Direct LSC method for determination of bio-origin by C-14 measurement

The aim of the research was to test the generalized direct liquid scintillation spectrometry (LSC) method for bio-origin determination by measurement of C-14. Examples of diversified items with known and unknown bio-origin were measured by liquid scintillation counting and analyzed by procedures, developed for fuel samples. Bio-origin of fuels, lubricants and monomer resins were successfully determined via direct LSC method after simple sample preparation with acceptable accuracy and trueness despite their diversity in color, viscosity, density or chemical composition.

     

Establishment of rapid LSC method for direct alpha/beta measurements in waters

Development of rapid gross alpha/beta screening in waters has been presented. Modification of conventional ASTM method assumed direct mixing of samples with liquid scintillation cocktail, without any sample pretreatment. Optimization of method involved sample-to-cocktail ratio determination based on the achieved detection limit and quench level of sample as well as the optimal value of pulse shape analysis discriminator investigation. Results of calibration experiments and method’s validity measurements are presented. Direct alpha/beta method provides deviations <40% from reference values, but offers advantages over conventional alpha/beta measurements, it is ultra fast, simple and inexpensive test for efficient screening of water samples.     

Rapid method for the determination of fluoride in liquids

A rapid procedure has been developed for the determination of total fluoride in liquids. The samples are burned in a modified BECKMAN oxy-hydrogen burner The fluoride is scrubbed out of the products of combustion and determined in any conventional manner     

Comparison of two methods for 14C analysis from essential oils using LSC

Natural essential oil sample obtained from basil (Ocinum basilicum), and ethanol sample obtained from wine were measured to determine ¹⁴C specific activity, using two different sample preparation methods, and liquid scintillation counting method. The paper describes the use of two preparation methods, direct measurement method and CO₂ absorption method, and the results obtained for this comparative study. Depending on carbon content of the sample and bubbling time, different correction factors of carbon mass trapped in liquid scintillation cocktail were established for CO₂ absorption method.

     

Ion-selective electrodes for the determination of ionic liquids in water using direct potentiometry

Ion-selective electrodes (ISEs) with membranes based on ion exchangers plasticized with o-nitrophenyl octyl ether (NPOE), diethyl sebacate (DES), or dibutyl phthalate (DBP) are used for the determination of ionic liquids (ILs) in water. The membrane composition is optimized with respect to the ion-exchanger concentration and the plasticizer.     

Optimization of experimental variables in the dabsyl chloride derivatization of biogenic amines for their determination by RP-HPLC

Summary In the last few years special attention has been paid to the pre-column derivatization of biogenic amines with dabsyl chloride because proper experimental conditions for this reaction are very important. In this study, an experimental design (Doehlert design) was used to optimize the variables involved in the dabsylation of the following amines: histamine, tyramine, phenylethylamine, tryptamine, cadaverine, putrescine, spermidine, and spermine. The optimum experimental conditions for forming the dabsyl derivatives are: reagent concentration, 1.75.10⁻³ M; pH, 8.2; temperature, 70°C; heating time (t _h ), 21 min. Under these conditions good chromatographic repeatability is obtained.     

Optimization of chromatographic parameters for the determination of biogenic amines in wines by reversed-phase high-performance liquid chromatography

A method suitable for the determination of eight biogenic amines (histamine, tyramine, phenylethylamine, tryptamine, cadaverine, putrescine, spermidine and spermine) in wines has been developed. The method involves derivatization of the amines by treatment with dabsyl chloride, after which the derivates were analysed by reversed-phase liquid chromatography with gradient elution and spectrophotometric detection at 446 nm. Different variables affecting separation were optimized. Validation of the method included calibration experiments, the addition of standards amines for the determination of recovery and repeatability tests. Good linearity of the responses was obtained up to 500 microg l(-1), except for putrescine (up to 2100 microg l(-1)). The detection limits ranged between 10 and 60 microg l(-1) for standard solutions. The method was successfully applied to the analysis of five Spanish wines.     

A method for 237Np determination with LSC in the experiment of neptunium sorption onto bentonite

A method was developed for the determination of ²³⁷Np with liquid scintillation counting (LSC) in the batch experiment of neptunium sorption onto bentonite. Before we use the pulse shape analysis (PSA) technique to discriminate α/β emission, a new approach was developed to set the optimum PSA by measuring a mixed α/β emitters sample and a background sample. The mathematic treatment of neptunium spectrum indicated that at the selected PSA-level of 38 approximately 86 % of the total α emission is detected, which is suitable for the determination of samples in the batch sorption experiments. Moreover, we confirmed that, at mass to volume radio 0–10 g/L the bentonite suspension in samples has a little impact on LSC determination. Thus, sorption percentage can be easily obtained by counting equivalent amount of suspension and supernatant from the same sample. Therefore, ²³⁷Np samples of batch sorption experiments could be detected with LSC quickly and effectively.     

14 MeV INAA nitrogen determination in coal conversion liquids

Fast neutron activation analysis has been used for the direct determination of nitrogen in coal conversion liquids. In our previous work on coals, solid standards such as N-1-naphthylacetamide. NBS SRM 912 urea and NBS SRM 148 nicotinic acid were used for nitrogen determinations. In this work, a set of organic liquids was selected and evaluated for use as nitrogen standards in the analysis of coal-derived liquids. The use of the liquid standards minimizes problems associated with maintaining uniform irradiation and counting geometries and self absorption differences related to varying matrix densities. The standard liquids were selected using criteria of high boiling point, well-defined stoichiometry, high-purity, non-hygroscopic nature and simple C−H−N elemental compositions. Excellent agreement between the 14 MeV INAA data and calculated stoichiometric values has been demonstrated for liquids with nitrogen contents from 1.89 to 39.95%. The liquid standards have been used to determine nitrogen in a set of typical coal conversion liquids and several international standards.     

Routine method for the determination of the optical constants of liquids

A modification of the Kramera-Kronig method is used to obtain the spectra of the absorption and refraction indices, k and n, of benzene, chloroform and carbon tetrachloride from their infrared attenuated total-internal-reflectance spectra. The existing software of the Fourier-transform infrared spectrometer is applied for the calculation. For medium-strength bands with k between 0.004 and 0.3, agreement with earlier values is within a few percent, whereas for strong bands, the present k values are about 20% lower.     

Optimization and validation of a method for the direct determination of catechin and epicatechin in red wines by HPLC/fluorescence

The present paper describes a direct procedure for the determination of catechin and epicatechin concentrations in red wines employing reverse-phase high performance liquid chromatography (RP HPLC) and detection by fluorescence. The method was performed using a sample volume of 10 µL without dilution. The separation process employed a Chromolith performance RP-18e (100 mm × 4.6 mm) column, and the mobile phase was composed of solvent A: methanol-acetic acid-water (90:8:2) and solvent B: water-acetic acid-methanol (10:2:88) at a flow rate of 1.0 mL min^− 1. Linearity was observed in the range of 1 to 30 mg L^− 1, with limits of detection and quantification of 0.27 and 0.89 mg L^− 1, respectively, for catechin and 0.33 and 1.01 mg L^− 1, respectively, for epicatechin. The precisions estimated by the relative standard deviation were 3.34 and 1.09% for catechin concentrations of 0.5 and 20 mg L^− 1 respectively and 2.82 and 0.49% for epicatechin concentrations of 0.5 and 20 mg L^− 1, respectively. The evaluation of the accuracy was done using an addition/recovery assay. Four wine samples were used, and the recoveries varied from 105 to 108% for catechin and from 97 to 119% for epicatechin. The method was applied to the analysis of red wine samples collected from the São Francisco region, Bahia State, Brazil. Nine samples were analyzed, and the catechin and epicatechin concentrations varied from 7.51 to 73.20 and from 5.08 to 43.32 mg L^− 1, respectively. The concentrations found agree with data reported in the literature.     

Capillary zone electrophoresis of proteins applying ionic liquids for dynamic coating and as background electrolyte component

The use of ionic liquids in capillary electrophoresis, either as coating material or as components of the background electrolyte needs systematic standardization to set up optimal conditions. Excellent separation of the proteins was achieved using 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF₄]) or 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) ionic liquids using the properly made ionic-liquid–water binary mixtures for the experiments. The binary mixture has a distinctly stable and well perceptible low pH, which depends on the concentration of the ionic liquid, and on the preparation time of the mixture. Optimal conditions for the electrophoretic separation were obtained upon a multivariate analysis of the experimental parameters (applied voltage, migration time, concentration, and type of the ionic liquid). The standardized condition provides a low electroendosmotic flow toward the anode, which, however, did not hinder the proteins to migrate toward the cathode. The migration of cytochrome c, lysozyme, myoglobin, trypsin, and apo-transferrin at a pH around 2, far below the isoelectric points of the proteins, showed RSD values of the migration times less than 7.5% and less than 6.5% when using [emim][BF₄] or [bmim][BF₄], respectively, either in run-to-run or day-to-day experiments. The determination of the extent of the EOF is not possible with the commonly used EOF markers, due to interaction with the ionic-liquid constituents. The interaction of the ionic liquids with the proteins influences the migration order in zone electrophoresis. This method has been applied successfully for the analyses of real biological samples such as proteins from egg whites and human tears.     

An optimized direct method for the determination of carboxylic acids in beverages by HPLC

Summary A direct method for the simultaneous determination of tartaric, malic, lactic, acetic, citric, shikimic, fumaric and succinic acids in fruit juices and wines by isocratic reversed phase HPLC is reported.The variables (pH, ionic strength, flow and temperature) have been optimized by a modification of the original simplex method. The separation factor (s) and calibrated resolution product (r^*) have been used as criteria for selectivity optimization. After validation, the method has been applied to the determination of carboxylic acids in apple, orange and lemon juices, white and red wines and musts during the fermenation process.     

A new ultra-pressure liquid chromatography method for the determination of biogenic amines in cheese

A fast and reliable ultra-performance liquid chromatography (UPLC™) method for the determination of biogenic amines (ethanolamine, methylamine, agmatine, histamine, dimethylamine, ethylamine, octopamine, pyrrolidine, dopamine, isopropylamine, propylamine, tyramine, putrescine, butylamine, cadaverine, tryptamine, 2-phenylethylamine, 3-methylbutylamine, spermidine, spermine) in cheese was established. After pre-column derivatization with 6-aminoquinolyl-N-hydroxy-succinimidyl carbamate (AQC), 20 primary and secondary biogenic amines were separated on an Acquity™ UPLC™ column (BEH C₁₈, 1.7 μm; 2.1 mm × 50 mm) within 9 min. Limits of detection (mg/100 g cheese) ranged from 0.04 (ethanolamine) to 1.62 (spermine), and limits of quantification were between 0.16 (ethanolamine) and 6.09 (spermine). The UPLC™ method was applied to the analysis of 58 cheese samples as retailed in Austria. About 13.8% of samples had a histamine content above 10 mg/100 g, and 22.4% had a tyramine content above 10 mg/100 g. Moreover, 8.6% of samples had a putrescine or cadaverine content higher than 10 mg/100 g. The total concentration of biogenic amines in two cheese samples was about 194 mg/100 g. Thus, obligatory monitoring of biogenic amines should be considered to ensure quality of cheese in future.     

A kinetic method for the direct determination of cellobiose hydrolysis by β-glucosidases

TheSomogyi—Nelson colorimetric method is applied in a new manner which is more suitable for following the kinetics of cellobiose hydrolysis catalyzed by -glucosidase (EC 3.2.1.21). TheSomogyi—Nelson colour reagent, which is a mixture of the solutions of the reagent ofSomogyi and that ofNelson in a volume ratio of 1:1, is added to the enzyme-substrate solution at the very start of the reaction. The colour reagent reacts with the product (D-glucose). Under the reaction conditions (0.1M acetate buffer,pH = 5.0 and temperature 37°C) the colour reagent does not affect the enzyme activity. The method excludes any inhibition of the product, owing to the continuous removal of the latter by the colour reagent. The method suggested has been applied to monitor cellobiose hydrolysis with -glucosidase, contained in four cellulase enzyme preparations from various fungal sources. The values of theMichaelis parameters (Km, V) were determined.

---

Eine kinetische Methode zur Verfolgung der Hydrolyse von Cellobiose durch ß-Glucosidasen

Zusammenfassung Die kolorimetrische Methode nachSomogyi undNelson wird nach einem neuen Verfahren zur Verfolgung der Kinetik der hydrolytischen Spaltung von Cellobiose, katalysiert durch -Glucosidase (EC 3.2.1.21), angewandt. Das Farbreagenz nachSomogyi undNelson (Mischung der Reagenzien vonSomogyi undNelson im Volumenverhältnis 1:1) wird der Enzym-Substrat-Lösung zu Beginn der Reaktion hinzugefügt. Das Farbreagenz tritt mit derD-Glukose in Reaktion, wobei unter den gegebenen Reaktionsbedingungen (0,1M Azetatpuffer,pH = 5,0 und 37°C) die Enzymaktivität nicht beeinflußt wird. Die entwickelte Methode wurde zur Verfolgung der Hydrolyse von Cellobiose durch ß-Glucosidasen, die in vier Enzympräparaten aus verschiedenen Pilzstämmen enthalten waren, angewandt. Es wurden dieMichaelis-Parameter (Km, V) bestimmt.

     

A new method for the determination of biogenic amines in cheese by LC with evaporative light scattering detector

This paper presents a new LC method with evaporative light scattering detection (ELSD), for the separation and determination of the biogenic amines (histamine, spermidine, spermine, tyramine, putrescine and β-phenylethylamine) which are commonly present in cheese, as their presence and relative amounts give useful information about freshness, level of maturing, quality of storage and cheese authentication. The LC-ELSD method is validated by comparison of the results with those obtained through LC-UV determination, based on a pre-column dansyl chloride derivatisation step. The obtained data demonstrate that both methods can be interchangeably used for biogenic amines determination in cheese. The new LC-ELSD method shows good precision and permits to achieve, for standard solutions, limit of detection (LOD) values ranging from 1.4 to 3.6 mg L⁻¹ and limit of quantitation (LOQ) values ranging from 3.6 to 9.3 mg L⁻¹. The whole methodology, comprehensive of the homogenization-extraction process and LC-ELSD analysis, has been applied in the analysis of a typical Calabria (Southern Italy) POD cheese, known as Caciocavallo Silano. The most aboundant amine found was histamine, followed, in decreasing order, by tyramine, spermine, putrescine, β-phenylethylamine and spermidine, for a total amount of 127 mg kg⁻¹. This value does not represent a possible risk for consumer health, according to the toxicity levels reported in literature and regarded as acceptable.