Interactions between cement clinkers and clay minerals are crucial to the much lower strength of cement-based stabilized clays than concrete or mortar.In this paper,the kaolinite-based and montmorillonite-based clays ...Interactions between cement clinkers and clay minerals are crucial to the much lower strength of cement-based stabilized clays than concrete or mortar.In this paper,the kaolinite-based and montmorillonite-based clays were respectively stabilized by tricalcium silicate(C3S)and tricalcium aluminate(C3A),and measured by the unconfined compressive strength(UCS),29Si/27Al solid state nuclear magnetic resonance(SS-NMR),Fourier transform infrared spectroscopy(FTIR),and transmission electron microscope(TEM)to probe the clinker-clay mineral interaction from macro-mechanical,mineralogical,and microstructural perspectives.The results show that C3A-stabilized samples gain strength rapidly in the first 3 d but are only 20%e60%of the strength of C3S-stabilized ones after 60 d.Microstructures reveal that montmorillonite shows better pozzolanic reactivity due to its superior Sichain and lattice substitution compared to kaolinite.This interaction domains the engineering performance of stabilized clays,benefiting the design of stabilizer referring to as the industrial by-products and clay minerals.展开更多
Some proteins perform their biological functions by changing their material states through liquid-liquid phase separation.Upon phase separation,the protein condenses into a concentrated liquid phase and sometimes into...Some proteins perform their biological functions by changing their material states through liquid-liquid phase separation.Upon phase separation,the protein condenses into a concentrated liquid phase and sometimes into a gel phase,changing its dynamic properties and intermolecular interactions,thereby regulating cellular functions.Although the biological significance of this phenomenon has been widely recognized by researchers,there is still a lack of a comprehensive understanding of the structural and dynamic properties of the protein in the condensed phase.In this phase,molecules usually contain domains with varied dynamic properties and undergo intermediate exchanges.Magic angle spinning(MAS)solid-state NMR(SSNMR)experiments are very powerful in studying rigid protein polymers such as amyloid.The incorporation of solution-like experiments into SSNMR and the development of J-coupling based MAS SSNMR techniques extend its ability to study partially mobile segments of proteins in a condensed liquid or gel phase which are not visible by solution NMR or dipolar-coupling based SSNMR.Therefore,it has been applied in studying protein condensation and has provided very important information that is hard to obtain by other techniques.展开更多
Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked pol...Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.展开更多
Coal has a highly complex chemical structure,similar to polymers,coal is a macromolecular structure composed of a large number of“similar compounds”,which is called the basic structural unit.Understanding coal struc...Coal has a highly complex chemical structure,similar to polymers,coal is a macromolecular structure composed of a large number of“similar compounds”,which is called the basic structural unit.Understanding coal structure is the basis of its transformation and utilization.Shendong(SD)coal was analyzed by FTIR,XRD,XPS,and NMR.The results show that SD coal normalized structure formula is C_(100)H_(68.5)O_(35.7)N_(1.2)S_(0.2)and the average number of aromatic rings is 1.98.-CH_(2)-content accounts for about 82%in aliphatic CeH region,and the ratio of ether bond CeO,aromatic ether C-O and C=O is about 2:1:11 in oxygen-containing functional group region.The d_(002),L_(C),L_(a)and N_(C)of S_(D)coal microcrystalline structure parameters are 0.1832 nm,1.4688 nm,2.0852 nm and 9.017,respectively.Aromatic carbon and aliphatic carbon ratios of SD coal are 55.67%and 29.97%,aromatic cluster size and average methylene chain length are 0.224 and 1.817.Based on these structural parameters,molecular model of SD coal was constructed with^(13)C SSNMR experimental spectra as a reference.The model was constructed with an atom composition of C_(214)H_(214)O_(49)N_(2)S.展开更多
Antimicrobial peptides(AMP)are small proteins that play critical roles in host defense against microbe invasion.Many AMPs disrupt the cellular membrane of microbe,while the mechanism of action of AMPs can be very soph...Antimicrobial peptides(AMP)are small proteins that play critical roles in host defense against microbe invasion.Many AMPs disrupt the cellular membrane of microbe,while the mechanism of action of AMPs can be very sophisticated.Solid-state NMR(SSNMR)technique is powerful in characterizing the mechanism of AMPs in vivo and in vitro.This review summarizes the recent advance of SSNMR technique in AMP mechanisms characterization.We highlight the sample preparation approaches,the SSNMR spectroscopic methods,and a number of outstanding examples of AMP mechanisms elucidated via SSNMR spectroscopy.展开更多
Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fller...Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fllers dispersed in polymer solid electrolytes are consid-ered to be one of the most promising candidate electrolytes for high-performance solid-state lithium batteries.Understanding the local environments and the conduction pathway/dynamics of Lit is essential for the design of high-performance CSEs.Nuclear magnetic resonance(NMR)is a non-invasive quantitative technique that has unique ca-pabilities in providing molecular structure information,morphological evolution,and measuring the movement of ions at different time scales.Therefore,for battery re-searchers,an accurate and comprehensive under standing of the basic principles and experimental design of solid-state NMR(SSNMR)is of great significance for investigating the abundant molecular structure and dynamics information in CSEs.The specific appli-cations of the SSNMR technique in CSEs are briefly introduced in this present review.展开更多
Layered rare earth hydroxides(LREHs)are a novel class of two-dimensional materials with potential applications in various fields.The exchange reactions with organic anions are typically the first step for the function...Layered rare earth hydroxides(LREHs)are a novel class of two-dimensional materials with potential applications in various fields.The exchange reactions with organic anions are typically the first step for the functionalization of LREHs.Although the laminar structures seem to be clear for anion-exchanged compounds,the state of intercalated organic anions and their interactions with cationic rare earth hydroxide layers remain unclear.Herein,we demonstrate that the use of 13C solid-state nuclear magnetic resonance(ssNMR)spectroscopy enables to extract key information on the state of intercalated organic anions such as their local chemical environment,stacking,and dynamics,which are often difficult or impossible to obtain previously.In combination with powder X-ray diffraction and ab initio density functional theory calculations,the intercalation chemistry of two representative layered yttrium hydroxides with selected monovalent organic anions was studied in detail.The products can undergo secondary exchange with a divalent organic anion,depending on the match between the basal spacing of two phases,i.e.,the replacement of benzenesulfonate(BS^(-)),2,4-dimethylbenzene sulfonate(DMBS^(-)),and 4-ethylbenzene sulfonate(EBS)with 2,6-naphthalene disulfonate(NDS^(2-))is allowed due to the insignificant change in basal spacing after exchange,while the replacement of very long dodecyl benzene sulfonate(DBS^(-))and dodecyl sulfate(DS)with NDS^(2-)is forbidden.The results therefore provide valuable insights into the structure-property relationships of LREH-based functional materials.展开更多
The methanol-to-olefins(MTO)reaction offers an alternative pathway for the production of low-carbon olefins from non-oil feedstocks.Fundamental research has been impeded by a lack of comprehensive understanding of its...The methanol-to-olefins(MTO)reaction offers an alternative pathway for the production of low-carbon olefins from non-oil feedstocks.Fundamental research has been impeded by a lack of comprehensive understanding of its underlying mechanism,despite the significant progress made in industry.In-situ solid-state nuclear magnetic resonance(ss NMR)spectroscopy has emerged as a pivotal tool,offering crucial insights into key species under real-time operando conditions.Furthermore,the host–vip interaction between zeolites or surface species residing on zeolites and the reactant/active intermediates is revealed by the combination of in-situ^(13)C MAS NMR and 2D correlation spectroscopy.Moreover,recent technological advancements in hyperpolarization(HP)methods,including HP^(129)Xe NMR and dynamic nuclear polarization(DNP),have significantly improved the sensitivity of ssNMR,enabling detailed structural and kinetic analysis as well as the detection of trace species.In this feature article,we summarized recent advancements in(in-situ)ssNMR spectroscopy applied to MTO reaction processes,encompassing mechanistic investigations at various stages and the intricate host–vip interactions.These theoretical insights into the dynamic evolution of MTO reactions lay a solid foundation for the optimization of catalytic processes and the development of efficient catalysts,thereby advancing the techniques towards more sustainable and economical production route for olefins.展开更多
Bone is a hierarchical architecture that consists of both inorganic and organic components.The organic components,including collagen and numerous non-collagenous biomolecules,are crucial for maintaining the mechanical...Bone is a hierarchical architecture that consists of both inorganic and organic components.The organic components,including collagen and numerous non-collagenous biomolecules,are crucial for maintaining the mechanical strength and physiological functions of bone.The native structures of organic components and especially the mutual interactions between different components are important questions to be addressed.Among different analytical techniques,solid-state nuclear magnetic resonance(SSNMR)spectroscopy is a powerful tool to reveal the chemical and interactional information at an atomic level.Recent advancements of SSNMR technology and experimental protocols have brought great advances in understanding the molecular details in native bones.In this review,we summarize the progresses on the SSNMR studies of various organic components in the bone matrix.In the first part,we review the studies on collagen from four different aspects:(1)waterassociated molecular dynamics;(2)the intrahelical/interhelical interactions in collagen residues;(3)the interactions between collagen and citrate;and(4)the cross-linking between collagen and inorganic surface.In the second part,we review the studies on the non-protein biomolecules including sugar species,citrate,lipids,and nucleic acids.In the end,we propose an outlook of future directions for SSNMR investigations on bones.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.52278334,42272322,and 52209136).
文摘Interactions between cement clinkers and clay minerals are crucial to the much lower strength of cement-based stabilized clays than concrete or mortar.In this paper,the kaolinite-based and montmorillonite-based clays were respectively stabilized by tricalcium silicate(C3S)and tricalcium aluminate(C3A),and measured by the unconfined compressive strength(UCS),29Si/27Al solid state nuclear magnetic resonance(SS-NMR),Fourier transform infrared spectroscopy(FTIR),and transmission electron microscope(TEM)to probe the clinker-clay mineral interaction from macro-mechanical,mineralogical,and microstructural perspectives.The results show that C3A-stabilized samples gain strength rapidly in the first 3 d but are only 20%e60%of the strength of C3S-stabilized ones after 60 d.Microstructures reveal that montmorillonite shows better pozzolanic reactivity due to its superior Sichain and lattice substitution compared to kaolinite.This interaction domains the engineering performance of stabilized clays,benefiting the design of stabilizer referring to as the industrial by-products and clay minerals.
基金supported by the National Natural Science Foundation of China(No.32171185,No.31770790)the National Key R&D Program of China(No.2017YFA0504804).
文摘Some proteins perform their biological functions by changing their material states through liquid-liquid phase separation.Upon phase separation,the protein condenses into a concentrated liquid phase and sometimes into a gel phase,changing its dynamic properties and intermolecular interactions,thereby regulating cellular functions.Although the biological significance of this phenomenon has been widely recognized by researchers,there is still a lack of a comprehensive understanding of the structural and dynamic properties of the protein in the condensed phase.In this phase,molecules usually contain domains with varied dynamic properties and undergo intermediate exchanges.Magic angle spinning(MAS)solid-state NMR(SSNMR)experiments are very powerful in studying rigid protein polymers such as amyloid.The incorporation of solution-like experiments into SSNMR and the development of J-coupling based MAS SSNMR techniques extend its ability to study partially mobile segments of proteins in a condensed liquid or gel phase which are not visible by solution NMR or dipolar-coupling based SSNMR.Therefore,it has been applied in studying protein condensation and has provided very important information that is hard to obtain by other techniques.
基金financially supported by the National Natural Science Foundation of China(Grant No.22325405,22321002,22279153)Liaoning Revitalization Talents Program(XLYC1807207,XLYC2203134)DICP I202104。
文摘Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.
基金financed by the Department of education of Gansu Province:Young Doctor Fund Project(2022QB-029)the Fundamental Research Funds for the Central Universities(31920240125-06,31920240059)+1 种基金the Scientific Research Project of Introducing Talents of Northwest Minzu University(xbmuyjrc202215,xbmuyjrc202216)the National Natural Science Foundation of China(22178289).
文摘Coal has a highly complex chemical structure,similar to polymers,coal is a macromolecular structure composed of a large number of“similar compounds”,which is called the basic structural unit.Understanding coal structure is the basis of its transformation and utilization.Shendong(SD)coal was analyzed by FTIR,XRD,XPS,and NMR.The results show that SD coal normalized structure formula is C_(100)H_(68.5)O_(35.7)N_(1.2)S_(0.2)and the average number of aromatic rings is 1.98.-CH_(2)-content accounts for about 82%in aliphatic CeH region,and the ratio of ether bond CeO,aromatic ether C-O and C=O is about 2:1:11 in oxygen-containing functional group region.The d_(002),L_(C),L_(a)and N_(C)of S_(D)coal microcrystalline structure parameters are 0.1832 nm,1.4688 nm,2.0852 nm and 9.017,respectively.Aromatic carbon and aliphatic carbon ratios of SD coal are 55.67%and 29.97%,aromatic cluster size and average methylene chain length are 0.224 and 1.817.Based on these structural parameters,molecular model of SD coal was constructed with^(13)C SSNMR experimental spectra as a reference.The model was constructed with an atom composition of C_(214)H_(214)O_(49)N_(2)S.
基金a research grant from the Natural Science and Engineering Research Council of Canadaan equipment grant from the Canada Foundation for Innovationfunding from the Canada Research Chair pro-gram
基金supported by the National Key Research and Development Program of the Ministry of Science and Technology,People's Republic of China(contract number 2016YFA0501203)the National Natural Science Foundation of China(21874004,31470727)the Interdisciplinary Medicine Seed Fund of Peking University,and the Fundamental Research Funds for the Central University.
文摘Antimicrobial peptides(AMP)are small proteins that play critical roles in host defense against microbe invasion.Many AMPs disrupt the cellular membrane of microbe,while the mechanism of action of AMPs can be very sophisticated.Solid-state NMR(SSNMR)technique is powerful in characterizing the mechanism of AMPs in vivo and in vitro.This review summarizes the recent advance of SSNMR technique in AMP mechanisms characterization.We highlight the sample preparation approaches,the SSNMR spectroscopic methods,and a number of outstanding examples of AMP mechanisms elucidated via SSNMR spectroscopy.
基金This work was supported by the National Natural Science Foundation of China(Grant No.22075064,No.21673065,No.21611130177).
文摘Solid electrolytes have received widespread attention due to their higher safety than liquid electrolytes in the past decades.In particular,organic-inorganic composite solid electro-lytes(CSEs)in which inorganic fllers dispersed in polymer solid electrolytes are consid-ered to be one of the most promising candidate electrolytes for high-performance solid-state lithium batteries.Understanding the local environments and the conduction pathway/dynamics of Lit is essential for the design of high-performance CSEs.Nuclear magnetic resonance(NMR)is a non-invasive quantitative technique that has unique ca-pabilities in providing molecular structure information,morphological evolution,and measuring the movement of ions at different time scales.Therefore,for battery re-searchers,an accurate and comprehensive under standing of the basic principles and experimental design of solid-state NMR(SSNMR)is of great significance for investigating the abundant molecular structure and dynamics information in CSEs.The specific appli-cations of the SSNMR technique in CSEs are briefly introduced in this present review.
基金supported by the National Natural Science Foundation of China(grant no.21904071 and 22071115)the Open Funds(T151904)the State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics of China.
文摘Layered rare earth hydroxides(LREHs)are a novel class of two-dimensional materials with potential applications in various fields.The exchange reactions with organic anions are typically the first step for the functionalization of LREHs.Although the laminar structures seem to be clear for anion-exchanged compounds,the state of intercalated organic anions and their interactions with cationic rare earth hydroxide layers remain unclear.Herein,we demonstrate that the use of 13C solid-state nuclear magnetic resonance(ssNMR)spectroscopy enables to extract key information on the state of intercalated organic anions such as their local chemical environment,stacking,and dynamics,which are often difficult or impossible to obtain previously.In combination with powder X-ray diffraction and ab initio density functional theory calculations,the intercalation chemistry of two representative layered yttrium hydroxides with selected monovalent organic anions was studied in detail.The products can undergo secondary exchange with a divalent organic anion,depending on the match between the basal spacing of two phases,i.e.,the replacement of benzenesulfonate(BS^(-)),2,4-dimethylbenzene sulfonate(DMBS^(-)),and 4-ethylbenzene sulfonate(EBS)with 2,6-naphthalene disulfonate(NDS^(2-))is allowed due to the insignificant change in basal spacing after exchange,while the replacement of very long dodecyl benzene sulfonate(DBS^(-))and dodecyl sulfate(DS)with NDS^(2-)is forbidden.The results therefore provide valuable insights into the structure-property relationships of LREH-based functional materials.
基金the financial support provided by the National Key Research and Development Program of China(2022YFE0116000)the National Natural Science Foundation of China(22241801,22022202,22032005,22288101,21972142,21991090,21991092,and 21991093)Dalian Outstanding Young Scientist Foundation(2021RJ01)。
文摘The methanol-to-olefins(MTO)reaction offers an alternative pathway for the production of low-carbon olefins from non-oil feedstocks.Fundamental research has been impeded by a lack of comprehensive understanding of its underlying mechanism,despite the significant progress made in industry.In-situ solid-state nuclear magnetic resonance(ss NMR)spectroscopy has emerged as a pivotal tool,offering crucial insights into key species under real-time operando conditions.Furthermore,the host–vip interaction between zeolites or surface species residing on zeolites and the reactant/active intermediates is revealed by the combination of in-situ^(13)C MAS NMR and 2D correlation spectroscopy.Moreover,recent technological advancements in hyperpolarization(HP)methods,including HP^(129)Xe NMR and dynamic nuclear polarization(DNP),have significantly improved the sensitivity of ssNMR,enabling detailed structural and kinetic analysis as well as the detection of trace species.In this feature article,we summarized recent advancements in(in-situ)ssNMR spectroscopy applied to MTO reaction processes,encompassing mechanistic investigations at various stages and the intricate host–vip interactions.These theoretical insights into the dynamic evolution of MTO reactions lay a solid foundation for the optimization of catalytic processes and the development of efficient catalysts,thereby advancing the techniques towards more sustainable and economical production route for olefins.
基金supported by the National Natural Science Foundation of China(Nos.21922410,22072133,and 22275159)Zhejiang Provincial Natural Science Foundation(No.LR19B050001)Zhejiang Provincial Natural Science Foundation(No.LQ20H170002).
文摘Bone is a hierarchical architecture that consists of both inorganic and organic components.The organic components,including collagen and numerous non-collagenous biomolecules,are crucial for maintaining the mechanical strength and physiological functions of bone.The native structures of organic components and especially the mutual interactions between different components are important questions to be addressed.Among different analytical techniques,solid-state nuclear magnetic resonance(SSNMR)spectroscopy is a powerful tool to reveal the chemical and interactional information at an atomic level.Recent advancements of SSNMR technology and experimental protocols have brought great advances in understanding the molecular details in native bones.In this review,we summarize the progresses on the SSNMR studies of various organic components in the bone matrix.In the first part,we review the studies on collagen from four different aspects:(1)waterassociated molecular dynamics;(2)the intrahelical/interhelical interactions in collagen residues;(3)the interactions between collagen and citrate;and(4)the cross-linking between collagen and inorganic surface.In the second part,we review the studies on the non-protein biomolecules including sugar species,citrate,lipids,and nucleic acids.In the end,we propose an outlook of future directions for SSNMR investigations on bones.
