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Enzymatic and Non-Enzymatic Response during Nitrosative Stress in Escherichia coli

Rohan Nath
Rohan Nath
, 
Swarnab Sengupta
Swarnab Sengupta
 e 
Arindam Bhattacharjee
Arindam Bhattacharjee
   | 25 giu 2022
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Pubblicato online: 25 giu 2022
Pagine: 81 - 93
Ricevuto: 01 nov 2021
Accettato: 01 apr 2022
DOI: https://doi.org/10.2478/am-2022-0008
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© 2022 Rohan Nath et al., published by Sciendo
This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Fig. 1

Mechanism of action of flavohemoglobin under aerobic and anaerobic condition in presence of nitrating agentUnder aerobic condition Fe(II) present in Hmp remains associated with O2 to form Fe(II) O2 complex. Under nitrosative stress in presence of NO, it forms nitrosyldioxyl complex (Fe[II]OONO) and this complex ultimately breaks down to nitrate (NO3−) and heme group returns back to its original state [Fe(III)]. Under anaerobic condition, NO• reacts with Fe(II) and Fe(III)NO− is formed. Fe(III)NO− is again broken down to NO− and then it is converted to N2O via dimeric species.
Mechanism of action of flavohemoglobin under aerobic and anaerobic condition in presence of nitrating agentUnder aerobic condition Fe(II) present in Hmp remains associated with O2 to form Fe(II) O2 complex. Under nitrosative stress in presence of NO, it forms nitrosyldioxyl complex (Fe[II]OONO) and this complex ultimately breaks down to nitrate (NO3−) and heme group returns back to its original state [Fe(III)]. Under anaerobic condition, NO• reacts with Fe(II) and Fe(III)NO− is formed. Fe(III)NO− is again broken down to NO− and then it is converted to N2O via dimeric species.

Fig. 2

Mechanism of action of cytochrome c peroxidesSequential transformation of peroxynitrite (ONOO−) to nitrite NO2). The nitrite (NO2) formed by the action of Compound I (Cmpd I) diffuses out of the cell by the action of CompoundII (Cmpd II).
Mechanism of action of cytochrome c peroxidesSequential transformation of peroxynitrite (ONOO−) to nitrite NO2). The nitrite (NO2) formed by the action of Compound I (Cmpd I) diffuses out of the cell by the action of CompoundII (Cmpd II).

Fig. 3

Mechanism of action of flavorubredoxinNO• can be reduced to N2O by two mechanisms involving the [Fe2+-O-Fe2+]. (A) via formation of NO2−, (B) Formation of N2O from NO• via formation of [Fe3+-O-Fe3+-NO2−] as intermediate.
Mechanism of action of flavorubredoxinNO• can be reduced to N2O by two mechanisms involving the [Fe2+-O-Fe2+]. (A) via formation of NO2−, (B) Formation of N2O from NO• via formation of [Fe3+-O-Fe3+-NO2−] as intermediate.

Fig. 4

Mechanism of action of catalaseCatalase has the Fe(III) center which helps in quenching of nitric oxide and peroxynitrite. When catalase encounters NO•, Compound I ([Cat-Fe(IV) = O]+·) is formed due to oxidation by NO•. When such Compound I again reacts with another NO•, nitrite (NO2−) is formed as end product. On the other hand, when catalase encounters peroxynitrite ((ONOOH), Compound II ([Cat-Fe(IV) = O+·NO2]) is formed which breaks down to nitrite (NO3−).
Mechanism of action of catalaseCatalase has the Fe(III) center which helps in quenching of nitric oxide and peroxynitrite. When catalase encounters NO•, Compound I ([Cat-Fe(IV) = O]+·) is formed due to oxidation by NO•. When such Compound I again reacts with another NO•, nitrite (NO2−) is formed as end product. On the other hand, when catalase encounters peroxynitrite ((ONOOH), Compound II ([Cat-Fe(IV) = O+·NO2]) is formed which breaks down to nitrite (NO3−).

Fig. 5

Mechanism of action of CuZn-SOD(1) Generation of superoxide (O2−) from oxygen by the addition of one electron. (2) The formed superoxide is used up by Cu2+Zn2+SOD where Cu2+ is reduced to Cu+ with the formation of molecular oxygen (O2). The reduced Cu+ of CuZn-SOD is again oxidized to Cu2+ with the formation of H2O2. In this way CuZn-SOD inhibits the formation of ONOO− from NO and O2−.
Mechanism of action of CuZn-SOD(1) Generation of superoxide (O2−) from oxygen by the addition of one electron. (2) The formed superoxide is used up by Cu2+Zn2+SOD where Cu2+ is reduced to Cu+ with the formation of molecular oxygen (O2). The reduced Cu+ of CuZn-SOD is again oxidized to Cu2+ with the formation of H2O2. In this way CuZn-SOD inhibits the formation of ONOO− from NO and O2−.

Fig. 6

Mechanism of action of cytochrome c nitrite reductaseCytochrome c nitrite reductase encounter NO• and {FeNO}6 is formed with the removal of water, followed by the formation of {FeNO}8 by removing 2 electrons. After that Fe(II)-HNO complex is formed which reduced to hydroxylamine (NH2OH). Hydroxylamine is again reduced to ammonia (NH3).
Mechanism of action of cytochrome c nitrite reductaseCytochrome c nitrite reductase encounter NO• and {FeNO}6 is formed with the removal of water, followed by the formation of {FeNO}8 by removing 2 electrons. After that Fe(II)-HNO complex is formed which reduced to hydroxylamine (NH2OH). Hydroxylamine is again reduced to ammonia (NH3).

Fig. 7

Predicted mechanism of action of hybrid cluster proteinThis predicted figure shows the mode of action of Hcp via two different mechanisms. In one pathway, the [4Fe2+-2S-2O] containing Hcp can react with NO and Fe2+ is oxidized to Fe3+with the formation of NO2−. NO2− can again react with another NO2− and N2O is formed as the end product. In another mechanism, [2Fe2+−2S] containing Hcp can react with NO and NH2OH (hydroxylamine) is formed which may get converted to ammonia (NH3). In this reaction also Fe2+ is oxidized to Fe3+ but it can again come back to its normal state.
Predicted mechanism of action of hybrid cluster proteinThis predicted figure shows the mode of action of Hcp via two different mechanisms. In one pathway, the [4Fe2+-2S-2O] containing Hcp can react with NO and Fe2+ is oxidized to Fe3+with the formation of NO2−. NO2− can again react with another NO2− and N2O is formed as the end product. In another mechanism, [2Fe2+−2S] containing Hcp can react with NO and NH2OH (hydroxylamine) is formed which may get converted to ammonia (NH3). In this reaction also Fe2+ is oxidized to Fe3+ but it can again come back to its normal state.

Fig. 8

Basic working principle of GSH under nitrosative stressUnder normal physiological condition, GGSG (oxidized glutathione) converts to GSH (reduced glutathione) by the action of GRX (glutaredoxin). Under nitrosative stress, GSH reacts with NO and stores the NO in the form of GSNO. It can again be transported outside the cell via GSH transporter or GSNO can be broken down to GSSG by the activity of GSNOR (blue arrow).
Basic working principle of GSH under nitrosative stressUnder normal physiological condition, GGSG (oxidized glutathione) converts to GSH (reduced glutathione) by the action of GRX (glutaredoxin). Under nitrosative stress, GSH reacts with NO and stores the NO in the form of GSNO. It can again be transported outside the cell via GSH transporter or GSNO can be broken down to GSSG by the activity of GSNOR (blue arrow).
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