Investigation of unloading rock failure under differentσ_(2)facilitates the control mechanism of excavation surrounding rock.This study focused on single-sided unloading tests of granite specimens under true triaxial...Investigation of unloading rock failure under differentσ_(2)facilitates the control mechanism of excavation surrounding rock.This study focused on single-sided unloading tests of granite specimens under true triaxial conditions.The strength and failure characteristics were studied with micro-camera and acoustic emission(AE)monitoring.Furthermore,the choice of test path and the effect ofσ_(2)on fracture of unloading rock were discussed.Results show that the increasedσ_(2)can strengthen the stability of single-sided unloading rock.After unloading,the rock’s free surface underwent five phases,namely,inoculation,particle ejection,buckling rupture,stable failure,and unstable rockburst phases.Moreover,atσ_(2)≤30 MPa,the b value shows the following variation tendency:rising,dropping,significant fluctuation,and dropping,with dispersed damages signal.Atσ_(2)≥40 MPa,the tendency shows:a rise,a decrease,a slight fluctuation,and final drop,with concentrated damages signal.After unloading,AE energy is mainly concentrated in the micro-energy range.With the increasedσ_(2),the micro-energy ratio rises.In contrast,low,medium and large energy ratios drop gradually.The increased tensile fractures and decreased shear fractures indicate that the failure mode of the unloading rock gradually changes from tensile-shear mode to tensile-split one.The fractional dimension of the rock fragments first increases and then decreases with an inflection point at 20 MPa.The distribution of SIF on the planes changes asσ_(2)increases,resulting in strengthening and then weakening of the rock bearing capacity.展开更多
Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,...Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.展开更多
The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its a...The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its atomic specificity and versatility in studying gas,liquid,and solid,allows the study of electrolyte solution,catalyst and catalyst-adsorbate interfaces.When applied in operando,NMR can offer molecular-level insights into various electrochemical processes.Operando NMR has been applied extensively in battery research,but relatively underexplored for electrocatalysis in the past two decades.In this mini review,we first introduce the operando electrochemical NMR setups,categorized by different probe designs.Then we review the applications of operando NMR for monitoring the electrolyte solution and the catalyst-adsorbate interface.Considering the high environmental impact of electrochemical conversion of CO_(2)into value-added products,we zoom in to the use of operando NMR in studying electrochemical CO_(2)reduction.Finally,we provide our perspective on further developing and applying operando NMR methods for understanding the complex reaction network of Cu-catalyzed electrochemical CO_(2)reduction.展开更多
Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric press...Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric pressure.The dragline silk fiber,which is essentially a spider's lifeline,surpasses the strength of a steel wire of equivalent thickness.Regrettably,humans have yet to replicate this process to produce fibers with similar high strength and elasticity in an eco-friendly manner.Therefore,it is of utmost importance to thoroughly comprehend the extraordinary structure and fibrillation mechanism of silk,and leverage this understanding in the manufacturing of high-strength,high-elasticity fibers.This review will delve into the recent progress in comprehending the structure of silks derived from silkworms and spiders,emphasizing the distinctive attributes of solidstate NMR.展开更多
Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such ...Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.展开更多
The measurement of nuclear magnetic resonance(NMR)porosity is affected by temperature.Without considering the impact of NMR logging tools,this phenomenon is mainly caused by variations in magnetization intensity of th...The measurement of nuclear magnetic resonance(NMR)porosity is affected by temperature.Without considering the impact of NMR logging tools,this phenomenon is mainly caused by variations in magnetization intensity of the measured system due to temperature fluctuations and difference between the temperature of the porous medium and calibration sample.In this study,the effect of temperature was explained based on the thermodynamic theory,and the rules of NMR porosity responses to temperature changes were identified through core physics experiments.In addition,a method for correcting the influence of temperature on NMR porosity measurement was proposed,and the possible factors that may affect its application were also discussed.展开更多
Aqueous film-forming foams(AFFFs)are the primary source of toxic perfluoroalkyl and polyfluoroalkyl substances(PFAS)in wastewater.Thus,it is urgent to develop a facile and fast method for identifying fluorosurfactants...Aqueous film-forming foams(AFFFs)are the primary source of toxic perfluoroalkyl and polyfluoroalkyl substances(PFAS)in wastewater.Thus,it is urgent to develop a facile and fast method for identifying fluorosurfactants in commercially available AFFFs.In this work,fluorine nuclear magnetic resonance(^(19)F NMR)spectroscopy was optimized to measure AFFFs directly with the extra addition of 5%D_(2)O as the locking reagent,and high-quality spectra could be acquired within 4 min(0.1%fluorosurfactant content).Recovery experiments demonstrated that the use of different AFFFs had no marked influence on the quantitative analysis of fluorosurfactants.Such method works with low-field NMR spectroscopy(1.4 T)as well.Two-dimensional(2D)^(19)F COSY NMR was used to make signal assignments for different fluorosurfactant derivatives.The optimized ^(19)F NMR could quantify the commercially available fluorosurfactants in different AFFFs,identify them being in either the perfluorooctane sulfonate(PFOS)or fluorotelomer sulfonic acid(FTS)categories,and distinguish the head-group of PFOS and FTS derivatives,which exhibits great potentials in the developments of relevant commercial detections.展开更多
Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chro...Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics.Numerous microbial rhodopsins have been discovered,contributing to diverse functions and colors.Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins.This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field.We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy.展开更多
Tannin was extracted from different subspecies of Acacia nilotica,Acacia nilotica nilotica(Ann),Acacia nilotica tomentosa(Ant)and Acacia nilotica adansonii(Ana).The aim was to elucidate their structure and evaluate th...Tannin was extracted from different subspecies of Acacia nilotica,Acacia nilotica nilotica(Ann),Acacia nilotica tomentosa(Ant)and Acacia nilotica adansonii(Ana).The aim was to elucidate their structure and evaluate their reactivity as bioadhesives in the wood industry.The extracts were prepared by hot water extraction(90°C tem-perature).Their gel time with paraformaldehyde was used atfirst to compare their reactivity.The tannin contents and the percentage of total polyphenolic materials in different solutions of the extracts spray dried powder were determined by the hide powder method.Concentrated solutions(47%)were tested by both MALDI ToF,13CNMR.The thermomechanical analysis(TMA)was performed to evaluate their modulus of elasticity(MOE)at different pHs.The gel times of all the three tannin extracts showed that their reactivity and it was com-parable to other known procyanidin/prodelphinidin tannin extract types.Ana,Ann and Ant showed highest per-cent of total polyphenolic materials at 70%,64%,and 57%,respectively.The 13CNMR spectra showed that the three subspecies of condensed tannins were mainly constituted of procyanidins(PC)and prodelphinidins(PD)in slightly different ratios.Ann(56.5%PC and 43.4%PD),Ant(57%PC and 43%PD)and Ana(58%PC and 42%PD).MALDI–TOF spectra showed the presence offlavonoid monomers,and oligomers some of which linked to short carbohydrates monomers or dimers.TMA revealed that the three types of tannins had high MOE at their initial pH(5).展开更多
Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this w...Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this work was to contribute to the understanding of the properties of Paraberlinia bifoliolata tannin by Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy MALDI-TOF/MS and Carbon 13 Nuclear Magnetic Resonance(13C NMR).The chemical composition of tannin extracted from Paraberlinia bifoliolata bark was determined,as was the mechanical strength of the resin hardened with Acacia nilotica extracts.Yield by successive water extraction was 35%.MALDI-TOF/MS analysis revealed the presence of three new compounds in this tannin,previously unknown in this family of extracts.These are 3-hydroxyproline acid,N-methyl-4-hydroxypipecolic acid and N-methyl-5-dihydroxypipecolic acid.The identification of the above molecules means that this tannin can be used for industrial applications,as a resin in the manufacture of particleboard and in the formulation of green corrosion inhibitors.This information is reinforced by 13C NMR spectrometry,which indicates the presence of several polyflavonoid units,confirming the condensed nature of the tannin.Thermomechanical analysis of the resin formed by the purified tannin of Paraberlinia bifoliolata to which a vegetal biohardener has been added provided a Modulus of Elasticity(MOE)value of 4840 MPa at 150℃,confirming its possible use as a binder resin in the manufacture of wood panels as well as for the formulation of a corrosion inhibitor.展开更多
基金This work was supported by the Scientific Research Project of Anhui Province Universities,China(No.YJS20210388)the National Natural Science Foundation of China(Nos.51974009,52004006,and 52004005)+2 种基金the Major Science and Technology Special Project of Anhui Province,China(No.202203a07020011)the Collaborative Innovation Project of Anhui Province Universities,China(No.GXXT-2021-075)the Huaibei City Science and Technology Major Program(No.Z2020005).
文摘Investigation of unloading rock failure under differentσ_(2)facilitates the control mechanism of excavation surrounding rock.This study focused on single-sided unloading tests of granite specimens under true triaxial conditions.The strength and failure characteristics were studied with micro-camera and acoustic emission(AE)monitoring.Furthermore,the choice of test path and the effect ofσ_(2)on fracture of unloading rock were discussed.Results show that the increasedσ_(2)can strengthen the stability of single-sided unloading rock.After unloading,the rock’s free surface underwent five phases,namely,inoculation,particle ejection,buckling rupture,stable failure,and unstable rockburst phases.Moreover,atσ_(2)≤30 MPa,the b value shows the following variation tendency:rising,dropping,significant fluctuation,and dropping,with dispersed damages signal.Atσ_(2)≥40 MPa,the tendency shows:a rise,a decrease,a slight fluctuation,and final drop,with concentrated damages signal.After unloading,AE energy is mainly concentrated in the micro-energy range.With the increasedσ_(2),the micro-energy ratio rises.In contrast,low,medium and large energy ratios drop gradually.The increased tensile fractures and decreased shear fractures indicate that the failure mode of the unloading rock gradually changes from tensile-shear mode to tensile-split one.The fractional dimension of the rock fragments first increases and then decreases with an inflection point at 20 MPa.The distribution of SIF on the planes changes asσ_(2)increases,resulting in strengthening and then weakening of the rock bearing capacity.
基金the Basic Research Project(C123000,C210200,C310200,&C421000)of the Korea Basic Science Institute(KBSI)funded by the Korea Ministry of Science and ICT(MSIT)the Technology Development Program to Solve Climate Changes through the National Research Foundation of Korea(NRF)funded by MSIT(NRF-2021M1A2A2038141).O.H.Han thanks to Prof.I.S.Yang at Ewha Womans University for insightful discussion.
文摘Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.
基金support from Radboud University Start-up and NWO Open Competition ENW-M grant (OCENW.M.21.308)support from China Scholarship Council
文摘The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its atomic specificity and versatility in studying gas,liquid,and solid,allows the study of electrolyte solution,catalyst and catalyst-adsorbate interfaces.When applied in operando,NMR can offer molecular-level insights into various electrochemical processes.Operando NMR has been applied extensively in battery research,but relatively underexplored for electrocatalysis in the past two decades.In this mini review,we first introduce the operando electrochemical NMR setups,categorized by different probe designs.Then we review the applications of operando NMR for monitoring the electrolyte solution and the catalyst-adsorbate interface.Considering the high environmental impact of electrochemical conversion of CO_(2)into value-added products,we zoom in to the use of operando NMR in studying electrochemical CO_(2)reduction.Finally,we provide our perspective on further developing and applying operando NMR methods for understanding the complex reaction network of Cu-catalyzed electrochemical CO_(2)reduction.
基金support by a JSPS KAKENHI,Grant-in-Aid for Scientific Research(C),Grant Number JP19K05609.
文摘Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric pressure.The dragline silk fiber,which is essentially a spider's lifeline,surpasses the strength of a steel wire of equivalent thickness.Regrettably,humans have yet to replicate this process to produce fibers with similar high strength and elasticity in an eco-friendly manner.Therefore,it is of utmost importance to thoroughly comprehend the extraordinary structure and fibrillation mechanism of silk,and leverage this understanding in the manufacturing of high-strength,high-elasticity fibers.This review will delve into the recent progress in comprehending the structure of silks derived from silkworms and spiders,emphasizing the distinctive attributes of solidstate NMR.
基金Guangdong Basic and Applied Basic Research Found ation(Guangdong Province,China)general project for the financial support。
文摘Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.
基金This paper is supported by“National Natural Science Foundation of China(Grant No.42204106)”.
文摘The measurement of nuclear magnetic resonance(NMR)porosity is affected by temperature.Without considering the impact of NMR logging tools,this phenomenon is mainly caused by variations in magnetization intensity of the measured system due to temperature fluctuations and difference between the temperature of the porous medium and calibration sample.In this study,the effect of temperature was explained based on the thermodynamic theory,and the rules of NMR porosity responses to temperature changes were identified through core physics experiments.In addition,a method for correcting the influence of temperature on NMR porosity measurement was proposed,and the possible factors that may affect its application were also discussed.
基金financially supported by the“National Key R&D Program of China”(No.2022YFC3004900)“Basic Research Fund of TFRI”(No.2022SJ07)。
文摘Aqueous film-forming foams(AFFFs)are the primary source of toxic perfluoroalkyl and polyfluoroalkyl substances(PFAS)in wastewater.Thus,it is urgent to develop a facile and fast method for identifying fluorosurfactants in commercially available AFFFs.In this work,fluorine nuclear magnetic resonance(^(19)F NMR)spectroscopy was optimized to measure AFFFs directly with the extra addition of 5%D_(2)O as the locking reagent,and high-quality spectra could be acquired within 4 min(0.1%fluorosurfactant content).Recovery experiments demonstrated that the use of different AFFFs had no marked influence on the quantitative analysis of fluorosurfactants.Such method works with low-field NMR spectroscopy(1.4 T)as well.Two-dimensional(2D)^(19)F COSY NMR was used to make signal assignments for different fluorosurfactant derivatives.The optimized ^(19)F NMR could quantify the commercially available fluorosurfactants in different AFFFs,identify them being in either the perfluorooctane sulfonate(PFOS)or fluorotelomer sulfonic acid(FTS)categories,and distinguish the head-group of PFOS and FTS derivatives,which exhibits great potentials in the developments of relevant commercial detections.
基金supported in part by JSPS KAKENHI Grant Numbers in Japan(JP21H05229 to I.K.)JST CREST(JPMJCR21B2)The authors also thank Nobuko Yamaguchi for the financial support.
文摘Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics.Numerous microbial rhodopsins have been discovered,contributing to diverse functions and colors.Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins.This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field.We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy.
基金the fund provided by NAPATA program,jointly funded by France campus and the Ministry of Higher Education and Scientific research,SudanLab facilities provided by LERMAB which is supported by a grant of the French Agence Nationale de la Recherche(ANR)in the ambit of the laboratory of excellence(Labex)ARBRE is also aknowledged.
文摘Tannin was extracted from different subspecies of Acacia nilotica,Acacia nilotica nilotica(Ann),Acacia nilotica tomentosa(Ant)and Acacia nilotica adansonii(Ana).The aim was to elucidate their structure and evaluate their reactivity as bioadhesives in the wood industry.The extracts were prepared by hot water extraction(90°C tem-perature).Their gel time with paraformaldehyde was used atfirst to compare their reactivity.The tannin contents and the percentage of total polyphenolic materials in different solutions of the extracts spray dried powder were determined by the hide powder method.Concentrated solutions(47%)were tested by both MALDI ToF,13CNMR.The thermomechanical analysis(TMA)was performed to evaluate their modulus of elasticity(MOE)at different pHs.The gel times of all the three tannin extracts showed that their reactivity and it was com-parable to other known procyanidin/prodelphinidin tannin extract types.Ana,Ann and Ant showed highest per-cent of total polyphenolic materials at 70%,64%,and 57%,respectively.The 13CNMR spectra showed that the three subspecies of condensed tannins were mainly constituted of procyanidins(PC)and prodelphinidins(PD)in slightly different ratios.Ann(56.5%PC and 43.4%PD),Ant(57%PC and 43%PD)and Ana(58%PC and 42%PD).MALDI–TOF spectra showed the presence offlavonoid monomers,and oligomers some of which linked to short carbohydrates monomers or dimers.TMA revealed that the three types of tannins had high MOE at their initial pH(5).
基金supported by the Institut de la Francophonie pour le Developpement Durable(IFDD/Canada)/Projet de Deploiement des Technologies et Innovations Environnementales(PDTIE)funded by Organisation Internationale de la Francophonie(OIF)the Organisation of African,Caribbean and Pacific States and the European Union(EU)(FED/220/421-370)the Local Materials Promotion Authority(MIPROMALO)of the Ministry of Scientific Research and Innovation of Cameroon who made it possible for this scientific work to be carried out.
文摘Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this work was to contribute to the understanding of the properties of Paraberlinia bifoliolata tannin by Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy MALDI-TOF/MS and Carbon 13 Nuclear Magnetic Resonance(13C NMR).The chemical composition of tannin extracted from Paraberlinia bifoliolata bark was determined,as was the mechanical strength of the resin hardened with Acacia nilotica extracts.Yield by successive water extraction was 35%.MALDI-TOF/MS analysis revealed the presence of three new compounds in this tannin,previously unknown in this family of extracts.These are 3-hydroxyproline acid,N-methyl-4-hydroxypipecolic acid and N-methyl-5-dihydroxypipecolic acid.The identification of the above molecules means that this tannin can be used for industrial applications,as a resin in the manufacture of particleboard and in the formulation of green corrosion inhibitors.This information is reinforced by 13C NMR spectrometry,which indicates the presence of several polyflavonoid units,confirming the condensed nature of the tannin.Thermomechanical analysis of the resin formed by the purified tannin of Paraberlinia bifoliolata to which a vegetal biohardener has been added provided a Modulus of Elasticity(MOE)value of 4840 MPa at 150℃,confirming its possible use as a binder resin in the manufacture of wood panels as well as for the formulation of a corrosion inhibitor.
