Even under low external force,a few macromolecules of a polymer have to be much more highly stressed and fractured first due to the inherent heterogeneous microstructure.When the materials keep on working under loadin...Even under low external force,a few macromolecules of a polymer have to be much more highly stressed and fractured first due to the inherent heterogeneous microstructure.When the materials keep on working under loading,as is often the case,the minor damages would add up,endangering the safety of use.Here we show an innovative solution based on mechanochemically initiated reversible cascading variation of metal-ligand complexations.Upon loading,crosslinking density of the proof-of-concept metallopolymer networks autonomously increases,and recovers after unloading.Meanwhile,the stress-induced tiny fracture precursors are blocked to grow and then restored.The entire processes reversibly proceed free of manual intervention and catalyst.The proposed molecular-level internal equilibrium prevention mechanisms fundamentally enhance durability of polymers in service.展开更多
Manipulating the structure self-reconstruction of transition metal sulfide-based(pre)catalysts during the oxygen evolution reaction(OER) process is of great interest for developing cost-effective OER catalysts,which r...Manipulating the structure self-reconstruction of transition metal sulfide-based(pre)catalysts during the oxygen evolution reaction(OER) process is of great interest for developing cost-effective OER catalysts,which remains a central challenge. Here we realize a deep structure self-reconstruction of natural chalcopyrite to unlock its OER performance via mechanochemical activation. Compared with the manually milled counterpart(CuFeS_(2)-HM), the mechanically milled catalyst(CuFeS_(2)-BM) with a reduced crystallinity exhibits a 7.11 times higher OER activity at 1.53 V vs. RHE. In addition, the CuFeS_(2)-BM requires a low overpotential of 243 mV for generating 10 mA cm^(-2) and exhibits good stability over 24 h. Further investigations suggest that the excellent OER performance of CuFeS_(2)-BM mainly originates from the decreased crystallinity induced the in situ deep structure self-reconstruction of the originally sulfides into the electroactive and stable metal(oxy)hydroxide phase(e.g., a-Fe OOH) via S etching under OER conditions. This study demonstrates that regulating the crystallinity of catalysts is a promising design strategy for developing highly efficient OER catalysts via managing the structure self-reconstruction process, which can be further extended to the design of efficient catalysts for other advanced energy conversion devices. In addition, this study unveils the great potentials of engineering abundant natural minerals as cost-effective catalysts for diverse applications.展开更多
The vigorous development of two-dimensional(2D)materials brings about numerous opportunities for lithiumion batteries(LIBs)due to their unique 2D layered structure,large specific surface area,outstanding mechanical an...The vigorous development of two-dimensional(2D)materials brings about numerous opportunities for lithiumion batteries(LIBs)due to their unique 2D layered structure,large specific surface area,outstanding mechanical and flexibility properties,etc.Modern technologies for production of 2D materials include but are not limited to mechanochemical(solid-state/liquid-phase)exfoliation,the solvothermal method and chemical vapor deposition.In this review,strategies leading to the production of 2D materials via solid-state mechanochemistry featuring traditional high energy ball-milling and Sichuan University patented pan-milling are highlighted.The mechanism involving exfoliation,edge selective carbon radical generation of the 2D materials is delineated and this is followed by detailed discussion on representative mechanochemical techniques for tailored and improved lithium-ion storage performance.In the light of the advantages of the solid-state mechanochemical method,there is great promise for the commercialization of 2D materials for the next-generation high performance LIBs.展开更多
The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directl...The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directly synthesized by reactive ball milling(RBM) of Li3N and Mg powder mixture with a molar ratio of 2:1 under hydrogen pressure of 9 MPa.More than 8.8 wt%hydrogen was absorbed during the RBM process.The phases and structural evolution during the in situ hydrogenation process were analyzed by means of in situ solidgas absorption and ex situ X-ray diffraction(XRD) measurements.It is determined that the hydrogenation can be divided into two steps,leading to mainly the formation of a lithium magnesium imide phase and a poorly crystallized amide phase,respectively.The H-cycling properties of the as-milled composite were determined by temperature-programmed dehydrogenation(TPD) method in a closed system.The onset dehydrogenation temperature was detected at 125℃,and it can reversibly desorb 3.1 wt% hydrogen under a hydrogen back pressure of 0.2 MPa.The structural evolution during dehydrogenation was further investigated by in situ XRD measurement.It is found that Mg(NH_(2))_(2)phase disappears at about 200 ℃,and Li_(2)Mg_(2)N_(3)H_(3),LiNH_(2),and Li_(2)MgN_(2)H_(2)phases coexist at even 300 ℃,revealing that the dehydrogenation process is step-wised and only partial hydrogen can be desorbed.展开更多
Metastasis is the leading cause of death in people with cancer. In the series of steps comprising metastasis process, mechanochemistry plays crucial roles. In this review, we introduced the mechanical factors in cance...Metastasis is the leading cause of death in people with cancer. In the series of steps comprising metastasis process, mechanochemistry plays crucial roles. In this review, we introduced the mechanical factors in cancer cell metastasis, intracellular mechanical sensors and methods for measuring the mechanical forces of tumor cells. The recent researches on the contribution of mechanochemistry to metastasis and future perspectives were summarized.展开更多
Integrins are a large family of adhesion molecules broadly expressed on the surface of a wide variety of cells as heterodimers.Binding of integrins to ligands provides anchorage and signals for the cell,making them pr...Integrins are a large family of adhesion molecules broadly expressed on the surface of a wide variety of cells as heterodimers.Binding of integrins to ligands provides anchorage and signals for the cell,making them prime candidates for mechanosensing molecules.To elucidate how force regulates integrin/ligand dissociation,we used molecular mechanics experiments展开更多
With the progress of science and technology,China has gradually attached importance to research and exploration in chemistry,and the achievements in exploring mechanochemistry are also quite significant.Therefore,it i...With the progress of science and technology,China has gradually attached importance to research and exploration in chemistry,and the achievements in exploring mechanochemistry are also quite significant.Therefore,it is necessary to study and explore mechanochemistry.This article mainly discusses the application of mechanochemistry in powder and some silicate materials,as well as in special ceramics,and provides a brief introduction to provide reference for relevant researchers.展开更多
Peri-annulation is recognized as an influential structural motif in accessing functional molecular materials.However,efficient synthetic access to peri-annulated structures remains challenging.Herein,we show that mech...Peri-annulation is recognized as an influential structural motif in accessing functional molecular materials.However,efficient synthetic access to peri-annulated structures remains challenging.Herein,we show that mechanochemistry is a valuable synthetic tool to achieve this goal.It is comparatively better than activation through microwave irradiation and conventional solution-phase reactions.The synthesized materials are molecularly curved nanographenes containing sulfur and selenium atoms.The curvature comes from the use of corannulene as the central building block,upon which the benzothiophene or benzoselenophene are peri-annulated through the palladium-catalyzed direct arylation reactions.Peri-annulation endows the nanographene structures with better optical properties as compared to other annulation chemistries.展开更多
Mechanically interlocked molecules(MIMs)are prototypical molecular machines with parts that enable controlled,large-amplitude movement with one component positioned relative to another.Incorporating MIMs into polymeri...Mechanically interlocked molecules(MIMs)are prototypical molecular machines with parts that enable controlled,large-amplitude movement with one component positioned relative to another.Incorporating MIMs into polymeric matrices is promising for the designing of functional materials with unprecedented properties.However,the central issue is the challenges involved with establishing the mechanistic linkage between the single-molecule and the bulk material.Herein,we explore the mechanochemical properties and energetic details of a linear poly[2]catenane with strong intercomponent hydrogen bonding(IHB)revealed by single-molecule force spectroscopy.Our results showed that the individual linear poly[2]catenane chain exhibited typical sawtooth pattern,corresponding to the reversible unlocking and relocking transitions under external force or upon stimulations to dissociate or re-form the strong IHB.Furthermore,when a poly[2]catenane-based polymer gel was prepared using a thiol-ene click reaction between thiol-ended poly[2]catenane and a low-molecule-weight cross-linker,the resultant gel showed excellent mechanical adaptability and dynamic properties,which correlated well with the molecular-level observations.The unique poly[2]catenane structure also contributed to the gel formation with an extraordinary IHB-mediated swelling behavior and shape memory property.Thus our present results demonstrate the functioning of bulk material in a linear tandem manner from the behavior of a single molecule,a finding which should be applicable to other systems with versatile properties and promising applications.展开更多
A way of directly repairing spent lithium-ion battery cathode materials is needed in response to environmental pollution and resource depletion.In this work,we report a green repair method involving coupled mechano-ch...A way of directly repairing spent lithium-ion battery cathode materials is needed in response to environmental pollution and resource depletion.In this work,we report a green repair method involving coupled mechano-chemistry and solid-state reactions for spent lithium-ion batteries.During the ball-milling repair process,an added manganese source enters into the degraded LiMn_(2)O_(4)(LMO)crystal structure in order to fill the Mn vacancies formed by Mn deficiency due to the Jahn–Teller effect,thereby repairing the LMO's chemical composition.An added carbon source acts not only as a lubricant but also as a conductor to improve the material's electrical conductivity.Meanwhile,mechanical force reduces the crystal size of the LMO particles,increasing the amount of active sites for electrochemical reactions.Jahn–Teller distortion is successfully suppressed by cation disorder in the LMO material.The cycling stability and rate performance of the repaired cathode material are thereby greatly improved,with the discharge specific capacity being more than twice that of commercial LMO.The proposed solid-state mechanochemical in situ repair process,which is safe for the environment and simple to use,may be extended to the repair of other waste materials without consuming highly acidic or alkaline chemical reagents.展开更多
The serendipitous discovery of dumb-bell-shaped C_(120) under high-speed vibration milling conditions is described.The mechanochemical protocol has been employed to synthesize the He-,H_(2)-or H_(2)O-encapsualted C_(1...The serendipitous discovery of dumb-bell-shaped C_(120) under high-speed vibration milling conditions is described.The mechanochemical protocol has been employed to synthesize the He-,H_(2)-or H_(2)O-encapsualted C_(120),the cross-dimer C_(130),trimer C_(180),bridged C_(60) dimers as well as products from many other reactions of fullerenes,carbon nanotubes and graphenes.Mechanochemistry extended to various reactions of non-fullerene molecules is briefly discussed.展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have attracted phenomenal attention because of their superior optoelectronic performances.The combination of their structural tunability and material stabi...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have attracted phenomenal attention because of their superior optoelectronic performances.The combination of their structural tunability and material stability offers an unprecedented opportunity to engineer materials with unique functionalities.However,developing a rapid and effective design method for introducing luminescence into dielectric switch and realizing controllable regulation has been an enormous challenge.Thus far,materials with tunable optoelectronic multichannel response have not been successfully implemented.In this study,we successfully developed a facile and effective mechanochemical method for realizing the integration and regulation of luminescence and dielectric switch in 2D perovskites,which is unprecedented for the design of dielectric switching materials.The mild external mechanical stimuli enabled the formation of Mn ion-doped 2D hybrid perovskites(Cyclopropylammonium)2Pb1-xMnxBr4 with excellent dielectric switch and rapidly controllable luminescence of highly efficient blue light,white light,pink light,and orange light.This work will provide a new perspective on the rapid and effective design of multifunctional materials and can inspire the future development of low-cost and high-efficiency electronics.展开更多
Comprehensive Summary Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years,as the mechanochemical generation of reactive species has a great potential in developin...Comprehensive Summary Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years,as the mechanochemical generation of reactive species has a great potential in developing different polymeric materials for various purposes,such as stress detection,self-healing,self-strengthening,controllable degradation and release of small molecules.In this review,we first discuss the recent progress on polymer mechanochemistry of the reactive species that are generated from the mechanochemical reactions of mechanophores.Five types of reactive species,including radical,zwitterion,ionic,carbene and neutral intermediates,and their applications were reviewed in detail.Since mechanochemical reactions are sensitive to the mechanophore structure and polymer framework,we then discuss how mechanophore isomerism,polymer structure,polymer attachment point,and polymer architecture influence the mechanophore activation.At last,we provide our perspectives on the polymer mechanochemistry of reactivespecies.展开更多
Polymer mechanochemistry has rapidly evolved since the mid-20o0s.Recent advancements highlight the development of mechanophore platforms for the controlled release of bioactive payloads and the exploration of biocompa...Polymer mechanochemistry has rapidly evolved since the mid-20o0s.Recent advancements highlight the development of mechanophore platforms for the controlled release of bioactive payloads and the exploration of biocompatible activation strategies.These platforms,ranging from furan-maleimide Diels-Alder adducts to disulfide motifs withβ-carbonate linkages,demonstrate promising prospects in targeted drug delivery.Additionally,supramolecular assemblies and free radical-generating mechanophores present innovative avenues for potential therapeutic applications.Biocompatible activation methods,notably high-intensity and/or low-intensity focused ultrasound,hold potential for in vivo applications.However,challenges persist in comprehending the fundamental physics of ultrasound and its utilization for activation.展开更多
The field of polymer mechanochemistry has been revolutionized by implementing force-responsive functional groups—mechanophores.The rational design of mechanophores enables the controlled use of force to achieve const...The field of polymer mechanochemistry has been revolutionized by implementing force-responsive functional groups—mechanophores.The rational design of mechanophores enables the controlled use of force to achieve constructive molecular reactivity and material responses.While a variety of mechanophores have been developed,this Mini Review focuses on cyclobutane,which has brought valuable insights into molecular reactivity and dynamics as well as innovations in materials.We discuss its reactivity and mechanism,dynamics and stereoselectivity,as well as impacts on material properties.展开更多
Mechanochemistry has been recognized as an efficient and sustainable methodology to provide a unique driven force and reaction environments under ambient and neat conditions for the construction of functionalized mate...Mechanochemistry has been recognized as an efficient and sustainable methodology to provide a unique driven force and reaction environments under ambient and neat conditions for the construction of functionalized materials possessing promising properties.Among them,highly porous conjugated scaffolds with attractive electronic conductivities and high surface areas are one of the representative categories exhibiting diverse taskspecific applications,especially in electrochemical energy storage.In recent years,the mechanochemistry-driven procedures have been deployed to construct conjugated scaffolds with engineered structures and properties leveraging the tunability in chemical structures of building blocks and polymerization capability of diverse catalysts.Therefore,a thorough review of related works is required to gain an in-depth understanding of the mechanochemical synthesis procedure and property-performance relationship of the as-produced conjugated scaffolds.Herein,the mechanochemistry-driven construction of conjugated porous networks(CPNs),the carbon-based materials(e.g.,graphite and graphyne),and carbon supported single atom catalysts(CS-SACs)are discussed and summarized.The electrochemical performance of the afforded conductive scaffolds as electrode materials in supercapacitors and alkali-ion batteries is elucidated.Finally,the challenges and potential opportunities related to the construction of conjugated scaffolds driven by mechanochemistry are also discussed and concluded.展开更多
Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of ...Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of CIP in water.The influence of various additives(CaO,Fe_(2)O_(3),SiO_(2),Al,and Fe)on CIP degradation efficiency was investigated.Additionally,six types of composite additives(Fe-CaO,Fe-Fe_(2)O_(3),Fe-SiO_(2),Fe-Al,Al-SiO_(2),and Al-CaO)were explored,with the composite of 20%Fe and 80%SiO_(2) exhibiting notable performance.The impacts of additive content,pH value,and co-existing ions on CIP degradation efficiency were investigated.Furthermore,the effectiveness of MCT in degrading other medical pollutants(norfloxacin,ofloxacin,and enrofloxacin)was verified.The transformations and changes in the crystal structure,oxidation state,microstructure,and morphology of the Fe-SiO_(2) composite additive were characterized using X-ray diffraction,X-ray photoelectron spectroscopy,and scanning electron microscopy techniques.This study proposed a sigmoid trend kinetic model(the Delogu model)that better elucidates the MCT process.Three plausible degradation pathways were discussed based on intermediate substance identification and pertinent literature.This study not only establishes a pathway for the facile degradation of CIP pollutants through MCT but also contributes to advancements in wastewater treatment methodologies.展开更多
Traditional chemical processes often generate substantial waste,leading to significant pollution of water,air,and soil.Developing ecofriendly chemical methods is crucial for economic and environmental sustainability.M...Traditional chemical processes often generate substantial waste,leading to significant pollution of water,air,and soil.Developing ecofriendly chemical methods is crucial for economic and environmental sustainability.Mechano-driven chemistry,with its potential for material recyclability and minimal byproducts,is well-aligned with green chemistry principles.Despite its origins over 2000 years ago and nearly 200years of scientific investigation,mechano-driven chemistry has not been widely implemented in practice.This is likely due to a lack of comprehensive understanding and the complex physical effects of mechanical forces,which challenge reaction efficiency and scalability.This review summarizes the historical development of mechano-driven chemistry and discusses its progress across various physical mechanisms,including mechanochemistry,tribochemistry,piezochemistry,and contact electrification(CE)chemistry.CE-induced chemical reactions,involving ion transfer,electron transfer,and radical generation,are detailed,emphasizing the dominant role of radicals initiated by electron transfer and the influence of ion transfer through electrical double layer(EDL)formation.Advancing efficient,eco-friendly,and controllable green chemical technologies can reduce reliance on traditional energy sources(such as electricity and heat)and toxic chemical reagents,fostering innovation in material synthesis,catalytic technologies,and establishing a new paradigm for broader chemical applications.展开更多
Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a n...Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a new way to access degradable polyethylene materials with a low content of in-chain ester units via mechanochemical backbone editing.Initially,ester groups are incorporated as side groups through catalytic copolymerization of ethylene with a cyclobutene-fused lactone monomer(CBL),yielding polyethylene materials with high molecular weights and adjustable thermomechanical properties.Subsequent solid-state ball-milling treatment selectively introduces side-chain ester groups into the main chain of the polyethylene materials via force-induced cycloreversion of the cyclobutane units.Under acidic conditions,hydrolysis of the resultant polyethylene materials with in-chain ester units facilitates further degradation into oligomers.展开更多
Ultrasound(US),as an efficient and non-invasive trigger,has been extensively explored in drug delivery and has many advantages,such as deep penetration,low invasiveness,and high biochemical precision.These advantages ...Ultrasound(US),as an efficient and non-invasive trigger,has been extensively explored in drug delivery and has many advantages,such as deep penetration,low invasiveness,and high biochemical precision.These advantages demonstrate the immense clinical potential of ultrasound.This study aimed to provide a comprehensive analysis of ultrasound-induced shear forces that exhibit covalent/non-covalent bond cleavage and reactive oxygen species(ROS)-mediated remote control of nanocarriers.By doing so,we can gain a deeper understanding of the vital role,significant advantages,and untapped potential of ultrasound in molecular-level drug activation.Furthermore,clinical translation faces challenges such as the low drug-loading capacity of polymer chains,frequency compatibility between ultrasound parameters and biological systems,insufficient ROS generation,and biocompatibility of current sonosensitizers.To solve these problems,ultrasound mechanochemistry has emerged as a versatile therapeutic modality to promote the development of medical treatments.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52033011,51773229,51873235).
文摘Even under low external force,a few macromolecules of a polymer have to be much more highly stressed and fractured first due to the inherent heterogeneous microstructure.When the materials keep on working under loading,as is often the case,the minor damages would add up,endangering the safety of use.Here we show an innovative solution based on mechanochemically initiated reversible cascading variation of metal-ligand complexations.Upon loading,crosslinking density of the proof-of-concept metallopolymer networks autonomously increases,and recovers after unloading.Meanwhile,the stress-induced tiny fracture precursors are blocked to grow and then restored.The entire processes reversibly proceed free of manual intervention and catalyst.The proposed molecular-level internal equilibrium prevention mechanisms fundamentally enhance durability of polymers in service.
基金financially supported by the National Natural Science Foundation of China (21777045, 61875119)the Australian Research Council (ARC) Future Fellowship (FT160100195)+3 种基金the Foundation of Shenzhen ScienceTechnology and Innovation Commission (SSTIC)(2020231312, JCYJ20190809144409460)the Natural Science Funds for Distinguished Young Scholar of Guangdong Province,China (2020B151502094)the China Scholarship Council (CSC) for the scholarship support。
文摘Manipulating the structure self-reconstruction of transition metal sulfide-based(pre)catalysts during the oxygen evolution reaction(OER) process is of great interest for developing cost-effective OER catalysts,which remains a central challenge. Here we realize a deep structure self-reconstruction of natural chalcopyrite to unlock its OER performance via mechanochemical activation. Compared with the manually milled counterpart(CuFeS_(2)-HM), the mechanically milled catalyst(CuFeS_(2)-BM) with a reduced crystallinity exhibits a 7.11 times higher OER activity at 1.53 V vs. RHE. In addition, the CuFeS_(2)-BM requires a low overpotential of 243 mV for generating 10 mA cm^(-2) and exhibits good stability over 24 h. Further investigations suggest that the excellent OER performance of CuFeS_(2)-BM mainly originates from the decreased crystallinity induced the in situ deep structure self-reconstruction of the originally sulfides into the electroactive and stable metal(oxy)hydroxide phase(e.g., a-Fe OOH) via S etching under OER conditions. This study demonstrates that regulating the crystallinity of catalysts is a promising design strategy for developing highly efficient OER catalysts via managing the structure self-reconstruction process, which can be further extended to the design of efficient catalysts for other advanced energy conversion devices. In addition, this study unveils the great potentials of engineering abundant natural minerals as cost-effective catalysts for diverse applications.
基金financially supported by the National Natural Science Foundation of China(No.51933007,51673123)the National Key R&D Program of China(No.2017YFE0111500)the Program for Featured Directions of Engineering Multidisciplines of Sichuan University(No.2020SCUNG203)。
文摘The vigorous development of two-dimensional(2D)materials brings about numerous opportunities for lithiumion batteries(LIBs)due to their unique 2D layered structure,large specific surface area,outstanding mechanical and flexibility properties,etc.Modern technologies for production of 2D materials include but are not limited to mechanochemical(solid-state/liquid-phase)exfoliation,the solvothermal method and chemical vapor deposition.In this review,strategies leading to the production of 2D materials via solid-state mechanochemistry featuring traditional high energy ball-milling and Sichuan University patented pan-milling are highlighted.The mechanism involving exfoliation,edge selective carbon radical generation of the 2D materials is delineated and this is followed by detailed discussion on representative mechanochemical techniques for tailored and improved lithium-ion storage performance.In the light of the advantages of the solid-state mechanochemical method,there is great promise for the commercialization of 2D materials for the next-generation high performance LIBs.
基金financially supported by the Beijing Science and Technology Program(No.D141100002014002)the European COST Action(No.MP1103)
文摘The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directly synthesized by reactive ball milling(RBM) of Li3N and Mg powder mixture with a molar ratio of 2:1 under hydrogen pressure of 9 MPa.More than 8.8 wt%hydrogen was absorbed during the RBM process.The phases and structural evolution during the in situ hydrogenation process were analyzed by means of in situ solidgas absorption and ex situ X-ray diffraction(XRD) measurements.It is determined that the hydrogenation can be divided into two steps,leading to mainly the formation of a lithium magnesium imide phase and a poorly crystallized amide phase,respectively.The H-cycling properties of the as-milled composite were determined by temperature-programmed dehydrogenation(TPD) method in a closed system.The onset dehydrogenation temperature was detected at 125℃,and it can reversibly desorb 3.1 wt% hydrogen under a hydrogen back pressure of 0.2 MPa.The structural evolution during dehydrogenation was further investigated by in situ XRD measurement.It is found that Mg(NH_(2))_(2)phase disappears at about 200 ℃,and Li_(2)Mg_(2)N_(3)H_(3),LiNH_(2),and Li_(2)MgN_(2)H_(2)phases coexist at even 300 ℃,revealing that the dehydrogenation process is step-wised and only partial hydrogen can be desorbed.
基金supported by grants from the National Natural Science Foundation of China (Nos. 21778055, 21573250, 61501039)Beijing Natural Science Foundation (Nos. L172048, 2162017)+2 种基金Beijing Municipal Education Commission (No. KM201710015005)the Chinese Academy of Sciences (Nos. QYZDB-SSW-SLH024, YZ201424)the Program for Young Outstanding Scientists of ICCAS (No. Y41Z011)
文摘Metastasis is the leading cause of death in people with cancer. In the series of steps comprising metastasis process, mechanochemistry plays crucial roles. In this review, we introduced the mechanical factors in cancer cell metastasis, intracellular mechanical sensors and methods for measuring the mechanical forces of tumor cells. The recent researches on the contribution of mechanochemistry to metastasis and future perspectives were summarized.
基金supported by US National Institutes of Health grant R01 AI44902by a Scientist Development Grant 0735224Na Pre-doctoral Fellowship from the American Heart Association
文摘Integrins are a large family of adhesion molecules broadly expressed on the surface of a wide variety of cells as heterodimers.Binding of integrins to ligands provides anchorage and signals for the cell,making them prime candidates for mechanosensing molecules.To elucidate how force regulates integrin/ligand dissociation,we used molecular mechanics experiments
文摘With the progress of science and technology,China has gradually attached importance to research and exploration in chemistry,and the achievements in exploring mechanochemistry are also quite significant.Therefore,it is necessary to study and explore mechanochemistry.This article mainly discusses the application of mechanochemistry in powder and some silicate materials,as well as in special ceramics,and provides a brief introduction to provide reference for relevant researchers.
基金supported by the Ministry of Education Singapore under the AcRF Tier 2(MOE-T2EP10221-0002)the Ministry of Research,Innovation and Digitalization under Romania's National Recovery and Resilience Plan PNRR-Ⅲ-C9-2022-I8 Program with Project code 167/15.11.22。
文摘Peri-annulation is recognized as an influential structural motif in accessing functional molecular materials.However,efficient synthetic access to peri-annulated structures remains challenging.Herein,we show that mechanochemistry is a valuable synthetic tool to achieve this goal.It is comparatively better than activation through microwave irradiation and conventional solution-phase reactions.The synthesized materials are molecularly curved nanographenes containing sulfur and selenium atoms.The curvature comes from the use of corannulene as the central building block,upon which the benzothiophene or benzoselenophene are peri-annulated through the palladium-catalyzed direct arylation reactions.Peri-annulation endows the nanographene structures with better optical properties as compared to other annulation chemistries.
基金We are grateful to acknowledge the National Basic Research Program(2013CB834502,2013CB834503)the National Natural Science Foundation of China(91527301,21434005,21525418,51773179,11302190,and 11432012)the Open Project of State Key Laboratory of Supramolecular Structure and Materials(sklssm201611)for financial support.
文摘Mechanically interlocked molecules(MIMs)are prototypical molecular machines with parts that enable controlled,large-amplitude movement with one component positioned relative to another.Incorporating MIMs into polymeric matrices is promising for the designing of functional materials with unprecedented properties.However,the central issue is the challenges involved with establishing the mechanistic linkage between the single-molecule and the bulk material.Herein,we explore the mechanochemical properties and energetic details of a linear poly[2]catenane with strong intercomponent hydrogen bonding(IHB)revealed by single-molecule force spectroscopy.Our results showed that the individual linear poly[2]catenane chain exhibited typical sawtooth pattern,corresponding to the reversible unlocking and relocking transitions under external force or upon stimulations to dissociate or re-form the strong IHB.Furthermore,when a poly[2]catenane-based polymer gel was prepared using a thiol-ene click reaction between thiol-ended poly[2]catenane and a low-molecule-weight cross-linker,the resultant gel showed excellent mechanical adaptability and dynamic properties,which correlated well with the molecular-level observations.The unique poly[2]catenane structure also contributed to the gel formation with an extraordinary IHB-mediated swelling behavior and shape memory property.Thus our present results demonstrate the functioning of bulk material in a linear tandem manner from the behavior of a single molecule,a finding which should be applicable to other systems with versatile properties and promising applications.
基金This work was supported by the National Natural Science Foundation of China(51972030,52102207)Beijing Natural Science Foundation(Z220021)+2 种基金the National Key R&D Program of China(2021YFB3800300)the Joint Funds of the National Natural Science Foundation of China(U2130204)Beijing Outstanding Young Sci-entists Program(BJJWZYJH01201910007023).
文摘A way of directly repairing spent lithium-ion battery cathode materials is needed in response to environmental pollution and resource depletion.In this work,we report a green repair method involving coupled mechano-chemistry and solid-state reactions for spent lithium-ion batteries.During the ball-milling repair process,an added manganese source enters into the degraded LiMn_(2)O_(4)(LMO)crystal structure in order to fill the Mn vacancies formed by Mn deficiency due to the Jahn–Teller effect,thereby repairing the LMO's chemical composition.An added carbon source acts not only as a lubricant but also as a conductor to improve the material's electrical conductivity.Meanwhile,mechanical force reduces the crystal size of the LMO particles,increasing the amount of active sites for electrochemical reactions.Jahn–Teller distortion is successfully suppressed by cation disorder in the LMO material.The cycling stability and rate performance of the repaired cathode material are thereby greatly improved,with the discharge specific capacity being more than twice that of commercial LMO.The proposed solid-state mechanochemical in situ repair process,which is safe for the environment and simple to use,may be extended to the repair of other waste materials without consuming highly acidic or alkaline chemical reagents.
基金The continuous financial support from the Chinese Academy of Sciences and National Science Foundation of China(Nos.20125205,20772117,21132007,21372211)for our mechanochemistry study is acknowledged.
文摘The serendipitous discovery of dumb-bell-shaped C_(120) under high-speed vibration milling conditions is described.The mechanochemical protocol has been employed to synthesize the He-,H_(2)-or H_(2)O-encapsualted C_(120),the cross-dimer C_(130),trimer C_(180),bridged C_(60) dimers as well as products from many other reactions of fullerenes,carbon nanotubes and graphenes.Mechanochemistry extended to various reactions of non-fullerene molecules is briefly discussed.
基金the National Natural Science Foundation of China(21991141)the Natural Science Foundation of Zhejiang Province(LZ20B010001)Zhejiang Normal University。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have attracted phenomenal attention because of their superior optoelectronic performances.The combination of their structural tunability and material stability offers an unprecedented opportunity to engineer materials with unique functionalities.However,developing a rapid and effective design method for introducing luminescence into dielectric switch and realizing controllable regulation has been an enormous challenge.Thus far,materials with tunable optoelectronic multichannel response have not been successfully implemented.In this study,we successfully developed a facile and effective mechanochemical method for realizing the integration and regulation of luminescence and dielectric switch in 2D perovskites,which is unprecedented for the design of dielectric switching materials.The mild external mechanical stimuli enabled the formation of Mn ion-doped 2D hybrid perovskites(Cyclopropylammonium)2Pb1-xMnxBr4 with excellent dielectric switch and rapidly controllable luminescence of highly efficient blue light,white light,pink light,and orange light.This work will provide a new perspective on the rapid and effective design of multifunctional materials and can inspire the future development of low-cost and high-efficiency electronics.
基金support from the National Natural Science Foundation of China(22201198 and 21925107)funding from the Natural Science Foundation of JiangsuProvince(BK20220506).
文摘Comprehensive Summary Polymer mechanochemistry on reactive species has attracted more and more attentions over the past 20 years,as the mechanochemical generation of reactive species has a great potential in developing different polymeric materials for various purposes,such as stress detection,self-healing,self-strengthening,controllable degradation and release of small molecules.In this review,we first discuss the recent progress on polymer mechanochemistry of the reactive species that are generated from the mechanochemical reactions of mechanophores.Five types of reactive species,including radical,zwitterion,ionic,carbene and neutral intermediates,and their applications were reviewed in detail.Since mechanochemical reactions are sensitive to the mechanophore structure and polymer framework,we then discuss how mechanophore isomerism,polymer structure,polymer attachment point,and polymer architecture influence the mechanophore activation.At last,we provide our perspectives on the polymer mechanochemistry of reactivespecies.
基金financially supported by the National Natural Science Foundation of China(22271061)the startup funds from State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science at Fudan University。
文摘Polymer mechanochemistry has rapidly evolved since the mid-20o0s.Recent advancements highlight the development of mechanophore platforms for the controlled release of bioactive payloads and the exploration of biocompatible activation strategies.These platforms,ranging from furan-maleimide Diels-Alder adducts to disulfide motifs withβ-carbonate linkages,demonstrate promising prospects in targeted drug delivery.Additionally,supramolecular assemblies and free radical-generating mechanophores present innovative avenues for potential therapeutic applications.Biocompatible activation methods,notably high-intensity and/or low-intensity focused ultrasound,hold potential for in vivo applications.However,challenges persist in comprehending the fundamental physics of ultrasound and its utilization for activation.
基金supported by the National Science Foundation(CHE-2204079)supported by the National Science Foundation(DGE-2152210)+1 种基金Foundation for a Sloan Research Fellowship(FG-2023-20341)the Camille and Henry Dreyfus Foundation for a Camille Dreyfus Teacher-Scholar Award(TC-24-087)。
文摘The field of polymer mechanochemistry has been revolutionized by implementing force-responsive functional groups—mechanophores.The rational design of mechanophores enables the controlled use of force to achieve constructive molecular reactivity and material responses.While a variety of mechanophores have been developed,this Mini Review focuses on cyclobutane,which has brought valuable insights into molecular reactivity and dynamics as well as innovations in materials.We discuss its reactivity and mechanism,dynamics and stereoselectivity,as well as impacts on material properties.
基金supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,Materials Sciences,and Engineering Division
文摘Mechanochemistry has been recognized as an efficient and sustainable methodology to provide a unique driven force and reaction environments under ambient and neat conditions for the construction of functionalized materials possessing promising properties.Among them,highly porous conjugated scaffolds with attractive electronic conductivities and high surface areas are one of the representative categories exhibiting diverse taskspecific applications,especially in electrochemical energy storage.In recent years,the mechanochemistry-driven procedures have been deployed to construct conjugated scaffolds with engineered structures and properties leveraging the tunability in chemical structures of building blocks and polymerization capability of diverse catalysts.Therefore,a thorough review of related works is required to gain an in-depth understanding of the mechanochemical synthesis procedure and property-performance relationship of the as-produced conjugated scaffolds.Herein,the mechanochemistry-driven construction of conjugated porous networks(CPNs),the carbon-based materials(e.g.,graphite and graphyne),and carbon supported single atom catalysts(CS-SACs)are discussed and summarized.The electrochemical performance of the afforded conductive scaffolds as electrode materials in supercapacitors and alkali-ion batteries is elucidated.Finally,the challenges and potential opportunities related to the construction of conjugated scaffolds driven by mechanochemistry are also discussed and concluded.
基金supported by the National Key Research and Development Program of China(Grants No.2021YFC2902701,2021YFC2902100,2019YFC1805600,2018YFC1801800)the Fundamental Research Funds for the Central Universities(Grant No.2022QN1051)+1 种基金the Shandong Provincial Major Science and Technology Innovation Project(Grant No.2021CXGC011206)the Key Project of the National Natural Science Foundation of China(Grant No.52130402).
文摘Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of CIP in water.The influence of various additives(CaO,Fe_(2)O_(3),SiO_(2),Al,and Fe)on CIP degradation efficiency was investigated.Additionally,six types of composite additives(Fe-CaO,Fe-Fe_(2)O_(3),Fe-SiO_(2),Fe-Al,Al-SiO_(2),and Al-CaO)were explored,with the composite of 20%Fe and 80%SiO_(2) exhibiting notable performance.The impacts of additive content,pH value,and co-existing ions on CIP degradation efficiency were investigated.Furthermore,the effectiveness of MCT in degrading other medical pollutants(norfloxacin,ofloxacin,and enrofloxacin)was verified.The transformations and changes in the crystal structure,oxidation state,microstructure,and morphology of the Fe-SiO_(2) composite additive were characterized using X-ray diffraction,X-ray photoelectron spectroscopy,and scanning electron microscopy techniques.This study proposed a sigmoid trend kinetic model(the Delogu model)that better elucidates the MCT process.Three plausible degradation pathways were discussed based on intermediate substance identification and pertinent literature.This study not only establishes a pathway for the facile degradation of CIP pollutants through MCT but also contributes to advancements in wastewater treatment methodologies.
基金supported by the National Natural Science Foundation(Grant No.22479016)。
文摘Traditional chemical processes often generate substantial waste,leading to significant pollution of water,air,and soil.Developing ecofriendly chemical methods is crucial for economic and environmental sustainability.Mechano-driven chemistry,with its potential for material recyclability and minimal byproducts,is well-aligned with green chemistry principles.Despite its origins over 2000 years ago and nearly 200years of scientific investigation,mechano-driven chemistry has not been widely implemented in practice.This is likely due to a lack of comprehensive understanding and the complex physical effects of mechanical forces,which challenge reaction efficiency and scalability.This review summarizes the historical development of mechano-driven chemistry and discusses its progress across various physical mechanisms,including mechanochemistry,tribochemistry,piezochemistry,and contact electrification(CE)chemistry.CE-induced chemical reactions,involving ion transfer,electron transfer,and radical generation,are detailed,emphasizing the dominant role of radicals initiated by electron transfer and the influence of ion transfer through electrical double layer(EDL)formation.Advancing efficient,eco-friendly,and controllable green chemical technologies can reduce reliance on traditional energy sources(such as electricity and heat)and toxic chemical reagents,fostering innovation in material synthesis,catalytic technologies,and establishing a new paradigm for broader chemical applications.
基金financially supported by the National Natural Science Foundation of China(No.52473097)the Fundamental Research Funds for the Central Universities(No.24X010301678)Shanghai Jiao Tong University 2030 Initiative(No.WH510363002/002)。
文摘Incorporating a low density of ester units into the backbone of polyethylene materials enhances their sustainability and recyclability while maintaining the main material properties of polyethylenes.Here we report a new way to access degradable polyethylene materials with a low content of in-chain ester units via mechanochemical backbone editing.Initially,ester groups are incorporated as side groups through catalytic copolymerization of ethylene with a cyclobutene-fused lactone monomer(CBL),yielding polyethylene materials with high molecular weights and adjustable thermomechanical properties.Subsequent solid-state ball-milling treatment selectively introduces side-chain ester groups into the main chain of the polyethylene materials via force-induced cycloreversion of the cyclobutane units.Under acidic conditions,hydrolysis of the resultant polyethylene materials with in-chain ester units facilitates further degradation into oligomers.
基金financially supported by the Young Scientists Fund of the National Natural Science Foundation of China(No.22305173)Young Scientists Fund of the Natural Science Foundation of Tianjin(No.S25QNM009)+2 种基金Tianjin University Independent Innovation Fund(No.2025XSU-0008)the National Natural Science Foundation of China(No.22475151)Xiaomi Young Talents Program。
文摘Ultrasound(US),as an efficient and non-invasive trigger,has been extensively explored in drug delivery and has many advantages,such as deep penetration,low invasiveness,and high biochemical precision.These advantages demonstrate the immense clinical potential of ultrasound.This study aimed to provide a comprehensive analysis of ultrasound-induced shear forces that exhibit covalent/non-covalent bond cleavage and reactive oxygen species(ROS)-mediated remote control of nanocarriers.By doing so,we can gain a deeper understanding of the vital role,significant advantages,and untapped potential of ultrasound in molecular-level drug activation.Furthermore,clinical translation faces challenges such as the low drug-loading capacity of polymer chains,frequency compatibility between ultrasound parameters and biological systems,insufficient ROS generation,and biocompatibility of current sonosensitizers.To solve these problems,ultrasound mechanochemistry has emerged as a versatile therapeutic modality to promote the development of medical treatments.
