Free electron laser-Fourier transform ion cyclotron resonance mass spectrometry facility for obtaining infrared multiphoton dissociation spectra of gaseous ions

Valle, Jose; Eyler, John R.; Oomens, Jos; Moore, David T.; Meer, A. F. G. van der; Helden, Gert von; Meijer, Gerard; Hendrickson, Christopher L.; Marshall, Alan G.; Blakney, Greg T.

doi:10.1063/1.1841953

Cited by 297 publications

(249 citation statements)

References 74 publications

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“…2 are recorded in the fingerprint range in a FT-ICR-MS coupled to an ESI ion source and the IR beamline of the Free Electron Laser for Infrared eXperiments (FELIX). [34][35][36] LC (499%) purchased from Sigma Aldrich is used without further purification. To produce the metal complexes, a 0.2 mM solution of LC in methanol is mixed with 1-6 mM metal chloride or nitrate salt solutions in water.…”

Section: Experimental and Computational Techniquesmentioning

confidence: 99%

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

Günther

Nieto

Berden

et al. 2014

Phys. Chem. Chem. Phys.

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Infrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal-lumichrome ionic complexes, M q+ LC n with M q+ = Li + , Na + , K + , Rb + , Cs + , Ag + (n = 1), and Mg 2+ (n = 2), are recorded in the fingerprint range. The complexes are generated in an electrospray ionization source coupled to an ion cyclotron mass spectrometer and the IR free electron laser FELIX. Vibrational and isomer assignments of the IRMPD spectra are accomplished by density functional theory calculations at the B3LYP/cc-pVDZ level, which provide insight into the structure, binding energy, bonding mechanism, and spectral properties of the complexes. The two major binding sites identified involve metal bonding to the oxygen atoms of the two available carbonyl groups of LC (denoted O2 and O4). The more stable O4 isomer benefits from an additional interaction with the lone pair of the nearby N5 atom of LC. While M + LC with alkali metals are mainly stabilized by electrostatic forces, the Ag + LC complex reveals additional stabilization arising from partly covalent contributions. Finally, the interaction of Mg 2+ ions with LC is largely enhanced by the doubled positive charge. The frequencies of the CQO stretching modes are a sensitive indicator of both the metal binding site and the metal bond strength.

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Section: Experimental and Computational Techniquesmentioning

confidence: 99%

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

Günther

Nieto

Berden

et al. 2014

Phys. Chem. Chem. Phys.

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“…Ions of the formula [M 2 (NO 3 ) 5 ] -(M 2 ϭ Mg 2 , MgCa, Ca 2 , or Sr 2 ) are generated using ESI in a Micromass Z-Spray source. Ions are injected into a home-built Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer described in detail elsewhere [18].…”

Section: Esi Ft-icr Mass Spectrometrymentioning

confidence: 99%

IRMPD spectroscopy of anionic group II metal nitrate cluster ions

Leavitt

Dain

Steill

et al. 2009

J. Am. Soc. Mass Spectrom.

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Anionic group II metal nitrate clusters of the formula [M 2 (NO 3 ) 5 ] -, where M 2 ϭ Mg 2 , MgCa, Ca 2 , and Sr 2 , are investigated by infrared multiple photon dissociation (IRMPD) spectroscopy to obtain vibrational spectra in the mid-IR region. The IR spectra are dominated by the symmetric and the antisymmetric nitrate stretches, with the latter split into high and low-frequency components due to the distortion of nitrate anion symmetry by interactions with the cation. Density functional theory (DFT) is used to predict geometries and vibrational spectra for comparison to the experimental spectra. Calculations yield two stable isomers: the first one contains two terminal nitrate anions on each cation and a single bridging nitrate ("mono-bridging"), while the second structure features a single terminal nitrate on each cation with three bridging nitrate ligands ("tri-bridging"). The tri-bridging isomer is calculated to be lower in energy than the mono-bridging one for all species. Theoretical spectra of the tri-bridging structure provide a better qualitative match to the experimental infrared spectra of T he combination of ion-trapping mass spectrometers and free-electron lasers tunable through the mid-infrared region of the electromagnetic spectrum have provided invaluable access to the vibrational spectra of discrete, gas-phase metal complexes [1][2][3][4][5][6][7][8][9][10]. It is generally difficult to acquire a conventional linear absorption spectrum of species commonly investigated by mass spectrometry because of the low ion concentrations. However, use of an action spectroscopy approach allows photon absorption to be monitored by measuring fragmentation yields that result from wavelength-specific infrared multiple-photon dissociation (IRMPD) [11][12][13].Using the uranyl (UO 2 2ϩ ) and the europium (Eu 3ϩ ) cations, our group produced the first vibrational spectra of gas-phase metal nitrate anions of the formula [UO 2 (NO 3 ) 3 ] -and [Eu(NO 3 ) 4 ] - [14]. These experiments were carried out at the FOM Institute for Plasma Physics in Nieuwegein, The Netherlands, using the free electron laser for infrared experiments (FELIX). FELIX provides a tunable, high-intensity beam of photons across the mid-IR range to a high-resolution mass spectrometer. The IRMPD spectra of both the uranyl and europium nitrate anions are dominated by the antisymmetric nitrate stretch ( 3 ), which is split into low and high-frequency components corresponding to the O-N-O (O-atoms involved in bonding with the metal), and (non-coordinating) NϭO stretches respectively. Previous studies have shown that the splitting of the 3 (⌬ 3 ) is proportional to the interaction strength between the metal and the nitrate ligands [15,16]. In the uranyl and europium nitrate anions, ⌬ 3 was found to be 264 cm -1 and 273 cm -1 respectively [14].In a later study, IRMPD spectroscopy was used to record vibrational spectra of anionic group II metal nitrate complexes of the formula [M(NO 3 ) 3 ] -where M ϭ Mg 2ϩ , Ca 2ϩ , Sr 2ϩ , and Ba 2ϩ [17]. By observ...

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“…The experiments were carried out on a laboratory-built 4.7 Tesla actively shielded Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, described in detail elsewhere [29]. This mass spectrometer is coupled to the beam line of the free electron laser for infrared experiments (FELIX) [30], thus enabling IR spectroscopy experiments on ions in the gas phase.…”

Section: Experimental and Calculationsmentioning

confidence: 99%

Observation of zwitterion formation in the gas-phase H/D-exchange with CH₃OD: Solution-phase structures in the gas phase

Polfer

Dunbar

2007

J. Am. Soc. Mass Spectrom.

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Infrared spectroscopy of gas-phase singly deuterated [Trp ϩ K] ϩ (formed by H/D exchange with CH 3 OD) shows that some (ϳ20%) kinetically stable zwitterionic (ZW) conformer is formed, based on the diagnostic antisymmetric CO stretch of the deprotonated carboxylate moiety, as (CO 2 Ϫ ), at 1680 cm Ϫ1 . A majority of the deuterated [Trp ϩ K] ϩ is found to be in the charge solvation (CS) conformation, with deuterium exchange occurring on both the acid and amino groups, which is consistent with H/D scrambling. Interestingly, H/D exchange with the more basic ND 3 reagent did not result in the stabilization of a kinetically stable zwitterion, although it is not clear yet what causes this observation. The result for CH 3 OD shows that H/D exchange can in fact alter the structure of the analyte and, hence, care needs to be taken when interpreting gas-phase H/D exchange studies. Moreover, this result shows the possibility of forming solution-phase structures that are thermodynamically disfavored in the gas phase, thus opening a new area of study. (HDX) is one of the most popular techniques for the structural elucidation of biomolecules in mass spectrometry and has been widely implemented for both solution [1][2][3][4] and gas phase studies [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. In solution, the extent of HDX can be directly related to the solvent accessibility of amino acid residues in proteins. However, in the gas phase there are many structural parameters apart from the surface availability that affect the HDX rates, as illustrated in a recent HDX study on ion-mobilityselected charge states of bovine ubiquitin [17]. Systematic studies on small peptide systems showed that the difference in proton affinity of the biomolecules and deuterated donor reagent plays a crucial role in the HDX mechanism [7][8][9][10]19]. Beauchamp and coworkers [9] suggested that lower basicity reagents, such as D 2 O and CH 3 OD, proceed via a "relay" mechanism [20] for protonated peptides, while the higher basicity ND 3 reagent gives rise to an "onium" mechanism [21]. In the case of amino acids cationized by an alkali metal ion rather than a proton, polar deuterating ligands such as D 2 O can exchange via a similar relay mechanism involving charge solvation-zwitterion (CS-ZW) isomerization [18]. Modeling of observed HDX processes and quantum chemical calculations of the potential surfaces have made a strong circumstantial case that ZW structures are traversed in many cases during HDX with basic partners like D 2 O, CH 3 OD, and ND 3 [14,16,18]. Nevertheless, computations also generally indicate that the bare ZW is sufficiently disfavored energetically that its equilibrium presence in the M ϩ /amino acid would be negligible [22,23].Here, we show unambiguous spectroscopic evidence that bare ZW can in fact be kinetically trapped as a result of the HDX of [Trp ϩ K] ϩ with CH 3 OD. Infrared multiple-photon dissociation (IR-MPD) spectroscopy of metal-tagged amino acids and peptides has already been shown to be a powerful probe for CS ...

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Free electron laser-Fourier transform ion cyclotron resonance mass spectrometry facility for obtaining infrared multiphoton dissociation spectra of gaseous ions

Cited by 297 publications

References 74 publications

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

IRMPD spectroscopy of anionic group II metal nitrate cluster ions

Observation of zwitterion formation in the gas-phase H/D-exchange with CH₃OD: Solution-phase structures in the gas phase

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Free electron laser-Fourier transform ion cyclotron resonance mass spectrometry facility for obtaining infrared multiphoton dissociation spectra of gaseous ions

Cited by 297 publications

References 74 publications

IRMPD spectroscopy of metalated flavins: structure and bonding of Mq+–lumichrome complexes (Mq+ = Li+–Cs+, Ag+, Mg2+)

IRMPD spectroscopy of metalated flavins: structure and bonding of Mq+–lumichrome complexes (Mq+ = Li+–Cs+, Ag+, Mg2+)

IRMPD spectroscopy of anionic group II metal nitrate cluster ions

Observation of zwitterion formation in the gas-phase H/D-exchange with CH3OD: Solution-phase structures in the gas phase

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IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

IRMPD spectroscopy of metalated flavins: structure and bonding of M^q+–lumichrome complexes (M^q+ = Li⁺–Cs⁺, Ag⁺, Mg²⁺)

Observation of zwitterion formation in the gas-phase H/D-exchange with CH₃OD: Solution-phase structures in the gas phase