Properties of a furan ring-opening reaction in aqueous micellar solutions for selective sensing of mesalazine.

A novel and efficient non-azo formation based method was developed for trace sensing of mesalazine (MES), a pharmaceutical aromatic amine. MES was simply coupled with a Meldrum's activated furan (MAF) reagent via a furan ring opening reaction to form a colored product. The intense purple colored solution was detected at 575 nm. The reaction of MES with MAF was monitored by employing 1H NMR spectroscopy and mass spectrometry. In addition, density functional theory (DFT) was applied to optimize the structure of the colored product and its λmax (the wavelength of maximum absorbance) in dimethyl sulfoxide and water. The colored product was considered in three possible structures, and the most possible structures in dimethyl sulfoxide and in water were identified by employing the DFT calculations. Both of the most possible structures indicated only a local excitation in their λmax and no charge transfer was observed. However, one of the structures in dimethyl sulfoxide presented charge transfer properties occurring through NCCC moiety. A univariate optimization method was also used to attain the optimum condition for analysis. In addition, the dependence of the analytical response on the three main affecting parameters (reaction time (X1), Triton X-100 concentration (X2) and MAF concentration (X3)) was identified by employing a central composite design (CCD) approach. The CCD study showed that the analytical response depends complexly on the parameters. Beer's law was obeyed within the range of 0.06-9.30 µg mL-1 of MES (155 fold linearity) at 575 nm, under the optimum condition introduced by the CCD approach. Also, the limit of detection was obtained 0.04 µg mL-1 of MES. The method showed precision (as relative standard deviation) and accuracy (as recovery) within the ranges of 0.6-3.2 % and 96.3-100.8%, respectively. Various organic and inorganic species, amino-pharmaceuticals, and amino acids were tested to evaluate the selectivity of the method. The selectivity of the analytical method was satisfactory. The method was successfully applied for detection of MES in various water matrices and pharmaceutical tablets.

Screen printed carbon electrode modified with a copper@porous silicon nanocomposite for voltammetric sensing of clonazepam.

The work describes an electrochemical sensor for the determination of the tranquilizer clonazepam (CZP) in serum and pharmaceutical preparations. A screen printed carbon electrode (SPCE) was modified with copper nanoparticles anchored on porous silicon (PSi). The surface of the SPCEs modified with the Cu/PSi nanostructure was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoemission spectroscopy, energy dispersive X-ray spectroscopy and field-emission scanning electron microscopy. Cyclic and differential pulse voltammetric methods were used for the electrochemical studies and electrochemical detection, respectively. Several parameters controlling the performance of the modified SPCE were optimized. The peak current values (at a potential of -0.52 V) were used to construct calibration plots. Under the optimum conditions, the calibration plot is linear in the 0.05-7.6 µM CZP concentration range, and the detection limit is 15 nM. The sensor is reproducible, repeatable, highly selective and sensitive. It was successfully applied to the determination of CPZ in spiked serum and in drugs. Graphical abstract Scheme of electrochemical reduction of clonazepam on the designed copper@porous silicon modified screen printed carbon electrode (CuNPs/PSi/SPCE). This electrode was employed for the determination of clonazepam in tablets and human blood plasma using differential pulse voltammetry.

Extraction and Trace Analysis of Trihalomethanes in Water Samples Using Zein@Fe3O4 Nanocomposite.

This study presents a simple dispersive solid phase extraction (DSPE) technique combined with headspace thermal desorption (HSTD) for extraction and determination of the most significant trihalomethanes (THMs), bromodichloromethane, bromoform, chloroform and dibromochloromethane, in water samples by using Zein@Fe3O4 nanocomposite coupled with gas chromatography/micro electron capture detection (GC-MECD). Various parameters affecting the DSPE-HSTD performance were investigated and optimized. The obtained results revealed that under optimum conditions, LOD and LOQ values were in the range of 0.1-0.36, 0.3-1.08 µg L-1, respectively. The intra-day and inter-day precisions of the method at a concentration of 10 µg L-1 for each analyte (n = 5) were obtained in the range of 5.69-6.70% and 6.12-7.34%, respectively. Finally, the proposed method was successfully applied for extraction and determination of four THMs in drinking water samples.

Palladium nanoparticles in electrochemical sensing of trace terazosin in human serum and pharmaceutical preparations.

In this approach, palladium nanoparticle film was simply fabricated on the surface of carbon paste electrode by electrochemical deposition method. The film was characterized using scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The prepared electrode exhibited an excellent electrocatalytic activity toward detection of trace amounts of terazosin, which is an antihypertensive drug. Under the optimum experimental conditions, a linear range of 1.0×10-8-1.0×10-3molL-1 with a detection limit of 1.9×10-9molL-1 was obtained for determination of terazosin using differential pulse voltammetry as a sensitive method. The efficiency of palladium nanoparticle film on the surface of carbon paste electrode successfully proved for determination of terazosin in pharmaceutical sample and human serum sample with promising recovery results. The effect of some foreign species has been studied.

Preparation of magnetite/poly(styrene-divinylbenzene) nanoparticles for selective enrichment-determination of fenitrothion in environmental and biological samples.

In the present study, a cross-linked nano-sized spherical magnetic poly(styrene-divinylbenzene) is synthesized and used as an adsorbent for enrichment-determination of fenitrothion. A miniemulsion polymerization procedure was used to prepare the adsorbent. The magnetic adsorbent was characterized by FT-IR, SEM and TEM. The prepared magnetic adsorbent nanoparticles were mixed with magnetite nanoparticles for faster and more efficient magnetic precipitation. The reduced fenitrothion was coupled with 3-methyl-2-benzothiazolinone hydrazone and then the blue colored complex was extracted. The blue derivative of fenitrothion was eluted by a 1 mL aliquot of 1-propanol prior to spectrophotometry at 571 nm. Beer's law was obeyed in the range of 2-230 ng mL(-1) of fenitrothion with relative standard deviation and recovery in the ranges of 0.9-5.1% and 97.2-100.0%, respectively. Selectivity of the method was evaluated, and the method was successfully applied to the determination of fenitrothion in various water, soil, urine and human plasma samples.

Dodecylbenzene sulfonate-coated magnetite nanoparticles as a new adsorbent for solid phase extraction-spectrophotometric determination of ultra trace amounts of ammonium in water samples.

A new method was proposed for the determination of ammonium based on the preconcentration with dodecylbenzene sulfonate modified magnetite nanoparticles. Ammonium was oxidized to nitrite by hypobromite and then the nitrite produced was determined spectrophotometrically, using sulfabenzamide and N-(1-naphthyl) ethylenediamine after solid phase extraction. The azo dye produced was desorbed by an appropriate small volume of sodium hydroxide prior to the absorbance measurement. The linear calibration graphs were obtained in the concentration range of 0.03-6.00 ng mL(-1) ammonium. The relative standard deviation and recovery percents were 1.0 and 99.0, respectively, for 1.0 ng mL(-1) ammonium, and the limit of detection was 3.2 ng L(-1) ammonium. The interfering effects of a large number of diverse ions on the determination of ammonium were studied. The method was applied to the determination of ammonium in various types of water resources. The results revealed a high efficiency for the recommended ammonium determination method.

H-point standard addition method--first derivative spectrophotometry for simultaneous determination of palladium and cobalt.

H-point standard addition method (HPSAM) has been applied for simultaneous determination of palladium and cobalt in trace levels, using disodium 1-nitroso-2-naphthol-3, 6-disulphonate (nitroso-R salt) as a selective chromogenic reagent. Palladium and cobalt in the neutral pHs form red color complexes with nitroso-R in aqueous solutions and making spectrophotometric monitoring possible. Simultaneous determination of palladium and cobalt were performed by HPSAM--first derivative spectrophotometry. First derivative signals at the two pairs of wavelengths, 523 and 589 nm or 513 and 554 nm were monitored with the addition of standard solutions of palladium or cobalt, respectively. The method is able to accurately determine palladium/cobalt ratio 1:10 to 15:1 (wt/wt). Accuracy and reproducibility of the determination method on the various amounts of palladium and cobalt known were evaluated in their binary mixtures. To investigate selectivity of the method and to ensure that no serious interferences were observed the effects of diverse ions on the determination of palladium and cobalt were also studied. The recommended procedure was successfully applied to real and synthetic cobalt or palladium alloys, B-complex ampoules, a palladium-charcoal mixture and real water matrices.

Zero-crossing second derivative spectrophotometry for simultaneous determination of palladium and nickel using 1-(2-pyridylazo)-2-naphthol in mixed micellar solutions.

1-(2-Pyridylazo)-2-naphthol (PAN) has been used for the simultaneous determination of nickel and palladium at trace levels. PAN complexes of nickel and palladium in the pH 1.98 form red and green colored complexes, respectively, which are soluble in aqueous 4:1 Triton X-100 to sodium dodecylsulfate (SDS) micellar media with total detergent concentration of 3.2%. Under optimum conditions, calibration graphs for the simultaneous determination by second derivative spectrophotometry were obtained. Zero crossing second derivative spectrophotometry at 668 and 572 nm, respectively for palladium and nickel was used for the simultaneous determination. The method is able to determine palladium to nickel ratio 70:1 to 1:6 (Wt/Wt), accurately. Accuracy and reproducibility of the determination method on the known various amounts of palladium and nickel in their binary mixtures were tested. Effects of diverse ions on the determination of palladium and nickel to investigate selectivity of the method also were studied.

Spectrophotometric and AAS determination of trace amounts of cobalt after preconcentration by using alpha-benzilmonoxime-microcrystalline naphthalene.

The formed cobalt-a-benzilmonoxime complex was adsorbed onto microcrystalline naphthalene. Then it was determined by zero and first derivative spectrophotometry and by atomic absorption spectrophotometry (AAS) after dissolving into chloroform and methylisobutylketone (MIBK), respectively. Under optimum conditions, cobalt in the range of 1.0 - 20.0, 0.4 - 30.0 and 2.5 - 50.0 microg could be determined by spectrophotometry, first derivative spectrophotometry and AAS method, respectively. By the method, a preconcentration factor equal to approximately 30 for cobalt was obtained. The effect of diverse ions on the determination of 5.0 microg cobalt was also studied. The method was successfully applied to some pharmaceuticals and synthetic alloy samples.

H-point standard addition method for the selective simultaneous determination of nickel and copper using 1-(2-pyridylazo)-2-naphthol in Tween 80 micellar media.

The H-point standard addition method (HPSAM) has been applied for the simultaneous determination of nickel and copper in trace levels, using 1-(2-pyridylazo)-2-naphthol (PAN) as a chromogenic reagent in aqueous Tween 80 micellar media. Under the optimum condition, the simultaneous determinations of nickel and copper by HPSAM were performed. The absorbances at one pair of wavelengths, 548 and 579 nm, were monitored with the addition of standard solutions of copper. The method is able to accurately determine copper-to-nickel ratios of 15:1 to 1:10 (Wt/Wt). The effects of diverse ions on the determination of nickel and copper to investigate the selectivity of the method were also studied. The recommended procedure was successfully applied to some water and alloy samples.

Second and first-derivative spectrophotometry for efficient simultaneous and individual determination of palladium and cobalt using 1-(2-pyridylazo)-2-naphthol in sodium dodecylsulfate micellar media.

1-(2-Pyridylazo)-2-naphthol (PAN) has been used for the simultaneous and individual determination of palladium and cobalt at trace levels. PAN complexes of palladium and cobalt at neutral pH form green-color neutral complexes, which are soluble in aqueous SDS micellar media. Under optimum conditions, calibration graphs for individual determinations by zero and first-derivative spectrophotometry, and also for simultaneous determinations by second-derivative spectrophotometry were obtained. A zero-crossing method using second-derivative spectrophotometry at 628 or 578 and 614 nm, respectively, for cobalt and palladium was used for simultaneous determinations. The method is able to determine the cobalt-to-palladium ratio, 5:1 to 1:10 (Wt/Wt), accurately. The accuracy and reproducibility of the determination method for various known amounts of cobalt and palladium in their binary mixtures were tested. The effects of diverse ions on the determination of cobalt and palladium to investigate the selectivity of the method were also studied. The recommended procedures were applied to a synthetic binary alloy, cobalt in vitamin B12 and B-complex ampoules, a Co2O3-Co3O4 laboratorial chemical mixture, some synthetic cobalt-alloy samples, a Pd-charcoal catalyst, and some synthetic palladium alloys.

A facile spectrophotometric method for cobalt determination using alpha-benzilmonoxime in sodium dodecylsulfate micellar solutions.

Alpha-benzilmonoxime in sodium dodecylsulfate micellar media has been used for the spectrophotometric determination of cobalt at pH 9.0. The linear range of calibration is 0.05-1.50 microg cm(-3) of cobalt at 380 nm with molar absorptivity of 3.72 x 10(4) dm3 mol(-1) cm(-1), which is about 1.5-times greater than that of the alpha-benzilmonoxime extraction based method. The relative standard deviations, recoveries, detection limit and effects of diverse ions on the determination of cobalt were studied. These analytical results were satisfactory. The method was successfully applied to the determination of cobalt in the various samples.