镍－PAN极谱络合吸附波的研究

在含有５０％乙醇,２０×ｌ０￣－５ｍｏｌ／Ｌ１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）的０．１ｍｏｌ／ＬＮＨ＿４Ａｃ缓冲溶液（ｐＨ７．２）中,Ｎｉ（Ⅱ）－ＰＡＮ络合物在单扫示波极谱仪上产生一灵敏的导数极谱波,峰电位在－０．６５ｖ（ｖｓＳＣＥ）,峰电流与Ｎｉ（Ⅱ）浓度在３．０×１Ｏ￣－９～４．０×１０￣－６ｍｏｌ／Ｌ范围内呈线性关系,检测限达２×１Ｏ￣－９ｍｏｌ／Ｌ。机理研究表明,峰电流是由吸附在电极表面的络合物中的ＰＡＮ经不可逆还原而产生的。方法已应用于钢中镍的测定,结果满意。     

铱－钼酸盐－罗丹明B缔合显色反应的研究

在聚乙烯醇（ＰＶＡＶＡ）存在下,铱与钼酸盐和罗丹明Ｂ（ＲＢ）形成离了缔合物。缔台物的最大吸收位于５７０ｎｍ摩尔吸光系数ε８．３６×１０￣５’Ｌ·ｍｏｌ￣－１·ｃｍ￣－１,服从比尔定率范围为０～２．７５μｇｌｒ／２５ｍｌ。测定２．０μｇ铱的相对标准偏差为２．５％（ｎ＝７）,检出限４３ｎ／ｍｌ（ｎ＝１２）。测定铱的适宜条件为ＣＨＣｌＯ＿４＝０．９３ｍｏｌ／Ｌ,Ｃ＿ＭｏＯ￣２－＿４９．０×１０～－４ｍｏｌ／Ｌ,Ｃ＿ＲＢ＝３．３×ｌ０￣－５ｍｏｌ／Ｌ,ＰＶＡＯ０８％。试验了３０多种共存离子的影响,除形成杂多酸元素     

二安替比林基－（2－溴）苯基甲烷与钒（Ⅴ）的显色反应研究

合成并鉴定了二安替比林基─（２─溴）苯基甲烷（ＤＡＯＢＭ）,研究了它与钒（Ⅴ）的显色条件。在Ｔｗｅｅｎ─８０和Ｍｎ（Ⅱ）存在下,ＤＡＯＢＭ与Ｖ（Ⅴ）在Ｈ３ＰＯ４（１＋１０）介质中生成橙色产物,λｍａｘ＝４９０ｎｍ,ε＝１．５５×１０６Ｌ·ｍｏｌ－１·ｃｍ－１,Ｖ（Ⅴ）的浓度在０．１～０．９μｇ／２５ｍｌ范围内符合比尔定律。方法用于中草药和矿样中钒的测定,结果满意。     

1－（－2－吡啶偶氮）－2－萘酚修饰碳糊电极测定铜的研究

本文报道１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）修饰碳糊电极在乙酸盐缓冲液（ｐＨ５．０）中,与铜离子生成电后性螯合物,并吸收在电极表面,经介质交换到０．１ｍｏｌ／ＬＫＣｌ中,用微分脉冲伏安法测定,用－０．１５Ｖ出现一灵敏的还原峰。用正交试验优化法研究了测定铜的最佳条件。其相对柯准偏差３．２７％。这一方法用于阳极泥中铜的测定,回收率为９４．３％。还用双电位阶跃计时库仑法,循环伏安法研究了ＰＡＮ修饰碳糊电极与Ｃｕ（Ⅱ）的反应机理,获得良好的结果。     

5—（2－噻唑）偶氮－8－氨基喹啉的合成及光度法测定微量钴

合成了新试剂５－（２－噻唑）偶氮８－氨基喹啉（ＴＡＡＱ），测定了它的酸离解常数，并用于光度法测定微量钴。在ＣＴＭＡＢ存在下，０．０４～０．０２ｍｏｌ／１ＮａＯＨ介质中，ＴＡＡＱ与Ｃｏ￣２＋形成１：３的深蓝色络合物，最大吸收峰位于６３０ｎｍ，摩尔吸光系数ε＝１．２３×１０￣５１．ｍｏｌ￣－１·ｃｍ￣－１。Ｃｏ￣２＋在０～１０μｇ／２５ｍｌ范围内符合比尔定律。方法具有较好的选择性，已用于ＶＢ＿（１２）及矿石分析，结果满意。     

钯－钼酸铵－丁基罗丹明B显色反应体系的研究

本文提出了一种新的光度测定论的方法。该方法基于在聚乙烯醇（ＰＶＡ）存在下,钯与钼酸盐和丁基罗丹明Ｂ（ＢＲＢ）反应形成离子缔合物。缔合物的最大吸收位于５８０ｎｍ,摩尔吸光系数ε为３．１４×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）,钯量在０～４ｕｇ／２５ｍｌ范围内服从比尔定律。缔合物中ｐｄ：ＢＲＢ＝１：４,体系至少可稳定１０ｈ,测定钯的适宜条件是：Ｃ＿（ＨＣＯ４）＝１．６ｍｏｌ／Ｌ,Ｃ＿（ＢＲＢ）＝３．８×１０￣（－５）ｍｏｌ／Ｌ,ＰＶＡ０．０８％。考察了３０多种共存离子的影响。本法用于碳基和铝基催化剂中     

吸附溶出伏安法测定痕量钒

在０．０１ｍｏｌ／ＬＨａｃ－ＮａＡｃ和１．２×ｌ０－５ｍｏｌ／Ｌ乙醛酸缩氨基硫脲（ＧＡＴＳＣ）体系中，Ｖ（Ⅴ）产生一灵敏的还原波，峰电位是－０．８９ｖ（υｓ．ＳＣＥ），峰高与Ｖ（Ⅴ）的浓度在２．０×１０－８～１．６×１０－６ｍｏｌ／Ｌ范围内呈直线关系，检测限是６０×１０－９ｍｏｌ／Ｌ。     

偶氮溴膦－PSN直接测定钢铁中稀土总量

,Ｖ（Ⅴ）（２．５）,Ｗ（Ⅵ）（２）,Ｚｒ（Ⅳ）（０．０７）,Ｚｎ２＋（３）,Ｆｅ３＋（１５）,ＥＤＴＡ（２００）,酒石酸（７５０）,ＳＯ（９０）,草酸（２５）。（＊Ｎｂ含量高时加１ｍｌ２０％酒石酸掩蔽;加０．５ｍｌ５％苯羟乙酸和２滴３０％过氧化氢掩蔽）。２．５工作曲线于５０ｍｌ容量瓶中,加１０ｍｌ盐酸（１＋３）,用水稀至刻度,摇匀。分取５ｍｌ数份各置于２５ｍｌ容量瓶中,并分别加入０～２０μｇ铈,加２ｍｌ偶氮溴膦－ＰＳＮ,以下按实验方法测量吸光度。３样品分析称取０．１ｇ试样置于１００ｍｌ锥形瓶中,加５ｍｌ     

碲钨杂多酸——罗丹明B测定痕量碲的研究

利用碲钨杂多酸－罗丹明Ｂ（ＲＢ）－聚乙烯醇体系建立了分光光度测定痕量碲的新方法，确定了测定碲的适宜条件为〔Ｈ２ＳＯ４〕＝１．２０ｍｏｌ／Ｌ，〔ＷＯ２－４〕＝１．２×１０－４ｍｏｌ／Ｌ，〔ＲＢ〕＝５．０×１０－５ｍｏｌ／Ｌ和ＰＶＡ０．０８％。在ＰＶＡ存在下碲钨杂多酸与罗丹明Ｂ形成１∶９的离子缔合物，其最大吸收位于５６５ｎｍ，表观摩尔吸光系数ε＝１．７６×１０７，离子缔合物至少稳定２４０ｈ。测定碲的线性范围为０～０．１６μｇ／２５ｍｌ，对０１２μｇ／２５ｍｌ碲测定的相对标准偏差１．３％（ｎ＝１０）。考察了４０多种共存离子的影响，大多数常见元素不干扰，允许５００倍量Ｓｅ（Ⅳ）；４０倍量Ｃｕ２＋，Ｂｉ３＋存在。本法灵敏度高，重现性和选择好，用于烟尘中碲的测定，结果与电分析法吻合。     

离子交换色谱法测定砷黄铁矿浸取溶液中砷（V）和砷（Ⅲ）

本文是在含有硫酸铁（０．１－０．５ｍｏｌ／Ｌ），硝酸铁（０．１－０．２ｍｏｌ／Ｌ），硫酸（０．３－１．０ｍｏｌ／Ｌ）和硝酸（０．１－０．３ｍｏｌ／Ｌ）的提金浸取液中用Ｈ＾＋型阳离子交换柱分离样品溶液中的Ｆｅ（Ⅱ），Ｆｅ（Ⅲ）和其它共存阳离子；然后用带电导检测器的离子色谱仪测定含量范围为０．２－１０ｇ／Ｌ的亚砷酸根和砷酸根。本法测定了硫酸盐和其它共存阴离子存在时对Ａｓ（Ｖ）的影响；并比较了几种洗脱液     

Synthesis and biological investigations of 1-(tetrahydropyran-2'-yl)- and 1-(tetrahydrofuran-2'-yl)benzimidazoles and 1/2-(tetrahydropyran-2'-yl)- and 1/2-(tetrahydrofuran-2'-yl)benzotriazoles

Sets of benzimidazole and benzotriazole derivatives bearing on position 1 or 2 a tetrahydrofuranyl or tetrahydropyranyl moieties were prepared through the addition of the suitable benzazoles on 2,3-dihydrofuran and 3,4-dihydro-2H-pyran. The reactions were carried on either without solvent or in carbon tetrachloride solution. In the last case some peculiar chlorinated side products were isolated and characterized. Twenty compounds were screened for in vitro antitumoral and anti-HIV-1 activities and found poorly active or completely inactive. On the other hand several compounds exhibited good tracheal relaxant activity in vitro; compound 8, 11, 16, 24 and 26 resulted more active than theophylline in this test, while compound 11 was comparable to amrinone till the concentration of 3 micrograms/ml. Finally, compound 5 resulted endowed with a strong diuretic and saluretic activity at the dose of 3 mg/Kg, thus representing a new lead for discovering new diuretic agents.     

Synthesis and biological investigations of 2-(tetrahydropyran-2'-yl) and 2-(tetrahydrofuran-2'-yl)benzimidazoles

A set of benzimidazole derivatives bearing on position 2 a tetrahydropyranyl or tetrahydrofuranyl residue was prepared and tested for antitumoral, anti HIV-1 and other pharmacological activities. While the anti-HIV activity was completely lacking, moderate antitumoral activity was found in a few compounds; particularly the 5,6-dichloro-2-(tetrahydropyran-2-yl)-benzimidazole (8) was able to inhibit the growth of 19 cell lines of humane tumors at near micromolar concentration. On the other hand compounds 4, 6-8 and 10 exhibited significant tracheal relaxant activity in vitro at concentration 3-10 micrograms/ml, thus resulting superior to theophylline and comparable to amrinone.     

Tyrosinaemia type I and NTBC (2-(2-nitro-4-trifluoromethylbenzoyl)-1,3-cyclohexanedione)

In tyrosinaemia type I (McKusick 276700), fatal liver disease results either because of liver failure during infancy or early childhood or because of development of hepatocellular carcinoma during childhood or adolescence. This is caused by toxic metabolites which accumulate because of deficiency of fumarylacetoacetase, the last enzyme in the tyrosine catabolic pathway. NTBC is a potent inhibitor of 4-hydroxyphenylpyruvate dioxygenase and has been shown to efficiently prevent tyrosine degradation, and production of succinylacetone, in patients with tyrosinaemia. Since the first trial of NTBC treatment for tyrosinaemia type I in 1991, over 220 patients have been treated by the drug using a protocol which includes regular follow-up with reports of clinical and laboratory investigations to the study centre in Gothenburg, where additional analysis of critical variables is done on regularly collected samples. The course of the disease in patients with acute tyrosinaemia has changed dramatically. Only 10% of the patients have not clinically responded to NTBC treatment. In half of these patients, successful liver transplantation has been performed which has further reduced the mortality rate during infancy to 5%. The international NTBC study has now been going for 5 years and data have emerged that indicate a decreased risk for early development of hepatocellular carcinoma in patients who started treatment at an early age. There are now 101 patients aged 2-8 years who have started NTBC treatment before 2 years of age, and no cancer has developed after 2 years of age among these patients. However, there is no safe age with respect to occurrence of liver cancer, which has been recognized at diagnosis at 1 year of age in one patient and after a few months of treatment in an infant who was given NTBC at 5 months of age.     

2-(2-苯并咪唑基)-6-甲基吡啶-1，1'-联萘-2，2'-双二苯膦铜(I)配合物

以[Cu(CH₃CN)₄](ClO₄)、1, 1’-联萘-2, 2’-双二苯膦(BINAP)和2-(2-苯并咪唑基)-6-甲基吡啶(Hbmp)为起始原料,合成得到一例铜(I)单核配合物[Cu(Hbmp)(BINAP)](ClO₄) (1), 并对其结构和光物理性质进行了表征。X-射线单晶衍射表明,配合物1的一价铜离子与Hbmp上的2个N和BINAP上的2个P相连接,产生一个以一价铜离子为中心的变形四面体。配合物1在340~450 nm范围有一个弱的低能量宽吸收,其归属于Cu(I)到Hbmp的金属到配体电荷转移(MLCT)跃迁。配合物1在溶液和固态均具有良好的光致发光性质。      

Synthesis and biological activities of optically active 6-[3-(3,4-dimethoxybenzylamino)-2-hydroxypropoxy]-2(1H)-quinolinone (OPC-18790)

The enantiomers of 6-[3-(3,4-dimethoxybenzylamino)-2-hydroxypropoxy]-2(1H)-quinolinon e (OPC-18790), a novel cardiotonic agent, were synthesized and evaluated for positive inotropic activity. The key intermediates, 2,3-epoxypropoxy derivatives, were obtained by the alkylation of 6-hydroxy-2(1H)-quinolinone with optically active epichlorohydrin and subsequent ring closure. In an in vitro study, the (R)-(+)-isomer was about 10-fold more potent than the (S)-(-)-isomer.     

5-Br-PADAT和3,5-Br_2-PADAT作为络合滴定指示剂的应用

研究了 5 [(5 溴 2 吡啶 )偶氮 ] 2 ,4 二氨基甲苯和 5 [(3,5 二溴 2 吡啶 )偶氮 ] 2 ,4 二氨基甲苯作为直接滴定铜和以铜为回滴剂的指示剂的应用 ,以及以前者为指示剂滴定铜与锌等离子总量 ,并借助掩蔽剂以提高选择性 ,成功应用于铜合金等样品的分析。     

5—Br—PADAT和3,5—Br2—PTDAT作为络合滴定指示剂的应用

研究了５－「（５－溴－２－吡啶）偶氮」－２,４－二氨基甲苯和５－「（３,５－二溴－２－吡啶）偶氮」－２,４－二氨基甲苯作为直接滴定铜和以铜为回滴剂的批示剂的应用,以及以前者为指示剂滴定铜与锌等离子总量,并借助掩蔽剂以提高选择性,成功应用于铜合金等样品的分析。     

Ti(Ⅳ)-Fe(Ⅲ)-H2O2-棓化青体系动力学光度法测定钛(Ⅳ)

在H2SO4介质中,铁(Ⅲ)能催化H2O2氧化棓化青褪色,钛(Ⅳ)对该催化反应有显著的催化作用,据此建立了测定痕量钛(Ⅳ)的动力学分析新方法。研究了该反应的最佳条件和动力学参数。以钛(Ⅳ)为催化剂的Fe(Ⅲ)-H2O2-棓化青催化反应体系中,对棓化青为假零级反应,对钛(Ⅳ)为一级反应,测得没有钛(Ⅳ)和有钛(Ⅳ)反应体系的表观活化能分别为79.75 kJ/mol和49.82 kJ/mol。该方法测定钛(Ⅳ)的检出限为0.01μg/mL,测量范围为0.03~0.16μg/mL,可用于废水样品中痕量钛(Ⅳ)测定。