Non-destructive gamma-spectrometry analysis of cosmogenic radionuclides in fragments of the Ko?ice meteorite

Results of analysis of cosmogenic radionuclides (^57,58,60Co, ⁵⁴Mn, ⁴⁶Sc, ²²Na, ⁴⁸V and ²⁶Al) in fragments of the Ko?ice meteorite are presented and discussed. Analyses were carried out using a low-level HPGe-spectrometer placed in a lead-iron-copper shield. Twelve meteorite fragments were available for the analysis with masses from 27 to 2,163?g. The lowest massic activities were observed for ⁴⁶Sc (down to 0.1?mBq/g), and the highest for ²²Na (up to 2?mBq/g). The measured radionuclide activities showed differences between fragments, as indicated mainly by the ⁶⁰Co data, which were caused by different positions of meteorite fragments from the center of the meteorite body.     

Refinement of Pu parent–daughter isotopic and concentration analysis for forensic (dating) purposes

Plutonium (Pu) metal samples from an interlaboratory exchange exercise and simulated swipe samples were dated using plutonium–uranium (Pu–U) and plutonium–americium (Pu–Am). Metal data were evaluated for consistency and the swipe data against its source material. Metal ages based on ²³⁹Pu versus ²³⁵U and ²⁴⁰Pu versus ²³⁶U agreed to within a few percent, while the ²³⁸Pu–²³⁴U and ²⁴¹Pu–²⁴¹Am measurements had larger uncertainties. Swipe ages compared favorably with the material’s known history. Neptunium (²³⁷Np) analyses were examined in the context of the ²⁴¹Pu–²⁴¹Am–²³⁷Np system to estimate whether Np can provide insights on material from which Am, Np, and U were removed.     

Fluorometric determination of sugars using fluorescein-labeled concanavalin A–glycogen conjugates

The fluorescence of fluoresceinisothiocyanate-labeled concanavalin A (FITC-Con A) was quenched by forming an FITC-Con A–glycogen conjugate and dequenched upon addition of sugars to the conjugate solution due to disaggregation of the conjugate. However, fluorescence quenching was barely observed upon formation of FITC-Con A–dextran conjugate. The sugar-induced fluorescence response of the FITC-Con A–glycogen conjugate depended significantly on the type of sugar: methylated α-D-glucose and α-D-mannose both induced high and rapid responses, while the responses to D-mannose and D-glucose were moderate. In contrast, no response was observed in the presence of D-galactose due to a lack of affinity to Con A. Thus, it is apparent that D-glucose and other sugars can be detected via the fluorescence of the FITC-Con A–glycogen conjugate.      

Triad sequence determination of ethylene–propylene copolymers – application of quantitative 13C NMR

A methodology for acquiring fully quantitative ¹³C{¹H} NMR spectra for high performance ethylene–propylene copolymers has been proposed. To minimize the spectral acquisition time without sacrificing spectral quality, different amounts of chromium(III)acetylacetonate relaxation agent has been added to optimize its concentration. The study demonstrates the critical setting of delay time for determining six triad distributions from eight discrete set of resonances which otherwise leads to inaccurate determination of triad concentrations. It allows precise integral measurements of low intensity resonances depending on copolymer composition, and significant reduction of experimental time.     

Quantitative determination of cationic modified polysaccharides on hair using LC–MS and LC–MS–MS

Cationic polysaccharides containing N-hydroxypropyl-N,N,N-trimethylammonium substituents are widely used as conditioning agents for hair-care products. A sensitive method has been developed for the quantitation of these polymers. After acidic extraction from hair the polysaccharides are hydrolyzed using trifluoroacetic acid. The cationic monoglycosides are determined using liquid chromatography–tandem mass spectrometry (LC–MS–MS). The developed method is independent of hair treatment. Even hair cut from test persons after customary hair wash can be analyzed. After treatment of natural and bleached hair tresses using a real-life treatment procedure 180 g and 300 g of polymer per gram hair were quantified, respectively. Additionally the fragmentation mechanism of the cationic N-hydroxypropyl-N,N,N-trimethylammonium group during electrospray ionization was investigated. A mass loss of 60 Da in combination with loss of a single charge is observed and associated with cleavage of trimethylamine and a proton. It is assumed that this process is promoted by the anionic counter-ion which might be hydroxide in an aqueous environment.     

Accurate determination of naturally occurring radionuclides in Philippine coal-fired thermal power plants using inductively coupled plasma mass spectrometry and γ-spectroscopy

There is an increased interest in measuring naturally occurring radioactive materials (NORM) like coal, fly ash considering health hazards caused by naturally occurring radionuclides. This paper presents activity concentration (AC) of ²²⁶Ra, ²²⁸Ra, ²³²Th, ²³⁸U and ⁴⁰K in feed coal, bottom and fly ash samples from Philippines coal-fired thermal power plants using inductively coupled plasma mass spectrometry (ICP-MS) and high-purity germanium gamma spectroscopy (HPGe γ-spectroscopy). Coal, bottom and fly ash samples were digested using a microwave oven with a mixture of HNO₃, HClO₄ and HF. Uranium (²³⁸U) and thorium (²³²Th) ACs were also analyzed from samples using ICP-MS. A good correlation was found for the measurement of U and Th using both techniques (R² = 0.97 and 0.94 respectively). ICP-MS measurements showed the highest AC of ²³²Th and ²³⁸U in fly ash and lowest for feed coal samples. With HPGe γ-spectroscopy measurements, highest AC (in Bq kg^{− 1}) of ²²⁶Ra, ²²⁸Ra, ²²⁸Th and ⁴⁰K, were noticed in fly ash followed by bottom ash and feed coal. ICP-MS method is rapid for the measurement of uranium and thorium in comparison to γ-spectroscopy as secular equilibrium is not required. Activity concentrations of bottom and fly ash samples were found to be within the reported values worldwide and below the International Atomic Energy Agency recommended values for regulatory control.     

Liquid–liquid microextraction and spectrophotometric determination of anionic surfactants using Astra Phloxine FF

A novel and simple procedure for determination of anionic surfactants has been developed. The method is based on the reaction of sodium dodecyl sulphate (SDS) with Astra Phloxine FF reagent at pH 3–8, followed by liquid–liquid microextraction of the formed ion associate into an organic phase containing a mixture of carbon tetrachloride and dichloroethane (4:1, v/v) and subsequent UV-Vis detection at 555 nm. The calibration plot was linear in the range 0.006–0.29 mg L^?1 of SDS. The limit of detection (LOD), calculated based on 3s, is 0.002 mg L^?1. The method was applied to the determination of anionic surfactants in real wastewater samples.     

Solvent extraction and extraction–voltammetric determination of phenols using room temperature ionic liquid

The phenolic compounds phenol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dinitrophenol, 1-naphthol, 2-naphthol, and 4-chlorophenol are extracted nearly quantitatively from aqueous solution into the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF₆) in molecular form at pH<pK_a. Picric acid is extracted efficiently in anionic form. Recovery of pyrocatechol and resorcinol is much lower. The effect of pH, phenol concentration, and volume ratio of aqueous and organic phases were studied. Ionic liquid BMImPF₆ is shown to be suitable for extraction–voltammetric determination of phenols without back-extraction or addition of support electrolyte. The electrochemical window of BMImPF₆ at various electrodes was determined, and voltammetric oxidation of phenols and reduction of nitrophenols in BMImPF₆ was studied.     

Potentiometric determination of ascorbic acid in water–acetonitrile solution using pyrite and chalcopyrite electrodes

Journal of Solid State Electrochemistry - Performance characteristics of the solid-state potentiometric sensors, based on natural sulfide minerals pyrite and chalcopyrite, are assayed in aqueous...     

Picogram determination of estrogens in water using large volume injection gas chromatography–mass spectrometry

In this study, a simple and efficient large volume injection gas chromatography–mass spectrometry (GC-MS) method, via a programmable-temperature vaporizer (PTV) inlet, has been developed and applied in the determination of estrogens in environmental water samples without a prior derivatization process. Three commonly used estrogens estrone, 17 β-estradiol and 17 α-ethynylestradiol were selected as target compounds for this study. It has been demonstrated that the type of gas chromatograph liner and the initial inlet temperature can greatly affect the response intensity of estrogens. Three different types of PTV liners have been studied; the multibaffle liner generated the strongest response intensities towards the estrogen analytes. The results showed that the response intensities of estrogens reduced sharply while the initial inlet temperature increased. Various instrument conditions and sample preparation methods were studied in detail. The optimized method has been validated with good linearity, precision and accuracy. The method detection limit of each estrogen was found to be 0.041 ng/L for estrone, 0.046 ng/L for 17 β-estradiol and 0.031 ng/L for 17 α-ethynylestradiol. To the best of our knowledge, these results represent the best sensitivities achieved for estrogens analyzed in water samples via traditional GC-MS method without a derivatization process. This method has been successfully applied in the analyses of different water samples.     

Methods of determination of sulfur yperite–DNA adducts

A review of publications on methods for the determination of sulfur yperite adducts with DNA in different biological samples (whole blood, urine, organ and tissue homogenates) is presented. Methods of formation and structures of the most important adducts are considered. Methods of the isolation and hydrolysis of adducts with DNA from biological samples are summarized.     

Voltammetric determination of uric acid by using gold nanotubule electrode

Gold nanotubule membranes were prepared by using electroless deposition of gold within the pores and surfaces of polycarbonate track-etched membranes.And the gold nanotubule membrane was used as an electrode for determination of uric acid in urine samples for the first time.In Britton-Robinson buffer of pH 4.56,uric acid exhibited well-defined differential pulse voltammograms.And the interference between coexistent ascorbic acid and uric acid was overcome owing to the attractive ability of the gold nanotubule electrode to yield a large anodic peak difference ca.0.404 V(vs.SCE).The proposed method was then applied to the determination of uric acid in urine without any pretreatment.     

Trace determination of EDTA from water samples using dispersive liquid–liquid microextraction coupled with HPLC-DAD

Dispersive liquid–liquid microextraction (DLLME) in conjunction with high-performance liquid chromatography-diode array detection (HPLC-DAD) has been applied to the extraction and determination of EDTA in sediments and water samples. The effect of extraction, nature and volume of disperser solvent, pH value of sample solution, extraction time and extraction temperature were investigated. Under the optimal conditions the analytical range of EDTA was from 3.0 to 50.0 μg L^?1 with a correlation coefficient of 0.9982 and a detection limit of 1.7 μg L^?1. The relative standard deviation (RSD) was less than 5.4% (n?=?5), and the recovery values were in the range of 89–95%. The simplicity, high enrichment, high recovery and good repeatability are the main advantages of the method presented. The DLLME-HPLC-DAD method was successfully applied to the analysis of EDTA in aqueous samples.     

Application of dispersive liquid–liquid microextraction for the determination of donepezil in urine by HPLC using a core–shell column

A rapid and novel method combining dispersive liquid–liquid microextraction and high-performance liquid chromatography coupled with fluorescence detection was developed for the determination of donepezil in human urine. Parameters affecting extraction efficiency and chromatographic determination, such as the type and volume of the extraction and disperser solvent, pH of sample for dispersive liquid–liquid microextraction, mobile-phase composition, pH, column oven temperature, and flow rate for chromatographic determination, were evaluated and optimized. Using a C₁₈ core–shell column (7.5 × 4.6?mm, 2.7?μm), the determination of donepezil was accomplished within 5?min. Under optimum conditions, developed method was linear in the range of 0.5–25?ng?mL^?1 with the correlation coefficient >0.99. Limit of detection was 0.15?ng?mL^?1. The relative standard deviation at three concentration levels (2, 12.5, and 20?ng?mL^?1) was less than 11% with accuracy in the range of 96.9–102.8%. The results of this study demonstrate that the use of dispersive liquid–liquid microextraction and core–shell column can be considered as a powerful tool for the analysis of donepezil in human urine.     

Solid-phase extraction of personal care products using mixed-ligand metal–organic framework combined with spectrophotometric determination

The adsorption of personal care products (diclofenac sodium and chlorhexidine digluconate) on a mixed-ligand metal–organic framework based on a complex of nickel terephthalate with 2,2'-bipyridine was investigated by solid-phase extraction in combination with spectrophotometric analysis.     

The determination of β-agonist residues in bovine tissues using liquid chromatography–tandem mass spectrometry

We aimed to develop a rapid, simple and reproducible method based on LC–tandem mass spectrometry (LC–MS/MS) to analyze β-agonist residues (clenbuterol, zilpaterol, ractopamine and isoxsuprine) in bovine tissues. The method was validated in accordance with the European Council Decision 2002/657/EC. The samples were homogenized, and then 10 mL of an acetate buffer was added to a 5-g sample. The sample was then centrifuged at 12,000 rpm and filtered. Sodium hydroxide (2 m ) was added to adjust pH of the sample that was centrifuged again. The extract was filtered through a solid-phase extraction column. The residue was re-dissolved in 250 μL acetonitrile and then subjected to LC–MS/MS. The separation was done on a C₁₈ column. The mobile phase consisted of 0.1% formic acid in deionized water and 0.1% formic acid in methanol. The mean recoveries of β-agonists were in the range of 84.3%–119.1% with relative standard deviations (%RSDs) of 0.683%–4.05%. Decision limits and detection capabilities of the analytes ranged from 0.0960 to 4.9349 μg/kg and from 0.0983 to 5.0715, respectively. This method was used to detect four β-agonists in 100 bovine muscle, 100 liver and 100 kidney tissues from a slaughterhouse. No residue was found above the maximum residue limit level.     

Colorimetric determination of 8-hydroxy–2′-deoxyguanosine using label-free aptamer and unmodified gold nanoparticles

We report on a sensitive and specific method for the visual and colorimetric detection of 8-hydroxy-2′-deoxyguanosine (8-OHdG) in human urine by using the 8-OHdG-aptamer (Apt) as the recognition element. The aptamer was adsorbed on the surface of gold nanoparticles which enhances their stability. On addition of 8-OHdG, the conformation of the aptamer changes to form a G-quadruplex structure, thereby losing the ability to protect the nanoparticles and causing a color change from red to blue. The conformational changes were also studied by circular dichroism. The response is linearly dependent on the concentration of 8-OHdG in the range from 5.6 to 282 nM, the limit of detection is 1.7 nM, the relative standard deviation ranges from 1.1 to 4.2 % (for n?=?6), and the recoveries range from 95.9 to 104.9 %. The method paves the way for visual analysis of samples without the use of costly instruments.

A concise synthesis of tetrahydroisoquinoline-1-carboxylic acids using a Petasis reaction and Pomeranz–Fritsch–Bobbitt cyclization sequence

A sequence of two reactions: the Petasis reaction, in which an aminoacetaldehyde acetal was used as the amine component, followed by Pomeranz–Fritsch–Bobbitt cyclization, has been shown to be a convenient and simple method for the synthesis of tetrahydroisoquinoline-1-carboxylic acids. Using this method several acids have been prepared in good to excellent yields and characterized as hydrochloride salts.