Versatile Metalloporphyrin‐Based Electrochemical Sensing Applications: From Small Gasotransmitters to Macromolecules

Abstract

At the beginning of his youthful sixth decade, this work is dedicated to Prof. Dr. Fabio Doctorovich. He is distinctive in organometallic chemistry. During his successful career, he has been studying the reactivity and application of metalloporphyrins. Metalloporphyrins are organometallic complexes that exhibit, through synthetic modifications, the ability to tune their optical and electrochemical properties and their selectivity towards a particular molecule or ion. For this reason, they are systems extremely useful as electrochemical sensors to detect and quantify a wide variety of analytes with high selectivity, even in real samples such as food, water, biological fluids, or pharmaceutical compounds. This review presents an up-to-date list of reports in which metalloporphyrins are used as electrochemical sensors. In addition to compiling a comprehensive and up-to-date list of reported sensors that utilize metalloporphyrins, this work aims to provide an overview of currently available tools and techniques for the detection of various chemical species through similar approaches, which are constantly being developed.

Controlling Chirogenic Effects in Porphyrin Based Supramolecular Systems: Theoretical Analysis Versus Experimental Observations

“…Generally, for application in sensors (due to synthetic and supramolecular reasons, for example to make additional interaction points, etc. ), porphyrins with some peripheral substituents (often it is phenyl or naphthyl rings in meso positions) are conventionally used [10,12,24,87–90] . These substituents can prevent free rotation of a guest by creation of steric hindrance or formation of additional non‐covalent bonds.…”

“…), porphyrins with some peripheral substituents (often it is phenyl or naphthyl rings in meso positions) are conventionally used. [10,12,24,[87][88][89][90] These substituents can prevent free rotation of a guest by creation of steric hindrance or formation of additional non-covalent bonds. The latter occurs when substituents have additional functional groups, like OH, NH 2 , COOH, etc., which are able to make noncovalent bonds with a guest to form a supramolecule.…”

Update on Endogenous HNO Production: An Exploration of Unanswered Questions and Challenges

“…In recent work, the reaction between NO * and thiols has been studied with the main objective of evaluating whether HNO is a reaction intermediate. Our analysis focused on the reactions of NO * with 1-hexanethiol (R 6 SH), cysteine (Cys), benzenethiol (PhÀ SH), and benzeneselenol (PhÀ SeH), using Mn(III) 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinate (Mn(III)TCPP) as a scavenger for HNO, [95] an HNOselective electrode, [96][97][98] and ab initio methods. The results revealed that the reaction is first order in both reagents and that the HNO production rate varies in the following order: PhÀ SeH > PhÀ SH @ R 6 À SH > Cys.…”