Ultra-clean ternary Au/Ag/AgCl nanoclusters favoring cryogenic temperature-boosted broadband SERS ultrasensitive detection.

Exploring multifunctional surface-enhanced Raman scattering (SERS) substrates with high sensitivity, broadband response property and reliable practicability should be required for ultrasensitive molecular detection in complex environments, which is heavily dependent on the photo-induced charge transfer (PICT) efficiency realized on the desirable nano-architectures. Herein, we introduce ultra-clean ternary Au/Ag/AgCl nanoclusters (NCs) with broadband resonance crossing the visible light to near-infrared region created by one step laser irradiation of mixed metal ion solution. Interestingly, the surface defects and interaction among these unique cluster-like ternary nanostructures would be further enhanced by thermal annealing treatment at 300°C, providing higher broadband SERS activities than the reference ternary nanoparticles under 457, 532, 633, 785, and 1064 nm wavelengths excitation. More importantly, the further promoted SERS activities of the resultant Au/Ag/AgCl NCs with achievable ∼5-fold enhancement than the initial one can be conventionally realized by simplistically declining the temperature from normal 20°C to cryogenic condition at about -196°C, due to the lower temperature-suppressed non-radiative recombination of lattice thermal phonons and photogenerated electrons. The cryogenic temperature-boosted SERS of the resultant Au/Ag/AgCl NCs enables the limit of detection (LOD) of folic acid (FA) biomolecules to be achieved as low as 10-12 M, which is obviously better than that of 10-9 M at room temperature condition. Overall, the smart Au/Ag/AgCl NCs-based broadband SERS sensor provides a new avenue for ultrasensitive biomolecular monitoring at cryogenic condition.

Double profound enhancements of Cu2O nano-octahedrons connected by intertwined Ag nanovines for elevating SERS activity toward ultrasensitive pesticide detection.

Recently, hybrid plasmonic metal/semiconductor-based surface-enhanced Raman scattering (SERS) has attracted ever-increasing attention due to its combined characteristics of electromagnetic (EM) enhancement and chemical (CM) enhancement, holding great potential for trace molecular detection. Herein, we demonstrate an interesting heterostructure by linking Cu2O nano-octahedrons with intertwined Ag nanovines (NVs). The obtained Ag NVs/Cu2O heterostructures exhibit excellent SERS activity, which is about 2.7 and 7.0 times higher than that of monodispersed Ag or Au nanoparticles (NPs) modified Cu2O. The intertwined Ag NVs among adjacent Cu2O octahedrons serve as efficient electron transport channels, which can obviously promote the separation of electrons and holes, reduce the recombination of photogenerated carriers, and then improve the CM enhancement effect. Meanwhile, the accumulated electrons on plasmonic NVs can effectively optimize the collective oscillation of electrons and further improve the EM enhancement. The optimal SERS substrate possesses fascinating multifunctional SERS properties, including ultra-low detection limit (CV, 10-14 M), excellent anti-interference capability and selectivity. Finally, the established nanosensor can be effectively applied for the quantitative detection of pesticide thiram molecules in soil and biological samples, with low detection limits of 0.48 ng g-1 and 10-7 M, respectively. The proposed work demonstrates a high-performance SERS heterostructure with both improved CM enhancement and enhanced EM effect by linking adjacent Cu2O nano-octahedrons with Ag NVs, which is particularly suitable for ultrasensitive residual pesticide detection in real-world environment.

Silk fibroin fibers decorated with urchin-like Au/Ag nanoalloys: a flexible hygroscopic SERS sensor for monitoring of folic acid in human sweat.

Surface-enhanced Raman scattering (SERS) spectroscopy has become a powerful and sensitive analytical tool for the detection and assessment of chemical/biological molecules in special scenarios. Herein we propose a flexible hygroscopic SERS biocompatible sensor based on the silk fibroin fibers (SFF) decorated with urchin-like Au/Ag nanoalloys (NAs). The hybrid SFF-Au/Ag NAs with a stronger absorbance capacity (500∼1100 nm) and excellent hygroscopicity provide a remarkable higher near-infrared (NIR)-SERS activity than that of bare urchin-like Au/Ag NAs. The interesting NIR-SERS sensor enables the limit of detection (LOD) of folic acid (FA) to be achieved at nanomolar (nM, 10-9 M) level, facilitating the ultrasensitive monitoring of FA in human sweat and offering reliable real-time personal health management in the near future.

Alloyed AuPt nanoframes loaded on h-BN nanosheets as an ingenious ultrasensitive near-infrared photoelectrochemical biosensor for accurate monitoring glucose in human tears.

Photo-electro-chemical (PEC) glucose biosensor has recently attracted extensive attention due to the double advantages of both photocatalysis via photon energy utilization and electrocatalytic oxidation through extra electric field. Compared with previous shorter wavelength (violet-visible) light-induced PEC reaction, the anticipated near infrared (NIR, >~700 nm) excited PEC biosensor with multiple fascinating features should be more suitable for clinical diagnostic biology. Herein, we report an ingenious NIR-PEC biosensor by loading alloyed Au5Pt9 nanoframes on two dimensional (2D) hexagonal boron nitride (h-BN) nanosheets. The obtained h-BN/Au5Pt9 nanoframes exhibit a remarkable higher NIR-PEC activity in comparison with other as-prepared h-BN/AuPt references. The improved PEC performance is attributed to the enhanced synergetic coupling effect between Au5Pt9 nanoalloys and constitutionally stable h-BN that gives rise to a stronger absorbance capacity and pronounced localized surface plasmon resonance (LSPR) in visible-NIR region as well as high free-electron mobility of framework-like Au/Pt. Interestingly, the obtained h-BN/Au5Pt9 nanoframes excited by 808 nm NIR light provide superior PEC accuracy and sensitivity as compared to visible or other NIR light irradiation. Then, the novel 808 nm NIR-PEC biosensor was used for precise glucose monitoring in human tears with a detectable concentration of 0.03~100 µM and a low detection limit of 0.406 nM. Undoubtedly, the proposed h-BN/Au5Pt9 nanoframes as an appealing NIR-PEC glucose biosensor can possess greater potential values for practical glucose monitoring in biomedicine.

Cu2O nanocubes-grafted highly dense Au nanoparticles with modulated electronic structures for improving peroxidase catalytic performances.

Based on the intermediate states of metal ions in metal oxide nanomaterials (NMs) that acted as the primary active species, the design of high-performance nanozymes has greatly stimulated current research in diverse biomedical applications. Herein, Cu2O nanocubes-grafted highly dense Au nanoparticles (NPs) was developed as an appealing nanozyme for H2O2 colorimetric sensor and antioxidant detections. The obtained Au/Cu2O heterostructures show efficient electron-transfer from metallic NPs to Cu2O nanocubes owing to the difference of Fermi energy between two components. The modulated electronic structure of Au/Cu2O hybrids enables them to possess enhanced peroxidase catalytic activity for the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) in the presence of H2O2, which is about 32% higher than that of pristine Cu2O nanocubes. Then, an excellent H2O2 colorimetric sensor was established by using Au/Cu2O heterostructures with a low limit of detection (LOD) of 0.054 µM, which is much lower than the H2O2 allowance level of US FDA regulations (ca.15 µM, 0.05 wt%). The obtained Au/Cu2O nanoproducts exhibit pronounced long-time stability with 95% peroxidase activity maintained after keeping them for 30 days, while residual 64.5% via Cu2O nanocubes. Furthermore, we assessed the anti-oxidative behavior of three natural antioxidants (tannic acid, gallic acid, tartaric acid) with the LODs as low as 0.039, 0.16 and 1.55 µM, respectively, and the antioxidant capacity in the following order: tannic acid > gallic acid > tartaric acid. Therefore, it is believed that the as-prepared Au/Cu2O nanozymes have promising potential applications in fields of biomedicine and food safety.