Brnsted酸性离子液体催化醛(酮)与二元醇的缩合反应

研究了以Bro¨nsted酸性离子液体1-正丁基-3-甲基咪唑磷酸二氢盐(BMImH2PO4)为催化剂,在不使用其它有机溶剂且无需脱水的条件下,于室温下进行醛(酮)与二元醇的缩合反应,得到了由中至高的转化率和高选择性.产物1,3-二口恶戊烷可以和反应物自动分层,后处理操作简单.过量的醇与离子液体可以多次重复使用,且醛(酮)的转化率无明显降低.     

Spectrophotometric determination of thorium in food using 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid

A new highly sensitive and selective chromogenic reagent, 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid (1), was synthesized and applied to the spectrophotometric determination of trace thorium. In 5 mL of a 6 M perchloric acid medium, which greatly increases the selectivity, thorium reacts with 1 to form a 1: 2 green complex, having a sensitive absorption peak at 670 nm. Under optimal conditions, Beer’s law is obeyed over the range from 0 to 0.8 μg/mL Th(IV) and the apparent molar absorptivity is 2.09 × 10⁵ L/mol cm. It is found that, uranium(VI), Ti(IV), heavy rare earths, and most of other common metal ions do not interfere. The method has been tested on the determination of thorium in food samples with satisfactory results. The text was submitted by the authors in English.     

GC-MS监测生活饮用水输配水管材及防护材料中溶出的挥发性有机物

我国的生活饮用水行业中,目前常使用的管材分为金属类管材和非金属类管材两种。由于金属类管材本身的化学特性,行业内必须在此类管材的内壁上进行防腐处理,通常采用一些高分子防腐涂料。可用于给水行业的涂料品种繁多,涂料质量好坏直接影响到水质。我们针对一些常用产品作了浸泡试验,用吹扫捕集-GC-MS方法对水中溶出的可挥发性有机物进行了检测,发现一些产品在水中溶出了大量的甲苯、乙苯、二甲苯、甲乙苯等苯系物,且浸泡30d后仍有溶出物。这些物质长期存在会导致人体中枢神经系统紊乱,严重危害人体健康。行业内关于水源水中此类有机物污染的监测比较充分,而对于防护涂料可能污染水质的状况并未引起足够重视。     

Electrochemistry of metallofullerene films: the major isomer of Dy@C82

Solution-cast films of the major isomer of Dy@C(82) (Dy@C(82)(I)) have been studied by cyclic voltammetry (CV) in acetonitrile. The films are found to display pronounced and stable redox responses in solution. The reduction/reoxidation processes exhibit large splittings between the first two reduction and reoxidation waves. However, a pair of reversible oxidation and rereduction waves is observed after the reoxidation of a reduced film. The characteristics and the inter-relationship of these waves are uncovered by the CV technique, scanning electron microscopy (SEM), and UV/Vis-NIR spectra. A possible mechanism is proposed for the film electrode processes, which emphasizes the redox-induced structural reorganization of the metallofullerene film by the incorporation and expulsion of electrolyte ions into and out of the film. The influence of the counter ion diffusivity and the ion-pair stability on the electrochemical activity of the metallofullerene film has also been indicated.     

1,4-双(9-O-奎宁)-2,3-二氮杂萘-OsO4催化烯烃的不对称氨羟化反应

在氧化-供氮试剂N-氯代氨基甲酸苄酯存在下,1,4-双(9-O-奎宁)-2,3-二氮杂萘-OsO4催化剂在5种烯烃的不对称氨羟化反应中表现出极高的对映选择性(85%～99%e.e.)和区域选择性,产率48%～68%.     

Synthesis and Magnetic Properties of Binuclear Mn（Ⅱ）Complexes with Alkoxide Bridge

ＳｙｎｔｈｅｓｉｓａｎｄＭａｇｎｅｔｉｃＰｒｏｐｅｒｔｉｅｓｏｆＢｉｎｕｃｌｅａｒＭｎ（Ⅱ）ＣｏｍｐｌｅｘｅｓｗｉｔｈＡｌｋｏｘｉｄｅＢｒｉｄｇｅＹａｎＳｈｉ－ｐｉｎｇ；ＦａｎＢｏ；ＬｉａｏＤａｉ－ｚｈｅｎｇ；ＪｉａｎｇＺｏｎｇ－ｈｕｉａｎｄＷａｎｇ...     

SHAPE MEMORY EFFECT OF PU IONOMERS WITH IONIC GROUPS ON HARD-SEGMENTS

SMPU （shape memory polyurethane） non-ionomers and ionomers, synthesized with poly（c-caprolactone） （PCL）, 4, 4＇-diphenylmethane diisocyanate （MDI）, 1,4-butanediol （BDO）, dimethylolpropionic acid （DMPA） were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content.     

LiCl—HOAc和LiCl—HOAc—H2O体系（25℃）相图

测定了LiCl-HOAc和LiCl-HOAc-H_2O体系25℃时的溶度,绘制了溶度图.在LiCl-HOAc体系的相图中有LiCl及LiCl·1/2HOAc2种固相,后者是固液异成分化合物,体系中未发现LiCl·5HOAc或LiCL·HOAc的生成.LiCl-HOAc-H_2O体系25℃时的相图中有3种固相,即LiCl·H_2O、LiCl和LiCl·(1/2)HOAc.相变LiCl·H_2O→LiCl→LiCl·(1/2)HOAc表明HOAc在该三元体系中具有盐溶、脱水和溶剂合3种作用.此结果提供了一种制备无水LiCl的新方法.     

Quantitative determination of glucose in blood plasma by homonuclear proton decoupled water attenuation transverse relaxation Carr-Purcell-Meiboom-Gill (WATR-HDCPMG) NMR spectroscopy

Glucose in 5% D₂O/95% H₂O solution was successfully determined quantitatively by measurements of the ¹H NMR peak height (intensity) of the single peaks at δ(¹H) = 5.22 and 4.64 ppm corresponding to the α-D and the β-D-glucose spectrum, respectively. The single peaks were obtained from decoupling of the high field part of the AX spectrum of the α-D- or the β-D-glucose by incorporation of time shared homonuclear decoupling in the WATR-CPMG method (WATR-HDCPMG) without re-attenuation of the water peak. The method was applied to the determination of total glucose in blood plasma from human subjects undergoing oral glucose tolerance test (OGTT) in the teaching hospital. The results compared favorably with those obtained from the standard glucose oxidase method obtained in a hospital pathology laboratory. The accuracy of the results obtained using the WATR-HDCPMG method was within 3.5% of the glucose oxidation method.     

Novel preparation of organic polymer-based monolithic column by microwave irradation

Microwave irradiation was firstly attempted for the preparation of organic-based monoliths of poly（styrene-divinylbenzene- methacrylic acid）, which single step in situ polymerization was carried out during 15 min. The colunm permeability, electrophoretic and chromatographac behaviors were comparatively evaluated using pressure-assisted CEC, GEC and low pressure-driven separation modes. The largest theoretical plates for the preparing column could be close to 18,0000 plates/m for thiourea in the mode of p-CEC. It provided a viable alternative to traditional initiation means for the perparation of monolithic capillary columns.