三硝基均苯三酚及其碱金属盐晶体的周期性密度泛函理论研究

对三硝基均苯三酚(TNPG)及其碱金属盐晶体进行DFT-B3LYP周期性计算研究, 求得其能带和电子结构, 探讨了结构-性能关系. 研究结果表明, 晶胞结构参数的计算值与实验值吻合较好. TNPG的导电性介于半导体和绝缘体之间, 而其碱金属盐均为半导体. 金属离子的引入使TNPG阴离子和金属阳离子通过配位键形成三维无限网状结构, 这种网状结构与晶体的半导体性质相关联. TNPG及其碱金属盐的前线轨道主要是由C—NO₂的原子轨道组成, 配位水和金属离子对前线轨道的组成没有贡献. TNPG碱金属盐的带隙均比TNPG的小, 根据“最易跃迁原理”可推测碱金属盐均比TNPG敏感, 这与实验事实相符. 同时, 金属离子的引入增大了酚羟基上的氧原子的活性, 这也可能是导致碱金属盐比TNPG敏感的原因之一.     

分子间作用力对咪唑盐介晶相性质的影响

通过对咪唑环1位(N1)取代烷基、3位(N3)取代基及阴离子的修饰合成了一系列具有近晶A (SmA)相的咪唑类离子液晶. 利用差示扫描量热法、单晶衍射、小角度X射线衍射等手段研究了咪唑盐的介晶相温度范围、介晶态的结构, 并测量了部分咪唑盐的各向异性导电率. 结果表明, 咪唑环N1取代烷基、N3取代基及咪唑盐的阴离子会改变分子间范德华力和氢键, 从而对咪唑盐的介晶相性质产生影响. 此外, 当乙烯基引入到咪唑环N3位置时, 咪唑盐相邻的层结构之间形成π-π堆积作用, 不仅有利于介晶态的形成, 同时使氟硼酸类离子液晶具有最大的层间距和最小的各向异性导电率. 这一结果表明, 调控离子液晶的性质时必须综合考虑各种分子间作用力的影响.     

（＋）-α-苯乙胺磷钨杂多化合物的合成、表征和催化不对称环氧化性能

以Keggin型12-磷钨酸和( )-α-苯乙胺为原料,通过水热法合成了具有Keggin结构的( ).α-苯乙胺磷钨酸盐(C8H12-N)3PW12O40.通过红外光谱、核磁共振波谱、紫外光谱、元素分析和热重分析等技术对合成产物进行了结构、组成和热稳定性的表征和考察,证实了合成产物为( )-α-苯乙胺磷钨酸盐.以顺丙烯磷酸-α-苯乙胺盐环氧化合成(1R,2S).环氧丙基磷酸-a-苯乙胺盐为探针反应,考察了(C8H12N)3PW12O40催化不对称环氧化性能.结果表明,在催化剂用量为2.00%和反应温度为50℃时,产物环氧丙基磷酸苯乙胺盐的收率为64%,(1R,2S)-环氧丙基磷酸苯乙胺盐的对映选择性ee值为10.8%.     

碘酸铯的晶体结构

大多数碘酸盐具有良好的电光、非线性光学和压电性能,因此,人们对碘酸盐的结构和性能进行了广泛的研究,已测定了锂、钠、钾、铷等碱金属碘酸盐的晶体结构,并观察到CsIO_3粉末也具有较强的倍频效应.由于难以生长单晶和结构上呈现赝立方对称性,至今人们还未确定出其晶体结构.因此,碱金属碘酸盐随碱金属原子半径的增大,其晶体结构类型发生变化的规律并没有完全阐明,解决 CsIO_3的晶体结构,对了解碱金属碘酸盐结构类型的变化具有一定的意义.     

二铁氧还盐和四铁氧还盐的电子结构

本文采用CNDO/2-SD方法计算了二铁氧还盐及四铁氧还盐的电子结构.与Roussin 红盐及Roussin 黑盐的电子结构比较,相似之处为:在铁局部对称性为四面体的簇合物中, Fe-Fe间相互作用主要由铁的s,p电子的σ贡献产生, 金属d轨道的π相互作用在占有轨道区间同时具有成键和反键贡献, 因而对骨架的形成几乎无贡献. 骨架μ2-S桥含有孤对电子,有形成μ3-S桥的可能, 但以桥硫孤对电子贡献为主的轨道都不是前线轨道. 不同之处在于端基为SH的簇合物骨架电子的非定域性较端基为NO时更强. 二核簇合物Fe与端基SH的成键能力比与NO的小, 因而在自兜反应中容易失去端基SH而形成封闭型结构.     

四种新型柔性吡啶基配合物的合成、结构及配体构象与配合物结构的关系

合成了柔性配体3-吡啶甲酸-1,2-乙二酯(3-pyridinecarboxylic acid 1,2-ethanediyl ester,pcaede),并将其分别与Co盐和Hg盐进行组装,得到4个新配合物[Co(pcaede)2Cl2.2CH3CN.H2O]n(1),[Co(pcae-de)2Cl2.H2O]n(2),[Hg(pcaede)I2]n(3)和[Hg(pcaede)Br2]n(4),对其进行了元素分析、红外光谱及X射线单晶结构分析.配合物1和2为含有孔道的一维链状结构,配合物3是1D内消旋螺旋链,配合物4则是锯齿形1D链状结构.研究结果显示,孔道中填充的溶剂分子和平衡阴离子对配合物的组装有显著的影响.此外对4个配合物中配体的构象进行了理论计算.     

弱碱K~2CO~3体系中酚酞盐的结构特征

用红外光谱、核磁共振谱鉴定了弱碱K~2Co~3体系和强碱KOH体系中制备的酚酞钾盐, 在弱碱K~2Co~3体系中, 酚酞成盐以完全内酯式结构为特性, 而在强碱KOH体系中,酚酞成盐主要是醌式结构。从而发现成盐反应中所使用的碱本身的性质是决定生成酚酞盐结构的关键因素。     

Ferrihydrite的亚微观结构对反应活性的影响

以Fe(III)盐为原料、NaOH为沉淀剂、采用三种方法调控制备了ferrihydrite, 借助X射线衍射(XRD)、红外光谱(IR)、差热分析(DTA)及其在稀盐酸中的溶解速率等手段对其结构进行了表征, 探讨了ferrihydrite的形成环境对其亚微观结构及其反应活性的影响. 结果表明, 不同方法制备的ferrihydrite的亚微观结构不同, 恒pH条件下制备的ferrihydrite结构与α-Fe2O3结构最为相似, 更易转化为α-Fe2O3粒子.     

1,2,3-三氨基胍二硝基胍盐的合成与量子化学研究

以1,2,3-三氨基胍盐酸盐和二硝基胍为原料,制备了一种新型含能离子盐1,2,3-三氨基胍二硝基胍盐,并对其结构进行了表征. 运用密度泛函理论（DFT）方法,在B3LYP/6-31+G^**水平下计算得到了该盐的几何结构、自然原子电荷分布、前线轨道能量及红外光谱,同时计算了热容、焓及熵等热力学参数,并分析了这些参数和温度之间的函数关系;利用Born-Haber循环求得该化合物的生成热为150.54 kJ/mol;利用Monte-Carlo方法预测了该化合物的理论密度为1.56 g/cm³;基于以上数据进一步计算得到该化合物的爆速为7.81 km/s,爆压为24.74 GPa.     

水热-热解法制备具有一维结构的Co3O4多晶

采用温和的水热-热解法, 在一定温度下, 通过调节Na2CO3溶液和可溶性钴盐的摩尔比控制产物的形貌, 得到具有一维结构的水热产物. 以该产物为前驱体制备了具有一维结构的Co3O4多晶. 以六次甲基四胺、尿素等代替Na2CO3溶液作为沉淀剂, 均得到了一维纳米结构的Co3O4, 表明CO2-3在水镁石CoO2层间的嵌入是得到一维结构水热产物的关键.     

几类醚化物的水溶性、碱水溶解性和酸解活性

本文对几类典型醚类化合物的水溶性、碱水(5%的Na₂SiO₃·9H₂O)溶解性和酸解活性进行了初步研究,查阅了这些醚类化合物的水溶性,并测定了其碱水溶解性、临界碱水不可溶醚当量以及在微量酸存在条件下的酸解活性,研究结果表明,对一般醚类化合物而言,当醚键中不含p-π共轭时其临界水不溶醚当量为116,临界碱水不溶醚当量为102;当醚键中含p-π共轭时其临界水不溶醚当量在56-100之间,临界碱水不溶醚当量在56-72之间,这些数据对光/热成像用活性醚化物阻溶/促溶剂的分子设计以及碱显影成像制版具有重大的指导意义。     

异丁烯与对氯甲基苯乙烯正离子共聚合研究

以四氯化钛(TiCl4)、二氯乙基铝(AlEtCl2)、倍半铝(AlEt1.5Cl1.5)、三氯化铝(AlCl3)等路易斯酸为共引发剂,水或枯基醇(CumOH)为引发剂,在-80℃下的正己烷/二氯甲烷(V/V=6/4)的混合溶剂内,研究了异丁烯(IB)与对氯甲基苯乙烯(p-CMS)的正离子共聚合.利用示差凝胶渗透色谱仪(GPCRI)以及核磁氢谱(1H-NMR)对共聚物的表观分子量及分子量分布、共聚组成等进行分析,采用KelenTüd?s与Yezreielv-Brokhina-Roskin法计算了单体竞聚率,初步探讨了p-CMS与IB正离子共聚合的反应机理.结果表明,AlEtCl2、AlEt1.5Cl1.5、AlCl3均可催化大分子间的烷基化反应,产生凝胶;TiCl4作为共引发剂,可以得到无凝胶单峰分布共聚物;邻位氯甲基苯乙烯(o-CMS)不能参与共聚,p-CMS的共聚活性较低,IB与p-CMS的单体竞聚率为rIB=4.67,rp-CMS=0.70;随反应时间延长,共聚物中p-CMS的含量及共聚物分子量均逐渐增加;p-CMS单体自身几乎不参与引发,共聚到大分子链后,苄基氯缓慢参与引发,形成支化.提高共聚合温度至-60和-40℃,聚合速率降低,p-CMS的引发活性未发生明显变化.     

Imidazo[2,1-b]benzothiazoles. II. Synthesis and antiinflammatory activity of some imidazo[2,1-b]benzothiazoles

3-[2-[p-(Un)substituted phenyl]imidazo [2,1-b]benzothiazol-3- yl]propionic acid derivatives (2a--e) were prepared via the interaction of the corresponding 2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazoles (1a--e) with acrylic acid in the presence of acetic anhydride and acetic acid. Esterification of 2a--e produced methyl esters (3a--e). Upon the interaction of 3a with m-chloroperbenzoic acid, the S-dioxide (4a) was obtained. Compound 5a was prepared from 4a by alkaline hydrolysis. Vilsmeier formylation for 1a--e produced novel [2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazol-3- yl]formaldehyde derivatives (6a--e). Derivatives 6a--e reacted with ethyl bromoacetate to give ethyl 3-hydroxy-3-[2-[p-(un)substituted phenyl]imidazo[2,1-b]benzothiazol- 3-yl]propionate esters (7a--e). Compound dl-7a was resolved with l-(+)-tartaric acid. Compounds 2a--e showed weak or no activity in the carrageein-induced paw edema assay. Compound 4a significantly inhibited the leakage of pontamine-sky blue dye into the peritoneal cavity of mice, in the capillary permeability inhibition assay. Compound 5a inhibited the writhing by 62% in the acetic acid-induced writhing assay.     

Higher-order equation-of-motion coupled-cluster methods for electron attachment

High-order equation-of-motion coupled-cluster methods for electron attachment (EA-EOM-CC) have been implemented with the aid of the symbolic algebra program TCE into parallel computer programs. Two types of size-extensive truncation have been applied to the electron-attachment and cluster excitation operators: (1) the electron-attachment operator truncated after the 2p-1h, 3p-2h, or 4p-3h level in combination with the cluster excitation operator after doubles, triples, or quadruples, respectively, defining EA-EOM-CCSD, EA-EOM-CCSDT, or EA-EOM-CCSDTQ; (2) the combination of up to the 3p-2h electron-attachment operator and up to the double cluster excitation operator [EA-EOM-CCSD(3p-2h)] or up to 4p-3h and triples [EA-EOM-CCSDT(4p-3h)]. These methods, capable of handling electron attachment to open-shell molecules, have been applied to the electron affinities of NH and C2, the excitation energies of CH, and the spectroscopic constants of all these molecules with the errors due to basis sets of finite sizes removed by extrapolation. The differences in the electron affinities or excitation energies between EA-EOM-CCSD and experiment are frequently in excess of 2 eV for these molecules, which have severe multideterminant wave functions. Including higher-order operators, the EA-EOM-CC methods predict these quantities accurate to within 0.01 eV of experimental values. In particular, the 3p-2h electron-attachment and triple cluster excitation operators are significant for achieving this accuracy.     

Syntheses, structures, and anion-binding properties of two novel calix[2]benzo[4]pyrroles

Calix[2]benzo[4]pyrrole m-6 and p-6, each containing two dipyrromethane moieties and two m-phenylene or p-phenylene units, respectively, were readily synthesised from pyrrole, 1,3- and 1,4-bis(1,1'-dimethylhydroxymethyl)benzene, (m-4 and p-4, respectively) and acetone. Macrocycles m-6 and p-6 were tested as receptors for a selection of anions, such as acetate, dihydrogenphosphate and fluoride. The X-ray structures of m-6 and p-6 and those of the complexes m-6F(-), m-6Cl(-) and m-6CH(3)COO(-) (with an nBu(4)N(+) counterion) were also determined.     

Cyclopropenylidene carbene ligands in palladium catalysed coupling reactions: carbene ligand rotation and application to the Stille reaction

Reaction of [Pd(PPh(3))(4)] with 1,1-dichloro-2,3-diarylcyclopropenes gives complexes of the type cis-[PdCl(2)(PPh(3))(C(3)(Ar)(2))] (Ar = Ph 5, Mes 6). Reaction of [Pd(dba)(2)] with 1,1-dichloro-2,3-diarylcyclopropenes in benzene gave the corresponding binuclear palladium complexes trans-[PdCl(2)(C(3)(Ar)(2))](2) (Ar = Ph 7, p-(OMe)C(6)H(4)8, p-(F)C(6)H(4)9). Alternatively, when the reactions were performed in acetonitrile, the complexes trans-[PdCl(2)(NCMe)(C(3)(Ar)(2))] (Ar = Ph 10, p-(OMe)C(6)H(4)11 and p-(F)C(6)H(4)) 12) were isolated. Addition of phosphine ligands to the binuclear palladium complex 7 or acetonitrile adducts 11 and 12 gave complexes of the type cis-[PdCl(2)(PR(3))(C(3)(Ar)(2))] (Ar = Ph, R = Cy 13, Ar = p-(OMe)C(6)H(4), R = Ph 14, Ar = p-(F)C(6)H(4), R = Ph 15). Crystal structures of complexes 6·3.25CHCl(3), 10, 11·H(2)O and 12-15 are reported. DFT calculations of complexes 10-12 indicate the barrier to rotation about the carbene-palladium bond is very low, suggesting limited double bond character in these species. Complexes 5-9 were tested for catalytic activity in C-C coupling (Mizoroki-Heck, Suzuki-Miyaura and, for the first time, Stille reactions) and C-N coupling (Buchwald-Hartwig amination) showing excellent conversion with moderate to high selectivity.     

N－丙烯酰基－N＇－苯基脲及其衍生物的合成与聚合反应

 以三种合成路线分别合成了含有脲键的一类单体，Ｎ－丙烯酰基－Ｎ’－苯基脲（ＡＰＵ）、Ｎ－甲基丙烯酰基－Ｎ’－苯基脲（ＭＰＵ）、Ｎ－甲基丙．烯酰基－Ｎ’－对甲苯基脲（ＭＴＵ），通过单体的自由基聚合与共聚合，制备了均聚物和共聚物，经ＩＲ、１Ｈ—ＮＭＲ表征和ＴＧＡ、ＤＳＣ测定．     

Synthesis,chemical nuclease activity,and in vitro cytotoxicity of benzimidazole-based Cu(Ⅱ)/Co(Ⅱ) complexes

In this study, novel mono/di-nuclear Cu(p-2-bmb)(OH)(ClO₄) (1) and Co₂(p-2-bmb)₂Cl₄ (2) (p-2-bmb=1- ((2-(pyridin-2-yl)-benzoimidazol-1-yl)methyl)-1H-benzotriazole) complexes with the nitrogen heterocyclic benzimidazole-based ligand were synthesized and characterized. The two complexes showed antiproliferative effects in various carcinoma cell lines, especially complex 1 in the SMMC7721 tumor cell line. Complex 1 was also able to pass through the cell membrane and enter the nucleus and mitochondrion. An analysis of in vitro chemical nuclease activity revealed that complex 1 partially intercalated to calf thymus DNA and exhibited strong unwinding activity against pBR322 superhelical plasmid DNA. The comet assay and flow cytometry analysis confirmed that 1 caused extensive DNA damage and arrested SMMC7721 tumor cells at G2/M phase of the cell cycle, leading to loss of mitochondrial membrane potential and apoptosis. These results suggest that these benzimidazole-based metal complexes could be potential anti-cancer agents.     

叔丁基二甲硅氧基苯硼酸及羟基苯硼酸的制备

以邻、间、对三种溴酚为原料, 经叔丁基二甲基氯硅烷保护酚基后制成格氏试剂, 然后与硼酸酯反应, 选择性水解得到了邻、间、对-叔丁基二甲硅氧基苯硼酸, 收率分别为51%, 44%和40%. 将对位、间位的硼酸酯中间体3a, 3b用强酸水解可得到间羟基苯硼酸(产率65%)和对羟基苯硼酸(产率14%), 但发现它们极难纯化, 这是由于羟基硼酸极易生成苯二酚之故.     

Azo-Derivatives of Gossypol and Its Imines

Azo-coupling of diazotized aromatic amines with gossypol and gossypolimines was studied. The physicochemical properties and interferon-inducing activity of the products were determined. It was found that the interferon-inducing activity depended on the reaction type, the position of functional groups (o-, m-, p-) in the added substituents, and the dose and contact time of the compounds with the cells.