Utility of solid-phase spectrophotometry for determination of dissolved iron(II) and iron(III) using 2,3-dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline

A new simple, very sensitive, selective and accurate procedure for the determination of trace amounts of iron(II) by solid-phase spectrophotometry (SPS) has been developed. The procedure is based on fixation of iron(II) as 2,3-dichloro-6-(3-carboxy-2-hydroxy-1-naphthylazo)quinoxaline on a styrene-divinylbenzene anion-exchange resin. The absorbance of resin sorbed iron(II) complex is measured directly at 743 and 830nm. Iron(III) was determined by difference measurements after reduction of iron(III) to iron(II) with hydroxylamine hydrochloride. Calibration is linear over the range 1.0-20 microgL(-1) of Fe(II) with relative standard deviation (R.S.D.) of 1.65% (n=10.0). The detection and quantification limits for 100mL sample system are 280 and 950 ngL(-1) using 0.5 g of the exchanger. The molar absorptivity and Sandell sensitivity are also calculated and found to be 2.86 x 10(6)Lmol(-1)cm(-1) and 0.0196 ngcm(-2), respectively. The proposed procedure has been successfully applied to determine iron(II) and iron(III) in tap, mineral and well water samples.     

Utility of some pi-acceptors for spectrophotometric determination of gatifloxacin in pure form and in pharmaceutical preparations

Four simple, quick and sensitive methods are described for the spectrophotometric determination of gatifloxacin. The methods are based on the reaction of gatifloxacin as n-electron donor with 7,7,8,8-tetracyanoquinodimethane (TCNQ); 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ); chloranilic acid (CLA) and p-chloranil (CL) as pi-acceptors to give highly colored complex species. The colored products are quantitated spectrophotometrically at 460, 841, 530 and 545 nm for DDQ, TCNQ, CLA and CL, respectively. Optimization of the different experimental conditions is described. Beer's law is obeyed in the concentration ranges 5-60, 1.5-18, 30-360 and 20-240 microg ml(-1) of gatifloxacin, but for more accurate analysis, Ringbom optimum concentration range was found to be 7.5-55, 3-16, 35-350 and 25-230 microg ml(-1) of gatifloxacin for DDQ, TCNQ, CLA and CL, respectively. The limits of detection and quantification were calculated and the relative standard deviations for different concentrations of gatifloxacin using various acceptors were <1.28%. The association constants of 1 : 1 complexes and standard free energy changes using Benesi-Hildebrand plots were studied. The proposed methods were successfully applied to the determination of gatifloxacin in pharmaceutical dosage forms without interference from common additives encountered.     

Rare event probabilities in stochastic networks

The paper is dealing with estimation of rare event probabilities in stochastic networks. The well known variance reduction technique, called Importance Sampling (IS) is an effective tool for doing this. The main idea of IS is to simulate the random system under a modified set of parameters, so as to make the occurrence of the rare event more likely. The major problem of the IS technique is that the optimal modified parameters, called reference parameters to be used in IS are usually very difficult to obtain. Rubinstein (Eur J Oper Res 99:89–112, 1997) developed the Cross Entropy (CE) method for the solution of this problem of IS technique and then he and his collaborators applied this for estimation of rare event probabilities in stochastic networks with exponential distribution [see De Boer et al. (Ann Oper Res 134:19–67, 2005)]. In this paper, we test this simulation technique also for medium sized stochastic networks and compare its effectiveness to the simple crude Monte Carlo (CMC) simulation. The effectiveness of a variance reduction simulation algorithm is measured in the following way. We calculate the product of the necessary CPU time and the estimated variance of the estimation. This product is compared to the same for the simple Crude Monte Carlo simulation. This was originally used for comparison of different variance reduction techniques by Hammersley and Handscomb (Monte Carlo Methods. Methuen & Co Ltd, London, 1967). The main result of the paper is the extension of CE method for estimation of rare event probabilities in stochastic networks with beta distributions. In this case the calculation of reference parameters of the importance sampling distribution requires numerical solution of a nonlinear equation system. This is done by applying a Newton–Raphson iteration scheme. In this case the CPU time spent for calculation of the reference parameter values cannot be neglected. Numerical results will also be presented. This work was supported by grant from the Hungarian National Scientific Research Grant OTKA T047340.     

Synthesis of 1,2,4-triazolopyridazines,isoxazolofuropyridazines, and tetrazolopyridazines as antimicrobial agents

Through current and previous researches, it was found that the derivatives of pyridazine, isoxazole, tetrazole, quinazoline, hydrazinyl, and 1,2,4-triazole have many pharmacological activities. Thus, a series of novel furopyridazinones ( 7 ), isoxazolopyridazine ( 8 ), sub-benzylidene-furopyridazinones ( 9a-c ), isoxazolofuropyridazines ( 10a-c ), 3-chloro-(pyridin-4-ylmethylene)-dihydropyridazines ( 11 ), tetrazolopyridazines ( 12 ), pyridazinoquinazolinones ( 13 ), piperazinyl/morpholino-pyridazines ( 14a,b ), hydrazinyl-pyridazines ( 15 ), and 1,2,4-triazolo-pyridazines ( 16a,b ) in good yields (72%-90%) were synthesized from substituted ethyl 4-oxo-4-phenylbutanoate ( 2 ), 6-phenyl-4,5-dihydropyridazinone ( 3 ), and 6-phenyl-4-(pyridin-4-ylmethylene)-4,5-dihydropyridazinone ( 4 ) as beginning materials. All the chemical structures of the new compounds have been demonstrated by different spectroscopy analyses such as infrared, NMR, mass spectrum, and elemental analysis. Also, the activities of the newly prepared compounds were tested against many types of bacteria and fungi in vitro. Hence, 1,2,4-triazolopyridazines ( 16a,b ), isoxazolofuropyridazines ( 10a-c ), tetrazolopyridazines ( 12 ), Piperazinyl/morpholinyl-pyridazines ( 14a,b ) displayed the most efficient antimicrobial activities compared with the cefotaxime sodium and nystatin as standard drugs.     

Large scale investigation of chemical composition, structure and corrosion mechanism of bronze archeological artefacts from Mediterranean basin

A large number of Cu-based archaeological artefacts from the Mediterranean basin have been selected for investigation of their chemical composition, metallurgical features and corrosion products (i.e. the patina).The guidelines for the selection of the Cu-based artefacts have taken into account the representativeness of the Mediterranean archaeological context, the manufacturing technique, the degradation state and the expected chemical composition and structure of the objects.The results show wide variation of the chemical composition of the alloys that include all kinds of ancient Cu-based alloys such as low and high tin, and also leaded bronzes, copper and copper-iron alloys.The examination of the alloy matrix shows largely different metallurgical features thus indicating the use of different manufacturing techniques for producing the artefacts. The results of the micro-chemical investigation of the patina show the structures and the chemical composition of the stratified corrosion layers where copper or tin depletion phenomenon are commonly observed with a remarkably surface enrichment of some soil elements such as P, S, Ca, Si, Fe, Al and Cl. This information indicates the strict interaction between soil components and corrosion reactions and products. In particular, the ubiquitous and near constant presence of chlorine in the corrosion layers is observed in the patina of the archaeological Cu-based artefacts found in different contexts in Italy, Turkey, Jordan, Egypt, Spain and Tunisia. This latter occurrence is considered dangerous because it could induce a cyclic corrosion reaction of copper that could disfigure the artefact.The micro-chemical and micro-structural results also show that another source of degradation of the bronze archaeological artefacts, are their intrinsic metallurgical features whose formation is induced during the manufacturing of the objects, carried out in ancient times by repeated cycles of cold or hot mechanical work and thermal treatments. These combined treatments induce crystallisation and segregation phenomena of the impurities along the grain boundaries and could cause mechanical weakness and increase the extent of the inter-granular corrosion phenomena. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

Impact of ethylene carbonate on electrical properties of PVA/(NH4)2SO4/H2SO4 proton-conductive membrane

A new proton-conductive membrane (PCM) based on poly (vinyl alcohol) and ammonium sulfate (NH₄)₂SO₄ complexed with sulfuric acid and plasticized with ethylene carbonate (EC) at different weight percent were prepared by casting technique. The structural properties of these electrolyte films were examined by XRD studies. The XRD patterns of all the prepared polymer electrolytes reveal the amorphous nature of the films. ac conductivity and dielectric spectra of the electrolyte were studied with changing EC content from weight 0.00 to 0.75 g. A maximum conductivity of 7.3 × 10⁻⁵ S cm⁻¹ has been achieved at ambient temperature for PCM containing 0.25 g of ethylene carbonate. The electrical conductivity σ, dielectric constant ε′ and dielectric loss ε″ of PCM in frequency range (100 Hz to 100 KHz), and temperature range (300–400 K) were carried out. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions. The electrolyte with the highest electrical conductivity was used in the fabrication of a solid-state electrochemical cell with the configuration (Mg/PCM/PbO₂). Various cell parameters ldensity, and current density were determined. The fabricated cells gave capacity of 650 μAh and have an internal resistance of 11.6 kΩ.