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    This study introduces an electrochemical surface plasmon resonance (SPR) method for sensitive detection of redox processes. The technique enhances signal readout for low-concentration biomolecular assemblies and interfacial redox reactions.

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    Area of Science:

    • Electrochemistry
    • Surface Plasmon Resonance (SPR)
    • Biomolecular Assemblies

    Background:

    • Conventional SPR struggles with weak optical signals from low-concentration redox processes.
    • Detecting redox changes in molecular assemblies requires enhanced sensitivity and robustness.

    Purpose of the Study:

    • To develop an electrochemical SPR technique for improved detection of redox processes.
    • To optimize SPR signal readout for low-concentration biomolecular assemblies.

    Main Methods:

    • Combined cyclic voltammetry with wavelength/angle-tuned SPR.
    • Utilized a silver/gold bilayer electrode for enhanced signal.
    • Employed cytochrome c as a model redox probe.
    • Performed polarized angular reflectance and transfer-matrix calculations.

    Main Results:

    • Optimized SPR detection sensitivity by tuning excitation wavelength and refractive index.
    • Identified optimal detection within the SPR response linear region and at the redox probe's absorption band.
    • Achieved accurate, wavelength-dependent optical constants (552-785 nm).

    Conclusions:

    • The developed electrochemical SPR method enables highly sensitive detection of biomolecular assemblies.
    • Facilitates real-time probing of interfacial redox processes with enhanced sensitivity and electrochemical robustness.