轻希土硫氰酸盐与2,3,11,12,-四苯基-1,4,7,10,13,16-六氧-2,11-十八环二烯配合物的合成及XPS研究

合成了六种轻希土硫氰酸盐与标题不饱和冠醚的新固体配合物,进行了元素分析,摩尔电导率、DTA、UV、IR和XPS等表征。对Ln(NCS)_3·L和Ln(NCS)_3的XPS研究中,得到它们组成原子芯能级电子(Ln3d_(5/2),Ols,Nls,S2p)的结合能信息;观察到除Y3d_(5/2)外Ln3d_(5/2)(Ln=La、Ce、Pr、Nd、和Sm)的伴峰结构,Ln3d_(5/2)结合能与原子序数呈线性关系,并推断类似化合物Pm3d_(5/2)结合能在1035eV附近.     

聚合物-Ni(II)膜电极的研究

Ni(Ⅱ)离子可与聚8羟基喹啉、聚邻氨基酚、聚邻苯二胺和聚苯胺络合。聚合物-Ni(Ⅱ)膜电极的循环伏安图有明显的氧化还原蜂, 和彼此相似的电化学特性。聚8羟基喹啉膜(聚邻氨基酚, 聚邻苯二胺)可用以交换Ni(Ⅱ)与H~+离子和分离Ni(Ⅱ)、Co(Ⅱ)和Fe(Ⅱ)离子。     

铜（Ⅱ）－4－（吡啶－2′－甲基）－1，4，7，10－四氮杂环十三烷－11，13－二酮－α－氨基酸（5－取代邻菲罗啉）三元配合物的稳定性研究

用ｐＨ法在２５．０±０．１℃，Ｉ＝０．１ｍｏｌ·ｄｍ－３ＫＮＯ３条件下，测定铜（Ⅱ）－４－（吡啶－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮－α－氨基酸（５－取代邻菲罗啉）三元配合物的稳定常数；比较了带吡啶甲基二氧四胺大环配体和二氧四胺大环配体与Ｃｕ（Ⅱ）的配位能力、配位方式；研究了该三元体系配合物稳定性与配体α－氨基酸酸碱强度之间的直线自由能关系；探讨了Ｃｕ（Ⅱ）和５－取代邻菲罗啉之间的ｄ－ｐ反馈π键以及邻菲罗啉取代基Ｈａｍｍｅｔｔ诱导效应与该三元配合物稳定性之间的关系。讨论了４－（吡啶－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮和４－（喹啉－２′－甲基）－１，４，７，１０－四氮杂环十三烷－１１，１３－二酮与Ｃｕｘｐｈｅｎ所形成配合物的不同空间结构及其对配合物稳定性产生的影响。     

Crystal Structure and Molecular Absolute Configuration of （＋）－Isocedranol （C_（15）H_（26）O）

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅａｎｄＭｏｌｅｃｕｌａｒＡｂｓｏｌｕｔｅＣｏｎｆｉｇｕｒａｔｉｏｎｏｆ（＋）－Ｉｓｏｃｅｄｒａｎｏｌ（Ｃ_（１５）Ｈ_（２６）Ｏ）￥ＬｉｕＪｉｅ；ＣｈｅｎＭｉｎ－Ｑｉｎ（ＣｅｎｔｅｒｏｆＡｎａｌｙｓｉｓ＆Ｍｅａｓｕｒｅｍ...     

3，19－二羟基－1－硫杂－5，8，11，14，17－五氧杂环二十烷的醚化与缩聚反应

３，１９－二羟基－１－硫杂－５，８，１１，１４，１７－五氧杂环二十烷（简称二羟基硫杂２０－冠－６）在一缩二乙二醇二甲醚和氢化钠存在下可与卤代烷顺利地进行醚化反应，得到双己氧基、双十二烷氧基、双十六烷氧基、双节氧基和双烯丙氧基硫杂２０－冠－６，同时也得到了单己氧基、单十二烷氧基、单十六烷氧基和单辛氧基单羟基疏杂２０－冠－６副产物。二羟基硫杂冠醚可顺利地与丁二酰氯缩聚，得到主链含硫杂冠醚基团的聚酯     

自由基链式亲核取代反应(S_(RN)1)的进展

本文评述了自由基链式亲核取代反应的最近进展。内容包括:脂肪族化合物和芳香族化合物按S_(RN)l进行的反应及其机理。     

Modified modeling of the effect of pH and viscosity on the mass transfer in hydrophobic hollow fiber membrane contactors

This paper studied the effect of pH and the viscosity of feed solution on the mass transfer in two different specifications of hydrophobic hollow fiber membrane contactors. Experimental results showed that the pH of the feed had a significant effect on the rate of mass transfer, the flux and the removal efficiency of easily ionized volatile compounds (VCs), such as ammonia. In unbuffered feed solutions, both the resistance of membrane and the resistance of feed side were affected by the pH of feed and both of them had contributions to the overall mass transfer. A model, , was proposed to predict the effect of pH and gave good agreement with the experimental data for the two contactors. The relationship between viscosities and the mass transfer coefficient could be described by . Based on our experiments, the change of the viscosities in the concentration range of ammonia from 50 to 10,000 mg l⁻¹ caused about 3–4% variation of the mass transfer coefficients. Moreover, it may be more suitable to use the equilibrium concentrations of volatile species instead of the total concentrations of VCs to estimate mass transfer coefficients, removal efficiency and flux. Experimental results also revealed that the choice of the pH of feed might be one of the most crucial factors for removing easily ionized VCs, such as ammonia, from water and wastewater.     

Characterization of low molecular weight components of [(ViMe2SiO1/2)x(PhSiO3/2)y(SiO4/2)z], [(ViMe2SiO1/2)x(SiO4/2)y], and [(SiO4/2)x(HO1/2)y(tBuO1/2)z] silsesquioxanes by electrospray ionization fourier transform mass spectrometry (ESI-FTMS)

This paper describes the characterization of low molecular weight components of four materials using electrospray ionization Fourier transform mass spectrometry (ESI-FTMS). The materials in the current study are [(ViMe₂SiO_1/2)_x(PhSiO_3/2)_y(SiO_4/2)_z] (MTQ), [(ViMe₂SiO_1/2)_x(SiO_4/2)_y] (MQ), and [(SiO_4/2)_x(HO_1/2)_y(^tBuO_1/2)_z] (Q) silsesquioxanes. Accurate mass measurements coupled with knowledge of resin chemistry afforded siloxane composition determination that was used to propose specific structures for the oligomers. Branched or linear (T_nQ_mM_n+2m+2), and monocyclic (T_nQ_mM_n+2m) structures are predominant structures for the low molecular weight species in MTQ. For MQ and Q, more condensed structures, such as partially opened cage structures (Q_mM_2m?6 and Q_mM_2m?8), were identified. The differences between MQ, Q, and MTQ are likely attributed to differences in intrinsic structure and reactivity of T and Q building blocks. The structural information obtained for these oligomeric species will ultimately provide a better understanding of new resin materials and their associated physical properties.     

Effects of matrix-assisted laser desorption/ionization experimental conditions on quantitative compositional analysis of ethylene oxide/propylene oxide copolymers

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has the potential to become a valuable tool for the compositional analysis of copolymers. For a copolymer composed of structurally very similar building blocks with minor chain length changes, one would expect the relative peak intensities observed in the MALDI mass spectra to reflect its composition, at least within a narrow mass range. However, we show that variations in experimental conditions in MALDI can have a significant effect on the mass spectral appearance of a copolymer. The effects of concentration, laser power, type of matrices and solvents on mass spectra of an ethylene oxide/propylene oxide copolymer are illustrated. These somewhat surprising results show that great care needs to be exercised when interpreting copolymer spectra for compositional analysis, even for copolymers with structurally similar monomers. This work also points out that further studies are needed to better understand and optimize spectral acquisition conditions for reliable copolymer compositional analysis by MALDI.