Cooperativity broadly manifests itself from biology to society. Biology uses the language of non-covalent chemistry and supramolecular self-assembly to communicate to each other and the outside environment. In materials science, non-covalent self-assembly offers a versatile and modular strategy in generating functional architectures that often display dynamic, cooperative behaviors in response to environmental stimuli. Recently, our lab has discovered several unique cooperative systems with all-or-nothing bistable states without intermediates. In one example, an anti-Hofmeister trend was shown where chaotropic anions induced 'phase out' of cationic block copolymers in contrary to 'phase in' for protein solubilization. In another example, hydrophobic micellization drove divergent proton distribution of transistor-like ultra-pH sensitive nanoprobes with a Hill coefficient of 51, by far the largest reported in the literature. We are using these systems to learn how the alphabets of self-assembly (e.g., hydrophobic, hydrogen bonding and electrostatic interactions) are constructed together to create the 'language of cooperativity'.
- Li Y, Wang YG, Huang G, Ma X, Gao J. A Surprising Chaotropic Anion-Induced Supramolecular Self-Assembly of Ionic Polymeric Micelles. Angew. Chem. Int. Ed. 2014, 53, 8074-8078. PDF
- Ma X, Wang YG, Zhao T, Li Y, Su LC, Wang Z, Huang G, Sumer BD, Gao J. Ultra-pH Sensitive Nanoprobe Library with Broad pH Tunability and Fluorescence Response. J. Am. Chem. Soc. 2014, 136, 11085-11092. (Selected as ACS Editor's Choice) PDF
- Huang X, Huang G, Zhang SR, Sagiyama K, Togao O, Ma X, Wang Y, Li Y, Soesbe TC, Takahashi M, Sherry AD, Gao J. Multi-Chromatic pH-Activatable 19F-MRI Nanoprobes with Binary ON/OFF pH Transitions and Chemical Shift Barcodes. Angew. Chem. Int. Ed. 2013, 52, 8074-8078. PDF
- Li Y, Zhao T, Wang C, Lin Z, Huang G, Sumer BD, Gao J. Molecular basis of cooperativity in pH-triggered supramolecular self-assembly. Nature Comm. 2016, 7, 13214. PDF
- Li Y, Wang Y, Huang G, Gao J. Cooperativity Principles in Self-Assembled Nanomedicine. Chem. Rev. 2018, 118, 5359-91. PDF
- Wilhelm J, Wang Z, Sumer BD, Gao J. Exploiting nanoscale cooperativity for precision medicine. Adv. Drug Deliv. Rev. 2020, 158, 63-72. PDF