This paper is a review of the kinetic method for the determination of thermochemical values for gas-phase molecules. In addition, we have explored the utility of the kinetic method to obtain meaningful relative binding energies of macromolecules for polyatomic substrates using a system comprising poly(methylmethacrylate) (PMMA) oligomers and doubly protonated diaminoalkanes. The major factors which determined the suitability of the kinetic method for this system were identified as (i) the structural arrangement of the parent ion complex, (ii) possible reverse activation barriers and (iii) the evaluations of A(AS‡). Molecular mechanics/molecular dynamics simulations, together with ion mobility spectrometry, suggests the parent ion complexes represent a relatively equal sharing of the substrate between the two PMMA oligomers within the complex and that the two PMMA oligomers interact almost exclusively with the substrate and not with each other. Tandem mass spectrometry of the trimeric parent complexes resulted in one PMMA unit leaving as a neutral which suggests very limited coulombic repulsion (which would contribute to a reverse activation barrier). The drift times of PMMA–diaminoalkane complexes that were generated directly by electrospray ionization mass spectrometry or by dissociation of a trimeric PMMA–diaminoalkane–PMMA complex were found to be identical and when, combined with molecular mechanics/molecular dynamics simulations, suggested that the product PMMA–diaminoalkane dication has the same conformation as it does when part of a trimeric complex. This is evidence for A(AS‡) ≈ A(AS) and using a statistical mechanics approach, A(AS) ≈ 0. The effective temperature variable in the kinetic method expression was found to decrease as a function of the size of the trimeric complex, suggesting that the population distribution of the dissociating ensemble of complexes narrows as size increases.
HolmesJ.L.AubryC.MayerP.M., Assigning Structures to Ions in Mass Spectrometry.CRC Press, Boca Raton, USA (2007).
2.
KebarleP., “Ion thermochemistry and solvation from gas phase ion equilibria”, Ann. Rev. Phys. Chem.28, 445 (1977). doi: 10.1146/annurev.pc.28.100177.002305
3.
ErvinK.M., “Experimental techniques in gas-phase ion thermochemistry”, Chem. Rev.101, 391 (2001). doi: 10.1021/cr990081l
4.
LongJ.MunsonB., “Proton affinities of some oxygenated compounds”, J. Am. Chem. Soc.95, 2427 (1973). doi: 10.1021/ja00789a002
5.
WilsonM.S.McCloskeyJ.A., “Chemical ionization mass spectrometry of nucleosides. Mechanisms of ion formation and estimations of proton affinity”, J. Am. Chem. Soc.97, 3436 (1975). doi: 10.1021/ja00845a026
6.
HoyauS.NorrmanK.McMahonT.B.OhanessianG., “A quantitative basis for a scale of Na+ affinities of organic and small biological molecules in the gas phase”, J. Am. Chem. Soc.121, 8864 (1999). doi: 10.1021/ja9841198
7.
GapeevA.DunbarR.C., “Cation-π interactions and the gas-phase thermochemistry of the Na+/phenylalanine complex”, J. Am. Chem. Soc.123, 8360 (2001). doi: 10.1021/ja010351t
8.
Meot-NerM., “The ionic hydrogen bond. 3. Multiple NH+ … O and CH+ … O bonds. Complexes of ammonium ions with polyethers and crown ether”, J. Am. Chem. Soc.105, 4912 (1983). doi: 10.1021/ja00353a012
9.
WuR.McMahonT.B., “An investigation of the ion–molecule interactions of protonated glycine with ammonia by high pressure mass spectrometry and ab initio calculations”, Can. J. Chem.83, 1978 (2005). doi: 10.1139/v05-205
10.
ChowdhuryS.HeinisT.GrimsrudE.P.KebarleP., “Entropy changes and electron affinities from gas-phase electron transfer equilibrial A− + B = A + B−”, J. Phys. Chem.90, 2747 (1986). doi: 10.1021/j100403a037
DunbarR.C., “BIRD (blackbody infrared radiative dissociation): Evolution, principles, and applications”, Mass Spectrom. Rev.23, 127 (2004). doi: 10.1002/mas.10074
13.
CooksR.G.KrugerT.L., “Intrinsic basicity determination using metastable ions”, J. Am. Chem. Soc.99, 1279 (1977). doi: 10.1021/ja00446a059
14.
SzulejkoJ.E.McMahonT.B., “A pulsed electron beam, variable temperature, high pressure mass spectrometric re-evaluation of the proton affinity difference between 2-methylpropene and ammonia”, Int. J. Mass Spectrom.109, 279 (1991). doi: 10.1016/0168-1176(91)85109-Y
15.
Meot-NerP.H.M.HunterE.P.FieldF.H., “Bonding energies in association ions of aromatic compounds. Correlations with ionization energies”, J. Am. Chem. Soc.100, 5466 (1978). doi: 10.1021/ja00485a034
16.
PriceW.D.SchnierP.D.WilliamsE.R., “Tandem mass spectrometry of large biomolecule ions by blackbody infrared radiative dissociation”, Anal. Chem.68, 859 (1996). doi: 10.1021/ac951038a
17.
SchnierP.D.PriceW.D.JockushR.A.WilliamsE.R., “Blackbody infrared radiative dissociation of bradykinin and its analogues: Energetics, dynamics, and evidence for salt-bridge structures in the gas phase”, J. Am. Chem. Soc.118, 7178 (1996). doi: 10.1021/ja9609157
18.
KitovaE.N.BundleD.R.KlassenJ.S., “Thermal dissociation of protein–oligosaccharide complexes in the gas phase: Mapping the intrinsic intermolecular interactions”, J. Am. Chem. Soc.124, 5902 (2002). doi: 10.1021/ja017213o
19.
DunbarR.C.McMahonT.B., “Activation of unimolecular reactions by ambient blackbody radiation”, Science279, 194 (1998). doi: 10.1126/science.279.5348.194
20.
DrahosL.VékeyK., “How closely related are the effective and the real temperature?”, J. Mass Spectrom.34, 79 (1999). doi: 10.1002/(SICI)1096-9888(199902)34:2<79::AID-JMS793>3.0.CO;2-V
21.
GrecoF.LiguoriA.SindonaG.UccellaN., “Gas-phase proton affinity of deoxyribonucleosides and related nucleobases by fast atom bombardment tandem mass spectrometry”, J. Am. Chem. Soc.112, 9092 (1990). doi: 10.1021/ja00181a009
22.
WuZ.FenselauC., “Proton affinity of arginine measured by the kinetic approach”, Rapid Commun. Mass Spectrom.6, 403 (1992). doi: 10.1002/rcm.1290060610
23.
HolmesJ.L.AubryC.MayerP.M., “Proton affinities of primary alkanols: An appraisal of the kinetic method”, J. Phys. Chem. A103, 705 (1999). doi: 10.1021/jp984094z
24.
EberlinM.N.KotiahoT.ShayB.J.YangS.S.CooksR.G., “Gas-phase Cl+ affinities of pyridines determined by the kinetic method using multiple stage (MS3) mass spectrometry,”J. Am. Chem. Soc.116, 2457 (1994). doi: 10.1021/ja00085a028
25.
YangS.S.ChenG.MaS.CooksR.G.GozzoF.C.EberlinM.N., “Relative carbonyl isocyanate cation [OCNCO]+ affinities of pyridines determined by the kinetic method using multiple-stage (MS3) mass spectrometry”, J. Mass Spectrom.30, 807 (1995). doi: 10.1002/jms.1190300605
26.
ChengX.WuZ.FenselauC., “Collision energy dependence of proton-bound dimer dissociation: Entropy effects, proton affinities, and intramolecular hydrogen-bonding in protonated peptides”, J. Am. Chem. Soc.115, 4844 (1993). doi: 10.1021/ja00064a052
27.
WuZ.FenselauC., “Gas-phase basicities and proton affinities of lysine and histidine measured from the dissociation of proton-bound dimers”, Rapid Commun. Mass Spectrom.8, 777 (1994). doi: 10.1002/rcm.1290080923
28.
CerdaB.A.HoyauS.OhanessianG.WesdemiotisC., “Na+ binding to cyclic and linear dipeptides. Bond energies, entropies of Na+ complexation, and attachment sites from the dissociation of Na+-bound heterodimers and ab initio calculations”, J. Am. Chem. Soc.120, 2437 (1998). doi: 10.1021/ja972417j
29.
NoldM.J.CerdaB.A.WesdemiotisC., “Proton affinities of the N- and C-terminal segments arising upon the dissociation of the amide bond in protonated peptides”, J. Am. Soc. Mass Spectrom.10, 1 (1999). doi: 10.1016/S1044-0305(98)00120-2
30.
ArmentroutP.B., “Entropy measurements and the kinetic method: A statistically meaningful approach”, J. Am. Soc. Mass Spectrom.11, 371 (2000). doi: 10.1016/S1044-0305(00)00102-1
31.
HahnI.-S.WesdemiotisC., “Protonation thermochemistry of [beta]-alanine: An evaluation of proton affinities and entropies determined by the extended kinetic method”, Int. J. Mass Spectrom.222, 465 (2003). doi: 10.1016/S1387-3806(02)01018-7
32.
GrabowyJ.A.D.MayerP.M., “Entropy changes in the dissociation of proton-bound complexes: A variational RRKM study”, J. Phys. Chem. A108, 9726 (2004). doi: 10.1021/jp0483829
33.
WuZ.FenselauC., “Proton affinities of poly-glycines assessed by using the kinetic method”, J. Am. Soc. Mass Spectrom.3, 863 (1992). doi: 10.1016/1044-0305(92)80011-9
34.
KaltashovI.A.FabrisD.FenselauC.C., “Assessment of gas phase basicities of protonated peptides by the kinetic method”, J. Phys. Chem.99, 10046 (1995). doi: 10.1021/j100024a055
35.
RenJ.TanJ.P.HarperR.T., “Gas-phase acidities of cysteine–polyalanine peptides, I: A3,4CSH and HSCA3,4”, J. Phys. Chem. A113, 10903 (2009). doi: 10.1021/jp903594a
36.
MorishettiK.K.HuangB.D.S.YatesJ.M.RenJ., “Gas-phase acidities of cysteine–polyglycine peptides: The effect of the cysteine position”, J. Am. Soc. Mass Spectrom.21, 603 (2010). doi: 10.1016/j.jasms.2009.12.008
37.
CaseD.A.DardenT.A.CheathamT.E.IIISimmerlingC.L.WangJ.DukeR.E.LuoR.MerzK.M.PearlmanD.A.CrowleyM.WalkerR.C.ZhangW.WangB.HayikS.RoitbergA.SeabraG.WongK.F.PaesaniF.WuX.BrozellS.TsuiV.GohlkeH.YangL.TanC.MonganJ.HornakV.CuiG.BerozaP.MathewsD.H.SchafmeisterC.RossW.S.KollmanP.A., Amber 9.University of California, San Francisco, CA, USA (2006).
38.
WangJ.WolfR.M.CaldwellJ.W.KollmanP.A.CaseD.E., “Development and testing of a general amber force field”, J. Comput. Chem.25, 1157 (2004). doi: 10.1002/jcc.20035
39.
WilsonS.R.CuiW., “Applications of simulated annealing to peptides”, Biopolymers29, 225 (1990). doi: 10.1002/bip.360290127
40.
MeslehM.F.HunterJ.M.ShvartsburgA.A.SchatzG.C.JarroldM.F., “Structural information from ion mobility measurements: Effects of the long-range potential”, J. Phys. Chem.100, 16082 (1996). doi: 10.1021/jp961623v
CaseyJ.AlhazmiA.MayerP.M., “Conformation effects on the dissociation of ionized polymers”, Eur. J. Mass Spectrom.11, 557 (2005). doi: 10.1255/ejms.779
43.
MontaudoG.LattimerR.P., Mass Spectrometry of Polymers.CRC Press, Boca Raton, FL (2002).
44.
AlhazmiA.M.MayerP.M., “Protonating polymer oligomers in the gas phase to change fragmentation pathways”, J. Am. Soc. Mass Spectrom.20, 60 (2009). doi: 10.1016/j.jasms.2008.09.014
45.
FouquetT.HumbelS.CharlesL., “Tandem mass spectrometry of trimethylsilyl-terminated poly(dimethylsiloxane) ammonium adducts generated by electrospray ionization”, J. Am. Soc. Mass Spectrom.22, 649 (2011). doi: 10.1007/s13361-010-0073-9
46.
MayerP.M.MartineauE., “Gas-phase binding energies for non-covalent Aβ-40 peptide/small molecule complexes from CID mass spectrometry and RRKM theory”, PCCP13, 5178 (2011). doi: 10.1039/c0cp02149k
47.
RenaudJ.B.MartineauE.MironovG.G.BerezovskiM.V.MayerP.M., “The collaborative role of molecular conformation and energetics in the binding of gas-phase non-covalent polymer/amine complexes”, PCCP14, 165 (2012). doi: 10.1039/c1cp22936b
48.
MayeuxC.GalJ.-F.CharlesL.MassiL.MariaP.-C.Tammiku-TaulJ.LohuE.-L.BurkP., “A study of the cesium cation bonding to carboxylate anions by the kinetic method and quantum chemical calculations”, J. Mass. Spectrom.45, 520 (2010). doi: 10.1002/jms.1735
49.
RenaudJ.B.MartineauE.MironovG.G.BerezovskiM.V.MayerP.M., “The collaborative role of molecular conformation and energetics in the binding of gas-phase non-covalent polymer/amine complexes”, PCCP14, 7 (2012). doi: 10.1039/c1cp22936b
