Partial least squares-near infrared determination of pesticides in commercial formulations

A solvent free, fast and environmentally friendly near infrared-based methodology (NIR) was developed for pesticide determination in commercially available formulations. This methodology was based on the direct measurement of the diffuse reflectance spectra of solid samples and a multivariate calibration model (partial least squares, PLS) to determine the active principle concentration in commercial formulations. The PLS calibration set was built on using the spiked samples by mixing different amounts of pesticide standards and powdered samples. Buprofezin, Diuron and Daminozide were used as test analytes. Concentration of Buprofezin in the samples was calculated employing a 4-factors PLS calibration using the spectral information in the range between 2231–2430 and 1657–1784 nm. For Diuron determination a 1-factor PLS calibration model using the spectral range 1110–2497 nm, after a linear removed correction. Daminozide determination was carried out employing a 4-factors PLS model using the spectral information in the ranges 1644–1772 and 2014–2607 nm without baseline correction. The root mean square errors of prediction (RMSEP) found were 1.1, 1.7 and 0.7% (w/w) for Buprofezin, Diuron and Daminozide determination, respectively. The developed PLS-NIR procedure allows the determination of 120 samples/h, does not require any sample pre-treatment and avoids waste generation.     

Partial least squares modeling of combined infrared, 1H NMR and 13C NMR spectra to predict long residue properties of crude oils

Research has been carried out to determine the potential of partial least squares (PLS) modeling of mid-infrared (IR) spectra of crude oils combined with the corresponding ¹H and ¹³C nuclear magnetic resonance (NMR) data, to predict the long residue (LR) properties of these substances. The study elaborates further on a recently developed and patented method to predict this type of information from only IR spectra. In the present study, PLS modeling was carried out for 7 different LR properties, i.e., yield long-on-crude (YLC), density (D_LR), viscosity (V_LR), sulfur content (S), pour point (PP), asphaltenes (Asph) and carbon residue (CR). Research was based on the spectra of 48 crude oil samples of which 28 were used to build the PLS models and the remaining 20 for validation. For each property, PLS modeling was carried out on single type IR, ¹³C NMR and ¹H NMR spectra and on 3 sets of merged spectra, i.e., IR + ¹H NMR, IR + ¹³C NMR and IR + ¹H NMR + ¹³C NMR. The merged spectra were created by considering the NMR data as a scaled extension of the IR spectral region. In addition, PLS modeling of coupled spectra was performed after a Principal Component Analysis (PCA) of the IR, ¹³C NMR and ¹H NMR calibration sets. For these models, the 10 most relevant PCA scores of each set were concatenated and scaled prior to PLS modeling. The validation results of the individual IR models, expressed as root-mean-square-error-of-prediction (RMSEP) values, turned out to be slightly better than those obtained for the models using single input ¹³C NMR or ¹H NMR data. For the models based on IR spectra combined with NMR data, a significant improvement of the RMSEP values was not observed neither for the models based on merged spectra nor for those based on the PCA scores. It implies, that the commonly accepted complementary character of NMR and IR is, at least for the crude oil and bitumen samples under study, not reflected in the results of PLS modeling. Regarding these results, the absence of sample preparation and the straightforward way of data acquisition, IR spectroscopy is preferred over NMR for the prediction of LR properties of crude oils at site.     

Determination of soil properties using Fourier transform mid-infrared photoacoustic spectroscopy

Photoacoustic spectroscopy (PAS) is based on the absorption of electromagnetic radiation by analyte molecules, and this technique has emerged as a valuable tool for the study of materials like biological, chemical and geological samples. In this paper, Fourier transform mid-infrared photoacoustic spectroscopy (FTIR-PAS) was used in the prediction of soil properties. Air-dried soil samples (n = 56) from Fengqiu Ecology Experimental Station Chinese Academy of Sciences were involved in this experiment, and FTIR-PAS spectra of these soil samples were recorded. These FTIR-PAS spectra indicated abundant soil information, but overlapping of absorption made it difficult to make direct measurement of soil properties. Partial least squares (PLS) models based on soil FTIR-PAS spectra was developed to predict available nitrogen (N), phosphorus (P), potassium (K) and organic matter content of soil. 42 soil samples were firstly used in leave-one-out cross-validation, and calibration error, calibration coefficient, validation error and ratio of standard deviation to prediction error (RPD) were obtained to optimize the PLS factor number; then based on the optimized PLS models the soil properties of the other 14 soil samples were predicted. The calibration statistics showed that the PLS model was suitable to use in the prediction of available N, P, K and organic matter content of soil. This prediction technique was non-destructive, and no sample pre-treatment was needed, which made FTIR-PAS a very promising method for fast evaluation of soil properties as well as soil quality.     

Classification and determination of total protein in milk powder using near infrared reflectance spectrometry and the successive projections algorithm for variable selection

This paper proposes a methodology for the classification and determination of total protein in milk powder using near infrared reflectance spectrometry (NIRS) and variable selection. Two brands of milk powder were acquired from three Brazilian cities (Natal-RN, Salvador-BA and Rio de Janeiro-RJ). The protein content of 38 samples was determined by the Kjeldahl method and NIRS analysis. Principal component regression (PCR) and partial least squares (PLS) multivariate calibrations were used to predict the total protein. Soft independent modeling of class analogy (SIMCA) was also used for full-spectrum classification, resulting in almost 100% classification accuracy, regardless of the significance level adopted for the F-test. Using this strategy, it was feasible to classify powder milk rapidly and nondestructively without the need for various analytical determinations. Concerning the multivariate calibration models, the results show that PCR, PLS and MLR-SPA models are good for predicting total protein in powder milk; the respective root mean square errors of prediction (RMSEP) were 0.28 (PCR), 0.25 (PLS), 0.11 wt% (MLR-SPA) with an average sample protein content of 8.1 wt%. The results obtained in this investigation suggest that the proposed methodology is a promising alternative for the determination of total protein in milk powder.     

Kinetic spectrophotometric determination of hyoscine butylbromide in pure form and in pharmaceutical formulations

A simple and sensitive kinetic method was described for the determination of hyoscine butylbromide in pharmaceutical preparations. The method is based upon a kinetic investigation of the oxidation reaction of the drug with alkaline potassium permanganate at room temperature for a fixed time of 15 min. The absorbance of the colored manganate ion was measured at 610 nm. The absorbance–concentration plot was rectilinear over the range of 1.0–10 μg mL^?1 (r = 0.9999) and detection limit of 0.092 μg mL^?1. The concentration of hyoscine butylbromide was calculated using the corresponding calibration equation for the fixed-time method. The determination of hyoscine butylbromide by the fixed-concentration and rate constant methods is also feasible with the calibration equations obtained but the fixed-time method has been found to be more applicable. The different experimental parameters affecting the development and stability of the colors were carefully studied and optimized. The proposed method was applied to the determination of hyoscine butylbromide in pharmaceutical formulations. The results obtained were in good agreement with those obtained using the official British Pharmacopeial method (2004).     

Determination of the iodine value and the free fatty acid content of waste animal fat blends using FT-NIR

This study determined iodine value (IV) and free fatty acids (FFA) content of four different animal fat wastes and their blends using Fourier transform near-infrared spectroscopy (FT-NIR). Chemometric analysis by partial least squares (PLS) regression was used to correlate spectral data with IV and FFA reference values of the samples. The effects of four spectra pre-processing (first derivative (FD), second derivative (SD), multiplicative scatter correction (MSC) and vector normalization (VN)) methods were investigated to predict the reproducibility and robustness of the PLS-NIR model developed. A set of 70% of animal fat wastes and their blends were used for developing PLS calibration models for measuring IV and FFA content using the remaining 30% samples as an independent test set validation. The coefficient of determination (R²), the root mean square error estimation (RMSEE), and the residual prediction deviation (RPD) were used as indicators for the predictability of the PLS models. PLS-NIR models developed using first derivative and second derivative spectral preprocessing methods were the best for both IV and FFA content analysis (For IV, FD; R² = 0.9870, RMSEE = 1.40 gI₂/100 g, RPD = 8.76, SD; R² = 0.9892, RMSEE = 1.28 gI₂/100 g, RPD = 9.64 while For FFA, FD; R² = 0.9991, RMSEE = 0.195%, RPD = 34.00, SD; R² = 0.9993, RMSEE = 0.182%, RPD = 36.8). Overall, the results of this study demonstrate the suitability of FT-NIR spectroscopy for the quality control analysis of feedstocks for biodiesel production.     

Kinetic spectrophotometric determination of pravastatin in drug formulations via derivatization with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl)

A simple and sensitive kinetic spectrophotometric method for the quantitative analysis of pravastatin sodium (PVS) in pure and pharmaceutical formulations has been described. The method is based on the formation of colored product between PVS and 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) in acetone medium at 55 ± 2 °C. The reaction is followed spectrophotometrically by measuring the increase in absorbance at 462 nm as a function of time. The initial rate and fixed time methods were adopted for constructing the calibration curves. The linearity ranges were found to be 15.0–50.0 and 10.0–70.0 μg mL^?1 for initial rate and fixed time methods, respectively. The limits of detection for initial rate and fixed time methods are 0.029 and 0.086 μg mL^?1, respectively. Both methods have been applied successfully for the estimation of PVS in commercial dosage forms with no interference from the excipients. The results are compared with the HPLC pharmacopoeial method.     

The response characteristics of tetrazolium violet solutions to gamma irradiation

The dosimetry characteristics of various solutions of tetrazolium violet, TV, (2,5-diphenyl-3-(1-naphthyl)-2H-tetrazolium chloride) to gamma irradiation are reported. The optical absorption spectra of these solutions show peaks between 400 and 600 nm with a shoulder at around 550 nm. The dose response of the optical absorbance values of aqueous and aqueous-alcoholic solutions containing different concentrations of TV was measured in the 250 Gy up to 75 kGy dose range. The formation of formazan product was observed due to radiolytic reduction in both solutions. Its formation was found more pronounced in N₂-saturated as well as in alkaline solutions. The results indicate that the 1 mM TV solution can be used for food irradiation and medical sterilization dosimetry at gamma irradiation facilities.     

Assessment of soil quality of arable soils in Hungary using DRIFT spectroscopy and chemometrics

Nowadays, there is a great demand for precise, sensitive and adequate indicators for evaluating the quality of soils. In spite of recent developments in this field, a fast, non-destructive method for soil quality assessment has not yet been evaluated. The objective of this study was to investigate the possibility of using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy to estimate soil quality in the form of soil quality index (SQI). A set of soil samples (n = 89) was scanned and regression was carried out using a combination of DRIFT spectroscopy and partial least-squares (PLS). The reliability of the DRIFT-PLS calibration model (n = 53) was acceptable (coefficient of determination, R² = 0.49; residual prediction deviation, RPD = 1.4) for the estimating of the SQI values. The validation of the calibration model using a validation set (n = 36) of unknown samples also resulted in good acceptability with R² = 0.68 and RPD = 1.85. The DRIFT-PLS based model could provide a rapid, cheap estimate of SQI values and subsequently of soil quality by taking into account the integrated effects of the mineralogical and organic components of the soil. This approach could be useful to monitor soil quality under conditions where the analysis of a large number of soil samples is required.     

Characterization and quantification of secondary metabolite profiles in leaves of red and white clover species by NIR and ATR-IR spectroscopy

Different varieties of two clover species (Trifolium pratense L. and Trifolium repens L.), cultivated in 2008 and 2009 were analysed by near-infrared (NIR) and mid-infrared (MIR) spectroscopy for establishing a fast and reliable quantification protocol for isoflavones and phenolic acids. Based on HPLC–UV/MS reference data, good results were obtained by PLS regression for the prediction of total isoflavone (R² = 0.90) as well as for glycitin content (R² = 0.88). Because of the lower concentration of formononetin and phenolic acids, their prediction quality was generally slightly lower (R² = 0.73 and R² = 0.64, respectively) compared to those of the isoflavones. The applicability of ‘leave one out’ cross validation for such a large data set is proven by comparison to an averaged randomized test-set validation leading to similar results. Additionally, the large sample set (n = 624) was screened by hierarchical cluster analysis allowing a fast evaluation of influences resulting from different cultivation parameters on the isoflavone and phenolic acid content. Climatic changes (cultivation year, date of harvest) seem to have the most impact on the metabolic profile as indicated by higher variability in the referring spectra when both cultivation years were simultaneously regarded. This work offers a new vibrational spectroscopic approach for the qualitative and quantitative determination of isoflavone and phenolic acid profiles, directly performed in the plant material without any laborious sample preparation and time-consuming chromatography. Once validated by HPLC reference, MIR and NIR spectroscopy can be used for the reliable prediction of secondary metabolites in clover as well as for fast screening and pre-evaluation of the diversity of a large sample set, aiming to reduce analytical costs, chemical waste and expenditure of time.     

Onboard calibration igneous targets for the Mars Science Laboratory Curiosity rover and the Chemistry Camera laser induced breakdown spectroscopy instrument

Accurate characterization of the Chemistry Camera (ChemCam) laser-induced breakdown spectroscopy (LIBS) on-board composition targets is of prime importance for the ChemCam instrument. The Mars Science Laboratory (MSL) science and operations teams expect ChemCam to provide the first compositional results at remote distances (1.5–7 m) during the in situ analyses of the Martian surface starting in 2012. Thus, establishing LIBS reference spectra from appropriate calibration standards must be undertaken diligently. Considering the global mineralogy of the Martian surface, and the possible landing sites, three specific compositions of igneous targets have been determined. Picritic, noritic, and shergottic glasses have been produced, along with a Macusanite natural glass. A sample of each target will fly on the MSL Curiosity rover deck, 1.56 m from the ChemCam instrument, and duplicates are available on the ground. Duplicates are considered to be identical, as the relative standard deviation (RSD) of the composition dispersion is around 8%. Electronic microprobe and laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) analyses give evidence that the chemical composition of the four silicate targets is very homogeneous at microscopic scales larger than the instrument spot size, with RSD < 5% for concentration variations > 0.1 wt.% using electronic microprobe, and < 10% for concentration variations > 0.01 wt.% using LA ICP-MS. The LIBS campaign on the igneous targets performed under flight-like Mars conditions establishes reference spectra for the entire mission. The LIBS spectra between 240 and 900 nm are extremely rich, hundreds of lines with high signal-to-noise, and a dynamical range sufficient to identify unambiguously major, minor and trace elements. For instance, a first LIBS calibration curve has been established for strontium from [Sr] = 284 ppm to [Sr] = 1480 ppm, showing the potential for the future calibrations for other major or minor elements.     

A multimodal spectrometer for Raman scattering and near-infrared absorption measurement

Raman and infrared (IR) spectroscopy are complementary spectroscopic techniques. However, measurement of Raman and IR spectra are commonly carried out on separate instruments. A dispersive system that enables both Raman spectroscopy and NIR spectroscopy was designed, built, and tested. The prototype system measures spectral ranges of 2600–300 cm⁻¹ and 752–987 nm for Raman and NIR channels, respectively. A wavelength accuracy better than 0.6 nm and spectral resolution better than 1 nm (14.4 cm⁻¹ for Raman channel) could be achieved with our configuration. The linearity of spectral response was better than 99.8%. The intensity stability of the instrument was found to be 0.7% and 0.4% for Raman and NIR channels, respectively. The performance of the instrument was evaluated using binary aqueous solutions of ethanol and ovalbumin. It was found that ethanol concentrations (2–10%) could be predicted with a root mean squared error of prediction (RMSEP) of 0.45% using Raman peak height at 882.2 cm⁻¹. Quantification of ovalbumin concentration (8–16 g/L) in aqueous solutions and in denatured states yielded RMSEP values of 1.05 g/L and 0.74 g/L, respectively. Using concentration as external perturbation in two-dimensional correlation spectroscopy (2DCOS), heterospectral correlation analysis revealed the relationship between NIR and Raman spectra.     

Determination of NiII(3-OMe-salophene) in MCF7 and HT29 cancer cell lines using HR-CS-AAS and in serum albumin using LC with monolithic silica

A high-resolution continuum source atomic absorption spectrometric method was developed and validated for the determination of Ni^II(3-OMe-salophene) (a complex with anticancer activity in vitro) in MCF7 and HT29 cancer cell lines. The primarily most sensitive line 232.003 nm was selected for analysis. Compared to the standard nickel, the absorbance values obtained for Ni^II(3-OMe-salophene) complex was at least 93% at the upper end of linear range of the calibration curve. The use of common matrix modifiers including magnesium nitrate, palladium nitrate, ammonium hydrogen phosphate, lanthanum chloride and calcium nitrate brought no significant improvement in the GF AAS measurement. The dynamic linear working range of the calibration curve was found to be between 2.16 and 12.0 μg L^? 1 (ppb). This covers a concentration range of the complex from 0.036 μM to 0.204 μM. Typical coefficients of variation (n = 6) ranged from 0.2% to 6.7% for Ni in Ni^II(3-OMe-salophene). Detection and quantitation limits were 0.65 and 2.16 μg L^? 1 (ppb), respectively. The proposed method has been successfully applied to the analysis of Ni^II(3-OMe-salophene) complex in cell lines of breast cancer (MCF7) and colon cancer (HT29). However, being based on the determination of nickel in the salophene complex, the method was unsuitable for the quantitation of Ni^II(3-OMe-salophene) in serum albumin, which originally contains significant amount of nickel. For this purpose, a high performance liquid chromatographic method with a monolithic silica RP-18e column has been developed to quantitate the complex in serum albumin. The developed chromatographic method depends on detecting the whole complex in serum rather than the bounded nickel. A mobile phase consisting of 25 mM phosphate buffer pH 3/methanol (30:70, v/v) was pumped at a flow rate of 1 mL min^? 1. The eluted complex was monitored at a wavelength of 250 nm. The dynamic linear working range of the calibration curve for the developed LC method was found to be between 100 and 20,000 μg L^? 1 (0.23–46.18 μM). Detection and quantitation limits were 30 and 100 μg L^? 1 (ppb), respectively.     

Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE

ELYSE is a fast kinetics center created for pulse radiolysis with picosecond time-resolution. The facility is a 4–9 MeV electron accelerator using a subpicosecond laser pulse to produce an electron pulse from a Cs₂Te semiconductor photocathode and RF gun technology for the electron acceleration. The pulse duration is around 5 ps at low charge (<2 nC) and high energy (9 MeV), and is under routine conditions 10 ps at higher charge (5 nC) and >8 MeV. The dark current at the target is less than 1% of the pulse photocurrent.Time-resolved absorbance measurements in cells placed in front of the electron beam are achieved using pulsed laser diodes, or a xenon flash lamp as light sources, and photodiodes connected to a 3 GHz transient digitizer or a streak camera (250–800 nm range and 3.7 ps time resolution) as detection instruments. In addition, the synchronization between the laser beam and the electron beam is exploited to measure the absorbance by a pump-probe set-up, the pump being the electron pulse produced by the laser pulse, and the probe being part of the laser beam (120 fs–3 ps) delayed by a variable optical line.     

LIF technique offers the potential for the detection of cadmium-induced alteration in photosynthetic activities of Zea Mays L.

The laser-induced fluorescence spectra of leaves of Zea mays L. plants treated with different concentrations (0.01, 0.10 and 1.00 mM) of cadmium were recorded in region 650–800 nm using 488 nm line of Argon Ion laser as excitation source and PMT as detector. Besides this, blue-green fluorescence and Chl fluorescence were also measured using third harmonic (355 nm) of Nd:YAG laser as excitation source and 320 M monochromator with intensified charge coupled device as a detector in the region 400–800 nm. These spectra have been used to analyse the effect of several doses of cadmium on the photosynthetic activities of Z. mays L. plants. The fluorescence intensity ratios (FIR) of control as well as treated Z. mays L. were calculated by evaluating curve-fitted parameters using Gaussian spectral function. In addition, growth parameters like photosynthetic pigments content were also estimated. The chlorophyll fluorescence intensity ratio F685/F735 excited by both 488 and 355 nm lines are strongly correlated with photosynthetic pigments content (total chlorophyll and carotenoids) and their ratios. Consequently, there also existed a correlation between the blue-green fluorescence intensity ratio F470/F540 and photosynthetic pigments content.     

Densities and derived thermodynamic properties of 1-heptanol and 2-heptanol at temperatures from 313 K to 363 K and pressures up to 22 MPa

Experimental densities were determined in liquid phase for 1-heptanol and 2-heptanol at temperatures from 313 K to 363 K and pressures up to 22 MPa using a vibrating tube densimeter. Water and nitrogen were used as reference fluids for the calibration of the vibrating tube densimeter. The uncertainties of the experimental measurements in the whole range of reported data are estimated to be ±0.03 K for temperature, ±0.008 MPa for pressure, and ±0.20 kg · m^?3 for density. The experimental data are correlated using a short empirical equation of six parameters and the 11-parameter Benedict–Webb–Rubin–Starling equation of state (BWRS EoS) using a least square optimization. Statistical values to evaluate the different correlations are reported. Published density data of 1-heptanol are compared with values calculated with the 6-parameter equation using the parameters obtained in this work. The experimental data determined here are also compared with an available correlation for 1-heptanol. Densities of 2-heptanol at high pressure were not found in the literature and the data reported here represent the first set of data reported in the literature. Isothermal compressibilities and isobaric thermal expansivity are calculated using the 6-parameter equation for both alcohols within uncertainties estimated to be ±0.025 Gpa^?1 and ±4 × 10^?7 K^?1, respectively.     

Trace level quantification of 1-(3-chloropropyl)-4-(3-chlorophenyl)piperazine HCl genotoxic impurity in trazodone using LC–MS/MS

A selective and sensitive liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed for the quantitative determination of 1-(3-chloropropyl)-4-(3-chlorophenyl)piperazine HCl (CCP HCl) a process related impurity in trazodone. The method provided excellent sensitivity at a typical target analyte level of <0.1 ppm, when the API samples were prepared at 5.0 mg/mL. The CCP HCl sample was analyzed on a C18 symmetry (100 mm × 4.6 mm, 3.5 μm) column interfaced with a triple quadruple tandem mass spectrometer operated in a multiple reaction monitoring (MRM) mode. Positive electro spray ionization (ESI) was employed as the ionization source and the mobile phase used was 5.0 mM ammonium acetate–acetonitrile (30:70, v/v). The injection precision of the lowest concentration standards was excellent with %RSD-1.42%. The calibration curve showed good linearity over the concentration range of 0.03–1.5 ppm with a correlation coefficient of >0.9996. Limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.01 and 0.03 ppm, respectively. The developed method was validated as per ICH guidelines in terms of LOD, LOQ, linearity, precision, accuracy, specificity and robustness.     

Phase equilibrium data and thermodynamic modelling of the system (propane + DMF + methanol) at high pressures

Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {propane + N,N-dimethylformamide (DMF) + methanol}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour–liquid (VLE), liquid–liquid (LLE) and vapour–liquid–liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng–Robinson equation of state with the Wong–Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.     

New,simple and validated kinetics spectrophotometric method for determination of moxifloxacine in its pharmaceutical formulations

The objective of this research was to develop a kinetic spectrophotometric method for determination of moxifloxacine (MOXF) in pure form and pharmaceutical formulations. The method was based on the formation of a colored N-vinyl chlorobenzoquinone derivative of MOXF by its reaction with 2,3,5,6-tetrachloro-1,4-benzoquinone in presence of acetaldehyde.The formation of the colored product was monitored spectrophotometrically by measuring the absorbance at 652 nm. Factors affecting the reaction were studied and optimized. The stoichiometry of the reaction was determined, and the reaction pathway was postulated. The activation energy of the reaction was calculated and found to be 6.65 kJ mol^?1. Under the optimized conditions, the initial rate and fixed time (at 5 min) methods were utilized for constructing the calibration graphs. The graphs were linear in concentration ranges 5–100 and 15–150 μg ml^?1 with limit of detection of 2.0 and 5.0 μg ml^?1 for the initial rate and fixed time methods, respectively. The analytical performance for both methods was fully validated, and the results were satisfactory. No interference was observed from the excipients that are commonly present in the pharmaceutical formulations. The proposed method was successfully applied to the determination of MOXF in its pharmaceutical formulations. The label claim percentages were 101.25 ± 0.73% and 100.92 ± 0.65% for the initial rate and fixed time method, respectively. Statistical comparison of the results with those obtained by a reference spectrophotometric method showed excellent agreement between the accuracy and precision of the two methods. The proposed method has great value in its application to the analysis of MOXF in quality control laboratories.     

Multipumping flow system for improving hydride generation atomic fluorescence spectrometric determinations

The advantages of using membrane micropumps rather than peristaltic pumps to introduce both sample and reagent solutions for hydride generation atomic fluorescence spectrometry are discussed. Arsenic was used as a test analyte to check the performance of the proposed manifold. Sample and reagent consumption was reduced 8–9 fold compared with continuous mode measurements made with peristaltic pumps, with no deterioration in sensitivity. The calibration graph was linear in the 0.05 to 2.5 μg l^− 1 As range using peak area as the analytical signal and maximum gain in the detector setting. A limit of detection (3σ) of 0.02 μg l^− 1 and relative standard deviation values close to 2% for 10 independent measurements of a 1 μg l^− 1 As solution were obtained. The sampling frequency increased from 45 to 102 h^− 1 with the subsequent saving in carrier gas used and reduction in wastes generated. The instrumental modification, which could be used for other elements currently determined by atomic fluorescence spectrometry, will permit hydride generators of more reduced dimensions to be constructed.