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111.
The synthesis of 2-phenylsparteine-N16-oxide (7) and its perchlorate salt (7-H+) was carried out. On the basis of spectral data, and by comparison with appropriate sparteine-N-oxides, the mechanism of formation and the structures of the two new compounds were proposed. It was found, the basicity of the new N-oxide is unexpectedly high and comparable to the basicity of quaternary ammonium hydroxides. The structure and the strength of intramolecular H-bond in 7-H+ makes 7 an excellent “catcher” proton or specific ”sponge” proton. 相似文献
112.
Estimating the pore size distribution of activated carbons from adsorption data of different adsorbates by various methods 总被引:1,自引:0,他引:1
Gauden PA Terzyk AP Rychlicki G Kowalczyk P Cwiertnia MS Garbacz JK 《Journal of colloid and interface science》2004,273(1):39-63
Experimental adsorption isotherms of four adsorbates (N2, Ar, C6H6, and CCl4) as well as adsorption enthalpy (C6H6 and CCl4) measured on two strictly microporous carbons are used to evaluate the porosity of adsorbents (i.e., pore size distributions (PSDs) and average pore diameter ( Lav )). The influence of the diameter of adsorbates ( dA) as well as of the temperature ( T ) is analyzed in order to explain the differences or similarities between the above-mentioned quantities for all systems. Proposed previously, the general relationships between the parameters of the Dubinin-Astakhov (DA) isotherm equation (the characteristic energy of adsorption ( E0 ) and the exponent of this equation ( n )) and the average slit-width of carbon micropores are investigated. Moreover, the thermodynamic verification of the Horvath-Kawazoe (HK) theory and the ND model is presented based on data of the adsorption and enthalpy of adsorption of benzene and carbon tetrachloride on two carbons. Finally, the pore diameters calculated from calorimetry data using the Everett and Powl method and those calculated applying the recently developed equations are compared. In our opinion the change of apparent PSD should be monitored by performing a series of isotherm measurements from high (equal and higher than room temperature) to low temperatures (ca. 77.5 K) as was presented in the current study. Moreover, the analysis of the experimental data leads to the conclusion that the entropy of C6H6 and CCl4 can approach to the values characteristic of quasi-solid (a partially ordered structure). Therefore, this behavior of the adsorbate should be taken into consideration in the theoretical assumptions of model and its thermodynamic verification. 相似文献
113.
M. Mucha 《Colloid and polymer science》1994,272(9):1090-1097
The miscibility of polyethylene oxide (PEO) with oligoester and polyester resin, the morphology of the blends and the kinetics of PEO crystallization in the blends were studied by optical microscopy and differential scanning calorimetry. The blends were found to be miscible with uncured resin at 60°C. After isothermal crystallization of PEO from liquid oligoester or UV cured polyester about 20% of the PEO material is still dissolved in the resin and it is incorporated between lamellae or in the interspherulitic regions. It was observed that the growth rate of PEO spherulites and the degree of crystallinity of PEO in the blends decreases very fast together with a decrease of the PEO content and the progress of the resin crosslinking. 相似文献
114.
The FOGO method is used to calculate proton affinities and lithium cation affinities. The molecules of primary interest in this study are the methyl-substituted amines. In addition, the lithium cation affinity of HF, H2O, CH3OH, H2CO, and HCN are calculated for comparison. Geometries of all species are fully optimized with a double-zeta (DZ) basis set, including polarization on hydrogen and the first-row elements by floating orbitals. Comparison with experimental values demonstrates that structural data and proton affinities resulting from this type of ab initio calculation are of chemical accuracy. The lithium cation affinities are also reasonably well reproduced, but the small experimental differences are not within the accuracy, which can be expected from this type of calculation. 相似文献
115.
Dzygiel A Rzeszotarska B Masiukiewicz E Cmoch P Kamieński B 《Chemical & pharmaceutical bulletin》2004,52(2):192-198
Methyl 5-amino-1H-[1,2,4]triazole-3-carboxylate hydrochloride (1). and free ester (2). were obtained and 2 was reacted with Ac(2)O to give the acetylated products 3-6. Compounds 1-6 were studied using HPLC, GC-MS, FTIR and multinuclear NMR spectroscopy, including the cross-polarisation magic angle spinning (CPMAS) technique. The results of the acetylation of 2 were compared to those of the acetylation of 5-amino-1H-[1,2,4]triazole, and for 2 a significant decrease in the susceptibility to acetylation was found. The reaction of 2 with Ac(2)O at 20 degrees C, regardless of the amount and the concentration of the latter, including neat Ac(2)O, proceeds fully regioselectively and leads to one product: methyl 1-acetyl-5-amino-1H-[1,2,4]triazole-3-carboxylate (3). In sharp contrast to 5-amino-1H-[1,2,4]triazole, neither an additional monoacetylated isomer, whether annular or exocyclic, nor any diacetylated derivative could be detected. The diacetylation of 2 requires the process to be carried out in neat boiling Ac(2)O and, as in the case of 5-amino-1H-[1,2,4]triazole, gives two diacetylated isomers. These are methyl 1-acetyl-3-(acetylamino)-1H-[1,2,4]triazole-5-carboxylate (4) and 1-acetyl-5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (5). Hypothetical pathways of their formation have been suggested. A mixture of 4 and 5 upon hydrolysis of the ring acetyl group gives the monoacetylated derivative methyl 5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (6). The spectroscopic, structural and conformational characteristics of compounds 1-6 have been given and methods for their preparation have been provided. 相似文献
116.
Maria?NowakowskaEmail author Krzysztof?Szczubia?ka Miros?aw?Gr?bosz 《Colloid and polymer science》2004,283(3):291-298
The interactions between copolymers of sodium styrene sulfonate (SSS) and N-isopropylacrylamide (NIPAM), anionic polyelectrolytes, and dodecyltrimethylammonium chloride (DTAC), a cationic surfactant, were studied in aqueous solutions of various ionic strengths. The copolymers were found to be thermoresponsive, showing a lower critical solution temperature (LCST). The influence of the polymer composition, the surfactant concentration, and the ionic strength on the LCST was studied. The surfactant was found to interact strongly with the polymer, forming mixed polymer-surfactant micelles. The critical aggregation concentration (cac) of the polymer-surfactant system was found from fluorescence spectroscopy using pyrene as a fluorescent probe. A strong dependence of the anionic polyelectrolyte-cationic surfactant interactions on the structure of the ionic comonomer was observed. 相似文献
117.
meso-Tetraphenylporphyrin (and its derivatives), in the reaction with fuming yellow nitric acid (d=1.53), form either 5-(4-nitroaryl)-10,15,20-triarylporphyrin, 5,10-bis(4-nitroaryl)-15,20-diarylporphyrin, or 5,10,15-tris(4-nitroaryl)-20-arylporphyrin, depending on the reaction temperature (0-20 °C), amounts of the acid used, and reaction time. The above nitroporphyrins react, in the presence of a base (t-BuOK) at 0 °C, with carbanions (which bear nucleophugal groups at the carbanionic center: −CH(Cl)SO2Tol, −CH(Br)SO2Tol, and −CH(Cl)SO2NMe2), leading to the nucleophilic substitution of hydrogen in one or more of the meso-nitroaryl rings. By this route, the preparation of the highly substituted ‘synthetic’ porphyrins (bearing up to ten O-, N-, Cl-, or C-substituents) was demonstrated. 相似文献
118.
Krzysztof Maruszewski Marek Jasiorski Witold Wacławek Wiesław Stręk Marek Lisowski 《Journal of Sol-Gel Science and Technology》1998,13(1-3):585-586
A series of silicate xerogels with entrapped chiral amino acids have been obtained via sol-gel technology. The transparent, glassy samples obtained exhibit chirality in the bulk due to the presence of the entrapped asymmetric molecules. Measurements of the optical activity of the doped xerogel samples revealed that the entrapment did not significantly influence the optical activity observed for liquid solutions of the amino acids. Thus, the sol-gel method enables the preparation of amorphous optical materials exhibiting properties of strictly spatially defined molecular systems. Apart from the obvious optical applications, such porous materials with asymmetric centers might find interesting applications in chiral chemical syntheses and separations. 相似文献
119.
5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R(P) and S(P) absolute configuration, respectively. [reaction: see text] 相似文献
120.
Piotr Kirszensztejn Wlodzimierz Zmierczak 《Reaction Kinetics and Catalysis Letters》1994,52(2):467-474
This study is concerned with the effect of various amounts of Sn species in modifying the dispersity of Al2O3–SnO2 supported platinum catalysts by application of hydrogen chemisorption in a pulse chromatographic system, as well as determination of activity in water-gas shift reaction (WGS). 相似文献