Role of distal arginine residue in the mechanism of heme nitrite reductases

Sarkar, Ankita; Bhakta, Snehadri; Chattopadhyay, S; Dey, Abhishek

doi:10.1039/d3sc01777j

“…Heme nitrite reductase produces NO and ammonium ion and is a key enzyme of nitrogen cycle. Recently, an arginine residue was reported to assist substrate binding and donate a proton during the catalysis [167].…”

Section: Arginine In the Active Sites Of Enzymesmentioning

confidence: 99%

Biological importance of arginine: A comprehensive review of the roles in structure, disorder, and functionality of peptides and proteins

Gupta,

Uversky

2024

International Journal of Biological Macromolecules

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Pendant Proton‐Relays Systematically Tune the Rate and Selectivity of Electrocatalytic Ammonia Generation in a Fe‐Porphyrin Based Metal–Organic Framework

Ghatak,

Shanker,

Sappati

et al. 2024

Angewandte Chemie

0

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Electrocatalytic nitrite reduction (eNO2RR) is a promising alternative route to produce ammonia (NH3). Until now, several molecular catalysts have shown capability to homogeneously reduce nitrite to NH3, while taking advantage of added secondary‐sphere functionalities to direct catalytic performance. Yet, realizing such control over heterogeneous electrocatalytic surfaces remains a challenge. Herein, we demonstrate that heterogenization of a Fe‐porphyrin molecular catalyst within a 2D Metal‐Organic Framework (MOF), allows efficient eNO2RR to NH3. On top of that, installation of pendant proton relaying moieties proximal to the catalytic site, resulted in significant improvement in catalytic activity and selectivity. Notably, systematic manipulation of NH3 faradaic efficiency (up to 90%) and partial current (5‐fold increase) was achieved by varying the proton relay‐to‐catalyst molar ratio. Electrochemical and spectroscopic analysis show that the proton relays simultaneously aid in generating and stabilizing of reactive Fe‐bound NO intermediate. Thus, this concept offers new molecular tools to tune heterogeneous electrocatalytic systems.

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Pendant Proton‐Relays Systematically Tune the Rate and Selectivity of Electrocatalytic Ammonia Generation in a Fe‐Porphyrin Based Metal–Organic Framework

Ghatak,

Shanker,

Sappati

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

Electrocatalytic nitrite reduction (eNO2RR) is a promising alternative route to produce ammonia (NH3). Until now, several molecular catalysts have shown capability to homogeneously reduce nitrite to NH3, while taking advantage of added secondary‐sphere functionalities to direct catalytic performance. Yet, realizing such control over heterogeneous electrocatalytic surfaces remains a challenge. Herein, we demonstrate that heterogenization of a Fe‐porphyrin molecular catalyst within a 2D Metal‐Organic Framework (MOF), allows efficient eNO2RR to NH3. On top of that, installation of pendant proton relaying moieties proximal to the catalytic site, resulted in significant improvement in catalytic activity and selectivity. Notably, systematic manipulation of NH3 faradaic efficiency (up to 90%) and partial current (5‐fold increase) was achieved by varying the proton relay‐to‐catalyst molar ratio. Electrochemical and spectroscopic analysis show that the proton relays simultaneously aid in generating and stabilizing of reactive Fe‐bound NO intermediate. Thus, this concept offers new molecular tools to tune heterogeneous electrocatalytic systems.

show abstract

Role of distal arginine residue in the mechanism of heme nitrite reductases

Abstract: Heme nitrite reductases reduce NO2- by e-/2H+ to NO or by 6e-/8H+ to NH4+ which are key steps in the global nitrogen cycle. The 2nd sphere residues like Arginine (with...

Cited by 3 publications

References 73 publications

Biological importance of arginine: A comprehensive review of the roles in structure, disorder, and functionality of peptides and proteins

Biological importance of arginine: A comprehensive review of the roles in structure, disorder, and functionality of peptides and proteins

Pendant Proton‐Relays Systematically Tune the Rate and Selectivity of Electrocatalytic Ammonia Generation in a Fe‐Porphyrin Based Metal–Organic Framework

Pendant Proton‐Relays Systematically Tune the Rate and Selectivity of Electrocatalytic Ammonia Generation in a Fe‐Porphyrin Based Metal–Organic Framework

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