Article
Engineering, Chemical
Sergey V. Sukhomlinov, Guido Kickelbick, Martin H. Mueser
Summary: Using molecular dynamics simulations based on density-functional theory, this study investigates stress and temperature-induced chemical reactions in systems containing triphosphoric acid and zinc phosphate molecules. The findings reveal that the nature of the products depends on the applied conditions, with isotropic and shear stress leading to different (zwitter-) ionic products. Thermal cycles also generate free ions, but these reactions are endothermic instead of exothermic like stress-induced transitions. The study also shows that before zinc atoms change their coordination under stress, proton mobility increases, and the hydrostatic stress required for this process is reduced with increasing shear. These findings have implications for understanding the impact of stress on material properties.
Article
Chemistry, Multidisciplinary
Rony Schwarz, Charles E. Diesendruck
Summary: Unstrained CC bond activation and functionalization have been achieved in homopolymers using mechanochemical methods, allowing the introduction of different end groups. This approach is versatile for various polymer chemistries and can be used to synthesize drug-polymer conjugates.
Article
Chemistry, Multidisciplinary
Daniel Eppel, Alpay Eryigit, Matthias Rudolph, Margit Brueckner, Frank Rominger, Abdullah M. Asiri, A. Stephen K. Hashmi
Summary: Starting from a [(C-MeO<^>N<^>C)AuCl] complex as precursor, a direct substitution by C,H-activation from sp-, sp(2)- or sp(3)-C,H-bonds under basic conditions in a planetary ball mill was achieved. This protocol provides an easy access to a highly valued complex class with extraordinary photophysical properties without the need for pre-functionalization of the starting materials or expensive transition metal catalysts, making it appealing for industrial purposes. The methodology was also successfully applied to chelate type [(tpy)AuCl2] complexes, demonstrating its versatility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Environmental Sciences
Xinze Geng, Yufeng Duan, Shilin Zhao, Jiwei Hu, Weimeng Zhao
Summary: Current approaches for Mechanochemical bromination (MCB) modified fly ash have been focusing on the efficiency and mechanism of mercury removal. Results showed that the activation mechanism of MCB mainly enhances the mercury removal ability of fly ash due to the generation of C-Br with activated carbon and M-Br on hematite.
Article
Chemistry, Multidisciplinary
Yudi Zhang, Zi Wang, Tatiana B. Kouznetsova, Ye Sha, Enhua Xu, Logan Shannahan, Muge Fermen-Coker, Yangju Lin, Chuanbing Tang, Stephen L. Craig
Summary: Metallocenes are attractive mechanophores due to their stability in the absence of force but reactivity under tension. Covalently bridging the cyclopentadienyl ligands of ferrocenes in a polymer alters their mechanochemical reactivity, leading to faster dissociation through a peeling mechanism. Distal attachments can restrict dissociation mechanism to peeling, increasing dissociation rate constant by several orders of magnitude.
Article
Chemistry, Multidisciplinary
Viktoria Nemethova, Dominika Kristofikova, Maria Meciarova, Radovan Sebesta
Summary: Asymmetric organocatalysis is a powerful method that provides access to valuable compounds while considering green chemistry principles. The use of solvent-free mechanochemical conditions in organocatalytic transformations brings additional benefits in terms of yields, selectivities, and overall sustainability. This overview discusses the development of mechanochemistry as a vehicle for asymmetric organocatalysis, highlighting the advantages and limitations of the reactions, as well as possibilities for target compound synthesis.
Article
Chemistry, Applied
Satenik Mkrtchyan, Michal Jakubczyk, Suneel Lanka, Muhammad Yar, Khurshid Ayub, Mohanad Shkoor, Michael Pittelkow, Viktor O. Iaroshenko
Summary: In this study, two mild, solvent-free mechanochemical coupling transformations of CF3 group with nitro compounds were successfully demonstrated, leading to amides or Schiff bases. Ytterbia was used as a catalyst to facilitate the process, which involves C-F bond activation and the use of Si-based reductants/oxygen scavengers. This work represents the first example of utilizing mechanical energy to promote the transformation of the inert CF3 group into other functionalities.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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
Chemistry, Multidisciplinary
Maria Carta, Leonarda Vugrin, Goran Miletic, Marina Juribasic Kulcsar, Pier Carlo Ricci, Ivan Halasz, Francesco Delogu
Summary: Mechanochemical transformations are commonly induced by mechanical processing in ball mills. This study reveals that even a single ball impact can cause trimerization in the powder of a square planar bis(dibenzoylmethanato)Ni-II coordination compound. Through systematic experiments and analysis using Raman spectroscopy, the transformation in the powder compact is quantitatively mapped, and bulk reaction kinetics are deduced from multiple individual impacts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Sehye Min, Beomsoon Park, Jantakan Nedsaengtip, Soon Hyeok Hong
Summary: The mechanochemical fluorination of unactivated C(sp(3))-H bonds has been achieved using N-fluorobenzenesulfonimide as both a precursor of the hydrogen-atom-transfer reagent and a bench-stable fluorine source. Control experiments have confirmed the essential role of mechanical energy in this reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Javier F. Reynes, Valerio Isoni, Felipe Garcia
Summary: Mechanochemistry provides an environmentally friendly platform for developing sustainable chemical processes. Researchers have shown numerous examples of beneficial mechanochemical applications at both laboratory and preparative scales. However, scaling up mechanochemical processes is still a nascent discipline and needs further exploration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)
Review
Environmental Sciences
Ewelina Grabias-Blicharz, Wojciech Franus
Summary: This review article focuses on the mechanochemistry of coal fly ash (CFA) and highlights the issue of fly ash from municipal solid waste (MSW). Fly ash is primarily used in the construction industry, chemical synthesis, and environmental engineering. However, the recycling rate for fly ash is low, and most of it ends up being landfilled. Mechanochemical processing of fly ash offers an eco-friendly, inexpensive, and efficient method for utilizing this abundant waste material.
SCIENCE OF THE TOTAL ENVIRONMENT
(2023)
Article
Chemistry, Multidisciplinary
Tomislav Stolar, Sasa Grubesic, Nikola Cindro, Ernest Mestrovic, Krunoslav Uzarevic, Jose G. Hernandez
Summary: Research shows that the combination of prebiotically plausible minerals and mechanochemical activation can oligomerize glycine at ambient temperature in the absence of water. Additionally, raising the reaction temperature contributes to increasing the degree of oligomerization, along with the formation of the undesired cyclic glycine dimer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Michael Walter, Dominic Linsler, Tobias Koenig, Chris Gaebert, Stefan Reinicke, Michael Moseler, Leonhard Mayrhofer
Summary: Controlled formation and breaking of weak chemical bonds is a versatile method for modifying material properties. Anthracene [4+4] cycloadducts can be formed by light and opened by external forces. Theoretical study reveals that rupture of the [4+4] inter-anthracene bonds dominates the transition barriers, while other bonds only come into play at extremely large forces. Experimental results on [4+4]-linked anthracene polymers support the reversible re-formation of [4+4] cycloaddition bonds after mechanochemical bond breaking due to applied shear stress.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Adam A. L. Michalchuk, Franziska Emmerling
Summary: Mechanochemical transformations offer environmentally friendly routes for synthesis, increasing reaction speed and selectivity. Time-resolved in situ (TRIS) approaches have provided new insights into mechanochemical reactions, revealing new features and advancing our understanding through the combination of complementary techniques.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ana M. Belenguer, Adam A. L. Michalchuk, Giulio I. Lampronti, Jeremy K. M. Sanders
Summary: Solid amines were shown to act as catalysts for disulfide-based dynamic combinatorial chemistry using ball mill grinding for the first time. The efficiency of different amines as catalysts varied, and the final mechanochemical equilibrium was affected by factors other than the catalyst choice during ball mill grinding.
Article
Chemistry, Multidisciplinary
Kevin Linberg, Franziska Emmerling, Adam A. L. Michalchuk
Summary: Time-resolved in situ X-ray diffraction has revolutionized the study of mechanochemical transformations, but using poly(methyl methacrylate) jars can significantly alter the kinetics of mechanochemical polymorphism, necessitating a better understanding of these effects.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Adam A. L. Michalchuk
Summary: This paper investigates the relationship between energy absorption and chemical transformations in mechanochemical reactions, focusing on the model system LiN3. The study reveals that mechanical impact can induce significant thermal excitation in crystalline LiN3, leading to marked changes in its electronic structure and chemical reactivity. The findings pave the way for an ab initio approach to studying elementary processes in mechanochemical reactions involving crystalline solids.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Paolo P. Mazzeo, Giulio Lampronti, Adam A. L. Michalchuk, Ana M. Belenguer, Alessia Bacchi, Franziska Emmerling
Summary: The debate on the mechanisms behind mechanochemical reactions via ball mill grinding is still ongoing. Accurately measuring the microstructural evolution and phase composition of materials under milling conditions is crucial for understanding the kinetics and driving forces of mechanochemical transformations. Investigating standard samples helps determine the instrumental contribution to X-ray powder diffraction peak broadening.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Kevin Linberg, Bettina Roder, Dominik Al-Sabbagh, Franziska Emmerling, Adam A. L. Michalchuk
Summary: Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. Little is known about controlling solid forms through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system, this study demonstrates that mechanochemistry can induce polymorphism in molecular solids under conditions different from conventional thermal transition points.
FARADAY DISCUSSIONS
(2023)
Editorial Material
Chemistry, Physical
Alexander Angerhofer, Thomas Auvray, Viktor Balema, Matej Balaz, James D. Batteas, Richard G. Blair, Elena Boldyreva, Carsten Bolm, Lars Borchardt, Tristan H. Borchers, Adam B. Braunschweig, Duncan L. Browne, Robert W. Carpick, Maria Ciaccia, Stephen Craig, Franziska Emmerling, Michael Ferguson, Cecilia Fiore, Tomislav Friscic, Sven Gratz, Ivan Halasz, Ehsan Hamzehpoor, Hajime Ito, Stuart James, Jeung Gon Kim, Frederic Lamaty, Giulio Lampronti, Danielle Laurencin, Jamie Leitch, Erli Lu, Stipe Lukin, James Mack, Lucia Maini, Ashlie Martini, Paolo P. Mazzeo, Adam A. L. Michalchuk, Sebastien Mittelette, Sharmarke Mohamed, Audrey Moores, Aldo de Jesus Mortera-Carbonell, Karthik Nagapudi, Allan Niidu, Francesco Puccetti, Martin Stahorsky, Leonarda Vugrin
FARADAY DISCUSSIONS
(2023)
Article
Materials Science, Multidisciplinary
Jada Ravi, Torvid Feiler, Amit Mondal, Adam A. L. Michalchuk, C. Malla Reddy, Biswajit Bhattacharya, Franziska Emmerling, Rajadurai Chandrasekar
Summary: Fluorescent plastically bendable crystals are promising for fabricating photonic integrated circuits due to their optical attributes and mechanical compliance. These crystals can act as active and passive waveguides in various geometries, allowing for input-selective and direction-specific signal transduction.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Physical
Imogen L. Christopher, Colin R. Pulham, Adam A. L. Michalchuk, Carole A. Morrison
Summary: Impact-sensitivity predictions based on the vibrational up-pumping model reveal a strong dependence on polymorphs for RDX. One high-pressure form formed during shock-wave experiments is notably more susceptible to mechanical initiation. The variations in impact sensitivity can be attributed to vibrational mode hardening and differences in the molecular conformation of RDX in different polymorphs.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Ana M. Belenguer, Adam A. L. Michalchuk
Summary: A potentially transformative route for purifying enantiomers using a simple ball milling procedure has been discovered in this study.
Article
Chemistry, Multidisciplinary
Kevin Linberg, Paulina Szymoniak, Andreas Schoenhals, Franziska Emmerling, Adam A. L. Michalchuk
Summary: We demonstrate that mechanochemically driven polymorphic transformations can have significantly long induction periods, which can be adjusted by changing the energy of ball milling. The design and interpretation of ball milling experiments need to consider the unexpected kinetics arising from unique energetic phenomena in the solid state. Through detailed thermal analysis and DFT simulations, we find that these long induction periods are associated with mechanical activation processes. Additionally, we show that pre-activation of reagents can also affect the length of induction periods. This discovery opens up a new dimension for controlling polymorphic transformations in organic crystals, and we expect mechanical activation to have broader implications in organic solid-state mechanochemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Torvid Feiler, Nobuhiro Yasuda, Adam A. L. Michalchuk, Franziska Emmerling, Biswajit Bhattacharya
Summary: Through a combination of μ-focus synchrotron X-ray diffraction and ab initio simulation, we have investigated for the first time the atomistic origin of elastic bending in a single-component organic crystal, which exhibits fascinating behavior with potential for developing advanced technologies.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Biswajit Bhattacharya, Adam A. L. Michalchuk, Dorothee Silbernagl, Nobuhiro Yasuda, Torvid Feiler, Heinz Sturm, Franziska Emmerling
Summary: This study presents a detailed mechanistic study on the elasto-plastic flexibility in molecular solid, and proposes an atomistic origin for this mechanical behavior. The findings suggest a close link between elastic and plastic bending, and bridge the gap between contested mechanisms, proposing its applicability as a general mechanism for elastic and plastic bending in organic molecular crystals.
Article
Chemistry, Multidisciplinary
Ana M. Belenguer, Giulio I. Lampronti, Adam A. L. Michalchuk, Franziska Emmerling, Jeremy K. M. Sanders
Summary: In this study, we demonstrate the reversible, selective, and quantitative transformation between three crystalline polymorphs using a disulfide system and ball mill grinding. We discovered a previously unknown polymorph and found that a contaminant as low as 1.5% mol mol(-1) acting as a template is necessary for the transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different grinding conditions and by surface interactions with small amounts of added solvent.
Article
Chemistry, Physical
Ekaterina K. Kosareva, Radmir Gainutdinov, Adam A. L. Michalchuk, Ivan Ananyev, Nikita Muravyev
Summary: Using atomic force microscopy (AFM), the microscopic initiation behavior of four prototypical energetic materials was studied. The softest materials were found to behave dynamically on the surface in response to mechanical deformation. Increased humidity was found to reduce the rate of surface rearrangement, potentially explaining the desensitization of energetic materials when wetted. Surface dynamics were found to influence a material's ability to dissipate excess energy, acting as a buffer towards mechanical initiation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
