On the Moisture Absorption Capability of Ionic Liquids.

Due to their many attractive physicochemical properties, ionic liquids (ILs) have received extensive attention with numerous applications proposed in various fields of science and technology. Despite this, the molecular origins of many of their properties, such as the moisture absorption capability, are still not well understood. For insight into this, we systematically synthesized 24 types of ILs by the combination of the dimethyl phosphate anion with various types of alkyl group-substituted cyclic cations─imidazolium, pyrazolium, 1,2,3-triazolium, and 1,2,4-triazolium cations─and performed a detailed analysis of the dehumidification properties of these ILs and their aqueous solutions. It was found that these IL systems have a high dehumidification capability (DC). Among the monocationic ILs, the best performance was obtained with 1-cyclohexylmethyl-4-methyl-1,2,4-triazolium dimethyl phosphate, whose DC (per mol) value is 14 times higher than that of popular solid desiccants like CaCl2 and silica gel. Dicationic ILs, such as 1,1'-(propane-1,3-diyl)bis(4-methyl-1,2,4-triazolium) bis(dimethyl phosphate), showed an even better moisture absorption, with a DC (per mol) value about 20 times higher than that of CaCl2. Small- and wide-angle X-ray scattering measurements of eight types of 1,2,4-triazolium dimethyl phosphate ILs were performed and revealed that the majority of these ILs form nanostructures. Such nanostructures, which vary with the identity of the IL and the water content, fall into three main categories: bicontinuous microemulsions, hexagonal cylinders, and micelle-like structures. Water in the solutions exists primarily in polar regions in the nanostructures; these spaces function as water pockets at relatively low water concentrations. Since the structure and stability of the aggregated forms of the ILs are mainly governed by the interactions of nonpolar groups, the alkyl side chains of the cations play an important role in the DC and temperature-dependent equilibrium water vapor pressure of the IL solutions. Our experimental findings and molecular dynamics simulation results shed light on the moisture absorption mechanism of the IL aqueous solutions from a molecular perspective.

Ionic liquid/water interfacial localization of a green fluorescent protein fused to a tryptophan-rich peptide.

We report that several tryptophan-rich peptides exhibit an affinity for a hydrophobic ionic liquid (IL) (1-ethyl-3-methylimidazolium bis-trifluoromethanesulfonyl imide), and that green fluorescent protein (GFP) fused to a peptides, "SSSWWSWWWW" (SW1) or "SWWWWSWWWW" (SW2), containing serine (S) and tryptophan (W) at the C terminus localized at the IL/water interface. While GFPs without W-rich peptide distributed only in water phase, SW1- and SW2-GFPs were accumulated at the interface. The localization of SW1-GFP showed biphasic behavior, and most distinctive localization was observed at 7.1 µM. The localization of SW2-GFP presumably occurred at largely lower concentration (≤0.5 µM) than that of SW1-GFP, which difference was due to the higher hydrophobicity of SW2 peptide.

Unconventional salt trend from soft to stiff in single neurofilament biopolymers.

We present persistence length measurements on neurofilaments (NFs), an intermediate filament with protruding side arms, of the neuronal cytoskeleton. Tapping mode atomic force microscopy enabled us to visualize and trace at subpixel resolution photoimmobilized NFs, assembled at various subunit protein ratios, thereby modifying the side-arm length and chain density charge distribution. We show that specific polyampholyte sequences of the side arms can form salt-switchable intrafilament attractions that compete with the net electrostatic and steric repulsion and can reduce the total persistence length by half. The results are in agreement with present X-ray and microscopy data yet present a theoretical challenge for polyampholyte interchain interactions.

Virus-templated photoimprint on the surface of an azobenzene-containing polymer.

A photoimprint-based immobilization process is presented for cylindrical viruses on the surface of an azobenzene-bearing acrylate polymer by using atomic force microscopy (AFM). Tobacco mosaic virus (TMV), 18 nm in diameter and ca. 300 nm in length, was employed as a model virus. First, a droplet of an aqueous solution containing TMV was placed on the acrylate polymer surface. After drying the droplet, the polymer surface was irradiated with light at a wavelength of 470 nm from blue-light-emitting diodes. Finally, the surface was washed by aqueous solution with detergents. The polymer surface was observed at each step by AFM. TMV was shown to embed itself gradually on the polymer surface during photoirradiation in a time scale of tens of minutes because of the formation of the surface groove complementary to the shape of TMV. Analysis of immobilization efficiency of TMV on the polymer surface by the immunological enzyme luminescence indicated that efficiency increased proportional to the photoirradiation time. In these experimental conditions, the absorption band of the azobenzene moiety remained constant before and after the photoirradiation. These results show that TMV is physically held on the complementary groove formed on the polymer surface by the photoirradiation.

Orientation control of photo-immobilized antibodies on the surface of azobenzene-containing polymers by the introduction of functional groups.

In our photo-induced immobilization technique for an antibody (IgG) using azopolymers, the introduction of COOH and NMe(2) into the azopolymers, which can introduce surface charges, strongly affected the immobilization properties such as the efficiency of immobilization and the activity of the immobilized IgG (i.e., the orientation of the immobilized IgG). The introduction of COOH promoted a more active orientation of the immobilized IgG. The orientation was determined during the adsorption process onto the azopolymer surface in solution before photo-immobilization, and was maintained during the photo-immobilization. The surface charge of the azopolymer appears to be an important factor for IgG orientation, which involves electrostatic interactions between its Fab and the azopolymer surface.

Molecular scale imaging of F-actin assemblies immobilized on a photopolymer surface.

A photo-immobilization based process is presented for direct imaging of hierarchical assemblies of biopolymers using atomic force microscopy (AFM). The technique was used to investigate the phase behavior of F-actin aggregates as a function of concentration of the divalent cation Mg2+. The data provided direct experimental evidence of a coil-on-coil (braided) structure of F-actin bundles formed at high Mg2+ concentrations. At intermediate Mg2+ concentrations, the data showed the first images of the two-dimensional nematic rafts discovered by recent x-ray studies and theoretical treatments.

Molecular-shape imprinting and immobilization of biomolecules on a polymer containing azo dye.

We demonstrate a novel technique for molecular imprinting and immobilization on a surface of a polymer containing azo dyes (azopolymer). The azopolymer was found to be capable of immobilizing micrometer- and nanometer-scale macromolecules (e.g., lambda-DNA, immunoglobulin G (IgG), bacterial protease, and 1-mum polystyrene particles) through photoirradiation with blue-wavelength light. Fluorescence and atomic force microscopy studies revealed that the azopolymer surface deformed along with the shape of the macromolecules, holding them in place after photoirradiation. The desorption of the immobilized macromolecules from the azopolymer surface in an aqueous medium was observed to be very slow, on the time scale of 10 min to weeks, depending on the photoirradiation time. Immunological and enzymatic studies showed that IgG and bacterial protease immobilized on the azopolymer surface retained their original functionality. These results suggest that the azopolymer physically, not chemically, binds the macromolecules because of the increase in contact area between the macromolecules and the azopolymer surface after photoirradiation.