Amber R. Solangi

Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles.

We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well.

Quantitative separation of oxytocin, norfloxacin and diclofenac sodium in milk samples using capillary electrophoresis.

A simple, sensitive and rapid method has been developed for simultaneous separation and quantification of three different drugs: oxytocin (OT), norfloxacin (NOR) and diclofenac (DIC) sodium in milk samples using capillary electrophoresis (CE) with UV detection at 220 nm. Factors affecting the separation were pH, concentration of buffer and applied voltage. Separation was obtained in less than 9 min with sodium tetraborate buffer of pH 10.0 and applied voltage 30 kV. The separation was carried out from uncoated fused silica capillary with effective length of 50 cm with 75 microm i.d. The carrier electrolyte gave reproducible separation with calibration plots linear over 0.15-4.0 microg/mL for OT, 5-1000 microg/mL for NOR and 3-125 microg/mL for DIC. The lower limits of detection (LOD) were found to be 50 ng/mL for OT, and 1 microg/mL for NOR and DIC. The method was validated for the analysis of drugs in milk samples and pharmaceutical preparations with recovery of drugs within the range 96-100% with RSD 0.9-2.8%.

Comparison of Diffusivity Data Derived from Electrochemical and NMR Investigations of the SeCN¯/(SeCN)2/(SeCN)3¯ System in Ionic Liquids

Electrochemical studies in room temperature ionic liquids are often hampered by their relatively high viscosity. However, in some circumstances, fast exchange between participating electroactive species has provided beneficial enhancement of charge transport. The iodide (I¯)/iodine (I(2))/triiodide (I(3)¯) redox system that introduces exchange via the I¯ + I(2) ⇌ I(3)¯ process is a well documented example because it is used as a redox mediator in dye-sensitized solar cells. To provide enhanced understanding of ion movement in RTIL media, a combined electrochemical and NMR study of diffusion in the {SeCN¯-(SeCN)(2)-(SeCN)(3)¯} system has been undertaken in a selection of commonly used RTILs. In this system, each of the Se, C and N nuclei is NMR active. The electrochemical behavior of the pure ionic liquid, [C(4)mim][SeCN], which is synthesized and characterized here for the first time, also has been investigated. Voltammetric studies, which yield readily interpreted diffusion-limited responses under steady-state conditions by means of a Random Assembly of Microdisks (RAM) microelectrode array, have been used to measure electrochemically based diffusion coefficients, while self-diffusion coefficients were measured by pulsed field gradient NMR methods. The diffusivity data, derived from concentration and field gradients respectively, are in good agreement. The NMR data reveal that exchange processes occur between selenocyanate species, but the voltammetric data show the rates of exchange are too slow to enhance charge transfer. Thus, a comparison of the iodide and selenocyanate systems is somewhat paradoxical in that while the latter give RTILs of low viscosity, sluggish exchange kinetics prevent any significant enhancement of charge transfer through direct electron exchange. In contrast, faster exchange between iodide and its oxidation products leads to substantial electron exchange but this effect does not compensate sufficiently for mass transport limitations imposed by the higher viscosity of iodide RTILs.

Phosphomolybdate-doped-poly(3,4-ethylenedioxythiophene) coated gold nanoparticles: synthesis, characterization and electrocatalytic reduction of bromate.

Phosphomolybdate, H3PMo12O40, (PMo12)-doped-poly(3,4-ethylenedioxythiophene) (PEDOT) coated gold nanoparticles have been synthesized in aqueous solution by reduction of AuCl4(-) using hydroxymethyl EDOT as a reducing agent in the presence of polystyrene sulfonate and PMo12. The resulting PMo12-doped-PEDOT stabilized Au nanoparticles are water soluble and have been characterized by UV-visible spectroscopy, scanning electron microscopy and electrochemistry. Glassy carbon electrodes modified with these Au nanoparticles show excellent stability and catalytic activity towards the reduction of bromate in an aqueous electrolyte solution containing 10mM H2SO4 and 0.1M Na2SO4.

Distribution and Risk Assessment of Polycyclic Aromatic Hydrocarbons in Vegetables Grown in Pakistan

Distribution and risk assessment of eight priority polycyclic aromatic hydrocarbons (PAHs) contents have been examined in different varieties of vegetables grown in Pakistan. The results showed that the total PAH contents were higher for root vegetables like potato and carrot (∼13 μg/kg) and relatively lower for turnip (10.9 μg/kg), respectively while for the fruit vegetables, all the peels were found to be more contaminated than cores. The ratio of total PAH concentrations in peels with respect to those of cores is found to be 1.45, 1.26, 1.31, 1.44, 1.40, and 1.36 for potato, turnip, carrot, eggplant, cucumber, and bitter gourd, respectively. For leafy vegetables, cabbage showed maximum PAH (11.6 μg/kg) as compared to the cores of fruit vegetables. Among individual PAH congeners, anthracene showed higher levels in all vegetables. For benzo(a)anthracene, maximum concentration (3.44±2.10 μg/kg) was encountered in turnip cores. Highest benzo(e)pyrene concentration was found in potato (3.19±1.67 μg/kg) followed by turnip (2.74±1.22 μg/kg). Benzo(b)fluoranthene and benzo(k)fluoranthene showed relatively lower levels in all samples studied. All the concentrations of PAHs are presented on a fresh weight basis. The results of human exposure of PAH by consumption of these vegetables showed that cumulative dietary exposure of Pakistani population to PAHs from vegetables ranges from 0.25 μg/p/d to 1.16 μg/p/d.

Selectivity of Brij-35 in Micellar Liquid Chromatographic Separation of Positional Isomers

Implementation of Brij-35, a nonionic surfactant, as a mobile phase for separation of positional isomers is investigated. Chromolith C-18 SpeedROD is used as a stationary phase. The effect of surfactant and organic modifier (propanol) concentration on the separation of some selected isomers is studied and evaluated in terms of linear solvation energy relationship (LSER). Shape selectivity is assessed by α value of sorbic and benzoic acid, which is found to be 1.339 by using mobile phase composed of 0.5% aqueous solutions of Brij-35 and propanol in 9 : 1. Isomers of parabens, nitroanilines, nitrophenols, and quinolinols are successfully separated using mobile phases composed of various percentages of surfactant and propanol. System constants for nonionic MLC using LSER analysis show that hydrogen bond basicity and dipolarity may be major contributors to selectivity, while excess molar refraction helps fine-tuning the separation which also imparts unique selectivity to nonionic surfactants as compared to ionic ones.

A MEKC method for naringenin from natural and biological samples

The work reported describes the development of a micellar electrokinetic chromatographic (MEKC) method for the determination of naringenin in real samples including grapefruit juice and human blood serum using a PDA detector. The effects of different CE parameters such as concentration and pH of the running buffer, voltage, injection time and concentration of sodium dodecyl sulfate (SDS) were optimized. Under the optimized conditions, naringenin could be well determined within 6 min using 40 mM borate buffer, 40 mM SDS at pH 9.0, at an applied voltage of 25 kV. For the quantitative determination of naringenin (flavonoid aglycone) in grapefruit juice, the naringin (flavonoid glycoside) was hydrolysed and the resulting aglycone was identified and quantified. The calibration curve was linear in the studied concentration range of 0.1 to 50 μg mL−1 (R2 = 0.995). The detection limit and the limit of quantification were found to be 0.05 and 0.19 μg mL−1, respectively.

Cathodic stripping voltammetry of pipemidic acid and ofloxacin in pharmaceutical dosages and human urine

Sensitive cathodic stripping voltammetric methods have been developed for two quinolone antibacterial drugs, pipemidic acid (PIP) and ofloxacin (OFL) using hanging mercury drop electrode as working electrode vs. Ag/AgCl reference electrode. The methods were developed for the determination of drugs individually as well as simultaneously. 0.1 M and 0.01 M hydrochloric acid was used as medium for PIP and OFL, respectively, 0.1 M potassium chloride was used as base electrolyte. Reduction waves were observed for PIP within −700 mV to −800 mV and for OFL within −1100 mV to −1200 mV. Linear calibration ranges for PIP and OFL were observed within 10–100 μg ml−1 with detection limits of 50 ng ml−1 and 1 μg ml−1, respectively. Relative standard deviations (RSD) for the analysis of 10 gµg ml−1 of PIP and OFL (n = 6) were 0.5% and 1.4%, respectively. The presence of glucose, lactose, sorbitol, gum arabic, starch, magnesium stearate, methylparaben and propylparaben did not affect the determinations of both PIP and OFL. The methods were used for the analysis of pharmaceutical preparations and the results indicated relative deviation of 0.5–5.5% from labeled values with RSD within 0.49–2.5%. PIP and OFL could also be determined simultaneously, and were determined from spiked human urine.

Preparation of polyaniline montmorillonite clay composites for the removal of diethyl hexyl phthalate from aqueous solutions

ABSTRACT The work presents the synthesis of polyaniline functionalized montmorillonite (PANI/MMT) clay composites and evaluation of their performance as an adsorbent for the mitigation of toxic diethyl hexyl phthalate (DEHP) from water. The formation of composite was confirmed by different analytical techniques such as FTIR, zeta potential analysis, XRD, SEM, and AFM. The adsorption capacity of PANI/MMT was superior to MMT. DEHP followed partition mechanism on PANI/MMT whereas MMT favored surface adsorption mechanism. The performance of PANI/MMT for DEHP removal was unaffected by the change in pH of solution, change in salinity, and hardness contents in aqueous system and consecutive adsorption desorption cycles compared to MMT. Furthermore, both PANI/MMT and MMT exhibited greater adsorption capacities as compared to the previously published work and showed satisfactory performance in real water samples.

Highly Selective Determination of Perchlorate by a Calix[4]arene based Polymeric Membrane Electrode

This article describes a versatile application of 25,27-bis-N-(N,N-diethyl-2-aminoethyl)carbonylmethoxy-26,28-dihydroxycalix[4]arene (4) as an ionophore for the preparation of perchlorate ion-selective electrode. The electrode exhibits a Nernstian response over the perchlorate concentration range of 1.0×10−9 – 1.0×10−1 M with a slope of 59.24 ± 0.5 mV per decade of the concentration. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot is 3.04×10−9 M. The electrode shows good selectivity toward perchlorate with respect to many common anions. The response time of the sensor was 5–10 s and it has maximum life time of 2 months in the acidic pH. The electrode was used to determine perchlorate in real water samples. The interaction of the ionophore with perchlorate ions is also demonstrated by UV–vis spectroscopy.