Heterogeneous copper‐catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β‐keto sulfones

An efficient and practical route to β‐keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM‐41‐supported Schiff base‐pyridine bidentate copper (II) complex [MCM‐41‐Sb,Py‐Cu (OAc)₂] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β‐keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)₂. MCM‐41‐Sb,Py‐Cu (OAc)₂ is also easy to recover and is recyclable up to eight times with almost consistent activity.     

Kinetic study of the reaction of nucleophilic cyclopropanation of C60 fullerene with halogenated maleopimarimide

The kinetics of nucleophilic fullerene cyclopropanation by halomethyl ketones with a diterpene fragment has been studied by the Bingel method, and the influence of the biologically active cyclopropanating agent on the process has been estimated. It has been revealed that favorable conditions for carrying out the reaction result in maximum monofunctionalized methanofullerenes formation with the maximum yield.     

La2O3对TiAl合金激光熔覆γ/Cr7C3/TiC 复合材料涂层组织与性能的影响

研究了添加不同含量稀土氧化物La2O3对TiAl合金预涂NiCr-Cr3C2混合粉末激光熔覆复合材料涂层组织、耐磨性及抗氧化性能的影响，分析了La2O3的作用机理。结果表明，激光熔覆涂层的组织主要由大量较规则初生块状Cr2C3，细小粒状或树枝状TiC以及γ／Cr2C3共晶组成；随着La2O3的加入，初生相明显细化、球化，共晶组织数量增多，适当的(质量分数4％）La2O3的添加能提高涂层的硬度、韧性和耐磨性，并改善其抗氧化性能。这主要是由于稀土元素对显微组织的细化和涂层的净化作用，显微组织的细化提高了涂层的强度、韧性和硬度，而涂层的净化可以降低其夹杂物的含量，进而提高氧化膜的致密性和附着性，这些都有利于提高其耐磨性和抗氧化性。     

醋酸甲羟孕酮与β-环糊精包络作用的光谱研究及应用

用紫外吸收、荧光光谱法对水溶液中β－环糊精（β－ＣＤ）与醋酸甲羟孕酮（ＭＡ）主客体包络物的光谱行为进行了研究．利用改进的Ｂｅｎｅｓｉ－Ｈｉｌｄｅｂｒａｎｄ法测定了包络物的形成常数，初步探讨了某些水溶性一元醇的引入对该包络物形成及荧光性质的影响，并提出了测定ＭＡ的高灵敏度荧光光度新方法，方法的最低检出限为８．９×１０－９ｍｏｌ·Ｌ－１．用该法测定样品中ＭＡ的结果令人满意，回收率为９７．９％～１０１．７％，平均回收率为９９．９％（ｎ＝５）     

阴-非离子表面活性剂存在下在DMF介质中用镉试剂2B测定银的研究

本文研究了在阴-非离子表面活性剂SDS-TritonX-100存在下,用Cadion 2B分光光度法测定银,发现DMF介质的增溶、增敏、增稳效果均好.配合物的最大吸收波长为560nm,表现摩尔吸光系数为1.23×10~5L·mol~(-1)·cm~(-1),Ag(Ⅰ)在0—18μg/25ml范围内服从比耳定律.该方法操作简便、快速,选择性好,可直接用于废水中微量银的测定,结果满意.     

Cu（Ⅱ）,Fe（Ⅲ）,Co（Ⅱ）含硫Schiff碱配合物的合成与性质

本文合成了四种新配合物:二氯化双苯甲醛缩氮基硫脲合铜(Ⅱ)(Cu~Ⅱ(Betsc—H)_2Cl_2),三氯化水杨醛缩氨基硫脲合铁(Ⅲ)(Fe~Ⅲ(Satsc—H_2)Cl_3,二氯化双对二甲氨基苯甲醛缩氨基硫脲合钴(Ⅱ)(Co~Ⅱ(Dmabtsc—H)_2Cl_2·H_2O)及双对硝基苯甲醛缩氨基硫脲合钴(Ⅱ)醋酸盐(Co~Ⅱ(Nitsc—H)(Nitsc)(Ac))。用元素分析和IR测定了化合物的组成,并进行了吸放O_2和CO的试验。     

添加助剂的钙钛矿型氧化物NdMO_3上的甲烷氧化偶联——Ⅱ.15% Li_2O/NdMO_3(M=Cr、Mn、Fe、Co、Ni)上的OCM反应研究

在添加了15%Li_2O的NdMO_3(M=Cr、Mn、Fe、Co、Ni)上进行了甲烷氧化偶联(OCM)反应研究.通过改变反应气中CH_4:O_2浓度比,在氧化态和“脱氧态”催化剂上的CH_4脉冲反应,探讨了表面吸附氧和晶格氧在OCM反应中的作用以及NdMO_3中不同金属离子(M)对OCM反应活性的影响等.     

自由基C69N及双体(C69N)2结构和电子光谱的理论研究

用INDO系列方法对自由基C₆₉N(Cs)及双体(C₆₉N)₂(C₂h)进行了理论研究,结果表明:笼骨架上N的掺入使C₇₀笼发生畸变,N向笼外突出,与氮相连的碳(6-6环上的C)自旋密度较大,2个C₆₉N自由基在这个碳上以C-C单键连接,形成双体为C₂h对称性,N与附近的3个碳均以单键连接,并不断开。理论计算的电子光谱与实验吻合较好,(C₆₉N)₂易分解为单体C₆₉N.     

An improved method for assay of vitamin C in fish feed and tissues

Summary A method was devised to assay four forms of vitamin C: L-ascorbic acid (AA), dehydroascorbic acid (DHA), ascorbate-2-mono- and polyphosphate (AMP, APP), as well as ascorbate-2-monosulphate (AMS), in sample series of different fish tissues and feed. Direct and indirect detection were combined. Sample extractions were carried out with 0.2 mol L⁻¹ sodium acetate buffer (pH 4.8) and extracts were deproteinized after different chemical or enzymatic reactions, with perchloric acid. The DHA was reduced to AA with dithioerythritol (DTE). Ascorbate oxidase enzyme was used for the detection of background and an acidic phosphatase enzyme for the hydrolysis of different phosphate esters. Ascorbate-2-sulphate was detected directly with help of coinjection of the compound. Chromatographic analysis was carried out with a single column isocratic reverse phase method. The mobile phase was an aqueous buffer of 0.04 M sodium-acetate, 0.05 mM EDTA, 0.5 mM tetrabutylammonium dihydrogen phosphate (TBA) adjusted to pH 3.76 with 85% H₃PO₄ and with 24 mL methanol added to 1000 mL. C-18 columns were used with 0.6 mL min⁻¹ flow rate at 23°C. The vitamin C forms were detected by UV absorption at 250 nm. The determination limit was 1.0–5.0 μg g⁻¹ in AA equivalent. The standard deviations were between 1–6% and depended on the concentrations of vitamin C forms and tissues. Recoveries were between 90–96% in samples. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997