烯烃氢甲酰化催化剂活性物种的原位1H NMR研究

The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process.     

以硫醚为主链的螯合树脂研究Ⅰ.4-氨基安替吡啉树脂和乙基原磺酸基树脂的合成及吸附性能

聚环硫氯丙烷或环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联预聚物，将交联预聚物与4－氨基安替吡啉（4AAP）或乙基原磺酸钾（PEA）反应，制得四种侧链带氨基安替吡啉，乙基原碘酸基的新型螯合树脂。它们对贵金属具有优良的吸附性能和高的吸附选择性。并通过X－射线光电子能谱初步探讨了树脂对金属离子的螯合作用。     

CRYSTAL AND MOLECULAR STRUCTURE OF THE COMPLEX OF METHOXYCARBONYLETHYLTIN TRICHLORIDE WITH SALICYLIDENE－M－TOLUIDINE

ＣＲＹＳＴＡＬＡＮＤＭＯＬＥＣＵＬＡＲＳＴＲＵＣＴＵＲＥＯＦＴＨＥＣＯＭＰＬＥＸＯＦＭＥＴＨＯＸＹＣＡＲＢＯＮＹＬＥＴＨＹＬＴＩＮＴＲＩＣＨＬＯＲＩＤＥＷＩＴＨＳＡＬＩＣＹＬＩＤＥＮＥ－Ｍ－ＴＯＬＵＩＤＩＮＥＦａｎｇＸｉｎＦＵ；ＸｉｕＪｕａｎＬＩ；Ｈ...     

The thermal conductivity of alumina nanoparticles dispersed in ethylene glycol

The thermal conductivities of several nanofluids (dispersions of alumina nanoparticles in ethylene glycol) were measured at temperatures ranging from 298 to 411 K using a liquid metal transient hot wire apparatus. Our measurements span the widest range of temperatures that have been investigated to date for any nanofluid. A maximum in the thermal conductivity versus temperature behavior was observed at all mass fractions of nanoparticles, closely following the behavior of the base fluid (ethylene glycol). Our results confirm that additional temperature contributions inherent in Brownian motion models are not necessary to describe the temperature dependence of the thermal conductivity of nanofluids. Our results also show that the effect of mass or volume fraction of nanoparticles on the thermal conductivity of nanofluids can be correlated using the Hamilton and Crosser or Yu and Choi models with one adjustable parameter (the shape factor in the Hamilton and Crosser model, or the ordered liquid layer thickness in the Yu and Choi model).     

Synthesis of four diastereomeric 3,5-dialkoxy-2,4-dimethylalkanals by a simple extension of the non-aldol aldol process to bis(propionates)

[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base.     

高分子固体电解质研究进展

高分子固体电解质具有质轻、粘弹性了、易成膜等许多无机电解质和有机溶剂电解质所不可比拟的优点，近年来得到了很大的发展，这种新型材料的应用主要集中开发全固态锂电池和锂离子电池。本文对ＳＰＥ的电性能，离子传导特性以及提高ＳＰＥ性能的途径等作了综述，并对其发展前景作了简要探讨。     

射频磁控溅射CNx薄膜的结构与衬底温度关系的研究

使用射频磁控溅射方法在不同衬底温度下（ts=室温，350，500℃）于Si(001)衬底上沉积了CNx膜，并利用拉曼（Raman)光谱、傅里叶变换红外光谱（FTIR）及X射线衍射光电子能谱（XPS）对CNx膜的化学结合状态与温度的关系进行了研究。Raman光谱结果表明，随衬底温度（ts) 增加，D带向低频方向移动，G带向高频方向移动；它们的半高宽分别由375和150cm^-1减小至328和142cm^-1；ID／IG由3．76减小至2.88。FTIR谱中除无序D带（1400cm^-1)和石墨G带（1570cm^-1)外，还有－700cm^-1,～2210cm^-1(C=N),2330cm^-1(C-O)及3255－3351cm^-1(N-H)等峰。XPS测试结果表明：随衬底温度增加，N与C的物质的量比由0.49下降至0.38，sp^2(C-N)组分与sp^3(C-N)组分强度比呈增大趋势。低温（350℃）退火并未对CNx膜的化学结合状态产生较大影响；高温（900℃）退火样品则显示出较好的结晶化程度。     

Highly effective and recyclable dendritic ligands for the enantioselective aryl transfer reactions to aldehydes

[reaction: see text] A series of chiral pyrrolidinylmethanol-based dendritic ligands were synthesized for application in enantioselective aryl transfer reactions to aldehydes with the (ArBO)3/ZnEt2 system in up to 98% ee.     

Convenient and Efficient Synthesis of L—Rhamnopyranosyl Phosphoramidates via H—Phosphonate

It is known that saccharides linked to proteins via a phosphoester hinge can function as immunological determinants. Under regular physiological conditions, it has been suggested that the role of phosphonate group is to direct the protease towards basic substrates1. Phosphoramidon a, which was isolated from a culture filtrate, is a potent inhibitor of the thermolysin, a metallo-endopeptidase. It is a glycosylated dipeptide, which has a L-rhamnose attached to the N-terminal of Leu-Trp dipep…     

Chemical species produced in the reaction between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline and their iron(II) complexes: preparation and some spectrometric studies

Chemical species obtained by reaction of 5-amino-1, 10-phenanthroline with ethanedial (glyoxal) are reported with regard to their preparation, chemical composition and spectrometric characterization (UV-visible, infrared and liquid secondary ion mass spectrometry). Products of the reaction are postulated to be a mixture of species with molecular weights of 339, 371,480 and 524 u. Chemical reactions leading to these products and possible structural formulas for each of these species are presented. The iron complexes of these ligands, because of their extremely low solubility in most solvents, find application as redox mediators when incorporated in carbon paste electrodes, particularly for sensing in continuous-flow systems.