文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性...文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性螺旋聚异腈poly(150-150/3n)。通过核磁共振氢谱(1 H nuclear magnetic resonance,1 H NMR)、氟核磁共振谱(19F nuclear magnetic resonance,19F NMR)等手段对聚合物的结构进行表征,使用圆二色光谱(circular dichroism,CD)、荧光光谱及圆偏振发光(circularly polarized luminescence,CPL)光谱对聚合物的光学性质进行表征,发现共聚物poly(150-150/3n)为一类具有CPL效应的高分子材料。展开更多
Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we dev...Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.展开更多
文摘文章使用手性大分子引发剂poly-150引发手性单体1与非手性单体2共聚得到侧基有活泼酯修饰的共聚物poly(150-150/2n),采用后修饰的方法将羟基修饰的荧光分子3a、3b、3c与poly(150-150/2n)进行酯交换反应,即可得到不同荧光基团修饰的手性螺旋聚异腈poly(150-150/3n)。通过核磁共振氢谱(1 H nuclear magnetic resonance,1 H NMR)、氟核磁共振谱(19F nuclear magnetic resonance,19F NMR)等手段对聚合物的结构进行表征,使用圆二色光谱(circular dichroism,CD)、荧光光谱及圆偏振发光(circularly polarized luminescence,CPL)光谱对聚合物的光学性质进行表征,发现共聚物poly(150-150/3n)为一类具有CPL效应的高分子材料。
基金the funding support from the Smart Medicine and Engineering Interdisciplinary Innovation Project of Ningbo University(No.ZHYG003)。
文摘Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.
