title: Spatiotemporal Control of Supramolecular Self-Assembly and Function.
abstract: The enzyme-triggered self-assembly of peptides has flourished in controlling the self-assembly kinetics and producing nanostructures that are typically inaccessible by conventional self-assembly pathways. However, the diffusion and nanoscale chemical gradient of self-assembling peptides generated by the enzyme also significantly affect the outcome of self-assembly, which has not been reported yet. In this work, we demonstrated for the first time a spatiotemporal control of enzyme-triggered peptide self-assembly. By simply adjusting the temperature, we could change both the catalytic activity of the enzyme of phosphatase and their aggregation states. The strategy kinetically controls the production rate of self-assembling peptides and spatially controls their distribution in the system, leading to the formation of nanoparticles at 37 °C and nanofibers at 4 °C. The nanofibers showed ∼10 times higher cellular uptake by 3T3 cells than the nanoparticles, thanks to their higher stability and more ordered structures. Using such spatiotemporal control, we could prepare optimized nanoprobes with low background fluorescence, rapid and high cellular uptake, and high sensitivity. We postulate that this strategy would be very useful in general for preparing self-assembled nanomaterials with controllable morphology and function.
authors.affiliation: State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, People's Republic of China.|College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Design, Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Jie
authors.initials: J
authors.lastname: Zhan
authors.affiliation: State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Yanbin
authors.initials: Y
authors.lastname: Cai
authors.affiliation: State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Shenglu
authors.initials: S
authors.lastname: Ji
authors.affiliation: College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Design, Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Shuangshuang
authors.initials: S
authors.lastname: He
authors.affiliation: College of Physics, Nanjing University , Nanjing 210093, People's Republic of China.
authors.forename: Yi
authors.identifier: http://orcid.org/0000-0003-1493-7868
authors.initials: Y
authors.lastname: Cao
authors.affiliation: State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Dan
authors.initials: D
authors.lastname: Ding
authors.affiliation: College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Design, Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Ling
authors.initials: L
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials, Ministry of Education, College of Life Sciences, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, People's Republic of China.|College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Design, Nankai University , Tianjin 300071, People's Republic of China.
authors.forename: Zhimou
authors.identifier: http://orcid.org/0000-0003-2967-6920
authors.initials: Z
authors.lastname: Yang
keywords: diffusion; enzyme; kinetics; molecular probe; peptide; self-assembly