Search

Optically responsive materials are present in everyday life, from screens to sensors. However, fabricating large-area, fossil-free materials for functional biocompatible applications is still a challenge today. Nanocelluloses from various sources, such as wood, can provide biocompatibility and are emerging candidates for templating organic optoelectronics. Silver (Ag) in its nanoscale form shows excellent optical properties. Herein, we combine both materials using thin-film large-area spray-coating to study the fabrication of optical response applications. We characterize the Ag nanoparticle formation by X-ray scattering and UV–vis spectroscopy in situ during growth on the nanocellulose template. The morphology and optical properties of the nanocellulose film are compared to the rigid reference surface SiO2. Our results clearly show the potential to tailor the energy band gap of the resulting hybrid material.

It is theoretically predicted and hypothesized that the charge density and size of spherical nanoparticles are the key factors for their adsorption onto oppositely charged surfaces. It is also hypothesized that the morphology and charge of the surface are of great importance. In-plane 2D (silica) or a volumetric 3D (regenerated TEMPO-oxidized cellulose model surfaces) distribution of charged groups is expected to influence charge compensation and, thus, the adsorption behavior.In this work, self-stabilized nanolatexes with a range of cationic charge densities and sizes were synthesized through reversible addition - fragmentation chain-transfer (RAFT) polymerization coupled with polymerization-induced self-assembly (PISA). Their adsorption onto silica and anionic cellulose model surfaces was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D).Experiments and theory agree and show that the size of the nanolatex and the difference in charge density compared to the substrate determine the charge compensation and, thus, the surface coverage. Highly charged or large nanolatexes overcompensate the surface charge of non-porous substrates leading to a significant repulsive zone where other particles cannot adsorb. For porous substrates like cellulose, the vertical distribution of charged groups in the 3D volume prevents overcompensation and thus increases the adsorption. This systematic study investigates the isolated effect of surface charge and size and paves the way for on-demand particles specifically designed for a surface with particular characteristics.

Green chemistry 23(5), 2113 - 2122 (2021). doi:10.1039/D0GC04266H, The polymerization of a bio-based terpene-derived monomer, sobrerol methacrylate (SobMA), was evaluated in the design of polymeric nanoparticles (nanolatexes). Their synthesis was accomplished by using emulsion polymerization, either by free-radical polymerization in the presence of a cationic surfactant or a cationic macroRAFT agent by employing RAFT-mediated polymerization-induced self-assembly (PISA). By tuning the length of the hydrophobic polymer, it was possible to control the nanoparticle size between 70 and 110 nm. The average size of the latexes in both wet and dry state were investigated by microscopy imaging and dynamic light scattering (DLS). Additionally, SobMA was successfully copolymerized with butyl methacrylate (BMA) targeting soft-core nanolatexes. The comparison of the kinetic profile of the cationically stabilized nanolatexes highlighted the differences of both processes. The SobMA-based nanolatexes yielded high Tg ��� 120 ��C, while the copolymer sample exhibited a lower Tg ��� 50 ��C, as assessed by Differential Scanning Calorimetry (DSC). Thereafter, the nanolatexes were adsorbed onto cellulose (filter paper), where they were annealed at elevated temperatures to result in polymeric coatings. Their morphologies were analysed by Field Emission Scanning Electron Microscopy (FE-SEM) and compared to a commercial sulfate polystyrene latex (PS latex). By microscopic investigation the film formation mechanism could be unravelled. Water contact angle (CA) measurements verified the transition from a hydrophilic to a hydrophobic surface after film formation had occured. The obtained results are promising for the toolbox of bio���based building blocks, focused on sobrerol-based monomers, to be used in emulsion polymerizations either for tailored PISA���latexes or facile conventional latex formation, in order to replace methyl methacrylate or other high Tg-monomers., Published by RSC, Cambridge