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

2，23-二乙基-8，17-二卟啉的扩链（2-乙氧羰基乙基）-3，7，12，13，18，22，22-六甲基卟啉（H_3sap），通过三吡咯烷衍生物与联吡咯缩合反应合成了卟啉衍生物，并建立了测定阴离子和金属离子的高选择性方法，卟啉与氟化物在680 nm激发下产生增强的荧光在450 nm波长下，氟离子通过离子对络合物[H_5sapF]^+的形成，在低至十亿分之一水平的条件下，该反应发生。由于本方法是基于氟离子与sappyrin的直接反应，因此相对于氟离子200倍量的铝（III）离子和2000倍量的铁（III）离子不会干扰氟离子的测定。将该方法应用于多种水样中氟离子的测定，并采用停流法研究了详细的反应机理。计算了生成和分散的速率常数和活化能， ...更多信息 [H<@D25@> D2 sap F]<@D1+@>D1的缔合反应为：k<@D2f@>D2=（1.53 ± 0.03）× 10 <@D17@>D1 mol<@D1-1@>D1 dm<@D13@>D1 s<@D1-1@>D1（25 ℃），Δ H <@D1*@>D1=24.1（]SY ±-. 0.3 kJ mol D1，Δ D1=-26.6（）SY ±.（1）1.0J mol D_1 K D_1，K D_2 =（4.08 ± 0.05）J mol D_1 K D_2 =（4.08 ± 0.05）J mol D_2 =（4.05 ± 0.05）J mol D [）0.08）x10<@D15@>D1（25 ℃），DELTAH<@D1（]SY.Thermod. D_（1）=4.79（±）SY. [）0.10 kJ mol<@D1-1@>D1，DELTAS<@D1（] SY. D_（1）=4.79（±）SY. [）0.10 J mol<@D1-1@>D1 K<@D1-1@>D1.其速率常数比氟离子质子化的速率常数小10000倍。结果表明，存在一个预平衡的变形sapphyrin结构接受氟离子。锌（Ⅱ）配合物的生成和解离速率常数为kD_2 =（11.8 ± 0.01）。[）0.2）× 10 <@D14@>D1（25 ℃）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，Δ TAS <@D1（] SY. [）@>D1=127（]SY.+-. [)3J mol<@D1-1@> D1，k <@D2 b @>D2=7.66（]SY ±-. [）0.71（25 ℃），Δ H <@D1（]SY.Thermod. D_1 =82.9（±）SY. [）6.5kJ mol<@D1-1@>D1，DELTAS<@D1（] SY. [）@>D1=126（]SY.+-. [)22 J摩尔D1 K摩尔D1锌（Ⅱ）络合物的生成速率是锌（Ⅱ）卟啉生成速率的1000倍，但仍小于锌（Ⅱ）水溶液解离速率的100倍，氟离子对络合物被氯仿萃取，其化学形态为[H_4sapF ^-]，也有荧光。少

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 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。

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 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。