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
In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom...In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom-made optical probe and with our custom-made 450 watts (W) monochromatic light sources. The molecular photochemistry including twisted intramolecular charge-transfer-excited-state (TICT) of the EMABPB in several solvents has been investigated. These results indicate that the aminoborane demonstrates multiple configurations in CD3Cl and CD2Cl2 resulting in the shifts of the signals of the alkyl groups on the nitrogen and boron. This indicates that there are some time-dependent changes at constant temperature over the irradiation interval. At ﹣60°C and the presence of light (λ = 265 nm), we observed a large change in the populations of the two sites, and this by itself indicates a modification in the rotation around the boron nitrogen bond in the excited state. By considering the existence of the TICT state, many important energy technologies may be developed with higher efficiency by controlling the back-electron transfer processes.展开更多
The aim of the present work has been to characterize, by NMR-based metabolic profiling, extravirgin olive oils (EVOOs) from a subarea (Salento) of Apulia, leader EVOO producer among the Italian regions. According to t...The aim of the present work has been to characterize, by NMR-based metabolic profiling, extravirgin olive oils (EVOOs) from a subarea (Salento) of Apulia, leader EVOO producer among the Italian regions. According to the European Union (EU) definition, Protected Designation of Origin (PDO) products are mostly closely linked to the concept of terroir due to the place of origin, climate and local know-how. Moreover, the authenticity and traceability of several products such as olive oils with specific geographical origin require to be preserved by analytical methods. In this regard, about a hundred EVOO samples (monovarietal and blend samples, cultivars Ogliarola Salentina and Cellina di Nardò, basis of “Terra d’Otranto” PDO, campaign 2012-2013) were therefore analyzed by 1H NMR spectroscopy and multivariate statistical analysis. Both unsupervised (PCA) and supervised (OPLS-DA) statistical analyses allowed differentiation of monocultivar oils and blends characterization. Other features such as the age of the trees (young, 100 years) could also be investigated. Cellina samples showed a higher content of aldehydic and phenolic compounds, while Ogliarola samples were characterized by NMR signals in the range of δH 6.5 - 5.6, which could be ascribed to higher carotenoids content. Higher polyphenols and polyunsaturated fatty acid content were also found in young over secular tree EVOOs.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
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
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
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
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
Nitrogen-14(^(14)N)overtone(OT)spectroscopy under fast magic angle spinning(MAS)conditions(>60 kHz)has emerged as a powerful technique for observing correlations and distances between ^(14)N and ^(1)H,owing to the ...Nitrogen-14(^(14)N)overtone(OT)spectroscopy under fast magic angle spinning(MAS)conditions(>60 kHz)has emerged as a powerful technique for observing correlations and distances between ^(14)N and ^(1)H,owing to the absence of the first-order quadrupolar broadenings.In addition,^(14)N^(OT) allows selective manipulation of ^(14)N nuclei for each site.Despite extensive theoretical and experimental studies,the spin dynamics of ^(14)N^(OT) remains under debate.In this study,we conducted experimental investigations to assess the spin dynamics of ^(14)N^(OT) using the rotational-echo saturation-pulse double-resonance(RESPDOR)sequence,which monitors population transfer induced by a^(14)N^(OT) pulse.The ^(14)N^(OT) spin dynamics is well represented by a model of a two-energy-level system.Unlike spin-1/2,the maximum excitation efficiency of ^(14)N^(OT) coherences of powdered solids,denoted by p,depends on the radiofrequency field(rf-field)strength due to orientation dependence of effective nutation fields even when pulse lengths are optimized.It is also found that the p factor,contributing to the ^(14)N^(OT) spin dynamics,is nearly independent of the B0 field.Consequently,the filtering efficiency of RESPDOR experiments exhibits negligible dependence on B0 when the ^(14)N^(OT) pulse length is optimized.The study also identifies the optimal experimental conditions for ^(14)N^(OT)/^(1)H RESPDOR correlation experiments.展开更多
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.
文摘In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom-made optical probe and with our custom-made 450 watts (W) monochromatic light sources. The molecular photochemistry including twisted intramolecular charge-transfer-excited-state (TICT) of the EMABPB in several solvents has been investigated. These results indicate that the aminoborane demonstrates multiple configurations in CD3Cl and CD2Cl2 resulting in the shifts of the signals of the alkyl groups on the nitrogen and boron. This indicates that there are some time-dependent changes at constant temperature over the irradiation interval. At ﹣60°C and the presence of light (λ = 265 nm), we observed a large change in the populations of the two sites, and this by itself indicates a modification in the rotation around the boron nitrogen bond in the excited state. By considering the existence of the TICT state, many important energy technologies may be developed with higher efficiency by controlling the back-electron transfer processes.
文摘The aim of the present work has been to characterize, by NMR-based metabolic profiling, extravirgin olive oils (EVOOs) from a subarea (Salento) of Apulia, leader EVOO producer among the Italian regions. According to the European Union (EU) definition, Protected Designation of Origin (PDO) products are mostly closely linked to the concept of terroir due to the place of origin, climate and local know-how. Moreover, the authenticity and traceability of several products such as olive oils with specific geographical origin require to be preserved by analytical methods. In this regard, about a hundred EVOO samples (monovarietal and blend samples, cultivars Ogliarola Salentina and Cellina di Nardò, basis of “Terra d’Otranto” PDO, campaign 2012-2013) were therefore analyzed by 1H NMR spectroscopy and multivariate statistical analysis. Both unsupervised (PCA) and supervised (OPLS-DA) statistical analyses allowed differentiation of monocultivar oils and blends characterization. Other features such as the age of the trees (young, 100 years) could also be investigated. Cellina samples showed a higher content of aldehydic and phenolic compounds, while Ogliarola samples were characterized by NMR signals in the range of δH 6.5 - 5.6, which could be ascribed to higher carotenoids content. Higher polyphenols and polyunsaturated fatty acid content were also found in young over secular tree EVOOs.
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.
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 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.
文摘Nitrogen-14(^(14)N)overtone(OT)spectroscopy under fast magic angle spinning(MAS)conditions(>60 kHz)has emerged as a powerful technique for observing correlations and distances between ^(14)N and ^(1)H,owing to the absence of the first-order quadrupolar broadenings.In addition,^(14)N^(OT) allows selective manipulation of ^(14)N nuclei for each site.Despite extensive theoretical and experimental studies,the spin dynamics of ^(14)N^(OT) remains under debate.In this study,we conducted experimental investigations to assess the spin dynamics of ^(14)N^(OT) using the rotational-echo saturation-pulse double-resonance(RESPDOR)sequence,which monitors population transfer induced by a^(14)N^(OT) pulse.The ^(14)N^(OT) spin dynamics is well represented by a model of a two-energy-level system.Unlike spin-1/2,the maximum excitation efficiency of ^(14)N^(OT) coherences of powdered solids,denoted by p,depends on the radiofrequency field(rf-field)strength due to orientation dependence of effective nutation fields even when pulse lengths are optimized.It is also found that the p factor,contributing to the ^(14)N^(OT) spin dynamics,is nearly independent of the B0 field.Consequently,the filtering efficiency of RESPDOR experiments exhibits negligible dependence on B0 when the ^(14)N^(OT) pulse length is optimized.The study also identifies the optimal experimental conditions for ^(14)N^(OT)/^(1)H RESPDOR correlation experiments.
