[화학] 망간포르피린을 함유한 고분자형 이온선택성 막전극의 감응 메카니즘

Response mechanism for the chloride-selective membrane doped with 5, 10, 15, 20-tetraphenyl(porphyrinato)manganase(III) chloride(Mn(TPP)Cl) in PVC/DOS matrix is proposed by examining the visible spectra of the corresponding optode membrane. The visible spectra of Mn(TPP)Cl-doped membrane placed in a...

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Veröffentlicht in:Punsŏk kwahak 1996, Vol.9 (3), p.270-278
Hauptverfasser: 홍영기(Young Ki Hong), 강유라(You Ra Kang), 신대호(Dae Ho Shin), 신두순(Doo Soon Shin), 차근식(Geun Sig Cha), 남학현(Hakhyun Nam)
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Sprache:kor
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Zusammenfassung:Response mechanism for the chloride-selective membrane doped with 5, 10, 15, 20-tetraphenyl(porphyrinato)manganase(III) chloride(Mn(TPP)Cl) in PVC/DOS matrix is proposed by examining the visible spectra of the corresponding optode membrane. The visible spectra of Mn(TPP)Cl-doped membrane placed in aqueous solution show that the chloride ligand is easily replaced with water molecule. When other halogen ions, such as $F^-$, $Br^-$ and $I^-$, are added to the sample solution, they replace the water ligand, exhibiting distinctive change in the Soret band of Mn(TPP). On the other hand, bulky anions, such as SCN and salicylate, do not form a bond with the central metal. These results suggests that the potentiometric response of Mn(TPP)-based membrane results either from the ligand exchange (water with halides) at the central metal or from the counter ion exchange (chlorides with bulky lipophilic anions) around the positively charged porphyrin molecule in membrane phase. It was also noted that both hydration enthalpies of anions and their binding constants to Mn(TPP) play critical role in determining the potentiometric selectivity pattern of the membrane. 5, 10, 15, 20-tetraphenyl(porphyrinato)manganase(III) chloride(Mn(TPP)Cl)를 감응성 물질로 사용하는 염화이온 선택성 전극의 감응 메카니즘을 동일한 막 조성을 갖는 optode의 가시광선 스펙트럼 변화를 관찰하여 연구하였다. 고분자막 내에서 망간포르피린의 리간드인 염화이온은 물분자와 치환되며, 시료 용액의 할로겐족 음이온들은 고분자막으로 들어와 망간포르피린에 치환된 물분자 리간드를 다시 치환함으로써, 그리고 살리실산과 같은 지용성 음이온들은 포르피린 주변의 염화이온들과 이온 교환을 함으로써 감응전위를 발생하는 것으로 보인다. 또한 각 음이온들에 대한 선택성을 결정하는 중요한 요소는 망간포르피린-음이온 리간드의 결합상수와 음이온의 수화엔탈피의 균형에 의하여 결정되는 것임을 확인할 수 있었다.
ISSN:1225-0163
2288-8985