Cobalt-free cathode material SrFe0.9Nb0.1O3−δ for intermediate-temperature solid oxide fuel cells

A cobalt-free cubic perovskite oxide, SrFe_0.9Nb_0.1O_3?δ (SFN) was investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD results showed that SFN cathode was chemically compatible with the electrolyte Sm_0.2Ce_0.8O_1.9 (SDC) for temperatures up to 1050 °C. The electrical conductivity of SFN sample reached 34–70 S cm^?1 in the commonly operated temperatures of IT-SOFCs (600–800 °C). The area specific resistance was 0.138 Ω cm² for SFN cathode on SDC electrolyte at 750 °C. A maximum power density of 407 mW cm^?2 was obtained at 800 °C for single-cell with 300 μm thick SDC electrolyte and SFN cathode.     

Simultaneous determination of thirty non-steroidal anti-inflammatory drug residues in swine muscle by ultra-high-performance liquid chromatography with tandem mass spectrometry

An ultra-high-performance liquid chromatography with tandem mass spectrometric detection (UHPLC–MS/MS) method was established for the simultaneous determination of residues of thirty non-steroidal anti-inflammatory drugs (NSAIDs) in swine muscle. The samples were extracted with acetonitrile and phosphoric acid. The extracts were defatted with n-hexane, and then purified by HLB solid-phase extraction cartridge. Analysis was carried out on UHPLC–ESI-MS/MS working with multiple reaction monitoring mode with polarity switching. Limits of detection were between 0.4 μg/kg and 2.0 μg/kg, and limits of quantification were between 1.0 μg/kg and 5.0 μg/kg. The recoveries of NSAIDs were between 61.7% and 125.7% at spiked levels of 1.0–500 μg/kg. The repeatability was less than 8% and the within-laboratory reproducibility was not more than 12.3%. The method was reliable, convenient and sensitive.     

UV-absorption and fluorimetric methods for the determination of alprazolam in pharmaceutical formulation

The development of UV and fluorescence spectrophotometric methods for the quantitative determination of alprazolam in dosage forms using As(III)?SDS system. The two simple and sensitive, spectrophotometric and spectrofluorimetric methods were developed for the determination of alprazolam (ALP) in tablets. These methods are based on formation of ALP?As(III) complex in the presence of SDS. The UV-spectrum of 30% methanolic solution of ALP (5 × 10^?5 M) at pH 6.5 (Mclivaine buffer) was run between 200 and 380 nm. The absorption spectrum of ALP exhibits two peaks with a λ_max. at 255 nm and a weak band at 325 nm. When the spectra of the drug were run at varying pH in the region 200–380 nm, one isosbestic point at 290 nm was observed, which indicated the presence of two ionic conditions in solution. The complex exhibited an absorption maximum at 265 nm and emission peak at 520 nm with respect to the excitation wavelength of 325 nm. The spectrophotometric method was found to be linear in 8.0–17.0 μg ml^?1 range with detection limit of 13.520 μg ml^?1, while 0.05–9.5 μg ml^?1 range was with detection limit of 1.048 × 10^?2 μg ml^?1 by spectrofluorimetric method. The mean percentage recovery of the added quantity was found to be 99.54 (spectrophotometric method) and 100.22 (spectrofluorimetric method) and the %RSD are lower than 0.478 and 0.296 determined spectrophotomerically and spectrofluorimtrically, respectively. This indicates that the proposed method is accurate. The apparent ionization constant of ALP was found to be 9.29. The spectra, experimental conditions were set followed by determination stoichiometry, stability constant and thermodynamic parameters of the As(III), Co(II), Ni(II), and Zn(II) complexes with ALP at pH 6.5. The proposed methods have been successfully applied to the assay of ALP in tablets and the results were statistically evaluated.     

A simple and sensitive spectrophotometric method for the determination of trace amounts of nitrite in environmental and biological samples using 4-amino-5-hydroxynaphthalene-2,7-disulphonic acid monosodium salt

A very simple, sensitive, fairly selective and rapid spectrophotometric method for the determination of trace amounts of nitrite has been described. This method is based on the diazotized intramolecular coupling of electrophilic diazonium cation with the phenolic group of 4-amino-5-hydroxynaphthalene-2,7-disulphonic acid monosodium salt (AHNDMS) in a phosphate buffer solution of pH 7.5. The cyclic product has a purple color with maximum absorbance at 560 nm and is stable for 6 h. Optimum reaction conditions and other important analytical parameters for the maximum color development were established. Beer's law was found to obey for nitrite in the concentration range of 0.1–1.6 μg ml^?1 with molar absorptivity of 2.6 × 10⁴ l mol^?1 cm^?1 and Sandell's sensitivity of 0.0075 μg ml^?1. The effect of interfering ions on the determination is described. The recommended method was applied for the determination of nitrite in different water, soil and human saliva samples. The performance of the recommended method was evaluated in terms of Student's t-test and variance ratio F-test, which indicated the significance of proposed method over the reference method.     

The investigation of the interactions between CdSe quantum dots and human serum albumin by resonance Rayleigh scattering and second-order scattering spectra

Human serum albumin (HSA) was the most abundant protein in human plasma and has significant physiological function. In Tris–HCl buffer solution (pH 7.4), water-soluble semiconductor CdSe quantum dots (QDs) reacted with HSA and the products resulted in a great enhancement of the intensity of resonance Rayleigh scattering (RRS) and second-order scattering (SOS). Based on this, a new method was developed to investigate the interactions between QDs and HSA. The parameters with regard to determination were optimized, and the reaction mechanism was discussed. Under optimal conditions, the increments of scattering intensity (ΔI) were directly proportional to the concentrations of HSA in the range of 0.4–48.0 μmol L^?1. The detection limits were 0.10 μmol L^?1 for RRS method and 0.25 μmol L^?1 for SOS method. The proposed method was sensitive, simple and rapid. It has been successfully applied to the determination of HSA in human urine samples. Analytical results obtained with this novel assay were satisfactory.     

anti-Tuberculosis natural products: synthesis and biological evaluation of pyridoacridine alkaloids related to ascididemin

There is an urgent need for novel therapeutics possessing new modes of action to treat tuberculosis (TB) infections. In this study we report on the synthesis and biological evaluation of a series of pyrido[2,3,4-kl]acridin-6-one alkaloids related to the anti-TB (MIC 0.35 μM) but cytotoxic (IC₅₀ <0.14 μM) marine natural product ascididemin (1). The most interesting compounds identified were 21 and 24, which were found to inhibit the growth of Mycobacterium tuberculosis (Mtb) H₃₇Rv with MIC 2.0 μM, but with negligible cytotoxicity towards Vero and P388 cells (IC₅₀>25 μM). Another analogue (10) was evaluated against a range of singly-drug-resistant strains of Mtb and was found to exhibit no cross-resistance. These results suggest that the pyrido[2,3,4-kl]acridin-6-one skeleton may provide a useful scaffold for future studies directed towards possible anti-TB drugs.     

Novel poly (neutral red) nanowires as a sensitive electrochemical biosensing platform for hydrogen peroxide determination

Poly (neutral red) nanowires (PNRNWs) have been synthesized for the first time by the method of cyclic voltammetric electrodeposition using porous anodic aluminum oxide (AAO) template and were examined by scanning electron microscopy (SEM) and transmission electron microscope (TEM). Moreover, horseradish peroxidase (HRP) was encapsulated in situ in PNRNWs (denoted as PNRNWs–HRP) by electrochemical copolymerization for potential biosensor applications. The PNRNWs showed excellent efficiency of electron transfer between the HRP and the glassy carbon (GC) electrode for the reduction of H₂O₂ and the PNRNWs–HRP modified GC electrode showed to be excellent amperometric sensors for H₂O₂ at −0.1 V with a linear response range of 1 μM to 8 mM with a correlation coefficient of 0.996. The detection limit (S/N = 3) and the response time were determined to be 1 μM and <5 s and the high sensitivity is up to 318 μA mM⁻¹ cm⁻².     

Magnesium lactate mixed with EVA polymer/paraffin as an EPR dosimeter for radiation processing application

The dosimetric characteristics of γ-radiation-induced defects in magnesium lactate (ML) rods (3.5 mm×10 mm) formulated by mixing ML with molten mixtures of paraffin wax and EVA copolymer have been investigated using electron paramagnetic resonance (EPR). The EPR spectrum of irradiated ML rods was characterized by a quartet signal with the spectroscopic splitting g-factor of 2.0048±0.0003 at 0.4 mT. The useful dose range of the rod dosimeter was 100 Gy to 80 kGy. The mass attenuation coefficient, μ/ρ, and the mass energy-absorption coefficient, μ_en/ρ, versus energy in the range of 10 keV to 20 MeV indicate that the prepared ML dosimeter is typically adipose tissue equivalent overall this energy range. The overall combined uncertainties (at 2σ) associated with routine dose monitoring in the dose range of 0.1–10 kGy and 10–80 kGy were found to be 6.14% and 6.36%, respectively.     

Validated voltammetric method for the determination of some antiprotozoa drugs based on the reduction at an activated glassy carbon electrode

A sensitive electrochemical procedure based on reduction of secnidazole (I), tinidazole (II) and ornidazole (III) at a glassy carbon electrode (GCE) was introduced. A study of the variation of the peak current with solution variables such as pH, ionic strength, concentration of drugs, possible interference, and instrumental variables such as scan rate, pulse amplitude, preconcentration time, accumulation potential, has resulted in the optimization of the reduction signal for analytical purposes. Linear calibration plots were obtained over the concentration ranges of 50–800, 50–750 μg mL^?1 for I, and both (II, III) respectively, in Britton–Robinson buffer of pH 7. The relative standard deviations of five replicate measurements of 1.0 and 10.0 μg mL^?1 of I, II and III concentrations were 4.7%, 4.9% and 5.3%, and 2.2%, 2.6% and 2.8%, respectively. The limits of detection (LOD) for I, II and III were found to be 2 × 10^?10, 3 × 10^?10 and 2.5 × 10^?10 mol L^?1 and limits of quantification (LOQ) for I, II and III were found to be 4.0 × 10^?8, 1.2 × 10^?8 and 4.4 × 10^?8 mol L^?1, respectively. The optimal conditions were: E_acc = ?0.9 V, t_acc = 30 s, scan rate = 20 mV s^?1, pulse-height = 90 mV and Britton–Robinson buffer of pH 7. The method was applied for the determination of the cited drugs both in raw materials and in pharmaceutical preparations with satisfactory results and compared with the official reference method. Complete validation of the proposed method was also done.     

HPLC-PDA analysis of ACE-inhibitors,hydrochlorothiazide and indapamide utilizing design of experiments

A simple, rapid, precise, accurate and sensitive high performance liquid chromatographic method has been developed for simultaneous determination of ACE inhibitors with hydrochlorothiazide and indapamide in pharmaceutical formulations. ‘Design of Experiments’ (DoE) using ‘central composite design’ (CCD) was applied to facilitate method development and optimization. Mobile phase was optimized utilizing response surface methodology using Design Expert software. Chromatographic separation was achieved on Hypersil®-Gold C₁₈ (100 × 4.6 mm, 3 μm, Thermo Fisher Scientific, USA), column at 25 °C. The mobile phase was 58% buffer (5 mM KH₂PO₄, containing triethylamine 0.25 ml/L), 25% acetonitrile and 17% methanol (pH adjusted to 2.8 ± 0.1). The analysis was performed at 215 nm. The mobile phase flow rate was 1.0 ml/min and injection volume 10 μl. The method was validated for linearity, limits of quantitation and detection, accuracy, precision, ruggedness and robustness as per the International Conference on Harmonization (ICH) guidelines. Calibration curves (for lisinopril, hydrochlorothiazide, captopril, imidapril, perindopril, indapamide and trandolapril) were linear in the concentration range of 5–35 μg/ml. The limit of detection and limit of quantitation for experimental drugs ranged from 0.03 to 0.61 and 0.08–1.84 μg/ml respectively.     

Enantiomeric separation of a melatonin agonist Ramelteon using amylose-based chiral stationary phase

A new simple isocratic chiral liquid chromatographic method was developed for the enantiomeric purity of Ramelteon[(S)-N-[2-(1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-yl) ethyl]-propionamide], a melatonin agonist in bulk drugs. The chromatographic separation was achieved on Chiralpak AD-H, 250 mm × 4.6 mm, 5 μm column using a mobile phase system consisting of n-hexane, ethanol and methanesulfonic acid in the ratio of 900:100:0.1 (v/v/v). The mobile phase was pumped on the column at the flow rate of 1 mL min^?1. Addition of methane sulfonic acid in the mobile phase enhanced chromatographic efficiency and resolution between the enantiomers. The resolution between the enantiomers was found to be more than four. The developed method was subsequently validated and proved to be accurate and precise. The experimentally established limit of detection and quantification of (R)-enantiomer were found to be 25.5 and 77.2 ng ml^?1, respectively, for 20 μl injection volumes. The percentage recovery of (R)-enantiomer was ranged from 98.5 to 101.9 in bulk drug samples of Ramelteon. The stability of Ramelteon sample in analytical solution was checked for about 48 h at room temperature and was found to be stable for about 48 h. The proposed method was found to be suitable and accurate for the quantitative determination of (R)-enantiomer in drug substance.     

Bismuth nano-powder electrode for trace analysis of heavy metals using anodic stripping voltammetry

In the present work, a more sensitive and conveniently usable electrode sensor for a trace analysis of heavy metal was developed by using Bi nanopowder synthesized by levitational gas condensation (LGC) method. It was observed from the TEM image that the Bi nanopowder is spherical in shape with a size of nearly 50 nm. The XRD pattern revealed intense peaks which can be indexed as a rhombohedral structure of Bi without any other diffraction peaks corresponding to an oxide or an impurity. This indicates that the resulting nanopowder synthesized by the LGC method is a highly crystallized Bi with a high purity. The square wave anodic stripping voltammograms (SWASV), experimentally measured for the Bi nanopowder electrode, showed well-defined and highly reproducible electrochemical responses relating to the stripping of Cd and Pb. The detection limit of the electrode was estimated to be 0.15 μg/l and 0.07 μg/l for Cd and Zn, respectively, on the basis of the signal-to-noise characteristics (S/N = 3) of the response for the 1.0 μg/l solution under a 10 min accumulation.     

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).     

Novel luminescent nanoparticles for DNA detection

Highly luminescent LaF₃:Ce³⁺/Tb³⁺ nanocrystals were successfully prepared and surface functionalized via Layer-by-Layer technology. These as-prepared nanocrystals are highly resistant to photobleaching and pretty dispersible in aqueous solution. Due to the efficient luminescence quenching of the nanocrystals by nucleic acids, a facile fluorescence quenching method was developed for the detection of trace amount of nucleic acids. Under optimal conditions, the fluorescence intensity was proportional to the DNA concentration over the range of 0.60–25.0 μg mL^?1 for calf thymus DNA (ct-DNA) and 0.60–30.0 μg mL^?1 for herring sperm DNA (hs-DNA), respectively. The corresponding detection limit is 0.21 μg mL^?1 for ct-DNA and 0.31 μg mL^?1 for hs-DNA, respectively. The results indicated that the reported method is simple and rapid with wide linear range. Also, the recovery and relative standard deviation of this method are reasonable and satisfactory.     

RP-HPLC-DAD method for the determination of phenylepherine,paracetamol, caffeine and chlorpheniramine in bulk and marketed formulation

A simple, specific and accurate isocratic RP-HPLC-DAD method was developed for the simultaneous determination of phenylephrine, paracetamol, caffeine and chlorpheniramine in bulk and tablet dosage form. The four contents are present in variable concentrations and have variable chromatographic behavior making the process of analysis very difficult. For present studies a reversed-phase C-18 column (150 mm × 4.5 mm i.d., particle size 5 μm) with mobile phase consisting of acetonitrile, methanol and 10 Mm phosphate buffer 16:22:62 (v/v) (pH of buffer 2.5 ± 0.02, adjusted with ortho phosphoric acid) was used. The flow rate was 1.0 ml/min and eluents were monitored at 280 nm. The mean retention times of phenylephrine, paracetamol, caffeine and chlorpheniramine were found to be 1.8, 3.1, 5.2 and 10.9 min, respectively. The method was validated in terms of linearity, range, specificity, accuracy, precision and robustness. The proposed method was successfully applied to the estimation of phenylephrine, paracetamol, caffeine and chlorpheniramine in combined tablet dosage form.     

Determination of copper,lead, cadmium and zinc content in commercially valuable fish species from the Persian Gulf using derivative potentiometric stripping analysis

This study was performed to determine the concentrations of cadmium, lead, copper and zinc in the edible muscle of pelagic (Scomberomorus commerson, Chirocentrus dorab, Sphyraena jello, Rachycentron conadum, Thunus tonggol, and Tenualosa ilisha) and demersal (Nemipterus japonicas, Epinephelus coioides, Platycephalus indicus, Psettodes erumei, Pomadasys argenteus, and Acanthopagrus latus) fish species from the Persian Gulf during winter and summer. The samples were analyzed by the derivative potentiometric stripping technique; and the results were expressed as μg/g of wet weight. The obtained range of metals in fish species was 0.024–0.111 μg/g for cadmium, 0.057–0.471 μg/g for lead, 0.799–4.790 μg/g for copper and 3.226–11.390 μg/g for zinc. The study revealed that seasonal variation influenced the concentration of metals in the samples. The highest concentration of cadmium, lead, copper and zinc was found in Platycephalus indicus (0.147 μg/g), Acanthopagrus latus (0.534 μg/g), Psettodes erumei (5.294 μg/g) and Psettodes erumei (13.528 μg/g) in winter, respectively. Moreover, demersal fish species had higher cadmium, lead and zinc concentrations, but lower copper content than pelagic ones. Our study demonstrated that the estimated daily and weekly intakes of lead, copper and zinc, and estimated monthly intake of cadmium via consumption of fish flesh were below the PTDI, PTWI and PTMI values established by FAO/WHO.     

The determination of trace lead in drinking water by flow injection spectrophotometry

Lead is the non-essential trace element in the human body, and it has been confirmed that drinking water is one of the sources of lead in human body. In the research, based on the sensitive colour reaction of lead with I^?–EV⁺–PVA, a simple, sensitive, accurate and portable method for the determination of trace lead in drinking waters was proposed. Chemicals and physicals had been optimized in detail. The apparent molar absorption coefficient was up to 7.4 × 10⁵ mol L^?1 cm^?1. The developed method provided a linearity range over 5–80 μg L^?1. The regression deviation was between 0.71% and 2.33%. The 3σ detection limit was 0.9 μg L^?1. Close to the quantitation limit for the analyte the relative standard deviation was 1.10% (n = 10) at 40 μg L^?1. The method developed here for analysis of lead yielded results that were comparable with those of the GFAAS.     

Determination of triclosan,triclocarban and methyl-triclosan in aqueous samples by dispersive liquid–liquid microextraction combined with rapid liquid chromatography

In this study, dispersive liquid–liquid microextraction (DLLME) combined with ultra-high-pressure liquid chromatography (UHPLC)–tunable ultraviolet detection (TUV), has been developed for pre-concentration and determination of triclosan (TCS), triclocarban (TCC) and methyl-triclosan (M-TCS) in aqueous samples. The key factors, including the kind and volume of extraction solvent and dispersive solvent, extraction time, salt effect and pH, which probably affect the extraction efficiencies were examined and optimized. Under the optimum conditions, linearity of the method was observed in the range of 0.0500–100 μg L^?1 for TCS, 0.0250–50.0 μg L^?1 for TCC, and 0.500–100 μg L^?1 for M-TCS, respectively, with correlation coefficients (r²) > 0.9945. The limits of detection (LODs) ranged from 45.1 to 236 ng L^?1. TCS in domestic waters was detected with the concentration of 2.08 μg L^?1. The spiked recoveries of three target compounds in river water, irrigating water, reclaimed water and domestic water samples were achieved in the range of 96.4–121%, 64.3–84.9%, 77.2–115% and 75.5–106%, respectively. As a result, this method can be successfully applied for the rapid and convenient determination of TCS, TCC and M-TCS in real water samples.     

Assessments of lifetimes and photoionization cross-sections at 10.6 μm of nd Rydberg states of Rb measured in a magneto-optical trap

By using IR laser photoionization in a magneto-optical trap, radiative lifetimes of rubidium Rydberg nd states (n = 16–20) have been measured. The measured lifetimes are: 4.63 μs for the 16d state, 5.39 μs (17d), 6.74 μs (18d), 8.06 μs (19d) and 8.99 μs (20d). The experimental values are in agreement with previous theoretical calculations. The reported method allows also for a measurement of the photoionization cross-sections of the specified Rydberg states at 10.6 μm. In this case the experimental values (ranging from 39 Mb for the 16d state to 30 Mb for the 20d state) look inconsistent with theoretical calculations.     

Direct determination of arsenate based on its electrocatalytic reduction at the poly(aniline-co-o-aminophenol) electrode

It was found that the copolymer poly(aniline-co-o-aminophenol) (PANOA) can strongly catalyze the reduction of arsenate in a NaCl solution, which was proved by cyclic voltammetry and the determination of activation energy. On the basis of the electrocatalytic reduction of arsenate, the PANOA copolymer was used as a probe to determine directly arsenate. The electrocatalytic activity of the PANOA electrode toward As(V) reduction strongly depended on the pH and the applied potential. Under the optimal conditions, the PANOA electrode can be used to determine directly As(V) concentration in a wide linear range (n = 19) of 0.949 and 495 μM with a correlation coefficient of 0.995 and a limit of detection of 0.495 μM. The sensitivity of the electrode was 0.192 μA μM^?1 cm^?2. The PANOA electrode had the good storage stability and a less negative operation potential of ?0.15 V (vs. SCE).