Molecular dynamics simulations of model polyethylene chains with various lengths up to 4000 CH2 units were performed. Our results verified that the modification of force fields to demonstrate the collapse stages in th...Molecular dynamics simulations of model polyethylene chains with various lengths up to 4000 CH2 units were performed. Our results verified that the modification of force fields to demonstrate the collapse stages in the folding process is not necessary. The transition between the stages of chain folding became sharp, and the clusters became stable as the chain became longer.展开更多
Lamellar crystal thickness lc of isotactic polybutene-1(it-PB1)have been investigated for crystal-lization in the melt over a wide range of crystallization temperature T from 40°C to 90°C by small angle X-ra...Lamellar crystal thickness lc of isotactic polybutene-1(it-PB1)have been investigated for crystal-lization in the melt over a wide range of crystallization temperature T from 40°C to 90°C by small angle X-ray scattering experiments and density measurements.The crystal thickness lc demonstrates two linear dependences on inverse supercooling and a transition from one dependence to the other has been observed around T=65°C.Each of the two dependences obeys the nucleation theory in the high and low supercooling ranges,respec-tively.Chain folding free energy q determined from the low supercooling range is larger than that determined from the high supercooling range.Possible mechanisms for the transition are discussed taking account of entropy of chain folding directions.展开更多
Using an ultra-sensitive differential scanning calorimetry (US-DSC), we have investigated the folding and aggregation behaviors of poly(N-isopropylacrylamide) (PNIPAM) chains in dilute and semidilute solutions. In the...Using an ultra-sensitive differential scanning calorimetry (US-DSC), we have investigated the folding and aggregation behaviors of poly(N-isopropylacrylamide) (PNIPAM) chains in dilute and semidilute solutions. In the heating process, the intrachain folding and interchain aggregation simultaneously occur in the dilute solutions, and the ratio of intrachain folding increases with decreasing concentra-tion. In the semidilute solutions, PNIPAM chains show limited interchain aggregation with elevated temperature, because most of the PNIPAM chains have been collapsed at lower temperature. In an ex-tremely dilute solution, PNIPAM chains undergo a single folding transition in the heating process. By extrapolating heating rate and concentration to zero, we have obtained the phase transition tempera-ture (TS) and enthalpy change (△HS) of the single chain folding. △HS is higher than that for a phase transition involving intrachain collapse and interchain aggregation, indicating that a single chain fold-ing can not be taken to be a macroscopic phase transition.展开更多
Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm.Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters c...Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm.Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters complex energy landscapes,leading to the potential occurrence of misfolding issues.While noncovalent crosslinking can circumvent this issue,the resulting single-chain nanoparticles exhibit lower structural stability compared to their covalently crosslinked counterparts.In this study,we present a novel approach for the synthesis of single-chain nanoparticles,achieved through the combination of non-covalent and covalent intramolecular crosslinking.Cyanostilbenes grafted onto the linear polymer form intrachain non-covalent stacks aided by hydrogen bonds,leading to the formation of non-covalently crosslinked single-chain nanoparticles.These nanoparticles undergo conversion to covalently crosslinked nanostructures through subsequent photo-irradiation using[2+2]photocycloaddition,a process facilitated by the supramolecular confinement effect.Consequently,the resulting single-chain nanoparticles demonstrate both intrachain folding efficiency and substantial stability,offering significant potential for advancing applications across diverse fields.展开更多
文摘Molecular dynamics simulations of model polyethylene chains with various lengths up to 4000 CH2 units were performed. Our results verified that the modification of force fields to demonstrate the collapse stages in the folding process is not necessary. The transition between the stages of chain folding became sharp, and the clusters became stable as the chain became longer.
基金Professor Miyaji of Kyoto University for valuable advice and encouragement.
文摘Lamellar crystal thickness lc of isotactic polybutene-1(it-PB1)have been investigated for crystal-lization in the melt over a wide range of crystallization temperature T from 40°C to 90°C by small angle X-ray scattering experiments and density measurements.The crystal thickness lc demonstrates two linear dependences on inverse supercooling and a transition from one dependence to the other has been observed around T=65°C.Each of the two dependences obeys the nucleation theory in the high and low supercooling ranges,respec-tively.Chain folding free energy q determined from the low supercooling range is larger than that determined from the high supercooling range.Possible mechanisms for the transition are discussed taking account of entropy of chain folding directions.
基金Supported by the National Natural Science Funds for Distinguished Young Scholar (Grant No. 20474060)Major State Basic Research Development Program of China (Grant No. 2007CB936401)
文摘Using an ultra-sensitive differential scanning calorimetry (US-DSC), we have investigated the folding and aggregation behaviors of poly(N-isopropylacrylamide) (PNIPAM) chains in dilute and semidilute solutions. In the heating process, the intrachain folding and interchain aggregation simultaneously occur in the dilute solutions, and the ratio of intrachain folding increases with decreasing concentra-tion. In the semidilute solutions, PNIPAM chains show limited interchain aggregation with elevated temperature, because most of the PNIPAM chains have been collapsed at lower temperature. In an ex-tremely dilute solution, PNIPAM chains undergo a single folding transition in the heating process. By extrapolating heating rate and concentration to zero, we have obtained the phase transition tempera-ture (TS) and enthalpy change (△HS) of the single chain folding. △HS is higher than that for a phase transition involving intrachain collapse and interchain aggregation, indicating that a single chain fold-ing can not be taken to be a macroscopic phase transition.
基金supported by the National Natural Science Foundation of China(Nos.22371272 and 22301295)the Fundamental Research Funds for the Central Universities(Nos.YD2060002036 and WK5290000004)+1 种基金International Partnership Program of the Chinese Academy of Sciences(No.123GJHZ2022064MI)the Collaborative Innovation Program of Hefei Science Center,CAS(No.2022HSC-CIP014)。
文摘Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm.Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters complex energy landscapes,leading to the potential occurrence of misfolding issues.While noncovalent crosslinking can circumvent this issue,the resulting single-chain nanoparticles exhibit lower structural stability compared to their covalently crosslinked counterparts.In this study,we present a novel approach for the synthesis of single-chain nanoparticles,achieved through the combination of non-covalent and covalent intramolecular crosslinking.Cyanostilbenes grafted onto the linear polymer form intrachain non-covalent stacks aided by hydrogen bonds,leading to the formation of non-covalently crosslinked single-chain nanoparticles.These nanoparticles undergo conversion to covalently crosslinked nanostructures through subsequent photo-irradiation using[2+2]photocycloaddition,a process facilitated by the supramolecular confinement effect.Consequently,the resulting single-chain nanoparticles demonstrate both intrachain folding efficiency and substantial stability,offering significant potential for advancing applications across diverse fields.
