Derivatization for liquid chromatography-mass spectrometry

“…It is well known that the derivatization of various functional groups is beneficial to LC-MS analyses 20 just as it is to ambient ionization 16 and both of these topics are the subjects of recent reviews 18,20 .…”

Section: Introductionmentioning

confidence: 99%

Molecular labels for analysis of amines and diols by spray based ionization-mass spectrometry

Ayrton

Cooks

Pugia

2016

Analyst

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A family of imidazolium and pyridinium salts was synthesized for the purpose of labeling amines and 1,2-diols for highly sensitivite analysis by mass spectrometry. The chosen mass labels are shown to serve as effective reporters when bound to particles functionalized with amines or 1,2-diols and the binding is reversible. The straightforward synthetic route allows analogous internal standards to be generated quickly. Solvents amenable to electrospray ionization facilitate the rapid liberation of imidazolium and pyridinium mass labels from particles by hydrolysis in aqueous acid, while the acetal bond remains stable in anhydrous or buffered aqueous solution. Detection of the labels is demonstrated at 1 nM and quantitation of mass labels released from particles is also demonstrated.

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“…21 However, not all the isotope internal standards are commercially available and the 86 synthesis of isotope internal standards is typically difficult. To circumvent these problems, in-vitro 87 isotope labeling methods have been developed for non-targeted quantitative profiling of 88 metabolites.…”

Section: Introduction 48mentioning

confidence: 99%

Metal Oxide-Based Selective Enrichment Combined with Stable Isotope Labeling-Mass Spectrometry Analysis for Profiling of Ribose Conjugates

Chu

Huang

et al. 2015

Anal. Chem.

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Some modified ribonucleosides in biological fluids have been evaluated as cancer-related metabolites. Detection of endogenous modified ribonucleosides in biological fluids may serve as a noninvasive cancers diagnostic method. However, determination of modified ribonucleosides is still challenging because of their low abundance and serious matrix interferences in biological fluids. Here, we developed a novel strategy for comprehensive profiling of ribose conjugates from biological fluids using metal oxide-based dispersive solid-phase extraction (DSPE) followed with in vitro stable isotope labeling and double neutral loss scan-mass spectrometry analysis (DSPE-SIL-LC-DNLS-MS). Cerium dioxide (CeO2) was used to selectively recognize and capture ribose conjugates from complex biological samples under basic environment. The enriched ribose conjugates were subsequently labeled with a pair of isotope labeling reagents (acetone and acetone-d6). The glucosidic bond of acetone labeled ribose conjugates is readily ruptured, and the generated ribose that carries an isotope tag can be lost as a neutral fragment under collision induced dissociation (CID). Since the light (acetone) and heavy (acetone-d6) labeled compounds have the same chemical structures and can generate different neutral loss fragments (NL 172 and 178 Da), it is therefore highly convenient to profile ribose conjugates by double neutral loss scan mode in mass spectrometry analysis. In this respect, the light and heavy labeled compounds were ionized at the same condition but recorded separately on MS spectra, which can significantly improve the detection specificity and facilitate the identification of ribose conjugates. Using the developed DSPE-SIL-LC-DNLS-MS strategy, we profiled the ribose conjugates in human urine, and 49 ribose conjugates were readily identified, among which 7 ribose conjugates exhibited significant contents change between healthy controls and lymphoma patients. The DSPE-SIL-LC-DNLS-MS strategy combines the selective enrichment, stable isotope labeling, and double neutral loss scan - MS analysis, which therefore can efficiently minimize false positive results, facilitate the relative quantification, and notably increase the numbers of identified ribose conjugates in biological fluids samples. Taken together, this study established a promising strategy for the effective profiling of urinary modified ribonucleosides, and simultaneous evaluation of the contents change of multiple modified ribonucleosides should provide more accurate and conclusive results for the use of urinary modified ribonucleosides as indicators of cancers.

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Derivatization for liquid chromatography-mass spectrometry

Cited by 205 publications

References 158 publications

Technology and methodology of DNA adducts analysis

Technology and methodology of DNA adducts analysis

Molecular labels for analysis of amines and diols by spray based ionization-mass spectrometry

Metal Oxide-Based Selective Enrichment Combined with Stable Isotope Labeling-Mass Spectrometry Analysis for Profiling of Ribose Conjugates

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