Surface-Enhanced Raman Scattering Enantioselective Detection of Gastric Cancer-Related d-Amino Acids in Saliva Based on Enzyme-Mediated Cascade Reaction.

The unusual d-amino acids (d-AAs), as the counter enantiomer of usual l-amino acids (l-AAs), have evoked increasing attention because of their potential relevance with diseases. Accordingly, it is essential to establish sensitive and selective detection methods for d-AAs without the interferences from l-AAs. The surface-enhanced Raman scattering (SERS) technique is efficacious for the detection of molecules but routinely ineffective in enantiomeric differentiation. d-Proline (d-Pro) and d-alanine (d-Ala) are regarded as biomarkers of gastric cancer. Herein, Raman-active boronate modified SERS chips are constructed to develop a d-amino acid oxidase (DAAO)-mediated cascade reaction-based SERS enantioselective assay for d-Pro and d-Ala. The principle is that DAAO selectively catalyzes the deamination of d-Pro and d-Ala, and the produced H2O2 oxidizes boronate to present a new SERS peak at 883 cm-1 for quantitative analysis in a ratiometric way. A linear range from 20 to 400 µmol/L and a limit of detection down to 14.8 µmol/L are reached. In addition, interferences from l-AAs and many other possible species coexisting in biofluids with the detection of d-Pro and d-Ala are ignorable. Enzyme-mediated cascade reaction-based SERS chips are further utilized for saliva sample analysis, and the total levels of d-Pro and d-Ala in salivary samples from gastric cancer patients are much higher than those of healthy persons. This work provides a solution for SERS enantioselective analysis and noninvasive screening chiral biomolecules for disease diagnosis.

Efficient removal of copper and silver ions in electroplating wastewater by magnetic-MOF-based hydrogel and a reuse case for photocatalytic application.

Direct discharge of electroplating wastewater containing hazardous metal ions such as Cu2+ and Ag + results in environmental pollution. In this study, we rationally prepare a magnetic composite hydrogel consisted of Fe3O4, UiO-66-NH2, chitosan (CTS) and polyethyleneimine (PEI), namely Fe3O4@UiO-66-NH2/CTS-PEI. Thanks to the strong attraction between the amino group and metal cations, the Fe3O4@UiO-66-NH2/CTS-PEI hydrogel shows the maximum adsorption capacities of 321.67 mg g-1 for Cu2+ ions and 226.88 mg g-1 for Ag + ions within 120 min. As real scenario, the Fe3O4@UiO-66-NH2/CTS-PEI hydrogel exhibits excellent removal efficiencies for metallic ions even in the complicated media of actual electroplating wastewater. In addition, we explore the competitive adsorption order of metal cations by using experimental characterization and theoretical calculations. The optimal configuration of CTS-PEI is also discovered with the density functional theory, and the water retention within hydrogel is simulated through molecular dynamics modeling. We find that the Fe3O4@UiO-66-NH2/CTS-PEI hydrogel could be reused and after 5 cycles of adsorption-desorption, removal efficiency could maintain 80%. Finally, the Ag+ accumulated by hydrogel are reduced to generate a photocatalyst for efficient degradation of Rhodamine B. The novel magnetic hydrogel paves a promising path for efficient removal of heavy metal ions in wastewater and further resource utilization as photocatalysts.