Catalytic Oxidation of Methanol to Formaldehyde Catalyzed by Iron Complex with N3S3-type Tripodal Ligand.

A Fe3+ complex with N3S3-type tripod ligand, 1, reacts with O2 in CH3OH to generate formaldehyde, which has been studied structurally, spectroscopically, and electrochemically. Complex 1 crystallizes as an octahedral structure with crystallographic C3 symmetry around the metal, with Fe-N=2.2917(17) Å and Fe-S=2.3574(6) Å. UV-vis spectrum of 1 in CH3OH under Ar shows an intense band at 572 nm (ϵ 4,100 M-1cm-1), which shifts to 590 nm (ϵ 2,860 M-1cm-1) by the addition of O2, and a new peak appeared at 781 nm (ϵ 790 M-1cm-1). Such a spectral change is not observed in CH2Cl2. Cyclic voltammogram (CV) of 1 in CH2Cl2 under Ar gives reversible redox waves assigned to Fe2+/Fe3+ and Fe3+/Fe4+ couples at -1.60 V (ΔE=69 mV) and -0.53 V (ΔE=71 mV) vs Fc/Fc+, respectively. In contrast, in CH3OH, the reversible redox waves, albeit accompanied by a positive shift of the Fe2+/Fe3+ couple, are observed at -1.20 V (ΔE=85 mV) and -0.53 V (ΔE=64 mV) vs Fc/Fc+ under Ar. Interestingly, a catalytic current was observed for the CV of 1 in CH3OH in the presence of CH3ONa under Ar, when the sweep rate was slowed down.

Molecular dynamics simulations for interfacial structure and affinity between carboxylic acid-modified Al2O3 and polymer melts.

Controlling the dispersion state of nanoparticles in a polymer matrix is necessary to produce polymer nanocomposites. The surface modification of nanoparticles is used to enable their dispersion in polymers. Moreover, molecular dynamics (MD) simulations are useful for revealing the interfacial properties between nanoparticles and polymers to aid in the design of materials. In this study, the effect of surface coverage, modifier length, and polymer species on the interfacial structure and affinity between surface-modified Al2O3 and polymer melts were investigated using all-atom MD simulations. Hexanoic, decanoic, and tetradecanoic acids were used as surface modifiers, and polypropylene (PP), polystyrene (PS), and poly (methyl methacrylate) (PMMA) were used as polymers. The work of adhesion Wadh and the work of immersion Wimm were selected as quantitative measures of affinity. Wadh was calculated using the phantom-wall approach, and Wimm was calculated by simply subtracting the surface tension of polymers γL from Wadh. The results showed that Wadh and Wimm were improved by surface modification with low coverage, owing to a good penetration of the polymer. The effect of modifier length on Wadh and Wimm was small. Whereas Wadh increased in the following order: PP < PS < PMMA, Wimm increased as follows: PMMA < PS < PP. Finally, the trend of Wadh and Wimm was organized using the Flory-Huggins interaction parameter χ between the modifier and the polymer. This study demonstrates that the interfacial affinity can be improved by tuning the surface coverage and modifier species depending on the polymer matrix.

Preparations of trans- and cis-µ-1,2-Peroxodiiron(III) Complexes.

The iron(II) complex with cis,cis-1,3,5-tris(benzylamino)cyclohexane (Bn3CY) (1) has been synthesized and characterized, which reacted with dioxygen to form the peroxo complex 2 in acetone at -60 °C. On the basis of spectroscopic measurements for 2, it was confirmed that the peroxo complex 2 has a trans-µ-1,2 fashion. Additionally, the peroxo complex 2 was reacted with benzoate anion as a bridging agent to give a peroxo complex 3. The results of resonance Raman and 1H-NMR studies supported that the peroxo complex 3 is a cis-µ-1,2-peroxodiiron(III) complex. These spectral features were interpreted by using DFT calculations.

Evaluation of the work of adhesion at the interface between a surface-modified metal oxide and an organic solvent using molecular dynamics simulations.

Advancing the practical applications of surface-modified nanoparticles requires that their dispersion in solvents can be controlled. The degree of dispersion depends on the affinity between surface-modified nanoparticles and solvents, which can be quantified using the work of adhesion at the interface. Herein, the affinity between a surface-modified inorganic solid and an organic solvent was evaluated by calculating the work of adhesion at the interface. The phantom-wall method, which is a thermodynamic route for evaluating the work of adhesion at an interface using molecular dynamics simulations, was applied to the decanoic acid-modified Al2O3/hexane interface. Molecular dynamics simulations were performed for flat interface systems to focus on the interactions between substances that affect the affinity on the surface. As a result, the surface coverage of decanoic acid was found to affect the work of adhesion, with a maximum value of 45.66 ± 0.75 mJ/m2 at a surface coverage of 75%. An analysis of the mass density profiles of Al2O3, decanoic acid, and hexane in the vicinity of the interface showed that the increase in the work of adhesion with the surface coverage was due to the penetration of hexane molecules into the decanoic acid layer on the Al2O3 surface. At a surface coverage of 75%, some hexane molecules were trapped in the layer of oriented decanoic acid molecules. These results suggested that the interfacial affinity can be enhanced by controlling the surface modification so that the solvent can penetrate the layer of the modifier.

Thermal dewetting behavior of polystyrene composite thin films with organic-modified inorganic nanoparticles.

The thermal dewetting of polystyrene composite thin films with oleic acid-modified CeO2 nanoparticles prepared by the supercritical hydrothermal synthesis method was investigated, varying the nanoparticle concentration (0-30 wt %), film thickness (approximately 50 and 100 nm), and surface energy of silanized silicon substrates on which the composite films were coated. The dewetting behavior of the composite thin films during thermal annealing was observed by an optical microscope. The presence of nanoparticles in the films affected the morphology of dewetting holes, and moreover suppressed the dewetting itself when the concentration was relatively high. It was revealed that there was a critical value of the surface energy of the substrate at which the dewetting occurred. In addition, the spatial distributions of nanoparticles in the composite thin films before thermal annealing were investigated using AFM and TEM. As a result, we found that most of nanoparticles segregated to the surface of the film, and that such distributions of nanoparticles contribute to the stabilization of the films, by calculating the interfacial potential of the films with nanoparticles.

Combined substituent number utilized machine learning for the development of antimicrobial agent.

The utilization of machine learning has a potential to improve the environment of the development of antimicrobial agents. For practical use of machine learning, it is important that the conversion of molecules information to an appropriate descriptor because too informative descriptor requires enormous computation time and experiments for gathering data, whereas a less informative descriptor has problems in validity. In this study, we utilized a descriptor only focused on substituent. The type and the position of substituents on the molecules that have a 4-quinolone structure (11,879 compounds) were converted to the combined substituent number (CSN). While the CSN does not include information on the detailed structure, physical properties, and quantum chemistry of molecules, the prediction model constructed by machine learning of CSN indicated a sufficient coefficient of determination (0.719 for the training dataset and 0.519 for the validation dataset). In addition, this CSN can easily construct the unknown molecules library which has a relatively consistent structure by recombination of substituents (32,079,318 compounds) and screening of them. The validity of the prediction model was also confirmed by growth inhibition experiments for E. coli using the model-suggested molecules and commercially available antimicrobial agents.

Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation.

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.

Rigorous kinetic model considering positional specificity of lipase for enzymatic stepwise hydrolysis of triolein in biphasic oil-water system.

A rigorous kinetic model describing the stepwise triglyceride hydrolysis at the oil-water interface, based on the Ping Pong Bi Bi mechanism using suspended lipase having positional specificity, was constructed. The preference of the enzyme to cleave to the ester bonds at the edge and the center of the glycerol backbone of the substrates (tri-, di- or monoglyceride) was incorporated in the model. This model was applied to the experimental results for triolein hydrolysis using suspended Porcine pancreatic lipase (an sn-1,3 specific lipase) and Candida rugosa lipase (a non-specific lipase) in a biphasic oil-water system under various operating conditions. In order to discuss the model's advantages, other models that do not consider the positional specificity of the lipase were also applied to our experimental results. The model considering the positional specificity of the lipase gave results which fit better with the experimental data and described the effect of the initial enzyme concentration, the interfacial area, and the initial concentrations of triolein on the entire process of the stepwise triolein hydrolysis. This model also gives a good representation of the rate for cleaving the respective ester bonds of each substrate by each type of lipase.

Synthesis of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) with low polydispersity using ultrasonic irradiation.

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) having low polydispersity was synthesized in mixed solvent of ethanol and water using ultrasonic irradiation without any chemical polymerization initiator. The effects of the volume fraction of ethanol in the solvent, the molar ratio of two monomers, the monomer concentration and the ultrasonic power intensity on the time courses of the conversion to the polymer, the number average molecular weight, and the polydispersity of synthesized polymer were investigated in order to determine the optimal conditions to synthesize the copolymers with a narrow molecular weight distribution (i.e. low polydispersity). The optimum volume fraction of ethanol in the solvent was 60 vol% to synthesize the copolymers with a low polydispersity. A higher ultrasonic power intensity resulted in a faster polymerization rate and a lower number average molecular weight. The polydispersity was less than 1.5 for all ultrasonic power intensities up to 450 W/dm3 applied in this work. A higher monomer concentration gave a faster polymerization rate and a higher number average molecular weight. The polydispersity was less than 1.5 when the monomer concentration was lower than 0.4 mol/dm3. A higher molar ratio of N-isopropylacrylamide resulted in a higher polymerization rate and a lower number average molecular weight. The copolymers with polydispersity less than 1.5 can be obtained regardless of the molar ratio of N-isopropylacrylamide. The copolymers synthesized by the ultrasonic polymerization method had a high temperature responsibility.

Control of molecular weight distribution in synthesis of poly(2-hydroxyethyl methacrylate) using ultrasonic irradiation.

Poly(2-hydroxyethyl methacrylate) (PHEMA) was synthesized using ultrasonic irradiation without any chemical initiator. The effect of the ultrasonic power intensity on the time course of the conversion to polymer, the number average molecular weight, and the polydispersity were investigated in order to synthesize a polymer with a low molecular weight distribution (i.e., low polydispersity). The conversion to polymer increased with time. A higher ultrasonic power intensity resulted in a faster reaction rate. The number average molecular weight increased during the early stage of the reaction and then gradually decreased with time. A higher ultrasonic intensity resulted in a faster degradation rate of the polymer. The polydispersity decreased with time. This was because the degradation rate of a polymer with a higher molecular weight was faster than that of a polymer with a lower molecular weight. A polydispersity below 1.3 was obtained under ultrasonic irradiation. By changing the ultrasonic power intensity during the reaction, the number average molecular weight can be controlled while maintaining low polydispersity. When the ultrasonic irradiation was halted, the reactions stopped and the number average molecular weight and polydispersity did not change. On the basis of the experimental results, a kinetic model for synthesis of PHEMA under ultrasonic irradiation was constructed considering both polymerization and polymer degradation. The kinetic model was in good agreement with the experimental results for the time courses of the conversion to polymer, the number average molecular weight, and the polydispersity for various ultrasonic power intensities.

Pretreatment combining ultrasound and sodium percarbonate under mild conditions for efficient degradation of corn stover.

Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US-SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US-SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US-SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US-SP pretreated biomass without the formation of microbial inhibitor furfural.

Kinetics of ultrasonic disinfection of Escherichia coli in the presence of titanium dioxide particles.

The ultrasonic disinfection of Escherichia coli was carried out in the presence of anatase-type TiO2 particles, and the effectiveness of the combination of ultrasonic irradiation with TiO2 addition was verified. The rate constant was determined from the plot of the common logarithm of the survival cell ratio versus the ultrasonic irradiation time using first-order kinetics. In the absence of particles, the rate constant was proportional to the ultrasonic power. When ultrasonic disinfection was carried out in the presence of TiO2 particles, which have a radical generation ability, the rate of disinfection was remarkably faster than that in the absence of TiO2. In the presence of silica particles, which have no radical generation ability, the rate of disinfection was the same as that in the absence of TiO2. These results suggest that the radical generation ability of TiO2 appeared as a result of the ultrasonic irradiation. The effect of the amount of TiO2 on the rate of disinfection was also examined. The rate constant for disinfection in the presence of TiO2 was saturated to a certain value and was represented using the Langmuir-type equation. The proposed model well describes the effects of the ultrasonic power and the amount of TiO2 on the rate constant for disinfection.

Kinetics of ultrasonic degradation of phenol in the presence of TiO2 particles.

The degradation of phenol by ultrasonic irradiation in the presence of TiO2 was investigated in complete darkness. The effects of amount of TiO2 and the combination of TiO2 addition with gas (air or oxygen) supply on the degradation kinetics of phenol and the formation of the reaction products were examined. The degradation rate of phenol increased with the amount of TiO2. As the dissolved oxygen concentration increased by supplying oxygen, the degradation rate of phenol also increased. A kinetic model for the disappearance of phenol was proposed. The model takes into account the OH radical formation by direct water degradation, indirect degradation by oxygen atom and indirect degradation by TiO2 catalysis. The calculated results explained well the fact that a higher amount of TiO2 and dissolved oxygen concentration gave faster disappearance rate.

Enhanced binding activity of nuclear antioxidant-response element through possible formation of Nrf2/Fos-B complex after in vivo treatment with kainate in murine hippocampus.

To evaluate whether in vivo glutamate signals modulate signaling processes mediated by antioxidant-response element (ARE), we examined ARE binding in nuclear extracts from the hippocampus after in vivo treatment of mice with kainate. Enhancement of ARE binding was found at 2 h to 3 days after kainate treatment. Supershift analysis indicated possible involvement of Nrf2, Fos-B, and c-Fos in ARE binding in hippocampal nuclear extracts obtained from kainate-treated animals. On super-supershift analysis by combination of these antibodies, ARE probe/protein complex was shifted by the anti-Fos-B antibody alone, but not by the anti-c-Fos antibody alone, and further addition of the anti-Nrf2 antibody dramatically eliminated binding of the complex shifted by the anti-Fos-B antibody in hippocampal nuclear extracts from kainate-treated animals. Kainate treatment induced a profound increase in levels of c-Fos and Fos-B, without markedly affecting that of Nrf2 in nuclear extracts from the hippocampus. Co-localization of Nrf2 with both Fos-B and c-Fos was found in neuronal cell layers of the hippocampus in kainate-treated animals. RT-PCR analysis revealed that kainate treatment increases glutathione-S-transferase mRNA level in the hippocampus. Taken together, kainate signals may enhance nuclear ARE binding through an interaction between constitutive Nrf2 with inducible Fos-B expressed in murine hippocampus.

Possible role of inter-domain salt bridges in oligopeptidase B from Trypanosoma brucei: critical role of Glu172 of non-catalytic ß-propeller domain in catalytic activity and Glu490 of catalytic domain in stability of OPB.

Oligopeptidase B (OPB) is a member of the prolyl oligopeptidase (POP) family of serine proteases. OPB in trypanosomes is an important virulence factor and potential pharmaceutical target. Characteristic structural features of POP family members include lack of a propeptide and presence of a ß-propeller domain (PD), although the role of the ß-PD has yet to be fully understood. In this work, residues Glu(172), Glu(490), Glu(524) and Arg(689) in Trypanosoma brucei OPB (Tb OPB), which are predicted to form inter-domain salt bridges, were substituted for Gln and Ala, respectively. These mutants were evaluated in terms of catalytic properties and stability. A negative effect on kcat/Km was obtained following mutation of Glu(172) or Arg(689). In contrast, the E490Q mutant exhibited markedly decreased thermal stability, although this mutation had less effect on catalytic properties compared to the E172Q and R689A mutants. Trypsin digestion showed that the boundary regions between the ß-PD and catalytic domains (CDs) of the E490Q mutant are unfolded with heat treatment. These results indicated that Glu(490) in the CD plays a role in stabilization of Tb OPB, whereas Glu(172) in the ß-PD is critical for the catalytic activity of Tb OPB.

Aggregation behavior of latex particles in shear flow confined between two parallel plates.

In this study, the aggregation and breakup behaviors of latex particles in shear flow confined between two parallel plates were investigated using an in situ observation apparatus with a laser scanning confocal microscope. To investigate the effects of shear rate and the gap width between two parallel plates on the size and structure of the aggregates in the steady state, the distributions of the projected cross-sectional area and perimeter-based fractal dimension of the aggregates were measured. As a result, the average size of the aggregates decreases as shear rate increases and the gap width decreases due to the hydrodynamic effect acting on the aggregates. The size distributions of the aggregates become narrow as the gap width decreases. In addition, the fractal dimension, that is, the structure of the aggregates, was almost independent of shear rate and the gap width and approximately 1.2, which suggests that the aggregates are relatively compact.