Atomically flat single terminated oxide substrate surfaces

Scientific interest in atomically controlled layer-by-layer fabrication of transition metal oxide thin films and heterostructures has increased intensely in recent decades for basic physics reasons as well as for technological applications. This trend has to do, in part, with the coming post-Moore era, and functional oxide electronics could be regarded as a viable alternative for the current semiconductor electronics. Furthermore, the interface of transition metal oxides is exposing many new emergent phenomena and is increasingly becoming a playground for testing new ideas in condensed matter physics. To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chemically mixed nature and also often polar. In this review, we summarize the surface treatment procedures to accomplish atomically flat surfaces with single terminating layer for various metal oxide substrates. We particularly focus on the substrates with lattice constant ranging from 4.00 Å to 3.70 Å, as the lattice constant of most perovskite materials falls into this range. For materials outside the range, one can utilize the substrates to induce compressive or tensile strain on the films and explore new states not available in bulk. The substrates covered in this review, which have been chosen with commercial availability and, most importantly, experimental practicality as a criterion, are KTaO₃, REScO₃ (RE = Rare-earth elements), SrTiO₃, La_0.18Sr_0.82Al_0.59Ta_0.41O₃ (LSAT), NdGaO₃, LaAlO₃, SrLaAlO₄, and YAlO₃. Analyzing all the established procedures, we conclude that atomically flat surfaces with selective A- or B-site single termination would be obtained for most commercially available oxide substrates. We further note that this topmost surface layer selectivity would provide an additional degree of freedom in searching for unforeseen emergent phenomena and functional applications in epitaxial oxide thin films and heterostructures with atomically controlled interfaces.     

Signal-Induced Release of Guests from a Photolatent Metal–Phenolic Supramolecular Cage and Its Hybrid Assemblies

The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with Cu^II ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and Cu^II. We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non-covalent engineering of MSN surfaces that should be suitable for various applications in materials science.     

Colorimetric determination of Cu2+ in simulated wastewater using naphthalimide-based Schiff base

A new Cu²⁺-selective colorimetric sensor was developed by combining the chromophore 3-hydroxynaphthalimide with diaminomaleonitrile. The sensor showed Cu²⁺-selective colorimetric signaling behavior in dimethylsulfoxide, indicated by a solution color change from yellow to pink, which was readily discernible without any external devices. Practical application of the sensor to the detection of Cu²⁺ in an aqueous solution containing other environmentally relevant metal ions by selective two-phase liquid-liquid extraction with ethyl acetate was possible. Particularly, extractive signaling of Cu²⁺ in simulated semiconductor wastewater with a readily-usable smartphone as a colorimetric data capture and analysis tool was successfully conducted.     

Cloning,Expression, and Biochemical Characterization of a Novel Acidic GH16 β-Agarase,AgaJ11, from <Emphasis Type="Italic">Gayadomonas joobiniege</Emphasis> G7

A novel β-agarase AgaJ11 belonging to the glycoside hydrolase (GH) 16 family was identified from an agar-degrading bacterium Gayadomonas joobiniege G7. AgaJ11 was composed of 317 amino acids (35 kDa), including a 26-amino acid signal peptide, and had the highest similarity (44 % identity) to a putative β-agarase from an agarolytic marine bacterium Agarivorans albus MKT 106. The agarase activity of purified AgaJ11 was confirmed by zymogram analysis. The optimum pH and temperature for AgaJ11 activity were determined to be 4.5 and 40 °C, respectively. Notably, AgaJ11 is an acidic β-agarase that was active only at a narrow pH range from 4 to 5, and less than 30 % of its enzymatic activity was retained at other pH conditions. The K _m and V _max of AgaJ11 for agarose were 21.42 mg/ml and 25 U/mg, respectively. AgaJ11 did not require metal ions for its activity, but severe inhibition by several metal ions was observed. Thin layer chromatography and agarose-liquefying analyses revealed that AgaJ11 is an endo-type β-agarase that hydrolyzes agarose into neoagarohexaose, neoagarotetraose, and neoagarobiose. Therefore, this study shows that AgaJ11 from G. joobiniege G7 is a novel GH16 β-agarase with an acidic enzymatic feature that may be useful for industrial applications.     

Chemical hybridization of imidized waterborne polyurethane with silica particle

Chemical hybrids of imidized waterborne polyurethane (WPU) with silica nanoparticle were synthesized by UV cure. Imide groups were introduced into the hard segment of UV curable WPU by extending the NCO-terminated prepolymers with pyromellitic dianhydride where chemical hybridization by UV cure was made between the acrylate-terminated polyurethane prepolymer and vinyltrimethoxysilane-silica oligomer. It was found that imidization of WPU and imidized WPU-silica hybrids showed remarkably high mechanical and dynamic mechanical properties at room and elevated temperatures as well as thermal stability.     

Enhancement of CO2 sorption uptake on hydrotalcite by impregnation with K2CO3

The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics.     

Preparation of MoO3/Pt electrodes by electrodeposition for a direct methanol fuel cell

MoO₃/Pt binary catalysts with various Mo/Pt ratios were prepared by an electrodeposition method for use as the anode in a direct methanol fuel cell. Pt was electrodeposited onto indium tin oxide (ITO) substrate, and then MoO₃ was electrodeposited from an Mo-peroxo electrolyte on the top of Pt with different deposition times. The crystallinity of synthesized films was analyzed by X-ray diffraction (XRD), and the oxidation state of both the platinum and molybdenum were determined by X-ray photoelectron spectroscopy (XPS) analyses. Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM/EDS) was employed to investigate the surface morphology and composition. The catalytic activity and stability for methanol oxidation were measured using cyclic voltammetry and chronoamperometry in a mixture of 0.5 M H₂SO₄ and 0.5 M CH₃OH aqueous solution. Electrocatalytic activity for CO oxidation was also evaluated in a 0.5-M H₂SO₄ solution. The addition of a proper amount of MoO₃ was found to significantly improve both the catalytic activity and stability for methanol oxidation.     

Keratinolytic enzyme-mediated biodegradation of recalcitrant feather by a newly isolated Xanthomonas sp. P5

We isolated and characterized a novel feather-degrading Xanthomonas sp. P5 with keratinolytic activity. In improved medium containing 0.1% (w/v) feather, maximal keratinolytic activity was observed at 5 days (69.0 ± 0.6 U/mL). This value was 7.1-fold higher than the yield in basal feather medium. The strain P5 degraded feather completely after 7 days. Feather degradation resulted in free thiol group, soluble protein and amino acids formation, indicating that sulfitolysis and proteolysis may be responsible for feather degradation by the strain P5. Total free amino acid concentration in the cell-free supernatant was around 188.6 μM. Asparagine, methionine, histidine and threonine were the major amino acids released in the culture. Xanthomonas sp. P5 exhibited multiple plant growth-promoting attributes such as siderophore, indoleacetic acid, ammonia, hydrolytic enzyme and antifungal activity. Our results indicate that Xanthomonas sp. P5 could be not only used to upgrade the nutritional value of recalcitrant feather waste but is also a potential candidate for the development of biofertilizer or biocontrol agent applicable to crop plant soil.     

Optimizing Dilute-Acid Pretreatment of Rapeseed Straw for Extraction of Hemicellulose

Biological conversion of biomass into fuels and chemicals requires hydrolysis of the polysaccharide fraction into monomeric sugars prior to fermentation. Hydrolysis can be performed enzymatically or with mineral acids. In this study, dilute sulfuric acid was used as a catalyst for the pretreatment of rapeseed straw. The purpose of this study is to optimize the pretreatment process in a 15-mL bomb tube reactor and investigate the effects of the acid concentration, temperature, and reaction time. These parameters influence hemicellulose removal and production of sugars (xylose, glucose, and arabinose) in the hydrolyzate as well as the formation of by-products (furfural, 5-hydroxymethylfurfural, and acetic acid). Statistical analysis was based on a model composition corresponding to a 3³ orthogonal factorial design and employed the response surface methodology to optimize the pretreatment conditions, aiming to attain maximum xylan, mannan, and galactan (XMG) extraction from hemicellulose of rapeseed straw. The obtained optimum conditions were: H₂SO₄ concentration of 1.76% and temperature of 152.6 °C with a reaction time of 21 min. Under these optimal conditions, 85.5% of the total sugar was recovered after acid hydrolysis (78.9% XMG and 6.6% glucan). The hydrolyzate contained 1.60 g/L glucose, 0.61 g/L arabinose, 10.49 g/L xylose, mannose, and galactose, 0.39 g/L cellobiose, 0.94 g/L fructose, 0.02 g/L 1,6-anhydro-glucose, 1.17 g/L formic acid, 2.94 g/L acetic acid, 0.04 g/L levulinic acid, 0.04 g/L 5-hydroxymethylfurfural, and 0.98 g/L furfural.     

Synthesis,characterization, and catalytic application of a zinc(II) complex bearing a pyrazole-based ligand

The reaction between ZnCl₂ and N,N-bis[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-1-phenylethylamine (bdmppea) affords [(bdmppea)ZnCl₂], whose structure has been determined by X-ray crystallography. The [(bdmppea)ZnEt₂] complex in situ prepared by the reaction between [bdmppea] and ZnEt₂ exhibited high activity toward the polymerization reaction of rac-lactide at room temperature. However, its activity decreased sharply with decreasing temperature. Stereospecificity of this catalyst characterized by heterotacticity (P_r) was determined by homonuclear decoupled NMR spectroscopy, which value was ∼0.58.