Gas-phase ion - Molecule reactions of neutral C-60 with the plasmas of alkyl methyl ethers and primary alcohols

The gas-phase ion-molecule reactions of C-60 with the methoxymethyl ion [CH3O=CH2](+) and the 1-hydroxyethyl ion [CH3CH=OH](+) generated under the self-chemical-ionization (self-CI) conditions of alkyl methyl ethers and primary alcohols were studied in the ion source of a mass spectrometer. The adduct ions [C60C2H5O](+) and protonated molecules [C60H](+) were observed as the major products of C-60 with the plasma of alkyl methyl ethers. On the contrary, the reactions of C-60 With the plasmas of primary alcohols produced few corresponding adduct ions. The AM1 semiempirical molecular orbital calculations were carried out on 14 possible structures. The calculated results showed that the most stable structure among the possible isomers of [C60C2H5O](+) is the [3+2] cycloadduct. According to experimental and theoretical results, the pathway for the formation of the adduct was presented.

The chemistry of alpha-oxo ketene cyclic dithioacetal .36. Studies on silica G catalyzed decomposition of adducts of beta,beta-1,3-propylenedithio-alpha,beta-unsaturated arylketones with grignard reagents

beta, beta-1, 3-Piopylenedithio-alpha, beta-unsaturated arylketones 2 via chemoselective 1,2-addition with allyl or benzyl Grignard reagents afforded the corresponding carbinols 3 and 4. Catalysed by silica gel, the carbinols 3 and 4 were converted to the beta,gamma-unsaturated arylketones 5, 6. The mechanism and reaction condition were discussed.

MODIFIED POLYSULFONES .1. SYNTHESIS AND CHARACTERIZATION OF POLYSULFONES WITH UNSATURATED END-GROUPS

Chloro-terminated polysulfones with various molecular weights were modified with poly(ethylene oxide) and poly[(ethylene oxide)(propylene oxide)] macromers carrying alpha-hydroxyl and omega-allyl end groups via classical polycondensation reactions. The pr

THE CATALYTIC ACTIVITY OF HETEROPOLY ACIDS (SALTS) AND MONO-LACUNARY HETEROPOLY TUNGSTOPHOSPHORIC COMPOUND IN THE OXIDATION OF ALCOHOLS

The catalytic activity of heteropoly compounds in the oxidation of benzyl alcohol and cyclohexa nol under phase transfer conditions has been studied. The catalytic activity of six kinds of heteropoly acids with Keggin structure will drop by the order of GeMo12 (H4GeMo12O40). PW12, PMo12, SiMo12, GeW12 and SiW12. When the three protons of H3PW12O40 Were replaced by Na+ step by step, the catalytic activity will raise gradually with the drop of acidity. The addition of base and trace amount of sulfuric acid to the reaction system resulted in an increase of catalytic activity. It was found that catalytic activity of mono-lacunary heteropoly compounds is higher than that of the primary heteropoly acids (or salts). The catalytic oxidation system of HPA-H2O2-PTC is very active in the oxidation of benzyl alcohol ana cyclohexanol, but it has little activity in the oxidation of inactive compounds such as n(or iso)-proplalcohol. n-butyl alcohol and n-hexanol. Solvent has great effect on reaction, when polar compounds such as water were used as solvent, the catalytic activity is better than that when non-polar compounds were used as solvent.

Sea surface temperature reconstruction for the middle Okinawa Trough during the last glacial-interglacial cycle using C-37 unsaturated alkenones

C-37 unsaturated alkenones were analyzed on a core retrieved from the middle Okinawa Trough. The calculated U-37(K') displays a trend generally parallel with those of the oxygen isotopic compositions of two planktonic foraminiferal species, Neogloboquadrina dutertrei and Globigerinoides sacculifer, suggesting that in this region, SST has varied in phase with global ice volume change since the last glacial -interglacial cycle. The U-37(K')-derived SST ranged from ca. 24.0 to 27.5 degrees C, with the highest value 27.5 degrees C occurring in marine isotope stage 5 and the lowest similar to 24.0 degrees C in marine isotope stage 2. This trend is consistent with the continental records from the East Asian monsoon domain and the marine records from the Equatorial Pacific. The deglacial increase of the U-37(K')-derived SST is similar to 2.4 degrees C from the Last Glacial Maximum to the Holocene. (c) 2007 Elsevier B.V. All rights reserved.

Determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatisation with carbazole-9-N-acetic acid and chromatographic behaviour of alcoholic derivatives

Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

Trichloroacetimidate as an efficient protective group for alcohols

The trichloroacetimidate is disclosed to be a general and efficient protective group for alcohols, which can be deprotected under mild acidic, basic, or neutral conditions, and has orthogonal stability with the acetate and tert-butyldimethylsilyl (TBS) protections.

Numerical Analysis of Rainfall Infiltration in the Slope with a Fracture

With the finite volume method, a 2D numerical model for seepage in unsaturated soil has been established to study the rainfall infiltration in the fractured slope.The result shows that more rain may infiltrate into the slope due to existing fracture and then the pore pressure rises correspondingly. Very probably, it is one of the crucial factors accounting for slope failure. Furthermore a preliminary study has been conducted to investigate the influence of various fracture and rainfall factors such as the depth, width and location of a crack, surface condition, rainfall intensity and duration. Pore pressure and water volumetric content during the transient seepage are carefully examined to reveal the intrinsic mechanism.

Experimental study on pore pressure in rock-soil slope during reservoir water level fluctuation

A test system was developed for measuring the pore pressure in porous media, and a new model was devised for the pore pressure testing in both saturated and unsaturated rock-soil. Laboratory experiments were carried out to determine the pore pressure during water level fluctuation. The variations of transient pore pressure vs. time at different locations of the simulated rock-soil system were acquired and processed, and meanwhile the deformation and failure of the model are observed. The experiment results show that whether the porous media are saturated or not, the transient pore pressure is mainly dependent on the water level fluctuation, and coupled with the variation of the stress field.