Dynamic behaviour of river colloidal and dissolved organic matter through cross-flow ultrafiltration system

Through cross-flow filtration (CFF) with a 1-kDa regenerated cellulose Pellicon 2 module, the ultrafiltration characteristics of river organic matter from Longford Stream, UK, were investigated. The concentration of organic carbon (OC) in the retentate in the Longford Stream samples increased substantially with the concentration factor (cf), reaching approximately 40 mg/L at cf 15. The results of dissolved organic carbon (DOC) and colloidal organic carbon (COC) analysis, tracking the isolation of colloids from river waters, show that 2 mg/L of COC was present in those samples and good OC mass balance (77-101%) was achieved. Fluorescence measurements were carried out for the investigation of retentate and permeate behaviour of coloured dissolved organic materials (CDOM). The concentrations of CDOM in both the retentate and permeate increased with increasing cf, although CDOM were significantly more concentrated in the retentate. The permeation model expressing the correlation between log[CDOM] in the permeate and logcf was able to describe the permeation behaviour of CDOM in the river water with regression coefficients (r(2)) of 0.94 and 0.98. Dry weight analysis indicated that the levels of organic colloidal particles were from 49 to 71%, and between 29 and 51% of colloidal particles present were inorganic. COC as a percentage of DOC was found to be 10-16% for Longford Stream samples.     

Microwave-assisted extraction followed by gas chromatography-mass spectrometry for the determination of endocrine disrupting chemicals in river sediments

A method for the simultaneous measurement of trace amounts of phenolic xenoestrogens, such as 2,4-dichlorophenol (2,4-DCP), 4-tert-butyl-phenol (BP), 4-tert-octylphenol (OP), 4-nonylphenol (NP), pentachlorophenol (PCP) and bisphenol A (BPA), in water samples was developed using stir bar sorptive extraction (SBSE) with in situ derivatization followed by thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS) analysis. The conditions for derivatization with acetic acid anhydride were investigated. A polydimethylsiloxane (PDMS)-coated stir bar and derivatization reagents were added to 10 ml of water sample and stirring was commenced for 10-180 min at room temperature (25 degrees C) in a headspace vial. Then, the extract was analyzed by TD-GC-MS. The optimum time for SBSE with in situ derivatization was 90 min. The detection limits of 2,4-DCP, BP, OP, NP, PCP and BPA were 2, 1, 0.5, 5, 2 and 2 pg ml(-1), respectively. The method showed good linearity over the concentration ranges of 10, 5, 2, 20, 10 and 10-1000 pg ml(-1) for 2,4-DCP, BP, OP, NP, PCP and BPA, respectively, and the correlation coefficients were higher than 0.99. The average recoveries of those compounds in river water samples were equal to or higher than 93.9% (R.S.D. <7.2%) with correction using the added surrogate standards. This simple, accurate, sensitive and selective method can be used in the determination of trace amounts of phenolic xenoestrogens in river water samples.     

Targeting the Substrate Binding Site of E. coli Nitrile Reductase QueF by Modeling,Substrate and Enzyme Engineering

Nitrile reductase QueF catalyzes the reduction of 2‐amino‐5‐cyanopyrrolo[2,3‐d]pyrimidin‐4‐one (preQ₀) to 2‐amino‐5‐aminomethylpyrrolo[2,3‐d]pyrimidin‐4‐one (preQ₁) in the biosynthetic pathway of the hypermodified nucleoside queuosine. It is the only enzyme known to catalyze a reduction of a nitrile to its corresponding primary amine and could therefore expand the toolbox of biocatalytic reactions of nitriles. To evaluate this new oxidoreductase for application in biocatalytic reactions, investigation of its substrate scope is prerequisite. We report here an investigation of the active site binding properties and the substrate scope of nitrile reductase QueF from Escherichia coli. Screenings with simple nitrile structures revealed high substrate specificity. Consequently, binding interactions of the substrate to the active site were identified based on a new homology model of E. coli QueF and modeled complex structures of the natural and non‐natural substrates. Various structural analogues of the natural substrate preQ₀ were synthesized and screened with wild‐type QueF from E. coli and several active site mutants. Two amino acid residues Cys190 and Asp197 were shown to play an essential role in the catalytic mechanism. Three non‐natural substrates were identified and compared to the natural substrate regarding their specific activities by using wild‐type and mutant nitrile reductase.     

Investigation of the influence of different commercial softeners on the stability of poly(lactic acid) fabrics during storage

We have studied the potential degradation of poly(lactic acid)-based fabrics treated with commercial softeners and stored under two sets of conditions for one year. Initial wet-processing caused a fall in molecular weight of about 28%, irrespective of after-treatment. Storage at 40 °C and 80% RH produced further degradation which, with few exceptions, was aggravated by the presence of softeners. Ultimately, all samples degraded beyond the point of commercial usefulness. No clear distinction could be made between the effects of softeners having differing compositions. In contrast, fabrics stored under milder conditions of 23 °C and 50% RH showed no significant time-dependent polymer degradation, irrespective of the treatment applied. There were slight changes in tensile properties and some evidence of physical structural effects having occurred, which we attribute to physical aging. However, we do not believe these to be so serious as to call into question the long-term viability of PLA-based textile products.     

The application of neutron powder diffraction techniques for crystallographic studies at high pressures

Abstract

For phase transition studies, neutron powder diffraction offers a number of important advantages over x-ray based techniques, for example ab-initio structural determination. There are two distinct methods using either monochromatic angular dispersive geometry on a reactor cold source or time-of-flight energy-dispersive techniques requiring a pulsed neutron source. Both techniques offer comparable resolution but have differing advantages for high pressure studies. Recent studies illustrate the benefits of the two methods and the application of these to solve unknown crystal structures.     

Condensation in a capped capillary is a continuous critical phenomenon

We show that condensation in a capped capillary slit is a continuous interfacial critical phenomenon, related intimately to several other surface phase transitions. In three dimensions, the adsorption and desorption branches correspond to the unbinding of the meniscus from the cap and opening, respectively, and are equivalent to 2D-like complete-wetting transitions. For dispersion forces, the singularities on the two branches are distinct, owing to the different interplay of geometry and intermolecular forces. In two dimensions we establish precise connection, or covariance, with 2D critical-wetting and wedge-filling transitions: i.e., we establish that certain interfacial properties in very different geometries are identical. Our predictions of universal scaling and covariance in finite capillaries are supported by extensive Ising model simulation studies in two and three dimensions.     

The effect of non-uniform bending deformation on the stability of circumferential growth of through-wall cracks in brass tubes

Experimental results on the stability of circumferential growth of through-wall cracks in brass tubes, show that non-uniform bending can adversely affect the crack stability criterion. The results are relevant to the important technological problem of crack stability in 304 stainless steel pipes used in Boiling Water Reactors.     

Critical and phase-equilibrium properties of an ab initio based potential model of methanol and 1-propanol using two-phase molecular dynamics simulations

Two-phase molecular dynamics simulations employing a Monte Carlo volume sampling method were performed using an ab initio based force field model parameterized to reproduce quantum-mechanical dimer energies for methanol and 1-propanol at temperatures approaching the critical temperature. The intermolecular potential models were used to obtain the binodal vapor-liquid phase dome at temperatures to within about 10 K of the critical temperature. The efficacy of two all-atom, site-site pair potential models, developed solely from the energy landscape obtained from high-level ab initio pair interactions, was tested for the first time. The first model was regressed from the ab initio landscape without point charges using a modified Morse potential to model the complete interactions; the second model included point charges to separate Coulombic and dispersion interactions. Both models produced equivalent phase domes and critical loci. The model results for the critical temperature, density, and pressure, in addition to the sub-critical equilibrium vapor and liquid densities and vapor pressures, are compared to experimental data. The model's critical temperature for methanol is 77 K too high while that for 1-propanol is 80 K too low, but the critical densities are in good agreement. These differences are likely attributable to the lack of multi-body interactions in the true pair potential models used here.     

Crystal deformation in aromatic polyesters

A study has been carried out of the changes in the x-ray diffraction patterns which occur when oriented fibers or tapes of poly(trimethylene terephthalate) (3GT) and poly-(tetramethylene terephthalate) (4GT) are subjected to mechanical tensile stress. Although the polymers show very different behavior in detail, in both cases comparatively large reversible lattice strains are observed (～ several %). The diffraction pattern of 3GT changes monotonically with increasing macroscopic strain, suggesting that the lattice responds immediately to the applied stress, and deforms as though it were a coiled spring. In 4GT, on the other hand, there is no detectable change in the x-ray diffraction pattern at low macroscopic strains, i.e., low values of the applied stress. At higher stresses, changes in the pattern occur which suggest a definite change in the crystal structure. Finally at the highest values of applied stress, the lattice deformations cease to increase. A preliminary discussion is presented of the relationship of these x-ray diffraction results to the mechanical stress–strain behavior.