Dynamics of ammonium and ammonia in solutions is closely related to the metabolism of arnrnoniac compounds, therefore plays an important role in various biological processes. NMR measurements indicated that the reorie...Dynamics of ammonium and ammonia in solutions is closely related to the metabolism of arnrnoniac compounds, therefore plays an important role in various biological processes. NMR measurements indicated that the reorientation dynamics of NH4＋ is faster in its aqueous solution than in rnethanol, which deviates from the Stokes-Einstein-Debye rule since water has higher viscosity than methanol. To address this intriguing issue, we herein study the reorientation dynamics of ammonium ion in both solutions using numerical simulation and an extended cyclic Markov chain model. An evident decoupling between translation and ro- tation of methanol is observed in simulation, which results in the deviation of reorientation from the Stokes-Einstein-Debye rule. Slower hydrogen bond （HB） switchings of ammonium with rnethanol comparing to that with water, due to the steric effect of the rnethyl group, remarkably retards the jump rotation of ammonium. The observations herein provide useful insights into the dynamic behavior of ammonium in the heterogeneous environments including the protein surface or protein channels.展开更多
The stress response of amorphous polymers in the glass transition region shows apparent temperature and rate dependence.With increasing loading rate,amorphous polymers also exhibit a clear ductile-brittle transition o...The stress response of amorphous polymers in the glass transition region shows apparent temperature and rate dependence.With increasing loading rate,amorphous polymers also exhibit a clear ductile-brittle transition of tensile failure.The rate-dependent behaviors originate from intrinsic relaxations,ranging from perturbation of molecular bonds between polymer segments to reptation of polymer chains.In this work,we develop a constitutive model that incorporates segmental and chain dynamics into the deformation of bond and polymer networks,respectively.The dynamic scission of polymer chains is also incorporated into the theoretical framework to describe the damage evolution and ultimate failure of polymers.A comparison between theoretical predictions and experiments shows that the present model is able to simultaneously capture the observed rate-dependent features,including the transition from glassy state to rubbery state,strain hardening,and failure threshold.展开更多
基金supported by the National Key Research and Development Program of China(2017YFA0206801)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000 and XDB10040304)the National Natural Science Foundation of China(No.21373201and No.21433014)
文摘Dynamics of ammonium and ammonia in solutions is closely related to the metabolism of arnrnoniac compounds, therefore plays an important role in various biological processes. NMR measurements indicated that the reorientation dynamics of NH4＋ is faster in its aqueous solution than in rnethanol, which deviates from the Stokes-Einstein-Debye rule since water has higher viscosity than methanol. To address this intriguing issue, we herein study the reorientation dynamics of ammonium ion in both solutions using numerical simulation and an extended cyclic Markov chain model. An evident decoupling between translation and ro- tation of methanol is observed in simulation, which results in the deviation of reorientation from the Stokes-Einstein-Debye rule. Slower hydrogen bond （HB） switchings of ammonium with rnethanol comparing to that with water, due to the steric effect of the rnethyl group, remarkably retards the jump rotation of ammonium. The observations herein provide useful insights into the dynamic behavior of ammonium in the heterogeneous environments including the protein surface or protein channels.
基金supported by the National Natural Science Foundation of China(Grant Nos.12022204,12002302 and 12072316)the Zhejiang Provincial Natural Science Foundation of China(Grant No.LQ21A020008)the Fundamental Research Funds of Zhejiang Sci-Tech University(Grant No.2021Q039).
文摘The stress response of amorphous polymers in the glass transition region shows apparent temperature and rate dependence.With increasing loading rate,amorphous polymers also exhibit a clear ductile-brittle transition of tensile failure.The rate-dependent behaviors originate from intrinsic relaxations,ranging from perturbation of molecular bonds between polymer segments to reptation of polymer chains.In this work,we develop a constitutive model that incorporates segmental and chain dynamics into the deformation of bond and polymer networks,respectively.The dynamic scission of polymer chains is also incorporated into the theoretical framework to describe the damage evolution and ultimate failure of polymers.A comparison between theoretical predictions and experiments shows that the present model is able to simultaneously capture the observed rate-dependent features,including the transition from glassy state to rubbery state,strain hardening,and failure threshold.
