Gas chromatographic determination of amino acids via one-step phase-transfer catalytic pentafluorobenzylation–preconcentration

Fiamegos, Yiannis C.; Stalikas, Constantine D.

doi:10.1016/j.chroma.2006.01.074

Cited by 23 publications

(11 citation statements)

References 40 publications

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“…Although a nucleophile at alkaline pH, diphenylamine did not react with PFBBr [13], possibly because of steric hindrance. Of the reacting analytes, phenol (log P 1.48) was the most hydrophilic analyte and HA (log P 7.15) was the most lipophilic.…”

Section: Model Compoundsmentioning

confidence: 79%

“…Some reports in the literature suggested that a combination of EA with SPAD [22][23][24]26] was a possible approach to improving the yield for derivatization of polar analytes. A review of that literature justified our selection of the TBA cation [13,24,26]. Some of the reported studies included direct comparisons of TBA with other cations [13,24].…”

Section: Effect Of Tba On Yield Of Pentafluorobenzylationmentioning

confidence: 98%

“…A review of that literature justified our selection of the TBA cation [13,24,26]. Some of the reported studies included direct comparisons of TBA with other cations [13,24].…”

Section: Effect Of Tba On Yield Of Pentafluorobenzylationmentioning

confidence: 98%

“…In typical PTC or EA (PTC/EA) the ionized analyte forms a lipophilic ion pair with a counter-ion of the opposite charge [11][12][13][14][15]. The ion pair is extracted into an immiscible organic solvent containing reagent where the reaction occurs, thus combining extraction and derivatization into a single step.…”

Section: Introductionmentioning

confidence: 99%

“…Phase transfer catalysis (PTC) or extractive alkylation (EA) [11][12][13][14] combines extraction and derivatization in a single step and simplifies sample preparation that involves AD. In typical PTC or EA (PTC/EA) the ionized analyte forms a lipophilic ion pair with a counter-ion of the opposite charge [11][12][13][14][15].…”

Section: Introductionmentioning

confidence: 99%

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Effect of Tetrabutylammonium Cation on Solid-Phase Analytical Derivatization as a Function of Analyte Lipophilicity

2011

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Analytical derivatizations (AD) can increase the sensitivity of analyses-including those with mass spectrometric detection-by as much as three orders of magnitude. The extra steps required, however, are a possible impediment to their use. To simplify AD we investigated solid-phase analytical derivatization (SPAD) of compounds with diverse structures by using pentafluorobenzyl bromide (PFBBr) as the reagent. Model compounds were organic acids (e.g. phenols, chlorophenols and carboxylic acids) which were simultaneously extracted and derivatized from 0.1 M NaOH onto a polystyrene-divinylbenzene resin (XAD-4) as their pentafluorobenzyl (PFB) derivatives. Test analytes ranged in molecular weight from 94 for phenol to 266 for pentachlorophenol and octanol-water partition coefficients (log P) values ranged from 1.48 for phenol to 7.15 for hexadecanoic acid. Under SPAD conditions, reaction rates rapidly increased with log P, but yields for less lipophilic compounds, although precise, were unacceptably low. Use of the tetrabutylammonium (TBA) cation as a phase transfer catalyst increased the yield of compounds with low log P; but, unexpectedly, as the log P of the analyte increased, the phase transfer catalyst caused a decrease in yield. The data from this study define the log P range of compounds that require TBA for optimal yield and the log P range of compounds for which TBA compromises yield. This insight led to a simple, two-step, one-pot technique that gave high yields of the PFB derivatives for the entire range of analytes studied. SPAD first extracted/derivatized the lipophilic analytes from aqueous solution onto the solid phase. Extraction/derivatization of the polar analytes followed upon addition of TBA to the reaction mixture. The PFB ethers and esters of the entire range of analytes were then eluted from the XAD-4. The two-step procedure was faster, used less reagent and required lower temperature than comparable methods in the literature. With the twostep procedure, pentafluorobenzylation of phenols and carboxylic acids from water gave yields in excess of 88% with the exception of phenol and pentachlorophenol which were recovered in 57 and 44%, respectively. For all analytes, relative standard deviations were below 15%. The effect of matrix on yield varied between zero and a decline in recoveries of approximately 20-30% depending on the analyte and concentrations of NaCl or humic acid. In the presence of matrix components relative standard deviations remained below 20%.

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Section: Model Compoundsmentioning

confidence: 79%

Section: Effect Of Tba On Yield Of Pentafluorobenzylationmentioning

confidence: 98%

“…A review of that literature justified our selection of the TBA cation [13,24,26]. Some of the reported studies included direct comparisons of TBA with other cations [13,24].…”

Section: Effect Of Tba On Yield Of Pentafluorobenzylationmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effect of Tetrabutylammonium Cation on Solid-Phase Analytical Derivatization as a Function of Analyte Lipophilicity

2011

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A sensitive fluorescence reagent, 2‐[2‐(7H‐dibenzo[a,g]carbazol‐7‐yl)‐ethoxy]ethyl chloroformate, for amino acids determination in Saussurea involucrate and Artemisia capillaris Thunb using high‐performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/electrospray ionization source

Sun

Song

et al. 2010

Biomedical Chromatography

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Recent researches shows that amino acids (AA) are not only cell signaling molecules but are also regulators of gene expression and the protein phosphorylation cascade. More precise analysis of AA composition is reckoned to be one of the most important applications in the biomedical and pharmaceutical fields. In this paper, we develop a sample, sensitive and mild method using 2-[2-(7H-dibenzo[a,g]carbazol-7-yl)-ethoxy]ethyl chloroformate (DBCEC) as A labeling reagent for AA determination by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) and identification with mass spectroscopy. The maximum excitation and emission wavelengths for DBCEC-AA derivatives were 300 and 395 nm, respectively. This method, in conjunction with a gradient elution, offered a baseline resolution of 20 AA on a reversed-phase Hypersil BDS C(18) column. LC separation for the derivatized AA showed good reproducibility, and all AA were found to give excellent linear responses with correlation coefficients > 0.9993. The calculated detection limits with a 25.0 fmol injection of each AA (at a signal-to-noise ratio of 3:1) ranged from 2.62 to 22.6 fmol. This method was applied to determine the AA composition in Saussurea involucrate and Artemisia capillaris Thunb. Meanwhile, this method exhibits a powerful potential for trace analysis of AA from biomedicine, foodstuff and other complex samples.

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Overview of chromatographic and electrophoretic methods for the determination of branched‐chain amino acids

Yin

Adams

Schepdael

2023

J of Separation Science

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The significance of branched‐chain amino acids in diseases was clearly shown over the years. This review aims to describe the available techniques for their analytical determination. The article provides examples of the use of various analytical methods. The methods are divided into two categories: derivatization and non‐derivatization approaches. Separation is achieved through different chromatography or capillary electrophoresis techniques and can be combined with different detectors such as flame ionization, ultraviolet, fluorescence, and mass spectrometry. It compares the application of various derivatization reagents or detection as such for different detectors.

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Gas chromatographic determination of amino acids via one-step phase-transfer catalytic pentafluorobenzylation–preconcentration

Cited by 23 publications

References 40 publications

Effect of Tetrabutylammonium Cation on Solid-Phase Analytical Derivatization as a Function of Analyte Lipophilicity

Effect of Tetrabutylammonium Cation on Solid-Phase Analytical Derivatization as a Function of Analyte Lipophilicity

Overview of chromatographic and electrophoretic methods for the determination of branched‐chain amino acids

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