Lubrication Properties of Ammonium-Based Ionic Liquids Confined between Silica Surfaces Using Resonance Shear Measurements.

To evaluate the friction properties of new lubrication systems, two types of ammonium-based ionic liquids (ILs), N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate ([DEME][BF4]) and N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethanesulfonyl) imide ([DEME][TFSI]), were investigated by resonance shear measurements (RSM) and reciprocating type tribotests between silica (glass) surfaces. RSM revealed that an IL layer of ca. 2 nm in thickness was maintained between the silica surfaces under an applied load of 0.40 mN ∼ 1.2 mN. The relative intensity of the RMS signal indicated that the friction of the system was lower for [DEME][BF4], 0.12, than that of [DEME][TFSI], 0.18. On the other hand, the friction coefficients µk obtained from the tribotests of [DEME][BF4] were lower than that of [DEME][TFSI] for sliding velocities in the range of 5.0 × 10(-4) m s(-1) to 3.0 × 10(-2) m s(-1) under applied loads of 196-980 mN. The friction coefficients obtained by the tribotest are discussed with reference to the RSM results.

Synthesis of mesoporous metal oxide by the thermal decomposition of oxalate precursor.

A synthesis method was newly developed to prepare mesoporous transition metal oxides by thermal decomposition of transition metal oxalates, and the method was advantageous in its versatility, low cost, and environmental friendliness. Various mesoporous transition metal oxides were successfully synthesized by the newly developed method, such as magnetic γ-Fe2O3, CoFe2O4, and NiFe2O4, MnxOy, Co3O4, and NiO. Morphology, structure, and magnetic property of the synthesized mesoporous transition metal oxides were characterized by XRD, TG-DTA, SEM, TEM, quantum design SQUID, and N2 sorption techniques. From the dependency of the heating rate, calcination time, and calcination temperature on the metal oxide structures, it was revealed that the calcination temperature was the major factor to determine the final mesoporous structure of the metal oxides. The mesoporous structures were well constructed by their corresponding metal oxide nanoparticles resulting from oxalate thermal decomposition.

Mechanical and Lubrication Properties of Double Network Ion Gels Obtained by a One-Step Process.

Human joints support us to reduce the impact on our body and move them smoothly. As they are composed of gel-like structures, gel materials with soft and resilient properties are expected, as lubricants, to provide high efficiency and a long lifetime for mechanical parts. While double network gels including ionic liquids as swelling agents possess high mechanical strength and stable low friction under high temperature or vacuum, their fabrication process is complex and time-consuming. In this study, we applied one-pot synthesis to a double network ion gel (DNIG) to obtain a thin gel film by a simple coating method and examined its thermal, mechanical and tribological properties. The DNIG was obtained by one-pot synthesis (DNIG-1) combining polycondensation of tetraethoxysilane and radical polymerization of methyl methacrylate to form silica and poly(methyl methacrylate) as a 1st and 2nd network, respectively. Such obtained DNIG-1 was characterized and compared with DNIG obtained by a conventional two-step process (DNIG-2). Thermogravimetric analysis and the compressive stress-strain test showed high thermal stability and mechanical strength of DNIG-1. As friction at the glass/DNIG-1 interface showed high friction compared with that at glass/DNIG-2, various counterface materials were applied to examine their effect on the friction of DNIG-1. As SUS304/DNIG-1 showed much lower friction compared with glass/DNIG-1, the difference in the friction was presumably due to the different adsorption forces and compatibility between the materials.

In Situ Surface-Initiated Atom-Transfer Radical Polymerization Utilizing the Nonvolatile Nature of Ionic Liquids: A First Attempt.

In this paper, in situ surface-initiated atom-transfer radical polymerization (SI-ATRP) based on both an open and a coated system, without using volatile reagents, was developed to overcome the limited usage of ATRP due to the necessity of sealing. Nonvolatile ionic liquid (IL)-type components were used, specifically N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide as the polymerizable monomer and N,N-diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide as the polymerization solvent. In the experiment, the reversible-deactivation radical polymerization characteristics are properly ensured in nonvolatile ATRP solution coated on silicon wafer as thin liquid film, to form concentrated polymer brushes (CPBs). The average molecular weight and molecular-weight distribution of the polymer produced in the liquid film and formed on silicon wafer were measured by gel permeation chromatography, which confirms that the polymerization reaction occurred as designed. Furthermore, it is clarified that the surface of the polymer brush synthesized in situ swollen by IL also exhibited low friction characteristics, comparable to that synthesized in a typical immersion process. This paper is the first to establish the effectiveness of in situ preparation for CPBs by using the coating technique.

Nanoporous Waveguide Spectroscopy for the Estimation of Enzyme Adsorption on Mesoporous Silica.

Mesoporous silica is considered as promising host material for enzymes due to its uniform pore size of enzyme dimensions and tunable surface chemical properties. In this study, we applied nanoporous waveguide (NPWG) spectroscopy to observe adsorption dynamics of heme proteins with different molecular size within mesoporous silica film modified with different surface functional groups. Since NPWG spectroscopy provides kinetic information and rough quantification of adsorption amount, it is useful to study the adsorption process of enzymes within inorganic nanoporous materials.

Trinucleotide duplex formation inside a confined nanospace under supercooled conditions.

Self-assembly of nucleotides of fewer than three base pairs is often found in protein-nucleotide conjugations, despite their energetic instability, and is regarded as the potential starting point for the creation of artificial hydrogen-bonded supramolecular complexes. Here we report duplex formation of 3-mer DNA fragments confined within silica mesopores modified with a positively charged trimethyl aminopropyl monolayer, and their further stabilization under supercooled conditions (T<273 K). We load 3-mer DNA fragments with donor- or acceptor-dye into modified silica mesopores and examine their hybridization behaviours using FRET measurements. The FRET results clearly reveal that efficient duplex formation through at least two A-T base pairs can be achieved at 233 K. Enthalpy changes for duplex formation are found to be nearly equal between complementary and single-mismatched 3-mer DNA duplexes. These results confirm confined mesoscale cavities to be a novel low-temperature reaction space for hydrogen-bonded supramolecular complexes.

Encapsulation of PEG-modified myoglobin in hydrophobic mesoporous silica as studied by optical waveguide spectroscopy.

The purpose of this study is to apply optical waveguide (OWG) spectroscopy to characterize the encapsulation behavior of enzymes modified with polyethylene glycol (PEG), i.e. pegylation, in a hydrophobic mesoporous silica film. For that purpose, pegylated myoglobin (PEG-Mb) was introduced into the silica mesopores modified with octadecylsilyl (ODS) groups and studied by OWG spectroscopy. OWG spectroscopy confirmed that the hydrophobic interaction between the PEG group and the surface ODS group promoted the encapsulation of PEG-Mb into the hydrophobic silica mesopores. The surface density of ODS affected the adsorbed amount of PEG-Mb and the higher surface density of the ODS group resulted in the suppression of adsorption and diffusion of PEG-Mb inside the pore. Since the desorption rate of PEG-Mb was found to be much slower than the adsorption rate, the pegylation of an enzyme could be effective for the enzyme encapsulation into the hydrophobic mesoporous silica host.

Adsorption and desorption dynamics of sodium dodecyl sulfate at the octadecylsilane layer on the pore surface of a mesoporous silica film observed in-situ by optical waveguide spectroscopy.

The purpose of this study is to apply optical waveguide (OWG) spectroscopy to observe adsorption and desorption dynamics occurring in a surfactant-templated mesoporous silica film. For that purpose, a mesoporous silica (MS) film with open accessible pores (pore diameter, ca. 6 nm) was formed on an aluminum (Al) layer deposited on a glass substrate, and the pore surface of the MS film was modified with octadecylsilane (ODS). The resulting ODS-modified MS (ODS-MS) and Al multilayer film showed a clear waveguide coupling dip in the reflection spectrum. The position of the waveguide coupling dip was red-shifted as the amount of sodium dodecyl sulfate within the ODS-MS layer increases. These results indicate the usefulness of OWG spectroscopy for the study of adsorption/desorption dynamics occurring in MS materials.