Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis
Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis
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DOI：
10.1021/acs.analchem.6b04179
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发表时间：
2017-04-04
影响因子：
7.4
通讯作者：
Ogawa, Takuji
中科院分区：
文献类型：
--
作者：
Lisak, Grzegorz;Tamaki, Takashi;Ogawa, Takuji
本工作揭示了卟啉二聚体在电分析中的应用，如离子的电位测定。它也提出了一个问题，目前的超能斯特反应的发生的看法，作为一个离子选择性膜内的单个卟啉的可能dirnerization的结果。为了研究，四种不同的卟啉二聚体被用作离子载体，即，游离碱-游离碱、Zn-Zn、Zn-游离碱和游离碱-Zn。由于锌-游离碱和游离碱-锌卟啉二聚体携带阴离子和阳离子敏感的卟啉单元，它们在离子选择电极中的应用被用于阴离子和阳离子敏感的传感器。对于添加的亲脂性盐，发现两种卟啉二聚体都具有阴离子和阳离子敏感性。这允许使用一个单一的分子作为新型的多功能的lorophore（阴离子和阳离子选择性），简单地通过改变膜的组成。所有阴离子敏感的传感器是高氯酸盐敏感的，而阳离子选择性传感器是银敏感的。传感器的选择性主要取决于卟啉二聚体的离子选择性膜。此外，发现基于阳离子敏感二聚体的传感器的选择性显著上级针对基于单个卟啉单元的传感器（卟啉二聚体的前体）测量的选择性。因此，单卟啉的二聚化实际上可能是增加或调节卟啉选择性的因素。此外，在阳离子敏感传感器的情况下，选择性极大地依赖于二聚体中卟啉单元的顺序。这开辟了一种新的途径，调控和调节传感器的灵敏度和选择性，通过应用复杂的卟啉系统与一个以上的卟啉单元与混合敏感卟啉。
This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dirnerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile lorophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation- sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor, to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.