PF—吐温—80分光光度法测定钼的方法研究

在０．０５－０．４ｍｏｌ．Ｌ＾－１盐酸溶液中，吐温－８０存在下，钼与苯基萤光酮生成橙色配合物，在该配合物的第二吸收峰测量，其表观摩尔吸光系数ε＝１．１×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，测得配合物组成比为Ｍｏ＝ＰＦ＝１：１。在２５ｍＬ溶液中含钼０－８μｇ范围时遵守比耳定律。有色配合的稳定６ｈ以上。此法用于矿石中微量钼的测定，结果令人满意。     

酸性品红分光光度法测定蛋白质的研究

在ＰＨ１．８的ＫＨ２ＰＯ４－Ｈ３ＰＯ４缓冲介质中,蛋白质与酸性品红结合使染料的吸光度下降。蛋白质浓度Ｃ在０．４０－４．００ｍｇ·Ｌ＾－１和８．００－４０．００ｍｇ·Ｌ＾－１范围内,吸光度的降低与蛋白质浓度（Ｃ）呈线性关系,回归方程分别为△Ａ＝０．０１４０Ｃ＋０．０５３４和△Ａ＝０．０１０９Ｃ＋０．０８９５,相关系数ｒ依次为０．９９６５和０．９９９３,方法用于奶粉和麦片中蛋白质的测定,结果满意。     

锆(Ⅳ)-桑色素-曲拉通显色反应的研究与应用

本文提出在曲拉通Ｘ－１００存在下,以桑色素为显色剂吸光光度法测定痕量锆的新方法。在「Ｈ＾＋」＝０．５－２．０ｍｏＬ的ＨＣｌ介质中形成三元配合物,其最大吸收波长为λｍａｘ＝４３０ｎｍ,摩尔吸光系数ε４３０＝９．８×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,锆量在０－１５μｇ／２５ｍＬ范围内遵守比耳定律,该方法简捷、准确,应用于铝合金中痕量锆的测定,共存离子不干扰,测定令人满意。     

DBC-偶氮胂光度法测定人发中微量铋

ＤＢＣ－偶氮胂对铋的灵敏度较高且选择性好，在０．２－１．０ｍｏｌ／Ｌ硝酸介质中与Ｂｉ形成配位比为１：２的紫红色配合物，λｍａｘ＝６３０ｎｍ，ε６３０＝８．８×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。铋量在０－＝１０μｇ／１０ｍＬ范围内符合比耳定律。用于人发中微量的铋的测定，操作简便，结果满意。     

苯基荧光酮在混合表面活性剂体系中铜、铝的分光光度法同时测定

本文对在溴代十六烷基三甲铵和吐温８０混合表面活性剂中苯基荧光酮分光光度法同时测定铜和铝进行了研究。实验表明，在磷酸介质中，ｐＨ＝６．８－７．４范围内，苯基荧光酮与铜、铝形成稳定的络合物。铜络合物最大吸收波长为６００ｎｍ，εＣｕ６００＝６．６３×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，线性范围为０—５μｇ／２５ｍＬ；铝络合物最大吸收波长为５６４ｎｍ，εＡｌ５６４＝１．０１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，线性范围０—６μｇ／２５ｍＬ。方法灵敏度高，选择性好，用于水及健康人体冻干血浆中铜、铝回收率的测定，结果满意。     

一种新型尾式卟啉吡啶季铵盐对锌离子显色反应的研究

本文研究了一种新型尾式卟啉吡啶季铵盐５－「４－（４－吡啶丁氧基）苯基」－１０,１５,２０－三（４－氯苯基）卟啉溴化物与锌的反应条件。ＰＨ＝１０．０,在吡啶存在下于沸水浴中加热１５ｍｉｎ,其与Ｚｎ＾２＋形成１：１配合物,其最大吸收波长位于４２８．６ｎｍ,在此条件下试剂的最大吸收波长在４１８．２ｎｍ,相差１０ｎｍ,配合物摩尔吸光系数４．６４×１０＾５Ｌ·ｍｏｌ·ｃｍ＾－１,锌在０－１．２μｇ／１０ｍＬ     

2—溴甲基萘荧光和室温磷光性质研究

研究了２－溴甲基萘（２－ＢｒＭＮ）的荧光及磷光性质。２－溴甲基萘是一种优良的荧光试剂,λｅｘ／λｅｍ＝２７４／３３４ｎｍ,其浓度在１．０×１０＾－６～１．２×１０＾－４ｍｏｌ·Ｌ＾－１范围内与荧光强度呈良好的线性关系,相关系数ｒ＝０．９９９,最低检测限为４．７×１０＾－８ｍｏｌ·Ｌ＾－１。以β－环糊精（β－ＣＤ）作保护剂和１,２－二溴丙烷（ＤＢＰ）为重原子微扰剂的２－ＢｒＭＮ／β－ＣＤ／ＤＢＰ体系     

卡托普利测定新方法的研究

基于卡托普利将Ｃｏ＾２＋的为Ｃｕ,新生的Ｃｕ可一新铜试剂形成黄色络合物,提出了间接分光度法法测定药物中卡托利析新方法。在ＰＨ３－８内,卡托普利浓度在０－２８μｇ／ｍＬ内有从比耳定律,测定的表观摩尔吸光系数ε为８．１３×１０＾３Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。方法简便、快速,用地药物中卡托普利的测定,结果与钨蓝比色法一致。     

新显色剂8-喹啉偶氮槲皮素的合成及其与Fe(Ⅲ)显色反应的研究

本文研究了新显色试剂８－喹啉偶氮槲皮素的合成方法及其理化性质,显色性能和与Ｆｅ（Ⅲ）的显色反应条件,在ＴｗｅｅＮ－８０存在下,ＰＨ＝１０．３的ＮＨ３－ＮＨ４Ｃｌ缓冲介质中,Ｆｅ（Ⅲ）与８－ＱＡＱ的络合物在５００ｎｍ处有最大吸收,表观摩尔吸光系数为１．０６×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,Ｆｅ（Ⅲ）含量在０－２．６μｇ／１０ｍＬ范围内符合比耳定律。在室温下,络合物至少稳定１５ｈ,络合比为１：３     

新型卟啉吡啶季铵盐与铜(Ⅱ)显色反应的研究

本文研究了在不使用表面活性剂情况下,新型卟啉试剂溴化５－［４－（４－吡啶丁氧基）苯基］－１０,１５,２０－三（４－甲氧基苯基）卟啉与铜（Ⅱ）的显色反应。结果表明,ｐＨ＝５－７时,铜（Ⅱ）与此卟啉形成了稳定配合物,其表观摩尔吸光系数为２．３７×１０５Ｌ·ｍｏｌ－１·ｃｍ－１,铜浓度在０－１．２μｇ／１０ｍＬ范围内服从比耳定律。配合物组成的摩尔比为Ｃｕ∶卟啉吡啶季铵盐＝１∶２,本方法应用于环境水样中铜的测定,结果满意     

N,N-二[(二苯基膦)甲基]-2-吡啶胺溴化铜(Ⅰ)配合物的合成和光谱

合成了一种新配体N,N-二[(二苯基膦)甲基]-2-吡啶胺(L)及其双核铜(Ⅰ)配合物(CuBrL)2(1),采用1HNMR、吸收光谱、质谱和元素分析等方法对化合物进行表征,并通过X射线单晶衍射确定配合物1的晶体结构。该晶体结构属三斜晶系,P-1空间点群。配合物1是中心对称的双核Cu(Ⅰ)配合物,中心离子Cu(Ⅰ)采取扭曲四面体空间构型,分别与配体L的两个P原子和两个桥联的Br原子配位;其中Cu-Cu距离为0.3060nm,大于两个铜原子的范德华半径之和,因此不存在Cu-Cu相互作用。密度泛函理论(DFT)计算表明1的HOMO电子密度主要集中于铜和卤素原子,而LUMO电子密度分布在配体(L)上。研究工作表明,配合物1的最低能级激发态通过金属到配体电荷跃迁(MLCT)和卤素到配体的电荷跃迁(XLCT)两种机制形成。     

2-(2-喹啉偶氮)-1，5-苯二酚光度法测定铜的研究

合成了新试剂 2 - ( 2 -喹啉偶氮 ) - 1,5-苯二酚 ( QADHB) ,并研究了其与铜的显色反应 ,在溴化十六烷基三甲胺 ( CTMAB)存在下 ,p H=4 .0邻苯二甲酸氢钾缓冲介质中 ,QADHB与铜反应生成 2∶ 1稳定络合物 ,λmax=540 nm,ε=2 .12× 10 4 L·mol-1·cm-1。铜含量在 0— 30 μg/ 2 5m L内符合比耳定律 ,该方法用于环境样品中铜的测定 ,结果令人满意     

新显色剂3,5-二(1-羧基-4,5-二甲氧基-2-苯氨基偶氮基)苯甲酸与铜(Ⅱ)的显色反应

研究了新显色剂3,5-二(1-羧基-4,5-二甲氧基-2-苯氨基偶氮基)苯甲酸(CDMOBAABA)与铜(Ⅱ)的显色反应。在TritonX-100存在下,于pH9.5的NH3-NH4Cl缓冲介质中,CDMOBAABA与铜(Ⅱ)形成棕红色配合物。试剂与络合物的最大吸收波长分别为450nm和540nm。表观摩尔吸光系数为2.43×105L·mol-1.cm-1。铜(Ⅱ)含量在0—20μg/25mL范围内符合比耳定律。该方法用于铝合金样品中铜的测定,结果与原子吸收光谱法相吻合,相对标准偏差1.89%。     

Spectroscopic Study of the Interaction of Mitoxantrone with Copper(I), Copper(II), and Neocuproine

Both reductive and oxidatlve mode of metabolism have been hypothesized for the antitumor agent mitoxantrone. This work aims to better understand the redox properties of mitoxantrone in the presence of the physiological redox couple, copper(I)/copper(II), by means of polarograpy and spectrophotometry. The first quasi-reversible one-electron reduction of mitoxantrone to the semiquinone and the second reduction to the hydroquinone have been shown to be considerably affected by copper. Visible spectra of mitoxantrone-copper mixtures in nitrogen and oxygen purged solutions taken in a one-week period exhibit varying degrees of complexation and oxido-reduction.

When copper(II), neocuprolne and mitoxantrone are mixed in a certain ratio in pH 7. 4 phosphate buffer solution, two new peaks at 584 and 632 nm emerge in the spectra indicating a ternary charge transfer complex. The complex atoichiometry was established as Cu(IT): neocuproine: tritoxan-trone = 2:4:1 by Job's method of continuous variations. The ternary complex is sensitive to the relative concentrations of mitoxantrone and copper(II), an excess of the latter giving rise to complete red ox products. This complex may be important in modeling the drug's oxidative mode of ant tumor action.     

Preparation of copper–silicon dioxide nanoparticles with chemical vapor synthesis

Atmospheric pressure chemical vapor synthesis was used to produce copper nanoparticle composites in an amorphous silicon dioxide, i.e., either copper nanoparticles coated with amorphous silicon dioxide or copper nanoparticles embedded in amorphous silicon dioxide matrix. Synthesized metal–organic copper(I) complex was used as a precursor that provided well-defined ratio (1:2) of copper and silicon. The thermal decomposition of the Cu(I) complex molecule leads to homogenous nucleation and formation of copper nanoparticles which are subsequently coated with Si/SiO₂ in the gas phase. The decomposition was greatly enhanced when reductive atmosphere, i.e., H₂/N₂ 10 v% were used instead of pure nitrogen. A narrow size distribution with the geometric mean diameter of the particle agglomerates around 30 nm was observed while the primary size of the copper core particles was around 5 nm.     

X-ray absorption spectral investigations on mixed-valence copper complexes of penicillamine and cysteamine

The X-ray K-absorption spectra of copper in some of its complexes involving ligands like penicillamine (known detoxicating agent for heavy metal poisoning) and cysteamine (a known radiation protector) have been investigated using a 40 cm curved crystal spectograph. These complexes are described in the literature as being mixed-valence [1, 2]. The copper-penicillamine complex shows two distinct edges, K₁ and K₂, indicating mixed-valency in the complex. The cysteamine complexes do not show any splitting of the edges. In one of the cysteamine complexes, which is said to involve molecular oxygen, the magnitudes of shifts of the main edge and principal absorption maximum fall close to copper (II) compounds whereas in the other complex, these shifts are in the range of copper (I) compounds. The probable reasons for the observed deviations have been discussed.     

Direct observation of radical intermediates during electron transfer between DNA and a ternary copper complex

The photoinduced electron transfer (PET) reaction within a ternary copper complex [Cu(phen)(Htrp)]⁺ (Htrp: l-tryptophanato; phen: 1,10-phenanthroline) (1) and in presence of DNA has been studied in homogeneous buffer medium and in reverse micelles. An intramolecular electron transfer occurs within the photoexcited complex (1) from tryptophan to phen. The copper complex can displace ethidium bromide from DNA backbone and on photoexcitation can oxidize DNA in a deoxygenated environment due to intermolecular electron transfer, although the intramolecular electron transfer is thermodynamically favorable. A prominent magnetic field effect (MFE) has been found even in homogeneous aqueous medium for the triplet born radicals both in case of intra and intermolecular electron transfer reactions. In case of intramolecular electron transfer the observation of MFE is similar to that of linked donor-acceptor system. However the observation of MFE for the intermolecular electron transfer between non-covalently bound complex-DNA systems is rather rare. Some non-covalent weak interaction, e.g. hydrophobic interaction between the phen ligand and DNA base pairs and electrostatic force of attraction between [Cu(phen)(Htrp)]⁺ complex and DNA may lead to partial intercalation of the copper complex within DNA that is responsible for such a rare observation.     

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO₄) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B ₀ = 8000 G). The degree of orientation of these complexes is rather high (S _z = 0.76) and close to that of systems with a complete ordering (S _z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH₄, N₂H₄ · H₂O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.     

析相光度法测定铁(Ⅲ)的研究

本研究了铁（Ⅲ）－ＰＥＧ（聚乙二醇－２０００）－铬锖Ｒ－Ｎａ２ＳＯ４体系的上光度法并应用于测定Ｆｅ（Ⅲ）。最适酸并为４．５￣６．５（ＮａＡｃ－ＨＡｃ）缓冲溶液,其络合物的最大吸收位于５６０ｎｍ,表观摩尔吸光系数为５．３６×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,Ｆｅ（Ⅲ）浓度在０￣４μｇ范围内服从比尔定律,铁与铬菁Ｒ形成组成为１：２的稳定络合物。该方法用于蔡叶中铁的测定,获得了满意的结果。