芴类蓝光材料的长波发射问题研究进展

有机电致发光技术在通信、信息、显示和照明等领域显现出巨大的商业应用前景, 十几年来一直是光电信息领域的研究热点之一. 相对于无机电致发光材料, 有机电致发光材料具有许多优点. 芴作为一种具有刚性平面联苯结构的化合物, 由于具有宽的能隙、高的发光效率和结构上易于修饰等特点, 是一类受到各方面广泛关注的蓝光材料. 芴类蓝光材料的一个缺点是薄膜在空气中退火或器件在长时间运行后会出现长波发射, 严重影响其综合电致发光性能. 目前认为是由分子间激基缔合物、芴酮或者两者共同作用引起了该长波发射. 经过各方努力, 芴类蓝光材料的长波发射问题趋向于被完全解决. 本文结合自己的工作, 从材料合成的角度综述了国内外在研究芴类蓝光材料的长波发射问题方面所取得的进展, 并对下一步需要研究的热点问题作了展望.     

芴类电致发光材料研究进展

有机电致发光材料是光电信息功能材料领域的研究热点之一。相比于无机电致发光材料,有机电致发光材料具有很多的优势.芴类化合物作为一类具有刚性平面联苯结构的电致发光材料,由于具有宽的能隙、高的发光效率等特点,备受各方面的关注.本文结合作者的工作,从材料合成的角度介绍了国内外在研究该类材料方面所取得的一些最新进展,并对一些有待进一步研究的问题做了展望.     

电光高分子材料的最新研究进展

电光高分子材料由于其在光电子信息领域的潜在应用前景已得到了广泛关注和深入研究.本文在简要介绍电光效应及其材料等相关知识的基础上,综述了最近几年来电光高分子材料的研究进展,主要包括生色团的设计与合成,以及掺杂型、侧链型、主链型、交联型、互穿网络型和树枝型等聚合物材料体系的设计与合成.     

9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴的光电性质

芴类化合物作为有机电致发光材料近年来引起了人们的广泛关注, 其具有高亮度和高工作效率等性能. 本论文采用量子化学方法研究了一种新型的芴类发光材料, 9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴的光电性质. 具体研究内容包括基态和激发态几何结构、前线分子轨道、能隙、电离能、电子亲和势、重组能以及吸收光谱和发射光谱等. 理论计算结果表明, 9,9-二-(3-(9-苯咔唑基))-2,7-芘基芴发射光谱为450.6 nm, 其在电致发光器件应用上是一种具有开发前景和实用价值的蓝光发光材料.     

二阶非线性光学聚合物材料

非线性光学材料是一类具有很高实用价值的功能材料。综述了聚合物二阶非线性光学材料的研究、极化聚合物在实用化研究方面取得的新进展,介绍了提高极化聚合物生色团高温取向稳定性、设计合成光损失较小的生色团以及优化聚合物主体的新方法。     

聚合物电致发光材料及其发光颜色调节的研究进展

聚合物电致发光材料已成为功能材料研究领域的一个热点.与无机材料和有机小分子材料相比,聚合物发光材料具有来源广泛、易加工成型、通过分子结构设计可调节发光颜色等优点,成为制备大面积、低成本、全色柔性显示器件的首选材料.本文介绍了聚合物发光材料的发光机理及调节发光颜色的常用方法,综述了聚对苯乙炔类、聚对苯类、聚芴类等多种共轭聚合物发光材料的合成及发光颜色调节的研究现状,并对聚合物发光材料的发展趋势以及聚合物电致发光器件的制备进行了评述和展望.     

咔唑及其衍生物在蓝光OLED中的应用

咔唑及其衍生物因其特有的电学性能、电化学性能和光物理性能而被广泛研究。由于这类材料不仅可以作为良好的空穴传输材料,而且在咔唑化合物的不同位置引入电子传输修饰基团,可以使得电子和空穴更加易于注入,并且可以很好地调节两者的平衡,因此,咔唑及其衍生物被认为是一类重要的蓝光荧光材料。咔唑及其衍生物不仅可以以小分子形式应用到蓝光荧光材料、蓝光磷光材料和热致延迟荧光材料,同样可以以高分子形式应用到蓝光荧光材料中。近年来,关于咔唑及其衍生物发光材料的合成及应用成为蓝光OLED研究的热点。本文综述了近年来国内外小分子咔唑及其衍生物作为蓝光有机电致发光主体材料的研究状况,对其分子结构设计光、电子轨道结构、物理性质、热学性质、电化学性质及器件性能等方面作了详细归纳比较,同时归纳了含咔唑结构的聚合物蓝光有机电致发光材料的研究进展,最后展望了咔唑基蓝光有机电致发光主体材料的发展前景和趋势。从光电转换效率及价格方面来说,热致延迟荧光材料和聚合物(含咔唑类基团)发光材料是最具有前景的蓝光OLED材料。     

聚甲基丙烯酸(N-羟基琥珀酰亚胺)酯的簇聚诱导发光研究

不含普通发光单元的非典型生色团发光化合物因其基础研究重要性和广泛的应用前景引起了人们的极大兴趣.其中许多化合物还具有独特的聚集诱导发光（Aggregation-induced emission,AIE）特性.然而其发光机理仍然存在争议.在此前的研究中,提出了簇聚诱导发光（clustering-triggered emission,CTE）机理,即非典型生色团的簇聚和电子共享来解释这些体系的发光和AIE现象.为进一步验证这一假说,设计合成了不含传统生色团的聚甲基丙烯酸（N-羟基琥珀酰亚胺）酯（PNHSMA）.其稀溶液基本不发光,但浓溶液,纳米聚集体,固体粉末均发射蓝光,呈现出AIE性质.通过与其单体甲基丙烯酸（N-羟基琥珀酰亚胺）酯（NHSMA）的发光行为对比及单体单晶结构解析,利用CTE机理很好地解释了其光物理行为.     

利用聚合物自组装实现绿色荧光蛋白生色团的荧光增强

根据绿色荧光蛋白的发光原理,采用聚乙二醇与聚甲基丙烯酸甲酯的两亲性两嵌段聚合物通过自组装包覆生色团的方式,模拟了绿色荧光蛋白发光,考察了组装行为对光学性能的影响,并将其用于细胞成像.通过核磁共振、高分辨质谱、傅里叶变换红外光谱、凝胶渗透色谱、紫外-可见吸收光谱及荧光光谱等表征了生色团分子和聚合物的结构及性能.生色团紫外最大吸收在371 nm,荧光最大发射峰在428 nm.聚合物和生色团进行组装后,其紫外吸收消失,而最大荧光发射峰强度大大增强,且发生了约70 nm的红移,这是因为组装使得生色团的自由旋转受到了限制,且生色团共平面性增加.动态光散射(DLS)和透射电镜(TEM)证明了纳米粒子的结构和尺寸.由于尺寸适合且具有较好的荧光性能,纳米粒子成功应用于细胞成像.这种绿色荧光蛋白生色团的简单自组装方式在生物成像领域具有良好应用前景.     

基于芴的蓝色电致发光材料研究进展

新型有机及高分子光电材料的制备与器件设计是目前国际上一个十分活跃的领域。与液晶平面显示器相比,有机和高分子电致发光平面显示器（OLED和PLED）具有主动发光、无角度依赖性、对比度好、轻、薄、能耗低等显著特点,具有广阔的应用前景。红、绿、蓝3原色是实现有效全色显示的必备条件。与红光和绿光材料相比,蓝光材料的效率、稳定性和色纯度都与前两者相去甚远。开发好的蓝光材料不仅可以作为OLED或PLED中的发光层,还可作为主体来掺杂制备绿光和白光光源。在蓝光材料中,基于芴的齐聚物和高分子拥有良好的热稳定性、高荧光量子效率和优异的电致发光特性,但其存在电荷注入与传输困难、易发生聚集、C9位易被氧化等缺点,这些缺点正是导致器件效率低、色纯度低、光谱稳定性差的原因。综述了基于芴的蓝光小分子和高分子的研究进展,主要针对含有电子给体、受体的齐聚芴和聚芴的材料设计、合成及电致发光性能,结果表明,既含空穴传输又含电子传输片段的材料比相应的只含电子给体或受体的材料性能更佳。     

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.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。