Issue 1, 2024

The enhanced electrocatalytic performance of nanoscopic Cu6Pd12Fe12 heterometallic molecular box encaged cytochrome c

Abstract

Designing molecular cages for atomic/molecular scale guests is a special art used by material chemists to harvest the virtues of the otherwise vile idea known as “the cage”. In recent years, there has been a notable surge in research investigations focused on the exploration and utilization of the distinct advantages offered by this art in the advancement of efficient and stable bio-electrocatalysts. This usually is achieved through encapsulation of biologically accessible redox proteins within specifically designed molecular cages and matrices. Herein, we present the first successful method for encaging cytochrome c (Cyt-c), a clinically significant enzyme system, inside coordination-driven self-assembled Cu6Pd12Fe12 heterometallic hexagonal molecular boxes (Cu-HMHMB), in order to create a Cyt-c@Cu-HMHMB composite. 1H NMR, FTIR, and UV-Vis spectroscopy, ICP-MS, TGA and voltammetric investigations carried out on the so-crafted Cyt-c@Cu-HMHMB bio-inorganic composite imply that the presented strategy ensures encaging of Cyt-c in a catalytically active, electrochemically stable and redox-accessible state inside the Cu-HMHMB. Cyt-c@Cu-HMHMB is demonstrated to exhibit excellent stability and electrocatalytic activity toward very selective, sensitive electrochemical sensing of nitrite exhibiting a limit of detection as low as 32 nanomolar and a sensitivity of 7.28 μA μM−1 cm−2. Importantly, Cyt-c@Cu-HMHMB is demonstrated to exhibit an excellent electrocatalytic performance toward the 4ē pathway oxygen reduction reaction (ORR) with an onset potential of 0.322 V (vs. RHE) and a Tafel slope of 266 mV dec−1. Our findings demonstrate that Cu-HMHMB is an excellent matrix for Cyt-c encapsulation. We anticipate that the entrapment-based technique described here will be applicable to other enzyme systems and Cyt-c for various electrochemical and other applications.

Graphical abstract: The enhanced electrocatalytic performance of nanoscopic Cu6Pd12Fe12 heterometallic molecular box encaged cytochrome c

Supplementary files

Article information

Article type
Paper
Submitted
15 Jūl. 2023
Accepted
16 Nov. 2023
First published
16 Nov. 2023

Nanoscale, 2024,16, 411-426

The enhanced electrocatalytic performance of nanoscopic Cu6Pd12Fe12 heterometallic molecular box encaged cytochrome c

S. Nabi, F. A. Sofi, Q. Jan, A. Y. Bhat, P. P. Ingole, M. Bayati and M. A. Bhat, Nanoscale, 2024, 16, 411 DOI: 10.1039/D3NR03451H

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