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.

The resemblance between colloidal and molecular polymerization reactions has been recognized as a powerful tool for the fundamental studies of polymerization reactions, as well as a platform for the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle (NP) ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes and compositions. In the present work, we have developed a method 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.

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.

The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and nanospheres (dye-labeled spherical latex nanoparticles, NPs) was studied in aqueous suspensions and in solid films. In mixed CNC-latex suspensions, phase separation into an isotropic latex-NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of latex NPs. Drying the mixed suspension resulted in CNC-latex films with planar disordered layers of latex NPs, which alternated with chiral nematic CNC-rich regions. In addition, fluorescent latex NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of latex NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties.

We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase.