self-assembled material; self-assembly; molecular simulation; supramolecular polymer; multiscale system; molecular modeling; dynamic materials; hierarchical structure; self-assembled fiber; supramolecular fiber
Bochicchio Davide, Pavan Giovanni M. (2018), Accelerated Atomistic Simulations of a Supramolecular Polymer in Water, in arXiv
Casellas N. M., Pujals S., Bochicchio D., Pavan G. M., Torres T., Albertazzi L., García-Iglesi (2018), From Isodesmic to Highly Cooperative: Reverting Supramolecular Polymerization Mechanism in Water by Fine Monomer Design., in Chemical Communications
Torchi Andrea, Bochicchio Davide, Pavan Giovanni M. (2018), How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure− Dynamics−Property Relationships From Coarse- Grained Simulations., in Journal of Physical Chemistry B
, 122, 4169.
Bochicchio Davide, Pavan Giovanni M. (2018), Molecular Modelling of Supramolecular Polymers, in Advances in Physics: X
, 3, 1436408..
Bochicchio Davide, Pavan Giovanni M. (2017), From cooperative self-assembly to water-soluble supramolecular polymers using coarse-grained simulations, in ACS Nano
, 11, 1000-1011.
Bochicchio Davide, Pavan Giovanni M. (2017), Effect of Concentration on the Supramolecular Polymerization Mechanism via Implicit-Solvent Coarse-Grained Simulations of Water-Soluble 1,3,5-Benzenetricarboxamide, in Journal of Physical Chemistry Letters
, 8, 3813.
Bochicchio Davide, Salvalaglio Matteo, Pavan Giovanni M. (2017), Into the Dynamics of a Supramolecular Polymer at Submolecular Resolution, in Nature Communications
, (8), 147.
Fredy J.W., Mendez-Ardoy A., Kwangmettatam S., Bochicchio D., Matt B., Stuart M. C. A., Huskens J., Katsonis N., Pavan G.M., Kudernac T. (2017), Molecular photoswitches mediating the strain-driven disassembly of supramolecular tubules, in Proceedings of the National Academy of Sciences of the United States of America
, 114, 11850.
Garzoni Matteo, Baker Matthew B., Leenders Christianus M. A., Voets Ilja K., Albertazzi Lorenzo, Palmans Anja R. A., Meijer E. W., Pavan Giovanni M. (2016), Effect of H-bonding on order amplification in the growth of a supramolecular polymer in water, in J. Am. Chem. Soc.
, 138, 13985-1399.
Synthetic supramolecular polymers are composed of monomeric units that self-assemble in ordered fashion via non-covalent interactions. These self-assembled materials constitute a versatile alternative to covalent polymers for many applications (biomedical, cosmetics, foodstuff, etc.) thanks to their bio-inspired and superior properties (e.g., self-healing) and their dynamic and responsive nature. However, the rules to design these systems are not well understood. The major challenge is to understand how small modifications in the monomer structure can produce large changes in the self-assembled material. This is fundamental to design supramolecular polymers in which the final properties are controlled by the molecular information stored in the self-assembling units. Usually, libraries of self-assembling molecules are created and the resulting supramolecular materials are evaluated in an assay through an expensive and repetitive experimental process. Nevertheless, in water solution it often extremely difficult, if not impossible, to obtain clear understanding of the interactions governing the self-assembly process. Molecular modeling is a fundamental support to the study of supramolecular polymers. Recently, we have developed a modeling approach based on all-atom molecular dynamics simulations to understand the effect of small changes in the monomer structure on the dynamics of the supramolecular polymer in water (Nat. Commun. 2015, 6, 6234): a direct structure/dynamics/property relationship. Focusing on 1,3,5-benzenetricarboxamide (BTA) monomers, a synthetic analog self-assembling into supramolecular fibers in water, our models demonstrated optimal consistency with the experiments and allowed for a detailed characterization of the supramolecular fibers and of the interactions controlling self-assembly in water. Comparison between fibers of achiral or chiral BTA monomers provided a direct link between the chiral information stored into the monomers and supramolecular polymer helicity, persistency and dynamic behavior. Together with a remarkable advance in the field, this preliminary study also proposed new exciting questions: How can we modify the monomers to control the final structure and the dynamic behavior of the supramolecular polymer? How can we transmit the structural information stored in the monomers to the supramolecular polymer to obtain controlled macroscale structural and dynamic properties in water? The aim of this project proposal is to expand our simulation strategy to model the effect of two key parameters on the behavior of the water-soluble supramolecular polymer:•Changing the monomers structure: Carbohydrate-decorated BTAs offer an example of achiral core decorated with an intrinsically chiral functionality, and the promise for highly-soluble and biocompatible supramolecular materials •Supramolecular copolymers: Mixing achiral and chiral monomers (BTAs) into a supramolecular copolymer provides an interesting case to study how the monomers transmit the chiral information to the supramolecular material in water We devised a computational approach to tackle these two points in a systematic way. The modeling strategy presented herein will allow for a multi-scale description of the mechanisms that govern the transmission of the information stored into the monomers to the supramolecular material, controlling the final properties. The computational effort required for this project will benefit from the precious collaboration of the experimental group of Prof. E.W. “Bert” Meijer (TU/e, Eindhoven, NL), a world-leading research group in the field. The obtained results will produce outstanding innovation in the fields of self-assembling materials and supramolecular chemistry, and will pave the way for the rational design of water-soluble supramolecular polymers with controlled properties.