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141.
Van Der Eycken E Appukkuttan P De Borggraeve W Dehaen W Dallinger D Kappe CO 《The Journal of organic chemistry》2002,67(22):7904-7907
Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed. 相似文献
142.
Summary The general objective is to provide an alternative methodology based on capillary electrophoresis (CE) to characterize flavonoids from honey and hence determine its botanical origin. The specific objective is to compare the separation of flavonoids by CE with those achieved by HPLC to assess CE as an alternative technique for the determination of honey flavonoids. Fourteen different flavonoids isolated from honey were analysed by MECC and compared to the HPLC separations. It was difficult to find specific experimental conditions to separate all the flavonoids from honey in a single MEKC run. Three chromatographic conditions are optimized and, depending on the flavonoid markers sought in honey, the appropriate detection method should be chosen. Compared to the HPLC results, it is clear that CE could be an alternative technique in honey flavonoids analysis and particularly in the study of its geographical and floral origin. 相似文献
143.
Vanommeslaeghe K Van Alsenoy C De Proft F Martins JC Tourwé D Geerlings P 《Organic & biomolecular chemistry》2003,1(16):2951-2957
Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur. 相似文献
144.
A. Van Baalen C.J. Groenenboom H.J. De Liefde Meijer 《Journal of organometallic chemistry》1974,74(2):245-253
The synthesis and the properties of the complexes Cp2TaCl2, Cp2M(allyl), Cp2M(1-methylallyl) and Cp2M(2-methylallyl) with M Nb, Ta are described. The complex Cp2TaCl2 has one unpaired electron per tantalum atom, while the allyl complexes are diamagnetic. The IR and PMR spectra indicate that the allyl group is π-bonded to the metal. The mass spectra of the complexes are discussed; the thermal stability of the Cp2Nb- and Cp2Ta-(allyl) complexes was investigated by differential thermal analysis. The properties of the niobium and tantalum complexes are compared with those of the corresponding titanium complexes. 相似文献
145.
Ehsan A. H. Gomaa H. Schut A. Van Veen M. Mohsen U. Fromm P. Morshuis 《Journal of Radioanalytical and Nuclear Chemistry》1996,211(1):77-83
Using the positron annihilation lifetime technique, the annihilation parameters have been measured for epoxy and high density polyethylene (HDPE) as a function of AC electric field strength and the exposure time. The lifetime spectra have been resolved into three components, the longest component (I33) is attributed to the pick-off annihilation of o-Ps in the amorphous regions. The intermediate one (I22) is due to the annihilation of free positrons, while the shorter component (I11) stems from self annihilation of p-Ps. In HDPE, the o-Ps parameters 3 andI
3 are measured as a function of electric field strengths in the range from 10 to 100 kV/cm exposed for 24 hours. A decrease inI
3 of 8% is observed from zero to 50 kV/cm followed by an increase of the same order from 50 to 100 kV/cm. By investigating the effect of the exposure time from 2 to 24 hours at 16 and 50 kV/cm, the effect is confirmed and is attributed to the inhibition of o-Ps formation at lower field strength. In epoxy, the effect or exposure time onI
3 at 166 and 133 kV/cm shows a similar behavior as in HDPE. At 133 kV/cmI
3 decreases by only 2.5%. On the other hand, the changes in 3 occur at short exposure times. Again at large times the saturation is obtained. These effects are attributed to the expansion of free volume (increase of 3) competing at longer exposure times with other phenomena, such as liberation of free radicals, which reduce the o-Ps intensityI
3 through the conversion to p-Ps. The reactions between o-Ps and free radicals might also lead to free positrons, which could explain the increase ofI
2 and the decrease of 3 at longer exposure times. 相似文献
146.
147.
Reducing end sugar residues in maltodextrins and arabinoxylans are determined as alditol acetates by gas-liquid chromatography following reduction, acid hydrolysis and acetylation of the samples. After this conversion to alditol acetates, the reducing end sugars are thus separated from their acetylated aldose counterparts. The method allows to identify individual reducing end sugars quantitatively and is a good alternative for colorimetric reducing sugar assays and 1H-NMR analysis. To demonstrate the advantages of the method, an application in a study of enzymic solubilisation and degradation of water unextractable arabinoxylan from a flour squeegee fraction is described. 相似文献
148.
Charles E. Hudson Liberty DeLeon Don Van Alstyne David J. McAdoo 《Journal of the American Society for Mass Spectrometry》1994,5(12):1102-1106
The transition state (TS) for loss of CH4 from protonated acetaldehyde has been located at the second-order Moller-Plesset (MP2)/6-31G(d,p) level of theory. The activation energy is predicted to be 263.9 kJ/mol starting from the more stable form (methyl and hydrogen E) and 261.6 kJ/mol starting from the less stable form (methyl and hydrogen Z) that is required for reaction. The products (methane and the formyl ion) are predicted to lie 136.6 kJ/mol below the TS for their formation. MP2 methods underestimate the heats of formation of both the TS and the reaction products by about 40 kJ/mol when compared with experiment. Restricted Hartree-Fock (RHF) calculations give much more accurate relative energies. The MP2 TS leads directly to fragmentation and is described as a protonation of the methyl group by the acidic proton on oxygen. Under RHF theory the reaction is stepwise. An RHF TS similar to the MP2 TS leads to a nonclassical intermediate (which is stable at this level of theory) that has one of the C---H bonds protonated. This mechanism (protonation of an alkyl group) appears to be a general one for high energy 1,2 eliminations from organic cations. (J Am Soc Mass Spectrom 1994, 5, 1102-1106) 相似文献
149.
The amidinoethylation of alcohols takes place by the addition of sodium alkoxides 2 (R1 = Me, Et) to the CC double bond of a variety of N,N'-substituted-propenamidines 1 (Method A). This illustrates the activation of the CC double bond by the conjugated amidine function and provides a new class of Michael acceptors for alcohols. However, this activation is poorer than with other nucleophiles or Michael acceptors. The amidinoethylation makes available 3-alkoxy-N,N'-substituted-amidines not easily accessible by other classical methods. However, it is demonstrated that the general N,N'-substituted-amidine synthesis via the nitrilium salts can also apply to nitrile compounds having an alkoxygroup present on the molecule (method B). Since the cyanoethylation of alcohols (4) is a very fast and facile reaction the method B is the preferred strategy for the synthesis of 3-alkoxy-N,N'-substituted-propanamidines 3. 相似文献
150.
The mass spectra of some N-methylpyridinium, quinolinium, isoquinolinium and phenanthridinium salts (R+X?) 1 The salt will be represented by R+X? or RX, R+ being the organic moiety, with its associated mass and X- the inorganic anion. are analyzed (X? = I? or ClO4?). For X? = I?, thermal decomposition gives rise mainly to the superimposed spectra of CH3I and the free base. Hence, iodide salts cannot be determined specifically by their mass spectra. When an α-methyl group is present, e.g. 2-methylpyridinium methiodide, elimination of HI becomes an important thermal process. For X? = ClO4?, the same pattern is observed, but in addition a generally important peak at [R + 15] is present. This peak is due to the oxidation, mainly α to the nitrogen of the organic moiety by the ClO4? ion, giving rise to the corresponding amide. In some cases, chlorination of the organic moiety has been observed as well as double oxidation. The thermal processes for the perchlorate salts are characteristic and are useful in the elucidation of the quaternary structure. 相似文献