Preparation and shaping of solid acid SO_4^(2-)/TiO_2 and its application for esterification of propylene glycol monomethyl ether and acetic acid

The solid acid SO_4^(2-)/TiO_2 was prepared by immersion method and applied for synthesis of propylene glycol methyl ether acetate(PMA) through esterification reaction of propylene glycol monomethyl ether(PM)and acetic acid(HAc). The optimal catalyst preparation condition was determined by orthogonal analysis of parameters in a five-factor and four-level test. The obtained solid acid catalysts were characterized in detail by means of X-ray powder diffraction, thermogravimetry, pyridine adsorbed IR analysis, scanning electron microscopy, and BET surface area method. Synthesis of PMA was studied in this paper through experimental investigation of reaction conditions such as temperature, molar ratio of reactants, catalyst dosage and agitation speed. Based on its possible reaction mechanism, a pseudo-homogeneous kinetic model was established and its activation energies E_a^+ and E_a^-,65.68 × 10~3J·mol^(-1) and 57.78 × 10~3J·mol^(-1), were estimated. To prepare shaped solid acid catalyst SO_4^(2-)/TiO_2, the shaping method of impregnation–shaping–impregnation was applied. The optimal molding formulation of solid acid catalyst, obtained from the orthogonal test, was found to be binder 7 wt%, reinforcing agent 20 wt%, pore forming material 2.5 wt%, and lubricant 4 wt%.The results of performance test of catalyst demonstrated that the shaped solid acid catalyst exhibited high activity and stability.

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO_2/MgO and SnO_2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether （DME） in the temperature range of 275 to 300 ℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate （MF） and dimethoxyethane （DMET） of 19.1% and 59.0% respectively were obtained at 275 ℃.

Stereoselective Synthesis of (+)-△~5-Dehydrosugiyl Methyl Ether

A stereoselective synthetic route to △~5-dehydrosugiyl methyl ether was developed from (S)-(-)-α-cyclocitral, DDQ as a better oxidant for enone was used.

Total Synthesis of 16-Acetoxy-6,7-didehydroferruginyl Methyl Ether

An efficient synthetic route have been developed to 16-acetoxy-6,7-didehydroferruginyl methyl ether.

SYNTHESIS AND CHARACTERIZATION OF A NEW COMBLIKE POLYMER BASED ON POLY (VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reacting monomethyl ether of poly(ethylene glycol) with poly(vinyl methyl ether-alt-maleic anhydride) and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solvent for the esterification in order to obtain a completely soluble product. The synthesis process was traced through by LR. Compared with the model compounds, the presumed structure of this comblike polymer has been proved to be valid by C-13 NMR The comb polymer is a white rubbery solid. It can be dissolved in butanone and THF, and manifests good film forming ability.

Obovatachalcone和(±)-Obovatin Methyl Ether的全合成

以苯甲醛和2,4,6-三羟基苯乙酮一水合物为起始原料,经 C -异戊烯基化、氧化环化、碘甲烷保护羟基、羟醛缩合反应以及催化关环等步骤,以7.2%和5.7%的总收率实现了两个天然吡喃类黄酮obovatachalcone和(±)-obovatin methyl ether的全合成,其结构经^1H NMR,^13C NMR,IR和HR-MS(ESI)确证。

A Synthesis, Process Optimization, and Mechanism Investigation for the Formation of Polyoxymethylene Dimethyl Ethers

Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM_(3-6) and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content(less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMM_n were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMM_n from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.

Synthesis of dimethyl ether from methane mediated by HBr

Dimethyl ether （DME） was synthesized from methane through a two-step process, in which CH3Br was prepared from the oxidative bromination reaction of methane in the presence of HBr and oxygen over a Rh-SiO2 catalyst and then, in the second step, CH3Br was hydrolyzed to DME over a silica supported metal chloride catalyst. 12 mol%ZnCl2/SiO2 catalyst was found to be the most active, but it deactivated because of Cl- losing.

Methoxyl methyl ether isoamylene quercetin, a quercetin derivative, protects rat aorta endothelial cells against oxidation and apoptosis

Methoxyl methyl ether isoamylene quercetin （MIAQ） is one of the newly synthesized quercetin derivatives. The present study investigated the effect of MIAQ on rat aorta endothelial cells （RAECs） injured by hydrogen peroxide （H2O2）, as well as the potential mechanisms. We observed that MIAQ at 2.5-10μmol/L significantly enhanced the viability of injured RAECs, and the effect was more potent than quercetin and ct-tocopherol. However, M1AQ at the same concentration failed to show anti-oxidant activity in a cell-free system. In H2O2-injured endothelial cells treated with MIAQ （5-10μmol/L）, the level of nitric oxide （NO） and malondialdehyde was decreased, and the activities of superoxide dismutase and glutathione peroxidase was enhanced. In addition, RAECs treated with MIAQ （2.5-10 μmol/L） exhibited significant inhibiting apoptosis. In conclusion, MIAQ had protective effect on RAECs, possibly through increasing NO production and antioxidases activities, as well as inhibiting apoptosis. These findings suggest that MIAQ is possibly beneficial in the prevention of atherosclerosis and other diseases related to endothelial injury.

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Pol

The phase behavior of the aqueous solution of poly(vinyl methyl ether) (PVME) sensitive to temperature and the modification of the behavior by using poly(acrylic acid) (PAA) have been studied by ultrasonic attenuation measurements and fluorescence probe techniques. It has been observed that PVME solution is transparent at room temperature and becomes turbid upon heating. The solution turns clear again as soon as the temperature is decreased to room temperature. The heating and cooling process can be repeated for many times. The phase behavior of the solution sensitive to temperature is attributed to the conformational changes of the polymer. PVME may adopt an open coil conformation at room temperature. With this conformation, the polymer is well miscible with the solvent, water, and thereby the system is a real solution. The polymer may adopt a compact coil conformation when the temperature is higher than a specific value, which is called the LCST (the lower critical solution temperature) of PVME. In this case, the polymer tangles to each other and forms various aggregates, which can scatter incident light and ultrasonic waves greatly, resulting in the phase separation. Introduction of PAA decreases the temperature sen-sitivity of the phase behavior of the polymer. The nature of the inhibition is attributed to the complexation of PAA with PVME and the strong hydrophilicity of PAA. Results from fluorescence probe studies are in accordance with those from ultrasonic attenuation measurements, indicating again that the ultrasonic attenuation method can be suc-cessfully used for the qualitative studies of polymer conformations and complexation between polymers.

A Facile Approach to Synthesis of the Di-O-methyl Ethers of （-）-Agatharesinol, （-）-Sugiresinol, （＋）-Nyasol and （＋）-Tetrahydronyasol

The facile enantioselective synthesis of the di-O-methyl ethers of （-）-agatharesinol （1b）, （-）-sugiresionl （2b）, （＋）-nyasol （3b） and （＋）-tetrahydronyasol （4） were achieved in high yield. The absolute configuration of （＋）-3a was confirmed via first total synthesis of （＋）-3b and （＋）-4.

Thermo-responsive cellulose papers grafted with poly(di(ethylene glycol)methyl ether methacrylate)

Novel thermo-responsive cellulose papers were prepared via grafting poly(di(ethylene glycol)methyl ether methacrylate)(PDEGMA)by activators regenerating electron transfer(ARGET)and atom transfer radical polymerization(ATRP).Attenuated total refraction Fourier-transform infrared spectroscopy(ATR-FTIR)and scanning electron microscopy(SEM)measurements of the modified paper showed that PDEGMA brushes were successfully grafted on the paper surface.The thermal stability of the papers before and after grafting was evaluated by thermogravimetric analysis(TGA).The PDEGMA-grafted paper exhibited a two-step thermal degradation process,and presented thermo-responsive characteristics.It was hydrophilic at room temperature but changed rapidly to highly hydrophobic when the temperature rose above 50℃.

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether （MTBE） to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high （2.00×10^4 mg/L） to low （2 mg/L）. The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00× 10^4-2.00× 10^4 mg/L （the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5）. Low concentrations （2-500 rag/L） stimulated algal growth up to the greatest effect of 85%-200% when the concentration of MTBE was 50-100 mg/L during day 3-5. The toxicity of MTBE （72-120 h EC50） was 6.65×10^3-9.58×10^3 mg/L for C. ellipsoidea and that is 1.14× 10^4-2.00× 10^4 mg/L for A. floc-aquae. We found that the toxicity and ecological risk of MTBE for the algal community structure were low and the toxicity was influenced by the duration time of the test.

Synergistic activity of lawsone methyl ether in combination with some antibiotics and artocarpin against methicillin-resistant Staphylococcus aureus, Candida albicans, and Trychophyton rubrum

Objective: One appealing strategy to overcome and prevent resistant problem is the use of combined two or more antibacterial substances. Lawsone methyl ether(LME) is the naphthoquinone found in the leaves of Impatiens balsamina. The objective of this study is to determine the interaction of LME with some antibiotics(ampicillin, tetracycline, norfloxacin, and clotrimazole) and a natural compound, artocarpin against methicillin-resistant Staphylococcus aureus(MRSA), Candida albicans, and Trychophyton rubrum.Methods: A broth microdilution method was used to determine the minimum inhibition concentration(MIC). Synergistic effects were evaluated at their own MIC using the checkerboard method and time-kill assay.Results: LME showed moderate antibacterial activity against MRSA with MIC value of 15.6 μg/mL, and exhibited strong antifungal activities against T. rubrum and C. albicans with MIC values of 7.8 and 3.9 μg/m L,respectively. The interaction of LME with the natural compound artocarpin against MRSA produced a synergy with fractional inhibitory concentration index(FICI) value of 0.31, while the combination of LME and clotrimazole exhibited synergy against C. albicans and T. rubrum with FICI values of 0.38 and 0.24, respectively. The time-kill assays confirmed that the compounds in combination enhanced their antimicrobial activities against the resistant microorganisms with different degrees.Conclusion: LME in combination with clotrimazole exhibited synergy effect against C. albicans and T.rubrum. In combination with artocarpin, it showed synergy effect against MRSA.

Aerobic degradation of methyl tert-butyl ether by a Proteobacteria strain in a closed culture system

The contamination of methyl ten-butyl ether （MTBE） in underground waters has become a widely concerned problem all over the world. In this study, a novel dosed culture system with oxygen supplied by H2O2 was introduced for MTBE aerobic biodegradation. After 7 d, almost all MTBE was degraded by a pure culture, a member of β-Proteobacteria named as PMI, in a closed system with oxygen supply, while only 40% MTBE was degraded in one without oxygen supply. Dissolved oxygen （DO） levels of the broth in closed systems respectively with and without H2O2 were about 5-6 and 4 mg/L. Higher DO may improve the activity of monooxygemase, which is the key enzyme of metabolic pathway from MTBE to tert-butyl alcohol and finally to CO2, and may result in the increase of the degrading activity of PM1 cell. The purge and trap GC-MS result of the broth in closed systems showed that tea-butyl alcohol, isopronol and acetone were the main intermediate products.

Genotoxicity and Embryotoxicity Study of Bicyclol Methyl Ether, Main Impurity in Bicyclol

Objective: To assess the genotoxicity and embryotoxicity of bicyclol methyl ether(BME), the main impurity in bicyclol. Methods: Five concentrations of BME(0.5, 5, 50, 500 and 5000 μg/plate) were used in the Ames test to detect gene mutation. In the chromosome aberration test, Chinese hamster lung cells were used to detect chromosomal aberration of BME(15, 30, 60, 120 μg/m L) with or without S9 mixture. Embryotoxicity test was also conducted to determine any embryotoxicity of BME(7.5, 22.5, 67.5 μg/L) using zebrafish embryos. Results: No significant differences were observed in the Ames test and the chromosome aberration test in the BME groups compared with the vehicle control group. The zebrafish embryos toxicity test also showed no embryo development toxicity of BME, including hatching rate, body length, pericardial area and yolk sac area. Conclusions: Bicyclol methyl ether has no genotoxicity in vitro and embryotoxicity in zebrafish embryos, and the impurity in bicyclol is qualified.

Hydration Heat Effect of Cement Pastes Modified with Hydroxypropyl Methyl Cellulose Ether and Expanded Perlite

Hydration heat effect of cement pastes and mechanism of hydroxypropyl methyl cellulose ether （HPMC） and expanded perlite in cement pastes were studied by means of hydration exothermic rate, hydration heat amount, FTIR and TG-DTG. The results show that HPMC can significantly delay the hydration induction period and acceleration period of cement pastes. As mixing amount increased, hydration induction period of cement pastes enlarged and accelerated period gradually went back. At the same time, the amount of hydration heat gradually decreased. Expanded perlite had worse delay effects and less change of hydration heat amount of cement pastes than HPMC. HPMC changed the structure of C-S-H during cement hydration. The more amount of HPMC, the more obvious effect. However, EXP had little influence on the structure of C-S-H. At the same age, the content of Ca （OH）2 in cement pastes gradually decreased as the mixing amount increase of HPMC and expanded perlite, and had better delay effect than that single-doped with HPMC or expanded perlite when HPMC and expanded nerlite were both dooed in cement pastes.

Determination of methyl tert-butyl ether(MTBE) in Chinese fuels by gas chromatography/mass spectrometry and gas chromatography/flame ionization detector

A method was developed to determine the concentration of methyl tert-butyl ether(MTBE) in gasoline, diesel and heating oil by gas chromatography(GC) with mass spectrometry(GC-MS) or flame ionization detection(FID). The diluted gasoline was directly injected into the GC, and the complete separation of MTBE from co-eluting hydrocarbons was not required. GC/MS or GC/FID method can be used to analyze MTBE in different concentration range and have good consistency.

Molecular dynamics simulations of the hydration of poly(vinyl methyl ether):Hydrogen bonds and quasi-hydrogen bonds

Atomistic detailed hydration structures of poly(vinyl methyl ether)(PVME) have been investigated by molecular dynamics simulations under 300 K at various concentrations. Both radial distribution functions and the distance distributions between donors and acceptors in hydrogen bonds show that the hydrogen bonds between the polymer and water are shorter by 0.005 nm than those between water molecules. The Quasi-hydrogen bonds take only 7.2% of the van der Waals interaction pairs. It was found the hydrogen bonds are not evenly distributed along the polymer chain,and there still exists a significant amount(10%) of ether oxygen atoms that are not hydrogen bonded to water at a concentration as low as 3.3%. This shows that in polymer solutions close contacts occur not only between polymer chains but also between chain segments within the polymer,which leads to inefficient contacts between ether oxygen atoms and water molecules. Variation of the quasi-hydrogen bonds with the concentration is similar to that of hydrogen bonds,but the ratio of the repeat units forming quasi-hydrogen bonds to those forming hydrogen bonds approaches 0.2. A transition was found in the demixing enthalpy at around 30% measured by dynamic testing differential scanning calorimetry(DTDSC) for aqueous solutions of a mono-dispersed low molecular weight PVME,which can be related to the transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ～27%. The transition of the fractions of hydrogen bonds and quasi-hydrogen bonds at ～27% can be used to explain the demixing enthalpy transition at 30% at a molecular scale. In addition,at the concentration of 86%,each ether oxygen atom bonded with water is assigned 1.56 water molecules on average,and 'free' water molecules emerge at the concentration of around 54%.

2D-Cell Experiment on Methyl Tert-Butyl Ether Transport in Saturated Zone of Groundwater

As an additive of gasoline,methyl ten-butyl ether(MTBE)has a higher solubility in water,which is about 20 times as high as that of benzene.This characteristic results in MTBE dissolving out of the gasoline into the soil and groundwater.Due to relative unique physicochemical behavior of MTBE it would be an ideal candidate for use in environmental forensic investigations.In order to study the transport and distribution of MTBE in saturated zone of ground water,a two-dimensional experimental cell was setup to simulate the real environment of the groundwater flow.The effects of soil and groundwater flow velocity on the MTBE transport were investigated.The results show that the mobile distance of MTBE in vertical direction was smaller than that in horizontal direction paralleling with the groundwater flow.Because the main dynamics of groundwater flow direction was convection and dispersion,the movement of MTBE is also diffusion in the vertical direction.In addition,the transport of MTBE was more quick in high permeability porous media,and the increase of groundwater flow velocity can accelerate the MTBE plume development,but the irregularity and randomness of the plume are enhanced synchronously.These research results can give some helps for the investigation of MTBE movement in the groundwater,also can make some references for other petroleum contamination behavior.