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31.
A surface counterion titration method was used to monitor the interaction of monovalents cations (Li(+), Na(+), TMA(+)) with the surface of alumina-coated TiO(2) particles in concentrated media at different pH and electrolyte concentrations. This method allows measuring separately the negative and positive contribution to the surface charge. It showed that Cl(-) and TMA(+) are indifferent ions, but Li(+) and Na(+) specifically adsorb on the non-ionized alumina surface sites. The binding sequence of cations is Li(+)>Na(+)>TMA(+) at all ionic strengths investigated and is consistent with the structure-making and structure-breaking model developed a few decades ago. Polyacrylic acid (PAA) previously neutralized with the corresponding hydroxide (LiOH, NaOH, TMAOH) has been adsorbed on the alumina surface at different pH. The polymer counterion has a significant influence on the polymer adsorption. The sequence of the surface coverage as a function of the polymer counterion follows the order Li-PAA > Na-PAA > TMA-PAA. The much higher surface coverage with Li-PAA and Na-PAA compared to TMA-PAA is explained by the specific adsorption of Li-PAA and Na-PAA on the nonionized alumina surface sites, the same way LiCl and NaCl do.  相似文献   
32.
Novel large polyazadioxime molecules 4,5,8,9-tetraaza-3,6,7,10-tetramethyl -3,5,7,9-dodecatetraene-2, 11-dione-2, 11-dioxime (H2doxN4) and 4,5,8,9,12, 13-hexaaza-3,6,7,10,11,14-hexamethyl-3, 5,7,9,11,13-hexadecahexane-2,15-dione-2, 15-dioxime (H2doxN6) were synthesized. The molecular geometries of these molecules as well as smaller dioxime molecules, H2dox and H2doxN2 were optimized by using modified intermediate neglect of differential overlap (MNDO) calculations. The optimized conformations for all the molecules under study are close to the all-E, all-s trans conformation of C2h symmetry group. However, the energy barriers of internal rotation around the N-N single bonds were found to be low. Therefore some distortions of the polyazabackbone through internal rotation the N-N bonds have been evidenced. By infrared and Raman spectroscopies in the solid state as well as in solution. From the MNDO calculations and vibrational spectroscopy, the polyaza chain molecules under study appear as a poorly conjugated system and can be represented as a sequence of single and double bond alternation.  相似文献   
33.
β-(trichloromethyl)-β-propiolactone (CCl3-PL), β-(trifluoromethyl,methyl)-β-propiolactone (CF3, Me-PL) and β-(trifluoromethyl,ethyl)-β-propiolactone (CF3,Et-PL) have been obtained by the reaction of ketene with chloral, 1,1,1-trifluoroacetone and 1,1,1-trifluorobutanone, respectively. Chiral catalysis lead to optically active monomers. The enantiomeric excess of the lactones has been measured by 1H-NMR spectroscopy, in the presence of 2,2,2-trifluoro-1-(9-anthryl)ethanol or an europium chiral shift reagent. Polymerizations have been carried out in bulk or in toluene, at 60°C or 80°C, using mainly organometallic initiators. The Polymers become insoluble and crystalline at enantiomeric excesses over 80% for CCl3-PL and 70% for CF3,Me-PL. Melting temperatures were recorded from 238 to 268°C for poly(CCl3-PL) and from 78 to 100°C for poly(CF3,Me-PL), depending upon the molecular weight and the enantiomeric excess. The 13C-NMR specroscopy of poly(CCL3-PL) indicates that the polymerization of the corresponding lactone leads to polymers of increasing degrees of isotacticity with the enantiomeric excess of the monomer.  相似文献   
34.
The electron impact mass spectra of two series of 5-oxo-tetrahydro-5H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates and 7-oxo-tetrahydro-7H-thiazolo [3,2-a]pyrimidine-6-ethylcarboxylates were measured and fragmentation patterns examined. Structures were assigned from analysis of oxo molecular ion fragmentations. Compounds of the 5-oxo series gave an [M – CO2C2H5]+ fragmentation whereas compounds of the 7-oxo series gave three characteristic cleavages. This decomposition was confirmed for one pair of isomers by high-resolution mass spectrometry and unimolecular mass-analysed ion kinetic energy spectrometry. Electron impact mass spectrometry is a convenient method for assigning structures of 5- and 7-oxo regioisomers of tetrahydrothiazolo[3,2-a]pyrimidine-6-carboxylates.  相似文献   
35.
Abstract— Extracts of Neurospora crassa contain photoreactivating enzyme by the criteria of ability to split thymine-containing dimers and to increase the transforming ability of u.v.-irradiated Hemophilus influenzae DNA. The latter activity is heat-labile and is destroyed by trypsin. The action spectrum of such in vitro photoreactivation is a simple one (with a single maximum at 405 nm in the range 313 to 436 nm), differing from the more complicated in vitro spectra for yeast and Escherichia coli. However, the in vitro Neurospora spectrum coincides closely with the in vivo spectrum for this organism, suggesting that there is little or no “indirect” photoreactivation in Neurospora. It is concluded that the Neurospora photoreactivating enzyme is probably of a different type than those of yeast and Escherichia coli.  相似文献   
36.
In the title compound, [TbCl(C27H35N3)2(H2O)](ClO4)2·2C2H6O, the TbIII ion has a coordination number of eight, composed of two tridentate substituted‐ter­pyridine ligands, a water mol­ecule and a bound Cl? anion. The first coordination shell can be described as a distorted bicapped trigonal prism. The dihedral angles between pyridine rings belonging to the same tpy ligand range from 5.2 (5) to 16.8 (5)°.  相似文献   
37.
Bifunctional derivatives of the alkaloid galanthamine, designed to interact with both the active site of the enzyme acetylcholinesterase (AChE) and its peripheral cation binding site, have been assayed with Torpedo californica AChE (TcAChE), and the three-dimensional structures of their complexes with the enzyme have been solved by X-ray crystallography. Differences were noted between the IC(50) values obtained for TcAChE and those for Electrophorus electricus AChE. These differences are ascribed to sequence differences in one or two residues lining the active-site gorge of the enzyme. The binding of one of the inhibitors disrupts the native conformation of one wall of the gorge, formed by the loop Trp279-Phe290. It is proposed that flexibility of this loop may permit the binding of inhibitors such as galanthamine, which are too bulky to penetrate the narrow neck of the gorge formed by Tyr121 and Phe330 as seen in the crystal structure.  相似文献   
38.
In the presence of a catalytic amount of BH3·Me2S, TiCl4 or Me3SiCl, LiBH4 or NaBH4 are capable of hydroborating alkenes by following the unusual order of decreasing reactivity: tetramethylethylene > 1-methylcyclohexene > cyclohexene; the key step of the catalytic cycle is the exchange reaction between LiBH4 and the mono- or dialkylboranes resulting from hydroboration of the more substituted alkenes with BH3.  相似文献   
39.
A synthesis of the alkylidene cyclopentenone prostaglandin TEI 9826 has been realized. The synthesis involved the preparation of the chiral 1,5-diene 8 using a stereoselective Claisen rearrangement from the allylic alcohol 6 giving the ester 7 after vinylation. Then a key RCM reaction allowed the preparation of the cyclopentenol 9 which, after oxidation, gave the cyclopentenone 10, precursor of the prostaglandin.  相似文献   
40.
Three homologous series of semi-perfluorinated liquid crystals: 4-(2,2,3,3,4,4,4-heptafluoro-butyloxycarbonyl)phenyl, 4-(2,2,3,3,4,4,5,5-octafluoropentyloxycarbonyl)phenyl and 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxycarbonyl)phenyl 4-[(n-perfluoroalkyl)alkyloxy]benzoates have been synthesized. Their mesomorphic properties were studied by DSC, microscopic observation and X-ray diffraction. Their layer spacings are smaller than the molecular length (L). The ratio dSA/L is about 0.7. The crystal structure of two derivatives of the first family have also been investigated. In both structures the molecules pack in smectic C-like sheets where neighbouring molecules are antiparallel, interacting through dipolar and van der Waals forces. The interactions between contiguous sheets, through the ends of perfluorinated chains are very weak. The X-ray diffraction results on the mesophases and on the crystalline structures of two compounds of the first family are compared. From this, we propose a model of the smectic phases with a zig-zag structure.  相似文献   
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