A new approach to qualitative analysis of organophosphorus pesticide residues in cucumber using a double gas chromatographic system: GC-pulsed-flame photometry and retention time locking GC-mass spectrometry

A qualitative method for the screening of organophosphorus pesticides (OPs) that could present in different types of vegetables has been established and validated. A typical multi-residue extraction procedure of OPs using ethyl acetate and sodium sulphate has been applied. No clean-up was required after extraction, and concentrated extracts were analysed by gas chromatography with pulsed-flame photometric detection (GC-PFPD). Confirmation of compound identities was performed by gas chromatography with mass spectrometric detection (GC-MSD) in the electron impact (EI) mode with full scan acquisition. Retention time locking (RTL) software was used in order to improve the method capability of identification and confirmation. Spiked samples at pesticide concentrations equal to the maximum residue level (MRL) were used to check chromatographic performance and for validation studies. The proposed method allows a rapid and accurate identification of the studied OPs until the ng ml(-1) range for those whose use is forbidden, and above their MRL concentration for the rest.     

Mixtures of nonionic and anionic surfactants: interactions with low-molecular-mass homopeptides

The interaction between low molecular-mass homopeptides and mixtures of nonionic and anionic surfactants has been assessed by using reversed-phase thin-layer chromatography. The relative strength of interaction for mixtures of sodium dodecylsulfate and tridecylalcohol diglycolate (GNX) at the molar ratios of 8:2, 6:4, 4:6 and 2:8 has been calculated and its relationship with the physicochemical parameters (number of amino acid units, hydrophobicity, side chain bulkiness, electronic characteristics) of peptides has been computed by stepwise regression analysis. Each peptide interacted with each surfactant mixture the strength of interaction markedly depending on both the character of the peptide and the composition of the surfactant mixture. The hydrophobicity and electronic properties of the amino acid units exerted the highest influence on the strength of interaction at the highest concentration of the nonionic surfactant (GNX) whereas the number of amino acid units in the peptide molecule and the bulkiness of the amino acid side chain governed the strength of interaction at the lowest concentration of GNX.     

Atomic spectroscopy for detection in thermal analysis

An atomic absorption spectrophotometer is coupled to a conventional thermoanalytical quartz furnace as used for TG and DTG to detect the thermally evolved products. In this combined system, the dry aerosol (smoke) obtained by cooling the vapour evolved is transported from the furnace to the flame for metal-specific atomic absorption detection. The particular design of the furnace outlet promotes the formation of stable aerosols. Optimum experimental conditions were determined, using zinc chloride solution, by varying the specimen mass, the heating rate and the flow rate of the furnace gas at a linear temperature program. The absorbancevs. temperature curves obtained with this method for various zinc compounds are compared with the corresponding DTG curves. The applicability of the technique for studying heterogeneous reactions with carbon tetrachloride and hexane vapours is presented. The utilization of an atomic absorption spectrophotometer equipped with a quartz cuvette for detecting the thermal evolution of mercury vapours is described, as well as detection potentials by molecular absorption (for NO and NH₃) and light scattering (for smoke evolved from organic matter). The results obtained with the suggested methods may, in some respects, valuably complement the results achieved with DTG and with flame ionization detection.

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Zusammenfassung Ein Atomabsorptionsspektrometer wurde mit einem konventionellen thermoanalytischen Quarzofen gekoppelt um thermische Abspaltprodukte nachzuweisen. In diesem kombinierten System wird das durch Kühlung des entwickelten Dampfes erhaltene Aerosol (Rauch) vom Ofen in die Flamme für den metallspezifischen Atomabsorptionsnachweis übergeleitet. Die spezielle Ausbildung der Austrittsöffnung gewährleistet die Bildung eines stabilen Aerosols. Die optimalen Versuchsbedingungen wurden durch Zinkchloridlösungen bei Anderung der Probenmasse, der Aufheizgeschwindigkeit und der Strömungsgeschwindigkeit des Ofengases im linearen Temperaturprogramm ermittelt. Die mit dieser Methode für verschiedene Zinkverbindungen erhaltenen Absorptions—Temperatur-Kurven wurden mit den entsprechenden DTG-Kurven verglichen. Die Anwendbarkeit dieser Technik bei dem Studium heterogener Reaktionen mit Kohlenstofftetrachlorid und Hexandämpfen wird gezeigt. Der Einsatz eines mit einer Quarzküvette zum Nachweis der thermischen Entwicklung von Quecksilberdampf versehenen Atomabsorptionsspektrometers wird beschrieben, sowie die Nachweisgrenze durch molekulare Absorption (für NO und NH₃) und Lichtstreuung (für aus organischem Material entwickelten Rauch). Die bei den beschriebenen Methoden erhaltenen Ergebnisse können, in mancher Hinsicht, die durch DTG und Flammenionisationsnachweis erhaltenen Ergebnisse wertvoll ergänzen.

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- , , . (), , . . , . — , , -. . - , , , ( NO NH₃) ( , ). , , , - .

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Presented in part at the 24th Hungarian Conference on Analytical Sptecroscopy, Miskolc, June 15–18, 1981. Abstracts pp. 159–162.

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The authors wish to express their thanks to S. Gál for his assistance in the present application of the temperature programmer developed by him and his group, and for the valuable discussions on the subject. Thanks are also due to K. Tomor and J. Kmives who participated in the comparative thermoanalytical measurements and their analysis.     

Simple and rapid determination of the drug naproxen in pharmaceutical preparations by heavy atom-induced room temperature phosphorescence

A simple, selective and sensitive heavy atom-induced room temperature phosphorimetric method (HAI-RTP) is described for the determination of naproxen (NAP) in pharmaceutical preparations. The phosphorescence signals are a consequence of intermolecular protection when analytes are, exclusively, in presence of a heavy atom salt and sodium sulfite as an oxygen scavenger to minimize RTP quenching. These variables selection constitute the basis of a HAI-RTP method for the determination of naproxen (detection limit 17.6 ng ml(-1); 1.71% relative standard deviation at 250 ng ml(-1)). The method has been applied satisfactorily to the analysis of pharmaceutical preparations.     

Distribution of mercury in soil organic matter fractions obtained by dissolution/precipitation method

Sequential multistep procedure, usually used for the fractionation and characterization of soil organic matter was tested for Hg content in the individual steps and fractions. Under general laboratory conditions serious problems have arosen during the attempt in the Hg mass balance calculation. Several sources of Hg contamination were recognized. The most serious was the background concentration of Hg even in research grade chemicals (what is in general not declared) and laboratory air. The work on operational Hg speciation as non-humic bound, humic acid, fulvic acid bound proceeds from the established status-quo on distribution of mercury of soil organic matter.     

Cyclodextrin Solubilization of the Antibacterial Agents Triclosan and Triclocarban: Effect of Ionization and Polymers

The natural β-cyclodextrin (βCD) and its complexes have limited solubility in aqueous solutions. This low aqueous solubility, as well as low aqueous solubility of the guest molecule (i.e. triclosan or triclocarban (TCC)), can result in low complexation efficiency (CE). The purpose of this study was to enhance the apparent intrinsic solubility (S ₀) of the guest molecule and its βCD complexes through ionization and addition of auxiliary compounds such as polymers, amino acids and metal ions. Both triclosan (pK _a 7.9) and TCC (pK _a 12.7) are weak acids. Addition of ethanol to the complexation medium enhanced S ₀ of both triclosan and TCC but at the same time ethanol lowered the stability constant (K _c ) of their βCD complexes resulting in overall lowering of CE. Addition of small amount of water-soluble polymers enhanced the βCD solubilization of both guests, and addition lysine enhanced the solubilization of TCC. Ionization of triclosan resulted in significant enhancement of CE and enhanced triclosan release from tablets containing triclosan/βCD complex. The effect of ionization was not as pronounced in the case of TCC.This revised version was published online in July 2005 with a corrected issue number.     

Characterization of anthocyanin extracts from maize kernels

The aim of the present work is to characterize the pigments present in the kernel of four native maize varieties related to the races Arrocillo, Cónico, Peruano, and Purepecha to determine their possible use as natural dyes. Total anthocyanin content is determined by a conventional spectrophotometric method, and anthocyanin analysis is done by high-performance liquid chromatography. The stability of the pigment at pH is also evaluated. The four maize samples contained anthocyanin in both the pericarp and aleurone layer. Total anthocyanin content among samples ranged from 54 mg/100 g of sample to 115 mg/100 g of sample. Anthocyanin profiles are almost the same among the four samples. Differences are observed only in the relative percentage of each anthocyanin. The anthocyanins identified are cyanidin-3-glucoside, pelargonidin- 3-glucoside, peonidin-3-glucoside, cyanidin-3-(6" malonylglucoside), and cyanidin-3-(3",6"-dimalonylglucoside). Anthocyanin extracts showed similar behavior in solutions with different pH. From pH 1-6 lambdamax values are maintained almost constant; however, above this pH value, a marked increase is observed in the bathochromic shifts, but the bluish color did not continue to change above pH 8.     

Regulation of the excitation energy utilization in the photosynthetic apparatus of chlorina f2 barley mutant grown under different irradiances

Acclimation of the photosynthetic apparatus of chlorophyll b-less barley mutant chlorina f2 to low light (100 micromolm(-2)s(-1); LL) and extremely high light level (1000 micromolm(-2)s(-1); HL) was examined using techniques of pigment analysis and chlorophyll a fluorescence measurements at room temperature and at 77 K. The absence of chlorophyll b in LL-grown chlorina f2 resulted in the reduction of functional antenna size of both photosystem II (by 67%) and photosystem I (by 21%). Chlorophyll fluorescence characteristics of the LL-grown mutant indicated no impairment of the utilization of absorbed light energy in photosystem II photochemistry. Thermal dissipation of excitation energy estimated as non-photochemical quenching of minimal fluorescence (SV(0)) was significantly higher as compared to the wild-type barley grown under LL. Despite impaired assembly of pigment-protein complexes, chlorina f2 was able to efficiently acclimate to HL. In comparison with chlorina f2 grown under LL, HL-grown chlorina f2 was characterized by unaffected maximal photochemical efficiency of photosystem II (F(V)/F(M), doubled content of both beta-carotene and the xanthophyll cycle pigments and considerably reduced efficiency of excitation energy transfer from carotenoids to chlorophyll a. The enormous xanthophyll cycle pool size was however associated with reduced SV(0) capacity. We suggest that the substantial part of the xanthophyll cycle pigments is not bound to the remaining pigment-protein complexes and acts as filter for excitation energy, thereby contributing to the efficient photoprotection of chlorina f2 grown under HL.     

Al2O3-coated 3-N-propylpyridinium chloride silsesquioxane polymer film: preparation and electrochemical property study of adsorbed cobalt tetrasulfophthalocyanine

Porous Al2O3 presenting a specific surface area of SBET = 105 m2 g(-1) was coated with 3-N-propylpyridinium chloride silsesquioxane polymer. The ion exchange capacity of this polymer grafted onto an Al2O3 surface, resulting in a material designated as AlSiPy(+)Cl-, was 1.09 mmol g(-1). Furthermore, a cobalt(II) tetrasulfophthalocyanine anionic complex was immobilized on the chemically modified surface by an ion exchange reaction with a yield of 40 micromol g(-1) (the surface density of the electroactive species is 3.80 x 10(-11) mol cm(-2)). The electrochemical properties of the material obtained, AlSiPy/CoTsPc, were tested for the catalytic oxidation of oxalic acid at 0.77 V vs SCE in 1.0 mol l(-1) KCl solution. Furthermore, a chronoamperometric technique was used with the electrode to test its potential use as a sensor for oxalic acid. The electrode response to oxalic acid concentrations between 1.0 and 3.5 mmol l(-1) was linear with an estimated detection limit of 0.5 mmol l(-1). The charge transfer resistance of the material, measured using the electrochemical impedance spectroscopy technique, was 43 Omega cm2.     

Cerium hybrid silica coatings on stainless steel AISI 304 substrate

AISI 304 Stainless Steel is widely used in different industrial fields because of its mechanical and corrosion properties. However, its tendency to corrosion in presence of halide ions limits the applications. One strategy to improve the corrosion resistance is the use of coatings barriers containing corrosion inhibitors in their formulation. The lanthanides present attractive green and corrosion properties for the substitution of chromates, which are the most common substances used as corrosion protection. However, these compounds are highly toxic, and an intense effort is being undertaken to replace them. Cerium is a good alternative because of its relatively low cost and abundance. It fulfils the basics requirements for being considered an alternative inhibitor: the ions form insoluble hydroxides and they present low toxicity. Inorganic and hybrid sol-gel coatings have been developed to increase the corrosion resistance of metals and they provide an excellent vehicle for the incorporation of secondary phases including particles and metal ions as cerium ions. The aim of this work was to study the influence of the incorporation of cerium ions in hybrid silica sol-gel coatings deposited on AISI 304 stainless steel as substrate as a potential replacement of chromate treatments. This system should combine the barrier protection effect of silica coating with the corrosion inhibitor effect of the cerium ions inside the coatings. After 7 days of immersion in NaCl, coated substrates showed lower current densities than the bare steel, although the coatings produced from Ce (III) salts experience a slight weakening in time and those obtained from Ce (IV) chemicals evidence an enhance in the coating performance, probably due to the plugging of corrosion products in the defective areas of the film.