GEOCHEMISTY OF BICYCLIC ALKANES IN SEDIMENTS, COAL AND CRUDE OILS

By using GC-MS to analyze the extracts of source rocks, coal and crude oil samplesformed in different sedimentary environments in China, New Zealand and Australia, twenty-two compounds of five types of bicyclic alkanes have been dis covered in the samples. Thispaper makes an exposition of stereochemical structure, abundance and distributive features ofthese compounds and their relation to sedimentary environments and thermal evolution. Furt-thermore, it demonstrates how the abundance ratios of bicyclic alkanes to steranes and ter-panes, drimane to homodramane and the relative abundance of C_(15),C_(16),C_(12)-C_(14) series of bicyclic-alkane compounds can be used to judge and determine types of oil and gas forming environ-ments (the depositive environments of source rocks from which the oil and gas wereformed), characteristics of source rocks and degree of maturation.     

C_(30)-C_(32) LANOSTANES——A NOVEL SERIES OF TETRACYCLIC TRITERPENOID HYDROCARBONS IDENTIFIED IN CHINESE TERTIARY LACUSTRINE SEDIMENTS

A series of novel tetracyclic triterpanes based on the lanostane skeleton, ranging in cars-bon number from C_(30) to C_(32), were identified for the first time in Eocene lacustrine depo-its of Biyang Depression, China. These compounds have been identified by GC, GC- MS, andcoinjection with authentic standard, as 8β(H), 9α(H)- lanostane (C_(30)), 24-methyl- lanostane(C_(31)) and 24- ethyl- lanostane (C_(32)). Mechanisms are proposed for the origin and geologicalfate of these compounds. To the best of our knowledge, this is the first confirmed occur-rence of lanostanes in the sedimentary record.     

Crystal Structures,Thermal Behaviors and Biological Activities of Acylhydrazone Compounds Containing Pyrazine Rings and Halogen Atoms

Three new kinds of acylhydrazone compounds(C_(12)H_(10)FN_5O·H_2O,1;C_(12)H_(10)Cl N_5O·2CH_3COOH,2;C_(12)H_(10)Br N_5O,3)were synthesized by the reaction of 2-amino-3-pyrazinecarbohydrazide(C_5H_7N_5O)with halogenated benzaldehyde(C_7H_5OX,X=F,Cl,Br).The structures of the three compounds were characterized by elemental analysis,~1H NMR,IR and X-ray diffraction.X-ray single-crystal diffraction presents that the three compounds all belong to triclinic system,P1 space group.Thermal gravity analyses show that three compounds have excellent thermal stabilities and all the thermal decomposition temperature of maximum weight loss was around 300°C.The interactions of the compounds with CT-DNA were investigated by UV-Vis spectrum,fluorescence spectrum and viscosity measurement.All the results suggest that three compounds could bind with CT-DNA through intercalation.The fluorescence spectrum was also used to study the interactions of three compounds with BSA.It was proved that all the compounds could quench the intrinsic fluorescence of BSA via a static quenching process.Compound 2 displays the strongest binding ability both in the reaction with CT-DNA or BSA.Antimicrobial test was carried on Escherichia coli,Staphylococcus aureus and Salmonella,and 2 is more effective against S.aureus.But in MTT assay,1 shows better cytotoxity activity against A549cells.     

Synthesis of Schiff Base-type Liquid Crystalline Crown Ethers Containing Dibenzo-18-Crown-6 Unit

The synthesis and characterization of novel Schiff base liquid crystalline crown ethers prepared from the intermediates 4-(4‘-alkoxylbiphenyl-4-carbonyl)benzaldehyde, cis- and trans-4,4‘-diaminodibenzo-18-crown-6 are described. The structure of these compounds have been well characterized by elemental analysis, IR, ^1H NMR and MS spectroscopy. The liquid-crystalline behavior of these compounds was also inverstigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) with a heating stage and polarimetric analysis.     

STUDIES ON ORGANOMETALLIC COMPOUNDS OF TITANIUM,ZIRCONIUM AND HAFNIUM——THE SYNTHESES AND PROPERTIES OF BIS (CYCLOPENTADIENYL) AND BIS (METHYLCYCLOPENTADIENYL) DI(ARYL)-METAL DERIVATIVES

Aryllithium reacts with Cp_2MCl_2 and Cp'_2 MCl_2 (C_p=η~5-C_5H_5, C_P′=η~5-CH_3C_5H_4:M=Ti, Zr, Hf) respectively to prepare a series of new bis (cyclopentadienyl), bis (methy-lcyclopentadienyl) diaryl derivatives of titanium, zirconium and hafnium. The hydrolysicreaction of these organometallic compounds are studied, the derivatives of zirconium andhafnium can be easily hydrolyzed with the exception of that of titanium. They react withhydrogen chloride, acetyl chloride, bromine and haloacids to form the respective bis(cyclo-pentadionyl) dihalides of these metals. The NMR and IR spectra were discussed in regardto the structure of (η~5--CH_3C_5H_4)_2 MAr_2 and (η~5--CH_3C_5H_4)_2 MX_2.     

IONIC CONDUCTIVITY AND CATALYTIC PERFORMANCE OF A_2BO_4/La_2O_3 CATALYSTS FOR OXIDATIVE COUPLING OF METHANE

A series of La_2O_3 cartalysts modified by A_2BO_4 compounds with supe-rionic conductivity were prepared. It was observed that the addition of A_2BO_4compounds to La_2O_3 enhances C_2 yields, and the C_2 yields over the modified cat-alysts are intimately related with their conductivities. The effects of A_2BO_4compounds on the conductivity and catalytic performance were discussed. Onlywhen ion A has high conductivity, can the catalyst show good catalytic perfor-mance. A mechanism for interpreting the significant effects of alkali metals wasproposed.     

The Synthesis, Reaction and Crystal Structures of Ethyltetramethylcyclopentadienylruthenium Compounds

Pentamethylcyclopentadienyl-trimethylphosphine-metal compounds play an important role in the activation studies of saturated hydrocarbons. A method to synthesize ethyltetramethylruthenium compounds was established, which started from the reaction of RuCl_3. H_2O with ethyltetramethylcyclopentadiene to give a dimer compound of 2. When 2 was reacted with different amounts of trimethylphosphine, compounds 3 [C_5Me_4EtRu(PMe_3)Cl_2] and 4 [(C_5Me_4Et)Ru(PMe_3)_2Cl] were obtained. Compound 3 is a 17-electron species which is in formula similar to Bergman's Ir compound used in hydrocarbon activation reaction, but might be more reactive because of its unsaturated electron structure. The crystal structure analysis of compounds 2, 3 and 4, showed that the ruthenium atom was coordinated in a "threeleg-piano-stool" geometry in all the three compounds. The Ru—Cl bond in 3 and 4 was lengthened, making it labile to other substitution reactions.     

Synthesis,Characterization and Properties of Bipolar Triphenylamine Charge Transport Materials

Four bipolar triphenylamine(TPA) charge transport materials were constructed by introducing imidazole and trifluoroacetyl groups into the TPA units, and characterized by the nuclear magnetic resonance spectrum(NMR) and mass spectrometry(MS). Among them, 4-(2-(1,3-trifluoroacetyl)imidazole)-phenyl-4,4?-di(4-methoxyphenyl)amine(2 Me OTPA-IOS, 1) was determined by X-ray single-crystal diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 24.338(5), b = 9.565(2), c = 11.456(2) ?, β = 99.427(3)°, Mr = 565.47, V = 2631.0(8) ?3,Z = 4,Dc = 1.428 g/cm3, μ = 0.125 mm–1, F(000) = 1160, the final R = 0.0559 and wR = 0.1265 for 5150 observed reflections with I 2σ(I). The optimized configurations of the target compounds were obtained by quantum chemical calculation, and the bipolarity of transportable holes and electrons was predicted by the frontier molecular orbital(HOMO and LUMO), which was further confirmed by the time of flight(TOF) method. In addition, the introduction of the terminal flexible chain enhances the solubility, thermal stability(DSC and TGA) and film-forming property of all compounds, and the frontier orbital energy of the solid film of the compounds was also tested(UV-vis and PYS). Thus, these compounds have the bipolarity of transportable holes and electrons and show good solubility and thermal stability.     

Fluorescence chemosensors with pyrene and their interaction with nucleotide phosphate

A group of fluorescence chemosensor with pyrene, compounds (Ⅰ), (Ⅱ) and (Ⅲ), were synthesized The fluorescence spectra and the lifetime of these compounds were carefully measured. The fluorescence quenching spec tra of pyrenyl butyric acid, compounds (Ⅰ), (Ⅱ) and (Ⅲ) by different nucleotide phosphates, AMP ADP, ATP dTTP, were also recorded and studied. The quenching and the stability constants were calculated by Stern-Volmer equa tion and eq. (2), respectively. The mechanism of interaction between fluorescence chemosensor and nucleotide phos phate was didscussed based on the comparison of the results obtained with the CPK model of free molecules of these com pounds in the ground state.     

Synthesis and Thermal Properties of Three Energetic Ion Salts of 3,6-Bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]-1,2,4,5-tetrazine

Three energetic ion salts of 3,6-bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]-1,2,4,5-tetrazine(BTATz), namely, methylamine salt(compound 1), ethylenediamine salt(compound 2), and diethylamine salt(compound 3), were synthesized and characterized by elemental analysis, Fourier transform infrared spectrometry, NMR spectroscopy, and ^13C NMR spectroscopy. The crystal structure of compound 1 was determined by single-crystal X-ray crystallography, and structural analysis revealed that it belonged to the monoclinic system with P21/c space group. In addition, the thermal behavior of the three compounds was studied by differential scanning calorimetry and thermogravimetry techniques. The thermal decomposition peak temperatures of the compounds were 574.89, 545.60, and 606.72 K, indicating that the three ion salts exhibited good thermal stability. Tlie kinetic mechanism equations of the main decomposition process and the entropy of activation(△S^≠), enthalpy of activation(△H^≠), and Gibbs free energy of activation(△G^≠) of the three compounds were also obtained. Moreover, the thermal safety of the compounds was evaluated by the values of the self^accelerated decomposition temperature(Tsadt)5 thermal ignition temperature(TTIT), and critical temperature of thermal explosion(7b). The results showed that all the compounds demonstrated good thermal safety, and the thermal safety of compound 3 was better than that of the others.     

(n-C18H37NH3)2MCl4热容的测定

在差示扫描量热仪(DSC仪)上, 采用扫描热焓法测定物质的热容, 实验精度达到±1%左右. 在190-410 K温度区间内, 测定了四氯合金属酸(Ⅱ)正十八铵(n-C_(18)H_(37)NH_3)_2MCl_4(M=Mn和Zn; 简称C_(18)M)的热容. 同时测定了C_(18)M的固-固相变焓和相变熵. 本文报导了C_(18)M每隔5 K的热力学函数.     

单取代二茂铁西佛碱型液晶化合物的合成及介晶性研究

报道了两个系列二茂铁衍生物，FcC_6H_4N＝CHC_6H_4OC_nH_(2n+1)（系列I） 和FcC_6H_4N＝CHC_6H_4O_2CC_6H_4OC_nH_(2n+1)（系列II）（Fc:ferrocenyl；n = 2，4，6，8，10，12，14，16），并通过DSC和热台偏光显微镜对其介晶性进行 了研究。系列I不具有介晶性，系列II呈较窄的液晶温度范围。其结果显示分子的 刚性部分长度对介晶性有重要影响。     

四氯合铜酸二烷基铵相变的热分析和红外光谱

用DSC和TG研究了(n-C_nH_(2n+1)NH_3)_2CuCl_4(n=7-12)(记为C_nM)配合物的热稳定性和固-固相变。由红外光谱讨论了C_9Cu三个相的性质。发现C_nM的热稳定性呈奇偶效应; 主相变峰温随链长增长而升高; 相变总ΔH和ΔS也随链增长而加大; 当n≤9时, 高温相为部分无序相; 而n≤10时, 高温相为构象无序相。C_9Cu的主相变主要源自链间堆积结构变化。而在307.7 K的相变主要与烃链有序-无序变化有关。     

Syntheses，Structures and Spectroscopic Properties of Mo（W）－Cu－S－Cluster Compounds with Dialkyldithiocarbamate Ligands

Ｓｙｎｔｈｅｓｅｓ，ＳｔｒｕｃｔｕｒｅｓａｎｄＳｐｅｃｔｒｏｓｃｏｐｉｃＰｒｏｐｅｒｔｉｅｓｏｆＭｏ（Ｗ）－Ｃｕ－Ｓ－ＣｌｕｓｔｅｒＣｏｍｐｏｕｎｄｓｗｉｔｈＤｉａｌｋｙｌｄｉｔｈｉｏｃａｒｂａｍａｔｅＬｉｇａｎｄｓＣａｏＲｏｎｇ；ＬｅｉＸｉｎ－Ｊｉ...     

轴向为烷氧基配位的萘酞菁硅配合物的光谱及光稳定性

轴向为烷氧基配位的萘酞菁硅配合物的光谱及光稳定性;萘酞菁硅;轴向烷氧基配位;光谱性质;光稳定性     

紫外光照下C_(60)与聚苯乙烯直接反应合成C_(60)-聚苯乙烯衍生物及电子自旋共振（ESR）研究

在室温，紫外光照下溶液相中C_(60)与聚苯乙烯的直接反应合成得聚苯乙烯的 C_(60)加合物。衍生物中C_(60)的含量可由C_(60)的投料比来控制。得到了产物经 UV－Vis，FTIR，GPC，TGA及DSC等波谱表片，测得产物的分子量比母体聚苯乙烯的 分子量稍高。对溶液相的反应进行了现场的ESR研究，得到强的PSC_(60)~(-·)的 自由基信号，g值为2.0024。同时对C_(60)和聚苯乙烯混合物固相体系的光照反应 进行了ESR测试。结果表明在反应过程中及最终产物中均存在稳定的C_(60)-高分子 链烃基自由基阴离子RC_(60)~(-·)。表明了反应的自由基机理。     

一些三唑类化合物的合成及其生物活性的研究

一些唑类化合物的广谱、高效、强内吸性杀菌作用和植物生长调节作用正受到人们广泛的关注。为筛选合成上简易,且有较高生物活性的化合物,作者设计了下列三类1,2,4-三唑和苯并1,2,3-三唑类化合物。其化学结构通式如下:     

咪唑基离子液体Br[C_(14)im](CH_2)_4[C_(14)im]Br对PP结构与性能的影响

应用Gemini型咪唑基离子液体和聚丙烯(PP)熔融共混,制备出Gemini型咪唑基离子液体改性PP,并对改性PP的结构与性能进行了表征与测试.研究结果表明,Br[C14im](CH2)4[C14im]Br添加到PP中后,起到了异相成核的作用,同时使PP晶体结晶度减小;添加离子液体的样品熔融峰温,结晶峰温与纯样相近,同时离子液体也诱导了PP中α晶的生成;Gemini型咪唑基离子液体可以提高PP的抗静电性能,加入量为3 phr时,表面电阻率为8.97×109Ωcm,抗静电性能优良;此外,添加离子液体后样品拉伸强度有所降低,冲击强度有所提高,断裂伸长率有所下降,降低了PP的玻璃化温度,说明离子液体对PP有增塑作用.     

杂多化合物的红外光谱研究

本文研究了与Ｋｅｇｇｉｎ结构相关的３１种３大系列（２：１８系列，１：１１系列和双系列）杂多化合物的红外光谱，它们是：ＮＰ２Ｗ１８（Ｎ＝（ＣＨ３）４Ｎ＾＋，（Ｃ２Ｈ５）４Ｎ＾＋，（Ｃ４Ｈ９）４Ｎ＾＋），ＭＰ２Ｗ１８（Ｍ＝Ｌｉ＾＋，Ｎａ＾＋，Ａｇ＾＋，Ｃｕ＾２＋）；ＫｎＺＷ１１（Ｚ＝Ｐ，Ｂ，Ｇｅ，Ｓｉ），ＭＳｉＷ１１（Ｍ＝Ｍｎ，Ｚｎ，Ｃｕ，Ｃｏ，Ｎｉ）和Ｍ（ＰＷ１１）２（Ｍ＝Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅ