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31.
A chemically bonded cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase (CSP) was prepared by a radical polymerization reaction. The prepared CSP was packed into fused-silica capillaries with inner diameter of 75 microm to perform enantiomer separations in CEC. The electrochromatographic behavior of the CSP was investigated. On the prepared CSP, high EOF could be generated under acidic mobile phases, which represented an advantage for the separation of acidic enantiomers. Several neutral, acidic, and basic enantiomers were resolved on the prepared CSP under aqueous mobile phases. The column efficiencies were between 20,000 and 100,000 plates/m, which were much higher than those of HPLC. In addition, it was observed that the separation of some enantiomers benefited from the adoption of THF as mobile phase modifier. 相似文献
32.
Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C1 and C18 alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (Ds) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C1 and C18 ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate Ds values under various RPLC conditions. The Ds values can be estimated with a mean square deviation of about 25–30%. The agreement between the Ds values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C1 and C18 ligands and that the contribution of each ligand is proportional to the ligand density. 相似文献
33.
采用密度泛函理论方法,在TZ2P-STO基组水平下,对金属四重键化合物M2Cl4(PMe3)4(M=Cr,Mo,W)和Mo2X4(PMe3)4(X=F,Cl,Br,I)的几何结构进行优化,分析了电子结构,并运用TDDFT方法对其低占据激发态进行了计算.考虑相对论效应的ZORA方法能够较好地重现M2X4(PMe3)4的几何结构.M2X4(PMe3)4的电子结构分析表明其d电子的组态为σ^2π^4δ^2,前线轨道能级顺序为πlig〈πd/σd〈δd〈δd^*.金属原子和卤素配体的改变虽然使轨道能量发生变化,但没有影响轨道的排布顺序.TDDFT方法对M2Xa(PMe3)4δd→δd^*和π→δd^*跃迁能量的计算较为准确,对πlig→δd^*(LMCT)跃迁能量的计算误差较大.金属原子、卤素配体以及相对论效应对激发能的影响可以根据分子轨道能级的变化给予解释. 相似文献
34.
Junyong Wu Jingchang Zhang Zhaoxu Wang Weiliang Cao 《International journal of quantum chemistry》2007,107(9):1897-1906
By counterpoise‐corrected optimization method, the interactions of BrCl with the first‐row hydrides (HF, H2O, NH3) have been investigated at the MP2/6–311++G(3d,3p) level. To understand that the X? Br‐type (X = F, O, N) structure is more stable than the corresponding hydrogen‐bonded structure in these complexes, the electronic properties were also investigated. Symmetry‐adapted perturbation theory (SAPT) analysis has been carried out to understand the nature of the weak hydrogen bond and X? Br‐type interactions. On the other hand, for the weak hydrogen‐bonded complexes and the X? Br‐type complexes charges transfer is well correlated with the total induction energies. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
35.
通过控制新集料掺加比例、泡沫沥青用量、水泥剂量、集料温度和抗剥落剂等,研究各因素对冷再生泡沫沥青混合料的路用性能和水稳定的影响,并揭示其微观机理.结果表明,旧料利用率、泡沫沥青用量、水泥剂量和抗剥落剂宜分别控制在50%~75%、 2.5%~3.0%、 1.0%~1.5%和0.5%左右.此外,适当提高集料温度,有助于提高泡沫沥青分散均匀性,从而提升冷再生泡沫沥青混合料的水稳定性.泡沫沥青用量和水泥剂量是冷再生泡沫沥青混合料水稳定的关键因素.尽量使泡沫沥青分散均匀,避免产生结团现象,是保证冷再生泡沫沥青混合料水稳定性的基础,进一步通过水泥补强作用,可获得良好的水稳定性. 相似文献
36.
采用套管法(PET)制备Bi系高温超导带材,进行了冷压工艺的优化研究。试验结果表明,Bi系带材所能承受的压力有一个限值,若超过这个限值后,密度虽可提高,但晶粒破碎严重Jc值反而降低,带材优化的冷压工艺参数是838℃/60h+冷压+838℃/60h。第1次压力为2GPa,第2次2.5GPa;冷压压下速率为1.5×10^-4mm/s。同时研究还表明冷压的主要作用是提高带材的致密度和晶粒取向度,最终改善 相似文献
37.
The catalase (fromAspergillus niger) has been immobilized by a chemical method on the pous SiO2 modified with γ-aminopropyltrietoxysilane, followed with glutaraldehyde and by a physical method in alginate and γ-carrageenan
gel. Optimum support:enzyme ratios and pH values were determined for modified SiO2 in a series of immobilization reactions of catalase in the presence of the crosslinking agent glutaraldehyde, and for alginate
and γ-carrageenan in the presence of hemoglobin and bovine serum albimine. pH and temperaturedependent activity variations
and the stability properties of immobilized catalase preparations were investigated. Rate constants for H2O2 decomposition and catalase deactivation were determined. The decomposition rate of H2O2 used in the cold pasteurizatioan of milk were investigated in a discontinuous batch type reactor system. Activity half-lives
of immobilized catalase were determined. 相似文献
38.
Alessandro D'Aprano Ines Dorina Donato Vincenzo Turco Liveri 《Journal of solution chemistry》1989,18(8):785-793
Static dielectric constants, refractive indices and viscosities of 1-pentanol +2-methyl-2-butanol mixtures were measured at 5, 25 and 45°C. The results show that the mixing of the two isomers modifies the polarizability and the resistence of viscous flow of the system depending on the composition and temperature. Short range intermolecular interactions producing hetero-alcohol open dimers are considered. 相似文献
39.
40.
反相键合相高效液相色谱法分离测定萘普生 总被引:1,自引:0,他引:1
建立了分离测定萘普生和溴代萘普生的反相键合相高效液相色谱法。采用ODS柱,以添加50mmol/L乳酸并用高氯酸调节pH为2.5的80%甲醇-水溶液作为流动相,以苯甲酸为内标物,测定了不对称合成工艺产物中萘普生和溴代萘普生的含量。方法的准确度分别为99.83%~102.07%(萘普生)和99.0%~100.83%(溴代萘普生),相对标准偏差分别小于2.58%(萘普生)和3.64%(溴代萘普生)。方法可用于工艺条件的选择和质量检测。 相似文献