Article
Chemistry, Multidisciplinary
Arun-Libertsen Lawzer, Thomas Custer, Jean-Claude Guillemin, Robert Kolos
Summary: While the archetypal free phosphinidene, H-P, has been studied for over a century, reports on uncomplexed, univalent phosphorus compounds are very sparse. Here, the production of HCCP in solid argon through UV-induced rearrangement and subsequent dehydrogenation of phosphapropyne, CH3CP, was demonstrated. The migration of hydrogen atoms along the CCP backbone of CH3CP resulted in the production of previously unobserved species 1-phosphapropadiene, CH2=C=PH, followed by the ethynylphosphine, HCCPH2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zexian Li, Minyan Wang, Zhuangzhi Shi
Summary: An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed, generating valuable multisubstituted perfluoroalkylated compounds in a single step. Mechanistically, photoinduced alkyl radical addition to an alkene leads to migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center, followed by generation of a C-radical bearing two electron-withdrawing groups and reduction by a hydrogen donor to complete the domino sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Javier Ramos-Soriano, Alfonso Perez-Sanchez, Sergio Ramirez-Barroso, Beatriz M. Illescas, Khalid Azmani, Antonio Rodriguez-Fortea, Josep M. Poblet, Cormac Hally, Santi Nonell, David Garcia-Fresnadillo, Javier Rojo, Nazario Martin
Summary: In this study, an ultra-long-lived triplet state with a mean lifetime of 93 ms in an aqueous phase at room temperature was discovered. Different tridecafullerenes were synthesized and characterized, confirming aggregation in water. The study also revealed that the inner solvation of multifullerenes varies depending on their molecular design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Monika M. Lindner, M. Wasim Alachraf, Benjamin Mitschke, Philipp Schulze, Markus Leutzsch, Benjamin List
Summary: A method for converting aldehydes into arenes is designed, involving the reaction of aldehydes to form fulvenes, followed by photochemical and platinum-catalyzed rearrangements into Dewar benzene derivatives, which finally isomerize into the desired arenes. Computational studies support the feasibility of this route, but fulvene irradiation unexpectedly results in isomerization into spiro[2.4]heptadienes. The mechanistic investigation of this unusual photorearrangement provides access to various spiro[2.4]heptadienes with different substituents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Johanna Proessdorf, Christian Jandl, Thomas Pickl, Thorsten Bach
Summary: It was found that while 2-alk-omega-enyloxy-sustituted benzaldehydes do not display any photochemical reactivity at the arene core, the respective iminium perchlorates undergo efficient reactions under certain conditions, leading to products with different molecular structures and stereochemical features.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zheng-Chun Yin, Chuang Niu, Mingjie Li, Wen-Rui Liu, Guan-Wu Wang
Summary: Regioselective electrochemical hydroalkylations of [60]fullerene-fused furochromenone with alkyl halides under different acidic conditions unexpectedly afford three types of tetra-functionalized [60]fullerene derivatives in high yields. These products have been characterized by spectroscopic data and single-crystal X-ray analysis, and two of them show diagnostic UV-vis spectra. A plausible reaction mechanism has been proposed to elucidate the formation of hydroalkylation products in the presence of different acids.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Applied
Shulei Pan, Marco T. Passia, Xianliang Wang, Peng Wu, Ding Ma, Carsten Bolm
Summary: NH-sulfoximines can react with carbenes generated from diazo compounds under blue light irradiation to undergo rapid Wolff rearrangement and form N-acylated products in good yields. The reaction conditions are mild, and no base, oxidant, or metal catalyst is required.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Polymer Science
Azra Kocaarslan, Gorkem Yilmaz, Gokhan Topcu, Levent Demirel, Yusuf Yagci
Summary: This study demonstrates the use of a new photochemical ligation process as a versatile approach for various applications such as cross-linking polymerization, functionalization of polymer chain ends, and surface modification of different materials. The process involves the formation of urethane linkages through the reaction of photochemically in situ generated isocyanates with hydroxyl moieties. The intermediates and obtained materials were characterized using NMR, FTIR, TGA, and TEM analyses, showing the potential for future applications in fabricating complex macromolecular structures, biomaterials, and gels.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Luke D. Elliott, Kevin Booker-Milburn, Alastair J. J. Lennox
Summary: This study demonstrates a rare example of a photo/thermal daisy-chained process, with the first visible-light-mediated excited state coupled with thermal cascade reaction conducted as a fully continuous process. The synthetic utility of flow chemistry is further showcased by the isolation of a reactive intermediate at quantities not possible under batch conditions.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Review
Biochemistry & Molecular Biology
Nischal Karki, Satyam Vergish, Brian D. Zoltowski
Summary: The review examines the differences in photochemistry and signal transduction in plant and animal CRYs, identifying potential modes of convergent evolution within these lineages that may reveal conserved signaling pathways. Recent data provides clarity on potential mechanisms of signal transduction in magnetoreception, addressing the conflicts regarding CRY photochemistry and signal transduction.
Article
Multidisciplinary Sciences
Keri A. Steiniger, Tristan H. Lambert
Summary: A new tandem electrochemical/electrophotocatalytic reaction is developed to olefinate aldehydes and ketones with a broad range of unactivated alkenes under nonbasic conditions. This method involves the oxidation-induced denitrogenation of cyclic diazenes to form stable 1,3-distonic radical cations that rearrange to yield the olefin products.
Article
Biochemistry & Molecular Biology
Ewa Wagner-Wysiecka, Paulina Szulc, Elzbieta Luboch, Jaroslaw Chojnacki, Pawel Sowinski, Katarzyna Szwarc-Karabyka
Summary: This study presents the preparation and characterization of products resulting from the photochemical and thermochemical rearrangements of certain azoxybenzocrown compounds. The structures of these compounds were determined using various spectroscopic methods, and their ability to bind and recognize metal cations was also investigated.
Article
Chemistry, Multidisciplinary
Yoshifumi Hashikawa, Shu Okamoto, Yasujiro Murata
Summary: The nucleophilic addition of phosphites to a cage-opened fullerene C-60 derivative led to the formation of alpha-hydrophosphates and enol phosphates as kinetic and thermodynamic products, respectively. Unlike classical Abramov reactions, which yield phosphonates with a P-C bond, these products feature a P-O bond. Theoretical calculations suggested that charge delocalization of zwitterionic intermediates along with the pi-framework facilitates the phospha-Brook rearrangement, resulting in the formation of nonclassical Abramov products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yoshifumi Hashikawa, Yasujiro Murata
Summary: Partial zipping of a fullerene orifice was achieved through water-mediated thermal rearrangement, with the addition of B(C6F5)(3) found to facilitate the reaction. Extending the reaction time led to decarbonylation and the formation of a new orifice structure. Computational study suggested that the formation of a carboxylic acid and Fischer-type carbene played a key role in the C-C bond cleavage/reformation processes during the rearrangement.
Article
Chemistry, Multidisciplinary
Julian Baars, Isabelle Grimm, Dirk Blunk, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A 12-step total synthesis of the natural product dysiherbol A was achieved, revealing the need for revision of the originally proposed structure and absolute configuration. The synthesis involved key steps including Cu-catalyzed addition/enolate-trapping, Au-catalyzed double cyclization, and late installation of the C5-bridgehead methyl group. Spectroscopic measurements confirmed the identity of the synthetic compound with the natural product but with an opposite molecular rotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jiangjiexing Wu, Zhenzhen Wang, Xin Jin, Shuo Zhang, Tong Li, Yihong Zhang, Hang Xing, Yang Yu, Huigang Zhang, Xingfa Gao, Hui Wei
Summary: This study investigates the relationship between structure and oxidase-mimicking activity using metal-organic frameworks, demonstrating a linear free energy relationship in MIL-53(Fe) nanozymes with increasing Hammett sigma(m) values leading to higher activity. This Hammett-type structure-activity relationship is also shown to be applicable to a range of substrates, metals, and MOF types, providing insight into catalytic mechanisms and potential for developing high-performance nanomaterials.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Xiangqin Meng, Dandan Li, Lei Chen, Helen He, Qian Wang, Chaoyi Hong, Jiuyang He, Xingfa Gao, Yili Yang, Bing Jiang, Guohui Nie, Xiyun Yan, Lizeng Gao, Kelong Fan
Summary: The pyrite peroxidase nanozyme demonstrates ultra-high affinity for H2O2 and possesses intrinsic glutathione oxidase-like activity, resulting in abundant production of (OH)-O-center dot and depletion of reduced glutathione, inducing apoptosis and ferroptosis of tumor cells. It shows potential for effective therapeutic application in tumor catalytic therapy.
Review
Chemistry, Multidisciplinary
Xiaomei Shen, Zhenzhen Wang, Xuejiao J. Gao, Xingfa Gao
Summary: Nanozymes are inorganic nanomaterials with enzyme-like catalytic activities. The research on nanozymes is a hot topic in interdisciplinary science involving materials, chemistry, and biology. DFT calculations have played an increasingly important role in exploring the mechanisms and kinetics of nanozymes by providing atomistic-level insights into the microscopic processes. This review summarizes the research progress and focuses on the computational studies that complement experimental findings and promote the understanding of nanozyme mechanisms and kinetics.
ADVANCED MATERIALS
(2023)
Article
Multidisciplinary Sciences
Wenhui Gao, Jiuyang He, Lei Chen, Xiangqin Meng, Yana Ma, Liangliang Cheng, Kangsheng Tu, Xingfa Gao, Cui Liu, Mingzhen Zhang, Kelong Fan, Dai-Wen Pang, Xiyun Yan
Summary: We report a carbon dot (C-dot) superoxide dismutase (SOD) nanozyme with a catalytic activity comparable to that of natural enzymes. The SOD-like activity of C-dot nanozyme relies on specific chemical modifications and conjugated carbonyl groups for binding and electron transfer. Furthermore, the C-dot SOD nanozymes exhibit intrinsic targeting ability to oxidation-damaged cells and effectively protect neuron cells in the ischemic stroke mouse model.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Qiao-Zhi Li, Huizhen Fan, Zhenzhen Wang, Jia-Jia Zheng, Kelong Fan, Xiyun Yan, Xingfa Gao
Summary: Currently, the research on catalysts that catalytically cut phos-phoester bonds using nanomaterials (NMs) is mainly limited to NMs consisting of high-valent metal ions, and a universal theory guiding the discovery of such NM catalysts is still lacking. This study investigates the mechanisms, kinetics, activity descriptors, and theoretical models for predicting the catalytic activities of arbitrary metal and metal-oxide NMs through density functional theory calculations and experiments. The results provide a systematic understanding of previously reported NM catalysts and theoretical guidelines for further optimization and screening of these catalysts.
Article
Engineering, Biomedical
Xuejiao J. Gao, Jun Yan, Jia-Jia Zheng, Shengliang Zhong, Xingfa Gao
Summary: In this study, a method for predicting the catalytic activities of materials towards tumor therapy was developed. This method combines adsorption-energy-based descriptors and criteria with density functional theory calculations and machine learning models. The method allows for efficient screening of 2D materials for catalytic therapy and will greatly contribute to the development of catalytic nanomaterials for medical applications.
ADVANCED HEALTHCARE MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Huizhen Fan, Jiajia Zheng, Jiaying Xie, Juewen Liu, Xingfa Gao, Xiyun Yan, Kelong Fan, Lizeng Gao
Summary: Nanozymes have great potential as alternatives to natural enzymes, but their practical use is limited by their low catalytic activity compared to natural enzymes. This study employed a surface engineering strategy using charge-transferrable ligands, such as polystyrene sulfonate (PSS), to improve the specific activity of Ru nanozymes. The modified Ru nanozyme exhibited a peroxidase-like specific activity double that of horseradish peroxidase. The modified Ru-peroxidase nanozyme was successfully used to develop an immunoassay with significantly increased detection sensitivity compared to traditional enzyme-linked immunosorbent assay.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Guolong Xing, Jingjuan Liu, Yi Zhou, Shuai Fu, Jia-Jia Zheng, Xi Su, Xingfa Gao, Osamu Terasaki, Mischa Bonn, Hai I. Wang, Long Chen
Summary: Conductive metal-organic frameworks (c-MOFs) with excellent electrical conductivities and charge transport properties were synthesized using contorted hexabenzocoronene (c-HBC) derivatives as nonplanar and highly soluble ligands. Three c-MOFs with different geometries and packing modes were obtained, among which c-HBC-12O-Cu exhibited the highest intrinsic electrical conductivity and all c-HBC-based c-MOFs showed high charge carrier mobilities. This work provides a systematic and modular approach to enhance the structure and charge transport properties of c-MOFs using nonplanar and highly soluble ligands.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Xuejing Cui, Xiaoyu Wang, Xueling Chang, Lin Bao, Junguang Wu, Zhiqiang Tan, Jinmei Chen, Jiayang Li, Xingfa Gao, Pu Chun Ke, Chunying Chen, Catherine Murphy
Summary: Carbon-based nanomaterials (CNMs) have been found in humans, and their integration into the endogenous carbon flow through the gut microbiota has been uncovered. The gut microbiota ferments CNMs, incorporating inorganic carbon into organic butyrate. Butyrate-producing bacteria prefer CNMs as their carbon source, and excessive butyrate derived from microbial CNMs fermentation affects the function of intestinal stem cells. This study highlights the need to assess the transformation of CNMs and their health risk via the gut-centric physiological and anatomical pathways.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Multidisciplinary
Takahiro Tsuchiya, Makoto Higashibeppu, Yasuhiro Mazaki
Summary: The construction of 1,2-position-connected azulene oligomers was achieved, and the crystal packing structure of terazulene was analyzed. The helical and syn-type structure with terminal azulene overlap was found to be more stable. Fused terazulenes (1,2''-closed and 1,8''-closed) were synthesized by Pd-catalyzed C-H/C-Br arylation, and their structures were analyzed using X-ray crystallography. The 1,8''-closed terazulene showed anti-aromatic properties according to Nucleus-independent chemical shift (NICS) calculations.
Article
Chemistry, Physical
Zhenzhen Wang, Huan Meng, Xuejiao J. Gao, Jia-Jia Zheng, Xingfa Gao
Summary: The Hammett equation is commonly used for theoretical modeling of the substituent effects on catalytic activities of metal-organic frameworks (MOFs). However, its application to MOF catalysts faces challenges due to unknown transferability of empirical parameters. In this study, a linker orbital energy model is proposed, which offers a simple way to estimate the remote electronic substituent effects on MOF catalysis and demonstrates its general applicability to MOFs based on extensive literature review. The model can be utilized for designing the catalytic activities of metal nodes in MOFs by manipulating the electronic properties of linkers and substituents.
NPJ COMPUTATIONAL MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Xuejiao J. Gao, Yuliang Zhao, Xingfa Gao
Summary: Developing biocompatible catalytic nanomaterials to target cancer reactive oxygen species (ROS) has provided a promising alternative chemotherapy strategy. Despite progress in synthesizing inorganic nanomaterials with potential therapeutic functions, the chemicobiological mechanisms underlying ROS-targeted catalysis and subsequent cancer therapeutic functions of nanomaterials remain elusive. This study proposes catalytic signal transduction theory to bridge the gap between catalytic activities and medical functions of inorganic nanomaterials, providing theoretical tools for the design and screening of candidate nanomaterials for cancer therapy.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Wei Xu, Jia-Jia Zheng, Yu-An Li, Xingfa Gao, Xiaobo Ji, Yi-Ge Zhou
Summary: The electrochemical processes of individual PB particles were investigated using nano-impact electrochemistry, revealing the kinetic mechanism of each oxidation/reduction reaction through theoretical simulation. The partially contradictory conclusion between single-particle analysis and the ensemble-averaged measurement was discussed. These findings contribute to a better understanding of the electrochemical processes of cathode materials with multiple redox centers and facilitate the development of effective strategies to optimize these materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Cong Liu, Lin Gui, Jia-Jia Zheng, Yong-Qiang Xu, Benli Song, Li Yi, Yijiang Jia, Ayijiang Taledaohan, Yuji Wang, Xingfa Gao, Zeng-Ying Qiao, Hao Wang, Zhiyong Tang
Summary: Metaloxide nanozymes have emerged as the most promising candidates for treating oxidative stress-mediated disorders, but their current efficacy is insufficient. This study introduces an intrinsic strain-mediated ultrathin ceria nanoantioxidant, which exhibits enhanced SOD-mimetic and total antioxidant activities. In vivo experiments demonstrate that these ultrathin ceria nanoplates can significantly improve the treatment of ischemic stroke, outperforming the commonly used drug edaravone.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chunyu Li, Peng Li, Leyun Li, Dingjia Wang, Xingfa Gao, Xuejiao J. Gao
Summary: The effects of cations in tetrahedral and octahedral sites on the electronic structures of spinels were systematically investigated, with results showing that octahedrally coordinated B cations have notable influence on the electronic structures of spinels. Jahn-Teller active ions Fe2+, Ni2+, Mn3+, Ni3+, Cr4+, and Fe4+ can remarkably reduce the band gaps of spinels and change their electroconductibilities. These findings provide theoretical insights into the electronic properties of 3d transition metal spinels.
