Article
Chemistry, Physical
Sai Wang, Pei Xu, Xu Zhu
Summary: CO2 radical anion is a highly reductive species that can add a carbonyl group to unsaturated C-C bonds and synthesize acids. It is usually generated through the direct reduction of CO2 gas or from formate salts via hydrogen atom transfer. This concept highlights recent developments in the carboxylation of alkenes using CO2 and/or formate as carbonyl sources, with the CO2 radical anion species playing a significant role in the carboxylation step.
Article
Chemistry, Multidisciplinary
Craig S. S. Day, Stephanie J. J. Ton, Clemens Kaussler, Daniel Vronning Hoffmann, Troels Skrydstrup
Summary: Here, a methodology for accessing isotopically labeled esters and amides from carbonates and carbamates utilizing an oxygen deletion strategy is reported. The methodology employs a decarboxylative carbonylation approach using C-12 or C-13 carbon monoxide generated ex situ in near stoichiometric amounts for isotope labeling. The reaction demonstrates a broad scope, functional group tolerance, and high yields, exemplified by the synthesis of structurally complex molecules. Additionally, a complementary method for the catalytic in situ generation of CO from CO2 liberated during decarboxylation is developed as a proof-of-concept approach for converting CO2-derived compounds to CO-containing frameworks. Mechanistic studies provide insights into the catalytic steps and the impact of ligand choice for overcoming challenges in low-pressure carbonylation methodologies, aiding the development of future methodologies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Mathematics, Applied
Henrik Garde, Nuutti Hyvonen
Summary: This work presents numerical methods for solving Calderon's problem using series reversions. By reversing the series of the forward map, a family of methods for solving the inverse problem is obtained, and the convergence of these methods is proven. The introduced numerical methods have the same computational complexity as solving the linearized inverse problem.
MATHEMATICS OF COMPUTATION
(2022)
Article
Chemistry, Physical
Victor Babin, Alex Talbot, Alexandre Labiche, Gianluca Destro, Antonio Del Vecchio, Charles S. Elmore, Frederic Taran, Antoine Sallustrau, Davide Audisio
Summary: A photocatalytic approach for carbon isotope exchange using [C-13]CO2 and [C-14]CO2 without the need for structural modifications. The mild conditions required for this traceless transformation contrast with previous harsh thermal methods.
Article
Mathematics, Applied
Henrik Garde, Nuutti Hyvonen
Summary: This study presents explicit series reversions for the solution of Calderon's problem and derives a family of numerical methods to improve the accuracy of the solution by reversing the Taylor series of the forward map. The convergence of these numerical methods is shown under conditions that ensure the invertibility of the Frechet derivative of the forward map. The introduced numerical methods have the same computational complexity as solving the linearized inverse problem.
MATHEMATICS OF COMPUTATION
(2022)
Review
Chemistry, Multidisciplinary
Yuto Sumida, Hirohisa Ohmiya
Summary: Visible-light-mediated chemical processes have been extensively studied, leading to cutting-edge synthetic chemistry by controlling radical generation and excited-state transformations. While photoredox chemistry is important, it often involves photocatalysts and redox processes, complicating reactions. A breakthrough in this field is the development of a system free of photocatalysts, providing more straightforward and energetically efficient methods.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Odey Bsharat, Michael G. J. Doyle, Maxime Munch, Braeden A. Mair, Christopher J. C. Cooze, Volker Derdau, Armin Bauer, Duanyang Kong, Benjamin H. Rotstein, Rylan J. Lundgren
Summary: The isotopic labelling of small molecules is crucial for drug development and biochemical processes. However, the labelling of carbon-labelled alpha-amino acids is difficult and time-consuming, resulting in high cost and scarcity of C-labelled products. This study demonstrates that aldehydes can catalyse the isotopic carboxylate exchange of alpha-amino acids with *CO2, providing a new method for late-stage C-11 radiolabelling.
Article
Chemistry, Organic
Euan B. McLean, David T. Mooney, David J. Burns, Ai-Lan Lee
Summary: A mild and inexpensive method for direct hydrodecarboxylation of aliphatic carboxylic acids has been developed, which does not require metals, light, or catalysts, making the protocol operationally simple and more sustainable.
Article
Chemistry, Multidisciplinary
Yong Zhao, Nikolaj L. Hansen, Yao-Tao Duan, Meera Prasad, Mohammed S. Motawia, Birger L. Moller, Irini Pateraki, Dan Staerk, Soren Bak, Karel Miettinen, Sotirios C. Kampranis
Summary: Researchers have identified a compound called celastrol in the roots of Tripterygium wilfordii, which has potential as an effective treatment for obesity. They have also developed a synthetic method for celastrol, allowing it to be produced from table sugar. This study demonstrates the successful combination of plant biochemistry, metabolic engineering, and chemistry for the scalable synthesis of complex specialized metabolites.
Article
Multidisciplinary Sciences
Annica Saaret, Benoit Villiers, Francois Stricher, Macha Anissimova, Melodie Cadillon, Reynard Spiess, Sam Hay, David Leys
Summary: The authors report an alternative pathway for isobutene bioproduction by modifying the mevalonate pathway to convert glucose to isobutene, with the final step catalyzed by an evolved ferulic acid decarboxylase enzyme. Directed evolution of the enzyme resulted in variants with significantly increased activity, with changes in the substrate binding pocket responsible for the improved selectivity. Isobutene cycloelimination is found to be rate limiting and strictly dependent on the presence of the 3-methyl group, as suggested by solution and computational studies.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Yuqing Fu, Xian Suo, Zhenzhen Yang, Sheng Dai, De-en Jiang
Summary: This study investigates the interaction between CO2 and malononitrile carbanion using computational and simulation methods. The results show that CO2 prefers physical interaction with the nitrile group and that the two -CN groups can attract two CO2 molecules with equal strength. The presence of an alkali metal ion enhances the interaction between CO2 and the carbanion. Therefore, ionic liquids based on malononitrile carbanion may have potential applications in carbon capture.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Organic
Trung Hieu Do, Supasorn Phaenok, Darunee Soorukram, Tina Modjinou, Daniel Grande, Thi Thanh Tam Nguyen, Thanh Binh Nguyen
Summary: Malonic acid and its derivatives, known for undergoing monodecarboxylation under mild conditions as a C-2 synthon, have been found to have a new application as a C-1 synthon through double decarboxylation promoted by sulfur and dimethyl sulfoxide. In the presence of amines as nucleophiles, a wide range of thioureas, thioamides, and N-heterocycles are produced in good to excellent yields under mild heating conditions.
Article
Engineering, Biomedical
Thomas Laumon, Elie Courvalin, Geoffrey Dagod, Pauline Deras, Mehdi Girard, Orianne Martinez, Camille Maury, Hugues Weber, Xavier Capdevila, Jonathan Charbit
Summary: The study aims to evaluate the interdependence between extracorporeal blood flow and gas flow in predicting CO2 removal and reduction of mechanical ventilation time under extracorporeal respiratory support. The linear regression models reveal that the product of extracorporeal blood flow and gas flow is linearly associated with CO2 removal and reduction of mechanical ventilation time.
Review
Oncology
Avantika Tripathi, Anjali Kashyap, Greesham Tripathi, Joni Yadav, Rakhi Bibban, Nikita Aggarwal, Kulbhushan Thakur, Arun Chhokar, Mohit Jadli, Ashok Kumar Sah, Yeshvandra Verma, Hatem Zayed, Amjad Husain, Alok Chandra Bharti, Manoj Kumar Kashyap
Summary: The reversion of tumor cells to normal cells is on the brink of becoming a reality, thanks to advancements in molecular techniques, but customized precision techniques are still needed for further insights.
BIOMARKER RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Haifa Shamseldin Mohamed Salim, Ibrahim Mohamed Ahmed, Mustafa Abbas Mustafa
Summary: Sudanese Fula crude oil from the western region is highly viscous and acidic, with high amounts of heteroatoms and low sulfur content. The molecular composition and treatment of the acid fraction are influenced by temperature and catalyst. Thermal treatment at 200 degrees C reduces acidity, while catalytic treatment with transition metal catalyst results in a significant reduction in acidic oils.
Article
Biochemistry & Molecular Biology
Yasaman Heidari, Graeme W. Howe, Ronald Kluger
BIOORGANIC CHEMISTRY
(2016)
Article
Chemistry, Multidisciplinary
Graeme W. Howe, Adelle A. Vandersteen, Ronald Kluger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Multidisciplinary
Adelle A. Vandersteen, Graeme W. Howe, Barbara Sherwood Lollar, Ronald Kluger
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Biochemistry & Molecular Biology
Michael Bielecki, Graeme W. Howe, Ronald Kluger
Article
Chemistry, Organic
Yuyang Li, Ronald Kluger
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Hematology
Aizhou Wang, Serena Singh, Binglan Yu, Donald B. Bloch, Warren M. Zapol, Ronald Kluger
Article
Biochemistry & Molecular Biology
Michael Bielecki, Graeme W. Howe, Ronald Kluger
Review
Chemistry, Organic
Yuyang Li, Ronald Kluger
SYNTHESIS-STUTTGART
(2019)
Article
Chemistry, Multidisciplinary
Shaoyuan Zhou, Bach T. Nguyen, John P. Richard, Ronald Kluger, Jiali Gao
Summary: This study reveals that the decarboxylation reactions of organic carboxylate compounds in aqueous and dimethylformamide solutions are influenced by solvent effects. A linear relationship was found between decarboxylation rates and Gibbs energies, suggesting diminishing recombination barriers in dimethylformamide. Protonation of carbanions by the solvent has large free energy barriers, allowing the competing exchange of isotope-labeled CO2 to be reversible in dimethylformamide. The intricate interplay of carbanion stability and solute-solvent interaction in decarboxylation and carboxylation could be beneficial in designing novel materials for CO2 capture.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Correction
Chemistry, Multidisciplinary
Shaoyuan Zhou, Bach T. Nguyen, John P. Richard, Ronald Kluger, Jiali Gao
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Nathan Wu, Ronald Kluger
Summary: The rates of fluoride elimination and iodination of the Breslow intermediate derived from 2-(1-hydroxy-2,2,2-trifluoroethyl)-thiamin provide important information about the reactivity of this class of intermediates. The results give insights into the rates of reactions and the acid-base properties of the intermediate. Comparison with enzyme-catalyzed reactions further highlights the differences in reaction pathways.
BIOORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Soeren Rindfleisch, Matthias Krull, Jon Uranga, Tobias Schmidt, Fabian Rabe von Pappenheim, Laura Liliana Kirck, Angeliki Balouri, Thomas Schneider, Ashwin Chari, Ronald Kluger, Gleb Bourenkov, Ulf Diederichsen, Ricardo A. Mata, Kai Tittmann
Summary: This study presents crystallographic snapshots of human OMPDC in complex with substrate, analogues, transition-state analogues, and products, revealing that substrate carboxylate is protonated and forms a favorable low-barrier hydrogen bond with a negatively charged residue. The catalytic prowess of OMPDC primarily results from the transition-state stabilization by electrostatic interactions of the enzyme with charges spread over the substrate. These findings have relevance for the design of (de)carboxylase catalysts.
Article
Chemistry, Organic
Yuju Kim, Ronald Kluger
Summary: Chemical cross-linking of human adult hemoglobin prevents dissociation and enables it to be an acellular oxygen carrier, but may lead to hypertension. By specific chemical reactions, bis-tetramers can be formed to block the interaction with nitric oxide.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Yuyang Li, Ronald Kluger
Article
Chemistry, Multidisciplinary
Michael Bielecki, Ronald Kluger
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2017)