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Improving the stability of porous materials for practical applications is highly challenging. Aluminosilicate zeolites are utilized for adsorptive and catalytic applications, wherein they are sometimes exposed to high-temperature steaming conditions (∼1000 °C). As the degradation of high-silica zeolites originates from the defect sites in their frameworks, feasible defect-healing methods are highly demanded. Herein, we propose a method for healing defects to create extremely stable high-silica zeolites. High-silica (SiO

Catalytic conversion of methane (CH4) to light olefins is motivated by increasing recoverable reserves of methane resources, abundantly available in natural gas, shale gas, and gas hydrates. The development of effective processes for conversion of CH4 to light olefins is still a great challenge. The interface of ZSM-5 zeolite and TiO2 nanoparticles is successfully constructed in their core–shell particles via mechanochemical treatment with high shear stress. The oxidative coupling of methane at a low temperature under application of an electric field may be induced by the O2 activation via electrons running through the surface of TiO2 located at the interface of TiO2 and zeolite particles. Moreover, C3H6 was also produced by the ethylene to propylene (ETP) reaction catalyzed by Bronsted acid sites in the ZSM-5 zeolite within core–shell particles.

The liver possesses a high regenerative capacity. Liver regeneration is a compensatory response overcoming disturbances of whole-body homeostasis provoked by organ defects. Here we show that a vagus-macrophage-hepatocyte link regulates acute liver regeneration after liver injury and that this system is critical for promoting survival. Hepatic Foxm1 is rapidly upregulated after partial hepatectomy (PHx). Hepatic branch vagotomy (HV) suppresses this upregulation and hepatocyte proliferation, thereby increasing mortality. In addition, hepatic FoxM1 supplementation in vagotomized mice reverses the suppression of liver regeneration and blocks the increase in post-PHx mortality. Hepatic macrophage depletion suppresses both post-PHx Foxm1 upregulation and remnant liver regeneration, and increases mortality. Hepatic Il-6 rises rapidly after PHx and this is suppressed by HV, muscarinic blockade or resident macrophage depletion. Furthermore, IL-6 neutralization suppresses post-PHx Foxm1 upregulation and remnant liver regeneration. Collectively, vagal signal-mediated IL-6 production in hepatic macrophages upregulates hepatocyte FoxM1, leading to liver regeneration and assures survival., The mechanisms underlying the regenerative capacity of the liver are not fully understood. Here, the authors show that the acute regenerative response to liver injury in mice is regulated by the communication involving the vagus nerve, macrophages, and hepatocytes, leading to hepatic FoxM1 activation and promotion of overall survival.

The adsorption–desorption isotherms and relaxation curves of water in chromium terephthalate metal–organic frameworks (MOFs), MIL-101, were measured by the gravimetric method at 298 K and 1 atm. Th...

The purpose of this study was to clarify nitrogen (N) leaching behavior as affected by snowmelt percolation in an Andosol soil planted with an established apple orchard, with the aim of supporting fertilization management that preserves the soil environment while maximizing apple production. Simultaneous measurements of electrical conductivity (EC), pH, NO3-N, and NH4-N (inorganic-N concentration) of the apple orchard soil pore water were taken. The adsorption nature of NO3-N and NH4-N were also monitored using Langmuir type and Logistic type adsorption isotherms. Numerical analysis relevant to the spatiotemporal dynamics of inorganic-N in soil pore water was also conducted during the growing and non-growing period for apples. The level of soil pore water EC resulting from fertilizer application was characteristically altered by downward leaching over time. Regarding the NO3-N concentration of soil pore water in the investigated area with heavy snow accumulation, the bulk of the fertilizer applied from January to July 2016 was leached down to z = 100 cm within 5 to 6 months. In the apple orchard during and after snowfall, the numerical results revealed that when NO3-N

Bis-bidentate ligand H4LB featuring two o-amidophenol noninnocent units was used to synthesize novel binuclear complexes [(LR)MIII(•LB•)MIII(LR)](ClO4)2, M = Fe (1) and Co (2, 3), with HLR (R = CH3, Cl) being the facially coordinating tetradentate coligands. Upon the synthesis, the fully reduced amidophenolate form of the ligand (LB)4– becomes oxidized, resulting in the formation of a rare example of a biradical (•LB•)2– bridge connecting two metal ions, as supported by X-ray crystallography. The electronic structures of the complexes have been probed by Mossbauer spectroscopy, magnetic susceptibility measurements, and electron paramagnetic resonance (EPR) spectroscopy. Species 1 contains two high-spin Fe(III) ions (S = 5/2) each coupled strongly antiferromagnetically (|J| > 150 cm–1; Ĥ = −2JŜ1Ŝ2) with a semiquinone π-radical (S = 1/2) form of the bridging (•LB•)2– ligand. The effective S = 2 spins of each [Fe(III)+R●] monomeric unit are then weakly ferromagnetically coupled with J = +0.22 cm–1. Species 2...

Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

In this study, an N-heterocyclic carbene (NHC)-based metallosurfactant (MS), NHC-PdMS, was synthesized, where Pd(II) was bound to the NHC framework via a robust Pd-carbene bond with NEt3 as a co-ligand. Surface tension measurements revealed that the critical micelle concentration (CMC) of NHC-PdMS (1.8×10-4 M) was one order of magnitude lower than that of its MS precursor (imidazolium bromide). Coordination of the MS precursor and NEt3 to Pd(II) also influenced micelle size; the hydrodynamic diameters of NHC-PdMS and the MS precursor were observed to be 25.8±5.6 nm and 2.5±0.3 nm, respectively. Furthermore, small angle X-ray scattering measurements indicated that NHC-PdMS exhibited liquid crystalline behavior above 26 wt%, with a spacing ratio of 1:2:3 for the first, second, and third Bragg peaks. To understand the role of the reactive interface, NHC-PdMS was also applied to aqueous catalytic reactions. Owing to its low CMC value, a catalytic amount of NHC-PdMS (3 mol%) provided the reactive interface, which facilitated the aqueous Mizoroki-Heck reaction of various aryl iodides and styrene in good yields (72-95%). These results suggest that MS formation results in a drastic change in selfassembling properties, which are important for the development of highly reactive chemical interfaces in water.

Hierarchically nanostructured, coral-like carbons with uniform spherical ∼50 nm pores and

This study represents a systematic framework supporting the development of a structure-based lumping kinetic model useful for designing, simulating, and optimizing refinery reactors. Utilizing the wealth of the available data and information provided by petroleomics, the framework comprises strategies for analyzing and reducing a large and complicated elementary kinetic reaction model as well as generating lumps in light of the structure and reactivity of the species included in the feedstock and product mixtures. A structure-based model developed by applying the framework cannot only predict yield but can also provide the structure-based composition of the product mixture. A case study on the hydrodesulfurization of light gas oil (LGO-HDS) was used to illustrate the applicability of the framework. The developed LGO-HDS structure-based kinetic model can describe reaction behavior and predict product distribution with high accuracy.

Oxidase activities of a μ-hydroxidodimanganese(III) system involving a series of tetradentate capping ligands H2LR1,R2 with a pair of phenolate arms have been investigated in the presence of 3,5-di-tert-butylcatechol (H2DBC) as a coligand cum-reductant. The reaction follows two distinctly different paths, decided by the substituent combinations (R1 and R2) present in the capping ligand. With the ligands H2Lt-Bu,t-Bu and H2Lt-Bu,OMe, the products obtained are semiquinonato compounds [MnIII(Lt-Bu,t-Bu)(DBSQ)]·2CH3OH (1) and [MnIII(Lt-Bu,OMe)(DBSQ)]·CH3OH (2), respectively. In the process, molecular oxygen is reduced by two electrons to generate H2O2 in the solution, as confirmed by iodometric detection. With the rest of the ligands, viz., H2LMe,Me, H2Lt-Bu,Me, H2LMe,t-Bu, and H2LCl,Cl, the products initially obtained are believed to be highly reactive quinonato compounds [MnIII(LR1,R2)(DBQ)]+, which undergo a domino reaction with the solvent methanol to generate products of composition [MnIII(LR1,R2)(BMOD)]...

The cyclic lipopeptide surfactin (SF) is one of the promising environmental friendly biosurfactants abundantly produced by microorganisms such as Bacillus subtilis. SF shows excellent surface properties at various pH, together with lower toxicity and higher biodegradability than commonly used petroleum-based surfactants. However, the effect of the dissociation degree of SF on self-assembly is still incompletely understood, even though two acidic amino acid residues (Asp and Glu) are known to influence eventual surface and biological functions. Here, we report changes in the secondary structure of SF induced by increased pH, and the effect on protease activity. We found that the β-sheet and β-turn formation of SF are significantly enhanced through increased dissociation of Asp and Glu as revealed by a titration experiment of SF solution to estimate apparent pK1 and pK2 values together with circular dichroism spectroscopy. We also studied the activity of the common detergent enzyme subtilisin in SF solution at above its pK2 (pH 7.6) to understand the role of the dissociation degree in the interaction with the protein. The mixing of SF having a unique cyclic topological feature with subtilisin suppressed the decrease in protease activity observed in the presence of synthetic surfactants such as sodium dodecyl sulfate and polyoxyethylene alkyl ether. Thus, SF has great potential for use in laundry detergent formulations, to improve the stability and reliability of detergent enzymes.

Uniformity in thickness and electronic properties of superconducting niobium titanium nitride (NbTiN) thin films is a critical issue for upscaling superconducting electronics, such as microwave kinetic inductance detectors for submillimeter wave astronomy. In this article we make an experimental comparison between the uniformity of NbTiN thin films produced by two DC magnetron sputtering systems with vastly different target sizes: the Nordiko 2000 equipped with a circular $\varnothing$ 100 mm target, and the Evatec LLS801 with a rectangular target of 127 mm $\times$ 444.5 mm. In addition to the films deposited staticly in both systems, we have also deposited films in the LLS801 while shuttling the substrate in front of the target, with the aim of further enhancing the uniformity. Among these three setups, the LLS801 system with substrate shuttling has yielded the highest uniformity in film thickness ( $\pm$ 2%), effective resistivity (decreasing by 5% from center to edge), and superconducting critical temperature ( $T_{\mathrm{c}}$ = 15.0 K–15.3 K) over a $\varnothing$ 100 mm wafer. However, the shuttling appears to increase the resistivity by almost a factor of 2 compared to static deposition. Surface SEM inspections suggest that the shuttling could have induced a different mode of microstructural film growth.

Meso- and/or macroporous zeolites have received particular attention because the presence of secondary meso- and/or macropores, in addition to the intrinsic micropores of zeolites, can provide addi...

With adoption of the petroleomics concept, significant effort has been made to create extensive databases of molecular structures and chemical and physical properties of complex petroleum mixtures. By collation of the available information provided by petroleomics, this study develops a new structure-based lumping kinetic model for hydrodesulfurization (HDS) of light gas oil. An advanced experimentation system, analytical technique, and computer software tool are employed to generate the necessary data. The model contains 16 structure-based lumps, each of which includes species having a similar structure and reactivity. The model allows for the tracking of changes in molecular structure type of the input and output mixtures during HDS. Its prediction capability is validated over a wide range of HDS operation temperatures (200–375 °C).

Aims Evaluation of the retinal microcirculation is key to understanding retinal vasculopathies, such as diabetic retinopathy. Laser speckle flowgraphy (LSFG) has recently enabled us to directly evaluate the vascular resistance in both retinal vessels and capillaries, non-invasively. We therefore assessed whether retinal vessel blood flow and/or the capillary microcirculation are associated with blood flow in the cervical arteries in diabetic patients without severe retinopathy. Methods We enrolled 110 type 2 diabetes patients, with no or mild non-proliferative diabetic retinopathy, in this prospective cross-sectional study. We measured the resistivity indices (RIs) of the retinal vessel and capillaries by LSFG and those of cervical arteries by Doppler ultrasonography, followed by analyzing associations. Results The RIs of not only the carotid but also vertebral arteries were associated with those of retinal vessel blood flow and the retinal capillary microcirculation. Multiple regression analyses revealed these associations to be independent of other explanatory variables including age and diabetes duration. Conclusions We obtained novel and direct evidence demonstrating a close association between the retinal microcirculation and cervical artery hemodynamics in diabetic patients. These findings suggest shared mechanisms to underlie micro- and macro-angiopathies. Thus, high vascular resistance of cervical arteries may be a risk of developing retinopathy.

The thermal dependence of salinity-gradient-driven energy conversion by reverse electrodialysis using a mesoporous silica thin film with pores ca. 2-3 nm in diameter was studied in a temperature range of 293-333 K. As the temperature increases, the surface charge density of mesopores increases owing to an increase in the zeta potential of the pore walls, which in turn increases the concentration of counter-ions in the electrical double layer. The ion mobility also increases with increasing temperature owing to a decrease in the liquid viscosity. As a result, the temperature increase improves the ion conductance of mesopores both in the surface-charge-governed regime at low ion concentrations and in the bulk regime at high ion concentrations. However, further increases in temperature induce bubble nucleation. In particular, in highly concentrated salt solutions, hydrophobic patches appear on the pore surfaces because of the salting-out effect and mask the surface charge. The weakened polarity in mesopores allows more co-ions to enter them, decreasing the potential difference across the film, resulting in a serious deterioration of the energy conversion efficiency. The thermal dependence of the performance characteristics of mesoporous-silica-based nanofluidic devices was also evaluated.

It is well known that helium (He) molecules that remain inside micropores after free-space calibration at a low temperature (77.4 K) affect the shape of an adsorption isotherm, especially in a very low relative pressure region. This negative effect of the remaining He leads to a misunderstanding of the porous characteristics, such as micropore size distribution and surface properties. However, it is still believed that such erroneous interpretations are limited to narrow microporous materials such as activated carbon and measurements at low temperatures, namely the measurement of the adsorption of N2 and Ar at their boiling points. Here we report a systematic investigation of the influence of free-space calibration using He on microporous, mesoporous and non-porous materials. Zeolite Y, mesoporous silica, carbon black and aerosil 200 were used for the measurements. N2, H2O and CO2 adsorption isotherms were measured at 77.4, 298 and 298 K, respectively. Free-space calibration was carried out before and after the isotherm measurement for each sample. Although the influence of the He that remained in the sample was small for the non-porous sample, the shape of the isotherms for the other samples in a low relative pressure region was rather affected by the timing of the free-space calibration even for the mesoporous sample, and at an ambient temperature.

The cyclization of amphiphiles has emerged as an attractive strategy for inducing remarkable properties in these materials without changing their chemical composition. In this study, we successfully synthesized three cyclic polyoxyethylene dodecyl ethers (c-POEC12's) with different ring sizes and explored the effects of their topology on their surface and self-assembly properties related to their function, comparing them with those of their linear counterparts (l-POEC12's). The surface activity of the c-POEC12's remained almost constant despite the change in their hydrophobic and hydrophilic balance (HLB) value, while that of the l-POEC12's decreased with an increase in the HLB value as general surfactants. In contrast to the normal micelles seen in the case of the l-POEC12's (3.4-9.7 nm), the cyclization of the POEC12's resulted in the formation of large spherical structures 72.8-256.8 nm in size. It also led to a dramatic decrease of 28 °C in the cloud point temperature. Furthermore, the cyclization of the POEC12's markedly suppressed the rate of protease hydrolysis caused by the surfactants. The initial rate of reduction of a detergent enzyme from Bacillus licheniformis was increased by more than 40% in the case of c-POE600C12 and c-POE1000C12, even though they exhibited surface activities almost equal to or higher than those of their linear counterparts. These results suggest that cyclization induces unusual aqueous behaviors in POEC12, making the surfactant milder with respect to detergent enzymes while ensuring it exhibits increased surface activity.

A surface-active N-heterocyclic carbene (NHC) ligand with an octaethylene glycol monomethyl ether and n-dodecyl chain was synthesized. The NHC and its Pd complex behaved as a general surfactant, and hydrophobic oily substrates such as iodobenzene and styrene were emulsified in water, resulting in the acceleration of the Mizoroki–Heck reaction under heterogeneous conditions. Our results demonstrated that the reactive emulsion interface rendered by the surface-active NHC is effective for the aqueous Mizoroki–Heck reaction.

New nickel(II) complexes containing 4-chromone N (4)-substituted thiosemicarbazone ligands of the type [Ni(L 1–3 ) 2 ](NO 3 ) 2 ·H 2 O ( 1 – 3 ) [4-chromone-4-methylthiosemicarbazone (L 1 ), 4-chromone-4-phenylthiosemicarbazone (L 2 ), 4-chromone-4-cyclohexylthiosemicarbazone (L 3 )] were synthesized and characterized by analytical and various spectroscopic techniques. The single crystal X-ray diffraction study of the complex 1 revealed a distorted octahedral geometry around the metal center. The new complexes were subjected to biological investigations such as DNA/protein interaction studies and in vitro cytotoxic study against human breast cancer cell line (MCF-7). The DNA binding by fluorescence spectral study showed that the complexes bind to DNA via intercalation binding mode. Protein binding studies using fluorescence spectroscopy showed that the new complexes could bind strongly with bovine serum albumin (BSA). The complexes have good anticancer activity against MCF-7 cancer cell line due to the terminal substituted thiosemicarbazones.

The coordination behavior of 2-oxo-1,2-dihydroquinoline-3-carbaldehyde hydrazone ligands in ruthenium(II) and the catalytic activity of newly synthesized complexes have been studied. The complexes [RuCl(CO)(PPh3)2(L1)] (1), [RuCl(CO)(AsPh3)2(L1)] (2), [RuCl(CO)(PPh3)2(L2)] (3) and [RuCl(CO)(AsPh3)2(L2)] (4) were synthesized by reactions of [RuHCl(CO)(EPh3)3] (E = P or As) precursors with hydrazone ligands and characterized by analytical and spectroscopic methods. The molecular structure of complex 2 was identified by means of single-crystal X-ray diffraction analysis. The structural analysis revealed that all the complexes possess a distorted octahedral geometry with the ligand coordinating in a uni-negative bidentate NO fashion. Further, the catalytic efficiency of the complexes have been investigated in the case of direct amidation of alcohols with amines. The influence of base, reaction temperature and catalyst loading in the amidation reaction was also evaluated. Notably, complex 3 was found to be very efficient catalyst towards amidation of alcohols with amine. A variety of aromatic (hetero) amines and alcohols with various functional groups have also been successfully used for amidations.

Leptin resistance is an important mechanism underlying the development and maintenance of obesity and is thus regarded as a promising target of obesity treatment. Plasminogen activator inhibitor 1 (PAI-1), a physiological inhibitor of tissue-type and urokinase-type plasminogen activators, is produced at high levels in adipose tissue, especially in states of obesity, and is considered to primarily be involved in thrombosis. PAI-1 may also have roles in inter-organ tissue communications regulating body weight, because PAI-1 knockout mice reportedly exhibit resistance to high fat diet (HFD)-induced obesity. However, the role of PAI-1 in body weight regulation and the underlying mechanisms have not been fully elucidated. We herein studied how PAI-1 affects systemic energy metabolism. We examined body weight and food intake of PAI-1 knockout mice fed normal chow or HFD. We also examined the effects of pharmacological inhibition of PAI-1 activity by a small molecular weight compound, TM5441, on body weight, leptin sensitivities, and expressions of thermogenesis-related genes in brown adipose tissue (BAT) of HFD-fed wild type (WT) mice. Neither body weight gain nor food intake was reduced in PAI-1 KO mice under chow fed conditions. On the other hand, under HFD feeding conditions, food intake was decreased in PAI-1 KO as compared with WT mice (HFD-WT mice 3.98 ± 0.08 g/day vs HFD-KO mice 3.73 ± 0.07 g/day, P = 0.021), leading to an eventual significant suppression of weight gain (HFD-WT mice 40.3 ± 1.68 g vs HFD-KO mice 34.6 ± 1.84 g, P = 0.039). Additionally, TM5441 treatment of WT mice pre-fed the HFD resulted in a marked suppression of body weight gain in a PAI-1-dependent manner (HFD-WT-Control mice 37.6 ± 1.07 g vs HFD-WT-TM5441 mice 33.8 ± 0.97 g, P = 0.017). TM5441 treatment alleviated HFD-induced systemic and hypothalamic leptin resistance, before suppression of weight gain was evident. Moreover, improved leptin sensitivity in response to TM5441 treatment was accompanied by increased expressions of thermogenesis-related genes such as uncoupling protein 1 in BAT (HFD-WT-Control mice 1.00 ± 0.07 vs HFD-WT-TM5441 mice 1.32 ± 0.05, P = 0.002). These results suggest that PAI-1 plays a causative role in body weight gain under HFD-fed conditions by inducing hypothalamic leptin resistance. Furthermore, they indicate that pharmacological inhibition of PAI-1 activity is a potential strategy for alleviating diet-induced leptin resistance in obese subjects.

Hi-tech industrial or biotechnological laser applications request for picosecond pulsed 2-μm laser generating sub-1-J pulses in >kHz repetition range. At HiLASE center the development of the laser system with target to generate 1-J picosecond pulses with 1-kHz repetition rate has started. In this paper, we present a concept of the laser system and demonstrate recent results from the first part of the laser – the holmium fiber oscillator. The holmium fiber front-end is pumped by a continuous wave

Hybrid organic-inorganic layered perovskites are typically nonporous solids. However, the incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates micropores between the perovskite layers. In this study, we increase in the micropore volume in layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g., ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their micropore volume decreases by as much as 43%. Through the variation of amine fraction, the micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature below 20 K, thus indicating that the obtained perovskites maintain their functions as layered perovskites.

Recent research has demonstrated how the economically and environmentally benign organic structure-directing agent (OSDA)-free synthesis of zeolite beta—based on the seed-assisted method—exhibits superior properties in applications as antibacterial agents, catalysts and adsorbents in comparison with conventional zeolite beta. One possible way to take advantage of OSDA-free beta is to apply the material in energy-efficient capture of carbon dioxide (CO 2 ) from a variety of large emission sources. For this reason, we have investigated the CO 2 adsorption–desorption properties of OSDA-free beta for the first time. The results of elemental analysis, N 2 and CO 2 adsorption–desorption, evaluation of the isosteric heat of adsorption and solid-state NMR measurements have shown that OSDA-free beta exhibited higher crystallinity, larger pore volume and higher aluminum (Al) as well as sodium (Na) cation content with enhanced homogeneity in Al distribution within the *BEA framework as compared to the conventional TEA-directed beta synthesized using tetraethylammonium hydroxide (TEAOH). These unique properties of OSDA-free beta resulted in significant improvements of CO 2 adsorption–desorption capability over a wide pressure region under moderate temperature in comparison with conventional zeolite beta.

We have investigated the adsorption and desorption of water in two-dimensional hexagonal mesoporous silica (MPS) with three different pore dimensions. All the adsorption–desorption isotherms exhibited type V behavior with significant hysteresis. Hysteresis was observed in the transient region between the layer adsorption state and the pore filling state, where capillary condensation and evaporation occurred. When the relative humidity is changed in steps from the onset point of capillary condensation and capillary evaporation, the relaxation curves of water uptake and release were measured at 298 K using a gravimetric method. For all MPSs, the relaxation rates of water uptake and release increased as the magnitude of the stepwise change in relative humidity increased. The relaxation curves of some MPSs could be well fitted by the exact solution of the Fickian diffusion equation at a small stepwise change in relative humidity. On the other hand, the adsorbed mass is proportional to the square root of time ...

To estimate effective doses for members of the public exposed to external radiation from radioactive cesium (134Cs and 137Cs) deposited on the ground by the Fukushima nuclear accident, we calculate the conversion coefficients for converting activity concentration to effective dose rate by using the Particle and Heavy Ion Transport Code System. The data were produced from different age groups within the public (newborns; 1-, 5-, 10-, and 15-year-old children; and adults) for the situations in which radioactive cesium is distributed uniformly in the soil over a planar area and at specific depths of 0.0, 0.5, 2.5, 5.0, 10.0, and 50.0 g/cm2. On the basis of the results, we also derive the conversion coefficients for exponentially distributed volumetric sources. In addition, we obtain the conversion coefficients that give the effective dose accumulated over the first and second months, the first year, and over a lifetime (50 years) because of the contamination remaining on the ground. These calculations indica...

The tsunami that followed the Great East Japan Earthquake in 2011 caused catastrophic salt damage to agricultural lands in Tohoku district on the Pacific coast of Japan. Large amounts of water would be required to leach away the salt from the salt-damaged farmlands. In addition, the salt cannot be washed away by using natural water sources such as rivers and ponds because the irrigation infrastructure, such as water canals, was destroyed and has not yet been repaired. Therefore, it is important to develop new salt-removal techniques to restore agricultural lands without using large amounts of water. We tested a new technique for salt removal: scraping the soil, followed by exposure of the soil to natural rainfall. In the test plots, which were located in a paddy field, soluble salt in the soil accumulated on the soil surface through evaporation. Next, the top 2 cm of the soil surface was scraped away, and the scraped soil was placed in open-topped plastic boxes that were exposed to natural rainfall. Soil electrical conductivity, exchangeable sodium percentage, and ion content decreased exponentially as cumulative rainfall increased. In addition, soil electrical conductivity decreased below the upper threshold limit required for crop cultivation after cumulative rainfall surpassed 217 mm, about 50 days after the start of the experiment. Therefore, our technique may be used to remove salt from agricultural soils in a relatively short time.

Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

A new simple and efficient process for synthesizing tetraalkoxysilanes (TROS) directly from silica and alcohols was developed using molecular sieves as dehydrating agents. Using this method, a variety of TROS (R = ethoxy, n-propoxy, or n-butoxy) were obtained over 70% yields within 6 h. We also employed various natural silica sources in this process for practical applications.

Low temperature magnetic properties were investigated on the gold nano particles (GNP) with an average size of 11.5 nm, assembled with molecules of ruthenium complex (Ru0) and phenylboronic acid (B0) by the proton nuclear resonance (1H-NMR) and susceptibility measurements. The temperature dependence of the NMR shift and the uniform susceptibility was described as the sum of the Curie-Weiss term and a positive constant term. From the former, the average number of Ru0 on each GNP was estimated to be 118, which is 23 % of the calculation. The finite positive constant term shows a clear contrast with the well-known fact that the bulk gold is diamagnetic. Finally, a disappearance of the motional narrowing effect in the proton NMR spectra below 60 K indicates that the wavering motion of Ru0 complexes on GNP at room temperature is frozen at low temperatures., Comment: ieee transactions on magnetics, in press

Substituting effect of CF3 to the Ru-based binuclear complex [{RuIII(acac)2}2(μ-OEt)2], in which S = 1/2 spin dimer takes the singlet ground state have been investigated by means of the magnetic susceptibility χ and the longitudinal nuclear spin relaxation rate T1-1 of 1H/19F-NMR. In CF3-substituted complex [{RuIII(fhma)2}2(μ-OMe)2], we have observed the prominent magnetic response both in χ and T1−1. This behavior is attributed to the slight change in the Ru valence state due to the substitution.

Relations among absorption of pump beam, quantum defect and thermal load were investigated for pump wavelengths of 968 nm and near 940 nm in two independent, real-time measurement experiments complemented with thermal distribution simulation. Saturation of absorption at 969 nm pumping for non-lasing operational regime, which affects temperature rise and exists independently of the thin disk type, disk head construction, pump power and pump beam diameter is reported. Disk temperature dependence of absorption, quantum defect and disk geometry and large difference between absorption, disk temperature and o-o efficiency at both pump wavelengths are discussed.

We show that boron-doped epitaxial graphene can be successfully grown by thermal decomposition of a boron carbide thin film, which can also be epitaxially grown on a silicon carbide substrate. The interfaces of B4C on SiC and graphene on B4C had a fixed orientation relation, having a local stable structure with no dangling bonds. The first carbon layer on B4C acts as a buffer layer, and the overlaying carbon layers are graphene. Graphene on B4C was highly boron doped, and the hole concentration could be controlled over a wide range of 2 × 1013 to 2 × 1015 cm-2. Highly boron-doped graphene exhibited a spin-glass behavior, which suggests the presence of local antiferromagnetic ordering in the spin-frustration system. Thermal decomposition of carbides holds the promise of being a technique to obtain a new class of wafer-scale functional epitaxial graphene for various applications.

Thick mesoporous silica (MPS) films with sufficient mechanical strength and high porosity were prepared on aluminum plates by using electrophoretic deposition (EPD) with the addition of a small amount of polyvinylbutyral (PVB, 3.5–8.0 wt%) as binder. The porosity of the MPS films was approximately 50 vol%. The film thickness could be controlled by the deposition conditions, and a thickness of ca. 50 μm is reasonable for effectively using the whole MPS film. These MPS films exhibited good water vapor adsorption-desorption properties and sufficient stability for more than 150 adsorption-desorption cycles. When used in dehumidification applications, these MPS films had a dehumidification rate of 6.3 g-H2O/g-MPS per hour, with an adsorption-desorption cycle as short as 2 min even when a low temperature of 60 °C was used to regenerate the adsorbent.

Heterobimetallic compounds [L'OV(V)(μ-O)M(III)L]n (n = 1, M = Mn, 1-5; n = 2, M = Fe, 6 and 7) containing a discrete unsupported V(V)-O-M(III) bridge have been synthesized through a targeted synthesis route. In the V-O-Mn-type complexes, the vanadium(V) centers have a square-pyramidal geometry, completed by a dithiocarbazate-based tridentate Schiff-base ligand (H2L'), while the manganese(III) centers have either a square-pyramidal (1 and 3) or an octahedral (2 and 5) geometry, made up of a Salen-type tetradentate ligand (H2L) as established by X-ray diffraction analysis. The V-O-Mn bridge angle in these compounds varies systematically from 155.3° to 128.1° in going from 1 to 5 while the corresponding dihedral angle between the basal planes around the metal centers changes from 86.82° to 20.92°, respectively. The V-O-Fe-type complexes (6 and 7) are tetranuclear, in which the two dinuclear V(μ-O)Fe units are connected together by apical iron(III)-aryl oxide interactions, forming a dimeric structure with a pair of Fe-O-Fe bridges. The X-ray data also confirm the V═O → M canonical form to contribute predominantly on the overall V-O-M bridge structure. The molecules in solution also retain their heterobinuclear composition, as established by electrospray ionization mass spectrometry and (51)V NMR spectroscopy. Electrochemically, these complexes are quite interesting; the manganese(III) complexes (1-5) display three successive reductions (processes I-III), each with a monoelectron stoichiometry. Process I is due to a Mn(III)/Mn(II) reduction (E1/2 ranges between -0.32 and -0.05 V), process II is a ligand-based reduction, and process III (E1/2 = ∼1.80 V) owes its origin to a V(V)O/V(IV)O reduction; all potentials are versus Ag/AgCl. The iron(III) compounds (6 and 7), on the other hand, show at least four irreversible processes, appearing at Epc = -0.20, -1.0, -1.58, and -1.68 V in compound 6 (processes IV-VII), together with a reversible process (process VIII) at E1/2 = -1.80 V (ΔEp = 80 mV). While the first two of these are due to Fe(III)/Fe(II) reductions at the two iron(III) centers of these tetranuclear cores, the reversible reduction at a more negative potential (ca. -1.80 V) is due to a V(V)O/V(IV)O-based electron transfer.

A new series of nickel(II) complexes of the type [Ni(L)2] (1–6) has been synthesized by using the 3,3-dialkyl/aryl-1-(2,4-dichlorobenzoyl)thiourea ligands, and characterized by analytical and spectral (NMR, FT-IR and UV–Vis) techniques. The structures of the ligands (HL1, HL2 and HL3) and complexes (2 and 5) have been confirmed by single crystal X-ray diffraction studies. The interaction of the nickel(II) complexes (2–5) with calf thymus (CT) DNA and bovine serum albumin (BSA) protein was investigated using UV–Vis and fluorescence spectroscopic methods. Absorption and emission spectral studies indicate that complex 2 interacts with CT DNA and BSA protein more strongly than the other complexes (3, 4 and 5). Complexes 2 and 5 exhibited good cytotoxicity against A549 and HT29 cell lines at 50 μM concentration.

The plant stress hormone abscisic acid (ABA) is critical for several abiotic stress responses. ABA signaling is normally repressed by group-A protein phosphatases 2C (PP2Cs), but stress-induced ABA binds Arabidopsis PYR/PYL/RCAR (PYL) receptors, which then bind and inhibit PP2Cs. X-ray structures of several receptor-ABA complexes revealed a tunnel above ABA's 3' ring CH that opens at the PP2C binding interface. Here, ABA analogs with sufficiently long 3' alkyl chains were predicted to traverse this tunnel and block PYL-PP2C interactions. To test this, a series of 3'-alkylsulfanyl ABAs were synthesized with different alkyl chain lengths. Physiological, biochemical and structural analyses revealed that a six-carbon alkyl substitution produced a potent ABA antagonist that was sufficiently active to block multiple stress-induced ABA responses in vivo. This study provides a new approach for the design of ABA analogs, and the results validated structure-based design for this target class.

A calculation system for the estimation of decontamination effects (CDE) is developed in the present work to aid in the effective planning of decontamination procedures. This system calculates dose...

We investigated the CO2 adsorption of mesoporous ceria under high humidity. In the presence of co-adsorbed water, mesoporous ceria sustained reversible CO2 adsorption–desorption behavior with a hig...

Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future.

The new chiral ligands (R)-/(S)-N-((1-phenylethyl)carbamothioyl)benzamide (L1/L2), (R)-/(S)-N-((1-phenylethyl)carbamothioyl)thiophene-2-carboxamide (L3/L4), and (R)-/(S)-N-((1-phenylethyl)carbamothioyl)furan-2-carboxamide (L5/L6) were synthesized, characterized, and used to prepare novel chiral Ru(II) complexes. The chiral Ru(II) complexes 1–6 were obtained from reactions between the chiral ligands L1–L6 and [RuCl2(p-cymene)2]2. The complexes were characterized by analytical and spectroscopic (NMR, FT-IR, electronic) techniques. The solid-state structures of the ligands L1 and L3 and complexes 1, 4, and 6 were determined by single-crystal X-ray diffraction methods. In all of the complexes, the ligand is bound to the Ru(II) center only via the sulfur donor atom. This monodentate coordination of the acylthiourea ligands was observed for the first time with ruthenium. The Ru(II) complexes 1–6 all act as efficient catalysts for the asymmetric transfer hydrogenation of aromatic ketones in the presence of 2-pro...

The construction of a novel electrochemical sugar recognition system using a tris(acetylacetonato)ruthenium complex and phenylboronic acid assembled on gold nanoparticles is described. This system showed excellent sensitivity compared to those by the assembly on the dendrimer and optical recognition.

The synthesis, structure and biological studies of cobalt(III) complexes supported by NNS-tridentate ligands are reported. Reactions of 2-acetylpyridine N-substituted thiosemicarbazone (HL(1-3)) with [CoCl2(PPh3)2] resulted [Co(L(1-3))2]Cl (1-3) which were characterized by elemental analysis and various spectral studies. The molecular structure of the complex 1 has been determined by single crystal X-ray diffraction studies. In vitro DNA binding studies of complexes 1-3 carried out by fluorescence studies and the results revealed the binding of complexes to DNA via intercalation. The binding constant (Kb) values of complexes 1-3 from fluorescence experiments showed that the complex 3 has greater binding propensity for DNA. The DNA cleavage activity of the complexes 1 and 3 were ascertained by gel electrophoresis assay which revealed that the complexes are good DNA cleavage agents. Further, the interactions of the complexes with bovine serum albumin (BSA) were also investigated using fluorescence spectroscopic method, which showed that the complexes 1-3 could bind strongly with BSA. The antioxidant property of the complexes was evaluated to test their free-radical scavenging ability. Furthermore, in vitro cytotoxicity of the complexes against MCF-7 and A431 cell lines was assayed which showed higher activity and efficiently vanished the cancer cells even at low concentrations.

Ruthenium(II) complexes with 2-acetylpyridine-thiosemicarbazones (L1–L4) were synthesized and characterized by analytical and spectral (FT-IR, UV–vis, NMR [1H, 13C and 31P], and ESI-Mass) methods. Systematic biological investigations, free radical scavenging, anticancer activities, and DNA cleavage studies, were carried out for the complexes. Antioxidant studies showed that the complexes have significant antioxidant activity against DPPH, hydroxyl, nitric oxide radicals and hydrogen peroxide assay. The in vitro cytotoxicity of complexes against breast cancer (MCF-7) cell line was assayed showing high cytotoxicity with low IC50 values indicating their efficiency in destroying the cancer cells even at very low concentrations. The DNA cleavage studies showed that the complexes efficiently cleaved DNA.

We report for the first time, the successful synthesis of siliceous ferrierites with SiO 2 /Al 2 O 3 = 138.8–324 by the hydrothermal treatment of aluminosilicate gel with the introduction of pyridine and easy-to-handle sodium fluoride (NaF). It has been found that pure siliceous ferrierites exhibit well-defined plate-like morphologies with sufficient micropore volume. Moreover, in terms of the adsorption of water vapor, siliceous ferrierites (SiO 2 /Al 2 O 3 ⩾ 208) exhibit significantly higher hydrophobicity than commercially available siliceous zeolite (ZSM-5, HSZ-890HOA, SiO 2 /Al 2 O 3 = 1880). This work provides a promising approach for the preparation of siliceous ferrierites with a simple synthesis system, and this finding will help to broaden the practical applicability of ferrierites.