1-芳基-2-丙酮的合成研究

以芳香胺为原料, 经重氮化和改进的Meerwein芳基取代反应, 合成了一系列的1-芳基-2-丙酮, 其中1-(3,5-二三氟甲基苯基)-2-丙酮是一个新化合物. 改进后的方法简化了合成步骤, 提高了收率, 可方便地用于在苯环上具有不同取代基的芳基丙酮的合成.     

腰果酚的紫外光固化机理和固化膜性能

研究了腰果酚在无光引发剂条件下的紫外光固化反应,并用IR、UV、元素分析、GPC等分析手段分析了腰果酚的紫外光固化机理及其固化膜性能。结果表明:在紫外光辐照下,腰果酚通过侧链发生氧化聚合反应,和酚羟基的邻对位失去质子形成的自由基引起的苯环缩合反应,最终形成体型高聚物。腰果酚的紫外光固化膜的常规物理机械性能、抗溶剂性、耐化学介质腐蚀性、热稳定性和抗紫外线性能均优于腰果酚醛缩聚物(PC)涂膜。     

Enantioselective Addition of Phenylacetylene to Aldehydes Catalyzed by Polymer-Supported Sulfonamide

Enantioselective formation of C-C bonds is an area of intense research. Among them, the asymmetric addition of alkynyl reagents to aldehydes is very useful for the synthesis of chiral secondary propargyl alcohols.[1] Recently, many significant homogeneous chiral ligands have been disclosed,[2,3] but very few efficient heterogeneous catalysts have been reported. Herein, we report our research results in the asymmetric addition of phenylacetylene to aldehydes catalyzed by polymer-supported chiral sulfonamide.     

Theoretical Study on the Antioxidant Activity of Curcumin

The computational results for curcumin at the B3LYP/6-31G(d,p) level show that the enol form of curcumin is more stable than the diketo form because of an intramolecular hydrogen bond, which extends the conjugation effect in the enol chain, formed in the enol structure. Cis-diketone form can not be obtained, presumably due to the strong repulsion between the carbonyl dipoles aligned in parallel. According to the phenolic O-H bond dissociation enthalpy, curcumin in its most stable form can be suggested to be a relatively good antioxidant. In order to avoid overcoming H-bond interaction and to improve the antioxidant activity of curcumin, a catechol moiety was incorporated into curcumin for designing a novel antioxidant. It is found that the designed molecule is much more efficient to scavenge radical than curcumin, comparable to vitamin E. Moreover, the ionization potential of the designed molecule is similar to that of curcumin, indicating that the designed molecule can not display the prooxidant effect.     

PRODUCTION OF LIGHTOLEFINS FROM CO_2 HYDROGENATION OVER Fe/SILICALITE-2 CATALYST Ⅱ. PROMOTION EFFECT OF MnO PROMOTER

IntroductionItilasbeenshot'-nthattileadditionofMnOpromotertoFocatal}stcanresultinaremarkableimprovementinthesclectivit}'to11ghtalkenesforCOh}!drogenationll'l.Ho-c'cvcr.thecadetofMnOonCH4formationandCOconversionisvery'ambigUouslltolMoreover.MnOpromotergrca…     

含侧链手性噁唑硼烷催化还原苯乙酮对映选择性的理论研究

用AMI方法研究了含侧链手性恶唑硼烷催化苯乙酮还原反应的对映选择性机理 及其取代基和构型对对映选择性的影响。计算结果表明，含侧链手性恶唑硼烷催化 还原苯乙酮的反应机理与Corey等人提出的机理相符合，在此类硼催化剂的作用下 ，苯乙酮还原产物的绝对构型以R型为主。当恶唑硼烷环N(3)，B(2)上无取代基时 ，C(4)，C(5)位的取代基及其构型是不对称催化反应对映选择性的主要影响因素。     

凝胶渗透色谱法测定聚丙烯腈共聚物分子量中宽分布校正法的应用

应用宽分布校正法对凝胶渗透色谱(GPC)进行了校正，将校正曲线用于聚丙烯腈(PAN)共聚物分子量的计算。对扣除色谱峰扩展效应前后的测试结果与乌氏粘度法测得的数据进行比较。结果表明，应用宽分布校正法时，必须扣除色谱峰扩展效应，才能得到较为准确的测试结果。     

Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes

The potential energy surfaces for the butoxy radical dissociation into R·＋O on the six low-lying electronic states have been determined with the combined CASSCF and MR-CI methods. The isomerization reactions between the different conformers of 1- and 2-butoxy radicals at the X and B states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non-radiative decay mechanisms of butoxy radicals at the B state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t-butoxy radical would predissociate via the B/C intersection. As to 1- and 2-butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the B state are much lower than those of the B/C intersections, resulting in the predominance of the isomerization in the decay of the B state for 1- and 2-butoxy radicals.     

The solid state reactions of o-aminobenzoic acid with Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Mn(Ⅱ) acetate hydrate at room temperature

The solid-solid state reactions of o-aminobenzoic acid with Zn(OAc)2.2H2O, Cu(OAc)2 .H2O, Ni(OAc)2.4H2O and Mn(OAc)2.4H2O result in the formation of corresponding complexes M(OAB)2 (M = Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Mn(IⅡ)). XRD, IR and elemental analysis methods have been used to characterize the solid products. The activation energies of these reactions, which are calculated from the kinetic data obtained by means of the isothermal electrical conductivity measurement method, have been found to increase in the order: Cu(OAc)2.H2O(37.7 kJ.mol-1)~Mn(OAc)2.4H2O (39.7kJ.mol-1) < Zn(OAc)2.2H2O (56.3 kJ.mol-1) < Ni(OAc)2.4H2O (85.2 kJ.mol-1). The trend is related to their crystal structures.     

Amperometric Biosensor for Hydrogen Peroxide Based on Electrodeposited Sub-micrometer Gold Modified Glassy Carbon Electrode

IntroductionAmperometricbiosensorofhydrogenperoxideisofpracticalimportancebecauseofitswideapplicationsinchemical,biological,clinical,environmentalandmanyotherfields.Forimprovementofsensor抯quality,vari-ouskindsofchemicalmodificationmethodshavebeendevelopedforreducingredoxoverpotentialsofH2O2atelectrodesurfaces,increasingthedetectionsensitivity,linearrange,stabilityandlivetime.Ithasbeenshownthattheuseofsub-micrometersizedmetalparticlessuchasPt-blackcansignificantlyimprovethequalityofthebiosens…