PB@PDA nanocomposites as nanolabels and signal reporters for separate-type cathodic photoelectrochemical immunosensors in the detection of carcinoembryonic antigens.

Photoelectrochemical (PEC) immunoassays exhibiting high sensitivity and decent operability have considerable potential in areas such as cancer diagnostics. In particular, cathodic PEC configurations can prevent interference from reductive substances, which can occur in biological samples; however, challenges remain in terms of sensitivity and operability. In this study, separate-type PEC immunoassays were developed for carcinoembryonic antigen (CEA) by combining microplate-based immune recognition and off-on cathodic PEC detection. Polydopamine (PDA)-coated Prussian blue (PB) nanoparticles (PB@PDA NPs) were used as signal tags to label the detection antibody. The PB NPs and PDA captured on the microplates both disassembled under strongly alkaline conditions to generate redox-active electron acceptors. The disassembled products were quantitatively transferred to PEC detection cells and synergistically enhanced the PEC current with microstructured BiOI, which operated as a cathodic semiconductor electrode. As proof of principle, carcinoembryonic antigen (CEA) was applied to elucidate the potential application of PEC immunoassay in clinical diagnosis, and the obtained linear range of the sensor was 0.001-100 ng mL-1 with the detection limit of 54.9 fg mL-1 (S/N = 3). The proposed separate-type off-on PEC strategy showed high sensitivity and decent operability for CEA detection, indicating its potential for the identification of other tumor markers.

Spectroscopic Investigation and Nanoscale Characterization of Epinephrine Autooxidation under Alkaline Conditions.

Melanins are intriguing biomaterials with unique physical and chemical properties. Due to the insoluble nature of the synthetic melanins prepared from different precursors, such as 3,4-dihydroxy-phenylalanine (DOPA) and dopamine (DA), it is still challenging to reveal the structure-property relationships. In this work, the autoxidation of epinephrine (EP) under basic conditions was investigated from the perspective of supramolecular chemistry, and the formed soluble epinephrine-melanin (EPM) was characterized on the nanoscale. The supramolecular aggregate nature of oxidation products has been identified on the basis of spectroscopic investigations. A two-dimensional sheet-like morphology with highly ordered in-plane stacking structures was observed for the first time, and the thickness of the nanosheet increased with increasing EPM concentration. More importantly, in contrast to the well-known monotonic absorption profiles of synthetic melanins, EPM shows featured and unusual pH-responsible absorption profiles in the near-ultraviolet region (UVA). The decrease in pH can induce the disappearance of the absorption in the lower-energy band and the reduction of aggregate size. The oxidative and aggregation kinetic processes of EP were investigated in three different alkaline systems by the combination of absorption and fluorescence spectroscopies. The oxidation process of EP shows concentration- and buffer-dependent behaviors. The unusual absorption properties of EPM were exploited for the fabrication of transparent UV-shielding chitosan biofilms and gelatin hydrogels. Extensive research on the molecular structures, supramolecular exciton coupling, and material-oriented property exploitation of EPM is highly anticipated.