The interaction between poly(N-isopropylacrylamide) and salts in aqueous media: The “salting-out” phenomenon as studied by attenuated total reflection/fourier transform infrared spectroscopy

The effect of two strong salting-out salts (Na₂SO₄ and K₂SO₄) on the temperature-induced phase-separation process in aqueous solutions of poly(N-isopropylacrylamide) (PNIPA) was examined by attenuated total reflectance/Fourier transform infrared spectroscopy, differential scanning calorimetry, and viscosity measurements. On the basis of these measurements, a detailed scenario of the phase-separation process was deduced. The phase-separation scenario of solutions containing PNIPA and water was altered in the presence of sulfate ions. Here, the sulfate ions induced partial intrachain collapse, manifested by a relatively compact structure well below the lower critical solution temperature. This led to a more gradual, smooth phase transition, with temperature-resolved intrachain collapse and interchain aggregation and a lesser extent of hysteresis. Although at the macrolevel one may not be able to differentiate among various scenarios altering the solvent into a poor solvent, the aforementioned microlevel measurements provided a way to expose the difference between raising the temperature and adding cosolutes. Follow-up studies on the effect of salting-in salts will be presented. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 33–46, 2004     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Statistical thermodynamics evaluation of polymer–polymer miscibility

The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004     

PURIFICATION OF L-METHIONINE AND N-ACETYL-D-METHIONINE FROM THE MIXTURE OF ENZYMATICALLY DEACYLATED N-ACETYL-DL-METHIONINE

1. INTRODUCTION Methionine, namely 2-amido-4-thiomethyl butyric acid with a structure of CH3SCH2CH2CHCOOH, is one of the essential amino acids and has two natural enantionmers, D and L-methionine. The mixture of L- and D-isomers can be used as analeptics or nutritive additives to maintain the equilibrium of amino acids of feed [1,2]. L-methionine can release active methyl and accelerate the synthesis of choline, which further speeds up the conversion of the lipid accumulated in liv…     

Kinetic Studies on the Reaction of Sodium Hexa-cyanoferrate(II) Complex with Peroxydisulfate Anion

Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant …     

Studies on the Adsorption of Asymmetrical Triblock Copolymers by Scheutjens-Fleer Theory and Monte Carlo Simulation

The adsorption of asymmetrical triblock copolymers from a non-selective solvent on solid surface has been studied by using Scheutjens-Fleer mean-field theory and Monte Carlo simulation method on lattice model. The main aim of this paper is to provide detailed computer simulation data, taking A8-kB20Ak as a key example, to study the influence of the structure of copolymer on adsorption behavior and make a comparison between MC and SF results. The simulated results show that the size distribution of various configurations and density-profile are dependent on molecular structure and adsorption energy. The molecular structure will lead to diversity of adsorption behavior. This discrepancy between different structures would be enlarged for the surface coverage and adsorption amount with increasing of the adsorption energy. The surface coverage and the adsorption amount as well as the bound fraction will become larger as symmetry of the molecular structure becomes gradually worse. The adsorption layer becomes thicker with increasing of symmetry of the molecule when adsorption energy is smaller but it becomes thinner when adsorption energy is higher. It is shown that SF theory can reproduce the adsorption behavior of asymmetrical triblock copolymers. However, systematic discrepancy between the theory and simulation still exists.The approximations inherited in the mean-filed theory such as random mixing and the allowance of direct back folding may be responsible for those deviations.     

Elliptic and parabolic problems in unbounded domains

We consider elliptic and parabolic problems in unbounded domains. We give general existence and regularity results in Besov spaces and semi‐explicit representation formulas via operator‐valued fundamental solutions which turn out to be a powerful tool to derive a series of qualitative results about the solutions. We give a sample of possible applications including asymptotic behavior in the large, singular perturbations, exact boundary conditions on artificial boundaries and validity of maximum principles. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An approach to deciding the observational equivalence of Algol-like languages

We prove that the observational equivalence of third-order finitary (i.e. recursion-free) Idealized Algol (IA) is decidable using Game Semantics. By modelling the state explicitly in our games, we show that the denotation of a term M of this fragment of IA is a compactly innocent strategy-with-state, i.e. the strategy is generated by a finite view function f_M. Given any such f_M, we construct a real-time deterministic pushdown automaton (DPDA) that recognizes the complete plays of the knowing-strategy denotation of M. Since such plays characterize observational equivalence, and there is an algorithm for deciding whether any two DPDAs recognize the same language, we obtain a procedure for deciding the observational equivalence of third-order finitary IA. Restricted to second-order terms, the DPDA representation cuts down to a deterministic finite automaton; thus our approach gives a new proof of Ghica and McCusker’s regular-expression characterization for this fragment. Our algorithmic representation of program meanings, which is compositional, provides a foundation for model-checking a wide range of behavioural properties of IA and other cognate programming languages. Another result concerns second-order IA with full recursion: we show that observational equivalence for this fragment is undecidable.     

3-正则图的分割问题是NP-完全问题

证明了3-正则图的最小平分问题和最小α-分割问题都是NP-完全问题.