INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation a...INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation and phasetransitions of polymers. A description of the conformational state transition requires questions about; 1) howmany stable conformational states for a specific σ bond; 2) the barriers between the states; 3) the mechanismof the conformational transition; 4) any cooperative behavior during the transition. Flory and his coworkers展开更多
The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based ...The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based adiabatic geometric optimization method and the one-dimensional transmission combined with three-dimensional correction approximation(OTCTCA)method.The numerical results show that for the 4,40-dipyridyl with a p-conjugated phenyl-phosphoryl or diphenylsilyl side group,the pyridyl vertically anchors on the second atomic layer of the pyramid-shaped Au tip electrode at small inter-electrode distances by laterally pushing the apical Au atom aside,which induces stronger pyridyl-electrode coupling and high-conductance state of the formed junctions.As the inter-electrode distance increases,the pyridyl shifts to the apical Au atom of the tip electrode.This apical Au atom introduces additional scatterings to the tunneling electrons and significantly decreases the conductance of the junctions.Furthermore,for the 4,40-dipyridyl with a phenyl-phosphoryl side group,the probability of manifesting the high-conductance state is decreased due to the oxygen atom reducing the probability of the pyridyl adsorbing on the second layer of Au tip electrode.In contrast,for the 4,40-dipyridyl with a nonconjugated cyclohexyl-phosphoryl side group,the steric hindrance from the bulky cyclohexyl group leads the molecule to preferentially form the O-Au contact,which prevents both the high conductance and mechanically induced conductance switching of the junction.Our results provide a theoretical understanding of the side-group effects on electronic transport properties of single-molecule junctions,offering an alternative explanation for the experimental observations.展开更多
A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polyconde...A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polycondensation in m-cresol.This PI is a semicrystalline polymer.Lots of short fine fibric crystals with length and diameter about 20、μm and 1、μm respectively disperse randomly in the PI film. The optical textures and the X-ray diffraction patterns of the PI solution and film show that the PI main chains are in the extended conformation and pack parallel to each other, and the pendent biphenyl ester groups occupy the space between the main chain layers,more or less perpendicular to the main chains.At the same time, mechanical and thermally stable properties of the PI film were investigated. The excellent mechanical properties of general polyimide films are reasonably maintained, the polyimide film with pendent groups showes higher tensile strength and modulus and lower T g. TGA study showes a typical two-step weight loss behavior corresponding to the pyrolysis of pendent groups and main chains of the PI,respectively.展开更多
文摘INTRODUCTION The conformational state transition of polymer chains relates to crystallization processes, migration ofthe chains in solution, fluctuation of the end-to-end distance of random coils, and the relaxation and phasetransitions of polymers. A description of the conformational state transition requires questions about; 1) howmany stable conformational states for a specific σ bond; 2) the barriers between the states; 3) the mechanismof the conformational transition; 4) any cooperative behavior during the transition. Flory and his coworkers
基金supported by the National Natural Science Foundation of China(Grant Nos.12474286,22173052,and 12204281).
文摘The forming processes of 4,40-dipyridyl-based single-molecule junctions and mechanically induced conductance switching as well as the side-group effects are systematically investigated by applying the ab initio-based adiabatic geometric optimization method and the one-dimensional transmission combined with three-dimensional correction approximation(OTCTCA)method.The numerical results show that for the 4,40-dipyridyl with a p-conjugated phenyl-phosphoryl or diphenylsilyl side group,the pyridyl vertically anchors on the second atomic layer of the pyramid-shaped Au tip electrode at small inter-electrode distances by laterally pushing the apical Au atom aside,which induces stronger pyridyl-electrode coupling and high-conductance state of the formed junctions.As the inter-electrode distance increases,the pyridyl shifts to the apical Au atom of the tip electrode.This apical Au atom introduces additional scatterings to the tunneling electrons and significantly decreases the conductance of the junctions.Furthermore,for the 4,40-dipyridyl with a phenyl-phosphoryl side group,the probability of manifesting the high-conductance state is decreased due to the oxygen atom reducing the probability of the pyridyl adsorbing on the second layer of Au tip electrode.In contrast,for the 4,40-dipyridyl with a nonconjugated cyclohexyl-phosphoryl side group,the steric hindrance from the bulky cyclohexyl group leads the molecule to preferentially form the O-Au contact,which prevents both the high conductance and mechanically induced conductance switching of the junction.Our results provide a theoretical understanding of the side-group effects on electronic transport properties of single-molecule junctions,offering an alternative explanation for the experimental observations.
文摘A novel polyimide(PI) containing pendent biphenyl ester groups was synthesized from 3,5-diaminobenzoic-4′-biphenyl ester (DABBE)and 3,3′,4,4′-oxydiphthalic dianhydride(ODPA) by a one-step high-temperature polycondensation in m-cresol.This PI is a semicrystalline polymer.Lots of short fine fibric crystals with length and diameter about 20、μm and 1、μm respectively disperse randomly in the PI film. The optical textures and the X-ray diffraction patterns of the PI solution and film show that the PI main chains are in the extended conformation and pack parallel to each other, and the pendent biphenyl ester groups occupy the space between the main chain layers,more or less perpendicular to the main chains.At the same time, mechanical and thermally stable properties of the PI film were investigated. The excellent mechanical properties of general polyimide films are reasonably maintained, the polyimide film with pendent groups showes higher tensile strength and modulus and lower T g. TGA study showes a typical two-step weight loss behavior corresponding to the pyrolysis of pendent groups and main chains of the PI,respectively.
