Analytical and Physical
Room: MR 1121 B
- INSTITUTION AND LOCATION DEGREE YEAR(s) FIELD OF STUDY
- University of North Carolina, Chapel Hill B.S. 1957-1961 Chemistry
- Massachusetts Institute of Technology Ph. D. 1961-1965 Chemistry
- Free University of Brussels Postdoc. 1965-1966 Electrochemistry
Analytical and Physical ChemistryTel. (212) 650-8363
Fax: (212) 650-6848
Our research activities involve the investigation of electrochemical systems of interest in biochemical redox processes , in energy conversion such as solar to electrical energy ( electrochemical solar cells ) , chemical to electrical energy ( fuel cells), and electrical to chemical energy ( electrosynthesis), and in molecular electronics such as molecules bound to Ag or Au metal clusters.
Electrochemical electron transfer reactions are unique ways to make novel chemical species and to modify metal surfaces with adsorbed layers with unusual properties, e.g., layers of conducting polymers . We investigate the structure and dynamics of adsorbed molecules on metal surfaces using the insitu technique of surface enhanced Raman spectroscopy (SERS). To further this end, we have developed unique single scan and pump-probe time-resolved SERS (TRSERS) methods to investigate transient structural changes for adsorbed molecules undergoing molecular change in the nanosecond, microsecond, and millisecond time domain after an electrode potential pulse or a laser light pulse. Our studies have shown that it is possible to obtain detailed mechanistic information about the structure and dynamics of reacting molecules on metal surfaces. We are also using ab initio molecular orbital calculations to study the properties of individual molecules and of metal cluster/molecule systems.
Another area of interest is in the redox and complexation reactions which take place at the active sites of enzymes, especially those enzymes which contain iron porphyrins and vitamin B12 compounds as prosthetic groups. Our investigations in this area involves the study of the redox and ligand binding reactions of vitamin B12 (cobalamin) compounds in solution and at the active site of vitamin B12 dependent enzymes using Raman and electrochemical techniques. We are especially interested in the reactions of nitric oxide and nitrous oxide with these cobalamin systems. The in vitro studies are designed to help understand reactions which occur at the active site of the enzyme- methionine synthase , which has a methyl-B12 cofactor. We are also using electronic structure calculations to model cobalamin reactions in these enzymes.
B.S., University of North Carolina (Chapel Hill), 1961
Ph. D., Massachusetts Institute of Technology, 1965
Post Doctoral, University of Brussels, Belgium, 1965-66
Professor, 1981 - present, The City College of CUNY
Associate Professor, 1974 - 1980, City College of CUNY
Associate Professor, 1972-74, University of South Florida
Assistant Professor, 1969-72, University of South Florida
Instructor, 1966-69, Harvard University
Faria, P. A., R. L., Chen, X., W., and Lombardi, J. R., Birke, R. L., Langmuir, 16 , 394 (2000) , A Surface-Enhanced Raman and ab Initio Study of Spectra of Lumazine Molecules http://pubs3.acs.org/acs/journals/doilookup?i\in_10.1021/la991351y
Zheng, D. , and Birke, R. L, J. Am Chem. Soc,123 , 437 (2001) , Spectroscopic Evidence for Nitric Oxide Binding with Cob(II)alaminhttp://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/ja015682k
Vivoni, A., Birke, R. L, and Lombardi, J. R., , Spectrochimica Acta, part A , 57 , 535 (2001), " Optimization of Force Constants with a Urey-Bradley Force Field Avoiding Normal Mode Crossings".
Mileykovskaya, E., Dowhan, W., Birke, R. L., Zheng, D., Lutterodt, L. , and Haines, T. H. , " FEBS Let., 507 , 187 (2001), "Cardiolipin binds to nonyl acridine orange by aggregating the dye at exposed hydrophobic domains on bilayer surfaces
Zheng, D. , Yan, L., and Birke, R. L, ", Inorg. Chem.,41 , 2548 (2002), Electrochemical and Spectral Studies of the Reactions of Aquocobalamin with Nitric Oxide and Nitrite Ion http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/ic010802a
Rywkin, S., Hosten, C. M., Lombardi, J. R., Birke, R. L., Langmuir, 18 , 5869 (2002), Surface-Enhanced Resonance Raman Scattering and Voltammetry Study of the Electrocatalytic Reduction of Oxygen by the -Oxo Dimer of Iron(III) Tetra-4-N-methylpyridylporphyrin http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/la011334k
Zheng, D. , and Birke, R. L, J. Am Chem. Soc, 31, 9066 (2002), The Reaction of Nitric Oxide with Glutathionylcobalamin http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/ja017684a
Chen, S.-P; Hosten, C. M; Lombardi, R. L. and Birke, R. L. Langmuir , 18(25) , 9888-9900 ( 2002),
SERS Investigation of NAD+ on a Silver Electrode, http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/la020235j
Vivoni, A. ; Birke, R. L. ; Foucault, R. and Lombardi, J. R. , J. Phys. Chem. B, 107, 5547-5557 ( 2003), Ab Initio Frequency Calculations of Pyridine Adsorbed on an Adatom Model of a SERS Active Site of a Silver Surface http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/jp027642o
Foucault, R; Birke , R. L. and Lombardi, J. R. Langmuir, 19, 8818-8827( 2003). SERS of Surfactants in Monolayer and Multibilayer Forms on an Electrified Ag Surface ,http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/la034631t
Kim, M.-H.; Yan, L.; Birke, R. L. and M.-Z. Czae, " Differential Pulse Polarography for a First-Order EC process and Its Diagnostic Parameters ," Electroanalysis, 15, 1541-1553 ( 2003).
Birke, R. L.; Huang, Q.; Spataru, T.; Gosser, D. K., Jr., J. Am. Chem. Soc. (2006) 128(6); 1922-1936 . Electroreduction of a Series of Alkylcobalamins: Mechanism of Stepwise Reductive Cleavage of the Co-C Bond , http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/ja054479c
Spataru, T.; Birke, R. L. J. Electroanal. Chem. ( 2006), 593, 74-86 " The effect of solvent on the electrode process of methylcobalamine as studied by cyclic voltammetry , "doi:10.1016/j.jelechem.2006.03.032
Spataru, T.; Birke, R, L. J. Phys. Chem. A (2006) 110 (28): 8599-8604 , Carbon-Cobalt Bond Distance and Bond Cleavage in One-Electron Reduced Methylcobalamin :Failure of the DFT Method, http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/jp062741d
Wang, M., Teslova, T.; Xu, F; Spataru, T; Lombardi, J. R., Birke. R. L.; Leona, M. J. Phys. Chem. C (2007) 111, 3038-3043, Raman and Surface Raman Scattering of 3-Hydroxflavone http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/jp062100i
Wang, M.; Spataru, T; DOI: 10.1002/jrs.1695 J. Phys. Chem. C (2007) 111, 3044-3052, Time-Resolved Surface Enhanced Raman Scattering Studies of 3-Hydroxflavoneon a Ag Electrode. http://pubs3.acs.org/acs/journals/doilookup?in_doi=0.1021/jp0650937
Teslova, T.; Corredor, C.; Livingstone, R.; F; Spataru, T; Birke. R. L. ; Lombardi, J. R.; Canamares, M. V. Leona, M. (2007) J. Raman Spectrosc., (2007) 38, 802-818, Raman and Surface-Enhanced Raman Spectra of flavone and several Hydroxy Derivatives. DOI: 10.1002/jrs.1695
Lombardi, R. L. and Birke, R. L. , J. Chem. Phys. (2007) 126, 244709, Time-dependent picture of the charge-transfer contributions to surface Raman spectroscopy, doi:10.1063/1.2748386
86. . Lombardi, R. L. and Birke, R. L., “ A Unified Approach to Surface-Enhanced Raman Spectroscopy” , J. Phys. Chem. C 112, 5605-5617 (2008)
87. Chenal, Cat ; Birke, R. L.; Lombardi , J. R. “Determination of the Degree of Charge-Transfer Contributions to Surface Enhanced Raman Spectroscopy”, ChemPhysChem, 9, 1617-1623 (2008) .
88. Canamares, M. V.; Chenal, Cat; Birke, R. L.; Lombardi, J. R. “ DFT, SERS, and Single-Molecule SERS of Crystal Violet”, J. Phys. Chem. C 112, 20295-20300 (2008).
89. Lombardi, J. R. ; Birke, R. L “ A Unified View of Surface-Enhanced Raman Scattering” Acc. of Chem. Res., 42, 734-742 ( 2009).
90. . Lombardi, R. L. and Birke, R. L., “ Excitation Profiles and Continuum in SERS: Identification of Fano Line Shapes” , J. Phys. Chem. C 114, 7812-7815 (2010)
91. Birke, R. L. ; Znamenskiy, V. ; and Lombardi, R. L. “ A Charge-transfer surface enhanced Raman scttering model from time-dependent density functional theory calculations on a Ag10-pyridene complex ” , J. Chem. Phys. 132 , 214707(2010).
92. Lombardi, R. L., Birke, R. L., Haran, G., “ Single Molecule SERS Spectral Blinking and Vibronic Coupling” , J. Phys. Chem. C 115, 4540-4545 (2011)
93. . Lombardi, R. L. and Birke, R. L., “The theory of surface-Enhanced Raman Scattering” , J. Chem. Phys. , 136, 144704 (2012)
94. Eisenberg, A.; Likhtina , Y.; Znamenskiy, V.; Birke , R. L. , “ Electronic Spectroscopy and Computational Studies of Glutathionylco(III)balamin” , J. Phys. Chem. A. , 116, 6851-6869 (2012)
95. Lombardi, J. R.; Birke, R. L. , “ Theory of Surface-Enhanced Raman Scattering Semiconductors”, J. Phys. Chem. C 118, 11120-11130 (2014)
96. Birke, R. L. and Lombardi, J. L., “ Simulation of SERS by a DFT study: a comparison of static and near-resonance Raman for 4-mercaptopyridine on small Ag clusters” , J. Opt. 17 114004 (14 pp) (2015)
97. Birke, R. L.; Lombardi, J. R. ; Saidi, W. A. , Norman, P. , “Surface Enhanced Raman Scattering due to Charge Transfer Resonances: a Time-Dependent Density Functional Theory Study of Ag13-4-Mercaptopyridine”, J. Phys. Chem. C , 120, ASAP (2016)
98. Sajan, A. ; Birke, R. L. , “The Reductive Cleavage Mechanism and Complex Stability of Glutathionyl-Cobalamin in Acidic Media”, Electroanalysis, 28 web (2016)