希土元素与β-丙氨酸席夫碱双核配合物的合成、表征及催化活性

合成了未见报道的九种希土元素与水杨醛缩-β-丙氨酸(H₂L)的双核配合物。元素分析及摩尔电导值等表明此系列新配合物组成为［Ln₂(HL)₃NO₃］(NO₃)₂·nH₂O，［Ln=La,Pr, Nd, Sm, Gd，n=2; Ln=Tb, Er, Yb, Y, n=4］，钆、钇的配合物分属轻、重希土组。运用热重-差热分析、紫外及红外光谱、核磁     

三甘氨酸双11钨硅双核稀土杂多配合物的合成与性质

利用一缺位杂多酸对一维链式配合物的断链取代反应,合成了未见文献报道的以甘氨酸为桥联配体的双核稀土杂多配合物,其结构简式为K₁₀[(O₃₉W₁₁Si)RE(Gly)₃RE(SiW₁₁O₃₉)]·9H₂O(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Y;Gly=NH₃⁺CH₂COO<     

［Ln(DMSO)7Cl］［BPh4］2 (Ln=La、 Nd、 Sm、 Eu、 Gd、 Tb、 Dy、 Tm)的合成、性质及［Eu(DMSO)7Cl］［BPh4］2的晶体结构

以二甲亚砜(DMSO)作配体与三价希土离子配位,选用四苯硼酸根BPh₄^-作为大阴离子,合成了一系列希土配合物［Ln(DMSO)₇Cl］［BPh₄］₂ (Ln=La、 Nd、 Sm、 Eu、 Gd、 Tb、 Dy、 Tm),并用元素分析,红外光谱对其进行表征,采用单晶X-射线四圆衍射测定了［Eu(DMSO)₇Cl］［BPh₄］₂的晶体     

(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷与镧系硝酸盐、硫氰酸盐配合物的合成表征和CD谱

合成了共15个未见文献报道的三价镧系离子与手性氮杂冠醚(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷(以下以L(+)表示)的配合物Ln(NO₃)₃·L(+)·H₂O(Ln=La、Ce、Pr、Nd); Ln(SCN)₃·L(+)·H₂O(Ln=La、Pr、Nd、Sm、Eu、Gd-Er、Yb)。对所合成配合物进行了元素分析、电导、红外、可见吸收光谱、比旋光度和圆二色谱(CD谱)的测试，并对配合物的有关物理化学性质进行了讨论。     

三甲基胺氧化物希土配合物的振动光谱和配位结构研究

用三甲基胺氧化物(TMAO)与希土高氯酸盐和硝酸盐反应，制得了组成为：［Ln(TMAO)₆］(ClO₄)₃和［Ln(TMAO)₃(NO₃)］(NO₃)₂, (Ln=La、Nd、Sm、Gd)的配合物。用摩尔电导、IR、Raman光谱结合GF矩阵力常数及INDO分子轨道计算对其配位结构进行了研究。     

[La(CCl3COO)3(bipy)·H2O]2和Tb(CCl3CO)3(bipy)2·H2O混配 配合物的合成及其结构测定

利用不同溶剂合成并测定了希土三氯醋酸盐与α,α'-联吡啶(bipy)不同比例的配合物(Ⅰ)La:bipy=1:1,[La(CCl₃COO)₃(bipy)·H₂O]₂和(Ⅱ)Tb:bipy=1:2,Tb(CCl₃COO)₃(bipy)₂·H₂O,结构测定表明配合物(Ⅰ)与(Ⅱ)均为三斜晶系,中心离子La(或Tb)具有配位数为8的畸变四方反棱柱多面体;但是配合物(Ⅰ)形成具有对称中心的二聚体。     

3-醛基水杨酸缩氨基硫脲希土配合物的合成、表征及抑菌活性研究

新配体3-醛基水杨酸缩氨基硫脲(简称HL)，由3-醛基水杨酸和氨基硫脲合成。并用此配体与三价希土醋酸盐反应，合成了9个组成为［REAc₂L］·nH₂O(RE=Y、La、Nd、Sm、Eu、Gd、Ho、Er、Yb, n=2～4)的新配合物。所有化合物均经元素分析、IR、UV、摩尔电导。¹H NMR和差热—热重分析等表征，并对配体和配合物的抑菌活性进行了测试。     

镧系元素(La、Tb、Dy)的喹啉氧基乙酰胺配合物的结构及荧光性质

合成并通过单晶衍射表征了3个稀土配合物[LaL₂(NO₃)₃]·CH₃CN(1),[Ln(L)(NO₃)₃(H₂O)](Ln=Tb (2), Dy (3), L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺)。在配合物1中,十二配位的La(Ⅲ)离子采取扭曲的二十面体配位构型,分别与来自2个酰胺配体L的4个氧原子和2个氮原子,及3个双齿配位硝酸根配位。配合物2和3的结构与拥有相同有机配体的Pr、Nd、Sm、Eu、Gd和Er配合物同构。在每个配合物中,十配位的稀土离子与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位,拥有扭曲的双帽四方反棱柱配位构型。固态配合物2和3在可见区发射强荧光。     

镧系元素(La、Tb、Dy)的喹啉氧基乙酰胺配合物的结构及荧光性质

合成并通过单晶衍射表征了3个稀土配合物[LaL₂(NO₃)₃]·CH₃CN(1),[Ln(L)(NO₃)₃(H₂O)](Ln=Tb(2),Dy(3),L=N-苯基-2-(5-氯-8-喹啉氧基)乙酰胺)。在配合物1中,十二配位的La(Ⅲ)离子采取扭曲的二十面体配位构型,分别与来自2个酰胺配体L的4个氧原子和2个氮原子,及3个双齿配位硝酸根配位。配合物2和3的结构与拥有相同有机配体的Pr、Nd、Sm、Eu、Gd和Er配合物同构。在每个配合物中,十配位的稀土离子与来自1个配体L的2个氧原子和1个氮原子,3个双齿配位硝酸根和1个水分子配位,拥有扭曲的双帽四方反棱柱配位构型。固态配合物2和3在可见区发射强荧光。     

3—磺基—4—羟基香豆素希土化合物的合成及性质

在不同条件下制得三种类型的希土与3-磺基-4-羟基香豆素(H₂SHC)化合物,元素分析确定了它们的组成分别为Ln(HSHC)₃·9H₂(Ln=La,Pr,Nd,Gd,Dy,Er,Yb,Y),Ln₂(SHC)₃.nH₂O(Ln:La,Pr,Nd,Sm,Gd,N:4或6)和Na₃Ln(SHC)₃·H₂O(Ln=Er,Yb).并通过它们的摩尔电导戌\重,溶解度,红外光谱和电子吸收光谱对各种化合物进行了结构和性质的研究。     

AMIDO- AND AMINO-ALKYLATION OF SULFIMIDES,SULFOXIMIDES, AND SULFODIIMIDES

Abstract

Sulfimides, Sulfoximides and Sulfodiimides are polyfunctional compounds with nucleophilic/basic nitrogen and acidic hydrogen adjacent to sulfur. From these Mannich-type-reaction products 1 were prepared. For example, amidomethylation on nitrogen was achieved either directly via three-component condensation (pathway (a) or, after conversion of the S-Imide into the sodium salt by treatment with N-chloromethyl-amides (pathway (b)). With highly reactive methylene-iminium halides pathway (b) provided N-aminomethylated sulfoximides, the stability of which mainly depends on the substituents on sulfur. Surprisingly stable, however, are their monoquaternary salts. These are of pharmaceutical interest with respect to anticholinergic and antihistamine activity, which was found in this series and will briefly be discussed. Of similar interest but spasmolytically less active are C-Mannich-bases of type 2 as well as N-aminoalkylated sulfodiimides 3, which were synthesized by different reaction routes.     

POLYHEDRAL METALLOPHOSPHONATES AND -SILICATES: SYNTHESIS,FUNCTIONALIZATION, AND TRANSFORMATIONS

We synthesized molecular cyclic and polyhedral precursors to aluminophosphate and silicate materials and studied their substitution and nonhydrolytic sol-gel reactions.     

NEMATICIDAL,INSECTICIDAL, ANTIFERTILITY,ANTIFUNGAL AND ANTIBACTERIAL ACTIVITIES OF SALICYLANILIDE SULPHATHIAZOLE AND ITS MANGANESE,SILICON AND TIN COMPLEXES

A facile synthesis and studies on the stereochemistry and biochemical aspects of some organosilicon(IV), organotin(IV), and manganese(II) complexes derived from imine having N^∪N^∪O donor system is reported. The imine was prepared by the condensation of salicylanilide with sulphathiazole. This imine reacts with organosilicon(IV)chloride, organotin(IV)chloride, and hydrated manganese(II) chloride to yield compounds having M─O and M←N bonds. The structures of the compounds have been elucidated by physicochemical and spectral (IR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, ¹¹⁹Sn NMR, and ESR) studies, which clearly point to a trigonal bipyramidal geometry around silicon(IV) and tin(IV), and tetrahedral geometry around manganese(II), as the active lone pair of the nitrogen is also included in the coordination sphere. In the search for better fungicides and bactericides, studies were conducted to assess the growth-inhibiting potential of the synthesized complexes against various pathogenic fungal and bacterial strains. These complexes are highly active against nematode (Meloidogyneincognita) and insect (Trogodermagranarium). The activity will be increased with increasing concentration. These studies demonstrate that the concentrations reached levels that are sufficient to inhibit and kill the pathogens. All compounds have also been found to act as sterilizing agents by reducing the production of sperm in male mice.     

CHEMOSELECTIVE ACETYLATION OF ALCOHOLS,AMINES, AND THIOLS WITHOUT CATALYST AND SOLVENT

Microwave induced rapid and selective acetylation of alcohols, amines and thiols with acetic anhydride was carried out under non-catalytic and solvent free conditions.     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

SOME NEW S-, S,S- AND N,S-SUBSTITUTED 2-NITRODIENES AND BUTADIENYL-SUBSTITUTED PIPERAZINES

Nitrodiene 1 reacted with 2a, b and gave the novel compounds 3a, b, 4a, b, and 5a. Monosubstituted diene compound 3a gave the compounds 9a with morpholine, 11a with piperidine, and 13a with homopiperazine. Compound 3a gives the thioether compound 15 by the reaction with the dithiol (HS─(CH₂)₂─O─(CH₂)₂─SH) in ethanol containing sodium hydroxide.     

COMPARATIVE STUDIES ON THE LETHAL, MUTAGENIC, AND RECOMBINOGENIC EFFECTS OF ULTRAVIOLET-A,-B,-C, AND VISIBLE LIGHT WITH AND WITHOUT 8-METHOXYPSORALEN IN Saccharomyces cerevisiae

Abstract
Genetic effects of UV-A, UV-B, UV-C, and the combination of 8-methoxypsoralen (8MOP) with UV-A or visible light were studied in the haploid strain XV185–14C and diploid strain D5 of Saccharomyces cerevisiae. The induction of his+, lys+, and horn+ reverse mutations was measured in strain XV185–14C. In strain D5 we measured the induction of genetically altered colonies, particularly twin spot colonies arising from a mitotic crossing-over. UV-C and UV-B induced point mutations at the three loci in the haploid strain and mitotic crossing-over and other genetic alterations in the diploid strain. UV-C was more mutagenic and recombinogenic than UV-B. UV-A or visible light alone did not induce genotoxic effects at the doses tested. However, UV-A plus 8-MOP produced lethal and mutagenic effects in the haploid strain XV185–14C, although mutagenic activity was less than that of UV-B. Visible light plus 8-MOP also induced genotoxic effects in strain XV185–14C. In the diploid strain D5, UV-A plus 8-MOP induced a higher frequency of genetic alterations than UV-B at comparative doses. Visible light plus 8-MOP was also genetically active in strain D5. The haploid strain was more sensitive to the lethal effects of UV-C, UV-B, UV-A, and impure visible light plus 8-MOP than the diploid strain.     

COMPLEX FORMATION BETWEEN PYRENE AND THE NUCLEOTIDES GMP, CMP, TMP AND AMP

Pyrene has been found to form ground and excited electronic state complexes of 1:1 stoichi-ometry with GMP, CMP, TMP and AMP. The values of their ground state association constants are 45 M^-1, 13M^-1, 14 M^-1, and 52 M^-1 respectively. The fluorescence of pyrene is strongly quenched by GMP, CMP, and TMP but only slightly by AMP. Fluorescence quenching analysis has yielded the values 87M^-1, 73 M^-1, and 154 M^-1 for the excited state association constants with GMP, CMP, and TMP, respectively. The corresponding values for the excited state second-order rate constant for complex formation are: 3.3 times 10⁹M^-1 s^-1 4.1 times 10⁹M^-1 s^-1, and 4.0 times 10⁹M^-1 s^-1. The probabilities of complex formation per collision between an excited pyrene molecule and a nucleotide are: 0.52, 0.64, and 0.63. The values for the excited state rate constant for dissociation of the complex are: 3.8 times 10⁷s^-1 5.6 times 10⁷s^-1, and 2.6 times 10⁷s^-1. The possibility is discussed that partial transfer of charge from pyrene to nucleotide may be playing a role in the complex formation process.     

COACERVATION,COMPLEX-COACERVATION AND FLOCCULATION

The mechanism of coacervation is reexamined in the light of recent studies on the polar (i.e., hydrogen-bonding) components of interfacial Interactions in aqueous media. The differences and similarities between coacervation, complex coacervation and flocculation are outlined and illustrated with a number of examples.     

COMPARATIVE STUDIES ON THE LETHAL, MUTAGENIC, AND RECOMBINOGENIC EFFECTS OF ULTRAVIOLET-A,-B,-C, AND VISIBLE LIGHT WITH AND WITHOUT 8-METHOXYPSORALEN IN Saccharomyces cerevisiae

Genetic effects of UV-A, UV-B, UV-C, and the combination of 8-methoxypsoralen (8-MOP) with UV-A or visible light were studied in the haploid strain XV185-14C and diploid strain D5 of Saccharomyces cerevisiae. The induction of his+, lys+, and hom+ reverse mutations was measured in strain XV185-14C. In strain D5 we measured the induction of genetically altered colonies, particularly twin spot colonies arising from a mitotic crossing-over. UV-C and UV-B induced point mutations at the three loci in the haploid strain and mitotic crossing-over and other genetic alterations in the diploid strain. UV-C was more mutagenic and recombinogenic than UV-B. UV-A or visible light alone did not induce genotoxic effects at the doses tested. However, UV-A plus 8-MOP produced lethal and mutagenic effects in the haploid strain XV185-14C, although mutagenic activity was less than that of UV-B. Visible light plus 8-MOP also induced genotoxic effects in strain XV185-14C. In the diploid strain D5, UV-A plus 8-MOP induced a higher frequency of genetic alterations than UV-B at comparative doses. Visible light plus 8-MOP was also genetically active in strain D5. The haploid strain was more sensitive to the lethal effects of UV-C, UV-B, UV-A, and impure visible light plus 8-MOP than the diploid strain.