Analysis of alkyl nitrites by capillary gas chromatography-mass spectrometry

Bal, T.S.; Gutteridge, Daniel; Hiscutt, A.A.; Johnson, Bruce M.; Oxley, I.

doi:10.1016/s0015-7368(88)72828-5

Cited by 9 publications

(5 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After completing the forensic investigation, we attempted to establish an analytical method for the determination of IBN and related compounds. Alkyl nitrites have been analyzed by derivatization methods, GC with direct injection, HS-GC, , solid-phase microextraction GC, or infrared spectrometry . In this paper, IBN was determined by HS-GC.…”

Section: Resultsmentioning

confidence: 99%

Pitfalls in the Toxicological Analysis of an Isobutyl Nitrite-Adulterated Coffee Drink

Seto¹,

Kataoka²,

Tsuge³

et al. 2000

Anal. Chem.

View full text Add to dashboard Cite

A forensic investigation was carried out on one poisoning case, where cyanide was first detected in an evidence sample of a canned coffee drink. A more complete study revealed that it had been adulterated with isobutyl nitrite (IBN) and not cyanide. We examined the detectivity of IBN and related compounds by headspace gas chromatography and capillary electrophoresis. IBN decomposes to isobutyl alcohol (iBuOH) and nitrite in aqueous solution, and under higher temperature and more acidic conditions, the rate of this reaction becomes more rapid. IBN was also produced by the esterification of iBuOH with nitrite below pH 5. Cyanide was produced in a coffee solution by the addition of nitrite below pH 6. An IBN-spiked canned coffee drink solution was stored at 4 degrees C and periodically analyzed for IBN, iBuOH, nitrite, nitrate, and cyanide. Since the IBN level decreased rapidly, iBuOH was produced in an almost 90% molar yield. Nitrite production reached a maximum of 40% molar recovery on the first day and then gradually disappeared. The nitrate level reached a plateau of approximately 60% molar recovery. Cyanide was also detected, and its level at the 14th day was approximately 0.26% molar recovery. These findings suggest that, in a coffee drink solution, IBN undergoes hydrolysis to produce iBuOH and nitric acid, which is oxidized to nitrate and also produces cyanide through the nonspecific oxidation of organic compounds under acidic conditions.

show abstract

Section: Resultsmentioning

confidence: 99%

Pitfalls in the Toxicological Analysis of an Isobutyl Nitrite-Adulterated Coffee Drink

Seto¹,

Kataoka²,

Tsuge³

et al. 2000

Anal. Chem.

View full text Add to dashboard Cite

show abstract

“…Procedures to analyze alkyl nitrites include mass spectrometry, gas chromatography, infrared spectroscopy (4)(5)(6). However, to the best of our knowledge, little work has been done to determine the set of impurities which are present in street samples due to degradation by light and/or humidity.…”

Section: Resultsmentioning

confidence: 99%

In-Depth Headspage GC/MS Analysis of Alkyl Nitrites

Ripani¹,

Nichetti²,

Rossi³

et al. 1999

Canadian Society of Forensic Science Journal

View full text Add to dashboard Cite

Alkyl nitrites are widely abused for recreational purposes, as sexual stimulants, and to improve the physical performance in discotheque dancing. These chemicals are easily available because, with the exception of amyl nitrite, they are not controlled by Italian legislation. Alkyl nitrites are SUbject to photochemical and oxidation reactions. Therefore, the street samples usually contain a high number of chemical components. In the present paper, we report and discuss the synthesis and photochemical degradation of alkyl nitrites, and propose a fast and efficient head space / gas chromatography / mass spectrometry (HS/GC/MS) method for the identification of the degradation products. RESUME L'abus des nitrites d'alkyle est tres repandu recreationnellement comme stimulants sexuels ainsi que pour amellorer une performance physique dans les discos. Ces produits chimiques sont facilement disponibles en Italie car, aI'exception du nitrite d'amyle, ils ne se retrouvent pas dans la categorie des drogues reglementees. Les nitrites d'alkyle sont sensibles a des degradations photochimiques et oxydatives.

show abstract

“…Both headspace injection and liquid injection modes were evaluated to compare their effects on the method sensitivity of TBN. Both nitrogen (N 2 ) and helium (He) were screened as carrier gases. ,,,, Since no improvement in analysis time was observed with He over N 2 as a carrier gas and some loss in efficiency with N 2 could be tolerated, N 2 was chosen as the carrier gas due to its greater availability and reduced cost. The flow rate in the finalized method was set to 4.0 mL min –1 .…”

Section: Experimental Sectionmentioning

confidence: 99%

“…Table lists the various reported GC methods to quantify alkyl nitrites in different matrices. − Oxley et al, Schiavone et al, and other researchers have performed a thorough qualitative analysis of alkyl nitrites and their structural isomers using detailed mass fragmentation patterns in headspace (HS) gas chromatography–mass spectrometry (GC–MS). − However, the fragmentation pattern of alkyl nitrites overlaps with that of the corresponding degradant alcohols, resulting in complex and nonquantitative data. In some studies, alkyl nitrites have been quantified as alcohols using GC since alkyl nitrites are easily converted to their corresponding alcohols. , Ikeda et al reported extractive alkylation using pentafluorobenzyl bromide (PFBBr) for alkylation and subsequent GC–MS quantification of nitrite and nitrate inorganic anions .…”

Section: Introductionmentioning

confidence: 99%

Low-Level Quantification of tert-Butyl Nitrite in a Pharmaceutical Intermediate

Patel

Chokkalingam

Das

et al. 2021

Org. Process Res. Dev.

View full text Add to dashboard Cite

A sensitive, reliable, and reproducible headspace gas chromatography-flame ionization detection method was developed and validated to detect and quantify low levels of tert-butyl nitrite (TBN). TBN is a reagent commonly used by synthetic chemists for nitrogen insertion reactions and is also a potential mutagenic impurity due to a structurally alerting nitrite group. However, there is an inherent analytical challenge in the quantification of TBN due to its chemical instability in solution (e.g., degradation of TBN to tert-butyl alcohol, TBA, in protic solvents). The proposed methodology is based on stabilizing TBN in solution by adding imidazole to a sample diluent before static headspace gas chromatographic analysis. The gas chromatography method utilizes a high-polarity poly(ethylene glycol) stationary phase that provides the resolution of TBN from an interference peak in the sample matrix and facilitates the attainment of the required sensitivity of the TBN peak. The limit of detection (LOD) and limit of quantitation (LOQ) of this method were established as 0.05 μg mL −1 (0.05 ppm) and 0.15 μg mL −1 (0.15 ppm), respectively. Method validation experiments indicated excellent analytical performance of the method with respect to specificity (resolution of ∼2.2 from a matrix interference peak), linearity (range: 16.7−1000% of the working concentration), precision (relative standard deviation, RSD, of 1.0% for n = 6 at LOQ level), and recovery (94% at LOQ level). This is the first report of a practical strategy to stabilize TBN for its trace-level quantification.

show abstract

Analysis of alkyl nitrites by capillary gas chromatography-mass spectrometry

Cited by 9 publications

References 6 publications

Pitfalls in the Toxicological Analysis of an Isobutyl Nitrite-Adulterated Coffee Drink

Pitfalls in the Toxicological Analysis of an Isobutyl Nitrite-Adulterated Coffee Drink

In-Depth Headspage GC/MS Analysis of Alkyl Nitrites

Low-Level Quantification of tert-Butyl Nitrite in a Pharmaceutical Intermediate

Contact Info

Product

Resources

About