Infrared multiple photon dissociation (IRMPD) spectroscopy and its potential for the clinical laboratory

Carlo, Matthew J.; Patrick, Amanda L.

doi:10.1016/j.jmsacl.2021.12.004

Cited by 14 publications

(20 citation statements)

References 115 publications

(123 reference statements)

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“…This inquiry originates from the current, increasing interest in the application of IR spectroscopy as a versatile analytical tool to clarify the structural features of small (bio)molecules involved in relevant metabolic functions. 31 , 37 − 41 …”

Section: Introductionmentioning

confidence: 99%

“…In addition, quantum chemical calculations have been performed to sample low-energy candidate isomers and to obtain optimized geometrical and electronic structures and linear IR absorption spectra. This inquiry originates from the current, increasing interest in the application of IR spectroscopy as a versatile analytical tool to clarify the structural features of small (bio)molecules involved in relevant metabolic functions. ,− …”

Section: Introductionmentioning

confidence: 99%

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IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid

et al. 2022

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Genistein is a naturally occurring polyphenol belonging to the family of flavonoids with estrogenic properties and proven antioxidant, anti-inflammatory, and hormonal effects. Genistein and its derivatives are involved in radical scavenging activity by way of mechanisms based on sequential proton-loss electron transfer. In view of this role, a detailed structural characterization of its bare deprotonated form, [geni-H] − , generated by electrospray ionization, has been performed by tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy in the 800–1800 cm –1 spectral range. Quantum chemical calculations at the B3LYP/6-311+G(d,p) level of theory were carried out to determine geometries, thermochemical data, and anharmonic vibrational properties of low-lying isomers, enabling to interpret the experimental spectrum. Evidence is gathered that the conjugate base of genistein exists as a single isomeric form, which is deprotonated at the most acidic site (7-OH) and benefits from a strong intramolecular H-bond interaction between 5-OH and the adjacent carbonyl oxygen in the most stable arrangement.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid

et al. 2022

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“…The IR-FEL is generated by the strong interaction of SR with the successive electron beam and is transmitted from a coupling hole in the center of a resonant mirror to a laboratory. A remarkable feature of the IR-FEL is that it gives intense vibrational excitation energy to the corresponding functional group's mode-selectively, which can induce multi-photon absorption and dissociation reactions for various molecules in gas, liquid, and solid phases [23][24][25][26]. We have previously found that cellulose fibers can be dissociated, and glucose and low-molecular weight oligosaccharides can be recovered using an IR-FEL tuned to 9.1 µm (νC-O), 7.2 µm (δH-C-O), and 3.5 µm (νC-H) [27].…”

Section: Introductionmentioning

confidence: 99%

Degradation of Lignin by Infrared Free Electron Laser

et al. 2022

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Lignin monomers have attracted attention as functional materials for various industrial uses. However, it is challenging to obtain these monomers by degrading polymerized lignin due to the rigid ether linkage between the aromatic rings. Here, we propose a novel approach based on molecular vibrational excitation using infrared free electron laser (IR-FEL) for the degradation of lignin. The IR-FEL is an accelerator-based pico-second pulse laser, and commercially available powdered lignin was irradiated by the IR-FEL under atmospheric conditions. Synchrotron-radiation infrared microspectroscopy analysis showed that the absorption intensities at 1050 cm−1, 1140 cm−1, and 3400 cm−1 were largely decreased alongside decolorization. Electrospray ionization mass chromatography analysis showed that coumaryl alcohol was more abundant and a mass peak corresponding to hydrated coniferyl alcohol was detected after irradiation at 2.9 μm (νO-H) compared to the original lignin. Interestingly, a mass peak corresponding to vanillic acid appeared after irradiation at 7.1 μm (νC=C and νC-C), which was supported by our two-dimensional nuclear magnetic resonance spectroscopy analysis. Therefore, it seems that partial depolymerization of lignin can be induced by IR-FEL irradiation in a wavelength-dependent manner.

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“…Vibrational resonances are highly sensitive to details of the molecular structure, such that closely related isomeric molecular ions can often be differentiated on the basis of their IR spectra. Indeed, a range of studies have shown that IRIS can distinguish isomeric small molecules [16][17][18][19][20][21][22][23][24][25][26][27][28] , including several phase-I drug metabolites [29][30][31] . A significant advantage in comparison to techniques based on MS/MS fragmentation patterns is that gas-phase IR spectra can be reliably and efficiently predicted using quantum-chemical calculations based on density functional theory (DFT).…”

Section: Introductionmentioning

confidence: 99%

Identification of drug metabolites with infrared ion spectroscopy – application to midazolam in vitro metabolism

Outersterp

Martens

Berden

et al. 2022

Preprint

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The identification of biotransformation products of drug compounds is a crucial step in drug development. Over the last decades, liquid chromatography-mass spectrometry (LC-MS) has become the method of choice for metabolite profiling because of its high sensitivity and selectivity. However, determining the full molecular structure of the detected metabolites, including the exact biotransformation site, remains challenging on the basis of MS alone. Here we explore infrared ion spectroscopy (IRIS) as a novel MS-based method for the elucidation of metabolic pathways in drug metabolism research. Using the drug midazolam as an example, we identify several biotransformation products directly from an in vitro drug incubation sample. We show that IR spectra of the aglycone MS/MS fragment ions of glucuronide metabolites establish a direct link between detected phase I and phase II metabolites. Moreover, using quantum-chemically computed IR spectra of candidate structures, we are able to assign the exact sites of biotransformation in absence of reference standards. Additionally, we demonstrate the utility of IRIS for structural elucidation by identifying several ring-opened midazolam derivatives formed in an acidic environment.

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Infrared multiple photon dissociation (IRMPD) spectroscopy and its potential for the clinical laboratory

Abstract: Graphical abstract

Cited by 14 publications

References 115 publications

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid

Degradation of Lignin by Infrared Free Electron Laser

Identification of drug metabolites with infrared ion spectroscopy – application to midazolam in vitro metabolism

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