PMID- 35527726
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20220716
IS  - 2046-2069 (Electronic)
IS  - 2046-2069 (Linking)
VI  - 12
IP  - 21
DP  - 2022 Apr 28
TI  - Oxidative dehalogenation of trichlorophenol catalyzed by a promiscuous artificial 
      heme-enzyme.
PG  - 12947-12956
LID - 10.1039/d2ra00811d [doi]
AB  - The miniaturized metalloenzyme Fe(iii)-mimochrome VI*a (Fe(iii)-MC6*a) acts as an 
      excellent biocatalyst in the H(2)O(2)-mediated oxidative dehalogenation of the 
      well-known pesticide and biocide 2,4,6-trichlorophenol (TCP). The artificial 
      enzyme can oxidize TCP with a catalytic efficiency (k (cat)/K (TCP) (m) = 150 000 
      mM(-1) s(-1)) up to 1500-fold higher than the most active natural metalloenzyme 
      horseradish peroxidase (HRP). UV-visible and EPR spectroscopies were used to 
      provide indications of the catalytic mechanism. One equivalent of H(2)O(2) fully 
      converts Fe(iii)-MC6*a into the oxoferryl-porphyrin radical cation intermediate 
      [(Fe(iv)[double bond, length as m-dash]O)por (+)], similarly to peroxidase 
      compound I (Cpd I). Addition of TCP to Cpd I rapidly leads to the formation of 
      the corresponding quinone, while Cpd I decays back to the ferric resting state in 
      the absence of substrate. EPR data suggest a catalytic mechanism involving two 
      consecutive one-electron reactions. All results highlight the value of the 
      miniaturization strategy for the development of chemically stable, highly 
      efficient artificial metalloenzymes as powerful catalysts for the oxidative 
      degradation of toxic pollutants.
CI  - This journal is (c) The Royal Society of Chemistry.
FAU - Zambrano, Gerardo
AU  - Zambrano G
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
FAU - Sekretareva, Alina
AU  - Sekretareva A
AUID- ORCID: 0000-0001-7312-0116
AD  - Department of Chemistry - Angstrom, Uppsala University Lagerhyddsvagen 1 75120 
      Uppsala Sweden.
FAU - D'Alonzo, Daniele
AU  - D'Alonzo D
AUID- ORCID: 0000-0002-2857-8600
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
FAU - Leone, Linda
AU  - Leone L
AUID- ORCID: 0000-0001-7293-1814
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
FAU - Pavone, Vincenzo
AU  - Pavone V
AUID- ORCID: 0000-0001-6432-0802
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
FAU - Lombardi, Angela
AU  - Lombardi A
AUID- ORCID: 0000-0002-2013-3009
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
FAU - Nastri, Flavia
AU  - Nastri F
AUID- ORCID: 0000-0002-3390-9822
AD  - Department of Chemical Sciences, University of Napoli Federico II Via Cintia 
      80126 Napoli Italy flavia.nastri@unina.it +39-081674090 +39-081674419.
LA  - eng
PT  - Journal Article
DEP - 20220504
PL  - England
TA  - RSC Adv
JT  - RSC advances
JID - 101581657
PMC - PMC9067433
COIS- The authors declare no conflict of interest. The funders had no role in the 
      design of the study; in the collection, analyses, or interpretation of data; in 
      the writing of the manuscript, or in the decision to publish the results.
EDAT- 2022/05/10 06:00
MHDA- 2022/05/10 06:01
PMCR- 2022/05/04
CRDT- 2022/05/09 03:46
PHST- 2022/02/07 00:00 [received]
PHST- 2022/04/13 00:00 [accepted]
PHST- 2022/05/09 03:46 [entrez]
PHST- 2022/05/10 06:00 [pubmed]
PHST- 2022/05/10 06:01 [medline]
PHST- 2022/05/04 00:00 [pmc-release]
AID - d2ra00811d [pii]
AID - 10.1039/d2ra00811d [doi]
PST - epublish
SO  - RSC Adv. 2022 May 4;12(21):12947-12956. doi: 10.1039/d2ra00811d. eCollection 2022 
      Apr 28.