Charged cesium iodide clusters doped with mono-, di- and triglycine serve as a model system for sea salt aerosols containing biological molecules. Here, we investigate reactions of these complexes under infrared irradiation, with spectra obtained by infrared multiple photon dissociation. The cluster ions are generated via electrospray ionization and analyzed in the cell of a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Depending on the cluster size and peptide length, loss of HI or loss of a glycine unit is observed. The experimental measurements are supported by quantum chemical calculations. We show that N-H and O-H stretching modes dominate the spectrum, with large shifts depending on local interactions, namely due to interaction with iodide anions or intramolecular hydrogen bonding. Both experiment and theory indicate that several isomers are present in the experimental mixture, with different infrared fingerprints as well as dissociation pathways.
DunbarRCBerdenGMartensJKet al.Divalent metal-ion complexes with dipeptide ligands having Phe and His side-chain anchors: effects of sequence, metal ion, and anchor. J Phys Chem A2015; 119: 9901–9909.
2.
DunbarRCMartensJBerdenGet al.Complexes of Ni(II) and Cu(II) with small peptides: deciding whether to deprotonate. Phys Chem Chem Phys2016; 18: 26923–26932.
3.
DunbarRCPolferNCBerdenGet al.Metal ion binding to peptides: oxygen or nitrogen sites?Int J Mass Spectrom2012; 330-332: 71–77.
4.
DunbarRCMartensJBerdenGet al.Water microsolvation can switch the binding mode of Ni(II) with small peptides. J Phys Chem Lett2017; 8: 2634–2638.
5.
PeckelsenKMartensJBerdenGet al.Gas-phase complexes of Ni2+ and Ca2+ with deprotonated histidylhistidine (HisHis): A model case for polyhistidyl-metal binding motifs. J Mol Spectrosc2017; 332: 38–44.
6.
DunbarRCBerdenGOomensJ. How does a small peptide choose how to bind a metal ion? IRMPD and computational survey of CS versus iminol binding preferences. Int J Mass Spectrom2013; 354-355: 356–364.
7.
DunbarRCOomensJBerdenGet al.Metal ion complexes with HisGly: comparison with PhePhe and PheGly. J Phys Chem A2013; 117: 5335–5343.
8.
DunbarRCSteillJDPolferNCet al.Metal cation binding to gas-phase pentaalanine: divalent ions restructure the complex. J Phys Chem A2013; 117: 1094–1101.
9.
DunbarRCSteillJDPolferNCet al.Peptide bond tautomerization induced by divalent metal ions: characterization of the iminol configuration. Angew Chem Int Ed Engl2012; 51: 4591–4593.
10.
DunbarRCSteillJDOomensJ. Encapsulation of metal cations by the PhePhe ligand: a cation-π ion cage. J Am Chem Soc2011; 133: 9376–9386.
11.
DunbarRCSteillJDOomensJ. Chirality-induced conformational preferences in peptide-metal ion binding revealed by IR spectroscopy. J Am Chem Soc2011; 133: 1212–1215.
12.
DunbarRCSteillJDOomensJ. Conformations and vibrational spectroscopy of metal-ion/polylalanine complexes. Int J Mass Spectrom2010; 297: 107–115.
13.
DunbarRCSteillJDOomensJ. Cationized phenylalanine conformations characterized by IRMPD and computation for singly and doubly charged ions. Phys Chem Chem Phys2010; 12: 13383–13393.
14.
DunbarRCSteillJDPolferNCet al.Peptide length, steric effects, and ion solvation govern zwitterion stabilization in barium-chelated di- and tripeptides. J Phys Chem B2009; 113: 10552–10554.
15.
DunbarRCHopkinsonACOomensJet al.Conformation switching in gas-phase complexes of histidine with alkaline earth ions. J Phys Chem B2009; 113: 10403–10408.
16.
DunbarRCSteillJDPolferNCet al.Dimeric complexes of tryptophan with M2+ metal ions. J Phys Chem A2009; 113: 845–851.
17.
PolferNCOomensJDunbarRC. Alkali metal complexes of the dipeptides PheAla and AlaPhe: IRMPD spectroscopy. Chem Phys Chem2008; 9: 579–589.
18.
DunbarRCPolferNCOomensJ. Gas-phase zwitterion stabilization by a metal dication. J Am Chem Soc2007; 129: 14562–14563.
19.
ForbesMWBushMFPolferNCet al.Infrared spectroscopy of arginine cation complexes: direct observation of gas-phase zwitterions. J Phys Chem A2007; 111: 11759–11770.
20.
PolferNCOomensJMooreDTet al.Infrared spectroscopy of phenylalanine Ag(I) and Zn(II) complexes in the gas phase. J Am Chem Soc2006; 128: 517–525.
PolferNCPaizsBSnoekLCet al.Infrared fingerprint spectroscopy and theoretical studies of potassium ion tagged amino acids and peptides in the gas phase. J Am Chem Soc2005; 127: 8571–8579.
23.
BalajO-PKapotaCLemaireJet al.Vibrational signatures of sodiated oligopeptides (GG–Na+, GGG–Na+, AA–Na+ and AAA–Na+) in the gas phase. Int J Mass Spectrom2008; 269: 196–209.
24.
ChangTMBerdenGOomensJet al.Halide anion binding to Gly3 Ala3 and Leu3. Int J Mass Spectrom2015; 377: 440–447.
25.
PrellJSFlickTGOomensJet al.Coordination of trivalent metal cations to peptides: Results from IRMPD spectroscopy and theory. J Phys Chem A2010; 114: 854–860.
26.
Finlayson-PittsBJPittsJN. Chemistry of the upper and lower atmosphere: theory, experiments, and applications, San Diego, CA: Academic Press, 2007.
27.
O’DowdCDSmithMHConsterdineIEet al.Marine aerosol, sea-salt, and the marine sulphur cycle: a short review. Atmos Environ1997; 31: 73–80.
28.
ElderingASolomonPASalmonLGet al.Hydrochloric acid: A regional perspective on concentrations and formation in the atmosphere of Southern California. Atmos Environ Part A1991; 25: 2091–2102.
29.
DasguptaPKCampbellSWAl-HorrRSet al.Conversion of sea salt aerosol to NaNO3 and the production of HCl: Analysis of temporal behavior of aerosol chloride/nitrate and gaseous HCl/HNO3 concentrations with AIM. Atmos Environ2007; 41: 4242–4257.
30.
LaskinAMoffetRCGillesMKet al.Tropospheric chemistry of internally mixed sea salt and organic particles: Surprising reactivity of NaCl with weak organic acids. J Geophys Res2012; 117: D15302.
31.
Finlayson-PittsBJ. The tropospheric chemistry of sea salt: a molecular-level view of the chemistry of NaCl and NaBr. Chem Rev2003; 103: 4801–4822.
32.
VogtRElliottCAllenHCet al.Some new laboratory approaches to studying tropospheric heterogeneous reactions. Atmos Environ1996; 30: 1729–1737.
33.
LauxJMHemmingerJCFinlayson-PittsBJ. X-ray photoelectron spectroscopic studies of the heterogenous reaction of gaseous nitric acid with sodium chloride kinetics and contribution to the chemistry of the marine troposphere. Geophys Res Lett2012; 21: 1623–1626.
34.
BersenkowitschNKOnčákMvan der LindeCet al.Photochemistry of glyoxylate embedded in sodium chloride clusters, a laboratory model for tropospheric sea-salt aerosols. Phys Chem Chem Phys2018; 20: 8143–8151.
35.
BersenkowitschNKOnčákMHellerJet al.Photodissociation of Sodium Iodide Clusters Doped with Small Hydrocarbons. Chem Eur J. 2018; 24: 12433–12443.
MartinTP. Alkali halide clusters and microcrystals. Phys Rep1983; 95: 167–199.
38.
WhettenRLHomerMLLiXet al.Reactions of alkali-halide clusters. Ber Bunsenges Phys Chem1992; 96: 1120–1125.
39.
LintuluotoM. Theoretical study on the structure and energetics of alkali halide clusters. Theochem2001; 540: 177–192.
40.
HomerMLLivingstonFEWhettenRL. Molecular adsorption-desorption reactions of ammonia on alkali halide clusters and nanocrystals. J Phys Chem1995; 99: 7604–7612.
41.
LintuluotoM. Theoretical study on the adsorption of NH3 to alkali halide clusters. J Phys Chem A2000; 104: 6817–6823.
42.
FatemiDJBloomfieldLA. Photoelectron spectroscopy of sodium iodide clusters containing single hydroxyl ions or water molecules. Phys Rev A2002; 66: 1607.
43.
ZhangQCarpenterCJKemperPRet al.On the dissolution processes of Na2I+ and Na3I2+ with the association of water molecules: mechanistic and energetic details. J Am Chem Soc2003; 125: 3341–3352.
44.
BarnettRNLandmanU. Water adsorption and reactions on small sodium chloride clusters. J Phys Chem1996; 100: 13950–13958.
45.
YamabeSKounoHMatsumuraK. A mechanism of the ion separation of the NaCl microcrystal via the association of water clusters. J Phys Chem B2000; 104: 10242–10252.
46.
TsurutaMFuruyaAOhnoKet al.Adsorption of small molecules with the hydroxyl group on sodium halide cluster ions. J Phys Chem A2010; 114: 1432–1436.
47.
OuyangHLarriba-AndaluzCOberreitDRet al.The collision cross sections of iodide salt cluster ions in air via differential mobility analysis-mass spectrometry. J Am Soc Mass Spectrom2013; 24: 1833–1847.
48.
BladesATPeschkeMVerkerkUHet al.Hydration energies in the gas phase of select (MX)mM+ ions, where M+= Na+, K+, Rb+, Cs+, NH4+ and X–= F–, Cl–, Br–, I–, NO2–, NO3–. Observed magic numbers of (MX)mM+ ions and their possible significance. J Am Chem Soc2004; 126: 11995–12003.
49.
AguadoAAyuelaALópezJMet al.Theoretical study of small (NaI)n clusters. J Phys Chem B1997; 101: 5944–5950.
50.
AguadoAAyuelaALópezJMet al.Ab initio calculations of structures and stabilities of (NaI)nNa+ and (CsI)nCs+ cluster ions. Phys Rev B1998; 58: 9972–9979.
51.
MisaizuFTsurutaMTsunoyamaHet al.Size-dependent structures of NanIn-1+ cluster ions with a methanol adsorbate: a combined study by photodissociation spectroscopy and density-functional theory calculation. J Chem Phys2005; 123: 161101.
52.
LiXWhettenRL. Ultraviolet absorption bands of ionic compound clusters: onset of crystalline structures in [Csn+1In]+ n = 1–13. J Chem Phys1993; 98: 6170–6175.
53.
ParryISKartouzianAHamiltonSMet al.Chemical reactivity on gas-phase metal clusters driven by blackbody infrared radiation. Angew Chem Int Ed Engl2015; 54: 1357–1360.
54.
HermesACHamiltonSMCooperGAet al.Infrared driven CO oxidation reactions on isolated platinum cluster oxides, PtnOm+. Faraday Discuss2012; 157: 213.
55.
HermesACHamiltonSMHopkinsWSet al.Effects of coadsorbed oxygen on the infrared driven decomposition of N2O on isolated Rh5+ clusters. J Phys Chem Lett2011; 2: 3053–3057.
56.
HamiltonSMHopkinsWSHardingDJet al.Infrared induced reactivity on the surface of isolated size-selected clusters: dissociation of N2O on rhodium clusters. J Am Chem Soc2010; 132: 1448–1449.
LengyelJOnčákMHerburgerAet al.Infrared spectroscopy of O˙- and OH- in water clusters: evidence for fast interconversion between O˙- and OH˙OH. Phys Chem Phys2017; 19: 25346–25351.
59.
HerburgerAvan der LindeCBeyerMK. Photodissociation spectroscopy of protonated leucine enkephalin. Phys Chem Phys2017; 19: 10786–10795.
60.
CalvoFParneixP. Amplification of anharmonicities in multiphoton vibrational action spectra. Chem Phys Chem2012; 13: 212–220.
61.
ParneixPBasireMCalvoF. Accurate modeling of infrared multiple photon dissociation spectra: the dynamical role of anharmonicities. J Phys Chem A2013; 117: 3954–3959.
62.
GrantERSchulzPASudboASet al.Is multiphoton dissociation of molecules a statistical thermal process?Phys Rev Lett1978; 40: 115–118.
63.
MakarovAAPetrovaIYRyabovEAet al.Statistical Inhomogeneous Broadening of Infrared and Raman Transitions in Highly Vibrationally Excited XY6 Molecules. J Phys Chem A1998; 102: 1438–1449.
64.
OomensJSartakovBGMeijerGet al.Gas-phase infrared multiple photon dissociation spectroscopy of mass-selected molecular ions. Int J Mass Spectrom2006; 254: 1–19.
PrellJSChangTMBilesJAet al.Isomer population analysis of gaseous ions from infrared multiple photon dissociation kinetics. J Phys Chem A2011; 115: 2745–2751.
67.
PrellJSCorreraTCChangTMet al.Entropy drives an attached water molecule from the C- to N-terminus on protonated proline. J Am Chem Soc2010; 132: 14733–14735.
68.
ZhaoYTruhlarDG. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Account2008; 120: 215–241.
69.
SzentpályLvon, FuentealbaPPreussHet al.Pseudopotential calculations on Rb+2, Cs+2, RbH+, CsH+ and the mixed alkali dimer ions. Chem Phys Lett1982; 93: 555–559.
BalajOPBergCBReitmeierSJet al.A novel design of a temperature-controlled FT-ICR cell for low-temperature black-body infrared radiative dissociation (BIRD) studies of hydrated ions. Int J Mass Spectrom2009; 279: 5–9.
73.
DunbarRC. BIRD (blackbody infrared radiative dissociation): evolution, principles, and applications. Mass Spectrom Rev2004; 23: 127–158.
74.
FoxBSBeyerMKBondybeyVE. Black body fragmentation of cationic ammonia clusters. J Phys Chem A2001; 105: 6386–6392.
75.
SchnierPDPriceWDJockuschRAet al.Blackbody infrared radiative dissociation of bradykinin and its analogues: energetics, dynamics, and evidence for salt-bridge structures in the gas phase. J Am Chem Soc1996; 118: 7178–7189.
76.
SenaMRiverosJM. The unimolecular dissociation of the molecular ion of acetophenone induced by thermal-radiation. Rapid Commun Mass Spectrom1994; 8: 1031–1034.
77.
ThölmannDTonnerDSMcMahonTB. Spontaneous unimolecular dissociation of small cluster ions, (H3O+)Ln and Cl–(H2O)n (n = 2-4), under Fourier transform ion cyclotron resonance conditions. J Phys Chem1994; 98: 2002–2004.
78.
SchindlerTBergCNiedner-SchatteburgGet al.Protonated water clusters and their black body radiation induced fragmentation. Chem Phys Lett1996; 250: 301–308.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
