Determination of iphosphamide and seven metabolites in blood plasma,as stable trifluoroacetyl derivatives,by electron capture chemical ionization GC-MS

A method is described for the determination of the antitumor agent iphosphamide and seven of its metabolites in the plasma of cancer patients by multiple ion monitoring (MIM) GC-MS, mainly using the electron capture chemical ionization mode, of stable methyl and/or trifluoroacetyl derivatives. The metabolites determined were 2- and 3-dechloroethyliphosphamide, 4-ketoiphosphamide, carboxyiphosphamide, iphosphamide mustard, and two previously undetected metabolites, chloroethylamine and 1,3-oxazolidine-2-one. The isolation of the acidic and neutral metabolites was performed by solid phase extraction on to C₁₈ adsorbent at pH 4. The weakly acidic iphosphamide mustard, isolated under these conditions with a yield of ca 50%, was measured as a stable methyltrifluoroacetyl derivative, in contrast to the corresponding phosphoramide mustard of the isomer cyclophosphamide which decomposes during derivatization. Chloroethylamine and 1,3-oxazolidine-2-one were isolated with high yield by liquid extraction with ethyl acetate at pH 10. Selective measurement of several metabolite derivatives with similar retention times was performed by multiple ion monitoring MS of specific ion masses, using a methyl phenyl siloxane capillary column previously employed in the study of cyclophosphamide metabolites. Quantitation of metabolites in patient plasma samples could be performed in the concentration range 3 ng to 20 μg per ml of original plasma.     

中国南海海绵化学成份研究Ⅱ—B·C

从中国南海西沙群岛永胜岛附近海域采集到的一种海绵(种属未定)分离到两种新的三羟基长链酰胺类化合物S—Ⅱ(C_(49)H_(99)NO_4,M=765,m.p.138-140℃)和S—Ⅲ(C_(45)H_(93)NO_4,M=723,m.p.92—93℃),通过对它们的IR,MS,~1HNMR,~(13)CNMR及~(13)CNMR DEPT等波谱数据分析,S—Ⅱ和S—Ⅲ的结构分别确定为N-(1-乙基-3,22-二羟基)二十二烷基-2-甲基-4-羟基二十四脂肪酸酰胺和N-(1-羟甲基-2-乙基-4-甲基-3,18-二羟基)十九烷基—二十三脂肪酸酰胺。     

应用化学专业《化工原理》课程教学改革探索

为了适应社会需求的变化和发展，提高学生的工程意识和实践能力，对应用化学专业《化工原理》课程存在的问题与现状进行了分析，探索了该课程教学内容、教学方法、教学手段和实践性教学环节等方面的改革，并在教学实践中予以完善与深化。     

高频等离子体化学气相淀积法制备TiO2超细粒子

利用ＴｉＣｌ４＋Ｏ２体系，在高频等离子体化学气相淀积反应器中合成了纯度高、粒度细的ＴｉＯ２粒子。考察了工艺条件对ＴｉＯ２粒子物性的影响；探讨了ＴｉＯ２粒子晶型控制的方法，金红石型质量分数可通过工艺条件控制；探讨了ＴｉＯ２粒子晶型控制的方法。金红石型质量分数可通过工艺条件控制，减少ＴｉＯ２单体浓度可提高金红石型质量分数；也可通过在原料ＴｉＣｌ４中添加ＡｌＣｌ３等晶型转化剂，使可转化为单一金红石型Ｔｉ     

The Fundamental Experiments of Red Tide Chemical Forecast

Many food algae and red tide algae were cultivated in the f/2 medium, and the nitric oxide (NO) concentration of the medium and the cell density were determined. The experiments on algae were conducted when different concentrations of NO were added into the medium using two methods. The results show that low concentrations of NO were self-produced by marine algae during the exponential growth period and were about nmol/L level. But at the end of the period, i.e., 2 or 3 days before the cell density reaches the maximum, an NO peak appeared, with the NO concentration reaching 10 nmol/L. The NO threshold concentration exists according to the influence of exogenous NO on the marine phytoplankton growth. One type is the threshold concentration that can promote algae growth, and its value is between 10 and 1 nmol level, or even lower. The other type can inhibit the phytoplankton growth, which is about μmol level or higher. The results indicate that red tide algae are far more sensitive to NO than are food algae. The fundamental experimental outcome above may provide a new clue for red tide chemical forecast by inspecting the NO change.     

HCHO-(DL-苹果酸)-BrO-3-Mn2+-H2SO4体系化学振荡反应动力学研究

研究了HCHO参与下的(DL-苹果酸)-BrO-3-Mn2+-H2SO4化学振荡反应体系的非线性动力学行为,考察了该体系中各反应物的初始浓度范围及主要影响因素. 结果表明,在5.0×10-5～1.0×10-2 mol·L-1范围内, HCHO对振荡反应的诱导期和周期有较大影响,且HCHO浓度的对数lnc(HCHO)与诱导期倒数的对数ln(1/tin)及周期倒数的对数ln(1/tp)均存在线性关系. 诱导期和周期的表观活化参数分别为70.87,55.71 kJ·mol-1. 另外还对HCHO参与下的可能振荡反应机理进行了探讨.     

论化学武器的危害及其防护

化学武器虽然早已被国际公约禁止,但有些国家并没有放弃研制和生产,国际恐怖组织也在利用化学武器制造恐怖袭击或进行恐怖威胁。因此,充分认识化学武器对人类的危害,做好防护和防范工作具有重要的现实意义。     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.     

On the Donor Ability of the Phosphaneiminato Substituent and Cube Formation with Transition Metal Fragments

The particular role of the phosphaneiminato ligand as a donor is investigated for a) nitrenes (phosphinidenes) and carbenes and b) cubane formation with transition metals. Accordingly, and as shown for the case a) the ligand is a stronger π‐donor than an amino group and can be considered as a special case of imine‐type substituents. The latter are very effective in π‐donation. In the case b), i.e. the cubane formation with transition metals, one has to consider transition metals with a partially or completely filled d‐shell (with electrons). Hence depending on the transition metal, cubanes are build with weak ferromagnetic coupled or closed shell systems. For the cubanes with closed shell character the matter of insertion of halide anions is discussed. In the last chapter of the review the bond stretching in the dithionitrosyl complexes with rhenium is characterized.     

针剂头孢曲松钠对B-Z化学振荡反应的影响及其分析检测

研究了针剂头孢曲松钠对经典的B-Z化学振荡体系的扰动,结果表明头孢曲松钠的浓度与扰动后振荡周期的改变量存在一定的线性关系,其线性范围为6.15×10-7~5×10-3mol/L,最低检测限为6.25×10-8mol/L.探讨了针剂头孢曲松钠对化学振荡反应扰动的可能机理.