A simple, rapid and sensitive method for the determination of atorvastatin calcium in pharmaceutical preparations using two modified carbon paste electrodes was developed. One electrode (sensor A) is based on ion-pair of atorvastatin with 5,6-diaminouracil hydrochloride (ATS-DAUH) and the other (sensor B) is based on atorvastatin with picric acid (ATS-PC). Among three different solvent mediators tested, dioctylphthalate (DOPH) exhibited a proper behavior including Nernstian slopes of the calibration curve at 58.76 ± 0.8 and 57.48±1 mV per decade for sensors A and B. The response times were 10 and 12 s, detection limits 1.3 × 10−6 and 2.2 × 10−6 M; the concentration range 2.5 × 10−6-7.9 × 10−2 M and 3.0 × 10−6 to 7.9 × 10−2 M respectively. The present electrodes show good discrimination of atorvastatin calcium from several inorganic, organic ions, sugars and some common excipients. The sensors were applied for the determination of atorvastatin calcium in pharmaceutical preparations using standard addition and the calibration curve methods. The results obtained were satisfactory with excellent percentage recovery comparable and sometimes better than those obtained by other routine methods for the assay. The proposed potentiometric methods offer the advantages of simplicity, accuracy, automation feasibility and applicability to turbid and colored sample solutions.
A greener analytical procedure based on automated flow through system with an optical sensor is proposed for determination of Co(II). The flow through system consisted of polymer inclusion membrane (PIM) containing potassium thiocyanate (KSCN) that was placed between the measuring cell and fixed with optical sensor probe as an optical sensor for monitoring of Co(II) at 625 nm. In the presence of Co(II) ions, the colourless membrane changes to blue. The sensing membrane was prepared by incorporating SCN into a non plasticized PIM. The prepared PIM were found to be homogenous, transparent and mechanically stable. The optode shows reversible optical response in the range of 1.00 × 10−6 – 1.00 × 10−3 mol L−1 with detection limit of 6.10 × 10−7 mol L−1. The optode can be regenerated by using 0.1 mol L−1 of ethylenediaminetetraacetic acid (EDTA). The main parameters of the computer controlled flow system incorporating the flow-through optode, a multi-port selection valve and peristaltic pump were optimized too. The calculated Relative Standard Deviation (R.S.D) of the repeatability and reproducibility of the method are 0.76% and 4.73%, respectively. This green system has been applied to the determination of Co(II) in wastewater samples with reduced reagents and samples consumption and minimum waste generation.
A convenient colorimetric and ratiometric fluorescent probe based on BODIPY derivative for cyanide detection has been synthesized, whose structural contains a dicyanovinyl group used as a sensing unit. Among the tested analytes, such as CN−, F−, Cl−, Br−, I−, ClO4−, AcO−, NO3−, H2PO4− HSO4−, S2− and N3−, only CN− could react with dicyanovinyl moiety by nucleophilic addition, which disrupted the π-conjugation of the probe and hindered the intramolecular charge transfer (ICT), leading a blue shift of absorption and fluorescence spectrum and a concomitant color change from yellow to light pink. The detection limit of this probe was calculated to be 0.98 μM, which is lower than the maximum concentration in drinking water (1.9 μM) permitted by the World Health Organization (WHO). Moreover, the probe showed excellent selectivity and anti-interference ability towards CN− over other anions. The reaction mechanism was fully supported by 1H NMR and MS spectrum.
Analysis of emission from laser-induced plasma has a unique capability for quantifying the major and minor elements present in any type of samples under optimal analysis conditions. Chemometric techniques are very effective and reliable tools for quantification of multiple components in complex matrices. The feasibility of laser-induced breakdown spectroscopy (LIBS) in combination with multivariate analysis was investigated for the analysis of environmental reference materials (RMs). In the present work, different (Certified/Standard) Reference Materials of soil and plant origin were analyzed using LIBS and the presence of Al, Ca, Mg, Fe, K, Mn and Si were identified in the LIBS spectra of these materials. Multivariate statistical methods (Partial Least Square Regression and Partial Least Square Discriminant Analysis) were employed for quantitative analysis of the constituent elements using the LIBS spectral data. Calibration models were used to predict the concentrations of the different elements of test samples and subsequently, the concentrations were compared with certified concentrations to check the authenticity of models. The non-destructive analytical method namely Instrumental Neutron Activation Analysis (INAA) using high flux reactor neutrons and high resolution gamma-ray spectrometry was also used for intercomparison of results of two RMs by LIBS.
Sensors based on Ag/α-Fe2O3 nanoparticles have been prepared by the coprecipitation method for sensing methyl mercaptan at room temperature. X-ray diffraction patterns of samples matched perfectly with characteristic peaks of hematite with no peaks assigned to Ag even at the highest concentration. STEM images and EDX analysis revealed the presence of Ag nanoparticles (from 2 to 5 nm) which were highly dispersed onto α-Fe2O3 surface with an Ag/Fe ratio from 0.014 to 0.099. The Ag nanoparticles were deposited on the hematite surface. Sensing tests of Ag-loaded hematite nanoparticles showed much higher response signal than the unmodified sensor. Hematite loaded with 3%(Wt) Ag showed the highest response with a linear dependence from 20 to 80 ppm. The sensor also depicted a good selectivity and stability during 4 days with short recovery time. The high dispersion of reduced Ag evaluated by XPS analysis played an important chemical role in the sensing mechanism that favored the contact of CH3SH with oxygen.
In this work, Ni/Ni nanoparticles were immobilized on modified nanoclay then, the resultant nanocomposite was used as a sorbent for separation of dibenzothiophene. The concentration of dibenzothiophene was determined with UV–vis spectrophotometry at 287 nm. Different parameters affecting the separation of dibenzothiophene such as: the ratio of Ni/NiO nanoparticles to nanoclay, amounts of Ni/NiO nanoparticles and nanoclay, stirring time of dibenzothiophene solution on the sorbent, type of eluent, eluent volume, elution time, stirring time for preparing the sorbent were optimized. The obtained results were shown quantitative desorption of dibenzothiophene performed using ethanol as eluent. A linear concentration range of 0.5–15 mg/L was obtained with a detection limit of 0.047 mg/mL. The sorbent capacity was found to be 32 mg/g. Relative standard deviation was ±1.4 for six replicated determination of 5 mg/g of dibenzothiophene. The optimized procedure was successfully used for a crude oil sample.
Polypyrrole-Sn(IV)arsenotungstate (PPy-SnAT) conductive nanocomposite cation exchange have been synthesized by in-situ chemical oxidative polymerization of polypyrrole with Sn(IV)arsenotungstate (SnAT). PPy-SnAT nanocomposite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-Ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive x-ray (EDX) and thermogravimetric analysis (TGA). The ion exchange capacity (IEC) and DC electrical conductivity of nanocomposite was found to be 2.50 meq/g and 5.05 × 10−1 S/cm respectively. The nanocomposite showed appreciable isothermal stability in terms of DC electrical conductivity retention under ambient condition up to 130 °C. The nanocomposite cation exchange based sensor for detection of formaldehyde and ammonia vapours were fabricated at room temperature. It was revealed that the resistivity of the nanocomposite increases on exposure to higher percent concentration of ammonia and lower concentration of formaldehyde at room temperature (25 °C).
Highly chlorinated benzenes, produced in the presence of organic matter and chlorine, are considered PCDD/Fs precursors, and are used as cost and time convenient substitute indicators for the indirect measurement of the latter. In this study penta- and hexa-chlorobenzene are quantified for the determination of the organochloride load of fly ash from solid recovered fuel incineration. Some of the chlorobenzenes are formed under ‘de novo’ conditions, through heterogeneous (ash particles/flue gases) reactions and are therefore deeply incorporated within fly ash. Accelerated solvent extraction (ASE) and ultrasonic solvent extraction (USE), along with the equivalent clean-up methods suggested by literature were compared to traditional Soxhlet. The extraction efficiencies achieved were 83 ± 7.5% for Soxhlet, 111 ± 19% for PFE, and 67 ± 17% for ultrasonication. Soxhlet extraction and clean-up through a multilayer silica gel column gave more precise results compared to the other sample preparation methods. Furthermore, performance comparison of gas chromatography fitted with either a mass spectrometer operated in single ion monitoring mode (GC-MS-SIM), or electron capture detector (GC- ECD) highlighted that ECD can be used for measuring chlorobenzenes traces down to 0.21 ng g−1, when the equivalent LOQ for MS-SIM was 3.26 ng g−1. The results further suggest that ECD can provide better peak integration than MS-SIM in the detection of chlorobenzenes in fly ash extracts, due to the detector's sensitivity to halogenated compounds.
The second generation of Bioenergy: a study of CPO liquid waste-based biodiesel production technology has been conducted. The aims of this study were to obtain biodiesel from Industrial liquid waste of CPO processing and to identify the kind of methyl-ester compound of the biodiesel. The production of biodiesel was applied in two steps of reactions; esterification reaction using H2SO4 and transesterification using CaO catalyst at 60 °C for 2 h. GC-MS analysis result showed that methyl ester from liquid waste of CPO contains methyl hexadecanoate 12.87%, methyl 9-octadecanoate 19.98%, methyl octadecanoate 5.71%, and methyl 8,11-octadecadienoate 10.22%.
This paper reports the development and optimization of micro-matrix solid-phase dispersion (micro-MSPD) of nine polychlorinated biphenyls (PCBs) in mussel samples (Mytilus galloprovincialis) by using a two-level factorial design. Four variables (amount of sample, anhydrous sodium sulphate, Florisil and solvent volume) were considered as factors in the optimization process. The results suggested that only the interaction between the amount of anhydrous sodium sulphate and the solvent volume was statistically significant for the overall recovery of a trichlorinated compound, CB 28. Generally most of the considered species exhibited a similar behaviour, the sample and Florisil amounts had a positive effect on PCBs extractions and solvent volume and sulphate amount had a negative effect. The analytical determination and confirmation of PCBs were carried out by using GC-ECD and GC-MS/MS, respectively. The method was validated having satisfactory precision and accuracy with RSD values below 6% and recoveries between 81 and 116% for all congeners. The optimized method was applied to the extraction of real mussel samples from two Galician Rías.
Trace amounts of Cr, Zn, Cd, and Pb were determined by metal furnace atomic absorption spectrometry using absorption tubes. Various absorption tubes were designed as roof- and tube-types, and fixed above the metal furnace in order to extend the light path length. Aqueous standards and samples were injected in the metal furnace and atomized in a metal atomizer with an absorption tube (6 cm length, 15.5 mm diameter). The used of an absorption tube resulted in an enhancement of the atomic absorbance. The ratios of absorbance values with and without the roof- and tube-type absorption tubes were 1.33 and 1.11 for Cr; 1.42 and 1.99 for Zn; 1.66 and 1.98 for Cd; and 1.31 and 1.16 for Pb, respectively. The use of an absorption tube was effective for Zn and Cd analysis, as the absorbance values for these low boiling point metals doubled. The proposed method was successfully applied in the determination of Zn in tap water.
A precise, accurate, specific, linear, rugged and robust analytical method was developed and validated for estimation of process and degradant impurities of Rosuvastatin calcium (RSC) in Rosuvastatin calcium tablets. 150 mm length column, 4.6 mm diameter and 3.5μ particle size with C18 stationary phase and pH3.0 phosphate buffer as mobile phase. Column was maintained at 30 °C.All impurities are monitored at 248 nm.Impurities are separated in gradient elution mode. All degradant impurities of RSC (Anti-isomer, 5-ketoacid, lactone and meglumine adduct), process impurity (Imp-A) are well separated. Unknown impurity (Meglumine adduct) formed during stability studies was isolated using preparative HPLC and structure was characterized by NMR and Mass spectrometry (LC-MS and HRMS) studies. Method is capable of separating and estimating all the degradant and process impurities.
It is well known that surfactant-suspended carbon nanotube (CNT) samples can be purified by centrifugation to decrease agglomerates and increase individually-dispersed CNTs. However, centrifugation is not always part of protocols to prepare CNT samples used in biomedical applications. Herein, using carboxylated multi-walled CNTs (cMWCNTs) suspended in water without a surfactant, we developed a Boehm titrimetric method for the analysis of centrifuged cMWCNT suspensions and used it to show that the surface acidity of oxidized carbon materials in aqueous cMWCNT suspensions was enriched by ∼40% by a single low-speed centrifugation step. This significant difference in surface acidity between un-centrifuged and centrifuged cMWCNT suspensions has not been previously appreciated and is important because the degree of surface acidity is known to affect the interactions of cMWCNTs with biological systems.
A naphthalo-1, 8-bis[(2,4-dinitrophenyl)hydrazone] sensor (K) was synthesized and characterized using UV–vis, 1H NMR and fluorescence spectroscopy. The sensor showed strong colorimetric and spectral response upon the molar addition of acetate or fluoride ion (AcO− or F−) in acetonitrile. The complexed state (KF or KAcO) of the system showed significant reversibility properties, both in color and spectra, upon the addition of small traces of water. Subsequently, in addition to sensing of fluoride or acetate ions, the complexed KF or KAcO adducts can be used in colorimetric signaling of water traces in different organic mediums. In order to have more understanding of the interaction between K and the anions, the study was supplemented using density functional theory computations.
We investigated the process of a bromination reaction of malonic acid and methylmalonic acid in the Belousov-Zhabotinsky reaction by using a quartz crystal microbalance (QCM). The process involves an enolization reaction as a rate-determining step. We found that, in the step, the variation of Br2 concentration induced an exactly quantitative shift of a resonant frequency of the QCM, based on the change of the surface mass on the QCM and the solution viscosity and density. This new finding enabled us to estimate the reaction rate constants and the thermodynamic parameters of the enolization reaction due to a QCM measurement. The values measured by the QCM were in good agreement with those measured by a UV-spectrophotometer. As a result, we succeeded to develop a new measurement method of a nonlinear chemical reaction.
Infrared sample digestion technology has been rapidly developed in recent years and its application and digestion performance on a variety of ores of base metals was assessed in this study, using a 6-channel infrared digester. Digestion times of 10 min or less were achieved for all base metal ores investigated, including oxides, sulfides, and silicates of Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, W, and Zn. Performance criteria for all samples were excellent, reflected in z values of less than 2 in all cases. Various acid digestion methods were developed for the selected ore samples under high intensity infrared radiation and delivered virtually complete recoveries of all of the elements of interest. Chromite, the notoriously refractory chromium ore was digested within 10 min and gave 100% recovery of chromium. These digestions were accomplished without resorting to perchloric acid and, for most sample types, without hydrofluoric acid, significantly improving the workplace safety for analysts. Between-channel variation of the analyte recoveries from the 6-channel unit were generally below 2%, suggesting that the digestion methods developed with this platform provide reproducible results to meet various sample preparation demands. The high speed and analyte recovery of these digestions makes this methodology especially attractive for prospectors and developers who demand rapid and reliable results from exploration samples.
A sensitive, specific and fast method to quantify 3α-hydroxytibolone in human plasma using deuterated 3α-hydroxytibolone (d5) as internal standard is described. The analyte and the internal standard were extracted from plasma (900 μL) by liquid-liquid extraction using ethyl ether/hexane (50/50, v/v) and ammonium hydroxide (50%). The extracts were analyzed by high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry without derivatization. Chromatography was performed isocratically on a Gemini-NX™ C18 5 μm (150 × 4.6 mm i. d.) column. The method had a chromatographic run time of 3.75 min and a linear calibration curve over the range 1–100 ng/mL. The limit of quantification validated was 1 ng/mL. This method was used to assess the bioequivalence between two different tibolone oral formulations: Livolon (1.25 mg tablet) provided by Biolab Sanus Farmacêutica (Brazil), as the test formulation, and Libiam™ (1.25 mg tablet) produced by Libbs Farmacêutica (Brazil), as the reference formulation. A single 3.75 mg dose of each formulation was administered to 46 postmenopausal female healthy volunteers. The study was conducted in an open, randomized, two-period crossover balanced design with a 2 week washout interval between the doses. The 90% confidence interval for Cmax, AUC(0-last) and AUC(0-inf) individual test/reference ratios were 97.48–111.51, 95.35–103.20 and 96.42–103.86, respectively. It is concluded that Livolon (1.25 mg tablet) is bioequivalent to Libiam™ (1.25 mg tablet), with regards to both rate and extent of absorption.
Liquid-based miniaturized techniques have received a lot of attention recently resulting in the development of the liquid phase microextraction (LPME) and dispersive liquid-liquid microextraction (DLLME) techniques each offering unique benefits over the other technique. Herein we report a combination of the two techniques for the extraction of hexestrol and atrazine from aqueous systems. The method sets off with the DLLME thereafter a hollow fibre filled with the organic solvent is introduced for the extraction of the pre-extracted analytes in the dispersed organic solvent. The method was modified further by introducing a second extracting solvent in place of the disperser solvent. Under the optimum conditions, namely, toluene in the acceptor phase, 1:1 chloroform:toluene (v/v) as a dispersed solvent, 15% NaCl, with the 15 min extraction time, the method achieved satisfactory enrichment factors (87- and 62-fold); sufficiently low detection limits of 0.018 μg/mL and 0.016 μg/mL using the flame ionization detector, while 0.072 and 0.063 ng/mL were obtained using single ion monitoring mass spectrometry detector, for atrazine and hexestrol, respectively; with sufficient linearity (R2 ≥ 0.9959). Although the compounds were not detected in the river water sample, satisfactory recoveries (111–115%) were achieved indicating the method did not suffer any negative matrix effect.
A rapid and simple method for the separation and determination of five polycyclic aromatic hydrocarbons (PAHs) in water is described. The procedure is based on the selective extraction of the PAHs on the surface of modified magnetic nanoparticles using a solid-phase dispersion technique. The PAHs-loaded magnetic nanoparticles were separated from the aqueous phase with a magnet and then quantified by HPLC. The modified extraction method successfully replaced conventional extraction methods. The partitioning of the analyte between the sub-micron magnetic nanoparticles (solid phase) and the liquid phase occurs as the solid moves through the samples as a colloidal sol. The detection limits were in the range 0.14–0.31 ng/L, with recoveries ranging from 88% to 96%. The as-synthesized magnetic nanoparticles showed good stability and high extraction recoveries for the adsorption-desorption of PAHs, even after recycling four times. The procedure was successfully applied to PAHs determinations in real water samples.
An efficient and fast method based on isopropyl 2-[(isopropoxycarbothiolyl)disulfanyl] ethane thioate (IICDET) were used for the speciation and determination of trace amount of Cr(III and VI) in human biological samples by cloud point assisted dispersive ionic liquid –liquid microextraction (CP-DILLME). Cr(VI) has carcinogenic effects, so, speciation of chromium in human body such as blood cells is very important. The cloudy solution was achieved by the mixture of acetone and IL ([C8MIM][PF6]) in human blood samples containing Cr(III) ions that were already complexed by IICDET at pH 4.5. After reduction Cr(VI) to Cr(III) by ascorbic acid, chromium speciation was obtained based on total chromium determination by electro thermal atomic absorption spectrometry (ET-AAS) and difference between total Cr and Cr(III) content. In addition, Cr speciation in human blood cells was calculated based on IICDET/CP-DILLME and hematocrit blood test (HCT). After optimized conditions, the enrichment factor (EF), Linear range and limit of detection (LOD) was obtained 25.2, 0.02–1.75 μg L−1 and 5.4 ng L−1 in human biological samples respectively. The validation of methodology was achieved by certified reference material (CRM) and ICP-MS technique.
