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71.
72.
Noble PF Cayre OJ Alargova RG Velev OD Paunov VN 《Journal of the American Chemical Society》2004,126(26):8092-8093
Novel colloidosome microcapsules with aqueous gel cores and integral shells of rodlike polymeric particles have been prepared and characterized. The synthesis is based on templating water-in-oil emulsions stabilized by rodlike particles followed by gelling of the aqueous phase, dissolution of the oil phase in ethanol, and redispersion of the obtained colloidosome capsules in water. Such capsules may find applications as vehicles for delivery and controlled release of drugs, cosmetics, and food supplements. 相似文献
73.
Michielin O Zoete V Gierasch TM Eckstein J Napper A Verdine G Karplus M 《Journal of the American Chemical Society》2002,124(37):11131-11141
A conformational analysis of a stereochemically complete set of peptide analogues based on a cis-enediol unit is presented. The cis-enediol unit, which can replace a two or a three amino acid segment of a peptide, contains two "side chains", four asymmetrical carbon atoms, and six free dihedral angles. To determine the accessible conformational space, the molecules are divided into three fragments, each containing two free dihedral angles. The energy surfaces are computed for all dihedral angle values, and the possible conformations of the cis-enediol unit analogues are built using all combinations of the surface minima. Such a "build-up" procedure, which is very fast, is able to reproduce 75% of the minima obtained from a full dihedral angle exploration of the conformational space. The cis-enediol unit minima are compared with the corresponding di- and tripeptide minima; all peptide minima can be closely matched by a cis-enediol unit minimum of low energy (less than 2.2 kcal/mol above the lowest energy conformer). However, there are low energy minima of the cis-enediol unit that have no corresponding minima in peptides. The results are shown to depend strongly on the chirality of the analogues. The ability of each of the stereoisomers to mimic natural peptides, evaluated by the present approach, is correlated with its experimental activity in a renin inhibition assay. 相似文献
74.
John Fielden Patrick T. Gunning De-Liang Long Margaret Nutley Arkady Ellern Paul Kgerler Leroy Cronin 《Polyhedron》2006,25(18):3474-3480
The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H2O)(NO3)](NO3) (1), and [Zn(DDOP)(H2O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode. 相似文献
75.
76.
Vladimir Klenwchter Jaroslav Drobnik Leroy Augenstein 《Photochemistry and photobiology》1967,6(2):133-146
Abstract— We have investigated the effects of solvent and pH on the absorption and emission propertied of various 6- and 9-substituted purines as a means of examining the nature of the directed not only at deteriming the relative energies of (π,π*) and (π,π*) states, but in particular, at examining the nature and energies of the two lowest-lying (π,π*) states. For examplem, the attachment of a methyl or ribosyl group to the N9 of purine does not change the relative energies of the lowest-lying (π,π*) and (π,π*) states; thus, the latter is the singlet of lowest energy. However, the lowest singles in derivatives formed by substitution at C6 are(π,π*) states—i.e. there is no long-wavelength tail in the absorption spectra and florescence is comparable in intensity to phosphorescence. Further the absence of emission from neutaral adenine at room temperature is due to temperature quenching. Both lowest (π–π*) transtions. are contained under a common envelope and cannot be resolved in the absorption spectra. The shoulder observed in some of these compounds on the long-wavelength slope of absorption envelope is vibrational in nature. Consideration of the effects of solvents on absorption and the analysis of luminescence spectra make it possible to locate the relative position of these (π–π*) transitions within the common envelope. In compounds with an -H on N9 and a free (aza) N1 (e.g. adenine, anionic hupoxanthine) the weaker, solvent-sensitive (W) band has a higher energy then the more intense, solvent-insensitive (S) band. When N1 is protonated, (e.g., in hypoxanthine or cationic adenine) and/or when methyl or ribosyl is substituted at N9, the order of these bands is inverted due ot a red shift of the W band. This shift is most apparent in the 9-substituted hypoxanthines, where in non-polar solvents the W band can be readily resolved in the absoption spectra. This inversion results in a red shift of both fluorescence and phophorescence and an increase of the P/F ratio. When chlorine or iodine is attached at C6 only phosphorescence having a very short lifetime appears due to heavy atom enhancement of single—triplet transitions. 相似文献
77.
Hauke Harms Julien Rime Olivier Leupin Stephan J. Hug Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):217-222
A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production
above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to
0.5 μM. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at
a concentration of 0.25 g L−1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much
stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate
solution at a concentration of 10 mg L−1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading
to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because
depolymerization occurred. In the presence of 0.4 mg L−1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite
adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 μM
EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved
state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water
filtration through a mixture of sand and iron granules. 相似文献
78.
Sénéchal K Maury O Le Bozec H Ledoux I Zyss J 《Journal of the American Chemical Society》2002,124(17):4560-4561
Thermally stable dipolar and octupolar (D2d, D3) NLO-phores are readily accessible by combining one, two, or three 4,4'-bis(dialkylaminostyryl)-[2,2']-bipyridyl ligands with zinc(II) salts. The off-resonant beta0 values point out the superiority of octupoles versus dipoles in terms of nonlinearity/transparency tradeoff. The octahedral tris(bipyridyl)zinc(II) complex exhibits a very large beta0 value (241 x 10-30 esu), which is the largest ever reported for octupolar molecules. 相似文献
79.
Robert H. Higgins Quentin L. Eaton Leroy Worth Myra V. Peterson 《Journal of heterocyclic chemistry》1987,24(1):255-259
Cyclization of either the tetrahydropyranyl or trimethylsilyl ether of 1-(alkylamino)-3-chloro-2-propanols 1 followed by cleavage of the azetidinyl ether provides a general method for the preparation of 1-alkyl-3-azetidinols. Unhindered amines provide a more facile preparation of derivatives of 1 , or its ethers, than do hindered amines, while hindered derivatives of 1 undergo more facile ring closure. 相似文献
80.
An efficient preparation of N-methyl-O-tert-butylhydroxylamine hydrochloride has been settled, which allowed the synthesis of modified Weinreb amides. Nucleophilic addition of organolithium and Grignard reagents on these N-tert-butoxy-N-methylamides afforded efficiently the corresponding ketones and reduction with DIBAL furnished the corresponding aldehydes in good yields up to 97%. 相似文献