PO Elementary Steps

Table I. Selected Elementary Steps of the PO Reaction.

Elementary Step
Rate Equation
Rate Constant

Included in BFSO

1. NADH + O₂ + H⁺ à NAD^· + H₂O₂ k₁[NADH][O₂] 3.0 M^-1s^-1

2. H₂O₂ + Per³⁺ à coI k₂[H₂O₂][Per³⁺] 1.8 × 10⁷ M^-1s^-1

3a. coI + NADH à coII + NAD^· k_3a[coI][NADH] 4.0 × 10⁴ M^-1s^-1

3b. coII + NADH à Per³⁺ + NAD^· k_3b[coII][NADH] 2.6 × 10⁴ M^-1s^-1

4. NAD^· + O₂ à NAD⁺ + O₂^- k₄[NAD^·][O₂] 2.0 × 10⁷ M^-1s^-1

5a. O₂^- + Per³⁺ à coIII k_5a[O₂^-][Per³⁺] 1.7 × 10⁷ M^-1s^-1

5b. 2O₂^-+2H⁺ à H₂O₂ + O₂ k_5b[O₂^-]² 2.0 × 10⁷ M^-1s^-1

6. coIII + NAD^· à coI + NAD⁺ k₆[coIII][NAD^·] Variable^a

7. NADH_stock à NADH(liquid) k₇[NADH]_stock Variable^b

8. NADH + O₂^- à NAD^· + H₂O₂ k₈ [NADH][O₂^-] 3.0 × 10² M^-1s^-1

9a, 9b. O₂(gas) à
ß O₂(liquid) k_9a[O₂]_eq - k_-9b[O₂] Variable^c

10. 2NAD^· à (NAD)₂ k₁₀[NAD^·]² Variable ^d

11. Per^{3 +}+NAD^· à Per²⁺ + NAD⁺ k₁₁[Per³⁺][NAD^·] 1.8 × 10⁶ M^-1s^-1

12. Per²⁺ + O₂ à coIII k₁₂[Per²⁺][O₂] 1.0 × 10⁵ M^-1s^-1

Not Included in BFSO

14. coIII à coII + H₂O₂ k₁₄[coIII] 2.0 × 10^-3s^-1

15. Per³⁺ + O₂^- à Per³⁺ + O₂^- k₁₅[coIII] 2.2 × 10^-3s^-1

Notes:
a. DCP Simulations: k₆ = 1.2-2.25 × 10⁸ M^-1s^-1. NADH Input Simulations: k₆ = 9 × 10⁷ M^-1s^-1.
b. DCP Simulations: k₇[NADH]_liq = 1.143 × 10^-7 Ms^-1. NADH Input Simulations: k₇ [NADH]_liq = 1.0-1.32 × 10^-7 Ms^-1.
c. DCP Simulations: k_9a = 7.3 × 10^-5 Ms^-1; k_9b = 3.73 × 10^-3 s^-1; O₂(gas) = 855 mM. NADH Input Simulations: k_9a = 7.2 × 10^-5 Ms^-1; k_9b = 6.0 × 10^-3 s^-1; O₂(gas) = 1000 mM.
d. DCP Simulations and "Low pH" NADH Input Simulations: k₁₀ = 10⁸ M^-1s^-1. "High" pH NADH Input Simulations: k₁₀ = 6 × 10⁷ M^-1s^-1.

Elementary Step			Rate Equation	Rate Constant
Included in BFSO
1. NADH + O₂ + H⁺	à	NAD^· + H₂O₂	k₁[NADH][O₂]	3.0 M^-1s^-1
2. H₂O₂ + Per³⁺	à	coI	k₂[H₂O₂][Per³⁺]	1.8 × 10⁷ M^-1s^-1
3a. coI + NADH	à	coII + NAD^·	k_3a[coI][NADH]	4.0 × 10⁴ M^-1s^-1
3b. coII + NADH	à	Per³⁺ + NAD^·	k_3b[coII][NADH]	2.6 × 10⁴ M^-1s^-1
4. NAD^· + O₂	à	NAD⁺ + O₂^-	k₄[NAD^·][O₂]	2.0 × 10⁷ M^-1s^-1
5a. O₂^- + Per³⁺	à	coIII	k_5a[O₂^-][Per³⁺]	1.7 × 10⁷ M^-1s^-1
5b. 2O₂^-+2H⁺	à	H₂O₂ + O₂	k_5b[O₂^-]²	2.0 × 10⁷ M^-1s^-1
6. coIII + NAD^·	à	coI + NAD⁺	k₆[coIII][NAD^·]	Variable^a
7. NADH_stock	à	NADH(liquid)	k₇[NADH]_stock	Variable^b
8. NADH + O₂^-	à	NAD^· + H₂O₂	k₈ [NADH][O₂^-]	3.0 × 10² M^-1s^-1
9a, 9b. O₂(gas)	à ß	O₂(liquid)	k_9a[O₂]_eq - k_-9b[O₂]	Variable^c
10. 2NAD^·	à	(NAD)₂	k₁₀[NAD^·]²	Variable ^d
11. Per^{3 +}+NAD^·	à	Per²⁺ + NAD⁺	k₁₁[Per³⁺][NAD^·]	1.8 × 10⁶ M^-1s^-1
12. Per²⁺ + O₂	à	coIII	k₁₂[Per²⁺][O₂]	1.0 × 10⁵ M^-1s^-1
Not Included in BFSO
14. coIII	à	coII + H₂O₂	k₁₄[coIII]	2.0 × 10^-3s^-1
15. Per³⁺ + O₂^-	à	Per³⁺ + O₂^-	k₁₅[coIII]	2.2 × 10^-3s^-1
Notes: a. DCP Simulations: k₆ = 1.2-2.25 × 10⁸ M^-1s^-1. NADH Input Simulations: k₆ = 9 × 10⁷ M^-1s^-1. b. DCP Simulations: k₇[NADH]_liq = 1.143 × 10^-7 Ms^-1. NADH Input Simulations: k₇ [NADH]_liq = 1.0-1.32 × 10^-7 Ms^-1. c. DCP Simulations: k_9a = 7.3 × 10^-5 Ms^-1; k_9b = 3.73 × 10^-3 s^-1; O₂(gas) = 855 mM. NADH Input Simulations: k_9a = 7.2 × 10^-5 Ms^-1; k_9b = 6.0 × 10^-3 s^-1; O₂(gas) = 1000 mM. d. DCP Simulations and "Low pH" NADH Input Simulations: k₁₀ = 10⁸ M^-1s^-1. "High" pH NADH Input Simulations: k₁₀ = 6 × 10⁷ M^-1s^-1.