2-(Ⅳ,Ⅳ-二羧甲基)-氨甲基4-氯酚铜(Ⅱ)的合成、结构与催化降解聚丙烯酰胺性能研究

合成了2-(N,N-二羧甲基)氨甲基4-氯酚,进而在水溶液中合成了其铜(Ⅱ)配合物,通过X-射线单晶衍射法测定了晶体结构.配合物中心Cu(Ⅱ)为五配位四方锥结构,在该配合物的晶体结构中存在两种构象异构体,相互问隔通过分子问氢键连接,延伸为一维链状结构.催化性能研究表明该配合物对H<,2>O<,2>的氧化降解聚丙烯酰胺有...     

希土硝酸盐与TTA和TPPO三元配合物的合成、表征和晶体结构

本文报道在无水乙醇中合成了TTA和TPPO与除Tm和Lu外的整个系列希土离子的三元配合物。实验发现,对于La、Ce形成组成为RE(NO_3)_2(TTA)(TPPO)_3的配合物;而对于其余希土离子则得到组成为RE(NO_3)(TTA)_2(TPPO)_2的配合物。培养出了Pr(NO_3)(TTA)_2(TPPO)_2配合物的单晶,测定了它的分子和晶体结构。根据结构数据讨论了配合物的红外和紫外光谱。     

[La(CCl_3COO)_3·dipy·H_2O]_2配合物的电子结构和化学键

作者曾系统研究[Ln(CCl_3COO)_3·dipy·H_2O]2配合物的合成和性质,并测定了[La(CCl_3COO)_3·dipy·H_2O]_2的晶体结构(待发表)。本文用量子化学INDO方法探讨镧配合物的电子结构和化学键。程序和参数见文献[1]。分子结构采用晶体结构数据。计算模型取配合物的一半,用HCOO~-代CCl_3COO~-,这样的近似对结果可能有影响,但在讨论羧基与La配位以及双聚机理时使图象更为简明清晰。分子骨架结构见图1,其中HCO_1O_5~-的一个氧     

Cd(ATZ)4( H2O)2] ( PA)2· 2H2O的合成、晶体结构和热分解机理研究

合成了以 5 -氨基四唑为配体的镉配合物 [Cd(ATZ) 4(H2 O) 2 ](PA) 2 ·2H2 O ,并对其进行了晶体结构测定 .测定结果表明 ,该配合物分子具有中心对称性 ,每个Cd2 +分别与 2个水分子中的氧原子和 4个 5 -氨基四唑 (ATZ)分子中的 4-位氮原子配位 ,形成六配位畸变八面体结构 ;在配合物分子间存在大量氢键 ,增加了整个晶体结构的稳定性 .通过DSC和TG -DTG分析 ,提出了标题化合物的热分解机理     

两个salen型卤代希夫碱Ni(Ⅱ)配合物的合成、晶体结构及Hirshfeld表面分析（英文）

通过硝酸镍与卤代希夫碱在甲醇溶液中反应,合成了2个Ni(Ⅱ)希夫碱配合物[Ni(3,5-Cl-salcy)](1)和[Ni(3-Cl-salcy)](2),(3,5-Cl-salcyH2=N,N′-(±)-双(3,5-二氯水杨基)-1,2-环己二胺;3-Cl-salcyH2=N,N′-(±)-双(3-氯水杨基)-1,2-环己二胺)。通过X射线衍射测定了2个配合物的结构。结构分析表明2个配合物的基本单元均为Ni(Ⅱ)离子通过与希夫碱配体的[N2O2]原子配位构成相似的平面型单核配合物。Platon软件分析表明配合物1中并不存在任何氢键,配合物2也仅存在非经典氢键。通过Hirshfeld表面分析法对2个配合物晶体结构中弱交换作用的分析结果表明,虽然卤原子构成的氢键相对较弱,但是C-H…X在稳定三维超分子晶体结构中起着非常重要的作用;此外,通过2个配合物的对比发现,配体中卤原子数量的不同对于晶体中弱交换作用的占比可以起到非常重要的影响。     

Y—Al双金属稀土配合物的合成和晶体结构

稀土化合物和烷基铝反应的研究,不仅对揭示f轨道的本质且对阐明稀土配位催化聚合烯烃的催化剂结构都有重要意义。Grcco等曾报道C_8H_8Ce(μ-O-i-C_3H_7)_2Al(C_2H_5)_2配合物,但尚未见晶体结构数据。 本文介绍了一种新的Y-Al双金属配合物的合成和培养晶体的方法。用四圆衍射仪确定了它的晶体结构,并用~1H NMR、ESCA等方法研究了配合物中钇的价态。     

[Cd(ATZ)~4(H~2O)~2](PA)~2·2H~2O的合成、晶体结构 和热分解机理研究

合成了以5-氨基四唑为配体的镉配合物[Cd(ATZ)~4(H~2O)~2](PA)~2·2H~2O,并对其进行了晶体结构测定。测定结果表明,该配合物分子具有中心对称性,每个Cd^2^+分别与2个水分子中的氧原子和4个5-氨基四唑(ATZ)分子中的4-位氮原子配位,形成六配位畸变八面体结构;在配合物分子间存在大量氢键,增加了整个晶体结构的稳定性。通过DSC和TG-DTG分析,提出了标题化合物的热分解机理。     

SCN-桥联的铜配合物：抗肿瘤活性及对肿瘤细胞耗氧的影响

合成和表征了一种新的N-苯基二吡啶甲基胺(phdpa)铜配合物[(phdpa)Cu(SCN)](ClO4)。X-衍射晶体结构数据显示配合物中铜原子与配体phdpa中3个N原子、SCN-中S原子和邻近分子中SCN-中N原子配位,形成扭曲八面体结构。生物活性数据显示该铜配合物抑制HepG-2细胞的生长,半数抑制率为10.4μmol.L-1。进一步机理研究数据显示这种SCN-桥联的铜配合物能诱导HepG-2细胞核的分裂,降低其耗氧量和ROS的含量,这表明该铜配合物是一种能影响HepG-2细胞氧代谢的多功能配合物。     

Schiff碱吡啶-2-甲醛缩氨基脲铅(Ⅱ)配合物的合成和晶体结构

缩氨基脲(或含硫)希夫碱及其配合物具有抗病毒、抗菌、抗麻风病等生物活性[1-3],因而引起了人们极度大的关注[4-6]。为了拓宽缩氨基脲及其配合物的研究领域,进一步了解该类化合物的结构特征,本文报道了Schiff碱吡啶-2-甲醛缩氨基脲铅(Ⅱ)配合物的合成和晶体结构。1实验部分1·1试剂和仪器吡啶-2-甲醛、盐酸氨基脲、硝酸铅、乙醇、乙酸钠等均为分析纯。VarioEL元素分析仪(德国ELEMENTAR公司),美国N icolet 50XB傅立叶红外光谱,AVANCE AV500MHz核磁共振仪,R igaku Mercury CCD衍射仪。1·2希夫碱吡啶-2-甲醛缩氨基脲(PNS)的合成…     

η~6-芳烃稀土有机配合物的合成、结构及性能研究——Ⅱ.Sm(η~6-CH_3C_6H_5)(η~2-AlCl_4)_3的合成及晶体结构

在前报中,从对η~6-苯钐配合物Sm(η~6-C_6H_5)(η~2-AlCl_4)_3的晶体结构测定,得到配合物中Sm-C键平均键长为2.92 ,这一结果,与Cotton报道的Sm(η~6-C_6Me_6)(η~6-AICI_4)_3中的Sm-C键平均键长(2.89 )相比,明显地增大了。可见,配体芳烃与相应的稀土有机配合物的结构有着密切的关系。为了进一步了解苯环上甲基取代数目对这类配合物结构的影响规律,我们以甲苯为配体,研究了η~6-甲苯钐有机配合物的合成及晶体结构。     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。