DNA-driven assembly of nanoscale objects has emerged as a powerful platform for the creation of materials by design via self-assembly. Recent years have seen much progress in the experimental realization of this approach for three-dimensional systems. In contrast, two-dimensional (2D) programmable nanoparticle (NP) systems are not well explored, in part due to the difficulties in creating such systems. Here we demonstrate the use of charged liquid interfaces for the assembly and reorganization of 2D systems of DNA-coated NPs. The absorption of DNA-coated NPs to the surface is controlled by the interaction between a positively charged lipid layer and the negatively charged DNA shells of particles. At the same time, interparticle interactions are switchable, from electrostatic repulsion between DNA shells to attraction driven by DNA complementarity, by increasing ionic strength. Using in situ surface X-ray scattering methods and ex situ electron microscopy, we reveal the corresponding structural transformation of the NP monolayer, from a hexagonally ordered 2D lattice to string-like clusters and finally to a weakly ordered network of DNA cross-linked particles. Moreover, we demonstrate that the ability to regulate 2D morphology yields control of the interfacial rheological properties of the NP membrane: from viscous to elastic. Theoretical modeling suggests that the structural adaptivity of interparticle DNA linkages plays a crucial role in the observed 2D transformation of DNA-NP systems at liquid interfaces.

Structurally tunable two-dimensional (2D) arrays of nanoscale objects are important for modulating functional responses of thin films. We demonstrate that such tunable and ordered nanoparticles (NP) arrays can be assembled at charged air-water interfaces from nanoparticles coated with polyelectrolyte chains, DNA. The electrostatic attraction between the negatively charged nonhybridizing DNA-coated gold NPs and a positively charged lipid layer at the interface facilitates the formation of a 2D hexagonally closed packed (HCP) nanoparticle lattice. We observed about 4-fold change of the monolayer nanoparticle density by varying the ionic strength of the subphase. The tunable NP arrays retain their structure reasonably well when transferred to a solid support. The influence of particle's DNA corona and lipid layer composition on the salt-induced in-plane and normal structural evolution of NP arrays was studied in detail using a combination of synchrotron-based in situ surface scattering methods, grazing incidence X-ray scattering (GISAXS), and X-ray reflectivity (XRR). Comparative analysis of the interparticle distances as a function of ionic strength reveals the difference between the studied 2D nanoparticle arrays and analogous bulk polyelectrolyte star polymers systems, typically described by Daoud-Cotton model and power law scaling. The observed behavior of the 2D nanoparticle array manifests a nonuniform deformation of the nanoparticle DNA corona due to its electrostatically induced confinement at the lipid interface. The present study provides insight on the interfacial properties of the NPs coated with charged soft shells.

Polymer nanocomposites can be used to study confinement effects on the polymer glass transition temperature (Tg) in a controlled manner by varying interparticle spacing. Using gold nanoparticles in polymethylmethacrylate, we show how the polymer Tg can be tuned by variation of the nanoparticle-polymer interface width (sigma), keeping interparticle spacing fixed. We report the first experimental observation of a crossover in the sign of Tg deviation for confined polymers by variation of sigma and propose a model to explain the dependence of crossover width on the spatial extent of cooperatively rearranging regions.

Nanomaterials have emerged as an area of interest motivated by potential applications of these materials in light emitting diodes, solar cells, polarizers, light -stable colour filters, optical sensors, optical data communication and optical data storage. Nanomaterials are of particular interest as they combine the properties of two or more different materials with the possibility of possessing novel mechanical, electronic or chemical behaviour. Understanding and tuning such effects could lead to hybrid devices based on these nanocomposites with improved optical properties. We have prepared polymer nanocomposites of well-defined compositions and studied the optical properties of powders and their thin films. UV-vis absorption spectroscopy on nanocomposite powders and spectroscopic ellipsometry measurements on thin films was used to study the effect of interfacial morphology, interparticle spacing and finite size effects on optical properties of nanocomposites. Systematic shift in the imaginary part of the dielectric function can be seen with variation in size and fraction of the gold nanoparticle. The thickness of the film also plays a significant role in the tunability of the optical spectra.

We present results of temperature dependent measurements of dynamics of polymer grafted nanoparticles with high grafting density with star polymerlike morphology. We observed for the low grafting density and hence low functionality sample, a dynamically arrested state with lowering of temperature, similar to what was conjectured earlier. However the high grafting density sample shows liquidlike relaxation at all measured temperatures. Possible origin of dynamical arrest in the two grafting density sample is discussed.