Journal of the American Chemical Society
Page 12 of 15
constants of TAML activators relative to the peroxidase enzymes
(5) Chahbane, N.; Popescu, D.ꢀL.; Mitchell, D. A.; Chanda, A.;
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Lenoir, D.; Ryabov, A. D.; Schramm, K.ꢀW.; Collins, T. J. Green
Chem. 2007, 9, 49ꢀ57.
is academically enticing. However, in comparing the utility of
TAML activators and peroxidases, it is important to recognize
that a typical TAML activator enjoys a large advantage in terms
of atom economy, comprising ~1% the mass of HRP, a particularꢀ
(
6) Collins, T. J.; GordonꢀWylie, S. W.; Horwitz, C. P. 2000,
30
U.S. 5,847,120.
ly light peroxidase enzyme.
Third, since both catalyst inactivation (k ) and the activation of
(7) Chanda, A.; Ryabov, A. D.; Mondal, S.; Alexandrova, L.;
Ghosh, A.; HangunꢀBalkir, Y.; Horwitz, C. P.; Collins, T. J. Chem.
Eur. J. 2006, 12, 9336ꢀ9345.
i
peroxide (k ) vary directly with substrate oxidation (k ), k and k
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are also directly proportional. Again, at neutral pH catalyst activaꢀ
tion is typically rate determining in TAML processes. Here too,
activators capable of greater overall rates of substrate oxidation
controlled by the catalyst activation step display proportionally
increased rates of inactivation providing further evidence that all
three proportionalities derive from a common electronic origin.
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(
8) Mills, M. R.; AriasꢀSalazar, K.; Baynes, A.; Shen, L. Q.;
Churchley, J.; Beresford, N.; Gayathri, C.; Gil, R. R.; Kanda, R.;
Jobling, S.; Collins, T. J. Scientific Reports 2015, 5, 10511.
(
9) Kundu, S.; Chanda, A.; Thompson, J. V. K.; Diabes, G.;
In conclusion, this general evaluation of peroxide oxidation proꢀ
cesses delivers considerable insight into how TAML catalysis
works. The study exemplifies the wellꢀestablished approach of
using knowledge of the key rate constants, k , k and k here, that
Khetan, S. K.; Ryabov, A. D.; Collins, T. J. Catal. Sci. Technol. 2015,
5, 1775ꢀ1782.
(10) Kundu, S.; Chanda, A.; Khetan, S. K.; Ryabov, A. D.;
Collins, T. J. Env. Sci. Technol. 2013, 47, 5319ꢀ5326.
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we call “technical performance parameters”, to generate robust
LFER analyses that give valuable insight into the forces underlyꢀ
ing each while bolstering the limited literature of catalyst inactivaꢀ
(
11) Kundu, S.; Chanda, A.; EspinosaꢀMarvan, L.; Khetan, S.
1
K.; Collins, T. J. Catal. Sci. Technol. 2012, 2, 1165ꢀ1172.
tion. In principle, this approach could have wider utility for probꢀ
ing the reactivity of other synthetic catalysts in oxidation, reducꢀ
tion or other processes.
(
12) Shen, L. Q.; Beach, E. S.; Xiang, Y.; Tshudy, D. J.; Khaniꢀ
na, N.; Horwitz, C. P.; Bier, M. E.; Collins, T. J. Env. Sci. Technol.
011, 45, 7882ꢀ7887.
2
ASSOCIATED CONTENT
(
13) Beach, E. S.; Malecky, R. T.; Gil, R. R.; Horwitz, C. P.;
Supporting Information is available free of charge on the ACS
publications website at http://pubs.acs.org.
Collins, T. J. Catal. Sci. Technol. 2011, 1, 437ꢀ443.
(14) Beach, E. S.; Duran, J. L.; Horwitz, C. P.; Collins, T. J.
Ind. Eng. Chem. Res. 2009, 48, 7072ꢀ7076.
Synthesis of 4; details of kinetic data collection.
AUTHOR INFORMATION
(
15) Chanda, A.; Khetan, S. K.; Banerjee, D.; Ghosh, A.; Colꢀ
lins, T. J. J. Am. Chem. Soc. 2006, 128, 12058ꢀ12059.
Corresponding Authors
(
16) Banerjee, D.; Markley, A. L.; Yano, T.; Ghosh, A.; Berget,
tc1u@andrew.cmu.edu; ryabov@andrew.cmu.edu
P. B.; Minkley, E. G.; Khetan, S. K.; Collins, T. J. Angew. Chem. Int.
Ed. 2006, 45, 3974ꢀ3977.
Notes
The authors declare no competing financial interests.
(17) Gupta, S. S.; Stadler, M.; Noser, C. A.; Ghosh, A.; Steinꢀ
hoff, B.; Lenoir, D.; Horwitz, C. P.; Schramm, K.ꢀW.; Collins, T. J.
Science 2002, 296, 326ꢀ328.
ACKNOWLEDGMENTS
TJC thanks the Heinz Endowments for funding. MRM is a CMU
(18) Emelianenko, M.; Torrejon, D.; Denardo, M. A.; Ryabov,
A. D.; Collins, T. J. J. Math. Chem. 2014, 52, 1460ꢀ1476.
1
Presidential Fellow. The H NMR spectrometers of the Departꢀ
ment of Chemistry NMR Facility were purchased in part with
funds from the NSF (CHEꢀ0130903).
(
19) Warner, G. R.; Mills, M. R.; Enslin, C.; Pattanayak, S.;
Panda, C.; Panda, T. K.; Gupta, S. S.; Ryabov, A. D.; Collins, T. J.
Chem. Eur. J. 2015, 21, 6226ꢀ6233.
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Ryabov, A. D.; Collins, T. J. J. Am. Chem. Soc. 2009, 131, 18052ꢀ
8053.
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