Abstract
Response surface methodology (RSM) was used to optimize the oxidizing the omeprazole sulfide to (S)-omeprazole catalyzed by environmentally friendly catalyst soybean pod peroxidase (SPP) in cetyltrimethylammonium bromide (CTAB)/isooctane/n-butyl alcohol/water water-in-oil microemulsions. With the initial concentration of SPP of 3200 U ml−1, the conversion of the omeprazole sulfide, the (S)-omeprazole yield and ee were 93.75%, 91.56% and 96.08%, respectively, under the optimal conditions: Wo of 15.85, the concentration of H2O2 of 22.44 mM and reaction temperature of 49.68 °C, respectively. The proposed mechanism of asymmetric sulfoxidations catalyzed by SPP involves three concomitant mechanisms as follows: (1) a two-electron reduction of SPP-I, (2) a single-electron transfer to SPP-I and (3) nonenzymatic reactions. Based on the proposed mechanism which is reasonable and can express the oxidations, the reaction system includes five enzymatic and two nonenzymatic reactions. With 5.44% of the average relative error, a kinetic model based on the mechanisms fitting observed data very well was established, and the SPP-catalyzed reactions including both the two-electron reduction and the single-electron transfer mechanisms obey ping-pong mechanism with substrate and product inhibition, while nonenzymatic reactions follow a power law. This study has also demonstrated the feasibility of SPP as a substitute with low cost, excellent enantioselectivity and better thermal stability.
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Abbreviations
- Sa :
-
Hydrogen peroxide
- A0 :
-
Initial concentration of hydrogen peroxide, mM
- Sb :
-
5-Methoxy-2-(((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)thio)-1H-benzoimidazole, Omeprazole thioether, 5-methoxy-2-(((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)thio)-1H-benzo[d]imidazole
- B0 :
-
Initial concentration of Sb, mM
- Sc :
-
Cation radical of Sb, Omeprazole sulfide cation
- E0 :
-
Initial concentration of peroxidase, U ml−1
- ee:
-
Enantiomeric excess, %
- K1, K10, K19 :
-
Kinetic parameter, dimensionless
- K2, K3, K6 :
-
Kinetic parameter, mM−1
- K4, K5, K7 :
-
Kinetic parameter, mM−2
- K8 :
-
Kinetic parameter, mM−3
- K9 :
-
Kinetic parameter, h−1 U−1 ml mM1−2K10
- K12, K14, K16 :
-
Kinetic parameter, h−1 U−1 ml mM−1
- K11, K13, K15, K17 :
-
Kinetic parameter, h−1 U−1 ml mM−2
- K18 :
-
Kinetic parameter, h−1 U−1 ml mM1−K19
- KK1 KK2:
-
∑K sum of Kappa constant, dimensionless
- PR :
-
(R)-enantiomer of P
- PS :
-
(S)-enantiomer of P, esomeprazole
- P:
-
5-Methoxy-2-[(4-methoxy-3,5-dimethylpyridin-2-yl) methylsulfinyl]-1H-benzoimidazole, Omeprazole
- Q:
-
H2O
- R:
-
Dication radical of Sb
- Wo:
-
Water/CTAB, mol
- Y(i):
-
Relative residual or yield of Sa, Sb, PS, PR, C and R, for i = 1–6, respectively, dimensionless
- Ysimulij :
-
Simulated residual or yield of Sa, Sb, PS and PR, for i = 1–4, j = 1–12, dimensionless
- Yexpi j :
-
Experimental residual or yield of Sa, Sb, PS and PR, for i = 1–4, j = 1–12, dimensionless
- T:
-
Time, hour
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Acknowledgements
This work was supported by the National Natural Science Foundation of China [Grant Numbers 21546004 and 21576145], China Scholarship Council (Grant Number: 201908370079) and Shandong Provincial Key R&D Program [Grant Numbers 2019GSF107027, 2019GNC106028 and 2019GSF107033].
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HT and YYZ designed and wrote the manuscript; YSD, DPL, ZYW, HLL, XG, FYW revised the manuscript.
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Tang, H., Zhang, Y., Deng, Y. et al. Optimization of Synthesis of (S)-Omeprazole Catalyzed by Soybean Pod Peroxidase in Water-in-Oil Microemulsions Using RSM. Catal Lett 152, 720–731 (2022). https://doi.org/10.1007/s10562-021-03681-x
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DOI: https://doi.org/10.1007/s10562-021-03681-x