A preconcentration and determination methodology for vanadium at trace levels in parenteral solutions was developed. Cloud point extraction was successfully employed for the preconcentration of vanadium prior to inductively coupled plasma atomic optical emission spectrometry (ICP-OES) coupled to a flow injection (FI) system. The vanadium was extracted as vanadium-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol [V-(5-Br-PADAP)] complex, at pH 3.7 mediated by micelles of the nonionic surfactant polyoxyethylene (5.0) nonylphenol (PONPE 5.0). The extracted surfactant-rich phase (100 mul) was mixed with 100 mul of ethanol and this final volume injected into ICP-OES for the vanadium determination. Under these conditions, the 50 ml sample solution preconcentration allowed raising an enrichment factor of 250-fold; however, it was possible to obtain a theoretical enrichment factor of 500-fold. The lower limit of detection (LOD) obtained under the optimal conditions was 16 ng l(-1). The precision for 10 replicate determinations at the 2.0 mug l(-1) V level was 2.3% relative standard deviation (RSD), calculated with the peak heights. The calibration graph using the preconcentration system for vanadium was linear with a correlation coefficient of 0.9996 at levels near the detection limits up to at least 50 mug l(-1). The method was successfully applied to the determination of vanadium in parenteral solution samples. 相似文献
The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1). 相似文献
In this paper, an inventory problem where the inventory cycle must be an integer multiple of a known basic period is considered. Furthermore, the demand rate in each basic period is a power time-dependent function. Shortages are allowed but, taking necessities or interests of the customers into account, only a fixed proportion of the demand during the stock-out period is satisfied with the arrival of the next replenishment. The costs related to the management of the inventory system are the ordering cost, the purchasing cost, the holding cost, the backordering cost and the lost sale cost. The problem is to determine the best inventory policy that maximizes the profit per unit time, which is the difference between the income obtained from the sales of the product and the sum of the previous costs. The modeling of the inventory problem leads to an integer nonlinear mathematical programming problem. To solve this problem, a new and efficient algorithm to calculate the optimal inventory cycle and the economic order quantity is proposed. Numerical examples are presented to illustrate how the algorithm works to determine the best inventory policies. A sensitivity analysis of the optimal policy with respect to some parameters of the inventory system is developed. Finally, conclusions and suggestions for future research lines are given.
Journal of Optimization Theory and Applications - In this paper, we propose a numerical approach for solving composite primal-dual monotone inclusions with a priori information. The underlying a... 相似文献
Journal of Optimization Theory and Applications - In this paper, we provide sufficient optimality conditions for convex optimal control problems with mixed constraints. On one hand, the data... 相似文献
The primary purpose of this paper is to study join-continuous frames. We present two representation theorems for them: one in terms of -subframes of complete Boolean algebras and the other in terms of certain Priestley spaces. This second representation is used to prove that the topological spaces whose frame of open sets is join-continuous are characterized by a condition which says that certain intersections of open sets are open. Finally, we show that Priestley's duality can be viewed as a partialization of the dual adjunction between the categories of, respectively, bitopological spaces and biframes, stated by B. Banaschewski, G. C. L. Brümmer and K. A. Hardie in [5].This work was partially supported by Centro de Matemáíica da Universidade de Coimbra. 相似文献
In this paper we derive the existence of multiple solutions for boundary value problems of the type $$u\prime \prime + f\left( {t,u} \right) = 0,u\left( 0 \right) = 0,u\left( \pi \right) = 0$$ , in terms of the behaviour of the ratiof(t,u)/u nearu=0 and near infinity. The nonlinear termf is assumed to be locally Lipschitz inu, so that the shooting method can be used. (AMS Subject Classification: 34B15). 相似文献
In this paper we consider a family of convex sets in , , , , satisfying certain axioms of affine invariance, and a Borel measure satisfying a doubling condition with respect to the family The axioms are modelled on the properties of the solutions of the real Monge-Ampère equation. The purpose of the paper is to show a variant of the Calderón-Zygmund decomposition in terms of the members of This is achieved by showing first a Besicovitch-type covering lemma for the family and then using the doubling property of the measure The decomposition is motivated by the study of the properties of the linearized Monge-Ampère equation. We show certain applications to maximal functions, and we prove a John and Nirenberg-type inequality for functions with bounded mean oscillation with respect to
We prove that if is a ``strongly quasihomogeneous" free divisor in the Stein manifold , and is its complement, then the de Rham cohomology of can be computed as the cohomology of the complex of meromorphic differential forms on with logarithmic poles along , with exterior derivative. The class of strongly quasihomogeneous free divisors, introduced here, includes free hyperplane arrangements and the discriminants of stable mappings in Mather's nice dimensions (and in particular the discriminants of Coxeter groups).