杂多化合物催化性能的研究—第四周期过渡金属取代的钼磷三元杂多化合物在环己烯氧化反应中的催化作用

过渡金属单取代的杂多化合物［（ｎ－Ｃ４Ｈ９）４Ｎ］８－ｎ［ＰＺｎ＋ＢｒＭｏ１１Ｏ３９］（Ｚ＝Ｍ２＋ｎ、Ｆｅ３＋、Ｃｏ２＋、Ｎｉ２＋、Ｃｕ２＋）对以过氧化氢为氧化剂的环己烯氧化反应具有良好的催化性能．基于动力学、红外光谱及电化学方法的研究，对反应机理作了讨论．认为这类取代的杂多化合物与Ｈ２Ｏ２作用形成了活性中间体，活性中心为参与取代的过渡金属离子．     

聚乙二醇辛基苯基醚—铁（Ⅱ）—过氧化氢化学发光体系研究及应用

本报道了聚乙二醇辛基苯基醚（ＯＰ）－Ｆｅ（Ⅱ）－Ｈ２Ｏ２化学发光体系，建立了高等反悔一测定微量铁的化学发光新方法，检出限为７．６×１０＾－８ｍｏｌ／Ｌ，线性响应的浓度范围为１．０×１０＾－７－１．０×１０＾－３ｍｏｌ／Ｌ，该法所受金属离子孤干扰小，用于实际水样及铜精矿样品的全铁的测定，结果令满意。     

Ti（Ⅳ）－F~－－邻硝基苯基荧光酮－氯化十六烷基吡啶四元体系显色反应的研究

本文较详细研究了在Ｈ＿２ＳＯ＿４介质中，Ｔｉ（Ⅳ）－Ｆ￣－－ｏ－ＮＰＦ－ＣＰＣ体系水相光度法测定痕量钛的新方法。四元体系的最大吸收峰在５６５ｎｍ处，表观摩尔吸光系数为２．１×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），Ｓａｎｄｅｌｌ灵敏度为２．２８×１０￣（－４）μｇＴｉ／ｃｍ￣２。钛含量在０～４μｇ／２５ｍＬ范围内遵守比尔定律。方法用于土壤、粮食、牧草、蔬菜和中草药中钛的测定，结果满意。     

CoHR--H2O2-鲁米诺化学发光体系与应用

研究了钛铁试剂（Ｈ２Ｒ２－）与Ｃｏ（Ⅱ）形成的配合物ＣｏＨＲ－,对Ｈ２Ｏ２氧化鲁米诺的增强作用,基于此建立了钴的化学发光分析新方法。新方法Ｃｏ（Ⅱ）的检出限为１．２９×１０９ｇ／Ｌ,工作曲线线性范围为５×１０８～１．０×１０５ｇ／Ｌ,检测１×１０７ｇ／ＬＣｏ（Ⅱ）离子的相对标准偏差为２．５％以内。直接用于制药厂废水中微量钴的测定,结果满意     

N—（β—羧丙酰基）异鲁米诺的电致化学发光行为及其机理探讨

本进行了Ｎ－（β－羧丙酰基）异鲁米诺的电致化学发光行为的研究。采用正矩形液脉冲电压，在ＫＯＨ－ＫＣｌ－Ｈ２Ｏ２－（ｐＨ１１．６）介质中，Ｎ－（β－羧丙酰基）异鲁米诺测定的线性范围为４．０×１０＾－１０￣７．０×１０＾－８ｍｏｌ／Ｌ，检出限为２．０×１０＾－１０ｍｏｌ／Ｌ。本对此体系的电致化学发光机理进行了探讨。     

一种基于形成杂多核络合物的荧光增敏效应的研究：Ⅲ.锰（Ⅱ）,钴（…

本研究了Ｍｎ＾２＋和Ｃｏ＾２＋对７－（８－羟基－３，６－二磺基萘偶氮）－８－羟基喹啉－５－磺酸－硼砂反应体系的混合荧光增敏作用。实验条件下，荧光增敏强度满足线性加和关系的范围是：Ｍｎ＾２＋浓度０￣２．９×１０＾－７ｍｏｌ／Ｌ；Ｃｏ＾２＋浓度０￣８．８～１０＾－７ｍｏｌ／Ｌ；总浓度不超过１．０×１０＾－６ｍｏｌ／Ｌ。检出限量为Ｍｎ＾２＋４．５×１０＾－９ｍｏｌ／Ｌ和Ｃｏ＾２＋１．４×１０＾－８ｍｏ     

高灵敏反相流动注射化学发光法测定抗坏血酸

基于抗坏血酸对Ｆｅ２＋－Ｌｕｍｉｎｏｌ－Ｏ２体系化学发光的抑制效应，利用反相流动注射技术，建立了一个测定抗坏血酸的高灵敏化学发光新方法。该法检出限达２×１０－１０ｇ／ｍＬ；抗坏血酸浓度在 １×１０－９～１× １０－６ｇ／ｍＬ范围内与体系化学发光强度减小量呈良好线性相关；相对标准偏差为１．９％（Ｃ＝５×１０－８ｇ／ｍＬ，ｎ＝１１）。     

Ti（Ⅳ）—F^——邻硝基苯基荧光酮—氯化十六烷基吡啶四元体系显色反应…

本较详细研究了在Ｈ２ＳＯ４介质中，Ｔｉ（Ⅳ）－Ｆ＾－－ｏ－ＮＰＦ－ＣＰＣ体系水相光度法测定痕量钛的新方法。四元体系的最大吸收峰在５６５ｎｍ处，表观摩尔吸光系数为２．１×１０＾５Ｌ．ｍｏｌ＾－＾１．ｃｍ＾－＾１，Ｓａｎｄｅｌｌ灵敏度为２．２８×１０＾－＾４μｇＴｉ／ｃｍ＾２。钛含量在０－４μｇ／２５ｍＬ范围内遵宁比尔定律。方法用于土壤，粮食，牧草，蔬菜和中草药中钛的测定，结果满意。     

测定钴的化学发光新体系

研究了新吖啶衍生物９，１０－二甲基吖啶氟磺酸盐的化学发光特性。建立了测定Ｃｏ６２＋的化学发光新体系。方法线性范围为１．０×１０＾－１０－１．０×１０＾－７ｇ／ｍＬ；检测限为５．０×１０＾－１１ｇ／ｍＬＣｏ＾２＋。测定５．０×１０＾－９ｇ／ｍＬＣｏ６２＋的相对标准偏差为６．０％。方法选择性好，用于自来水，江水，池塘水中痕量钴的测定，结果令人满意。     

MoO_2Br_2体系催化丁二烯聚合中烯丙基卤素的作用

ＭｏＯ２Ｂｒ２－Ａｌ（ｉ－Ｂｕ）２ＯＰｈＣＨ３（－ｍ）体系催化丁二烯１，２－聚合过程中添加Ｃ３Ｈ５Ｘ（Ｘ＝Ｃｌ、Ｂｒ和Ｉ）对聚合物分子量有较好的调节作用，其中以Ｃ３Ｈ５Ｂｒ的调节作用最强，Ｍｎ从１７．５×１０５降至３．５×１０５，但对催化活性有一定的影响．在测定催化体系的ＵＶ光谱、（１３）Ｃ－ＮＭＲ谱、聚合活性和聚合动力学参数的基础上，讨论了Ｃ３Ｈ５Ｘ在催化体系中的行为．     

Studies on Mechanism of Chemiluminescence Reaction of 2, 6, 7-Trihydroxyl-9-(4'-chlorophenyl )-3-fluorone

1INTRoDUCTIONPhenylfluoroneisanimportanttypeofreagentinanalytica1chemistry"~'>.Themoleculesofthisreagenthavearigidplanarstructuret5'6i,sotheenergyofmolecularorbitsofthereagentscanbecalculatedbyHuckelmolecularorbitalmethod(HMO).WehadtriedtoassigndissociationconstantsforsomesuchreagentsbyacombinedspectrophotometricandHMOmethodt7'8i.Them.thodissimpleandtheresultsaresatisfactory.Inthispaper,apossiblemechanismforcatalyticchemiluminescencere-actionofCl-PFisproposedonthebasisofstudyingchemil…     

Chemometrics-assisted simultaneous determination of cobalt(II) and chromium(III) with flow-injection chemiluminescence method

In this paper, a flow-injection chemiluminescence (CL) system is proposed for simultaneous determination of Co(II) and Cr(III) with partial least squares calibration. This method is based on the fact that both Co(II) and Cr(III) catalyze the luminol-H(2)O(2) CL reaction, and that their catalytic activities are significantly different on the same reaction condition. The CL intensity of Co(II) and Cr(III) was measured and recorded at different pH of reaction medium, and the obtained data were processed by the chemometric approach of partial least squares. The experimental calibration set was composed with nine sample solutions using orthogonal calibration design for two component mixtures. The calibration curve was linear over the concentration range of 2 x 10(-7) to 8 x 10(-10) and 2 x 10(-6) to 4 x 10(-9) g/ml for Co(II) and Cr(III), respectively. The proposed method offers the potential advantages of high sensitivity, simplicity and rapidity for Co(II) and Cr(III) determination, and was successfully applied to the simultaneous determination of both analytes in real water sample.     

Luminol-K2S2O8体系中金属离子化学发光行为的研究

报导了在自行设计的流动注射式化学发光分析仪上,对Luminal-K2S2O8体系中32种金属离子的化学发光行为的系统研究.确定了对金属离子的最优测定条件以及大多数金属离子的检出极限和线性范围.     

Potentiometric, spectroscopic and thermal studies on the metal chelates of 1-(2-thiazolylazo)-2-naphthalenol

The synthesis and characterization of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pd(II) and UO2(II) chelates of 1-(2-thiazolylazo)-2-naphthalenol (TAN) were reported. The dissociation constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 degrees C and 0.1 M ionic strength. The solid complexes were characterized by elemental and thermal analyses, molar conductance, IR, magnetic and diffuse reflectance spectra. The complexes were found to have the formulae [M(L)2] for M = Mn(II), Co(II), Ni(II), Zn(II) and Cd(II); [M(L)X].nH2O for M = Cu(II) (X = AcO, n = 3), Pd(II) (X = Cl, n = 0) and UO2(II) (X = NO3, n = 0), and [Fe(L)Cl2(H2O)].2H2O. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONN donor sites of the naphthyl OH, azo N and thiazole N. An octahedral structure is proposed for Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II) and UO2(II) complexes and a square planar structure for Cu(II) and Pd(II) complexes. The thermal behaviour of these chelates shows that water molecules (coordinated and hydrated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as E*, delta H*, delta S* and delta G* are calculated from the TG curves.     

A new chemiluminescence system for determination of cobalt

The chemiluminescence of the reaction of tartaric acid with hydrogen peroxide in the presence of Co(II) in alkaline buffer media has been examined. The maximum emission wavelength is 460 nm. The kinetic curve of the chemiluminescence system has been modelled with a computer, and the reaction conditions have been optimized. Foreign ions, such as Fe(II), Cr(III) and Mn(II), interfere when present in more than 10-fold ratio to Co(II), but several ions can be tolerated when present in higher ratios to Co(II). The concentration range of linear response is from 3.5 x 10(-9) to 2.0 x 10(-6) g/ml, and the detection limit is 4 x 10(-11) g/ml. The procedure has been satisfactorily applied to determine trace cobalt in human blood serum.     

基于纳米TiO2的化学发光法检测铁(Ⅱ)

铁(Ⅱ)能在具有催化活性的纳米TiO2表面产生化学发光辐射,表面活性剂十六烷基三甲基溴化铵(CTAB)的存在能显著增敏此发光强度。此外,纳米氧化钛也能增强Fenton反应的化学发光强度,据此,建立了纳米TiO2-CTAB-Fenton化学发光新体系检测铁(Ⅱ)的新方法。在优化条件下,亚铁离子在1.0×10-8~1.0×10-6mol/L浓度范围内与其化学发光强度呈现良好的线性关系,对1.0×10-7mol/L浓度的亚铁离子平行测定5次,相对标准偏差为3.9%,检出限为4.0×10-9mol/L。文中还对化学发光反应机理进行了初步探讨。     

鲁米诺-过氧化氢化学发光体系测定利福平

基于鲁米诺在碱性条件下可以被H2O2氧化产生化学发光,利福平对此化学发光具有增敏作用这一现象,结合流动注射技术建立了一种直接测定利福平的流动注射化学发光新方法.该方法的线性范围在1.0×10-6～2.0×10-8g·mL-1,检出限为3.0×10-9g·mL-1,对5.0×10-7g·mL-1的利福平连续进行11次平行测定,其相对标准偏差为3.0%.该法已成功测定了利福平胶囊及眼药水中利福平的含量.     

活性炭负载的钴基催化剂催化费托合成反应一步合成C1-C18混合醇：二氧化硅助剂的作用

采用费托合成反应以及X射线衍射、H2程序升温还原、CO脉冲化学吸附和N2物理吸附表征手段研究了SiO2助剂对活性炭负载的钴基催化剂上生成C1?C18混合醇的影响。结果表明, SiO2的添加抑制了钴物种的还原,但提高了钴物种的分散度,同时抑制了金属钴颗粒在反应过程中的团聚,从而显著提高了催化剂的活性。适量SiO2的添加促进了碳化钴的生成,从而提高了总醇选择性。重要的是,通过SiO2抑制钴物种的还原,导致大量二价钴物种的生成,从而有助于CO插入到碳链中间体中而使高碳醇容易生成。     

Unsymmetric bimetal(II) complexes: Synthesis, structures and catalytic behaviors toward ethylene

A series of unsymmetric bimetal(II) (Fe, Co and Ni) complexes ligated by 2-methyl-2,4-bis(6-iminopyridin-2-yl)-1H-1,5-benzodiazepines were synthesized and characterized by IR spectra and elemental analysis, while a representative nickel(II) complex (5a) was determined by single-crystal X-ray crystallography. These iron(II) complexes were found to exhibit good activities for ethylene oligomerization and polymerization in the presence of MMAO and afforded α-olefins in high selectivity, and the composition of oligomers followed the Schluz-Flory distribution. The nickel(II) complexes mainly dimerize ethylene with considerable activity. The influences of coordinative ligands and reaction parameters were fully investigated on the catalytic activity and properties of these complexes.     

Phase separation in liquid crystalline mesophases of [Co(H2O)6]X2:P65 Systems (X = NO3-, Cl-, or ClO4-)

Transition-metal aqua complex salts [M(H2O)6]X2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co(H2O)6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O)6](NO3):[Co(H2O)6](ClO4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O)6]X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co(H2O)6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere.