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Controlling Water-Soluble Supramolecular Polymers - Toward Rational Design Using Molecular Modeling

English title Controlling Water-Soluble Supramolecular Polymers - Toward Rational Design Using Molecular Modeling
Applicant Pavan Giovanni Maria
Number 162827
Funding scheme Project funding (Div. I-III)
Research institution Dipartimento Tecnologie Innovative (DTI) Scuola universitaria professionale della Svizzera italiana (SUPSI)
Institution of higher education University of Applied Sciences and Arts of Southern Switzerland - SUPSI
Main discipline Material Sciences
Start/End 01.03.2016 - 28.02.2018
Approved amount 199'400.00
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All Disciplines (2)

Discipline
Material Sciences
Physical Chemistry

Keywords (10)

self-assembled material; self-assembly; molecular simulation; supramolecular polymer; multiscale system; molecular modeling; dynamic materials; hierarchical structure; self-assembled fiber; supramolecular fiber

Lay Summary (Italian)

Lead
I polimeri supramolecolari sintetici sono composti da unità monomeriche che si auto-assemblano in modo ordinato tramite interazioni non covalenti. Questi materiali auto-assemblati costituiscono un’alternativa versatile ai polimeri covalenti convenzionali per varie applicazioni (biomedicina, energia, cosmesi, alimentare, etc.) grazie alle loro superiori proprietà bio-ispirate (abilità di auto-ripararsi, etc.) e la loro natura dinamica e reattiva. Tuttavia, I principi di progettazione di questi sistemi non sono ben compresi. La sfida principale è capire come piccole modifiche nella struttura del monomero possano produrre grandi cambiamenti nel materiale auto-assemblato. Ciò è fondamentale per progettare polimeri supramolecolari in cui le proprietà finali siano controllate dalle informazioni molecolari immagazzinate nelle unità auto-assemblanti (monomeri).
Lay summary

Obiettivi

Il nostro obiettivo principale è quello di comprendere in dettaglio come la struttura del monomero controlli le proprietà del polimero auto-assemblato a livello multi-scala. Questo è molto difficile, e spesso impossibile, da otterere a livello sperimentale, soprattutto in acqua. Concentrandoci su 1,3,5-benzenetricarboxamide (BTA), un monomero sintetico che auto-assembla in acqua formando fibre supramolecolari, svilupperemo modelli molecolari e utilizzeremo simulazioni al computer per studiare l'effetto di modifiche sistematiche della struttura molecolare dei monomeri sulle proprietà del polimero supramolecolare. I nostri risultati computazionali saranno confrontati con gli esperimenti condotti dai nostri collaboratori, al fine di fornire un quadro completo su scale multiple di questi sistemi supramolecolari in soluzione acquosa.

 

Contesto scientifico e sociale

I polimeri supramolecolari idrosolubili, ottenuti attraverso l'auto-assemblaggio a temperatura ambiente di monomeri studiati ad hoc, costituiscono una piattaforma versatile per ottenere in modo conveniente materiali avanzati con proprietà affascinanti. L'elevato controllo strutturale e cinetico che può essere raggiunto in tali strutture promette un impatto reale in molti campi tecnologici.

Direct link to Lay Summary Last update: 17.12.2015

Lay Summary (English)

Lead
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, energy, cosmetics, foodstuff, etc.) thanks to their superior bio-inspired 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.
Lay summary

Aims of the research project at the start of research and results after completion of the project

Aims of the research project at the start of research and results after completion of the project

Aims of the research project at the start of research and results after completion of the project

Objectives

Our main objective is to understand in detail how the structure of the monomer controls the properties of the self-assembled polymer on a multiscale level. This is very difficult and often impossible at experimental level, especially in water. Focusing on 1,3,5-benzenetricarboxamide (BTA) monomers, a synthetic analog self-assembling into supramolecular fibers in water, we will develop molecular models and use computer simulations to systematically investigate the effect of changing the molecular structure of the monomers on the properties of the supramolecular polymer. Our computational results will be compared to the experiments from our collaborators, providing a comprehensive multiscale picture of these supramolecular systems in water solution.

  

Scientific and societal context

Synthetic water-soluble supramolecular polymers, obtained through the self-assembly at room temperature of ad hoc designed monomers, constitute a versatile platform to obtain advanced materials with fascinating properties in convenient way. The high structural and kinetic control that can be achieved for such structures constitutes the promise for real breakthroughs in many technological fields.

Direct link to Lay Summary Last update: 17.12.2015

Responsible applicant and co-applicants

Employees

Name Institute

Publications

Publication
Accelerated Atomistic Simulations of a Supramolecular Polymer in Water
Bochicchio Davide, Pavan Giovanni M. (2018), Accelerated Atomistic Simulations of a Supramolecular Polymer in Water, in arXiv, 1803.10491.
From Isodesmic to Highly Cooperative: Reverting Supramolecular Polymerization Mechanism in Water by Fine Monomer Design.
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, xx.
How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure− Dynamics−Property Relationships From Coarse- Grained Simulations.
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.
Molecular Modelling of Supramolecular Polymers
Bochicchio Davide, Pavan Giovanni M. (2018), Molecular Modelling of Supramolecular Polymers, in Advances in Physics: X, 3, 1436408..
From cooperative self-assembly to water-soluble supramolecular polymers using coarse-grained simulations
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.
Effect of Concentration on the Supramolecular Polymerization Mechanism via Implicit-Solvent Coarse-Grained Simulations of Water-Soluble 1,3,5-Benzenetricarboxamide
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.
Into the Dynamics of a Supramolecular Polymer at Submolecular Resolution
Bochicchio Davide, Salvalaglio Matteo, Pavan Giovanni M. (2017), Into the Dynamics of a Supramolecular Polymer at Submolecular Resolution, in Nature Communications, (8), 147.
Molecular photoswitches mediating the strain-driven disassembly of supramolecular tubules
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.
Effect of H-bonding on order amplification in the growth of a supramolecular polymer in water
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.

Collaboration

Group / person Country
Types of collaboration
Prof. E. W. "Bert" Meijer group - Eindhoven University of Technology Netherlands (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Swiss Conference on Supramolecular Polymers Poster Coarse grained simulations of dynamically adaptive supramolecular polymers 01.02.2018 Fribourg, Switzerland Bochicchio Davide;
The Science of Surfaces, Interfaces and Nanostructures (SAOG) Talk given at a conference Multiscale modelcular modeling of dynamic materials and surfaces 01.02.2018 Fribourg, Switzerland Pavan Giovanni Maria;
International Molecular Machines Nobel Prize Conference Poster Into Bioinspired Dynamic Materials at Submolecular Resolution Using Molecular Modeling 19.11.2017 Groningen, Netherlands Pavan Giovanni Maria; Bochicchio Davide;
Seminar Individual talk Into dynamic supramolecular polymers at submolecular resolution using molecular modeling 17.11.2017 University of Groningen, Netherlands Pavan Giovanni Maria;
Seminar Individual talk Into dynamic supramolecular polymers at submolecular resolution using molecular modeling 16.11.2017 University of Twente, Netherlands Pavan Giovanni Maria;
Swiss Conference on Supramolecular Polymers Talk given at a conference Into dynamic supramolecular polymers at submolecular resolution 06.11.2017 Fribourg, Switzerland Pavan Giovanni Maria;
Seminar Individual talk Into dynamic supramolecular polymers using molecular modeling 27.02.2017 University College London, Great Britain and Northern Ireland Pavan Giovanni Maria; Bochicchio Davide;
Seminar Individual talk Into dynamic supramolecular polymers using molecular modeling 25.01.2017 TU/e, Netherlands Pavan Giovanni Maria;
Seminar Individual talk Multiscale modelling of bioinspired selfassembled materials 20.11.2016 Ben Gurion University, Israel Pavan Giovanni Maria;
Seminar Individual talk Multiscale modelling of bioinspired selfassembled materials 18.11.2016 Tel Aviv University, Israel Pavan Giovanni Maria;


Associated projects

Number Title Start Funding scheme
175735 Multiscale Modeling of Self-Assembled Polymeric Nanocarriers Responding to Specific Protein Stimuli 01.03.2018 Project funding (Div. I-III)

Abstract

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.
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