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Modification of bio macromolecules with six-valent osmium complexes and electrochemical analysis of the modified products
Abstract
This review is focused on the reaction of 1,2-diols with ligand complexes of six-valent osmium [Os(VI)L] (where L is a nitrogenous ligand) and possibilities of electrochemical analysis of yielded products. A number of biologically important molecules, such as mono-, oligo-and polysaccharides, RNA and glycoproteins, belong to compounds containing 1,2-diol in their structure. These compounds react with Os(VI)L yielding relatively stable ligand osmate esters which are electrochemically active and suitable to the electrochemical analysis. The ligand osmate esters give redox peaks at the mercury and carbon electrodes. The redox peaks are due to the electrochemical reduction or oxidation of osmium atoms. The osmate esters with some ligands give catalytic peaks at the mercury electrodes. The catalytic peak is due to the catalytic hydrogen evolution and is very sensitive. With the catalytic peak it is possible to measure picomolar concentrations in some cases. We have used reactions of Os(VI)L for the analysis of glycans and glycoproteins in relation to their great importance in biomedicine. © 2018, Czech Society of Chemical Engineering. All rights reserved.
... Catalytic hydrogen evolution (CHE) has been utilized in studies involving various biomolecules both unmodified (proteins [27], nucleic acids [7] or aminosugars [8]) and chemically modified (e.g., nucleic acids, proteins or carbohydrates labelled with osmium [28][29][30] or platinum [31] complexes, or DNA bearing sulfur-containing unnatural bases [21]). The catalytic character of the hydrogen evolution reactions, involving reduction of high numbers of protons per a single catalytically active moiety, offers particularly high sensitivities of detection of the catalysts. ...
Electrodeposition of silver amalgam particles (AgAPs) on various substrates represents a prospective approach to the development of a novel detection system applicable in the study of various electrochemically active substances, including nucleic acids and proteins. Herein, a double pulse chronoamperometric deposition of AgAPs on in-house fabricated screen-printed silver electrodes (SPAgE) has been optimized using the voltammetric signal of a model electrochemically reducible organic nitro-compound, 4-nitrophenol (4-NP). The surface morphology of SPAgE-AgAP was monitored by scanning electron microscopy with an energy dispersive X-ray spectrometer. A compact three-electrode sensor consisting of the working (substrate) SPAgE, counter graphite, and pseudo-reference Ag|AgCl electrodes was designed for analysis of electrochemically reducible compounds in a 96-well plate with about 150-μl sample volume per well. Herein optimized SPAgE-AgAP allowed detection of 4-NP down to 1 μmol l⁻¹ using cyclic voltammetry. Advantageously, differential pulse voltammetry at SPAgE-AgAP allowed highly sensitive detection of artificial nucleosides dTPT3 and d5SICS (developed to expand genetic alphabet in semi-synthetic organisms) using their catalytic hydrogen evolution signals, with limits of detection of 0.4 pmol l⁻¹. Moreover, these artificial nucleosides were easily detectable in the excess of natural nucleosides down to molar ratio 1:12000. Using constant current chronopotentiometric stripping and the catalytic peak H, we further demonstrated detection of a protein, bovine serum albumin, at the SPAgE-AgAP. Thus, we present the SPAgE-AgAP as a potent tool applicable in simple, fast, and sensitive electrochemical detection of reducible or catalytically active species, with prospective applications in hot research areas including chemical and synthetic biology.
... Catalytic hydrogen evolution (CHE) has been utilized in studies involving various biomolecules both unmodified (proteins [27], nucleic acids [7] or aminosugars [8]) and chemically modified (e.g., nucleic acids, proteins or carbohydrates labelled with osmium [28][29][30] or platinum [31] complexes, or DNA bearing sulfur-containing unnatural bases [21]). The catalytic character of the hydrogen evolution reactions, involving reduction of high numbers of protons per a single catalytically active moiety, offers particularly high sensitivities of detection of the catalysts. ...
Electrodeposition of silver amalgam particles (AgAPs) on various substrates offers perspective tool in development of novel electrochemical detection system applicable even in direct bioelectrochemistry of nucleic acids or proteins. Herein, a double pulse chronoamperometric deposition of AgAPs on in-house fabricated screen-printed silver electrodes (SPAgE) has been optimized using voltammetric signal of model electrochemically reducible organic nitro-compound, 4-nitrophenol, and scanning electron microscopy with energy dispersive X-ray spectrometer. This compact sensor including graphite counter and Ag|AgCl pseudo-reference electrode was design for highly effective analysis of electrochemically reducible compounds in 96-well plate with about 150-µl sample volume per well. The SPAgE-AgAP offers detection of 4-NP down to 5 µmol.l<sup>−1</sup> using cyclic voltammetry in acetate buffer pH 5.0. Advantageously, differential pulse voltammetry at SPAgE-AgAP allows highly sensitive detection system of unnatural nucleosides dTPT3 and d5SICS, which successfully expanded genetic alphabet of recently studied semi-synthetic organism, with limits of detection 0.1 pg.µl<sup>−1</sup> in 0.05 mol.l<sup>−1</sup> hydrochloric acid. Moreover, these artificial nucleosides are detectable in the mixture with natural nucleosides up to weight ratio 1 : 15 000. SPAgE-AgAP may be potentially utilized in simple, fast and sensitive electrochemical detection of organic nitro compounds and free or in DNA harbored dTPT3 and/or d5SICS, what may contribute in successful research and development of semi-synthetic organism perspective in chemical and synthetic biology.
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