International Journal of Mass Spectrometry 354-355 (2013) iv-xviii

Contents lists available at ScienceDirect

International Journal of Mass Spectrometry

ER journal homepage: www.elsevier.com/locate/ijms

ELSEVI

Contents

1-1 Publisher’s note

Rob van Daalen

Forward

2-2 Special Issue Image

3-3

Editors forward

Mike Bowers, Scott McLuckey 4-4 Personal foreword Helmut Schwarz

Regular Articles 5-14

An anatomy of the two-state reactivity concept: Personal reminiscences in memoriam of Detlef Schréder

Sason Shaik

Elsevier B.V. http://dx.doi.org/10.1016/S1387-3806( 13)00384-9

International Journal of Mass Spectrometry 354-355 (2013) iv-xviii

Contents lists available at ScienceDirect

International Journal of Mass Spectrometry

ER journal homepage: www.elsevier.com/locate/ijms

ELSEVI

Contents

1-1 Publisher’s note

Rob van Daalen

Forward

2-2 Special Issue Image

3-3

Editors forward

Mike Bowers, Scott McLuckey 4-4 Personal foreword Helmut Schwarz

Regular Articles 5-14

An anatomy of the two-state reactivity concept: Personal reminiscences in memoriam of Detlef Schréder

Sason Shaik

Elsevier B.V. http://dx.doi.org/10.1016/S1387-3806( 13)00384-9

Contents

15-18 Aspects of bonding in small gold clusters Xiao-Gen Xiong, Wen-Hua Xu, Jun Li, Pekka Pyykk6

19-25

New Strategies for resolving oligosaccharide isomers by exploiting mechanistic and thermochemical aspects of fragment ion formation

Andres Guerrero, Carlito B. Lebrilla

@ Human milk isomeric oligosaccharides were studied by MALDI FT-ICR. @ IRMPD tandem-MS experiments varying the irradiation period were performed. @ Sodium affinities and fragmentation paths were used to interpret the spectra. @ Pure isomers and mixtures of these oligosaccharides were distinguished. @ The rationale described can be used to resolve other isomeric species.

26-32

Presentation of a homobifunctional azo-reagent for protein structure analysis by collision-induced dissociative chemical cross- linking: Proof-of-principle

Francesco Falvo, Lukas Fiebig, Mathias Schafer

@ Azo-containing compound used as a ClD-labile reagent for chemical cross-linking (XL). @ CID of peptide-azo-peptide ions yields N, loss and open shell peptide product ions. @ ESI-MS" of t Sequerce specitc fragment ions > peptde prnary structure interpeptide and intrapeptide XL demonstrates proof-of-principle. @ The distonic nature of peptide en

radical cations is proved by ion-molecule reactions.

CID-MS? | | CID-MS?

33-38

Isolation and characterization of a peroxo manganese (Ill)

dioxygen reaction intermediate using cryogenic ion vibrational

predissociation " a Cryogenic lon Vibrational Spectroscopy of a Peroxo Manganese Complex Arron B. Wolk, Christopher M. Leavitt, Joseph A. Fournier,

Michael Z. Kamrath, Gayan B. Wijeratne, Timothy A. Jackson,

Mark A. Johnson

@ We present the infrared predissociation spectrum of peroxo manganese intermediate. @ The species were electrosprayed and cooled in a cryogenically cooled ion trap. @ Action spectra on N, adducts give a side on binding motif of the O, adduct. @ Comparison with '*O, substitution and harmonic spectra confirms assignment. @ Isolation of reactive intermediates will pave way for cluster mediated chemistry.

v ‘ . IRMPD me » Peptoe. +" NO CH, Ms? -N, - 33.5 Da HyC~ L J Lo J | | | | a. 700 80) 1100 1300 1800 E Proton Energy em on bewing mode

Contents

39-45 Reactions of 0,7* with CO,, OCS and CS,

Michael A. Parkes, Jessica F. Lockyear, Stephen D. Price

@ First investigation of reactivity of O,?* with triatomic molecules. @ Electron transfer dominates O,** + CO, reactivity. @ Bond-forming reactivity was observed following 0,?*+ OCS collisions. @ Concerted double-electron transfer major reaction channel follow- ing collisions with CS..

46-53 lon chemistry of sulfuryl fluoride: An experimental and theoretical

study on gas-phase reactions involving neutral and ionized SO,F, / 2c

Paola Antoniotti, Paola Benzi, Lorenza Operti, Roberto Rabezzana, = at

Stefano Borocci, Maria Giordani, Felice Grandinetti =

@ The gas-phase ion chemistry of SO,F, was studied by ITMS and theoretical calculations. @ The 1 7

distonic ion SO,F,* activates H,, H,O and CH, by hydrogen-atom abstraction. @ FSO,*(x = 0-2) ton eee »

activate the H—NH, bond with formation of O,S—NH,.. a oa

54-61 Protonated pyrimidine nucleosides probed by IRMPD spectroscopy

Antonello Filippi, Caterina Fraschetti, Flaminia Rondino, Susanna Piccirillo, Vincent Steinmetz, Leonardo Guidoni, Maurizio Speranza

62-69

Halide adducts of 1,3,5-trinitrobenzene: Vibrational signatures and role of anion-7 interactions

Barbara Chiavarino, Maria Elisa Crestoni, Philippe Maitre, Simonetta Fornarini

@ Fluoride and chloride complexes with 1,3,5-trinitrobenzene (TNB) are obtained. e TNB-F

conforms to a strongly covalent o-complex structure. @ TNB-CI- displays an off-center binding of 2 - y chlorine, described as weakly covalent. @ Also TNB-I- and TNB-Br~ present IR features consistent with a weak o-binding motif.

vi ma | a2 s*e%e ~ ] protonated | | ©2-protonated $027 355272585 2967 3065 see2 Vid cmt * 1300 1400 cm’

Contents

70-77

Effect of the Asn side chain on the dissociation of deprotonated peptides elucidated by IRMPD spectroscopy

Josipa Grzetic, Jos Oomens

@ Non-oxazolone b-type fragments identified for deprotonated peptides. @ b-Type anions from Asn-containing peptides have succinimide structure. @ b, and b, anions investigated. @ IR spec- troscopy distinguishes between imide and isoimide structures.

78-86

Collisions of low-energy ions Ar* and N,* with room-temperature and heated surfaces of tungsten, beryllium, and a mixed beryllium- tungsten thin film

Alan Keim, Martina Harnisch, Paul Scheier, Zdenek Herman

87-98

Guided ion-beam and theoretical studies of the reaction of Os* (®D) with O,: Adiabatic and nonadiabatic behavior

Christopher S. Hinton, Murat Citir, P.B. Armentrout

@ The Os*(®D) + O, reaction is examined by guided ion-beam tandem mass spectrometry. @ The bond energy of OsO* is determined as 4.96 + 0.02 eV. @ Formation of OsO,* is observed as the sequential exothermic reaction of OsO* with O,. @ The nature of the bonding for OsO* and OsO,” is explored theoretically. @ Explanations for the unusual two features in the OsO* cross section are explored.

Cross Section (10°16 cm?)

Energy (eV, CM)

99-104

The reaction of the hydrogen-bridged radical cation [NH,C=O—H—O=CH,]"* with dioxygen

Karl J. Jobst, Johan K. Terlouw, Julien De Winter, Pascal Gerbaux

vii 800 1000 1200 1400 1600 1800cm Energy (eV, Lab) 01 1 10 100 4 J i ! \ 2 ° 0 A 0.01 0.1 1 10 5 £

Contents

105-112

Reactions of V,O,,* cluster ions with simple inorganic *H2 Homolytic H-H splitting Water formation 4™10 and organic molecules a

Zhen Yuan, Yan-Xia Zhao, Xiao-Na Li, Sheng-Gui He ’ (x) V,O,* +H,0 @ Reactions of V,O,,." ions with H,, CO, CH,, CH,, CH,, and GH, were studied ee by QH-TOF-MS. @ The homolytic H—H splitting rather than the water forma- ho tion was identified. @ Double oxygen atom transfer reaction with C,H, was e ee oe identified. @ The increased velocity of the cluster ions favors the oxygen atom bd

transfer reaction with C,H,.

113-122

Toward extension of the gas-phase basicity scale by novel pyridine containing guanidines

Zoran Glasovac, Fabijan PavoSevic¢, Vjekoslav Strukil, Mirjana Eckert-Maksi¢, Maria Schlangen, Robert Kretschmer

@ The gas-phase basicities were measured by the entropy corrected kinetic method. @ Novel compounds - a useful set of the reference bases for further extension of the basicity scale. @ Experimental GBs correlate well with the pK,,, of the H-bond accepting groups. @ The gas-phase basicities were calculated using MP2 and DFT approaches.

123-128

Applications of switching reagent ions in proton transfer reaction on = ” mass spectrometric instruments for the improved selectivity of a si — explosive compounds

Philipp Sulzer, Bishu Agarwal, Simone Jiirschik, Matteo Lanza, Alfons Jordan, Eugen Hartungen, Gernot Hanel, Lukas Mark,

Tilmann D. Mark, Ram6n Gonzalez-Méndez, Peter Watts, 7" i @ We present a method for the highly selective detection of explosives with a PTR-MS instrument. vere

@ lon-molecule reaction processes for TNT, TNB, PETN and RDX are investigated utilising 0,” and NO* as reagent ions. @ Reagent ion switching time (H,0*, 0,” and NO*) is determined to be about 10s.

129-138

Differential ion mobility separation of isomers for threshold collision-induced dissociation measurements

John P. van Nostrand, Vladimir Romanov, Justin Kai-Chi Lau, Udo H. Verkerk, Alan C. Hopkinson, K.W. Michael Siu

@ Mobility separated TCID using a modified triple quadrupole MS. @ Proof-of-concept experiments using silver complexes of ortho-para and cis-trans isomers. @ Excellent agreement of experimental

bond dissociation energies of pure isomers, mobility separatedisomer mixtures and DFT modeling calculations.

lon Count

viii ax ge is ox 2 H | | —— HO Chemistry

Contents

139-143

Monitoring hydrogen sulfide in simulated breath of anesthetized

subjects

Gregory K. Koyanagi, Vitaliy Kapishon, Voislav Blagojevic, *80,--2+s0,-

Diethard K. Bohme $0,—2+s0 5

@ We applied negative ion APCI mass spectrometry to the quantification of simulated breath con- taining air, water vapor, N,O and CO,. @ We added CHCI, to mimic the influence of halocarbons associated with the breath of anesthetized subjects. @ Both SO,” and SO,” were observed to be sensitive to H,S down to about 1 ppt (trillion). The observed ratio of [SO,~] to [SO,"] was found to be themost useful monitor of H,S. @ SH” was found to be suppressed by CO, and so unsuitable for H,S quantification in breath.

144-151

Dissociation of CuH** and ZnH* complexes of ethylenediamine and their N-methylated homologues: Family and neighbours, but not the same

Karl J. Jobst, Johan K. Terlouw, Paul J.A. Ruttink, Peter C. Burgers

@ Complexes of CuH** and ZnH* with H,NCH,CH,NH, eliminate Cu(0)° and Zn(0). @ Experiment te D and theory agree that the associated TS is larger for the zinc complex. @ The high TS for the zinc af. mi complex allows competition with NH, loss. @ N-methyl substitution has no effect on the behaviour | en

of the CuH** complex ions. @ In contrast, N-methyl substituted complexes with ZnH* predomi- en

nantly loses ZnH,.

152-158

Electron capture dissociation of a self-assembled tetranuclear metallosupramolecular complex in the gas phase

Rainer Hovorka, Marianne Engeser, Arne Liitzen

159-164 Tunable infrared laser desorption and ionization of fullerene films T.C. Cheng, S.T. Akin, C.J. Dibble, S. Ard, M.A. Duncan

@ Fullerene films are excited with infrared lasers and ions (positive and negative) are detected with time-of-flight mass spectrometry. @ The mechanism of infrared desorption and ionization is investigated with different samples and IR wavelengths. @ Tunable IR studies provide desorbed ion infrared spectra of C,, revealing new vibrational combination bands.

ix [H,S} (ppm) Oo, (51) mz 61 + NH, | } Ag

x Contents

165-174

Unimolecular dissociation characteristics of cationic .,**, .*.. * complexes between nicotinic acid and Cu(II) and Ni(II) ~~ ON

Héloise Dossmann, Carlos Afonso, Jean-Claude Tabet, Einar Uggerud

@ We have formed and characterized ML{(L-H)’ complexes.@Wefindpreferencefor | metal coordination by the carboxylate group. @ Collisionally induced dissociation - pat

(Ni +

gives CO, loss as the primary product. @ The dissociation patterns are consistent = re ad with the known chemistry of Cu?* and Ni’.

175-180

C—C bond formation between CO,°° and allyl alcohol: tq o A mechanistic study

Robert F. Héckendorf, Kirsten Fischmann, Qiang Hao, o é. ° Christian van der Linde, O. Petru Balaj, Chi-Kit Siu, => Martin K. Beyer =

@ Evidence for covalent C—C bond formation is found in reactions of CO,~(H,0O), with pe Na

C,H,OH. @ Nanocalorimetry and DFT calculations indicate weak bond. @ Reaction product HOC,H,COO™ is stabilized by H atom transfer from neutral C,H.OH. @ Calculated potential energy surfaces explain experimentally observed reactions.

181-187

Gas phase dissociation behavior of acyl-arginine peptides William M. McGee, Scott A. McLuckey

188-192

Structure of C,HF* and C,F,* fragment ions from fluorobenzenes: Electronic spectra in 6 K neon matrices

Karol Filipkowski, Jan Fulara, John P. Maier

@ Absorptions of HC,F* and HC,F* in neon matrixes were observed for the first time. @ The electronic transition of FC,F* is identified at 569.3 nm. @ The electronic transition of HC,F* is identified at 586.3 nm. @ Structures are determined as linear carbon chains terminated with heteroatoms.

L A

| |

e Ni INAH -H-CO,) | - CAN 2NAH - (Cu + INAH - NICO. co | co j mr

‘

ye

seo 580 /nr

Contents

193-203

Compositional and structural investigation of HCN polymer through high resolution mass spectrometry

Jean-Yves Bonnet, Roland Thissen, Maéliss Frisari,

Véronique Vuitton, Eric Quirico, Francois-Régis Orthous-Daunay, Odile Dutuit, Léna Le Roy, Nicolas Fray, Hervé Cottin,

Sarah M. Horst, Roger V. Yelle

204-210

Infrared spectroscopy of trapped molecular dications below 4 K Juraj JaSik, Jan Zabka, Jana Roithova, Dieter Gerlich

@ A new ion trapping instrument is presented in which ions can be cooled to temperatures below 4 K. @ Low temperatures and high helium densities allow in situ addition of He to the studied ions. @ Helium tagging allows obtaining infrared predissociation spectra of highly reactive species such as small hydrocarbon dications.

Rel. number of fragments

2900 2950 3000 3050 3100 wavenumbers/cm

car 0 BP w4PT T

211-218

Strategies for the gas phase modification of cationized arginine via ion/ion reactions

Boone M. Prentice, William M. McGee, John R. Stutzman, Scott A. McLuckey

@ Sodium cationized arginine-containing peptides are reactive with sulfo-NHS acetate. @ Protonated peptide analogs exhibit no such gas phase reactivity. @ Sodium cationization does not enhance lysine amino acid reactivity. @ Sodium cationization can be done in solution or in the gas phase via cation exchange. @ CID of acetylated arginine can form ornithine to induce site-specific fragmentation.

219-228

Counter-ion and solvent effects in electrospray ionization of solutions of alkali metal and quaternary ammonium salts

Konrad Koszinowski, Friederike Lissy

@ Observation of significant ion-pairing effects in ESI. @ ESI from protic and aprotic solvents. @ Variation of analyte, counter-ion, solvent, and concentration.

Relative ES! response

xi = 3 NBu,” NBu,” o1 NEt ai — NEt 0.00001 0.00001 001 o1 1 10 a1 1 10 > Cing/(mmol Cino/ (mmol L-*) 4

Contents

229-234

C—H and C—C bond activation reactions in silver alkynyl cluster were,

cations, RC=CAg,* CD3!C George N. Khairallah, Kirsty A. Saleeba, Sharon Chow, Wilhelm Eger, oar Craig M. Williams, Richard A.]. O’Hair

@ Silver alkynyl cations RC=CAg,* (R = H, Me, Et, Pr, Bu, Bu and Ph) were “synthesized” in the gas

phase. @ These cations fragment via a range of pathways including C—H and C—C bond activation.

@ H/D scrambling is not involved in the C—C bond activation pathway of CD,CH,CH,C=CAg,* and

CD,CD,CH,C=CAg,*. @ Formation of Ag,H" involves regiospecific C—H bond activation of the CH, AgoX* adjacent to the CH, group in CH,CH,CH,C=CAg,°.

CID X=HorD

235-241

Conformational changes of small PAMAM dendrimers asafunction .. of their charge state: A combined electrospray mass spectrometry, cs = 240 A’ >

traveling-wave ion mobility and molecular modeling study 3 te CCS = 220 A + 1+

Aura Tintaru, Sabrina Pricl, Laetitia Denbigh, Xiaoxuan Liu, Ling Peng, 2 wiht, +2 5 i,

Laurence Charles

@ Dendrimer conformation changes were revealed by their ESI-MS charge state distribution. CCS = 205 A? aia aa

@ Most stable conformation of each charge state was determined by molecular modeling.

mz @ Theoretical collision cross sections were supported by experimental data. @ The extend of den-

drimer swelling was shown to depend on the PAMAM architecture.

242-248

Bis(diphenylphosphino)methane ligated gold cluster cations: Synthesis and gas-phase unimolecular reactivity

Athanasios Zavras, George N. Khairallah, Richard A.J. O’Hair

via condensed phase synthesis. @ These and organometallic clusters [Au,L' (CH( PPh,),)]"* (x = 5, ¥ S Led

y =3,n=2;x-=14,y =6,n = 3) were observed via ESI/MS. @ Their unimolecular chemistry was

examined via CID and ECD. @ A range of pathways appear for CID including dppm loss, cluster — fragmentation and C—P bond activation of dppm. @ The main ECD reaction was charge reduction f fh 3) NaBH,

which was sometimes followed by ligand loss or C—P bond activation of dppm. .

249-256 Gas-phase structures of phosphopeptide ions: A difficult case

Frantisek Turecek, Christopher L. Moss, loannis Pikalov, Robert Pepin,

Kerim Gulyuz, Nicolas C. Polfer, Matthew F. Bush, Jeffery Brown, Oe

Jonathan Williams, Keith Richardson enh B3LYP

@ We elucidated structures of gas-phase phosphopeptide ions. @ lon mobility data were compat- i cae =e A

ible with calculated structures. @ Action IR spectroscopy was difficult to interpret. | V

xii aot

Contents

257-262

Gas phase reactivity of iron pentacarbony! with anionic metal clusters

Matthew A. Henderson, J. Scott McIndoe

@ Iron pentacarbonyl was reacted with an activated anionic metal cluster. @ Up to three iron atoms

were added, making nearly saturated product ions. @ The ligated products could be stripped down to a bimetallic core.

) +Fe(CO), ~— +Fe(CO),; [HsRu,(CO),}-

263-270

Understanding the reactivity bottleneck in the spin-forbidden reac- tion FeO* + H, — Fe* + H,O

Jeremy N. Harvey, David P. Tew

@ Accurate coupled-cluster energies are reported for the title reaction. @ The crossing point between quartet and sextet surfaces is located. @ Non-adiabatic statistical rate theory calculations are performed. @ The H—H bond splitting transition state is predicted to be rate-limiting.

271-174

Decorating (C,,),*, » = 1-3, with CO, at low temperatures: Sterically enhanced physisorption

A. Mauracher, A. Kaiser, M. Probst, S. Z6ttl, M. Daxner, J. Postler, M.M. Goulart, F. Zappa, D.K. Bohme, P. Scheier

@ Physisorption of CO, to C,, monomer, dimer and trimer cations is observed for the first time in the mass spectra of He nanodroplets sequentially doped with C,,. and CO, and exposed to electron ionization at 50 eV. @ Stability anomalies apparent for (C,,).* (CO,), and (C,,),*(CO,), are consis- tent with preferentialadsorption to the “groove” in the dimer and the two “dimples” in the trimer cations. @ This is illustrated vividly with a computed visualization of the physisorption.

275-280

A novel projection approximation algorithm for the fast and accurate computation of molecular collision cross sections (IV). Application to polypeptides

Christian Bleiholder, Stephanie Contreras, Michael T. Bowers

@ The PSA method gives cross sections within experimental error over an extended temperature range for short peptide sequences. @ The method is robust for structures derived from different levels of theory.

xiii a Ge Se | ite | 1) {| | Mil Min

Contents

281-287

LAACP-MSi

Bioimaging of copper deposition in Wilson’s diseases mouse liver by laser ablation inductively coupled plasma

mass spectrometry imaging (LA-ICP-MSI)

Pornwilard M-M, Uta Merle, Ralf Weiskirchen, J. Sabine Becker

@ LA-ICP-MSI allows accurate metal measurement in mouse liver tissue. @ Wilson's disease . disease influences homeostasis of several trace metals in liver. @ LA-ICP-MSI provides a new diagnostic option in experimental and clinical hepatology.

288-291

Native electrospray ionization and electron-capture dissociation for comparison of protein structure in solution and the gas phase Hao Zhang, Weidong Cui, Michael L. Gross

@ Method to compare protein structure in gas phase and solution by mass spectrometry. @ Method “%y utilizes native ESI and electron-capture dissociation top-down MS. @ ECD fragmentation correlates B-factor

with high B-factor from X-ray crystallography. zions

292-302

Fragmentation, structure, and energetics of small

sodium formate clusters: Evidence for strong influence 1

-

Agnes Révész, Tibor Andras Rokob, Gabor Maasz, os 3

Laszl6 Mark, Helga Hevér, Laszl6 Drahos, Karoly Vékey ie ;

@ Several NaOOCH clusters exhibit structures different from those of alkali halides. @ |NaOOCH],Na* behaves as an “anti-magic” cluster in the mass spectrometer. @ Dissociation energies cannot explain the abundances and fragmentation patterns. @ The relatively compact tetramer becomes unfavorable due to entropic effects.

[NaOOCH],,Na*

303-311

Formation of polynuclear copper complexes of gua- ~ nine-based nucleobases in the gas phase studied by ** ESI-MS

* [(Cu,dGuo So)”

Cu-separation (4) # [(Cu,dGuo PY (1)

700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 mz

Daniela Ascenzi, Pietro Franceschi, Graziano Guella, Paolo Tosi

@ We demonstrate production of polynuclear copper complexes in ESI sprayed solutions. @ Complexes are observed in ESI of H,O/CH,OH solutions of deoxy- guanosine and CuSO,. @ High resolution MS, MS?, ion mobility experiments yield chemical and structural information. @ Complexes contain up to 4 Cu(II) ions and up to 3 sulphate anion acting as bridging agents.

xiv ga 4 unfavored

Contents

312-317

Increasing confidence of LC-MS identifications by utiliz- ing ion mobility spectrometry

Kevin L. Crowell, Erin S. Baker, Samuel H. Payne, Yehia M. Ibrahim, Matthew E. Monroe, Gordon W. Slysz, Brian L. La- Marche, Vladislav A. Petyuk, Paul D. Piehowski, William F. Danielson III, Gordon A. Anderson, Richard D. Smith

@ Database created with mass, elution time, drift time, and charge state for pep-

tides. @ IMS provides a 3rd dimension of separation for increased confidence in identifications. @ Addition of the IMS dimension discerns peptides that were previously impossible.

Average # of Peptides

318-325

The binding of Ca?*, Co?*, Ni?*, Cu?*, and Zn?* cations to [Angl+CasH)” angiotensin | determined by mass spectrometry based on amin techniques

Matthew S. Glover, Jonathan M. Dilger, Feifei Zhu, David E. Clemmer

@ Angiotensin |-metal interactions are examined by ion mobility and CID. @ Metal- |

binding sites are proposed. @ Metal-binding sites influence the populations of conformations. ee Terao ee = Collision Cross Section Collision Cross Section

@ We examine populations of conformations before and after collisional activation.

326-332

Gas-phase reactivity of sulfate esters and analogs: Why is the sulfur

Unfavorable approach center unreactive?

Thiago C. Correra, José M. Riveros

@ The energy profiles of nucleophilic reactions of ester sulfates and sulfur analogs were calculated at the DFT level. @ Nucleophilic displacement at C and a elimination in agreement with experi- mental results. @ Displacement at S is predicted as favorable for several cases but not observed } experimentally. @ Electrostatic repulsion inhibits the formation of the $,2@S reaction complex. “a % y& @ The oxygen atoms around the S center repel the approaching nucleophile. -

333-341

Influence of heteroanion and ammonium cation size on the composition and gas-phase fragmentation of polyoxovanadates

Grant E. Johnson, Naila M. Al Hasan, Julia Laskin

@ ESI-MS/MS of polyoxovanadates (POVs) synthesized in solution with different heteroanions and ammonium cations. @ Ammonium cations have a minor influence on the size of POVs synthesized in solution. @ Heteroanions have a pronounced effect on the size, composition and ionic charge state of POVs. @ Fragmentation pathways of representative POVs containing ammonium cations were investigated. @ Larger ammonium cations have a stronger interaction with vanadium oxides than smaller ones.

xv Data Proces.ing Without (MS | Pipeline 200 20 3% . DT stimated FDR (% p » J HO’\ @ ‘OH ~ ° ° \ ; om /

Contents

342-345

Structures and energies of C,S,4(q = +1, 0, —1) isomers. A theoretical study

Paul Jerabek, Gernot Frenking

346-355

infrared multiple photon dissociation action spectroscopy of alkali ' metal cation-cyclen complexes: Effects of alkali metal cation size AEX. fe fx pox on gas-phase conformation Na’ _Rb’

C.A. Austin, Y. Chen, C.M. Kaczan, G. Berden, J. Oomens, M.T. Rodgers

@ IRMPD action spectra of alkali metal cation-cyclen complexes to Na*, K*, Rb*, and Cs* are | f A 4 measured in a FT-ICR MS. @ Linear IR spectra of alkali metal cation-cyclen complexes are calcu- || W, LU Lf lated at the B3LYP/def2-TZVPPD level of theory. @ Measured IRMPD spectra of alkali metal cation- ont

cyclen complexes agree well with linear IR spectra of C,(++++) conformers. @ IRMPD yields are directly correlated with size of alkali metal cation and inversely correlated with strength of binding. @ ESI produces primarily ground-state C,(++++) conformers of M*(cyclen), and a minor population of C.(+++-) conformers.

M’(cyclen)

Yield

Frequency

356-364

How does a small peptide choose how to bind a metal ion? IRMPD and computational survey of CS versus Iminol binding preferences - a

Robert C. Dunbar, Giel Berden, Jos Oomens

365-371

Composition and size dependent methane dehydrogenation on 10 binary gold-palladium clusters

>

2 08 Sandra M. Lang, Anja Frank, Thorsten M. Bernhardt @ The reactions of free gold-palladium clusters Au,Pd*, AuPd,*, and Au,Pd,* with methane 2 04) Au,Pd; —~A Pd} have been investigated in an ion trap experiment. @ Methane binding energies are determined. z 0 2 |Pac111) | @ AuPd,* dehydrogenates methane and a mechanism for the catalytic ethylene formation is - | au(111) ‘ Pre proposed. @ The results are compared to the bare gold Au,,*(n = 2-4) and palladium Pd,,*(m = 2-4) 0.0+

Number of Pd atoms in Au,,Pd),

xvi \ { 2.095 1.613 1.508 1.613 1.156 1.508 ( ] > 1.515 90 \ M"*Ala, | 2% 3 5 3 metabligand BOE (kJ mol") é

Contents

372-377

The way toward theoretical description of state-selected reactions of O* with methane

J. Hrusak, |. Paidarova

@ The reactions of O*(?D,2P) with methane were studied by ab initio MCSCF method. @ 19 lowest electronic states were considered on the doublet potential energy surfaces. @ Scans were performed which allow visualization of the qualitative features of the reaction profile based on synoptical atom manipulation. @ Dramatic reduction of the computational effort is a clear advantage of this approach.

378-390

Fragmentation reactions of Si,Cl,** in the gas phase—A quantum- chemical and mass-spectrometric assessment

Elie M.L. Fink, Alexander Schieffer, Robert Berger, Max C. Holthausen

@ Fragmentations and isomerizations of Si,Cl,** were characterized by theory and experiment. @ Different fragmentation pathways were measured by MI and CA mass spectrometry. @ Appearance energies of various fragment ions were determined. @ C1,Si-SiCI,,,,°) and chlorobridged SiC1,-SiClm*”) species (m = 1,2) coexist.

SiCI} + SiCl; SiCI + SiCl; and

SiCI}" + SiCI,

391-397

Protein adsorption on thermoplastic elastomeric surfaces: A quantitative mass spectrometry study

Madalis Casiano-Maldonado, Goy Teck Lim, Xiaopeng Li, Darrell H. Reneker, Judit E. Puskas, Chrys Wesdemiotis

@ Protein adsorption on tissue engineering surfaces quantified by mass spectrometry. @ Quantities in the range of 0.1-400 pmol/cm? were detected by MALDI-ToF MS. @ Adsorption on nonpolar surfaces increases with protein and surface hydrophobicity. e Amount adsorbed maximizes at the isoelectric point and decreases with protein size. @ Electrospun surface morphologies adsorb more protein than molded surfaces.

Proteins on electrospun fibers

398-405

The mobile proton in biomolecular clusters: Tripeptides and vanillic acid

Osama Abdelrahman, Barbara Grotemeyer, Jiirgen Grotemeyer

@ We investigated the biomolecular cluster ions formed in a supersonic jet by resonance enhanced multi photon ionization. @ Fragmentation of the biomolecular cluster ions leads to the formation of protonated peptide ions. @ It is shown that the ionization of the cluster is described by a dissocia- tive proton transfer to the N-terminal end of the peptide by isotopic labeling. @ Fragmentation of the protonated peptides is conducted through a proton chain walk.

xvii

appronching

4

| —

1*° TS}; 2°

>

&

2

Contents

406-413

The dissociation behaviour of a singly and doubly charged (cationised) aza-crown ether/metalloporphyrin- oO conjugate: Metal-induced reactivity and Coulomb explosions

Jing Li, Katharina Duerr, Marc S. von Gernler, Norbert Jux, Ivana Ivanovic-BurmazoviC, Thomas Drewello

crown ether

@ The dissociation of aza-crown ether/metalloporphyrin-conjugates was examined by CID.

@ Different central metals (Fe/Mn) and guest ions (H*,Na*,K*) were studied.

@ Energy-dependent experiments were performed for the monocationic species. @ The central metal (Fe/Mn) influences the dissociation reaction of the monocations. @ The dissociation of the dications depends on the nature of the guest ion.

414-435 Publication List

Michael Bowers

436-437

CURRICULUM VITAE - Dr. habil. Detlef Schréder, IOCB, Czech Republic

Michael Bowers

xvili we 4 An) fe OD = OO | =Fe,M