PFG-NMR measurements of the self-diffusion coefficients of water in equilibrium poly(HEMA-co-THFMA) hydrogels

The self-diffusion coefficients for water in a series of copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA, swollen with water to their equilibrium states have been studied at 310 K using PFG-NMR. The self-diffusion coefficients calculated from the Stejskal-Tanner equation, D-obs, for all of the hydrated polymers were found to be dependent on the NMR storage time, as a result of spin exchange between the proton reservoirs of the water and the polymers, reaching an equilibrium plateau value at long storage times. The true values of the diffusion coefficients were calculated from the values of D-obs, in the plateau regions by applying a correction for the fraction of water protons present, obtained from the equilibrium water contents of the gels. The true self-diffusion coefficient for water in polyHEMA obtained at 310 K by this method was 5.5 x 10(-10) m(2) s(-1). For the copolymers containing 20% HEMA or more a single value of the self-diffusion coefficient was found, which was somewhat larger than the corresponding values obtained for the macroscopic diffusion coefficient from sorption measurements. For polyTHFMA and copolymers containing less than 20% HEMA, the PFG-NMR stimulated echo attenuation decay curves and the log-attenuation plots were characteristic of the presence of two diffusing water species. The self-diffusion coefficients of water in the equilibrium-hydrated copolymers were found to be dependent on the copolymer composition, decreasing with increasing THFMA content.

Rational combinatorial chemistry-based selection, synthesis and evaluation of an affinity adsorbent for recombinant human clotting factor VII

The selection, synthesis and chromatographic evaluation of a synthetic affinity adsorbent for human recombinant factor VIIa is described. The requirement for a metal ion-dependent immunoadsorbent step in the purification of the recombinant human clotting factor, FVIIa, has been obviated by using the X-ray crystallographic structure of the complex of tissue factor (TF) and Factor VIIa and has directed our combinatorial approach to select, synthesise and evaluate a rationally-selected affinity adsorbent from a limited library of putative ligands. The selected and optimised ligand comprises a triazine scaffold bis-substituted with 3-aminobenzoic acid and has been shown to bind selectively to FVIIa in a Ca2+-dependent manner. The adsorbent purifies FVIIa to almost identical purity (>99%), yield (99%), activation/degradation profile and impurity content (∼1000 ppm) as the current immunoadsorption process, while displaying a 10-fold higher static capacity and substantially higher reusability and durability. © 2002 Elsevier Science B.V. All rights reserved.

Copper transfer from the Cu(I) chaperone, CopZ, to the repressor, Zn(II)CopY: Metal coordination environments and protein interactions

Extracellular copper regulates the DNA binding activity of the CopY repressor of Enterococcus hirae and thereby controls expression of the copper homeostatic genes encoded by the cop operon. CopY has a CxCxxxxCxC metal binding motif. CopZ, a copper chaperone belonging to a family of metallochaperones characterized by a MxCxxC metal binding motif, transfers copper to CopY. The copper binding stoichiometries of CopZ and CopY were determined by in vitro metal reconstitutions. The stoichiometries were found to be one copper(l) per CopZ and two copper(l) per CopY monomer. X-ray absorption studies suggested a mixture of two- and three-coordinate copper in Cu(1)CopZ, but a purely three-coordinate copper coordination with a Cu-Cu interaction for Cu(1)(2)CopY. The latter coordination is consistent with the formation of a compact binuclear Cu(l)-thiolate core in the CxCxxxxCxC binding motif of CopY. Displacement of zinc, by copper. from CopY was monitored with 2,4-pyridylazoresorcinol. Two copper(l) ions were required to release the single zinc(II) ion bound per CopY monomer. The specificity of copper transfer between CopZ and CopY was dependent on electrostatic interactions. Relative copper binding affinities of the proteins were investigated using the chelator, diethyldithiocarbamic acid (DDC). These data suggest that CopY has a higher affinity for copper than CopZ. However, this affinity difference is not the sole factor in the copper exchange: a charge-based interaction between the two proteins is required for the transfer reaction to proceed. Gain-of-function mutation of a CopZ homologue demonstrated the necessity of four lysine residues on the chaperone for the interaction with CopY. Taken together, these results suggest a mechanism for copper exchange between CopZ and CopY.

The effectiveness of parent management training to increase self-efficacy in parents of children with Asperger syndrome

This study was a trial of an intervention programme aimed to improve parental self-efficacy in the management of problem behaviours associated with Asperger syndrome. The intervention was compared across two formats, a I day workshop and six individual sessions, and also with a non-intervention control group. The results indicated that, compared with the control group, parents in both intervention groups reported fewer problem behaviours and increased self-efficacy following the interventions, at both 4 weeks and 3 months follow-up. The results also showed a difference in self-efficacy between mothers and fathers, with mothers reporting a significantly greater increase in self-efficacy following intervention than fathers. There was no significant difference between the workshop format and the individual sessions.

The differential role of alcohol expectancies, drinking refusal self-efficacy and coping resources in predicting alcohol consumption in community and clinical samples

This study explored the relationship between coping, alcohol expectancies and drinking refusal self-efficacy in predicting drinking behaviour in both community and clinical samples. These variables were found to have differential effects in their association with frequency and volume of alcohol consumption across the two samples. Generally, drinking refusal self-efficacy was a more salient factor in relation to frequency and volume of community drinking, while coping and expectancies were more strongly associated with frequency of drinking sessions by problem drinkers. The interaction between expectancies and drinking refusal self-efficacy was related to volume of consumption in both groups, while coping and expectancies interacted in their association with frequency in the clinical group. The findings are discussed with regard to the different patterns of cognitive variables governing the decision to drink and the amount consumed in each drinking session, which may differentiate community and problem drinkers.

Organic microcavity light-emitting diodes with metal mirrors: dependence of the emission wavelength on the viewing angle

Organic microcavity light-emitting diodes typically exhibit a blueshift of the emitting wavelength with increasing viewing angle. We have modeled the shift of the resonance wavelength for several metal mirrors. Eight metals (Al, Ag, Cr, Ti, Au, Ni, Pt, and Cu) have been considered as top or bottom mirrors, depending on their work functions. The model fully takes into account the dependence of the phase change that occurs on reflection on angle and wavelength for both s and p polarization, as well as on dispersion in the organic layers. Different contributions to the emission wavelength shift are discussed. The influence of the thickness of the bottom mirror and of the choice and thickness of the organic materials inside the cavity has been investigated. Based on the results obtained, guidelines for a choice of materials to reduce blueshift; are given. (C) 2002 Optical Society of America.

Assessing the self-heating behaviour of Callide coal using a 2-metre column

A 2-m, adiabatic column has been successfully refurbished and recommissioned for coal self-heating research at The University of Queensland. Subbituminous coal from the Callide Coalfields reached thermal runaway in just under 19 days from a starting temperature of 20-22 degreesC. The coal was loaded as two layers, with an R-70 index of 2.73 degreesC h(-1) and 5.90 degreesC h(-1) for the upper layer and lower layer respectively. Initially, a hotspot developed in the upper layer between 120 and 140 cm from the air inlet due to moisture adsorption. After 7 days, self-heating in the lower half of the column began to take over, consistent with the higher R-70 index of this coal. The location of the final hotspot was approximately 60 cm from the air inlet. Further tests on Australian coals, with the column, will enable a better understanding of coal self-heating under conditions closely resembling mining, transport and storage of coal. The results from the column will also provide industry with the information needed to manage the coal self-heating hazard. (C) 2002 Elsevier Science Ltd. All rights reserved.