2,3-二羟基萘钼多酸有机衍生物的合成及1H NMR和IR谱学研究

本文对二种新合成的2，3－二羟基萘二钼和四钼多酸有机衍生物[n-Bu)4N]2[Mo2O5(OC10H6O)2](Ⅰ）和[n-Bu)4N]2[Mo4O10(OC10H6O)2(OCH3)2](Ⅱ)进行了红外光谱与核磁共振波谱研究，发现[Mo2O5]^2 中钼氧多桥键的红外振动频率较[Mo4O10(OCH3)2]^2 中钼氧多桥键的红外振动频率红移，而在配合物Ⅱ中2，3－二羟基中芳环的^1H化学位移较配合物Ⅰ中向低场移动。同时还发现含二钼配位中心[Mo2O5]^2 的[Mo2O5(OC10H6O)2]^2-与含四钼配位中心[Mo4O10(OCH3)2]^2 的[Mo4O10(OC10H6O)2(OCH3)2]^2-生成条件的差异仅仅只在反应体系的pH值的微小变化，说明钼多酸有机衍生物阴离子是对体系酸碱度极为敏感的物质。     

Electrochemical studies of 1,5-dihydroxynaphthalene as substrate for voltammetric enzyme immunoassay

Immunoassay is one of the biochemical analytical techniques using the specific antigen antibody com-plexation for analytical purposes. It has extensive ap-plication in clinical diagnostics, prevention and cure of diseases, and virus diagnostics. The presentation and progress of immunoassay methodology are one of the greatest achievements of bioanalytical chemistry. It is estimated that several-hundred millions of immuno-analytical determinations are carried out every year all over the world. E…     

1—（5—硝基—2—吡啶偶氮）2，7—萘二酚吸光光度法测定微量钴

报道了 1 (5 硝基 2 吡啶偶氮 ) 2 ,7 萘二酚与钴的显色反应 ,结果表明 ,在Tween 80存在下 ,pH 5 .2 6.5时试剂与钴形成稳定的蓝色配合物 ,其最大吸收波长位于 63 5nm ,表观摩尔吸光系数为 6.44× 10 4 L·mol- 1·cm- 1,配合物中钴与试剂的组成比为 1∶2 ,钴浓度在 0 5 μg/10ml范围内服从比耳定律。方法用于标准钢、金川精矿等试样中钴的测定 ,结果满意。     

高纯度2,6-二羟基萘的制备工艺

以便宜的2,6-萘二磺酸钠为原料,通过一步混合碱高温碱熔法合成高纯度2,6-二羟基萘。 N₂气保护下,添加苯酚或抗氧剂1010防止过度氧化焦油的产生,能显著提高2,6-二羟基萘收率。 较佳反应条件为:2,6-萘二磺酸钠与混合碱的质量比1:3,混合碱中氢氧化钠和氢氧化钾质量比2:1,使用0.5 g苯酚或抗氧剂1010,反应温度345 ℃,反应时间2 h,碱熔收率达到86.3%。 经过甲醇-水混合溶剂精制,2,6-二羟基萘纯度能达到99%。     

铜-5-Br-PAND-Triton X-100体系析相法测定天然水中痕量铜

研究了显色剂１－「（５－溴－２－吡啶）偶氮」－２,７－萘二酚（简称５－Ｂｒ－ＰＡＤＮ）在ＴｒｉｔｏｎＸ－１００存在下,用浊点析相分光光义法测定天然水中痕量铜（Ⅱ）。在ＰＨ８．３－９．７的氮水－氯化铵缓冲溶液中,配合物最大吸收波长为λｍａｘ＝５４３ｎｍ,相当于Ｓａｎｄｅｌｌ灵敏度为０．０００１４μｇ／ｃｍ,铜量在０－２０μｇ／２５０ｍＬ范围内符合比尔这律,方法已用于测定天然水中的痕量铜。     

Construction and structural analysis of mono- and heterobimetallic bis(titanate) molecular cages

To explore the utility of bis(dihydroxynaphthalene) ligands for the construction of supramolecular structures, we demonstrated the preparation of cage-shaped complexes by combining these ligands with hexacoordinate titanium(IV). The reaction of biphenylenebis(dihydroxynaphthalene) with TiO(acac)₂ proceeded in the presence of N-methylmorpholine in DMF and an M₂L₃-type cage was obtained by self-organization. As an extension of this work, the preparation of heterobimetallic molecular cages was examined by using combinations of titanium(IV), palladium(II) or platinum(II), and pyridyldihydroxynaphthalenes. Ti(IV)/Pd(II) cages were prepared in one pot by treatment of the pyridyldihydroxynaphthalene ligands with TiO(acac)₂ followed by PdCl₂(MeCN)₂. In the preparation of Ti(IV)/Pt(II) cages, platinum(II)-bridged bis(dihydroxynaphthalene) ligands were isolated in advance from the reaction of pyridyldihydroxynaphthalene ligand precursors with K₂PtCl₄, which were then deprotected and reacted with TiO(acac)₂ in the same conditions as those for biphenylenebis(dihydroxynaphthalene). The precise structures of the Ti(IV)/Pd(II) and Ti(IV)/Pt(II) heterobimetallic cages were fully elucidated by X-ray crystallographic analysis.     

Preparation and properties of new polyimides and polyamides based on 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene

A novel, trifluoromethyl‐substituted, bis(ether amine) monomer, 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene, was synthesized through the nucleophilic displacement of 2‐chloro‐5‐nitrobenzotrifluoride with 1,4‐dihydroxynaphthalene in the presence of potassium carbonate in dimethyl sulfoxide, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new fluorine‐containing polyimides with inherent viscosities of 0.57–0.91 dL/g were prepared by reacting the diamine with six commercially available aromatic dianhydrides via a conventional, two‐step thermal or chemical imidization method. Most of the resulting polyimides were soluble in strong polar solvents such as N‐methylpyrrolidone and N,N‐dimethylacetamide (DMAc). All the polyimides afforded transparent, flexible, and strong films with good tensile properties. These polyimides exhibited glass‐transition temperatures (T_g's) (by DSC) and softening temperatures (by thermomechanical analysis) in the ranges of 252–315 and 254–301 °C, respectively. Decomposition temperatures for 5% weight loss all occurred above 500 °C in both air and nitrogen atmospheres. The dielectric constants of these polyimides ranged from 3.03 to 3.71 at 1 MHz. In addition, a series of new, fluorinated polyamides with inherent viscosities of 0.32–0.62 dL/g were prepared by the direct polycondensation reaction the diamine with various aromatic dicarboxylic acids by means of triphenyl phosphite and pyridine. All the polyamides were soluble in polar solvents such as DMAc and could be solution‐cast into tough and flexible films. These polyamides had T_g's between 228 and 256 °C and 10% weight‐loss temperatures above 400 °C in nitrogen or air. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2377–2394, 2004     

Microwave Assisted One-pot Synthesis of 2-Amino-4H-chromenes and Spiropyrano[2,3-d]pyrimidine

A convenient and efficient method using microwave assisted one pot synthesis reactions for synthesis of 4H‐benzo[f]chromenes by the reaction of aromatic aldehydes with a mixture of malononitrile and naphthols was examined. The synthesis of spiropyrano[2,3‐d]pyrimidines by the reaction of isatin with malononitrile and barbituric acid and/or thiobarbituric acid was investigated. The versatility of the method was also examined through the reaction of aromatic aldehydes and malononitrile with various reagents.     

2,6-二碘-4-硝基偶氮胂分光光度法测定微量铋

研究了显色剂 2 (2 胂酸基苯偶氮 ) 7 (2 ,6 二碘 4 硝基苯偶氮 ) 1,8 二羟基 3,6 萘二磺酸与铋的显色反应。在 0 .6mol LHClO4 介质中 ,试剂与铋生成的深色络合物 ,最大吸收波长 6 33nm ,摩尔吸光系数为1 2 0× 10 5L·mol- 1 ·cm- 1 ,灵敏度高 ,常见的金属离子允许量大 ,选择性好。Bi 0～ 0 .8mg L范围内符合比耳定律 ,以NaCl褪色试样空白为参比 ,分光光度法测定纯铜及铜合金中的微量铋 ,方法简便 ,结果可靠