NMR imaging of water sorption into poly(hydroxyethyl methacrylate-co-tetrahydrofurfuryl methacrylate)

The diffusion of water into a series of hydroxyethyl methacrylate, HEMA, copolymers with tetrahydrofurfuryl methacrylate, THFMA, has been studied over a range of copolymer compositions using NMR imaging analyses. For polyHEMA the diffusion was found to be consistent with a Fickian model. The mass diffusion coefficient of water in polyHEMA at 37 degreesC was determined from the profiles of the diffusion front to be 1.5 x 10(-11) m(2) s(-1), which is less than the value based upon mass uptake, 2.0 x 10(-11) m(2) s(-1). The profiles of the water diffusion front obtained from the NMR images showed that stress was induced at the interface between the rubbery and glassy regions which led to formation of small cracks in this region of the glassy matrix of polyHEMA and its copolymers with mole fractions of HEMA greater than 0.6. Water was shown to be able to enter these cracks forming water pools. For copolymers of HEMA and THFMA with mole fractions of HEMA less than 0.6 the absence of cracks was attributed to the ability of the THFMA sequences to undergo stress relaxation by creep.

Thermal characterization of copolymers obtained by radiation grafting of styrene onto poly(tetrafluoroethyleneperfluoropropylvinylether) substrates: thermal decomposition, melting behavior and low-temperature transitions

Differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA) have been used to study the thermal decomposition, the melting behavior and low-temperature transitions of copolymers obtained by radiation-induced grafting of styrene onto poly (tetrafluoroethylene- perfluoropropylvinylether) (PFA) substrates. PFA with different contents of perfluoropropylvinylether (PPVE) as a comonomer have been investigated. A two step degradation pattern was observed from TGA thermograms of all the grafted copolymers, which was attributed to degradation of PSTY followed by the degradation of the PFA backbone at higher temperature. One broad melting peak can be identified for all copolymers, which has two components in the samples with higher PPVE content. The melting peak, crystal-crystal transition and the degree of crystallinity of the grafted copolymers increases with radiation grafting up to 50 kGy, followed by a decrease at higher doses. No such decrease was observed in the ungrafted PFA samples after irradiation. This indicated that the changes in the heats of transitions and crystallinity at low doses are due to the radiation effects on the microstructure of PFA (chain scission), whereas at higher doses the grafted PSTY is the driving force behind these changes. (C) 2001 Elsevier Science Ltd. All rights reserved.

Molecular weight changes and scission and crosslinking in poly(dimethyl siloxane) on gamma radiolysis

The molecular weight changes which occur on the gamma -radiolysis of poly(dimethyl siloxane) under vacuum between 77 and 373 K and in air at 303 K have been investigated using triple detection GPC to obtain the complete molecular weight distributions for the irradiated samples and to determine the number and weight average molecular weights. The results have been interpreted in terms of the relative yields of scission and crosslinking. The total yields for crosslinking predominate over those for scission at all the temperatures investigated for radiolysis under vacuum. Based on a solid-state Si-29 NMR analysis of PDMS irradiated under vacuum at 303 K, which yielded a value of G(Y) of 1.70, the values of G(S) = 1.15 +/-0.2 and G(H) = 1.45 +/-0.2 were obtained for radiolysis under vacuum at 303 K. For radiolysis in air at 303 K, crosslinking was also predominant, but the nett yield of crosslinking was much less than that observed for radiolysis under vacuum. Under the conditions of the radiolysis in air at 303 K, because of the low solubility of oxygen in PDMS, it is likely that the radiation chemistry is limited by oxygen diffusion. (C) 2001 Elsevier Science Ltd. All rights reserved.

The use of NMR for determination of new structures in irradiated TFE/PMVE fluoropolymers

The radiation chemistry of two TFE/PMVE copolymers with TFE mole fractions of 0.66 and 0.81 has been studied under vacuum using Co-60 gamma -radiation over absorbed dose ranges up to 4.2 MGy. The radiolysis temperature was 313 K for both TFE/PMVE copolymers. New structure formation in the copolymers was identified by solid-state F-19 NMR and the G-values for new chain ends of 2.1 and 0.5 and for branching sites of 0.9 and 0.2 have been obtained for the TFE/PMVE with TFE mole fractions of 0.66 and 0.81, respectively. The relative yields of-O-CF3 and -CF2-CF3 chain ends were found to be proportional to the copolymer composition, but the yields of the -CF2-CF3 chain ends and -CF- branch points mere not linearly related ia the composition. rather they wets correlated with the radical yields measured at 77 K. (C) 2001 Elsevier Science Ltd. All rights reserved.

Coffee and alcohol consumption and the risk of pancreatic cancer in two prospective United States cohorts

Although most prospective cohort studies do not support an association between coffee consumption and pancreatic cancer, the findings for alcohol are inconsistent. Recently, a large prospective cohort study of women reported statistically significant elevations in risk of pancreatic cancer for both coffee and alcoholic beverage consumption. We obtained data on coffee, alcohol, and other dietary factors using semiquantitative food frequency questionnaires administered at baseline (1986 in the Health Professionals Follow-Up Study and 1980 in the Nurses’ Health Study) and in subsequent follow-up questionnaires. Data on other risk factors for pancreatic cancer, including cigarette smoking, were also available. Individuals with a history of cancer at study initiation were excluded from all of the analyses. During the 1,907,222 person-years of follow-up, 288 incident cases of pancreatic cancer were diagnosed. The data were analyzed separately for each cohort, and results were pooled to compute overall relative risks (RR). Neither coffee nor alcohol intakes were associated with an increased risk of pancreatic cancer in either cohort or after pooling the results (pooled RR, 0.62; 95% confidence interval, 0.27–1.43, for >3 cups of coffee/day versus none; and pooled RR, 1.00; 95% confidence interval, 0.57–1.76, for >=30 grams of alcohol/day versus none). The associations did not change with analyses examining different latency periods for coffee and alcohol. Similarly, no statistically significant associations were observed for intakes of tea, decaffeinated coffee, total caffeine, or alcoholic beverages. Data from these two large cohorts do not support any overall association between coffee intake or alcohol intake and risk of pancreatic cancer.

Effects of alcohol consumption on indices of iron stores and of iron stores on alcohol intake markers

Background: Alcohol increases body iron stores. Alcohol and iron may increase oxidative stress and the risk of alcohol-related liver disease. The relationship between low or safe levels of alcohol use and indices of body iron stores, and the factors that affect the alcohol-iron relationship, have not been fully characterized. Other aspects of the biological response to alcohol use have been reported to depend on iron status. Methods: We have measured serum iron, transferrin, and ferritin as indices of iron stores in 3375 adult twin subjects recruited through the Australian Twin Registry. Information on alcohol use and dependence and smoking was obtained from questionnaires and interviews. Results: Serum iron and ferritin increased progressively across classes of alcohol intake. The effects of beer consumption were greater than those of wine or spirits. Ferritin concentration was significantly higher in subjects who had ever been alcohol dependent. There was no evidence of interactions between HFE genotype or body mass index and alcohol. Alcohol intake-adjusted carbohydrate-deficient transferrin was increased in women in the lowest quartile of ferritin results, whereas adjusted gamma -glutamyltransferase, aspartate aminotransferase, and alanine aminotransferase values were increased in subjects with high ferritin. Conclusions: Alcohol intake at low level increases ferritin and, by inference, body iron stores. This may be either beneficial or harmful, depending on circumstances. The response of biological markers of alcohol intake can be affected by body iron stores; this has implications for test sensitivity and specificity and for variation in biological responses to alcohol use.

Adherence with naltrexone prescription advice in hospital outpatient alcohol rehabilitation programme

Background: The anti-craving drug, naltrexone, is used as a pharmacotherapeutic adjunct in the treatment of alcohol dependence. In addictive disorders, compliance issues remain central. There are limited data on compliance with naltrexone treatment regimens within formalized rehabilitation programs and even less data that identifies factors that have an impact on this. Objective: To study patient adherence to naltrexone medication regimens and examine whether patients' reported pre-treatment alcohol use, dependence severity and measures of psychological health are predictive of medication compliance. Method: Fifty outpatients meeting DSM IV criteria for alcohol dependence enrolled in 12-week rehabilitation programme. This included cognitive behavioural therapy (CBT) and naltrexone, 50 mg orally daily. Measures included: pharmacy prescription pick-up including number of tablets dispensed, programme attendance and patient pre-treatment alcohol use variables. Measures of psychological health included somatic symptoms, anxiety, social dysfunction and depression as measured by the General Health Questionnaire (GHQ-28). Results: Classifying the sample into compliant (greater than or equal to 90% medication pick-up) and less compliant groups, 66% of subjects were naltrexone-compliant. Pre-treatment alcohol use variables were not predictive of compliance. Although social dysfunction and depression tended towards poorer prescription filling, measures of psychological distress (GHQ-28) did not identify factors predictive of medication non-compliance. One patient withdrew from treatment because of naltrexone-induced dysphoria. Conclusion: Patients with alcohol dependence demonstrated high levels of anti-craving medication compliance, good rehabilitation programme participation and favourable outcomes. Naltrexone was well tolerated. Medication compliance in this study group compared well with those of other hospital populations with chronic disorders. Factors predictive of anti-craving medication compliance in alcohol dependence require further study.

Outpatient cognitive behavioural therapy programme for alcohol dependence impact of naltrexone use on outcome

Objective: Cognitive-behavioural therapy (CBT) has been effectively used in the treatment of alcohol dependence. Clinical studies report that the anticraving drug naltrexone, is a useful adjunct to treatment. Currently, few data are available on the impact of adding this medication to programmes in more typical, outpatient, and rehabilitation settings. The objective of this study was to examine the impact on outcome of adding naltrexone to an established outpatient alcohol rehabilitation program which employed CBT. Method: Fifty patients participated in an established 12-week, outpatient, 'contract'-based alcohol abstinence programme which employed CBT. They also received naltrexone 50 mg orally daily (CBT + naltrexone). Outcomes were compared with 50 historical, matched controls, all of whom participated in the same programme without an anticraving medication (CBT alone). All patients met DSM-IV criteria for alcohol dependence. Results: Programme attendance across the eight treatment sessions was lower in the CBT alone group (p < 0.001). Relapse to alcohol use occurred sooner and more frequently in the CBT alone group (p < 0.001). Rehabilitation programme completion at 12 weeks was 88% (CBT + naltrexone) compared with 36% for (CBT alone) (p < 0.001). Alcohol abstinence at 12 weeks was 76% (CBT + naltrexone) compared with 18% (CBT alone) (p < 0.001). Conclusion: When employing the same outpatient rehabilitation programme and comparing outcomes using matched historical controls, the addition of naltrexone substantially improves programme attendance, programme completion and reported alcohol abstinence. In a typical outpatient programme, naltrexone addition was associated with significantly improved programme participation, better outcomes and was well tolerated.

Molecular motion in nanocomposites of poly(ethylene oxide) and montmorillonite

Motion of chains of poly(ethylene oxide) within the interlayer spacing of 2:1 phyllosilicate/montmorillonite was studied with H-1 and C-13 NMR spectroscopy. Measurements of the H-1 NMR line widths and relaxation times across a large temperature range were used to determine the effect of bulk thermal transitions on polymer chain motion within the nanocomposites. The results were consistent with previous reports of low apparent activation energies of motion. Details of the frequency and geometry of motion were obtained from a comparison of the C-13 cross-polarity/magic-angle spinning spectra and relaxation times of the nanocomposite with those of the pure polymer. (C) 2001 John Wiley & Sons, Inc.

Helping the female partners of men abusing alcohol: a comparison of three treatments

Aim. To evaluate the effectiveness of three approaches to assisting the female partners of male problem drinkers with the stress imposed by the male's drinking. Design. Participants were assigned randomly via random number tables to one of three treatment conditions: supportive counselling, stress management or alcohol-focused couples therapy. Setting. The intervention took place at the Behaviour Research and Therapy Centre (BRTC), The University of Queensland. This research and training centre offers outpatient psychology services to the community. Participants. Sixty-one married women whose husbands drank heavily. Participants reported protracted alcohol problems, severe impact of alcohol on social functioning and severe marital distress. Measurement. The women's stress, alcohol consumption by the male, and relationship functioning were assessed at pre- and post-treatment and at 6-month follow-up. Interventions. All three treatments involved 15 1-hour sessions with the woman. In the alcohol-focused couple therapy, attempts were made to engage the man in these sessions. Results. Contrary to our predictions, there were few differences between the treatments. All three treatments were associated with reductions in the women's reported stress, with trends for somewhat greater reduction in the women's stress in the stress management and alcohol-focused couples therapy conditions than for supportive counselling. None of the treatments produced clinically significant reductions in men's drinking or relationship distress. Conclusion. The treatments ease stresses and burden but do not improve drinking or relationships. Limited power in the design restricted the capacity to detect differential treatment effects.

Exploiting the versatility of human cytochrome P450 enzymes: The promise of blue roses from biotechnology

The cytochrome P450 (P450) enzymes involved in drug metabolism are among the most versatile biological catalysts known. A small number of discrete forms of human P450 are capable of catalyzing the monooxygenation of a practically unlimited variety of xenobiotic substrates, with each enzyme showing a more or less wide and overlapping substrate range. This versatility makes P450s ideally suited as starting materials for engineering designer catalysts for industrial applications. In the course of heterologous expression of P450s in bacteria, we observed the unexpected formation of blue pigments. Although this was initially assumed to be an artifact, subsequent work led to the discovery of a new function of P450s in intermediary metabolism and toxicology, new screens for protein engineering, and potential applications in the dye and horticulture industries.