(Li,Ca,A)_2SiO_4:Eu,Bi发光体的合成和发光性能的研究(A=Al,Y,La,Gd)

为了寻找新的发光基质材料,用高温固相反应合成了(Li,Ca,A)_2SiO_4:Eu,Bi系列发光体(A=Al,Y,La,Gd).通过激发光谱和发射光谱的测试.首次在碱土金属硅酸盐体系中研究了Al,Y,La,Gd等三价金属离子对Bi~(3+)、Eu~(3+)发光特性和Bi~(3+)敏化Eu~(3+)发光性能的影响,得到了良好的基质组成.实验结果表明.基质中适当含量的Gd~(3+)可大幅度提高Eu~(3+)的发光强度,使~5D_0-~7F_2发射强度增加6倍.Bi~(3+)对Eu~(3+)有很好的敏化作用,以A=Gd或Al时较好,对~5D_0-~7F_1辐射跃迁的敏化效果尤为突出.     

A WATER-SOLUBLE RUBRENE DERIVATIVE: SYNTHESIS, PROPERTIES AND TRAPPING OF 1O2 IN AQUEOUS SOLUTION

Abstract A rubrene derivative has been synthesized as a new trap for singlet oxygen in aqueous solution. Photooxygenation and evolution of the endoperoxide under various conditions have been investigated. This trap may be used either as a colorimetric test or as a specific one by isolation of the endoperoxide.     

(Li,Ca,A)2SiO4:Eu,Bi发光体的合成和发光性能的研究(A=Al,Y,La,Gd)

为了寻找新的发光基质材料,用高温固相反应合成了(Li,Ca,A)₂SiO₄:Eu,Bi系列发光体(A=Al,Y,La,Gd).通过激发光谱和发射光谱的测试.首次在碱土金属硅酸盐体系中研究了Al,Y,La,Gd等三价金属离子对Bi³⁺、Eu³⁺发光特性和Bi³⁺敏化Eu³⁺发光性能的影响,得到了良好的基质组成.实验结果表明.基质中适当含量的Gd³⁺可大幅度提高Eu³⁺的发光强度,使⁵D₀-⁷F₂发射强度增加6倍.Bi³⁺对Eu³⁺有很好的敏化作用,以A=Gd或Al时较好,对⁵D₀-⁷F₁辐射跃迁的敏化效果尤为突出.     

Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

STUDIES ON PREPARATION OF GAS FOR METHANOL SYNTHESIS BY METHANE REFORMING WITH STEAM AND CO_2 Ⅱ.ACTIVITY AND STABILITY OF SUPPORTED NICKEL CATALYSTS

lntroductionMethanolissynthesizedbyblendgasofCOandH2.FeedstockgasformethanolsynthesismustbeinlinewiththefollowingstoichiometricrelationtR=(H2-Co2)/(Co CO2)52Inaddition,thecontentofCo2shouldbelowerthan8%ll1.MethanereformingwithsteamandCO2canproducethequalifiedsynthesisgasformethanolsynthesisinindustry.ComParedwithtndtionalsteaInrefotheng,thefeedstocksynthsisgasproducedbymethanreformingwithsteamandCO2docsnotneedseparaingandcanbedirectlyusedinmethanolsynthesis.Therefore,thecostofmethanolca…     

STUDIES ON THE REACTION OF SULFUR,SELENIUM AND TELLURIUM WITH SODIUM HYDROXIDE UNDER PHASE TRANSFER CATALYSIS(Ⅱ).A CONVENIENT METHOD FOR THE SYNTHESIS OF BI(ACYL)DISULFIDES

A simple and general method for the synthesis of bi(acyl)disulfides isreported.Sulfur is allowed to react with sodium hydroxide to give sodium disulfideat 65℃ under PTC,which can react with acyl halides to afford bi(acyl)disulfides ingood to excellent isolated yields.The effects of solvents and phase transfercatalysts are discussed.     

芳香胺及其氮氧化物合希土配合物的研究 V.2, 2''—联喹啉—N, N''—二氧化物合硝酸希土固体配合物的合成及其性质

在无水乙醇和氯仿混合溶剂中使重希土硝酸盐与2,2′—联喹啉—N,N′—二氧化物(BiqO_2)作用,制得了固体配合物Ln(BiqO_2)(NO_3)_3·2H_2O(Ln=Tm,Yb,Lu,Y)。通过元素分析、X光粉末衍射物相分析、差热—热重分析、红外光谱、紫外光谱、溶解性及摩尔电导测定,研究了配合物的组成及其有关性质。     

镍基气凝胶催化CH4-CO2重整制取合成气反应的研究Ⅱ.制备方法对Ni/CeO2-Al2O3催化剂反应性能的影响

采用浸渍法、溶胶 凝胶过程与普通干燥、超临界干燥过程相结合的方法制备了三种 82 3K焙烧的NiO CeO2 Al2 O3 体系催化剂 ,分别为浸渍型催化剂 (iNCA5 5 0 )、干凝胶催化剂 (xNCA5 5 0 )和气凝胶催化剂 (aNCA5 5 0 ) ,考察了它们在CH4 CO2 重整反应中的催化性能及反应的稳定性 ,采用TG、TEM、XPS等手段研究了反应前后催化剂的结构性质。研究结果表明 ,在 10 73K、CH4 CO2 =1∶1、180 0 0mL h·g的反应条件下 ,三种催化剂中aNCA5 5 0在CH4 CO2 重整反应过程中的积碳量较大 ,但却具有最好的反应稳定性 ;aNCA5 5 0具有较大积碳量与其表面酸量较大、酸性较强及较大镍分散度有关 ,然而由于它具有较大的积碳容量和很强的金属抗烧结能力 ,因此保持了较好的反应稳定性。催化剂积碳和金属镍烧结导致催化剂表面活性中心数目减少是催化剂失活的主要原因。     

SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMICAL STUDIES OF MONO- AND DINUCLEAR COMPLEXES OF NICKEL(II) AND COBALT(II) WITH HEXADENTATE LIGANDS HAVING N2P4 DONOR ATOMS. CRYSTAL STRUCTURE OF [Ni(BDPE)]ClO4)2. CH2Cl2

Abstract

A series of mono- and dinuclear complexes of Ni(II) and Co(II) with two hexadentate ligands α,α′-bis(bis(2-(diphenylphosphino)ethyl)amino)ethane(BDPE) and α,α′-bis(bis(2-(diphenylphosphino)ethyl)-amino)-m-xylene (BDPX) were synthesized and chracterized by means of elemental analyses, molar conductance, magnetic susceptibilities, infrared, electronic and ³¹P NMR data. The molecular structure of a mononuclear Ni(II) complex, [Ni(BDPE)](CIO₄)₂.CH₂Cl₂, was established by single-crystal X-ray diffraction methods. Crystal data: C₅₉H₆₂NiCl₄N₂O₈P₄, M = 1250.98, orthorhombic, space group Pbca, V= 11834.3(7) Å3, Z= 8, a= 10.817(1), b = 31.683(7), c=34.538(1) Å, final R 0.055 (R w = 0.057) for 3118 observed reflections. The Ni(II) ion exists in a slightly distorted square planar geometry, the coordination sites being two phosphorous and two tertiary nitrogen atoms of the ligand. Electrochemical studies of the complexes were also carried out.     

乙烯系单体自由基聚合的阻聚效应——ⅩⅣ.4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶-1-氧自由基低聚物的合成及对丙烯酸阻聚的研究

研究了数均分子量10~3～5×10~3的聚甲基丙烯酸甲酯的制备及其在甲醇镁存在下和2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基(TMHPO·)间的酯交换反应,合成了聚-4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶-1-氧自由基(PMTMPO·)低聚物。同时观察了4-甲基丙烯酰氧基2,2,6,6-四甲基哌啶的调聚反应,同样制得PMTMPO·低聚物。利用IR、EPR和TGA技术对PMTMPO·进行了表征。评价了PMTMPO·对AIBN引发的丙烯酸(AA)自由基聚合的影响,表明PMTMPO·对AA有良好的阻聚功效。     

STUDIES ON BIPYRIDINIUM SALTS AND THEIR POLYMERS Ⅰ. SYNTHESIS OF 4, 4''-(1, 4-PHENYLENE-)BIS-[N-ALKYL (ARYL)-2, 6-DIPHENYL-] PYRIDINIUM SALTS AND THEIR POLYMERS FROM CORRESPONDING BIPYRYLIUM SALT*

The reaction of pyrylium salt with primary amine has been utilized to synthesize 4,4'-bipyri-dinium salts and pyridinium polymers. Seven new 4,4'-(1,4-phenylene-) bis-[N-alkyl(aryl)-2,6-diphenyl-] pyridinium perchlorates 4 and five corresponding bipyridinium polymers 5 were preparedwith good yields from 4,4'-(1,4-phenylene-) bis-(2,6-diphenyl-) pyrylium perchlorate 3. Preliminarytests have been made for their redox behavior and catalytic activity.     

9, 10-Secocholesta-(5Z)-5,8(14), 10(19)-trien-3β-ol und 18-Nor-14β-methyl-9,10-secocholesta-(5E)-5, 10(19), 13(17)-trien-3β-ol,zwei neue Doppelbindungsisomere des Vitamins D3. Strukturelle Abwandlungen am Vitamin D3: 5. Mitteilung [1]

9,10-Secocholesta-(5 Z )-5,8(14),10(19)-triene-3β-ol and 18-Nor-14β-methyl-9,10-secocholesta-(5 E )-5,10(19), 13(17)-trien-3β-ol, two new double bond isomers of vitamin D₃ . Structural modifications of vitamin D₃: 5. Communication [1] The present paper reports the synthesis and structure elucidation of the two title compounds. Treatment of the 4-phenyl-1,2,4-triazolin-3,5-dione adducts of vitamin D₃ with BF₃O (C₂H₅)₂ and KOH/butanol yields these two new vitamin D₃ double bond isomers.     

Chemistry of o-Benzoquinones and Masked o Benzoquinones VII.: Regioselective and Stereoselective Cycloadditions of 6, 7-Dipropyl- and 8, 9-Eipropyl-1, 4-Dioxaspiro[4.5] deca-6, 8-Di-En-2, 10-Dione with Monosubstituted Ethylenes

The cycloadditions of the titled two masked o-benzoquinones, 2 and 3 , with monosubstituted ethylenes including ethyl acrylate, styrene, ethyl vinyl ether and 1-hexene were studied. The reactions proceeded with high stereoselectivity and regioselectivity to give endo head-to-head adducts when ethyl acrylate, styrene and ethyl vinyl ether were used as addenda. In the case of 1-hexene, the reaction with 2 took place with high regioselectivity but low stereoselectivity to afford endo as well as exo head-to-head adducts while the reaction with 3 occurred with less regioselectivity to produce presumably all the eight possible isomers. The regiochemistry of the adducts were determined by the ¹H nmr analysis of their hydrolysis products, bicyclo[2,2,2]oct-5-en-2,3-diones 6 , and the subsequent photolysis products, 1,3-cyclohexadienes 7 . The stereochemistry was established by the study of the lanthanide induced shifts of compounds 6a-6f with Fu(fod)₃. The regioselectivity and stereoselectivity of these cycloaddition reactions were explained in terms of frontier molecular orbital theory and steric effect. The present study provides also a facile method to prepare regioselectively bicyclo[2, 2, 2]oct-5-en-2,3-diones (stereo-selectively also) and 1,3-cyclohexadienes from unsymmetric catechols via masked o-benzoquinones.