Analysis Of Carbonyl Compounds Research Articles

Fixed-Charge Generation Derivatization for the Analysis of Carbonyl Compounds by Electrospray Ionization Mass Spectrometry

The fixed-charge generation derivatization approach based on a reaction with ω-N,N-dimethylaminoalkylamines followed by quaternization with alkyl halides was applied to the analysis of aliphatic aldehydes and ketones, as well as ketosteroids by electrospray ionization (ESI) mass spectrometry. Both stages of reaction proceed quantitatively, and the registered ESI mass spectra of the products contain abundant peaks of the corresponding ammonium cations. In most cases, the dissociation of the last named compounds under collision activation results only in the loss of the terminal trialkylamino group as a neutral species. Such predictable fragmentation can be used for developing of highly sensitive methods of analysis based on selected reaction monitoring.

Analysis of Carbonyl Compounds in Ambient Air by a Microreactor Approach.

Aldehydes including formaldehyde, acetaldehyde, and acrolein are toxic organic components of air pollution that cause lung cancer and cardiovascular disease with chronic exposure. The commonly used method for determining the levels of carbonyl compounds based on the derivatizing agent 2,4-dinitrophenylhydrazine is of limited use for ketones and unsaturated aldehydes because of issues such as low capture efficiencies, unstable derivatives, and long sample collection times. This work details the analysis of carbonyls in ambient air by a microreactor approach. The microreactor is fabricated on a silicon wafer and has thousands of micropillars in a microfluidic channel for uniformly distributing the air flow through the channel. The surfaces of the micropillars are coated with a quaternary ammonium aminooxy reagent, 2-(aminooxy)ethyl-N,N,N-trimethylammonium iodide (ATM), for chemoselective capture of carbonyl compounds by means of oximation reactions. ATM–carbonyl adducts are eluted from the microreactor and directly analyzed by Fourier transform ion cyclotron resonance mass spectrometry and ultrahigh-performance liquid chromatography–mass spectrometry. More than 20 carbonyls were detected in ambient air samples. Acetone, 2-butanone, acetaldehyde, and formaldehyde were the most abundant carbonyls in ambient air of the studied urban areas.

Development, validation and application of an UFLC-DAD-ESI-MS method for determination of carbonyl compounds in soybean oil during continuous heating

A method was developed for the extraction and UFLC-DAD-ESI-MS analysis of carbonyl compounds (CCs) in oils heated to 180°C. Different parameters were evaluated, and the best results were 1.5ml of acetonitrile as the extraction solvent, manual stirring for 3min and 30min of sonication time. The method was validated using soybean oil samples spiked with CCs at concentration levels ranging from 0.2 to 10.0μg.mL−1. The average recoveries in the lowest concentration level ranged from 70.7% to 85.0%. Detection limits ranged from 0.03 to 0.1μg.mL−1, and the quantification limit was 0.2μg.mL−1 for all compounds. When the method was applied to samples of heated oil, the CCs identified were 4-hydroxy-2-nonenal, 2,4-decadienal, 2,4-heptadienal, 4-hydroxy -2-hexenal, acrolein, 2-heptenal, 2-octenal, 4,5-epoxy-2-decadal, 2-decenal, and 2-undecenal, with the first three mentioned presenting the highest mean concentrations after heating, specifically 36.9, 34.8 and 22.6μg.g−1 of oil, respectively.

Development of a sampling method for carbonyl compounds released due to the use of electronic cigarettes and quantitation of their conversion from liquid to aerosol

In this study, an experimental method for the collection and analysis of carbonyl compounds (CCs) released due to the use of electronic cigarettes (e-cigarettes or ECs) was developed and validated through a series of laboratory experiments. As part of this work, the conversion of CCs from a refill solution (e-solution) to aerosol also was investigated based on mass change tracking (MCT) approach. Aerosol samples generated from an e-cigarette were collected manually using 2,4-dinitrophenylhydrazine (DNPH) cartridges at a constant sampling (puffing) velocity of 1Lmin−1 with the following puff conditions: puff duration (2s), interpuff interval (10s), and puff number (5, 10, and 15 times). The MCT approach allowed us to improve the sampling of CCs through critical evaluation of the puff conditions in relation to the consumed quantities of refill solution. The emission concentrations of CCs remained constant when e-cigarettes were sampled at or above 10puff. Upon aerosolization, the concentrations of formaldehyde and acetaldehyde increased 6.23- and 58.4-fold, respectively, relative to their concentrations in e-solution. Furthermore, a number of CCs were found to be present in the aerosol samples which were not detected in the initial e-solution (e.g., acetone, butyraldehyde, and o-tolualdehyde).

Direct Analysis of Free and Sulfite-Bound Carbonyl Compounds in Wine by Two-Dimensional Quantitative Proton and Carbon Nuclear Magnetic Resonance Spectroscopy.

Recent developments that have accelerated 2D NMR methods and improved quantitation have made these methods accessible analytical procedures, and the large signal dispersion allows for the analysis of complex samples. Few natural samples are as complex as wine, so the application to challenges in wine analysis look promising. The analysis of carbonyl compounds in wine, key oxidation products, is complicated by a multitude of kinetically reversible adducts, such as acetals and sulfonates, so that sample preparation steps can generate complex interferences. These challenges could be overcome if the compounds could be quantified in situ. Here, two-dimensional ((1)H-(1)H) homonuclear and heteronuclear ((13)C-(1)H) single quantum correlations (correlation spectroscopy, COSY, and heteronuclear single quantum coherence, HSQC) nuclear magnetic resonance spectra of undiluted wine samples were observed at natural abundance. These techniques achieve simultaneous direct identification and quantitation of acetaldehyde, pyruvic acid, acetoin, methylglyoxal, and α-ketoglutaric acid in wine with only a small addition of D2O. It was also possible to observe and sometimes quantify the sulfite, hydrate, and acetal forms of the carbonyl compounds. The accuracy of the method was tested in wine samples by spiking with a mixture of all analytes at different concentrations. The method was applied to 15 wine samples of various vintages and grape varieties. The application of this method could provide a powerful tool to better understand the development, evolution, and perception of wine oxidation and insight into the impact of these sulfite bound carbonyls on antimicrobial and antioxidant action by SO2.

A versatile probe for chemoselective capture and analysis of carbonyl compounds in exhaled breath

We describe an aminooxy reagent for the capture of trace aldehyde and ketone volatile organic compounds (VOCs) in exhaled breath.

Evaluation of Ternary Mobile Phases for the Analysis of Carbonyl Compound Derivatives Using High-Performance Liquid Chromatography

In this study, the feasibility of ternary mobile phases was examined in a high-performance liquid chromatography (HPLC)-based analysis of carbonyl compounds (CCs). To test the performance of different ternary phases, the liquid phase standards containing a 15 aldehyde/ketone-DNPH(o) mix were analyzed through a series of five-point calibration experiments. For this comparison, three types of ternary mobile phases were prepared initially by mixing water (W) with two of the following three organic solvents: isopropanol (I), methanol (M), and tetrahydrofuran (T). The resulting three types of ternary phases (named as WIM, WTM, and WIT) were tested and evaluated in relation to the water content or in terms of methanol-to-water ratio (M/W). The results derived by the three ternary phases revealed that the optimal resolution was attained near maximum water content, while those of WIT consistently suffered from poor resolution problems. The relative performances of WIM and WTM phases, if assessed by three key operating parameters (sensitivity, retention time, and resolution), were found to be reliable for most selected CCs with the decreasing M/W ratio.

Analysis of carbonyl compounds in sea buckthorn for the evaluation of triglyceride oxidation, by enzymatic hydrolysis and derivatisation methodology

Carbonyl compounds formed in sea buckthorn berry (Hippophae rhamnoides) and oil samples as a result of lipid oxidation were determined by enzymatic hydrolysis followed by derivatisation with 2,4-dinitrophenylhydrazine and analysed by LC–UV and electrospray ionisation (ESI) tandem mass spectrometry (MS/MS). Several classes of carbonyl compounds such as saturated, unsaturated, linear and branched aldehydes and ketones, aromatic aldehyde, dicarbonyls and carboxy aldehydes were identified based on fragmentation pattern, molecular weight and retention time. The lower carbonyls such as formaldehyde, acetaldehyde and acetone were found to be predominant in the berry samples and acetaldehyde was found to be the most abundant carbonyl. In the sea buckthorn pulp oil sample, longer aldehydes and carboxy aldehydes dominated, thus clearly demonstrating the benefit of the enzymatic step when analysing oxidation products originating from triglycerides.

Effect of HPLC binary mobile phase composition on the analysis of carbonyls

The relative performance of the binary mobile phase in the high-performance liquid chromatography analysis of carbonyl compounds (CCs) was tested using the liquid-phase standards containing 15 aldehyde/ketone-DNPH mixture. The Hichrome column was employed for the analysis of CCs at a flow rate of 1.5 mL min( - 1). The binary mobile phases prepared using both acetonitrile/water (AW) and a possible alternative of methanol:water (MW) mixture were examined by their calibration results. The data derived from these two binary phases were then evaluated in terms of three key variables (i.e., resolution, relative sensitivity, and retention time). The relative water content (or the water to organic solvent ratio (W/A) or (W/M)) of the binary phase was found as the key variable for the performance. The results indicate that the optimal resolution of AW combination was attained consistently for most composition, while MW generally suffered from overpressure problem. The changes of water content in the AW mixture led to the changes of all three variables in the quantitative analysis of CCs. The obtained results confirm that the AW mixture should be the optimal elutant for the CC analysis, as other simple binary compositions like MW are limited in many respects.

Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic–ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives

An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC–ITMS). Selecting specific fragment ions within the electron ionization (EI +) mass spectra of these oxime derivatives as precursor ions for MS–MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, ( E)-2-alkenals, ( E, E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI + mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.

Estimation of Uncertainty in the Analysis of Carbonyl Compounds by HPLC‐UV Using DNPH Derivatization

This work describes the estimation of uncertainty following the “bottom‐up” approach for the quantification process of thirteen carbonyl compounds, as 2,4‐dinitrophenylhydrazone derivatives, by high performance liquid chromatography with ultraviolet detection (HPLC‐UV). These results are compared with the ones obtained using gas chromatography‐mass spectrometry (GC‐MS). A study of the linear range was established and validation was performed for both methods using statistical analysis of several indicative parameters. In terms of validation data, precision (RSD<7.8% for HPLC‐UV and <20% for GC‐MS), and accuracy (relative error <8.3% for HPLC‐UV and <7.3% for GC‐MS) were obtained under day to day conditions. The results of the estimation of uncertainty for both methods demonstrated that the contributions due to the preparation of the standard solutions are not significant. The uncertainty associated with the estimation of the compound concentrations from the calibration curves are similar for both methodology, or slightly lower when HPLC‐UV is used. The cause of higher uncertainty and, especially, when GC‐MS is used, is the repeatability of the measurements.

The determination of carbonyl compounds in air using a robotic sampling preparation system integrated to a gas chromatograph with a nitrogen-phosphorus detector.

A totally automated solid phase extraction gas chromatography procedure was developed for the sampling and analysis of carbonyl compounds in air. In this system, two PrepStation modules were used, one for the preparation and elution of 2,4-dinitrophenylhydrazine silica cartridges, and the other for air sampling. The sample collected by the sampling module was eluted to an autosampler vial in the PrepStation module and then transferred to the gas chromatograph for analysis via a robotic arm. The sampling module was modified to enable air sampling via an external pump. A typical run by this technique required 142 min, 100 min for air sampling and 42 min for the other operations, including a GC analysis time of 25 min. Recoveries of at least 85% were obtained for all compounds studied. The detection limits for formaldehyde, acetaldehyde and acetone were 2.2, 2.7 and 2.2 ppbv, respectively. All operations, including the conditioning of the cartridges, were performed without any intervention from the analyst.

Isolation and analysis of carbonyl compounds as oximes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIsolation and analysis of carbonyl compounds as oximesJames W. VoghCite this: Anal. Chem. 1971, 43, 12, 1618–1623Publication Date (Print):October 1, 1971Publication History Published online1 May 2002Published inissue 1 October 1971https://doi.org/10.1021/ac60306a007RIGHTS & PERMISSIONSArticle Views238Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (634 KB) Get e-Alerts Get e-Alerts