Raman imaging,as a molecular spectroscopy technique,has been widely studied and applied in research fields such as life sciences and food safety due to its excellent specificity and high resolution.However,its develop...Raman imaging,as a molecular spectroscopy technique,has been widely studied and applied in research fields such as life sciences and food safety due to its excellent specificity and high resolution.However,its development still faces challenges such as weak signals,slow acquisition speed,and insufficient penetration depth.In recent years,the rapid development of aggregate science has provided new insights for addressing these limitations.Aggregation-induced emission(AIE)materials exhibit enhanced signals in the aggregated state,which may compensate for the inherent weak Raman signals.This article reviews the cutting-edge progress of Raman imaging technology and its current status in cross-disciplinary research with aggregate science,emphasizing the strategy of constructing AIE-Raman dual-responsive probes through molecular engineering to achieve functional complementarity between fluorescence localization and Raman quantification,thereby significantly improving detection sensitivity and specificity.These probes have demonstrated single-cell resolution and high spatiotemporal accuracy in applications such as tumor surgical navigation,diagnosis and treatment of drug-resistant bacteria,and dynamic monitoring of organelles.We also analyze the bottlenecks in this field,such as biological safety and the complexity of molecular design,and outline the future development directions,including intelligent responsive probes,artificial intelligence-assisted analysis,and multimodal fusion platforms.The integration of Raman imaging and AIE sheds new light in the field of medical imaging.展开更多
A multi-stimuli-responsive hydrogel,P(VI-co-MAAC-NE),was successfully constructed by covalently integrating the aggregation-induced emission(AIE)moiety(Z)-N-(4-(1-cyano-2-(4-(diethylamino)phenyl)vinyl)-phenyl)methacry...A multi-stimuli-responsive hydrogel,P(VI-co-MAAC-NE),was successfully constructed by covalently integrating the aggregation-induced emission(AIE)moiety(Z)-N-(4-(1-cyano-2-(4-(diethylamino)phenyl)vinyl)-phenyl)methacrylamide(NE)into a dynamic hydrogen-bonding network composed of 1-vinylimidazole(VI)and methacrylic acid(MAAC)groups.The dense hydrogen-bonding network not only provides enhanced mechanical robustness,but also significantly enhances the AIE effect of NE by restricting its molecular motion.Under various external stimuli,the hydrogen bonds within the hydrogel network undergo reversible dissociation and reformation,thus enabling synergistic modulation of the hydrogel’s mechanical properties and luminescence behavior.Specifically,organic solvents disrupt the hydrogen-bonding network and the aggregation of the AIE moiety NE,resulting in macroscopic swelling and fluorescence quenching of the hydrogel.In strongly acidic conditions,protonation of NE molecules suppresses the intramolecular charge transfer(ICT)process,yielding a blue-shifted emission band accompanied by intense blue fluorescence;in highly alkaline environments,deprotonation of carboxyl groups induces hydrogel swelling and disperses NE aggregates,leading to pronounced fluorescence quenching.Moreover,the system exhibits thermally activated shape-memory behavior:heating above the glass transition temperature(T_(g):ca.62℃)softens the hydrogel to allow programmable reshaping,and subsequent hydrogen bond reformation at ambient conditions locks in the resultant geometries without sacrificing the hydrogel’s fluorescence performance.By capitalizing on these multi-stimuli-responsive characteristics and shape-memory behavior,the potential of hydrogel P(VI-co-MAAC-NE)for advanced information encryption and anti-counterfeiting applications is demonstrated.This work not only provides a versatile material platform for sensing and information storage,but also offers new insights into the design of intelligent soft materials integrating AIE features with dynamically regulated supramolecular network structures.展开更多
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Raman imaging,as a molecular spectroscopy technique,has been widely studied and applied in research fields such as life sciences and food safety due to its excellent specificity and high resolution.However,its development still faces challenges such as weak signals,slow acquisition speed,and insufficient penetration depth.In recent years,the rapid development of aggregate science has provided new insights for addressing these limitations.Aggregation-induced emission(AIE)materials exhibit enhanced signals in the aggregated state,which may compensate for the inherent weak Raman signals.This article reviews the cutting-edge progress of Raman imaging technology and its current status in cross-disciplinary research with aggregate science,emphasizing the strategy of constructing AIE-Raman dual-responsive probes through molecular engineering to achieve functional complementarity between fluorescence localization and Raman quantification,thereby significantly improving detection sensitivity and specificity.These probes have demonstrated single-cell resolution and high spatiotemporal accuracy in applications such as tumor surgical navigation,diagnosis and treatment of drug-resistant bacteria,and dynamic monitoring of organelles.We also analyze the bottlenecks in this field,such as biological safety and the complexity of molecular design,and outline the future development directions,including intelligent responsive probes,artificial intelligence-assisted analysis,and multimodal fusion platforms.The integration of Raman imaging and AIE sheds new light in the field of medical imaging.
文摘A multi-stimuli-responsive hydrogel,P(VI-co-MAAC-NE),was successfully constructed by covalently integrating the aggregation-induced emission(AIE)moiety(Z)-N-(4-(1-cyano-2-(4-(diethylamino)phenyl)vinyl)-phenyl)methacrylamide(NE)into a dynamic hydrogen-bonding network composed of 1-vinylimidazole(VI)and methacrylic acid(MAAC)groups.The dense hydrogen-bonding network not only provides enhanced mechanical robustness,but also significantly enhances the AIE effect of NE by restricting its molecular motion.Under various external stimuli,the hydrogen bonds within the hydrogel network undergo reversible dissociation and reformation,thus enabling synergistic modulation of the hydrogel’s mechanical properties and luminescence behavior.Specifically,organic solvents disrupt the hydrogen-bonding network and the aggregation of the AIE moiety NE,resulting in macroscopic swelling and fluorescence quenching of the hydrogel.In strongly acidic conditions,protonation of NE molecules suppresses the intramolecular charge transfer(ICT)process,yielding a blue-shifted emission band accompanied by intense blue fluorescence;in highly alkaline environments,deprotonation of carboxyl groups induces hydrogel swelling and disperses NE aggregates,leading to pronounced fluorescence quenching.Moreover,the system exhibits thermally activated shape-memory behavior:heating above the glass transition temperature(T_(g):ca.62℃)softens the hydrogel to allow programmable reshaping,and subsequent hydrogen bond reformation at ambient conditions locks in the resultant geometries without sacrificing the hydrogel’s fluorescence performance.By capitalizing on these multi-stimuli-responsive characteristics and shape-memory behavior,the potential of hydrogel P(VI-co-MAAC-NE)for advanced information encryption and anti-counterfeiting applications is demonstrated.This work not only provides a versatile material platform for sensing and information storage,but also offers new insights into the design of intelligent soft materials integrating AIE features with dynamically regulated supramolecular network structures.
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.
