Biohybrid Organic Heterostructure Based on Chlorophyll-Bacteriochlorophyll Aggregates for Ecofriendly Hydrogen Production

Hydrogen energy is an abundant, clean, sustainable and environmentally friendly renewable energy source. Therefore, the production of hydrogen by photocatalytically splitting water on semiconductors has been considered in recent years as a promising and sustainable strategy for converting solar energy into chemical energy to replace conventional energy sources and to solve the growing problem of environmental pollution and the global energy crisis. However, highly efficient solar-driven photocatalytic hydrogen production remains a huge challenge due to the poor visible light response of available photocatalytic materials and the low efficiency of separation and transfer of photogenerated electron-hole pairs. In the present work, organic heterojunction structures based on bacteriochlorophyll (BChl) and chlorophyll (Chl) molecules were introduced and used for solar-driven photocatalytic hydrogen production from water under visible light. Also, noble metal-free photocatalyst was successfully constructed on Ti₃C₂T_x nanosheets by simple successive deposition of Chl and BChl, which was used for the photocatalytic splitting water to hydrogen evolution reaction (HER). The results show that the optimal BChl@Chl@Ti₃C₂T_x composite has a high HER performance with 114 μmol/h/g_cat, which is much higher than the BChl@Ti₃C₂T_x and Chl@Ti₃C₂T_x composites.     

Bipolar Electrode-based Electrochromic Devices for Analytical Applications – A Review

Bipolar electrode-based (BPE-based) electrochromic devices have garnered increasing attention in the past decade. These BPE-based electrochromic devices have been used for analytical health monitoring, point-of-care (POC) diagnostics, and chemical sensing. In this review, we highlight recent progress made regarding BPE-based electrochromic devices constructed for these analytical applications. Various, available electrochromic materials are summarized in the first section, after which the different device types (e. g., paper-based and self-powered) are discussed. Biological- and chemical-based analytical demonstrations of these devices are then reviewed. Finally, we conclude this review with a perspective on the future developments of BPE-based electrochromic devices in analytical applications.     

Novel synthesis of heterocyclic spirans by tandem cycloaddition to sulfur-containing heterocumulenes

Novel Ni(C0)₄-promoted tandem cycloadditions of diphenylcyclo- propenone to isothiocyanates and to CS₂ were found to provide new heterocyclic spirans, pyrroline-2-one-5-spiro-5′-thiolene-4′-ones and a thiolene-2-one-5-spiro-5′-thiolene-4′-one, respectively, in moderate yields.     

Synthesis of 5H-pyrido[2,3-a]phenoxazin-5-one and 5H-pyrido[3,2-a]phenoxazin-5-one derivatives

The 5H-pyrido[2,3-a]phenoxazin-5-one derivatives and 5H-pyrido[3,2-a]phenoxazin-5-one derivatives were prepared by the condensation of substituted 2-aminophenols with 6,7-dibromo-5,8-quinolinequinone followed by dehalogenation in the presence of sodium hydrosulfite dissolved in aqueous pyridine under a nitrogen atmosphere.     

Molecular interactions between lipid bilayers and a water-soluble polymer

Molecular interactions between lipid bilayers (liposomes) and chondroitin sulfate C (CS), a water soluble polymer, have been investigated in terms of zeta-potential, particle size, microscopic-viscosity, microscopic-polarity of liposomes and permeability of calcein. Microscopic morphology is dramatically changed by the addition of CS to the positively charged liposomes (Pos.L), while it is not changed by the addition to uncharged liposomes (Unc.L) or negatively charged liposomes (Neg.L). The absolute value of the particle size of Pos.L increases with the addition of CS, while the zeta- potential of Pos.L decreases. Permeability of Pos.L decreases with an increase in the concentration of CS. Phase transition temperature of Pos.L is changed after the addition of CS. These values, however, are not changed for the other liposomes by the addition of CS. The results of gel filtration chromatography show that CS is absorbed on the Pos.L surface. Microscopic viscosity is also increased by the addition of CS to Pos.L due to the adsorption of CS.     

Development of a new software for the X-ray structural analysis of polymer crystals by utilizing the X-ray imaging plate system

A software and some useful tools have been developed for identifying individual x-ray reflectional peaks recorded with an x-ray imaging plate system. These techniques were applied to analyze the crystal structure of uniaxially oriented polymer samples. Characteristic features of the present method may be summarized as follows. (1) The indexing of the observed reflections and the determination of the unit cell parameters can be made easily on the display of the computer. (2) The integrated intensity of the individual component of the overlapped reflections can be evaluated quantitatively through the curve separation technique. The R_merge's for the equivalent reflections were 5–6%, indicating the exact evaluation of the integrated intensities. (3) The thus obtained reflectional data were successfully utilized for the extraction of the initial structural models by the direct method. The actual applications have been made for orthorhombic polyethylene, trigonal polyoxymethylene, and isotactic polybutene-1, giving the refined crystal structures including even the positions of hydrogen atoms in some cases. The reliability factors were 12, 5, and 15%, respectively, for these three polymer cyrstals. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1677–1700, 1997     

Biodegradation of chitin with enzymes and vital components

Chitin from squid pen was effectively degraded by the chitinase from Bacillus sp. PI-7S, while the degradation of chitin with lysozyme proceeded very slowly. Among the various vital components studied, the degradation of chitin from squid pen was performed not by canine serum, canine tela subcutanea, canine tela liver, and equine serum but by bovine serum and caprine serum. Noteworthy is the fact that chitin sponge subcutaneously implanted in dog reported not to have chitinase was degraded in ca. 14 days.     

Vanadium-binding protein in a vanadium-rich ascidian Ascidia sydneiensissamea: CW and pulsed EPR studies

Some of the ascidians belonging to the suborder Phlebobranchia accumulate vanadium ion efficiently from seawater. Clarification of the mechanism of this surprisingly efficient metal-accumulation system is desirable. Two mutually similar vanadium-binding proteins (vanabin1 and vanabin2) have recently been isolated from a vanadium-rich ascidian Ascidia sydneiensis samea. In this study, the vanadium-binding properties of vanabin2 have been investigated by X-band CW EPR and pulsed EPR spectroscopy. CW EPR spectra of samples containing various ratios of VO2+ and vanabin2 invariably exhibited a usual mononuclear-type VO2+ EPR signal with the intensity dependent on the ratio [vanabin]/[V]. EPR titration has shown that vanabin2 can bind up to approximately 23.9 vanadium ions per one molecule, almost all of which ( approximately 84%) are in a mononuclear VO2+ state as estimated by EPR quantitation. Electron spin-echo envelope modulation (ESEEM) spectra of VO-vanabin2 exhibited reasonably intense peaks attributable to amine nitrogen. This is consistent with the fact that vanabin2 is a lysine-rich protein (14 lysines out of 91 amino acids). The present study reveals the uniqueness of vanabin2, which can bind a large number of metal ions in a mononuclear fashion in contrast to the situation for ferritin and metallothionein.