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Noninvasive on-skin electrodes record the electrical potential changes from human skin, which reflect body condition and are applied for healthcare, sports management, and modern lifestyle. However, current on-skin electrodes have poor conformal properties under sweaty condition in real-life because of decreased electrode-skin adhesion with sweat film at the interface. Here, we fabricated biocomposite electrodes based on silk fibroin (SF) through interfacial polymerization, which is applicable on sweaty skin. Interfacial polymerized conductive polypyrrole (PPy) and SF are structurally interlocked and endow the whole electrode with uniform stretchability. Existence of water results in similar Young's modulus of SF to the skin and enhanced interfacial adhesion. It keeps the electrodes conformal to skin under sweaty condition and allows reliable collection of ambulatory electrophysiological signals during sports and sweating. Wearable devices with these electrodes were used to acquire continuous and stable real-time electrocardiography (ECG) signals during running for 2 h. The collected signals can provide information for sports management and are also analyzed by artificial intelligence to show their potential for intelligent human emotion monitoring. Our strategy provides opportunities to record long-term continuous electrophysiological signals in real-life conditions for various smart monitoring systems.

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