Synthesis, characterisation, reactivity and in vitro antiamoebic activity of hydrazone based oxovanadium(IV), oxovanadium(V) and mu-bis(oxo)bis{oxovanadium(V)} complexes

Binuclear, mu-bis(oxo)bis{oxovanadium(V)} complexes [(VOL)2(mu-O)2](2 and 7)(where HL are the hydrazones Hacpy-nah I or Hacpy-fah II; acpy = 2-acetylpyridine, nah = nicotinic acid hydrazide and fah = 2-furoic acid hydrazide) were prepared by the reaction of [VO(acac)2] and the ligands in methanol followed by aerial oxidation. The paramagnetic intermediate complexes [VO(acac)(acpy-nah)](1) and [VO(acac)(acpy-fah)](6) have also been isolated. Treatment of [VO(acac)(acpy-nah)] and [VO(acac)(acpy-fah)] with aqueous H2O2 yields the oxoperoxovanadium(V) complexes [VO(O2)(acpy-nah)](3) and [VO(O2)(acpy-fah)](8). In the presence of catechol (H2cat) or benzohydroxamic acid (H2bha), 1 and 6 give the mixed chelate complexes [VO(cat)L](HL =I: 4, HL =II: 9) or [VO(bha)L](HL =I: 5, HL =II: 10). Complexes 4, 5, 9 and 10 slowly convert to the corresponding oxo-mu-oxo species 2 and 7 in DMF solution. Ascorbic acid enhances this conversion under aerobic conditions, possibly through reduction of these complexes with concomitant removal of coordinated catecholate or benzohydroxamate. Acidification of 7 with HCl dissolved in methanol afforded a hydroxo(oxo) complex. The crystal and molecular structure of 2.1.5H2O has been determined, and the structure of 7 re-determined, by single crystal X-ray diffraction. Both of these binuclear complexes contain the uncommon asymmetrical {VO(mu-O)}2 diamond core. The in vitro tests of the antiamoebic activity of ligands I and II and their binuclear complexes 2 and 7 against the protozoan parasite Entamoeba histolytica show that the ligands have no amoebicidal activity while their vanadium complexes 2 and 7 display more effective amoebicidal activity than the most commonly used drug metronidazole (IC50 values are 1.68 and 0.45 microM, respectively vs 1.81 microM for metronidazole). Complexes 2 and 7 catalyse the oxidation of styrene and ethyl benzene effectively. Oxidation of styrene, using H2O2 as an oxidant, gives styrene epoxide, 2-phenylacetaldehyde, benzaldehyde, benzoic acid and 1-phenyl-ethane-1,2-diol, while ethyl benzene yields benzyl alcohol, benzaldehyde and 1-phenyl-ethane-1,2-diol.     

Immunogenic Potential and Therapeutic Efficacy of Multi-Epitope Encapsulated Silk Fibroin Nanoparticles against Pseudomonas aeruginosa-Mediated Urinary Tract Infections

Pseudomonas aeruginosa (P. aeruginosa) causing urinary tract infections (UTIs) are a major concern among hospital-acquired infections. The need for an effective vaccine that reduces the infections is imperative. This study aims to evaluate the efficacy of a multi-epitope vaccine encapsulated in silk fibroin nanoparticles (SFNPs) against P. aeruginosa-mediated UTIs. A multi-epitope is constructed from nine proteins of P. aeruginosa using immunoinformatic analysis, expressed, and purified in BL21 (DE3) cells. The encapsulation efficiency of the multi-epitope in SFNPs is 85% with a mean particle size of 130 nm and 24% of the encapsulated antigen is released after 35 days. The vaccine formulations adjuvanted with SFNPs or alum significantly improve systemic and mucosal humoral responses and the cytokine profile (IFN-γ, IL-4, and IL-17) in mice. Additionally, the longevity of the IgG response is maintained for at least 110 days in a steady state. In a bladder challenge, mice treated with the multi-epitope admixed with alum or encapsulated in SFNPs demonstrate significant protection of the bladder and kidneys against P. aeruginosa. This study highlights the promising therapeutic potential of a multi-epitope vaccine encapsulated in SFNPs or adjuvanted with alum against P. aeruginosa infections.     

A combined CFD modeling with population balance equation to predict pressure drop in venturi scrubbers

A venturi scrubber is one of the most important devices for air pollution control. Although there are different models for predicting the pressure drop in venturi scrubbers, most of them have some defects and cannot predict the pressure drop correctly. In this study, for the first time, an Eulerian–Eulerian computational fluid dynamics (CFD) model is combined with a population balance equation to predict the pressure drop in venturi scrubbers. This simulation takes into account a multiple size group model for droplet dispersion and droplet size distribution, which is based on a population balance equation. Flow field has been calculated by solving the time averaged continuity and Navier–Stokes equations along with the standard k–ε turbulence model. The equations included drag, turbulent dispersion, and buoyancy forces. The calculated pressure drop with and without considering the population balance equation was compared with the experimental data to evaluate the accuracy of the CFD modeling. The size distribution of droplets in the venturi scrubber was studied at different points for different liquid to gas ratios and throat gas velocities. The results show that the maximum break-up of droplets happens at the liquid injection point. Finally, the effects of nozzle diameter and nozzle arrangement on pressure drop in venturi scrubbers were investigated.     

Effect of ceria and zirconia nanoparticles on mechanical behavior of nanocomposite hybrid coatings

Epoxy-silica based hybrid nanocomposite coatings have been developed with different organicinorganic contents by sol–gel process. Various ratios of ceria and zirconia colloidal dispersions as inorganic nanoparticles are uniformly distributed in the hybrid sol. The hybrid sols are prepared by hydrolysis and condensation of 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetraethylorthosilicate (TEOS) in acidic solution using bisphenol A (BPA) and 1-methyl-imidazol (MI). A thin layer of each sol is coated on a micro-glass slide and 1050 aluminum alloy as substrates. The effect of alkoxysilane precursors (i.e. TEOS and GPTMS) and inorganic to organic molar ratio are investigated. Nanoindentation and dynamic mechanical analysis (DMA) performed to characterize the mechanical properties of the coatings in nanorange scale. It is revealed that all hybrid nanocomposite coatings had appropriate flexibility and strong interfacial interaction with the aluminum alloy substrate. It is proposed that the ceria and zirconia nanoparticles can be bonded to the surrounding of siloxane ring which can be induced high restriction in polymeric chain mobility in dynamic mechanical analysis. Nanoindentation tests showed that by increasing the inorganic phase in the nanocomposite, both elastic modulus and hardness increase, especially they are very intense in the higher levels of inorganic content.     

Spectrophotometric Determination of Metoclopramide in Pharmaceutical Preparations

A simple and rapid spectrophotometric method for the determination of metoclopramide is described. The method is based upon simple diazotization reactions with nitrite and aniline as the coupling reagent. The absorbance was measured at 410 nm. The method was optimized for acidity, the amount of reagents required, and the amount of sodium hydroxide. The range of linearity was 0.5–12.0 µg/mL. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations without any interference from common excipients.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 711–714.Original English Text Copyright © 2005 by Shah, Rasul Jan, Azam Khan, Amin.The text was submitted by the authors in English.     

Applications of Inorganic Polymeric Materials II: Polysilanes

Polysilanes which cover one of the most attractive and challenging fields, are high molecular weight polymers with inorganic elements in their backbone. These materials have silicon atoms in their main chain and exhibit unique properties resulting from the easy delocalization of sigma electrons in the Si─Si bonds. There are many technical uses as well as applications of these materials such as precursors of silicon carbide ceramics; a strengthening agent in porous ceramic; imaging materials in microlithography; photoiniting in radical reactions; and photoconducting, conducting, and semiconducting which are due to the unusual mobility of sigma electrons. In this work, the main structural features, properties, and some other important and recent applications of polysilanes are discussed.     

Synthesis and characterizations of ultra-small ZnS and Zn(1-x)Fe(x)S quantum dots in aqueous media and spectroscopic study of their interactions with bovine serum albumin

This work reports a new experimental methodology for the synthesis of ultra small zinc sulfide and iron doped zinc sulfide quantum dots in aqueous media. The nanoparticles were obtained using a simple procedure based on the precipitation of ZnS in aqueous solution in the presence of 2-mercaptoethanol as a capping agent, at room temperature. The effect of Fe(3+) ion concentration as dopant on the optical properties of ZnS was studied. The size of quantum dots was determined to be about 1nm, using scanning tunneling microscopy. The synthesized nanoparticles were characterized by X-ray diffraction, UV-Vis absorption and photoluminescence emission spectroscopies. The presence and amount of iron impurity in the structure of Zn((1-x))Fe(x)S nanocrystals were confirmed by atomic absorption spectrometry. A blue shift in band-gap of ZnS was observed upon increasing incorporation of Fe(3+) ion in the iron doped zinc sulfide quantum dots. The photoluminescence investigations showed that, in the case of iron doped ZnS nanoparticles, the emission band of pure ZnS nanoparticles at 427nm shifts to 442nm with appearance of a new sharp emission band around 532nm. The X-ray diffraction analysis indicated that the iron doped nanoparticles are crystalline, with cubic zinc blend structure, having particle diameters of 1.7±022nm. Finally, the interaction of the synthesized nanoparticles with bovine serum albumin was investigated at pH 7.2. The UV-Vis absorption and fluorescence spectroscopic methods were applied to compare the optical properties of pure and iron doped ZnS quantum dots upon interaction with BSA. It was proved that, in both cases, the fluorescence quenching of BSA by the quantum dots is mainly a result of the formation of QDs-BSA complex in solution. In the steady-state fluorescence studies, the interaction parameters including binding constants (K(a)), number of binding sites (n), quenching constants ( [Formula: see text] ), and bimolecular quenching rate constants (k(q)) were determined at three different temperatures and the results were then used to evaluate the corresponding thermodynamic parameters ΔH, ΔS and ΔG.     

Synthesis and solution properties of new metal-free and metallo-phthalocyanines containing four bis(indol-3-yl)methane groups

Metallo-phthalocyanines bearing four bis(indol-3-yl)methane groups were successfully prepared by reaction of the corresponding phthalonitriles with anhydrous metal salts [Zn(CH₃COO)₂, NiCl₂ and CoCl₂] in the presence of a catalytic amount of DBU in 2-(dimethylamino)ethanol. The metal-free phthalocyanine was obtained by treating a mixture of the phthalonitrile derivative in similar conditions but in the absence of a metal salt. All of these phthalocyanines are soluble in DMSO, DMF, and pyridine. The products were characterized by IR, NMR, and UV-vis spectroscopy, MALDI-TOF-MS, and thermogravimetric analysis. The aggregation properties of the phthalocyanines were investigated at different concentrations in DMSO. All the phthalocyanines showed monomeric behavior in solution.     

A New Aluminium Hydroxide Coating on Fused Silica Fiber for the Determination of 1,4-Dioxane in Surfactants and Detergents Using HS-SPME-GC

This paper presents a simple and convenient analytical method for determination of 1,4-dioxane in surfactants and detergents by using a novel SPME fiber. For the preparation of the fiber, the surface of a fused silica capillary tubing was modified by means of aluminium tri-tert-butoxide in a straightforward grafting process. The surface of our proposed fiber provides a Lewis acid–base interaction with analyte functional groups. The main factors affecting the extraction were optimized by using a central composite design method, which leads to the following optimum conditions: extraction temperature of 34?°C, extraction time of 4?min, equilibrium time of 13?min, and salt content of 25% (w/v). The optimum conditions showed a linear range from 0.005 to 60?μg?g^?1. LOD and LOQ of the proposed method were estimated to be 0.0015 and 0.005?μg?g^?1, respectively. This method was also applied for the analysis of some real samples including ethoxylated fatty alcohol, sodium lauryl ether sulfate, dish-washing agents, and shampoos by using the standard addition method.