Investigation into pH-responsive self-assembled monolayers of acylated anthranilate-terminated alkanethiol on a gold surface

This article describes the preparation of pH-responsive self-assembled monolayers (SAMs) of acylated anthranilate-terminated alkanethiol. These monolayers are formed by chemisorption of the alkanethiol molecules onto a gold surface, resulting in different wetting properties of the surfaces depending upon the pH. By using various characterization techniques (e.g., infrared spectroscopy, cyclic voltammetry, contact angle measurements, and surface energy analysis), we have found that the changes in the wetting properties originate from the different surface structures of the monolayers in different pH environments. From surface energy analysis, we found that the disperse components of the surface energy on such SAMs predominate after treatment with pH 1 water, whereas the polar components of the surface energy on such SAMs predominate after treatment with pH 13 water. It is greatly anticipated that this line of research will provide new insight into the mechanism behind pH-responsive properties, facilitating the design and synthesis of new surface-active molecules for the fabrication of pH-responsive functional surfaces.     

Separation of cationic polymer particles and characterization of avidin-immobilized particles by capillary electrophoresis

Cationic polymer microparticles have received much attention especially in the field of biotechnology, such that their analysis and separation have become important. So far, the separation of cationic polymer particles with different size using CE has not been achieved and the cationic particles migrated as if they are negatively charged, probably due to electrostatic interaction between capillary wall and cationic polymer particles. In this paper, the separation of cationic polymer microparticles by CE was investigated in detail. The separation of cationic particles with different size was achieved in CE by taking into account the interaction between sample particles and the inner surface of capillaries. By employing a poly(vinyl alcohol)-coated capillary, a better size separation of amine-modified latex particles was obtained compared to a Polybrene-coated capillary. It was elucidated that the composition, concentration, and pH of the background solution were also important factors in the separation of colloidal particles to avoid the surface adsorption and the characteristic aggregation of polymer particles. Furthermore, the CE analysis was applied to the characterization of cationic protein-immobilized particles.     

Evaluation of left ventricular function with cardiac magnetic resonance imaging using Fourier fitting

The aims of this study were to investigate the applicability of Fourier fitting in the magnetic resonance (MR) evaluation of left ventricular (LV) function and to determine the optimal number of harmonics for fitting. Cine cardiac MR imaging was performed in 10 subjects, and an LV time–volume curve was generated. Fourier fitting was applied to the original curve using 1–10 harmonics, and the qualities of the time–volume curve and first-derivative curve were evaluated. LV functional parameters were calculated from curves generated with and without fitting. The quality of the original time–volume curve was good, and Fourier fitting had no substantial effect on functional parameters obtained directly from the time–volume curve such as ejection fraction. The first-derivative curve generated without fitting showed substantial artificial fluctuation. The application of Fourier fitting depressed the fluctuation and tended to decrease estimates of peak ejection rate and peak filling rate. Five or six harmonics appeared to be appropriate for obtaining a high-quality first-derivative curve. In conclusion, Fourier fitting was indicated to aid in reducing the artificial fluctuation of the first-derivative curve generated from cine cardiac MR imaging and to contribute to the evaluation of functional parameters derived from the first-derivative curve.     

Fundamental studies on enhancement and blinking mechanism of surface-enhanced Raman scattering （SERS） and basic applications of SERS biological sensing

We review recent our results in the fundamental study of surface-enhanced Raman scattering （SERS） with emphasis on experiments that attempted to identify the enhancement and blinking mechanism using single Ag nanoparticle dimers attached to dye molecules. These results are quantitatively discussed in the framework of electromagnetic mechanism. We also review recent our results in basic SERS applications for biological sensing regarding detections of cell surface molecules and distinction of disease marker molecules under single cell and single molecule level.     

Sugar Binding Effects on the Enzymatic Reaction and Conformation Near the Active Site of Pokeweed Antiviral Protein Revealed by Fluorescence Spectroscopy

In various trials for elucidating the physiological function of pokeweed antiviral protein (PAP), studies on the interaction with sugar are essential. The fluorescence titration curves showed that PAP retained the strong affinity against N-acetylglucosamine (NAG) and two sites in one PAP molecule co-operatively participated in the binding. In the complex of PAP with NAG, Trp208 located at the entrance lid site of substrate came closer to Tyr72 about 0.3 Å. Furthermore, the fluorescence anisotropy decay measurement demonstrated that the segmental rotation of Trp208 was enlarged by the binding of PAP with NAG. Such conformational changes around the active site closely correlate with the enzymatic activity of PAP. The N-glycosidase activity of PAP was enhanced more than two times in the presence of NAG. The obtained results consistently suggested the enzymatic activity of PAP would be regulated through the conformation change near the active site induced by the binding with NAG.     

Effect of laser annealing using high repetition rate pulsed laser on optical properties of phosphorus-ion-implanted ZnO nanorods

The effect of high repetition rate pulsed laser annealing with a KrF excimer laser on the optical properties of phosphorus-ion-implanted zinc oxide nanorods has been investigated. The recovery levels of phosphorus-ion-implanted zinc oxide nanorods have been measured by photoluminescence spectra and cathode luminescence images. Cathode luminescence disappeared over 300 nm below the surface due to the damage caused by ion implantation with an acceleration voltage of 25 kV. When the annealing was performed at a low repetition rate of the KrF excimer laser, cathode luminescence was recovered only in a shallow area below the surface. The depth of the annealed area was increased along with the repetition rate of the annealing laser. By optimizing the annealing conditions such as the repetition rate, the irradiation fluence and so on, we have succeeded in annealing the whole damaged area of over 300 nm in depth and in observing cathode luminescence. Thus, the effectiveness of high repetition rate pulsed laser annealing on phosphorus-ion-implanted zinc oxide nanorods was demonstrated.     

Spatiotemporal alteration of phospholipids and prostaglandins in a rat model of spinal cord injury

We determined quantitative and qualitative alterations in lipids during the occurrence and progression of spinal cord injury (SCI) in rats to identify potential clinical indicators of SCI pathology. Imaging mass spectrometry (IMS) was used to visualize twelve molecular species of phosphatidylcholine (PC) on thin slices of spinal cord with SCI. In addition, twelve species of phospholipids and five species of prostaglandins (PGs) were quantified by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) of lipid extracts from control/injured spinal cords. Unique distribution patterns were observed for phospholipids with different fatty acid compositions, and distinct dynamic changes were seen in both their amounts and their distributions in tissue as tissue damage resulting from SCI progressed. In particular, PCs containing docosahexaenoic acid localized to the large nucleus in the anterior horn region at one day post-SCI and rapidly decreased thereafter. In contrast, PCs containing arachidonic acid (AA-PCs) were normally found in the posterior horn region and were intensely and temporarily elevated one week after SCI. Lysophosphatidylcholines (LPCs) also increased at the same SCI stage and in regions with elevated AA-PCs, indicating the release of AA and the production of PGs. Moreover, LC-ESI-MS/MS analysis of lipid extracts from the spinal cord tissue at the impact site demonstrated a peak in PGE2 that reflected the elevation/reduction pattern of AA-PCs and LPC. Although further investigation is required, we suggest that invasive immune cells that penetrated from the impaired blood-brain barrier at 1-2 weeks post-SCI may have produced LPCs, released AA from AA-PCs, and produced PGs in SCI tissue at sites enriched in AA-PCs/LPC.     

The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy

The first electronic transition (?←X?) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The ?←X? transition energies of 1 M electrolyte solutions are higher (Li(+): 8.024 eV and Cs(+): 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the ?←X? transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H(+), Li(+), and Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the ?←X? transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated ?←X? transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the ?←X? transition bands measured by ATR-FUV spectroscopy.     

Correction of quadratic phase error in two-wavelength digital holographic interferometry using laser diodes

We present the correction of a quadratic phase error in two-wavelength digital holographic interferometry using laser diodes. This phase error arises from numerical reconstructions of wavefronts from digital holograms based on the Fresnel diffraction integral. To correct the quadratic phase error, it is numerically produced by computer on the basis of the theoretical prediction and is subtracted from the phase difference map in two-wavelength digital holographic interferometry. Experimental results show that the method of correction in this paper is useful for two-wavelength digital holographic interferometry using laser diodes.     

Adsorption and dissociation of water on LaB6(100) investigated by surface vibrational spectroscopy

The chemisorption of water (H₂O and D₂O) on a LaB₆(100) surface was studied with reflection absorption infrared spectroscopy (RAIRS) and high resolution electron energy loss spectroscopy (HREELS). The clean surface was exposed to H₂O and D₂O at temperatures from 90 K to room temperature, and spectra were acquired after heating to temperatures as high as 1200 K. It was found that water molecularly adsorbs on the surface at 90 K as a monomer at low coverages and as amorphous solid water at higher coverages. Water adsorbs dissociatively at room temperature to produce surface hydroxyl species as indicated by OH/OD stretch peaks at 3676/2701 cm^?1. Room temperature adsorption also reveals low frequency loss features in HREEL spectra near 300 cm^?1 that are quite similar to results obtained following the dissociative adsorption of O₂. In the latter case, the loss features were attributed to the LaO stretch of O atoms bridge-bonded between two La atoms. In the case of dissociative adsorption of H₂O, the low frequency loss features could be due to either the LaO vibrations of adsorbed O or of adsorbed OH.