Substituted benzeneboronic acids for the gas chromatographic determination of bifunctional compounds with electron-capture detection

Poole, Colin F.; Singhawangcha, S.; Zlatkis, A.

doi:10.1016/s0021-9673(00)89953-7

Cited by 37 publications

(6 citation statements)

References 35 publications

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“…1. Although nonselective when compared to the use of boronic acids 5 HFBI was the derivatization reagent of choice; HFBI makes volatile all coextracted compounds with -OH or -NH groups thereby minimizing contamination of the GC column and injector; the mass spectra of 3-MCPD-HFBI derivatives contains a greater number of diagnostic ions than the corresponding alkyl or phenyl boronic acid. 8,9 A number of diols were evaluated as internal standards for the quantification of 3-MCPD; 3-fluoro-1,2-propandiol formed GC stable derivatives with HFBI but was found to be unstable in some low pH extracts; 3-bromo-1,2-propandiol was unstable to HFBI; 3-methoxy-1,2-propandiol, butane diol and other homologous diols occurred naturally in some HVP's.…”

Section: Resultsmentioning

confidence: 99%

“…Analytical methods used to determine 3-MCPD include: gas chromatography (GC) of an alkyl or phenyl boronic acid derivative with electron-capture detection, 5,6 flame ionization detection 7 and mass detection; 8,9 GC of a heptafluorobutyrate derivative with electron-capture detection; 10 GC of the underivatized diol with electrolytic conductivity detection 11 or mass detection. 12 However none of these methods are of sufficient sensitivity or selectivity for the determination of µg/kg levels of 3-MCPD in HVP.…”

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confidence: 99%

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Determination of the Chloropropanols, 3-Chloro-1,2-propandiol and 2-Chloro-1,3-propandiol, in Hydrolysed Vegetable Proteins and Seasonings by Gas Chromatography/Ion Trap Tandem Mass Spectrometry

Hamlet

Sutton

1997

Rapid Commun. Mass Spectrom.

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This paper reports on the development of a highly selective method for the determination of parts-per-billion (µg/kg) levels of 3-chloro-1,2-propandiol (3-MCPD) in hydrolysed vegetable proteins (HVP) using gas chromatography/ion trap mass spectrometry operating in the tandem mass spectrometry (MS/MS) mode. Samples were extracted into 5M sodium chloride solution and partitioned into diethyl ether using Extrelut® 20 solid phase columns. Dried and concentrated extracts were derivatized with heptafluorobutyrylimidazole (HFBI) prior to determination by gas chromatography ion trap (GC/IT) MS/MS. Multiple reaction monitoring was used to monitor the parent/daughter ion transitions of the analytes and the stable isotope internal standard (3-chloro-1,2-propandiol-d 7 ). Calibration was linear over the range 5.0-500 pg/µL with correlation coefficients of 0.999 routinely obtained. The results showed that the method was capable of detecting 3-MCPD below 5 µg/kg in HVP when analysed by GC/ITMS/MS.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Determination of the Chloropropanols, 3-Chloro-1,2-propandiol and 2-Chloro-1,3-propandiol, in Hydrolysed Vegetable Proteins and Seasonings by Gas Chromatography/Ion Trap Tandem Mass Spectrometry

Hamlet

Sutton

1997

Rapid Commun. Mass Spectrom.

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“…It has been our experience with the solution technique that boronate derivatives are not formed with bifunctional ketone compounds, 1,3-disubstituted aromatic compounds, dicarboxylic acids or aliphatic compounds with functional groups separated by more than two methylene units (i. e. 15carbon atom systems) [2,3]. The derivatives formed with aromatic carboxylic acids degrade rapidly on standing in solution.…”

Section: February 1979mentioning

confidence: 99%

“…However, some derivatives are unstable in solution and the need to isolate bifunctional compounds from biological fluids prior to the formation of derivatives is a limitation on the general use of these reagents. Using two new boronic acids, 2,4-dichlorobenzeneboronic acid [2] and 44odobutaneboronic acid [3], some novel methods of derivative formation were investigated with a representative series of bifunctional compounds. The sandwich injection technique was studied as a means of eliminating solution degradation and extractive derivatization as a means of isolation and derivative formation of aqueous solutions.…”

Section: Introductionmentioning

confidence: 99%

Versatile derivatization reactions with 4‐lodobutaneboronic and 2,4‐dichlorobenzeneboronic acids

Singhawangcha

Poole

Zlatkis

1979

J. High Resol. Chromatogr.

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“…Phenylboronic acid-diol derivatives have also been analyzed by gas chromatography and mass spectroscopy (13) and the interaction between boronic acids and diols has been extensively studied (14). Aqueous boric acid mobile phases were initially used to separate diols by paper chromatography and by electrophoresis (15).…”

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confidence: 99%

Manipulation of Stationary-Phase Acid-Base Properties by a Surface-Buffering Effect

Lochmüller

Hill

1986

ACS Symposium Series

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The presence of residual amine groups in sur face bound, silica-based phenylboronic acid phases lowers the apparent pK a of the acid groups. This "surface buffering" effect permits boronate-saccharide complexation chemistry to occur at much lower pH values than is typically the case. The broader implications of the de liberate use of such effects are discussed.Lochmuller, Wilder and Marshall ( 1 ) observed an apparent lowering of the pKa for surface-bound quinazolines using photothermal spectrometric titration approach and further evidence for the mechanism of this change in acid base behavior has recently been reported by Lochmuller and Hill (2). It appears that sitesite interactions (charge repulsion) and "surface buffering" by residual amine groups combine to produce the apparent change. Mat lin and Davidson (3 ) also observed interactions between the neutral species picramidopropyl and propylamine in a "mixed", bonded phase by photοthermal spectrometry.One of the problems with silica-based chromatographic materials is their relatively high solubility in mobile phases of pH higher than 7.5 units. It is interesting to speculate that at least for some important ionic equilibria, the acid-base chemistry of bound molecules might be manipulated by deliberately intro ducing a "surface buffering" effect.We chose to explore this possibility by studying the complexation of saccharides by boronic acid anion because of the importance of saccharides and the nor mally high pH conditions required (pH 8-10) Gilham had postulated that the local positive or negative charges on cellulose in fluenced the pKa of phenylboronic acid at low mobile phase ionic strength (4 ).In addition, Lochmuller and Amoss first demon strated the advantage of "mixed" bonded phases in systems where the complexation constants are large and contribute to poor trans fer kinetics (5 ). Later Karger used this approach to improve the performance of bound metal complex phases (6).Partial derivati zation of amine silicas might be expected to improve the efficien cies obtained with boronate phases by the same reasoning.

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Substituted benzeneboronic acids for the gas chromatographic determination of bifunctional compounds with electron-capture detection

Cited by 37 publications

References 35 publications

Determination of the Chloropropanols, 3-Chloro-1,2-propandiol and 2-Chloro-1,3-propandiol, in Hydrolysed Vegetable Proteins and Seasonings by Gas Chromatography/Ion Trap Tandem Mass Spectrometry

Determination of the Chloropropanols, 3-Chloro-1,2-propandiol and 2-Chloro-1,3-propandiol, in Hydrolysed Vegetable Proteins and Seasonings by Gas Chromatography/Ion Trap Tandem Mass Spectrometry

Versatile derivatization reactions with 4‐lodobutaneboronic and 2,4‐dichlorobenzeneboronic acids

Manipulation of Stationary-Phase Acid-Base Properties by a Surface-Buffering Effect

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