FTIR studies of adsorption and photocatalytic decomposition under UV irradiation of dimethyl sulfide on calcium hydroxyapatite

The adsorption and photocatalytic decomposition under UV irradiation of dimethyl sulfide ((CH₃)₂S: DMS) on synthetic colloidal calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂: Hap) particles were examined by in vacuo IR measurements. The adsorption isotherms of DMS on Hap exhibited the Langmuir type. The saturated adsorbed amount of DMS was increased with increasing the outgassing temperature of Hap, showing a maximum of 2.4 molecules/nm² at 250 °C. Similar tendency could be observed for change in area intensity of surface P-OH bands of Hap estimated from in vacuo IR measurements against outgassing temperature. By adsorption of DMS, the surface P-OH bands of Hap weakened while the CH bands due to DMS appeared. These results revealed that the DMS was adsorbed on surface P-OH groups of Hap. When the UV light was irradiated to the DMS-adsorbed Hap, the surface P-OH bands revived and the CH bands weakened. This fact strongly indicated the photocatalytic decomposition of DMS took place on surface P-OH groups of Hap, which was thought to be due to the formation of surface P-OH radicals by UV irradiation.     

Multifunctional Hydrophobized Microparticles for Accelerated Wound Healing after Endoscopic Submucosal Dissection

Endoscopic submucosal dissection (ESD) provides strong therapeutic benefits for early gastrointestinal cancer as a minimally invasive treatment. However, there is currently no reliable treatment to prevent scar contracture resulting from ESD which may lead to cicatricial stricture. Herein, a multifunctional colloidal wound dressing to promote tissue regeneration after ESD is demonstrated. This sprayable wound dressing, composed of hydrophobized microparticles, exhibits the multifunctionality necessary for wound healing including tissue adhesiveness, blood coagulation, re‐epithelialization, angiogenesis, and controlled inflammation based on hydrophobic interaction with biological systems. An in vivo feasibility study using swine gastric ESD models reveals that this colloidal wound dressing suppresses fibrosis and accelerates wound healing. Multifunctional colloidal and sprayable wound dressings have an enormous therapeutic potential for use in a wide range of biomedical applications including accelerated wound healing after ESD, prevention of perforation, and the treatment of inflammatory diseases.     

Resistance switch employing a simple metal nanogap junction

In recent years, several researchers have reported the occurrence of reversible resistance switching effects in simple metal nanogap junctions. A large negative resistance is observed in the I-V characteristics of such a junction when high-bias voltages are applied. This phenomenon is characteristic behaviour on the nanometre scale; it only occurs for gap widths slightly under 13?nm. Furthermore, such a junction exhibits a non-volatile resistance hysteresis when the bias voltage is reduced very rapidly from a high level to around 0?V, and when the bias voltage is reduced slowly. This non-volatile resistance change occurs as a result of changes in the gap width between the metal electrodes, brought about by the applied bias voltage.     

Important role of blood rheology in atherosclerosis of patients with hemodialysis

Concerning a role of blood rheology for atherosclerosis in patients with hemodialysis (HD), little data are available. It may be due to the fact that the method for evaluating rheologic properties of circulating blood has been limited. We examined blood rheology in 118 HD patients by using microchannel array flow analyzer that makes it possible to directly observe the flow of blood cell elements through the microchannel. Transit time (T(B)) of heparinized whole blood through slit pores (7 x 30 microm) was used as an index of rheology and related with various inflammatory biomarkers such as high-sensitive CRP (hsCRP), monocyte chemotactic protein-1, osteopontin, or fibrinogen (Fg). Moreover, as a surrogate marker of atherosclerosis, carotid intima-media thickness (IMT) and aortic stiffness evaluated by brachial-ankle pulse-wave velocity (baPWV) were studied. In HD patients, T(B) had strong positive correlations with hsCRP (r = 0.427; p < 0.00001), Fg (r = 0.452; p < 0.00001), and osteopontin (r = 0.227; p < 0.0134). Further, T(B) was significantly well correlated with IMT (r = 0.400; p < 0.0001) and PWV (r = 0.470; p < 0.0001). Multivariate regression analysis showed that baPWV, IMT, Fg, hematocrit, white blood cell count, and CRP were chosen as significant explanatory factors for T(B.) These results suggest that blood rheology may play an important role for atherosclerosis in patients with HD.     

Resonance acoustoelasticity measurement of stress in thin plates

A computer-driven, swept-frequency measurement technique is developed on the basis of resonance birefringence acoustoelasticity to evaluate the stresses in thin plates. The resonance frequency depends on the thickness and the elastic wave velocity; they change with stress because of the Poisson effect and the acoustoelastic effect. The resonance frequency is obtained from the spectral response curve in the electric impedance of the piezoelectric transducer. The frequency displacement induced by acoustically coupling the transducer can be minimized by employing the resonance peak closest to the transducer fundamental frequency. To illustrate the method, the residual stress is measured in butt-welded aluminum alloy plates and is compared with the results of conventional methods.     

Synthesis and Electrochemical Behavior of Regioisomeric Bismethanofullerene Derivatives

A series of regioisomeric bis-methanofullerenes (diethyl [60]fullerenobisacetate) were prepared by reaction of the sulfonium ylide with C₆₀. Seven stable resultant regioisomers were completely isolated on a preparative HPLC and identified by FT-IR, UV-vis, TOF-MS, and ¹H and ¹³C NMR measurements. The structures of these bisadducts were assigned based on 1) the relationship of the polarities of the regioisomers with the elution order from HPLC; 2) a comparison of their UV-vis spectra with those of corresponding Bingel-Hirsch bisadducts; and 3) the identification of their molecular symmetries by their ¹H and ¹³C NMR spectra. The electrochemical properties of the resultant regioisomeric bismethanofullerene, derivatives were investigated through cyclic voltammetry (CV). The bisadducts exhibited more negative reduction potential than the pristine C₆₀. Trans-2- and cis-3- bisadducts had the least negative potential E¹_1/2 of all the other bisadducts.     

Surface structure and visible light photocatalytic activity of titanium–calcium hydroxyapatite modified with Cr(III)

The synthetic titanium–calcium hydroxyapatite (Ti–CaHap) particles were treated with different concentrations of aqueous Cr(NO₃)₃·9H₂O solution and the materials obtained were characterized by a variety of conventional techniques. The crystal structure and particle morphology of Ti–CaHap were essentially not altered by treating with Cr(III) solution. With increasing the Cr(III) concentration, the amount of Cr(III) in the products was increased and that of Ca(II) was decreased. XPS results revealed that the surface state of Cr of Ti–CaHap was trivalent. These facts allow us to infer that the Cr(III) was doped by substitution of surface Ca(II) of Ti–CaHap. Besides, IR results proved that increasing the Cr(III) concentration developed the surface Cr–OH band while the surface Ti–OH and P–OH bands of Ti–CaHap vanished. This imply that the formation of surface P–O-Cr(OH)₂ and Ti–O–Cr(OH)₂ groups, resulting the Cr(OH)₃-like layer on the surface of Ti–CaHap particles. The Cr(III)-doped Ti–CaHap possessed the absorption peaks at 446 and 623 nm in vis range in addition to the UV absorption of charge transfer transition of O^2? → Ti⁴⁺. The vis absorption peaks developed on raising the Cr(III) concentration. The photocatalytic decomposition of acetaldehyde into CO₂ over Cr(III)-doped Ti–CaHap was detected under vis irradiation and the activity was lowered by the formation of Cr(OH)₃-like layer on the particle surface.     

Strain-mediated phase control and electrolyte-gating of electron-doped manganites

A prototype Mott transistor, the electric double layer transistor with a strained CaMnO(3) thin film, is fabricated. As predicted by the strain phase diagram of electron-doped manganite films, the device with the compressively strained CaMnO(3) exhibits an immense conductivity modulation upon applying a tiny gate voltage of 2 V.     

Mapping the "forbidden" transverse-optical phonon in single strained silicon (100) nanowire

The accurate manipulation of strain in silicon nanowires can unveil new fundamental properties and enable novel or enhanced functionalities. To exploit these potentialities, it is essential to overcome major challenges at the fabrication and characterization levels. With this perspective, we have investigated the strain behavior in nanowires fabricated by patterning and etching of 15 nm thick tensile strained silicon (100) membranes. To this end, we have developed a method to excite the "forbidden" transverse-optical (TO) phonons in single tensile strained silicon nanowires using high-resolution polarized Raman spectroscopy. Detecting this phonon is critical for precise analysis of strain in nanoscale systems. The intensity of the measured Raman spectra is analyzed based on three-dimensional field distribution of radial, azimuthal, and linear polarizations focused by a high numerical aperture lens. The effects of sample geometry on the sensitivity of TO measurement are addressed. A significantly higher sensitivity is demonstrated for nanowires as compared to thin layers. In-plane and out-of-plane strain profiles in single nanowires are obtained through the simultaneous probe of local TO and longitudinal-optical (LO) phonons. New insights into strained nanowires mechanical properties are inferred from the measured strain profiles.     

Calculation of photogenerated carrier escape rates from GaAs/AlGa1-xAs quantum wells

We present a new theory for photogenerated carrier escape rates from single quantum wells, as a function of an applied electric field, that includes thermionic emission, direct tunneling, and tunneling via thermal occupation of upper subbands, and compare the results for GaAs/Al_xGa_1-xAs quantum wells with recent experiments. We account for the two dimensional (2D) density of states below the barrier, assume thermal equilibrium of carriers within the well, allow for the possibility of strain in the well and/or barrier, and include the contribution to electron thermionic emission from indirect conduction band minima. Our expressions for thermionic emission reduce, in the limit of large well width, to those derived by assuming a three-dimensional (3D) density of states. The results for electron emission from GaAs/Al_xGa_1-xAs quantum wells with x=0.2 and x=0.4 barriers at room temperature agree well with experiment. For wells with x=0.2 barriers, thermally assisted tunneling overtakes thermionic emission around 40 kV/cm, while for wells with x=0.4 barriers thermionic emission from the L valley conduction band minima dominates for fields less than 70 kV/cm. For holes we show that the escape rates are very sensitive to the in-plane effective masses, and results using simple expressions for the in-plane masses that do not include light/heavy-hole mixing agree poorly with experiment. The agreement with experiment is improved using in-plane masses that include light/heavy-hole mixing, particularly for wells with high barriers. We suggest that agreement with experiment would be improved by using more accurate in-plane hole masses for all of the subbands