Ultrahigh Surface-enhanced Raman Scattering Research Articles

Synergistic enhancement of ultrahigh SERS activity via Cu2O@Ag Core-Shell structure for accurate label-free identification of breast tumor subtypes

Conventional methodology for accurate identification of breast tumor subtypes is complex and time-consuming. Label-free SERS (surface-enhanced Raman scattering) enables rapid detection of biomolecules and provides intrinsic fingerprint information of analytes. Exploring reliable SERS bioprobes with high sensitivity and repeatability is essential for efficient typing of cancer cells. In this study, a novel core-shell noble metal-semiconductor Cu2O@Ag heterostructure with uniform morphology and outstanding SERS activity for label-free detection has been proposed. The Cu2O@Ag SERS substrates exhibit exceptional sensitivity to detect 4 nitrophenthiol (4NTP) at extreme low concentration (10−15 M), and the SERS spectra demonstrate excellent selectivity and repeatability (RSD ≈ 8.84%). The enhancement mechanism is attributed to the synergistic enhancement of photoinduced charge transfer and boosted surface plasmon resonance effect, confirmed by reduced fluorescence lifetime of methylene blue on SERS substrates and enhanced electromagnetic field intensity via finite-difference time-domain computational simulation. The ultrahigh sensitivity and good signal stability endow Cu2O@Ag SERS bioprobe potential for accurate detection of four breast cancer cells subtypes. The rich fingerprint information from SERS spectra is processed using linear differentiation analysis, revealing a high accuracy of 93.3% for subtypes classification. These results demonstrate an excellent SERS bioprobe with high sensitivity and repeatability for precision diagnosis has been developed.

Design and fabrication of Zn@ZnO@Ag chip for Raman scattering analysis of norfloxacin in liquid milk, fish and animal feeds.

A novel and easy-to-prepare plasmonic nanoparticles doped semiconductor substrate-Zn@ZnO@Ag chip with ultra-high surface-enhanced Raman scattering (SERS) activity was fabricated for label-free, rapid and sensitive analysis of norfloxacin. The Zn@ZnO array was synthesized by surface oxidation at low temperature, followed by in-situ reduction to form leaf-like AgNPs on Zn@ZnO array without extra reducing agent, thus fabricating a Zn@ZnO@Ag chip. The ultra-high SERS activity is attributed to the synergistic effect of semiconductor characteristics of ZnO and surface plasmon resonance properties of leaf-like AgNPs. The possible enhancement mechanism was verified by density functional theory simulations. The proposed SERS method showed a wide linear range (3.0-500.0μg/L) and low limit of detection (0.8μg/L) for norfloxacin analysis. High sensitivity, good selectivity and acceptable recoveries (82.7-113.6%) in real sample analysis were obtained. This study offers a promising SERS chip-based platform for norfloxacin detection in the field.

3D Plasmonic Ensembles of Graphene Oxide and Nobel Metal Nanoparticles with Ultrahigh SERS Activity and Sensitivity

We describe a comparison study on 3D ensembles of graphene oxide (GO) and metal nanoparticles (silver nanoparticles (AgNPs), gold nanoparticles (GNPs), and gold nanorods (GNRs)) for surface-enhanced Raman scattering (SERS) application. For the first time, GNRs were successfully assembled on the surfaces of GO by means of electrostatic interactions without adding any surfactant. The SERS properties of GO/AgNPs, GO/GNPs, and GO/GNRs were compared using 2-mercaptopyridine (2-Mpy) as probing molecule. We found that GO/AgNPs and GO/GNPs substrates are not suitable for detecting 2-Mpy due to the very strongπ-πstacking interaction between the 2-Mpy molecules andsp2carbon structure of GO. Conversely, the GO/GNRs substrates show ultrahigh SERS activity and sensitivity of 2-Mpy with the detection limit as low as ~10-15 M, which is ~2-3 orders of magnitude higher than that of the corresponding GNRs.

Wrinkled Nanoporous Gold Films with Ultrahigh Surface-Enhanced Raman Scattering Enhancement

Amplified by plasomonic nanostructured metals, Raman intensity of organic molecules and biomolecules can be dramatically improved, particularly at "hot spots" where intense electromagnetic fields are produced in the vicinity of narrow nanogaps between metallic nanostructures. Therefore, developing new substrates with a high density of "hot spots" has been the recent topic of intense study. Here we report wrinkled nanoporous gold films that contain abundant Raman-active nanogaps produced by deformation and fracture of nanowire-like gold ligaments. This novel nanostructure yields ultrahigh surface enhanced Raman scattering for molecule detection.