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Boronic Acid-Functionalized MOFs Enable Ultrasensitive Proteomic Profiling of Ultratrace Plasma for Triple-Negative
Shuang Zhang1,2, Zhixiao Xu1,2, Haoni Yan1
1Department of Anesthesiology and Surgical Intensive Care Unit, Xinhua Hospital, School of Medicine and School of Biomedical Engineering, Shanghai Jiao Tong University, Shanghai200030, People's Republic of China.
Abstract:
Blood-based proteomics holds great promise for noninvasive disease diagnostics, yet remains constrained by large sample requirements, laborious preprocessing, and limited sensitivity. Here, we present a streamlined workflow for ultratrace plasma sample proteomics (UPSP) utilizing boronic acid-functionalized metal-organic frameworks (MOFs) that enable efficient protein enrichment from just 1 μL plasma through synergistic nitrogen-boronate complexation, cation-π interaction, and O-Eu coordination. UPSP eliminates the need for high-abundance protein depletion and peptide fractionation, achieving robust and reproducible quantification of over 500 proteins per microliter with high interassay precision (R2 = 0.986) and low variability (CV < 20% for >65% of proteins). We demonstrate the utility of UPSP in a clinical context by profiling plasma from triple-negative breast cancer (TNBC) and healthy controls. Integrated with machine learning, the platform achieved a diagnostic accuracy of 0.93 for TNBC. UPSP provides a versatile and scalable platform for deep proteome profiling of trace-volume biospecimens, with broad applicability in biomarker discovery, longitudinal monitoring, and scarce-sample scenarios.