Determination of acrolein and other carbonyls in cigarette smoke using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine

A new method for the determination of acrolein and other carbonyls in cigarette smoke using a dual cartridge system has been developed. Each cartridge consists of reagent-impregnated silica particles. The first contains hydroquinone (HQ) for the inhibition of acrolein polymerization, while the second contains 2,4-dinitrophenylhydrazine (DNPH) for the derivatization of carbonyls. Smoke samples were firstly drawn through the cartridge containing HQ-impregnated silica (HQ-silica) and then through the DNPH-impregnated silica (DNPH-silica). Acrolein in the sample was completely trapped in the first HQ-silica cartridge. Some other airborne carbonyls were also trapped by the HQ-silica, and those that pass through were trapped in the second DNPH-silica cartridge. Extraction was performed in the reverse direction to air sampling. When solvent was eluted through the dual-cartridges, excess DNPH was washed into the HQ bed where it reacted with acrolein and other trapped carbonyls to form the corresponding hydrazone derivatives. All of the hydrazones derived from airborne carbonyls were completely separated and measured using high-performance liquid chromatography. This HQ-DNPH-method can be applied for the determination of acrolein and other α,β-unsaturated aldehydes, such as crotonaldehyde, in cigarette smoke.     

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation

Aldehydes and ketones readily react with 2,4-dinitrophenylhydrazine (2,4-DNPH) to form the corresponding hydrazones. This reaction has been frequently used for the quantification of airborne carbonyl compounds. Since unsymmetrical aldehydes and ketones are known to form isomeric 2,4-dinitrophenylhydrazones (syn/ anti-isomers), the influence of isomerization on the practicability and accuracy of the 2,4-DNPH-method using 2,4-dinitrophenylhydrazine-coated solid sorbent samplers has been studied with three ketones (methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and methyl isobutyl ketone (MIBK)). With all three ketones the reaction with 2,4-DNPH resulted in mixtures of the isomeric hydrazones which were separated by HPLC and GC and identified by mass spectroscopy and ¹H nuclear magnetic resonance spectroscopy. The isomers show similar chromatographic behaviour in HPLC as well as in GC, thus leading to problems in quantification and interpretation of chromatographic results.     

Spectrofluorimetric determination of formaldehyde in air after collection onto silica cartridges coated with Fluoral P

In the present work, a sensitive and selective fluorimetric method for formaldehyde determination in air samples is described. The method is based in the reaction between formaldehyde and Fluoral P producing 3,5-diacetyl-1,4-dihydrolutidine, which, when excited at 410 nm, emits fluorescence at 510 nm.The Fluoral P was prepared by the reaction of 0.3 ml of acetic acid, 0.2 ml of acetylacetone and 15.4 g of ammonium acetate. Then, the volume was completed to 100 ml with deionized water. The Fluoral P obtained, if stored under refrigeration in the dark, can be used, safely, for 60 days.The calibration curve obtained with concentrations of formaldehyde in the range of 12 to 192 ng ml⁻¹ (n=9) was Intensity=1.11C+0.06 (R²=0.9920). In the quantification of formaldehyde, air samples were passed at 1 l min⁻¹, during 120 min, through glass impingers containing 40 ml of Fluoral P, followed by direct fluorescence measuring, or through two SEP PAK silica cartridges, coated with Fluoral P. The cartridges were eluted with 10 ml of Fluoral P solution and quantified by spectrofluorimetry. Under these conditions, the detection limit (S/N=3) obtained was 2.0 ng ml⁻¹.The new methodology was validated by comparison with a well-known HPLC method in which formaldehyde was collected into SEP PAK C18 cartridges coated with 2,4 dinitrophenylhydrazine. The application of the t_95% test did not show significant differences between the HPLC and either fluorimetric methodologies.This method has been used in the determination of gas phase formaldehyde in both indoor and outdoor sites. For the indoor site, the measured concentrations were in the range of 9.0 to 67.7 μl l⁻¹, while for the outdoor site they were in the range of 16.8 to 38.8 μl l⁻¹. Further, due to the ease of handling in field studies, the SEP PAK cartridges coated with Fluoral P were used. The formaldehyde concentrations thus determined, in outdoor sites, were in the range of 2.09 to 25.1 μl l⁻¹. The main advantage of this analytical procedure is its selectivity for formaldehyde, without interferences from bisulfite and other aldehydes, especially acetaldehyde, and low blank level, resulting in low detection limits. In addition, very little sample preparation is required.     

2,4-Dinitro-3,5,6-trideuterophenylhydrazones for the quantitation of aldehydes and ketones in air samples by liquid chromatography-mass spectrometry

The quantification of carbonyl compounds in air samples using an internal calibration approach with stable isotope-labelled standards and HPLC-atmospheric pressure chemical ionization MS analysis is presented. 2,4-Dinitro-3,5,6-trideuterophenylhydrazine and various of its hydrazones have been synthesized and characterized for the first time. The respective stable isotope-labelled hydrazones of a series of aldehydes and ketones are applied as internal standards for the determination of the carbonyls in car exhaust samples. Various aldehydes are identified and quantified by MS detection. The results exhibit good agreement to quantification data obtained with UV detection.     

Interferences of nitrogen dioxide in the determination of aldehydes and ketones by sampling on 2,4-dinitrophenylhydrazine-coated solid sorbent

Summary The influence of nitrogen oxides on the practicability and accuracy of the determination of aldehydes and ketones in air samples using the DNPH-method was examined. Nitrogen dioxide reacts with 2,4-dinitrophenylhydrazine and the reaction products were identified as 2,4-dinitrophenylazide (main product) and 2,4-dinitrochlorobenzene (by-product). They have a similar chromatographic behaviour in high performance liquid chromatography (HPLC) as formaldehyde-2,4-DNP-hydrazone. The chromatographic separation of the reaction products and formaldehyde-2,4-dinitrophenylhydrazone was performed using different gradient systems. Problems which occur in nitrogen dioxide-containing air samples are discussed.     

Effect of the micellar surfactant nanoreactors on the reactions of 2,4-dinitrophenylhydrazine with some aldehydes

By thermogravimetry, the IR and electronic spectroscopy physicochemical characteristics of systems including aromatic aldehydes, 2,4-dinitrophenylhydrazine, and a surfactant were investigated. Selective solubilization effect of the cationic surfactant (cetylpyridinium chloride) micelles on the aci-form of hydrazone arising in the alkaline medium was found. The universal character of solubilization by the cationic surfactant micelles in the aromatic aldehyde—2,4-dinitrophenylhydrazine systems was shown by an example of the benzaldehyde derivatives with substituents of different nature. This effect leads to the increase in solubility of the reaction products and the aggregative stability of solutions.     

Evaluation of C18 adsorbent cartridges for sampling and derivatization of primary amines in air

The sampling efficiency of C₁₈ solid-phase extraction cartridges was investigated for methylamine, ethylamine, propylamine, butylamine and pentylamine, in air. Determination of these analytes was based on derivatization with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) on the solid support and fluorescence detection at λ_excitation=330 nm and λ_emission=440 nm of the eluted derivatives. The calibration model derived from aqueous standards was statistically comparable with the calibration model for air standards. Aqueous amines can be used as standards. The method was useful for calculating short-term exposure limits (STEL). A sampling time of 15 min at 30 ml min⁻¹ was employed. Good recoveries for amines alone and their mixtures were obtained from air and water samples, 98±14 and 97±12% (mean ), respectively. Recovery values were independent of amine concentration. The detection limits varied between 0.16 and 0.52 μg per sample (0.35 and 1.18 mg m⁻³, respectively) and the calibration graphs were linear in the range 0.5-2 μg per sample except for pentylamine, which was 1.5-5 μg per sample. The utility of the method was demonstrated for the estimation of methylamine in two generated air samples.     

Disturbance of the determination of aldehydes and ketones: Structural elucidation of degradation products derived from the reaction of 2,4-dinitrophenylhydrazine (DNPH) with ozone

None of the reaction products of ozone and DNPH immobilized on solid phase support have been identified yet. However, they can interfere with the determination of carbonyl compounds in ozone containing air when analysis is performed by sampling and derivatization with DNPH coated silica cartridges. To elucidate the structure of these compounds, DNPH silica cartridges were treated with synthetic air containing defined concentrations of ozone and eluted with acetonitrile. The products were characterized by HPLC-UV/Vis and nuclear magnetic resonance (NMR) spectroscopy. Three of the degradation products were identified as 2,4-dinitrophenol, 2,4-dinitroaniline and 1,3-dinitrobenzene. The identification was confirmed by comparison with commercially available standard compounds. The other elutable products were characterized as substituted aromatic compounds. The formation of all characterized products is consistent with a radical mechanism which has been previously discussed in the literature. Received: 9 September 1998 / Revised: 9 February 1999 / Accepted: 11 February 1999     

Interactions of aldehydes and ketones with the surface of fused silica capillary columns

By using gas chromatographic intermediate surface testing to study the surface properties of fused silica capillary tubing, the reversible adsorption of aldehydes and ketones on the fused silica surface has been observed for the first time. It is shown that this interaction can arise from the preferential interaction of carbonyl functional groups at bonded silanol sites on the surface. It is further shown that simple test mixtures containing aldehydes or ketones can be used to probe the concentration of water and bonded silanols on the surface and thus to evaluate capillary manufacturing processes and thermal and chemical surface treatments.     

Study of specific molding of silica gels with 2,4-dinitrophenylhydrazones of ketones

Conclusions Catalysts, prepared on silica gels that exhibit weak adsorption toward the molding compound, display selectivity during catalytic reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1855–1856, August, 1976.     

Quantification of 2,4-dinitrophenyl-hydrazones of low molecular mass aldehydes and ketones using HPLC

Summary This study was undertaken to evaluate the HPLC separation and quantification of several low molecular mass aldehydes and ketones, which may be produced during combustion in alcohol-fueled automobiles, by means of their dinitrophenylhydrazone derivatives. Stationary phases (ODS), mobile phase components (acetonitrile or methanol with water) and detection sensitivity at 254 and 365 nm were evaluated. Separation of eight dinitrophenylhydrazones could be achieved in approximately 20 minutes using a Zorbax ODS or a Supelcosil LC-PAH column with a MeOH:H₂O (7525 v/v) mobile phase. Complete separations were not obtained with either a Nova-Pack C-18 or an Ultrasphere ODS column. The use of acetonitrile-water mobile phases produces poorer resolution at all compositions tested. Quantification of the compounds by several methods was compared, with the lowest standard deviations being seen with the external than 1.5 pmol for each of the 2,4-dinitrophenylhydrazones in the test solution. The method is being applied to the analysis of aldehydes and ketones in the exhaust of automobile engines fueled by ethanolgasoline mixtures.Presented at the 19th ISC. Aix-en-Provence, France, September 13–18, 1992.     

Silica gel promotes reductions of aldehydes and ketones by N-heterocyclic carbene boranes

N-Heterocyclic carbene boranes (NHC-boranes) such as 1,3-dimethylimidazol-2-ylidine trihydridoborane (diMe-Imd-BH(3)) serve as practical hydride donors for the reduction of aldehydes and ketones in the presence of silica gel. Primary and secondary alcohols are formed in good yields under ambient conditions. Aldehydes are selectively reduced in the presence of ketones. One, two, or even all three of the boron hydrides can be transferred. The process is attractive because all the components are stable and easy to handle and because both the reaction and isolation procedures are convenient.     

Reaction of 2-silylmethylcyclopropyl ketones with in situ oxirane-derived aldehydes and formation of 2-hydroxymethyl tetrahydrofurans

The enolates formed from Lewis acid treatment of (2-trimethylsilylmethyl)cyclopropyl alkyl and aryl ketones reacted with aldehydes formed in situ from alkoxy-, aryl- and vinyl-substituted oxiranes to generate aldol products in good yields. Selected aldol products were conveniently transformed into highly substituted tetrahydrofurans under oxidative conditions.     

Determination of olefinic aldehydes and other volatile carbonyls in air samples by DNPH-coated cartridges and HPLC

Summary The collection of low-boiling olefinic aldehydes on 2,4-dinitrophenylhydrazine (DNPH)-coated adsorbents (silica cartridges and glass denuders) is examined. Concurrent formation of two different hydrazones by both acrolein and crotonaldehyde is reported and discussed. Identification and quantitation of these compounds do not represent a problem in HPLC analysis, because of their separation from other C₃ and C₄ carbonyl derivatives present in airborne sample extracts.     

Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization

A simple and sensitive method is described for the determination of picomolar amounts of C₁–C₉ linear aliphatic aldehydes in waters containing heavy metal ions. In this method, aldehydes were first derivatized with 2,4-dinitrophenylhydrazine (DNPH) at optimized pH 1.8 for 30 min and analyzed by HPLC with UV detector at 365 nm. Factors affecting the derivatization reaction of aldehydes and DNPH were investigated. Cupric ion, an example of heavy metals, is a common oxidative reagent, which may oxidize DNPH and greatly interfere with the determination of aldehydes. EDTA was used to effectively mask the interferences by heavy metal ions. The method detection limits for direct injection of derivatized most aldehydes except formaldehyde were of the order of 7–28 nM. The detection limit can be further lowered by using off-line C₁₈ adsorption cartridge enrichment. The recoveries of C₁–C₉ aldehydes were 93–115% with a relative standard deviation of 3.6–8.1% at the 0.1 μM level for aldehydes. The HPLC–DNPH method has been applied for determining aldehyde photoproducts from Cu(II)–amino acid complex systems.     

Influences of sampling volume and sample concentration on the analysis of atmospheric carbonyls by 2,4-dinitrophenylhydrazine cartridge

In this study, the analytical bias involved in the application of the 2,4-dinitrophenylhydrazine (2,4-DNPH)-coated cartridge sampling method was investigated for the analysis of five atmospheric carbonyl species (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde). In order to evaluate the potential bias of the sampling technique, a series of the laboratory experiments were conducted to cover a wide range of volumes (1–20 L) and concentration levels (approximately 100–2000 ppb in case of acetaldehyde). The results of these experiments were then evaluated in terms of the recovery rate (RR) for each carbonyl species. The detection properties of these carbonyls were clearly distinguished between light and heavy species in terms of RR and its relative standard error (R.S.E.). It also indicates that the studied analytical approach can yield the most reliable pattern for light carbonyls, especially acetaldehyde. When these experimental results were tested further by a two-factor analysis of variance (ANOVA), the analysis based on the cartridge sampling method is affected more sensitively by the concentration levels of samples rather than the sampling volume.     

Selective determination of trimethylamine in air by liquid chromatography using solid phase extraction cartridges for sampling

The selective determination of trimethylamine (TMA) in air by liquid chromatography is reported. Sampling is effected by flushing air through C18-packed solid-phase extraction (SPE) cartridges at a flow rate of 15 mL/min for 15 min. Next, TMA is desorbed from the cartridges and injected into the chromatographic system. The analyte is then selectively retained on a precolumn (20 mm x 2.1 mm i.d., packed with 30 microm, Hypersil C18 phase), and derivatized on-line by injecting 9-fluorenylmethyl chloroformate (FMOC). Finally, the TMA-FMOC derivative is transferred to the analytical column (125 mm x 4 mm i.d., LiChrospher 100 RP18, 5 microm), and monitored at 262 nm. The method was applied to the measurement of TMA in air in the 0.25-2.5 microg interval (equivalent to concentrations of TMA of 1.1-11 mg/m3), providing good linearity, reproducibility and accuracy. The mean recovery of TMA was (96 +/- 7%) (n = 12), and the limit of detection was 0.05 microg. The proposed procedure allows the selective determination of TMA in the presence of other primary and secondary short-chain aliphatic amines.     

Room-temperature Ru(II)-catalyzed transfer hydrogenation of ketones and aldehydes in air

Transfer hydrogenation (TH) of ketones and aldehydes was efficiently carried out in 2-propanol at room temperature by means of a ruthenium(II) complex catalyst bearing a 2-(benzoimidazol-2-yl)-6-(pyrazol-1-yl)pyridine ligand. TH of the ketone substrates proceeded in air, reaching final TOFs of up to 59,400 h⁻¹, and the reduction of aldehydes proceeded under a nitrogen atmosphere to achieve final TOFs of up to 5940 h⁻¹.