Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

Single-step synthesis of magnetic chitosan composites and application for chromate(Cr(Ⅵ))removal

Magnetic chitosan composites(Fe3O4@chitosan) were synthesized in one single-step, characterized and applied in Cr(VI) removal from water. With the increase of loading proportion of chitosan, Cr(Ⅵ) adsorption capacity of Fe3O4@chitosan composites increased from 10.771 to 21.040 mg/g. The optimum adsorption capacities of Cr(VI) on Fe3O4@chitosan-3 were found in a pH range of 3.0-5.0. Kinetic study results show that the adsorption process follows pseudo-second-order model, indicating that the rate-limiting step in the adsorption of Cr(Ⅵ) involves chemisorptions. Moreover, FT-IR spectra analysis confirms that the amine and hydroxyl groups of chitosan are predominantly responsible for binding. Results from this work demonstrate that the prepared Fe3O4@chitosan composites possess great potential in Cr(Ⅵ) removal from contaminated water.

One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO3H catalyst

The conversion of hemicellulose-derived xylose to furfuryl alcohol is a practical procedure for producing value-added chemicals from biomass.In this study,a bifunctional Cu/SBA-15-SO3 H catalyst was employed for the one-pot catalytic conversion of xylose to furfuryl alcohol with a yield of up to 62.6% at the optimized conditions of 140℃,4 MPa,and for 6 h in a biphasic water/n-butanol solvent.A high reaction temperature resulted in further hydrogenation to 2-methyl furan,while a high hydrogen pressure led to a side hydrogenation reaction to xylitol.The biphasic solvent allowed xylose solvation as well as furfuryl product extraction.The acidic-SO3 H sites and Cu sites co-existed,maintained a balance,and cooperatively catalyzed the cascade conversion.Excessive acidic sites and large pores could promote the xylose conversion,although a low furfuryl alcohol yield was obtained.This catalytic system could be potentially applied to the one-pot synthesis of furfuryl alcohol from hemicellulose-derived xylose.

Highly-dispersed iron element decorated nickel foam synthesized by an acid-free and one-pot method for enzyme-free glucose sensor

The highly-dispersed iron element decorated Ni foam was prepared by simple immersion in a ferric nitrate solution at room temperature without using acid etching, and characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM), EDAX spectrum(EDAX mapping) and Raman spectroscopy. The EDAX spectrum illustrated that iron element was highly-dispersed over the entire surface of nickel foam, and the Raman spectroscopy revealed that both Ni-O and Fe-O bonds were formed on the surface of the as-prepared electrode. Moreover, the iron element decorated Ni foam electrode can be used as non-enzymatic glucose sensor and it exhibits not only an ultra-wide linear concentration range of 1-18 mmol/L with an outstanding sensitivity of 1.0388 m A·mmol/(L·cm2), but also an excellent ability of stability and selectivity. Therefore, this work presents a simple yet effective approach to successfully modify Ni foam as non-enzymatic glucose sensor.

Fabrication of Pd-based metal-acid-alkali multifunctional catalysts for one-pot synthesis of MIBK

The one-pot synthesis of methyl isobutyl ketone（MIBK） from acetone using multifunctional catalysts is an important sustainable organic synthesis method with high atom and energy efficiency.Herein. we report a series of Pd supported on mixed metal oxide（MMO） catalysts with controllable acidic/basic/metallic sites on the surface. We study the relationship between the nature, synergy,and proximity of active sites and the catalytic performance of the multifunctional catalyst in the tandem reaction, in detail. In the existence of Lewis acid and base sites, the catalysts with medium-strength acidic/basic sites show preferred activity and/or MIBK selectivity. For multifunctional catalysts, the catalytic properties are more than just a collection of active sites, and the Pd/Mg_3Al-MMO catalyst possessing 0.1% Pd loading and ~0.4 acid/base molar ratio exhibits the optimal 42.1% acetone conversion and 37.2% MIBK yield, which is among the best reported so far for this tandem reaction under similar conditions. Moreover, the proximity test indicates that the intimate distance between acidic/basic/metallic sites can greatly shorten the diffusion time of the intermediate species from each active site, leading to an enhancement in the catalytic performance.

Combining Principal Component Regression and Artificial Neural Network to Predict Chlorophyll-a Concentration of Yuqiao Reservoir’s Outflow

In order to investigate the eutrophication degree of Yuqiao Reservoir, a hybrid method, combining principal component regression (PCR) and artificial neural network (ANN), was adopted to predict chlorophyll-a concentration of Yuqiao Reservoir’s outflow. The data were obtained from two sampling sites, site 1 in the reservoir, and site 2 near the dam. Seven water variables, namely chlorophyll-a concentration of site 2 at time t and that of both sites 10 days before t, total phosphorus(TP), total nitrogen(TN),...

Ope Pot Synthesis and Characterization of Safener R-28725

The title compound was synthesized by a one pot synthesis method with ethanolamine ,ketone and dichloroacetyl chloride. The product was characterization by IR, 1 HNMR,UV, and elementary analysis.

Microwave radiation one-pot synthesis of chloropropyl-functionalized mesoporous MCM-41

Chloropropyl-functionalized mesoporous MCM-41（MCM-41-（CH2）3Cl） was synthesized in alkaline medium by the microwave radiation one-pot method, using cetyltrimethy-lammoniumbromide （CTAB） as novel template, tetraethoxysilane （TEOS） as silica source, and chloropropyltriethoxysilane （C1PTES） as the coupling agent. The microstructure of MCM-41-（CH2）3Cl was characterized by the means of X-ray diffraction （XRD）, nitrogen absorption-desorption, Fourier transform infrared spectroscopy （FT-IR）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. The results show that a successful synthesis of MCM-41-（CH2）3Cl with well structure is obtained. The optimal microwave power is 120 W and the best microwave time is 50 rain. The dosage of chloropropyltriethoxysilane on the structure of chloropropyl-functionalzed MCM-41 was also investigated. It is found that the chloropropyltriethoxysilane volume between 0.8 mL and 1.6 mL is favorable for the formation of highly ordered MCM-41-（CH2）3Cl mesostructure.

Synthesis of Substituted u-Oxo-bis[tetra-phenyl porphyrinatoiron] Compounds from Free Base Porphyrins by a One-pot Method

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.

Al_(x)/HKUST-1 prepared by synthetic exchange as catalyst for reduction of NO by CO at low temperature

Al_(x)/HKUST-1(x=1/24,1/12,1/6,1/3),one of the bimetallic copper-based organic framework materials,was successfully prepared by the synthetic exchange method and characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),specific surface area(BET),thermogravimetric analysis(TG),infrared spectra(IR),X-ray photoelectron spectroscopy(XPS),and H_(2)-temperature programmed reduction(H_(2)-TPR).The findings indicated that Al_(x)/HKUST-1 maintained the octahedral morphology of its precursor(HKUST-1).The thermal stability and catalytic reduction ability of HKUST-1 skeleton were improved by doping aluminum(Al^(3+)).Al_(1/12)/HKUST-1 showed the best performance among all samples,with a nitric oxide(NO)conversion rate of 100%at 210℃(50℃lower than that of HKUST-1).The valence kind of Al,Cu,and O in Al_(1/12)/HKUST-1 did not change after the catalytic reaction,but the contents of Al,Cu,and O in different forms changed significantly.The catalytic process of the Al_(x)/HKUST-1 followed a Langmuir-Hinshelwood mechanism.

Filter Method and Its Consistency of Double-Star Position/SINS Integrated System

According to the characteristic of Beidou Double-star positing system (for short: Double-star position), the optimal predication model of Double-star position/SINS integrated system is put forward, which can make use of the delayed position in-formation from Double-star positioning system to predicate optimally for the integrated system, and then to correct SINS, and af-fords integrated results of some navigation parameters. In order to validate the consistency of the filter, the criteria for consistency of a filter is also studied, and the tested statistics are given, the experiment based on practical measured data shows that the filtering method is consistent with the integrated system.

Optimized One-Step Preparation of a Bioactive Natural Product,Guaiazulene-2,9-dione

We previously isolated a natural product, namely guaiazulene-2,9-dione showing strong antibacterial activity against Vibrio anguillarum, from a gorgonian Muriceides collaris collected in South China Sea. In this experiment, guaiazulene-2,9-dione was quantitatively synthesized with an optimized one-step bromine oxidation method using guaiazulene as the raw material. The key reaction condition including reaction time and temperature, drop rate of bromine, concentration of aqueous THF solution, respective molar ratio of guaiazulene to bromine and acetic acid, and concentration of guaiazulene in aqueous THF solution, were investigated individually at five levels each for optimization. Combined with the verification test to show the absolute yield of each optimization step, the final optimal condition was determined as: when a solution of 0.025 mmol m L-1 guaiazulene in 80% aqueous THF was treated with four volumes of bromine at a drop rate of 0.1 m L min-1 and four volumes of acetic acid at-5℃ for three hours, the yield of guaiazulene-2,9-dione was 23.72%. This was the first report concerning optimized one-step synthesis to provide a convenient method for the large preparation of guaiazulene-2,9-dione.

One-pot synthesis of cyclic aldol tetramer and ?, β-unsaturated aldol from linear aldehydes using quaternary ammonium combined with sodium hydroxide as catalysts

One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst（PTC）, quaternary ammonium, combined with sodium hydroxide as catalysts was investigated. Butanal was subjected for detail investigations to study the effect of parameters. It was found that the selectivity of cyclic aldol tetramer depends greatly on the operating conditions of the reaction, especially the PTC/butanal molar ratio. The average selectivity of 2-hydroxy-6-propyl-l, 3, 5-triethyl-3-cyclohexene-1-carboxaldehyde（HPTECHCA） was 54.41% using tetrabutylammonium chloride combined with 14%（mass fraction） Na OH as catalysts at 60 ℃for 2 h with a PTC-to-butanal molar ratio of 0.09：1. Pentanal was more likely to generate cyclic aldol tetramer compared with other aldehydes under the optimum experimental conditions. Recovery of the PTC through water washing followed by adding enough sodium hydroxide from the washings was also demonstrated.

Synthesis of 2-Methyl-4-methoxyaniline from o-Nitrotoluene Using Pt/C and Acidic Ionic Liquid as Catalyst System

2-Methyl-4-methoxyaniline （MMA） was synthesized by one-pot method through the hydrogenation and Bamberger rearrangement of o-nitrotoluene in methanol using acidic ionic liquid and 3% Pt/C as catalyst system. The effects of ionic liquid type, dosage of ionic liquid and 3% Pt/C, reaction temperature and reaction pressure on o-nitrotoluene conversion and MMA selectivity were investigated. The results indicated that the imidazolium-based acidic ionic liquid which contains SO3H-functionalized cation showed higher selectivity to MMA than other acidic ionic liquids used in this work. Using 1-（propyl-3-sulfonate）-3-methylimidazolium hydrosulfate （[HSO3-pmim][HSO4]） as the acid catalyst, the selectivity to MMA was as high as 67.6% at 97.8% of o-nitrotoluene conversion. As 3% Pt/C increased from 0.01 g to 0.025 g, the selectivity to MMA decreased from 73.4% to 62.5%, because of the hydrogenation of intermediate o-methyl-phenylhydroxylamine to o-toluidine becoming more dominant. An increase in hydrogen pressure also had obviously dramatic effect in lowering the MMA selectivity. After easy separation from the products, the catalyst system could be reused at least 3 times.

Normalization method for asphalt mixture fatigue equation under different loading frequencies

In order to analyze the effect of different loading frequencies on the fatigue performance for asphalt mixture,the changing law of asphalt mixture strengths with loading speed was revealed by strength tests under different loading speeds.Fatigue equations of asphalt mixtures based on the nominal stress ratio and real stress ratio were established using fatigue tests under different loading frequencies.It was revealed that the strength of the asphalt mixture is affected by the loading speed greatly.It was also discovered that the fatigue equation based on the nominal stress ratio will change with the change of the fatigue loading speed.There is no uniqueness.But the fatigue equation based on the real stress ratio doesn't change with the loading frequency.It has the uniqueness.The results indicate the fatigue equation based on the real stress ratio can realize the normalization of the asphalt mixture fatigue equation under different loading frequencies.It can greatly benefit the analysis of the fatigue characteristics under different vehicle speeds for asphalt pavement.

Modified Lindstedt-Poincaré Method for Obtaining Resonance Periodic Solutions of Nonlinear Non-autonomous Oscillators

A modified Lindstedt-Poincar＆#233; （LP） method for obtaining the resonance periodic solutions of nonlinear non-autonomous vibration systems is proposed in this paper. In the modified method, nonlinear non-autonomous equa-tions are converted into a group of linear ordinary differential equations by introducing a set of simple transformations. An approximate resonance solution for the original equation can then be obtained. The periodic solutions of primary, super-harmonic, sub-harmonic, zero-frequency and combination resonances can be solved effectively using the modi-fied method. Some examples, such as damped cubic nonlinear systems under single and double frequency excitation, and damped quadratic nonlinear systems under double frequency excitation, are given to illustrate its convenience and effectiveness. Using the modified LP method, the first-order approximate solutions for each equation are obtained. By comparison, the modified method proposed in this paper produces the same results as the method of multiple scales.

Exogenous carbon monoxide attenuates inflammatory responses in the small intestine of septic mice

AIM： To determine whether the carbon monoxide （CO）-releasing molecules （CORM）-Iiberated CO sup- press inflammatory responses in the small intestine of septic mice. METHODS： The C57BL/6 mice （male, n = 36; weight 20±2 g） were assigned to four groups in three re- spective experiments. Sepsis in mice was induced by cecal ligation and puncture （CLP） （24 h）. Tricarbonyl- dichlororuthenium （Ⅱ） dimer （CORM-2） （8 mg/kg, i. v.） was administrated immediately after induction of CLP. The levels of inflammatory cytokines [interleukin-1β （IL-1β） and tumor necrosis factor-α （TNF-α）] in tis- sue homogenates were measured with enzyme-linked immunosorbent assay. The levels of malondialdehyde （MDA） in the tissues were determined. The levels of nitric oxide （NO） in tissue homogenate were measured and the expression levels of intercellular adhesion mol- ecule 1 （ICAM-1） and inducible nitric oxide synthase （iNOS） in the small intestine were also assessed. NO and IL-8 levels in the supernatants were determined after the human adenocarcinoma cell line Caco-2 was stimulated by lipopolysaccharide （LPS） （10 g/mL） for 4 h in vitro. RESULTS： At 24 h after CLP, histological analysis showed that the ileum and jejunum from CLP mice in- duced severe edema and sloughing of the villous tips, as well as infiltration of inflammatory cells into the mu- cosa. Semi-quantitative analysis of histological samples of ileum and jejunum showed that granulocyte infil- tration in the septic mice was significantly increased compared to that in the sham group. Administration of CORM-2 significantly decreased granulocyte infiltration. At 24 h after CLP, the tissue MDA levels in the mid- ileum and mid-jejunum significantly increased com- pared to the sham animals （103.68 ± 23.88 nmol/ml vs 39.66 ± 8.23 nmol/mL, 89.66±9.98 nmol/mL vs 32.32 ± 7.43 nmol/mL, P 〈 0.01）. In vitro administra- tion of CORM-2, tissue MDA levels were significantly decreased （50.65±11.46 nmol/mL, 59.32 ± 6.62 nmol/mL, P 〈 0.05）. Meanwhile, the tissue IL-1β and TNF-α levels in the mid-ileum significantly increased compared to the sham animals （6.66±1.09 pg/mL vs 1.67±0.45 pg/mL, 19.34±3.99 pg/mL vs 3.98 ± 0.87 pg/mL, P 〈 0.01）. In vitro administration of CORM-2, tissue IL-1β and TNF-α levels were significantly de- creased （3.87 ± 1.08 pg/mL, 10.45±2.48 pg/mL, P 〈 0.05）. The levels of NO in mid-ileum and mid-jejunum tissue homogenate were also decreased （14.69 ± 2.45 nmol/mL vs 24.36 ± 2.97 nmol/mL, 18.47 ± 2.47 nmol/mL vs 27.33 ± 3.87 nmol/mL, P 〈 0.05）. The ex- pression of iNOS and ICAM-1 in the mid-ileum of septic mice at 24 h after CLP induction significantly increased compared to the sham animals. In vitro administration of CORM-2, expression of iNOS and ICAM-1 were sig- nificantly decreased. In parallel, the levels of NO and IL-8 in the supernatants of Caco-2 stimulated by LPS was markedly decreased in CORM-2-treated Caco-2 cells （2.22 ± 0.12 nmol/mL vs 6.25±1.69 nmol/mL, 24.97 ± 3.01 pg/mL vs 49.45± 5.11 pg/mL, P 〈 0.05）. CONCLUSION： CORM-released CO attenuates the inflammatory cytokine production （IL-1β and TNF-α）, and suppress the oxidative stress in the small intestine during sepsis by interfering with protein expression of ICAM-1 and iNOS.

Tripartition of Arbitrary Single-Qubit Information via a Class of Asymmetric Four-Qubit W State

A four-party scheme is put forward for a sender to partition arbitrary single-qubit information among three receivers by utilizing a class of asymmetric four-qubit W state as quantum channels. In the scheme the sender＇s quantum information can be recovered by the three receivers if and only if they collaborate together. Specifically, they collaborate to perform first two different 2-qubit collective unitary operations and then a single-qubit unitary operation. The scheme is symmetric and （3, 3）-threshold with regard to the reconstruction, for any receiver can be assigned to conclusively recover the quantum information with the other two＇s assistances.

Transatlantic Cooperation During the Second World War： The First Stages of Economic Cooperation During the ＂Phoney War＂

During the Second world war, the Franco-British cooperation included the organization of purchasing missions for airnautical material in the States. On 25 november 1939, a Franco-British agreement was set up to organize two purchasing missions in the United States under the control of a ＂Liaison Committee＂ supervised by the Treasury Secretary, Henry Morgenthau. Edouard Daladier, French Chief of Government, sent Ren6 Pleven to establish contacts with General Arnold （AirCorps）. The Franco-British financial contribution facilitated a main spurt in investments which help modernize the American products apparatus. First contacts were established on April 1940, to be delivered in September. While France had not be able to benefit from significant part of these orders, Great Britain would take over some units that were originally allocated to France. These contracts would later facilitate the development of transatlantic cooperation.

The relationship between nNOS and Cyt-c in mitochondria of glioma

Objective： The aim of this study was to investigate the association between neuronal nitric oxide synthase （nNOS） and the expression level of Cytochrome C （Cyt-c） in mitochondria. Methods： The pathological diagnosis of glioma and tumor classification was by HE staining, and we use immunohistochemistry method to analyse the level of nNOS in different pathological grade glioma and the expression level of Cyt-c in mitochondria meanwhile. Results： The levels of nNOS were highest in grade Ⅲ tumors, moderate in grade Ⅱ tumors, and lowest different in grade I tumors. There was significant difference of the nNOS levels among different pathological grade tumors （P 〈 0.05）. Furthermore, the similar phenomenon was observed in the expression level of Cyt-c in mitochondria （P 〈 0.05）. Conclusion： The expression level of nNOS and Cyt-c in mitochondria was significantly related to the pathological grade of glioma.