Flow-injection chemiluminescence determination of gentamicin: optimization by central composite design.

A simple and sensitive flow-injection chemiluminescence (CL) method has been developed for the determination of gentamicin sulfate. The method is based on the inhibitory effect of gentamicin on the CL emission accompanying oxidation of luminol by H2 O2 in an alkaline medium in the presence of Cu(II) as a catalyst. Inhibition was caused by the formation of a strong complex between analyte and the catalyst. Experimental variables, including the concentrations of luminol (µmol/L), H2 O2 (mol/L), Cu(II) (mol/L) and NaOH (mol/L), were optimized using a central composite design. Under optimum conditions, the plot of CL intensity versus gentamicin concentration was found to have two linear ranges. One range was at low concentrations from 1.0 to 10.0 mg/L and the other was from 10.0 to 30.0 mg/L. Precision was calculated by analyzing samples containing 5.0 mg/L gentamicin (n = 11) and the relative standard deviation (RSD) was 1.7%. Also, a high injection throughput of 120 samples/h was achieved. This method was successfully applied to the determination of gentamicin sulfate in pharmaceutical formulations and water samples.

CuO nanosheets-enhanced flow-injection chemiluminescence system for determination of vancomycin in water, pharmaceutical and human serum.

A novel, rapid and sensitive CuO nanosheets (NSs) amplified flow-injection chemiluminescence (CL) system, luminol-H2O2-CuO nanosheets, was developed for determination of the vancomycin hydrochloride for the first time. It was found that vancomycin could efficiently inhibit the CL intensity of luminol-H2O2-CuO nanosheets system in alkaline medium. Under the optimum conditions, the inhibited CL intensity was linearly proportional to the concentration of vancomycin over the ranges of 0.5-18.0 and 18.0-40.0 mg L(-1), with a detection limit (3σ) of 0.1 mg L(-1). The precision was calculated by analyzing samples containing 5.0 mg L(-1) vancomycin (n=11) and the relative standard deviation (RSD) was 2.8%. Also, a high injection throughput of 120 sample h(-1) was obtained. The CuO nanosheets were synthesized by a sonochemical method. Also, X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were employed to characterize the CuO nanosheets. The method was successfully employed to determine vancomycin hydrochloride in environmental water samples, pharmaceutical formulation and spiked human serum.

Simultaneous monitoring of photocatalysis of three pharmaceuticals by immobilized TiO2 nanoparticles: chemometric assessment, intermediates identification and ecotoxicological evaluation.

In this study, the photocatalytic degradation of a mixture of three pharmaceuticals, Metronidazole (MET), Atenolol (ATL) and Chlorpromazine (CPR), was quantified simultaneously during the UV/TiO2 process. The investigated TiO2 was Millennium PC-500 immobilized on ceramic plates by sol-gel based method. The partial least squares modeling was successfully applied for the multivariate calibration of the spectrophotometric data. The central composite design was applied to model and optimize the UV/TiO2 process. Predicted values of removal efficiency were found to be in good agreement with experimental values for MET, ATL and CPR (R(2)=0.947 and Adj-R(2)=0.906, R(2)=0.977 and Adj-R(2)=0.960 and R(2)=0.982 and Adj-R(2)=0.969, respectively). The optimum initial concentration of pharmaceuticals, reaction time and UV light intensity was found to be 10 mg L(-1), 150 min and 38.45 W m(-2), respectively. The main degradation intermediates of pharmaceuticals produced in this process were identified by GC-MS technique. The chronic ecotoxicity of pharmaceuticals was evaluated using aquatic species Spirodela polyrrhiza prior to and after photocatalysis. The TOC results (90% removal after 16 h) and ecotoxicological experiments revealed that the photocatalysis process could effectively mineralize and reduce the ecotoxicity of the pharmaceuticals from their aqueous solutions.

A novel selenium nanoparticles-enhanced chemiluminescence system for determination of dinitrobutylphenol.

A novel selenium nanoparticles (Se NPs)-amplified chemiluminescence (CL) reaction, Se NPs-potassium permanganate-dinitrobutylphenol (DNBP), for the determination of DNBP at gram per milliliter level is described. In the present study, it was found that direct reaction of DNBP with potassium permanganate (KMnO4) in the acidic mediums elicited light emission, which was greatly enhanced by selenium nanoparticles. Under optimum conditions, the CL intensity is linearly related to the concentration of DNBP in the range of 1.0×10(-7)-8.0×10(-5)g mL(-1) with a detection limit (3σ) of 3.1×10(-8) g mL(-1). The relative standard deviation for 11 determinations of 2.5×10(-5) gm L(-1) DNBP is 2.07%. The Se NPs were prepared by the chemical hydrothermal method. It was found that catalytic properties of Se NPs were higher than those of microparticles (MPs). In addition, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the Se NPs. Appropriate sensitivity, selectivity and precision were among notable features of the proposed method. The method was successfully applied to the determination of DNBP in the water samples of different origins. Moreover, the possible mechanism for the new CL reaction was also discussed.

Optimization of photocatalytic treatment of dye solution on supported TiO2 nanoparticles by central composite design: intermediates identification.

Optimization of photocatalytic degradation of C.I. Basic Blue 3 (BB3) under UV light irradiation using TiO(2) nanoparticles in a rectangular photoreactor was studied. The investigated TiO(2) was Millennium PC-500 (crystallites mean size 5-10 nm) immobilized on non-woven paper. Central composite design was used for optimization of UV/TiO(2) process. Predicted values of decolorization efficiency were found to be in good agreement with experimental values (R(2)=0.9686 and Adj-R(2)=0.9411). Optimization results showed that maximum decolorization efficiency was achieved at the optimum conditions: initial dye concentration 10mg/L, UV light intensity 47.2 W/m(2), flow rate 100 mL/min and reaction time 120 min. Photocatalytic mineralization of BB3 was monitored by total organic carbon (TOC) decrease, and changes in UV-vis and FT-IR spectra. The photodegradation compounds were analyzed by UV-vis, FT-IR and GC-mass techniques. The degradation pathway of BB3 was proposed based on the identified compounds.