Strategies to Achieve a Ferrocene-Based Polymer with Reversible Redox Activity for Chiral Electroanalysis of Nonelectroactive Amino Acids

2021 ◽  
Author(s):  
Datong Wu ◽  
Cong Ma ◽  
Fei Pan ◽  
Yongxin Tao ◽  
Yong Kong
Keyword(s):  
Amino Acids ◽  
Redox Activity ◽  
Reversible Redox

scholarly journals Electron Inventory of the Iron-Sulfur Scaffold Complex HypCD Essential in [NiFe]-Hydrogenase Cofactor Assembly

2021 ◽  
Author(s):  
Sven T. Stripp ◽  
Jonathan Oltmanns ◽  
Christina S. Müller ◽  
David Ehrenberg ◽  
Ramona Schlesinger ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Redox Activity ◽  
Construction Site ◽  
Iron Ion ◽  
Paramagnetic Resonance ◽  
Iron Sulfur ◽  
Reducing Conditions ◽  
Reversible Redox ◽  
Electron Paramagnetic ◽  
Redox Conversion

The [4Fe-4S] cluster containing scaffold complex HypCD is the central construction site for the assembly of the [Fe](CN)2CO cofactor precursor of [NiFe]-hydrogenase. While the importance of the HypCD complex is well established, not much is known about the mechanism by which the CN– and CO ligands are transferred and attached to the iron ion. We developed an efficient protocol for the production and isolation of the functional HypCD complex that facilitated detailed spectroscopic investigations. The results obtained by UV/Vis-, electron paramagnetic Resonance (EPR)-, Resonance Raman-, Fourier-transform infrared (FTIR), and Mössbauer spectroscopy provide comprehensive evidence for an electron inventory fit to drive multi-electron redox reactions. We demonstrate the redox activity of the HypCD complex reporting the interconversion of the [4Fe-4S]2+/+ couple. Additionally, we observed a reversible redox conversion between the [4Fe-4S]2+ and a [3Fe-4S]+ cluster. MicroScale thermophoresis indicated preferable binding between the HypCD complex and its interaction partner HypEF under reducing conditions. Together, these results suggest a redox cascade involving the [4Fe-4S] cluster and a conserved disulfide bond of HypD that may facilitate the synthesis of the [Fe](CN)2CO cofactor precursor on the HypCD scaffold complex.

A TTFV–pyrene-based copolymer: synthesis, redox properties, and aggregation behaviour

RSC Advances ◽  
2015 ◽  
Vol 5 (30) ◽  
pp. 23952-23956 ◽  
Author(s):  
Eyad A. Younes ◽  
Kerry-Lynn M. Williams ◽  
Joshua C. Walsh ◽  
Celine M. Schneider ◽  
Graham J. Bodwell ◽  
...  
Keyword(s):  
Ph Value ◽  
Redox Properties ◽  
The Self ◽  
Redox Activity ◽  
Repeat Units ◽  
Aggregation Behaviour ◽  
Reversible Redox ◽  
Conjugated Copolymer ◽  
External Stimuli ◽  
Self Aggregation

A new π-conjugated copolymer containing tetrathiafulvalene vinylogue and pyrene repeat units was synthesized and exhibited reversible redox activity, while the self-aggregation behaviour in the solution phase was responsive to external stimuli such as solvent and pH value.

scholarly journals Redox Activity of Ce(IV)-Substituted Polyoxometalates toward Amino Acids and Peptides

2020 ◽  
Vol 59 (15) ◽  
pp. 10569-10577
Author(s):  
Shorok A. M. Abdelhameed ◽  
Laurens Vandebroek ◽  
Francisco de Azambuja ◽  
Tatjana N. Parac-Vogt
Keyword(s):  
Amino Acids ◽  
Redox Activity

scholarly journals Ferrocene Introduced into 5-Methylresorcinol-Based Organic Aerogels

Polymers ◽  
2020 ◽  
Vol 12 (7) ◽  
pp. 1582 ◽  
Author(s):  
Ludmila V. Erkhova ◽  
Igor A. Presniakov ◽  
Michail I. Afanasov ◽  
Dmitry A. Lemenovskiy ◽  
Haojie Yu ◽  
...  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Exchange Process ◽  
Sol Gel ◽  
Supercritical Drying ◽  
Redox Activity ◽  
High Porosity ◽  
Reversible Redox ◽  
Amorphous Substrates ◽  
Structural Blocks ◽  
Organic Aerogels

The polycondensation sol–gel reaction of 5-methylresocinol and formaldehyde with additional compounds in reaction media is a relatively simple way to produce modified aerogels. In order to obtain aerogels with a large surface area and high porosity, the conditions for gel formation, the solvent exchange process before drying, and the supercritical drying process were optimized. A successful attempt was made to introduce ferrocene units into 5-methylresocinol-formaldehyde-based aerogels. The resulting aerogels are amorphous substrates, and no aggregated ferrocene units were found in their structures. All of the aerogel samples that were obtained are structurally similar despite differences in the original ferrocene units and their initial concentration. It was found that the inclusion limit of ferrocene structural blocks into an aerogel is ~6% wt. The structures of the inclusions in which all of the Fe atoms in the aerogel substrates were present in ferrocene/ferrocenium at an approximate ratio of 60/40 to 55/45 were confirmed by X-ray photoelectron spectroscopy and Mössbauer spectroscopy. Aerogels with ferrocene/ferrocenium inclusions are likely to exhibit reversible redox activity in reactions with gaseous reagents.

Reversible Redox Activity in Multicomponent Metal–Organic Frameworks Constructed from Trinuclear Copper Pyrazolate Building Blocks

2017 ◽  
Vol 139 (23) ◽  
pp. 7998-8007 ◽  
Author(s):  
Binbin Tu ◽  
Qingqing Pang ◽  
Huoshu Xu ◽  
Xiaomin Li ◽  
Yulin Wang ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Redox Activity ◽  
Reversible Redox ◽  
Metal Organic

Solvent-triggered stereoselectivity of α,α-cyclopropanation of amino acids in the Ni(ii) chiral coordination environment

2020 ◽  
Vol 49 (25) ◽  
pp. 8636-8644 ◽  
Author(s):  
Oleg A. Levitskiy ◽  
Olga I. Aglamazova ◽  
Yuri K. Grishin ◽  
Ksenia A. Paseshnichenko ◽  
Vadim A. Soloshonok ◽  
...  
Keyword(s):  
Amino Acids ◽  
Redox Activity ◽  
Coordination Environment ◽  
Diastereomeric Complexes

Unexpected solvent-controlled increase in stereoselectivity of glycine cyclopropanation within chiral Ni(ii) coordination environment was observed and rationalized. Cyclopropanated diastereomeric complexes exhibit stereodependent redox-activity.

Osmium Bipyridine-Containing Redox Polymers Based on Cellulose and Their Reversible Redox Activity

2011 ◽  
Vol 116 (1) ◽  
pp. 55-62 ◽  
Author(s):  
Hongliang Kang ◽  
Ruigang Liu ◽  
Huafeng Sun ◽  
Jieming Zhen ◽  
Qinmei Li ◽  
...  
Keyword(s):  
Redox Activity ◽  
Redox Polymers ◽  
Reversible Redox

Redox activity of some non-innocent amino acids

2013 ◽  
Vol 144 (7) ◽  
pp. 937-949 ◽  
Author(s):  
Kristína Matelková ◽  
Katrin Ossberger ◽  
Juraj Hudák ◽  
Jaroslav Vatrál ◽  
Roman Boča ◽  
...  
Keyword(s):  
Amino Acids ◽  
Redox Activity

scholarly journals Electron Inventory of the Iron-Sulfur Scaffold Complex HypCD Essential in [NiFe]-Hydrogenase Cofactor Assembly

2021 ◽  
Author(s):  
Sven T. Stripp ◽  
Jonathan Oltmanns ◽  
Christina S. Müller ◽  
David Ehrenberg ◽  
Ramona Schlesinger ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Redox Activity ◽  
Construction Site ◽  
Iron Ion ◽  
Paramagnetic Resonance ◽  
Iron Sulfur ◽  
Reducing Conditions ◽  
Reversible Redox ◽  
Electron Paramagnetic ◽  
Redox Conversion

The [4Fe-4S] cluster containing scaffold complex HypCD is the central construction site for the assembly of the [Fe](CN)2CO cofactor precursor of [NiFe]-hydrogenase. While the importance of the HypCD complex is well established, not much is known about the mechanism by which the CN– and CO ligands are transferred and attached to the iron ion. We developed an efficient protocol for the production and isolation of the functional HypCD complex that facilitated detailed spectroscopic investigations. The results obtained by UV/Vis-, electron paramagnetic Resonance (EPR)-, Resonance Raman-, Fourier-transform infrared (FTIR), and Mössbauer spectroscopy provide comprehensive evidence for an electron inventory fit to drive multi-electron redox reactions. We demonstrate the redox activity of the HypCD complex reporting the interconversion of the [4Fe-4S]2+/+ couple. Additionally, we observed a reversible redox conversion between the [4Fe-4S]2+ and a [3Fe-4S]+ cluster. MicroScale thermophoresis indicated preferable binding between the HypCD complex and its interaction partner HypEF under reducing conditions. Together, these results suggest a redox cascade involving the [4Fe-4S] cluster and a conserved disulfide bond of HypD that may facilitate the synthesis of the [Fe](CN)2CO cofactor precursor on the HypCD scaffold complex.

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