Novel composite membranes for gas separation: Preparation and performance

High performance composite membranes based on molecular sieving silica (MSS) were synthesized using sols containing silicon co-polymers (methyltriethoxysilane and tetraethylorthosilicate). Alpha alumina supports were treated with hydrochloric acid prior to sol deposition. Permselectivity of CO2 over CH4 as high as 16.68 was achieved whilst permeability of CO2 up to 36.7 GPU (10(-6) cm(3) (STP) cm(-2) . s(-1) . cm Hg-1) was measured. The best membrane's permeability was finger printed during various stages of the synthesis process showing an increase in CO2/CH4 permselectivity by over 25 times from initial support condition (no membrane film) to the completion of pore structure tailoring. Transport measurement results indicate that the membrane pretreated with HCl has highest permselectivity and permeation rate. In particular, there is a definite cut-off pore size between 3.3 and 3.4 angstroms which is just below the kinetic diameters of Ar and CH4. This demonstrates that the mechanism for the separation in the prepared composite membrane is molecular sieving (activated diffusion), rather than Knudsen diffusion.

Regional and total body bone mineral density in elite collegiate male swimmers

Back,ground To examine the role of long-term swimming exercise on regional and total body bone mineral density (BMD) in men. Methods. Experimental design: Cross-sectional. Setting: Musculoskeletal research laboratory at a medical center, Participants:We compared elite collegiate swimmers (n=11) to age-, weight-, and height-matched non-athletic controls (n=11), Measures: BMD (g/cm(2)) of the lumbar spine L2-4, proximal femur (femoral neck, trochanter, Ward's triangle), total body and various subregions of the total body, as well as regional and total body fat and bone mineral-free lean mass (LM) was assessed by dual-energy X-ray absorptiometry (DXA, Hologic QDR 1000/W). Results. Swimmers, who commenced training at 10.7+/-3.7 yrs (mean+/-SD) and trained for 24.7+/-4.2 hrs per week, had a greater amount of LM (p<0.05), lower fat mass (p<0.001) and percent body fat (9.5 vs 16.2 %, p<0.001) than controls. There was no significant difference between groups for regional or total body BRID, In stepwise multiple regression analysis, body weight was a consistent independent predictor of regional and total body BMD, Conclusions. These results suggest that long-term swimming is not an osteogenic mode of training in college-aged males. This supports our previous findings in young female swimmers who displayed no bone mass benefits despite long-standing athletic training.

An "openable," high-strength gradient set for orthopedic MRI

A novel three-axis gradient set and RF resonator for orthopedic MRT has been designed and constructed. The set is openable and may be wrapped around injured joints. The design methodology used was the minimization of magnetic field spherical harmonics by simulated annealing. Splitting of the longitudinal coil presents the major design challenge to a fully openable gradient set and in order to efficiently design such coils, we have developed a new fast algorithm for determining the magnetic field spherical harmonics generated by an are of multiturn wire. The algorithm allows a realistic impression of the effect of split longitudinal designs. A prototype set was constructed based on the new designs and tested in a 2-T clinical research system. The set generated 12 mT/m/A with a linear region of 12 cm and a switching time of 100 mu s, conforming closely with theoretical predictions. Preliminary images from the set are presented. (C) 1999 Academic Press.

Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2)center dot 6H(2)O (ox = oxalate), {[Ni-2(tren)(3)][ClO4](4)center dot H2O}(n), and [Ni-2(tren)(2)(aepd)][ClO4](4)center dot 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidi

Reaction of K-3[Cr(ox)(3)] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O. The polymeric complex {[Ni-2(tren)(3)][ClO4](4). H2O}(n) has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni-2(tren)(2)(aepd)][ClO4](4). 2H(2)O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon-carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300-4.2 K) and magnetization data (2, 4 K, H = 0-5 T) for {[Ni-2(tren)(3)][ClO4](4). H2O}(n) (300 K , 4.23 mu(B)) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = -1.8 cm(-1); \ D\ = 2 cm(-1)) at low temperature. For [Ni-3(tren)(4)(H2O)(2)][Cr(ox)(3)](2). 6H(2)O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.

Quantifying the influence of intra-aggregate concentration gradients on solute transport

The physical nonequilibrium of solute concentration resulting from preferential now of soil water has often led to models where the soil is partitioned into two regions: preferential flow paths, where solute transport occurs mainly by advection, and the remaining region, where significant solute transport occurs through diffusive exchange with the flow paths. These two-region models commonly ignore concentration gradients within the regions. Our objective was to develop a simple model to assess the influence of concentration gradients on solute transport and to compare model results with experiments conducted on structured materials. The model calculates the distribution of solutes in a single spherical aggregate surrounded by preferential now paths and subjected to alternating boundary conditions representing either an exchange of solutes between the two regions (a wet period) or no exchange but redistribution of solutes within the aggregate (a dry period). The key parameter in the model is the aggregate radius, which defines the diffusive time scales. We conducted intermittent leaching experiments on a column of packed porous spheres and on a large (300 mm long by 216 mm diameter) undisturbed field soil core to test the validity of the model and its application to field soils. Alternating wet and dry periods enhanced leaching by up to 20% for this soil, which was consistent with the model's prediction, given a fitted equivalent aggregate radius of 1.8 cm, If similar results are obtained for other soils, use of alternating wet and dry periods could improve management of solutes, for example in salinity control and in soil remediation.

Comparison of calcaneal ultrasound and DXA in young women

Purpose: The purpose of the study was to assess quantitative ultrasound (QUS) parameters in collegiate female gymnasts, a population whose training incorporates high-impact loading, which is particularly osteogenic, and to determine the discriminative capacity of this relatively new radiation-free technique compared with bone densitometry in a young healthy population. Methods: We studied 19 collegiate gymnasts and 23 healthy controls undergoing regular weight-bearing activity, matched for age (gymnasts 19.2 +/- 1.2, controls 19.9 +/- 1.6 yr) and body weight (gymnasts 56.7 +/- 3.7, controls 57.7 +/- 7.8 kg). QUS parameters of the calcaneus (broadband ultrasound attenuation (BUA), bone velocity (BV), and speed of sound (SOS)) were measured by a Walker Sonix UBA 575+. Bone mineral density (BMD; g.cm(-2)) of the lumbar spine, hip (Femoral neck, trochanter. Ward's triangle) and whole body was assessed by dual energy x-ray absorptiometry (DXA, Hologic QDR 1000/W). Data analysis included unpaired two-tailed Student's t-tests, analysis of variance, Pearson product-moment, and Spearman rank-order correlations. Results: Regional and whole body BMD of gymnasts was greater than controls (P < 0.001), with the difference being 7-28%. Average QUS parameters of the right and left calcaneus were also higher (P < 0.001) in the gymnasts. BUA, BV, and SOS were significantly (P < 0.001) correlated to each bone site with r = 0.54-0.79. Analysis of receiver operating characteristic (ROC) curves indicated no significant difference in sensitivity and specificity for QUS and DXA measures. Conclusions: These results indicate that QUS parameters of the calcaneus are higher in young women gymnasts compared to individuals who undergo regular weight-bearing activity and that QUS parameters are able to discriminate between these two groups in a similar manner as does regional and whole body BMD.

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

Variable temperature and pressure study of the aquation reactions of cobalt(III) and chromium(III) penta- and tetra-amines

Preparation of a series of specific penta- and tetra-amine derivatives of Co-III and Cr-III with a neutral leaving ligand has been carried out in order to accomplish a fine tuning of the associativeness/dissociativeness of their substitution reactions. Spontaneous aquation reactions of the neutral ligands have been studied at variable temperature and pressure. Although rate constants and thermal activation parameters show an important degree of scatter, the values determined for the activation volumes of the substitution process illustrate the mechanistic fine tuning that may be achieved for these reactions. In all cases, in the absence of important steric constraints in the molecule, electronic inductive effects seem to be the most important factor accounting for the dissociative shifts observed both for pentaamine (i.e.Delta V double dagger=+4.0 or +14.0 cm(3) mol(-1) and +5.2 or +16.5 cm(3) mol(-1) for the aquation of cis- or trans-[Co(MeNH2)(NH3)(4)(DMF)](3+) and cis- or trans-[CoL15(DMF)](3+) respectively, where L-15 represents a pentaamine macrocyclic ligand), and tetraamine systems (i.e.Delta V double dagger=+4.1 or +8.4 cm(3) mol(-1) and -10.8 or -7.4 cm(3) mol(-1) for the aquation of cis-[Co(NH3)(4)Cl(DMAC)](2+) (DMAC=dimethylacetamide) or cis-[Co(en)(2)Cl(DMAC)](2+) and cis-[Cr(NH3)(4)Cl(DMF)](2+) or cis -[Cr(en)(2)Cl(DMF)](2+)). From the results, clear evidence is obtained which indicates that, only when the situation is borderline I-a/I-d, or the steric demands are increased dramatically, dissociative shifts are observed; in all other cases electronic inductive effects seem to be dominant for such a tuning of the substitution process.

Assessment of limb muscle and adipose tissue by dual-energy X-ray absorptiometry using magnetic resonance imaging for comparison

OBJECTIVE: To use magnetic resonance imaging (MRI) to validate estimates of muscle and adipose tissue (AT) in lower limb sections obtained by dual-energy X-ray absorptiometry (DXA) modelling. DESIGN: MRI measurements were used as reference for validating limb muscle and AT estimates obtained by DXA models that assume fat-free soft tissue (FFST) comprised mainly muscle: model A accounted for bone hydration only; model B also applied constants for FFST in bone and skin and fat in muscle and AT; model C was as model B but allowing for variable fat in muscle and AT. SUBJECTS: Healthy men (n = 8) and women (n = 8), ages 41 - 62 y; mean (s.d.) body mass indices (BMIs) of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m2, respectively. MEASUREMENTS: MRI scans of the legs and whole body DXA scans were analysed for muscle and AT content of thigh (20 cm) and lower leg (10 cm) sections; 24 h creatinine excretion was measured. RESULTS: Model A overestimated thigh muscle volume (MRI mean, 2.3 l) substantially (bias 0.36 l), whereas model B underestimated it by only 2% (bias 0.045 l). Lower leg muscle (MRI mean, 0.6 l) was better predicted using model A (bias 0.04 l, 7% overestimate) than model B (bias 0.1 l, 17% underestimate). The 95% limits of agreement were high for these models (thigh,+/- 20%; lower leg,+/- 47%). Model C predictions were more discrepant than those of model B. There was generally less agreement between MRI and all DXA models for AT. Measurement variability was generally less for DXA measurements of FFST (coefficient of variation 0.7 - 1.8%) and fat (0.8 - 3.3%) than model B estimates of muscle (0.5-2.6%) and AT (3.3 - 6.8%), respectively. Despite strong relationships between them, muscle mass was overestimated by creatinine excretion with highly variable predictability. CONCLUSION: This study has shown the value of DXA models for assessment of muscle and AT in leg sections, but suggests the need to re-evaluate some of the assumptions upon which they are based.

Thermal and radiation curing of phenylethynyl terminated macromers

The thermal and gamma-irradiation induced curing of two phenylethynyl terminated composite resin systems, DFB/BPF and PETI5A, was investigated. Thermal curing of these matrix resin samples was performed at a temperature of 360 degrees C, gamma irradiation of the samples was conducted at 300 degrees C at a dose rate of 2.2 kGy h(-1). The reaction and subsequent loss of ethynyl groups in the resins for both cure methods was demonstrated by observing the decrease of the 2215 cm(-1) peak in the Raman spectra of the resins. Fully cured resin samples were found to have glass transition temperatures of 244-246 degrees C and 278-280 degrees C for DFB/BPF and PETI5A respectively. Similar relationships between T-g and fractional conversion were observed in both resins. The apparent polymerization rate, R-p, for thermal cure at 360 degrees C, was found to be 4.79 x 10(-2)% s(-1) in PETI5A and 3.22 x 10(-2)% s(-1) in DFB/BPF. Catastrophic degradation under nitrogen was observed to commence near 450 degrees C and 530 degrees C, with 5% weight losses occurring at 455 degrees C and 540 degrees C for DFB/BPF and PETI5A respectively. Gamma radiation induced cure at 300 degrees C was shown to be feasible, with full cure being reached with doses of 40 kGy for DFB/BPF and 100 kGy for PETI5A.

Base-catalysed rearrangements of 5-oxodihydroisoxazoles

Five distinct pathways for the reaction of isoxazol-5(2H)-ones with bases or nucleophiles have been reported, and are detailed herein. That investigated in greatest detail, and of greatest application in heterocyclic synthesis, is that of isoxazolones unsubstituted at C-3, in which the sequentially formed ketenimine, alpha-lactone and ketene may all react with a nucleophile.

Clinical measures of obesity and weight loss in men

OBJECTIVES: (?) To determine the relationship between waist circumference and body weight in overweight men both before and after participation in a weight loss program; and (2) to make recommendations for the appropriate use of these measures at various stages of weight toss. DESIGN: Weight and waist circumference measures were taken in two diverse groups of men both before and 1-2y after commencing a men's 'waist loss' program. Regression analyses were used to assess the relationship between weight and waist measures. SUBJECTS: One group of 42 retired Caucasian men from New South Wales, and one group of 45 indigenous men from the Torres Strait region of Northern Australia. RESULTS: There were differences in the relationships of weight and waist circumference before the program and change in weight and change in waist circumference after weight loss. These differences were similar in both groups of men (indigenous men and retired Caucasian men), with a 1 cm waist loss being on average equivalent to about 3/4 kg, but with wide variability, suggesting inter-individual variation in fat losses from different depots. This variation suggests that neither weight nor waist alone is a sufficient measure of fat loss for men. CONCLUSIONS: Weight and waist circumference should both be used at various stages in the clinical situation to assess change in body fat in men involved in obesity reduction.

FHA domain boundaries of the Dun1p and Rad53p cell cycle checkpoint kinases

Dun1p and Rad53p of the budding yeast Saccharomyces cerevisiae are members of a conserved family of cell cycle checkpoint protein kinases that contain forkhead-associated (FHA) domains. Here, we demonstrate that these FHA domains contain 130-140 residues, and are thus considerably larger than previously predicted by sequence comparisons (55-75 residues), In vivo, expression of the proteolytically defined Dun1p FHA domain, but not a fragment containing only the predicted domain boundaries, inhibited the transcriptional induction of repair genes following replication blocks, This indicates that the non-catalytic FI-IA domain plays an important role in the transcriptional function of the Dun1p protein kinase. (C) 2000 Federation of European Biochemical Societies.

Increasing the efficiency of solute leaching: impacts of flow interruption with drainage of the "preferential flow paths"

Most soils contain preferential flow paths that can impact on solute mobility. Solutes can move rapidly down the preferential flow paths with high pore-water velocities, but can be held in the less permeable region of the soil matrix with low pore-water velocities, thereby reducing the efficiency of leaching. In this study, we conducted leaching experiments with interruption of the flow and drainage of the main flow paths to assess the efficiency of this type of leaching. We compared our experimental results to a simple analytical model, which predicts the influence of the variations in concentration gradients within a single spherical aggregate (SSA) surrounded by preferential flow paths on leaching. We used large (length: 300 mm, diameter: 216 mm) undisturbed field soil cores from two contrasting soil types. To carry out intermittent leaching experiments, the field soil cores were first saturated with tracer solution (CaBr2), and background solution (CaCl2) was applied to mimic a leaching event. The cores were then drained at 25- to 30-cm suction to empty the main flow paths to mimic a dry period during which solutes could redistribute within the undrained region. We also conducted continuous leaching experiments to assess the impact of the dry periods on the efficiency of leaching. The flow interruptions with drainage enhanced leaching by 10-20% for our soils, which was consistent with the model's prediction, given an optimised equivalent aggregate radius for each soil. This parameter quantifies the time scales that characterise diffusion within the undrained region of the soil, and allows us to calculate the duration of the leaching events and interruption periods that would lead to more efficient leaching. Application of these methodologies will aid development of strategies for improving management of chemicals in soils, needed in managing salts in soils, in improving fertiliser efficiency, and in reclaiming contaminated soils. (C) 2000 Elsevier Science B.V. All rights reserved.

Effect of density on spatial distribution, pit formation and pit diameter of Myrmeleon acer Walker, (Neuroptera : Myrmeleontidae): patterns and processes

The effect of increasing population density on the formation of pits, their size and spatial distribution, and on levels of mortality was examined in the antlion Myrmeleon acer Walker. Antlions were kept at densities ranging from 0.4 to 12.8 individuals per 100 cm(2). The distribution of pits was regular or uniform across all densities, but antlions constructed proportionally fewer and smaller pits as density increased. Mortality through cannibalism was very low and only occurred at densities greater than five individuals per 100 cm(2). Antlions in artificially crowded situations frequently relocated their pits and when more space became available, individuals became more dispersed with time. Redistribution of this species results from active avoidance of other antlions and sand throwing associated with pit construction and maintenance, rather than any attempt to optimise prey capture per se.