电致发光金属配合物和有机小分子的合成与性能

本文以调控发光颜色、提高发光效率为目的，通过改变配体、中心金属离子、取代基等进行颜色调节；通过引入电子或空穴传输单元，实现发光分子的功能化进而改善载流子传输提高发光效率。文中主要以有机小分子和金属配合物为研究对象，它们本身都具有良好的发光性质。工作集中围绕以下几个问题展开：1、PPV齐聚物是一类高效发光的分子体系，如果在其中嵌入8一取代的哇琳单元对发光会有什么影响？2、使用含噁二唑（具有电子传输功能）的配体得到的金属配合物是否能同时拥有双重功能，即高效发光（金属配合物的特点）和优良的电子传输？3、由N2O-双齿配体转变成N，N-双齿配体，配合物的发光又会如何？4、稀土配合物具有高的光致发光效率，但电致发光效率非常低，能否通过咔哇或呛二吟功能化来改善载流子传输，提高电致发光效率？主要工作及取得的结果概述如下：1、经由Knoevenagel缩合反应合成了一系列共骊的2，21-（1，4-芳二乙烯基）双-8-取代喹啉。单晶X-射线衍射研究表明固态下存在分子间，π…π堆积相互作用，这对于载流子传输是比较有利的。喹啉8-位于的取代基的变化对发光影响不大，表明刚性共扼骨架对发光起主要贡献。改变中心的芳核，明显可以调控发光颜色。当存在分子内电荷转移时，与不存在的相比，发光显著红移。电致发光性质表明这些含双喳琳的PPV齐聚物是良好的发光和电子传输材料。2、存在分子内氢键的化合物2-（2-羟基苯基）-5-苯基-1，3，4-噁二唑（HOXD），具有激发态分子内质子转移（ESIPT）特性。在室温下，用365脚的紫外灯照射时表现强的兰色荧光。室温和低温（77K）下的磷光光谱表明它在固态下具有较强的磷光发射，与理论预测完全一致。多层电致发光器件ITO加PB／HOXD／BCP／Alq3／Mg：Ag最大亮度达到656cd／m2，电流效率为0．37cd／A。当把HoxD掺在cBP中时，亮度和效率都有一定程度的提高，达到870cd／m2和0.82cd／A。3、合成了含有德二哩配体（HOXD）的碱金属配合物MOxD（M=Li，Na，K）。我们发现配合物的发光颜色取决于中心金属离子，LiOXD是一个优良的蓝光材料，半峰宽是65nm，发射峰位在478nm，它也可以作为界面材料使用，起到和LIF相同的作用，即改善电子注入。同时作者首次报道了钠和钾的配合物可以用作发光材料。电致发光性质表明这些配合物是优良的蓝／绿色发光和电子注入／传输材料。4、使用从N双齿配体代替N，O-双齿配体（比如8-羟基喹啉），合成了含有2－（2-羟基喹啉）苯并咪唑的锌、铍和硼配合物。用硼配合物作为发光层的三层器件ITO/NPB/boron-complex／Alq3／LiF／A1所得到的光谱覆盖了从400到750nm的区域，表明获得了一个很好的白色发光。白光分别源于激子和激基复合物发光，由三种成分构成：来自于硼配合物的兰色发光（490nm）；来自于Alq3的发光（535nln）；NPB和BPh2（Pybm）界面形成的激基复合物发光（610nm）。器件最大亮度是110cd／m2最大效率是0.8cd／A。5、设计、合成了咔唑、噁二唑功能化的稀土馆配合物，期望通过改善空穴和电子传输来提高发光效率。含咔哇的配合物的双层器件发光光谱较宽，包括三价铺的特征发射和一个宽峰，可能是咔唑的发光。当使用TPD做空穴传输层时，噁二唑铺配合物的电致发光器件得到纯正明亮的红色发光，器件结构为ITO／TPD（40nm）／（OXD-PyBM）Eu（DBM）3（SOnm）／LiF（Inm）／Al（200m），启动电压为7.8V，在21v时达到最大亮度322cd／m2。亮度为57cd／m2和13．sv时电流效率最大，为1.9cd／A，对应外量子效率是1.7％。高的效率表明通过引入噁二唑基团，配合物的电子传输能力得到明显改善。6、初步研究了三线态发光的铱的金属有机配合物，得到了高亮度、高效率的绿色发光；对8-羟基喹啉锌配合物的高分子化也做了初步探讨。

关于固体表面上液体球冠的平衡条件问题——兼评“冷凝器壁面滴状冷凝的热力学机理及最佳接触角”等文章

对于第一类液滴(尺度远大于界面层的厚度),无论是远离固体壁面的液体球或附着在壁面上的球冠,其内外压力差(简称"附加压力")均适用经典Laplace公式,并且特别对球冠情况给出了一种新的整体性证明.还澄清有关争论:指出[曹治党、郭愚1999物理学报481823]一文对附壁面第一类液体球冠所推导出的附加压力与接触角有关的公式是错误的,而[闵敬春2002物理学报512730]是正确的。

Improvement of FEM's dynamic property

The discretization size is limited by the sampling theorem, and the limit is one half of the wavelength of the highest frequency of the problem. However, one half of the wavelength is an ideal value. In general, the discretization size that can ensure the accuracy of the simulation is much smaller than this value in the traditional finite element method. The possible reason of this phenomenon is analyzed in this paper, and an efficient method is given to improve the simulation accuracy.

氮杂环化合物的绿色合成研究

氮杂环化合物大多数都是具有生理活性的物质，例如喹喔啉化合物与苯二氮卓类化合物，因此研究氮杂环化合物骨架的构建方法具有一定意义。绿色化学的迅速发展迫切要求化学家发展清洁、经济和环境较友好条件下的有机合成方法。其中，水相反应与绿色固体酸催化剂的使用都是实现绿色有机合成的重要途径，它们非常具有潜力，近些年受到了广泛关注。本论文的主要工作是围绕水相及固体酸催化条件下两类具有生物活性的含氮杂环小分子的合成方法而开展的，具体包括以下内容： 1. 研究和探索出了两类绿色固体酸催化剂蒙脱土（Mont. K-10）和杂多酸(H4SiW12O40), 在水相条件下成功合成出喹喔啉化合物的有效方法。两个催化体系都以无毒无公害的水作反应溶剂，实验条件温和，操作安全简便，反应速度快，底物普适性强，产率高，且产物易分离收集。两类固体酸催化剂，对设备腐蚀性小，可回收循环使用，对环境无公害; 蒙脱土催化大部分底物能得到当量产率的产物，硅钨酸催化催化剂负载量小。 2. 实现了无溶剂条件下，以杂多酸（H3PW12O40）作催化剂，高效合成1,5-苯二氮卓衍生物的合成方法。该催化体系具有以下一些优势：实验条件温和，反应速度较快，底物普适性良好，产物易分离收集，反应过程中没有加入其它有机溶剂，绿色环保。 ‘Green Chemistry’ is currently a major issue of modern chemistry. It is widely acknowledged that there is a growing need for more environmentally acceptable processes in the chemical industry. New green catalysts and green reaction media are the important and efficient strategies in green chemistry. New green catalysts include solid acid catalysts, solid base catalysts, metal catalysts not only possess higher activity and selectivity, but also are easily separated from reaction system. Green reaction media include water, supercritical fluids and ionic liquids can not only substitute traditional toxic and harmed organic solvents, but also improve reaction activity and selectivity. Meanwhile water is a promising green reaction medium for use in modern chemistry because it has a number of advantages such as the cheapest solvent available on earth, being non-hazardous and non-toxic to the environment. Solid acids had also attracted much attention for realizing green chemistry due to their unique acidity, high activity and efficiency as organic catalysts. Nitrogen-containing heterocyclic compounds of different ring sizes such as quinoxaline and benzodiazepine are the important pharmacologically active compounds. Due to the wide biological significance of these compounds, the synthesis of these types of compounds have received a great deal of attention. Despite the large availability of methods to construct nitrogen-containing heterocyclic compounds, there is still a strong need to further explore green methods to efficiently and safely synthesize these compounds. Thus, we aim at developing efficient and green methodology for the synthesis of quinoxaline and benzodiazepine carried out under water condition with solid acid catalysts. The contents of this dissertation are listed as the following: 1. We have developed two catalytic systems for the synthesis quinoxaline via the condensation of an aryl 1,2-diamine with a 1,2-diketone compound in the presence of Mont. K-10 or H4SiW12O40 as a catalyst in water solvent. Both of these two methods can be applied to wide range of substrates, tolerating aryl 1,2-diamine/1,2-diketone with the electron donating/drawing substituent. Operational simplicity, the ambient conditions, use of an economically convenient catalyst, use of water as a desirable solvent, high yields and short reaction times are the key features of these two protocols. 2. We developed a convenient and efficient protocol for the synthesis of a variety of 1,5-benzodiazepines in high yields via condensation of aryl o-phenylenediamine derivatives with a variety of ketones using H3PW12O40 as a green recyclable and heterogeneous catalyst under solvent-free condition. The simple experiment procedure combined with ease of recovery and reuse of this catalyst make this procedure quite simple, more convenient and environmentally benign.

Radiosensitivity of hepatoma cell lines and human normal liver cell lines exposed in vitro to carbon ions and argon ions at the HIRFL

Human hepatoma (SMMC-7721) and normal liver (L02) cells were irradiated with c-rays, 12C6+ and 36Ar18+ ion beams at the Heavy Ion Research Facility in Lanzhou (HIRFL). By using the Calyculin-A induced premature chromosome condensation technique, chromatid-type breaks and isochromatid-type breaks were scored separately. Tumor cells irradiated with heavy ions produced a majority of isochromatid break, while chromatid breaks were dominant when cells were exposed to c-rays. The relative biological effectiveness (RBE) for irradiation-induced chromatid breaks were 3.6 for L02 and 3.5 for SMMC-7721 cell lines at the LET peak of 96 keVlm 1 12C6+ ions, and 2.9 for both of the two cell lines of 512 keVlm 1 36Ar18+ ions. It suggested that the RBE of isochromatid-type breaks was pretty high when high-LET radiations were induced. Thus we concluded that the high production of isochromatid-type breaks, induced by the densely ionizing track structure, could be regarded as a signature of high-LET radiation exposure.

A method on theoretical simulation of chromosome breaks in cells exposed to heavy ions

Background. The aim of this study is to assess an easy and quick method on simulating chromosome breaks in cells exposed to heavy charged particles. Methods. The theoretical value of chromosome break was calculated, and the validated comparison with the experimental value by using a premature chromosome condensation technique was done. Results. A good consistence was found to be appeared between the theoretical and experimental value. Conclusions. This suggested that a higher relative biological effectiveness of heavy ions was closely correlated with its physical characteristics and besides, a safe approach on predicting chromosome breaks in cells exposed to heavy ions at off-line environment come to be considered. Furthermore, three key factors influencing the theoretical simulation was investigated and discussed.

Deconfinement phase Transition including perturbative QCD corrections in (proto)neutron star matter

Deconfinement phase transition and neutrino trapping in (proto)neutron star matter are investigated in a chiral hadronic model (also referred to as the FST model) for the hadronic phase (HP) and in the color-flavor-locked (CFL) quark model for the deconfined quark phase. We include a perturbative QCD correction parameter alpha(s) in the CFL quark matter equation of states. It is shown that the CFL quark core with K-0 condensation forms in neutron star matter with the large value of alpha(s). If the small value of alpha(s) is taken, hyperons suppress the CFL quark phase and the HP is dominant in the high-density region of (proto)neutron star matter. Neutrino trapping makes the fraction of the CFL quark matter decrease compared with those without neutrino trapping. Moreover, increasing the QCD correction parameter alpha(s) or decreasing the bag constant B and the strange quark mass m(s) can make the fraction of the CFL quark matter increase, simultaneously, the fraction of neutrino in protoneutron star matter increases, too. The maximum masses and the corresponding radii of (proto)neutron stars are not sensitive to the QCD correction parameter alpha(s).

Biodosimetry estimate for high-LET irradiation

The purpose of this paper is to prepare for an easy and reliable biodosimeter protocol for radiation accidents involving high-linear energy transfer (LET) exposure. Human peripheral blood lymphocytes were irradiated using carbon ions (LET: 34.6 keV mu m(-1)), and the chromosome aberrations induced were analyzed using both a conventional colcemid block method and a calyculin A induced premature chromosome condensation (PCC) method. At a lower dose range (0-4 Gy), the measured dicentric (dics) and centric ring chromosomes (cRings) provided reasonable dose information. At higher doses (8 Gy), however, the frequency of dics and cRings was not suitable for dose estimation. Instead, we found that the number of Giemsa-stained drug-induced G2 prematurely condensed chromosomes (G2-PCC) can be used for dose estimation, since the total chromosome number (including fragments) was linearly correlated with radiation dose (r = 0.99). The ratio of the longest and the shortest chromosome length of the drug-induced G2-PCCs increased with radiation dose in a linear-quadratic manner (r = 0.96), which indicates that this ratio can also be used to estimate radiation doses. Obviously, it is easier to establish the dose response curve using the PCC technique than using the conventional metaphase chromosome method. It is assumed that combining the ratio of the longest and the shortest chromosome length with analysis of the total chromosome number might be a valuable tool for rapid and precise dose estimation for victims of radiation accidents.

Hyperon-hyperon interaction in relativistic mean field model

By using the new experimental data of Lambda Lambda potential, this paper has performed a full calculation for strange hadronic matter with different strangeness contents as well as its consequences on the global properties of neutron star matter in relativistic mean field model. It finds that the new weak hyperon - hyperon interaction makes the equations of state much stiffer than the result of the previous strong hyperon-hyperon interaction, and even stiffer than the result without consideration of hyperon -hyperon interaction. This new hyperon -hyperon interaction results in a maximum mass of 1.75M(circle dot) ( where M-circle dot stands for the mass of the Sun), about 0.2-0.5M(circle dot) larger than the previous prediction with the presence of hyperons. After examining carefully the onset densities of kaon condensation it finds that this new weak version of hyperon -hyperon interaction favours the occurrence of kaons in comparison with the strong one.

Correlation between initial chromatid damage and survival of various cell lines exposed to heavy charged particles

The biophysical characteristics of heavy ions make them a rational source of radiation for use in radiotherapy of malignant tumours. Prior to radiotherapy treatment, a therapeutic regimen must be precisely defined, and during this stage information on individual patient radiosensitivity would be of very great medical value. There are various methods to predict radiosensitivity, but some shortfalls are difficult to avoid. The present study investigated the induction of chromatid breaks in five different cell lines, including one normal liver cell line (L02), exposed to carbon ions accelerated by the heavy ion research facility in Lanzhou (HIRFL), using chemically induced premature chromosome condensation (PCC). Previous studies have reported the number of chromatid breaks to be linearly related to the radiation dose, but the relationship between cell survival and chromatid breaks is not clear. The major result of the present study is that cellular radiosensitivity, as measured by D-0, is linearly correlated with the frequency of chromatid breaks per Gy in these five cell lines. We propose that PCC may be applied to predict radiosensitivity of tumour cells exposed to heavy ions.

Survival and initial chromatid breakage in normal and tumour cells exposed in vitro to gamma rays and carbon ions at the HIRFL

Human hepatoma and normal liver cells were irradiated with C-12(6+) ion beams (linear energy transfer (LET) = 96 keV mu m(-1)) and gamma-rays at the Heavy Ion Research Facility in Lanzhou (HIRFL). The numbers and types of chromatid breaks were detected using the premature chromosome condensation technique. Irradiation with C-12(6+) ions produced a majority of isochromatid break types, while chromatid breaks were dominant for irradiation with gamma-rays. Experimental results showed that the initial level of chromatid breaks is clearly related to the absorbed dose from C-12(6+), ions and gamma-rays. The (12)C(6+)ions are relatively more effective at inducing initial chromatid breaks when compared with the gamma-rays. A relative biological effectiveness (RBE) of about 2.5 resulted for the induction of initial chromatid breaks by C-12(6+) ions relative to gamma-rays in both cell lines.

Radiobiological response of human hepatoma and normal liver cells exposed to carbon ions generated by Heavy Ion Research Facility in Lanzhou

Human hepatoma and normal liver cells were irradiated with C-12(6+), ion beams (LET= 96.05 keV/mu m) and gamma-rays at Heavy Ion Research Facility in Lanzhou (HIRFL). The chromatid breaks and break types were detected using the premature chromosome condensation technique. Our experimental results showed that chromatid breaks seem to have a good relation with C-12(6+) absorbed dose and C-12(6+) are more effective to induce chromatid breaks as compared to they-rays. For C-12(6+) ion irradiation the major break was isochromatid break, while chromatid breaks were dominant for gamma-ray irradiation. We also observed that the Relative Biology Effectiveness (RBE) of C-12(6+) ion is about 2.5 times higher than that of gamma-rays.

染色体断裂预测肿瘤细胞辐射敏感性

恶性肿瘤（癌症）是危及人类生命健康最严重的疾病之一，放射治疗是一种较为有效的治疗手段。不同种类细胞对射线的敏感性有很大区别，即使同一细胞在不同的细胞周期时相、同一器官的不同部位其辐射敏感性也存在着明显的差异。为了认识人类不同种类月γ瘤细胞对γ射线的辐射敏感性的差异以及正常人细胞接受Y射线照射后染色体的损伤及修复，本研究以染色体断裂为预测指标，应用CalyculinA诱导的早熟染色体凝集技术对肝癌细胞系SMMC-7721、胃癌细胞系BGC-823、宫颈癌细胞系HeL。、黑色素瘤细胞系A375、肝细胞系L02等五种人类肿瘤细胞对Y射线的辐射敏感性及人类正常肝细胞染色体损伤的动态修复过程进行了研究。发现：1．Y射线照射后，肿瘤细胞染色体断裂与吸收剂量及染色体断裂和细胞存活率之间存在正相关关系，其中，在相同吸收剂量下染色单体断裂数目远较等点染色单体数目多；2．正常肝细胞在经过射线照射后染色体断裂数目也与吸收剂量和细胞存活率之间存在正相关关系，经过4昆小时的修复，染色单体断裂85％以上得到了有效修复，等点染色单体断裂修复率小于15％。结果提示：γ射线诱导产生的染色体断裂可以作为预测细胞辐射敏感性的可靠指标；辐射诱发正常细胞的癌变可能与等点染色单体的不能有效修复存在着密切的联系。这不仅对于具有个案针对性的临床放射治疗有着极为重要的指导意义，而且对于恶性肿瘤的发病机理也有重要意义。

Hydrothermal stability and catalytic activity of aluminum-containing mesoporous ethane-silicas

Aluminum was incorporated into the mesoporous framework of ethane-silica by one-pot condensation of Al(OiPr)(3) with 1,2-bis(trimethoxysilyl)ethane using octadecyltrimethylammonium chloride as surfactant. Powder X-ray diffraction patterns, nitrogen sorption analysis, and TEM results reveal the formation of an ordered mesoporous material with uniform porosity. Al-27 MAS NMR confirms the incorporation of aluminum in the framework. The synthesized materials exhibit extremely high hydrothermal stability in boiling water (no obvious change of mesostructure and textural properties was observed even after refluxing in water for 100 h), which could be mainly contributed to the ethane-bridged mesoporous framework. The aluminum-containing mesoporous ethane-silicas are efficient catalysts for the alkylation of 2,4-di-tert-butylphenol by cinnamyl alcohol to yield a flavan.

Direct synthesis of Al-SBA-15 mesoporous materials via hydrolysis-controlled approach

Aluminum-substituted mesoporous SBA-15 (Al-SBA-15) materials were directly synthesized by a hydrolysis-controlled approach in which the hydrolysis of the silicon precursor (tetraethyl orthosilicate, TEOS) is accelerated by fluoride or by using tetramethyl orthosilicate (TMOS) as silicon precursor rather than TEOS. These materials were characterized by powder X-ray diffraction (XRD), N-2 sorption isotherms, TEM, Al-27 MAS NMR, IR spectra of pyridine adsorption, and NH3-TPD. It is found that the matched hydrolysis and condensation rates of silicon and aluminum precursors are important factors to achieve highly ordered mesoporous materials. Al-27 MAS NMR spectra of Al-SBA-15 show that all aluminum species were incorporated into the silica framework for the samples prepared with the addition of fluoride. A two-step approach (sol-gel reaction at low pH followed by crystallization at high pH) was also employed for the synthesis of Al-SBA-15. Studies show that the two-step approach could efficiently avoid the leaching of aluminum from the framework of the material. The calcined Al-SBA-15 materials show highly ordered hexagonal mesostructure and have both Bronsted and Lewis acid sites with medium acidity.