Article
Biochemistry & Molecular Biology
Chenjiao Huang, Wenwen Bao, Senhe Huang, Bin Wang, Chenchen Wang, Sheng Han, Chenbao Lu, Feng Qiu
Summary: In this study, two novel dimethoxy substituted asymmetric and cross-symmetric Co(II) porphyrin (PorCo) were prepared as model electrocatalysts for CO2 reduction. The intramolecular charge transfer of these push-pull type molecules facilitated electron mobility, resulting in higher CO2-to-CO Faradaic efficiency (FECO) and turnover frequency (TOF). Density functional theory (DFT) calculations confirmed the effectiveness of the methoxy group in enhancing CO2 reduction performance. This work provides a new pathway for the design of molecular catalysts to boost electrocatalytic CO2 reduction.
Article
Chemistry, Multidisciplinary
Xiao bin Gao, Yucheng Wang, Weicheng Xu, Huan Huang, Kuangmin Zhao, Hong Ye, Zhi-You Zhou, Nanfeng Zheng, Shi-Gang Sun
Summary: Metallic particles can inhibit the demetalation of Fe SACSs by acting as electron donors and strengthening the Fe-N bond, thereby preventing electrochemical Fe dissolution. Different types, forms, and contents of metal particles have varying effects on the Fe-N bond strength. Screening a particle-assisted Fe SACS resulted in a 78% reduction in Fe dissolution and enabled continuous operation for up to 430 hours in a fuel cell.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Benjamin D. Groff, James M. Mayer
Summary: This study demonstrates the generality of molecular scaling relationships in achieving faster catalysis at lower overpotentials. By independently controlling the characteristics of the catalyst and the buffer solution, both the maximum turnover frequency and the effective overpotential have been improved. The most optimal system is achieved with the most reducing catalyst and a weak buffered acid, which may seem counterintuitive.
Article
Chemistry, Physical
Isabel Barraza Alvarez, Yanyu Wu, Joel Sanchez, Yulu Ge, Mario V. Ramos-Garces, Tong Chu, Thomas F. Jaramillo, Jorge L. Colon, Dino Villagran
Summary: Intercalating CoTcPP into ZrP layers enhances the efficiency and catalytic stability of water oxidation reactions, with the electrochemical behavior being superior to pristine α-ZrP material.
SUSTAINABLE ENERGY & FUELS
(2021)
Article
Chemistry, Physical
Qi Hua, Kenneth E. Madsen, Anne Marie Esposito, Xinyi Chen, Toby J. Woods, Richard T. Haasch, Shuting Xiang, Anatoly Frenkel, Timothy T. Fister, Andrew A. Gewirth
Summary: The oxygen reduction reaction (ORR) activity of an Fe porphyrin on different supports in acid conditions was studied. It was found that the activity varies depending on the support, with XC72 showing the highest activity and pH dependence compared to MoS2 and g-C3N4. The support-electrolyte interaction was found to control the ORR activity.
Article
Electrochemistry
Ekrem Kaplan, Selin Gumrukcu, Metin Gencten, Yucel Sahin, Esin Hamuryudan
Summary: In this study, catalysts were prepared and attached to pencil graphite electrodes via electrochemical polymerization method, serving as electrocatalysts for the first time in the literature for electrochemical CO2 reduction. The results demonstrated that one of the catalysts significantly decreased the overpotential of CO2RR compared to the bare graphite electrode.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2021)
Article
Chemistry, Analytical
Varsha Singh, Pradeep S. Thakur, Vellaichamy Ganesan, Muniappan Sankar
Summary: A Zn(II) porphyrin polymer (ZnP-polymer) was successfully synthesized and characterized. The ZnP-polymer showed monomeric zinc porphyrin moieties and exhibited high selectivity and stability as an oxygen reduction reaction (ORR) catalyst for the production of H2O2. It has the potential to be used as a green and efficient catalyst for industrial-scale synthesis of H2O2.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Analytical
Hideto Moriyama, Genki Ogata, Haruma Nashimoto, Seishiro Sawamura, Yoshiaki Furukawa, Hiroshi Hibino, Hiroyuki Kusuhara, Yasuaki Einaga
Summary: Monitoring drug concentration in blood is crucial for safe and effective drug treatment. This study introduces a rapid electrochemical method using boron-doped diamond electrodes to determine the unbound drug concentration in human serum. The results show that this method can provide fast and reliable measurement within the clinical concentration range.
Article
Chemistry, Applied
Taejun Eom, Anzar Khan
Summary: This work discusses the synthesis and properties of monoazobenzene compounds with multiple electron-donating and electron-withdrawing substituents, showing that the position of these groups greatly influences the absorption spectrum. Changes in the arrangement of specific groups can lead to significant shifts in absorption maximum. Additionally, a reversible blue-shift phenomenon was observed under acidic conditions.
Article
Chemistry, Physical
Catalina Sandoval-Altamirano, Eduardo Berrios, Javier Morales, Christian Silva, German Gunther
Summary: Phenalenone and its derivatives have high singlet oxygen generation capacity through photosensitization. Efforts have been made to obtain phenalenones with red-shifted absorption while maintaining the ability to generate singlet oxygen. The presence of a dimethylamino substituent at positions 3 or 6 allows for modulation of singlet oxygen generation capacity and fluorescence. Both compounds show red-shifted absorption compared to phenalenone, with different solvent effects on their absorption and emission properties.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Analytical
Sergey M. Kuzmin, Svetlana A. Chulovskaya, Olga A. Dmitrieva, Nugzar Z. Mamardashvili, Oskar I. Koifman, Vladimir I. Parfenyuk
Summary: Polymer films based on 2H-5,10,15,20-tetrakis(3-aminophenyl)porphyrin have been successfully prepared and their catalytic activity in the oxygen electroreduction reaction has been demonstrated. The films exhibit a potential pathway for O-2 reduction and have the potential to be promising catalysts.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kento Kosugi, Hina Kashima, Mio Kondo, Shigeyuki Masaoka
Summary: A highly active copper-based catalyst for electrochemical CO2 reduction is reported. It achieves a maximum turnover frequency more than 1,000,000 times higher than other reported copper-based molecular catalysts at an overpotential of 0.85 V.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Amal Baqais, Hassan Ait Ahsaine
Summary: In this study, perfluorinated iron porphyrin catalyst was used for CO2 electroreduction reaction to selectively produce carbon monoxide in different bicarbonate electrolytes.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wenlin Zhang, Eva J. Meeus, Lei Wang, Lu-Hua Zhang, Shuangcheng Yang, Bas de Bruin, Joost N. H. Reek, Fengshou Yu
Summary: This study presents a strategy for synthesizing efficient oxygen reduction reaction (ORR) catalysts by precise regulation of the electronic states of catalytic sites through molecular engineering. The catalysts, based on mononuclear iron phthalocyanine supported on multi-walled carbon nanotubes with electron-donating functional groups, showed enhanced ORR performance compared to non-functionalized catalysts. Density functional theory calculations revealed that the coordination of electron-donating groups facilitated oxygen adsorption and activation.
Article
Electrochemistry
Laura Scarpetta-Pizo, Ricardo Venegas, Karina Munoz-Becerra, Lisa Munoz, Alejandro Toro-Labbe, Nadim Darwish, Ricardo Matute, Ruben Onate, Jose H. Zagal, Ingrid Ponce
Summary: Using reactivity predictors to enhance or control electrocatalytic activity is an interesting concept, especially for developing platinum metal group-free materials. In this study, FeN4 molecular catalysts were designed and synthesized to increase their catalytic performance for the ORR through the pull effect. Experimental findings revealed unexpected results, leading to a reconsideration of the interface effects on catalyst activity.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Md Estak Ahmed, Abhijit Nayek, Alenka Krizan, Nathan Coutard, Adina Morozan, Somdatta Ghosh Dey, Reiner Lomoth, Leif Hammarstrom, Vincent Artero, Abhishek Dey
Summary: With the price-competitiveness of solar and wind power, hydrogen technologies may change the game for a cleaner, defossilized, and sustainable energy future. Electrochemical production of hydrogen can be stored for long periods and converted back into power through fuel cells. The discovery of cheap and efficient catalysts, inspired by bioinspiration and iron-based catalysts, is crucial for the feasibility of this process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Abhijit Nayek, Md Estak Ahmed, Soumya Samanta, Souvik Dinda, Suman Patra, Somdatta Ghosh Dey, Abhishek Dey
Summary: One of the major goals of bioinorganic chemistry is to mimic the function of metalloenzymes. By utilizing heterogeneous electrochemistry and molecule design, it is possible to control both electron and proton transfer reactions. This control enables functional modeling of various important reactions and provides insights into unnatural bioinspired reactions and reorganization energy estimation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Aishik Bhattacharya, Arnab Kumar Nath, Arnab Ghatak, Abhijit Nayek, Souvik Dinda, Rajat Saha, Somdatta Ghosh Dey, Abhishek Dey
Summary: The reduction of SO2 by iron(II) tetraphenylporphyrin has been demonstrated, generating an intermediate [Fe-III-SO](+) species which releases SO. The SO obtained from the chemical reduction of SO2 can be evidenced in the form of a cheletropic adduct of butadiene resulting in an organic sulfoxide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Samir Chattopadhyay, Soumya Samanta, Ankita Sarkar, Aishik Bhattacharya, Suman Patra, Abhishek Dey
Summary: In-operando spectroscopic observation using SERRS-RDE is crucial for studying the mechanism of electrocatalytic reactions. However, current technology is limited to oxygen reduction reactions due to stability issues. This study presents a second-generation SERRS-RDE setup using Ag nanostructure-modified graphite electrode, which overcomes the stability issues and allows observation of intermediates in other reactions.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Abhishek Dey
Summary: Reducing CO2 selectively to a specific C1 product is challenging due to similar thermodynamic reduction potentials for different CO2 reductions. Inspired by nickel CO dehydrogenase (Ni-CODH), the use of bimetallic iron porphyrins bridged by a urea moiety enables fast and selective reduction of CO2 to CO. The mechanism appears to mimic Ni-CODH, where one metal binds and reduces CO2 while the other stabilizes the reduced species and facilitates C-O bond cleavage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sarmistha Bhunia, Arnab Ghatak, Atanu Rana, Abhishek Dey
Summary: Iron porphyrins with one or four tertiary amine groups in their second sphere show higher rates and selectivity in the electrochemical O2 reduction reaction (ORR) compared to iron tetraphenylporphyrin lacking these amines. The presence of these amine groups leads to protonation and lower overpotentials, enhancing the ORR rate. Heterogeneous aqueous conditions reveal changes in the rate-determining step (rds) of the ORR depending on the number of amine groups, with cleavage of the O-O bond being the rds in the presence of one amine group, while proton-coupled reduction becomes the rds with four amine groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Ecology
Rohan Sarkar, Anirban Bhowmick, Debsruti Dasgupta, Rounak Banerjee, Poushali Chakraborty, Abhijit Nayek, R. Sreelekshmi, Aritra Roy, Rituparna Sonowal, Amartya Baran Mondal, Anindita Bhadra
Summary: Dogs prioritize nutritionally valuable food while foraging alone, but also scavenge less valuable food. In the presence of intra-group competition, dogs transition from random to systematic foraging and eat first before sampling in groups. They adjust their behavior based on the patch quality and show reduced individual vigilance. These decisions support the optimal foraging theory and highlight the cognitive abilities and adaptability of dogs, which may have influenced domestication.
FRONTIERS IN ECOLOGY AND EVOLUTION
(2023)
Article
Chemistry, Inorganic & Nuclear
Aleksandra Wandzilak, Katarzyna Grubel, Kazimer L. Skubi, Sean F. Mcwilliams, Dimitrios Bessas, Atanu Rana, Stefan Hugenbruch, Abhishek Dey, Patrick L. Holland, Serena Debeer
Summary: This study successfully elucidated the characteristics and mechanism of the intermediate species during the cleavage of the strong triple bond of N2 by Diketiminate-supported iron complexes, using a range of spectroscopic techniques and computational models.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Piyali Sarkar, Sayan Sarkar, Abhijit Nayek, Nayarassery N. Adarsh, Arun K. Pal, Ayan Datta, Abhishek Dey, Pradyut Ghosh
Summary: This paper explores the advantage of a pre-organized pi-cavity of a Fe(II) complex in CO2 reduction by overcoming the high overpotential associated with the inert nature of the complex. The study demonstrates that a macrobicycle with a pi-cavity can enable CO2 reduction at a lower potential, providing a new series of molecular catalysts for the CO2 reduction reaction.
Article
Chemistry, Physical
Paramita Saha, Sudip Barman, Sk Amanullah, Abhishek Dey
Summary: Nitric oxide (NO) is a key intermediate in the nitrogen cycle, but there are limited molecular catalysts for its transformation. Heme nitrosyls, particularly the ferrous nitrosyl species, play important roles in the reduction of NO2 (-) to NH4 (+). This study investigates the effect of substituents on iron porphyrins on the reduction of NO, and demonstrates that the presence of -COOEt groups can shift the potential for electrochemical NO reduction, making it more physiologically relevant.
Article
Chemistry, Multidisciplinary
Ankita Sarkar, Snehadri Bhakta, Samir Chattopadhyay, Abhishek Dey
Summary: Heme nitrite reductases play a key role in the global nitrogen cycle by reducing NO2- to NO or NH4+. The presence of arginine residues in the second sphere of these enzymes is proposed to assist in substrate binding and provide protons for the reaction. This study investigates the role of guanidine arm attached to a synthetic ferrous porphyrin in reducing NO2-, and suggests that rapid re-protonation of arginine residues may trigger NO dissociation from the ferric nitrosyl species.
Article
Chemistry, Multidisciplinary
Soumya Samanta, Srijan Sengupta, Saptarshi Biswas, Sucheta Ghosh, Sudip Barman, Abhishek Dey
Summary: Heme dioxygenases play a crucial role in the biosynthesis of important biomolecules. In this study, the catalytic function of a ferrous heme dioxygen adduct was investigated using in situ resonance Raman spectroscopy. The results showed the accumulation of different species during the electrochemical ORR catalysis, mimicking the reaction of heme dioxygenases. This study provides important insights into the mechanism of biological catalysts and can inspire the design of more efficient artificial catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sandipan Jana, Puja De, Chinmay Dey, Somdatta Ghosh Dey, Abhishek Dey, Sayam Sen Gupta
Summary: This study reports a synthetic iron complex that mimics cytochrome P450 in water using H2O2 as the oxidant. It shows high selectivity in oxidizing unactivated C-H bonds in small organic molecules, with predictable stereoretention and moderate to high yields. The reactivity of this iron complex in water is about 300 times higher than in organic solvents.
Review
Chemistry, Multidisciplinary
Sk Amanullah, Paramita Saha, Abhishek Dey
Summary: Nature utilizes a variety of porphyrinoids to catalyze biological processes, and investigating their differences in electronic structure and reactivity is important. This article summarizes the role of synthetic metallo-porphyrinoids in catalyzing small molecule activation reactions and explores the synthetic routes to active-site mimics. The incorporation of second-sphere residues emulating basic amino acid residues also plays a crucial role.
CHEMICAL COMMUNICATIONS
(2022)