Search

Polymer solutions under shear flow are often observed in manufacturing processes. Classically, polymer behavior is represented by Kuhn’s bead-spring model, in which only the elongation of polymer chains is assumed. In recent years, the compression of polymer chains under shear flow has been reported. In this study, we investigated the behavior of polymer chains dissolved in various concentrations under shear flow. We measured the time variation of the fluorescence intensity emitted from a FRET (fluorescence resonance energy transfer) polymer, which enabled us to study the change in the distance between both ends of a polymer chain. The polymer chains appeared to stretch and compress depending on the concentration of the polymer solution. The results showed that the deformation of polymer chains was different from the classical theory. The FRET measurement is a promising diagnostic method for understanding the dynamics of polymer chains.

We propose a novel approach to analyze random walks in heterogeneous medium using a hybrid machine-learning method based on a gamma mixture and a hidden Markov model. A gamma mixture and a hidden Markov model respectively provide the number and the most probable sequence of diffusive states from the time series position data of particles/molecules obtained by single-particle/molecule tracking (SPT/SMT) method. We evaluate the performance of our proposed method for numerically generated trajectories. It is shown that our proposed method can correctly extract the number of diffusive states when each trajectory is long enough to be frame averaged. We also indicate that our method can provide an indicator whether the assumption of a medium consisting of discrete diffusive states is appropriate or not based on the available amount of trajectory data. Then, we demonstrate an application of our method to the analysis of experimentally obtained SPT data.

The curing process of poly(dimethylsiloxane) (PDMS) was microscopically investigated by the single-molecule tracking method based on the diffusion motion of fluorescent dye molecules adding to the PDMS layer stored at a temperature of 308K. The PDMS layer was completely cured at 900 min after adding a curing agent. We compared the time- and ensemble-averaged mean square displacements (MSDs) of the tracked molecules at 90, 510, and 900 min after adding the curing agent into the PDMS layer. The discrepancies were observed between the time- and ensemble-averaged MSDs, indicating weak ergodicity breaking. The spatially averaged diffusion coefficient exhibited a two-step decrease: first step was rapid decrease suggesting the extent of crosslinking, and second step was slow one suggesting the increase of crosslink density. The single-molecule trajectory scale analysis revealed the heterogeneous distribution of the diffusion coefficient. By calculating the heat map from the slope of moment scaling spectrum (MSS) of each single-molecule trajectory, cluster structures were recognized. The spatial correlation of the slope of MSS decreased with the time elapsed. These results suggested the existence of the heterogeneous structure in the PDMS layer during the curing process.

The Brownian motions of ZnS-AgInS2 (ZAIS) nanoparticles in a poly(dimethylsiloxane) (PDMS) layer were observed using the single-particle tracking (SPT) technique. The positions of each nanoparticle can be detected with spatial resolution of O(10 nm), and reflect the environment near each nanoparticles; thus, SPT can obtain information on the nanoscale structure or the spatial heterogeneity of the medium. In this study, ZAIS nanoparticles were illuminated by an excitation laser, and the emission of the nanoparticle was taken by using an EM-CCD camera. We analyzed each motion of the nanoparticle in the PDMS layer under two conditions: before and after adding a curing agent. The histograms of the diffusion coefficients had single peak for all of the particles in the layer before adding the curing agent and some particles in the layer after adding the one. On the other hand, the histogram of the other particles had two peaks. This indicates these particles diffused in the heterogeneous layer, showing spatial heterogeneous curing process in the layer.