Study of the carbonyl products of terpene/OH radical reactions: detection of the 2,4-DNPH derivatives by HPLC-MS

The oxidation of the terpenes - and -pinene, limonene and ³-carene by hydroxyl radicals has been investigated in a fast-flow reactor coupled to a liquid nitrogen trap for collecting the carbonyl compounds. Identification of the products was performed via 2,4-dinitrophenylhydrazone (DNPH) derivatization of the carbonyls to form the mono- and di-DNPH derivatives, which were analysed by high-performance liquid chromatographic (HPLC)-DAD (diode array detector) and HPLC-mass spectrometry (HPLC-MS). Both electrospray ionization [ESI(–)] and atmospheric pressure chemical ionization [APCI(–)] were suitable for the detection of the DNPH derivatives of formaldehyde, acetaldehyde, myrtanal, campholene aldehyde, perillaldehyde, acetone, nopinone, trans-4-hydroxynopinone and 4-acetyl-1-methylcyclohexene. Also the mono-DNPH derivatives of the dicarbonyl compounds pinonaldehyde, endolim and caronaldehyde could be identified. The MS² spectra generated in the ion trap of the mass spectrometer allowed us to distinguish between aldehydes and ketones on the basis of the characteristic fragment ion m/z 163 for the aldehydes. For the quantitative analysis of the mono-DNPH derivatives, ESI(–) in combination with single ion monitoring (SIM) detection showed the lowest detection limits. For the quantification of the dicarbonyl compounds, the acid-sensitive di-DNPH derivatives had to be formed by keeping the acidity in the acid-catalysed derivatization reaction at about 1.7 mM H₂SO₄. Detection of these dicarbonyl compounds can only be performed by APCI(–) with somewhat lesser sensitivity than by HPLC-DAD.     

Electrochemical Study of 2,4‐Dinitrophenylhydrazine as Derivatization Reagent and Aldehydes at Carbon Glassy Electrode

A selective method based on derivatization with 2,4‐dinitrophenylhydrazine (DNPH) is described for the determination of several carbonyl compounds. The factors affecting the derivatization reaction of aldehyde and DNPH were investigated. The product of the derivatization reaction has been characterized by UV/Vis spectrophotometry, NMR, infrared spectroscopy and cyclic voltammetry. Then, an electrochemical study for the determination of aldehyde‐2.4‐dinitrophenylhydrazone was performed at glassy carbon electrode (GCE) using square wave voltammetry (SWV). After the optimization of experimental parameters, the limits of detection (at 3σ ) obtained for all aldehyde‐2,4‐DNPH were varied from 15.82 to 78.39 μmol L⁻¹ and relative standard deviations were between 1.8 and 4.5%. Finally, the proposed method was applied to determine the aldehydes concentration in drinking water and orange juice samples with satisfactory results.     

Experimental choices for the determination of carbonyl compounds in air

The analysis of carbonyls in ambient air has received a great deal of scientific attention with the advancement of analytical techniques and increased demand for the build-up of its data base. In this review article, we have attempted to provide some insight into the relative performance of different instrumental approaches available for the analysis of ambient carbonyls with a major emphasis on high performance liquid chromatographic and gas chromatographic methods. Reported in several international standard procedures, derivatization of carbonyls with 2,4-dinitrophenylhydrazine (2,4-DNPH) with either an impinger or cartridges is the most commonly used method of HPLC detection. In this respect, a number of alternative hydrazine reagents have also been discussed for use with HPLC. In contrast, GC methods based on the combined application of adsorptive enrichment on solid sorbents and thermal desorption are examined with regard to their suitability for carbonyl analysis in air. Particular emphasis has been directed towards the advantages and drawbacks of these different instrumental techniques for ambient carbonyls. Based on this comparative approach, we discuss the suitability for each method for carbonyl analysis.     

Performance of a 2,4-DNPH coated annular denuder/HPLC system for formaldehyde monitoring in air

Summary The performance of annular denuders coated with 2,4-dinitrophenylhydrazine for collection of atmospheric HCHO has been evaluated by HPLC/UV analysis of samples coming from laboratory tests and field experiments. A number of parameters, such as collection efficiency at varying air humidity, detection limit, operative capacity and temporal self-consistency have been investigated to optimize the denuder behaviour under different weather conditions and to obtain short-term concentration profiles of HCHO. Deviations between measurements made simultaneously by the DNPH denuder method and differential optical absorption spectrometry (DOAS) have been found to average approximately 30% in the 0–5 ppb HCHO concentration range.     

Analysis of formose sugar and formaldehyde by high-performance liquid chromatography

Formose sugar and formaldehyde (HCHO) were analyzed using high-performance liquid chromatography (HPLC) utilizing a CarboPac PA1 column (Dionex) and pulsed amperometric detection. This HPLC system was unsuitable for the analysis of formose sugar and HCHO and thus reducing sugars and unconverted HCHO were determined by endowing them with charges through a derivatization method using 2,4-dinitrophenylhydrazine. The separation and detection of compounds were performed by three Chromolith RP-C18 columns (Merck) and diode array detection, at a wavelength of 360 nm ultraviolet light, respectively. Lower sugars (except HCHO) showed some instabilities when the derivatized samples were kept for the extended periods of time. For C₅ and consecutive higher sugars, a certain derivatization time was necessary. In the present case (formose reaction with partial HCHO conversion), approximately 18 h may be a reasonable compromise for the derivatization reaction. A derivatization agent to compound mole ratio of up to 100:1 was required to complete the derivatization of C₄ and higher sugars. However, the analysis of C₄ and consecutive higher sugars is problematic for example due to overlapping of peaks or branched-chain sugars.     

Towards a Non-Biased Formaldehyde Quantification in Leather: New Derivatization Conditions before HPLC Analysis of 2,4-Dinitrophenylhydrazine Derivatives

In leathers, formaldehyde is currently analyzed according to EN ISO 17226-1 standard, by reversed phase liquid chromatography after off-line precolumn derivatization with 2,4 dinitrophenylhydrazine (DNPH) in strong acidic conditions. We first demonstrate that this standard is not adapted to leather retanned with resins likely to release formaldehyde by hydrolysis. Indeed, formaldehyde content may be largely overestimated due to concomitant resin hydrolysis (in harsh acidic conditions) that releases formaldehyde during the derivatization step and during the waiting time on autosampler before analysis. Therefore, we thoroughly studied the derivatization step in order to propose new derivatization conditions. Replacing orthophosphoric acid by less acidic buffer solutions is not enough to avoid hydrolysis. A derivatization without adding acid is realized by solubilizing DNPH in acetonitrile instead of orthophosphoric acid. These conditions lead to a complete derivatization of formaldehyde in 3 h at 50 °C (in a water bath) while avoiding the hydrolysis of co-extracted dicyandiamide and melamine resins. The as-obtained leather extracts are stable over time. Formaldehyde contents found with this method agree with the formaldehyde content measured immediately at the end of derivatization reaction in standard conditions or with formaldehyde content measured by a home-designed flow injection analysis with acetylacetone online derivatization and UV detection.     

小麦粉中甲醛(吊白块)的测定方法研究

对小麦粉中甲醛提取方法、甲醛与2,4-二硝基苯肼的衍生化反应条件以及甲醛衍生物的提取净化方法进行了研究, 建立了一种小麦粉中甲醛(吊白块)的高压液相色谱测定方法.该方法在甲醛浓度为0.026～0.832 μg/mL范围内与其衍生物的色谱峰面积呈显著线性相关, 相关系数r=0.9986. 小麦粉中甲醛不同添加量的平均回收率＞99%;吊白块不同添加量的平均回收率＞94%(以甲醛量计). 重复测定相对标准偏差平均为4.5%, 甲醛的检出限为9.6 μg/L, 相当于小麦粉中甲醛的最小检出量为0.24 mg/kg.     

Short-term measurements of acrolein in ambient air

Summary A method has been developed for the determination of acrolein in air samples collected by a high-volume aqueous scrubber. The aldehyde is collected as the bisulfite adduct, which is decomposed before determination of acrolein by DNPH (2,4-dinitrophenylhydrazine) derivatization and HPLC. Approximately 95% of the acrolein reacts with DNPH within 3 h at DNPH:HSO₃ molar ratios of up to 10. The method appears promising for short-term air sampling at 8 L min^–1, enabling the achievement of a detection limit of 0.2 g m^–3 for acrolein.     

Using 2,4 DNPH-PVC membrane sensors for indirect determination of formaldehyde in urea glue and wastewater

Three simple, rapid, and sensitive ion-selective electrodes for indirect determination of free formaldehyde in urea glue and wastewater have been developed. The methods are based on the formation of the membrane sensors 2,4-dinitrophenylhydrazine-phosphtungestic acid (DNPH-PTA), 2,4-dinitrophenylhydrazine-phosphomolybdic acid (DNPH-PMA), and 2,4-dinitrophenylhydrazine-tetraphenylborate (DNPH-TPB) as neutral carriers. The sensors are stable and show fast potential responses of 30?s, and near-Nernstian cationic slopes of 56.2?±?0.5, 54.3?±?0.5, and 53.8?±?0.4?mV per decade of activity between pH 0.5 and 3.5 over a wide range of 2,4-dinitrophenylhydrazine concentrations (1?×?10^?5 to 1?×?10^?2?M). These sensors were used for indirect determination of formaldehyde over concentration range (1?×?10^?4 to 1?×?10^?1?M). The selectivity coefficients of the developed sensors indicate excellent selectivity for 2,4 DNPH over a large number of organic and inorganic species. The mediator o-nitrophenyloctyl ether has a significant affect on the lifetime of the fabricated sensors. The analytical applications of the proposed sensors showed good results for indirect determination of formaldehyde in formaldehyde solutions, wastewater solutions, and free formaldehyde in urea-formaldehyde liquid and powder glues. The results were compared favourably with that obtained by ASTM, colorimetric, and British Standard methods.     

Facile and Sensitive Spectrophotometric Determination of Chromium

Abstract

A simple, sensitive, and selective spectrophotometric method is developed for the determination of trace amounts of chromium(VI) in various samples. The method is based on oxidation of 2,4-dinitrophenylhydrazine (DNPH) by chromium in an acidic medium and coupling with β-naphthol to give a red-colored dye, having an absorbance maximum at 663 nm, and/or coupling with α-naphthol to give a violet-colored dye, having an absorbance maximum at 503 nm. The method obeys Beer's law in the concentration range 0.02–4.0µg mL^?1 and 0.05–9.0 µg mL^?1, respectively. The optimum reaction conditions and other important analytical parameters were established. Interference caused by various nontarget ions was also investigated. The proposed method is applied to the analysis of chromium(VI) in environmental, pharmaceutical, and steel samples. The performance of the proposed method is evaluated using the student's t and F -tests.