Construction of a Triphenyltetrazolium Liquid Membrane Ion Selective Electrode and its Analytical Application to the Assay of Vitamin C

 The construction of a liquid triphenyltetrazolium cation (TT⁺) ion-selective electrode (ISE) based on [TT⁺]₃[P(W₃O₁₀)₄] salt dissolved in 2-nitrotoluene is described. The liquid membrane electrode exhibits a rapid and almost Nernstian response to triphenyltetrazolium cations in the concentration range from 2×10⁻⁴ to 1×10⁻² mol l⁻¹. The Nernstian slope is 56–58 mV decade⁻¹ which remains constant for at least two months. The response is virtually unaffected by pH changes in the range 3–12. Major interferents are periodate and malate. Deviation from linearity is also observed in the presence of bromide, iodide and thiocyanate, due to their precipitation with triphenyltetrazolium cations. Analytical applications such as direct potentiometry for the determination of TT⁺ in aqueous solutions and indirect potentiometry for the assay of ascorbic acid (vitamin C) in pharmaceutical preparations are described. Ascorbic acid in the range of 150–500 mg l⁻¹, under specified experimental conditions, can be determined with mean relative error of 1.9%. Received February 25, 2000. Revision April 4, 2000.     

Adaptive station grouping: a highly efficient protocol for optical LANs

A new medium access control protocol for wavelength division multiplexing (WDM) Star Networks, which is capable of achieving a high performance under bursty traffic conditions, is introduced. According to the proposed protocol, the access of stations to the wavelengths is based on their grouping. A separate set of groups is maintained for each wavelength within the traffic stream. All the groups are granted permission to transmit on the corresponding wavelength in a round-robin fashion. The main objective of the grouping algorithm is to have in each group exactly one station which is ready to transmit on the corresponding wavelength, at any given time. In this way, idle slots and collisions are minimized and a nearly optimal throughput-delay performance is achieved. The grouping of stations is dynamically modified at each time slot according to the network feedback information. Due to the dynamic nature of the grouping algorithm, the protocol is capable of being adapted to the sharp changes of the stations’ traffic. Extensive simulation results are presented which indicate that the proposed protocol achieves a significantly superior performance than other well-known medium access control protocols for WDM Star Networks.     

Lecithin organogels used as bioactive compounds carriers. A microdomain properties investigation

Organogels were obtained by adding small amounts of water to a solution of lecithin in organic solvents. Either isooctane or isopropyl palmitate and isopropyl myristate were used as the continuous organic phase of the gels. EPR spectroscopy using both DSA membrane-sensitive and lipophilic spin probes was applied to define the dynamic structure of the surfactant monolayer and the continuous oil phase of lecithin organogels. It was found that by increasing the water quantity, an increase of the polar head area per lecithin molecule was induced, and as a consequence the total interface expanded. It was found that the use of esters as organic solvents induced a decrease of the size of the dispersed structures. The interconnection of the aqueous microdomains and their dynamics were monitored by both static and time-resolved fluorescence quenching spectroscopy using Ru(bipy)32+ as fluorophore and Fe(CN)63- as quencher. It was found that the rates of inter- and/or intra-micellar exchange of water molecules were very slow because they appeared quite immobilized close to the lecithin polar heads. According to the results of the dynamic studies, appropriate organogels were formulated and used to incorporate model bioactive compounds with medicinal or cosmetic interest such as caffeine and theophylline. When these systems were tested for trans-membrane diffusion, they showed a 24 h permeation of 20% and 35%, respectively.     

Adjoint wall functions: A new concept for use in aerodynamic shape optimization

The continuous adjoint method for the computation of sensitivity derivatives in aerodynamic optimization problems of steady incompressible flows, modeled through the k–ε turbulence model with wall functions, is presented. The proposed formulation leads to the adjoint equations along with their boundary conditions by introducing the adjoint to the friction velocity. Based on the latter, an adjoint law of the wall that bridges the gap between the solid wall and the first grid node off the wall is proposed and used during the solution of the system of adjoint (to both the mean flow and turbulence) equations. Any high Reynolds turbulence model, other than the k–ε one used in this paper, could also profit from the proposed adjoint wall function technique. In the examined duct flow problems, where the total pressure loss due to viscous effects is used as objective function, emphasis is laid on the accuracy of the computed sensitivity derivatives, rather than the optimization itself. The latter might rely on any descent method, once the objective function gradient has accurately been computed.     

Correlation between structural and electrical properties of heavily lithiated boron oxide solid electrolytes

Infrared and impedance measurements have been carried out on high lithium content boron oxide solid electrolytes xLi₂O–B₂O₃, with x = 3.0–4.5, in order to establish the correlation between their structural and electrical properties. The samples are two-phase materials, in which crystalline islands are scattered throughout the vitreous background phase. The evolution of structural and electrical properties with increasing x exhibits a marked differentiation around x = 4.0, which is associated with increasing crystallization in the material.     

Exponential lower bounds for finding Brouwer fix points

The computation of Brouwer fixed points is a central tool in economic modeling. Although there have been several algorithms for computing a fixed point of a Brouwer map, starting with Scarf's algorithm of 1965, the question of worst-case complexity was not addressed. It has been conjectured that Scarf's algorithm has typical behavior that is polynomial in the dimension. Here we show that any algorithm for computing the Brouwer fixed point of a function based on function evaluations (a class that includes all known general purpose algorithms) must in the worst case perform a number of function evaluations that is exponential in both the number of digits of accuracy and the dimension. Our lower bounds are very close to the known upper bounds.     

Normal and differential demasking flow-injection manifold for the direct spectrophotometric determination of zinc(II) in biological materials and pharmaceutical formulations

A normal and a differential demasking flow-injection (FI) manifold were developed and optimized for the spectrophotometric determination of microamounts of Zn(II) in biological materials and pharmaceutical formulations. The reported method is very sensitive, rapid, simple and it is based upon the reaction of Zn(II) with 2,2'-dipyridyl-2-pyridylhydrazone (DPPH) in a strongly basic medium to form a yellow-coloured complex (lambda max = 448 nm). By using the differential demasking manifold, the tolerance of the method to many cations was enhanced by a mean factor of 25. The obtained calibration graphs were linear in the range of 0-10 mg l-1 Zn(II), at a sampling rate of 120 injections h-1 in both cases. The precisions of both manifolds were very good (RSD = 0.6 and 0.8%, respectively) and the 3 sigma detection limits were quite satisfactory (cL = 4 and 6 ng ml-1 respectively). The method has been successfully applied to the determination of Zn(II) in serum, human hair and pharmaceutical formulations with recoveries ranging between 98.0 and 101.6%. The obtained results were also in excellent agreement with flame atomic absorption spectrometry (FAAS), since the mean relative error was er = 0.9%.     

Impedance modelling of two-phase solid-state ionic conductors. Part I—theoretical model and computer simulations

An equivalent circuit model is introduced to account for the impedance properties of solid state ionic conductors, composed of two distinct phases. The model is developed on the basis of physical arguments, regarding the micrometer-scale structure of the two-phase material system and the comparison of different possible equivalent circuit representations. The final equivalent circuit reduces to two simpler circuits, suitable for fitting experimental impedance spectra. Computer simulations are provided to demonstrate the non-Arrhenius behaviour, which is observed in the temperature dependence of the ohmic elements of the equivalent circuits used for data analysis. This complex dual-slope behaviour of the Arrhenius plot is in agreement with the predictions of the model. Finally, with the aid of mathematical calculations and illustrated by computer simulations, a modified Arrhenius plot evaluation procedure was developed to derive correctly the electrical properties of the individual constituent phases from impedance measurements.     

Nickel(II) and cobalt(II) complexes of 2,4-diaminothieno[2,3-d]-pyrimidines

Summary The reactions of methyl-2-amino-4-diethylamino thieno-[2,3-d]pyrimidine 6-carboxylate, methyl-2-amino-4-ethyl-phenylamine thieno-[2,3-d]pyrimidine-6-carboxylate) and methyl-2-amino, 4-morpholino-thieno-[2,3-d]pyrimidine-6-carboxylate with Ni^II and Co^II halides produced complexes of the general formula ML₂X₂ (where L is thieno pyrimidine and X is Cl or Br). The complexes were characterized by elemental analyses, conductivity and magnetic susceptibility measurements and spectroscopy. All of the complexes were found to have pseudotetrahedral structures with the metal coordinated through the N(1) site of the thieno-[2,3-d]-pyrimidine.     

Copper(II) oxalate and oxamate complexes

Reaction of Cu^II salts with phenanthroline and oxalate (ox) or oxamate (oxm) gives [Cu(phen)(ox)(H₂O)] · H₂O or [Cu(phen)(oxm)(H₂O)] · H₂O complexes while direct treatment of Cu^II salts with oxalate or oxamate gives [NH₄]₂[Cu(ox)₂] and [Cu(oxm)₂(H₂O)₂] respectively. The X-ray structures of one example of each system, aquo-oxamato-phenanthroline-copper(II)-dihydrate and the polymeric ammonium-bis(aquo)-tetraoxalato-dicopper(II)-dihydrate, are reported.