RSC Mechanochemistry最新文献

This work proposes the construction of chemical models based on the Gibbs composition triangle, which provides support for the proper interpretation of semiconductor synthesis under non-equilibrium processing, considering the pertinent variables of the system. It demonstrates how chemical models are constructed using experimental findings and theoretical insights and by incorporating data available in the literature. Then, an illustrative example is used to validate the construction, interpretation and application of a chemical model for obtaining PbTe via non-equilibrium process. This approach can be directly applied to forecast the formation of IV–VI and II–VI binary semiconductors, as well as the formation of ternary semiconductor solid solutions. However, it is exemplified—in this work—via the mechanochemical synthesis of PbTe. This work aims to construct a chemical model that maps the transformation from precursors to semiconductor material through the high-energy milling process.

The insertion of force-active molecules (mechanophores) with optical-switching properties into polymer chains has enabled the development of various mechanochromic polymers. Among them, colorimetric spiropyran (SP) has been the most extensively studied. However, the low extent of SP activation in bulk materials and the associated poor material mechano-sensitivity have hindered its broader applications. To address this challenge, we report the amplification of SP mechanophore activation in bulk materials through a tethering design. Two SP mechanophores were tethered through a long aliphatic linker, and the resulting molecule was employed as a crosslinker in silicone elastomer networks. This approach resulted in an enhancement of SP activation by more than twofold compared to its mono-SP counterpart. Additionally, we observed that increasing the number of added short linkers leads to greater tension constraints on these linkers, creating a self-reinforcing effect on mechanophore activation. We anticipate that this tethering strategy can be adapted to other non-scissile mechanophores in bulk studies.

Understanding the degradation mechanisms of perfluoropolyether (PFPE) lubricants is critical for the reliability of Heat-Assisted Magnetic Recording (HAMR) systems. In this study, we conducted ReaxFF reactive molecular dynamics simulations to investigate the role of diamond-like carbon (DLC) surfaces in PFPE degradation under confined shear and at elevated temperature. The results show that confined shear plays a more dominant role than temperature, with the decomposition rate constant increasing with shear velocity. PFPE degradation primarily initiates through C–OH bond rupture at end groups, typically after the OH group bonds to the DLC surfaces. Bonded PFPE molecules adopt bridge and loop conformations, both contributing comparably to degradation with increasing shear velocity, with bridges being slightly more sensitive to shear. Our analysis suggests that bridge dissociation is facilitated by shear-induced end-to-end stretching, while loop dissociation is driven by entanglement of conformationally flexible main chains. These insights provide guidance regarding further development of reliable HAMR systems.

Correction for ‘Mechanochemical synthesis of eucairite CuAgSe and investigation of physicochemical and transport properties’ by Dáša Drenčaková et al., RSC Mechanochem., 2025, 2, 246–255, https://doi.org/10.1039/D4MR00111G.

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We would like to take this opportunity to thank all of RSC Mechanochemistry’s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for RSC Mechanochemistry in 2024.

In this study, a mechanochemical adaptation of the McMurry coupling reaction was developed to synthesize ethylenes using Zn/TiCl₄/Et₃N as reagents. Leveraging solvent-free ball-milling conditions, the method achieved up to 97% yield across >23 substrates. The reaction was performed without inert gas protection in a Teflon milling jar and was found to be scalable and to accommodate various functional groups.

Plasmon-driven molecular jackhammers (MJHs) are a type of molecular machine that converts photon energy into mechanical energy. Upon insertion into lipid bilayers followed by near-infrared light activation, plasmon-driven MJH mechanically open cellular membranes through a process that is not inhibited by reactive oxygen species (ROS) inhibitors and does not induce thermal heating. The molecular mechanism by which the plasmon-driven MJH open and disassemble cellular membranes has not hitherto been established. Herein, we differentiate the mechanical mechanism in MJHs from the ROS-mediated chemical effects in photodynamic therapy or thermal effects in photothermal therapy. We further present a detailed molecular mechanism for the plasmon-driven MJH disassembly of lipid bilayers. The mechanical studies on plasmon-driven MJH disassembly processes on artificial lipid bilayers were done using ROS-unreactive saturated phytanoyl phospholipids. We were able to capture in real-time the lipid bilayer disassembly by MJHs using fluorescence confocal microscopy on saturated phospholipids in giant unilamellar vesicles.

Perfluorooctanoic acid (PFOA), recognized as a persistent organic pollutant, poses a serious threat to the environment and human health. Currently, mechanochemical degradation is considered a highly promising technology for the degradation of PFOA. This study systematically employs density functional theory (DFT) and the COGEF (COnstrained GEometry to simulate Forces) model to deeply investigate the impact of external forces on the degradation properties of PFOA molecules. Through quantum chemical calculations, we analyzed in detail the changes in the electronic structure, chemical reactivity, and decarboxylation reaction process of PFOA molecules under the influence of external forces. The results show that the application of external forces significantly alters the electronic density distribution of PFOA molecules, thereby enhancing their reactive activity, especially in terms of nucleophilicity and radical reactivity at the carboxylate end. Moreover, the application of external mechanical force reduces the Gibbs free energy change of the decarboxylation reaction, thereby making the reaction energetically favorable. This study not only theoretically elucidates the mechanism of mechanochemical degradation of PFOA, but also provides a basis for optimizing its mechanochemical degradation technology. In addition, this study also provides a systematic theoretical perspective for exploring the mechanisms of mechanochemical degradation.

Quininium aspirinate is mechanochemically prepared as a crystalline solid by liquid-assisted grinding, or as an amorphous phase (as determined by X-ray powder diffraction), by neat grinding or neat ball milling. Our previous work demonstrated using FT-IR spectroscopy that a mechanochemical reaction had occurred in the mechanically treated neat mixtures. Herein is reported that microcrystal electron diffraction (microED) afforded the discovery of two diffracting micron-size particles in the amorphous powder synthesized by manual grinding, among a majority of non-diffracting particles. Remarkably, microED data of one of them led to the known lattice parameters of quininium aspirinate. Furthermore, this so-called ‘X-ray amorphous’ phase quickly recrystallizes upon exposure to vapors of N,N-dimethylformamide, or hexane vapours (at a lower rate); but it remains amorphous for longer than 20 months when stored at ambient conditions in a closed container. The lattice parameters and the degrees of crystallinity of both recrystallized materials are identical within the experimental error. However, slightly more intense and better-resolved X-ray powder diffraction peaks are observed in the material recrystallized from N,N-dimethylformamide vapours than in the analogous phase recovered from hexane. As expected, Williamson–Hall graphs lead to a larger average crystalline domain size for the former solid. These results illustrate the use of microED for the investigation of structural features in amorphous phases, and the generic role of the solvent vapours in promoting their recrystallization.