Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

On the microhardness testing of electrically stressed poly(phenylene oxide): Polystyrene blends

Microhardness measurements have been performed on untreated (virgin) and electrically stressed, solvent‐cast laboratory‐prepared samples of pure poly(phenylene oxide) (PPO), pure polystyrene (PS), and PPO : PS polyblends with different weight proportions. Results of such measurement on untreated polyblend sample show that microhardness (H_v) increases with increase in the content of PS up to 10 wt %, which attributed to the existence of homogeneous phase morphology. However, this feature is not observable in samples containing higher content of PS. Electrical stress is found to modify considerably the mechanical property of polymer. The effect of electric field on the microhardness of such samples (PPO : PS :: 90 : 10) has been characterized by the existence of a peak. Trapping of charge carriers in electrically stressed samples imparts hardening to the polyblend up to an applied step field of 190 kV/cm. However, the excessive charging beyond this step field value destroys this characteristic. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nondegradative microextrusion of resorbable polyesters for pharmaceutical and biomedical applications: The cases of poly‐lactic‐acid and poly‐caprolactone

In recent years biodegradable polymers, particularly polyesters such as the poly(lactic acid) (PLA) and polycaprolactone (PCL), have gained high interests for their applicability in the biomedical and pharmaceutical fields where they're used for manufacturing various different resorbable devices, from tissue engineering scaffolds to controlled drug release systems. Despite many positive characteristics, processability of these materials still remains a critical issue as they easily tend to degrade during manufacturing. In this article we aimed to assess microextrusion as a nondegradative process for manufacturing PLA and PCL. The results we experimentally obtained, that are hereby presented, set a new point in the on‐going debate on degradation during processing of resorbable polymers as they allow to affirm that microextrusion leaves unmodified molecular weight distributions without producing any evident reductions in mean molecular weight. Microextrusion thus represents a risk‐free high molecular weight polymer processing solution for obtaining nondegraded products within pharmaceutical and biomedical production lines, such as for scaffolds for tissue engineering applications or drug delivery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Antimicrobial finishing of regular and modified polyethylene terephthalate fabrics

An effective two-stage method has been developed for imparting antimicrobial properties to regular polyethylene terephthalate (R-PET), polyethylene glycol modified polyethylene terephthalate (PEG-M-PET), R-PET/Cotton blend (R-PET/C) and PEG-M-PET/Cotton blend (PEG-M-PET/C) fabrics. The method consists of partial hydrolysis of the fabrics to create carboxylic groups in PET macromolecules followed by subsequent reaction with dimethylalkylbenzyl ammonium chloride (DMABAC) under alkaline conditions. The reaction conditions such as pH, reaction temperature and time, carboxylic content, and DMABAC concentration were studied. Characterization of the finished fabrics was carried out through scanning electron microscopy (SEM) and Fourier transform infrared spectra (FTIR). All the modified PET fabrics showed excellent antibacterial activity towards Gram-positive (Bacillus mycoides), Gram-negative (Escherichia coli), and nonfilamentous fungus (Candida albicans). The achieved antimicrobial functions on the PET fabrics are durable in repeated laundering processes. Even after laundering 10 times the fabrics could still provide more than 85% of its antimicrobial activity against B. mycoides, E. coli, and C. albicans. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

橡胶Mooney—Rivlin模型材料系数对轴向刚度影响分析

在橡胶小变形范围内，采用理论推断的方法，得到在相同硬度下橡胶Mooney—Rivlin模型材料系数由C2／C1决定的关系式。并采用ABAQUS有限元软件分析的方法，结合橡胶轴向刚度常规解，分析了C2／C1不同值对橡胶轴向刚度的影响进行，结果显示其影响呈现一定规律性。     

Memory of Distributed Computer Systems: Distinctive Features of Their Architectural-Structural Organization and Use

Distinctive features of architectural-structural organization and use of memory networks are considered with the aim of choosing an optimal configuration in designing distributed computer systems.     

Studies of substrate specificities of lipases from different sources

Although lipases are widely applied in a wide variety of reactions, available information on the factors that are responsible for the substrate specificities of lipases from different sources is scarce. In this paper, nine lipase‐producing microorganism strains were isolated from oil‐containing samples. The properties of these enzymes, including pH optima, temperature optima, thermal stability, and pH stability, vary significantly with the different sources from which these lipases were isolated. The substrate specificities of the nine lipases, including fatty acid and positional specificities, were also studied. The fatty acid specificities of the nine lipases were observably different toward 15 substrates with different carbon chain lengths, different saturation degrees and different side chains. The lipases from S₃ Penicillium citrinum (PCL), MJ₁ Aspergillus niger (ANL), MJ₂ Aspergillus oryzae (AOL), YM Bacillus coughing (BCL), S₉ Geotrichum candidum (GCL), and S₁₁ Candida lypolytica (CLL) showed the strongest specificities to short‐chain esters, and the other lipases showed strong selectivity for medium‐ or long‐chain and branched esters. The positional specificities were examined by analyzing the hydrolytic products of triolein catalyzed by the nine lipases, using TLC. The lipases can be mainly classified into two groups by their specificities for the ester bond at position 2 of triglycerides; one group can selectively hydrolyze the ester bond at position 2 of the triglycerides, the other group cannot. All these nine lipases were divided into four groups by hierarchical clustering analysis on the basis of the results of fatty acid and positional specificities.     

Direct synthesis and catalytic performance of ultralarge pore GaSBA-15 mesoporous molecular sieves with high gallium content

Mesoporous GaSBA-15 molecular sieves with different n_Si/n_Ga ratios have been directly synthesized using Pluronic 123 triblock polymer as a structure-directing agent by pH-adjusting method. The mesoporous materials have been characterized using ICP-AES, XRD, N₂ adsorption, ⁷¹Ga-MAS NMR, SEM and TEM. ICP-AES studies show a high amount of gallium incorporation on the silica pore walls. The structural and textural properties of calcined GaSBA-15 are characterized by XRD and N₂ adsorption. ⁷¹Ga MAS NMR results demonstrate that a high amount of tetrahedral-gallium could be substituted for Si in the framework of SBA-15. TEM and FE-SEM images show the uniform pore diameter and rope-like hexagonal mesoporous structure of GaSBA-15. These GaSBA-15 materials have been used as catalysts for vapour-phase t-butylation of 1,2-dihydroxybenzene (DHB) for selective synthesis of 4-t-butylcatechol (4-TBC) under different reaction conditions. GaSBA-15(10) gave the highest 93.2% conversion of DHB and 95.7% selectivity of 4-TBC as compared with other GaSBA-15 catalysts.