Spectrophotofluorimetric determination of aldehydes with dimedone and other reagents

Summary Two new reagents, dimedone and 1,3-cyclohexanedione, are introduced for the fluorimetric determination of aliphatic aldehydes. Six fluorimetric methods for the determination of formaldehyde and other aldehydes have been compared. Of the selective methods for the determination of formaldehyde the J-acid procedure is recommended when a high order of sensitivity is necessary, the 2,4-pentanedione method when a high order of selectivity is desirable. The dimedone procedures are recommended when it is necessary to analyze for aldehydes other than formaldehyde. However, the dimedone procedures are the most sensitive for the determination of formaldehyde and can be used for this purpose where conditions are appropriate and maximal sensitivity is necessary. These various procedures should also be useful in the analysis of various types of aldehyde precursors.

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Zusammenfassung Zwei neue Reagenzien für die fluorimetrische Bestimmung aliphatischer Aldehyde, Dimedon und 1,3-Cyklohexandion, wurden eingeführt. Sechs fluorimetrische Verfahren für die Bestimmung von Formaldehyd und anderen Aldehyden wurden verglichen. Von den selektiven Methoden zur Formaldehyd-bestimmung wird das Verfahren mit J-Säure (6-Amino-naphthol-3-sulfonsäure) empfohlen, wenn hohe Empfindlichkeit nötig ist, das Verfahren mit 2,4-Pentandion, wenn hohe Selektivität gewünscht wird. Die Dimedon-Methoden werden empfohlen, wenn andere Aldehyde als Formaldehyd bestimmt werden sollen. Aber diese Methoden sind die empfindlichsten für die Formaldehyd-bestimmung und können unter geeigneten Bedingungen für diesen Zweck verwendet werden, wenn maximale Empfindlichkeit gefordert wird. Die verschiedenen Verfahren sind auch für die Analyse verschiedener Aldehyd-Vorprodukte nützlich.

     

A thermometric method for determination of thlols in non-aqueous media. Comparison with other methods

A comparison is made between the determination of thiols in non-aqueous media by thermometric titration and two previously stabilised methods, a colour-indicator method and an official electrometric titration one. The study is applied to control the demercuritation of an industrial process. The obviation of the need to regenerate the transductor, which can be handled without any special care, constitutes a substantial advantage of the thermometric technique.     

Spectrophotofluorimetric determination of 3-carbon fragments and their precursors with anthrone. Application to air pollution

Summary Two modifications of an anthrone procedure for the characterization and determination of compounds and their precursors are described. Two main types of fluorescence spectra are obtained. The procedure for analysis of precursors works well for the aldopentoses; by comparison, aldo-and ketohexoses react poorly.Water-soluble fractions of airborne particulates were analyzed by the anthrone procedure. At least three families of compounds were found: two give fluorogens, of which one is a precursor, and a third gives a chromogen(s) absorbing at 423 and 540 nm.

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Zusammenfassung Zwei Modifikationen eines Verfahrens zum Nachweis und zur Bestimmung von Verbindungen mit den Gruppen und deren Ausgangsstoffen mit Hilfe von Anthron wurden beschrieben.Zwei Haupttypen von Fluoreszenzspektren wurden festgestellt. Das Verfahren zur Analyse von Stoffen, die Brenztraubenaldehyd-Derivate bilden, eignet sich gut für Aldopentosen, Aldo- und Ketohexosen reagieren vergleichsweise nur schwach.Wasserlösliche Fraktionen atmosphärischer Verunreinigungen wurden nach dem Anthronverfahren analysiert. Dabei wurden drei Arten von Verbindungen gefunden: zwei davon geben Fluorogene, darunter eines, das die Gruppe > CH · CO · CHO zu bilden vermag, die dritte gibt Chromogene, die bei 423 bzw. 540 nm absorbieren.

     

Quantum-chemical model for the photoisomerization of protonated schiff bases of formaldehyde and acrolein

By means of potential energy curves in the excited states we discuss the mechanism of trans-cis isomerization of protonated imine and enumine. For the higher homologues isomerization about the CN bond is highly improbable     

Rapid determination of polycyclic aromatic hydrocarbons in sewage sludges using microwave-assisted solvent extraction. Comparison with other extraction methods

The presence of toxic organic micropollutants in municipal sewage sludges is a major problem on account of risks associated with the agricultural use of the sludges and therefore maximum tolerance limits are imposed. The aim of our study was to develop a reliable and fast analytical procedure for the determination of polycyclic aromatic hydrocarbons in sewage sludges, using focused microwave-assisted extraction. Optimization of the extraction conditions was performed on real matrices. The results of a 2(3) factorial design showed that extraction time was the only influential factor. The selected conditions (30 W, 10 min, 30 ml solvent) were used for real sludges and a certified marine sediment, leading to recoveries of between 56 and 75%. Results of an interlaboratory test confirmed these values. Finally, the technique was compared to traditional techniques (Soxhlet, sonication), and the more recent pressurized liquid extraction technique. Focused microwave-assisted extraction remains an attractive alternative technique due to its rapidity, the low solvent volume required and its moderate investment cost.     

Comparison of macro-gravimetric and micro-colorimetric lipid determination methods

In order to validate a method for lipid analysis of small tissue samples, the standard macro-gravimetric method of Bligh-Dyer (1959) [E.G. Bligh, W.J. Dyer, Can. J. Biochem. Physiol. 37 (1959) 911] and a modification of the micro-colorimetric assay developed by Van Handel (1985) [E. Van Handel, J. Am. Mosq. Control Assoc. 1 (1985) 302] were compared. No significant differences were observed for wet tissues of two species of fish. However, limited analysis of wet tissue of the amphipod, Leptocheirusplumulosus, indicated that the Bligh-Dyer gravimetric method generated higher lipid values, most likely due to the inclusion of non-lipid materials. Additionally, significant differences between the methods were observed with dry tissues, with the micro-colorimetric method consistently reporting calculated lipid values greater than as reported by the gravimetric method. This was most likely due to poor extraction of dry tissue in the standard Bligh-Dyer method, as no significant differences were found when analyzing a single composite extract. The data presented supports the conclusion that the micro-colorimetric method described in this paper is accurate, rapid, and minimizes time and solvent use.     

Fluorometric determination of formaldehyde

A simple, selective and sensitive fluorometric method is presented for the determination of formaldehyde in water based on its reaction with 3,4-diaminoanisole in alkaline ethanol-water solution to give a strongly fluorescing Schiff base. The dependence of the fluorescence intensity on the solvent composition, quenching by acetic and sulphuric acid, heating time and interference by other compounds is discussed. The detection limit of the method is 0.6 μg/L. The recovery of formaldehyde spiked into river water is 93% with an R.S.D of 6.05% at a concentration level of 10 μg/L. Received: 18 November 1996 / Revised: 17 February 1997 / Accepted: 18 February 1997     

Fluorometric determination of formaldehyde

A simple, selective and sensitive fluorometric method is presented for the determination of formaldehyde in water based on its reaction with 3,4-diaminoanisole in alkaline ethanol-water solution to give a strongly fluorescing Schiff base. The dependence of the fluorescence intensity on the solvent composition, quenching by acetic and sulphuric acid, heating time and interference by other compounds is discussed. The detection limit of the method is 0.6 μg/L. The recovery of formaldehyde spiked into river water is 93% with an R.S.D of 6.05% at a concentration level of 10 μg/L.     

Spectrophotometric determination of formaldehyde

A new spectrophotometric method for the determination of micro amounts of formaldehyde in aqueous and methanol solutions is based on the oxidation of formaldehyde by hydrous silver oxide at pH 11-12.5 and oxidation of the metallic silver produced, with iron(III) in the presence of Ferrozine. The absorbance of the resulting iron(II)-Ferrozine complex at 562 nm is proportional to the amount of formaldehyde and corresponds to an apparent molar absorptivity of 5.58 x 10(4) 1.mole(-1).cm(-1).     

Spectrophotometric determination of formaldehyde by using formaldehyde dehydrogenase

A new method for the determination of formaldehyde by using formaldehyde dehydrogenase is described. The method is based on the quantitative oxidation of formaldehyde with oxidized nicotinamide adenine dinucleotide (NAD⁺), in the presence of formaldehyde dehydrogenase, to form the reduced dinucleotide (NADH). This enzyme does not require glutathione as a co-factor and the NADH produced, which is directly proportional to the concentration of formaldehyde in the assay solution, is then measured spectrophotometrically at 340 nm. Formaldehyde can be determined in the range 0.3–8.0 μg ml^?1 (1.0×10^?5–2.7× 10^?4 M) with a sensitivity of 0.216 absorbance/ μg ml^?1 (0.0065 absorbance/μM). Optimal conditions and the selectivity of this enzyme toward formaldehyde are described.     

Comparison of activation methods for mercury determination

A comparative study is made on different activation methods for mercury analysis. Mercury concentrations down to 0.1 ppm were determined instrumentally via the isotopes¹⁹⁷Hg (T=65 h) and²⁰³Hg (T=47 d). A high-resolution Ge(Li) detector was used in measuring the activity and a small computer for data reduction. Up to 500 samples were measured daily. Chemical separations were performed on samples with low mercury concentrations. Sensitivity of 0.01 ppm was attained by precipitating HgS from basic solutions and counting¹⁹⁷Hg on NaI(T1) detector. A new rapid instrumental method was also developed based on^199mHg (T=43 min). This short-lived isotope was activated with resonance neutrons. The sensitivity of the method is 0.5 μg and it requires only 1 hr.     

Development and comparison of different fluorimetric HPLC-methods with standard methods for the determination of formaldehyde in the atmosphere

Summary Three different fluorimetric methods for the measurement of atmospheric formaldehyde are described. The relatively unknown 2-diphenylacetylindan-1,3-dionhydrazine (DAIH) method was developed and optimized with an improved limit of detection of 2 ppbv corresponding to a sample volume of 7.5 L. Separation of lutidines necessary for the Nash method was successfully carried out and the separation time was reduced by a factor of 5. The detection limit of the Nash method was improved to 1 ppbv. In comparison, the N,N-diphenyl-1-naphthylamine-5-sulfonhydrazine (DNSH) method performed in a similar manner, reached an LOD of 0.5 ppbv. Finally, measurements made in candle smoke using the three different fluorimetric methods and three standard methods yielded very similar results.     

吖啶红动力学荧光法测定痕量甲醛

在H2SO4介质中，以KCIO3-吖啶红为指示反应，建立了测定甲醛的动力学荧光分析法。方法的线性范围为40～600μg／L，检出限为27μg／L。方法用于树脂整理特殊织物和动物标本室内空气中甲醛的测定，与标准方法乙酰丙酮分光光度法进行对照，所测结果经t-检验无显著性差异。     

Application of probe sonication extraction for the determination of linear alkylbenzene sulfonates from sewage sludge. Comparison with other extraction methods

A new method based on probe sonication extraction (USP) prior to high performance liquid chromatography (HPLC) has been developed for the determination of linear alkylbenzene sulfonates (LAS) from sewage sludge. The optimized method was designed to be cost effective compared to existing extraction methods (ultrasonic assisted extraction, Soxhlet or pressurized liquid extraction) which may require large quantities of organic solvents, or costly instrumentation or equipment.The main factors affecting the extraction efficiency (extractant volume, ultrasounds power and extraction time) were optimized using compost sludge. The detection limit of total LAS in the sludge was 10 mg kg^− 1. The extraction of C₁₀-C₁₃ homologues is carried out using an extraction time of 7 min with 10 mL of methanol. Liquid chromatography with fluorescence (FL) detector is used for determination of LAS homologues. A mobile phase acetonitrile-water containing 0.1 M NaClO₄ (65:35) and isocratic elution was used. Compounds were eluted over 6 min at a flow rate of 1 mL/min. Polar interferences are eluted between 0 and 2 min and no purification of the samples is required prior to the final determination by high performance liquid chromatography (HPLC). The recoveries of LAS in spiked sewage sludge were between 84.0% and 97.0%, which reflect the efficiency of the method for extraction of these analytes from sewage sludge. Concentration levels found were between 11,858 mg kg^− 1 for digested sludge and 2379 mg kg^− 1 for compost sludge.     

基于四环素荧光熄灭测定碘的研究

基于碘对荧光试剂四环素的荧光熄灭,建立了测定微量碘的荧光分析方法。在pH10的碱性介质中,最大激发/发射波长分别为400.0nm/509.0nm,四环素的荧光强度与碘浓度的对数呈良好的线性关系,测定碘浓度的线性范围为3.20×10^-7～1.00×10^-4mol/L,检出限为1.30×10^-8mol/L,常见的共存离子不干扰测定。该方法适用于食盐中微量碘含量的测定。     

Kinetic determination of formaldehyde and hexamethylenetetramine with a cyanide-selective electrode

An automatic potentiometric reaction-rate method is described for the determination of formaldehyde and hexamethylenetetramine. The formaldehyde reacts with cyanide, and the reaction rate is followed with a cyanide-selective electrode. The time required for the reaction to consume a fixed amount of cyanide, and therefore for the potential to increase by a preselected amount (8.0 mV), is measured automatically and related directly to the formaldehyde concentration. The average error for the determination of 60–300 μg of formaldehyde in a sample volume of 1.00 ml was about 1.3%. Amounts of hexamethyl-enetetramine in the range 50–250 μg in a sample volume of 0–050 ml were determined after acid hydrolysis to formaldehyde with an average error of about 1.6%. Measurement times were in the range 18–80 s for both determinations. The method has been applied to the determination of hexamethylenetetramine in pharmaceutical preparations.     

The fluorimetric determination of formaldehyde

A sensitive fluorimetric procedure for formaldehyde has been developed. The method, which can measure 0.01 μg formaldehyde, is based on the Hantzsch reaction between acetylacetone, ammonia, and formaldehyde. The product, 3,5-diacetyl-I,4-dihydrolutidine, is colored yellow and fluoresces yellow green. Infra-red spectra indicate that this compound is ionic in dilute solution and aggregated in concentrated solution. The Hantzsch reaction may be extended for the assay of other aldehydes, amines, and β-diketones.     

Spectrophotofluorimetric determination of terbium, europium and samarium with pivaloyltrifluoroacetone and tri-n-octylphosphine oxide in micellar solution of nona-oxyethylene dodecyl ether

The fluorescence intensities of terbium, europium and samarium complexes with several beta-diketone derivatives in the absence and presence of tri-n-octylphosphine oxide (TOPO) in micellar solution of nona-oxyethylene dodecyl ether (BL-9EX) were examined. The spectrophotofluorimetric determination of terbium (1.5-1500 ng/ml) has been investigated with pivaloyltrifluoroacetone (PTA) and TOPO in 0.5% micellar solution (pH 3.8-4.5) of BL-9EX. The excitation and emission wavelengths were 309 and 542 nm, respectively. Europium and samarium could be determined by a similar method.