A bioinspired naphthoquinone model of the quinones in photosynthetic reaction centers but bearing an intramolecular hydrogen-bonded carboxylic acid has been synthesized and characterized electrochemically, spectroscopically, and computationally to provide mechanistic insight into the role of proton-coupled electron transfer (PCET) of quinone reduction in photosynthesis. The reduction potential of this construct is 370 mV more positive than the unsubstituted naphthoquinone. In addition to the reversible cyclic voltammetry, infrared spectroelectrochemistry confirms that the naphthoquinone/naphthoquinone radical anion couple is fully reversible. Calculated redox potentials agree with the experimental trends arising from the intramolecular hydrogen bond. Molecular electrostatic potentials illustrate the reversible proton transfer driving forces, and analysis of the computed vibrational spectra supports the possibility of a combination of electron transfer and PCET processes. The significance of PCET, reversibility, and redox potential management relevant to the design of artificial photosynthetic assemblies involving PCET processes is discussed.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11445641 | PMC |
| http://dx.doi.org/10.1039/d4sc05277c | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Synergy of Copper Doping and Carbon Defect Engineering in Promoting C-C Coupling for Enhanced CO Photoreduction to Ethanol Activity.
ACS Appl Mater Interfaces
December 2024
Key Laboratory of Industrial Ecology and Environment Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, PR China.
Photocatalytic conversion of carbon dioxide (CO) to fuel provides an ideal pathway to achieving carbon neutrality. One significant hindrance in achieving the reduction of CO to higher energy density multicarbon products (C) was the difficulty in coupling C-C bonds efficiently. Copper (Cu) is considered the most suitable metal catalyst for C-C coupling to form C products in the CO reduction reaction (CORR), but it encounters challenges such as low product selectivity and slow catalytic efficiency.
View Article and Find Full Text PDFClean and sustainable extraction of gelatin: Effects of microwave and freeze-thaw on the crosslinking degree and hydrogen bond of fish skin collagen.
Food Chem
December 2024
College of Food Science, Southwest University, Chongqing 400715, China; Chongqing Key Laboratory of Speciality Food Co-Built by Sichuan and Chongqing, Chongqing 400715, China; Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, Chongqing 400715, China. Electronic address:
The traditional gelatin extraction methods (acid-base) may hinder to their green applications due to mass energy consumption and pollution. Herein, we constructed a clean and sustainable gelatin extraction method, investigated the molecular mechanism of microwave treatment (0-360 min) and freeze-thaw on the gelatin extraction from the perspective of the crosslinking degree and hydrogen bonds. Microwave (0-60 min) can improve the hydrolysis degree (DH) and expose more enzyme cleavage sites of collagen by destroying the intramolecular and intermolecular covalent crosslinking.
View Article and Find Full Text PDFExcited-state antioxidant activity for apigenin based on external electric field-modulated ESIPT behavior: TD-DFT and molecular docking calculations.
J Photochem Photobiol B
December 2024
College of Science, Northeast Forestry University, Harbin 150040, China. Electronic address:
Apigenin (Api), a flavonoid possessing dual features of antioxidant activity and intramolecular hydrogen bond (IMHB), is subjected to an external electric field (EEF) to investigate its excited-state antioxidant activity after excited state intramolecular proton transfer (ESIPT) behavior employing the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods, as well as molecular docking. The existence of IMHB is demonstrated by structural parameters and AIM topological analysis, where Api in the enol form under an EEF of +60 × 10 a.u.
View Article and Find Full Text PDFBenzimidazole analogues active against adult Schistosoma mansoni: SAR analyses, In vivo efficacy in mice, and preliminary mechanistic studies as potential inhibitors of hemozoin formation.
Eur J Med Chem
December 2024
Swiss Tropical and Public Health Institute, Kreuzstrasse 2, 4123, Allschwil, Switzerland; University of Basel, P.O. Box CH-4003, Basel, Switzerland. Electronic address:
For over three decades, praziquantel (PZQ) has been the mainstay chemotherapy for prevention and treatment of schistosomiasis. The excessive use of PZQ, coupled with the lack of advanced drug candidates in the current anti-schistosomiasis drug development pipeline, emphasizes the genuine need for new drugs. In the current work, we investigated the antischistosomal potential of a new series of compounds derived from the privileged benzimidazole scaffold, which exhibited low micromolar IC potency in the range of 1.
View Article and Find Full Text PDFTuning Fluorescence Properties of BIM Probes via Clay Integration: Targeting Rifampicin with improved selectivity.
Chem Asian J
December 2024
Birla Institute of Technology & Science Pilani - Hyderabad Campus, Chemistry department, Shameerpet, 500078, Hyderabad, INDIA.
The incorporation of photoactive organic dyes into layered inorganic materials enhances their optical and chemical properties, making them ideal for sensing applications. In this study, Bisindolyl methane (BIM)-based neutral probes were integrated with bentonite clay to explore their sensing capabilities. Probe 1 (unoxidized BIM) and Probe 2 (oxidized BIM) generally exhibited quenched luminescence in solution due to intramolecular rotations.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!