Teresa Heinz Professor of Green Chemistry
Green chemistry, green oxidation catalysis in water, inorganic chemistry, biomimetic chemistry of peroxidase enzymes, mechanisms of oxidation catalysis, novel approaches to water purification
We design homogeneous oxidation catalysts to activate the natural oxidants, hydrogen peroxide and oxygen. By following an iterative design protocol, we have developed TAML activators with iron as the active metal that are outstanding peroxidase mimics, but are only about 1% the size of the enzymes. Peroxidase enzymes are distributed widely in nature and activate hydrogen peroxide to oxidize organic substrates. We are continuing to develop our insight into how to control catalyst lifetime, reactivity and selectivity via ligand design and are producing new peroxidase mimics with targeted reactivity features. Students learn to design high performance oxidation catalysts and to apply synthetic organic and inorganic chemistry to enable their design work.
In water with hydrogen peroxide (or some other oxidizing agents), TAML activators produce exceptionally strong oxidizing systems that generally perform rapidly and are capable of large turnover numbers. The reaction chemistry is usually highly efficient in hydrogen peroxide use and appears to be primarily non-radical in nature. We design ways to kinetically isolate the various steps in the complex catalytic cycle and then measure the rate behavior as we work to construct a full quantitative picture of the catalysis. Students learn how to perform kinetic studies on complex catalytic systems including stopped-flow and conventional techniques.
TAML activators do their catalytic work at remarkably low concentrations, low micromolar to nanomolar. By using design understanding informed by mechanistic insight, we have been able to produce variants that oxidize many pollutants in water over a wide range of reaction conditions. The list includes persistent chlorinated phenols, natural and synthetic estrogens, active pharmaceutical agents, dyes and colored lignin fragments, chemical warfare agents, persistent explosives residuals, pesticides, and colored and smelly pollutants from the pulp and paper industry. High performance disinfection of hardy pathogens including bacterial spores and clostridia has also been discovered. Students learn how to follow these processes using a range of analytical techniques.
|Years||Position or Degree|
|2010–present||Teresa Heinz Professor of Green Chemistry Carnegie Mellon University|
|2001–2010||Thomas Lord Professor of Chemistry, Carnegie Mellon University|
|1988–1992||Associate Professor of Chemistry, Carnegie Mellon University|
|1981–1987||Assistant Professor of Chemistry, California Institute of Technology|
|1978–1980||Postdoctoral Fellow, Stanford University|
|1978||Doctor of Philosophy, University of Auckland|
|1975||Master of Science with First Class Honors, University of Auckland|
|1974||Bachelor of Science, University of Auckland|
|2013||Fellow, American Chemical Society|
|2010||Heinz Award for the Environment|
|2008||Honorary Fellow of the Royal Society of New Zealand|
|2008||Charles E. Kaufman Award of the Pittsburgh Foundation|
|2007||Award of the New York Metropolitan Catalysis Society|
|2007||Distinguished Alumnus Award, University of Auckland, New Zealand|
|2006||Fellow of the International Union of Pure and Applied Chemists|
|2004||Pittsburgh Award of the American Chemical Society|
|2004||Award of the Baylor University ACS Students Affiliates for Outstanding Achievements in Green chemistry|
|2002||Golden Goggles Award, Middle Tennessee State University|
|2001||Honorary Professor, University of Auckland, 2001|
|1998||Presidential Green Chemistry Challenge Award|
|1997||Award of the Japanese Society of Pure and Applied Coordination Chemistry|
|1997||Award of the Japanese Society of Pure and Applied Coordination Chemistry|
|1986||Alfred P. Sloan Research Fellow|
|1985||Camille and Henry Dreyfus Teacher-Scholar|
Sustainable Chemistry: Addressing the challenges of low dose adverse effects by everyday-everywhere chemicals through remediation of contaminants and design of safe products
Genoa R. Warner and Terrence J. Collins, In Integrative Environmental Medicine, 2017, Aly Cohen, Frederick Vom Saal (Ed); Andrew Weil (Series Ed.), Oxford University Press, Oxford: 978-0-19-049091-1 (ISBN).
Homogeneous Catalysis Under Ultra-Dilute Conditions: TAML/NaClO Oxidation of Persistent Metaldehyde
Tang, Liang; DeNardo, Matthew; Schuler, Christopher; Mills, Matthew; Gayathri, Chakicherla; Gil, Roberto; Kanda, Rakesh; Collins, Terrence, J. Am. Chem. Soc., 2016, 139, pp 879–887. DOI: 10.1021/jacs.6b11145
Unifying Evaluation of the Technical Performances of Iron-Tetra-amido Macrocyclic Ligand Oxidation Catalysts
Matthew A. DeNardo, Matthew R. Mills, Alexander D. Ryabov, and Terrence J. Collins, J. Am. Chem. Soc., 2016, 138, pp 2933–2936 DOI: 10.1021/jacs.5b13087
NaClO-Generated Iron(IV)oxo and Iron(V)oxo TAMLs in Pure Water
Mills, Matthew; Weitz, Andrew; Hendrich, Michael; Ryabov, Alexander; Collins, Terrence; J. Am. Chem. Soc., 2016, 138 (42), pp 13866–13869, DOI: 10.1021/jacs.6b09572
Use of a Battery of Chemical and Ecotoxicological Methods for the Assessment of the Efficacy of Wastewater Treatment Processes to Remove Estrogenic Potency
Nicola Beresford, Alice Baynes, Rakesh Kanda, Matthew R. Mills, Karla Arias-Salazar, Terrence J. Collins, Susan Jobling, J. Vis. Exp. (115), e54243, doi:10.3791/54243 (2016).
Minireview: Endocrine Disruptors: Past Lessons and Future Directions
Thaddeus T. Schug, Anne F. Johnson, Linda S. Birnbaum, Theo Colborn, Louis J. Guillette, Jr David, Crews, Terry Collins, Ana M. Soto, Frederick S. vom Saal, John A. McLachlan, Carlos Sonnenschein, and Jerrold J. Heindel, Molecular Endocrinology, (2016) 30 (8): pp 833-847, DOI: 10.1210/me.2016-1096
Iron Species in the Catalytic Oxidation of NADH and a Dye by O2 in AOT Reverse Micelles
Liang L. Tang, Alexander D. Ryabov, and Terrence J. Collins, Kinetic Evidence for Reactive Dimeric TAML ACS Catal. 2016, 6, pp 3713–3718; DOI: 10.1021/acscatal.6b00787
Kinetic Evidence for Reactive Dimeric TAML Iron Species in the Catalytic Oxidation of NADH and a Dye by O2 in AOT Reverse Micelles
Liang L. Tang, Alexander D. Ryabov, and Terrence J. Collins, ACS Catal., 2016, 6, pp 3713–3718; DOI: 1021/acscatal.6b00787
TAML/H2O2 Oxidative Degradation of Metaldehyde: Pursuing Better Water Treatment for the Most Persistent Pollutants
Tang, Matthew A. DeNardo, Chakicherla Gayathri, Roberto R. Gil, Rakesh Kanda, and Terrence J. Collins, Environ. Sci. Technol. 2016, 50, pp 5261−5268; DOI: 10.1021/acs.est.5b05518
Removal of ecotoxicity of 17α-ethinylestradiol using TAML/ peroxide water treatment
M. R. Mills, K. Arias-Salazar, Alice Baynes, L. Q. Shen, J. Churchley, N. Beresford, C. Gayathri, R. G. Gil, R. Kanda, S. Jobling, T. J. Collins, Sci. Rep., 2015, 5, pp 10511 -10511,: doi: 10.1038/srep10511
“Beheaded” TAML Activator: A Compromised Catalyst that Emphasizes the Linearity between Catalytic Activity and pKa
Mills, Matthew; Weitz, Andrew; Zhang, David; Hendrich, Michael; Ryabov, Alexander; Collins, Terrence A, Inorg. Chem., 2016, 55 (23), pp 12263–12269, DOI: 10.1021/acs.inorgchem.6b01988
Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeIIIFeIV Dimer and Associated Catalytic Chemistry
L. L. Tang, W. A. Gunderson, A. C. Weitz, M. P. Hendrich, A. D. Ryabov, T. J. Collins, J. Am. Chem. Soc., 2015, 137 (30), pp 9704–9715.
Reactivity and operational stability of N-tailed (‘biuret’) TAMLs in water through kinetic studies of the catalyzed oxidation of Orange II by H2O2. Synthesis and X-ray structure of an N-phenyl biuret TAML
G. R. Warner, M. R. Mills, C. Enslin, S. Pattanayak, C. Panda, T. K. Panda, S. Sen Gupta, A. D. Ryabov, T. J. Collins, Chem. Eur. J., 2015, 21(16), pp 6226–6233 (cover art).
Review of the Twenty-two Year Evolution of the First University Course in Green Chemistry: teaching future leaders how to create sustainable human societies.
T. J. Collins, J. Cleaner Production, 2015, pp 1–18: http://dx.doi.org/10.1016/j.jclepro.2015.06.136
Activation Parameters as Mechanistic Probes in the TAML Iron(V)– Oxo Oxidations of Hydrocarbons
Soumen Kundu, Jasper Van Kirk Thompson, Longzhu Q. Shen, Matthew R. Mills, Emile L. Bominaar, Alexander D. Ryabov, and Terrence J. Collins, Chem. Eur. J. 2015 21(4):pp 1803-10. doi: 10.1002/chem.201405024.