消除夹带溶胀的新液膜操作法

消除夹带溶胀的新液膜操作法曹汉瑾，褚莹，何彦涛，吴子生，严忠（东北师范大学化学系长春１３００２４）关键词液膜，油／水乳液，溶胀，夹带，包裹消除液膜操作中的夹带溶胀对液膜的工业化具有重要意义，夹带溶胀分为包裹溶胀和再液化溶胀。前者是乳状液滴上浮时将水相...     

溶剂浓度对PVDF相转换膜大孔结构的影响

提出决定大孔能否发展的初始分相点处溶剂浓度临界点的概念 ,认为初始分相点处较高的溶剂浓度有利于大孔的发展 ,溶剂浓度低于一定的界限后 ,大孔停止发展 ,转为海绵状结构 .实验考察了不同凝胶液组成下制得的PVDF中空膜的结构 ,建立了相应的传质模型 ,模拟不同制膜条件下初生态膜内的组成分布情况 ,根据初始分相点处溶剂浓度临界点的概念 ,预测膜的形态结构 .模拟结果与相应制膜条件下的电镜照片有很好的对应关系 ,证明了上述大孔形成机理的正确性 .     

MORPHOLOGIES AND GAS SEPARATION PROPERTIES OF MELT-SPUN ASYMMETRIC POLY(4-METHYL-1-PENTENE)HOLLOW FIBER MEMBRANES*

Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.     

A simple and easy access to 3-N-alkyl-5-vinyloxazolidinones mediated by palladium-phosphine catalysts

A new entry for the synthesis of 3-alkyl substituted 5-vinyloxazolidin-2-one derivatives 2 from cis-2-butenylene-1,4-dicarbonate 1 and primary amines mediated by palladium-phosphine catalysts is described. The scope and limitation, a plausible mechanism, and an asymmetric version of the reaction are also discussed.     

水中酚的膜萃取分离流动注射技术测定的研究

本文提出了硅橡胶膜在线萃取分离流动注射技术测定水样中苯酚的方法。由于水样中的苯酚透过硅橡胶进入萃取液的萃取量随时间的增加和温度的升高而增大，故采用停流技术及升高温度以降低酚的检出限。     

Diastereoselective hydroformylation of 2-substituted allylic o-DPPB-esters-on the origin of 1,2-asymmetric induction

2-Substituted secondary alcohol o-DPPB esters (o-DPPB=ortho-diphenylphosphanylbenzoyl) have been prepared and their o-DPPB-directed diastereoselective hydroformylation examined. It was found that the diastereoselectivity increased as a function of the steric demand of the substituents both at the stereogenic center and in the alkene 2-position. Hydrolytic cleavage of the o-DPPB group afforded-via the lactols 29-the corresponding lactones 30, the relative configurations of the vicinal stereogenic centers of which were ascertainable by 2D-NOESY spectroscopy. In addition, a crystal structure analysis of the hydroformylation product 2 d provided further confirmation of the relative configuration. Replacement of the ester carbonyl group of the o-DPPB by a methylene unit resulted in significantly worse diastereoselectivity in the course of the hydroformylation (34-->35), which indicates a decisive role for the ester carbonyl function. All the experimental observations were combined in a model of the origin of the 1,2-asymmetric induction during the title reaction. The key feature is the consideration of diastereomeric trigonal-bipyramidal rhodium-hydrido-olefin complexes I and II, capable on the basis of the Hammond postulate of acting as good models for the transition states of the selectivity-determining hydrometalation step. Investigation of these complexes by force-field methods indicated good correlation between theoretically predicted and experimentally determined diastereoselectivities.     

Asymmetric Synthesis in the Presence of Cyclodextrins

Oxidative couplings of 2-naphthol, 6-bromo-2-naphthol and2-naphthylamine were achieved at room temperature in the presence of H₂O₂, horseradish peroxidase and a suitable cyclodextrin.2-Thionaphthol behaved differently, yielding the corresponding disulfide. Yields of binaphthyl derivatives were generally excellent, and a fairly good enantiomeric excess was observed. Under similar reaction conditions methyl 2-(6-methoxy-2-naphthyl) propanoate, when treated with esterase in the presence of cyclodextrin, yielded naproxen (a well-known anti-inflammatory drug) with a good enantiomeric excess. No reaction product was detected in the absence of cyclodextrin. Cyclodextrins do not act as simple transfer agents.     

Reverse-docking as a computational tool for the study of asymmetric organocatalysis

A novel methodology for 'reverse-docking' a cationic peptide-based organocatalyst to a rigid anionic transition state (TS) model for the conjugate addition of azide to alpha,beta-unsaturated carbonyl substrates is described. The resulting docking poses serve as simplified TS models for enantioselective catalysis. Molecular mechanics-based scoring and ranking of the docking poses, followed by clustering and structural analysis, reveal a clear energetic preference for docking to the S-enantiomeric azidation TS model, in agreement with experiment. Clear energetic trends emerged from docking the catalyst to both enantiomers of all six azidation TS models of this study. Structural analysis of the most favorable pose suggests a mechanism for enantioselective catalysis that is consistent with principles of molecular recognition, catalysis, and experimental data.     

Resolution of seven-coordinate complexes

The crystal structures of [Pr(dbm)3H2O] (1), [Sm(dbm)3H2O] (2), and [Er(dbm)3H2O] (3) have been determined (dbm=dibenzoylmethane). They display seven-coordinate propeller-shaped molecules, which are chiral and crystallize as conglomerates in space group R3. Analysis of the crystal structures reveals supramolecular interactions, including formation of a quadruple helix, which explain how stereochemical information can be transferred between stacks of molecules. A method to quantify the ee in bulk samples of stereochemically labile compounds by using solid-state CD spectroscopy is described. Using this method, it has been shown that compounds 1-3 undergo total spontaneous resolution directly after synthesis, forming a microcrystalline reaction product that is essentially enantiopure. The resolution of bulk quantities of seven-coordinate complexes (without chiral or polydentate ligands) is thus reported for the first time. Because the crystallization starts without seeding, the overall preparation may be regarded as absolute asymmetric synthesis.     

Novel Membrane Potentiometric Thiocyanate Sensor Based on Tribenzyltin(IV) Dithiocarbamate

A novel PVC membrane ion‐selective electrode based on tribenzyltin(IV) dithiocarbamate [Sn(IV)–TBDTB] as neutral carrier was developed for thiocyanate (SCN^?) determination. The electrode exhibits a near‐Nernstian response for SCN^? with a slope of 62.8±2.0 mV per decade over a wide concentration range 1.0×10^?1–2.0×10^?6 mol L^?1 and a detection limit of 1.0×10^?6 mol L^?1 in MES–NaOH buffer, pH 6.0, at 25 °C. The electrode prepared with 1.5 wt.% Sn(IV)–TBDTB, 32.5 wt.% PVC and 66.0 wt.% 2‐nitrophenyloctyl ether (o‐NPOE) shows optimal response characteristics. Anti‐Hofmeister selectivity sequence for a series of anions shown by the electrode was as follows: SCN^?>Sal^?>I^?>ClO >phCOO^?>CH₃COO^?>Br^?>Cl^?>NO >NO >Citrate>SO₄^2?. The useful pH range for the electrode was found to be 3–7 with a response time 30–40 s. The electrode has been used for direct determination of thiocyanate in wastewater with satisfactory results.