导电聚苯胺呋喃的结构表征

碘掺杂聚苯胺呋喃是一类非共轭导电聚合物。用紫外吸收光谱、傅里叶变换红外吸收光谱、电子顺磁共振波谱、光电子能谱等对该聚合物的结构性质及导电机制进行了研究。     

含偶氮和席夫碱结构线性聚合物的合成及性能

以盐酸联苯胺为原料，经过重氮偶联、烷基化合成了预聚物，再与联苯胺反应生成主链同时含有偶氮和席夫碱结构的新型线性共轭聚合物，利用¹H NMR， FT-IR和HR-MS(ESI)对中间体及聚合物结构进行表征，通过紫外可见吸收光谱及荧光发射光谱对其光学性能进行了研究。     

芳香杂环聚合物紫外-可见光谱性质的理论研究

在AM₁方法优化构型的基础上,用ZINDO/CI方法计算了系列芳香杂环聚合物的紫外-可见光谱,探索分子结构与其光学性质之间的关系.理论计算结果表明,模型化合物ABPBO,PBO,PBOV和PBODV的紫外-可见光谱最大吸收波长(λ_max)依次增加,且相应吸收强度与分子链共轭长度相关.根据线性递变规律推导的理论λ_max值与其实验值(薄膜干态紫外吸收)符合得较好.由于质子化效应等环境因素,溶液中测量值较理论值和薄膜紫外吸收偏大.     

含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

氮桥双共轭体系中的交替竞争共轭

本文根据氮桥系列(Ⅸ)的紫外光谱,应用同系线性规律,定量地证明了在氮桥系列(Ⅸ)中,同系序数N≠m+n+4,因此氮不能同时与芳稠环及烯醛链共轭。紫外谱图的峰形,峰数及代基当量(△N_s)进一步证明了芳稠环与烯醛链互相竞争氮的独对p电子。当芳稠环链的长度m,达到使其竞争力大于烯醛链时,氮主要与芳环共轭,烯醛链只起代基的作用;当烯醛链的长度n,达到使其竞争力大于芳环时,氮则主要与烯醛链共轭,芳环只起代基的作用。随着两边链长m,n的交替增长,则出现竞争共轭的交替现象。     

含磺酸根侧链的聚苯乙炔-吡啶类共轭聚合物的荧光传感性能

利用Sonogashira偶合反应合成了两种新的含磺酸根侧链的聚苯乙炔-吡啶类共轭聚合物P1, P2. 通过紫外-可见吸收光谱和荧光光谱对其光学性质及Cu^2＋传感检测进行了研究. 结果表明, 按一定比例嵌段引入吡啶环的聚合物P1能有效地改善共轭主链的刚性, 提高检测的灵敏度, 使共轭聚合物具有更优异的荧光化学传感性能. 在甲醇溶剂中, P1 的荧光能被Cu^2＋有效地猝灭, 相对单体模型分子PESO₃, 其响应信号扩大222倍.     

带树枝状侧链聚苯乙炔的合成与结构表征

合成了带树枝状聚苯甲醚修饰基团的苯乙炔单体,在Rh[(nbd)Cl2]2催化剂的作用下得到了侧链带聚苯甲醚树枝的新型聚苯乙炔衍生物,用红外吸收光谱、核磁共振谱、紫外可见吸收光谱和凝胶渗透色谱表征了聚合物的结构.发现聚合物的重均分子量达到了57300,在氯仿、N,N-二甲基甲酰胺、四氢呋喃等有机溶剂中有良好的溶解性能.由于侧链上聚苯甲醚树枝体积庞大,聚合物主链采取立构规整的顺-顺式构象,紫外可见吸收光谱在440nm附近出现了显著的共轭主链的吸收肩峰;立构规整的顺-顺式构象使树枝状侧链形成了对主链保护的"夹套效应",聚合物热分解温度从聚苯乙炔母体的225℃提高到295℃.     

PBO聚合物紫外吸收光谱中环境因素影响的理论研究

芳杂环液晶高分子聚对亚苯基苯并二噁唑（PBO, poly(p-phenylene-2,6- benzobisoxazole)）的共轭平面结构赋予其光电性能而备受关注.实验结果表明其光电性能受其所处环境状态影响. 通过量子化学计算研究发现,PBO无论固态还是溶液状态的最大紫外吸收均较其本征值有所红移.对PBO二聚体模型以及其在强质子酸中所具有的质子化形态模型的紫外吸收光谱计算模拟的结果表明,PBO聚集态时的分子间相互作用,以及溶液中质子化效应均导致红移.质子化模型所得紫外吸收光谱能很好地阐释溶液中具有精细结构实测的紫外吸收光谱.     

一种新型哒嗪与N-戊烷基咔唑类聚合物的合成与表征

以二氯-1,3-双(二苯基磷)丙烷基镍(Ⅱ)为催化剂,通过3,6-二氯哒嗪格氏试剂与3,6-二溴-N-戊烷基咔唑共聚得到了一种新型共轭聚合物,并使用IR和1H-NMR等测试手段对单体和聚合物的结构进行了表征。该合成方法所得的共聚物收率为75%,共聚物在N,N-二甲基酰胺(DMF)、二甲基亚砜(DMSO)等极性溶剂和CF3COOH、CH3SO3H、HCOOH等常用有机酸中具有较好的溶解性。用红外(FT-IR)、紫外-可见吸收光谱(UV-vis)、荧光光谱(PL)、X射线衍射、循环伏安(CV)等对聚合物的吸收光谱特性、结晶性和电化学活性进行了探讨。结果表明:聚合物具有较高的发光强度,是一种还原型聚合物,结晶性比较差。     

三苯基吡啶-芴交替共轭聚合物的合成与光致发光性能研究

通过Suzuki偶合反应得到了两种间位连接的三苯基吡啶同分异构体和9,9-二辛基芴的交替共聚物PFOTPP1和PFOTPP2.并对它们的紫外-可见吸收光谱、光致发光光谱以及电化学性能等进行了初步研究.结果表明,将间位连接的三苯基吡啶基引入聚芴主链能使聚合物的LUMO能级降低,光致发光光谱发生蓝移,得到了两种有望应用于电致炼光发光器件的共轭聚合物蓝光发光材料.     

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.     

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。     

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.

     

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.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

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。