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
Biochemistry & Molecular Biology
Vanessza Judit Kolcsar, Gyorgy Szollosi
Summary: In this study, a convenient and green procedure for the preparation of N-heterocyclic compounds was developed using environmentally friendly processes and efficient catalysts. The application of mechanochemical activation significantly shortened the reaction time and improved the yield.
Article
Engineering, Mechanical
Jian Guo, Chen Xiao, Jian Gao, Gengzhuo Li, Hanqiang Wu, Lei Chen, Linmao Qian
Summary: The mechanical removal of GaN using diamond tip and mechanochemical removal using Al2O3 tip are described by the Archard equation and mechanically assisted Arrhenius-type kinetic model, respectively. Material removal under elastic contact with the assistance of interfacial mechanochemical reactions is evident. The critical activation volume and activation barrier are determined semiquantitatively by analyzing the mechanochemical reactions with Arrhenius-type kinetic model and Hertzian contact mechanics. The mechanical activation from the chemically active counter-surface facilitates the mechanochemical atomic attrition by altering the energy barrier of the reaction kinetics.
TRIBOLOGY INTERNATIONAL
(2021)
Article
Biology
Shijing Yu, Sarah Rempel, Negin Gholamipourbarogh, Christian Beste
Summary: This study reveals the temporally nested representational dynamics during the opening and closing of working memory gates using different EEG analysis methods. It also shows that these dynamics are attributable to a ventral stream-prefrontal cortex processing cascade.
COMMUNICATIONS BIOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Gyeonghyeon Choi, Eprillia Intan Fitriasari, Chiyoung Park
Summary: The study introduces a facile method to prepare electro-mechanochemically responsive soft gel composites with molecular gatekeeper-based nanocontainers. These composites exhibit self-healing ability and controlled guest molecule release in response to electrical and mechanical stimuli, allowing for remotely controllable drug-delivery applications.
Review
Biochemistry & Molecular Biology
Tatiana A. Akopova, Tatiana N. Popyrina, Tatiana S. Demina
Summary: This study reviews the application of mechanochemical approaches to modify polysaccharides. The considered approach is characterized by the ability to avoid toxic solvents, initiators, or catalysts, aligning with current global trends. Examples using various polysaccharides and their derivatives are used to analyze the mechanisms of chemical transformations, the structure and properties of the products, their solubility and swelling in different media, and their ability to self-organize and stabilize nanodispersed inorganic particles and biologically active substances.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(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)
Article
Multidisciplinary Sciences
Ruo-Xu Gu, Bert L. L. de Groot
Summary: The authors use MD simulations to investigate the effect of dewetting on the function and conformational transition of potassium channels. The results suggest that insufficient hydration obstructs ion permeation and leads to changes in the function and structure of the channels. This conclusion may be applicable to other ion channels as well.
NATURE COMMUNICATIONS
(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, Physical
Zhijie Cao, Michael Felderhoff
Summary: Ytterbium tetrahydroaluminate Yb(AlH4)3 was successfully synthesized via a mechanochemical procedure under hydrogen atmosphere, with its thermal decomposition proceeding through four stages. The first dehydrogenation step exhibited a relatively low apparent activation energy, while rehydrogenation tests showed unsuccessful rehydrogenations of the first decomposition step.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Multidisciplinary Sciences
Martina Alunni Cardinali, Laura Cartechini, Marco Paolantoni, Costanza Miliani, Daniele Fioretto, Luciano Pensabene Buemi, Lucia Comez, Francesca Rosi
Summary: Correlative Brillouin and Raman microspectroscopy (BRaMS) is used to monitor the chemical and physical changes of linseed oil during polymerization. The results provide important insights into the processes leading to the conversion of a fluid binder into a dry adhering film.
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, 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
Polymer Science
Devavrat Sathe, Hanlin Chen, Junpeng Wang
Summary: By investigating the effects of different substituents on cyclobutane on the polymers, this study reveals their impact on polymerization conversion and thermal properties. These findings are important for designing the next generation of chemically recyclable polymers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Stephen L. Craig
Summary: This paper summarizes the Faraday Discussions meeting on mechanochemistry, focusing on the fundamentals, applications, and future prospects in the context of broad themes.
FARADAY DISCUSSIONS
(2023)
Article
Polymer Science
Wenqi Wang, Brayan Rondon, Zeyu Wang, Junpeng Wang, Jia Niu
Summary: The study reports a general method for the organocatalyzed photocontrolled radical ring-opening cascade copolymerization of macrocyclic allylic sulfone and various types of vinyl monomers. This method provides a versatile approach to the wide range of degradable vinyl plastics with various structures and functions.
Article
Chemistry, Multidisciplinary
Tetsu Ouchi, Brandon H. Bowser, Tatiana B. Kouznetsova, Xujun Zheng, Stephen L. Craig
Summary: This study reports a double-network hydrogel that can increase acidity when strained and recover its initial shape after large deformation. By synthesizing a specific mechanoacid molecule and incorporating it into the hydrogel, the locking and releasing of acid through mechanochemical reactions are achieved.
MATERIALS HORIZONS
(2023)
Article
Polymer Science
Junfeng Zhou, Devavrat Sathe, Andrew Ciccotelli, Junpeng Wang
Summary: Helices are important structures in biomacromolecules and chiral catalysis. The unfolding of helical structures under mechanical force has attracted attention in recent years. This paper reports the design of a potential mechanophore, a Zn (II) bidipyrrin (BDPR-Zn) double helix, and its mechanochemical testing using pulsed ultrasonication. The results demonstrate the inertness of the BDPR-Zn unit under mechanical force and suggest possibilities for further design of force-induced helix unfolding.
JOURNAL OF POLYMER SCIENCE
(2023)
Review
Chemistry, Multidisciplinary
Junfeng Zhou, Tze-Gang Hsu, Junpeng Wang
Summary: The accumulation of plastic waste has resulted in severe environmental pollution due to inadequate recycling. While mechanical recycling can address this issue, it often compromises the material's molecular weight and mechanical properties, making it unsuitable for mixed materials. Chemical recycling, on the other hand, breaks down polymers into smaller constituents, enabling the creation of high-quality materials comparable to virgin polymers, and it can be applied to mixed materials. Mechanochemical degradation and recycling combine the advantages of mechanical techniques and chemical recycling to achieve efficient and scalable polymer recycling. This article serves as a summary of recent advancements in mechanochemical degradation and recycling of synthetic polymers, both commercially available and specially designed for more effective mechanochemical degradation. It also highlights the limitations of mechanochemical degradation and provides perspectives on overcoming these challenges towards a circular polymer economy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Junpeng Wang, Tatiana B. Kouznetsova, Jianshe Xia, Felipe Jimenez Angeles, Monica Olvera de la Cruz, Stephen L. Craig
Summary: Single-molecule force spectroscopy is a powerful tool for studying the properties of individual polymer strands. However, the weak attachment between the atomic force microscope tip and the analyte limits its efficiency. In this study, we developed a polyelectrolyte handle that provides strong attachment, high success rate, non-fouling detachment, and specific attachment locations along the polymer strand.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Julia Zhao, Eduard O. Bobylev, David J. Lundberg, Nathan J. Oldenhuis, Heng Wang, Ilia Kevlishvili, Stephen L. Craig, Heather J. Kulik, Xiaopeng Li, Jeremiah A. Johnson
Summary: Metal-organic cages/polyhedra (MOCs) are versatile building blocks for advanced polymer networks. This study introduces a novel polymer metal-organic cage (polyMOC) gel, which shows tunable stress-relaxation rates due to the different dynamics of metal-ligand exchange at the MOC level. Mixed-metal polyMOCs also exhibit relaxation behavior indicative of intrajunction cooperative interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Kelsie E. Wentz, Yunxin Yao, Ilia Kevlishvili, Tatiana B. Kouznetsova, Braden A. Mediavilla, Heather J. Kulik, Stephen L. Craig, Rebekka S. Klausen
Summary: Four unsaturated poly(carbooligosilane)s were synthesized by acyclic diene metathesis polycondensation of new oligosilane diene monomers. These polymers showed high trans internal olefin stereochemistry and molecular weights, and were further modified through postpolymerization epoxidation for single-molecule force spectroscopy studies. The single-chain elasticity of the polycarbooligosilanes decreased with increasing numbers of Si-Si bonds, as supported by quantum chemical calculations.
Article
Polymer Science
Patricia N. Johnson, Yunxin Yao, Xiao Huang, Ilia Kevlishvili, Stephen Schrettl, Christoph Weder, Heather J. Kulik, Stephen L. Craig
Summary: This study investigates the crosslinking of polymers through complexation with two different metal salts, and explores the impact of metal complexes on material properties. The material crosslinked with copper ions exhibits higher extensibility and fracture energy compared to the polymer crosslinked with iron. Computational results suggest that copper complexes are more labile and can more easily re-bind MeBip ligands.
Article
Polymer Science
Tetsu Ouchi, Wencong Wang, Brooke E. E. Silverstein, Jeremiah A. A. Johnson, Stephen L. L. Craig
Summary: The influence of strand length on deformation and tension in a polymer network was studied using mechanophore force probes. It was found that the critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but independent of the molecular length of the probes. The rate of decoloration during relaxation of the network was found to depend on the relaxing strain, indicating the effect of residual tension on the reversion reaction.
Article
Polymer Science
Haley K. Beech, Shu Wang, Devosmita Sen, Dechen Rota, Tatiana B. Kouznetsova, Akash Arora, Michael Rubinstein, Stephen L. Craig, Bradley D. Olsen
Summary: The study explores reactivity-guided fracture in polymer networks with different compositions of strands. It is found that increasing the content of less reactive strands has a negligible impact on the fracture energy until a certain threshold, after which the fracture energy sharply increases. The study also reveals that the loss of percolated network structure is a necessary criterion for crack propagation in polymer networks.
Article
Polymer Science
Zeyu Wang, Junpeng Wang
Summary: This study investigates the relationship between the structure and depolymerizability of graft polymers. Increasing side-chain length or grafting density is found to promote depolymerization. However, ball-milling-assisted depolymerization results in significant chain scissions and low monomer yield.
Article
Multidisciplinary Sciences
Yichen Yu, Robert T. O'Neill, Roman Boulatov, Ross A. Widenhoefer, Stephen L. Craig
Summary: This study reports a molecular scaffold in which the thermal isomerization rate of an alkene can be significantly increased by binding a metal ion to a remote receptor site. By constructing a mechanochemical model, the researchers quantitatively reproduced this acceleration effect and demonstrated the effectiveness of the formalism of force-coupled reactivity for the quantitative analysis of reaction kinetics at a molecular level.
NATURE COMMUNICATIONS
(2023)
