Near-infrared photoactive Yb-MOF functionalized with a large conjugate ionic liquid: synthesis and application for photoelectrochemical immunosensing of carcinoma embryonic antigen

Abstract

A novel near-infrared (NIR)-excited photoelectrochemical (PEC) immunosensor based on an ionic liquid functionalized metal organic framework (Yb-MOF) and gold nanoparticles (Au-NPs) was designed for the high-performance determination of carcinoembryonic antigen (CEA). The Yb-MOF was synthesized from the coordination of the Yb³⁺ metal ion with the 1,1′-(1,5-dihydropyrene-2,7-diyl)bis(3-(4-carboxybenzyl)-1H-imidazol-3-ium) bromide [DDPDBCBIm(Br)₂] ionic liquid by a hydrothermal method. To improve the photoelectric conversion efficiency of the Yb-MOF in the NIR region, the surface of the Yb-MOF was integrated with gold nanoparticles (AuNPs) to fabricate a Yb-MOF@AuNP nanocomposite through an in situ reduction of chloroauric acid with sodium borohydride. The NIR photoelectrochemical response of the Yb-MOF@AuNPs at 808 nm was enhanced 4-fold over the pristine Yb-MOF. Subsequently, a photoelectrochemical platform based on the Yb-MOF@AuNPs was constructed for loading the CEA antibody (anti-CEA). After cross-linking with glutaraldehyde followed by blocking with bovine serum albumin, a photoelectrochemical sensor for assaying CEA was fabricated. Upon specifically interacting with CEA, CEA can block the photogenerated electron–hole pair transfer and the mass transfer of ascorbic acid to the sensing interface, thus leading to a decrease in photocurrent response. The photocurrent variation can be used for determining CEA quantitatively. After optimizing the experimental conditions, the photocurrent variations before and after incubation with CEA were linearly correlated with the CEA concentration over the range of 0.005–15 ng mL⁻¹. The detection limit of CEA was calculated to be 0.25 pg mL⁻¹ (S/N = 3). The immunosensor was employed for the measurement of free CEA in clinical serum samples, and the results were very consistent with the values obtained by clinical tests. The NIR PEC immunosensor also demonstrated excellent accuracy and recovery, which corroborates its potential as a practical technique in clinical diagnosis.