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991.
Alvarez P Lastra E Gimeno J Bassetti M Falvello LR 《Journal of the American Chemical Society》2003,125(9):2386-2387
Intramolecular [2 + 2] cycloaddition of two C=C bonds in vinylidene complexes [Ru(eta5-C9H7){=C=C(R)H}(PPh3){kappa1-(P)-PPh2(C3H5)][BF4] affords cyclobutylidene complexes [Ru(eta5-C9H7){kappa2-(P,C)-(=CC(R)HCH2CHCH2PPh2)}(PPh3)][BF4], which can be also obtained by reaction of terminal alkynes with [Ru(eta5-C9H7)(PPh3){kappa3-(P,C,C)-PPh2(C3H5)}][PF6]. The reaction proceeds under mild conditions via vinylidene complexes, and the activation parameters were determined by kinetic studies. 相似文献
992.
Barry SJ Carr RM Lane SJ Leavens WJ Monté S Waterhouse I 《Rapid communications in mass spectrometry : RCM》2003,17(6):603-620
A simple method has been developed for the pre-column derivatisation of low molecular weight primary and secondary amines and carboxylic acids using quaternary nitrogen compounds to enhance their detection by liquid chromatography/electrospray ionisation mass spectrometry (LC/ESI-MS). The synthesis of seven novel quaternary nitrogen reagents is described. The derivatives are designed to be relatively small molecules to avoid some of the steric hindrance problems that may be associated with larger derivatisation reagents. The compounds have amine and carboxylic acid functional groups with which to derivatise carboxylic acids and amines, respectively. Two of the compounds contain a bromine atom in order to assess the advantages of a bromine isotope pattern in the mass spectra. This acts as a simple marker for derivatisation and enables data processing by cluster analysis.Activation of the carboxylic acid group was achieved by the use of either 1-chloro-4-methylpyridinium iodide (CMPI) or the more reactive 1-fluoro-4-methylpyridinium p-toluenesulphonate (FMP).1 Using both of these active reagents, the degree of nucleophilic substitution was investigated for the derivatisation of a variety of small molecules. Whilst giving some increase in the ESI-MS response for the derivatised compounds, the FMP itself acted as a derivatising reagent in a competing reaction. In the light of this finding, FMP was reacted with the test compounds separately and gave positive results as a derivatising reagent. Detection of the 'pre-charged' derivatives of amines and carboxylic acids by LC/ESI-MS was investigated with respect to their ESI response and chromatography. 相似文献
993.
The morphologically undifferentiated cells of nonregenerant callous tissue of Cereus peruvianus cultured in the original medium and in medium supplemented with tyrosine were used as an alkaloid source. Comparison of alkaloid
production by C. peruvianus plants and by callous tissues indicated that alkaloid levels were almost twice as high in callous tissues as in shoots of
C. peruvianus plants. The ratio of alkaloid concentration between mature plant and morphologically und ifferentiated cells of callous tissue
was 1∶1.7. A relationship between culture medium containing tyrosine and alkaloid production was also observed in the callous
tissues of C. peruvianus. Since increased alkaloid production may be induced by additional factors such as tyrosine, increasing levels of tyrosine
or other conditions of the culture medium may be considered factors for inducing higher alkaloid production by C. peruvianus callous tissues. 相似文献
994.
Sorption of spruce acetylated galactoglucomannans (GGM) onto different pulps, among which unbleached and peroxide-bleached mechanical pulps, and unbleached and bleached kraft (BK) pulps, was studied as a means of understanding the retention of acetylated GGMs in mechanical pulping and papermaking. The fibre surface coverage of lignin and carbohydrates was estimated by X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA). GGM sorption was clearly favoured on kraft pulps. Hardly any differences in sorption were, however, observed between unbleached and BK pulps, even if the surface coverage of lignin was lower on the bleached pulp. Neither thermomechanical pulp (TMP) nor chemithermomechanical pulp (CTMP) manufactured from spruce sorbed any acetylated GGMs. Peroxide bleaching of the pulp did not increase sorption. Only CTMP produced from aspen sorbed some GGMs. The anionic charge of neither chemical nor mechanical pulps influenced GGM sorption. 相似文献
995.
996.
A multiresidue method was developed for the de termination of 16 polycyclic aromatic hydrocarbons (PAHs) in unifloral and multifloral honeys. The analytical procedure is based on the matrix solid-phase dispersion of honey on a mixture of Florisil and anhydrous sodium sulfate in small glass columns and extraction with hexane-ethyl acetate (90 + 10, v/v) with assisted sonication. The PAH residues are determined by gas chromatography with mass spectrometric detection using selected-ion monitoring. Average recoveries for all the PAHs studied were in the range of almost 80 to 101%, with relative standard deviations of 6 to 15%. The limits of detection ranged from 0.04 to 2.9 microg/kg. The simultaneous extraction and cleanup of samples makes this method simple and rapid, with low consumption of organic solvents 相似文献
997.
Kerdelhué JL Langenwalter KJ Warmuth R 《Journal of the American Chemical Society》2003,125(4):973-986
Photolysis of p-tolyldiazirine (6) in the inner phase of a hemicarcerand with four butane-1,4-dioxy linker groups (5) in C(6)D(5)CD(3) at 77 K yields the 5-methylcycloheptatetraene hemicarceplex 5 circle 3b in 41% together with innermolecular reaction products resulting from an insertion of transient p-tolylcarbene (1b) into an acetal C-H or linker C-O bond of 5 and from the addition of 1b to an aryl unit of 5. The yield of incarcerated 3b increased up to 67% if 6 is photolyzed inside a hemicarcerand with deuterated spanners and butane-1,4-dioxy linker groups (d(48)-5). Hemicarceplex 5 circle 3b is not formed if the photolysis is carried out in CDCl(3). Incarcerated 3b is stable at room temperature in the absence of oxygen and is characterized by 1D and 2D NMR spectroscopy. In the presence of oxygen, 3b reacts quantitatively to yield toluene and CO(2). Upon heating solutions of d(48)-5 circle 3b in C(6)D(5)CD(3), 3b rearranges to 1b and m-tolylcarbene (18). Both tolylcarbenes immediately react with the surrounding host. From a product analysis and the measured rate constants for the thermal decomposition of d(48)-5 circle 3b in the temperature range 70-102 degrees C, the activation parameters for the 3b to 1b and 3b to 18 rearrangements are calculated (3b to 1b: DeltaG(373)++ = 27.3 +/- 1.4 kcal/mol, DeltaH(373)++ = 26.4 +/- 1.0 kcal/mol, TDeltaS(373)++ = -0.9 +/- 1.0 kcal/mol; 3b to 18: DeltaG(373)++ = 27.8 +/- 1.4 kcal/mol, DeltaH(373)++ = 19.7 +/- 1.0 kcal/mol, TDeltaS(373)++ = 8.1 +/- 1.0 kcal/mol). These values are compared with those calculated by Geise and Hadad at the B3LYP/6-311+G** level of theory (Geise, C. M.; Hadad, C. M. J. Org. Chem. 2002, 67, 2532-2540). The slightly higher inner phase activation free energy of the 3b to 18 rearrangement is explained through steric constraints imposed by the surrounding hemicarcerand on the transition state. The enthalpy-entropy compensation observed for the 3b to 18 rearrangement is discussed and interpreted as a result of a hemicarcerand and solvent reorganization along the reaction coordinate. It is taken as indirect evidence for the intermediacy of 2-methylbicyclo[4.1.0]hepta-2,4,6-triene in the 3b to 18 rearrangement. 相似文献
998.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
999.
Carballo R Casas JS García-Martínez E Pereiras-Gabián G Sánchez A Sordo J Vázquez-López EM 《Inorganic chemistry》2003,42(20):6395-6403
The reactions of methylacetoacetate and ethyl 2-methylacetoacetate thiosemicarbazones (H(2)L(A) and H(2)L(B), respectively) with [ReX(CO)(5)] and [ReX(CO)(3)(CH(3)CN)(2)] (X = Cl, Br) were explored under various experimental conditions. Besides the adducts fac-[ReX(CO)(3)(H(2)L)], in which the rhenium is coordinated to three carbonyl groups, the X anion, and the N,S-bidentate thiosemicarbazone ligand, the following complexes were also isolated: fac-[ReBr(CO)(3)(Hpyz(B))], the tetrameric complexes fac-[Re(pyz(A))(CO)(3)](4) and fac-[Re(pyz(B))(CO)(3)](4), and fac-[Re(pyz(B))(CO)(3)(H(2)O)] (where Hpyz(A) and Hpyz(B) are pyrazolones derived by cyclization of H(2)L(A) and H(2)L(B), respectively). The cyclization reactions were monitored by (1)H NMR spectroscopy and the complexes isolated were identified by elemental analysis, mass spectrometry, IR and (1)H NMR spectroscopy, and in some cases by X-ray diffractometry. The isolation and the full structural identification of the rather unusual fac-[ReBr(CO)(3)(Hpyz(B))], which contains the enol form of the pyrazolone ligand, affords new insight into the cyclization of thiosemicarbazones derived from beta-keto esters. 相似文献
1000.
This work focuses on the optimization of the rheological behavior of suspensions considering different solvent compositions. The effects of methyl ethyl ketone (MEK)/ethanol (E) solvent mixtures on reaction sialon suspensions were investigated by measuring sedimentation behavior, adsorption of dispersant, and flow behavior. It was shown that both the flow behavior and the sedimentation behavior strongly depended on selection of solvent composition. Using 3 wt% KD1 as dispersant, well-dispersed colloidal suspensions could be obtained in MEK-rich solvents. The suspensions with 60 vol% MEK/40 vol% E as solvent could be fitted to the Bingham model with very low yield stress, while suspensions with pure MEK or ethanol-rich mixtures as solvent showed pseudo plastic behavior with relatively high yield stress values. A model was proposed to explain the different flow behaviors of suspensions considering the different configurations of dispersant at particles' surfaces. 相似文献