Fe(ClO_4)_3氧化合成聚乙撑二氧-三噻吩

分别以Fe(Cl O4)3、FeCl3、Fe2(SO4)3作为氧化剂,对3′,4′-乙撑二氧-2,2′∶5′,2″-三噻吩(TET)进行了化学氧化聚合,并研究了聚合条件对聚合物结构和电化学性能的影响。利用红外光谱、紫外光谱、X射线衍射对聚合物进行了表征,采用循环伏安、恒电流充放电等电化学方法研究了聚合物的电化学性能。结果表明:当TET与Fe(Cl O4)3的摩尔比为1∶4,反应温度为18℃,反应时间为12 h时,聚3′,4′-乙撑二氧-2,2′∶5′,2″-三噻吩(PTET)具有更好的共轭结构和电化学性能,导电率可达1.47 S/m,比电容可达133 F/g。     

Two new chalcones from Fordia cauliflora

<正>Two new chalcones,β,2′,4′,5′-tetramethoxychalcone 1,andβ,2′,5′-trimethoxyfurano[4″,5″:3′,4′]-chalcone 2 were obtainedfrom an ethyl acetate-soluble fraction of ethanol extract of the stem of Fordia cauliflora.Their chemical structures were determinedby analysis of spectroscopic evidences.     

酰氨基硫脲及相关杂环衍生物的研究——ⅩⅩⅨ.2-(3’-溴苯胺基)-5-[5’-氨基-1’-(4"-氯苯基)-1’,2’,3’-三唑-4’-基]-1,3,4-噻二唑的晶体结构

经1-[5′-氨基-1′-(4″-氯苯基)-1′,2′,3′-三唑-4′-甲酰基]-4-(3′-溴苯基)-3-氨基硫脲在浓硫酸作用下制得2-(3′-溴苯胺基)5-[5′-氨基-1′-(4″-氯苯基)-1′,2′,3′-三唑-4′-基]-1,3,4-噻二唑化合物.该化合物的晶体结构经X射线衍射分析确定,化合物属三斜晶系,P1空间群,a=1.1784(2),b=1.4455(2),c=1.1353(1)nm;α=100.68(1),β=109.50(1),γ=79.89(1)°;V=1.7779nm~3;分子式C~(16)H_(11)BrClN_7S,M_r=448.75;D_c=1.673g/cm~3,Z=4,μ=58.16cm~(-1),最终偏离因子 R=0.084,R_w=0.086.分析化合物的键长,键角数据表明,该分子具有离域π键结构.     

含空穴传输基团三联吡啶(2,2′:6′,2″-terpyridine)衍生物铕配合物的合成及发光性能研究

以2,2′∶6′,2″-三联吡啶(L1)为基础,通过引入不同的空穴传输基团合成了4′-咔唑基-2,2′∶6′,2″-三联吡啶(L2),4′-二苯基胺基-2,2′∶6′,2″-三联吡啶(L3),4′-二(4-叔丁基苯基)胺基-2,2′∶6′,2″-三联吡啶(L4),4′-(N-苯基-1-萘基)胺基-2,2′∶6′,2″-三联吡啶(L5),4′-(N-苯基-2-萘基)胺基-2,2′∶6′,2″-三联吡啶(L6)5个N,N,N-三齿中性配体,然后以三氟乙酰噻吩丙酮(HTTA)作为第一配体合成了6种铕配合物。在369~373 nm激发条件下,配合物都表现出铕离子5D0-7FJ(J=0,1,2,3,4)的特征发射。引入不同的空穴传输基团后,在铕离子的周围形成了"光吸收天线"(light-harvesting antenna),不仅扩大了配合物吸收光能的范围、增强了配合物的吸收强度,而且提高了配合物的光致发光性能。其中含有咔唑基团的配合物具有最强的发光强度和最长的激发态寿命。     

Near-Infrared Hydrophobic Probes as Molecular Light Switch for CMC Determination of Triton X-100 Solution

The fluorescence behavior of two near-infrared (NIR) chromophores with linear alkyl chains of different lengths, 2-[4′chloro-7′(3″ethyl-2″benzothiaolinylidene)-3′,5′-(1″′3′″-propanediyl)-1′3′,5′-heptantriene-1′-yL]-3-ethylbenzothiazolium iodide (Probe Ⅰ) and 2-[4′chloro-7′(3″hexadecyl-2″benzothiazolinylidene)-3′,5′-(1′″,3′″-propanediyl)-1′,3′,5′-heptantriene-1′-yl]-3-ethylbenzothiazolium iodide (Probe Ⅱ), in aqueous solution containing different concentrations of surfactants was studied. The fluorescence of the probe with a short chain (probe Ⅰ) was completely quenched in water and aqueous solution containing a low concentration (below the critical micelle concentration,CMC) of surfactant Triton X-100. However, the fluorescence reappeared and reached maximum rapidly once the concentration of the surfactant approached the CMC. The probe with a long chain (probe II) displayed a similar fluorescence behavior but more dramatically fluorescent recovery in Triton X-100 system, which gave a direct in- dication for the micelle forming process and provided a simple method for the determination of the critical micelle concentration of the surfactant. The CMC values determined by this method were in good agreement with those obtained by other techniques. The fluorescence behavior of the two probes in other surfactant systems was also investigated.     

碳纳米管聚(3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩)复合材料的制备及其电化学性能研究

通过Stille反应合成了3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩(TET),并以其作为单体,采用化学氧化原位聚合方法在碳纳米管(CNT)的表面包覆新型聚(3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩)(PTET),制备了PTET-CNT纳米复合材料.通过TEM、SEM和IR对其进行了表征,并利用循环伏安、交流阻抗、恒电流充放电等电化学测试方法,比较研究了复合材料以及碳纳米管在0.1 mol/L四乙基四氟硼酸铵(Et4NPF4)的乙腈溶液中的电化学行为.实验结果表明,在电流密度为3 mA/cm2时,PTET-CNT复合材料的比电容为86 F/g,比原碳纳米管比电容20 F/g提高了3.3倍.基于这种复合材料的电容器的能量密度达到2.02 Wh/kg.     

1-芳酰基-4-(1''''-N-β-D-吡喃型糖基)氨基硫脲类化合物的合成(英文)

通过 2 ,3,4 ,6 四 O 乙酰基 β D 吡喃型葡萄糖异硫氰酸酯和 2 ,3,4 三 O 乙酰基 β D 吡喃型木糖异硫氰酸酯与取代的芳基酰肼的亲核加成反应合成了 1 0个 1 芳酰基 4 ( 1′ N 2′,3′,4′,6′ 四 O 乙酰基 β D 吡喃型葡萄糖基 )氨基硫脲和 7个 1 芳酰基 4 ( 1′ N 2′,3′,4′ 三 O 乙酰基 β D 吡喃型木糖基 )氨基硫脲 ,所得化合物的结构经元素分析 ,IR ,1 HNMR确证 .     

含吡唑啉酮三脚架结构的化合物及其稀土配合物的合成、表征及荧光性能

合成了一种含吡唑啉酮的三脚架结构化合物 1,1,1 三 { 1′ [2′ 氧杂 5′ 氧代 5′ ( 1″ 苯基 3″ 甲基吡唑啉酮 4″ 基 )戊基 ] }丙烷 (H3 L)及其 7个稀土配合物。通过元素分析、摩尔电导、质谱、红外光谱、核磁共振谱、荧光光谱等对H3 L及其稀土配合物的组成及性质进行了表征。分析结果表明 :H3 L的分子式为C45H50 N6O9,配合物的组成比为REL·0 5H2 O (RE =La ,Sm ,Eu ,Gd ,Tb ,Dy ,Yb) ;该三脚架形配体分别以醚氧、烯醇氧及吡唑酮环上的羰基氧与稀土离子进行配位 ,形成内配型配合物。荧光光谱分析表明SmL·0 5H2 O ,EuL·0 5H2 O ,TbL·0 5H2 O ,DyL·0 5H2 O配合物具有三价稀土离子的特征线状荧光 ,其中TbL·0 5H2 O的荧光强度最强 ,表明T(配体 )→5D4(Tb)能级更为匹配 ,从而进行分子内能量有效传递 ;由EuL·0 5H2 O的荧光光谱图形推测 ,Eu3 +离子在该配合物中处于非对称中心     

基于柔性多羧酸配体H3TCOPM构筑的Co(Ⅱ)配合物的合成与结构

以三苯甲烷-4,4′,4″-三羧酸(H_3TCOPM)为主配体,以含氮二齿配体4,4′-bipyridine(4,4′-bipy)为辅助配体,与Co(NO_3)_2·6H_2O通过溶剂热反应得到了2个配位聚合物{[Co_2(α-OH-TCOPM)(OH)(H_2O)_4]·DMF}_n(1)(α-OH-H_3TCOPM=三苯甲醇-4,4′,4″-三羧酸)和{[Co_3(α-OH-TCOPM)_2(4,4′-bipy)_3(H_2O)_6]·2H_2O}_n(2)。晶体结构分析表明,配合物1为四边形的二维层状结构,而配合物2为二维网状结构。采用红外光谱、粉末X射线衍射对配合物进行了表征,用热重分析仪研究了其热稳定性。     

A new biflavonoid from Selaginella labordei Hieron.ex Christ

A new biflavonoid,2,3-dihydro-5,5″,7,7″,4′-pentahydroxy-6,6″-dimethyl-[3′-O-4′″]-biflavone 1 and two known biflavonoids 2,3″-dihydroochnaflavone 2 and 2″,3″-dihydro-3′,3′″-biapigenin 3 were isolated from the herb of Selaginella labordei Hieron.ex Christ.Their structures were elucidated by spectroscopic methods.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.