Attogram-level detection and relative sensitivity of strong electrophores by gas chromatography with electron capture detection

Corkill, Jeffrey A.; Joppich, Markus; Kuttab, Simon; Giese, Roger W.

doi:10.1021/ac00240a029

Cited by 18 publications

(10 citation statements)

References 28 publications

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“…LODs at the attogram [110] and zeptomolar (200 • 10 −21 at an S/N of 3:1) levels [111] were demonstrated by GC-ECD and GC/EC-MS, respectively. An electrophore is a functional group (e.g., pentafluorophenyl-, -NO2) that enhances the EC crosssection to produce molecular anions and/or fragment negative ions.…”

Section: Improvements In Detectabilitymentioning

confidence: 97%

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Derivatization techniques for determination of carbonyls in air

Szulejko

Kim

2015

TrAC Trends in Analytical Chemistry

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Section: Improvements In Detectabilitymentioning

confidence: 97%

“…Giese and co-workers used electron-capture detectors (ECDs) or GC analysis of compounds/or derivatives containing electrophoric groups [110,111]. LODs at the attogram [110] and zeptomolar (200 • 10 −21 at an S/N of 3:1) levels [111] were demonstrated by GC-ECD and GC/EC-MS, respectively.…”

Section: Improvements In Detectabilitymentioning

confidence: 99%

Derivatization techniques for determination of carbonyls in air

Szulejko

Kim

2015

TrAC Trends in Analytical Chemistry

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“…Furthermore, sandwiching the bound carbohydrate guest between aromatic rings located atop of and below the H-bonding cavity should greatly increase the number of hostÀguest dispersion and CH´´´p interactions, as well as enhance favorable hydrophobic desolvation processes, thereby enabling stable carbohydrate complexation in aqueous solution [5]. , methyl 2-amino-5-iodobenzoate [31], 61 [44], methyl 2,5-diiodobenzoate [51], [PdCl 2 (dppf)]´CH 2 Cl 2 [52], and CuCl [53] were synthesized according to literature procedures. The octyl glycosides 63 ± 65, 67 [54], and 68 [55] were prepared according to known protocols [56].…”

Section: Synthetic Receptors For Monosaccharides and Disaccharides mentioning

confidence: 99%

Optically Active Cyclophane Receptors for Mono- and Disaccharides: The Role of Bidentate Ionic Hydrogen Bonding in Carbohydrate Recognition

Droz¹,

Neidlein²,

Anderson³

et al. 2001

HCA

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A new family of optically active cyclophane receptors for the complexation of mono-and disaccharides in competitive protic solvent mixtures is described. Macrocycles (À)-(R,R,R,R)-1 ± 4 feature preorganized binding cavities formed by four 1,1'-binaphthalene-2,2'-diyl phosphate moieties bridged in the 3,3'-positions by acetylenic or phenylacetylenic spacers. The four phosphodiester groups converge towards the binding cavity and provide efficient bidentate ionic H-bond acceptor sites (Fig. 2). Benzyloxy groups in the 7,7'-positions of the 1,1'-binaphthalene moieties ensure solubility of the nanometer-sized receptors and prevent undesirable aggregation. The construction of the macrocyclic framework of the four cyclophanes takes advantage of Pd 0 -catalyzed arylÐacetylene cross-coupling by the Sonogashira protocol, and oxidative acetylenic homo-coupling methodology (Schemes 2 and 8 ± 10). Several cleft-type receptors featuring one 1,1'-binaphthalene-2,2'-diyl phosphate moiety were also prepared (Schemes 1, 6, and 7). An undesired side reaction encountered during the synthesis of the target compounds was the formation of naptho[b]furan rings from 3-ethynylnaphthalene-2-ol derivatives, proceeding via 5-endo-dig cyclization (Schemes 3 ± 5). Computer-assisted molecular modeling indicated that the macrocycles prefer nonplanar puckered, cyclobutane-type conformations (Figs. 7 and 8). According to these calculations, receptor (À)-(R,R,R,R)-1 has, on average, a square binding site, which is complementary in size to one monosaccharide. The three other cyclophanes (À)-(R,R,R,R)-2 ± 4 feature, on average, wider rectangular cavities, providing a good fit to one disaccharide, while being too large for the complexation of one monosaccharide. This substrate selectivity was fully confirmed in 1 H-NMR binding titrations. The chiroptical properties of the cyclophanes and their nonmacrocyclic precursors were investigated by circular dichroism (CD) spectroscopy. The CD spectra of the acyclic precursors showed a large dependence from the number of 1,1'-binaphthalene moieties (Fig. 9), and those of the cyclophanes were remarkably influenced by the nature of the functional groups lining the macrocyclic cavity (Fig. 11). Profound differences were also observed between the CD spectra of linear and macrocyclic tetrakis(1,1'-binaphthalene) scaffolds, which feature very different molecular shapes (Fig. 10). In 1 H-NMR binding titrations with mono-and disaccharides (Fig. 13), concentration ranges were chosen to favor 1 : 1 hostÀguest binding. This stoichiometry was experimentally established by the curve-fitting analysis of the titration data and by Job plots. The titration data demonstrate conclusively that the strength of carbohydrate recognition is enhanced with an increasing number of bidentate ionic hostÀguest H-bonds (Table 1) in the complex formed. As a result of the formation of these highly stable H-bonds, carbohydrate complexation in competitive protic solvent mixtures becomes more favorable. Thus, cleft-type receptors (À)-(R)-7 and (À...

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“…The extremely low detection limits attainable with the electron capture detector are well illustrated by the response obtained with, among others, some derivatized iodothyronines and N, N-dipentafluorobenzoylpentafluoroaniline [130] ; these compounds showed detection limits at attogram levels. The development of new ECD labels which allow even lower detection limits than those currently obtained may only be a matter of time.…”

Section: Electron Capture Detectionmentioning

confidence: 81%

Derivatization reactions in the gas—liquid chromatographic analysis of drugs in biological fluids

Hulshoff¹,

Lingeman²

1984

Journal of Pharmaceutical and Biomedical Analysis

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Alkylation, acylation, silylation and other derivatization reactions applied to the gas chromatographic analysis of drugs in biological matrices are reviewed. Reaction conditions are discussed in relation to reaction mechanisms. Detector-oriented labelling of drugs, and derivatization with chiral reagents for the separation of enantiomers are surveyed. Data on the sample clean-up, derivatization and GLC analysis of more than 300 drugs and related compounds are listed.

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Attogram-level detection and relative sensitivity of strong electrophores by gas chromatography with electron capture detection

Cited by 18 publications

References 28 publications

Derivatization techniques for determination of carbonyls in air

Derivatization techniques for determination of carbonyls in air

Optically Active Cyclophane Receptors for Mono- and Disaccharides: The Role of Bidentate Ionic Hydrogen Bonding in Carbohydrate Recognition

Derivatization reactions in the gas—liquid chromatographic analysis of drugs in biological fluids

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