Photocatalytic Activity of a TiO<Subscript>2</Subscript> Photocatalyst Doped with C<Superscript>4+</Superscript> and S<Superscript>4+</Superscript> Ions Having a Rutile Phase Under Visible Light

C⁴⁺ and S⁴⁺-codoped titanium dioxide (TiO₂) having a rutile phase was prepared. By doping C⁴⁺ and S⁴⁺ ions into a TiO₂ lattice, the absorption edge of rutile TiO₂ powder was largely shifted from 400 to 700 nm. 2-Methylpyridine and methyleneblue were photocatalytically oxidized at high efficiency on C⁴⁺ and S⁴⁺-doped TiO₂ under visible light at a wavelength longer than 5 nm.     

Block copolymerization of tetrahydrofuran with δ-valerolactone by the samarium iodide-induced transformation

Summary Polymerization behavior of -valerolactone (VL) with alkylsamarium (RSmI₂) was studied, and its application to the block copolymerization of tetrahydrofuran (THF) with VL was examined. Polymerization of VL by butylsamarium gave the corresponding poly(VL) in good yield. The yield increased with increasing the concentration of VL and decreasing the polymerization temperature, resulting from the equilibrium between VL and poly(VL). The decrease in the molecular weight of poly(VL) by prolonging the polymerization time indicated the existence of back-biting reaction to form cyclic oligomers. The polymerization of VL with poly(THF)-macroanion obtained by the two-electron reduction of the propagation center of living poly(THF) with SmI₂ led to the block copolymer of THF with VL. The initiation efficiency of VL-polymerization was almost quantitative, and the unit ratio of THF and VL-segments could be controlled by both the polymerization time of THF and the amounts of VL.     

Photoinduced electron transfer in nanostructures of ultrathin polyimide films containing porphyrin moieties

Photoinduced electron transfer between porphyrin moieties and pyromellitimide fragments has been investigated in multi-layered structures of ultrathin polyimide films prepared by the Langmuir-Blodgett (LB) technique. The LB films were composed of three kinds of polyimides, which contained zinc tetraphenylporphyrin (ZnTPP) unit as an electron donor (D-layer), no chromophoric groups (S-layer), and pyromellitimide fragments as an electron acceptor (A-layer). The layered structure and orientational distribution of porphyrin moieties in the LB films were evaluated by surface plasmon measurement and absorption dichroism measurement, respectively. The thickness of monolayer was estimated to be 0.9 nm for the polyamic acid films and 0.4 nm for the polyimide films. The molecular plane of porphyrin moieties was oriented in the direction parallel to the substrate plane. In the multi-layered structures of polyimide LB films, the efficiencies of photoinduced electron transfer from porphyrin moieties to pyromellitimide fragments varied sharply with the number of spacing layers, indicating that the short-range interactions such as electron transfer could be controlled by the fabric of ultrathin films. The rate of electron transfer observed by the fluorescence quenching measurements was numerically simulated for the nanostructure using the Monte Carlo method.     

Development of a mass-producible on-chip plasmonic nanohole array biosensor

We have developed a polymer film based plasmonic device whose optical properties are tuned for measuring biological samples. The device has a circular nanohole array structure fabricated with a nanoimprint technique using a UV curable polymer, and then gold thin film is deposited by electron beam deposition. Therefore, the device is mass-producible, which is also very important for bioaffinity sensors. First the gold film thickness and hole depth were optimized to obtain the maximum dip shift for the reflection spectra. The dip shift is equivalent to the sensitivity to refractive index changes at the plasmonic device surface. We also calculated the variation in reflection spectra by changing the above conditions using the finite-difference time domain method, and we obtained agreement between the theoretical and experimental curves. The nanohole periodicity was adjusted from 400 to 900 nm to make it possible to perform measurements in the visible wavelength region to measure the aqueous samples with less optical absorption. The tuned bottom filled gold nanohole array was incorporated in a microfluidic device covered with a PDMS based microchannel that was 2 mm wide and 20 μm deep. As a proof of concept, the device was used to detect TNF-α by employing a direct immunochemical reaction on the plasmonic array, and a detection limit of 21 ng mL(-1) was obtained by amplification with colloidal gold labeling instead of enzymatic amplification.     

Towards Tuneable Retaining Glycosidase‐Inhibiting Peptides by Mimicry of a Plant Flavonol Warhead

Retaining glycosidases are an important class of enzymes involved in glycan degradation. To study better the role of specific enzymes in deglycosylation processes, and thereby the importance of particular glycosylation patterns, a set of potent inhibitors, each specific to a particular glycosidase, would be an invaluable toolkit. Towards this goal, we detail here a more in‐depth study of a prototypical macrocyclic peptide inhibitor of the model retaining glycosidase human pancreatic α‐amylase (HPA). Notably, incorporation of l ‐DOPA into this peptide affords an inhibitor of HPA with potency that is tenfold higher (K_i=480 pm ) than that of the previously found consensus sequence. This represents a first successful step in converting a recently discovered natural‐product‐derived motif, already specific for the catalytic side‐chain arrangement conserved in the active sites of retaining glycosidases, into a tuneable retaining glycosidase inhibition warhead.     

Synthesis of state machine diagrams from communication diagrams using Petri nets

Service-oriented architecture is an architecture style to build up a large-scale networked system composed of a set of components or functions, each of which is called a service. A problem to construct behavioral models of services from given global interaction specifications, called choreography, is known as the choreography realization problem. The constructed model is still an intermediate model in the process of system developments; the model will be corrected, modified, and enhanced further by designers. Therefore, we also have to consider readability of the constructed model. In this paper, we proposed a method to construct state machine models from choreographies described by a set of communication diagrams using Petri nets. The proposed method will try to use the composite states and the orthogonal regions of UML state machines for the readability.     

Resveratrol derivative-rich melinjo (Gnetum gnemon L.) seed extract suppresses multiple angiogenesis-related endothelial cell functions and tumor angiogenesis

Angiogenesis is a promising target for cancer prevention and treatment. This study aimed to determine the antiangiogenic effects of melinjo (Gnetum gnemon L.) seed extract and its resveratrol derivative components, such as gnetin C (GC), gnetin L (GL), gnemonoside A (GMA), gnemonoside C (GMC), and gnemonoside D (GMD). An ethanol extract of melinjo seeds (EEMS) and the two gnetins markedly inhibited the proliferation and tube formation of human umbilical vein endothelial cells (HUVEC) stimulated with vascular endothelial growth factor and basic fibroblast growth factor. The inhibitory effects of GC and GL were much stronger than those of resveratrol. GMC and GMD inhibited only proliferation, whereas GMA had almost no effect on the two endothelial cell functions. The EEMS and GC also reduced the cell viability of tube-forming HUVEC, with accompanying ERK1/2 inactivation, and suppressed the migration of HUVEC. Furthermore, dietary intake of EEMS significantly inhibited tumor angiogenesis in a mouse dorsal air sac assay. In conclusion, we found that the EEMS and its resveratrol derivatives, particularly GC, suppress multiple angiogenesis-related endothelial cell functions and/or tumor angiogenesis, indicating that the melinjo seeds and the natural resveratrol derivatives may be useful for cancer prevention and treatment.     

Analysis of the tilt angle of the moiré fringes produced by two inclined gratings in talbot interferometry

Abstract

Features of the moiré fringes produced by the inclined grating planes in Talbot interferometry are studied under the illumination of a plane wave. Inclinations of the two grating planes are introduced by rotating the beam-splitter and the detector gratings around the axes parallel to the line directions of each grating, when the line directions of the two grating are different. Theoretical analyses indicate that the tilt angle of the moiré fringes is sensitive to the inclination angle, and the analyses are supported by experimental results. Some simple and practical methods for judging and removing the inclinations are also discussed.     

Electrochemical surface plasmon resonance measurement based on gold nanohole array fabricated by nanoimprinting technique

In this paper, we describe our development of an electrochemical surface plasmon resonance (EC-SPR) measurement device based on a bottom-filled gold nanohole array. The polymer based gold nanohole array was fabricated with a UV nanoimprint technique and electron beam gold deposition. Direct reflection mode measurement was used to monitor the SPR dip in the reflection spectra. A cyclic voltammogram was also operated by using the standard three electrodes containing working electrode having a gold nanohole array and counter and reference electrodes. The gold nanohole array was modified with an osmium-poly(vinylpyridine)-wired horseradish peroxidase (Os-gel-HRP) film, and its redox state induced by the change in potential was monitored simultaneously. The redox state of the local film was obtained simply by scanning the sample substrate stage. The substrate modified with Os-gel-HRP film was incorporated in a microfluidic chip, and then the hydrogen peroxide was determined in terms of the redox change in the Os complex mediator from the slope of the SPR dip shift. The linear relation of hydrogen peroxide from 10 to 250 μM was successfully monitored, and a high conversion efficiency was realized.