三苯基锗不饱和烃基酸衍生物的合成和性质

随着倍半锗氧类化合物的合成及应用研究的日益广泛 ,含 Ge_ O键的烃基锗衍生物的合成及应用也逐渐引起了人们的关注 .1 984年 ,L ukevics等 [1]合成了具有抗癌活性的介吗川类化合物 ,1 990年Kakimoto等 [2 ] 报道了具有杀菌活性的环状烃基羧酸的合成与应用 .但是三烃基锗的膦酸类衍生物的合成及生物活性研究均未见文献报道 .为了研究该类化合物的生理活性 [3～ 5] ,本文以三苯基氯化锗和炔基 (烯基 )膦酸钠为原料 ,在苯中反应 ,合成了一系列双 - O- (三苯基锗 )炔基 (烯基 )膦酸酯和单 - O-三苯基锗炔基 (烯基 )膦酸 ,部分化合物初步生理…     

氯代二苯基锗杂环羧酸酯的合成与表征

以二苯基二氯化锗和杂环羧酸钠为原料,合成了8种氯代二苯基锗杂环羧酸酯Ph2Ge(Cl)O2CR(R=2-呋喃基,2－呋喃乙烯基,2－噻吩基,2－吡啶基,3－吡啶基,4－吡啶基,3－吲哚甲基,3－吲哚丙基）。利用元素分析,红外光谱、核磁共振谱和质谱表征了这些化合物的结构。结果表明杂环羧酸是以单齿形式与锗原子键合,生成了四配位的有机锗化合物,生物活性测试表明,该类化合物具有较高的体外抗癌活性。     

三苯基锗杂环羧酸酯的合成与表征

合成了8种三苯基锗杂环羧酸酯Ph~3GeO~2CR(R=2-呋喃、2-呋喃乙烯基、2-噻吩基、2-吡啶基、3-吡啶基、4-吡啶基、3-吲哚甲基、3-吲哚丙基),利用元素分析、红外光谱、核磁共振氢谱和质谱表征了这些化合物的结构。体外实验表明,这些化合物对MCF-7和WiDr癌细胞具有较好的抑制活性。     

二苯基锗杂环羧酸酯的合成、表征及生物活性研究

合成了8种二苯基锗杂环羧酸酯Ph2Ge(O2CR)2(R=2-呋喃基、2-呋喃乙烯基、2-噻吩基、2-吡啶基、3-吡啶基、4-吡啶基、3-吲哚甲基、3-吲哚丙基),利用元素分析、红外光谱、核磁共振氢谱和质谱表征了这些化合物的结构。体外实验表明,这些化合物对MCF-7、WidDr和EC癌细胞具有较好的抑制活性。     

双(三苯基锗)不饱和烃基膦酸酯的合成

随着倍半氧锗类化合物的合成及应用研究的日益广泛,含Ge-O键的烃基锗衍生物的合成及应用研究也逐渐引起了人们的关注,相继合成了各种类型具有抗癌活性的含Ge-O键的烃基锗类化合物[1～3].但烃基锗膦酸衍生物的合成及应用研究尚未见文献报道.为了探讨该类化合物的结构及生物活性,本文以三苯基氯化锗和烯(炔)基膦酸钠为原料,合成了8种双(三苯基锗)不饱和烃基膦酸酯.……     

双(三苯基锗)二元羧酸酯的合成和性质

通过三苯基氯化锗与二元羧酸钠反应合成了12种新的双(三苯基锗)二元羧酸酯。利用元素分析、红外光谱、核磁共振氢谱表征了这些化合物的结构,红外光谱测试表明,所有化合物中羧基是以单齿形式与锗原子配位。生物活性测试结构表明,该类化合物对MCF-7和WiDr癌细胞具有较高的体外抑制活性。     

极谱法测定蒙药那如三味丸中锗的研究

采用差分脉冲极谱法,在pH 1.50、含3,4 –二羟基苯甲醛(DHB)的H2SO4中,测得无机锗的峰电位为Ep=-0.54 V,Ge(Ⅳ)浓度在1.04×10 5～1.05×10 4 mol·L 1范围内与峰电流呈线性关系,利用该法用于测定蒙药那如三味丸中总锗、无机锗和有机锗,得到了满意的结果.     

电感耦合等离子体原子发射光谱法测定锡锗中间合金中锗

锡锗中间合金溶解于硝酸(1 1)及盐酸(1 4)中,溶解温度应在60℃以下,所得溶液中锗含量用电感耦合等离子体原子发射光谱(ICP-AES)测定,对测定条件作了试验并予以优化.最后选择栽气流量为0.6 L·min-1,试样溶液的介质及酸度为约2 mol·L-1盐酸溶液,分析谱线为265.118 nm.基体元素锡对锗的分析信号有增强作用,明显影响了锗测定结果的准确性.为克服此基体效应,在制备标准曲线时应用了基体匹配法.经试验,方法的回收率在96.0%～103.6%之间,测定结果的相对标准偏差(n=6)为0.53%.     

三苯基锗烯或炔基膦酸衍生物的合成

由三苯基氯化猪与烯或炔基膦酸盐反应,合成了８种新的三苯基锗烯基或炔基膦酸衍生物,利用元素分析,ＩＲ和ＨＮＭＲ表征了这些化合物的结构     

电感耦合等离子体发射光谱法测定锗精矿中锗量

建立了用硝酸、氢氟酸、磷酸溶解样品,电感耦合等离子体发射光谱法测定锗精矿中锗量的方法。试验选择209.426nm作为最优分析谱线,锗的检出限为0.006μg/mL,测定下限为0.020 μg/mL,在磷酸基体匹配的条件下测定,测定范围为1%-15%,与经典碘酸钾滴定法对比,数据一致,相对标准偏差<3%(n=11),加标回收率98%~101%,能够满足快速测定及批量处理锗精矿中1%-15%的锗含量的需求。     

Synthesis and structure of hydroxyisoxazolidines and derivatives of hydroxylamine and alkenals

The reactions of N-substituted hydroxylamines with alkenals serve as a method for the synthesis of the corresponding 2-substituted 3(5)-hydroxyisoxazolidines. The reaction pathway is determined by the nature of the substituent attached to the nitrogen atom. Ring-chain isomerism has been detected in these newly obtained compoundsTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1270–1276, September, 1987.     

Synthesis and characterization of triazenide and triazene complexes of ruthenium and osmium

Triazenide [M(eta2-1,3-ArNNNAr)P4]BPh4 [M = Ru, Os; Ar = Ph, p-tolyl; P = P(OMe)3, P(OEt)3, PPh(OEt)2] complexes were prepared by allowing triflate [M(kappa2-OTf)P4]OTf species to react first with 1,3-ArN=NN(H)Ar triazene and then with an excess of triethylamine. Alternatively, ruthenium triazenide [Ru(eta2-1,3-ArNNNAr)P4]BPh4 derivatives were obtained by reacting hydride [RuH(eta2-H2)P4]+ and RuH(kappa1-OTf)P4 compounds with 1,3-diaryltriazene. The complexes were characterized by spectroscopy and X-ray crystallography of the [Ru(eta2-1,3-PhNNNPh){P(OEt)3}4]BPh4 derivative. Hydride triazene [OsH(eta1-1,3-ArN=NN(H)Ar)P4]BPh4 [P = P(OEt)3, PPh(OEt)2; Ar = Ph, p-tolyl] and [RuH{eta1-1,3-p-tolyl-N=NN(H)-p-tolyl}{PPh(OEt)2}4]BPh4 derivatives were prepared by allowing kappa1-triflate MH(kappa1-OTf)P4 to react with 1,3-diaryltriazene. The [Os(kappa1-OTf){eta1-1,3-PhN=NN(H)Ph}{P(OEt)3}4]BPh4 intermediate was also obtained. Variable-temperature NMR studies were carried out using 15N-labeled triazene complexes prepared from the 1,3-Ph15N=N15N(H)Ph ligand. Osmium dihydrogen [OsH(eta2-H2)P4]BPh4 complexes [P = P(OEt)3, PPh(OEt)2] react with 1,3-ArN=NN(H)Ar triazene to give the hydride-diazene [OsH(ArN=NH)P4]BPh4 derivatives. The X-ray crystal structure determination of the [OsH(PhN=NH){PPh(OEt)2}4]BPh4 complex is reported. A reaction path to explain the formation of the diazene complexes is also reported.     

Mass and NMR spectra of haplophyllidine and perforine and of their derivatives

Conclusions The mass and NMR spectra of haplophyllidine, perforine, and their derivatives have been studied. The influence of the open and cyclic forms of the molecular ion on the nature of the fragmentation has been discussed. The main routes of fragmentation of the compounds considered are due to the presence of substituents at C₈ and C₄.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 273–279, 1969     

Investigation of adhesion and mobility of polyurethane and epoxy-rubber glues and adhesives

The values of activation parameters in uncured and cured epoxy resins, rubbers, and blends thereof are investigated. The dependences of activation energy and adhesion strength of epoxy-rubber compositions on rubber content are determined. The correlation of adhesion and activation energy values for polyurethane rubber and epoxy-rubber compositions is shown.     

Crystal and molecular structure of aroyl- and acetylhydrazones of acet- and benzaldehydes

Aroyl- and acetylhydrazones of acet- (I) and benzaldehydes (IV) and benzoylhydrazones of acet- (II) and benzaldehydes (III) were studied by x-ray structural and quantum-chemical methods in order to establish their structures. Compund (I) was the EEZ structure in the crystal. Calculations and spectral data showed that the EEE form occurs in nonpolar solvents and in the gas phase. According to crystallographic data molecules (I)–(IV) are the E-isomers (relative to the N-N bond) and the hydrazone fragments are planar. Intermolecular N-H...O H-bonds from in the crystals. The data obtained suggest that the majority of acylhydrazones are conformationally rigid on dissolution although exceptions do occur. Apparently the reasons for the difference of acetyl- and benzoylhydrazones in electrocarboxylation reactions are electronic and not steric factors.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 75–81, January, 1991.     

Preparation and characterization of diarylphosphazene and diarylphosphinohydrazide complexes of titanium, tungsten and ruthenium and phosphorylketimido complexes of rhenium

Reaction of the proligand Ph2PN(SiMe3)2 (L1) with WCl6 gives the oligomeric phosphazene complex [WCl4(NPPh2)]n, 1 and subsequent reaction with PMe2Ph or NBu4Cl gives [WCl4(NPPh2)(PMe2Ph)] (2) or [WCl5(NPPh2)][NBu4] (3), respectively. DF calculations on [WCl5(NPPh2)][NBu4] show a W=N double bond (1.756 A) and a P-N bond distance of 1.701 A, which combined with the geometry about the P atom suggests, there is no P-N multiple bonding. Reaction of L1 with [ReOX3(PPh3)2] in MeCN (X = Cl or Br) gives [ReX2(NC(CH3)P(O)Ph2)(MeCN)(PPh3)](X = Cl, 4, X = Br, 5) which contains the new phosphorylketimido ligand. It is bound to the rhenium centre with a virtually linear Re-N-C arrangement (Re-N-C angle = 176.6 degrees, when X = Cl) and there is multiple bonding between Re and N (Re-N = 1.809(7) A when X = Cl). The proligand Ph2PNHNMe2(L2H) reacts with [(C5H5)TiCl3] to give [(C5H5)TiCl2(Me2NNPPh2)] (6). An X-ray crystal structure of the complex shows the ligand (L2) is bound by both nitrogen atoms. Reaction of the proligands Ph2PNHNR2[R2 = Me2 (L2H), -(CH2CH2)2NCH3 (L3H), (CH2CH2)2CH2 (L4H)] with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave [RuCl2(eta6-p-MeC6H4iPr)L] {L = L2H (7), L3H (8), L4H (9)}. The X-ray crystal structures of 7-9 confirmed that the phosphinohydrazine ligand is neutral and bound via the phosphorus only. Reaction of complexes 7-9 with AgBF4 resulted in chloride ion abstraction and the formation of the cationic species [RuCl(6-p-MeC6H4iPr)(L)]+ BF4- {(L = L2H (10), L3H (11), L4H (12)}. Finally, reaction of complex 6 with [{RuCl(mu-Cl)(eta6-p-MeC6H4iPr)}2] gave the binuclear species [(eta6-p-MeC6H4iPr)Cl2Ru(mu2,eta3-Ph2PNNMe2)TiCl2(C5H5)], 13.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

Kinetics and mechanisms of chlorine dioxide and chlorite oxidations of cysteine and glutathione

Chlorine dioxide oxidation of cysteine (CSH) is investigated under pseudo-first-order conditions (with excess CSH) in buffered aqueous solutions, p[H+] 2.7-9.5 at 25.0 degrees C. The rates of chlorine dioxide decay are first order in both ClO2 and CSH concentrations and increase rapidly as the pH increases. The proposed mechanism is an electron transfer from CS- to ClO2 (1.03 x 10(8) M(-1) s(-1)) with a subsequent rapid reaction of the CS* radical and a second ClO2 to form a cysteinyl-ClO2 adduct (CSOClO). This highly reactive adduct decays via two pathways. In acidic solutions, it hydrolyzes to give CSO(2)H (sulfinic acid) and HOCl, which in turn rapidly react to form CSO3H (cysteic acid) and Cl-. As the pH increases, the (CSOClO) adduct reacts with CS- by a second pathway to form cystine (CSSC) and chlorite ion (ClO2-). The reaction stoichiometry changes from 6 ClO2:5 CSH at low pH to 2 ClO2:10 CSH at high pH. The ClO2 oxidation of glutathione anion (GS-) is also rapid with a second-order rate constant of 1.40 x 10(8) M(-1) s(-1). The reaction of ClO2 with CSSC is 7 orders of magnitude slower than the corresponding reaction with cysteinyl anion (CS-) at pH 6.7. Chlorite ion reacts with CSH; however, at p[H+] 6.7, the observed rate of this reaction is slower than the ClO2/CSH reaction by 6 orders of magnitude. Chlorite ion oxidizes CSH while being reduced to HOCl, which in turn reacts rapidly with CSH to form Cl-. The reaction products are CSSC and CSO3H with a pH-dependent distribution similar to the ClO2/CSH system.