Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

Jašíková, Lucie; Roithová, Jana

doi:10.1002/chem.201705692

Cited by 74 publications

(38 citation statements)

References 188 publications

(136 reference statements)

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“…As the resonant IR photons are absorbed, the absorbed energy is redistributed among many vibrational modes. This causes the internal energy to exceed a certain threshold, leading to fragmentation of the molecule’s covalent bonds or separation of the constituent identities of the noncovalent complexes [ 182 , 183 , 184 , 185 ]. The IRMPD spectrum can provide detailed information on basic structural features, secondary geometry of the molecular systems, and the position of the charge or bonding interactions when used in combination with theoretical calculations [ 185 ].…”

Section: Noncovalent CD Complexes In the Gas Phasementioning

confidence: 99%

Noncovalent Complexes of Cyclodextrin with Small Organic Molecules: Applications and Insights into Host–Guest Interactions in the Gas Phase and Condensed Phase

Lee

2020

Molecules

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Cyclodextrins (CDs) have drawn a lot of attention from the scientific communities as a model system for host–guest chemistry and also due to its variety of applications in the pharmaceutical, cosmetic, food, textile, separation science, and essential oil industries. The formation of the inclusion complexes enables these applications in the condensed phases, which have been confirmed by nuclear magnetic resonance (NMR) spectroscopy, X-ray crystallography, and other methodologies. The advent of soft ionization techniques that can transfer the solution-phase noncovalent complexes to the gas phase has allowed for extensive examination of these complexes and provides valuable insight into the principles governing the formation of gaseous noncovalent complexes. As for the CDs’ host–guest chemistry in the gas phase, there has been a controversial issue as to whether noncovalent complexes are inclusion conformers reflecting the solution-phase structure of the complex or not. In this review, the basic principles governing CD’s host–guest complex formation will be described. Applications and structures of CDs in the condensed phases will also be presented. More importantly, the experimental and theoretical evidence supporting the two opposing views for the CD–guest structures in the gas phase will be intensively reviewed. These include data obtained via mass spectrometry, ion mobility measurements, infrared multiphoton dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations.

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Section: Noncovalent CD Complexes In the Gas Phasementioning

confidence: 99%

Noncovalent Complexes of Cyclodextrin with Small Organic Molecules: Applications and Insights into Host–Guest Interactions in the Gas Phase and Condensed Phase

Lee

2020

Molecules

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“…For example, Figure shows intense signals of intermediate 5 and weak signals of compounds 6 – 9 . Their structures were assigned based on collision‐induced dissociation (CID) experiments (Figures S7 and S8), isotopic labeling (Figures S9, S43, and S44), and infrared photodissociation spectroscopy (Figures S1–S4 in the Supporting Information) . At short photolysis times, we detected the first low‐intensity signal at m/z 497 that corresponds to an adduct of 1 +32 mass units.…”

Section: Resultsmentioning

confidence: 99%

“…The structures of all relevant ions were determined based on their IR characteristics and other supporting methods, such as collision‐induced dissociation experiments or photofragmentation pattern . For clarity of the following text, these assignments, except for one example, are discussed in the chapter “Going Deeper: The Structural Assignment of Detected Ions” in Experimental Section, and the remaining details are provided in Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Photochemistry of a 9‐Dithianyl‐Pyronin Derivative: A Cornucopia of Reaction Intermediates Lead to Common Photoproducts

et al. 2020

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Leaving groups attached to the meso‐methyl position of many common dyes, such as xanthene, BODIPY, or pyronin derivatives, can be liberated upon irradiation with visible light. However, the course of phototransformations of such photoactivatable systems can be quite complex and the identification of reaction intermediates or even products is often neglected. This paper exemplifies the photochemistry of a 9‐dithianyl‐pyronin derivative, which undergoes an oxidative transformation at the meso‐position to give a 3,6‐diamino‐9H‐xanthen‐9‐one derivative, formic acid, and carbon monoxide as the main photoproducts. The course of this multi‐photon multi‐step reaction was studied under various conditions by steady‐state and time‐resolved optical spectroscopy, mass spectrometry and NMR spectroscopy to understand the effects of solvents and molecular oxygen on individual steps. Our analyses have revealed the existence of many intermediates and their interrelationships to provide a complete picture of the transformation, which can bring new inputs to a rational design of new photoactivatable pyronin or xanthene derivatives.

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“…The use of benchtop systems complements IRMPD measurements performed using free-electron lasers (FELs) that deliver infrared radiation usually within the range 600-2000 cm −1 with enough power to induce dissociation of selected trapped ions, 40 although higher harmonics can be used to extend the operational range of FELs. 64 However, these systems rely on linear electron accelerators to produce a relativistic beam to be injected into an undulator, and therefore are still very expensive and not easily implemented.…”

Section: Introductionmentioning

confidence: 99%

Development of a photoinduced fragmentation ion trap for infrared multiple photon dissociation spectroscopy

Penna

Cervi

Rodrigues‐Oliveira

et al. 2020

Rapid Comm Mass Spectrometry

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Rationale Methods for isomer discrimination by mass spectroscopy are of increasing interest. Here we describe the development of a three‐dimensional ion trap for infrared multiple photon dissociation (IRMPD) spectroscopy that enables the acquisition of the infrared spectrum of selected ions in the gas phase. This system is suitable for the study of a myriad of chemical systems, including isomer mixtures. Methods A modified three‐dimensional ion trap was coupled to a CO2 laser and an optical parametric oscillator/optical parametric amplifier (OPO/OPA) system operating in the range 2300 to 4000 cm−1. Density functional theory vibrational frequency calculations were carried out to support spectral assignments. Results Detailed descriptions of the interface between the laser and the mass spectrometer, the hardware to control the laser systems, the automated system for IRMPD spectrum acquisition and data management are presented. The optimization of the crystal position of the OPO/OPA system to maximize the spectroscopic response under low‐power laser radiation is also discussed. Conclusions OPO/OPA and CO2 laser‐assisted dissociation of gas‐phase ions was successfully achieved. The system was validated by acquiring the IRMPD spectra of model species and comparing with literature data. Two isomeric alkaloids of high economic importance were characterized to demonstrate the potential of this technique, which is now available as an open IRMPD spectroscopy facility in Brazil.

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Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

Cited by 74 publications

References 188 publications

Noncovalent Complexes of Cyclodextrin with Small Organic Molecules: Applications and Insights into Host–Guest Interactions in the Gas Phase and Condensed Phase

Noncovalent Complexes of Cyclodextrin with Small Organic Molecules: Applications and Insights into Host–Guest Interactions in the Gas Phase and Condensed Phase

Photochemistry of a 9‐Dithianyl‐Pyronin Derivative: A Cornucopia of Reaction Intermediates Lead to Common Photoproducts

Development of a photoinduced fragmentation ion trap for infrared multiple photon dissociation spectroscopy

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