Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers

The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Ho. man theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX ( where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-bPCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.

Longitudinal selenium status in healthy British adults: assessment using biochemical and molecular biomarkers

Human selenium (Se) requirements are currently based on biochemical markers of Se status. In rats, tissue glutathione peroxidase-1 (Gpx1) mRNA levels can be used effectively to determine Se requirements; blood Gpx1 mRNA levels decrease in Se-deficient rats, so molecular biology-based markers have potential for human nutrition assessment. To study the efficacy of molecular biology markers for assessing Se status in humans, we conducted a longitudinal study on 39 subjects (age 45 +/- 11) in Reading, UK. Diet diaries (5 day) and blood were obtained from each subject at 2, 8, 17 and 23 weeks, and plasma Se, glutathione peroxidase (Gpx3) enzyme activity, and selenoprotein mRNA levels were determined. There were no significant longitudinal effects on Se biomarkers. Se intake averaged 48 +/- 14 mu g/d. Plasma Se concentrations averaged 1.13 +/- 0.16 mu mol/l. Plasma Se v. energy-corrected Se intake (ng Se/kJ/d) was significantly correlated, but neither Gpx3 activity v. Se intake (ng Se/kJ/d) nor Gpx3 activity v. plasma Se was significantly correlated. Collectively, this indicates that subjects were on the plateaus of the response curves. Selenoprotein mRNAs were quantitated in total RNA isolated from whole blood, but mRNA levels for Gpx1, selenoprotein H, and selenoprotein W (all highly regulated by Se in rodents), as well selenoprotein P, Gpx3, and phospholipid hydroperoxide glutathione peroxidase were also not significantly correlated with plasma Se. Thus selenoprotein molecular biomarkers, as well as traditional biochemical markers, are unable to further distinguish differences in Se status in these Se replete subjects. The efficacy of molecular biomarkers to detect Se deficiency needs to be tested in Se-deficient populations.

Formation of crystalline macrocyclic phases during electrophilic precipitation-polycondensation syntheses of poly(arylene ether ketone)s

Elongated crystalline particles formed as by-products during poly(arylene ether ketone) synthesis by electrophilic precipitation-polycondensation of 4,4'-diphenoxybenzophenone with terephthaloyl chloride or isophthaloyl chloride, thought previously to be polymer-whiskers, have now been identified as macrocyclic phases. Single crystal X-ray analysis of the needle-like particles formed in the reaction with terephthaloyl chloride, using the microdiffraction technique with synchrotron radiation, revealed that they consist of a macrocylic compound containing ten phenylene units, i.e. the [2 + 2] cyclic dimer. An analogous structure has also been demonstrated for the corresponding macrocycle derived from the reaction of 4,4-diphenoxybenzophenone with isophthaloyl chloride. Chloroform extraction of the products of the two polycondensations dissolved the macrocyclic material (but not the linear polymer), and analysis of the extracts by MALDI-TOF mass spectrometry demonstrated the presence in both cases of homologous families of macrocyclic products. Higher yields of macrocycles were obtained under pseudo-high dilution conditions, enabling the [2 + 2] cyclodimers from reactions of 4,4'-diphenoxybenzophenone with both terephthaloyl and isophthaloyl chloride to be isolated as pure compounds and fully characterised. (C) 2003 Published by Elsevier Ltd.

Selenium supplementation of lactating dairy cows: effects on milk production and total selenium content and speciation in blood, milk and cheese

Forty multiparous Holstein cows were used in a 16-week continuous design study to determine the effects of either selenium (Se) source, selenised yeast (SY) (derived from a specific strain of Saccharomyces cerevisiae CNCM 1-3060) or sodium selenite (SS), or Se inclusion rate in the form of SY in the diets of lactating dairy cows on the Se concentration and speciation in blood, milk and cheese. Cows received ad libitum a total mixed ration (TMR) with a 1 : 1 forage: concentrate ratio on a dry matter (DM) basis. There were four diets (T-1 to T-4), which differed only in either source or dose of Se additive. Estimated total dietary Se for T, (no supplement), T-2 (SS), T-3 (SY) and T-4 (SY) was 0.16, 0.30, 0.30 and 0.45 mg/kg DM, respectively. Blood and milk samples were taken at 28-day intervals and at each time point there were positive linear effects of Se in the form of SY on the Se concentration in blood and milk. At day 112 blood and milk Se values for T-1 to T-4 were 177, 208, 248 and 279 +/- 6.6 and 24, 38, 57 and 72 +/- 3.7 ng/g fresh material, respectively, and indicate improved uptake and incorporation of Se from SY. In whole blood, selenocysteine (SeCys) was the main selenised amino acid and the concentration of selenomethionine (SeMet) increased with the increasing inclusion rate of SY In milk, there were no marked treatment effects on the SeCys content, but Se source had a marked effect on the concentration of SeMet. At day 112 replacing SS (T-2) with SY (T-3) increased the SeMet concentration of milk from 36 to 111 ng Se/g and its concentration increased further to 157ng Se/g dried sample as the inclusion rate of SY increased further (T-4) to provide 0.45 mg Se/kg TMR. Neither Se source nor inclusion rate affected the keeping quality of milk. At day 112 milk from T-1, T-2 and T-3 was made into a hard cheese and Se source had a marked effect on total Se and the concentration of total Se comprised as either SeMet or SeCys. Replacing SS (T-2) with SY (T-3) increased total Se, SeMet and SeCys content in cheese from 180 to 340 ng Se/g, 57 to 153 ng Se/g and 52 to 92 ng Se/g dried sample, respectively. The use of SY to produce food products with enhanced Se content as a means of meeting the Se requirements is discussed

Effect of dietary supplementation with selenium-enriched yeast or sodium selenite on selenium tissue distribution and meat quality in commercial-line turkeys

The objective of this study was to determine the concentration of total selenium (Se) and proportions of total Se comprised as selenomethionine (SeMet) and selenocysteine (SeCys) in the tissues of female turkeys offered diets containing graded additions of selenized-enriched yeast (SY), or sodium selenite (SS). Oxidative stability and tissue glutathione peroxidase (GSH-Px) activity of breast and thigh muscle were assessed at 0 and 10 days post mortem. A total of 216 female turkey poults were enrolled in the study. A total of 24 birds were euthanized at the start of the study and samples of blood, breast, thigh, heart, liver, kidney and gizzard were collected for determination of total Se. Remaining birds were blocked by live weight and randomly allocated to one of four dietary treatments(n548 birds/treatment) that differed either in Se source (SY v. SS) or dose (Con [0.2 mg/kg total Se], SY-L and SS-L [0.3mg/kg total Se as SY and SS, respectively] and SY-H [0.45mg total Se/kg]). Following 42 and 84 days of treatment 24 birds per treatment were euthanized and samples of blood, breast, thigh, heart, liver, kidney and gizzard were retained for determination of total Se and the proportion of total Se comprised as SeMet or SeCys. Whole blood GSH-Px activity was determined at each time point. Tissue GSH-Px activity and thiobarbituric acid reactive substances were determined in breast and thigh tissue at the end of the study. There were responses (P,0.001) in all tissues to the graded addition of dietary Se, although rates of accumulation were highest in birds offered SY. There were notable differences between tissue types and treatments in the distribution of SeMet and SeCys, and the activity of tissue and erythrocyte GSH-Px (P,0.05). SeCys was the predominant form of Se in visceral tissue and SeMet the predominant form in breast tissue. SeCys contents were greater in thigh when compared with breast tissue. Muscle tissue GSH-Px activities mirrored SeCys contents. Despite treatment differences in tissue GSH-Px activity, there were no effects of treatment on any meat quality parameter.

Reactions of methylvinyl and phenylvinyl ketones with a tricyclic ketone derived from 2-tetralone: characterization of crystalline products by X-ray diffraction

Base catalysed reaction of the tricyclic ketone (6 ⇌ 7) with methylvinyl ketone gave the tetracyclic ketols, 11, 13, 15, 16, and the pentacyclic ketols, 12, 17. With phenylvinyl ketone, the tetracyclic ketol (18) was formed. The stereostructures of the ketols were identified by X-Ray diffraction. The base-catalysed title reactions gave the cyclic ketols and derived compounds shown below whose structures were identified by X-ray diffraction.

Dielectric relaxation around the nematic-isotropic transition of liquid crystalline polymers

This study is concerned with a series of acrylate based side-chain liquid crystalline (LC) polymers. Previous studies have shown that these LC polymers have a preference for parallel or perpendicular alignment with respect to the polymer chain which depends on the length of the coupling chain joining the mesogenic unit to the polymer backbone. On the other hand, the dielectric relaxation of these side-chain LC polymers shows a strong relaxation associated to the mesogenic unit dynamics. For samples with parallel alignment, it was found that the dielectric relaxation of the nematic is weaker and broader than the relaxation of the isotropic. By contrast, for samples with perpendicular alignment, the isotropic to nematic transition reduces the broadening the relaxation and increases the relaxation strength. These two features are more evident for samples with short coupling units for which the dielectric relaxation observed appears to be strongly coupled with the backbone dynamics.

Liquid crystalline elastomers: the relationship between macroscopic behaviour and the level of backbone anisotropy

Nematic monodomain liquid crystalline elastomers have been prepared through in situ cross-linking of an acrylate based side-chain liquid crystalline polymer in a magnetic field. At the nematic–isotropic transition, the sample is found to undergo an anisotropic shape change. There is found to be an increase in dimensions perpendicular — and a decrease parallel — to the director, this is consistent with alignment of the polymer backbone parallel to the direction of mesogen alignment in the nematic state. From a quantitative investigation of this behaviour, we estimate the level of backbone anisotropy for the elastomer. As second measure of the backbone anisotropy, the monodomain sample was physically extended. We have investigated, in particular, the situation where a monodomain sample is deformed with the angle between the director and the extension direction approaching 90°. The behaviour on extension of these acrylate samples is related to alternative theoretical interpretations and the backbone anisotropy determined. Comparison of the chain anisotropy derived from these two approaches and the value obtained from previous small-angle neutron scattering measurements on deuterium labelled mixtures of the same polymer shows that some level of chain anisotropy is retained in the isotropic or more strictly weakly paranematic state of the elastomer. The origin and implications of this behaviour are discussed.

Orientation effects in monodomain nematic liquid crystalline polysiloxane elastomers

A series of monodomain liquid crystalline (LC) elastomers based on a polysiloxane were synthesised. These elastomers were prepared either with one or two cross-linking agents in the presence of a mechanical field. By using the real-time X-ray facility at the University of Reading (AXIS), we have shown that the nematic order parameter 〈P2 〉 is dependent on both the extension λ value and the degree of cross-linking. We have also shown that the monodomain elastomers, exhibiting permanent alignment and 〈P2 〉 values of about 0.5, can be prepared by using only one cross-linking agent making the synthesis of these monodomain LC elastomers much more simple and cost effective than that proposed by Küpfer.

Wide-angle X-ray scattering study of structural parameters in non-crystalline polymers

The paper presents an analysis of WAXS (wide-angle X-ray scattering) data which aids an understanding of the structure of non-crystalline polymers. Experimental results are compared with calculations of scattering from possible models. Evidence is presented which supports the view that the chains in molten PE do not lie parallel but have a conformation in accord with the predictions of energy calculations. However, the evidence indicates that in “molten” PTFE the chains lie parallel over distances well in excess of their diameters. WAXS-based proposals are made for the conformations of a-PMMA and a-PS.

Experimental separation of the coherent component of X-ray scattering prior to RDF analysis of non-crystalline polymers

An experimental method is described which enables the inelastically scattered X-ray component to be removed from diffractometer data prior to radial density function analysis. At each scattering angle an energy spectrum is generated from a Si(Li) detector combined with a multi-channel analyser from which the coherently scattered component is separated. The data obtained from organic polymers has an improved signal/noise ratio at high values of scattering angle, and a commensurate enhancement of resolution of the RDF at low r is demonstrated for the case of PMMA (ICI `Perspex'). The method obviates the need for the complicated correction for multiple scattering.

Conformational analysis of oriented non-crystalline polymers using wide angle X-ray scattering

A procedure is presented for obtaining conformational parameters from oriented but non-crystalline polymers. This is achieved by comparison of the experimental wide angle X-ray scattering with that calculated from models but in such a way that foreknowledge of the orientation distribution function is not required. X-ray scattering intensity values for glassy isotactic poly(methylmethacrylate) are analysed by these techniques. The method could be usefully applied to other oriented molecular systems such as liquid crystalline materials.

Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation