Synthesis, characterization and thermal analysis of polyaniline/ZrO2 composites

Conducting polyaniline-zirconium dioxide (PANI/ZrO₂) composites were synthesized by ‘in situ’ deposition technique in the presence of hydrochloric acid (HCl) as dopant by adding the fine grade powder (average particle size of approximately 20 nm) of ZrO₂ into the polymerization reaction mixture of aniline. The composites obtained were characterized by infrared spectra (IR) and X-ray diffraction (XRD) and thermogravimetric analysis (TGA). TG curves and DTG curves of the composites suggest that the thermal degradation process of PANI/ZrO₂ composites proceeds in two-steps and the composites are more thermally stable than that of the pure PANI. The improvement in the thermal stability for the composites is attributed to the interaction between PANI and ZrO₂, which restricts the thermal motion of PANI chains and shields the degradation of PANI in the composites.     

Chiral palladium template promoted asymmetric hydrophosphination reaction between diphenylphosphine and vinylphosphines

An organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two regioisomers are cocrystallized in a 1:1 ratio. The naphthylamine auxiliary could be removed chemoselectively from the template products by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes [(R)- or (S)-(prophos)PdCl(2)]. Subsequently, the (R)- and (S)-dichloro complexes undergo ligand displacement with aqueous cyanide to generate the corresponding optically pure diphosphine ligands in high yields. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.     

Determination of Size Distribution of Nano-particles by Capillary Zone Electrophoresis

A new method was developed for the determination of the size distribution of nano-particles by capillary zone electrophoresis (CZE). Scattering effect of nanoparticles was studied. This method for the determination of size distribution was statistical.     

直流放电制备CN自由基及其LIF探测

CN自由基是研究化学反应动力学的典型自由基，CN的动力学行为，如CN＋O2的反应已成为研究自由基－自由基反应的模型体系[1]，同时也在许多实际过程如燃烧过程，星际气体的形成过程中起着重要的作用[2，3]．利用含有CN的化合物进行光解、放电、与亚稳态原子分子进行传能反应是目     

富镧混合稀土对ZL101A合金组织和机械性能的影响

研究了富镧混合稀土对ＺＬ１０１Ａ合金的铸态、固溶态、Ｔ６状态、重熔态的组织和机械性能的影响，提出了混合稀土中入量低压铸造整体车轮合理的热处理状态。     

聚丙烯纤维辐射接枝进展

本文对聚丙烯纤维的辐射接枝方法、特征和机理、以及其研究进展和表征进行了扼要综述。     

甲醇／丙烷在ZSM－5分子筛上偶合转化过程的研究

考察了甲醇／低碳烷烃在ＺＳＭ－５分子筛上偶合转化为芳烃和低碳烯烃的反应过程。对特定的催化体系，存在一最佳原料配比，使反应的热效应近似为零。偶合转化时甲醇完全转化，低碳烷烃的转化率低；不同催化剂上偶合转化产物分布差别极大，与ＨＺＳＭ－５相比，Ｇａ改性后可获得较高的芳烃和低碳烯烃收率。     

Sorption behavior of Co(II) on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the presence of humic acid

The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al₂O₃ in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al₂O₃ in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al₂O₃ was attributed to strong surface binding of HA on γ-Al₂O₃ and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO⁻) _x Co^2−x . Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al₂O₃ in the presence of HA.     

PhenNO—TTA—乳化剂OP荧光光度法测定微量铕

研究了Ｅｕ（Ⅲ）－ＰｈｅｎＮＯ－ＴＴＡ－乳化剂ＯＰ体系的荧光性质及其用于微量铕的测定。该体系具有良好的分析特性，最低检测限可达７．０×１０＾－１４ｍｏｌ／Ｌ．     

Carbohydrate-binding module O-mannosylation alters binding selectivity to cellulose and lignin

Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies. In this study, we examine the impact of O-glycosylation on the binding selectivity of a model Family 1 carbohydrate-binding module (CBM), which has been shown to be one of the primary sub-domains responsible for non-productive lignin binding in multi-modular cellulases. Specifically, we examine the relationship between glycan structure and the binding specificity of the CBM to cellulose and lignin substrates. We find that the glycosylation pattern of the CBM exhibits a strong influence on the binding affinity and the selectivity between both cellulose and lignin. In addition, the large set of binding data collected allows us to examine the relationship between binding affinity and the correlation in motion between pairs of glycosylation sites. Our results suggest that glycoforms displaying highly correlated motion in their glycosylation sites tend to bind cellulose with high affinity and lignin with low affinity. Taken together, this work helps lay the groundwork for future exploitation of glycoengineering as a tool to improve the performance of industrial enzymes.

Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies.

The cell walls of terrestrial plants primarily comprise the polysaccharides cellulose, hemicellulose, and pectin, as well as the heterogeneous aromatic polymer, lignin. In nature, carbohydrates derived from plant polysaccharides provide a massive carbon and energy source for biomass-degrading fungi, bacteria, and archaea, which together are the primary organisms that recycle plant matter and are a critical component of the global carbon cycle. Across the various environments in which these microbes break down lignocellulose, a few known enzymatic and chemical systems have evolved to deconstruct polysaccharides to soluble sugars.^1–6 These natural systems are, in several cases, being evaluated for industrial use to produce sugars for further conversion into renewable biofuels and chemicals.From an industrial perspective, overcoming biomass recalcitrance to cost-effectively produce soluble intermediates, including sugars for further upgrading remains the main challenge in biomass conversion. Lignin, the evolution of which in planta provided a significant advantage for terrestrial plants to mitigate microbial attack, is now widely recognized as a primary cause of biomass recalcitrance.⁷ Chemical and/or biological processing scenarios of lignocellulose have been evaluated⁸ and several approaches have been scaled to industrial biorefineries to date. Many biomass conversion technologies overcome recalcitrance by partially or wholly removing lignin from biomass using thermochemical pretreatment or fractionation. This approach enables easier polysaccharide access for carbohydrate-active enzymes and/or microbes. There are however, several biomass deconstruction approaches that employ enzymes or microbes with whole, unpretreated biomass.^9,10 In most realistic biomass conversion scenarios wherein enzymes or microbes are used to depolymerize polysaccharides, native or residual lignin remains.^11,12 It is important to note that lignin can bind and sequester carbohydrate-active enzymes, which in turn can affect conversion performance.¹³Therefore, efforts aimed at improving cellulose binding selectivity relative to lignin have emerged as major thrusts in cellulase studies.^14–25 Multiple reports in the past a few years have made exciting new contributions to our collective understanding of how fungal glycoside hydrolases, which are among the most well-characterized cellulolytic enzymes given their importance to cellulosic biofuels production, bind to lignin from various pretreatments.^15,17 Taken together, these studies have demonstrated that the Family 1 carbohydrate-binding modules (CBMs) often found in fungal cellulases are the most relevant sub-domains for non-productive binding to lignin,^15,17,20,26 likely due to the hydrophobic face of these CBMs that is known to be also responsible for cellulose binding (Fig. 1).²⁷Open in a separate windowFig. 1Model of glycosylated CBM binding the surface of a cellulose crystal. Glycans are shown in green with oxygen atoms in red, tyrosines known to be critical to binding shown in purple, and disulfide bonds Cys8–Cys25 and Cys19–Cys35 in yellow.Furthermore, several studies have been published recently using protein engineering of Family 1 CBMs to improve CBM binding selectivity to cellulose with respect to lignin. Of particular note, Strobel et al. screened a large library of point mutations in both the Family 1 CBM and the linker connecting the catalytic domain (CD) and CBM.^21,22 These studies demonstrated that several mutations in the CBM and one in the linker led to improved cellulose binding selectivity compared to lignin. The emerging picture is that the CBM-cellulose interaction, which occurs mainly as a result of stacking between the flat, hydrophobic CBM face (which is decorated with aromatic residues) and the hydrophobic crystal face of cellulose I, is also likely the main driving force in the CBM-lignin interaction given the strong potential for aromatic–aromatic and hydrophobic interactions.Alongside amino acid changes, modification of O-glycosylation has recently emerged as a potential tool in engineering fungal CBMs, which Harrison et al. demonstrated to be O-glycosylated.^28–31 In particular, we have revealed that the O-mannosylation of a Family 1 CBM of Trichoderma reesei cellobiohydrolase I (TrCel7A) can lead to significant enhancements in the binding affinity towards bacterial microcrystalline cellulose (BMCC).^30,32,33 This observation, together with the fact that glycans have the potential to form both hydrophilic and hydrophobic interactions with other molecules, led us to hypothesize that glycosylation may have a unique role in the binding selectivity of Family 1 CBMs to cellulose relative to lignin and as such, glycoengineering may be exploited to improve the industrial performance of these enzymes. To test this hypothesis, in the present study, we systematically probed the effects of glycosylation on CBM binding affinity for a variety of lignocellulose-derived cellulose and lignin substrates and investigated routes to computationally predict the binding properties of different glycosylated CBMs.