有生物活性的稀土-腺苷三磷酸系列物的合成及其量子化学理论计算的研究

本文首次报道合成了稀土-腺苷三磷酸固态配合物RE(Ⅲ)-ATP(RE=Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)。运用红外、激光Raman、热分析、紫外、顺磁、X射线衍射、元素分析、配位滴定等技术测定了上述配合物的化学组成和分子结构,其分子式用通式表为[RE(Ⅲ)(HATP)(H_2O)_4]。采用量子化学INDO方法计算了系列物的电子结构,依据计算结果讨论了生物化学中高能磷酸键的本质。     

具有生物活性的金属配合物的研究——Ⅵ.3,6-二(二甲氨基)-二苯并碘六环镧反式-1,2-环己烷二胺四乙酸配合物的合成、性质及抗肿瘤活性

反式-1,2-环己烷二胺四乙酸(H_4DCTA)可作为体内锰中毒的解毒剂,它在溶液中与稀土离子的配合行为及体内载体效应和代谢机制均曾被研究。但H_4DCTA的稀土配合物作为抗癌药物的筛选以及其配阴离子[RE(DCTA)]-的抗衡离子是大体积有机阳离子的配合物的合成则未见报道。为此我们在完成了[C_(17)H_(20)N_2I][RE(EDTA)]·nH_2O[C_(17)H_(20)N_2I]_3[RE(Cit)_2]·nH_2O及[C_(17)H_(20)N_2I]_3[RE(NTA)_2]·nH_2O等多种配合物的     

三个含2,4-二氯苯乙酸配体的Mg(Ⅱ)、Ca(Ⅱ)和Cd(Ⅱ)配合物的合成及晶体结构（英文）

以2,4-二氯苯乙酸、4,4'-联吡啶分别和硫酸镁、氯化钙和硝酸镉反应,采用自然挥发法制备了3个配合物[Mg(DCBA)_2(H_2O)_4]·3(4,4'-bipy)(1)、[Ca(DCBA)(H_2O)_4]·DCBA·H_2O(2)和[Cd(DCBA)_2(H_2O)_2]·2H_2O(3)(DCBA=2,4-二氯苯乙酸,4,4'-bipy=4,4'-联吡啶),并对其进行了元素分析、红外光谱、热稳定性和X射线单晶衍射的表征,研究了配合物3的荧光性质。结果表明,配合物1、2和3均为零维结构,其中,配合物1中存在O-H…O、O-H…N、C-H…O、C-H…Cl和O-H…π氢键作用,而配合物2和3中存在O-H…O和C-H…Cl氢键作用,并以此分别形成了3D超分子结构。     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应（英文）

RE(CH_2SiMe_3)_3(THF)_2和1.5 equiv.(C_4H_3NHCH_2)_2NCH_3 (1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η~1:η~1:η~1-(C_4H_3NCH_2)_2NCH_3]RE{μ-η~5:η~5:η~1-(C_4H_3NCH_2)_2NCH_3}RE[η~1:η~1:η~1-(C_4H_3NCH_2)_2NCH_3](THF)[RE=Y(2),Er(3), Yb (4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

稀土高氯酸盐与1,10—二氮杂菲—1—氧化物的配合物研究

本研究合成出十三种稀土高氯酸盐与phenNO的配合物。元素分析确定配合物的组成为RE(phenNO)_4(ClO_4)_3·H_2O(RE=La、Pr、Nd,Sm～Lu)。对该系列配合物的红外光谱、紫外光谱、荧光光谱、热谱、摩尔电导等性质进行了研究。     

稀土与含硫有机配体配合物的研究 Ⅴ.哌啶荒酸重稀土配合物的制备与性质

在干燥的氮气氛中制备了重稀土与哌啶荒酸形成的7个固体配合物,确定其组成为C_5H_(10)NH_2[RE(S_2CNC_5H_(10)_4]·xH_2O(RE=Y,Tb～Er;x=2,6)和RE(S_2CNC_5H_(10))Cl_2·2H_2O(RE=Tm、Yb)。通过红外光谱、摩尔电导、差热-热重分析等对配合物进行了鉴定。结果表明,在该类配合物中配体通过硫原子以二齿形式与稀土离子配位。     

稀土与含硫有机配体配合物的研究(Ⅷ)——甘氨酸二硫代甲酸镍与稀土醋酸盐多核配合物的合成与性质

在乙醇—水溶液中,用稀土醋酸盐与氨基乙酸二硫代甲酸镍[H_2Ni(Gc)_2]反应,制备出14种稀土元素的多核配合物,通过元素分析确定了配合物的组成为RENi(Gc)_2·AC·H_2O(RE=La—Gd,除Ce、Pm外)和RE_2[Ni(Gc)_2]_3·xH_2O(RE=Tb—Lu,Y;x=4,8,10),研究了配合物的溶解性、红外光谱、X射线光电子能谱和核磁共振氢谱。     

具有生物活性的金属配合物的研究 Ⅲ.3-6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物的合成、性质及抗肿瘤活性

合成了十五种新的3,6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物,其化学式为:[C_(17)H_(20)N_2I]_3[RE(C_6H_5O_7)_2]·xH_2O(RE=La-Nd,x=5;Sm-Tb,x=4;Dy-Lu,Y,x=3)。利用X射线粉末衍射、热重-差热,红外光谱、紫外光谱、摩尔电导等对这些配合物进行了表征。试验表明,镧配合物对L_(7712)癌细胞DNA合成的抑制率(97.3％)明显高于其前体(C_(17)H_(20)N_2I~+·HCOO~-,72.5％;Na_3[La(C_6H_5O_7)_2],-16.5％)。     

三个金属-乳清酸配合物的合成、结构和氢键作用（英文）

嘧啶衍生物乳清酸作为一种生物小分子较少应用到金属-有机配合物的合成中。我们应用乳清酸与过渡金属盐反应,通过溶剂热方法合成了3个新颖的配合物:{[Cu(HOr)_2]·2NH_2(CH_3)_2}n (R-1)、[Co_2(HOr)_2(bipy)(H_2O)_6]·2H_2O (R-2)和{[Ni_2(HOr)_2(1,3-dpp)_2(H_2O)_2][Ni(HOr)(1,3-dpp)(H_2O)]2·(1,3-dpp)·2H_2O}n (R-3)(H_3Or=orotic acid,bipy=4,4′-bipyridine,1,3-dpp=1,3-di(4-pyridyl)propane)。应用X射线单晶衍射、元素分析、红外衍射、热重分析等对配合物进行了结构分析和表征。X射线单晶衍射分析表明:R-1是具有2D层结构的单核配合物,R-2为简单的单分子配合物,R-3则是由层和链组成的复杂三明治结构。这3个配合物均能通过分子间的氢键作用连接成三维的框架结构。     

基于水杨醛类席夫碱构筑的Fe(Ⅲ)、Co(Ⅲ)、混价Mn(Ⅱ)/Mn(Ⅲ)配合物的合成、晶体结构及磁性

以3-甲氧基水杨醛与乙醇胺缩合得到席夫碱化合物hmmpH_2(hmmpH_2=2-[(2-羟乙基亚氨基)甲基]-6-甲氧基苯酚),以hmmpH_2为配体合成了配合物[Fe_2(hmmp)_2(hmmpH)_2]·1.5CH_3CN·0.5H_2O(1)和[Co_2Na(hmmp)_2(N_3)_2(CH_3O)(CH_3OH)_2](2)。以3,5-二溴水杨醛与乙醇胺缩合得到化合物hmdbrpH_2(hmdbrpH_2=2-[(2-羟乙基亚氨基)甲基]-4,6-二溴苯酚),以hmdbrpH_2为配体合成了一个混价三核配合物[Mn(Ⅱ)Mn(Ⅲ)_2(hmdbrp)_2(O_2CPh)_4(CH_3OH)_2]·2CH_3CN·2CH_3OH(3)(HO_2CPh为苯甲酸)。对配合物分别进行了元素分析、X射线单晶衍射分析,还对1和3进行了磁性研究。单晶结构分析表明配合物1中2个六配位的Fe(Ⅲ)离子通过2个醇羟基氧原子相连形成二聚体结构,配合物2中Co(Ⅲ)也为六配位,通过2个甲醇中氧原子相连形成双核结构,配合物3为一混价三核锰结构,3个Mn离子呈线性排列。磁性测试表明配合物1中Fe(Ⅲ)离子之间存在反铁磁相互作用,配合物3的三核锰单元内Mn(Ⅱ)、Mn(Ⅲ)离子之间存在反铁磁相互作用。     

Furyl- and thienyl-silatranes and germatranes

We review our research on the synthesis and study of the physical and biological properties of furyl- and thienylgermatranes and -silatranes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 725–732, June, 1992.     

Review and patents and literature

The use of the insect cell/baculovirus expression system for producing recombinant proteins of bacterial, plant, insect, and mammalian origin has become widespread. The popularity of this eukaryotic expression system is due to many factors, including (1) potentially high protein expression levels, (2) ease and speed of genetic engineering, (3) ability to accommodate large DNA inserts, (4) protein processing similar to higher eukaryotic cells (e.g., mammalian cells), and (5) ease of insect cell growth (e.g., suspension growth). The following review of the literature discusses two engineering aspects of recombinant protein synthesis by insect cell cultures: bioreactor scale-up and insect cell line selection. Following this review patent abstracts and additional literature pertaining to expression of recombinant proteins in insect cell culture are listed.     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Preparation and photolysis of poly-p-ethylacrylophenone and poly-p-chloroacrylophenone and their copolymers with styrene and methyl methacrylate

Poly-p-ethylacrylophenone (PPEtAP) and poly-p-chloroacrylophenone (PPClAP) and their copolymers with styrene (PEtAP/S) and (PClAP/S) and with methyl methacrylate (PEtAP/MMA) and (PClAP/MMA) were prepared. Quantum yields of main-chain scissions at 366 nm at room temperature in benzene solution are of the same order as those of the unsubstituted polyacrylophenone and its copolymers. Substitution with chlorine and ethyl group in the para position compared to the unsubstituted polyacrylophenone and its copolymers leads to an increase of the lifetime for the n–π^* excited triplet state, as is evident from the measured quenching constants of photolysis. The low-temperature emission spectra of the copolymers are similar to the spectra of the model compounds in a polymer film. For the homopolymer, however, the character of the emission spectrum changes considerably.     

Concentrations and distributions of trace and minor elements in Chinese and Canadian coals and ashes

A total of 35 trace and minor elements including some of environmental significance were determined in each of a selection of 15 Chinese and 6 Canadian thermal coals and their ashes by using the SLOWPOKE-2 nuclear reactor facility of the University of Toronto. The concentrations and distributions of these constituents among the coals and their combustion products (viz. ash and volatile matter) are presented together with an interpretation of their significance in relation to the large scale combustion of these coals as thermal fuels in industrialized countries such as China and Canada. The detailed results showed wide variations in trace impurity concentrations (up to a factor of 100 and more) among the coals studied with few large differences between those of Chinese and Canadian origin except that the rare earths, Sc, Th, U, I, and Se were much higher in the former, other halogens, As and Na were lower. Values for elemental enrichment factors (EF) relative to normal crustal abundances indicated that only As(EF=13), Br(5.7), I(16), S(230), Sb(11) and Se(320) were appreciably enriched in coal. During static ashing at 750°C most of the halogens, S and Se were volatilized whereas most other inorganic constituents were highly retained and concentrated in the ash by factors of 6 to 11.