Although aggregation-induced emission(AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging,the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor e...Although aggregation-induced emission(AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging,the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood.Herein,we elucidate the mechanisms governing the tetraphenylethene(TPE)'s function(rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7.Our study shows that modulating the frontier orbital energy difference(ΔE(DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3,act as a rotor in Cy5 uniquely devoid of aggregation activation,or neither in Cy7.In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity.We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.展开更多
基金supported by National Natural Science Foundation of China(Nos.32371433 and W2411083)the National Key Research and Development Program of China(No.2022YFB3203800)+4 种基金Guang Dong Basic and Applied Basic Research Foundation(No.2023A1515030207)Key Research and Development Program of Shaanxi(No.2024SF2-GJHX-30)Innovation Capability Support Program of Shaanxi(No.2022TD-52)Dual-chain Integration Special Program of Qin Chuang Yuan Construction(No.23LLRH0070)Xidian University Specially Funded Project for Interdisciplinary Exploration(Nos.TZJH2024035,TZJH2024031)。
文摘Although aggregation-induced emission(AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging,the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood.Herein,we elucidate the mechanisms governing the tetraphenylethene(TPE)'s function(rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7.Our study shows that modulating the frontier orbital energy difference(ΔE(DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3,act as a rotor in Cy5 uniquely devoid of aggregation activation,or neither in Cy7.In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity.We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.
