石膏减水剂的吸附形态与分散稳定性研究

采用紫外吸收光谱分析、微电泳仪、光电子能谱分析技术研究了萘系、多羧酸系 2种类型减水剂在石膏表面的吸附特性、表面电化学性能及其对石膏浆体流动性的影响。结果表明 ,FDN、HC在石膏颗粒表面的吸附基本符合 L angm uir等温方程 ,FDN为物理吸附 ,HC为化学吸附。 FDN为平躺吸附 ,吸附量较大 ,吸附层的静电作用较强 ,空间位阻小 ,其分散作用主要取决于静电斥力 ,ζ电位主要取决于 FDN首层吸附量 ;多羧酸为梳状吸附 ,吸附量较小 ,静电效应较弱 ,但吸附层空间位阻较大。减水剂分散性取决于ζ电位静电斥力和吸附层空间位阻。由于水化产物对静电斥力的屏蔽效应 ,静电斥力分散作用的稳定性差 ,其流动度经时损失大。空间位阻的分散性受胶凝材料水化作用的影响较小 ,其稳定性优于静电斥力。     

Steric hindrance in immunolabelling

In this paper we describe immunocytochemical detection of PhoE pore protein in the outer membrane of E. coli K-12 cells in dependence of a variety of labelling approaches. Immuno-gold labelling on ultrathin cryosections showed a uniform, dense labelling of the outer membrane of all cells. However, using immunofluorescence, whole-mount or freeze-etch labelling methods, labelling was limited to less than 5% of the cell population. In order to understand this phenomenon, immunoincubated cells exhibiting less than 5% labelling were processed for cryo-ultramicrotomy. Reincubation of the sections with antibody and probe resulted in labelling of all of the cells. If an E. coli Gal-U mutant strain, defective in the lipopolysaccharide (LPS) carbohydrate chain length, was used, each approach rendered 100% labelling. From these results it is concluded that the antigenic sites of the PhoE pore protein are not accessible in intact ‘wild-type’ cells due to steric hindrance caused by the LPS carbohydrate chains. In cryosections this steric hindrance is partly precluded since antigenic determinants are exposed at the section surface in transversely cut membranes. Our results emphasize the necessity to compare results obtained by means of several, basically different approaches.     

Hydrogen storage of dual-Ti-doped single-walled carbon nanotubes

The hydrogen adsorption capacity of dual-Ti-doped (7, 7) single-walled carbon nanotube (Ti-SWCNTs) has been studied by the first principles calculations. Ti atoms show different characters at different locations due to local doping environment and patterns. The dual-Ti-doped SWCNTs can stably adsorb up to six H₂ molecules through Kubas interaction at the Ti₂ active center. The intrinsic curvature and the different doping pattern of Ti-SWCNTs induce charge discrepancy between these two Ti atoms, and result in different hydrogen adsorption capacity. Particularly, eight H₂ molecules can be adsorbed on both sides of the dual-Ti decorated SWCNT with ideal adsorption energy of 0.198 eV/H₂, and the physisorption H₂ on the inside Ti atom has desirable adsorption energy of 0.107 eV/H₂, ideal for efficient reversible storage of hydrogen. The synergistic effect of Ti atoms with different doping patterns enhances the hydrogen adsorption capacity 4.5H₂s/Ti of the Ti-doped SWCNT (VIII), and this awaits experimental trial.     

Bulky rigid substitutions: A route to high electron mobility and high solid-state luminescence efficiency of perylene diimide

In this paper, we report that a kind of perylene diimide derivative with bulky rigid substituents, 1,7-bis(p-tert-butylphenoxy)-N,N′-dicyclohexyl-perylene-3,4,9,10-tetracarboxylic diimide (TBPCHPDI) possesses both high electron mobility (1.8 cm² V⁻¹s⁻¹) and high fluorescence quantum yield (0.32) in the solid state. Through X-ray diffraction (XRD), UV–Vis absorption and fluorescence spectra, and differential scanning calorimetry (DSC) measurements, it is demonstrated that the above phenomenon can be ascribed to the unique crystal structure of TBPCHPDI: due to steric hindrance of bulky rigid substituents, the intermolecular π–π actions are neglectable, providing high luminescence efficiency; in the mean time, the spacing between perylene chromophores is still very short (3.47 Å), which is favorable for the hopping transportation of charge carrier from one molecule to neighboring molecule. Therefore, our finding would help design and synthesize novel organic semiconductive materials with potential applications in electrically pumped lasers which require high emission efficiency when large current density is applied.     

超支化镍系催化剂构效关系及催化乙烯齐聚机理

采用1.0G超支化大分子（1.0G）、3-取代水杨醛和NiCl₂·6H₂O为原料,依次经席夫碱反应和络合反应合成了3种新型具有不同取代基位阻的超支化水杨醛亚胺配体及其镍系催化剂,利用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）、紫外光谱（UV-vis）、电喷雾质谱（ESI-MS）及电感耦合等离子体质谱（ICP-MS）等方法对合成出产物的结构进行表征。考察了配体空间位阻、溶剂种类、助催化剂种类及反应条件对催化乙烯齐聚性能的影响。研究结果表明,配体空间位阻对催化乙烯齐聚性能有较大的影响,当以甲苯为溶剂、甲基铝氧烷（MAO）为助催化剂,在最佳反应条件下,超支化邻苯基水杨醛亚胺镍系催化剂催化乙烯齐聚的活性为2.81×10⁵g/(mol Ni·h),对高碳烯烃（C₁₀₊）的选择性为34.28%。此外,在超支化水杨醛亚胺镍系催化剂催化性能评价的基础上,对其催化乙烯齐聚的机理进行研究。     

亲和膜配基的结构和密度对胆红素吸附的影响

体内存在过量的胆红素会引起神经系统疾病,严重时危及生命,常用循环吸附法去除,但是多数胆红素与白蛋白形成复合物,难于拆分,导致血清胆红素的吸附去除率降低。以醋酸纤维素/聚乙烯基亚胺共混亲和膜(CA/PEI膜)为基质,通过戊二醛活化,引入间隔臂,固载具有一定特异性吸附的5种有机胺和8种氨基酸配基,强化血清胆红素的去除效果。研究结果表明,虽然改性膜的伯胺基含量仅为CA/PEI膜的1/3,但是因间隔臂的引入和配基特异性的增强,4种改性膜的胆红素吸附量提高了100%以上,并且提高了胆红素相对于蛋白的吸附选择性。增加胺基和疏水结构有利于胆红素的吸附;羧基不利于胆红素吸附;胆红素吸附还受到配基密度和空间位阻等诸多因素的影响。苯环等空间位阻较大的配基,不利于实际胆红素的吸附,且无法通过提高配基密度而提高其改性膜的胆红素吸附量,而含直链胺配基的己二胺(3-HMD)改性膜的胆红素吸附量随配基密度的提高而提高。     

位阻胺超重力脱硫技术评述

针对高含硫天然气的脱硫,介绍了位阻胺脱硫技术和超重力技术。将二者结合形成的位阻胺超重力脱硫技术,可以优化操作指标,降低建设投资,减少设备腐蚀,提高脱硫效率,具有良好的应用前景。     

Work stressors, role-based performance, and the moderating influence of organizational support.

As a test of the 2-dimensional model of work stressors, the present study proposed differential relationships between challenge stressors and hindrance stressors and role-based performance, which were expected to be moderated by organizational support. In a sample of 215 employees across 61 offices of a state agency, the authors obtained a positive relationship between challenge stressors and role-based performance and a negative relationship between hindrance stressors and role-based performance. In addition, organizational support moderated the relationship between challenge stressors and role-based performance but did not moderate the relationship between hindrance stressors and role-based performance. This suggests that organizations would benefit from increasing challenges in the workplace as long as they are supportive of employees and removing hindrances. Further implications for organizational theory and practice are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Tailoring of chiroptical properties of substituted polyanilines by controlling steric hindrance

Optically active polyorthoanisidine, polyorthotoluidine, polyorthoethylaniline and polyorthochloroaniline were synthesized with chemical polymerization of corresponding monomers in aqueous medium by using d- or l-camphorsulfonic acid (d- or l-CSA) as chiral dopant, ammonium persulfate as oxidant, and diaminodiphenylamine as initiator. By circular dichroism spectroscopic measurements, it was found that PANI exhibited generally a reversed chirality in comparison with the used chiral dopant, but the substituted PANIs had the same one as the chiral dopant. This revealed that the substituent at ortho position caused helical inversion of conformation in comparison with the parent PANI. Such effect was further confirmed by the influence of the copolymerization of aniline and its derivatives on the chirality of the copolymers. The effect of the substituent on the chirality of the copolymers was increased with the increase of the steric hindrance of the ortho substituent. A mechanism was proposed to explain the effects of steric hindrance on the chirality of PANIs. The clarified relationship between the steric hindrance and the chirality of the polymer can enable us to tailor the chiroptical properties of functional polymer materials for future application.     

新型阻燃增塑剂DCRP的合成及测试

催化条件下合成阻燃增塑剂 ＤＣＲＰ，确定了最佳工艺条件。