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991.
Zoran D. Matovi Vesna D. Mileti Miorad M. Vasojevi Milica Cvijovi Svetlana uri Svetlana K. Beloevi 《Monatshefte für Chemie / Chemical Monthly》2007,138(9):823-832
Summary. An iron(III) complex with the hexadentate ligand 1,3-propanediamine-N,N′-diacetate-N,N′-di-3-propionate (1,3-pddadp) was prepared, chromatographically isolated as its isomer trans(O5O6)-Cs[Fe(1,3-pddadp)] · 2H2O, and characterized. The trans(O5O6) configuration of the iron(III) compound was found to dominate and this geometry was established by means of IR spectroscopy
and Density Functional Theory (DFT). Structural data correlating the octahedral geometry of the [Fe(1,3-pddadp)]− unit and an extensive strain analysis are discussed in relation to the information obtained for similar complexes. Antibacterial
activities of the free ligand and its corresponding iron(III) complex towards common Gram-negative and Gram-positive bacteria are reported as well. 相似文献
992.
Optically pumped chemiluminescence of indole-3-acetic acid (IAA) was observed and studied. Rose Bengal (RB) was used as a photosensitizer. Long-lived chemiluminescence (CL) appeared after irradiation of the IAA/RB reaction mixture by monochromatic light at 550 nm (the maximum of RB absorption) or by visible light. The CL spectrum had a maximum at 480 nm. The kinetics of the CL decay were single exponential. Single-exponential kinetics were characterized by two experimentally measured values: initial CL intensity and exponential lifetime of the CL decay. We studied the influence of five parameters: (1) the rate of irradiation fluence, (2) the time of irradiation, (3) RIB concentration, (4) IAA concentration and (5) buffer pH on the initial CL intensity and the CL lifetime. Initial CL intensity was proportional to the rate of irradiation fluence and the concentration of RB. Saturation was observed in dependencies of initial CL intensity on the time of irradiation, the concentration of IAA and the buffer pH. The lifetime of the CL decay decreased with increasing pH and did not depend on the other four parameters. The mechanism explaining the experimental results was suggested and detailed kinetic analysis was performed to prove the proposed mechanism. Quantum yield of the CL and five rate constants that are involved in the mechanism were determined. 相似文献
993.
Katsyuba S Kovalenko V Chernova A Vandyukova E Zverev V Shagidullin R Antipin I Solovieva S Stoikov I Konovalov A 《Organic & biomolecular chemistry》2005,3(14):2558-2565
The IR and Raman spectra and conformations of calix[4]arene, thiacalix[4]arene and their p-tert-butyl derivatives have been analysed within the framework of scaled quantum mechanics (SQM). It is shown that the introduction of four p-tert-Bu groups into the calixarene molecules influences the relative energies of their conformers and the enthalpy of the cooperative intramolecular H-bonding (DeltaH(intra)) almost negligibly. DeltaH(intra), evaluated from Iogansen's rule, amounts to approximately 26-28 kcal mol(-1) for the calixarenes and approximately 20-21 kcal mol(-1) for the thiacalixarenes, which essentially exceeds the enthalpies of non-cooperative H-bonds formed by related phenols. As a result of this strong bonding, bands of stretching, bending and torsion vibrations of an eight-membered cyclic system (OH...)4 arise, e.g., two delta(OH)4 bands are observed in the IR spectra of the most highly symmetric C4 cone conformations of calix[4]arene and thiacalix[4]arene. The "duplication" of the number of OH infrared bands is a good new indicator of cooperativity of intramolecular H-bonding of the calixarenes. 相似文献
994.
Sviridenko FB Stass DV Kobzeva TV Tretyakov EV Klyatskaya SV Mshvidobadze EV Vasilevsky SF Molin YN 《Journal of the American Chemical Society》2004,126(9):2807-2819
This contribution reports the design and synthesis of a series of spin-labeled charge acceptors to produce three-spin systems of "radical ion/biradical ion" type in X-irradiated alkane liquids. This opens the way to study spin triads in experimental conditions, in which short-lived radical ion pairs are conventionally studied, thus offering optically detected techniques such as magneto-resonance OD ESR and level-crossing MARY spectroscopy. The structure of the synthesized 2-imidazoline-1-oxyl derivatives is A-Sp-R, where A is a positive or negative charge acceptor, R is a stable radical, and Sp is a hydrocarbon bridge. The set of 20+ compounds represent a convenient tool to construct experimental three-spin systems with various properties, e.g. with the "third" spin introduced into one or the other partner of the radical ion pair. The degree of exchange coupling between the two paramagnetic fragments in the biradical ion has been demonstrated to strongly depend on the type of the radical fragment R and the structure of the bridge Sp. As a result, a series of acceptors with systematically reduced exchange interaction has been synthesized, and optimal systems for the observation of low magnetic field effect have been found. In the most favorable case, an OD ESR signal from a spin triad living as short as ca. 100 ns has been registered as a single unresolved line. The exchange integral for this biradical anion (9) was estimated from OD ESR and ESR experiments to be ca. 10(3) G by the order of magnitude, which is much greater than the hyperfine couplings in the biradical ion but much smaller than the thermal energy kT. 相似文献
995.
Zayats M Pogorelova SP Kharitonov AB Lioubashevski O Katz E Willner I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6108-6114
N-(3-Aminopropyl)-N'-methyl-4,4'-bipyridinium is coupled to tiopronin-capped Au nanoparticles (diameter ca. 2 nm) to yield methyl(aminopropyl)viologen-functionalized Au nanoparticles (MPAV(2+)-Au nanoparticles). In situ electrochemical surface plasmon resonance (SPR) measurements are used to follow the electrochemical deposition of the bipyridinium radical cation modified Au nanoparticles on an Au-coated glass surface and the reoxidation and dissolution of the bipyridinium radical cation film. The MPAV(2+)-functionalized Au nanoparticles are also employed for the amplified SPR detection of NAD(+) and NADH cofactors. By SPR monitoring the partial biocatalyzed dissolution of the bipyridinium radical cation film in the presence of diaphorase (DP) NAD(+) is detected in the concentration range of 1x10(-4) M to 2x10(-3) M. Similarly, the diaphorase-mediated formation of the bipyridinium radical cation film on the Au-coated glass surface by the reduction of the MPAV(2+)-functionalized Au nanoparticles by NADH is used for the amplified SPR detection of NADH in the concentration range of 1x10(-4) M to 1x10(-3) M. 相似文献
996.
The reaction of copper with benzyl bromides in dipolar aprotic solvents has been studied. There are no linear or other simple relations between ε, 1/ε, Y, P, n, and the rate of reaction. The activity of the solvent is determined by donor number (DN) in reaction under consideration. The kinetic and thermodynamic parameters of the reaction of copper with benzyl bromide in dimethyl sulfoxide (DMSO) have been clarified. Hammett plots of log (k/k°) vs. the substituent constant σ gave good correlations (ρ = 0.18, Sρ = 0.02, r = 0.961 in dimethyl sulfoxide and ρ = 0.21, Sρ = 0.02, r = 0.947 in dimethylacetamide (DMAA)). The structure of the organic group has little effect on the rate of reaction of benzyl bromide with copper. The Hammett ρ value also depends on DN. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 496–501, 2005 相似文献
997.
Svetlana Knežević R. Milačič Marjan Veber 《Analytical and bioanalytical chemistry》1998,362(1):162-166
A procedure was developed for the preconcentration and determination of aluminium and copper in dialysis concentrates at
the ng cm–3 level. The preconcentration was achieved on microcolumns filled with Chelex-100 resin adjusted to a pH of 4.0. Five repetitive
cycles of the sample through the column ensured a sufficient contact time for quantitative retention of aluminium and copper
ions. The retained ions were eluted with HNO3 (0.5 mol dm–3). Aluminium and copper were determined in the eluate by Zeeman ETAAS using the standard addition technique. The procedure
was performed under clean room conditions (class 10,000), The reliability of the results was evaluated by recovery tests,
using dialysis concentrates spiked with aluminium and copper. The recoveries obtained ranged from 86 to 106% for aluminium
and from 92 to 97% for copper. Using the recommended procedure, the LOD of aluminium and copper in dialysis concentrates (preconcentration
factor 2) was found to be 0.5 ng cm–3 and 0.2 ng cm–3, respectively.
Received: 19 December 1997 / Revised: 10 March 1998 / Accepted: 28 March 1998 相似文献
998.
Farrell S Ronkainen-Matsuno NJ Halsall HB Heineman WR 《Analytical and bioanalytical chemistry》2004,379(3):358-367
The suitability of a microelectrode as the detector for a small-volume, bead-based enzyme-labeled immunoassay for later use in a microfluidic device was investigated. The microelectrode helps to overcome consumption of the electroactive species by the electrode (depletion) that is encountered with macroelectrodes such as the rotating disk electrode (RDE) and allows the volume of the detection cell to be reduced. Microelectrodes also allow the chemical reactions to be monitored in real time due to the electrodes close proximity to the assay site. A bead-based sandwich immunoassay for mouse IgG was developed with alkaline phosphatase (AP) as the enzyme label, p-aminophenyl phosphate (PAPP) as the enzyme substrate, and microelectrode detection. The diffusion coefficient of the product of enzymatic hydrolysis, p-aminophenol (PAP), was determined to be 7.2±0.9×10–6 cm2 s–1. The detection limits were determined for free (0.52 ng mL–1) and bead-bound AP (10 ng mL–1). The number of binding sites for AP per bead was calculated to be 9.6×104 molecules/bead, and under saturation conditions the minimum detectable number of beads was 2500. Lower detection limits could be achieved with the microelectrode than the RDE while maintaining similar reproducibility. The microelectrode also made it possible to work with lower sample volumes (down to 10 L) than with the RDE (minimum volume of 40 L). Depletion of PAP was not observed with the microelectrode. The results obtained here with a microelectrode showed great promise for later use of microelectrodes in microfluidic devices with limited sample volumes. RDE detection cannot be used in a microfluidic system due to its complex set-up that includes a motor for rotation.Abbreviations: Ab
Antibody - Ag
Antigen - AP
Alkaline phosphatase - NSA
Nonspecific adsorption - PAP
p-aminophenol - PAPP
p-aminophenyl phosphate - RDE
Rotating disk electrode - NSA
Nonspecific adsorption - PBS
Phosphate-buffered saline 相似文献
999.
The total synthesis of the natural product RK-397 is based on a new synthetic strategy for assembling polyacetate structures, by efficient cross-coupling of nucleophilic terminal alkyne modules with electrophilic epoxides bearing another alkyne at the opposite terminus. The natural product is constructed from four principal modules: a polyene precursor for carbons 3-9, and three alkyne-terminated modules for carbons 10-16, 17-22, and 23-33. Each module is prepared with control of all stereochemical elements, and the alkynyl alcohols obtained from alkyne-epoxide couplings are converted into 1,3-diols by a sequence of hydroxyl-directed hydrosilylation, C-Si bond oxidation, and stereoselective ketone reduction with induction from the beta-hydroxyl group. The highly convergent nature of our synthetic pathway and the flexibility of the modular synthesis strategy for virtually any stereoisomer can provide access to other members of the polyene-polyol macrolides, including stereoisomers of RK-397. 相似文献
1000.
Novikov Vladimir P. Tarasenko Svetlana A. Samdal Svein Vilkov Lev V. 《Structural chemistry》2000,11(2-3):111-120
Gas electron diffraction data are applied to determine the geometrical parameters of the octamethylcyclotetrasilane molecule using a dynamic model in which the ring puckering is treated as a large amplitude motion. The structural parameters and parameters of the potential function were refined, taking into account the relaxation of the molecular geometry estimated from ab initio calculations at the Hartree–Fock level of theory using a 6-311G** basis set. The potential function has been described as V() = V
0[(/
e
)2 – 1]2 with V
0 = 1.0 ± 0.5 kcal/mol and
e
= 28.3 ± 1.9°, where is the puckering angle of the ring. The geometric parameters at the minimum of V() (r
a in Å, in degrees and errors given as three times the standard deviations including a scale error) are as follows: r(Si—C)av = 1.894(3), r(Si—Si) = 2.363(3), r(C—H) = 1.104(3), CSiC = 109.5(6), SiSiSi = 88.2(2), SiCH = 111.7(6), C = 4.1, where the tilt C was estimated from ab initio constraints. The structural parameters are compared with those obtained for related compounds. 相似文献