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Manganese-Substituted α-Carbonic Anhydrase as an Enantioselective Peroxidase

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Book cover Bio-inspired Catalysts

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 25))

Abstract

Carbonic anhydrase binds a zinc ion in a hydrophobic active site using the imidazole groups of three histidine residues. The natural role of carbonic anhydrase is to catalyze the reversible hydration of carbon dioxide to bicarbonate, but it also catalyzes hydrolysis of esters with moderate enantioselectivity. Replacing the active-site zinc with manganese yielded manganese-substituted carbonic anhydrase (CA[Mn]), which shows peroxidase activity with a bicarbonate-dependent mechanism. In the presence of bicarbonate and hydrogen peroxide, CA[Mn] catalyzed the efficient oxidation of o-dianisidine with k cat /K M  = 1.4 × 106 M−1s−1, which is comparable to that for horseradish peroxidase, k cat /K M  = 57 × 106 M−1s−1. CA[Mn] also catalyzed the moderately enantioselective epoxidation of olefins to epoxides (E = 5 for p-chlorostyrene). This enantioselectivity is similar to that for natural heme-based peroxidases, but has the advantage that CA[Mn] avoids formation of aldehyde side products. CA[Mn] degrades during the epoxidation, limiting the yield of the epoxidations to <12%. Replacement of active-site residues Asn62, His64, Asn67, Gln92, or Thr200 with alanine by site-directed mutagenesis decreased the enantioselectivity showing that the active site controls enantioselectivity of the epoxidation.

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Abbreviations

Ala:

Alanine

Asn:

Asparagine

Asp:

Aspartic acid

BES:

N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid

CA:

Carbonic anhydrase

CA[Mn]:

Manganese-substituted bovine carbonic anhydrase mixture of isozymes

CAII[Mn]:

Manganese-substituted bovine carbonic anhydrase isoenzyme II

CiP:

Peroxidase from Coprinus cinereus

CPO:

Chloroperoxidase from Caldariomyces fumago

Mn:

Manganese

E :

Enantioselectivity

ee:

Enantiomeric excess

ESI-MS:

Electrospray ionization mass spectrometry

Gln:

Glutamine

Glu:

Glutamic acid

hCAII:

Human carbonic anhydrase isozyme II

His:

Histidine

HRP:

Horseradish peroxidase

ICP-AES:

Inductively coupled plasma atomic emission spectrometry

k cat :

Catalytic constant

K M :

Michaelis constant

Leu:

Leucine

PNPA:

4-Nitrophenyl acetate

Ser:

Serine

Trp:

Tryptophan

Thr:

Threonine

TOF:

Turnover frequency

TTN:

Total turnover number

Val:

Valine

VClPO:

Vanadium chloroperoxidase

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Author information

Authors and Affiliations

  1. Department of Biochemistry, Molecular Biology & Biophysics and the Biotechnology Institute, University of Minnesota, Saint Paul, MN 55108, USA, 1479 Gortner Avenue

    Qing Jing, Krzysztof Okrasa & Romas J Kazlauskas

Authors
  1. Qing Jing
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  2. Krzysztof Okrasa
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  3. Romas J Kazlauskas
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Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Basel, Townsville, Queensland, Australia

    Thomas R. Ward

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Jing, Q., Okrasa, K., Kazlauskas, R.J. (2009). Manganese-Substituted α-Carbonic Anhydrase as an Enantioselective Peroxidase. In: Ward, T.R. (eds) Bio-inspired Catalysts. Topics in Organometallic Chemistry, vol 25. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-87757-8_3

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