Chemical Properties of Expanded Porphyrins and their Application to Analytical Chemistry

膨胀卟啉的化学性质及其在分析化学中的应用

• 批准号: 05453071
• 负责人: TABATA Masaaki
• 金额: $ 4.74万
• 依托单位: Saga University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453071/
• 关键词: Porphyrins; Expanded porphyrin; Fluoride; Zinc; サフィリン; 蛍光分析法; イオン対生成速度

An Expanded Porphyrin, 2,23-diethyl-8,17-bis (2-ethoxycarbonylethyl) -3,7,12,13,18,22,22-hexamethylsapphyrin (H_3sap), was synthesized by condensation of tripyrrane derivative with bipyrrole and highly selective methods for the determination of anions and metal ions were developed.The sapphyrin reacts with fluoride to give out an enhanced fluorescence intensity at 680 nm on excitation at 450 nm in the presence of fluoride ion as small as parts per billion level via the ion-pair complex, [H_5sap F]^+ formation. Since the present method is based on a direct reaction of the fluoride ion with the sappyrin, a 200-fold amount of the aluminum (III) ion and 2000-fold amount of the iron (III) ion over the fluoride ion did not interfere with determination of the fluoride. The method was applied to determination of the fluoride ion in various water samples.The detailed reaction mechanism was studied by using stopped-flow method. The rate constants and activation energies for the formation and dis … More sociation reactions of[H<@D25@>D2sap F]<@D1+@>D1 were found to be k<@D2f@>D2=(1.53 0.03)x10<@D17@>D1 mol<@D1-1@>D1 dm<@D13@>D1 s<@D1-1@>D1(25ﾟC), DELTAH<@D1*@>D1=24.1(]SY.+-.[) 0.3 kJ mol<@D1-1@>D1, DELTAS<@D1*@>D1=-26.6(]SY.+-.[)1.0J mol<@D1-1@>D1 K<@D1-1@>D1, and k<@D2d@>D2=(4.08(]SY.+-.[)0.08)x10<@D15@>D1(25ﾟC), DELTAH<@D1(]SY.Thermod.[)@>D1=4.79(]SY.+-.[)0.10 kJ mol<@D1-1@>D1, DELTAS<@D1(]SY.Thermod.[)@>D1=4.79(]SY.+-.[)0.10 J mol<@D1-1@>D1 K<@D1-1@>D1. The rate constant is 10000 times smaller than that of the protanation of fluoride ion. The results suggest existence of a pre-equilibrium of a deformed sapphyrin structure to accept the fluoride ion. The rate constants for the formation and dissociation of zinc (II) complex were k<@D2f@>D2=(11.8(]SY.+-.[)0.2)x10<@D14@>D1(25ﾟC)mol<@D1-1@>D1 dm<@D13@>D1 s<@D1-1@>D1, DELTAH<@D1(]SY.Thermod.[)@>D1=82.0(]SY.+-.[)0.8 kJ mol<@D1-1@>D1, DELTAS<@D1(]SY.Thermod.[)@>D1=127(]SY.+-.[)3J mol<@D1-1@>D1 K<@D1-1@>D1, and k<@D2b@>D2=7.66(]SY.+-.[)0.71(25ﾟC), DELTAH<@D1(]SY.Thermod.[)@>D1=82.9(]SY.+-.[)6.5kJ mol<@D1-1@>D1, DELTAS<@D1(]SY.Thermod.[)@>D1=126(]SY.+-.[)22 J mol<@D1-1@>D1 K<@D1-1@>D1. The formation rate of zinc (II) complex is 1000 times as reactive as the zinc (II) porphyrin formation rate but is still smaller 100 times than the water dissociation from aqua zinc (II) ion.The fluoride ion-pair complex was extracted into chloroform and the chemical species is[H_4sap F^-]which also shows tfluoresence. Less

扩展的卟啉，2,23-二甲基-8,17-双（2-乙氧基苯基甲基）-3,7,12,13,18,22222222222222-22-22-甲基甲基甲基甲基甲基甲酰胺（H_3SAP）（H_3SAP），通过与高度衍生物的凝结相结合，并通过高度选择性方法合成，并通过高度选择性方法来确定。 sapphyrin与氟化物反应，在450 nm的兴奋时，在氟离子存在下，通过离子配合物（H_5SAP F]^+形成，在450 nm的兴奋时给出了增强的荧光强度。由于目前的方法是基于氟离子与奶油蛋白的直接反应，因此在氟化物离子上含有200倍的铝（III）离子和2000倍的铁（III）离子不会干扰确定氟离子。应用该方法来确定各种水样中的氟化物离子。使用停止流量方法研究了详细的反应机理。发现[H <@d25@> d2sap f] <@d1+@> d1的速率常数和激活能量是k <@d2f@> d2f@> d2 =（1.53 0.03）x10 x10 <@d17 <@d17@> d1@> d1@> d1 mol <@d1 col <@d1@d1 d1 d1 d1 d1 dm <@d1@d1（25@d1 c） deltah <@d1*@> d1 = 24.1（] k <@d2d@> d2 =（4.08（] sy。+ - 。[）0.08）x10 <@d15@> d1（25 c），deltah <@d1（] sy.thermod。[）@> d1@> d1 = 4.79（] deltas <@d1（] sy.thermod。[）@> d1 = 4.79（]sy。+ - 。[）0.10 j mol <@d1-1@> d1 k <@d1-1@>@> d1。速率常数比氟离子的原质量小10000倍。结果表明存在变形的sapphyrin结构的前平衡，以接受氟化离子。锌（II）复合物形成和解离的速率常数为k <@d2f@> d2 =（11.8（]SY。+ - 。[）0.2）x10 <@d14@> d1@> d1（25 c）mol <@d1-1-c） deltah <@d1（] sy.thermod。[）@> d1 = 82.0（] k <@d2b@> d2 = 7.66（] mol <@d1-1@> d1 k <@d1-1@> d1。锌（II）复合物的形成速率是锌（II）卟啉形成速率的1000倍，但仍然是水离子离子（II）离子的100倍。将氟离子-PAIR络合物提取到氯仿中，化学物种是化学物种[H_4SAP F^ - ]，这也显示出TfluoreSence。较少的

项目成果

Masaaki Tabata: "Thermochromism of Metal-Exchange Reaction between Zinc(II) and Mercury(II) Porphyrins" Zeit.Naturforschung. (in press). (1995)

Masaaki Tabata：“锌（II）和汞（II）卟啉之间金属交换反应的热致变色”Zeit.Naturforschung。

Masaaki Tabata at al.: "Kinetic Evidence for Short-lived Inter-mediates Formed in Metalloporphyrin Formation" J.Molecular Liquid. (in press). (1995)

Masaaki Tabata 等人：“金属卟啉形成中形成的短寿命中间体的动力学证据”J.Molecular Liquid。

M.Tabata;K.Suenaga: "Dynamic Recognition of Metal Ions by Porphyrin and 18-Crown-6" Supuramolecular Chem.22. 271-276 (1993)

M.Tabata；K.Suenaga：“卟啉和 18-Crown-6 对金属离子的动态识别”超分子化学.22。

Hitoshi Ohtaki et al.: "Direct Structural determination of the Short-lived Intermediate Formed in the Dynamic Incorporation of a Copper (II) Ion into a Mercury (II) Porphyrin by the Sstopped-flow EXAFS Method" J.Chem.Soc., Chem.Commun.1023-1025 (1994)

Hitoshi Ohtaki 等人：“通过 Sstopped-flow EXAFS 方法直接结构测定铜 (II) 离子动态掺入汞 (II) 卟啉中形成的短寿命中间体”J.Chem.Soc.，

Masaaki Tabata et al.: "An EXAFS Study on Metal-Substitution Reaction of Homodinuclear Mercury (II) Porphyrin with Copper (II) in Aqueous Solution" Bull.Chem.Soc.Jpn.67. 1608-1614 (1994)

Masaaki Tabata 等人：“水溶液中同核汞 (II) 卟啉与铜 (II) 的金属取代反应的 EXAFS 研究”Bull.Chem.Soc.Jpn.67。