New electron-capturing pentafluorophenyldialkylchlorosilanes as versatile derivatizing reagents for gas chromatography

Poole, Colin F.; Sye, Wen-Fa; Singhawangcha, S.; Hsu, Fong‐Fu; Zlatkis, A.; Arfwidsson, A.; Vessman, Jörgen

doi:10.1016/s0021-9673(01)91366-4

Cited by 30 publications

(5 citation statements)

References 18 publications

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“…It was hoped that reaction of β‐blockers with the chloromethyl(pentafluoro)methylsilyl reagents would form cyclic derivatives as with the CMDMS reagents but all attempts to achieve cyclization were unsuccessful. Spectra were similar to those of the iso ‐propyl analogs in that loss of the iso ‐propyl group produced major ions from derivatized alcohols but the ion was absent from the spectra of derivatized n ‐butanethiol, 3‐butenoic acid and aniline, and of only moderate abundance in the spectra of benzoic acid and phenol (Poole et al, ). In the presence of strong bases, the chloromethyl group could be displaced resulting in self‐condensation of the reagent.…”

Section: Other Silyl Derivativesmentioning

confidence: 90%

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Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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This review describes the mass spectral fragmentation of trimethylsilyl (TMS) and related alkylsilyl derivatives used for preparing samples for analysis, mainly by combined gas chromatography and mass spectrometry (GC/MS). The review is divided into three sections. The first section is concerned with the TMS derivatives themselves and describes fragmentation of derivatized alcohols, thiols, amines, ketones, carboxylic acids and bifunctional compounds such as hydroxy‐ and amino‐acids, halo acids and hydroxy ethers. More complex compounds such as glycerides, sphingolipids, carbohydrates, organic phosphates, phosphonates, steroids, vitamin D, cannabinoids, and prostaglandins are discussed next. The second section describes intermolecular reactions of siliconium ions such as the TMS cation and the third section discusses other alkylsilyl derivatives. Among these latter compounds are di‐ and trialkyl‐silyl derivatives, various substituted‐alkyldimethylsilyl derivatives such as the tert‐butyldimethylsilyl ethers, cyclic silyl derivatives, alkoxysilyl derivatives, and 3‐pyridylmethyldimethylsilyl esters used for double bond location in fatty acid spectra. © 2019 Wiley Periodicals, Inc. Mass Spec Rev 0000:1–107, 2019

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Section: Other Silyl Derivativesmentioning

confidence: 90%

“…These derivatives comprise one of a series investigated by Poole et al () for the GLC and GC/MS detection of small molecules. Molecular ions from derivatized butane‐2‐ol and n ‐butanethiol were of low abundance but a very prominent ion was present at [M − iso ‐C 3 H 7 • ] + .…”

Section: Other Silyl Derivativesmentioning

confidence: 99%

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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“…Aliquots of 0.5 mL and a protein concentration between 0.1 mg/L and 100 mg/L were mixed with 1.5 mL of 6 M HCl in a 2.2 mL Eppendorf tube and incubated at 110°C for 24 h. The hydrolyzates were dried under vacuum in a speedvac at room temperature for 12 h. For derivatization, the dried hydrolyzates were resuspended in 100 µL of tetrahydrofuran (Fluka), 100 µL of N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBST-FA) (Fluka) was added, and the mixture was incubated for 60 min at 60°C. Protic sites of amino acids (OH-, NH-, and SH-groups) were blocked by silylation to reduce dipole-dipole interactions and to increase volatility for GC separation (11). The use of MTBSTFA had the advantage that mostly neutral and volatile byproducts are formed that did not react with the column, hence enabling direct GC-MS analysis (12).…”

Section: Methodsmentioning

confidence: 99%

GC‐MS Analysis of Amino Acids Rapidly Provides Rich Information for Isotopomer Balancing

Dauner

Sauer

2000

Biotechnology Progress

221

205

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Gas chromatography-mass spectrometry (GC-MS) is a rapid method that provides rich information on isotopomer distributions for metabolic flux analysis. First, we established a fast and reliable experimental protocol for GC-MS analysis of amino acids from total biomass hydrolyzates, and common experimental pitfalls are discussed. Second, a suitable interface for the use of mass isotopomer data is presented. For this purpose, a general, matrix-based correction procedure that accounts for naturally occurring isotopes is introduced. Simulated and experimentally determined mass distributions of unlabeled amino acids showed a deviation of less than 3% for 89% of the analyzed fragments. Third, to investigate general properties of GC-MS-based isotopomer balancing, altered flux ratios through glycolysis and pentose phosphate pathway and/or exchange fluxes were simulated. Different fluxes were found to exert specific and significant influence on the mass isotopomer distributions, thus indicating that GC-MS data contain valuable information for metabolic flux analysis. Fourth, comparison of different methods revealed that GC-MS analysis provides the largest number of independent constraints on amino acid isotopomer abundance, followed by correlation spectroscopy and fractional enrichment analysis by nuclear magnetic resonance.

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“…Flophemesyl derivatives also have favorable advantages for GC/MS, producing diagnostic ions that carry more of the current than TMS derivatives. (55) …”

Section: Silylationmentioning

confidence: 99%

Chemical Reagents and Derivatization Procedures in Drug Analysis

Danielson

Gallagher

Bao

2008

Encyclopedia of Analytical Chemistry

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This article describes both pre‐ and postcolumn derivatization chemistry used in conjunction with either chromatography or capillary electrophoresis (CE) to facilitate the determination of drugs. Generally, only prederivatization is used in gas chromatography (GC), principally to enhance the volatility, temperature stability, and/or detectability. The GC section considers derivatization of drugs by reagent class: alkylation, acylation, and silylation. The GC sample‐handling section describes an approach that combines the extraction and derivatization steps together. Both pre‐ and postcolumn derivatization are common approaches for high‐performance liquid chromatography (HPLC) and many of these methods have been adapted for CE. Derivatization for HPLC is often directed toward aliphatic amines, carboxylic acids, or alcohols that are difficult to detect at low levels by absorbance, luminescence, or electrochemical means. In addition, small hydrophilic molecules upon prederivatization are often converted into larger more hydrophobic compounds, making reversed‐phase HPLC easier or even feasible. The HPLC section considers derivatization of drugs based on the following types: alkaloids, amines, antibiotics, barbiturates, carbonyl compounds and carboxylic acids, catecholamines, hydroxy compounds, steroids, and sulfur compounds. For the GC and HPLC sections, tables are included, giving the structures of the more important derivatizing agents, the analytes, and the corresponding reaction products. A brief rationale for derivatization chemistry with CE concludes this article. For CE, derivatization is often done to improve detectability as the path length for absorbance detection is very short and fluorescence can be effective using laser‐based systems.

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New electron-capturing pentafluorophenyldialkylchlorosilanes as versatile derivatizing reagents for gas chromatography

Cited by 30 publications

References 18 publications

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

GC‐MS Analysis of Amino Acids Rapidly Provides Rich Information for Isotopomer Balancing

Chemical Reagents and Derivatization Procedures in Drug Analysis

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