酰基吡唑啉酮缩邻苯二胺希土配合物的合成、表征及生物活性

酰基吡唑啉酮缩二胺是近年开发的双席夫碱试剂,对希土离子具有较高的萃取性能,并表现出一定的抗菌、抗病毒生物活性。由于这类试剂含有活性的羟基和亚胺基官能团,适于同各种金属离子配位。最近我们研究了酰基吡唑啉酮缩乙二胺配合物,发现它们具有一定的传递电子作用、光致发光作用和较强的抗菌生物活性。但缩芳香二胺双席夫碱配合物的研究较少,为进一步拓宽酰基吡唑啉酮类配合物的研究领域,本文合成了11种未见报道的希土元素与N,N'-双[1－苯基－3－甲基－5－氧－4－吡唑啉基）α-呋喃次甲基]邻苯二亚胺（（HPMαFP）2Pen)的配合物。研究了配合物的结构,一般性质和抗菌活性。     

呋喃甲酰基吡唑啉酮缩邻苯二胺铀(Ⅵ)钍(Ⅳ)配合物的合成、表征及生物活性

分别合成了U(Ⅵ)和Th(Ⅳ)与双席夫碱N，N’-双[(1-苯基-3-甲基-5-氧-4吡唑啉基α-呋喃次甲基]邻苯二亚胺(HPMα FP)2pen形成的新配合物．通过元素分析、红外光谱、紫外光谱、核磁共振谱及摩尔电导等方法测试，确定其组成为：[UO2(PMαFP)2pen]和[Th(PMαFP)2pen(NO3)2]．对新配合物的结构与性质进行了表征．抗菌实验表明，配合物具有一定的生物活性．     

含草酰胺桥的Cu(Ⅱ)-Fe(Ⅱ)和Cu(Ⅱ)-Zn(Ⅱ)双核配合物的合成、磁性及生物活性

以N,N'-双（3－氨基－2,2－二甲基丙基）草酰胺根阴离子（Me2oxpn)为桥联配体,分别端接N,N,N',N'-四甲基乙二胺（tmen)和2,9－二甲基－1,10－邻菲甲啉（Me2-phen);合成和表征了3种新的异双核配合和物[Cu(Me2oxpn)Fe(tmen)2]SO4(a),[Cu(Me2oxpn)Zn(tmen)2]SO4(b)和[Cu(Me2oxpn)Zn(Me2-phen)2]SO4(c)。经元素分析、红外光谱、电子光谱、电导及磁性测量等方法推定了这些配合物的结构。测定并研究了（a)的变温磁化率（4－300K）,求得交换参数J＝－12．96cm^-1,表明双核配合物中Cu(Ⅱ）-Fe(Ⅱ)离子间存在反铁磁超交换作用。测试了3个双核配合物的杀菌作用。     

HPMαFP及邻菲罗啉稀土混配配合物的合成与性质

首次合成了混配配合物RE(PMαFP)_3·Phen[RE为La、Pr、Nd、Sm、Eu、Gd、Tb,Dy、Ho、Er、Tm、Yb、Lu、Y;HPMαFP为1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑酮-5,Phen为邻菲罗啉]。通过元素分析、红外光谱等初步研究了这些配合物的组成和性质。     

4-[(N-甲基-N-羟乙基)氨基]苯甲醛缩氨基硫脲及其过渡金属配合物的合成及表征

本文报道了4－[(N－甲基－N－羟乙基）氨基]苯甲醛缩氨基硫脲（HL）及其金属配合物的合成,通过元素分析、红外光谱、紫外、核磁共振对配体和配合物进行了表征。配合物的组成为ML2（M=Ni(Ⅱ）、Cu（Ⅱ）、Zn（Ⅱ）、Cd（Ⅱ）、Pd（Ⅱ）。晶体结构分析表明配体分子中除了羟乙基偏离平面外,其余各原子几乎在一个平面上。晶体结构中存在N－H…O（N1…O1）和O－H…S氢键,形成一个二维网状结构。在与金属离子配合时,配体由硫酮式转变为硫醇式作为负一价二齿配体通过S和β-N与金属离子螯合,形成稳定的中性配合物。     

新型Schiff碱单核配合物的合成及光谱特征

首次报道了新型Schiff碱配合物-双[N,N’-亚乙基-2,2’-(苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]合单金属配合物MH_2L[M=Mn(Ⅱ)、Fe(Ⅲ)Cl、Cr(Ⅲ)Cl、Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)]的合成方法及光谱特征。     

新型Schiff碱单核及异双核配合物的合成及光谱特征

首次报道了新型Schiff碱配合物--双[N,N'-亚乙基-2,2'-(苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]合单金属配合物MH₂L[M=Mn(Ⅱ),Fe(Ⅲ)Cl,Cr(Ⅲ)Cl,Cu(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ)]及异双金属配合物MnML[M=Fe(Ⅲ)Cl,Cr(Ⅲ)Cl,Cu(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ)]的合成方法及光谱特征.     

酰基吡唑啉酮缩氨基硫脲Ni(Ⅱ),Co(Ⅲ)和Cr(Ⅲ)配合物的合成、表征及生物活性

合成了含硫席夫碱1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5缩氨基硫脲(HL)及其Ni(Ⅱ),Co(Ⅲ)和Cr(Ⅲ)配合物.元素分析及摩尔电导率表明,新配合物的组成为[NiL2]·C2H5OH,[CoL2]Cl·H2O,[CrL2]Cl·1/2H2O.运用红外光谱、紫外光谱、核磁共振谱和磁矩对配合物进行了表征.抗菌实验表明,配合物具有较强的抗菌生物活性.     

手性锌卟啉对咪唑类客体的分子识别及圆二色光谱的研究

研究了手性α,α,α,β－四－[邻（叔丁氧羰L－酪氨酸）氨基苯基]卟啉 锌[α,α,α,β-ZnT(o-Boc)TyrTAPP](1)和手性α,α,α,β－四－[邻（叔 丁氧羰L－丙氨酸）氨基苯基]卟啉锌[α,α,α,β-ZnT(o-BocAla)TAPP](2)对 咪唑、2－甲基咪唑、N－甲基咪唑和2－乙基－4－甲基咪唑的分子识别行为,分别 求得主体（1）对咪唑类分子识别的缔合常数顺序为K（Im)>K(2-MeIm)>K(N-MeIm) >K(2-Et-4-MeIm),主体（2）对咪唑类分子识别的缔合常数顺序为K（2－MeIm)>K (Im)>K(2-Ek-4-MeIm)>K(N-MeIm),并用圆二色光谱（CD）研究了主体1和2对咪唑 在客体在CHCl3中分子识别的光谱行为,与热力学的结果做了比较。     

酰基吡唑啉酮配合物的合成、结构、量化计算及生物活性

在溶液中合成了1－苯基－3－甲基－4－苯甲酰基－吡唑啉酮－5（HPMBP）的Co(Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Zn（Ⅱ）配合物,对配合物进行了元素分析和红外光谱表征。用X射线衍射方法测定了Zn(Ⅱ）配合物的晶体结构,用密度泛函方法对Co(Ⅱ）及Zn（Ⅱ）配合物进行了量子化计算,生物活性实验表明四种配合物对大肠杆菌和金黄色葡萄球菌均有一定的抗菌作用。     

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。     

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.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

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^-。     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.     

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.