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  • Physics  (10,646)
  • Engineering General  (9,884)
  • Atomic, Molecular and Optical Physics  (6,266)
  • Insulin
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  • 1
    ISSN: 1432-0428
    Keywords: Keywords GLP-1 ; Insulin ; pulsatility ; insulin secretion ; time series ; Type II diabetes ; human.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Aims/hypothesis. The enteric incretin hormone, glucagon-like peptide-1 (GLP-1), is a potent insulin secretagogue in healthy humans and patients with Type II (non-insulin-dependent) diabetes mellitus. In this study we assessed the impact of short-term GLP-1 infusion on pulsatile insulin secretion in Type II diabetic patients. Methods. Type II diabetic patients (n = 8) were studied in a randomised cross-over design. Plasma insulin concentration time series were obtained during basal conditions and during infusion with saline or GLP-1 (1.2 pmol/l · kg–1· min–1) on 2 separate days. Plasma glucose was clamped at the initial concentration by a variable glucose infusion. Serum insulin concentration time series were evaluated by deconvolution analysis, autocorrelation analysis, spectral analysis and approximate entropy. Results. Serum insulin concentrations increased by approximately 100 % during GLP-1 infusion. Pulsatile insulin secretion was increased as measured by secretory burst mass (19.3 ± 3.8 vs 53.0 ± 10.7 pmol/l/pulse, p = 0.02) and secretory burst amplitude (7.7 ± 1.5 vs 21.1 ± 4.3 pmol/l/min, p = 0.02). A similar increase in basal insulin secretion was observed (3.6 ± 0.9 vs 10.2 ± 2.2 pmol/l/min, p = 0.004) with no changes in the fraction of insulin delivered in pulses (0.50 ± 0.06 vs 0.49 ± 0.02, p = 0.84). Regularity of secretion was unchanged as measured by spectral analysis (normalised spectral power: 5.9 ± 0.6 vs 6.3 ± 0.8, p = 0.86), autocorrelation analysis (autocorrelation coefficient: 0.19 ± 0.04 vs 0.18 ± 0.05, p = 0.66) and the approximate entropy statistic (1.48 ± 0.02 vs 1.51 ± 0.02, p = 0.86). Conclusion/interpretation. Short-term stimulation with GLP-1 jointly increases pulsatile and basal insulin secretion, maintaining but not improving system regularity in Type II diabetic patients. [Diabetologia (2000) 43: 583–588]
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  • 2
    ISSN: 1432-1041
    Keywords: Key words Glibenclamide ; Insulin ; Proinsulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract Objective: We analysed the kinetics and effects of glibenclamide (Gb) on glucose, insulin and proinsulin secretion in two ethnic groups (10 in each) of type-2 diabetic patients, one of Caucasian, the other of Chinese origin. Background: Diabetes mellitus type 2 is a global disease affecting all ethnic groups. There are ethnic differences in both the prevalence and metabolic characteristics of the disease. Important interethnic pharmacodynamic and pharmacokinetic differences have been reported for several drugs. With few exceptions, detailed studies on sulphonylurea are lacking. Material and methods: The patients were studied on two occasions when either no Gb (control) or 1.25 mg Gb was administered i.v., immediately before the administration of a 75-g oral glucose tolerance test. Concentrations of insulin and proinsulin were determined by means of radioimmunoassay without cross-reactivities. Gb concentration was determined using high-performance liquid chromatography. Pharmacodynamic results were calculated using net areas under the curves, with basal values set as zero. A P value less than 0.05 was considered significant. Results: When glucose was administered orally without Gb, Chinese patients had higher plasma glucose increases at 10 min (7.6 mmol/l × min vs 2.6 mmol/l × min) and higher increases of plasma insulin levels than Caucasians at both 10 min (198 pmol/l × min vs 54 pmol/l × min) and 30 min (2286 pmol/l × min vs 1198 pmol/l × min). When Gb was administered, the plasma glucose increases were reduced, and the increases of serum insulin and proinsulin levels were greater in both ethnic groups. Compared with the basal values (−1 min), proinsulin/insulin ratios (RPI) were lowest at 10–30 min, followed by an increase. Chinese patients had higher increases of serum insulin levels at 10 min (1109 pmol/l × min vs 550 pmol/l × min) and a lower RPI at 30 min (6.0% vs 7.6%) and 240 min (15.0% vs 21.0%) relative to Caucasians. Serum Gb data were best fitted to a biexponential i.v. model. There were no interethnic differences in any of the pharmacokinetic parameters. Conclusion: In summary, following oral glucose administration without Gb, Chinese type-2 diabetic patients had higher plasma insulin levels but also higher plasma glucose levels during the first 10 min, which might reflect reduced insulin sensitivity or more rapid glucose absorption. Gb augmented glucose-induced release of both insulin and proinsulin in both ethnic groups; the effect on insulin secretion was more pronounced. In conclusion, minor pharmacodynamic but no pharmacokinetic differences were found between the two groups. It seems appropriate to employ the same dosage principles when using Gb in Caucasians and Chinese.
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  • 3
    ISSN: 1432-1076
    Keywords: Key words Arachnoid cyst ; Growth ; Growth hormone deficiency ; Growth hormone treatment ; Insulin ; Leptin ; Puberty ; Precocious puberty
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A suprasellar arachnoid cyst may cause disorders of growth, puberty and hypothalamic-pituitary function, due to the proximity of the cyst to the hypothalamic-pituitary area. A total of 30 patients (17 boys) with cyst diagnosed at 4.3 ± 1 years were routinely evaluated at 5.4 ± 1 years; 24 of them had one or multiple cyst derivations. Some 23 cases had an abnormal height, weight or puberty: short (〈−2SD, 5 cases) or tall (〉2SD, 10 cases) stature, overweight (body mass index, BMI, 〉2SD, 6 cases), central precocious puberty (10 cases) and/or no progression of pubertal development (3 cases). The growth hormone (GH) peaks after pharmacological stimulation test were low (〈10 μg/l) in 16 patients, confirmed by a second evaluation in 8/11 of them. The plasma free thyroxine was low in five patients, prolactin was high in two and the cortisol and concomitant plasma and urinary osmolalities were normal. BMI was correlated negatively with the GH peaks (r=−0.37, P 〈 0.01) and positively with the plasma leptin concentrations (r=0.55, P 〈 0.01). The plasma fasting insulin concentrations were also correlated negatively with the GH peaks (r=−0.55, P 〈 0.02) and positively with the plasma insulin-like growth factor I concentrations (r=0.64, P 〈 0.002). The adult height (12 cases) was at 4SD in 1 and 〈−2SD in 4 patients, two of whom had precocious puberty untreated with gonadotropin releasing hormone (GnRH) analogue, and two had untreated GH deficiency. The adult height of those treated was normal. One girl had primary amenorrhoea and two boys had low plasma testosterone, despite a normal gonadotropin response to a GnRH test. Conclusion Suprasellar arachnoid cysts may cause deficiencies of growth hormone and thyrotropin, stimulation of the hypothalamic-pituitary-gonadal axis, tall stature and/or overweight. These last two disorders may be due to hyperinsulinism, itself due to suprasellar arachnoid cyst.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of mammary gland biology and neoplasia 5 (2000), S. 19-30 
    ISSN: 1573-7039
    Keywords: Insulin ; transgenic ; knockout ; mammary ; IGF
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Transgenic and knockout mice have become valuable experimental systems with which tostudy specific molecular events within the mammary gland of an intact animal. These modelshave provided a wealth of information about the effects of a number of oncogenes and growthfactors. This review focuses on results obtained from the application of transgenic and knockoutmodels to determine the roles of insulin and insulin-like growth factors (IGF)3 in the regulationof mammary gland development, lactation and tumorigenesis. Transgenic models whichoverexpress IGF-I or -II display specific alterations in mammary gland development and an increasedincidence of mammary tumors. Analysis of mammary gland development in knockout micewhich are deficient in IGF-I or the IGF-I receptor supports the conclusion that the IGF systemis important for normal mammary gland development. This review discusses these observationsin detail and attempts to fit them into a larger picture of IGF and insulin action in themammary gland.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Annals of biomedical engineering 28 (2000), S. 102-109 
    ISSN: 1573-9686
    Keywords: Nitric oxide ; Superoxide ; Pancreatic cells ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract The onset of insulin-dependent diabetes mellitus (IDDM) is often associated with the infiltration of pancreatic cells by macrophages. Upon activation, macrophages release nitric oxide (NO) and superoxide (O 2 - ). These species or their reactive intermediates can be cytoxic, mutagenic, or carcinogenic. Previous studies have reported both positive and negative effects of extracellularly generated NO on insulin secretion and viability of pancreatic cells. Inherent problems of several previous studies assessing the effects of NO on insulin secretion include unsteady state NO concentration exposures and the generation of other potentially damaging species. In this study, these problems were eliminated by using a modified experimental system in which NO delivery was achieved via diffusion across a gas-permeable tube and O 2 - delivery was maintained using an enzymatic reaction. The delivery rates were constant, leading to steady state concentrations of NO and O 2 - in the experimental system. Based on reaction kinetics, a model was developed to predict NO, O 2 - and peroxynitrite ONOO- concentrations during the experiment. This study showed that NO, O 2 - and ONOO- at predicted concentrations as high as 2.8 μM, 0.25 μM, and 0.1 nM, respectively, do not affect the insulin secretion rates of βTC3 pancreatic cells over short times. © 2000 Biomedical Engineering Society. PAC00: 8717-d
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Annals of biomedical engineering 28 (2000), S. 812-823 
    ISSN: 1573-9686
    Keywords: C-peptide ; Population model ; Compartmental model ; Bayes estimation ; Markov chain Monte Carlo ; Insulin ; System identification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Technology
    Notes: Abstract When models are used to measure or predict physiological variables and parameters in a given individual, the experiments needed are often complex and costly. A valuable solution for improving their cost effectiveness is represented by population models. A widely used population model in insulin secretion studies is the one proposed by Van Cauter et al. (Diabetes 41:368–377, 1992), which determines the parameters of the two compartment model of C-peptide kinetics in a given individual from the knowledge of his/her age, sex, body surface area, and health condition (i.e., normal, obese, diabetic). This population model was identified from the data of a large training set (more than 200 subjects) via a deterministic approach. This approach, while sound in terms of providing a point estimate of C-peptide kinetic parameters in a given individual, does not provide a measure of their precision. In this paper, by employing the same training set of Van Cauter et al., we show that the identification of the population model into a Bayesian framework (by using Markov chain Monte Carlo) allows, at the individual level, the estimation of point values of the C-peptide kinetic parameters together with their precision. A successful application of the methodology is illustrated in the estimation of C-peptide kinetic parameters of seven subjects (not belonging to the training set used for the identification of the population model) for which reference values were available thanks to an independent identification experiment. © 2000 Biomedical Engineering Society. PAC00: 8715Aa, 0250Ga, 8714-g
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  • 7
    ISSN: 1439-6327
    Keywords: Key words Carbohydrate ; Osmolality ; Glycogen ; Insulin ; Glucose
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The rate of muscle glycogen synthesis during 2 and 4 h of recovery after depletion by exercise was studied using two energy equivalent carbohydrate drinks, one containing a polyglucoside with a mean molecular mass of 500 000–700 000 (C drink), and one containing monomers and oligomers of glucose with a mean molecular mass of approximately 500 (G drink). The osmolality was 84 and 350 mosmol · l−1, respectively. A group of 13 healthy well-trained men ingested the drinks after glycogen depleting exercise, one drink at each test occasion. The total amount of carbohydrates consumed was 300 g (4.2 g · kg−1) body mass given as 75 g in 500 ml water immediately after exercise and again 30, 60 ad 90-min post exercise. Blood glucose and insulin concentrations were recorded at rest and every 30 min throughout the 4-h recovery period. Muscle biopsies were obtained at the end of exercise and after 2 and 4 h of recovery. Mean muscle glycogen contents after exercise were 52.9 (SD 27.4) mmol glycosyl units · kg−1 (dry mass) in the C group and 58.3 (SD 35.4) mmol glycosyl units · kg−1 (dry mass) in the G group. Mean glycogen synthesis rate was significantly higher during the initial 2 h for the C drink compared to the G drink: 50.2 (SD 13.7) mmol · kg−1 (dry mass) · h−1 in the C group and 29.9 (SD 12.5) mmol · kg−1 (dry mass) · h−1 in the G group. During the last 2 h the mean synthesis rate was 18.8 (SD 33.3) and 23.3 (SD 22.4) mmol · kg−1 (dry mass) · h−1 in the C and G group, respectively (n.s.). Mean blood glucose and insulin concentrations did not differ between the two drinks. Our data indicted that the osmolality of the carbohydrate drink may influence the rate of resynthesis of glycogen in muscle after its depletion by exercise.
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  • 8
    ISSN: 1615-2573
    Keywords: Key words Creatine kinase isoenzyme ; Insulin ; Atenolol ; Diabetes mellitus ; Myocardium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The expression of mRNAs of creatine kinase (CK)-B and CK-M has been show to be affected by insulin, and myocardial CK-MB activity is suppressed in insulin-deficient rats. We investigated the dose-related effect of insulin on CK-MB activity in cardiac and skeletal muscles. Male Wistar rats were divided into three groups: (1) control group, (2) diabetic group, injected with 65 mg/kg streptozotocin for 4 weeks, and (3) atenolol group, administered 30 mg/kg per day atenolol. Each group was further divided into three subgroups and administered either saline, or 20 (Ins 20) or 30 (Ins 30) U/kg per day insulin. After 3 weeks, the isoenzyme activity of CK and lactate dehydrogenase (LDH) in the left ventricle of the heart (LV) and the major pectoral muscle (PM) was measured. Serum insulin increased and plasma glucose decreased in Ins 20 and Ins 30, dose-dependently, in all three groups. Both CK-MB and -BB activity in LV increased dose-dependently with insulin treatment in the control, diabetes, and atenolol groups, although these changes did not occur in skeletal muscles. CK-MB in LV correlated with the serum insulin levels in all rats, while no correlation was found in the skeletal muscles. These findings suggest that insulin possibly regulates the distribution of CK isoenzymes in rat heart muscle, and that the effect of insulin is not due to the sympathetic drive induced by hypoglycemia.
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  • 9
    ISSN: 1432-136X
    Keywords: Key words Fattening ; Food availability ; Insulin ; Glucagon ; Corticosterone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract To investigate the proximate influence of a changing food availability on the seasonal fattening of migratory birds, garden warblers (Sylvia borin) following postnuptial moult were food restricted once a week. Body mass, food intake, plasma hormone and metabolite levels were measured and compared to birds which always had ad libitum food access. The food-restricted birds increased their body mass significantly earlier than the controls. The accelerated fattening was initially not accompanied by hyperphagia and may be due to either an increased food utilisation efficiency or a reduced metabolic rate. An increase of basal glucagon and corticosterone and a decrease of insulin levels prior to fattening were not significant, however, they resulted in a significant decrease of the insulin:glucagon ratio. This ratio was also lower in food-restricted birds than in control birds and may account for the difference in the fattening progress. We conclude that seasonal fattening may be stimulated by a catabolic impulse which could be imposed in free-living birds by a decrease of food availability and/or by an increase of energy expenditure. A negative energy balance is hypothesised to be a common proximate factor affecting migratory as well as winter fattening.
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  • 10
    ISSN: 1432-2307
    Keywords: Key words Rat ; Pancreatic beta cell ; Insulin ; GLUT2 glucose transporter ; Glucokinase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Functional heterogeneity among pancreatic beta cells is a characteristic feature of the islets of Langerhans. Under physiological conditions, beta cells in the pancreas of fed rats exhibited heterogeneous immunohistochemical staining for insulin and glucokinase. Intracellular beta cell glucokinase staining was either faint or dense. In the pericapillary space beta cell glucokinase immunoreactivity had a polar orientation, with the highest density in cytoplasmic regions close to the blood vessels. Starvation resulted in a loss of heterogeneity with homogeneous insulin staining in all beta cells of the islets, and this was accompanied by a loss of heterogeneous glucokinase staining. The intracellular polarity of glucokinase staining in contact to blood vessels also disappeared after starvation. Refeeding resulted in the reappearance of intercellular heterogeneity. In dependence on the functional demand, the endocrine pancreas recruited insulin from beta cells according to a well-defined hierarchy, with an initial preferential mobilization of medullary beta cells. In the course of this process intracellular polarity of glucokinase staining reappeared in areas of the beta cell with functional contact to the GLUT2 glucose transporter in the plasma membrane. This can be regarded as the morphological correlate of an activation of the glucose signal recognition apparatus. Interestingly, the study also provides evidence that the changes in glucokinase distribution apparently preceded those in insulin distribution, which is in keeping with the central role of glucokinase as the glucose sensor of the pancreatic beta cell.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 36 (1999), S. 93-97 
    ISSN: 1432-5233
    Keywords: Key words Type 2 diabetes mellitus ; Insulin ; Acarbose ; Gliclazide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In this prospective study we aimed to compare insulin plus acarbose with insulin plus gliclazide with respect to their effect on insulin requirement, lipid profiles and body mass index (BMI) while achieving good glycemic control. Forty patients with type 2 diabetes mellitus who were on conventional insulin therapy (subcutaneous insulin therapy consisting of regular and NPH insulin, two times a day) were included in the study. They were randomized to double blind treatment with insulin in combination with gliclazide or acarbose for 6 months. For both groups, acceptable glycemic control was achieved at the end of study period. The mean HbA1c levels decreased from 8.32±0.26 to 7.13±0.18% in acarbose group and 8.6±0.15 to 7.48±0.21% in the gliclazide group. The difference between groups was not significant (P 0.29). In the acarbose group, total cholesterol and LDL concentration decreased significantly while other parameters did not change. In the gliclazide group, HDL levels decreased significantly from 46.6±2.48 mg/dl to 41.3±2.09 mg/dl (P 0.001) BMI increased significantly from 27.60±1.21 kg/m2 to 28.69±1.26 kg/m2. (P 0.003) Total daily insulin dose was not changed in the acarbose group significantly, but increased from 42.6±2.73 to 49.27±3.58 U/day, which was significant in gliclazide group of (P 0.016). In the acarbose group, there were no significant differences between responders and nonresponders with respect to fasting and stimulated C-peptide, HbA1c levels and baseline BMI values. But in the gliclazide group, baseline BMI values were significantly higher in the nonresponding group compared to responders (P 0.02). In conclusion, combination of insulin with acarbose can be a good alternative for type 2 diabetic patients on insulin therapy; seems more beneficial than combination with gliclazide; may have advantage of achieving good glycemic control without increasing insulin dose and BMI; also may have the advantage of providing a decrease in LDL level, which are all important to prevent atherosclerosis.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular medicine 77 (1999), S. 107-110 
    ISSN: 1432-1440
    Keywords: Key words Pancreatic islet transplantation ; Cryopreservation ; Conservation ; Insulin ; Nude mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cryopreservation is the only available technique for long-term storage of pancreatic islets. The freezing/thawing protocol may cause considerable loss of viable islet tissue and impair its function in vivo. The aim of this study was to investigate glucose and insulin levels after transplantation of fresh and cryo/thawed rat islets. Rat pancreatic islets were isolated following intraductal collagenase injection and Ficoll gradient purification. After isolation, islets were cultured for 24 h and then either transplanted or frozen after stepwise addition of DMSO according to Rajotte et al. and stored in liquid nitrogen. After rapid thawing islets were stepwise transferred into RPMI medium and cultured for another 24 h. The recipients were athymic mice with streptozotocine-induced diabetes. Two hundred fresh (n=13) or cryo/thawed (n=15) islets were transplanted beneath the renal capsule. Glucose levels were measured for 14 days and blood samples for insulin determination were obtained 15 min after i.p. glucagon (10 mg/kg) administration on day 14. Glucose levels were normalized (〈9 mmol/l) in all recipients within 3 days since transplantation. On day 14, mean fasting values±SE in fresh and cryo/thawed islet groups were 4.0±0.6 and 4.4±0.4 mmol/l, respectively (P〉0.05). Fasting insulin levels were higher in the cryo/thaw than in the fresh islet group (1.67±0.33 vs 0.57±0.13 ng/ml; P〈0.01). Post-glucagon levels did not differ significantly (1.45±0.24 vs 0.86±0.24 ng/ml; P=0.06). While glucagon significantly increased insulin levels (P〈0.01) in the fresh islet group, no change in insulin levels was observed (P〉0.05) in the cryo/thaw group. Immunohistochemical staining demonstrated fragmentation of viable islet tissue which was more apparent in the cryo/thaw group. We conclude that in a short-term study cryo/thawed rat islets produce higher insulin levels than fresh islets transplanted into nude mice. This may be due to better islet survival or loss of feed-back regulation.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Development genes and evolution 209 (1999), S. 447-450 
    ISSN: 1432-041X
    Keywords: Key words Bombyxin ; Insulin ; Bombyx mori ; Electroporation ; Cell-specific expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  A transgene reporter consisting of the bombyxin gene promoter and the green fluorescent protein coding region was introduced into intact brains of the silkworm Bombyx mori by in vitro electroporation. After in vitro culture of the brains, the fluorescence derived from the introduced reporter gene was observed in all cases in eight neurosecretory cells that had previously been identified as bombyxin-producing cells (BPCs). Although the fluorescence was not always observed in all cells, it was specific to BPCs, indicating that the reporter was under the control of the bombyxin gene promoter in a BPC-specific manner. Electroporatical introduction of a reporter gene was therefore found to be a suitable method for analyzing cell-specific expression in intact tissues and to be substitute for germ-line transmission of reporters in the transgenic system. Application of this technique enables us to analyze the cell-specific expression of transgene reporters within a few days and treat more than several dozens of the reporters within 1 month, which is difficult to do with the transgenic system.
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  • 14
    ISSN: 1432-2013
    Keywords: Key words Hypokalaemic periodic paralysis ; ATP-sensitive K+ channels ; Insulin ; Skeletal muscle ; Patch clamp
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  In the present work, we examined the effects of in vivo administration of insulin to rats made hypokalaemic by feeding a K+-free diet. The i.p. injection of insulin in the hypokalaemic rats provoked muscle paralysis within 3–5 h. Consistent with this observation, the skeletal muscle fibres of the paralysed rats were depolarized. In contrast, in the normokalaemic animals, insulin neither provoked paralysis nor produced significant fibre hyperpolarization. In the hypokalaemic rats, insulin almost completely abolished the sarcolemma adenosine triphosphate (ATP)-sensitive K+ currents without altering the sensitivity of the channels to ATP or glibenclamide. In contrast, in the normokalaemic rats, insulin enhanced ATP-sensitive K+ currents that became also resistant to ATP and glibenclamide. Our experiments indicate that the modulation of the sarcolemma ATP-sensitive K+ channels by insulin is impaired in the hypokalaemic state. This phenomenon appears to be related to the fibre depolarization and paralysis observed in the same animals.
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  • 15
    ISSN: 1432-1912
    Keywords: Key words Arterial smooth muscle ; Glucose ; Inducible NO synthesis ; Insulin ; Lean and obese Zucker rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin has been suggested to prevent the induction of nitric oxide synthase (NOS) in vitro in arterial smooth muscle, but whether such a mechanism is operative in vivo is not known. Therefore, we evaluated the sensitivity of smooth muscle NOS to induction by interleukin-1β (IL-1β) in aortic rings of lean and obese Zucker rats, a model of experimental hyperinsulinaemia. In order to modulate the insulin and glucose balance of the rats, a 22-week-long treadmill exercise was included in the study. The training attenuated weight gain and reduced blood glucose in the obese and lean rats, whereas the abnormally high plasma insulin of the obese rats remained unaffected. A 6-h incubation of aortic rings with IL-1β (10 ng/ml) increased cyclic GMP in smooth muscle by approximately threefold in all groups, and this effect was prevented by methylene blue. The contractile sensitivity of endothelium-denuded aortic rings to phenylephrine was reduced by incubation with IL-1β (1 ng/ml and 10 ng/ml) in the exercised obese and lean rats, whereas no significant change was observed in the sedentary groups. The aortic maximal contractile force induced by phenylephrine was reduced in sedentary and exercised obese rats by incubation with IL-1β, while no change was detected in the lean rats. The aortic relaxation to exogenous L-arginine was augmented by IL-1β in all groups, while the relaxation sensitivity to L-arginine after induction by IL-1β was enhanced by exercise in the obese but not in the lean rats. Finally, the relaxation to nitroprusside was not significantly affected by IL-1β in any of the study groups. In conclusion, since maximal contractile force generation to phenylephrine was reduced by IL-1β in the obese but not in the lean rats, the sensitivity of NOS to induction by IL-1β was higher in arterial smooth muscle of the obese than the lean Zucker rats. Thus, this model of hyperinsulinaemia was not associated with reduced sensitivity of smooth muscle NOS to induction by IL-1β. Regular exercise did not change plasma insulin concentrations, but it enhanced the action of insulin in both strains as reflected by reduced blood glucose, and increased the sensitivity of smooth muscle NOS to induction by IL-1β.
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  • 16
    ISSN: 1432-2013
    Keywords: Key words A6 cells ; Capacitance ; Hormones ; Insulin ; Membrane area ; Membrane traffic ; Renal epithelia ; Water permeability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The role of membrane traffic in the stimulation of apical Na+ permeability caused by increases in cytoplasmic cyclic AMP was assessed by measuring the effects of forskolin on transepithelial capacitance (C T), transepithelial conductance (G T), and short-circuit current (I sc) in A6 cultured toad kidney cells. Apical water permeability was probed by recording cell volume changes after reducing the osmolality of the apical bath. We found that forskolin does not increase the osmotic water permeability of the apical membrane of A6 cells, and thus does not stimulate the insertion of water channels. Comparison of the effects of forskolin and insulin on Na+ transport demonstrated that both agents produce reversible increases in C T, G T and I sc. G T and C T increased proportionally during the rising phase of the insulin response. However, a non-linear relationship between both parameters was recorded when forskolin was given in NaCl Ringer’s solution. The relationship between C T and G T became linear after the effects of forskolin on Cl– conductances were eliminated by substituting Cl– by an impermeant anion. In contrast, in Cl–-containing Na+-free solutions, the non-linearity became more pronounced. Successive additions of insulin and forskolin caused additive increases in C T. Because increases in C T and Na+ transport occurred in the absence of stimulation of water permeability and increases of C T and G T were directly proportional when Na+ was the major permeating ion across the apical membrane, we suggest that the increase in apical Na+ permeability in the presence of either forskolin or insulin is due to the insertion of channels residing in intracellular pools. In contrast, the increased Cl– permeability caused by forskolin may be related to the activation of channels already present in the membrane.
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  • 17
    ISSN: 1432-2277
    Keywords: Key words Cyclosporin A ; Langerhans ; Insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We investigated the effect of different doses of cyclosporin A (CyA) on glucose and insulin levels, as well as its residual effects on pancreatic islets ultrastructure after discontinuation of the drug. We studied four groups of Wistar rats. One control- (n = 5) and three experimental groups, n = 10 each, were treated with different doses of CyA IM for 14 days: group I, 5 mg/Kg; group II, 15 mg/Kg; and group III, 25 mg/Kg. Five animals of each group were sacrificed after 14 days, and the remaining five after 21 days to assess residual CyA effects. On the day of sacrifice, the rats underwent maltose absorption test, and glucose and insulin levels were measured. Pancreatic biopsies were obtained on day 21 to evaluate islets ultrastructure by electron microscopy. As a result, statistically significant, dose dependent (P 〈 0.05) increases in glucose and insulin levels were observed in CyA-treated groups. Groups II and III showed insulin levels significantly higher after fasting (P 〈 0.05) on day 14 comparing to the controls, while in groups I and II values returned to normal after CyA discontinuation. Group III showed persistently increased insulin levels on day 21. Pancreatic ultrastructural changes were observed only in group III. We can conclude that CyA effects on glucose and insulin levels were temporary and reversible at low doses. Ultrastuctural changes in the pancreatic islets may occur with high doses of CyA.
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  • 18
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    Rechtsmedizin 9 (1999), S. 190-192 
    ISSN: 1434-5196
    Keywords: Key words Hypoglycaemia factitia ; Insulin ; Diet ; Lethal outcome ; Schlüsselwörter Hypoglykaemia factitia ; Insulin ; Diät ; Tödlicher Verlauf
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine , Law
    Description / Table of Contents: Zusammenfassung Wir berichten über den Fall einer 28jährigen, nicht insulinpflichtigen nicht-Diabetikerin, in deren Anamnese eine hypoglykaemische Episode vor dem Todeseintritt bekannt wurde. Autoptisch wurde eine (heimliche) Applikation von Insulin durch letal hohe Insulinspiegel im zentralen und peripheren Blut mit Hypoglykaemie diagnostiziert. Nach der Anamnese, den Ergebnissen des Ermittlungsverfahrens und der Autopsie konnte die Applikation von Insulin aus suizidaler und homizidaler Absicht oder im Rahmen eines Münchhausen-Syndroms ausgeschlossen werden. Vielmehr handelte es sich in der Gesamtschau um eine Hypoglykaemia factitia aus diätetischen Gründen.
    Notes: Abstract The medical history of a 28-year-old non-insulin-dependent and non-diabetic patient with a hypoglycaemic episode before death is reported. At autopsy, an (surreptious) insulin administration was documented by lethally high serum insulin in central and peripheral blood during hypoglycaemia, According to the anamnesis, the judical inquiry and the autopsy findings, a suicidal intent, murder by insulin or Munchhausen-syndrome could be excluded. We therefore diagnosed a hypoglycaemia factitia caused by the diet.
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  • 19
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    European journal of applied physiology 79 (1999), S. 331-335 
    ISSN: 1439-6327
    Keywords: Key words Leptin ; Exercise Energy balance ; Insulin ; Glucocorticoids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In subjects who maintain a constant body mass, the increased energy expenditure induced by exercise must be compensated by a similar increase in energy intake. Since leptin has been shown to decrease food intake in animals, it can be expected that physical exercise would increase energy intake by lowering plasma leptin concentrations. This effect may be secondary either to exercise-induced negative energy balance or to other effects of exercise. To delineate the effects of moderate physical activity on plasma leptin concentrations, 11 healthy lean subjects (4 men, 7 women) were studied on three occasions over 3 days; in study 1 they consumed an isoenergetic diet (1.3 times resting energy expenditure) over 3 days with no physical activity; in study 2 the subjects received the same diet as in study 1, but they exercised twice daily during the 3 days (cycling at 60 W for 30 min); in study 3 the subjects exercised twice daily during the 3 days, and their energy intake was increased by 18% to cover the extra energy expenditure induced by the physical activity. Fasting plasma leptin concentration (measured on the morning of day 4) was unaltered by exercise [8.64 (SEM 2.22) 7.17 (SEM 1.66), 7.33 (SEM 1.72) 1μg · l−1 in studies 1, 2 and 3, respectively]. It was concluded that a moderate physical activity performed over a 3-day period does not alter plasma leptin concentrations, even when energy balance is slightly negative. This argues against a direct effect of physical exercise on plasma leptin concentrations, when body composition is unaltered.
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  • 20
    ISSN: 1435-232X
    Keywords: Key words Complex disease ; Carbohydrate ; Insulin ; Aboriginal populations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract We undertook a genome-wide scan using 190 markers with an average separation of 20 cM in 49 Canadian Oji-Cree sib pairs affected with type 2 diabetes. Four of these markers, one each on chromosomes 6, 8, 16, and 22, showed both suggestive linkage and suggestive association with type 2 diabetes in the Oji-Cree. None of these markers corresponded to any chromosomal region or marker that has so far been linked with type 2 diabetes in other populations. Thus, there might be several genetic loci that confer susceptibility to type 2 diabetes in this study sample. We are following up on these preliminary leads by increasing the density of the markers within these linked and associated regions, and also by increasing the number of study subjects. Also, we found instances in which there were wide disparities between the Oji-Cree and reference Caucasians with respect to marker heterozygosity. This suggests that a particular set of markers for genome-wide scanning will have different informativeness in different ethnic groups. Thus, different marker sets will likely be required for different ethnic groups in order to maximize their information content for linkage calculations.
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  • 21
    ISSN: 1432-5233
    Keywords: Key words Glucose ; Insulin ; Hyperinsulinaemia ; Blood flow
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin-mediated stimulation of blood flow to skeletal muscle has been proposed to be of major importance for insulin-mediated glucose uptake. The aim of this study was to investigate the relative importance of blood flow and glucose extraction as determinants of insulin-mediated glucose uptake in the human forearm. Forearm blood flow (FBF), glucose extraction and oxygen consumption were evaluated for 100 min during the euglycaemic hyperinsulinaemic clamp (92 mU/l) in nine healthy subjects. FBF was measured by venous occlusion plethysmography. Forearm glucose uptake increased sevenfold during the hyperinsulinaemia (P〈0.001). Forearm glucose extraction showed a minor increase during the first 10 min of hyperinsulinaemia, but the most marked increase took place between 10 and 20 min (+170%). Thereafter, only a minor further increase was seen. During the first 10 min of hyperinsulinaemia FBF was unchanged. Thereafter, FBF increased steadily to a plateau reached after 60 min (+50%, P〈0.001). A close relationship between whole body glucose uptake and FBF was seen at the end of the clamp (r = 0.75, P〈0.02), but at this time the relationship between whole body glucose uptake and forearm glucose extraction was not significant. The modest increase in O2 consumption seen at the beginning of the clamp (+19%) was not related to FBF during the early phase of the clamp. In conclusion, the early course of insulin-mediated glucose uptake in the human forearm was mainly due to an increase in glucose extraction. However, with time the insulin-mediated increase in blood flow increased in importance and after 100 min of hyperinsulinaemia FBF was the major determinant of glucose uptake.
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  • 22
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    Virchows Archiv 433 (1998), S. 495-504 
    ISSN: 1432-2307
    Keywords: Key words Insulinomas ; Prohormone convertases ; Carboxypeptidase H ; Insulin ; Proinsulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Sixty-seven insulinomas were investigated by immunohistochemistry using site-directed antibodies against insulin, proinsulin, chromogranin A, HISL-19, and four proteins directly or indirectly involved in the proteolytic processing of proinsulin: the prohormone convertases PC2 and PC3, carboxypeptidase H (CPH) and 7B2. Results were expressed in a six-grade score according to the frequency of immunoreactive tumour cells. Insulin was expressed by all tumours, appearing in either a diffuse or a polarized pattern and being detected in more than 30% of tumour cells in all cases but three. Proinsulin was also expressed in all tumours, with more than 50% of tumour cells immunoreactive in all cases but 5. It was consistently localized in the Golgi apparatus. In about half the cases, moreover, it also showed diffuse cytoplasmic staining, usually with a very sparse distribution. Trabecular and solid insulinomas did not present specific, homogeneous patterns of insulin immunostaining. However, insulin immunoreactivity was much more abundant in trabecular than in solid neoplasms, being present in virtually all tumour cells (score 6) in 50% and 8% of cases, respectively. Virtually all insulinomas expressed PC2, PC3, CPH and 7B2, usually in 30–100% of tumour cells, with a frequency significantly related to that of insulin. However, detection of PC2 and 7B2 was slightly less frequent than that of PC3 and CPH. In consecutive sections these proteins were found to be mostly co-localized with insulin and chromogranin A but not with proinsulin. They were heavily expressed in all 10 tumours with more than 10% of cells showing cytoplasmic proinsulin immunoreactivity, indicating that the leakage of proinsulin from the Golgi compartment is not associated with faulty expression of converting enzymes and possibly reflects a saturated processing capacity. HISL-19 immunoreactivity was found in both Golgi apparatus and insulin stores, indicating that the relevant antigen is different from all other proteins investigated. These results do not support a defect in expression or localization of proinsulin-processing enzymes in most insulinomas.
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  • 23
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    Acta neuropathologica 96 (1998), S. 144-150 
    ISSN: 1432-0533
    Keywords: Key words Neuropathy ; Hypoglycaemia ; Hyperglycaemia ; Insulin ; BB/Wor rat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To elucidate the pathophysiology of diabetic neuropathy many workers have examined nerve specimens from diabetic rats. While most workers found that animals with high blood glucose levels develop neuropathy, some researchers report that the peripheral nerves are normal in hyperglycaemic rats. Hypoglycaemia may also cause neuropathy. Some workers suggest that neuropathy is linked to fluctuations of the blood glucose level. In the present study we examine plantar nerves of diabetic BB/ Wor rats maintained on an eu-/hyperglycaemic or an eu-/ hypoglycaemic regime with insulin implants. Treatment with implants worked well. Light microscopic examination of nerve fibres in non-diabetic control rats and in eu-/ hyperglycaemic diabetic rats showed a normal picture. Preparations from eu-/hypoglycemic rats showed irregular myelin sheaths and signs of Wallerian degeneration. The lengths and diameters of the largest internodes were significantly subnormal. We conclude, that periodic moderate hypoglycaemia, but not periodic moderate hyperglycaemia, elicits neuropathy in diabetic BB/Wor rats treated with insulin implants.
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  • 24
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    Acta neuropathologica 96 (1998), S. 151-156 
    ISSN: 1432-0533
    Keywords: Key words Neuropathy ; Hypoglycemia ; Insulin ; implant ; Rat ; Electron microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Insulin-dependent diabetes mellitus is a chronic metabolic disease that causes long-term secondary complications such as neuropathy. The occurrence of diabetic neuropathy has generally been thought of as being associated with hyperglycaemia. However, in a previous light microscopic examination of plantar nerves in diabetic BB/Wor rats treated with insulin implants we found that eu-/hyperglycaemic rats present a normal picture, whereas eu-/hypoglycaemic rats show severe changes. The aim of the present work is to supplement our previous light microscopic report with electron microsocpic data from the lateral plantar nerve of normal, eu-/hyperglycaemic and eu-/hypoglycaemic BB/Wor rats. Under the electron microscope lateral plantar nerves collected from eu-/hyperglycaemic rats presented a qualitatively normal picture. In addition, the fibre numbers and the size distribution of the myelinated fibres were normal. In contrast, specimens from eu-/hypoglycaemic BB/Wor rats showed severe qualitative changes, interpreted as signs of axonal de- and regeneration. The total number of axons was somewhat subnormal and the sizes of the myelinated fibres were strongly shifted towards smaller diameters. These data confirm our previous light microscopic observations. We conclude that eu-/hypoglycaemic BB/Wor rats treated with insulin implants, but not similarly treated eu-/hyperglycaemic animals, develop a neuropathy in their plantar nerves.
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  • 25
    ISSN: 1432-041X
    Keywords: Key words Bombyxin ; Insulin ; Bombyx mori ; Multigene family ; Brain neurosecretory cell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Bombyxin G1 gene, a novel insulin-related peptide gene of the silkmoth Bombyx mori, has been identified. The G1 gene encodes a precursor peptide which shows 41–56% and 28% sequence identities with preprobombyxins previously characterized and human preproinsulin, respectively. The G1 gene forms a pair with bombyxin C2 gene with opposite transcriptional orientation in a bombyxin gene cluster. The bombyxin G1 mRNA in Bombyx brain was shown to locate in four pairs of medial neurosecretory cells.
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  • 26
    ISSN: 1432-0738
    Keywords: Key words Proliferation ; Epidermal growth factor (EGF) ; Insulin ; Hepatocyte ; Cyclosporin A
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cyclosporin A (CsA) at concentrations up to 1 μM induced apoptosis in a dose-dependent manner in cultured rat hepatocytes for 48 h in the presence of insulin and epidermal growth factor (EGF). The effect of CsA was evidenced by the DNA fragmentation pattern constituted by fragments of multiples of 180–200 base pairs, which is a characteristic of programmed cell death. The metabolic activity did not change significantly in the presence of 0.1 μM CsA and diminished to 49% of control in the presence of 1 μM CsA. Changes in the metabolic activity were correlated with a decrease in both [methyl-3H]thymidine uptake and DNA content, which reflects a decrease in the cell number. The treatment of cells with CsA (1 μM) decreased the metabolic activity/DNA content ratio by 24% with respect to dimethyl sulphoxide (DMSO) control, which also suggests, under these conditions, that the necrosis achieved is at most only 24%. In addition, the changes observed (apoptotic process, arrest of the cell cycle and apparition of a necrotic process) were correlated with an increase in the high-affinity guanosine triphosphatase (GTPase) enzymes.
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  • 27
    ISSN: 1432-1076
    Keywords: Key words Diabetes mellitus ; Infantile cystinosis ; Insulin ; C-peptide ; Chronic renal failure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Infantile cystinosis, a rare lysosomal storage disease of cystine, leads to Fanconi syndrome and end-stage renal failure. After renal transplantation, no recurrence of the disease occurs in the graft, but other organ involvement becomes evident later in life. Diabetes mellitus has been associated with cystinosis, but the mechanisms of impaired glucose tolerance have not yet been characterized. Here, we studied glucose tolerance, glucose constant decay (k-values), insulin and C-peptide by intravenous glucose tolerance test (IVGTT) in eight patients with infantile cystinosis (three with impaired GFR (CRF) and five after kidney transplantation (KTX)). For comparison, 15 age-matched children with CRF and 15 age-matched KTX patients were analysed. Both early and second insulin secretion phases were diminished in patients with infantile cystinosis, whereas in CRF, k-values were no different from control patients. After renal transplantation, k-values were significantly lower in cystinotic patients with a markedly reduced early insulin secretion phase. There was a significant negative correlation between k-values and age in patients with cystinosis. Repetitive IVGTTs in these patients demonstrated progressive but rather slow loss of first phase insulin secretion and C-peptide production, suggesting a slowly reducing secretion potential of the beta cell due to cystine storage. Conclusion Unlike type I diabetes mellitus, glucose intolerance in patients with infantile cystinosis is characterized by a slow, progressive loss of insulin secretion and C-peptide production. For these patients, the data indicate a 50% risk of developing glucose intolerance by the age of 18 years. We recommend to perform intravenous glucose tolerance tests at 5-year intervals.
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  • 28
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    European radiology 8 (1998), S. 849-857 
    ISSN: 1432-1084
    Keywords: Key words: Ultrasound ; Physics ; Vascular studies ; Vascular pathologies ; Ultrasonic contrast agents ; Clinical applications
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The choice of the optimal ultrasonic frequency for vascular studies is determined by the required resolution and penetration. Anatomical real-time two-dimensional imaging and blood flow studies provide complementary information. Intravascular scanning allows high-frequency ultrasound to be used, with correspondingly good spatial resolution. Contrast resolution is degraded by beam side lobes and the limited dynamic range of the ultrasonic pulse. The physics of ultrasonic scattering by blood, pulsed Doppler and duplex scanning and colour flow imaging performances determines the limits of clinical applications. Contrast agents enhance the echogenicity of blood, improving sensitivity and, through second harmonic detection, suppressing solid tissue echoes. Three-dimensional display, with segmentation by the presence of the flow signal, facilitates spatial perception. Clinical applications in vascular pathologies are summarised.
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  • 29
    ISSN: 1432-1440
    Keywords: Key words Postprandial hyperlipoproteinemia ; Lipoprotein lipase ; Insulin ; Apolipoprotein E ; Hyperlipoproteinemia type III
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Type III hyperlipoproteinemia (HLP) is a multifactorial disorder associated with homozygosity for the apolipoprotein (apo) E-2 allele. Factors which may promote the development of HLP include lipoprotein lipase (LPL) and hyperinsulinemia. These factors were investigated in eight patients with type III HLP and in nine normolipidemic controls. In vitro the interaction of apoE with LPL was analyzed in cell binding assays. All type III HLP patients showed delayed triglyceride (TG) clearance and remnant lipoprotein accumulation in an oral fat tolerance test. Normolipidemic apoE-2/2 controls revealed normal TG clearance comparable to apoE3/3 controls. HLP patients showed lower LPL activity and mass than controls. Analysis of the LPL gene revealed an Asn 291→Ser mutation in three patients and a –93 T-G substitution combined with an Asp 9→Asn mutation in one control subject. In addition to LPL abnormalities, postprandial hyperinsulinemia was observed in five out of eight patients. In vitro LPL compensated the defective function of apoE-2 in mediating remnant lipoprotein binding to cells. In summary, seven out of eight patients with type III HLP showed LPL abnormalities and/or postprandial hyperinsulinemia. Together with the in vitro data these findings support a coordinate effect of apoE and LPL for the manifestation of type III HLP. Hyperinsulinemia appears to be an additional factor important for disease expression.
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  • 30
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    Pflügers Archiv 435 (1998), S. 583-594 
    ISSN: 1432-2013
    Keywords: Key words GLP-1 ; cAMP ; Insulin ; Calcium ; NIDDM ; Glucagon ; Islet ; GIP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Glucagon-like peptide 1 is a gastrointestinally derived hormone with profound effects on nutrient-induced pancreatic hormone release. GLP-1 modulates insulin, glucagon and somatostatin secretion by binding to guanine nucleotide binding protein-coupled receptors resulting in the activation of adenylate cyclase and generation of cyclic adenosine monophosphate (cAMP). In the B-cell, cAMP, via activation of protein kinase A, interacts with a plethora of signal transduction processes including ion channel activity, intracellular Ca2+ handling and exocytosis of the insulin-containing granules. The stimulatory action of GLP-1 on insulin secretion, contrary to that of the currently used hypoglycaemic sulphonylureas, is glucose dependent and requires the presence of normal or elevated concentrations of the sugar. For this reason, GLP-1 attracts much interest as a possible novel principle for the treatment of human type-2 diabetes. Here we review the actions of GLP-1 on islet cell function and attempt to integrate current knowledge into a working model for the control of pancreatic hormone secretion.
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  • 31
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 919-930 
    ISSN: 0887-6266
    Keywords: α-relaxation ; cold crystallization ; poly(aryl-ether-ether-ketone) (PEEK) ; poly(ether-imide) (PEI) ; vitrification ; devitrification ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have established time-temperature transformation and continuous-heating transformation diagrams for poly(ether-ether-ketone) (PEEK) and PEEK/poly(ether-imide) (PEI) blends, in order to analyze the effects of relaxation control on crystallization. Similar diagrams are widely used in the field of thermosetting resins. Upon crystallization, the glass transition temperature (Tg) of PEEK and PEEK/PEI blends is found to increase significantly. In the case of PEEK, the shift of the α-relaxation is due to the progressive constraining of amorphous regions by nearby crystals. This phenomenon results in the isothermal vitrification of PEEK during its latest crystallization stages for crystallization temperatures near the initial Tg of PEEK. However, vitrification/devitrification effects are found to be of minor importance for anisothermal crystallization, above 0.1°C/min heating rate. In the case of PEEK/PEI blends, amorphous regions are progressively enriched in PEI upon PEEK crystallization. This promotes a shift of the α-relaxation of these regions to higher temperatures, with a consequent vitrification of the material when crystallized below the Tg of PEI. The data obtained for the blends in anisothermal regimes allow one to detect a region in the (temperature/heating rate) plane where crystallization proceeds in the continuously close proximity of the glass transition (dynamic vitrification). These experimental findings are in agreement with simple simulations based on a modified Avrami model coupled with the Fox equation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 919-930, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 977-982 
    ISSN: 0887-6266
    Keywords: compressed gases ; polymer ; plasticization ; high-pressure DSC ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A high-pressure differential scanning calorimetric technique is described for studying polymer plasticization by compressed gases at pressures to 100 atm. The in situ measurements avoid problems due to gas desorption encountered with conventional DSCs, thus providing an accurate way to determine the change in glass transition temperature, Tg, with pressure, p. The entire Tg-p curve can be established in less than 2 days. The glass transition was observed as a sharp step in the case of 100-200-μm thin samples, whereas thicker samples gave a broad transition; highly reproducible results were obtained for the thin samples. For PS-CO2, the measured Tgs under various pressures were found to be in good agreement with literature values. Results for the systems PS-HFC134a, PVC-CO2, and PC-CO2 are also reported. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 977-982, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1025-1035 
    ISSN: 0887-6266
    Keywords: polymer thin films ; thermosets ; microelectronics ; moisture ; physical aging ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.1 It was found that the post curing near but below Tg resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025-1035, 1998
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  • 34
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
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  • 35
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1129-1139 
    ISSN: 0887-6266
    Keywords: polymer diffusion ; ambient temperature ; fluorescence ; latex films ; poly(butyl methacrylate) ; poly((acetoacetoxy)ethyl methacrylate-co-ethylhexyl methacrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer diffusion across interfaces at room temperature (21°C) was analyzed by direct nonradiative energy transfer (DET) in labeled latex films. Two modellatex polymers were examined: poly(butyl methacrylate) [PBMA, Mw = 3.5 × 104, Tg (dry) = 21°C] and a copolymer of 2-ethylhexyl methacrylate with 10 wt % (acetoacetoxy)-ethyl methacrylate [P(EHMA-co-AAEM), Mw = 4.8 × 104, Tg (dry) = -7°C]. Little energy transfer due to polymer diffusion was detected for the P(EHMA-co-AAEM) latex samples in the dispersed state or dried to solids content below ca. 90%, but above 90% solids, diffusion occurs among particles. For PBMA, diffusion occurs only after the film is dried (〉97% solids) and aged. In the dry PBMA films, it requires 4-5 days at 21°C to reach a significant extent of mixing (fm = 0.3-0.4). This corresponds to an estimated penetration depth dapp of 30-40 nm and a mean apparent diffusion coefficient (Dapp) of 5 × 10-4 nm2/s. The corresponding Dapp value for the dry P(EHMA-co-AAEM) sample is 5 × 10-2 nm2/s, and it takes about 25-40 min for this polymer to reach fm of 0.3-0.4 with dapp of 20-30 nm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1129-1139, 1998
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  • 36
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1201-1209 
    ISSN: 0887-6266
    Keywords: polymer electrolytes ; NMR ; conductivity ; glasses ; Arrhenius and VTF dependences ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the temperature variation of conductivity and 1H NMR linewidth of (PEG)xNH4ClO4 (x = 20, 30, 46, 100, 200, & 1000) polymer electrolyte systems. The temperature dependence of the conductivity shows two distinct behaviors, the low temperature VTF dependence crossing over to Arrhenius dependence at higher temperatures. The departure from the VTF behavior is found to be composition dependent. NMR spectra indicate the presence of large fractions of crystalline regions that start to melt around the crossover temperature. We understand the deviation from the VTF behavior as a consequence of this crystalline to elastomer transition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1201-1209, 1998
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1227-1233 
    ISSN: 0887-6266
    Keywords: FTIR spectroscopy ; isotactic polystyrene ; crystallization process ; induction period ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227-1233, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2327-2337 
    ISSN: 0887-6266
    Keywords: surface tension ; surface energy ; contact angle ; liquid crystalline polymers ; thermotropic polymers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have determined the surface energies (γs) of two liquid crystalline polyesters (Vectra™ A-950 [Hoechst Celanese, NJ] and Xydar™ [Amoco, GA]) and one polyesteramide (Vectra™ B-950 [Hoechst Celanese, NJ]) using contact angle techniques at room temperature. These LCPs were dissolved in bis-trifluoromethyl phenol and spin coated upon glass slides to form thin films. The contact angle measurements were carried out employing a Ramé-Hart Contact Angle Goniometer (Ramé-Hart, NJ). Pure water, glycerol, formamide, and diiodomethane were chosen as the testing liquids. Various surface energy calculation models were utilized to analyze the surface energies of these LCP films. Experimental data suggest that surface energy values did match between two-liquid geometric and three-liquid acid-base approaches if the correct combinations of testing liquid were used. However, the three-liquid Lifshitz-van der Waals acid-base method is more suitable for the surface energy calculation of these three LCPs, and provides much more information (e.g., acidity and basity of LCP surfaces). The average surface energies of Vectra™ A-950, Vectra™ B-950, and Xydar™ are 41.0, 41.9, and 42.3 mJ/cm2, respectively. In addition, all these three LCPs should be classed as monopolar Lewis bases because their Lewis acid components, γ+, are negligible. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2327-2337, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2355-2369 
    ISSN: 0887-6266
    Keywords: fracture ; fatigue ; polyethylene ; molecular weight distribution ; short chain branch content ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stepwise fatigue crack propagation in a range of polyethylene resins, some of which are candidates for use in pipes for natural gas distribution, was studied. Examination of the effect of molding conditions on fatigue crack propagation in a pipe resin indicated that fast cooling under pressure produced specimens with the same crack resistance as specimens taken from a pipe extruded from this resin. The mechanism of stepwise crack propagation in fatigue was the same as reported previously for creep loading. Observations of the region ahead of the arrested crack revealed a complex damage zone that consisted of a thick membrane at the crack tip followed by a main craze with subsidiary shear crazes that emerged from the crack tip at an angle to the main craze. The effects of molecular parameters, such as molecular weight, comonomer content, and branch distribution, on the kinetics of fatigue crack propagation were examined. Correlation of creep and fatigue crack resistance made it possible to relate fatigue fracture toughness to molecular parameters by invoking concepts of craze fibril stability developed for creep. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2355-2369, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2379-2391 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; polymer micelle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated at different oil concentrations to ascertain the effect of composition on TPEG morphology and mechanical properties. The impact of thermal processing is also examined by comparing gels thermally quenched to 0°C or slowly cooled to ambient temperature. Transmission electron micrographs reveal that gels with 70 to 90 wt % oil exhibit styrenic micelles measuring ca. 24 nm in diameter. Variation in composition or cooling rate does not have any perceivable effect on micelle size or shape, whereas the rate at which the gels are cooled influences the extent of microstructural order and the time to rupture (tR) at constant strain. Dynamic rheological testing confirms the presence of a physically crosslinked network at TPEG compositions ranging from 70 to 90 wt % oil, independent of cooling rate. Results presented here suggest that the dynamic elastic shear modulus (G′) scales as tαR where α varies from 0.41 to 0.59, depending on cooling rate. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2379-2391, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2423-2433 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; nonrandom crosslinking ; molecular weight distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of the first-order Markovian statistics, we propose a general matrix formula for the weight-average molecular weight of crosslinked polymer systems, explicitly given by M̄w = M̄w,0 + WX0 (I - X)-1 Sf. This equation is valid for both step and chain-growth polymerizations, including those in a nonequilibrium state irrespective of the reactor types used. In the context of the present theory, the onset of gelation is simply stated as a point at which the largest eigenvalue of the matrix X reaches unity (i.e., det(I - X) = 0). The present theory provides a unified point of view for various types of gelling systems. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2423-2433, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2461-2470 
    ISSN: 0887-6266
    Keywords: dielectric relaxation spectroscopy ; thermosets ; interpenetrating polymer networks ; curing reaction ; temperature-modulated differential scanning calorimetry ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation spectroscopy (3 kHz ≤ ƒ ≤ 3 MHz), differential scanning calorimetry, and temperature-modulated calorimetry have been performed during isothermal curing of an epoxy network (diglycidylether of bisphenol A crosslinked with diaminodiphenyl methane), and of two thermoplast modified epoxy resins (semi-interpenetrating polymer networks) consisting of the epoxy network component and different amounts (10 and 20 wt %) of a linear high Tg polymer (polysulfone or polyethersulfone). During reaction, the homogeneous-mixtures phase separate into an epoxy-rich and a linear polymer-rich phase with different mobilities of the electrical dipoles. The complex dielectric permittivity is composed of a contribution from the ionic dc-conductivity and a contribution from relaxations of the permanent electrical dipoles in the two phases. The decrease of the dc-conductivity in the initial stage of cure is related to the time for gelation or vitrification. The contribution of the dipole relaxations to the dielectric permittivity reflects an increase of the relaxation times with curing time for both phases. The time-dependent changes in the complex dielectric permittivity are described by a simple two-phase model based on two Havriliak-Negami functions combined with Vogel-Fulcher equations for the description of the curing-time dependence of the relaxation times. The increase of the relaxation times in the phases during isothermal curing is incorporated by time-dependent Vogel temperatures. The latter are related to the time evolution of the glass-transition temperatures in the two phases measured independently by calorimetry. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2461-2470, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2483-2492 
    ISSN: 0887-6266
    Keywords: low-density polyethylene ; surface modification of polymers ; scanning force microscopy ; self-assembled monolayer of thiols ; chemical force microscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this article, we present the results of a study on the surface properties of chromic acid-oxidized low-density polyethylene (LDPE) by scanning force microscopy (SFM) and contact angle measurements. LDPE films were surface modified by a chromic acid treatment with subsequent annealing in argon and reconstruction in boiling water as described by Rasmussen, Stedronsky, and Whitesides [J. Am. Chem. Soc., 99, 4736 (1977)]. The LDPE oxidation in chromic acid was monitored in situ by contact mode SFM. Initially stacks of lamellae became exposed, and at later stages a granular morphology was observed. By tapping mode SFM, the sample roughness was shown to increase during the first 10 min of oxidation from initially ca. 20 nm to ca. 50 nm. Gold-coated SFM probes (tips) functionalized with self-assembled monolayers were used to determine the pull-off force characteristics in ethanol. Variations in the contact area between SFM tips and polymer surfaces that exposed sharp crystalline features were shown to obscure the results of pull-off force measurements. However, on annealed and subsequently reconstructed samples with lower roughness, the results of force measurements correlated well with the measured contact angles. Over the range of surface energies studied, the normalized pull-off force between carboxylic acid-modified tips and these smooth samples was shown to depend approximately linearly on the cosine of the contact angle. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2483-2492, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2499-2511 
    ISSN: 0887-6266
    Keywords: heat capacity ; poly(trimethylene terephthalate) ; entropy ; enthalpy ; free enthalpy ; heats of transition ; glass transition ; melting ; crystallinity ; rigid-amorphous fraction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heat capacity of poly(trimethylene terephthalate) (PTT) has been measured using adiabatic calorimetry, standard differential scanning calorimetry (DSC), and temperature-modulated differential scanning calorimetry (TMDSC). The heat capacities of the solid and liquid states of semicrystalline PTT are reported from 5 to 570 K. The semicrystalline PTT has a glass transition temperature of 331 K. Between 340 and 480 K, PTT can show exothermic ordering depending on the prior degree of crystallization. The melting endotherm of semicrystalline samples occurs between 480 and 505 K, with a typical onset temperature of 489 K (216°C). The heat of fusion of the semicrystalline samples is about 15 kJ mol-1. For 100% crystalline PTT the heat of fusion is estimated to be 30 ± 2 kJ mol-1. The heat capacity of solid PTT is linked to an approximate group vibrational spectrum and the Tarasov equation is used to estimate the heat capacity contribution due to skeletal vibrations (θ1 = 550.5 K and θ2 = θ3 = 51 K, Nskeletal = 19). The calculated and experimental heat capacities agree to better than ±3% between 5 and 300 K. The experimental heat capacities of liquid PTT can be expressed by: \documentclass{article}\pagestyle{empty}\begin{document}$ C^L_p(exp) $\end{document} = 211.6 + 0.434 T J K-1 mol-1 and compare to ±0.5% with estimates from the ATHAS data bank using contributions of other polymers with the same constituent groups. The glass transition temperature of the completely amorphous polymer is estimated to be 310-315 K with a ΔCp of about 94 J K-1 mol-1. Knowing Cp of the solid, liquid, and the transition parameters, the thermodynamic functions enthalpy, entropy, and Gibbs function were obtained. With these data one can compute for semicrystalline samples crystallinity changes with temperature, mobile amorphous fractions, and resolve the question of rigid-amorphous fractions.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2499-2511, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2551-2562 
    ISSN: 0887-6266
    Keywords: polytetrafluoroethylene ; virgin powder ; two-stage draw ; morphology ; tensile properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polytetrafluoroethylene (PTFE) virgin powder was ultradrawn uniaxially by a two-stage draw. A film, compression molded from powder below the melting temperature (Tm), was initially solid-state coextruded to an extrudate draw ratio (EDR) of 6-20 at an established optimum extrusion temperature of 325°C, near the Tm of 335°C. These extrudates from first draw were found to exhibit the highest ductility at 45-100°C for the second-stage tensile draw, depending on the initial EDR and draw rate. The maximum achievable total draw ratio (DRt, max) was 36-48. Such high ductility of PTFE, far below the Tg (125°C) and Tm, is in sharp contrast to other crystalline polymers that generally exhibit the highest ductility above their Tg and near Tm. The unusual draw characteristics of PTFE was ascribed to the existence of the reversible crystal/crystal transitions around room temperature and the low intermolecular force of this polymer, which leads to a rapid decrease in tensile strength with temperature. The structure and tensile properties of drawn products were sensitive to the initial EDR, although this had no significant influence on DRt,max. The most efficient and highest draw was achieved by the second-stage tensile draw of an extrudate with the highest EDR 20 at 100°C, as evaluated by the morphological and tensile properties as a function of DRt. The efficiency of draw for the cold tensile draw at 100°C was a little lower than that for solid-state coextrusion near the Tm. However, significantly higher tensile modulus and strength along the fiber axis at 24°C of 60 ± 2 GPa and 380 ± 20 MPa, respectively, were achieved by the two-stage draw, because the DRt,max was remarkably higher for this technique than for solid-state coextrusion (DRt,max = 48 vs. 25). The increase in the crystallite size along the fiber axis (D0015), determined by X-ray diffraction, is found to be a useful measure for the development of the morphological continuity along the fiber axis of drawn products.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2551-2562, 1998
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  • 46
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2597-2605 
    ISSN: 0887-6266
    Keywords: positron annihilation ; open space ; relaxation ; subsurface ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Open spaces in the subsurface region (〈10 μm) of very low density polyethylene were probed by a monoenergetic positron beam. From measurements of Doppler broadening spectra measurements of the annihilation radiation and the lifetime spectra of positrons as a function of incident positron energy, the size of the open spaces in the region of 0-3 μm was found to be larger than that in the deeper region. This was attributed to the cooperative motion of large segments of molecules which is activated near the surface. After the freezing in of such motions (below 230 K), although the lineshape parameter S in the bulk was almost constant, S in the region of 0-3 μm decreased with decreasing temperature. This discrepancy was associated with the presence of the open spaces with an excess content and the resultant contraction of amorphous structure near the surface. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2597-2605, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 755-761 
    ISSN: 0887-6266
    Keywords: positron annihilation lifetime spectroscopy ; free volume ; transition temperatures ; poly(silylenemethylene)s ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amorphous and crystalline poly(silylenemethylene)s with the repeating PhRSiCH2 (R : Me or Ph) units were characterized by positron annihilation lifetime spectroscopy (PALS) to gain insights into the molecular motions of these polymers. The temperature dependence of the ortho-positronium lifetime (τ3) and intensity (I3) was examined from 50 to 470 K for each sample. The glass transition temperature of each polymer was easily distinguished by a change in the slope of τ3 spectrum. Both polymers exhibited a steep drop of I3 at 130-140 K being probably assignable to the transition arising from the motions of phenyl groups, which was almost undetectable by means of differential scanning calorimetry or dynamic mechanical analysis. Several other transitions of these polymers detected by PALS are also discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 755-761, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 763-781 
    ISSN: 0887-6266
    Keywords: random copolyesters ; copolymers ; crystallization ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of poly(ethylene terephthalate co-1,4-cyclohexylene dimethylene terephthalate) [PET/CT] random copolyesters has been studied. The basis of this analysis was the triple melting behavior of PET homopolymers, which is commonly observed after a period of isothermal crystallization followed by linear heating in a differential scanning calorimeter. Both ET and CT homopolymers are able to crystallize, and as a consequence, the copolymer morphology depends on the ET/CT ratio. It has been reported that at low CT concentrations, the ET units can crystallize with complete rejection of the CT units and that at high CT concentrations, the CT units can cocrystallize with the ET units. In the present work, low CT concentrations were selected, as they are completely rejected from the ET crystals. The purpose was to further test the hypothesis that in the triple melting behavior of PET homopolymers, the second DSC melting endotherm is related to secondary species crystallized by material rejected from the primary crystals. This concept arose from our previous work, where it was speculated that increasing the average molecular-weight of PET would enhance molecular entanglement and increase secondary crystallization. This process would give rise to a higher amount of species being rejected from the main crystals, i.e., an increase of secondary crystallization would occur, and as a consequence the second melting endotherm would be enhanced. Similar to the effect of molecular weight, such behavior has been observed as a function of rejected copolymer content. This gives support to our previously proposed step-like crystallization and melting mechanism for PET homopolymers, and has the potential to be extended to other high temperature semicrystalline polymeric systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 763-781, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 357-371 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; molecular weight distribution ; branched polymers ; polymer modification ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A Markovian model is proposed for nonrandom branching reactions, by using free-radical polymerization that involves chain transfer to polymer as an example. Free-radical polymerizations are kinetically controlled; therefore, each primary polymer molecule experiences different history of branched structure formation. By assuming that the primary chains with the identical birth time conform to the same chain connection probabilities, the nonlinear structural development can be viewed as a system in which the primary chains formed at different birth times are combined into nonlinear polymers in accordance with the first-order Markov chain statistics. An explicit formula for the weight-average chain length is derived in a matrix form. The onset of gelation is simply stated as a point at which the largest eigenvalue of the transition matrix X reaches unity, i.e., det(X - I) = 0. This criterion for the onset of gelation can be considered as an extension of the Flory/Stockmayer theory to a nonequilibrium reaction system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 357-371, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 495-517 
    ISSN: 0887-6266
    Keywords: crystallization ; DSC ; multiple melting ; nascent morphology ; polyethylene ; synchrotron ; UHMW PE ; WAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nascent morphology of UHMW PE exhibits high melting point, high crystallinity, and increased WAXS line breadth relative to samples formed by melt crystallization. Different empirical relationships between crystal size and melting point are observed for nascent and molded samples. This differentiation is removed following nitric acid treatment of the nascent flake. Solid-state annealing behavior is differentiated by several regimes. Regime I is characterized by increasing crystallite dimensions and crystallinity at low annealing temperatures. Regime II[a] and II[b] is identified by double melting in DSC scans of moldings and nascent flake, respectively. The double melting is due to partial melting with incomplete recrystallization. Regime II[a] of moldings is differentiated from Regime II[b] of flake by an increase in melting point of the higher melting endotherm. Within Regime II[b], the partial melting of the nascent structure is sensitive to the distribution of morphological stability. Regime III is initiated at annealing temperatures approaching the zero heating rate melting point, and shows melting kinetics by DSC or time-resolved WAXS using synchrotron x-ray radiation. The superheat, partially associated with Regime III behavior, is sensitive to morphological heterogeneity and annealing history. Morphological models are discussed which highlight the role of noncrystalline regions and melting kinetics on the melting behavior of nascent form crystallinity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 495-517, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 567-572 
    ISSN: 0887-6266
    Keywords: surface ; interfaces ; diffusion ; polystyrene ; polyphenylene oxide ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Symmetric polydisperse (Mw = 23 × 104, Mw/Mn = 2.84) and monodisperse (Mw = 21 × 104, Mw/Mn 〈 1.05) polystyrene (PS), and asymmetric polydisperse PS/poly(2,6-dimethyl 1,4-phenylene oxide) (PPO) interfaces have been bonded in the vicinity of the glass transition temperature (Tg) of PS. In a lap-shear joint geometry, strength develops in all cases with time to the fourth power, which indicates that it is diffusion controlled. Strength developing at short times at the polydisperse PS/PS interface, at 90°C, is higher than that at the monodisperse interface, at 92°C (at Tg - 13°C in both cases), presumably due to the contribution of the low molecular weight species. The decrease of strength at the PS/PPO interface when the bonding temperature decreases from 113 to 70°C, i.e., from Tg + 10°C to Tg - 33°C of the bulk PS, indicates a high molecular mobility at the surface as compared to that in the bulk, and can be expressed by a classical diffusion equation, which is valid above Tg (of the surface layer). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 567-572, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 629-640 
    ISSN: 0887-6266
    Keywords: poly(acrylonitrile) ; two-stage draw ; morphology and tensile properties ; effect of molecular weight ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultradrawing of atactic poly(acrylonitrile) (PAN) was investigated for a Mv series, ranging 8.0 × 104-2.3 × 106. Samples for the draw were prepared from 0.5-30 wt % solutions of PAN in N,N′-dimethylformamide. The solutions were converted to a gel by quenching from 100 to 0°C. The dried gel films were initially drawn uniaxially by solid-state coextrusion (first-stage draw) to an extrusion draw ratio (EDR) of 16, followed by further tensile draw at 100-250°C (second-stage draw). The maximum total draw ratio (DRt,max) and tensile properties achieved by two-stage draw increased remarkably with sample Mv. Other factors affecting ductility were the solution concentration from which gel was made and the second-stage draw temperature. The effects of these variables became more prominent with increasing Mv. The temperature for optimum second-stage draw increased with sample Mv. Both the initial gel and the drawn products showed no small-angle X-ray long period scattering maximum, suggesting the absence of a chain-folded lamellae structure, which had been found in our previous study on the drawing of nascent PAN powder. The chain orientation function (fc) and sample density (ρs) increased rapidly with DRt in the lower range (DRt 〈 30) and approached constant values of fc = 0.980-0.996 and ρs = 1.177-1.181 g/cm3, respectively, at higher DRt 〉 30-100. The tensile modulus also showed a similar increase with DRt. The tensile strength increased linearly with DRt, reaching a maximum, and decreased slightly at yet higher DRt. The highest modulus of 28.5 GPa and strength of 1.6 GPa were achieved with the highest Mv of 2.3 × 106. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 629-640, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 681-692 
    ISSN: 0887-6266
    Keywords: high-density polyethylene ; nonisothermal crystallization kinetics ; plateau temperature ; regime transition ; crystallinity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The quiescent nonisothermal bulk crystallization kinetics of two high-density polyethylene resins were investigated by a modified light-depolarizing microscopy (LDM) technique. The technique allows studies at average cooling rates up to 2500°C/min. The polymer was found to crystallize at a pseudo-isothermal temperature even at these very high cooling rates. The overall bulk crystallization rate increased rapidly as the cooling rate and supercooling increased. Crystallization kinetics was analyzed by Avrami analysis. Avrami exponents near 3 suggested spherical growth geometry and instantaneous nucleation at predetermined sites. Observation of spherulites by optical microscopy together with a number density of spherulites that changed little with increase in cooling rate or supercooling supported this model of crystallization behavior. Analysis of the half-time of crystallization based on the Lauritzen and Hoffman secondary nucleation theory indicated that the regime II-III transition was found to occur at a degree of supercooling of approximately 22°C. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 681-692, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 727-741 
    ISSN: 0887-6266
    Keywords: liquid crystal polymer ; aromatic polyester ; molecular modeling ; Monte Carlo ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The condensed phase of the alternating copolyester of p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) is investigated by studying the room temperature packing arrangement of the copolymer chains. A molecular modeling methodology is employed with a Monte Carlo sampling of the configurational phase space. Realistic poly(HBA-alt-HNA) polymer chains are represented by an explicit atom representation of the HBA/HNA dimers. States are sampled from the NVT ensemble using a sampling scheme consisting of (1) valence and torsional variations, (2) rigid body rotations of the chain about the chain axis, and (3) rigid body translations of the chain. The effect of chain packing on the conformation of chains, as well as the relative intra- and intermolecular orientations of aromatic rings, is investigated. Correlation of chain positioning along the chain axis is dominated by aromatic rings maintaining a center-to-center plane of registry. These layers of aromatic units pack with a preference for edge-to-face orientations in a herringbone-type pattern and have an intermolecular ring angle between the pairs of aromatic rings in the unit cell that is ca. 68°. The aromatic rings, on average, are rotated 38° out from the b-c plane. The phenylene rings of these copolyesters are less restricted in their relative orientation in comparison to the naphthalene rings. Intramolecular orientational probability density distributions indicate a preference for staggering the successive aromatic rings along the chain, with a staggering angle of ca. 66°. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 727-741, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 797-803 
    ISSN: 0887-6266
    Keywords: polynorbornene ; gas separation ; membrane ; free volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of gas transport properties of novel polynorbornenes with increasing length of an aliphatic pendant group R (CH3—, CH3(CH2)3—, CH3(CH2)5—, CH3(CH2)9—) has been performed. These polymers were synthesized using novel organometallic complex catalysts via an addition polymerization route. This reaction route maintained the bridged norbornene ring structure in the final polymer backbone. Gas permeability and glass transition temperature were found to be higher than those for polynorbornenes prepared by ring-opening metathesis and reported in the literature. It was shown that for noncondensable gases such as H2 and He the selectivity over N2 decreased when the length of the pendant group increased, but remained relatively stable for the more condensable gases (O2 and CO2). The permeability coefficient is correlated well to the inverse of the fractional free volume of the polymers. The more condensable gases showed a deviation from this correlation for the longest pendant group, probably due to an increase of the solubility effect. This polymer series demonstrated a simultaneous increase in permeability and selectivity, uncommon for polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 797-803, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 805-813 
    ISSN: 0887-6266
    Keywords: collagen ; surfactants ; calorimetry ; segment-long-spacing ; anionic ; titration ; sodium lauryl sulfate ; castor oil ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Leather, a textile based on collagen, usually requires the addition of sulfated oils that have been recently found to cause instability when heated in critical manufacturing processes. Here reactions between collagen and sodium dodecyl sulfate (SDS), sulfated castor oil, or a synthetic sulfated oil are studied calorimetrically. Sodium lauryl sulfate below its critical micelle concentration (cmc) displayed an immediate exotherm due to equilibrium binding of the reagents with stoichiometry n = 12.6 ± 0.2, K = (2.02 ± 0.8) × 107 M-1, and enthalpy ΔH = 62 ± 2 Kcal/mol; and a delayed endotherm due to denaturation of collagen. The endotherms accompanying the reactions with sulfated oils with longer chains were smaller, with no apparent denaturation of collagen. The micellar nature of these surfactants was apparent from very large n for sulfated castor oil, 4082 ± 11 and a very small value of ΔH, 0.77 ± 0.01 cal/mol. The binding of sulfated castor oil at the polar bands of collagen crystallites, comprising extended molecules arranged side-by-side, was shown directly by electron microscopy. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 805-813, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 861-871 
    ISSN: 0887-6266
    Keywords: glass transition ; polymer blends ; free volume ; positron annihilation ; composition dependence of Tg ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-Vinyl Polybutadiene (HVBD)/cis-Polyisoprene (CPI) blends were characterized by Differential Scanning Calorimetry (DSC) and Positron Annihilation Lifetime Spectroscopy (PALS). A single DSC glass transition temperature Tg is observed, whose composition dependence strongly deviates from additivity, and shows an apparent cusp when the weight fraction of HVBD ≈ 0.75. The free-volume hole size, Vh, and the scaled fractional free volume, hps/C, = I3Vh were determined by PALS from the orthopositronium (o-Ps) intensities, I3, and lifetimes, τ3, over a temperature range encompassing Tg and the temperature at which “positronium bubble” formation occurs. In the glass, Vh and hps/C are smaller for CPI than for HVBD, but the thermal expansion coefficient for hole volume, αf, is larger in the melt for CPI than for HVBD; thus, an iso-hole volume temperature occurs in these blends at Tiso ≈ -34°C. Above and below Tiso, Vh and hps/C each show a negative departure from additivity. A quantitative interpretation of the cusp in the composition dependence of Tg can be obtained, via a modified analysis of Kovacs, using free-volume quantities from PALS, with the ratio of scaling constants CCPI/CHVBD as an adjustable parameter. At high temperatures, the positron bubble size is smaller in CPI than in HVBD. This agrees with the observation that the thermal expansivity of hole volume, and, hence the internal pressure are larger in the equilibrium melt of CPI. The effect of e+-irradiation on the o-Ps intensity was investigated. I3 decreases more rapidly in the melt as T → Tg, and then more slowly in the glass, suggesting that the effect is due to trapping of radical or ionic species which inhibit o-Ps formation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 861-871, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 373-381 
    ISSN: 0887-6266
    Keywords: pressure-sensitive adhesive ; PSA ; tackifier ; tack adhesion ; polyisoprene ; poly(ethylene-propylene) ; pulsed gradient spin echo-nuclear magnetic resonance ; PGSE-NMR ; diffusion ; n-butyl ester of abietic acid ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A detailed study of the mobility of a tackifying resin in a pressure-sensitive adhesive (PSA) has been done for the first time. The objective of this work is to relate changes in adhesive performance with tackifier loading to tackifier mobility. Tackifiers are low-molecular weight resins that improve the overall performance of PSAs. They increase the adhesive tack or the ability to form a bond of measurable strength after brief contact under slight applied pressure. In this study the diffusion of n-butyl ester of abietic acid (n-BEAA) in either polyisoprene (PI) (Mw = 195,000 Mw/Mn ∼ 1.05) or poly(ethylene-propylene) (PEP) (Mw = 40,000 Mw/Mn ∼ 2.30) was measured by Pulsed Gradient Spin Echo-Nuclear Magnetic Resonance (PGSE-NMR) as a function of both tackifier concentration and temperature. The concentration dependence of the tackifier's diffusion coefficient was weak for both systems. The weak variation in mobility with composition for the PI/n-BEAA system was consistent with that system's weak variation in tack with composition. On the other hand, blends of PEP/n-BEAA showed only modest variation in mobility, even though these adhesive systems showed appreciable enhancement of tack at intermediate compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 373-381, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 415-423 
    ISSN: 0887-6266
    Keywords: block copolymer ; polymeric micelle ; nanoparticle ; clonazepam ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Block copolymers consisting of poly(γ-benzyl L-glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) as the hydrophilic part were synthesized and characterized. Core shell type nanoparticles of the block copolymers (abbreviated GEG) were prepared by the dialysis method. Under fluorescence spectroscopy measurement, the GEG block copolymers were associated in water to form core shell type nanoparticles as polymeric micelles and the critical micelle concentrations (CMC) values of the block copolymers decreased with increasing PBLG chain length in the block copolymers. Transmission electron microscopy (TEM) observations revealed nanoparticles of spherical shapes. From dynamic light scattering (DLS) study, sizes of nanoparticles of GEG-1 and GEG-2 copolymer were 64.3 ± 28.7 nm and 28.9 ± 7.0 nm. The drug-loading contents of GEG-1 and GEG-2 nanoparticles were 15.2 and 8.3 wt %, respectively. These results indicated that the drug-loading contents were dependent on PBLG chain length in the copolymer. Then, the longer the PBLG chain length, the more the drug-loading contents. Release of clonazepam (CNZ) from the nanoparticles was slower in higher loading contents of CNZ than lower loading contents due to the hydrophobic interaction between PBLG core and CNZ. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 415-423, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1401-1417 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; Brownian dynamics ; shear flow ; extensional flow ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational and rheological dynamics of dilute solutions of polyelectrolyte macromolecules undergoing shear and extensional flow are modeled using Nonequilibrium Brownian Dynamics (NEBD) and Configuration-Biased Monte Carlo (CBMC) simulations. The mathematical model utilizes a bead-spring chain with charged beads that interact through a screened Debye-Hückel potential, and that also interact through stretching and bending forces. The diffusion (or Fokker-Planck) equation for the probability density of the positions of the beads of the chain is converted to a Stochastic Differential Equation (SDE), from which the simulation algorithm for the NEBD is obtained. The CBMC is used in the initial chain generation and in determining steady-state properties in elongational flows. Various conformational and rheological quantities, such as the stress and birefringence, are monitored, under both steady-state and transient conditions, with the primary independent variable being the salt concentration (parametrized through the Debye length) and the strength of interaction q, related to the degree of ionization of the chain. It is found that this model is able to describe qualitatively many of the experimentally observed features in such systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1401-1417, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1451-1463 
    ISSN: 0887-6266
    Keywords: bulk modulus ; heat capacity ; high-pressure ; poly(vinyl acetate) ; thermal conductivity ; transient hot-wire method ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal conductivity λ and heat capacity per unit volume of poly(vinyl acetate) (260 kg mol-1 in weight average molecular weight) have been measured in the temperature range 150-450 K at pressures up to 1 GPa using the transient hot-wire method, which yielded λ = 0.19 W m-1 K-1 at atmospheric pressure and room temperature. The bulk modulus K has been measured in the temperature range 150-353 K up to 1 GPa. At atmospheric pressure and room temperature, K = 4.0 GPa and (∂K/∂p)T = 8.3. The volume data were used to calculate the volume dependence of λ, \documentclass{article}\pagestyle{empty}\begin{document}$g = - \left( {\frac{{\partial \lambda /\lambda }}{{\partial V/V}}} \right)_T .$\end{document} The values for g of the liquid and glassy states were 3.0 and 2.7, respectively, and g of the latter was almost independent of volume and temperature. Theoretical models can predict the value for g of the glassy state to within 25%. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1451-1463, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 543-553 
    ISSN: 0887-6266
    Keywords: polyacrylonitrile ; polyimine ; isotacticity ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543-553, 1998
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  • 63
    ISSN: 0887-6266
    Keywords: poly(methylphenylsiloxane) ; poly(dimethylsiloxane) ; titania ; silica ; composites ; reinforced elastomers ; morphology ; stress-strain isotherms ; scattering intensities ; differential scanning calorimetry ; transmission electron microscopy ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The work reported in the preceding article in this series is extended by consideration of polysiloxane-ceramic composites based on atactic poly(methylphenylsiloxane) (PMPS) elastomers instead of poly(dimethylsiloxane). The former is noncrystallizable because of its stereochemically irregular structure, while the latter is crystallizable. In addition, some composites were prepared by the in situ precipitation of titania instead of silica. The resulting materials were characterized using differential scanning calorimetry, equilibrium stress-strain measurements in elongation, small-angle neutron scattering, and transmission electron microscopy. The moduli of the PMPS elastomers were found to increase significantly with increase in amount of either type of filler, with reinforcing upturns at high elongation in the case of the silica. Because the PMPS elastomers were amorphous, it is obvious that strain-induced crystallization is not required for these upturns in modulus. Titania did not give as good reinforcement as did silica, at least in the case of PMPS. Differences in interactions between the polymer and the two fillers are obviously important in this regard, but differences in particle morphology probably also contribute. Specifically, the titania “particles” were significantly larger than the silica particles when observed in TEM, and appeared to be much more porous. The actual domain size as measured by scattering, however, was only approximately 5% larger. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1191-1200, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1247-1260 
    ISSN: 0887-6266
    Keywords: polyimides ; thin films ; infrared spectroscopy ; molecular structure ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular structure of poly[biphenyl dianhydride-p-phenylenediamine] (BPDA-PDA) polyimide in ultrathin (3-300 nm) films on silicon has been characterized by polarized infrared spectroscopy in conjunction with ellipsometry and X-ray reflectivity measurements. In spite of the high degree of crystalline packing of the polymer chains, the results show that an unexpected and significant content of imide rings exhibit local structural perturbations, including out-of-plane twisting. Further, the fraction of perturbed rings increases with increasing film thickness while, in contrast, the high degree of in-plane uniaxial film symmetry and planar stacking of the chains remain constant with thickness. These results reveal a new structural aspect of localized ring disorder that arises within the otherwise well-ordered, chain-stacked structure of BPDA-PDA polyimide films. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1247-1260, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1987-1994 
    ISSN: 0887-6266
    Keywords: toughening ; impact strength ; blend ; nylon 6 ; core-shell impact modifier ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Super-tough nylon 6 was prepared by using maleic anhydride grafted polyethylene-octene rubber/semicrystalline polyolefin blend (TPEg) as an impact modifier. The morphology, dynamic mechanical behavior, mechanical properties, and toughening mechanism were studied. Results indicate that TPEg with a semicrystalline polyolefin core and a polyethylene-octane rubber shell, possesses not only a better processability of extruding and pelletizing with a lower cost, but also an improved toughening effect in comparison with the maleated pure polyethylene-octene rubber. The shear yielding is the main mechanism of the impact energy dissipation. In addition, the influence of melt viscosity of nylon 6 on toughening effectiveness was also investigated. High melt viscosity of matrix is advantageous to the improvement of notched Izod impact strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1987-1994, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2019-2024 
    ISSN: 0887-6266
    Keywords: divinylbenzene ; porous copolymer ; excess adsorption isotherm ; active centers ; adsorption azeotropic point ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorptive properties of four porous copolymers were investigated. They contained different functional groups in the internal structure. Adsorption measurements were made using the static method. Three two-component and one three-component solutions with different physicochemical properties were used. The adsorptive centers of the copolymers were evaluated based on the analysis of excess adsorption isotherms of the polar solution component. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2019-2024, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2057-2067 
    ISSN: 0887-6266
    Keywords: PTFE ; fillers ; UV radiation ; degradation ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The first part of a series of two, this paper analyzes the degradation of pure and filled PTFE under high energy UV radiation. The polymer morphology is first investigated using differential scanning calorimetry, highlighting the respective nucleating efficiency of TiO2 and CaF2 during polymer crystallization. Then, the various polymers are exposed to excimer laser radiation and observed under an optical microscope. The results indicate that the degradation is closely connected with microstructural parameters. In pure PTFE, scattering by crystallites and reflection on piles of lamellae control the nature and extent of the degradation. In filled PTFE, nature and concentration of fillers are the most important features governing degradation. When absorbing particles are added to PTFE, the damage is restricted to the surface and photothermal processes can modify the degradation from heterogeneous to ablative, depending on the filler content. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2057-2067, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2103-2109 
    ISSN: 0887-6266
    Keywords: ethylene-vinyl alcohol copolymers ; multiple-pulse proton NMR ; spin diffusion ; comonomer content ; crystallinity ; long spacing ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Capitalizing on the superior sensitivity of proton NMR, relatively rapid estimates of three parameters, namely, comonomer content, crystallinity, and long spacing, are determined for three ethylene/vinyl alcohol copolymers using solid-state proton NMR measurements. Multiple-pulse techniques are utilized (a) in conjunction with magic angle spinning for measuring comonomer content, (b) in conjunction with a T1xz relaxation measurement for determining crystallinity, and (c) in conjunction with a T1xz-based spin diffusion measurement for determining the long spacing. These three parameters, extracted from data collected in a total spectrometer time of about 20 min, are compared with similar parameters obtained using more conventional DSC, SAXS (including synchrotron), and solution-state NMR measurements. Agreement is found to be good. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2103-2109, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2141-2152 
    ISSN: 0887-6266
    Keywords: N-isopropylacrylamide ; fluorocarbon-containing comonomers ; linear latices ; microgel ; hydrophobicity and hydrophilicity ; transition heat ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of thermally responsive copolymers of N-isopropylacrylamide (NIPAAM) with a fluorinated hydrophobic comonomer, either hexafluoroisopropylmethacrylate (HFIPMA) or 2,2,3,3,4,4-hexafluorobutylmethacrylate (HFBMA) and a hydrophilic comonomer, methacrylic acid (MAA), were synthesized by emulsion polymerization. The chemical structures of the copolymers were studied by the IR technique. Dynamic light scattering (DLS) showed that aqueous latices of the copolymers exhibited swelling-deswelling changes typical to PNIPAAM; the degree of swelling as well as the temperature at which the polymers collapse depended on the chemical structure of the comonomers. Endotherms related to the contraction of the polymers were studied by differential scanning calorimetry (DSC). A combination of DLS and DSC results revealed that the hydrophobic and hydrophilic units in the copolymers strongly affected the swelling behavior, as well as the local environment of the PNIPAAM chains. The comonomer HFIPMA increased the hydrophobicity of NIPAAM, reduced the swelling, and caused coagulation of the copolymer of NIPAAM and HFIPMA at temperatures above the critical temperature. Hydrophobicity of HFIPMA also affected the rheological properties of the latex. The HFBMA comonomer increased the swelling of the latex particles. Methacrylic acid added into the associating copolymers made the copolymers to show polyelectrolyte behavior with an increase of swelling and a decrease of the enthalpy change upon the collapse. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2141-2152, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2197-2210 
    ISSN: 0887-6266
    Keywords: polycarbonate ; PMMA ; polyglutarimide ; crystallization ; segregation ; AFM ; SAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microstructure of amorphous polymer blends has been extensively studied in the past, but now there is a growing interest for polymer blends where one or more of the components can crystallize. In this study we investigate such blends, namely miscible polycarbonate (PC)/acrylic blends. Using small angle X-ray scattering (SAXS) measurements, combined with atomic force microscopy (AFM), electron microscopy (SEM), and optical microscopy, we demonstrate that the amorphous acrylic component mostly segregates inside the spherulites between the lamellar bundles (interfibrillar segregation). Varying the PC molecular weight or the mobility of the amorphous component (by changing its molecular weight and Tg) does not change the mode of segregation. So far qualitative predictions of the mode of segregation in semicrystalline polymer blends have been proposed using the δ parameter (the ratio between the diffusion coefficient D of the amorphous component in the blend and the linear crystallization rate G), introduced by Keith and Padden. Our results suggest that other parameters have to be considered to fully understand the segregation process. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2197-2210, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2247-2258 
    ISSN: 0887-6266
    Keywords: polyimide ; imidization ; interdiffusion ; PMDA/3,4′-ODA ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Para-, meta-, and mixed isomeric poly(amic ethyl ester) precursors of the polyimide based on pyromellitic dianhydride (PMDA) and 3,4′-oxydianiline (3,4′-ODA) were synthesized. The intrinsic viscosity of each of the isomers was measured in an NMP solution and found to be less than corresponding isomers derived from PMDA and 4,4′-oxydianiline (4,4′-ODA) precursors with comparable molecular weight. The imidization and solvent retention were measured as a function of imidization temperatures, Ti using forward recoil spectrometry (FRES). For samples cast from a single solvent, either N-methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO), no difference was observed in the temperature-dependent imidization behavior between the isomers. In all cases the imide fraction f increased as Ti increased, and reached a value of unity, i.e., full conversion at 400°C. At the same Ti, samples cast from DMSO showed a slightly higher f than samples cast from NMP. FRES and time of flight FRES (TOF-FRES) were used to measure the interdiffusion distance, w, of deuterium-labeled tracers into nondeuterated base layers of the polyimide of PMDA/3,4′-ODA treated at various Ti. The primary determinant of w for all isomers was Ti, and the particular isomer used as either the base or the tracer molecule did not seem to affect w. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2247-2258, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2275-2290 
    ISSN: 0887-6266
    Keywords: associative polymers ; rheology ; thickening ; hydrophobic ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological properties of hydrophobic alkali-soluble associative polymers (HASE) were studied using controlled rate (Mettler LS40) and controlled stress (TA CSL 500) rheometers. The effects of pH and polymer concentrations on the rheological properties of three HASE model polymer systems (i.e., HASE 5141, 5134, and 5142, with a degree of ethoxylation of 2.5, 10, and 40 mol, respectively) and a reference polymer without associative hydrophobes (MAAEA) were examined. As the pH is increased by addition of ammonia to greater than 5-6, the carboxyl groups ionize to carboxylate ions and the polymers become water soluble. The HASE polymers thicken mainly by hydrophobic association. Viscosity can increase by two to three orders of magnitude as pH is raised to 9. The degree of ethoxylation in the macromonomer controls the nature of the hydrophobic association junctions by altering the flexibility and hydrophobicity of the macromonomer. Optimum thickening efficiency is observed in the system with approximately 10 mol of an ethylene-oxide spacer between the polymer backbone and the macromonomer. Viscoelastic study shows that the maximum thickening efficiency also corresponds to the dominant elastic property observed in the system with 10 mol of EO. All the model systems except the control system without hydrophobe exhibit strain thickening of the viscous and elastic components. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2275-2290, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2311-2325 
    ISSN: 0887-6266
    Keywords: poly(ethylene oxide) ; crystallization ; AFM ; spherulites ; crystal growth ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The atomic force microscope (AFM) has been used to investigate morphological development during the crystallization of poly(ethylene oxide) (PEO) from the melt. PEOs with molecular weights of 1 × 105 and 7 × 106 were used. Height and amplitude images were recorded, using the tapping mode. For both polymers, the mode of spherulite development varied with the velocity of the growth front. For slow growth velocities, the growth of the crystallites was linear, with growth initially occurring by single lamellae, later developing into growth arms by screw dislocation spawning of crystallites. At intermediate growth velocities, stacks of lamellae develop rapidly. The splaying apart of adjacent crystals and growth arms is abundant. The operation of growth spirals was observed directly in this growth velocity range. The crystals formed by the giant screw dislocations diverge immediately from the original growth direction, providing a source of interlamellar splaying. At low and intermediate velocities, the front propagates by the advance of primary growth arms, with the regions between the arms filled in by arms growing behind the primary front. At the highest velocity observed here, the formation of lamellar bundles and immediate splaying results in recognizable spherulites developing at the earliest stages of crystallization. The change from linear growth to splaying and nonlinear growth are qualitatively explained in terms of driving force, elastic resistance and the presence of compositional and/or elastic fields in the melt. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2311-2325, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2349-2354 
    ISSN: 0887-6266
    Keywords: polyethylene ; slow crack growth ; γ-irradiation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of γ-irradiation on slow crack growth (SCG) in a medium density polyethylene (MDPE) was measured and compared with behavior of high density polyethylene (HDPE) and a recrystallized HDPE (RCHDPE). The three materials exhibited the same dependence on dose up to 3 Mrd. The HDPE became brittle above 50 Mrd. The resistance to SCG of MDPE and RCHDPE increased very rapidly with dose above 3 Mrd, until at 50-80 Mrd their resistance to SCG became extraordinarily high. This high resistance to SCG was accompanied by a transition from crazing to shear deformation at the root of a notch. It was found that for the same concentration, crosslinks are more effective than short chain branches for increasing resistance to SCG. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2349-2354, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1305-1312 
    ISSN: 0887-6266
    Keywords: poly(β-hydroxybutyrate) ; nonisothermal crystallization ; kinetics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetics of nonisothermal crystallization of poly(β-hydroxybutyrate) from melt and glassy states were performed by differential scanning calorimetry under various heating and cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that both Avrami treatment and a new method developed by combining the Avrami equation and Ozawa equation could describe this system very well. However, Ozawa analysis failed. By using an evaluation method, proposed by Kissinger, activation energies have been evaluated to be 92.6 kJ/mol and 64.6 kJ/mol for crystallization from the glassy and melt state, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1305-1312, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1393-1399 
    ISSN: 0887-6266
    Keywords: PNLC ; UV cure ; polyurethane acrylate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer network liquid crystals (PNLC) have been prepared from ultraviolet-curable polyurethane acrylate (PUA) and a nematic liquid crystal mixture (BL002). Effects of monoacrylate type on film morphology, temperature-dependent off-state transmittance, and electro-optic performance of the film have been studied. Among three types of monoacrylates incorporated (EHA(2-ethyl hexyl acrylate), MMA (methylmethacryalte), NVP (N-vinylpyrrolidone)), EHA-based PUAs gave the greatest polymer-LC phase separation, lowest threshold (V10), and operating (V90) voltages, and the effect was more pronounced in monoacrylate/triacrylate systems than in monoacrylate/diacrylate systems. Contact angle measurement offers a clue to the observed morphology and electro-optic behavior. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1393-1399, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1419-1422 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 78
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1443-1450 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; STEM ; dark field imaging ; chemical derivatization ; morphology ; semicrystalline ; amorphous ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Important chemical and mechanical properties in semicrystalline polymers are determined by the noncrystalline or nonordered regions. Hence, characterizing these regions is important in developing a morphological model to better define and predict the chemical and mechanical behavior of polymeric materials. With this objective, preferential tagging was accomplished by covalent linking of a heavy element to poly(ethylene terephthalate) (PET). In scanning transmission electron microscopy (STEM), contrast was obtained using a low concentration of thallium (0.4%), the tagging element, thus providing a map of the more accessible regions within the semicrystalline structure. Differential scanning calorimetry (DSC) and wide-angle x-ray scattering (WAXS) were used to characterize the PET film. Elemental analysis using energy dispersive x-ray analysis (EDAX) was used to confirm the presence of the heavy element in the tagged regions. The STEM imaging results were then compared with the characterization results from the DSC and WAXS measurements to gain an understanding of the domains and their size ranges in the semicrystalline microstructure of PET. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1443-1450, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1501-1506 
    ISSN: 0887-6266
    Keywords: intrachain coil-to-globule transition ; interchain aggregation ; laser light scattering ; poly(N-isopropylacrylamide) ; single-chain nanoparticle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coil-to-globule transition of two poly(N-isopropylacrylamide) (PNIPAM) ionomers with different ionic contents (0.8 and 4.5 mol %), but similar weight average molar masses, in deionized water was investigated by a combination of static and dynamic light scattering. In spite of the large difference in their ionic contents, both the ionomers have a nearly same lower critical solution temperature (LCST, ∼ 32.5°C). At temperatures higher than the LCST, the ionomer chains undergo a simultaneous intrachain coil-to-globule transition and interchain aggregation to form nanoparticles thermodynamically stable in water. The average size of the nanoparticles decreases respectively as the ionic content increases and the ionomer concentration decreases. The interchain aggregation can be completely suppressed in an extremely dilute ionomer solution (〈 ∼ 5 × 10-6 g/mL), so that the intrachain coil-to-globule transition leads to the collapse of the ionomer chains into individual single-chain nanoparticles. Our results clearly indicate that there is a hysteresis in the colling process (the globule-to-coil transition). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1501-1506, 1998
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  • 80
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    Keywords: near-infrared spectroscopy ; diffuse reflectance spectroscopy ; copolymer ; ethylene/vinyl acetate copolymer ; chemometrics ; multivariate data analysis ; principal component analysis ; partial least-squares regression ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Near-infrared (NIR) diffuse reflectance spectra have been measured by use of a rotating drawer for pellets of 12 kinds of ethylene/vinyl acetate (EVA) copolymers with vinyl acetate (VA, the comonomer) varying in the 7-44 wt % range. They are unambiguously discriminated from one another by a score plot of the principal component analysis (PCA) Factor 1 and 2, based upon the NIR spectra pretreated by multiplicative scatter correction (MSC). Principal component (PC) weight loadings for Factor 1 show that the discrimination relies largely upon bands due to the overtone and combination modes arising from the VA unit. We have found one “outlier” in the score plot and elucidated its spectral characteristics based upon PC weight loadings for Factor 2. Partial least-squares (PLS) regression has been applied to propose calibration models which predict the VA content in EVA. The models have been prepared for three kinds of pretreatment, the first derivative, the second derivative, and MSC; and four kinds of wavelength regions. The NIR spectra in the 1100-2200 nm region after the MSC treatment has given the best correlation coefficient and standard error of prediction (SEP) of 0.998 and 0.70%, respectively. The calibration models, prepared by NIR diffuse reflectance spectroscopy for the pellet samples, are compared with previously reported models by NIR transmission spectroscopy for the flowing molten samples, and with those by Raman spectroscopy for the pellet samples. PLS regression has also allowed us to predict melting points of the copolymers with the correlation coefficient and SEP of 0.997 and 0.78°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1529-1537, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1557-1566 
    ISSN: 0887-6266
    Keywords: polyesters ; PET ; PEN ; PEI ; 13C NMR ; dynamics ; nuclear relaxation times ; gas diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS 13C NMR. Proton T2, 13C T1ρ, and proton T1ρ decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T2 and 13C T1ρ measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T1ρ, on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of 13C T1ρ values on two different irradiating field strengths (H1 = 38 KHz, H1 = 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O2 and CO2 gas permeabilities in PET, PEI, and PEN. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1557-1566, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1625-1636 
    ISSN: 0887-6266
    Keywords: mechanical behavior ; block copolymers ; affine strain ; SAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Films of a blend of styrene-isoprene triblock copolymer and mineral oil have been simple-cast and roll-cast from a toluene solution. Their microstructure has been analyzed by transmission electron microscopy and small-angle X-ray scattering. The blend formed polystyrene spheres arranged on a body-centered cubic lattice in a matrix composed of polyisoprene and mineral oil, and the samples display large grain sizes and very long-range order. The roll-cast sample exhibits approximately uniaxial symmetry around the rolling direction, which corresponds to the [111] crystallographic direction of the lattice. The glassy spheres act as physical crosslinks of known crosslinking functionality in the soft rubbery matrix. The high-strain deformation mechanism of this oriented cubic material has been studied by a simultaneous tensile-SAXS experiment, where the sample was stretched up to 300% along the [111] direction. By monitoring the position of the (222) and (110) reflections, the deformation of the lattice is shown to be affine with the macroscopic deformation of the sample, and the Poisson's ratio is approximately 0.46. The first zero of the sphere form factor in the SAXS patterns remains also essentially unchanged up to 300% deformation indicating that the reinforcing glassy PS domains retain their spherical shape throughout the deformation. Deformation of the microstructure is totally reversible upon unloading. A model of {hk0} faults is proposed to describe the microstructural changes induced by high-strain deformation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1625-1636, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2671-2675 
    ISSN: 0887-6266
    Keywords: second normal stress difference ; melt rheology ; Doi-Edwards model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Flow birefringence is used to study stress relaxation following step strain deformations of a well entangled polyisoprene melt. The optical method employs multiple light paths to fully sample the three-dimensional stress tensor, and hence provides measurements of all three independent shear material functions (shear stress and both first and second normal stress differences). Experiments are complicated by multiple orders in retardation. However, data show that the ratio of the second to the first normal stress difference is a strain thinning function, with magnitude intermediate between the predictions of the Doi-Edwards model with and without independent alignment. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2671-2675, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2691-2702 
    ISSN: 0887-6266
    Keywords: surface segregation ; polyolefin copolymers ; deuterium labeling effect ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have examined the effect of deuterium labeling on surface interactions in mixtures of random olefinic copolymers [C4H8]1-x[C2H3(C2H5)]x. Based on surface segregation data we have determined a surface energy difference χs between pure blend constituents. In each binary mixture components have different fractions x1, x2 of the group C2H3(C2H5), and one component is labeled by deuterium (dx) while the other is hydrogenous (hx). The mixtures are grouped in four pairs of structurally identical blends with swapped labeled constituent (dx1/hx2, hx1/dx2). For each pair the surface energy parameter χs increases when the component with higher fraction x is deuterated, i.e., χs(dx1/hx2) 〉 χs(hx1/dx2) for x1 〉 x2. A similar pattern has been found previously for the bulk interaction parameter χ. This is explained by the solubility parameter formalism aided by the lattice theory relating the surface excess to missing-neighbor effect. χs has also an additional contribution, insensitive to deuterium swapping effect, and related to entropically driven surface enrichment in a more stiff blend component with a lower fraction x. Both enthalpic and entropic contributions to χs seem to depend on the extent of chemical mismatch between blend components. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2691-2702, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2725-2735 
    ISSN: 0887-6266
    Keywords: blending ; polymorphism ; syndiotactic polystyrene (s-PS) ; amorphous polystyrene (a-PS) ; PPO ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction and optical microscopy characterization were performed to evaluate the phenomenon of alteration of polymorphism of syndiotactic polystyrene (s-PS) in the presence of other blending miscible polymers: poly(2,6-dimethyl-p-phenylene oxide) (PPO) or atactic polystyrene (a-PS). Both α and β crystal forms were observed in the neat s-PS sample, but only β-form crystal was found in miscible blends of s-PS with a-PS or PPO. The order and neighboring chain segments of neat s-PS are different from those of s-PS/PPO or s-PS/a-PS blends; thus, it is plausible that the greater randomness in the melt state of s-PS/a-PS or s-PS/PPO blends might be unfavorable for formation of α-form crystals from melts. The final spherulitic morphology the s-PS/a-PS or s-PS/PPO blends suggests that the amorphous-state miscibility of does not change much the spherulitic structure of s-PS. The radial growth rate is, in general, depressed with the presence of blending miscible polymers in s-PS of equal Tg or PPO of higher Tg. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2725-2735, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1981-1986 
    ISSN: 0887-6266
    Keywords: polystyrene ; poly(2,6-dimethyl-1,4-phenylene oxide) ; blend ; molecular relaxation ; low temperature relaxations ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular relaxation behavior in terms of the α, β, and γ transitions of miscible PS/PPO blends has been studied by means of DMTA and preliminary work has been carried out using DSC. From DSC and DMTA (by tan δ), the observed α relaxation (Tα or Tg) of PS, PPO, and the blends, which are intermediate between the constituents, are in good agreement with earlier reports by others. In addition, the β transition (Tβ) of PS at 0.03 Hz and 1 Hz is observed at -30 and 20°C, respectively, while the γ relaxation (Tγ) is not observed at either frequency. The Tβ of PPO is 30°C at 0.03 Hz and is not observed at 1 Hz, while the Tγ is -85°C at 0.03 Hz and -70°C at 1 Hz. On the other hand, blend composition-independent β or γ relaxation observed in the blends may be a consequence of the absence of intra- or intermolecular interaction between the constituents at low temperature. Thus it is suggested that at low temperature, the β relaxation of PS be influenced solely by the local motion of the phenylene ring, and that the β or γ relaxation of PPO be predominated by the local cooperative motions of several monomer units or the rotational motion of the methyl group in PPO. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1981-1986, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2015-2018 
    ISSN: 0887-6266
    Keywords: branched polymer ; gelation ; chain transfer to polymer ; molecular weight distribution ; continuous stirred-tank reactor ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2033-2046 
    ISSN: 0887-6266
    Keywords: spacer conformation ; solid-state 13C NMR ; smectic ; poly(ester imide)s ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several poly(ester imide)s based on 4-N-(carboxyphenyl)trimellitimide, 4-N-(carboxyethenylphenyl)trimellitimide, 4-hydroxy-N-(4-hydroxyphenyl)phthalimide and long aliphatic spacers have been investigated by different solid-state NMR techniques. The conformations of the methylene units were studied by the γ-gauche effect of the 13C chemical shift. In the frozen smectic LC phase, an alternating sequence of trans-conformations and disordered segments is predominant. In contrast, the spacers in the smectic-crystalline phase are capable of forming ordered trans-trans conformations. The amount of tt-conformations is found to increase with the spacer length and depend on the packing of the mesogens and the type of linkage between mesogen and spacer. The thermal stability above 100°C and the segmental mobility of the tt-conformations, as measured by 13C/1H wide line separation NMR, suggest a ropelike arrangement of the spacers. The tt-sequences are located in the outer parts rather than in the center of the spacer layer. Dephasing delay experiments on analogous polymers, which are deuteriated selectively in the four central methylene groups of the spacers, prove that these segments do not contain tt-conformations. Consequently, the ordering is due to the molecular constrains exerted by the rigid mesogenic groups and not by lateral van der Waals interactions between adjacent spacer segments. In a random copolymer with two different spacer lengths, the shorter spacer is found to be more extended than in the corresponding homopolymer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2033-2046, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2095-2102 
    ISSN: 0887-6266
    Keywords: molecular motion ; polyisobutylene ; isolated chain ; ESR ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(isobutylene) (PIB) chains with a radical at the chain end were graft-copolymerized on the poly(tetrafluoroethylene) (PTFE) surface in vacuo at 77 K. The PIB chains tethered on the PTFE surface in vacuo were regarded as isolated chains from neighboring tethered PIB chains. The molecular motion of the ends of the isolated PIB chains was observed by an electron spin resonance (ESR) spectrometer in the temperature range from 3 to 125 K, which was lower than Tg of PIB, 200 K,1 and two motion modes were found: One is a quantum tunneling of the methyl group located at the chain end at 3 K, and the other is an interconformation transition with freely rotating methyl group at the end at 77 K, where the transition rate was estimated to be 15 MHz at that temperature. The transition rate increased with an increase in temperature. The activation energy of the transition was estimated to be 370 J/mol. The high mobility and low activation energy was attributed to the isolation of PIB chains in vacuo. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2095-2102, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3127-3136 
    ISSN: 0887-6266
    Keywords: block copolymers ; thin films ; patterned surfaces ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We present results from a numerical study of a coarse-grained model of diblock copolymer (BCP) thin films cast on a chemically patterned surface. The patterned surface contains chemical inhomogeneities with a repeat spacing length scale comparable to the linear size of the BCP molecules. We find that the orientation of the lamellae in the thin film and the overlap of the film morphology with the preassigned surface pattern is strongly influenced by the commensurability between the bulk unconstrained lamellar size λ*, and the linear size of the surface inhomogeneities w. PACS Numbers: 64.60.Cn, 61.41.+e, 64.60.My, 64.75.+g. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3127-3136, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2237-2246 
    ISSN: 0887-6266
    Keywords: polypyrrole film ; bending ; water vapor sorption ; diffusion ; anisotropic expansion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polypyrrole films containing perchlorate were electrochemically synthesized and the bending and recovery motion of the films obtained has been investigated. It was found that the thickness of the film and ambient relative humidity (RH) were crucial to the motion of film: An increase of the film thickness decreased the displacement of the bending but increased the bending stress. On the other hand, an increase of the ambient RH decreased both functions. The motion of film was caused by the difference of expansion on both sides of the film owing to anisotropic sorption of water vapor, which could be expressed by the diffusion-limited bending model. The diffusion coefficients calculated from the bending and recovery motion at 25°C, RH 50% were 12.2 × 10-8 cm2 s-1 and 3.5 × 10-8 cm2 s-1, respectively. The maximum expansion of the film surface calculated from the bending curve was about 0.36%. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2237-2246, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2267-2274 
    ISSN: 0887-6266
    Keywords: poly(ether ether kotone) ; polyimide ; miscibility ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Miscibility and crystallization behavior of solution-blended poly(ether ether ketone)/polyimide (PEEK/PI) blends were investigated by using DSC, optical microscopy and SAXS methods. Two kinds of PIs, YS-30 and PEI-E, which consist of the same diamine but different dianhydrides, were used in this work. The experimental results show that blends of PEEK/YS-30 are miscible over the entire composition range, as all the blends of different compositions exhibit a single glass transition temperature. The crystallization of PEEK was hindered by YS-30 in PEEK/YS-30 blends, of which the dominant morphology is interlamellar. On the other hand, blends of PEEK/PEI-E are immiscible, and the effect of PEI-E on the crystallization behavior of PEEK is weak. The crystallinity of PEEK in the isothermally crystallized PEEK/YS-30 blend specimens decreases with the increase in PI content. But the crystallinity of PEEK in the annealed samples almost keeps unchanged and reaches its maximum value, which is more than 50%. The spherulitic texture of the blends depends on both the blend composition and the molecular structure of the PIs used. The more PI added, the more imperfect the crystalline structure of PEEK. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2267-2274, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2301-2309 
    ISSN: 0887-6266
    Keywords: discrete dynamic compliance spectra ; nonlinear viscoelasticity ; creep ; stress relaxation ; constant strain rate tests ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present work reports a discrete, stress-dependent dynamic compliance spectra method which may be used to predict the mechanical response of nonlinear viscoelastic polymers during strain-defined processes. The method is based on the observation that the real and complex parts of the discrete dynamic compliance frequency components obtained from creep measurements are smooth, easily fit functions of stress. Comparisons between experimental measurements and model calculations show that the model exhibits excellent quantitative agreement with the basis creep measurements at all experimental stress levels. The model exhibits good quantitative agreement with stress relaxation measurements at moderate levels of applied strain. However, the model underestimates the experimental stress relaxation at an applied strain of 3.26%. The stress relaxation error appears to be a real material effect resulting from the different strain character of creep and stress relaxation tests. The model provides a good quantitative agreement with experimental constant strain rate measurements up to approximately 4% strain, after which the model underestimates the experimental flow stress. This effect is explained by the time dependence of the stress-activated configurational changes necessary for large strains in glassy polymers. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2301-2309, 1998
    Additional Material: 7 Ill.
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  • 94
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2339-2348 
    ISSN: 0887-6266
    Keywords: epoxy ; curing ; generating function ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The systems of diepoxides cured with primary amine in presence of an monoepoxide, monofunctional reactive, under equal stoichiometric ratio has been analyzed by a generating function method. The average degree of polymerization, which changed with time or conversion, and gel point were calculated. The profiles of the degree of polymerization and critical conversion are dependent on the content of and relative reactivities of epoxy groups. For a system with the same ratio, the critical epoxy conversion increases with increasing reactivity. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2339-2348, 1998
    Additional Material: 10 Ill.
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  • 95
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2371-2378 
    ISSN: 0887-6266
    Keywords: liquid crystalline ; polymers ; X-ray diffraction ; fibers ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis and a partial characterization of segmented liquid crystalline polymers with 3,3′-diallyl-4,4′-dihydroxybiphenyl unit in the rigid moiety is reported. The general formula of polymers is [-p-C6H4-COO-p-C6H3(R)-p-C6H3(R)-OOC-p-C6H4-O-(CH2)nO-]x, with n = 6, 8, 10, 12, and R = —CH2—CH=CH2. All polymers have nematic liquid-crystalline behavior. At room temperature, annealed fiber samples of polymers show a complex polymorphism. Three phases have been isolated with very large unit cells accommodating 6 or 12 chains. The projection of the molecular packing in a plane perpendicular to the c axis is characterized by the organization of chains in a two-dimensional hexagonal or quasi-hexagonal array. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2371-2378, 1998
    Additional Material: 6 Ill.
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  • 96
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2413-2421 
    ISSN: 0887-6266
    Keywords: positron annihilation ; polyimide ; ion implantation ; membrane ; permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 6FDA-pMDA polyimide membranes were implanted with 140 keV N+ ions to fluences between 2 × 1014 and 5 × 1015 cm-2. Variable energy positron annihilation spectra were taken and spectral features compared to previously reported changes in gas permeability and permselectivity of these membranes as a function of ion fluence. Positron data corroborate the explanation of these changes in terms of molecular damage caused by the implant: for fluences up to about 1 × 1015 cm-2, the concentration of irradiation-induced defects merely increases with implant fluence; while fluences exceeding this threshold value create a second type of positron annihilation site, thereby marking a distinct change in the structure of the polymer, which is responsible for the vast improvement of gas permselectivity data found at the same threshold fluence. PACS codes: 78.70.Bj - positron annihilation; 61.82.Pv - polymers, organic compounds; 61.72.Ww - doping and impurity implantation. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2413-2421, 1998
    Additional Material: 4 Ill.
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  • 97
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2435-2447 
    ISSN: 0887-6266
    Keywords: poly(vinylidene fluoride) ; carbon dioxide ; supercritical fluid ; diffusion ; partial molar volume ; solubility parameter ; mass sorption ; high pressure ; dilation ; Sanchez-Lacombe model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The article reports on the behaviour of poly(vinylidene fluoride) in carbon dioxide at 42°C and 80°C and in a pressure range of 0.1-30 MPa. Experimental techniques for the measurement of gas mass uptake and polymer dilatation are described and the corresponding data are reported as mass sorption and dilatation isotherms, respectively. The mass uptake experiment was also used to follow the evolution of the coefficient of diffusion of carbon dioxide into the polymer as a function of pressure or concentration. An analysis for the calculation of the partial molar volume of carbon dioxide as a function of pressure is also given, which shows that the ‘apparent’ partial molar volume of the carbon dioxide decreases with pressure to very low values, at high pressure. The computed values are significantly less than those for either the liquid or the solid phases of pure carbon dioxide, and also lower than some data previously reported for silicone elastomers. A consideration of the origins of this apparent anomaly is given in the conclusions. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2435-2447, 1998
    Additional Material: 10 Ill.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2471-2482 
    ISSN: 0887-6266
    Keywords: poly(3-hydroxybutyrate-co-3-hydroxyvalerate) ; fibers ; wide-angle X-ray diffraction ; birefringence ; infrared dichroism ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structure of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) fibers prepared by drawing and annealing processes has been analyzed through wide-angle X-ray diffraction (WAXD), density, infrared dichroism, and birefringence measurements. There are three different types of crystalline structure in these fibers: two of these are the two types of orthorhombic with different orientation modes (the ordinary c-axis orientation (c//Z), and the preferential orientation of c-axis to the direction perpendicular to the fiber axis (c⊥Z)); and the third is pseudohexagonal. The weight fractions of the three types of crystals and amorphous phase were analyzed combining the WAXD integrated intensity and density data. The relation between crystalline orientation factors obtained separately from the WAXD measurement and the infrared dichroic ratio is also discussed. The birefringence of these fibers shows negative and positive values, depending on drawing and annealing temperatures. Considering the intrinsic birefringence and weight fraction of the c//Z, c⊥Z, and pseudohexagonal crystals, birefringence of the amorphous phase was evaluated. The amorphous birefringence shows positive values and decreases with an increase in the annealing temperature. From the analyzed fiber structure, it was speculated that the c⊥Z and pseudohexagonal crystals are preferentially formed in the drawing process irrespective of the drawing temperature.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2471-2482, 1998
    Additional Material: 15 Ill.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2525-2535 
    ISSN: 0887-6266
    Keywords: disinterspersion ; modified Flory model ; degree of deswelling ; molecular weight of the linear polymer ; packing factor ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The osmotic deswelling of polymer networks swollen in a good solvent by transferring it into a solution of a linear polymer in the same solvent is investigated using the modified Flory model proposed previously. The predicted results obtained using this simple model are compared to the experimental data available in the literature. We further examine the variation of the degree of deswelling, the degree of swelling and the partition coefficient with the molecular weight, and the volume fraction of the linear polymer chains in the surrounding polymer solution. Also, the role of the packing factor is briefly discussed.© 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2525-2535, 1998
    Additional Material: 7 Ill.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2563-2571 
    ISSN: 0887-6266
    Keywords: thermodynamic melting temperature ; thermodynamic melting temperature extrapolation ; n-alkanes thermodynamic melting temperature ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The determination of the thermodynamic equilibrium melting point of a polymer (T0m) by the extrapolation of the melting temperature of its oligomers has been extensively studied in the case of n-alkanes. Nevertheless, a recent publication1 underlines the difficulty to realize this extrapolation. A new method is presented here, leading to an acceptable extrapolation of PE. The equation proposed may give a better value of Tm because the premelting phenomena is being considered in its development. Moreover, this method can be easily extended to a larger number of polymers, such as PEO, PEEK, PPS, etc.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2563-2571, 1998
    Additional Material: 14 Ill.
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