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981.
Biing-Jiun Uang I-Pin Fu Chyuan-Der Hwang Chun-Wei Chang Chun-Tzu Yang Der-Ren Hwang 《Tetrahedron》2004,60(46):10479-10486
A highly enantioselective addition of trimethylsilylcyanide to aldehydes catalyzed by chiral titanium complexes is described. The chiral titanium complexes were prepared in situ from Ti(OiPr)4 and β-hydroxyamide ligands, that could easily be synthesized from ketopinic acid and C2 symmetrical chiral diamines in a small number of steps. 相似文献
982.
A pseudo-first-order catalytic mechanism in which both reactant and product of a redox reaction are strongly immobilized
on an electrode surface is theoretically analysed under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV).
A mathematical procedure is developed under diffusionless conditions. The relationships between the properties of the voltammetric
response and both the kinetic parameters of the redox reaction and the parameters of the excitation signal are studied. The
phenomenon of the quasi-reversible maximum is discussed. A comparative study between SWV and SCV is presented and the limitations
and advantages of both techniques, from analytical and kinetic points of view, are discussed. The theoretical predictions
are experimentally confirmed by the redox reaction of azobenzene in the presence of hydrogen peroxide as an oxidizing agent.
Electronic Publication 相似文献
983.
A new ligand, 2-carboxybenzaldehyde-(4’-hydroxy)benzoylhydrazone(H2L) and its ZnII and NiII complexes have been synthesized and characterized on the basis of elemental analyses, molar conductivities, 1H-NMR, IR spectra and thermal analyses. In addition, DNA-binding properties of these two metal complexes were investigated
using spectrometric titrations, ethidium bromide displacement experiments, and viscosity measurements. The results show that
the two complexes, especially the NiII complex, strongly bind with calf-thymus DNA, presumably via an intercalation mechanism. The intrinsic binding constants of the ZnII and NiII complexes with DNA are 2.46 × 105 and 7.94 × 105
M
−1, respectively. 相似文献
984.
The photodissociation of methyl iodide in various matrices at low temperature was studied. The observed Raman spectra excited by 514.5 nm laser radiation showed that there were two different photolytically produced iodine species isolated in the matrices after illumination by a medium pressure mercury lamp. One species which was dominant at lower iodine concentrations and exhibited a progression with an ωe of 201 cm?1, belonged to the matrix isolated iodine monomer (I2). The other species, which was dominant at higher iodine concentrations with an ωe of approximately 180 cm?1, belonged to the iodine aggregate ((I2)n). Five progressions of resonance Raman or resonance fluorescence of these two species were also observed in the other matrices. The iodine aggregate in the methyl iodide matrix at 77 K was formed in a crystalline structure, while the photolytically generated iodine aggregate from CH3I/Ar (2/3) matrix at 10 K, after illumination with a mercury lamp, was in amorphous form. The rearrangement of photolytically produced iodine aggregate in methyl iodide matrix was observed as a function of the duration of illumination. Local heating effects of the laser radiation might induce the iodine monomer to aggregate in matrices. The photodissociation mechanism of methyl iodide in matrices is also proposed. 相似文献
985.
L.V. Natarajan Fredrick M. Stein Robert E. Blankenship Raymond Chang 《Chemical physics letters》1983,95(6):525-528
A study of the linear diehroism and fluorescence polarization of diphenylpolyenes (C6H5—(CH=CH)n—C6H5) with n = 1,2,3,4,6,8 in stretched polyethylene films shows that the polyenes orient in the anisotropic matrix with their transition dipole (emission and absorption, π → π*) aligned with the direction of stretch. The maximum dichroic ratio is observed for 1,6-diphenyl-1,3,5-hexatriene (DPH), with n = 3, whereas the values are substantially lower for n < 3 or n > 3. The high orientation of DPH and poor alignment of the higher polyenes may be accounted for in terms of the growing flexibility of the polyene chains with increasing chain length. The results justify the use of DPH as a convenient fluorescence probe for biological and synthetic membranes. 相似文献
986.
Separations of small ions were carried out under nonequilibrated conditions using capillaries treated with NaOH, HCl, or tris(hydroxymethyl)aminomethane (Tris) prior to analysis. For separations of benzoic acid isomers or acids and amines under weakly acidic conditions, capillaries flushed with 0.1 M NaOH and subsequently with running buffers prior to analysis were used. Separations of six benzoic acid isomers were accomplished in 4 min in 1 mM phosphate buffers, pH 4.01, containing 2.5 mM hydroxypropyl-beta-cyclodextrin. Without additives, the separation of biological amines and acids were also achieved in 10 min at pH 4.01. Capillaries treated with 0.1 M HCl prior to analysis were tested in separations of six phenols in 5 mM Tris solutions at pH 7.0. As a result of small electrophoretic mobilities of phenols against a small electroosmotic flow, resolution was optimized. We also found that reproducibility was improved using capillaries treated with HCl. The relative standard deviations of migration mobility of phenols were less than 1%, which were smaller than those obtained using capillaries treated with 0.1 M NaOH or Tris. 相似文献
987.
Jorge Pavez Maritza Páez Armelle Ringuedé Fethi Bedioui José H. Zagal 《Journal of Solid State Electrochemistry》2005,9(1):21-29
We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O2) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O2 reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O2 to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy. 相似文献
988.
Sorption of uranium by non-living water hyacinth roots 总被引:1,自引:0,他引:1
S. Shawky M. Abdel Geleel Ashraf Aly 《Journal of Radioanalytical and Nuclear Chemistry》2005,265(1):81-84
Summary Many studies have shown that water hyacinth (Eichhornia crassipes) roots can be used to accumulate high concentrations of organic as well as inorganic pollutants. They are currently used to remediate aquatic environments and aqueous solutions. In the present study, sorption of uranium from aqueous solutions by using dried roots of water hyacinth has been investigated. The sorption of uranium was examined as a function of initial concentration, pH, weight of roots and contact time. Five different concentrations 20, 40, 60, 80, and 100 μg . ml-1 were used. Sorption proves to be very rapid and depend on pH, weight of roots and concentration of uranium. Maximum sorption capacity of water hyacinth roots was 64,000 U6+ μg/g. The sorption of uranium by water hyacinth roots follows a Langmuir isotherm. 相似文献
989.
[reaction: see text] The carbamate-protected glycals of naturally occurring 3,4-cis-3-amino-2,3,6-trideoxyhexoses (l-daunosamine, d-saccharosamine, and l-ristosamine) were prepared from noncarbohydrate starting materials. The short, high-yield syntheses are based on the chemoselective insertion of a rhodium nitrene in an allylic C-H bond rather than in a C-H bond that is alpha to an oxygen substituent. 相似文献
990.
Ikejiri M Bernardo MM Meroueh SO Brown S Chang M Fridman R Mobashery S 《The Journal of organic chemistry》2005,70(14):5709-5712
[structure: see text] Matrix metalloproteinases (MMPs), of which 26 are known, have been implicated in a number of pathological conditions, including tumor metastasis. We have previously described the first mechanism-based inhibitor for MMPs (J. Am. Chem. Soc. 2000, 122, 6799-6800), which in chemistry mediated by the active site zinc ion selectively and covalently inhibits MMP-2, -3, and -9. Computational analyses indicated that this selectivity in inhibition of MMPs could be improved by design of new variants of the inhibitor class. We report herein the syntheses of methyl 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetate (3) and 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetic acid (4), and show that compound 3 serves as a mechanism-based inhibitor exclusively for MMP-2. This molecule should prove useful in delineating the functions of MMP-2 in biological systems. 相似文献