isopenicillin n synthase – proposed mechanism

1
HN S H COOH HN AA O O H H Fe 2+ His Asp His H 2 O G ln Fe 2+ His Asp His H 2 O OH 2 + ACV + O 2 HN S H COOH HN AA O O H H Fe 3+ His Asp His H 2 O O O N S H COOH HN AA O O H Fe 2+ His Asp His H 2 O O OH HN S H COOH HN AA O O H Fe 3+ His Asp His H 2 O O OH H N S H COOH HN AA O O H Fe 4+ His Asp His H 2 O O N S COOH HN AA O O H Fe 3+ His Asp His H 2 O OH N S COOH HN AA O O H Fe 2+ His Asp His H 2 O OH -IPN A B C D E F G H -H 2 O -H 2 O Isopenicillin N Synthase – Proposed Mechanism Trapped in year 2 Trapped in year 1 0 0.06 0.1 300 400 500 600 700 Wavelength (nm) A Fe(IV )-Oxo Fe(III)- Superoxo Velocity (mm/s) Spectroscopic Properties of the C-H Cleaving Intermediates

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Isopenicillin N Synthase – Proposed Mechanism. Trapped in year 2. Spectroscopic Properties of the C-H Cleaving Intermediates. Fe(IV)-Oxo. Fe(III)- Superoxo. Velocity (mm/ s ). Trapped in year 1. - PowerPoint PPT Presentation

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Page 1: Isopenicillin  N  Synthase – Proposed Mechanism

HNS

H COOH

HN

AA

O

OH

HFe2+

HisAsp

His

H2O

GlnFe2+

HisAsp

His

H2O

OH2 + ACV + O2HN

S

HCOOH

HN

AAO

OH

HFe3+

HisAsp

His

H2OO O

NS

HCOOH

HN

AAO

OH

Fe2+

HisAsp

His

H2OO OH

HNS

HCOOH

HN

AAO

OH

Fe3+

HisAsp

His

H2OO OH

HNS

HCOOH

HN

AAO

OH

Fe4+

HisAsp

His

H2O O

NS

COOH

HN

AAO

OH

Fe3+

HisAsp

His

H2O OH

NS

COOH

HN

AAO

OH

Fe2+

HisAsp

His

H2OOH

- IPNA B C

D

EFG

H

- H2O

- H2O

Isopenicillin N Synthase – Proposed Mechanism

Trapped in year 2

Trapped in year 1

0

0.06

0.1

300 400 500 600 700

2H-ACV zeroed

2.5ms20ms100ms200ms2s

Wavelength (nm)

Absorbance

Fe(IV)-Oxo

Fe(III)-Superoxo

Velocity (mm/s)

Spectroscopic Properties of the C-H Cleaving Intermediates