Evaluation of crystallization kinetics by means of DTA

The kinetics of bulk crystallization of Se_61.5Ge_{15 4}Sb_23.1 glasses was investigated from their thermal behaviour. In the thermal characterization of a glass the recrystallization temperature is highly dependent on both the rate of heating and the thermal history of the glass. Vitreous samples were prepared by quenching. From ratedependent curves it was found that the recrystallization process obeys first-order kinetics with an apparent activation enthalpy of 48±5 kcal/mole. Further analysis allows determination of both the activation enthalpy,H=90±4 kcal/mole, and the kinetic exponent of the Avrami equation,n=1.9±0.3.

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Zusammenfassung Die Kinetik der Massenkristallisation von Glas-Arten der Zusammensetzung Se_61.5Ge_15.4Sb_23.1 wurde an Hand ihres thermischen Verhaltens studiert. Bei der thermischen Charakterisireung von Glas hängt die Rekristallisationstemperatur stark sowohl von der Aufheizgeschwindigkeit als auch von der Wärmevorgeschichte des Glases ab. Glasige Proben wurden durch rasches Abkühlen hergestellt. Aus den geschwindigkeitsabhängigen Thermogrammen geht hervor, dass der Rekristallisierungsprozess der Kinetik erster Ordnung gehorcht, mit einer scheinbaren Aktivierungsenthalpie von 48±5 kcal/mol. Die weitere Analyse ermöglicht die Bestimmung sowohl der AktivierungsenthalpieH=90±4 kcal/mol als auch des kinetischen Exponentenn=1.9±0.3 der Avrami-Gleichung.

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Résumé Etude de la cinétique de la cristallisation dans la masse de verres Se_61.5Ge_15.4Sb_23.1 à partir de leur comportement thermique. La température de recristallisation dépend fortement tant de la vitesse de chauffage que de l'histoire thermique du verre. Des échantillons vitreux ont été préparés par refroidissement rapide. La recristallisation obéit à une cinétique du premier ordre, avec une enthalpie d'activation apparente de 48±5 kcal·mol^–1. Une analyse ultérieure permet de déterminer l'enthalpie d'activationH=90±4 kcal-mol^–1 ainis que l'exposant cinétiquen=1.9±0.3 de l'équation d'Avrami.

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Se_61.5Ge_15.4Sb_23.1 . , , . . , 48±5 /. H=90±4/ , n=1.9±0.3 .

     

Clinical analysis of human urine by means of potentiometric Electronic tongue

The Electronic tongue (ET) composed of different kind of potentiometric chemical sensors has been applied for the detection of urinary system dysfunctions and creatinine levels. The creatinine contents evaluated by ET were compared with those obtained by automated Jaffe’s method and GC-MS, obtaining a satisfying agreement for both methods. Partial least square regression discriminate analysis (PLS-DA) and feed forward back-propagation neural network (FFBP NN) classified 51 urine specimens from healthy volunteers in four classes, according to the creatinine content, showing that both techniques can satisfactorily differentiate urines according to this parameter. The best accuracy result of 92.2% correct classification of unknown samples was achieved with FFBP NN. Moreover, the possibility of ET system to distinguish between urine samples of healthy patients, and those with malignant and non-malignant tumor diagnosis of bladder has been shown.     

Simultaneous determination of cadmium and lead in urine by means of computerized potentiometric stripping analysis

In computerized potentiometric stripping analysis for cadmium and lead in urine the samples are acidified with hydrochloric acid to a total concentration equal to 0.5 M. The sample is pre-electrolyzed at —1.25 V vs. SCE for 2 min without prior sample heating or deoxygenation, the working electrode being a mercury pre-coated glassy-carbon electrode. The lead and cadmium concentrations are evaluated by means of standard addition. Detection limits are 1 nM for both elements. Results obtained by potentiometric stripping analysis and by solvent extraction/atomic absorption are compared for samples from unexposed persons and from one patient under penicillamine treatment. The relative merits of the potentiometric stripping, anodic stripping and atomic absorption techniques are discussed.     

Determination of tenuazonic acid in human urine by means of a stable isotope dilution assay

The content of tenuazonic acid in human urine was determined by a stable isotope dilution assay (SIDA) that was recently developed for the analysis of food commodities and extensively re-validated for urine matrix in this study. Linearity of the response curve was proven between molar ratios n(labeled standard)/n(analyte) of 0.02–100. The limits of detection and determination were 0.2 and 0.6 μg/L, respectively. The mean recovery of the stable isotope dilution assay was 102?±?3 % in the range between 1.0 and 100 μg/L. Interassay precision was 6.7 % (relative standard deviation of three triplicate analyses of a human urine sample during 3 weeks). The method was applied to two studies dealing with urinary excretion of tenuazonic acid: In the first study, tenuazonic acid was quantified in the 24-h urine of six volunteers from Germany (three female, three male) in a concentration range of 1.3–17.3 μg/L or 2.3–10.3 ng/mg^?1 creatinine, respectively. In the second study, two volunteers (one female, one male) ingested 30 μg tenuazonic acid by consumption of naturally contaminated whole meal sorghum infant cereals and tomato juice, respectively. The urinary excretion of the ingested tenuazonic acid was 54–81 % after 6 h, depending on matrix and volunteer. After 24 h, 87–93 % of the ingested amount of tenuazonic acid was excreted, but the fate of the remaining about 10 % is open. Thus, it is not possible to exclude potential health hazards for the consumer, completely.

In vivo Investigation of Plant-Cell Metabolism by means of natural-abundance 13C-NMR spectroscopy

Based on the natural abundance of ¹³C, in vivo ¹³C-NMR was used for the first time to monitor the metabolism of sucrose and hydroquinone ( 1 ) in cell suspensions of the plant Rauwolfia serpentina (L.) BENTH . ex KURZ . Cells converted sucrose extracellularly into α-D - and β -D -glucose as well as into β -D -fructofuranose and β -D -fructopyranose, respectively. The sugar mixture was completely taken up by the cells after 4 days. Hydroquinone fed at that time resulted in optimum conversion into its β -D -glucoside arbutin ( 2 ) within 10 h. A further metabolite, the primeveroside ( 3 ) of hydroquinone, appeared as a trace compound after 10 h. The formation of this diglycoside can be increased by further addition of sucrose.     

Quantitative analysis of benzene, toluene, and xylenes in urine by means of headspace solid-phase microextraction

A simple method for benzene, toluene, and xylenes (BTX) quantitative analyses in human urine was developed, using headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry detection in the single ion monitoring mode. The developed method is solventless, non-invasive, requires small volume of sample (1 ml), shows high selectivity, sensitivity, repeatability, and linearity (correlation coefficients >0.998), providing a useful alternative to assess human exposure to BTX compounds due to occupational reasons or eventual exposure to organic solvents. Detection limit varies from 0.28 to 0.5 ppb (v/v).     

Determination of oxolinic acid in cow's milk and human urine by means of a single-use phosphorimetric sensor

A single-use phosphorimetric drop plane sensor for the determination of oxolinic acid (OXA) is proposed. The sensor was formed by a 30x16 mm(2) rectangular strip of Mylar type polyester as solid support that contained a circular sensing zone, 6 mm in diameter and 20 mum in thickness, formed by PVC plasticized with tributylphosphate adhered to its surface. When the strip was introduced for 1 hour into a sample solution, the analyte was retained in the sensing zone, making it possible to directly measure the phosphorescence intensity emitted by the OXA in the solid phase, at lambda(exc)=330 nm and lambda(em)=449 nm. The variables that affect the construction of the sensor have been studied, along with the experimental variables that influence the fixation of the analyte in the sensor. The method's detection limit was 0.01 mg l(-1) with an applicable concentration range from 0.04 to 1.50 mg l(-1) and a repeatability of 2.6% at the concentration range of 0.8 mg l(-1). The method was applied to samples of human urine and cows' milk, with recovery percentages ranging between 97.6 and 108.7%.     

On the solution of diffusion controlled adsorption kinetics by means of orthogonal collocation

The problem of diffusion controlled adsorption kinetics is solved by orthogonal collocation for the Henry and the Langmuir isotherms. The dependence of the surface concentration of a surfactant on time is described by explicit formulae for the whole range of time. The results are compared with those obtained by power series expansions and finite difference methods and have a high accuracy for any time value. The method of orthogonal collocation has been shown to be very effective. It is suitable for applications to similar problems.     

Enzyme kinetics assay in ionic liquid-based reaction media by means of Raman spectroscopy and multivariate curve resolution

Enzymatic hydrolysis of p-nitrophenylphosphate by alkaline phosphatase in binary mixtures of water and 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF₄) was monitored with Raman microspectroscopy. Concentrations of emimBF₄ in the studied ionic liquid/water solvent systems ranged from 0 to 75% v/v. Multivariate curve resolution-alternating least squares (MCR-ALS) was successfully applied to the recorded Raman spectra in order to retrieve the concentration profiles and pure Raman spectra of the different species involved in the reaction. Michaelis-Menten constant (K_M) and maximum rate (V_max) of the reaction were calculated from the initial reaction phase for the different solvent systems studied, to investigate the effect of increasing concentration of the ionic liquid on the kinetic behavior. From this study, it was found that the ionic liquid inhibits the reaction under study decreasing both V_max and K_M.     

Characterization of differently bound water by means of the constants of thermal decomposition kinetics

Summary Compounds containing differently strong bound water molecules were investigated by thermogravimetry and derivative thermogravimetry. The following models were used: inorganic adsorbents, salts containing water of crystallization and a compound with structural water. The temperature interval, the stoichiometry of the water release were determined and kinetic parameters of the processes were calculated. These results could be brought into connection with the nature of the adsorption and crystallization water.

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Charakterisierung von verschieden gebundenem Wasser mit Hilfe der kinetischen Konstanten der thermischen Zersetzung

Zusammenfassung Thermogravimetrisch und durch derivative Thermogravinietrie wurden Verbindungen untersucht, die mit verschiedener Stärke gebundene Wassermoleküle enthalten: anorganische und organische Adsorbentien, Kristallwasser enthaltende Salze und Verbindungen mit Strukturwasser. Die Temperaturgebiete sowie die Stöchiometrie der Wasserfreisetzung wurden bestimmt und die kinetischen Parameter der Vorgänge ermittelt. Die Ergebnisse ließen sich zu der Natur des adsorptiven oder Kristallwassers in Beziehung bringen.

The authors thank Mr. P. Töke and Mr. M. Matula for running the computer program and Mrs. E. Borsay for the technical assistance.     

Inclusion kinetics of a nucleotide into a cyclodextrin cavity by means of ultrasonic relaxation

To examine a dynamic interaction between nucleotide and cyclic oligosaccharide, ultrasonic absorption measurements were carried out in aqueous solution containing beta-cyclodextrin (beta-CD) and adenosine 5'-monophosphate (AMP) in the frequency range of 0.8-95 MHz. A relaxational absorption was observed in the solution, although it was not found in the individual solution of beta-CD or AMP. From the concentration dependences of AMP on the relaxation time and the maximum absorption per wavelength, the cause of the relaxation was attributed to a perturbation of a chemical equilibrium associated with a complex formation between beta-CD (host) and AMP (guest). The rate constants for the formation and breakup processes of the complex were determined. Also, a standard volume change of the reaction was obtained. From comparisons of the obtained rate and thermodynamic parameters with those for beta-CD and various guests, it has been concluded that the adenine moiety is included in the beta-CD cavity and that the hydrogen bonds may play a role in the complex formation.     

沉淀双点滴定法测定盐酸左旋咪唑

以Ag^＋作滴定剂,分别用双点滴定法和传统电位滴定法对盐酸左旋咪唑片进行了测定。试液的配制采用了过滤和不过滤两种方法。测定结果表明：所有方法测得的结果均在《药典》允许的范围之内;本法测定结果与《药典》规定方法的对照偏差约为2%-3%;采用过滤和不过滤两种方法配制试液的测定结果之间的偏差约为1%。     

Automated determination of lead in urine by means of computerized flow potentiometric stripping analysis with a carbon-fibre electrode

Five different digestion procedures have been investigated. In the recommended procedure 5 ml of concentrated hydrochloric acid-nitric acid mixture (1:1) were added to a 5-ml urine sample. After 1 min the sample was diluted to 100 ml with distilled water. The sample was divided into two 50-ml samples and to one of them a standard addition of 10 microg/l. lead(II) was made. The two samples were analysed fully automatically by means of computerized flow potentiometric stripping analysis, the main features of the procedure being mercury-film precoating, electrolysis of the sample for 90 sec and subsequent stripping in 1M calcium chloride/0.1M hydrochloric acid. Tin and copper were found not to interfere if present at concentrations below 50 mg/l. but high concentrations of tin had to be masked by the addition of copper in order to form a copper-tin intermetallic compound. Complexing agents used in lead poisoning therapy did not interfere with the determination. The lead concentration in a Seronorm reference urine sample was found to be 93 microg/l. with a standard deviation of 8 microg/l. (n = 5), the certified value being 88 microg/l.     

Analysis of endogenous steroids in urine by means of multi-immunoaffinity chromatography and isotope ratio mass spectrometry for sports drug testing

Analytical and Bioanalytical Chemistry - Detecting the administration of naturally occurring but synthetically derived steroids (e.g., testosterone) in routine doping controls is particularly...