Analytical Chemistry Research最新文献

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).

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.

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.

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.

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%.

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.

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 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.

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.

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.