Héloïse Thérien-Aubin

Three-dimensional shape transformations of hydrogel sheets induced by small-scale modulation of internal stresses

Although Nature has always been a common source of inspiration in the development of artificial materials, only recently has the ability of man-made materials to produce complex three-dimensional (3D) structures from two-dimensional sheets been explored. Here we present a new approach to the self-shaping of soft matter that mimics fibrous plant tissues by exploiting small-scale variations in the internal stresses to form three-dimensional morphologies. We design single-layer hydrogel sheets with chemically distinct, fibre-like regions that exhibit differential shrinkage and elastic moduli under the application of external stimulus. Using a planar-to-helical three-dimensional shape transformation as an example, we explore the relation between the internal architecture of the sheets and their transition to cylindrical and conical helices with specific structural characteristics. The ability to engineer multiple three-dimensional shape transformations determined by small-scale patterns in a hydrogel sheet represents a promising step in the development of programmable soft matter.

Control of biofouling on reverse osmosis polyamide membranes modified with biocidal nanoparticles and antifouling polymer brushes

Thin-film composite (TFC) polyamide reverse osmosis (RO) membranes are prone to biofouling due to their inherent physicochemical surface properties. In order to address the biofouling problem, we have developed novel surface coatings functionalized with biocidal silver nanoparticles (AgNPs) and antifouling polymer brushes via polyelectrolyte layer-by-layer (LBL) self-assembly. The novel surface coating was prepared with polyelectrolyte LBL films containing poly(acrylic acid) (PAA) and poly(ethylene imine) (PEI), with the latter being either pure PEI or silver nanoparticles coated with PEI (Ag-PEI). The coatings were further functionalized by grafting of polymer brushes, using either hydrophilic poly(sulfobetaine) or low surface energy poly(dimethylsiloxane) (PDMS). The presence of both LBL films and sulfobetaine polymer brushes at the interface significantly increased the hydrophilicity of the membrane surface, while PDMS brushes lowered the membrane surface energy. Overall, all surface modifications resulted in significant reduction of irreversible bacterial cell adhesion. In microbial adhesion tests with E. coli bacteria, a normalized cell adhesion in the range of only 4 to 16% on the modified membrane surfaces was observed. Modified surfaces containing silver nanoparticles also exhibited strong antimicrobial activity. Membranes coated with LBL films of PAA/Ag-PEI achieved over 95% inactivation of bacteria attached to the surface within 1 hour of contact time. Both the antifouling and antimicrobial results suggest the potential of using these novel surface coatings in controlling the fouling of RO membranes.

Surface patterning of nanoparticles with polymer patches

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules, serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles, and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

Controlling the Degree of Polymerization, Bond Lengths, and Bond Angles of Plasmonic Polymers

Plasmonic polymers present an interesting concept that builds on the analogy between molecular polymers and linear chains of strongly interacting metal nanoparticles. Ensemble-averaged optical properties of plasmonic polymers are strongly influenced by their structure. In the present work, we formed plasmonic polymers by using solution-based assembly of gold nanorods (NRs) end-tethered with photoactive macromolecular tethers. By using postassembly ligand photo-cross-linking, we established a method to arrest NR polymer growth after a particular self-assembly time, and in this manner, using kinetics of step-growth polymerization, we achieved control over the average degree of polymerization of plasmonic polymers. Photo-cross-linking of ligands also enabled control over the internanorod distance and resulted in the increased rigidity of NR chains. These results, along with a higher structural integrity of NR chains, can be utilized in plasmonic nanostructure engineering and facilitate advanced applications of plasmonic polymers in sensing and optoelectronics.

Structural and Optical Properties of Self-Assembled Chains of Plasmonic Nanocubes

Solution-based linear self-assembly of metal nanoparticles offers a powerful strategy for creating plasmonic polymers, which, so far, have been formed from spherical nanoparticles and cylindrical nanorods. Here we report linear solution-based self-assembly of metal nanocubes (NCs), examine the structural characteristics of the NC chains, and demonstrate their advanced optical characteristics. In comparison with chains of nanospheres with similar dimensions, composition, and surface chemistry, predominant face-to-face assembly of large NCs coated with short polymer ligands led to a larger volume of hot spots in the chains, a nearly uniform E-field enhancement in the gaps between colinear NCs, and a new coupling mode for NC chains due to the formation of a Fabry-Perot resonator structure formed by face-to-face bonded NCs. The NC chains exhibited stronger surface-enhanced Raman scattering in comparison with linear assemblies of nanospheres. The experimental results were in agreement with finite difference time domain simulations.

Ion-Mediated Gelation of Aqueous Suspensions of Cellulose Nanocrystals

Nanofibrillar hydrogels are an important class of biomaterials with applications as catalytic scaffolds, artificial extracellular matrixes, coatings, and drug delivery materials. In the present work, we report the results of a comprehensive study of nanofibrillar hydrogels formed by cellulose nanocrystals (CNCs) in the presence of cations with various charge numbers and ionic radii. We examined sol-gel transitions in aqueous CNC suspensions and the rheological and structural properties of the CNC hydrogels. At a particular CNC concentration, with increasing charge and cation size, the dynamic shear moduli and mesh size in the hydrogel increased. These effects were ascribed to a stronger propensity of CNCs for side-by-side association. The resulting hydrogels had an isotropic nanofibrillar structure. A combination of complementary techniques offered insight into structure-property relationships of CNC hydrogels, which are important for their potential applications.

Colloidal cholesteric liquid crystal in spherical confinement

The organization of nanoparticles in constrained geometries is an area of fundamental and practical importance. Spherical confinement of nanocolloids leads to new modes of packing, self-assembly, phase separation and relaxation of colloidal liquids; however, it remains an unexplored area of research for colloidal liquid crystals. Here we report the organization of cholesteric liquid crystal formed by nanorods in spherical droplets. For cholesteric suspensions of cellulose nanocrystals, with progressive confinement, we observe phase separation into a micrometer-size isotropic droplet core and a cholesteric shell formed by concentric nanocrystal layers. Further confinement results in a transition to a bipolar planar cholesteric morphology. The distribution of polymer, metal, carbon or metal oxide nanoparticles in the droplets is governed by the nanoparticle size and yields cholesteric droplets exhibiting fluorescence, plasmonic properties and magnetic actuation. This work advances our understanding of how the interplay of order, confinement and topological defects affects the morphology of soft matter.

Copolymerization of metal nanoparticles: a route to colloidal plasmonic copolymers.

The resemblance between colloidal and molecular polymerization reactions is very useful in fundamental studies of polymerization reactions, as well as in the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes, and compositions. A method has been developed to apply strategies from molecular copolymerization to the co-assembly of gold nanorods with different dimensions into random and block copolymer structures (plasmonic copolymers). The approach was extended to the co-assembly of random copolymers of gold and palladium nanorods. A kinetic model validated and further expanded the kinetic theories developed for molecular copolymerization reactions.

Colloidal analogs of molecular chain stoppers

Significance Self-assembly of nanoparticles in polymer-like chains bears a strong similarity to polymerization reactions, in which monomer units are brought together by directional noncovalent interactions. Based on this similarity, the molecular concepts of polymer chemistry can be applied to achieve controllable nanoparticle assembly. On the other hand, the ability to visualize nanoparticle assemblies and to exploit characterization tools used in nanoscience offers a unique way to study polymerization reactions. Here we explore this twofold strategy for an exemplary system including the self-assembly of bifunctional metal nanorods in the presence of monofunctional nanoparticles (chain stoppers). The approach provided insight into the polymerization kinetics, side reactions, the distribution of species in the system, and the design rules for the synthesis of molecular chain stoppers. A similarity between chemical reactions and self-assembly of nanoparticles offers a strategy that can enrich both the synthetic chemistry and the nanoscience fields. Synthetic methods should enable quantitative control of the structural characteristics of nanoparticle ensembles such as their aggregation number or directionality, whereas the capability to visualize and analyze emerging nanostructures using characterization tools can provide insight into intelligent molecular design and mechanisms of chemical reactions. We explored this twofold concept for an exemplary system including the polymerization of bifunctional nanoparticles in the presence of monofunctional colloidal chain stoppers. Using reaction-specific design rules, we synthesized chain stoppers with controlled reactivity and achieved quantitative fine-tuning of the self-assembled structures. Analysis of the nanostructures provided information about polymerization kinetics, side reactions, and the distribution of all of the species in the reaction system. A quantitative model was developed to account for the reactivity, kinetics, and side reactions of nanoparticles, all governed by the design of colloidal chain stoppers. This work provided the ability to test theoretical models developed for molecular polymerization.

Coassembly of gold nanoparticles and cellulose nanocrystals in composite films.

Coassembly of nanoparticles with different size-, shape-, and composition-dependent properties is a promising approach to the design and fabrication of functional materials and devices. This paper reports the results of a detailed investigation of the formation and properties of free-stranding composite films formed by the coassembly of cellulose nanocrystals and shape-isotropic plasmonic gold nanoparticles. The effect of gold nanoparticle size, surface charge, and concentration on the structural and optical properties of the composite films has been studied. The composite films retained photonic crystal and chiroptical activity properties. The size and surface charge of gold nanoparticles had a minor effect on the structure and properties of the composite films, while the concentration of gold nanoparticles in the composite material played a more significant role and can be used to fine-tune the optical properties of materials derived from cellulose nanocrystals. These findings significantly broaden the range of nanoparticles that can be used for producing nanocomposite materials based on cellulose nanocrystals. The simplicity of film preparation, the abundance of cellulose nanocrystals, and the robust, free-standing nature of the composite films offer highly advantageous features and pave the way for the generation of functional materials with coupled optical properties.