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排序方式: 共有176条查询结果,搜索用时 171 毫秒
51.
Doble DM Melchior M O'Sullivan B Siering C Xu J Pierre VC Raymond KN 《Inorganic chemistry》2003,42(16):4930-4937
The thermodynamic stabilities of the Gd(III) complexes of five hexadentate ligands, which incorporate the 2,3-dihydroxyterephthalamide and 2,3-hydroxypyridonate chelating moieties, have been determined by potentiometric and spectrophotometric titration. The ligands were chosen to span a range of basicities while maintaining a similar tripodal structural motif, facilitating a study of the effect of ligand basicity on the thermodynamic stability of the Gd(III) complexes. The relative stability of the five complexes is found to be highly pH dependent, with the most acidic ligands forming the most stable complexes at low pH and more basic ligands forming more stable complexes at high pH. The most stable Gd(III) complex at a physiological pH of 7.4 is formed with a ligand of intermediate basicity and is of stability comparable to that of Gd(III) complexes that feature eight-coordinate amino-carboxylate ligands and are currently used as magnetic resonance imaging contrast agents in diagnostic medicine. A single-crystal X-ray structure of the intermediate compound 3-hydroxy-6-methyl-2-oxo-1,2-dihydropyridine-4-carboxylic acid ethyl ester is described: This compound crystallizes in the triclinic space group P1 with a = 7.4801(3) A, b = 8.0671(3) A, c = 8.3457(4) A, alpha = 72.242(2) degrees, beta = 80.693(2) degrees, gamma = 69.943(3) degrees, V = 449.60(3) A(3), Z = 2, and R = 0.042. 相似文献
52.
The ligand 2,6-dimethylphenylisocyanide (CNx) forms six complexes of the formula [Re(CO)3(CNx)(L)]+, where L = 1,10-phenanthroline (1), 5-chloro-1,10-phenanthroline (2), 5-nitro-1,10-phenanthroline (3), 5-methyl-1,10-phenanthroline (4), 5,6-dimethyl-1,10-phenanthroline (5), and 1,10-phenanthrolinopyrrole (6). The lowest-energy absorption peaks of the complexes red-shift in the order 1 < 2 < 3 < 4 < 5 < 6. The time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) computed singlet excited states in ethanol deviate by 1000 cm(-1) or less from the experimental UV-vis peaks. The complexes undergo reversible reductions and irreversible oxidations. The electronic energy gap increases in the order 3 < 2 < 1 < 4 < 5 < 6, which is the order of increasing electron-donating power of the phen substituents. The reduction potentials linearly correlate with the B3LYP calculated LUMO energies for 1-6. The complexes emit at room temperature and at 77 K except 3, which emits only at 77 K. The calculated (3)MLLCT energies are within 1100 cm(-1) from the experimental emission energies at 77 K. The 77 K emission curve-fitting analysis results agree with the computational assignment of the emitting state as 3MLLCT for 1-5 and 3LC for 6. The experimental 77 K emission energies and the calculated 3MLLCT state energies increase in the order 6 < 5, 3 < 2 < 4, 1. The 77 K emission lifetimes increase upon addition of substituents from 65 micros for 1 to 171 micros for 2, to 230 micros for 4 and 5, and to 322 micros for 3. The emission quantum yields at room temperature in solution are 0.77, 0.78, 0.83, 0.56, and 0.11 for complexes 1, 2, 4, 5, and 6, respectively. 相似文献
53.
Multinational supply chains operate in more than one country or tax jurisdiction and face decision problems concerned with trade flows of resources, products and services, transfer prices, and allocation of transport costs between their divisions. These decisions must consider, for the sake of optimality, corporate and governmental parameters such as the payment of dividends and royalties, ownership of and control over subsidiaries, income taxes differentials, duties and quotas, etc. In this paper, we generalize and extend the Theory of the Multinational Firm to the case of multinational supply chains. We propose a model that is more general and comprehensive than the previous ones proposed in the literature. To be more specific, our model integrates many of the previous research factors and includes new ones, such as transport costs and duty drawbacks, which are critical for supply chains that operate under international trade regulations. Under the maximization of the repatriated earnings objective, we study the optimality conditions of the corporate decision variables to derive managerial guidelines and to determine how decisions regarding trade quantities, transfer prices, and transport cost allocations affect the amount of taxes to be paid to host governments as well as the total after tax repatriated earnings of the corporation. 相似文献
54.
Y. Kudriatsev A. Villegas S. Gallardo G. Ramirez R. Asomoza V. Mishurnuy 《Applied Surface Science》2008,254(16):4961-4964
We investigated the work function (WF) change of a silicon surface being under cesium ion bombardment and simultaneous oxygen flooding with various oxygen pressures at the sample surface. It was found that WF of Cs+ ion sputtered Si decreases under oxygen flooding. This decrease provides an essential grow of secondary ion yields of some negative ions, sputtered from Si. At the same time Si− ion yield decreases approximately in two times. In the paper we have discussed possible explanations of our experimental data: we considered a surface composition change, formation of surface dipoles and work function change caused by oxygen adsorption, and their relationships between each other. 相似文献
55.
This paper presents a fully experimental study on melting, flow and weld strength development during ultrasonic welding of CF/PPS composites with integrated triangular energy directors. The main goal of this research was assessing whether the heating time to achieve maximum weld strength could be significantly reduced as compared to ultrasonic welding with flat energy directors. The main conclusion is that, in the specific case under study, the triangular energy directors did heat up, melt and collapse approximately two times faster than the time it took for the flat energy directors to melt and significantly flow. However the heating time needed to achieve maximum weld strength for the integrated triangular energy directors did not differ drastically from that for flat energy directors. This was caused by the fact that a fully welded overlap was not directly achieved right after the collapsing of the triangular energy directors. Instead a solidified resin-rich interface was created which needed to be re-melted as a whole in order to achieve a fully welded overlap and hence maximum weld strength. 相似文献
56.
57.
58.
Brendon Rhoades 《Discrete Mathematics》2010,310(4):869-876
We resolve affirmatively some conjectures of Reiner, Stanton, and White (2004) [12] regarding enumeration of transportation matrices which are invariant under certain cyclic row and column rotations. Our results are phrased in terms of the bicyclic sieving phenomenon introduced by Barcelo, Reiner, and Stanton (2009) [1]. The proofs of our results use various tools from symmetric function theory such as the Stanton-White rim hook correspondence (Stanton and White (1985) [18]) and results concerning the specialization of Hall-Littlewood polynomials due to Lascoux, Leclerc, and Thibon (1994, 1997) [5] and [6]. 相似文献
59.
Bueno C Villegas ML Bertolotti SG Previtali CM Neumann MG Encinas MV 《Photochemistry and photobiology》2002,76(4):385-390
The photophysics and photochemical behavior of the phenoxazin-3-one dyes, resazurin and resorufin, have been studied in aqueous solutions. The irradiation of resazurin in the presence of amines leads to deoxygenation of the N-oxide group, giving resorufin. This photoreaction is highly dependent on the amine structure and is efficient only in the presence of tertiary aliphatic amines. The absorption and fluorescence properties of these dyes are dependent on pH. At pH above 7.5 both dyes are in their anionic form. For resorufin this form is highly fluorescent (phiF = 0.75). At lower pH the fluorescence is strongly reduced. The N-oxide dye presents a very weak fluorescence quantum yield (0.11), which also is reduced at low pH. Flash photolysis experiments allowed characterization of the triplet state and the transients formed after irradiation of these dyes in the absence and presence of amines. The triplet quantum yields are 0.08 for resazurin and 0.04 for resorufin. The photodeoxygenation of N-oxide in the presence of amines occurs from the triplet state. 相似文献
60.
N. Carmona E. Herrero-Hernandez J. Llopis M. A. Villegas 《Journal of Sol-Gel Science and Technology》2008,47(1):31-37
Anhydrous cobalt(II) chloride has been encapsulated in several inorganic sol–gel matrices with different solvent/water ratios.
Sols were cast into cuvettes and hermetically closed. Such sol–gel materials were found to be sensitive to temperature in the 10–50 °C range showing a
change of colour. General characterisation of the sensitive materials was made by immersion into a thermostatic water bath
and recording of the corresponding visible spectra. The optical response consisted of a change in colour from light pink to
deep blue as the temperature increases. These temperature detectors behave as sensors showing good optical sensitivity in
the range mentioned above and reversibility for more than 30 cycles. The sensors response time is at about 15 min and their
lifetime is 2 months at least. These sol–gel materials have been designed to be applied for preservation and conservation
purposes. High temperatures and cyclical temperature changes can yield severe consequences for the correct preservation of
cultural heritage materials (textiles, archaeological ceramics and other remains, metallic objects and statues, stained glass
windows, etc.) both in museums and outdoors. 相似文献