铜(Ⅰ)配合物[Cu(C8H4O2F3S)(PPh3)2]合成、性质、晶体结构及反应机理的探讨

Reaction of copper powder with 2-thenoyltrifluoroacetone and PPh₃ yielded the complex [Cu(C₈H₄O₂F₃S)(PPh₃)₂], which have been characterized by elemental analysis and IR spectra. The crystal is monoclinic, space group P2₁/n , a=1.0584(1), b=1.6738(1), c=2.2728(9) nm; β =94.22(2); V =4.0152 nm 3; Z=4; D_c=1.299 g·cm^-3; R=0.048, R_W=0.054. Copper (Ⅰ) ion is coordinated by two O and two P atoms forming distorted tetrahedron.     

1''-苯基-3''-甲基-5''-氧代吡唑-4''-基乙醛酸希土配合物的合成及性质研究

本文采用电导、pH滴定法研究了乙醇-水溶液中希土与1′-苯基-3′-甲基-5′-氧代吡唑-4′-基乙醛酸(简称H₂A)的配位反应.合成了15种新的希土固态配合物.通过元素分析、化学分析、水份分析确定了配合物的化学组成为RE(HA)₃·nH₂O(RE=Ce、Pr、Sm、Tm、Lu、n=1;RE=La、Nd、Eu、Gd、Tb、Dy、Ho、Er、Yb、Y,n=1-2).并对配合物的红外光谱、核磁共振谱、热稳定性、紫外光谱、溶解性及摩尔电导进行了测定.     

离聚体的结构表征——Ⅴ.含氟离聚体中离子微区稳定性的研究

本文用DSC方法研究了羟酸型含氟离聚体中不同金属离子种类、可离子化基团含量、配位结构单元构型及离子微区大小对离聚体中离子微区稳定性的影响。实验表明:离聚体中金属离子配位能力愈强,羟酸含量愈高,离子微区尺寸愈大,则相应离聚体中离子微区稳定性愈大。铅高聚体>锌离聚体>钙离聚体>钠离聚体。     

配位聚合载体化催化剂ESR研究进展

本文概述了配位聚合载体化催化剂的ESR研究进展,介绍了载体研究、活性中心研究及计算机模拟技术研究方面的发展概况.     

Use of a chiral surfactant for enantioselective reduction of a ketone

The influence of a chiral surfactant and a polymer-supported chiral additive on reduction of ketones using sodium borohydride will be described. Initial preparations involved methylation of (S)-leucinol to give (2S)-N , N-dimethyl-2-amino-4-methyl-1-pentanol (1) (67%). The chiral surfactant (2) was synthesized by reacting (1) with bromohexadecane (71%). The functionalized styrene for the polymer-supported chiral additive (5) was synthesized by reacting (1) with 4-vinylbenzyl chloride. Polymerization was carried out with 10% of the functionalized monomer (4), 5% cross-linking agent divinylbenzene, and 85% styrene with AIBN as the initiator. The activity of the chiral surfactant and polymeric additive were examined by using them as additives in a standard reduction of 2-pentanone with sodium borohydride to yield (R)- and (S)-2-pentanol (3) (20%). The resulting alcohol was analyzed by polarimetry (ee 9.5%) and also esterified with (2S)-methylbutyric acid prior to characterization by NMR. 13C NMR indicated an enantiomeric excess of 5.2% when the chiral surfactant was used, and 7% when the polymeric additive was used.     

Preparation and characterization of C16 monolithic columns for capillary electrochromatography

A series of methacrylamide-based C16 monolithic columns were prepared and characterized to determine how their porous structural properties and chromatographic behavior are affected by the percentages of functional monomer, base monomer, and cross-linker in the polymerization solution. Baseline separation of 6 neutral compounds can be readily obtained in an optimized column. Furthermore, the effects of organic additive in the mobile phase, operating voltages, and temperature on retention behaviors and separation efficiencies were also studied. The separation mechanism is also discussed. High column efficiency and good reproducibility indicate that the monolithic columns hold considerable promise.     

Diffusion characteristics of a T-type microchannel with different configurations and inlet angles.

A series of symmetrical and asymmetrical microfluidic T-sensors with different inlet angles were fabricated to study the mixing characteristics of a T-type microstructure for generating concentration gradient. Computational fluid dynamics (CFD) simulations showed that the concentration gradient, transition zone and diffusion length were different for various configurations and inlet angles. Quick mix and sharp concentration gradient occurred in the asymmetrical structure with large inlet angle. The observed concentration gradients in the fabricated microchannel were consistent with the theoretical prediction. In this microstructure, stagnant zone and z-direction diffusion also affected the concentration gradient. Based on the simulation results, the microfluidic structure was optimized to generate desired concentration gradient for a cell-based study.     

A vacuum ultraviolet photoionization mass spectrometric study of acetone

The photoionization and dissociative photoionization of acetone have been studied at the photon energy range of 8-20 eV. Photoionization efficiency spectra for ions CH3COCH3+, CH3+, C2H3+, C3H3+, C3H5+, CH(2-)CO+, CH3CO+, C3H4O+, and CH3COCH2+ have been measured. In addition, the energetics of the dissociative photoionization has been examined by ab initio Gaussian-3 (G3) calculations. The computational results are useful in establishing the dissociation channels near the ionization thresholds. With the help of G3 results, the dissociation channels for the formation of the fragment ions CH3CO+, CH2CO+, CH3+, C3H3+, and CH3COCH2+ have been established. The G3 results are in fair to excellent agreement with the experimental data.