Rajendra R. Bhat

Controlling the assembly of nanoparticles using surface grafted molecular and macromolecular gradients

We report on the generation of assemblies comprising number density gradients of nanoparticles in two (2D) and three (3D) dimensions. These structures are fabricated by creating a surface-bound organic template which directs the spatial arrangement of gold nanoparticles. The 2D template is made of amine-terminated organosilane with a concentration gradient along the solid substrate. The 3D matrix comprises surface-anchored poly(acryl amide), whose molecular weight changes gradually on the specimen. In both cases, the composite is assembled at low pH, where the positively charged –NH3+ groups within the organic scaffold attract negatively charged gold nanoparticles. We use a battery of experimental tools to determine the number density of particles along the gradient substrate and in the case of 3D structures also their spatial distribution. For 2D gradient assemblies, we show that gold nanoparticle coverage on the surface decreases gradually as the concentration of substrate-bound aminosilane decreases. The number of particles in the polymer brush/particle hybrid is found to increase with increasing polymer molecular weight. We show that for a given grafting density of polymer brush, larger particles predominantly stay near the brush–air interface. In contrast, smaller nanoparticles penetrate deeper into the polymer brush, thus forming a 3D structure. Finally, we discuss possible applications of these nanoparticle gradient assemblies.

Tuning the number density of nanoparticles by multivariant tailoring of attachment points on flat substrates

We report on the organization of nanoparticles on a flat surface when there is strong yet tunable interaction between the particles and the surface. Specifically, we tailor the number density of citrate-stabilized gold nanoparticles on flat substrates by varying the concentration of the grafted amino groups on the surfaces and their degree of ionization. While the former effect is accomplished by decorating silica-based substrates with a molecular gradient of (3-aminopropyl)triethoxysilane (APTES), the latter effect is achieved by varying the degree of ionization of the −NH2 groups in APTES by varying the pH of the gold sol. We show that the measurement of particle number density on an APTES concentration gradient substrate at different pH values provides a simple, non-spectroscopic means to deduce the relative molecular concentration profile of APTES on the substrate.

Time dependence of lysozyme adsorption on end-grafted polymer layers of variable grafting density and length

A combined experimental and theoretical approach establishes the long-lived nature of protein adsorption on surfaces coated with chemically grafted macromolecules. Specifically, we monitor the time dependence of adsorption of lysozyme on surfaces comprising polymer assemblies made of poly(2-hydroxyethyl methacrylate) brushes grafted onto flat silica surfaces such that they produce patterns featuring orthogonal and gradual variation of the chain length (N) and grafting density (σ). We show that in the kinetically controlled regime, the amount of adsorbed protein scales universally with the product σN, while at equilibrium the amount of adsorbed protein is governed solely by σ. Surprisingly, for moderate concentrations of protein in solution, adsorption takes more than 72 h to reach an equilibrium, or steady state. Our experimental findings are corroborated with predictions using molecular theory that provides further insight into the protein adsorption phenomenon. The theory predicts that the universal behavior observed experimentally should be applicable to polymers in poor and theta solvents and to a limited extent also to good solvent conditions. Our combined experimental and theoretical findings reveal that protein adsorption is a long-lived phenomenon, much longer than generally assumed. Our studies confirm the previously predicted important differences in behavior for the kinetic versus thermodynamic control of protein adsorption.

Development of High-Throughput substrates for Generating Two-Dimensional Nanoparticles Assemblies and for Screening Protein Adsorption

We discuss methods leading to the fabrication of orthogonal substrates comprising surfaceanchored polymer brushes, in which the polymer brush grafting density and molecular weight vary independently in two mutually perpendicular directions. We demonstrate that these orthogonal polymer substrates can be used as intelligent combinatorial platforms that facilitate the spatial distribution of nanoparticles and allow screening of protein adsorption on surfaces.