Soft Matter

The ability to control nanoscale materials in response to specific stimuli is expected to have a significant impact in targeted drug delivery and advanced sensor design. Hence, we work extensively on the synthesis of the polymeric materials, via a range of new or established techniques, and also on the assembly of the materials into precise nanoparticles by a directed assembly approach. This extensive understanding on the assembly and morphology of polymeric materials is a key area of research in the Gianneschi group and allows us to incorporate proteins, peptides and nucleic acids into novel polymeric synthetic materials with the aim of programming morphology and function.

Directed Assembly

The Gianneschi group works extensively on directing the assembly of polymeric materials, where we utilize polymer dynamics, and/or synthetic design to build complexity. These systems work on a non-equilibrium hypothesis of dissipative adaptation in which it is proposed that aggregation state could be statistically selectable in a fluctuating system that is driven by an external driving force. This has led to the design and implementation of programmed micellar nanoparticles that can be deployed for sense-and-response applications. The result is a generic, fundamental method for finding and testing novel hierarchical materials by pushing the limits of our knowledge of non-equilibrium processes.

Phase Diagrams of Polynorbornene Amphiphilic Block Copolymers in Solution
Sarah A. Barnhill, Nia C. Bell, Joseph P. Patterson, Daniel P. Olds, and Nathan C. Gianneschi
Macromolecules, 2015, 48 (4), 1152–1161, DOI: 10.1021/ma502163j

Enzyme-Directed Assembly and Manipulation of Organic Nanomaterials
Michael E. Hahn and Nathan C. Gianneschi
Chem. Comm., 2011, 47, 11814-11821, DOI: 10.1039/C1CC15220C

Melanin

Melanin is a ubiquitous polymeric material found in nature. It has diverse basic functionality including energy dissipation, high refractive index of ~2.0, material toughness, and strong metal-binding capacity. Our work seeks to explore melanin in natural and synthetic systems to elucidate structure-function relationships, mimic and enhance its naturally-occurring functionalities, and control long-range supramolecular order for emergent functionality.

Mimicking Melanosomes: Polydopamine Nanoparticles as Artificial Microparasols
Yuran Huang, Yiwen Li , Ziying Hu, Xiujun Yue, Maria T. Proetto, Ying Jones, and Nathan C. Gianneschi*
ACS Cent. Sci., 2017, 3(6), 564–569, DOI: 10.1021/acscentsci.6b00230

Structure and Function of Iron-Loaded Synthetic Melanin
Yiwen Li,^† Yijun Xie,^† Zhao Wang,^† Nanzhi Zang, Fabio Carniato, Yuran Huang, Christopher M. Andolina, Lucas R. Parent, Treffly B. Ditri, Eric D. Walter, Mauro Botta, Jeffrey D. Rinehart,* and Nathan C. Gianneschi*
ACS Nano, 2016, 10 (11), 10186–10194, DOI: 10.1021/acsnano.6b05502

Stimuli-Responsive Structurally Colored Films from Bioinspired Synthetic Melanin Nanoparticles
Ming Xiao, Yiwen Li, Jiuzhou Zhao, Zhao Wang, Min Gao, Nathan C. Gianneschi*, Ali Dhinojwala*, and Matthew D. Shawkey*
Chemistry of Materials, 2016, 28 (15), 5516–5521, DOI: 10.1021/acs.chemmater.6b02127

Synthetic Polymeric Materials

The common thread that links most of the research projects in our group is the use of polymers and polymeric materials. We rely on a number of different polymerization methods to synthesize these materials including living and radical techniques such as Ring Opening Metathesis (ROMP), Reversible Addition-Fragmentation chain Transfer (RAFT) and Free Radical Polymerization. The robustness of these polymerization methods has allowed us to synthesize polymers and materials incorporating a diverse range of functional groups that are used to control and tune the properties of these materials for applications including delivery, imaging, sensing and catalysis. Projects in this area focus on the development of monomers, strategies for their polymerization and characterization, analysis and evaluation of the resulting polymeric materials.

ROMPISA: Ring-Opening Metathesis Polymerization-Induced Self-Assembly
Daniel B. Wright, Mollie A. Touve, Lisa Adamiak, and Nathan C. Gianneschi*
ACS Macro Letters, 2017, 6 (9), 925–929, DOI: 10.1021/acsmacrolett.7b00408

Polymer-Stabilized Perfluorobutane Nanodroplets for Ultrasound Imaging Agents
Yuran Huang, Alexander Vezeridis, James Wang, Zhao Wang, Matthew Thompson, Robert Mattrey, and Nathan C. Gianneschi*
J. Am. Chem. Soc., 2017, 139 (1), 15–18, DOI: 10.1021/jacs.6b08800

Polymeric Gd-DOTA Amphiphiles Form Spherical and Fibril-Shaped Nanoparticle MRI Contrast Agents
Lyndsay M. Randolph,� Clare L. M. LeGuyader,� Michael E. Hahn,� Christopher M. Andolina, Joseph P. Patterson, Robert F. Mattrey, Jill E. Millstone, Mauro Botta, Miriam Scadeng, Nathan C. Gianneschi*
Chemical Science, 2016, 7, 4230–4236, DOI: 10.1039/C6SC00342G