Adsorption Kinetics and Self-Assembled Structures of Aspergillus oryzae Hydrophobin RolA on Hydrophobic and Charged Solid Surfaces.

Hydrophobins are small secreted amphipathic proteins ubiquitous among filamentous fungi. Hydrophobin RolA produced by Aspergillus oryzae attaches to solid surfaces, recruits polyesterase CutL1, and thus promotes hydrolysis of polyesters. Because the N-terminal region of RolA is involved in the interaction with CutL1, the orientation of RolA on the solid surface is important. However, the kinetic properties of RolA adsorption to solid surfaces with various chemical properties remain unclear, and RolA structures assembled after the attachment to surfaces are unknown. Using a quartz crystal microbalance (QCM), we analyzed the kinetic properties of RolA adsorption to the surfaces of QCM electrodes that had been chemically modified to become hydrophobic or charged. We also observed the assembled RolA structures on the surfaces by atomic force microscopy and performed molecular dynamics (MD) simulations of RolA adsorption to self-assembled monolayer (SAM)-modified surfaces. The RolA-surface interaction was considerably affected by the zeta potential of RolA, which was affected by pH. The interactions of RolA with the surface seemed to be involved in the self-assembly of RolA. Three types of self-assembled structures of RolA were observed: spherical, rod-like, and mesh-like. The kinetics of RolA adsorption and the structures formed depended on the amount of RolA adsorbed, chemical properties of the electrode surface, and the pH of the buffer. Adsorption of RolA to solid surfaces seemed to depend mainly on its hydrophobic interaction with the surfaces; this was supported by MD simulations, which suggested that hydrophobic Cys-Cys loops of RolA attached to all SAM-modified surfaces at all pH values. IMPORTANCE The adsorption kinetics of hydrophobins to solid surfaces and self-assembled structures formed by hydrophobin molecules have been studied mostly independently. In this report, we combined the kinetic analysis of hydrophobin RolA adsorption onto solid surfaces and observation of RolA self-assembly on these surfaces. Since RolA, whose isoelectric point is close to pH 4.0, showed higher affinity to the solid surfaces at pH 4.0 than at pH 7.0 or 10.0, the affinity of RolA to these surfaces depends mainly on hydrophobic interactions. Our combined analyses suggest that not only the adsorbed amount of RolA but also the chemical properties of the solid surfaces and the zeta potential of RolA affect the self-assembled RolA structures formed on these surfaces.

Effect of the Microstructures on Vulcanized Rubber Frictions.

Vulcanized rubber is widely used in a wide range of applications because of its flexibility, durability, sealing properties, and high degree of friction. However, this high degree of friction can also become an issue, as it leads to the wearing and breakage of parts. In this report, we investigated the effects of the vulcanized rubber microstructures on friction force by using simple, anisotropic microstructures. The line and space master microstructures were prepared from a photoresist, and the structures were transferred to PDMS, PSt, and then Ni. After surface modification of the Ni microstructures by TEOS, the vulcanized rubber microstructures were fabricated by a simple hot press process with the TEOS-coated Ni microstructure molds. The structural parameters of the vulcanized rubber line and space microstructures were found to be successfully varied by elongation, and the structural deformations were also investigated by FEM simulations. Measurements of the frictional force of the vulcanized rubber microstructures revealed the friction coefficient was reduced by the surface microstructures and was affected by the directions of the contact because of the microstructure anisotropy. The reason for of these results can be explained by the changes in the contact area and hysteresis friction. These results suggest that the friction coefficients of vulcanized rubbers can be reduced by the simple surface microstructures that are applicable to a wide range of fields.

Proton conductivity dependence on the surface polymer thickness of core-shell type nanoparticles in a proton exchange membrane.

The proton exchange membrane (PEM) is the main component that determines the performance of polymer electrolyte fuel cells. The construction of proton-conduction channels capable of fast proton conduction is an important topic in PEM research. In this study, we have developed poly(vinylphosphonic acid)-block-polystyrene (PVPA-b-PS)-coated core-shell type silica nanoparticles prepared by in situ polymerization and a core-shell type nanoparticle-filled PEM. In this system, two-dimensional (2D) proton-conduction channels have been constructed between PVPA and the surface of silica nanoparticles, and three-dimensional proton-conduction channels were constructed by connecting these 2D channels by filling with the core-shell type nanoparticles. The proton conductivities and activation energies of pelletized PVPA-coated core-shell type nanoparticles increased depending on the coated PVPA thickness. Additionally, pelletized PVPA-b-PS-coated silica nanoparticles showed a good proton conductivity of 1.3 × 10-2 S cm-1 at 80 °C and 95% RH. Also, the membrane state achieved 1.8 × 10-4 S cm-1 in a similar temperature and humidity environment. Although these proton conductivities were lower than those of PVPA, they have advantages such as low activation energy for proton conduction, suppression of swelling due to water absorption, and the ability to handle samples in powder form. Moreover, by using PS simultaneously, we succeeded in improving the stability of proton conductivity against changes in the temperature and humidity environment. Therefore, we have demonstrated a highly durable, tough but still enough high proton conductive material by polymer coating onto the surface of nanoparticles and also succeeded in constructing proton-conduction channels through the easy integration of core-shell type nanoparticles.

Novel Filler-Filled-Type Polymer Electrolyte Membrane for PEFC Employing Poly(vinylphosphonic acid)-b-polystyrene-Coated Cellulose Nanocrystals as a Filler.

Low-acidity polymer electrolyte membranes are essential to polymer electrolyte fuel cells (PEFCs) and water electrolysis systems, both of which are expected to be next-generation energy and hydrogen sources. We developed a new type of high-performance polymer electrolyte membrane (PEM) in which the core particles are precisely electrolyte polymer coated and filled into binder resin. Cellulose nanocrystals (CNCs), which have attracted attention as light, rigid, and sustainable materials, were selected as the core material for the filler. The CNC surface was coated with a new block copolymer containing a proton conductive polymer of poly(vinylphosphonic acid) (PVPA) and a hydrophobic polymer of polystyrene (PS) using RAFT polymerization with particles (PwP) we developed. The pelletized fillers and the filler-filled polycarbonate membranes achieved proton conductivities of over 10-2 S/cm with lower activation energies and much weaker acidity than the Nafion membrane.

[Investigation of resection and coagulation times during transurethral resection of the prostate among operators determined using a time-measuring instrument].

We investigated resection and coagulation times for 123 patients with lower urinary tract symptoms suggestive of benign prostatic hyperplasia who underwent transurethral resection of the prostate (TUR-P) and their differences among surgeons. The numbers of cases of TUR-P in this study were 57 for Doctor A (experienced about 4000 cases), 60 for Doctor B (experienced about 100 cases) and 6 for a visiting physician (experienced about 50 cases). We measured resection and coagulation times by turning on a time-measuring instrument that was made using commercially available parts. There were significant differences in entire operation time, and operation, resection and coagulation times per resected weight of the tissue among the 3 doctors (Doctor A < Doctor B < visiting physician, p < 0.0001, Kruskal-Wallis test). The percentage of total operation time accounted for by resection time and coagulation time in TUR-P was 37% for doctor A, whereas it was 27% for doctor B and that for the visiting physician was 21% (p < 0.0001, Kruskal-Wallis test). Thus, for doctors with more experience resection time and coagulation time accounted for higher percentages of total operation time. The measuring instrument is inexpensive and has the potential to be a useful tool for checking a surgeon's skill.

[A study of 4,031 patients of transurethral resection of the prostate performed by one surgeon: learning curve, surgical results and postoperative complications].

A total of 4,031 patients who underwent transurethral resection of the prostate (TURP) performed by one surgeon between May 1979 and December 2003 were retrospectively examined to determine the improvement of the surgeon's skill in performing TURP assessed by using a learning curve, surgical results and postoperative complications. Analysis using the learning curve, which displayed the relationship between the number of TURP procedures and the speed of resection (i.e., the weight of tissue resected divided by the operation time), revealed that 81 operations were needed before the surgeon's skill reached a plateau in performing TURP. The means +/- standard deviations of the weight of tissue resected, operation time and speed of resection were 17.0 +/- 14.6 g, 21.0 +/- 13.5 minutes, 0.80 +/- 0.32 g/minutes, respectively. As the number of TURP procedures increased and the level of skill improved, the operation time was significantly reduced and the speed of resection was significantly increased. The incidences of postoperative complications were 2.4% for blood transfusion, 0.3% for the TURP syndrome, 1.5% for hemostatic procedures, 2.8% for bladder neck contracture, and 1.0% for urethral stricture. The incidences of transfusion and the TURP syndrome decreased as the surgeon's skill improved. The mortality rate was 0.1%.

Hydrothermal synthesis of inorganic-organic hybrid gadolinium hydroxide nanoclusters with controlled size and morphology.

A series of gadolinium hydroxide [Gd(OH)3] nanoclusters having different morphologies was synthesized in the presence of 3,4-dihydroxy hydrocinnamic acid (DHCA), an organic modifier, under subcritical water conditions. These well-shaped Gd(OH)3 clusters are composed of many nanorods in a parallel orientation, rather than a disordered aggregation of nanorods, which are linked together by organic DHCA molecules. Here DHCA works as an inter-linker to form these cluster-like structures through coordination bonds. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and SQUID magnetometry. We investigated the effect of the concentrations of DHCA and KOH on the size and morphology of the Gd(OH)3 clusters. Their possible formation mechanism is also briefly discussed.

Polymer Janus particles containing block-copolymer stabilized magnetic nanoparticles.

In this report, we show a simple route to fabricate Janus particles having magnetic nanoparticles inside them, which can respond and rotate along to magnetic fields. By solvent evaporation from the tetrahydrofran solution of polymer stabilized γ-Fe2O3 nanoparticles, polystyrene (PS), and polyisoprene containing water, aqueous dispersion of Janus microparticles were successfully prepared, and the γ-Fe2O3 nanoparticles were selectively introduced into the PS phase. We demonstrate rotation and accumulation of Janus particles by using a neodymium magnet.

Coating and dispersion of ceramic nanoparticles by UV-ozone etching assisted surface-initiated living radical polymerization.

Commercially available unmodified ceramic nanoparticles (NPs) in dry powder state were surface-modified and dispersed in almost single-crystal size. The surface-initiated living radical polymerization after just UV-ozone soft etching enables one to graft polymers onto the surface of ceramic NPs and disperse them in solvents. Furthermore, a number of NPs were dispersed with single-crystal sizes. The technique developed here could be applied to almost all ceramic NPs including metal nitrides.

Size exclusion chromatography of quantum dots by utilizing nanoparticle repelling surface of concentrated polymer brush.

We have found that the concentrated poly(methyl methacrylate) (PMMA) brush showed the very good nanoparticles (NPs) repellency in its good solvent, e.g. tetrahydrofuran (THF). Whereas the oil- and hydro-phobic (fluorinated), hydrophobic and hydrophilic surfaces adsorbed a lot of NPs. The repellency of NPs did not depend on the surface nature of the NPs. Preparing absorption free columns for size exclusion chromatography (SEC) may enable us to separate quantum dots (QDs) and NPs according to their size. By installing the concentrated PMMA brush into silica monolith columns, we tried to achieve SEC of QDs and NPs. The concentrated PMMA brush immobilized silica monolith columns were prepared by surface initiated atom transfer polymerization of MMA. As a result, we have succeeded in separating QDs according to their size. This SEC system may be advantageous because it can be used in good solvents of the brush regardless of the stability of the surface modifier layer on the NPs.

Size and size distribution balance the dispersion of colloidal CeO2 nanoparticles in organic solvents.

Colloidal CeO2 nanoparticles (HNPs) stabilized with a decanoic fatty acid self-assembled monolayer (SAM) (decHNPs) showed very good dispersibility, i.e., perfect dispersion in cyclohexane up to 20 wt%. However, the HNPs stabilized with a dodecanoic acid SAM (dodHNPs) did not show good dispersion, i.e., at most 0.2 wt%. Interestingly, when we mixed equal portions of 5 wt% decHNPs in cyclohexane and 2 wt% dodHNPs in cyclohexane, the mixture showed much better dispersion than 1 wt% of dodHNPs in cyclohexane. This might indicate that the size and size distribution of the major components of the HNP solution are the most dominant factors for determining the dispersibility of HNPs in solution.

Experimental verification of the Smoluchowski theory for a bimolecular diffusion-controlled reaction in liquid phase.

We report experimental verification of the Smoluchowski theory for diffusion-controlled reactions in solution at the steady-state limit. We have determined both the diffusion coefficients and the self-termination reaction rates of the diphenylmethyl radical simultaneously. Smoluchowski theory is insufficient to discuss the reaction rate for the self-termination reaction of the diphenylmethyl radical, so the reaction rate of an encounter complex based on the Collins-Kimball treatment is estimated.