INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its us...INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its use for structural analysis is quite limited due to the low natural abundance of^(13)C-^(13)C connectivity(~0.01%)and thus low sensitivity.Particularly,in semi-solids like rubbers,the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to^(13)C due to molecular motions induced averaging of^(1)H-^(13)C dipolar couplings.Herein,in this study,we demonstrate that transient nuclear Overhauser effect(NOE)can be used to efficiently enhance^(13)C signals,and thus enable rapid acquisition of two-dimensional(2D)^(13)C INADEQUATE spectra of rubbers.Using chlorobutyl rubber as the model system,it is found that an overall signalto-noise ratio(SNR)enhancement about 22%can be achieved,leading to significant timesaving by about 33%as compared to the direct polarization-based INADEQUATE experiment.Further experimental results on natural rubber and ethylene propylene diene monomer(EPDM)rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment.展开更多
基金support of National Natural Science Foundation of China(No.22173033,and 22241501)Natural Science Foundation of Guangdong Province,China(No.2023A1515011395).
文摘INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its use for structural analysis is quite limited due to the low natural abundance of^(13)C-^(13)C connectivity(~0.01%)and thus low sensitivity.Particularly,in semi-solids like rubbers,the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to^(13)C due to molecular motions induced averaging of^(1)H-^(13)C dipolar couplings.Herein,in this study,we demonstrate that transient nuclear Overhauser effect(NOE)can be used to efficiently enhance^(13)C signals,and thus enable rapid acquisition of two-dimensional(2D)^(13)C INADEQUATE spectra of rubbers.Using chlorobutyl rubber as the model system,it is found that an overall signalto-noise ratio(SNR)enhancement about 22%can be achieved,leading to significant timesaving by about 33%as compared to the direct polarization-based INADEQUATE experiment.Further experimental results on natural rubber and ethylene propylene diene monomer(EPDM)rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment.
