Grafting Of Nanoparticles Research Articles

Role of polymer graft stiffness in electrostatic-driven self-assembly of nanoparticles in solutions.

Self-assembly of nanoparticles (NPs) in solution has garnered tremendous attention among researchers because of their electrical, chemical, and optoelectronic properties at the macroscale with potential applications in bio-imaging, bio-medicine, and therapeutics. Control of size, shape, and composition at the nanoscale is important in tuning the material's bulk properties. The grafting of NPs with polymers enables us to tune such bulk material properties at the nano level by controlling their assemblies, especially in solutions. The stiffness of grafts plays a crucial role in tuning the self-assembly of spherical NPs grafted with polyions (PGNs). Many recent studies based on single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA) showed the potential applications of such assemblies. In this work, we have performed coarse-grained molecular dynamics (MD) simulations to understand the charge-driven self-assembly of PGNs by varying stiffness of polymer grafts, the grafting density, and graft length. Self-assembly of these PGNs leads to the formation of different structures driven by the rigidity of polyion chains and the electrostatic interactions. A dramatic change in morphological transitions can be achieved, ranging from rings, strings, and percolated structures and ordered to disordered aggregates by tuning the control parameters. The percolated structures form disordered structures upon annealing with potential applications in thermal under filling, neuromorphic devices, and biological systems including drug delivery, and therapeutics.

Green Advances in Wet Finishing Methods and Nanoparticles for Daily Textiles.

This work presented an overview of greener technologies for realizing everyday fabrics with enhanced antibacterial activity, flame retardancy, water repellency, and UV protection. Traditional methods for improving these qualities in textiles involved dangerous chemicals, energy and water-intensive procedures, harmful emissions. New strategies are presented in response to the current emphasis on process and product sustainability. Nanoparticles (NPs) are suggested as a potential alternative for hazardous components in textile finishing. NPs are found to efficiently decrease virus transmission, limit combustion events, protect against UV radiation, and prevent water from entering, through a variety of mechanisms. Some attempts are made to increase NPs efficiency and promote long-term adherence to textile surfaces. Traditional wet finishing methods are implemented through a combination of advanced green technologies (plasma pre-treatment, ultrasound irradiations, sol-gel, and layer-by-layer self-assembly methods). The fibrous surface is activated by adding functional groups that facilitate NPs grafting on the textile substrate by basic interactions (chemical, physical, or electrostatic), also indirectly via crosslinkers, ligands, or coupling agents. Finally, other green options explore the use of NPs synthesized from bio-based materials or hybrid combinations, as well as inorganic NPs from green synthesis to realize ecofriendly finishing able to provide durable and protective fabrics.

Interfacial Assembly of Tunable Anisotropic Nanoparticle Architectures

We propose a strategy for assembling spherical nanoparticles (NPs) into anisotropic architectures in a polymer matrix. The approach takes advantage of the interfacial tension between two mutually immiscible polymers forming a bilayer and differences in the compatibility of the two polymer layers with polymer grafts on particles to trap NPs within two-dimensional planes parallel to the interface. The ability to precisely tune the location of the entrapment planes via the NP grafting density, and to trap multiple interacting particles within distinct planes, can then be used to assemble NPs into unconventional arrangements near the interface. We carry out molecular dynamics simulations of polymer-grafted NPs in a polymer bilayer to demonstrate the viability of the proposed approach in both trapping NPs at tunable distances from the interface and assembling them into a variety of unusual nanostructures. We illustrate the assembly of NP clusters, such as dimers with tunable tilt relative to the interface and trimers with tunable bending angle, as well as anisotropic macroscopic phases, including serpentine and branched structures, ridged hexagonal monolayers, and square-ordered bilayers. We also develop a theoretical model to predict the preferred positions and free energies of NPs trapped at or near the interface that could help guide the design of polymer-grafted NPs for achieving target NP architectures. Overall, this work suggests that interfacial assembly of NPs could be a promising approach for fabricating next-generation polymer nanocomposites with potential applications in plasmonics, electronics, optics, and catalysis where precise arrangement of polymer-embedded NPs is required for function.

Hierarchical nanoparticle topography in amphiphilic copolymer films controlled by thermodynamics and dynamics.

This study systematically investigates how polymer composition changes nanoparticle (NP) grafting and diffusion in solvated random copolymer thin films. By thermal annealing from 135 to 200 °C, thin films with a range of hydrophobicity are generated by varying acrylic acid content from 2% (SAA2) to 29% (SAA29). Poly(styrene-random-tert butyl acrylate) films, 100 nm thick, that are partially converted to poly(styrene-random-acrylic acid), SAA, reversibly swell in ethanol solutions containing amine-functionalized SiO2 nanoparticles with a diameter of 45 nm. The thermodynamics and kinetics of NP grafting are directly controlled by the AA content in the SAA films. At low AA content, namely SAA4, NP attachment saturates at a monolayer, consistent with a low solubility of NPs in SAA4 due to a weakly negative χ parameter. When the AA content exceeds 4%, NPs sink into the film to form multilayers. These films exhibit hierarchical surface roughness with a RMS roughness greater than the NP size. Using a quartz crystal microbalance, NP incorporation in the film is found to saturate after a mass equivalence of about 3 close-packed layers of NPs have been incorporated within the SAA. The kinetics of NP grafting is observed to scale with AA content. The surface roughness is greatest at intermediate times (5-20 min) for SAA13 films, which also exhibit superhydrophobic wetting. Because clustering and aggregation of the NPs within SAA29 films reduce film transparency, SAA13 films provide both maximum hydrophobicity and transparency. The method in this study is widely applicable because it can be applied to many substrate types, can cover large areas, and retains the amine functionality of the particles which allows for subsequent chemical modification.

Mechanical and Frictional Properties of Nanoparticle Monolayers Grafted on Functionalized Mica Substrates

Normal and lateral forces between two opposing monolayers of grafted polymer nanoparticles (NPs) were measured using the Surface Forces Apparatus in a humid atmosphere. The NPs made of N, N-diethylacrylamide and 2-hydroxyethyl methacrylate have a hydrodynamic diameter of ca. 660 nm at 25 degrees C. The effect of surface roughness was studied by creating surface asperities using different NP grafting densities ranging from 0.41 to 2.63 NPs/mum (2). An increase in the NPs grafting density gave rise to an increase in surface roughness and to a deformation of the nanoparticles caused by the lateral pressure between neighboring particles. An elastoplastic behavior of the nanoparticles was observed for large grafting densities, while a purely elastic behavior was observed for small grafting densities. The lateral forces measured between two opposing NP monolayers sliding past each other followed Amontons' law for all grafting densities. The friction coefficient between the surfaces appeared to increase significantly with an increase in surface roughness, which was inherent to an increase in the elastoplastic behavior of the NP monolayers.