Ron Birke

Analytical and Physical Chemistry

Research

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.

Biosketch

Education:
    B.S., University of North Carolina (Chapel Hill), 1961
    Ph. D., Massachusetts Institute of Technology, 1965
    Post Doctoral,     University of Brussels, Belgium, 1965-66

Professional Experience
    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)alamin

 http://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-Hydroxflavone

on 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