丙氨酸—N—荒酸镍与稀土多核配合物的合成,表征和抗癌,抑菌活性研究

本文报道了稀土与丙氨酸－Ｎ－荒酸镍「Ｈ２ＮｉＬ２」多核配合物的合成和表征。     

稀土与氨基酸固体配合物的合成及生物活性的研究

用稀土硝酸盐与γ－甲基－α氨基戊酸（白氨酸，Ｃ６Ｈ（１３）ＮＯ２）制得了８种组成为ＲＥ（Ｌｅｕ）３（ＮＯ３）３·ｎＨ２Ｏ（ＲＥ＝Ｌａ、Ｃｅ、Ｐｔ、Ｎｄ、Ｓｍ、Ｅｕ、Ｙｂ、Ｙ，ｎ＝１～３）的新固体配合物；与δ－胍基－α氨基戊酸（精氨酸，Ｃ６Ｈ（１４）Ｎ４Ｏ２）制得了４种组成为ＲＥ（Ａｒｇ）ｎ（ＮＯ３）３．ｍＨ２Ｏ（ＲＥ＝Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ，ｎ＝２～３，ｍ＝１～３）的新固体配合物。经元素分析、ＩＲ、摩尔电导及核磁共振时配合物进行厂表征。选用部分稀上盐，配合物及氨基酸分别对５种细菌、２种霉菌进行了生物活性试验，证明稀士氨基酸配合物均具有抑菌或杀菌作用。     

稀土（Ⅲ）（4＇－溴－5＇－硝基苯并－15－冠－5）配合物的制备与表征

在乙腈和丙酮介质中合成了６种轻稀土硝酸盐与４＇－溴－５＇－硝基苯并－１５－冠－５（Ｌ）的固体配合物，经元素分析确定其组成为ＲＥ（ＮＯ＿３）＿３·Ｌ（ＲＥ＝－Ｌａ～Ｎｄ），Ｓｍ（ＮＯ＿３）＿３·Ｌ·Ｈ＿２Ｏ和Ｅｕ（ＮＯ＿３）＿３·Ｌ·ＣＨ＿３ＣＮ·４Ｈ＿２Ｏ，并进行了ＩＲ、ＵＶ、ＴＧ－ＤＴＡ、摩尔电导及Ｘ－射线粉末衍射物相分析等表征，探讨了冠醚苯基上引入双取代基（－Ｂｒ，－ＮＯ＿２）后对稀土离子配位作用的影响．     

稀土与1,4,7,10-四氧杂-13-氮杂-5∶6-苯并-十五烷-N-乙酸配合物的合成与表征

以邻苯二酚、２－氯乙醇、二乙醇胺和溴乙酸为原料，合成了一个新的配体——Ｎ－乙酸取代苯并氮杂冠醚。在无水乙醇中经置换反应，制得了九种稀土硫氰酸盐冠醚固体配合物，经元素分析确定其组成为ＲＥ（ＳＣＮ）２·Ｌ·２Ｈ２Ｏ（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｅｒ，Ｙ；Ｌ＝Ｎ－乙酸取代苯并氮杂冠醚）。用ＩＲ、ＵＶ－Ｖｉｓ和电导测定等方法，研究了配合物的配位结构和性质。     

铕和镧与吡啶－2，6－二甲酸配合物的NMR研究

合成了稀土铕、镧与吡啶－２，６二甲酸形成的二元配合物及铕与邻菲罗啉和吡啶－２，６二甲酸形成的三元配合物。经元素分析确定该配合物的组成分别为二元：Ｎａ３［Ｅｕ（ＤＰＣ）３］·２Ｈ２Ｏ，Ｎａ３［Ｌａ（ＤＰＣ）３］·２Ｈ２Ｏ；三元：ＮａＥｕ（ＤＰＣ）２·ｐｈｅｎ·４Ｈ２Ｏ。用核磁共振研究了配体与稀土的配位方式，讨论了诱导效应、屏蔽效应及稀土离子的顺磁性对配合物化学位移和ＮＭＲ谱图的影响。ＮＭＲ研究表明，三种配合物具有相似的对称结构和相同的化学位移变化规律。吡啶－２，６二甲酸中的羧酸以单齿配位（整个分子为三齿配位），二元配合物中，铕和镧的配位数均为９，三元配合物中，铕的配位数最低为８。     

钒（IV）与N,N,N‘,N“,N”—五苯并咪唑甲基二乙三胺多核配合物合…

合成了两种新的Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－五苯并咪唑甲基二乙三胺ＶＯ（Ⅱ）多核配合物并进行了元素分析，ＩＲ，ＵＶ－ｖｉｓＥＳＲ等表征。求得了配合物的自旋Ｈａｍｉｌｔｏｎ参数，两配合物中Ｖ（Ⅳ）的电子环境差别较大。体外抗癌活性和农药活性测定结果表明配合物具有一定生物活性。     

水合希土硝酸盐与本并及单环己基－12－冠－4配合物的合成、性质及晶体结构

在乙腈介质中合成了苯并－１２－冠－４（简称Ｂ－１２－Ｃ－４）和单环己基－１２－冠－４（简称Ｃｙ－１２－Ｃ－４）的六种希土配合物：ＲＥ（ＮＯ３）３·Ｂ－１２－Ｃ－４（ＲＥ＝Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ），ＲＥ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４（ＲＥ＝Ｌａ，Ｌｕ）．研究了它们的ＩＲ及１ＨＮＭＲ性质，并测定了四种单晶的结构．用ＩＮＤＯ法计算了Ｌｕ（ＮＯ３）３·Ｂ－１２－Ｃ－４，Ｌｕ（ＮＯ３）３·Ｃｙ－１２－Ｃ－４的电子结构．结果表明．Ｂ－１２－Ｃ－４与希土的配合物稳定性按Ｐｒ，Ｇｄ，Ｙｂ，Ｌｕ顺序减弱，并且Ｃｙ－１２－Ｃ－４与希土的配位能力大于Ｂ－１２－Ｃ－４．发现冠醚分子通过自身不同程度的扭曲，改变冠醚环空穴的大小，实现与不同大小的希土离子的配位作用．     

稀土组氨酸配合物的合成和性质研究

本文合成了十二个稀土与Ｌ－组氨酸（Ｌ－Ｈｉｓ）的固体配合物，元素分析结果表明配合物的组成为Ｌｎ（Ｈｉｓ）３（ＮＯ３）３２Ｈ２Ｏ（Ｌｎ＝Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｅｒ，Ｔｍ）。并通过配合物的ＩＲ、ＵＶ、Ｈ－ＮＭＲ、ＴＧ－ＤＴＡ、磁化率及在水中的摩尔电导等的研究，表征了这些配合物的物理化学性质，结果表明稀土组氨配合物中配体通过羟基氧原子与镧系离子配位。     

呋喃甲酰基吡唑啉酮双席夫碱稀土配合物的合成、表征及生物活性

合成了１１种新的稀土与Ｎ,Ｎ’－双「（１－苯基－３－甲基－５－氧－４－吡唑啉基）α－呋喃次甲基」乙二亚胺（ＨＰＭαＦＰ）２ｅｎ配合物。元素分析及摩尔电导值表明配合物的组成为「ＲＥ（ＨＰＭαＦＰ）２ｅｎ（ＮＯ３）２」ＮＯ３」ＮＯ３（ＲＥ＝Ｌａ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｔｂ,Ｄｙ,Ｈｏ,Ｅｒ,Ｙｂ,Ｙ）。用红外学谱、紫外学谱、磁共振谱和荧光光谱对配合物进行了表征,证实席夫碱配体以四齿形式配位,ＲＥ＾３     

希土发光配合物研究──Ⅰ．希土与邻菲罗啉－N－氧化物及丙烯酸三元配合物的合成、表征和荧光性质

合成了邻菲罗啉－Ｎ－氧化物（Ｌ１）及丙烯酸（ＨＬ２）与部分希土的三元配合物［ＲＥ（Ｌ１）（Ｌ２）３］（ＲＥ＝Ｌａ－Ｎｄ，Ｓｍ－Ｔｂ）。通过元素分析、红外光谱、紫外光谱、摩尔电导、热分析对该系列配合物进行了表征。研究了Ｅｕ（Ⅲ）、Ｓｍ（Ⅲ）配合物的荧光性质，讨论了阴离子对Ｅｕ（Ⅲ）配合物荧光性质的影响。     

SYNTHESIS,REACTIONS AND BIOLOGICAL ACTIVITY OF PHOSPHORUS-CONTAINING DERIVATIVES OF CHROMONE AND COUMARIN

Chromone and coumarin derivatives exhibit a wide spectrum of biological activity, including spasmolytic, antiarrhythmic, cardiothonic, antiviral, and anticancer properties. Phosphorus-containing chromone and coumarin derivatives form a novel group of compounds, possessing remarkable cytotoxicity and alkylating and anticancer activity against selected tumor cell lines. Derivatives containing a phosphorus atom at position 2 of a γ-pyrone ring are known to be efficient antibacterial agents.

This review presents methods developed for the synthesis of derivatives of chromone and coumarin that contain a phosphonate moiety. Among them, the reaction of derivatives of 2-hydroxyacetophenone with phosphonic compounds is the one most frequently used. Some analogues were characterized by X-ray crystallography.     

SYNTHESIS,SPATIAL STRUCTURE,AND NOOTROPIC ACTIVITY OF N-CYANOMETHYLANABASINE

Journal of Structural Chemistry - N-cyanomethylanabasine is prepared with an yield of 70% by the interaction of the alkaloid anabasine with glyconitrile. It is shown that the highest yield of the...     

碳铂类似物的合成,表征及对大鼠W—256肉瘤的抑制作用

合成了十八种〔PtA_2X〕·yH_2O,其中A分别为NH_3、CH_3NH_2、1/2乙二胺和1/2(2,3-二甲基-2,3-丁二胺),X分别为1,1-环丙烷二羧酸根(CPrDCA)、2-甲-1,1-环丙烷二羧酸根(2-M-CPrDCA)、2-甲-1,1-环丁烷二羧酸根(2-M-CBDCA)、1,2-环戊烷二羧酸根(CPDCA)和1,1-环已烷二羧酸根(CHDCA),并进行了表征。测定了配合物抑制大鼠W-256肉瘤的活性,发现配合物〔Pt(NH_3)_2X〕系列按X不同有以下的活性次序:CPrDCA>2-M-CPrDCA>CPDCA>CBDCA(碳铂)≥2-M-CBDCA。     

侧链含5-氟尿嘧啶甲壳胺的合成及其抗肿瘤活性的研究

本文报道了以不同分子量的甲壳胺为载体,制备了侧链含5-氟尿嘧啶的一系列高分子载体药物;通过定氮分析测定了H_2N-基的反应率;由IR、UV和~(13)C-NMR确定了载体药物的结构;模拟生理条件考查了在不同pH的缓冲溶液中5-氟脲嘧啶或其衍生物的水解释放率。体外初步实验结果表明,具有Ⅰ和Ⅱ结构的载体药物对艾氏腹水癌细胞有较强的杀伤作用。     

NEW SEMISYNTHETIC CEPHALOSPORINS WITH ANTIBACTERIAL,ANTIVIRAL AND ANTIFUNGAL ACTIVITY

Abstract

The synthesis of new derivatives of thiazolidine 2-alkylidene-4-on-5-acetamidocephalosporanic acids or thiazolidine 2-arylidenazino-4-on-5-acetamidocephalosporanic acids and their salts of general formula (I) has been achieved.     

SYNTHESIS AND ANTIBACTERIAL ACTIVITY OF SOME NEW PYRIDYL DIARYLSULFIDE AND DIARYLSULFONES

Abstract

Condensation of isonicotinaldehyde with 4-aminodiphenyl sulfides 1 and/or sulfones II gave 4-[N-[p-(diaryl/thio)]formimidoyl]-pyridine III and/or 4-[N-[p-(diarylsulfonyl)]-formimidoyl]pyridine IV. Cyclocondensation of mercaptoacetic acid on III and IV gave 3-[p-(diarylthio)]-2-(4-pyridyl)-4-thiazolidinones V and 3-[p-(diarylsulfonyl)]-2-(4-pyridyl)-4-thiazolidinones VI respectively. (Hetero/arylthio)-N-(6-methyl-2-pyridyl)-acetamides VIII have been synthesised via interaction of 6-methyl-2-chloroacetamido-pyridine VII with heterocyclic and/or aromatic mercaptans. Reaction of VII with piperidine and/or morpholine affords (IX). Biological activities of these compounds were tested.     

4,4'-DIMETHYLANGELICIN, A MONOFUNCTIONAL FUROCOUMARIN SHOWING HIGH PHOTOSENSITIZING ACTIVITY

Abstract— 4,4'-Dimethylangelicin, a monofunctional furocoumarin, showed a high photosensitizing activity on various biological substrates. The lethal effect on Escherichia coli B₄₈, a wild type strain, and the extent of DNA synthesis inhibition in Ehrlich ascites tumor cells, were not only much more pronounced than that observed with the previously studied monofunctional 4,5'-dimethylangelicin, but even higher than with bifunctional psoralen, 4,4'-Dimethylangelicin, contrary to the other methylangelicin, proved to be phototoxic on guinea pig skin and showed an evident mutagenic effect in E. coli WP₂, but to a much lower extent than psoralen.     

ORGANIC PHOSPHORUS COMPOUNDS 93.1 PREPARATION,PROPERTIES AND HERBICIDAL ACTIVITY OF 2-SUBSTITUTED 5-PHENOXY- AND 5-PYRIDY LOXY-PHENYLAMINOALKYLPHOSPHONIC-AND-PHOSPHINIC ACILAS WELL AS-PHOSPHINE OXIDE DERIVATIVES*

Abstract

Interaction of 4-phenoxy and 4-pyridyloxy substituted 1.2-dinitrobenzenes and aminoalkylphosphonates,-phosphinates, and -phosphine oxides produces mainly 5-phenoxy- and 5-pyridyloxy substituted 2-nitrophenylaminoalkyIphosphonates. -phosphinates and -phosphine oxides (Table I to IV and Figure 1 to 5). some of which show high herbicidal and plant growth regulating activity. The herbicidal activity increases from pyridyloxy-phenylaminoalkylphosphonates to phenoxy-phenylaminoalkyl-phosphonates, -phosphinates, -phosphine oxides. Of all the compounds tested the phosphine oxide 4a was at all concentrations the most active compound.     

铁酸盐的制备、表征及其催化性能的研究

采用空气氧化湿法制备了含Zn、 Ni、 Co的尖晶石型铁酸盐。运用XRD、IR、UV-DRS和TPR等方法对所制备的样品进行了表征。研究了铁酸盐的化学组成、结构和氧化还原性质。考察了铁酸盐对二氧化碳选择性氧化乙苯制苯乙烯的催化性能,并讨论了催化剂的结构、组成对反应活性的影响以及二氧化碳的作用。