Anand Viswanath

TiO2 nanocomposites with high refractive index and transparency

Transparent polymer nanocomposites with high refractive index were prepared by grafting polymer chains onto anatase TiO2 nanoparticlesvia a combination of phosphate ligand engineering and alkyne-azide “click” chemistry. Highly crystalline TiO2 nanoparticles with 5 nm diameter were synthesized by a solvothermal method and used as high refractive index filler. The synthesized phosphate-azide ligand anchors strongly onto the TiO2 nanoparticle surface and the azide end group allows for attachment of poly(glycidyl methacrylate) (PGMA) polymer chains through an alkyne-azide “click” reaction. The refractive index of the composite material increased linearly from 1.5 up to 1.8 by increasing the loading of TiO2 particles to 30 vol % (60 wt %). UV-vis spectra show that the nanocomposites exhibited a transparency around 90% throughout the visible light range. It was also found that the PGMA-grafted TiO2 nanoparticles can be well dispersed into a commercial epoxy resin, forming transparent high refractive index TiO2-epxoy nanocomposites.

Bimodal Surface Ligand Engineering: The Key to Tunable Nanocomposites

Tuning the dispersion of inorganic nanoparticles within organic matrices is critical to optimizing polymer nanocomposite properties and is intrinsically difficult due to their strong enthalpic incompatibility. Conventional attempts to use polymer brushes to control nanoparticle dispersion are challenged by the need for high graft density to reduce particle core-core attractions and the need for low graft density to reduce the entropic penalty for matrix penetration into the brush. We validated a parametric phase diagram previously reported by Pryamtisyn et al. (Pryamtisyn, V.; Ganesan, V.; Panagiotopoulos, A. Z.; Liu, H.; Kumar, S. K. Modeling the Anisotropic Self-Assembly of Spherical Polymer-Grafted Nanoparticles. J. Chem. Phys.2009, 131, 221102) for predicting dispersion of monomodal-polymer-brush-modified nanoparticles in polymer matrices. The theoretical calculation successfully predicted the experimental observation that the monomodal-poly(dimethyl siloxane) (PDMS)-brush-grafted TiO(2) nanoparticles can only be well dispersed within a small molecular weight silicone matrix. We further extended the parametric phase diagram to analyze the dispersion behavior of bimodal-PDMS-brush-grafted particles, which is also in good agreement with experimental results. Utilizing a bimodal grafted polymer brush design, with densely grafted short brushes to shield particle surfaces and sparsely grafted long brushes that favor the entanglement with matrix chains, we dispersed TiO(2) nanoparticles in high molecular weight commercial silicone matrices and successfully prepared thick (about 5 mm) transparent high-refractive-index TiO(2)/silicone nanocomposites.

Surface labeling of enveloped virus with polymeric imidazole ligand-capped quantum dots via the metabolic incorporation of phospholipids into host cells

We report a general method for the preparation of quantum dot-labeled viruses through a strain-promoted azide-alkyne cycloaddition (SPAAC) reaction. The quantum dot sample was functionalized with methacrylate-based polymeric imidazole ligands (MA-PILs) bearing dibenzocyclooctyne groups. Enveloped measles virus was labeled with azide groups through the metabolic incorporation of a choline analogue into the host cell membrane, and then linked with the modified QDs. The virus retained its infectious ability against host cells after the modification with MA-PIL capped QDs.

A methacrylate-based polymeric imidazole ligand yields quantum dots with low cytotoxicity and low nonspecific binding.

This paper assesses the biocompatibility for fluorescence imaging of colloidal nanocrystal quantum dots (QDs) coated with a recently-developed multiply-binding methacrylate-based polymeric imidazole ligand. The QD samples were purified prior to ligand exchange via a highly repeatable gel permeation chromatography (GPC) method. A multi-well plate based protocol was used to characterize nonspecific binding and toxicity of the QDs toward human endothelial cells. Nonspecific binding in 1% fetal bovine serum was negligible compared to anionically-stabilized QD controls, and no significant toxicity was detected on 24h exposure. The nonspecific binding results were confirmed by fluorescence microscopy. This study is the first evaluation of biocompatibility in QDs initially purified by GPC and represents a scalable approach to comparison among nanocrystal-based bioimaging scaffolds.

Synthesis of random terpolymers bearing multidentate imidazole units and their use in functionalization of cadmium sulfide nanowires

This work reports on a new random ternary polymerization method for the synthesis of multidentate imidazole polymers. The polymers can behave as ligands for the functionalization of cadmium sulfide nanowires. Due to the intrinsic differences in the electronegativity of the groups next to the vinyl bond, the vinyl groups displayed unique NMR signals, and allowed for the measurement of the individual monomer conversions in the random terpolymer system. The activated ester bearing terpolymer was postmodified with N-alkyl imidazole units, followed by the boc deprotection of the amine terminal groups. The resulting poly(imid-PEGMA-MAMamine) provided water solubility, dye loading capability as well as the ability to coordinate with metal chalcogenide surfaces using the imidazole units. Upon the attachment of a rhodamine dye, studies were performed to analyze the potential of such polymers to modify CdS nanowires using fluorescence microscopy. The fluorescence microscopy results provided confirmation of the polymeric ligand attachment, and sets the foundation for further optical studies using this system.