Article
Chemistry, Multidisciplinary
Jingshan Chai, Yu Zhao, Lina Xu, Qiushi Li, Xin-Yue Hu, Dong-Sheng Guo, Yang Liu
Summary: A novel strategy based on a polymeric inhibitor-encapsulated enzyme has been developed, which allows reversible control of the activity of native enzymes using light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kanna Fujishiro, Yuta Morinaka, Yohei Ono, Tsuyoshi Tanaka, Lawrence T. Scott, Hideto Ito, Kenichiro Itami
Summary: In this study, a lithium(0)-mediated mechanochemical anionic cyclodehydrogenation reaction was developed for the first time. The reaction could be easily performed using a conventional and easy-to-handle lithium(0) wire at room temperature, even under air, and achieved high yields in a short time. The study also comprehensively investigated the applicability and practicality of the protocol, as well as limitations, through computational studies and nuclear magnetic resonance analysis. Furthermore, novel nanographenes, including quinterrylene, were successfully synthesized using this method.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Wakana Sakai, Lori Gonnet, Naoki Haruta, Tohru Sato, Michel Baron
Summary: Mechanochemical reactions can produce unexpected results or product ratios compared to conventional reaction conditions. This study uses the Diels-Alder reaction between diphenylfulvene and maleimide as an example to theoretically explain the origin of mechanochemical selectivity. The application of external force can cause structural deformation, and we find that a mechanical force applied orthogonal to the reaction mode can lower the activation barrier by changing the potential energy curvature in the transition state. The endo-type pathway was found to be more mechanochemically favorable than the exo-type pathway in the Diels-Alder reaction, which is consistent with experimental observations.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Review
Biochemistry & Molecular Biology
Laszlo Jicsinszky, Federica Rossi, Roberto Solarino, Giancarlo Cravotto
Summary: Many scientists are seeking green alternatives to traditional synthetic methods. State-of-the-art ultrasonic and grinding techniques are already being used to produce organic compounds on an industrial scale. The unique properties of cyclodextrins, such as poor solubility and complexing properties, require special techniques. Green alternatives can eliminate or reduce the need for solvents, making classical synthetic methods more environmentally friendly. Mechanochemical reactions can facilitate the synthesis of cyclodextrin derivatives that are difficult to produce using traditional solution-chemistry methods. While not a universal solution, mechanochemistry shows promise for efficient synthesis.
Article
Chemistry, Multidisciplinary
Tamae Seo, Koji Kubota, Hajime Ito
Summary: Mechanochemical synthesis using transition-metal catalysts has advantages such as low solvent waste and short reaction times. However, the direct use of transition-metal catalysts in mechanochemical reactions without modifications limits the development of efficient cross-coupling processes. This study presents a new approach, using mechanochemistry-directed design to develop ligands for Suzuki-Miyaura cross-coupling reactions. The embedding of the ligand into a poly(ethylene glycol) polymer prevents catalyst deactivation and shows high catalytic activity at room temperature.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Molly E. McFadden, Ross W. Barber, Anna C. Overholts, Maxwell J. Robb
Summary: Naphthopyran undergoes a ring-opening reaction to generate colored merocyanine dyes after external stimulation, allowing exceptional control over their properties and stimuli-responsive behavior. Its applications as photoswitches in ophthalmic lenses have led to extensive research on its structure-property relationships. The discovery of mechanochromic behavior in naphthopyran has opened up new possibilities in polymer mechanochemistry.
Article
Chemistry, Physical
Meiling Chen, Yunpeng Long, Ruizhe Li, Zhongbiao Wu, Xiaole Weng
Summary: The atmospheric photochemical conversion of chlorinated volatile organic compounds (CVOCs) is crucial for aerosol formation and chlorine chemistry. However, the pathways and products of this conversion are not well understood. In this study, the conversion of chlorobenzene (CB) on gamma-Al2O3 mineral particles was used as a model reaction to investigate CVOC atmospheric chemistry. The results showed that CB can be degraded by gamma-Al2O3 under light, with the presence of SO2 inhibiting the conversion and NH3 facilitating it. Additionally, the study found that polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can be generated from the photochemical CB conversion, indicating a potential source of PCDD/Fs in atmospheric particulates.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Satenik Mkrtchyan, Viktor O. Iaroshenko
Summary: A three-component Pd-catalysed aminosulfonylation reaction of K2S2O5 and amine with aryl bromides or aromatic carboxylic acids was developed, utilizing mechanical energy. This strategy accommodates primary as well as secondary aliphatic and aromatic amines to provide a new shortcut to a wide range of sulfonamides. Studies on the reaction's scope and limitations revealed its tolerance of a vast range of functional groups and many structural patterns, enabling the reaction to be scaled up to gram quantities.
CHEMICAL COMMUNICATIONS
(2021)
Article
Thermodynamics
Aniele de Moura, Caroline Gaglieri, Luiz Carlos da Silva-Filho, Flavio Junior Caires
Summary: A new methodology for synthesizing a curcumin derivative was studied, which proved to be more efficient and environmentally friendly compared to traditional methods. The mechanochemical method was used, confirming the feasibility and advantages of this novel approach.
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2021)
Article
Chemistry, Multidisciplinary
Victoria S. Pfennig, Romina C. Villella, Julia Nikodemus, Carsten Bolm
Summary: A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill has been reported, followed by their reactions with CO2 or sodium methyl carbonate to provide aryl and alkyl carboxylic acids with yields up to 82%. The method stands out for its short reaction times and significantly reduced solvent amounts, with methoxy-substituted aryl bromides unexpectedly leading to major products being symmetric ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Yutaro Takaya, Yiyun Xiao, Yuki Tsunazawa, Mauricio Cordova, Chiharu Tokoro
Summary: This study investigates a mechanochemical method for the degradation of TBBPA and validates the degradation efficiency and rate through experiments. The research reveals that the mechanochemical degradation rate can be predicted by collision energy, providing a promising approach for the treatment of organic pollutants.
ADVANCED POWDER TECHNOLOGY
(2022)
Review
Chemistry, Multidisciplinary
Gennady I. Borodkin
Summary: This review summarizes and critically analyzes the data on the mechanochemical synthesis of halogen-containing organic compounds published mainly over the past 10 years. The established views about the methods of activation of mechanochemical halogenation reactions are discussed. The review considers the mechanochemical fluorination, chlorination, bromination, and iodination reactions of organic compounds. Special attention is given to reaction mechanisms, selectivity problems, and the consideration of mechanochemical approach as a promising trend of green chemistry.
RUSSIAN CHEMICAL REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Liangkun Pan, Long Zheng, Ye Chen, Zhihai Ke, Ying-Yeung Yeung
Summary: A mechanochemical method using hypervalent iodine reagents has been developed for the functionalization of olefins, enabling the synthesis of 1,3-dioxygenated compounds. Under similar reaction conditions with the addition of molecular iodine, 1,4-iodoalcohols can also be synthesized. These valuable products are difficult to achieve using traditional solution-phase methods. Mechanistic study suggests that the hypervalent iodine reagent may dimerize at the solid state and trigger the 1,3- and 1,4-difunctionalization reactions in an intermolecular cascade manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Hongyu Yan, Zhengyuan Zhang, Ming Xiao, Yuechuan Wang
Summary: This study develops a two-step bulk photopolymerization method to make multifunctional polyacrylic elastomers with ultra-strechability, hydrophobicity, self-healing, and adhesive properties. By adding a small amount of 1-ethynylcyclohexyl acrylate (ECA) into a common acrylate, these elastomers can be produced with desired properties. The environmental-friendly solvent-free approach expands their applications in various areas.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Antonino Curcio, Jian Wang, Zheng Wang, Zhiqi Zhang, Alessio Belotti, Simona Pepe, Mohammed B. Effat, Zongping Shao, Jongwoo Lim, Francesco Ciucci
Summary: The study demonstrates that coupling perovskites with MoS2 mechanochemically can overcome the kinetic limitation of the oxygen evolution reaction (OER) and improve its activity. MoS2 at the formed heterointerfaces acts as both an electron and a proton acceptor, facilitating deprotonation of the perovskite and leading to faster OER kinetics.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Molly E. McFadden, Maxwell J. Robb
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Multidisciplinary Sciences
Masanori Funabashi, Tyler L. Grove, Min Wang, Yug Varma, Molly E. McFadden, Laura C. Brown, Chunjun Guo, Steven Higginbottom, Steven C. Almo, Michael A. Fischbach
Article
Chemistry, Multidisciplinary
Molly E. McFadden, Maxwell J. Robb
Summary: The discovery of a 2H-naphtho[1,2-b]pyran mechanophore that produces a permanent merocyanine dye upon mechanochemical activation is reported. The irreversible nature of the mechanically generated merocyanine is attributed to a unique reaction involving the scission of an ester C-O bond. This permanent coloration offers new opportunities for sensing, force-recording applications, and fundamental studies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaoran Hu, Tian Zeng, Corey C. Husic, Maxwell J. Robb
Summary: A general mechanophore platform based on masked 2-furylcarbinol derivatives is described in this study, which can spontaneously decompose under mild conditions upon liberation via a mechanically triggered reaction, resulting in the release of functionally diverse molecular cargo with adjustable release kinetics. The platform demonstrates good selectivity and control, and efficient release of various cargo molecules can be triggered by ultrasound-induced mechanical force.
ACS CENTRAL SCIENCE
(2021)
Article
Polymer Science
Skylar K. Osler, Molly E. McFadden, Maxwell J. Robb
Summary: This study directly compares the reactivity of two isomeric naphthopyrans in solution and solid materials, finding that the 2H-naphthopyran produces a dye with slower reversion rate. By investigating the impact of naphthopyran isomerism on the mechanochromic properties, the study lays the foundation for the development of force-responsive polymers.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Brooke A. Versaw, Tian Zeng, Xiaoran Hu, Maxwell J. Robb
Summary: Mechanophores, stress-sensitive molecules that release small molecules from polymers, show great promise in achieving selective and controlled release of covalently bound payloads. While the field of polymer mechanochemistry is rapidly advancing, further fundamental and technological advancements are still needed for significant impact in this research area.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Polymer Science
Anna C. Overholts, Molly E. McFadden, Maxwell J. Robb
Summary: Accurate and quantitative characterization of structure-mechanochemical activity relationships is crucial for understanding mechanochemical reactivity and advancing the field of polymer mechanochemistry. Ultrasound-induced mechanical activation of polymers is a common method for studying mechanophore reactivity, but traditional methods for analyzing chain scission kinetics from GPC measurements may provide misleading results. This study demonstrates the importance of spectroscopic analysis in accurately determining mechanophore activation rates, highlighting the need for a unified approach to kinetic analysis in polymer mechanochemistry.
Article
Polymer Science
Corey C. Husic, Xiaoran Hu, Maxwell J. Robb
Summary: This study presents a new design of mechanophore polymer container that can release chemical payloads efficiently in non-proton solvent environments. The design incorporates a tethered primary alcohol and an intramolecular hydrogen bonding interaction between the alcohol and the carbonyl oxygen of a carbonate, reducing the activation energy for carbonate fragmentation and enabling molecular release. This design expands the application range of mechanically triggered release.
Article
Chemistry, Multidisciplinary
Molly E. McFadden, Skylar K. Osler, Yan Sun, Maxwell J. Robb
Summary: Multimodal mechanophores can distinguish between different stress states through color changes. In this study, we covalently linked polymer chains to naphthodipyran and generated the dual ring-opened dimerocyanine product with unique near-infrared absorption properties using mechanical force.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Infectious Diseases
Mingrong Yin, Zhipeng Tang, Xiaoran Hu, Yuyan Li, Longzong Guo, Xiaolong Sun, Shuang Chang, Peng Zhao, Yixin Wang
Summary: A cluster of artificially bred vultures in a zoo in Shandong Province, China exhibited emaciation and mortality, suggesting the presence of an immunosuppressive pathogen. Nucleic acid testing confirmed the presence of chicken infectious anemia virus (CIAV) in the dead vulture tissue. The isolated CIAV strain, SDTY2021-TJ, showed high pathogenicity in SPF chickens, causing significant mortality and immunosuppressive effects.
TRANSBOUNDARY AND EMERGING DISEASES
(2023)
Article
Polymer Science
Molly E. McFadden, Anna C. Overholts, Skylar K. Osler, Maxwell J. Robb
Summary: Understanding the relationship between structure and mechanochemical reactivity is crucial for designing new stimuli-responsive polymers. In this study, we validate an initial rates method that accurately determines rate constants for ultrasound-induced mechanochemical transformations. The experimental results support the effectiveness of this method in deconvoluting the kinetics of specific mechanophore activation from nonspecific chain scission.
Article
Chemistry, Multidisciplinary
Xuancheng Fu, Boyu Zhu, Xiaoran Hu
Summary: This paper presents a mechanical approach to induce atropisomerization in a parallel diarylethene molecule, resulting in distinct chemical reactivity of its antiparallel diastereomers. Under ultrasound-induced force field, a congested parallel diarylethene mechanophore in (R(a), S(a)) configuration with mirror symmetry is atropisomerized to antiparallel diastereomers with C(2) symmetry. The obtained stereochemistry-converted material exhibits symmetry-allowed reactivity towards conrotatory photocyclization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Skylar K. Osler, Molly E. McFadden, Tian Zeng, Maxwell J. Robb
Summary: Multi-modal mechanophores that react under mechanical force to produce unique absorption properties are of interest for force-sensing polymer design. In this study, a 2H-bis-naphthopyran mechanophore was investigated for its reactivity in generating thermally stable mono- and bis-merocyanine products upon mechanical activation. The force-mediated ester bond scission reaction followed by intramolecular hydrogen bonding plays a role in locking one merocyanine subunit in the open form, leading to the formation of an unusual trans merocyanine isomer. Unexpectedly, density functional theory calculations suggest a thermally reversible retro-cyclization reaction that may explain the mechanochemical generation of this isomer.
Article
Chemistry, Multidisciplinary
Tian Zeng, Xiaoran Hu, Maxwell J. Robb
Summary: In this study, a new mechanophore platform based on a masked 2-furylcarbinol derivative was reported, which efficiently releases phenol and arylamine payloads following mechanical activation. This platform incorporates a 5-aryloxy group as an electron-rich substituent to accelerate molecular release.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Brooke A. Versaw, Molly E. McFadden, Corey C. Husic, Maxwell J. Robb