In recent years, surface-enhanced Raman scattering (SERS) of a molecule/metal–semiconductor hybrid system has attracted considerable interest and regarded as the synergetic contribution of the electromagnetic and chemical enhancements from the incorporation of noble metal into semiconductor nanomaterials. However, the underlying mechanism is still to be revealed in detail. Herein, we report an irreversible accumulated SERS behavior induced by near-infrared (NIR) light irradiating on a 4-mercaptobenzoic acid linked with silver and silver-doped titanium dioxide (4MBA/Ag/Ag-doped TiO₂) hybrid system. With increasing irradiation time, the SERS intensity of 4MBA shows an irreversible exponential increase, and the Raman signal of the Ag/Ag-doped TiO₂ substrate displays an exponential decrease. A microscopic understanding of the time-dependent SERS behavior is derived based on the microanalysis of the Ag/Ag-doped TiO₂ nanostructure and the molecular dynamics, which is attributed to three factors: (1) higher crystallinity of Ag/Ag-doped TiO₂ substrate; (2) photo-induced charge transfer; (3) charge-induced molecular reorientation.

In this paper, we design a type of switchable metasurfaces by employing vanadium dioxide (VO₂), which possess tunable and diversified functionalities in the terahertz (THz) frequencies. The properly designed homogeneous metasurface can be dynamically tuned from a broadband absorber to a reflecting surface due to the insulator-to-metal transition of VO₂. When VO₂ is in its insulating state, the metasurface can efficiently absorb the normally incident THz wave in the frequency range of 0.535–1.3 THz with the average absorption of ~97.2%. Once the VO₂ is heated up and switched to its fully metallic state, the designed metasurface exhibits broadband and efficient reflection (>80%) in the frequency range from 0.5 to 1.3 THz. Capitalizing on such meta-atom design, we further extend the functionalities by introducing phase-gradients when VO₂ is in its fully metallic state and consequently achieve polarization-insensitive beam-steering and polarization-splitting, while maintaining broadband absorption when VO₂ is in insulating state.

Prostate cancer (PCa) is a leading cause of cancer-related death among males globally. To date, prostate-specific antigen (PSA), as a typical tumour marker, has been widely used in the early diagnosis of PCa. However, in practical clinical tests, high serum levels of PSA show a high probability for false-positive results, leading to misdiagnoses. In this study, we developed a new classification system for PCa, benign prostate hyperplasia (BPH) and healthy subjects by using a surface-enhanced Raman scattering (SERS)-based immunoassay of multiple tumour markers along with a support vector machine (SVM) algorithm. Silver nanoparticles (AgNPs) as immune probes and SiC@Ag@Ag-NPs SERS as immune substrates were constructed into a sandwich structure to serve as an ultrasensitive SERS-based immunoassay platform of tumour markers. With this assay, the limits of detection for PSA, prostate-specific membrane antigen (PSMA) and human kallikrein 2 (hK2) were as low as 0.46 fg mL-1, 1.05 fg mL-1 and 0.67 fg mL-1, respectively. Furthermore, the serum levels of PSA, PSMA and hK2 in clinical samples were successfully detected using the SERS-based immunoassay platform, and correct classifications of PCa, BPH and healthy subjects were feasible with help of the linear SVM algorithm. These results demonstrate the potential for improving the diagnostic accuracy of PCa. Overall, the linear SVM classification model with multiple tumour markers exhibited good classifications of PCa, BPH and healthy subjects, with a PCa diagnostic accuracy of 70% that was significantly superior to that of the linear SVM classification model based only on the serum level of PSA (50%). Therefore, combining the SERS-based immunoassay with pattern recognition technology can allow for comprehensive analyses of the serum levels of multiple tumour markers to effectively improve the diagnostic accuracy of cancer with potential applications in point-of-care testing.

An Ag@MSiO₂@Ag three core–shell architecture was synthesized by a facial hydrothermal method. The features of the sample were characterized by SEM, TEM, and AFM images, EDS analyses and absorption spectra. This novel nanostructure exhibited excellent SERS properties due to the formation of hot spots around the inner and outer Ag NPs, which were identified by theoretical calculations. A detection limit of the analyte molecule was obtained as low as 10⁻¹¹ M by using this SERS nanostructure. Moreover, the homogeneity of SERS signals from the three core–shell nanostructure was checked by Raman mapping. Our studies show that the unique Ag@MSiO₂@Ag three core–shell nanostructure has significant potential to realize a SERS substrate with both sensitivity and stability, which are important in SERS-based immunoassay.

Based on a sandwich structure consisting of nano-Si immune probes and a SiC@Ag SERS-active immune substrate, a kind of ultra-sensitive immunoassay protocol is presented to detect tumor markers in human serum. The nano-Si immune probes were prepared by immobilizing the detecting antibodies onto the surfaces of SiO₂-coated Si nanoparticles (NPs) which were modified with 3-(aminopropyl)trimethoxysilane, and the SiC@Ag SERS-active immune substrates were prepared by immobilizing the captured antibodies on Ag film sputtered on SiC sandpaper. To the best of our knowledge, it is the first time that Si NPs are directly used as Raman tags in an immunoassay strategy. And, the SiC@Ag SERS-active substrates exhibit excellent surface enhanced Raman scattering (SERS) performances with an enhancement factor of ∼10⁵, owing to the plasmonic effect of the Ag film on the rough surface of the SiC sandpaper. In our experiments, the sandwich immunoassay structure has been successfully applied to detect prostate specific antigen (PSA), α-fetoprotein (AFP) and carbohydrate antigen 19-9 (CA19-9) in a human serum sample and the limit of detections are as low as 1.79 fg mL⁻¹, 0.46 fg mL⁻¹ and 1.3 × 10⁻³ U mL⁻¹, respectively. It reveals that the proposed immunoassay protocol has demonstrated a high sensitivity for tumor markers in human serum and a potential practicability in biosensing and clinical diagnostics.