In this work, we examined the electrochemical behaviour of Cyt c and Zn Porph pre-and postconjugation to AuNPs. We determined that structural modifications in Cyt c, arising from its conjugation to AuNPs, brought about significant alterations in secondary and tertiary structures, with thiol-PEG-carboxyl functionalized AuNPs inducing the least changes. The structural modifications appear to be determined by either the proximity of Cyt c to the AuNP or the packing density. Surprisingly, covalent conjugation methods, which were expected to significantly alter the structure of Cyt c due to stronger bonding, caused less structural change than AuNP-MUA-Cyt c Ox electrostatic conjugation. ToF-SIMS confirmed that the conjugation method did not significantly impact the orientation of Cyt c. Instead, the ligand used in the conjugation process largely dictated This was necessary due to the complex shape of the voltammogram. DPV experiments were conducted on PBS (25 mM) and AuNPs, which did not show significant peaks. Therefore, any deviations from the DPV shape of PBS and AuNPs were attributed to the conjugated molecules. The DPVs were plotted in OriginPro (2018) (Figure SI 3A) and peak analysis was performed by selecting the "Peak Analyzer" from the "Analysis" tab. "Subtract Baseline" and "User-Defined Baseline Mode" were selected, and the 1st and 2nd derivatives were chosen as the methods for finding anchor points. Adjacent-averaging smoothing was used with a window size of 3, threshold of 0.05, and 8