Experimental analysis, modeling, and theoretical design of McMaster pore-filled nanofiltration membranes

A side-by-side comparison of the performance of McMaster pore-filled (MacPF) and commercial nanofiltration (NF) membranes is presented here. The single-salt and multi-component performance of these membranes is studied using experimental data and using a mathematical model. The pseudo two-dimensional model is based on the extended Nernst–Planck equation, a modified Poisson–Boltzmann equation, and hydrodynamic calculations. The model includes four structural properties of the membrane: pore radius, pure water permeability, surface charge density and the ratio of effective membrane thickness to water content. The analysis demonstrates that the rejection and transport mechanisms are the same in the commercial and MacPF membranes with different contributions from each type of mechanism (convection, diffusion and electromigration). Solute rejection in NF membranes is determined primarily by a combination of steric and electrostatic effects. The selectivity of MacPF membranes is primarily determined by electrostatic effects with a significantly smaller contribution of steric effects compared to commercial membranes. Hence, these membranes have the ability to reject ions while remaining highly permeable to low molecular weight organics. Additionally, a new theoretical membrane design approach is presented. This design procedure potentially offers the optimization of NF membrane performance by tailoring the membrane structure and operating variables to the specific process, simultaneously. The procedure is validated at the laboratory scale.     

Effect of temperature on the luminescence processes of SrAl2O4:Eu

The UV excited and persistent luminescence properties as well as thermoluminescence (TL) of Eu²⁺ doped strontium aluminates, SrAl₂O₄:Eu²⁺ were studied at different temperatures. Two luminescence bands peaking at 445 and 520 nm were observed at 20 K but only the latter at 295 K. Both Sr-sites in the lattice are thus occupied by Eu²⁺ but at room temperature efficient energy transfer occurs between the two sites. The UV excited and persistent luminescence spectra were similar at 295 K but the excitation spectra were different. Thus the luminescent centre is the same in both phenomena but excitation processes are different. Two TL peaks were observed between 50 and 250 °C in the glow curve. Multiple traps were, however, observed by preheating and initial rise methods. With longer delay times only the high temperature TL peak was observed. The persistent luminescence is mainly due to slow fading of the low temperature TL peak but the step-wise feeding process from high temperature traps is also probable.     

Modeling plane turbulent Couette flow

Among the salient features of shear-driven plane Couette flow is the constancy of the total shear stress (viscous and turbulent) across the flow. This constancy gives rise to a quasi-homogenous core region, which makes the bulk of the flow substantially different from pressure-driven Poiseuille flow. The present second-moment closure study addresses the conflicting hypotheses relating to turbulent Couette flow. The inclusion of a new wall-proximity function in the wall-reflection part of the pressure-strain model seems mandatory, and the greement with recent experimental and direct numerical simulation (DNS) results is encouraging. Analysis of model computations in the range 750 ≤ Re ≤ 35,000 and comparisons with low-Re DNS data suggest that plane Couette flow exhibits a local-equilibrium core region, in which anisotropic, homogeneous turbulence prevails. However, the associated variation of the mean velocity in the core, as obtained by the model, conflicts with the intuitively appealing assumption of homogeneous mean shear. The constancy of the velocity gradient exhibited by the DNS therefore signals a deficiency in the modeled transport equation for the energy dissipation rate.     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Atomic layer deposition in nanometer-level replication of cellulosic substances and preparation of photocatalytic TiO2/cellulose composites

TiO2 replicas of filter paper with nanometer-level accuracy were prepared by atomic layer deposition of thin conformal TiO2 coating, followed by a removal of the paper by air-anneal at 450 degrees C. Photocatalytic anatase TiO2/cellulose composites were also made by leaving the paper intact. The TiO2 films were deposited from Ti(OMe)4 and H2O at 150-250 degrees C. The photocatalytic activity of the TiO2/cellulose composite was verified by photocatalytic reduction of Ag(I) from an aqueous solution to Ag nanoparticles on the TiO2 surface. The TiO2/cellulose composites are mechanically more stable than the free-standing TiO2 replicas and are therefore potentially suitable as lightweight, high surface area photocatalysts.     

Speciation in the aqueous H+/H2VO4-/H2O2/picolinate system relevant to diabetes research

A detailed study of the quaternary aqueous H+/H2VO4-/H2O2/picolinate (Pi-) system has been performed at 25 degrees C in 0.150 M Na(Cl) medium using quantitative 51 V NMR (500 MHz) and potentiometric data (glass electrode). In the ternary H+/H2VO4-/Pi- system, six complexes have been found in the pH region 1-10. In the quaternary H+/H2VO4-/H2O2/Pi- system, eight additional complexes have been found. Generally, equilibria are fast in both systems. The rate of peroxide decomposition depends on the species in solution. Chemical shifts, compositions and formation constants for the species are given. Equilibrium conditions and the fit of the model to the experimental data are illustrated in distribution diagrams. Possible formation of mixed ligand species with imidazole, lactic acid and citric acid have been investigated and ruled out under the same experimental conditions. Structural proposals are given, based on 1)C NMR data and available crystal structures.     

Multicomponent polyanions. 57. Large-angle X-ray scattering study of aqueous molybdophenylphosphonate solutions

The radial distribution functions are calculated from large-angle X-ray scattering (LAXS) measurements for one concentrated aqueous molybdate/heptamolybdate solution and five aqueous molybdophenylphosphonate solutions (lithium chloride medium). Besides water and hydrated lithium, chloride, and molybdate ions, five species in all, having different nuclearities, are postulated to exist in the solutions, according to equilibrium studies using potentiometry and 31P NMR spectroscopy. The structures of the three polymolybdate species Mo7O24(6-), Mo8O26(4-), and (C6H5P)2Mo5O21(4-), for which the structures are determined crystallographically, are confirmed to exist also in aqueous solution. The principal structures of the remaining two complexes, (C6H5P)Mo6O21(OH2)5(2-) and (C6H5P)Mo7O25(OH2)4-, are elucidated with the use of structures of related species. Both anions have one group of four edge-sharing MoO6 octahedra and another group of two MoO6 octahedra connected by sharing corners, forming a bent unsymmetric six-membered ring, with the C6H5PO3 group placed on the crowded side of the ring. In the former, the group of two MoO6 octahedra is edge-shared, while in the latter, the group is face-shared, resulting in a ring small enough to tetrahedrally coordinate to the seventh molybdenum opposite the phenyl group.     

Antihydrophobic solvent effects: an experimental probe for the hydrophobic contribution to enzyme-inhibitor binding

The hydrophobic component to the binding affinities of one acyclic phosphinate (4) and three macrocyclic phosphonamidate inhibitors (1-3) to the zinc peptidase thermolysin was probed by varying the solvent composition. Increasing the percentage of ethanol in the buffer solution over the range 0-9% increases the inhibition constants, K(i), by up to an order of magnitude. This approach represents an experimental method for distinguishing solvation from conformational or other effects on protein-ligand binding. The size of the "antihydrophobic effect" is correlated with the amount of hydrophobic surface area sequestered from solvent on association of the inhibitor and enzyme, although it is attenuated from that calculated from the surface tension of ethanol-water mixtures. The results are consistent with the Lum-Chandler-Weeks explanation for the size dependence of the hydrophobic effect.     

The rate of reduction of selenium(VI) to selenium(IV) in hydrochloric acid

The reduction of selenium(VI) to selenium(IV) in 4, 5 and 6M hydrochloric acid was studied at temperatures between 50 and 95 degrees . The reaction rate was determined by measurement of the selenium(IV) formed, by continuous-flow hydride-generation atomic-absorption spectrometry. The most notable feature of the reaction is the strong increase in rate with increasing hydrogen-ion concentration and temperature. The rate increases initially with chloride concentration at constant acidity (mixtures of hydrochloric and perchloric acid) but levels off to an almost constant value at high chloride concentrations.     

Detection of environmental chemicals by SPR assay using branched cyclodextrin as sensor ligand

We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G₂βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G₂βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful for the repeated measurement.