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排序方式: 共有197条查询结果,搜索用时 15 毫秒
11.
Israel Zilbermann Avraham Meshulam Haim Cohen Dan Meyerstein 《Supramolecular chemistry》2013,25(2):325-332
Abstract The mechanisms and kinetics of oxidation of ascorbate, AH?, by Ni(III)Li aq and by LiNi(III) (HPO4)2 ? complexes (L1 = meso-(5,12)-7,7,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; L2 = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) in neutral aqueous solutions have been investigated. The oxidation of ascorbate by the LiNi(III) (HPO4)2 ? and Ni(III)L1 aq proceeds via two consecutive reactions well separated in time. The products of the first reaction are the A.? radical anion and the corresponding Ni(II) complex. The oxidations by the LiNi(III)(HPO4)2 ? complexes proceed via the outer sphere mechanism, whereas the detailed mechanism of reaction of Ni(III)L1 aq cannot be determined. The rate of reaction decreases with the increase in the concentration of phosphate, thus indicating that LiNi(III)(HPO4)(H2O)+ and LiNi(III)OH2+ are stronger oxidizing agents than LiNi(III)(HPO4)? 2. The oxidation of ascorbate by Ni(III)L2 aq proceeds via three consecutive reactions which are well separated in time. Thus the results clearly point out that this process occurs via the inner sphere mechanism. The first transient observed is tentatively identified as L2(H2O)Ni(II)(A.?)2+, i.e., an unexpected complex of the ascorbate anion radical. Also in this process the last transient observed is the A.? anion radical. The stabilization of the ascorbyl radical in a transient complex might be of biological significance. 相似文献
12.
We address the problem of scheduling in programs involving the production of multiple units of the same product. Our study was motivated by a construction program for fast naval patrol boats. Other applications of this problem include procurement of multiple copies of aircraft, spacecraft, and weapon systems. In this problem we must decide how many units of the product to assign to each of a number of available crews (individuals, teams, subcontractors, etc.). These types of problems are characterized by two potentially conflicting considerations: 1) the need to complete each unit by its contractual due date, and 2) learning effects. Because of the first consideration, there is a tendency to use multiple crews for simultaneous production, so that meeting due dates is assured. However, the second consideration encourages assigning many units to a single crew so that learning effects are maximized. We study this scheduling problem with two different penalty cost structures and develop models for both versions. The models trade-off the penalty associated with late deliveries and the savings due to learning (and possibly incentive payments for early completion). We discuss different heuristic algorithms — simulated annealing, a genetic algorithm, and a pair-wise swap heuristic — as well as an exhaustive search to determine a baseline for comparisons. Our computational results show that the pair-wise swap algorithm is the most efficient solution procedure for these models. 相似文献
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Suzuki Y Sarachik MP Chudnovsky EM McHugh S Gonzalez-Rubio R Avraham N Myasoedov Y Zeldov E Shtrikman H Chakov NE Christou G 《Physical review letters》2005,95(14):147201
Local time-resolved measurements of fast reversal of the magnetization of single crystals of Mn12-acetate indicate that the magnetization avalanche spreads as a narrow interface that propagates through the crystal at a constant velocity that is roughly 2 orders of magnitude smaller than the speed of sound. We argue that this phenomenon is closely analogous to the propagation of a flame front (deflagration) through a flammable chemical substance. 相似文献
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Raz Gvishi Avraham Englander Gadi Peleg 《Journal of Sol-Gel Science and Technology》2008,48(1-2):18-23
We present a feasibility study to apply terahertz (THz) spectroscopy and THz imaging as non-destructive diagnostic tools for sol–gel analysis, manufacturing and quality control. By performing THz spectroscopy on liquid and solid samples we were able to follow several key parameters during the sol–gel formation process and of the final product. Sol–gel transformations were monitored by THz absorption, whereas density changes have been observed through changes in refractive indices. Time domain spectroscopy (TDS), both in transmission and reflection geometries, was used to monitor the properties of fast sol–gel resins. THz imaging of gold coated, thin-film sol–gel enables us to determine inhomogeneities and defects in their internal structure. We demonstrated that THz spectroscopy can be implemented as an online analytical tool for multi-parameter evaluation of the sol–gel process during fabrication, and of the final product. 相似文献
17.
Bhaskar Godugu Pedatsur Neta Yamil Simón-Manso Stephen E. Stein 《Journal of the American Society for Mass Spectrometry》2010,21(7):1169-1176
A prominent dissociation path for electrospray generated tryptic peptide ions is the dissociation of the peptide bond linking
the second and third residues from the ammo-terminus. The formation of the resulting b2 and y
n−2 fragments has been rationalized by specific facile mechanisms. An examination of spectral libraries shows that this path
predominates in diprotonated peptides composed of 12 or fewer residues, with the notable exception of peptides containing
glutamine or glutamic acid at the N-terminus. To elucidate the mechanism by which these amino acids affect peptide fragmentation,
we synthesized peptides of varying size and composition and examined their MS/MS spectra as a function of collision voltage
in a triple quadrupole mass spectrometer. Loss of water from N-terminal glutamic acid and glutamine is observed at a lower
voltage than any other fragmentation, leading to cyclization of the terminal residue. This cyclization results in the conversion
of the terminal amine group to an imide, which has a lower proton affinity. As a result, the second proton is not localized
at the N-terminus but is readily transferred to other sites, leading to fragmentation near the center of the peptide. Further
confirmation was obtained by examining peptides with N-terminal pyroglutamic acid and N-acetyl peptides. Peptides with N-terminal
proline maintain the trend of forming b2 and y
n−2 because their ring contains an imine rather than imide and has sufficient proton affinity to retain the proton at the N-terminus. 相似文献
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The broad-band normal incidence UVB beam radiation has been measured at Neve Zohar, Dead Sea basin, using a prototype tracking instrument composed of a Model 501A UV-Biometer mounted on an Eppley Solar Tracker Model St-1. The diffuse and beam fraction of the solar global UVB radiation have been determined using the concurrently measured solar global UVB radiation. The diffuse fraction was observed to exceed 80% throughout the year. The application of the results of these measurements to the possible revision of the photoclimatherapy protocol for psoriasis patients at the Dead Sea medical spas is now under investigation. The suggested revision would enable the sun-exposure treatment protocol to take advantage of the very high diffuse fraction by allowing the patient to receive the daily dose of UVB radiation without direct exposure to the sun, viz. receive the diffuse UVB radiation under a sunshade. This would require an increase in sun-exposure time intervals, as the UVB radiation intensity beneath a sunshade is less than that on an exposed surface. 相似文献
20.