論文

The elasticity of Tetra-PEG chemical gel deformed by the oscillation of a laser-induced microbubble was obtained through comparison to a bubble dynamics model. An infrared nanosecond laser pulse was focused into the gel to nucleate a spherical microbubble whose subsequent free oscillation (at frequency of order (Formula presented.)) was recorded using a high-speed camera. The evolution of the bubble radius is found to be symmetric between the growth and shrinkage phases, suggesting that the gel structure is not damaged by finite-amplitude oscillations of the bubble. The radius evolution in the first collapse phase (from the maximal to the minimal size) was compared with the Rayleigh–Plesset (RP) equation equipped with neo-Hookean and quadratic Kelvin–Voigt (qKV) constitutive models, allowing for the determination of the shear modulus under high-frequency deformation. When the maximum radius of the bubble is sufficiently small, the measured shear modulus agrees with values from previous conventional rheometer studies, indicating frequency-independent behavior of the chemical gel above a certain deformation rate threshold. On the other hand, when the maximum radius exceeds a threshold, the neo-Hookean model fails to capture the elastic response, and comparison with the RP equation with the qKV model, reveals pronounced stiffening under large deformation.

Colloidal crystals have gathered wide attention as a model material for optical applications because of their feasibility in controlling the propagation of light by their crystal structure and lattice spacing as well as the simplicity of their fabrication. However, due to the simple interaction between colloids, the colloidal crystal structures that can be formed are limited. It is also difficult to adjust the lattice spacing. Furthermore, colloidal crystals are fragile compared to other crystals. In this study, we focused on polymer-grafted nanoparticles (PGNP) as a possible solution to these unresolved issues. We expected that PGNPs, composed of two distinct layers (the hard core of a nanoparticle and the soft corona of grafted polymers on the surface), will demonstrate similar behaviors as star polymers and hard spheres. We also predicted that PGNPs may exhibit polymorphism because the interaction between PGNPs strongly depends upon their grafting density and the length of the grafted polymer chains. Moreover, we expected that crystals made from PGNPs will be structurally tough due to the entanglement of grafted polymers. From exploration of crystal polymorphs of PGNPs by molecular dynamics simulations, we found face-centered cubic (FCC)/hexagonal close-packed (HCP) and body-centered cubic (BCC) crystals, depending on the length of the grafted polymer chains. When the chains were short, PGNPs behaved like hard spheres and crystals were arranged in FCC/HCP structure, much like the phase transition observed in an Alder transition. When the chains were long enough, the increase in the free energy of grafted polymers was no longer negligible and crystals were arranged in BCC structure, which has a lower density than FCC/HCP. When the chains were not too short or long, FCC/HCP structures were first observed when the volume fraction of system was small, but a phase transition occurred when the system was further compressed and the crystals arranged themselves in a BCC structure. These results most likely have laid strong foundations for future simulations and experimental studies of PGNP crystals.

We proposed an oil-sealed hydrogel microwell array for analysis of secretory components from isolated single cells. The purpose of our device is to realize the isolation of the secretory components during cell culture by combining the semi-permeable arginine-glycine-aspartate (RGD)-modified calcium alginate microwell and the oil sealing. We demonstrated the oil-sealing property, the impermeability to extracellular vesicles (EVs) or growth factor proteins (GFs), and the permeability to nutrients of our device by using three types of fluorescent particles with different diameters. We believe that our oil-sealed hydrogel microwell array will contribute to biomedical analysis on single-cell metabolism that helps to understand the mechanisms of various diseases.

We propose an oil-sealed, arginine-glycine-aspartic (RGD) -modified alginate hydrogel microwell array for the analysis of single-cell-derived extracellular vesicles and particles (EVPs) secreted by adherent cells cultured in enclosed spaces. Taking advantage of the mesh structure of alginate hydrogel, we developed a microwell array with size-selective permeability that allows nutrients to pass through the hydrogel while preventing EVPs from doing so. Continuous single-cell culture in sealed microwells (>19 days) has been achieved, while retaining the EVPs inside the microwells. The single-cell-derived EVPs were collected from sealed microwells using a glass capillary to analyze surface membrane proteins. We believe that our oil-sealed RGD-modified alginate hydrogel microwell array will contribute to revealing the heterogeneity of cells, thereby advancing our understanding of the mechanisms of various diseases.

We propose an oil-sealed arginine-glycine-aspartate (RGD)-modified hydrogel microwell array for analyzing exosomes secreted from single cells. Our device realizes the collection of exosomes from single cells in parallel. The size-selective permeation of the RGD-modified alginate hydrogel allows both stable cell culturing of single or few cells in closed wells and the confinement of exosomes secreted in each space. The nutrients (< 20 nm) that are necessary for cell culture can pass through the hydrogel, while exosomes (30-150 nm) do not permeate the walls of microwells. The cell culture property and the permeability of our device were examined, showing the capability to collect exosomes from single cells. We believe that our device would contribute to understanding the mechanisms of various diseases.

This paper proposes a force sensor that utilizes three-dimensional (3D) shape optimization and 3D printing technology. Introduction of micro-scale 3D printing technology have simplified the fabrication processes of microdevices with complex geometries. At the same time, there have also been advancements in the optimization of 3D structures to achieve desirable performances. This study combined these two technologies to develop a force sensor for measuring the force of a soft actuator. The force sensor combines a typical probe geometry with a laser displacement sensor. Due to the millimeter-order scale of the sensor, the low rigidity of the resin material causes undesired torsional deformation. Through 3D shape optimization, a beam design with more than 70 % torsional displacement reduction was achieved without changes in spring constant. Furthermore, a beam printed by a micro-scale 3D printer showed elasticity. The relationship between the input force and laser displacement sensor output showed linear characteristics, indicating its suitability as a force sensor.

© The Royal Society of Chemistry. Understanding and predicting the mechanisms underpinning the self-assembly of polymer-grafted nanoparticles (PGNPs) are important for controlling the engineering applications of these novel materials. The self-assembly of these materials is driven by their surfactancy, i.e., by the fact that the (inorganic) nanoparticles energetically dislike the (organic) polymer tethers. In previous work we developed a model in which a grafted polymer chain was treated as a rigid equivalent sphere (ES) which was impenetrable to the NPs, but completely penetrable to other ESs. This description, along with a geometric analogy with patchy particles, allowed us to facilely explain the self-assembly of PGNPs. However, since we model an ES as being completely penetrable to other ESs but impenetrable to the NPs the physical correspondence between a “real” grafted polymer and an ES is not clear. The application of the ES model to experiments and to computer simulations has therefore seen limited success, and only qualitative agreement has been obtained. In this paper, we develop a more realistic description, termed the modified ES (mES) model, based on the work of Daoud and Cotton on curved polymer brushes, which takes the impenetrability of the individual chain monomers into account. While this approach increases the complexity of our formalism, we find that the resulting mES model quantitatively captures computer simulation results on the structure of the PGNPs and also quantitatively explains their self-assembly over a broad range of conditions.

© 2018 American Chemical Society. Colloids grafted with a corona layer of polymers show glassy behavior that covers a wide range of fragilities, with this behavior being tunable through variations in grafting density and grafting chain length. We find that the corona roughness, which is maximized for long chain lengths and sparse grafting, is directly correlated to the concentration-dependence of the system relaxation time (fragility). Relatively rougher colloids result in stronger liquids because their rotational motions become orientationally correlated across the whole system even at low particle loadings leading to an essentially Arrhenius-like concentration-dependence of the relaxation times near the glass transition. The smoother colloids do not show as much orientational correlation except at higher densities leading to fragile behavior. We therefore propose that these materials are an ideal model to study the physical properties of the glass transition.

© 2019, The Society of Polymer Science, Japan. Abstract: The gelation process has been explained in the framework of percolation models. Although the percolation models accurately predict the gelation behaviors above the overlap concentration of prepolymers (c*0), they do not predict the gelation behaviors below c*0. We measured the osmotic pressure during the gelation of a series of model polymer gels, namely, tetra-polyethylene glycol (PEG) gels. The osmotic pressure decreased during the gelation reaction and was constant after the sol–gel transition. These results suggest that the clusters grow and fill the system at the sol–gel transition point. As a result, the gels behaved as semidilute systems regardless of the initial polymer concentration. This representation of the sol–gel transition at the overlap condition of the critical clusters corresponds well to the aggregation process predictrion. These results will help better understanding of general percolation problems in the dilute regime.