Article
Engineering, Environmental
Lu Bai, Ying Jiang, Deming Xia, Zongsu Wei, Richard Spinney, Dionysios D. Dionysiou, Daisuke Minakata, Ruiyang Xiao, Hong-Bin Xie, Liyuan Chai
Summary: The study investigated the kinetics and mechanisms of O-2(center dot-)-mediated PFCAs attenuation, with results indicating bimolecular nucleophilic substitution as the most likely thermodynamically feasible mechanism. As O-2(center dot-) approaches PFCA, the C-F bond is spontaneously stretched, leading to bond cleavage. The solvation mechanism was elucidated, showing that although less polar solvents enhance O-2(center dot-) nucleophilicity, they also decrease PFCAs desolvation process.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Jyoti Sharma, Pier Alexandre Champagne
Summary: This study investigated the mechanisms behind the reactions of elemental sulfur and polysulfides with cyanide and phosphines using DFT calculations. The proposed mechanisms include nucleophilic decomposition, unimolecular decomposition, scrambling reactions, and attack on thiosulfoxides. It was found that intramolecular cyclization is the most favorable decomposition pathway for long polysulfides, while short polysulfides can undergo a combination of unimolecular decomposition, nucleophilic attack, and scrambling pathways.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Sandra Rodriguez, Uxue Uria, Efraim Reyes, Liher Prieto, Marta Rodriguez-Rodriguez, Tomas Tejero, Pedro Merino, Jose L. Vicario
Summary: A synthetic approach to (+/-)-Ferrugine has been optimized in 8 steps starting from 5-aminocyclohept-1-ene, with the Bronsted acid-catalyzed pseudotransannular ring-opening of the epoxide as the key step. During attempts at enantioselective synthesis from enantiopure 2-hydroxy-8-azabicyclo[3.2.1]octane, it was found that the compound tends to racemize via an achiral symmetric aziridinium intermediate. This racemization process has been studied in detail using experimental and computational methods.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Alessandro Palmieri, Marino Petrini
Summary: The limited nucleophilic character and bidentate nature of unactivated nitroalkane anions make alkylation and allylation procedures troublesome. This review summarizes the most rewarding approaches, mainly based on metal-catalyzed processes involving purely ionic or mixed ionic-radical intermediates, that have been devised to overcome this limitation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Biochemistry & Molecular Biology
Arturo Gamonal Ruiz-Crespo, Laura Galan-Fernandez, Paloma Martinez-Martin, Juan Carlos Rodriguez-Ubis
Summary: A three-step synthetic route for the preparation of nonsymmetrical bisazolyl 2,4,6-trisubstituted pyridines with different substituents on the pyrazole, indazole, and pyridine heterocycles is described. These synthetic modules can serve as optimal building blocks for tuning the chelating and photophysical properties in complex compounds and metalloorganic structures.
Article
Chemistry, Multidisciplinary
Thomas Hansen, Alba Nin-Hill, Jeroen D. C. Codee, Trevor A. Hamlin, Carme Rovira
Summary: The development of small-molecule covalent inhibitors and probes has a significant impact on the field of chemical biology. This study investigates the reactivity and modulation of widely used electrophilic traps using quantum chemical approaches. The findings provide mechanistic insights and guidance for the design of covalent inhibitors and probes for enzymatic activity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Marian Mikolajczyk, Marek Cypryk, Bartlomiej Gostynski, Jakub Kowalczewski
Summary: The mechanisms of three selected identity substitution reactions at phosphorus and sulfur have been investigated using density functional theory (DFT). The results show that these reactions can occur via stepwise or synchronous mechanisms, and DFT method is useful in distinguishing between these mechanisms.
Article
Chemistry, Multidisciplinary
Ming-Xing Zhang, Lu Lin, Xiaofei Yang, Jun Yin, Jun Zhu, Sheng Hua Liu
Summary: A new class of complexes has been successfully synthesized and the reaction mechanism has been explored through experiments and DFT calculations. The substituents significantly affect the reaction rate, leading to the successful formation of the target complexes in the end.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Sebastian A. Cuesta, F. Javier Torres, Luis Rincon, Jose Luis Paz, Edgar A. Marquez, Jose R. Mora
Summary: In this study, the degradation mechanism of chloroacetanilide herbicides in the presence of four different nucleophiles was theoretically evaluated. The results showed that nucleophiles where a sulfur atom performs the nucleophilic attack are the most effective, and the R groups of the compounds have a negligible effect on the reaction process. Geometrical changes and electronic rearrangements were found to contribute significantly to the activation energy of the process.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Guanyu Zhang, Maodie Wang, Petia Bobadova-Parvanova, Frank R. Fronczek, Kevin M. Smith, M. Graca H. Vicente
Summary: The synthesis and reactivity of 3,8-dibromo-dodecafluoro-benzo-fused BOPHY 2 were reported in this study, with reactions involving various nucleophiles and Pd(0)-catalyzed cross-coupling reactions. The resulting perfluoro-BOPHY derivatives showed different reactivities under different conditions, indicating potential applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Crystallography
Alexander A. Lashkov, Polina A. Eistrich-Geller, Valeriya R. Samygina, Sergey V. Rubinsky
Summary: The mechanisms and substrate specificity of uridine phosphorylases were studied, revealing that the orientation and concentration effects of amino acid residues of the enzyme lower the activation barrier and contribute to the reaction under physiological conditions.
Article
Chemistry, Multidisciplinary
Leijie Zhou, Stefania Perulli, Marco M. Mastandrea, Patricia Llanes, Junshan Lai, Miquel A. Pericas
Summary: A polystyrene-supported version of the Denton catalyst has been developed for catalytic inversion of enantiopure secondary alcohols, showing high yields and enantioselectivity. The functional resin exhibits excellent recyclability and can be easily re-activated for extended use.
Article
Chemistry, Physical
Hayden T. Robinson, Timothy R. Corkish, Christian T. Haakansson, Peter D. Watson, Allan J. McKinley, Duncan A. Wild
Summary: Mass spectrometry and anion photoelectron spectroscopy were used to study the gas-phase SN2 reaction involving Br- and CH3I. The anion photoelectron spectra associated with the reaction intermediates were presented. High-level CCSD(T) calculations were utilized to investigate the reaction intermediates and rationalize the photoelectron spectra.
Article
Chemistry, Organic
Xiao-Ning Wang, Zhan-Cai Li, Yu Zhang, Bing-Xia Yan, Hong-Xing Zheng, Qiang Li, Chang-Qiu Zhao
Summary: A variety of menthyl-containing phosphinothioates were synthesized for the phosphorus-promoted cleavage of the C-S bond with lithium-naphthalene. The cleavage of C-S/P-S could be controlled by varying the amount of naphthalene and temperature. The retention of configuration about the P in P-S cleavage was utilized for stereospecific formation of the C-P bond.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Biochemistry & Molecular Biology
Divya Srivastava, Jouni Ahopelto, Antti J. Karttunen
Summary: The phonon properties and thermodynamics of four crystalline cellulose allomorphs have been investigated using dispersion-corrected density functional theory. The results show that the free energy differences between the cellulose allomorphs are small and the specific heat behavior is similar within the studied temperature range.
Article
Cardiac & Cardiovascular Systems
Hiran A. Prag, Laura Pala, Duvaraka Kula-Alwar, John F. Mulvey, Luping Du, Timothy E. Beach, Lee M. Booty, Andrew R. Hall, Angela Logan, Volha Sauchanka, Stuart T. Caldwell, Ellen L. Robb, Andrew M. James, Zhelong Xu, Kourosh Saeb-Parsy, Richard C. Hartley, Michael P. Murphy, Thomas Krieg
Summary: The study demonstrates that the more rapidly hydrolysable malonate ester prodrug MAM can effectively protect against cardiac I/R injury at reperfusion in a clinically relevant mouse model.
CARDIOVASCULAR DRUGS AND THERAPY
(2022)
Article
Cardiac & Cardiovascular Systems
Livia L. Camargo, Augusto C. Montezano, Misbah Hussain, Yu Wang, Zhiguo Zou, Francisco J. Rios, Karla B. Neves, Rheure Alves-Lopes, Fazli R. Awan, Tomasz J. Guzik, Thomas Jensen, Richard C. Hartley, Rhian M. Touyz
Summary: In this study, the role of NOX-induced oxidative stress in VSMCs in human hypertension was explored, with a focus on NOX5 and its connection to c-Src. The findings suggest that the NOX5/ROS/c-Src pathway plays a significant role in VSMC dysfunction in hypertension, and dampening this pathway may have therapeutic potential in reducing hypertension-associated vascular injury.
CARDIOVASCULAR RESEARCH
(2022)
Article
Cell Biology
Helmut Sies, Vsevolod V. Belousov, Navdeep S. Chandel, Michael J. Davies, Dean P. Jones, Giovanni E. Mann, Michael P. Murphy, Masayuki Yamamoto, Christine Winterbourn
Summary: This article discusses the key issues associated with identifying the physiological roles of oxidants, with a focus on H2O2 and O-2(.-). The article emphasizes the need for more precise measurement of oxidants and specific identification of their signaling targets. It also highlights the importance of inter-organellar communication and the contribution of environmental exposures. Development of tools for real-time detection and quantification of individual oxidants is crucial for achieving these goals.
NATURE REVIEWS MOLECULAR CELL BIOLOGY
(2022)
Article
Multidisciplinary Sciences
Dylan G. Ryan, Elena Knatko, Alva M. Casey, Jens L. Hukelmann, Sharadha Dayalan Naidu, Alejandro J. Brenes, Thanapon Ekkunagul, Christa Baker, Maureen Higgins, Laura Tronci, Efterpi Nikitopolou, Tadashi Honda, Richard C. Hartley, Luke A. J. O'Neill, Christian Frezza, Angus Lamond, Andrey Y. Abramov, J. Simon C. Arthur, Doreen A. Cantrell, Michael P. Murphy, Albena T. Dinkova-Kostova
Summary: Cells have evolved cytoprotective protein networks controlled by Nrf2 and Keap1 to overcome oxidative, inflammatory, and metabolic stress. Activation of Nrf2 facilitates metabolic reprogramming and mitochondrial adaptation, and fine-tunes the innate immune response in macrophages.
Review
Biochemistry & Molecular Biology
Michael P. Murphy, Edward T. Chouchani
Summary: Succinate, as a signaling modulator, plays multiple roles in biology due to its ability to reflect the redox state of the CoQ pool. Its equilibrium with the CoQ pool enables the communication of the mitochondrial status to the rest of the cell and other cells, explaining the emerging roles of succinate in biology.
NATURE CHEMICAL BIOLOGY
(2022)
Article
Oncology
Tania Capeloa, Joanna Krzystyniak, Donatienne D'Hose, Amanda Canas Rodriguez, Valery L. Payen, Luca X. Zampieri, Justine A. Van de Velde, Zohra Benyahia, Erica Pranzini, Thibaut Vazeille, Maude Fransolet, Caroline Bouzin, Davide Brusa, Carine Michiels, Bernard Gallez, Michael P. Murphy, Paolo E. Porporato, Pierre Sonveaux
Summary: This study investigates the potential of the mitochondria-targeted antioxidant MitoQ in inhibiting breast cancer metastasis. Using human breast cancer cells as models, the researchers demonstrate that MitoQ can inhibit cancer cell migration, invasion, clonogenicity, sphere formation, and spheroid stability. The findings of this study are important for future clinical research and evaluation of MitoQ for the prevention of breast cancer metastasis.
Article
Oncology
Tania Capeloa, Joanna Krzystyniak, Amanda Canas Rodriguez, Valery L. Payen, Luca X. Zampieri, Erica Pranzini, Francoise Derouane, Thibaut Vazeille, Caroline Bouzin, Francois P. Duhoux, Michael P. Murphy, Paolo E. Porporato, Pierre Sonveaux
Summary: Entry into the metastatic phase is devastating for cancer patients. Clinical studies have found that the mitochondria-targeted antioxidant MitoQ can prevent breast cancer metastasis and recurrence.
Article
Biochemistry & Molecular Biology
Fay M. Allen, Ana S. H. Costa, Anja Gruszczyk, Georgina R. Bates, Hiran A. Prag, Efterpi Nikitopoulou, Carlo Viscomi, Christian Frezza, Andrew M. James, Michael P. Murphy
Summary: The study developed a rapid fractionation procedure to stabilize the distribution of metabolites between mitochondria and the cytosol. The procedure revealed the compartmentation of mitochondrial metabolites in vivo and allows for the assessment of metabolite distribution between the cytosol and mitochondria in various situations.
Article
Multidisciplinary Sciences
Mario Gonzalez-Jimenez, Trent Barnard, Ben A. Russell, Nikita V. Tukachev, Uros Javornik, Laure-Anne Hayes, Andrew J. Farrell, Sarah Guinane, Hans M. Senn, Andrew J. Smith, Martin Wilding, Gregor Mali, Motohiro Nakano, Yuji Miyazaki, Paul McMillan, Gabriele C. Sosso, Klaas Wynne
Summary: It has been discovered that the boson peak in glasses, which is an excess in heat capacity or an additional peak in the terahertz vibrational spectrum, can be isolated in liquids of highly symmetric molecules using depolarized Raman scattering. This peak is linked to the formation of clusters consisting of about 20 molecules. These findings represent a significant step toward understanding the physics of vitrification.
NATURE COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Shinpei Uno, Alexander H. Harkiss, Roy Chowdhury, Stuart T. Caldwell, Tracy A. Prime, Andrew M. James, Brendan Gallagher, Julien Prudent, Richard C. Hartley, Michael P. Murphy
Summary: The targeting of bioactive molecules and probes to mitochondria can be achieved by coupling to the lipophilic triphenyl phosphonium (TPP) cation, which accumulates within mitochondria in response to the mitochondrial membrane potential. In this study, we investigated the effects of using a polyethylene glycol (PEG) linker instead of a simple alkane linker to enhance the water solubility of mitochondria-targeted compounds. We found that the use of PEG greatly improved the uptake of compounds by mitochondria and reduced adsorption to the mitochondrial inner membrane.
Correction
Multidisciplinary Sciences
Mario Gonzalez-Jimenez, Trent Barnard, Ben A. Russell, Nikita V. Tukachev, Uros Javornik, Laure-Anne Hayes, Andrew J. Farrell, Sarah Guinane, Hans M. Senn, Andrew J. Smith, Martin Wilding, Gregor Mali, Motohiro Nakano, Yuji Miyazaki, Paul McMillan, Gabriele C. Sosso, Klaas Wynne
NATURE COMMUNICATIONS
(2023)
Letter
Multidisciplinary Sciences
Valerie B. O'Donnell, Nils H. Schebb, Ginger L. Milne, Michael P. Murphy, Christopher P. Thomas, Dieter Steinhilber, Stacy L. Gelhaus, Hartmut Kuehn, Michael H. Gelb, Per-Johan Jakobsson, Ian A. Blair, Robert C. Murphy, Bruce A. Freeman, Alan R. Brash, Garret A. Fitzgerald
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Ben A. Russell, Mario Gonzalez-Jimenez, Nikita V. Tukachev, Laure-Anne Hayes, Tajrian Chowdhury, Uros Javornik, Gregor Mali, Manlio Tassieri, Joy H. Farnaby, Hans M. Senn, Klaas Wynne
Summary: This study discovered a single-component homogeneous molecular liquid that exhibits two comparable glass transitions, one associated with dynamic arrest of liquid properties and the other associated with the freezing out of intramolecular degrees of freedom.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Andrew M. James, Abigail A. I. Norman, Jack W. Houghton, Hiran A. Prag, Angela Logan, Robin Antrobus, Richard C. Hartley, Michael P. Murphy
Summary: A new mass spectrometry probe, CysTPP, has been developed to sensitively detect major acyl-CoAs in rat tissues, revealing the potential importance of longer-chain fatty acyl-CoAs in modifying protein residues non-enzymatically.
CELL CHEMICAL BIOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Nils Burger, Andrew M. James, John F. Mulvey, Kurt Hoogewijs, Shujing Ding, Ian M. Fearnley, Marta Loureiro-Lopez, Abigail A. Norman, Sabine Arndt, Amin Mottahedin, Olga Sauchanka, Richard C. Hartley, Thomas Krieg, Michael P. Murphy
Summary: This study found that Cys39 of ND3 is exposed in complex I during mitochondrial respiration, which has significant implications for our understanding of the A/D transition and the mechanism of complex I.
CELL CHEMICAL BIOLOGY
(2022)
