Determination of the Influence of Various Factors on the Character of Surface Functionalization of Copper(I) and Copper(II) Oxide Nanosensors with Phenylboronic Acid Derivatives

In this work, we attempt to determine the influence of the oxidation state of copper [Cu(I) Cu(II)], the nature of the interface (solid/aqueous solid/air), the incubation time, and the structure of N-substituted phenylboronic acids (PBAs) functionalizing the surface of copper oxide nanostructures (NSs) on the mode of adsorption. For this purpose, 4-[(-anilino)(phosphono)--methyl]phenylboronic acid (1-PBA) and its two analogues (2-PBA and bis{1-PBA}) and the copper oxide NSs were synthesized in a surfactant-/ion-free solution via a synthetic route that allows controlling the size and morphology of NSs. The NSs were characterized by scanning electron microscopy, ultraviolet-visible spectroscopy, Raman spectroscopy, and X-ray diffraction, which confirmed the formation of spherical CuO nanoparticles (CuONPs) with a size of 1.5 μm to 600 nm crystallized in a cubic cuprite structure and leaf-like CuO nanostructures (CuONSs) with dimensions of 80-180 nm in width and 400-700 nm in length and crystallized in a monoclinic structure. PBA analogues were deposited on the surface of the copper oxide NSs, and adsorption was investigated using surface-enhanced Raman spectroscopy (SERS). The changes in the orientation of the molecule relative to the substrate surface caused by the abovementioned factors were described, and the signal enhancement on the copper oxide NSs was determined. This is the first study using vibrational spectroscopy for these compounds.