Formation and Mechanism of Alkali Metal Porphyrins and their Application to Analytical Chemistry

碱金属卟啉的形成、机理及其在分析化学中的应用

• 批准号: 08454238
• 负责人: TABATA Masaaki
• 金额: $ 5.5万
• 依托单位: SAGA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454238/
• 关键词: Porphyrins; Lithium porphyrin; spectrophotometry; solvent extraction; serum; sea water; 分析; リチウムイオン; 吸光光度定量

A water-soluble porphyrin (2,3.7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin ; H<@D22@>D2obtpps<@D14-@>D1 ; H2P<@D14-@>D1) was synthesized and develped for the determination and separation of lithium ion in aqueous solution. Tne octabromo groups lower the basicity of the porphyrin by their eletron-withdrawing effect and enable the porphyrin to react with lithium ion in alkaline aqueous solution to form the lithium complex along with a shft of absorption maxima ; lmax (log epsilon/mol<@D1-1@>D1 dm<@D13@>D1 cm<@D1-1@>D1) of thg lithium porphyrin are 490.5 nm (5.31) and 734 nm (4.36). Sodium and potassium ions did not react with the porphyrin. The equilibrium constant for the reaction Li<@D1+@>D1+HP<@D15-@>D1 [LiP]<@D15-@>D1+H<@D1+@>D1 was found to be 10-8.81 and the condtional formation constant ofthe [LiP]<@D15-@>D1 at pH l3 is10<@D14.21@>D1.The [LiP]<@D15-@>D1 can be extracted into chloroform as an ion-pair complex with tetracuthylammonium ion (X<@D1+@>D1) and the extracted X<@D25@>D2LiP dissociates to X<@D24@>D2LiP<@D1-@>D1 and X<@D1+@>D1 in chlomform. The exttraction constant for the reaction of [LiP<@D15@>D1-]<@D2a@>D2+5[X<@D1+@>D1]<@D20@>D2(]SY.dblharw.[)[X<@D24@>D2LiP<@D1-@>D1]<@D20@>D2+[X<@D1-@>D1]<@D20@>D2 was found to be (8.4(]SY.+-。[)0.7) x 10<@D112@>D1 mol<@D1-4@>D1 dm<@D112@>D1, where subscripts of a and o denote chemical species in aqueous and organic phases, respectively. The above results were developed for the determination of lithium in serum, sea water and hot-spring water samples at a range of 0.07-0.7 mg dm<@D1-3@>D1 (1 x 10<@D1-5@>D1-1 x 10<@D1-4@>D1 mol dm<@D1-3@>D1). The interference of hevy metal ions was by N,N'-1,2-ethanediylbis-[N (carboxylmethyl)-glycinato] magnesium (II) ([Mg (edta)]<@D12-@>D1 or H<@D24@>D2 edta if sample contain magnesium (II) ion.

水溶性卟啉（2,3.7,8,12,13,17,17-18-OctaBromo-5,10,15,20-20-220-Tetrakis（4-硫酸苯基苯基）卟啉；水溶液中的锂离子。 Tne八尖剂组通过吸引埃特龙的效应降低了卟啉的碱性，并使卟啉能够与酒精水溶液中的锂离子反应，以形成锂络合物，并与吸收最大的shft一起形成锂络合物。 lmax（log epsilon/mol <@d1-1@> d1 dm <@d13@> d1 cm <@d1-1@> d1）的Thg卟啉是490.5 nm（5.31）和734 nm（4.36）。钠和钾离子与卟啉没有反应。反应的等效常数li <@d1+@> d1+hp <@d15-@> d1 [lip] <@d15-@@>@> d1+h <@d1+@> d1+@> d1是10-8.81，并且[lip] <@d15-@@d15-@@@d15-@@@@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@d1 <@ [lip] <@d15-@> d1可以作为离子-PAIR提取成氯仿，与四乙基肌离子（x <@d1+@> d1）和提取的x <@d25@> d25@> d25 lip隔离到x <@d24@d24@> d24@> d2 lip@> d2 lip@> d2 lip@> d1-@d1-@d1-@> d1 and x <@@@@@d1+@@d1+@d1 in。 [Lip <@d15@> d1-] <@d2a@> d2+5 [x <@@d1+@> d1] <@d20@> d2@> d2（] sy.dblharw。为（8.4（]sy。+ - 。[）0.7）x 10 <@d112@> d1 mol <@d1-4@> d1 dm <@d112@> d1，其中a和o分别在水性和有机阶段中表示化学物种。在0.07-0.7 mg dm <@d1-3@> d1（1 x 10 <@d1-5@> d1 x 10 <@d1 x 10 <@d1-4@> d1-4@> d1 mol dm <@d1 mol dm <@d1-3@> d1@@d1-3@@> d1）中，开发了上述结果是为了确定血清，海水和热量水样品中的锂。 Hevy金属离子的干扰是由N，N'-1,2-乙基甲基链球菌 - [N（羧甲基）-Glycinato]镁（II）（II）（[mg（edta）] <@d12-@@@@>@> d1或h <@d24@> d24@> d2 edta If Sampam If Sampamium（ii）iim（II）ion。

项目成果

M.Tabata and H.Ishimi: "Kinetics and Mechanism for the Formation and Dissociation Reaction of 21-(4-Nitrobenzyl)-5,10,15-20-tetrakisi (4-sulfonatophenyl)-23H-porpyrinatozinc (II) and-cadmium (II)" Bull.Chem. Soc.Jpn. 70. 1353-1359 (1997)

M.Tabata 和 H.Ishimi：“21-(4-硝基苯甲基)-5,10,15-20-四(4-磺基苯基)-23H-卟啉锌 (II) 和-的形成和解离反应的动力学和机制

Masaaki Tabata et al.: "Catalytic Reactions as Applied to Trace Analysis" Trend Anal.Chem.16. 132-139 (1997)

Masaaki Tabata 等人：“应用于痕量分析的催化反应”Trend Anal.Chem.16。

M.Tabata et al.: "Kinetics and Mechanism for the Formation and Dissociation Reaction of 21-(4-Nitrobenzyl)-5,10,15-20-tetrakisi(4-sulfonatophenyl)-23H-porpyrinatozinc(II) and" Bull.Chem.Soc.Jpn.70. 1353-1359 (1997)

M.Tabata 等人：“21-(4-硝基苯甲基)-5,10,15-20-四(4-磺基苯基)-23H-卟啉锌(II) 的形成和解离反应的动力学和机制”

Masaaki Tabata et al.: "Ion-Pair Extraction of Lithium Ion by a Water-Soluble Porphyrin" Anal.Sci.(Supplement). 119-122 (1997)

Masaaki Tabata 等人：“水溶性卟啉对锂离子的离子对萃取”Anal.Sci.（补充）。

Masaaki Tabata: "Reaction Mechanism of Mercury(II) with Protonated N-Substituted Porphyrin" Bull.Chem.Soc.Jpn.69. 1587-1592 (1996)

Masaaki Tabata：“汞(II)与质子化N-取代卟啉的反应机制”Bull.Chem.Soc.Jpn.69。