Effect of Mechanical Instability of Polymer Scaffolds on Cell Adhesion

The adhesion of fibroblast on polymer bilayers composed of a glassy polystyrene (PS) prepared on top of a rubbery polyisoprene (PI) was studied. Since the top PS layer is not build on a glassy, or firm, foundation, the system becomes mechanically unstable with decreasing thickness of the PS layer. When the PS film was thinner than 25 nm, the number of cells adhered to the surface decreased and the cells could not spread well. On a parallel experiment, the same cell adhesion behavior was observed on plasma-treated PS/PI bilayer films, where in this case, the surface was more hydrophilic than that of the intact films. In addition, the fluorescence microscopic observations revealed that the formation of F-actin filaments in fibroblasts attached to the thicker PS/PI bilayer films was greater than those using the thinner PS/PI bilayer films. On the other hand, the thickness dependence of the cell adhesion behavior was not observed for the PS monolayer films. Taking into account that the amount of adsorbed protein molecules evaluated by a quartz crystal microbalance method was independent of the PS layer thickness of the bilayer films, our results indicate that cells, unlike protein molecules, could sense a mechanical instability of the scaffold

Aggregation States of Polymers at Hydrophobic and Hydrophilic Solid Interfaces

Aggregation states of polystyrene (PS) and poly­(methyl methacrylate) (PMMA) at hydrophobic deuterated-octadecyltrichlorosilane (OTS-<i>d</i>) and hydrophilic SiO_x interfaces are discussed, focusing on the interaction strength between polymer and substrate. Sum-frequency generation spectroscopy revealed that PS exhibited oriented phenyl groups along the normal direction at the interface in a spin-coated film because of the centrifugal force generated during the film solidification process, whereas it did not in a solvent-cast film. This result was common for both hydrophobic and hydrophilic substrates. That is, the aggregation states of PS depended little on which kind of substrate was used. This is because the interaction between PS and the surfaces is weak. In the case of a PMMA film on the hydrophobic OTS-<i>d</i> substrate, the interfacial local conformation was also dependent on the method of film preparation. PMMA at the hydrophilic SiO_x interface, however, exhibited oriented ester methyl groups along the direction normal to the interface, regardless of the film preparation method. This is due to a stronger interaction via hydrogen bonding between carbonyl groups of PMMA and the substrate surface

The Impact of Polymer Dynamics on Photoinduced Carrier Formation in Films of Semiconducting Polymers

A better understanding of the carrier formation process in photosemiconducting polymers is crucial to design and construct highly functionalized thin film organic photodevices. Almost all studies published focus on the effect of structure on the photoinduced carrier formation process. Here, we study the dynamics of polymer chain impacts on the carrier formation process for a series of poly­(3-alkylthiophene)­s (P3ATs) with different alkyl side-chain lengths. The formation of polarons (<b>P</b>) from polaron pairs (<b>PP</b>) was accelerated at a temperature at which the twisting motion of thiophene rings occurs. Among all P3ATs employed, in P3AT with hexyl groups, or poly­(3-hexylthiophene) (P3HT), it was easiest to twist the thiophene rings and generate <b>P</b> from <b>PP</b>. The activation energy for <b>P</b> formation was proportional to that of thiophene ring motion. This makes it clear that chain dynamics, in addition to the crystalline structure, is a controlling factor for the carrier formation process in photosemiconducting polymers

Design of a Well-Defined Polyrotaxane Structure on a Glassy Polymer Surface

The polymer dynamics at the water interface play a crucial role in the manifestation of biorelated functions. One of the strategies for this is to form inclusion complexes of polymer chains with cyclic compounds. However, such an idea has been limited to bulk materials so far. Here we propose a preparation pathway for a polyrotaxane structure composed of poly­(ethylene oxide) (PEO) and α-cyclodextrin (CD) at the outermost surface of a glassy poly­(methyl methacrylate) film on the basis of the combination of a click reaction and the Langmuir–Blodgett method. The chain motion of PEO at the water interface could be regulated by threading of CD molecules on PEO and thereby the biological responses such as protein adsorption and platelet adhesion altered depending on the extent of complexation

Dynamics of Water-Induced Surface Reorganization in Poly(methyl methacrylate) Films

At the outermost surface, aggregation states of polymers generally tend to alter to their most stable ones in response to their surrounding environment. We here apply a time-resolved contact angle measurement to study the rate of the surface reorganization of poly­(methyl methacrylate) (PMMA) in water. By doing these measurements at various temperatures, it is possible to determine the apparent activation energy of the surface dynamics based on the relation of the surface relaxation time and temperature. Also, the sum-frequency generation spectroscopy revealed that the surface reorganization involves the conformational changes in the main chain part as well as the side chains. Hence, the dynamics observed here may reflect the segmental motion at the outermost region of the PMMA film, in which water plays as a plasticizer

Simple Surface Treatment of Cell-Culture Scaffolds with Ultrafine Bubble Water

We propose a novel method to treat polymeric scaffold surfaces for cell culture with water containing nanobubbles, called ultrafine bubbles (UFBs), with typical diameters less than 1 μm. A thin film of polystyrene (PS) prepared on a solid substrate was exposed to UFB water for 2 days at room temperature. The PS surface was characterized by X-ray photoelectron spectroscopy (XPS), static contact angle measurements in water, and atomic force microscopy (AFM). The surface chemical composition and wettability of PS films remained unchanged after treatment, so that aggregation states of PS at film surfaces remained unaltered by UFB water. On the other hand, after treatment, many UFBs were adsorbed on hydrophobic PS surfaces. To study the effect of UFBs on scaffold properties, the adsorption behavior of fibronectin, which is a typical extracellular matrix protein involved in cell adhesion and proliferation, was examined. While the effect on the adsorption was unclear, the structural denaturation of fibronectin was enhanced after UFB treatment, so that the proliferation of fibroblast cells on PS surfaces was promoted

Design of a Dynamic Polymer Interface for Chiral Discrimination

Enantioselective wetting of a chiral polymer film was demonstrated. The contact angle of chiral liquids on the film was strongly dependent on their chirality although their physical properties including surface tension were identical. Such wetting behavior resulted from the enantioselective surface reorganization involving local conformational change of the polymer chains at the liquid interface. The concept of “dynamic interface for chiral discrimination” has possible potential for the development of materials capable of chiral sensing, optical resolution, and asymmetric synthesis

Load-Induced Frictional Transition at a Well-Defined Alkane Loop Surface

Self-assembled monolayers (SAMs) have attracted considerable attention as a tool to confer desirable properties on material surfaces. So far, molecules used for the SAM formation are generally limited to linear ones and thus chain ends dominate the surface properties. In this study, we have successfully demonstrated unique frictional properties of a SAM composed of alkane loops from cyclic alkanedisulfide on a gold substrate, where both sulfurs are bound to gold. The frictional response was proportional to the load. However, once the load went beyond a threshold value, the frictional response became more dominant. Such a frictional transition was reversible and repeatable and was not discerned for a corresponding SAM composed of <i>n</i>-alkyl chains. The load-induced change in the frictional response from the alkane loops could be associated with the conformational change of the alkane loops. The present results differ from most studies, in which the surface properties are designed on the basis of functional chain end groups

Mesoscopic Heterogeneity in Pore Size of Supramolecular Networks

There has been a considerable interest in developing new types of gels based on a network of fibrous aggregate composed of low molecular weight gelators, also known as supramolecular gels (SMGs). Unlike conventional polymer gels with chemical cross-linking, the network formation in SMGs does not involve any covalent bonds. Thus, the network in SMGs has been often regarded as homogenous or less heterogeneous in comparison with that in chemically cross-linked polymer gels. In this study, we have experimentally verified the existence of the network heterogeneity even in SMGs. The thermal motion of probe particles in SMGs, which were prepared from aqueous dispersions of gelators having a different number of peptide residues, PalGH, PalG₂H, and PalG₃H, was tracked. The gels were spatially heterogeneous in terms of the network pore size, as evidenced by the variation in the particle motion depending on the location, at which a particle existed. With varying particle size, it was found that the characteristic length scale of the heterogeneity was in the order of (sub)­micrometers and was smaller in the order of the PalG₂H, PalG₃H, and PalGH gels

Glass Transition Behavior in Thin Polymer Films Covered with a Surface Crystalline Layer

Thin amorphous poly­(ethylene terephthalate) (PET) films covered with/without a crystallized surface layer were prepared onto silicon wafers. In the former and latter cases, the surface mobility in the film was depressed and enhanced, respectively. The glass transition temperature (<i>T</i>_g) of the amorphous PET film decreased with the reduction of the film thickness, exhibiting a remarkable nanoconfinement effect. However, once the surface region of the thin film was crystallized, or frozen in terms of the segmental motion, <i>T</i>_g of the films recovered to that of the bulk. Concurrently, the apparent activation energy of the segmental motion in the surface-crystallized film was in good accordance with the bulk value as well. These results make it clear that the mobility in the surface region plays an essential role in the glass transition of the thin films