Hilkka Kenttämaa Current Group Members Current Research Useful Links Home

Hilkka I. Kenttämaa                                                                                                    hilkka@purdue.edu

Title: Professor

Research Interests:
Organic Mass Spectrometry, Gas-Phase Ion Chemistry, Organic Reaction Intermediates.

Education, Positions, Awards:
B.S., 1977, Helsinki University, Finland
M.S., 1978, Helsinki University, Finland
Ph.Lic. (Licenciate of Philosophy), 1981, Helsinki University, Finland
Ph.D., 1986, Helsinki University, Finland

Research Scientist, Helsinki University, Finland, 1978-1986
Research Scientist, The Academy of Finland, 1981-1985
Postdoctoral Fellow, Purdue University, 1986
Assistant Research Scientist, Purdue University, 1987-1989
Dosentti (Special University Lecturer), Helsinki University, Finland, 1989-Present
Assistant Professor, Purdue University, 1989-1994
Associate Professor, Purdue University, 1994-1999
Full Professor, Purdue University, 1999-Present

Fellowship of the Academy of Finland, 1981-1985
Gustaf Komppa Award of the Finnish Chemical Society for the best Chemistry Ph.D. Thesis in Finland, 1985
Award of the American Society for Mass Spectrometry for a Young Academic Mass Spectroscopist, 1999
Young Faculty Award of Eli Lilly and Company, 1992
University Faculty Scholar, Purdue University, 2001-2006
Member, The Finnish Academy of Science, 2004-

Current Work and Activities

Mechanistic, kinetic and thermochemical studies are carried out on reaction intermediates that are important for example in organic and inorganic synthesis, carcinogenesis, and the action of antitumor drugs; e.g., radical cations, radicals, borocations, carbene ions, and phosphorus and antimony cations. Theoretical methods are used to complement experiments carried out using Fourier-transform ion cyclotron resonance mass spectrometry. New strategies are developed for the synthesis and study of interesting ions inside the mass spectrometer. Multiple-stage tandem mass spectrometry experiments are being developed for selective ionization and structural characterization of polyfunctional organic compounds, including amino acids, peptides, and sugars. The possibility to use functional group selective ion-molecule reactions in mass spectrometric analysis of organic compounds is being explored.

Selected Publications

"A New Reagent for Structure Specific Ion-Molecule Reactions. Dimethyl Diselenide", B.J. Beasley, R.L. Smith and H.I. Kenttämaa, J. Mass Spectrom. 30 (1995) 384-385.

"Differentiation of Stereoisomeric Diols by Using CH3OB+OCH3 in a Small Fourier-Transform Ion Cyclotron Resonance Mass Spectrometer", D.T. Leeck, T.D. Ranatunga, R.L. Smith, T. Partanen, P. Vainiotalo and H.I. Kenttämaa, Int. J. Mass Spectrom. Ion Processes141 (1995) 229-240.

"Gas-Phase Reactions of Dicoordicated Boron Cations with Alcohols", T. Ranatunga and H.I. Kenttämaa, Inorg. Chem. 34 (1995) 18-27.

"Gas-Phase Reactions of the 4-Dehydroanilinium Ion and Its Isomers", L.J. Chyall and H.I. Kenttämaa, J. Mass Spectrom. 30 (1995) 81-87.

"A General Method for the Synthesis of Charged Phenyl Radicals in the Gas Phase", R.L. Smith and H.I. Kenttämaa, J. Am. Chem. Soc. 117 (1995) 1393-1396.

"Reactivity of the Prototype Organosulfur Distonic Ion: CH2SH2+", P.K. Chou, R.L. Smith, L.J. Chyall, H.I. Kenttämaa, J. Am. Chem. Soc. 117 (1995) 4374-4378.

"The Site of Protonation of Aniline", R.L. Smith, L.J. Chyall, B. Beasley and H.I. Kenttämaa, J. Am. Chem. Soc. 117 (1995) 7971-7973.

"An Experimental and Theoretical Study of the Long-Lived Radical Cation of CH3OCH2CH2OH", J.M.H. Pakarinen, R.L. Smith, P. Vainiotalo, T.A. Pakkanen and H.I. Kenttämaa, J. Am. Chem. Soc. 118 (1996) 3914-3921.

"Structure and Reactivity of Selected Distonic Radical Cations", an invited chapter in "The Structure, Energetics, and Dynamics of Organic Ions", R.L. Smith, P.K. Chou, H.I. Kenttämaa, Wiley Series on Ion Chemistry and Physics, Editors: T. Baer, C.Y. Ng, and I. Powis, 1996, pp. 197-261.

"Methyl Propionate Radical Cation", J.M.H. Pakarinen, P. Vainiotalo, C.L. Stumpf, D.T. Leeck, P.K. Chou, and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 7 (1996) 482-489.

"Homolytic Se-H Bond Energy and Ionization Energy of Benzeneselenol and the Acidity of the Corresponding Radical Cation", D.T. Leeck, R. Li, L.J. Chyall and H.I. Kenttämaa, J. Phys. Chem. 100 (1996) 6608-6611.

"Unusual Reactivity of the Radical Cations of Some Simple Trivalent Organophosphorus Compounds Toward Dimethyl Disulfide and Dimethyl Diselenide", R.L. Smith, A. Schweighofer, H. Keck, W. Kuchen and H.I. Kenttämaa, J. Am. Chem. Soc. 118 (1996)1408-1412.

"Fluorine Substitution Enhances the Reactivity of Substituted Phenyl Radicals Toward Organic Hydrogen Atom Donors", Ruomei Li, R.L. Smith and H.I. Kenttämaa, J. Am. Chem. Soc. 118 (1996) 5056-5061.

"Distinguishing Conventional and Distonic Radical Cations by Using Dimethyl Diselenide", K.K. "Thoen, B.J. Beasley, R.L. Smith, H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 17(1996)1245-1250.

"Characterization of Long-Chain Carboxylic Acid Esters with CH3OBOCH3+ in a Small Fourier-Transform Ion Cyclotron Resonance Mass Spectrometer", K.K. Thoen, D.T. Tutko, T.D. Ranatunga and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 7 (1996) 1138-1143.

"Charged Phenyl Radicals", K.K. Thoen, R.L. Smith, J. Nousiainen, E.D. Nelson, and H.I. Kenttämaa, J. Am. Chem. Soc. 118 (1996) 8669-8676.

"The Prototypical Organophosphorus Ylidion CH2PH3+", A. Schweighofer, P.K. Chou, K.K. Thoen, V.K. Nanayakkara, H. Keck, W. Kuchen and H.I. Kenttämaa, J. Am. Chem. Soc. 118 (1996) 11893-11897.

"The Radical Cation of Trimethylphosphine Oxide", Li, R., Schweighofer, A. , Keck, H., Kuchen, W., Kenttämaa, H.I., Int. J. Mass Spectrom. Ion Processes 157/158 (1996) 293-303

"Disubstituted Boron Cations Cleave Carbonyl Bonds", T. Ranatunga, J.M. Kennady, and H.I. Kenttämaa, J. Am. Chem. Soc. 119 (1997) 5200-5207.

"Synthesis and Characterization of Aromatic Biradicals in the Gas Phase: a meta-Benzyne with an Inert Positively Charged Substituent and Its ortho- and para- Isomers", K.K. Thoen and H.I. Kenttämaa, J. Am. Chem. Soc. 119 (1997) 3832-3833.

"Reactions of Alkyl Halides with Distonic Acylium Radical Cations", R.L. Smith, K.K. Thoen, K.M. Stirk, and H.I. Kenttämaa, Int J. Mass Spectrom. Ion Processes 165/166 (1997) 315-325.

"Electron and Proton Transfer Reactions of Simple Aldehyde and Ketone Radical Cations and their Enol and Distonic Isomers in the Gas Phase", H.C.M. Byrd, L.M. Castro, Y.-Q. Yu, C.T. Hwang, and H.I. Kenttämaa, Int. J. Mass Spectrom. Ion Processes 167/168 (1997) 403-414.

"Stereoselective Chemical Ionization Mass Spectrometry: Reactions of CH3OPOCH3+ with Cyclic Vicinal Diols", K.K. Thoen, L. Gao, T.D. Ranatunga, P. Vainiotalo, and H.I. Kenttämaa, J. Org. Chem. 62 (1997) 8702-8707.

 "Disulfide Bond Cleavage in Neutral Substrates by the Dimethylene  Ketene Radical Cation inside a Mass Spectrometer", K.K. Thoen, D. Tutko, J. Pèrez, R.L. Smith and H.I. Kenttämaa, Int. J. Mass Spectrom. Ion Processes, 175 (1998) 173-177.

"Gas-Phase Reactivity of the 2,6- and 3,5-Dimethylenepyridinium Biradicals", E.D. Nelson, K.K. Thoen and H.I. Kenttämaa, J. Am. Chem. Soc. 120 (1998) 3792-3798.

"The Dimethylene Ketene Radical Cation", P.K. Chou, K.K. Thoen and H.I. Kenttämaa, J. Org. Chem. 63 (1998) 4470-4474.

"Synthesis of Charged Phenyl Mono- and Biradicals by Photolysis in a FT-ICR Mass Spectrometer", K.K. Thoen, J. Perez, J.J. Ferra, Jr. and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 9 (1998) 1135-1140.

"Reactions of tert-Butyl Isocyanide with Distonic Radical Cations", E.D. Nelson, R. Li and H.I. Kenttämaa, Int. J. Mass Spectrom. Ion Processes 185/186/187 (1999) 91-96.

"Intrinsic Acidity and Redox Properties of the Adenine Radical Cation", T. Hwang, C. Stumpf, Y.-Q. Yu and H.I. Kenttämaa, Int. J. Mass Spectrometry 182/183 (1999) 253-259 (invited article; a memorial issue in honor of Ben Freiser).

"Reactivity of a Substituted meta-Benzyne Biradical", K.K. Thoen and H.I. Kenttämaa, J. Am. Chem. Soc. 121 (1999) 800-805.

"Reactivity of the Gaseous Radical Cations of Trimethylenemethane and 2-Isopropylidenecyclopentane-1,3-diyl", P.K. Chou, L. Gao, S.L. Painter, S.C. Blackstock and H.I. Kenttämaa, J. Phys. Chem., submitted.

"Polar Effects on Iodine Atom Abstraction by Charged Phenyl Radicals (Distonic Radical Cations)", J.L. Heidbrink, K.K. Thoen and H.I. Kenttämaa, J. Org. Chem., in press.

"Reactivity of Cl-P+-Cl Toward Cyclic Organic Ethers", L. Ramirez-Arizmendi, Y.Q. Yu and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 10 (1999) 379-385.

"The 2,3- and 2,5-Dihydrofuran Radical Cations", Y.-Q. Yu, L. Gao, J.J. Nousiainen and H.I. Kenttämaa, J. Am. Chem. Soc., submitted.

"Charge Localization in Bis(9-azabicyclo[3.3.1]nonyl)sulfide Radical Cation, and Comparison of Gas and Solution Phase Reactions of NO+ with its Neutral Form", S.F. Nelsen, D.A. Trieber, II, M.A. Nagy, L. Gao and H.I. Kenttämaa, J. Phys. Chem., submitted.

"Determination of 3,3'-Dichlorobenzidine and Its Degradation Products in Environmental Samples with a Small Low-Field Fourier-Transform Ion Cyclotron Resonance Mass Spectrometer", M.C. Nyman, J. Perez, E.R. Blatchley III and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 10 (1999) 1152-1156.

"Photodegradation of 3,3'-Dichlorobenzidine in the Aqueous Environment", M.C. Nyman, K.S. Haber, H.I. Kenttämaa and E.R. Blatchley III, Environmental Science and Technology, submitted.

"Laser Desorption in Transmission Geometry Inside a Fourier-Transform Ion Cyclotron  Resonance Mass Spectrometer", J. Perez, C.J. Petzold, M.A. Watkins, W.E. Vaughn and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 10 (1999) 1105-1110.

"Diastereoselectivity in Gas-Phase Hydride Reduction Reactions of Ketones", A. Artau, Y. Ho, H. Kenttämaa and R.R. Squires, J. Am. Chem. Soc. 121 (1999) 7130-7137.

"Gas-Phase Reactions of the Dichlorocarbene Radical Cation", E.D. Nelson, S.E. Tichy and H.I. Kenttämaa, Perkin Trans. Actions II (11) (1999) 2267-2272 (invited article, a memorial issue in honor of Bob Squires).

"Gas-Phase Fragmentation of Di- and Tripeptides via Ion-Molecule Reactions with ClPCl+", Y.-Q. Yu, C.L. Stumpf and H.I. Kenttämaa, Int. J. Mass Spectrom., in press (invited article, a memorial issue in honor of Bob Squires).

"Laser-Induced Acoustic Desorption/Chemical Ionization in Fourier-transform Ion Cyclotron Resonance Mass Spectrometry", J. Perez, L.E. Ramirez-Arizmendi, C.J. Petzold, L.P. Guler, E.D. Nelson, and H.I. Kenttämaa, Int. J. Mass Spectrom, accepted.

“Reactivity of the Gaseous Radical Cations of Trimethylenemethane and 2-Iso-propylidenecyclopentane-1,3-diyl”, P.K. Chou, L. Gao, S.E. Tichy, S.L. Painter, S.C. Blackstock and H.I. Kenttämaa, J. Phys. Chem. A 104 (2000) 5530-5534.

“A meta-Benzyne Reacts as an Electrophile”, E.D. Nelson, A. Artau, J.M. Price and H.I. Kenttämaa, J. Am. Chem. Soc. 122 (2000) 8781-8782.

“An FT-ICT Study of the 3,5-Dehydrophenyl Cation”, E.D. Nelson and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 12 (2001) 258-267

“Polarity of the Transition State Controls the Reactivity of Related Charged Phenyl Radicals toward Atom and Group Donors”, S. E. Tichy, K.K. Thoen, J.M. Price, J.J. Ferra, Jr., C.J. Petucci and H.I. Kenttämaa, J. Org. Chem. 66 (2001) 2726-2733

“N-Terminal Derivatization and Fragmentation of Neutral Peptides via Ion-Molecule Reactions with Acylium Ions: Towards Gas-Phase Edman Degradation?”, G.E. Reid, S. Tichy, J. Perez, R.A.J. O’Hair, R.J. Simpson and H.I. Kenttämaa, J. Am. Chem. Soc. 123 (2001) 1184-1192

“Synthesis and Characterization of a Distonic Nitrene Ion: Gas-Phase Reactivity of Singlet and Triplet N-Phenyl-3-Nitrenopyridinium Ion”, S. Tichy, B.T. Hill, J.L. Campbell and H.I. Kenttämaa, J. Am. Chem. Soc. 123 (2001) 7923-7924.

“Hydrogen Atom Abstraction and Addition Dominate the Reactivity of Charged Phenyl Radicals Toward Monosubstituted Aromatic Substrates in the Gas Phase”, L.E. Ramirez-Arizmendi, L. Guler, J. Ferra, Jr., K. Thoen and H.I. Kenttämaa, Int.J. Mass Spectrom. 210/211 (2001) 511-520 (special issue to honor Nico Nibbering’s retirement).

“meta-Benzyne Reacts as an Electrophile”, E.D. Nelson, A. Artau, J.M. Price, S.E. Tichy, L. Jing and H.I. Kenttämaa, J. Phys. Chem. A 105 (2001) 10155-10168.

“An Examination of Barriered and Barrierless Hydrogen Atom Abstraction Reactions by Organic Radical Cations: the Cytosine Radical Cation”, J. Price, C. Petzold, H.C.M. Byrd, and H.I. Kenttämaa, Int. J. Mass Spectrom. 212 (2001) 455-466.

“Polar Effects Control Hydrogen Abstraction Reactions of Charged, Substituted Phenyl Radicals”, J. Heidbrink, L. Ramirez-Arizmendi, K.K. Thoen, L. Guler and H.I. Kenttämaa, J. Phys. Chem. A. 105 (2001) 7875-7884.

“Gas-Phase Reactions of Charged Phenyl Radicals with Nonvolatile, Thermally Labile Biomolecules Evaporated by Laser-induced Acoustic Desorption”, C.J. Petzold, L.E. Ramirez-Arizmendi, J.L. Heidbrink and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 13 (2002) 192-194.

“Photodechlorination of 3,3'-Dichlorobenzidine in Water”, M.C. Nyman, K.S. Haber, H.I. Kenttämaa and E.R. Blatchley III, J. Environ.Toxicol. Chem.  21 (2002) 500-506.

“Hydrogen Atom Abstraction Reactions of Charged Aromatic σ-Radicals Related  to the Active Intermediates of Enediyne Antitumor Drugs”, C. Petucci, M. Nyman and H.I. Kenttämaa, J. Am. Chem. Soc. 124 (2002) 4108-4115.

“Differentiation of Stereoisomeric Steroids by Reactions with Phosphenium Ions”, C. Petucci, L. Guler and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom., in press.

“A Mechanistic Study of Stereoselective the Gas-Phase Reactions of Phosphenium Ions  with cis- and trans-1,2-Diaminocyclohexanes”, R.S. Thompson, L. Guler, E.D. Nelson, Y.-Q. Yu and H.I. Kenttämaa, J. Org. Chem., accepted.

“An Experimental and Computational Study of the Gas-Phase Structures of Five-Carbon Monosaccharides”, L.P. Guler, Y.-Q. Yu, and H.I. Kenttämaa, J. Phys. Chem., accepted.

“Charge-site Effects on Reactions of Charged Phenyl Radicals”, C. Petzold, Nelson, E. Kenttämaa, H.I. J. Phys. Chem. A, submitted.

“Distonic Radical Cations”, a book chapter in the Encyclopedia of Mass Spectrometry, Vol. 5 (invited), to be published.

“Gas-Phase Reactions of Charged Phenyl Radicals with Nonvolatile, Thermally Labile Biomolecules Evaporated by Laser-induced Acoustic Desorption”, C.J. Petzold, L.E. Ramirez-Arizmendi, J.L. Heidbrink, J. Perez,  and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 13 (2002) 192-194.

           

“Photodechlorination of 3,3'-Dichlorobenzidine in Water”, M.C. Nyman, K.S. Haber, H.I. Kenttämaa and E.R. Blatchley III, J. Environ.Toxicol. Chem.  21 (2002) 500-506.

 

“Hydrogen Atom Abstraction Reactions of Charged Aromatic σ-Radicals Related  to the Active Intermediates of Enediyne Antitumor Drugs”, C. Petucci, M. Nyman and H.I. Kenttämaa, J. Am. Chem. Soc. 124 (2002) 4108-4115.

 

“Differentiation of Stereoisomeric Steroids by Reactions with Phosphenium Ions”, C. Petucci, L. Guler and H.I. Kenttämaa, J. Am. Soc. Mass Spectrom. 13 (2002) 362-370.

 

“A Mechanistic Study of Stereoselective Gas-Phase Reactions of Phosphenium Ions  with cis- and trans-1,2-Diaminocyclohexanes”, R.S. Thompson, L. Guler, E.D. Nelson, Y.-Q. Yu and H.I. Kenttämaa, J. Org. Chem.  67 (2002) 5076-5084.

 

“An Experimental and Computational Study of the Gas-Phase Structures of Five-Carbon Monosaccharides”, L.P. Guler, Y.-Q. Yu, and H.I. Kenttämaa, J. Phys. Chem. A 106 (2002) 6754-6764

                                               

“Charge-site Effects on the Radical Reactivity of Distonic Ions”, C. Petzold, E.N Nelson, H. Lardin, and .HI. Kenttämaa, J. Phys. Chem. A 106 (2002) 9767-9775.

 

“Chemical Properties of a para-Benzyne”, A.S. Amegayibor, J.J. Nash, A. S. Lee, J. Thoen, C. Petzold and H.I. Kenttämaa, J. Am. Chem. Soc.  124 (2002) 12066-12067.

 

“Distonic Radical Cations”, a book chapter in the Encyclopedia of Mass Spectrometry, Volume 1: Theory and Ion Chemistry, Volume Ed. P.B. Armentrout, Eds. M.L. Gross, R. Caprioli (ISBN 0-08-043802-4), Elsevier: New York, 2003 (invited).

 

“Reactivity of Substituted Charged Phenyl Radicals toward Components of Nucleic Acids”, L.E. Ramirez-Arizmendi, J.K. Heidbrink, L.P. Guler and H.I. Kenttämaa, J. Am. Chem. Soc. 125 (2003) 2272-2281.

 

“Experimental and Theoretical Characterization of the 3,5-Didehydrobenzoate Anion: A Negatively Charged meta-Benzyne”, J.M. Price, K.E. Nizzi, J.L. Campbell, H.I. Kenttämaa, M. Seierstad and C.J. Cramer, J. Am. Chem. Soc. 125 (2003) 131-140.

 

“Theoretical Estimations of the 298 K Gas-Phase Acidities of the Pyrimidine-based Nucleobases Uracil, Thymine and Cytosine”, Y. Huang and H.I. Kenttämaa, J. Phys. Chem. A.  107 (2003) 4893-4897.

 

“Characterization of Two Chloro-Substituted m-Benzyne Isomers: Effect of Substitution on Reaction Efficiencies and Products”, J.M. Price and H.I. Kenttämaa,  J. Phys.Chem. Soc. A 107 (2003) 8985-8995.

 

“Theoretical and Experimental Investigations on the Chemical Reactions of Positively Charged Phenyl Radicals with Cytosine and 1-Methylcytosine”, Y. Huang and H.I. Kenttämaa, J. Am. Chem. Soc. 125 (2003) 9878-9889.

 

“Radical Reactions of Didehydroarenes with a 1,4-Relationship”, S.A. Amegayibor, J.J. Nash and H.I. Kenttämaa, J. Am. Chem. Soc. 125 (2003) 14256-14257.

 

“Gas-Phase Radical-radical Recombination Reactions of Nitroxides with Substituted Phenyl Radicals”, J.L. Heidbrink, F.S. Amegayibor and H.I. Kenttämaa, Int. J. Chem. Kin. 36 (2004) 216-229.

 

“Quantitative Determination of the Selectivity of Five Different Phenyl Radicals in Hydrogen atom Abstraction from Ethanol”, L. Jing, L.P. Guler, John J. Nash, and H.I. Kenttämaa,  J. Am. Soc. Mass Spectrom. 15 (2004) 913-919.

 

“Analysis of Nonpolar Hydrocarbons by Using Chemical Ionization Combined with Laser-induced Acoustic Desorption Fourier-transform Ion Cyclotron Resonance Mass Spectrometry (LIAD/FT-ICR)”, J.L. Campbell, K.E. Crawford and H.I. Kenttämaa, Anal. Chem. 76 (2004) 959-963.

 

“Ion-Molecule Reactions for Mass Spectrometric Identification of Functional Groups in Protonated Oxygen-containing Monofunctional Compounds”, M.A. Watkins, J.M. Price, B.E. Winger and H.I. Kenttämaa, Anal. Chem. 76 (2004) 964-976.

 

“Theoretical Estimations of the 298 K Gas-Phase Acidities of the Purine-Based Nucleobases Adenine and Guanine”, Y. Huang and H.I. Kenttämaa, J. Phys. Chem. A 108 (2004) 4485-4490.