange at the nmr time scale with the free helices. At all drug-to-helix ratios studied, the ditercalinium was found in the bound form, whereas free and complexed oligonucleotides were in slow exchange, allowing resonance assignments through two-dimensional chemical exchange experiments.For d(GCGC)2 the strong upfield shifts induced on all aromatic protons of both the bases and the drug by complexation with ditercalinium suggest an interaction by intercalation of the two rings. However, the loss of twofold symmetry upon binding, as well as the chemical shift variation of the drug proton signals of one of the chromophores with temperature and concentration, favor a model in which the drug-nucleotide complexes have one ring of the drug intercalated and the other stacked on top of the external base pair. The intermolecular contacts between drug protons and nucleotide protons give a defined geometry for complexation that is consistent with the proposed model.In contrast, with d(CCTATAGG)2 several drug-nucleotide complexes were formed and a large increase in line broadening was observed at high drug-to-DNA ratios, precluding a detailed analysis of these complexes. However, the large upfield shift in the imino proton resonances together with the shielding of the ditercalinium ring protons favor a model with bis-intercalation of ditercalinium. This model is supported by the downfield shift of at least 4 out of 14 phosphorus signals. The results are compared with those obtained on ditercalinium binding to the homologous sequences d(CGCG)2 and d(TTCGCGAA)2, and discussed in terms of sequence specificity.
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  • 66
    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-Val (C10H19N3O4·3H2O; GAV) crystallizes in the monoclinic space group P21, with a = 8.052(2), b = 6.032(2), c = 15.779(7) Å, β = 98.520(1)°, V = 757.8 Å3, Dx = 1.312 g cm-3, and Z = 2. The peptide Gly-L-Ala-L-Leu (C11H21N3O4·3H2O; GAL) crystallizes in the orthorhombic space group P212121, with a = 6.024(1), b = 8.171(1), c = 32.791(1) Å, V = 1614 Å3, Dx = 1.289 g cm-3, and Z = 4. Their crystal structures were solved by direct methods using the program SHELXS-86, and refined to an R index of 0.05 for 1489 reflections for GAV and to an R index of 0.05 for 1563 reflections for GAL. The tripeptides exist as a zwitterion in the crystal and assume a near α-helical backbone conformation with the following torsion angles: ψ1 = -150.7°; φ2, ψ2 = -68.7°, -38.1°; φ3, ψ31, ψ32, = -74.8°, -44.9°, 135.9° for GAV; ψ1 = -150.3°; φ2, ψ2 = -67.7°, -38.9°; φ3, ψ31, ψ32 = -72.2°, -45.3°, 137.5°, for GAL. Both the peptide units in both of the tripeptides show significant deviation from planarity [ω1 = -171.3(6)° and ω2 = -172.0(6)° for GAV; ω1 = -171.9(5)° and ω2 = -173.2(6)° for GAL]. The sidechain conformational angles χ21 and χ22 are -61.7(5)° and 175.7(5)°, respectively, for valine, and the side-chain conformations χ12 and χ23's are -68.5(5)° and (-78.4(6)°, 159.1(5)°) respectively, for leucine. Each of the tripeptide molecule is held in a near helical conformation by a water molecule that bridges the NH3+ and COO- groups, and acts as the fourth residue needed to complete the turn by forming two hydrogen bonds. Two other water molecules form intermolecular hydrogen bonds in stabilizing the helical structure so that the end result is a column of molecules that looks like an α-helix.
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  • 67
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    Biopolymers 31 (1991), S. 435-447 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effective sphere approximation for modeling electrophoretic transport of macromolecules in highly porous gels (the “Ogston model”) is examined, and contrasted with similar mobility models for stiff and flexible solutes. Calculation of segmental depletion near gel obstacles of various shapes demonstrates the limited applicability of the effective sphere approach. For highly flexible chains, both theory and experiment reveal a nonunique mapping between mobility and molecular size when the molecular radius is comparable to that of gel fibers. Turning to mobility behavior in more concentrated gels, neither flexible or stiff macromolecules behave as spheres; for the particular case of flexible chains, the presence of entropic barriers in concentrated gels can be understood in terms of a simple random planes model for the gel structure.
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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: Differential scanning calorimetry studies of the effect of NaCl on protein-based polymer self-assembly has been carried out on six elastin-based synthetic sequential polypeptides- i.e., the polypentapeptide (L-Val1-L-Pro2-Gly3-L-Val4-Gly5)n and its more hydrophobic analogues (L-Leu1-L-Pro2-Gly3-L-Val4-Gly5)n and (L-Val1-L-Pro2-L-Ala3-L-Val4-Gly5)n; the polytetrapeptide (L-Val1-L-Pro2-Gly3-Gly4)n and its more hydrophobic analogue (L-IIe1-L-Pro2-Gly3-Gly4)n; and the polynonapeptide (a pentatetra hybrid), (L-Val1-L-Pro2-Gly3-L-Val4-Gly5-L-Val6-L-Pro7-Gly8-Gly9)n.Previous physical characterizations of the polypentapeptides have demonstrated the occurrence of an inverse temperature transition since increase in order of the polypentapeptide, as the temperature is raised from below to above that of the transition, has been repeatedly observed using different physical characterizations.In the present experiments, it is observed that the transition temperatures of the polypeptides studied are linearly dependent on NaCl concentration. The molar effectiveness of NaCl in shifting the transition temperature ΔTm/[N], is about 14°C/[N], with the dependence on peptide hydrophobicity being fairly small. Interestingly, however, the δΔQ/ [N] does depend on the hydrophobicity of a polypeptide.
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  • 69
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    New York : Wiley-Blackwell
    Biopolymers 31 (1991) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 70
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure and activity of a protein molecule are strongly influenced by the extent of hydration of its cavities. This is, in turn, related to the free energy change on transfer of a water molecule from bulk solvent into a cavity. Such free energy changes have been calculated for two cavities in a sulfate-binding protein. One of these cavities contains a crystallo graphically observed water molecule while the other does not. Thermodynamic integration and perturbation methods were used to calculate free energies of hydration for each of the cavities from molecular dynamics simulations of two separate events: the removal of a water molecule from pure water, and the introduction of a water molecule into each protein cavity. From the simulations for the pure water system, the excess chemical potential of water was computed to be -6.4 ± 0.4 kcal/mol, in accord with experiment and with other recent theoretical calculations. For the protein cavity containing an experimentally observed water molecule, the free energy change on hydrating it with one water molecule was calculated as -10.0 ± 1.3 kcal/mol, indicating the high probability that this cavity is occupied by a water molecule. By contrast, for the cavity in which no water molecules were experimentally observed, the free energy change on hydrating it with one water molecule was calculated as 0.2 ± 1.5 kcal/mol, indicating its low occupancy by water. The agreement of these results with experiment suggests that thermodynamic simulation methods may become useful for the prediction and analysis of internal hydration in proteins.
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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: The conformational possibilities of three different δ-selective opioid peptides, which are DPDPE , and DRE (Tyr-D-Met-Phe-His-Leu-Met-Asp-NH2, dermenkephalin), were explored using energy calculations. Sets of low-energy conformers were obtained for each of these peptides. The sets consisted of 61 structures for DPDPE, 32 for DCFPE, and 38 for DRE, including various types of rotamers of the Tyr and Phe side-chain groups. Comparison of the geometrical shapes of the conformers was performed for these sets using topographical considerations, i.e., examination of the mutual spatial arrangement of the N-terminal α-amino group, and of the Tyr and Phe side-chain groups. The results obtained suggest a model for the δ-receptor-bound conformer(s) for opioid peptides. The model suggests the placement of the Phe side chain in a definite position in space corresponding to the g- rotamer of Phe for peptides containing Phe4 and to the t rotamer for peptides containing Phe.3 The position of the Tyr1 side chain cannot be specified so precisely. The proposed model is in a good agreement with the results of biological testing of β-Me-Phe4-substituted DPDPE analogues that were not considered in the process of model construction.
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  • 72
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    Biopolymers 31 (1991), S. 835-843 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complete nmr and CD studies of two cyclic tetrapeptides with disulfide bonds, 1 and 2 bonds have been carried out in different solvents to investigate the formation and stabilization of β-turn structures and to determine the stereochemistry of the disulfide linkage. Both peptides have three-dimensional structures with a type II β-turn, as derived from quantitative nuclear Overhauser effect data. The combined use of CD and nmr indicates that the dihedral angle of the disulfide bridge is different in the two peptides, although the chirality is maintained.
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  • 73
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved studies of network self-organization from homogeneous solutions of the representative biostructural polymer agarose are presented. Solutions are temperature quenched and observed by several techniques. Consistent with previous suggestions by the authors, experiments at concentrations up to about 1.75% w/v provide direct kinetic evidence for the occurrence of at least two distinct processes, leading, in sequence, to self-assembly. These are as follows: (a) a liquid-liquid phase separation of the solution occurring via spinodal demixing and resulting in two sets of regions that have, respectively, higher and lower than average concentrations of random-coiled polymers; and (b) the subsequent 2 coils → double helix transition and accompanying cross-linking and gelation (due to branching of double helices), occurring in the high-concentration regions. The size of the high-concentration regions depends upon agarose concentration and quenching temperature, and is in the range from a fraction of micrometers to a few micrometers, in agreement with earlier experiments. Bundling of the double-helical segments is known to follow self-assembly and can be considered as a third step (gel curing). This follows from the thermo-dynamic instability of the helical segments in the solvent, behaving as a system of rod-like particles connected by more or less flexible joints.The two processes leading in succession to self-assembly are discussed in terms of a phase diagram consistent with available data. Their time scales differ remarkably. At the end of the first process, all polymers remain random coiled and freely drifting. Much later coil-helix transition is observed, always in coincidence with polymer cross-linking and gelation. The enhancement of concentration of random-coiled polymers in specific regions of the sol caused by spinodal demixing is thus a prerequisite for self-assembly of these biostructural gels in the concentration interval studied. Conceptually, concentration enhancements of this type can provide a new pathway for promotion of functional biomolecular interactions even at very low average concentrations. The mechanism will work identically if the region of instability is reached by varying the polymer concentration (e.g., by biosynthesis), rather than by temperature quenching.
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  • 74
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sample peptides Boc-Leu4-Aib-Leu4-OBzl and Boc-(Leu4-Aib)2-OBzl, were crystallized by the solvent-evaporation method. Both crystals are monoclinic, with space group of P21 and Z = 2. The cell parameters are a = 16.580(7), b = 21.105(7), c = 11.583(4) Å, and β = 104.90(3)° (Boc-Leu4-Aib-Leu4-OBzl), and a = 15.247(9), b = 19.04(l), c = 16.311(9) Å, and β = 117.10(1)° [Boc-(Leu4-Aib)2-OBzl]. Crystal structures were solved by the direct method and refined to R values of 0.096 (the former peptide) and 0.112 (the latter). Peptide backbones fold into a right-handed α-helix, except for the C-terminal Aib residue in Boc-(Leu4-Aib)2-OBzl. Both peptide molecules are stabilized by six (the former) or seven (the latter) intramolecular (5 → 1) hydrogen bonds, and arranged in the head-to-tail fashion, which makes an infinite column. In this column, one (the former) or two (the latter) intermolecular hydrogen bonds link the neighboring molecules. In the case of Boc-Leu4-Aib-Leu4-OBzl, the solvent molecule N, N-dimethylformamide was found in the difference Fourier map. There was a hydrogen bond between peptide and solvent molecule. Along the lateral direction, only hydrophobic contacts were observed between adjacent peptide molecules.
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  • 75
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    Biopolymers 31 (1991) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    Biopolymers 31 (1991), S. 1037-1047 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Clusters of ionizable groups are examined for conditions that develop cooperativity (1) on the binding of protons, and (2) on the binding of an associated ligand when the clusters are shared between domains or subunits in macromolecules. Cooperative binding isotherms for protons have long been observed (but not emphasized as cooperative binding) when studies have been done on clusters for the evaluation of metal ion complexation [A. E. Martell & M. Calvin (1952) Chemistry of the Metal Chelate Compounds, Prentice-Hall, Englewood Cliffs, New Jersey]. Reactions are formulated in this paper to show that anions, chelating to positively charged clusters, are also capable of developing the cooperative binding of protons. Extension of these simple reactions to those where clusters of ionizable groups are shared between domains of macromolecules provides models for cooperative binding, which include the allosteric, Bohr, anion, and cation effects in proteins.
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  • 77
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    Biopolymers 31 (1991), S. 1077-1086 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified molecular dynamics (MD) method in which atomic masses are weighted was developed previously for studying the conformational flexibility of neuroregulating tetra-peptide Phe-Met-Arg-Phe-amide (FMRF-amide). The method has now been applied to longer and constrained molecules, namely a disulfide-linked cyclic hexapeptide, c [CYFQNC], and its linear and [pseudo-cyclic] analogues. The sampling of dihedral conformational space of the linear hexapeptide in mass-weighted MD simulations was found to be improved significantly over conventional MD simulations, as in the case of the shorter FMRF-amide molecule studied previously. In the cyclic hexapeptide, the internal constraint of the molecule due to the intramolecular disulfide bond (hence the absence of free terminals in the molecule) does not adversely affect the significant improvement of conformational sampling in mass-weighted MD simulations over normal MD simulations. The pseudo-cyclic polypeptide is identical to the linear CYFQNC molecule in amino acid sequence (i.e., side chains of the cysteine residues are reduced), but the positions of its two terminal heavy atoms were held fixed in space such that the molecule has a nearly cyclic conformation. For this molecule, the mass-weighted MD simulation generated a wide range of polypeptide backbone conformations covering the internal dihedral degrees of freedom; moreover, the physical space of the pseudo-cyclic structure was also sampled in a complete revolution of the entire molecular fragment about the two fixed termini during the simulation. These characteristics suggest that mass-weighted MD can also be an extremely useful method for conformational analyses of constrained molecules and, in particular, for modeling loops on protein surfaces.
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  • 78
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-(3-dimethylaminopropyl) naphtho [2, 1-b] thiophene-4-carboxamide and the 6-substituted methoxy, methyl, fluoro, chloro, bromo, trifluoromethyl, and cyano derivatives have been shown to bind to DNA via intercalation with binding constants in the 35-900 × 103 range at 25°C, pH 7, and [Na+] = 0.019M . Both electron-donating and -withdrawing substituents enhance intercalation binding, but the binding affinity is most enhanced by the cyano substituent. Calorimetric titrations for calf thymus DNA differ dramatically from those reported for ethidium [Hopkins et al. (1990) Biopolymers Vol. 29, pp. 449-459]. Apparent enthalpy parameters (ΔHB) for intercalation are constant only at low coverage of sites and become much more positive as saturation is approached. In the plateau region, ΔHB values for the parent and the cyano-, fluoro-, chloro-, and bromo-substituted compounds are nearly the same (∼ -5.9 kcal/mol). For the methyl- (-6.8 kcal/mol) and methoxy- (-7.5 kcal/mol) substituted compounds, the ΔHB values are more exothermic than that for the un-substituted compound, whereas ΔHB for the trifluoromethyl compound is approximately 1 kcal/mol less exothermic. The corresponding ΔSB values, corrected for mixing effects, are in the 7-15-cal/deg/mol range and are approximately linearly related to ΔHB if the cyano derivative is excluded.
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  • 79
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    Biopolymers 31 (1991), S. 1159-1170 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report here a novel approach to label specifically one of the two cryptic, free sulfhydryl groups per subunit of human plasma fibronectin with either an 15N, 2H-maleimide spin label or a coumarinylphenyl maleimide fluorescent label. This permits the use of electron spin resonance (ESR) or fluorescence techniques to study molecular dynamics of fibronectin with the label attached to a single site per chain on the protein molecule. The method is based on our observation that upon adsorption of fibronectin to a gelatin-coated surface, the SH1 site, located between the DNA-binding and the cell-binding domains, is partially exposed, while the SH2 site, located within the carboxyl-terminal fibrin-binding domain, remains buried and unreactive. The procedures for the preparation of the selectively labeled fibronectins are described in detail. The physicochemical properties of these single-site labeled fibronectins, particularly as affected by high salt, heparin, surface binding, and temperature, were characterized by ESR spin-label and steady-state fluorescence techniques. The steady-state fluorescence measurement indicates that both local environments of SH1 and SH2 sites are relatively hydrophobic, and that the SH2 site is more hydrophobic than the SH1 site. The ESR results show that heparin or high salt induces an increase in the domainal flexibility in both SH1 and SH2 regions, perhaps through the disruption of domain-domain interactions in the fibronectin molecule, and that the former is more effective than the latter in producing such an effect. The observed heparin effect is reversible by addition of calcium ions in the SH2 regions but not in the SH1 regions. In addition, at temperatures above 44°C, both type III homologous regions containing the free sulfhydryl groups are shown to undergo denaturation and aggregation processes. The data presented here suggest that the newly developed method for differential labeling of the free sulfhydryl groups in fibronectin should be useful for mapping the spatial arrangement of structural domains in the protein molecule using spin-label-spin-probe and fluorescence energy transfer techniques.
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  • 80
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    Biopolymers 31 (1991), S. 1221-1228 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of electrophoretic separations of DNA restriction fragments by capillary electrophoresis in solutions of (hydroxyethyl) cellulose (HEC) were performed. Rheological studies were used to confirm that the entanglement threshold (Φ*) for the HEC solutions used is approximately 0.004 g/mL, in good agreement with theoretical predictions. A mesh size an order of magnitude smaller than that found in agarose gels (on a per weight basis) was calculated using polymer-entanglement theory and was confirmed by electrophoretic measurements. Electrophoretic migration was shown to follow the Ogston regime under most conditions. An approach for obtaining smaller mesh sizes is presented.
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  • 81
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    Biopolymers 31 (1991) 
    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 31 (1991), S. 1265-1271 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dynamic light scattering was used to characterize the diffusion of monodisperse polystyrene latex spheres (PLS) of different sizes (55-, 105-, and 265-nm radii) in column-purified 0.65 mg/mL actin solutions polymerized with 100 mM KCl in the absence and presence of various amounts of the actin-binding protein gelsolin. The gelsolin and its interaction with actin was initially studied to ensure that the gelsolin could be used to produce filament populations with well-defined mean lengths. Measurements with PLS diffusion probes present showed, in the absence of gelsolin, that the effective local microviscosity in the actin solutions was 5-20 times that of water and that a large fraction of the PLS are trapped within the pores of the actin filament network, as found previously [J. Newman, K. L. Schick, & K. S. Zaner, (1989) Biopolymers 28, 1969-1980]. As the molar ratio of gelsolin to actin was increased, the diffusion coefficients of the PLS approached those in pure water while the degree of PLS trapping went to zero. Measurements of the dependence of the PLS diffusion coefficients on the ratio of actin concentration to the semidilute overlap concentration showed, for the smaller PLS, a transition occurring near the mean global overlap concentration. These results reflect the dissolution of the actin network as the gelsolin concentration is increased and illustrate the role of gelsolin/actin interactions in the control of macromolecular transport within the periphery of cells.
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  • 83
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    Biopolymers 31 (1991), S. 1343-1346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 84
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of the antitumoral ellipticine derivative 2-methyl-9-hydroxyellipticinium acetate (elliptinium; NMHE) to DNA was analyzed by the combined use of DNase I foot-printing and spectroscopic methods. Using two fragments of pBR322 DNA, five discrete NMHE binding sites of 5-7 protected base pairs (bp) were detected by footprinting at 4°C on the analyzed regions. These corresponded to alternating pyrimidines and purines. The inactive derivative 2-methyl ellipticinium acetate L(NME) lacking a hydroxy group failed to demonstrate DNA protection even at low temperature. Ultraviolet-absorption and 1H-nmr analysis was performed using two autocomplementary octanucleotides d(TGACGTCA) (I) and d(ACTGCAGT) (II). The uv-absorption titrations resulted in an intercalative binding mode for NMHE in the oligomers. Analysis of the derived biphasic Scatchard plots yielded two binding sites corresponding to ∼6-bp and 2-bp sizes and characterized by apparent association constants K1 ∼ 108M-1 and K2 ∼ 106M-1, respectively. The 1H-nmr analysis of exchangeable (imino) protons and nonexchangeable protons performed in the one- and two-dimensional modes confirmed the intercalation of NMHE, and further revealed the existence of multiple sites on DNA. Assuming that imino resonance line width concerned the sole kinetic effects, 10-ms order lifetimes were estimated for the drug-oligonucleotide complexes at 7°C, pH 7, and 0.1 ionic strength. Finally examination of every drug-DNA spectra in the light of the footprinting results indicated that there was a preference for binding of NMHE to the CpG (octamer I) and TpG (octamers I and II) steps.
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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: We used time-dependent fluorescence energy transfer, time-dependent collisional quenching, and global analysis of the data resulting from these through-space and contact interactions to recover the end-to-end distance distributions and diffusion coefficients of flexible fluorescent molecules. The fluorescence decays of covalently linked tryptamine-acceptor and tryptamine-quencher pairs were measured by the frequency-domain method. These data were fit using numerical solutions of the differential equation, which predicts the time-and distance-dependent population of the excited state donors in the presence of energy transfer or collisional quenching, followed by transformation to the frequency domain for nonlinear least-squares comparison with the experimental data. We found that the energy transfer data for the donor-acceptor pair alone were adequate to recover the starting distribution and the end-to-end diffusion coefficient; however, the resolution is dramatically improved by the use of both the through-space and contact interactions.
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  • 86
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    Biopolymers 31 (1991), S. 1429-1435 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemically induced radical reactions involving the lateral sequences and the end macromolecular chain groups of hyaluronic acid in aqueous solutions at 293K were studied by EPR spin trapping technique with DMPO (5,5-dimethylpyrroline-1-oxide). In the first 1-10 minutes of irradiation EPR indicates spin adducts of two carbon centered radicals with the splitting constants of aN = 1.60 mT, aH = 2.51 mT and aN = 1.56 mT, aH = 2.28 mT. After longer irradiation time (over 10 minutes) dominate two further DMPO adducts of radicals centered on hetero-atoms with splitting constants of aN = 1.44 mT, an = 1.60 mT and of aN = 1-49 mT, aH = 1.49 mT. Simultaneously, molecular weight followed by SEC decreases, suggesting that UV irradiation leads to the breaking of interglycosidic bonds of hyaluronic acid main macromolecular chain.
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  • 87
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    Biopolymers 31 (1991), S. 1459-1459 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Biopolymers 31 (1991), S. 1483-1502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In describing the Na+ channel-gating kinetics, it is generally believed the Hodgkin-Huxley model is inadequate and other types of Markovian models are more appropriate. In this paper, we perform detailed kinetic analyses to find out whether the Hodgkin-Huxley model is really unacceptable. Specifically, we consider two models for the analyses: A five-state Markovian model that allows inactivation to take place before opening and a Hodgkin-Huxley eight-state model. The criteria used to check the goodness of the two models are (a) Akaike's information criterion; (b) χ2 tests on the waiting-time, open-time, and closed-time distributions, and the number of openings per record; and (c) comparison between all latency distributions and the probability of the open state predicted from the two models. In order to do this, we first develop a method of constructing probability density histograms of a specified event (e.g., waiting time, closed time, open time, number of openings per patch) from the multichannel patch-clamp recordings. The goodness of our method is checked by simulating multichannel patch recordings using a multinomial random number generator. Our kinetic analysis on the single Na+ channel recordings from the cardiac cells revealed that (a) on the basis of Akaike's information criterion, the Hodgkin-Huxley model is definitely a better model than the five-state model, but (b) on the basis of χ2 tests on the probability density functions, the latter model is slightly better than the former. We find no evidence that the Hodgkin-Huxley model is inferior to the five-state model for this cell type.
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  • 89
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    Biopolymers 31 (1991), S. 1543-1557 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA on the surface of the histone octamer in the native nucleosome core particle is modeled as a circumferentially wound elastic line on the surface of a cylinder. In a model for the radial transition, the line is allowed to straighten, and thus lose energy, by swinging off the surface, but it is impeded in such an excursion by a radial force field representing the attractive interaction between DNA and histone octamer. In a model for the axial transition, the line may straighten by becoming more parallel to a generator of the cylinder while remaining on the surface. In this mode of straightening, dimer-tetramer or tetramer-tetramer interfaces are disrupted, and the resulting energy gain impedes the transition. Both radial and axial transitions are predicted to occur in all-or-none fashion. We propose that these models are related to the abrupt transitions actually observed in the nucleosome core particle.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic recombination of nonreplicating phage λ-DNA, during infection of homoimmune lysogenic bacteria, was previously observed to be dramatically stimulated by prior uv irradiation of the phages, even when the Escherichia coli hosts lacked the major uv-photo-product excision-repair system (UvrABC). UvrABC-independent recombination of circular phage molecules depends on host MutHLS functions and on undermethylation of adenines at GATC sites in the phage DNA, and thus appears to be the result of “mismatch repair” of uv photoproducts. Recombinant frequencies pass through a relatively sharp maximum at 20 J/m2 and decrease at higher doses, whereas most plausible models for the process predict monotonic increases with dose, or a plateau at high uv doses. A uv-dose-dependent loss of biological activity (restriction) of all intracellular phage DNA was also observed previously. In order to provide a framework for testing possible explanations for the unusual recombinant-frequency vs uv-dose curve, a statistical model was constructed. This model includes probability terms for all possible one-exchange and two-exchange recombination processes, and incorporates the assumption that dimer recombinants are more susceptible to restriction than monomer parents (or recombinants), because of their larger target size. By adjustment of model parameters, particularly ∊, the efficiency per photoproduct of initiation of a recombinational exchange, a theoretical dose-response curve that agreed well with experiment was obtained. The best fit corresponded to ∊ = 0.035, close to the previously observed restriction efficiency of 0.053. In the calculations, the value for h0, the average length of heteroduplex DNA, was taken to be 0.5 λ units, i.e., about 25 kilobase pairs. This estimate for h0 was obtained here by analysis of the density distributions of the progeny of crosses between nonreplicating density-labeled λ-phage chromosomes, published by others [M. S. Fox, C. S. Dudney and E. J. Sodergren (1979) Cold Spring Harbor Symposium on Quantitative Biology, Vol. 43, pp. 999-1007].
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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: Effects of salt concentration on the stabilities of oligonucleotide helices are analyzed directly in terms of ΔΓN→yN ≡ ΓyNden - ΓNnat, the difference in the salt-nucleotide phosphate preferential interaction coefficients for the denatured state, having yN phosphate charges, and for the native state, having N phosphate charges (y = 1 for hairpin denaturation and y = 0.5 for dimer denaturation). Previous experimental studies of the denaturation of hairpin oligo-nucleotides (having 18 〈 N 〈 44) indicate significant differences between ΔΓN→N and ΔΓ∞, the value determined for the denaturation of the corresponding polynucleotide. These differences are thermodynamic manifestations of the oligoelectrolyte end effect. In contrast, the available data on the denaturation of oligonucleotide dimer helices (N ≤ 22) imply that differences between ΔΓ∞ and ΔΓN→0.5N, and hence oligoelectrolyte end effects, are small or negligible. To determine the origin of these apparently conflicting implications concerning the importance of oligoelectrolyte end effects, we have calculated the N dependence of ΓN from grand canonical Monte Carlo simulations for an idealized model of the structure and charge distribution of each oligomer conformation. Our calculations are in quantitative agreement with the experimental finding for d(TA) hairpin oligomers that - ΔΓN→N decreases linearly as N-1 increases, and with the extant experimental determinations of ΔΓN→0.5N. These results provide an illustration of how the large electrostatic end effects exhibited by the hairpin denaturation data are masked when ΔΓ∞ is compared with values of ΔΓN→0.5N for short dimer helices (N ≤ 22). For 0.5N 〉 24, - ΔΓN→0.5N is predicted to be a linear function of N-1 whose slope has the opposite sign from, and is more salt-concentration dependent than, the corresponding slope of - ΔΓN→N as a function of N-1. Our calculations also yield predictions about the N dependences of the individual values of ΓN that can be tested by determining Donnan coefficients from membrane dialysis equilibrium experiments. For long enough hairpin and dimer oligonucleotides (yN ≥ 24), in either native or denatured forms, we predict that the (positive) difference Γ∞ - ΓN increases linearly with increasing N-1. For smaller values of N the difference Γ∞ - ΓN continues to increase with increasing N-1.
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  • 92
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    Biopolymers 31 (1991), S. 1651-1667 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transient electric birefringence of two small DNA restriction fragments of the same molecular weight, one of which migrates anomalously slowly on polyacrylamide gels, has been investigated. Both fragments exhibit negative birefringence. The decay of the birefringence of the anomalously slowly migrating fragment is 8-9% faster than that of the normally migrating fragment. The faster birefringence decay of the anomalous fragment 12A persists under a variety of buffer conditions, suggesting that it is due primarily to static bending and/or curvature of fragment 12A. In reversing electric fields the absolute amplitude of the birefringence of fragments 12A and 12B decreased about 26% before returning to the steady state value. The minimum in the birefringence occurred faster than expected from the birefringence decay times and decreased with increasing electric field strength, suggesting that the minimum is due to a slow polarization of the ion atmosphere. For both fragments, the rise of the birefringence in the Kerr region is about 10% slower than the field-free decay. The buildup of the negative birefringence is preceded either by an interval when no birefringence is observed or by a small positively birefringent transient, suggesting that a small transverse ionic polarizability is also present. Both DNA fragments exhibit Kerr law behavior over most of the range of electric field strengths investigated. Analysis of the shapes of the saturation curves suggests that differences may exist in the polarization mechanisms of the two fragments.
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  • 93
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    Biopolymers 31 (1991), S. 1677-1687 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rabbit skeletal muscle myosin from the same rabbit was prepared by two different methods, and then purified by either Sephadex or hydroxylapatite chromatography. The resulting myosin samples were analyzed in 2-10 mM sodium pyrophosphate solutions at pH 9 using transient electric birefringence. The birefringence decay signals were fitted using a Fortran program called DISCRETE and two relaxation times, 49.7 ± 5.6 and 11.2 ± 2.5 μs, were determined. These relaxation times were independent of the method of myosin preparation, the method of myosin purification, the concentration of sodium pyrophosphate between 2 and 10 mM, the concentration of myosin between 0.08 and 1.59 mg/mL, and the temperature between 4.0 and 20.0°C, after correction to 20.0°C. The longer relaxation time is consistent with a rigid, linear myosin molecule. The shorter relaxation time is consistent with myosin that has a completely flexible hinge region in the myosin tail. Both relaxation times are inconsistent with the previously reported single relaxation time of myosin obtained by fitting the birefringence decay data to only 90% of the decay signal. By forcing some of the birefringence decay data in the present work to fit 90% of the decay signal with a single relaxation time, approximately the same relaxation time as previously reported was obtained.
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  • 94
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    Biopolymers 31 (1991), S. 1721-1726 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of deacetylation degree on heterogeneous molecular aggregation has been investigated for chitosan solution in 2 wt % acetic acid aqueous solution using rheological and small-angle x-ray scattering (SAXS) methods. Three samples of chitosan, which were designated CS62, CS79, and CS96, were used, and the deacetylation degrees of these samples were 0.62, 0.79 and 0.96, respectively.Rheological properties show that the systems of CS62 and CS96 are homogeneous, and the system of CS79 has a certain heterogeneous structure with a long-time relaxation mechanism. According to the SAXS measurement, the heterogeneous system has a fractal structure and the fractal dimension is about 1.3.
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  • 95
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    Biopolymers 31 (1991), S. 1727-1736 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational transition and the cation-binding properties of aqueous furcellaran (a gel-forming, low-sulfated polysaccharide of the carrageenan family) in various salts and salt mixtures was studied by optical rotation and by 133Cs-nmr. The results were compared with theoretical predictions based on the Poisson-Boltzmann cell model (PBCM). The conformational transition of furcellaran occurs in a single step, which implies a nonblocklike distribution of sulfate groups along the polymer chain. The chloride salts of sodium, lithium, and tetramethylammonium are equally potent in inducing helix formation of furcellaran, indicating that these ions act by nonspecific electrostatic interactions. In contrast, the potassium and cesium ions specifically promote helix formation and aggregation (gelation) of furcellaran. The divalent calcium and magnesium ions are nonspecific, but more potent than the nonspecific monovalent ions in inducing helices. Anions differ in their capacity to stabilize the furcellaran helix in the sequence Cl- 〈 NO3- 〈 Br- 〈 SCN- 〈 I-. The iodide and thiocyanate anions impede aggregation and gel formation. 133Cs-nmr chemical shifts indicate specific binding of cesium ions to the furcellaran helix. Thus, with respect to its ion specificity and ion-binding properties, furcellaran, with 0.6 sulfate group per repeating disaccharide, resembles κ-carrageenan (1 sulfate/disaccharide) but differs from ι-carrageenan (2 sulfates/disaccharide). The conformational transition temperatures of furcellaran are, however, generally higher than those of κ-carrageenan under comparable conditions, and in mixtures of the two polysaccharides, separate transitions still occur, indicating that no mixed helices are formed. The observed ion sensitivity and cation-binding properties of furcellaran agree with predictions, by the PBCM, for a K-carrageenan with a reduced charge density.
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  • 96
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution conformation of peptides rich in the α,α-dialkylated amino acid Aib has proven to be a subtle problem, not because of helix/coil transitions, but rather because of α-helical/310-helical competition. A special series of peptides containing 75% Aib has been synthesized that feature identical amino acid composition but differing sequences; they are sequence permutation isomers. Nuclear magnetic resonance hydrogen-bonding studies reveal that there is a sequence permutation induced transition between the two alternative helical forms within this set. The implications for the design and conformational prediction of helical Aib-rich peptides are discussed.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Through the joint use of CD, Fourier transform ir (FTIR), and attenuated total reflectance FTIR we have found that synthetic polypeptide models of the Plasmodium falciparum circumsporozoite (CS) protein repeat domain bind calcium ions in helicogenic environments. Ca2+-(NANP)n complexes (n ≥ 20) interact vectorially with model phospholipid membranes orienting their polypeptide axes preferentially along those of the lipid acyl chains. It is proposed that the P. falciparum CS protein central region, rather than acting as a molecular lure helping the parasite to evade host immune control, plays, as a specific Ca2+ macroligand, a critical functional role during attachment, invasion, and development of the malaria parasite in the hepatic cell.
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  • 98
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    Biopolymers 31 (1991), S. 631-635 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Minimal sequences of rubella E1 glycoprotein epitopes were previously identified as the tripeptide 250PER252 for the EP2 epitope, the tetrapeptide 260ADDP263 for the EP3 epitope, and the tripeptide 273EVW275 plus the octapeptide 278PVIGSQAR285 for the EP1 epitope.In order to establish for each epitope the shortest sequence that was able to give the maximum binding with human antirubella immunoglobulins, synthetic peptides with increasing number of residues flanking these essential parts of rubella E1 glycoprotein epitopes were synthesized and examined for their antigenic activity.Usually higher activity was observed with progressively longer homologues, whereas the additions of Pro-271, Pro-278 to 272GEVWVT277 peptide, and additions of Ala-248 to 249TPERP253and 249TPERPR254, led to an abrupt decrease in binding. Taken together, our results indicated that the antigenic activity of the whole antigen could be dissected and reproduced using synthetic peptides of appropriate structure for each epitope.
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  • 99
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational preference of Cα,α-diphenylglycinc (Døg) and Cα,α-dibenzylglycine (Dbz) residues was assessed in selected derivatives and small peptides by conformational energy computations, ir absorption, 1H-nmr, and x-ray diffraction. Conformational energy computations on the two monopeptides strongly support the view that these Cα,α-symmetrically disubstituted glycines are conformationally restricted and that their minimum energy conformation falls in the fully extended (C5) region. The results of the theoretical analyses appear to be in agreement with the solution and crystal-state structural propensities of three derivatives and seven di-and tripeptides.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational and ion-binding properties of two peptide fragments of 25 amino acid residues corresponding to the helix-loop sequences of domains I and III of calmodulin (CaM) were investigated by CD and Tb3+-mediated fluorescence spectroscopy. Both peptides exhibit very similar ion binding properties either in water or trifluoroethanol (TFE), and do not allow the differentiation of the two domains in the native protein in terms of their binding capacity. An aggregation phenomenon was observed in TFE with increase of the α-helical content. We suggest that the aggregation involves an interaction between the hydrophilic surfaces of amphiphilic α-helices in a way similar to inverse micelle formation.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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