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.

合成了水溶性卟啉(2，3.7，8，12，13，17，18-octabromo-5，10，15，20-tetrakis(4-sulfonatophenyl)porphyrin；H&lt；@D22@&gt；D2obtpps&lt；@D14-@&gt；d1；h2p&lt；@D14-@&gt；d1)，用于测定和分离水溶液中锂离子。八溴基团通过吸电子作用降低了卟啉的碱性，使其在碱性水溶液中与锂离子反应生成锂络合物，其最大吸收峰为：lmax(logepsilon/molgt；@d1-1@&gt；d1 dm&lt；@d13@&gt；d1 cm&lt；@d1-1@gt；d1)。钠、钾离子与卟啉不发生反应。反应Li&lt；@d1+@&gt；d1+HP&lt；@D15-@&gt；d1[LiP]&lt；d1+H&lt；@d1+@&gt；d1的平衡常数为10-8.81，在pH L3时，[Lip]@d15-@&gt；d1的条件生成常数为10&lt；@D14.21@&gt；d1。@d1+@&gt；d1)和提取的X&lt；@d25@&gt；D2LiP分离为X&lt；@d24@&gt；D2LiP&lt；@d1-@&gt；d1和@d1+@&gt；d1。[LiP&lt；@D15@&gt；D1-]&lt；@D2a@&gt；D2+5[X&lt；@D1+@&gt；D1]&lt；@D20@&gt；D2(]SY.dblharw.[)[X&lt；@D24@&gt；D2LiP&lt；@D1-@&gt；D1]&lt；@D20@&gt；D2+[X&lt；@D1-@&gt；D1]&lt；@D20@&gt；反应的萃取常数D2为(8.4(]sy.+-)。[)0.7)x10&lt；@D112@&gt；d1mol&lt；@d1-4@&gt；d1dm&lt；@D112@&gt；d1，其中a和o的下标分别表示水相和有机相中的化学物种。上述结果用于测定血清、海水和温泉水样中的锂，范围为0.07-0.7 mg dm&lt；@d1-3@&gt；d1(1×10&lt；@d1-5@&gt；d1-1 x 10&lt；@d1-4@&gt；d1moldm&lt；@d1-3@&gt；d1)。当样品中含有镁离子时，N，N‘-1，2-乙二基双-[N(羧甲基)-甘氨酸基]镁(II)([Mg(EDTA)]&lt；@D12-@&gt；d1或H&lt；@d24@&gt；D2EDTA)对Hevy金属离子的干扰。

项目成果

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。

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）。

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

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

M.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”