Article
Chemistry, Inorganic & Nuclear
Yijing Wang, Lijuan Yan, Xinyi Li, Shiqing Zhang, Jingjing Wei, Yongjun Liu
Summary: The study found that the Cys-Tyr cofactor is not essential for the oxidation activity of CDO, and its formation is just an accompanying reaction rather than a prerequisite for the oxidation reaction. This conclusion helps to understand the catalytic mechanism of CDO.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Henry P. Caldora, Zhenhua Zhang, Michael J. Tilby, Oliver Turner, Daniele Leonori
Summary: Phenols are important aromatic molecules widely found in natural products and used for the synthesis of high-value materials. However, obtaining highly substituted derivatives can be difficult, especially when their functionalization pattern does not match the reactivity of electrophilic aromatic substitution chemistry. This study presents a new and mechanistically distinct approach for phenol synthesis using saturated cyclohexanone precursors, which operates at ambient temperature under purple light irradiation and involves four sequential H-atom transfer processes in a dual catalytic manifold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Andreas S. Bommarius
Summary: While many oxidases are active and selective, they often lack stability for chemical synthesis or large-scale processing due to various stresses, such as loss of flavin co-enzyme, overoxidation in the presence of reactive oxygen species, or instability in the presence of air/water interfaces if the co-substrate oxygen is supplied by sparging.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Rahul Singh, Amreen K. Bains, Abhishek Kundu, Harshit Jain, Sudha Yadav, Dhananjay Dey, Debashis Adhikari
Summary: Borrowing hydrogen reactions by base metals have gained attention in green and sustainable chemistry. This study demonstrates that an earth-abundant nickel catalyst with a redox noninnocent azophenolate backbone can drive alcohol dehydrogenation through a radical pathway. Mechanistic investigations support substrate binding and the role of azophenolate hemilability. Quantitative analysis reveals the kinetic barrier and rate-determining step in the reaction.
Article
Chemistry, Inorganic & Nuclear
Chien-Wei Chiang, Yi-Hsien Chou, Chih-Hui Chou, Hung-Chi Chen, Jeng-Lung Chen, Liang-Ching Hsu, Wei-Hsiang Huang, Hung-Li Li, Yu-Hao Liu
Summary: This study investigates the mechanism of alcohol oxidation using a ferrocene-conjugated copper complex, offering valuable insights and potential for developing efficient and eco-friendly catalysts for chemical synthesis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pritam Mondal, Izumi Ishigami, Emilie F. Gerard, Chaeeun Lim, Syun-Ru Yeh, Sam P. de Visser, Gayan B. Wijeratne
Summary: Heme superoxides are versatile metallo-intermediates in biology, facilitating a wide range of oxidation and oxygenation reactions involving O-2(g). The electronic factors of heme center modulate the feasibility of proton-coupled electron transfer (PCET) processes, influencing both thermodynamic and kinetic parameters. Understanding these electronic effects is pivotal in biological heme systems and alternative energy applications.
Review
Chemistry, Medicinal
M. Saeed Mirzaei, Maxim Ivanov, Avat Arman Taherpour, Saber Mirzaei
Summary: Mechanism-based inactivation (MBI) refers to the metabolic bioactivation of xenobiotics by cytochrome P450s, leading to the formation of highly reactive intermediates that irreversibly inhibit the enzyme. Medicinal compounds undergoing MBI may result in drug-drug interactions and severe toxicity, as observed in clinical experiments. Advances in computational modeling have helped elucidate the activation mechanisms of various functional groups with MBI activity, providing valuable insights for drug design, toxicity prevention, and the discovery of inhibitors and catalysts.
CHEMICAL RESEARCH IN TOXICOLOGY
(2021)
Article
Biochemistry & Molecular Biology
Michela Lupi, Martina Onori, Stefano Menichetti, Sergio Abbate, Giovanna Longhi, Caterina Viglianisi
Summary: In this study, an efficient chemical resolution method was developed for the separation of racemic hydroxy substituted dithia-aza[4]helicenes. Enantiopure acids were used as resolving agents, leading to better diastereomeric separation. Highly optically pure products were obtained through subsequent manipulations.
Article
Biochemistry & Molecular Biology
Stefano Scurti, Daniele Caretti, Fabio Mollica, Erika Di Antonio, Riccardo Amorati
Summary: Phenol-capped SPIONs have been found to act as antioxidants, and this study investigates the underlying mechanism by studying their reaction with alkyl peroxyl radicals. It was found that the degree of purification affects the antioxidant effect, with SPIONs containing higher phenol content showing strong radical trapping activity. Thoroughly washed SPIONs had low reactivity towards peroxyl radicals.
Article
Biochemistry & Molecular Biology
Fabio Mollica, Lucia Bonoldi, Riccardo Amorati
Summary: The peroxidation of vegetable oils is a significant issue for the food and biodiesel industries, especially when the degree of unsaturation and temperature increase. Using phenols as additives is a common method to prevent oil peroxidation, but their effectiveness at high temperatures is not well understood.
Article
Biochemistry & Molecular Biology
Nunzio Cardullo, Filippo Monti, Vera Muccilli, Riccardo Amorati, Andrea Baschieri
Summary: Six bisphenol neolignans were synthesized and their antioxidant activity was evaluated. The derivatives showed varying effectiveness compared to the natural compound, depending on the presence and position of hydroxyl and alkyl groups. Compound 7 exhibited a significantly higher reaction rate with ROO• radicals than honokiol. The addition of 1,4-cyclohexadiene restored the antioxidant activity of compounds with quinonic oxidized forms by generating HOO• radicals. The combination of oxidized compounds with 1,4-cyclohexadiene showed increased antioxidant activity in some cases.
Article
Chemistry, Applied
Michela Lupi, Omar Salmi, Caterina Viglianisi, Stefano Menichetti
Summary: This article reports the conversion of N-thiophthalimido-arylphenothiazines 2 and triarylamines 3 to dithiabridged triarylamine hetero[4]helicenes 1 using catalytic amounts of chalcogen substituted Lewis Bases and hexafluoro isopropanol as hydrogen bond donor. The procedure provides good yields under mild reaction conditions without the need for excess Lewis Acids. It also presents a preliminary study on the control of the M and P absolute stereochemistry of helicenes 1 using enantiopure sulfur containing Lewis Bases from the natural chiral pool.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Linda Cerofolini, Kristian Vasa, Elisa Bianconi, Maria Salobehaj, Giulia Cappelli, Alice Bonciani, Giulia Licciardi, Anna Perez-Rafols, Luis Padilla-Cortes, Sabrina Antonacci, Domenico Rizzo, Enrico Ravera, Caterina Viglianisi, Vito Calderone, Giacomo Parigi, Claudio Luchinat, Antonio Macchiarulo, Stefano Menichetti, Marco Fragai
Summary: Several protein-drug conjugates are currently used in cancer therapy, relying on covalently attached cytotoxic organic compounds or non-covalent interactions. Human transthyretin (TTR) has been identified as a potential carrier protein for cytotoxic drug delivery. This study demonstrates the importance of integrating multiple biophysical and structural techniques, such as microscale thermophoresis, X-ray crystallography, and NMR. Solid-state NMR is particularly valuable in revealing ligand binding effects and their impact on macromolecular complex stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Alexandra Mavridi-Printezi, Arianna Menichetti, Dario Mordini, Riccardo Amorati, Marco Montalti
Summary: Artificial melanin-like nanoparticles combine strong antioxidant activity with versatile preparation methods, making them potential candidates for nanomedicine platforms. They have shown applications in preventing and treating important diseases such as cardiovascular disorders, neurological disorders, and even cancer. Further research should focus on understanding the interaction mechanisms between melanin-like nanoparticles and free radicals and reactive species, to design more effective and specific antioxidant nano-agents.
Article
Chemistry, Multidisciplinary
Fabio Santanni, Matteo Briganti, Giulia Serrano, Enrico Salvadori, Alessandro Veneri, Chiara Batistoni, Sofia F. Russi, Stefano Menichetti, Matteo Mannini, Mario Chiesa, Lorenzo Sorace, Roberta Sessoli
Summary: Sulfur-rich molecular complexes of dithiolene-like ligands are promising candidates for molecular spin qubits due to enhanced spin coherence properties in hydrogen-free environments. In this study, the mononegative 1,3,2-dithiazole-4-thione-5-thiolate (dttt-) ligand was used as an alternative to common dinegative dithiolate ligands. The synthesis and structural characterization of Cu2+, Ni2+, and Pt2+ complexes with this ligand were reported for the first time. XPS analysis indicated that intact molecules can be deposited on surfaces by sublimation, and AF exchange interactions mediated by S center dot center dot center dot S VdW interactions were observed.
Article
Chemistry, Multidisciplinary
Niccolo Giaconi, Lorenzo Poggini, Michela Lupi, Matteo Briganti, Anil Kumar, Tapan K. K. Das, Andrea L. L. Sorrentino, Caterina Viglianisi, Stefano Menichetti, Ron Naaman, Roberta Sessoli, Matteo Mannini
Summary: This study investigates the spin selectivity properties of a monolayer of a thioalkyl derivative on a gold surface and finds that it can act as a spin filter, discriminating flowing electrons according to their spin state based on the molecules' chirality. These results demonstrate that thioalkyl derivatives are important candidates for the development of chiral spintronic devices.
Article
Biochemistry & Molecular Biology
Luca Pincigher, Francesca Valenti, Christian Bergamini, Cecilia Prata, Romana Fato, Riccardo Amorati, Zongxin Jin, Giovanna Farruggia, Diana Fiorentini, Natalia Calonghi, Chiara Zalambani
Summary: Gamma-terpinene, alpha-terpinene, p-cymene, and myrcene are important components of essential oils extracted from many plants and spices. Myrcene, in particular, has potential anticancer activity, leading to cell proliferation arrest, decreased migration, morphological changes, and DNA damage in HeLa cells. Furthermore, myrcene is the only compound among the four that can interact with DNA.
Review
Biochemistry & Molecular Biology
Damiao P. de Sousa, Renan Oliveira S. Damasceno, Riccardo Amorati, Hatem A. Elshabrawy, Ricardo D. de Castro, Daniel P. Bezerra, Vitoria Regina V. Nunes, Rebeca C. Gomes, Tamires C. Lima
Summary: In this review, the authors provide an overview of the mechanisms of pharmacological action of essential oils and their components in various biological systems. They discuss the antioxidant, anti-inflammatory, antitumor, antimicrobial activities, as well as the mechanisms of action against various types of viruses. The data indicate that the chemical diversity in the composition of essential oils allows them to interfere with biological processes at different levels, making them a promising source for the development of new drugs.
Article
Biochemistry & Molecular Biology
Alexandra Mavridi-Printezi, Fabio Mollica, Rosa Lucernati, Marco Montalti, Riccardo Amorati
Summary: Experimental and theoretical studies show that the artificial allomelanin PDHN nanoparticles (PDHN-NP) have higher antioxidant efficiency compared to polydopamine nanoparticles (PDA-NP) due to catalytic cross-termination activity and a high reactivity with hydroperoxyl radicals (HOO), which is attributed to the presence of a H-bond network in PDHN-NP.
Article
Chemistry, Multidisciplinary
Riccardo Amorati, Yafang Guo, Bridgette Maria Budhlall, Carol Forance Barry, Dongmei Cao, Siva Sai Ramana Kumar Challa
Summary: The use of nanomaterials as inhibitors of autoxidation has attracted significant attention. In this study, a new CeO2-derived nanoporous material with excellent autoxidation inhibiting properties is reported, and a plausible chemical mechanism for radical trapping is proposed.