I：端羟基液体聚丁二烯的氯化 II：氯化端羟基液体聚丁二烯的固化

合成了一系列氯含量不同的氯化丁羟（氯含量为5％～68％）。利用红外光谱、核磁共振观察了氯含量不同的氯化丁羟的双键变化。通过氯含量－5反应时间的关系及上述观察结果表明；丁羟在四氯化碳中进行氯化，首先进行加成反应，待双键饱和后，进行取代反应。用红外光谱观察了丁羟在氯化反应中三种微观结构的变化，观察了氯化高顺式聚丁二烯的双键变化，对氯化丁羟的赤苏异构体的碳－氯键红外光密度比值，进行了分析。这些观察和分析说明；丁羟在四氯化碳中氯化，存在着顺－反异构化反应。较详细地研究了影响交联反应的主要因素，利用低聚物的特点，通过数均分子量和粘度表征了交联反应程度。从而观察到，交联反应伴随着氯化反应之中，交联程度随着反应液中羟浓度的提高，随着反应时间的延长而增大。在一定反应液浓度下交联程度可以减小到很低程度，得到完全可溶的氯化丁羟。反应温度对交联反应在20～76���范围无显著影响。提出了以氯乙醇为调节剂合成液体氯化丁羟的方法。实验结果说明，氯乙醇比文献中得到的乙醇在抑制交联反应，提高氯含量方面效果更好。氯化丁羟的羟值分析结果表明，丁羟的羟值在氯化反应中没有损失。这对氯化丁羟作为遥瓜型低聚物应用，在进行固化反应时，是非常重要的。随着溶剂介电常数的提高，出现凝胶的极限浓度也提高。根据这一实验和上述各项实验结果，基于烯类化合物氯化反应的一些基础研究工作。我们认为，在丁羟的氯化反应中，存在着两种反应机理；离子机理的加成，导致可溶氯化产物，自由基机理除加成外，导致交联，顺－反异构化反应。II 氯化丁羟与TDI的反应为二级反应。DBTDL（二月桂酸二丁基锡）对本固化反应有明显的催化效果。在100 ℃，以DBTDL为催化剂的固化反应中，氯化丁羟与TDI的反应速度常数为11.9 * 10~(-3)（升／克分子·秒），这个反应活化能为5.5千卡／克分子。合成了一系列的氯化丁羟聚氨酯。红外光谱测试结果表明，NH基分为两个红外吸收峰；3440 cm~(-1), 3310 cm~(-1)。高波频峰的为游离的NH基，低波频峰为缔合的NH基，其缔合度为88％。同时，表征了氯化丁羟聚氨酯的主要红外光谱吸收峰。研究了氯化丁羟聚氨酯的形态结构。透射电子微显镜示出氯化丁羟聚氨酯的微相分离区域结构，其硬段区域结构的尺寸大约趋于在0.7～1.6��范围内（硬段含量30％）。差热分析和示差扫描量热分析结果一致表明，氯化丁羟聚氨酯在60 ℃-90 ℃范围内有一宽而弱的吸热转变区，在115 ℃左右有一吸热峰，它们归因于硬段区域结构的热转变。宽角X光衍射实验没有观察到明显的结晶吸收峰的存在。这个实验结果主要与氯化丁羟聚氨酯的无规、侧基及不对称的结构特点有关。初步实验结果显示出，氯化丁羟聚氨酯具有优异的粘结性能，其抗剪强度约是丁羟聚氨酯的六倍。通过氧化锌的作用，可以提高氯化丁羟聚氨酯的抗张强度。因为粘结强度是水轮机耐磨耐汽蚀涂层研制中比较关键的因素，所以，这个实验结果是很有意义的。

I.茚基和环戊二烯基钕二氯化物-烷基铝二元体系催化丁二烯聚合反应动力学II.萘基钕及二环戊二烯基钕化合物的合成

本文研究所了四种钕化合物（茚基钕有机金属化合物C_9H_7NdCl_2·HCl·C_4H_8O，环戊二烯基钕有机金属化合物-C_5H_5NdCl_2·C_4H_8O，无水氯化钕络合物-NdCl_3·2C_4H_8O及NdCl_3·C_6H_5OH·C_4H_8O）与三异丁基铝（i-Ba_3Al）或一氢二异丁基铝（i-Bu_2AlH）所组成的二元催化体系中丁二烯聚合动力学。这些体系的动力学特点尚未被人们研究，通过实验揭示出一些新的规律，丰富了我们对稀土体系催化丁二烯聚合动力学的认识。研究中着重考察了聚合物活性链的变化条件，从而能较深刻地认识各体系的动力学特点，结果表明：C_9H_7NdCl_2·HCl·C_4H_8O，C_5H_5NdCl_2·C_4H_8O，NdCl_3·2C_4H_8O，NdCl_3·C_6H_5OH·C_4H_8O与i-Bu_2AlH所组成的二元催化体系中，当[Mo]=1.11克分子/升、[Nd]=1.12*10~(-4)克分子/升、[i-Bu_2AlH]\3.36*10~(-3)克分子/升、50 ℃聚合时为缓慢引发非稳态聚合反应。而当增加铝用量至[i-Bu_2AlH] = 6.72*10~(-3)克分子/升，C_9H_7NdCl_2·HCl·C_4H_8O体系转变为迅速引发稳态聚合反应，其余体系反应动力学行为无变化。各稀土钕催化体系动力学的差异主要是由配位体供电性不同产生的。当配位体供电性强时有利于降低稀土离子的正电荷，从而有利于烷基化反应和活性中心的形成和稳定，因此决定了各催化体系的不同动力学行为。C_9H_7NdCl_2·HCl·C_4H_8O体系当聚合温度、烷基铝浓度变化时以及Nd(naph)_3体系当温度变化时聚合物活性链状况会发生变化，从而改变了动力学行为。缓慢引发和迅速引发，稳态和非稳态间会发生转化而不是一成不变的。凝胶渗透色谱法应用于反应机理的研究不仅在理论上是可能的，在实践上是成功的。缓慢引发非稳态聚合（C_5H_5NdCl_2·C_4H_8O，NdCl_3·C_6H_5OH·C_4H_8O,NdCl_3·ZC_4H_8O），迅速引发非稳态聚合（Nd(naph)_3），迅速引发稳态聚合（C_9H_7NdCl_2·HCl·C_4H_8O）不同的动力学类型都具有不同的分子量分布特点。C_9H_7NdCl_2·HCl·C_4H_8O体系中丁二烯聚合速率方程为：K_p=K_p[C~*][M]. 50 ℃,[Nd]=1.12*10~(-4),[i-Bu_2AlH]=6.72*10~(-3)克分子/升条件下，丁二烯为快引发稳态聚合反应。此体系中活性中以浓度为2.43*10~(-6)克分子/升，催化剂有效利用率2%，链增长速率常数为81.42升/克分子，秒，聚合反应表观活化能为8.5±0.5千卡/克分子。聚合物顺-1，4结构均为98%左右。活性链平均寿命为7.22分钟。活性链对烷基铝的转移为主要链转移方式而对单体无明显转移。链转移速率常数为2.99升/克分子秒。

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

Diversities in hepatic HIF-1, IGF-I/IGFBP-1, LDH/ICD, and their mRNA expressions induced by CoCl2 in Qinghai-Tibetan plateau mammals and sea level mice

Ochotona curzoniae and Microtus oeconomus are the native mammals living on the Qinghai-TibetanPlateau of China. The molecular mechanisms of their acclimatization to the Plateau-hypoxia remain unclear. Expressions of hepatic hypoxia-inducible factor (HIF)-1 alpha, insulin-like growth factor-I (IGF-I)/IGF binding protein (BP)-1(IGFBP-1; including genes), and key metabolic enzymatic genes [lactate dehydrogenase (LDH)-A/isocitrate dehydrogenase (ICD)] are compared in Qinghai-Tibetan- Plateau mammals andsea- level mice after injection of CoCl2 (20, 40, or 60 mg/ kg) and normobaric hypoxia (16.0% O-2, 10.8% O-2, and 8.0% O-2) for 6 h, tested by histochemistry, Western blot analysis, ELISA, and RT-PCR. Major results are CoCl2 markedly increased 1) HIF-1 alpha only in mice, 2) hepatic and circulatory IGF-I in M. oeconomus, 3) hepatic IGFBP-1 in mice and O. curzoniae, and 4) LDH-A but reduced ICD mRNA in mice (CoCl2 20 mg/kg) but were unchanged in the Tibetan mammals. Normobaric hypoxia markedly 1) increased HIF-1 alpha and LDH-A mRNA in mice and M. oeconomus (8.0% O-2) not in O. curzoniae, and 2) reduced ICD mRNA in mice and M. oeconomus (8.0% O-2) not in O. curzoniae. Results suggest that 1) HIF-1 alpha responsiveness to hypoxia is distinct in lowland mice and plateau mammals, reflecting a diverse tolerance of the three species to hypoxia; 2) CoCl2 induces diversities in HIF-1, IGF-I/IGFBP-1 protein or genes in mice, M. oeconomus, and O. curzoniae. In contrast, HIF-1 mediates IGFBP-1 transcription only in mice and in M. oeconomus (subjected to severe hypoxia); 3) differences in IGF-I/IGFBP-1 expressions induced by CoCl2 reflect significant diversities in hormone regulation and cell protection from damage; and 4) activation of anaerobic glycolysis and reduction of Krebs cycle represents strategies of lowland-animals vs. the stable metabolic homeostasis of plateau- acclimatized mammals.

铂族元素分析方法研究及其在有关地质问题中的应用

Characterization of Platinum Group Elements (PGE) has been applied to earth, space and environmental sciences. However, all these applications are based on a basic prerequisite, i.e. their concentration or ratio in the research objects can be accurately and precisely determined. In fact, development in these related studies is a great challenge to the analytical chemistry of the PGE because their content in the geological sample (non-mineralized) is often extremely low, range from ppt (10~(-12)g/g) to ppt (10~(-9)g/g). Their distribution is highly heterogeneous, usually concentrating in single particle or phase. Therefore, the accurate determination of these elements remains a problem in analytical chemistry and it obstructs the research on geochemistry of PGE. A great effort has been made in scientific community to reliable determining of very low amounts of PGE, which has been focused on to reduce the level of background in used reagents and to solve probable heterogeneity of PGE in samples. Undoubtedly, the fire-assay method is one of the best ways for solving the heterogeneity, as a large amount of sample weight (10-50g) can be hold. This page is mainly aimed at development of the methodology on separation, concentration and determination of the ultra-trace PGE in the rock and peat samples, and then they are applied to study the trace of PGE in ophiolite suite, in Kudi, West Kunlun and Tunguska explosion in 1908. The achievements of the study are summarized as follows: 1. A PGE lab is established in the Laboratory of Lithosphere Tectonic Evolution, IGG, CAS. 2. A modified method of determination of PGE in geological samples using NiS Fire-Assay with inductively coupled plasma-mass spectrometry (ICP-MS) is set up. The technical improvements are made as following: (1) investigating the level of background in used reagents, and finding the contents of Au, Pt and Pd in carbonyl nickel powder are 30, 0.6 and 0.6ng/g, respectively and 0.35, 7.5 and 6.4ng, respectively in other flux, and the contents of Ru, Rh, Os in whole reagents used are very low (below or near the detection limits of ICP-MS); (2) measuring the recoveries of PGE using different collector (Ni+S) and finding 1.5g of carbonyl nickel is effective for recovering the PGE for 15g samples (recoveries are more than 90%), reducing the inherent blank value due to impurities reagents; (3) direct dissolving nickel button in Teflon bomb and using Te-precipitation, so reducing the loss of PGE during preconcentration process and improving the recoveries of PGE (above 60% for Os and 93.6-106.3% for other PGE, using 2g carbonyl nickel); (4) simplifying the procedure of analyzing Osmium; (5)method detection limits are 8.6, 4.8, 43, 2.4, 82pg/g for 15g sample size ofRu, Rh, Pd, Ir, Pt, respectively. 3. An analytical method is set up to determine the content of ultra-trace PGE in peat samples. The method detection limits are 0.06, 0.1, 0.001, 0.001 and 0.002ng/mL for Ru, Rh, Pd, Ir and Pt, respectively. 4. Distinct anomaly of Pd and Os are firstly found in the peat sampling near the Tunguska explosion site, using the analytical method. 5. Applying the method to the study on the origin of Tunguska explosion and making the following conclusions: (1) these excess elements were likely resulted from the Tunguska Cosmic Body (TCB) explosion of 1908. (2) The Tunguska explosive body was composed of materials (solid components) similar to C1 chondrite, and, most probably, a cometary object, which weighed more than 10~7 tons and had a radius of more than 126 m. 6. The analysis method about ultra-trace PGE in rock samples is successfully used in the study on the characteristic of PGE in Kudi ophiolite suite and the following conclusions are made: (1) The difference of the mantle normalization of PGE patterns between dunite, harzburgite and lherzolite in Kudi indicates that they are residual of multi-stage partial melt of the mantle. Their depletion of Ir at a similar degree probably indicates the existence of an upper mantle depleted Ir. (2) With the evolution of the magma produced by the partial melt of the mantle, strong differentiation has been shown between IPGE and PPGE; and the differentiation from pyroxenite to basalt would have been more and more distinct. (3) The magma forming ophiolite in Kudi probably suffered S-saturation process.