Direct analysis of sterols by derivatization matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and tandem mass spectrometry

Hailat, Iyad; Helleur, Robert

doi:10.1002/rcm.6766

Cited by 33 publications

(27 citation statements)

References 42 publications

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“…Other applications of MALDI TOF/TOF were also reported for carbohydrates and peptides [35, 36]. Whereas fatty acids have been investigated by MALDI TOF/TOF and their CID spectra are well understood, steroids and their conjugates have been far less investigated [37]. Here, we demonstrate, for the first time to our knowledge, the application of MALDI TOF/TOF instrumentation to induce CRF and enable structural characterization of sulfated steroids.…”

Section: Introductionmentioning

confidence: 65%

High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates

Yan

Ubukata

Cody

et al. 2014

J. Am. Soc. Mass Spectrom.

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A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (~10 keV, laboratory frame) that induced charge-remote fragmentations (CRF), a class of fragmentations particularly informative for lipids, steroids, surfactants, and peptides. Unfortunately, the capability for high-energy activation has largely disappeared with the demise of magnetic sector instruments. With the latest designs of tandem time-of-flight mass spectrometers (TOF/TOF), however, this capability is now being restored to coincide with the renewed interest in metabolites and lipids including steroid-sulfates and other steroid metabolites. For these metabolites, structure determinations are required at concentration levels below that appropriate for NMR. To meet this need, we explored CRF with TOF/TOF mass spectrometry for two groups of steroid sulfates, 3-sulfates and 21-sulfates. We demonstrated that the current generation of MALDI TOF/TOF instruments can generate charge-remote-fragmentations for these materials. The resulting collision-induced dissociation (CID) spectra are useful for positional isomer differentiation and very often allow the complete structure determination of the steroid. We also propose a new nomenclature that directly indicates the cleavage sites on the steroid ring with carbon numbers.

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Section: Introductionmentioning

confidence: 65%

High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates

Yan

Ubukata

Cody

et al. 2014

J. Am. Soc. Mass Spectrom.

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“…Likewise, long-chain alkenones and the corresponding U In addition to stratigraphic analysis of the biomarker record in sediments, LDI FTICR-MS may open new avenues for the examination of modern, spatially organized ecosystems, such as redox boundaries in sediments or microbial mats, where lipid biomarker and pigment analysis could reveal ultra-fine community composition. Several of these potentially interesting molecular targets for LDI FTICR-MS will require intense methodological development and possibly demand application of artificial matrix or derivatization techniques [e.g., sterols (67)], but could reward us with a transformative insight into the biomarker world.…”

Section: Resultsmentioning

confidence: 99%

Ultra-high-resolution paleoenvironmental records via direct laser-based analysis of lipid biomarkers in sediment core samples

Wörmer

Elvert

Fuchser

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and used in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single submillimeter-sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional liquid chromatography/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-μm resolution (∼4-y temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the ∼200-y de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and environmental factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments. molecular stratigraphy | solar cycle | laser desorption ionization | FTICR-MS | archaeal tetraether lipids M icrobial lipids in aquatic sediments reflect phylogeny, environmental conditions, and biogeochemistry of the water column in which they were produced. After sedimentation and because of the persistence of lipid structures in the sedimentary record, the information archived in these lipids remains available on geological time scales. Retrieval of this information from sediments and rocks has increasingly contributed to our understanding of past environments, microbial communities, and biogeochemical processes (e.g., refs. 1-5). Merged with the concept of molecular stratigraphy (2, 6), i.e., the analysis of selected biomarkers in solvent extracts of sediment samples in a stratigraphic framework, unique information can be gleaned regarding the temporal changes of past ecological and environmental conditions in aquatic systems. Because of analytical requirements, the temporal resolution is typically limited by centimeter-scale-sized samples, which, dependent on the depositional setting, tend to integrate time periods of decades to millennia, even in high-sedimentation settings such as the Santa Barbara Basin...

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“…MALDI-MS [15,16] has been tested for its applicability as a rapid screening technique. The challenges in MALDI-MS analysis of hydrophobic molecules such as cholesterol and its ester, steroids and coenzyme Q10 stem from the complexity and low ionization efficiencies of the target compounds.…”

Section: Introductionmentioning

confidence: 99%

Coumarins as new matrices for matrix-assisted laser-desorption/ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of hydrophobic compounds

Wang

Dai

Liu

et al. 2015

Analytica Chimica Acta

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Direct analysis of sterols by derivatization matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and tandem mass spectrometry

Cited by 33 publications

References 42 publications

High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates

High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates

Ultra-high-resolution paleoenvironmental records via direct laser-based analysis of lipid biomarkers in sediment core samples

Coumarins as new matrices for matrix-assisted laser-desorption/ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of hydrophobic compounds

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