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Symmetric and Asymmetric Twisted Nanorods with End-Tethered Polymer Chains

Applicant Zoppe Justin
Number 167900
Funding scheme Ambizione
Research institution Adolphe Merkle Institute Université de Fribourg
Institution of higher education University of Fribourg - FR
Main discipline Organic Chemistry
Start/End 01.03.2017 - 31.10.2020
Approved amount 621'890.00
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All Disciplines (3)

Discipline
Organic Chemistry
Physical Chemistry
Material Sciences

Keywords (8)

chirality; liquid crystals; cellulose nanocrystals; surface-initiated polymerization; self-assembly; polymer-tethered nanorods; cholesteric; hybrid materials

Lay Summary (German)

Lead
Eine der praktischsten Strategien um Materialien mit neuen Eigenschaften zu erzeugen, ist die Selbstassemblierung von chemischen Bausteinen in nanoskalige Strukturen. Die Bausteine selbstorganisierter Strukturen können aus kleinen Molekülen, Polymeren oder kolloidalen Partikeln bestehen. Besonders die Selbstassemblierung von Kolloiden bietet eine einfache Methode für die Herstellung komplexer, dreidimensionaler Materialstrukturen. Eine attraktive Klasse chiral-kolloidaler Bausteine sind Zellulose-Nanokristalle (CNCs), welche aus natürlichen, reichlich vorhandenen erneuerbaren Rohstoffen gewonnen werden. Eine im Vergleich zu anderen stabförmigen Nanopartikeln einzigartige Eigenschaft von CNCs ist die Bildung von Flüssigkristallphasen, deren Struktur bei der Herstellung von trockenen Filmen erhalten bleibt. Somit sind CNCs ein ideales Ausgangsmaterial für die Entwicklung neuartiger, poröser Materialien mit weiträumig chiraler Ordnung.
Lay summary

Inhalt und Ziel des Forschungsprojekts

Das Ziel dieses Forschungsprojektes ist die systematische Untersuchung selektiver Endgruppenmodifikation der Zellulose-Nanokristalle mit dem Ziel, die Selbstassemblierung in Flüssigkristallphasen zu kontrollieren, sowohl in kolloidalen Lösungen, als auch in Filmen. Entsprechend werden die Enden von CNCs unterschiedlicher Kristallstruktur mit einer Reihe von verschiedenen Polymerketten modifiziert, sodass stabförmige Nanopartikel mit asymmetrischen und symmetrischen Formen entstehen. Schlussendlich werden die Flüssigkristalleigenschaften der modifizierten CNCs sowohl in unterschiedlichen Lösungsmitteln als auch in festem Zustand untersucht.

Wissenschaftlicher und gesellschaftlicher Kontext des Forschungsprojekts

Die Einführung von Chiralität, oder Händigkeit, in solch poröse Feststoffe könnte zu wünschenswerten Eigenschaften für die Anwendung ergeben, zum Beispiel für asymmetrische Katalysatoren, enantioselektive Sorptionsmittel, Biosensoren und Optiken. Diese neuen Materialien könnten einen wichtigen Beitrag zur Überwindung gesellschaftlicher Herausforderungen leisten, wie beispielsweise im Gesundheitswesen, in der Energiewende und dem Klimawandel.

Direct link to Lay Summary Last update: 13.02.2017

Responsible applicant and co-applicants

Employees

Publications

Publication
Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs
Delepierre Gwendoline, Eyley Samuel, Thielemans Wim, Weder Christoph, Cranston Emily D., Zoppe Justin O. (2020), Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs, in Nanoscale, 12(33), 17480-17493.
Chemical modification of cellulose nanocrystal reducing end‐groups
Heise Katja, Delepierre Gwendoline, King Alistair, Kostiainen Mauri, Zoppe Justin, Weder Christoph, Kontturi Eero (2020), Chemical modification of cellulose nanocrystal reducing end‐groups, in Angewandte Chemie International Edition, anie.20200-anie.20200.
One-Component Nanocomposites Based on Polymer-Grafted Cellulose Nanocrystals
Wohlhauser Sandra, Kuhnt Tobias, Meesorn Worarin, Montero de Espinosa Lucas, Zoppe Justin O., Weder Christoph (2020), One-Component Nanocomposites Based on Polymer-Grafted Cellulose Nanocrystals, in Macromolecules, 53(3), 821-834.
Influence of the Salt Concentration on the Properties of Salt‐Free Polyelectrolyte Complex Membranes
Saikaew Rateeya, Meesorn Worarin, Zoppe Justin Orazio, Weder Christoph, Dubas Stephan Thierry (2019), Influence of the Salt Concentration on the Properties of Salt‐Free Polyelectrolyte Complex Membranes, in Macromolecular Materials and Engineering, 304(9), 1900245-1900245.
Stiffness‐Changing of Polymer Nanocomposites with Cellulose Nanocrystals and Polymeric Dispersant
Meesorn Worarin, Zoppe Justin O., Weder Christoph (2019), Stiffness‐Changing of Polymer Nanocomposites with Cellulose Nanocrystals and Polymeric Dispersant, in Macromolecular Rapid Communications, 40(9), 1800910-1800910.
Bio-Inspired, Self-Toughening Polymers Enabled by Plasticizer-Releasing Microcapsules
Meesorn W., Calvino C., Natterodt J.C., Zoppe J.O., Weder C. (2019), Bio-Inspired, Self-Toughening Polymers Enabled by Plasticizer-Releasing Microcapsules, in Advanced Materials, 1807212.
Recent advances and an industrial perspective of cellulose nanocrystal functionalization through polymer grafting
Kedzior Stephanie A., Zoppe Justin O., Berry Richard M., Cranston Emily D. (2018), Recent advances and an industrial perspective of cellulose nanocrystal functionalization through polymer grafting, in Current Opinion in Solid State and Materials Science.
Thermally Switchable Liquid Crystals Based on Cellulose Nanocrystals with Patchy Polymer Grafts
Risteen Bailey, Delepierre Gwendoline, Srinivasarao Mohan, Weder Christoph, Russo Paul, Reichmanis Elsa, Zoppe Justin (2018), Thermally Switchable Liquid Crystals Based on Cellulose Nanocrystals with Patchy Polymer Grafts, in Small, 1802060-1802060.
11 th Young Faculty Meeting, 5 th June 2018
Zoppe Justin O., Riniker Sereina, Merz Leo (2018), 11 th Young Faculty Meeting, 5 th June 2018, 72(7), 550-552, Swiss Chemical Society, Bern 72(7), 550-552.
Grafting Polymers from Cellulose Nanocrystals: Synthesis, Properties, and Applications
Wohlhauser Sandra, Delepierre Gwendoline, Labet Marianne, Morandi Gaëlle, Thielemans Wim, Weder Christoph, Zoppe Justin O. (2018), Grafting Polymers from Cellulose Nanocrystals: Synthesis, Properties, and Applications, in Macromolecules, 51(16), 6157-6189.
Polymer nanocomposites with cellulose nanocrystals made by co-precipitation
Natterodt Jens C., Shirole Anuja, Sapkota Janak, Zoppe Justin O., Weder Christoph (2017), Polymer nanocomposites with cellulose nanocrystals made by co-precipitation, in Journal of Applied Polymer Science, 45648-45648.
Cellulose Nanocrystals with Tethered Polymer Chains: Chemically Patchy versus Uniform Decoration
Zoppe Justin O., Dupire Alix Vaimiti Marie, Lachat Théo Gaston Gérard, Lemal Philipp, Rodriguez-Lorenzo Laura, Petri-Fink Alke, Weder Christoph, Klok Harm-Anton (2017), Cellulose Nanocrystals with Tethered Polymer Chains: Chemically Patchy versus Uniform Decoration, in ACS Macro Letters, 892-897.
Cellulose Nanocrystals: Surface Modification, Applications and Opportunities at Interfaces.
Natterodt Jens C., Petri-Fink Alke, Weder Christoph, Zoppe Justin (2017), Cellulose Nanocrystals: Surface Modification, Applications and Opportunities at Interfaces., in Chimia, 376.
Functionally Graded Polyurethane/Cellulose Nanocrystal Composites
Natterodt Jens C., Meesorn Worarin, Zoppe Justin O., Weder Christoph (2017), Functionally Graded Polyurethane/Cellulose Nanocrystal Composites, in Macromolecular Materials and Engineering, 1700661.

Collaboration

Group / person Country
Types of collaboration
Dr. Stephanie Kedzior Canada (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Dr. Alistair King, University of Helsinki Finland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
Prof. Eero Kontturi, Aalto University Finland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Prof. Elsa Reichmanis, Georgia Tech United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
- Exchange of personnel
Wim Thielemans Belgium (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Gaelle Morandi France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Emily Cranston Canada (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Dr. Tanja Zimmermann, Laboratory for Applied Wood Materials, EMPA Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Industry/business/other use-inspired collaboration
Prof. Stefan Spirk, TU Graz Austria (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Research Infrastructure
Prof. Harm-Anton Klok, Polymers Laboratory, EPFL Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
SCS Fall Meeting 2020 Talk given at a conference Patience is a Virtue: Self-Assembly and Physico-Chemical Properties of Cellulose Nanocrystal Allomorphs 25.08.2020 Virtual, Switzerland Delepierre Gwendoline;
KU Leuven-UBC Mini-Symposium on Cellulose Nanocrystals Talk given at a conference Towards Symmetrically and Asymmetrically functionalized Cellulose Nanocrystals 01.07.2020 Vancouver, Canada Delepierre Gwendoline;
2019 International Nanotechnology Conference for Renewable Materials Talk given at a conference Towards Symmetrically and Asymmetrically Functionalised Cellulose Nanocrystals 03.06.2020 Chiba, Japan Delepierre Gwendoline;
Burgess Lane Lecture Poster Self-assembly of cellulose nanocrystal polymorphs 02.03.2020 Vancouver, Canada Delepierre Gwendoline;
FriMat Day 2018 Talk given at a conference Symmetrically and asymmetrically functionalised cellulose nanocrystals 26.10.2018 Fribourg, Switzerland Delepierre Gwendoline;
Polycoll Meeting 2018 Poster Symmetrically and asymmetrically functionalised cellulose nanocrystals 05.10.2018 Lausanne, Switzerland Delepierre Gwendoline;
Swiss Chemical Society Fall Meeting 2018 Poster Symmetrically and asymmetrically functionalised cellulose nanocrystals 07.09.2018 Lausanne, Switzerland Delepierre Gwendoline;
Swiss NanoConvention 2018 Poster Symmetrically and asymmetrically functionalised cellulose nanocrystals 06.06.2018 Zürich, Switzerland Delepierre Gwendoline;
255th ACS National Meeting & Exposition Talk given at a conference Polymer nanocomposites with cellulose nanocrystals: Effects of polymer grafting and processing methods on thermomechanical properties 18.03.2018 New Orleans, USA, United States of America Zoppe Justin;
10th World Congress of Chemical Engineering - JOINT EVENT - NANOCELLULOSE Talk given at a conference Surface Engineering of Cellulose Nanocrystals via Controlled Radical Polymerization 01.10.2017 Barcelona, Spain Zoppe Justin;
5th EPNOE International Polysaccharide Conference 2017 Talk given at a conference Polymer grafting from cellulose nanocrystals: new synthetic pathways, properties and applications 20.08.2017 Jena, Germany Zoppe Justin;
253rd ACS National Meeting & Exposition Talk given at a conference Effect of cellulose nanocrystal chirality on the stereochemistry of surface-tethered polymers 02.04.2017 San Francisco, CA, United States of America Zoppe Justin;


Self-organised

Title Date Place
11th Young Faculty Meeting 05.06.2018 Bern, Switzerland

Communication with the public

Communication Title Media Place Year
Talks/events/exhibitions MIT 22nd EUROPEAN CAREER FAIR International 2018

Awards

Title Year
Wikimedia Science Competition, Swiss National Selection 2019, Category: Microscopy; 2nd place 2019
Best Talk Prize - FriMat Day 2018 2018

Abstract

One of the most practical strategies to produce nanoarchitectures in both two and three dimensions is through self-assembly. The building blocks of self-assembled structures span multiple length scales, from molecules and polymers to nanoparticles and macroscopic colloidal objects. Self-assembly of colloids, in particular, provides a simple means toward complex hierarchical structures, especially in three dimensions. Although still at its infancy, synthetic chiral colloids, such as twisted and helical nanoribbons/nanofibers, have started to emerge in nanoscience as a tool for synthetic materials with controlled handedness. One attractive class of chiral supracolloidal building blocks are cellulose nanocrystals (CNCs), which are readily extracted from naturally abundant renewable materials. Unique among rod-like chiral colloids, CNC chiral nematic (N*) liquid crystalline assemblies are preserved in dried films and have been utilized as templates for novel materials with mesoporous structures and long-range chiral order. Such chiral self-assembly concepts have contributed to recent developments in heterogeneous enantioselective catalysts, chiral plasmonics and stratified films with alternating chiral domains. Further development of chiral nanomaterials may lead to favorable properties for numerous applications including asymmetric catalysis, enantioselective separation/sorption media, chiral sensing, nanodevices/-machines and circular dichroism.Among the external factors that can be used to manipulate N* phases of CNCs, such as ionic strength, ultrasound, etc., surface chemical modification with tethered polymers remains less explored. This is probably because non-selective surface modification may have a negative impact on the formation of N* phases, as the packing density of nanorods would be disturbed by the presence of macromolecular layers. On the other hand, selective modification at the ends of nanorods with polymer tethers would still allow sufficient packing within N* phases. In fact, recent computer simulations have predicted the formation of N* phases of asymmetric polymer-tethered nanorods within a wide range of their phase diagram, even though the nanorods themselves were achiral. To date, there is no experimental platform available to support these theoretical descriptions of asymmetric nanorods with end-tethered polymer chains.The objective of the proposed research is to systematically investigate the selective-end group modification of colloidal nanorods as a means to manipulate their self-assembly into N* liquid crystalline phases, both in colloidal solution and in free-standing films. In this regard, CNCs represent an ideal platform, as the inherent directionality of individual cellulose chains, and therefore reducing end groups, can be controlled through chemical pre-treatments of raw cellulosic materials, resulting in different crystalline polymorphs, for example cellulose I and cellulose II. Through the acid hydrolysis of native cellulose I and cellulose II fibers, CNCs containing parallel and anti-parallel chains, respectively, will be produced as a new basis for symmetric and asymmetric chiral nanorods with end-tethered polymer chains.Important questions to be answered in this project to that objective are:•Do CNCs produced from cellulose II exhibit the same handedness (twist) as cellulose I?•Can the reducing end groups of CNCs be used as initiating sites for controlled radical polymerization toward colloidal analogues of rod-coil and coil-rod-coil block copolymers?•How do end-tethered polymer chains and symmetry affect the liquid crystalline behavior of CNCs?The development of symmetric and asymmetric CNCs with end-tethered polymer chains would not only provide an experimental platform to test recently developed theories of polymer-tethered nanorods, but also a fundamental understanding of the relationship between cellulose crystal structure, chirality and inversion over different length scales. As a unique nanomaterial with attractive thermomechanical and photonic properties, the development of CNC hybrids with end-tethered polymer chains will offer a new means to manipulate their liquid crystal ordering for chirality induction into porous solids. Finally, they could also provide new building blocks for novel supracolloidal concepts.
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