Re-entrant Bottom-up Filled Copper Nanowires Array for Triphase-assisted Electrochemical Sensing Hayeon Kim Fiber System Engineering Major Department of Fiber System Engineering Graduate School, Dankook University Advisor:Professor Kayoung Kim Quant...
Re-entrant Bottom-up Filled Copper Nanowires Array for Triphase-assisted Electrochemical Sensing Hayeon Kim Fiber System Engineering Major Department of Fiber System Engineering Graduate School, Dankook University Advisor:Professor Kayoung Kim Quantitative analyses of neurofilament lights (NfLs) and amyloid-β peptide1–40 (Aβ40) as diagnostic blood biomarkers are highly demanding for the assessment of Alzheimer’s disease (AD) patients in primary care settings. Here, I report stimuli-resistant nanowire arrays with tightly integrated solid–liquid–gas phases for the reliable photocathodic detection of both Nfls and Aβ40 in blood plasma. To achieve the resilient triple phase interfaces within the copper nanowire arrays (CuNWA), the wedge-shaped nanowire arrays featuring broad wire tops and tapered narrow bases was synthesized using bottom- up filling and area-selective pulse electrodeposition method. I systematically investigated the optimized synthesis parameters for forming the wedge-shaped architecture, including duty cycle, concentration of Cu2+ ion , and total pulse-on time. Multifaceted analyses including the Laplace pressure calculation and Young-Lippmann analyses revealed that the wedge-shaped CuNWA (W-CuNWA) retained the liquid–gas meniscus more effectively than the cylindrical architecture, when exposed to liquids of different surface tensions and to harsh electrochemical stress such as sustained current flow for 4 h and 500 repetitive voltage scanning. The results were attributed to the large ratio of the liquid– solid contact-line to the liquid–gas interfacial area in the wedge-shaped architecture, which effectively prevented the liquid flooding. The stabilized solid–liquid–gas contact boundaries in the W-CuNWA enhanced aerophilicity and enabled self-oxygen enrichment through atmosphere-connected air pockets, leading to the 3.4 times reduction of mass transport resistance and the 1.5-fold amplified electrochemical responses. The W- CuNWA conjugated with antibodies specific for the targeted biomarkers sensitively and reliably detected the NfL and Aβ40 down to clinically relevant picomolar levels.