Deformation induced evolution of plasmonic responses in polymer grafted nanoparticle thin films.

Multi-functional nanoparticle thin films are being used in various applications ranging from biosensing to photo-voltaics. In this study, we integrate two different numerical approaches to understand the interplay between the mechanical deformation and optical response of polymer grafted plasmonic nanoparticle (PGPN) arrays. Using numerical simulations we examine the deformation of thin films formed by end-functionalised polymer grafted nanoparticles subject to uniaxial elongation. The induced deformation causes the particles in the thin film network to rearrange their positions by two different mechanisms viz. sliding and packing. In sliding, the particles move in the direction of induced deformation. On the other hand, in packing, the particles move in a direction normal to that of the induced deformation. By employing a Green's tensor formulation in polarizable backgrounds for evaluating the optical response of the nanoparticle network, we calculate the evolution of the plasmonic response of the structure as a function of strain. The results indicate that the evolution of plasmonic response closely follows the deformation. In particular, we show that the onset of relative electric field enhancement of the optical response occurs when there is significant rearrangement of the constituent PGPNs in the array. Furthermore, we show that depending on the local packing/sliding and the polarization of the incident light there can be both enhancement and suppression of the SERS response.

Mechanical response of networks formed by end-functionalised spherical polymer grafted nanoparticles.

Via computer simulations we examine the mechanical response of hybrid polymer-particle networks composed of rigid spherical nanoparticles with long flexible polymer chains grafted onto their surface. The canopy of grafted polymer arms are end-functionalised such that interacting polymer-grafted nanoparticles (PGNs) form labile bonds when their coronas overlap. In the present study, the number of grafted arms, f, are such that the PGN brushes are in the small (f = 600) and intermediate curvature (f = 900 and 1200) regime with stable bonded interactions. To investigate the mechanical response of networks formed by these PGNs, controlled uniaxial elongation at a specified pulling rate is imposed on a 2-D network of PGNs placed on a hexagonal lattice. In the simulations, the force required to deform the network is measured as a function of the elongation and pulling rate imposed on the network until the network fails. By analysis of the force-strain curves and the rearrangement of the PGNs in the network we show that an increase in the number of grafted arms, pulling velocity and energy of the bonded interactions alters both the toughness and the mode of failure of the networks. In particular, we show that an increase in the number of grafted arms results in a reduction of toughness. Furthermore, analysis of the simulations of force relaxation after rapid extension indicates that the relaxation in deformed networks can be characterised by one or two time scales that depend on the number of grafted arms. The analysis of force-strain curves and force relaxation demonstrate the role of Deborah number, De, and the limitations in the use of a unique De in understanding the mechanical response of the networks respectively.

Effect of functional anisotropy on the local dynamics of polymer grafted nanoparticles.

End-functionalised polymer grafted nanoparticles (PGNs) form bonds when their coronas overlap. The bonded interactions between the overlapping PGNs depend on the energy of the bonds (U). In the present study, oscillatory deformation imposed on a simple system with interacting PGNs placed on the vertices of a triangle is employed to examine the local dynamics as a function of energy of the bonds and the frequency of oscillation relative to the characteristic rupture frequency, ω0 = 2πν exp(-U/kBT), of the bonds. In particular, the effect of functional anisotropy is studied by introducing bonds of two different energies between adjacent PGNs. A multicomponent model developed by Kadre and Iyer, Macromol. Theory Simul., 2021, 30, 2100005, that combines the features of effective interactions between PGNs, self-consistent field theory and master equation approach to study bond kinetics is employed to obtain the local dynamics. The resulting force-strain curves are found to exhibit a simple broken symmetry where Fx (γ,) ≠ -Fx (-γ,-) and Fy (γ,) ≠ Fy (-γ,-) in systems with functional anisotropy. Fourier analysis of the dynamic response reveals that functional anisotropy leads to finite even harmonic terms and systematic variation of both the elastic and dissipative response from that of the isotropic systems. Furthermore, the intra-cycle variations in the strain stiffening and shear thickening ratios obtained from the analysis indicate that functional anisotropy leads to anisotropic nonlinear response.

Designing mechanomutable composites: reconfiguring the structure of nanoparticle networks through mechanical deformation.

Via a new dynamic, three-dimensional computer model, we simulate the tensile deformation of polymer-grafted nanoparticles that are cross-linked by labile bonds, which can readily rupture and reform. For a range of relatively high strains, the network does not fail, but rather restructures into a stable, ordered structure. Within this network, the reshuffling of the labile bonds enables the formation of this new morphology. The results provide guidelines for designing mechano-responsive hybrid materials that undergo controllable structural transitions through the application of applied forces.

Modeling polymer grafted nanoparticle networks reinforced by high-strength chains.

Using a multi-scale computational approach, we determine the effect of introducing a small fraction of high-strength connections between cross-linked nanoparticles. The nanoparticles' rigid cores are decorated with a corona of grafted polymers, which contain reactive functional groups at the chain ends. With the overlap of neighboring coronas, these reactive groups can form weak labile bonds, which can reform after breakage, or stronger bonds, which rupture irreversibly and thus, the nanoparticles are interconnected by dual cross-links. We show that this network can be reinforced by the addition of high-strength connections, which model polymer arms bound together by bonds with energies on the order of 100 kBT. We demonstrate that in the course of these simulations, these high-strength connections can be treated as unbreakable chains. By subjecting networks with a random distribution of the unbreakable chains to tensile deformation at a constant strain-rate, we determine the distribution of strain at break and toughness. With even a small amount of unbreakable chains, the nanoparticle networks can survive strains far greater than the networks without these connections. Furthermore, networks containing the high-strength connections tend to form long, thin threads, which enable a larger strain at break. The findings provide guidelines for creating polymer grafted nanoparticles networks that could show remarkable strength and ductility.

Lattice animal model of chromosome organization.

Polymer models tied together by constraints of looping and confinement have been used to explain many of the observed organizational characteristics of interphase chromosomes. Here we introduce a simple lattice animal representation of interphase chromosomes that combines the features of looping and confinement constraints into a single framework. We show through Monte Carlo simulations that this model qualitatively captures both the leveling off in the spatial distance between genomic markers observed in fluorescent in situ hybridization experiments and the inverse decay in the looping probability as a function of genomic separation observed in chromosome conformation capture experiments. The model also suggests that the collapsed state of chromosomes and their segregation into territories with distinct looping activities might be a natural consequence of confinement.

Flexible ring polymers in an obstacle environment: Molecular theory of linear viscoelasticity.

We formulate a coarse-grained mean-field approach to study the dynamics of the flexible ring polymer in any given obstacle (gel or melt) environment. The similarity of the static structure of the ring polymer with that of the ideal randomly branched polymer is exploited in formulating the dynamical model using aspects of the pom-pom model for branched polymers. The topological constraints are handled via the tube model framework. Based on our formulation we obtain expressions for diffusion coefficient D, relaxation times tau, and dynamic structure factor g(k,t). Further, based on the framework we develop a molecular theory of linear viscoelasticity for ring polymers in a given obstacle environment and derive the expression for the relaxation modulus G(t). The predictions of the theoretical model are in agreement with previously proposed scaling arguments and in qualitative agreement with the available experimental results for the melt of rings.