Surface-enhanced Raman Scattering Hot Spots Research Articles

Three-dimensional surface-enhanced Raman scattering hotspots in spherical colloidal superstructure for identification and detection of drugs in human urine.

Rapid component separation and robust surface-enhanced Raman scattering (SERS) identification of drugs in real human urine remain an attractive challenge because of the sample complexity, low molecular affinity for metal surface, and inefficient use of hotspots in one- or two-dimensional (2D) geometries. Here, we developed a 5 min strategy of cyclohexane (CYH) extraction for separating amphetamines from human urine. Simultaneously, an oil-in-water emulsion method is used to assemble monodisperse Ag nanoparticles in the CYH phase into spherical colloidal superstructures in the aqueous phase. These superstructures create three-dimensional (3D) SERS hotspots which exist between every two adjacent particles in 3D space, break the traditional 2D limitation, and extend the hotspots into the third dimension along the z-axis. In this platform, a conservative estimate of Raman enhancement factor is larger than 10(7), and the same CYH extraction processing results in a high acceptability and enrichment of drug molecules in 3D hotspots which demonstrates excellent stability and reproducibility and is suitable for the quantitative examination of amphetamines in both aqueous and organic phases. Parallel ultraperformance liquid chromatography (UPLC) examinations corroborate an excellent performance of our SERS platform for the quantitative analysis of methamphetamine (MA) in both aqueous solution and real human urine, of which the detection limits reach 1 and 10 ppb, respectively, with tolerable signal-to-noise ratios. Moreover, SERS examinations on different proportions of MA and 3,4-methylenedioxymethamphetamine (MDMA) in human urine demonstrate an excellent capability of multiplex quantification of ultratrace analytes. By virtue of a spectral classification algorithm, we realize the rapid and accurate recognition of weak Raman signals of amphetamines at trace levels and also clearly distinguish various proportions of multiplex components. Our platform for detecting drugs promises to be a great prospect for a rapid, reliable, and on-spot analyzer.

Surface modification of SERS substrates with plasma-polymerized trimethylsilane nanocoating

Surface-enhanced Raman scattering (SERS) substrates were modified by depositing a nanometer-thick polymer coating on top of SERS-active surface. This thin hydrophobic nanocoating, achieved by low temperature plasma polymerization of trimethylsilane, was found to reduce surface energy of SERS substrate and in turn help relieve the analyte spreading on the surface of SERS substrates. Detection of melamine molecules with these surface-modified SERS substrates showed that this plasma nanocoating improved, not significantly though, SERS sensitivity in comparison with unmodified SERS substrates. It is believed that the increased hydrophobicity induced by this plasma nanocoating had two folds of beneficial effects on SERS sensitivity. First, the as-produced hydrophobic surface gave rise to preconcentration effect due to the reduced contact area between analyte molecules and the substrate surface. Second, the decreased surface energy of SERS substrates was helpful in placing analyte molecules in SERS hot spots. These two combined gains were deemed to outweigh the loss of SERS sensitivity caused by enlarged distance between metal surface and analyte molecules.

Silicon nanohybrid-based surface-enhanced Raman scattering sensors.

Nanomaterial-based surface-enhanced Raman scattering (SERS) sensors are highly promising analytical tools, capable of ultrasensitive, multiplex, and nondestructive detection of chemical and biological species. Extensive efforts have been made to design various silicon nanohybrid-based SERS substrates such as gold/silver nanoparticle (NP)-decorated silicon nanowires, Au/Ag NP-decorated silicon wafers (AuNP@Si), and so forth. In comparison to free AuNP- and AgNP-based SERS sensors, the silicon nanohybrid-based SERS sensors feature higher enhancement factors (EFs) and excellent reproducibility, since SERS hot spots are efficiently coupled and stabilized through interconnection to the semiconducting silicon substrates. Consequently, in the past decade, giant advancements in the development of silicon nanohybrid-based SERS sensors have been witnessed for myriad sensing applications. In this review, the representative achievements related to the design of high-performance silicon nanohybrid-based SERS sensors and their use for chemical and biological analysis are reviewed in a detailed way. Furthermore, the major opportunities and challenges in this field are discussed from a broad perspective and possible future directions.

Shedding Light on Surface-Enhanced Raman Scattering Hot Spots through Single-Molecule Super-Resolution Imaging.

Super-resolution imaging has recently been utilized to develop a better understanding of the properties of surface-enhanced Raman scattering (SERS) hot spots. SERS hot spots are much smaller than the diffraction limit of light, and therefore, obtaining a clear picture of the enhanced electromagnetic (EM) fields comprising these hot spots is a challenging task. In this Perspective, we discuss recent work applying super-resolution imaging to single-molecule SERS (SM-SERS) of rhodamine 6G (R6G) adsorbed to randomly assembled silver colloidal aggregates, allowing the shape, size, and local enhancement of the hot spots to be imaged with <5 nm resolution. The results are compared with studies applying super-resolution imaging to surface-enhanced fluorescence (SEF) of analytes diffusing into silver nanoparticle hot spots. Both studies show a strong correlation between emission intensity and position, allowing the EM field enhancements of SERS hot spots to be mapped with sub-5 nm resolution.

Correlated Super-Resolution Optical and Structural Studies of Surface-Enhanced Raman Scattering Hot Spots in Silver Colloid Aggregates

In order to advance the field of single-molecule surface-enhanced Raman scattering (SM-SERS), a better understanding of colloid morphology and hot spot properties in noble metal nanoparticle aggregates is crucial. We present super-resolution optical studies of surface-enhanced Raman scattering (SERS) from rhodamine 6G (R6G) molecules adsorbed onto silver colloid aggregates correlated with scanning electron microscope (SEM) images of those same aggregates. The scattering intensity maps of the SERS signal, obtained from the super-resolution fits, are overlaid with SEM topographical images of the colloids to map the shape of the SERS hot spot and the spatial origin of SERS intensity fluctuations with sub-5 nm resolution. These results have vital implications for developing reproducible and robust substrates capable of SM-SERS.

Gold Nanorod Arrays with Good Reproducibility for High-Performance Surface-Enhanced Raman Scattering

We have attempted to develop surface-enhanced Raman scattering (SERS) substrates by the use of two-dimensional (2D) Au nanorod arrays and to characterize the SERS-active sites of the Au nanostructures. We prepared two different types of 2D Au nanorod arrays by means of the anodic aluminum oxide (AAO) template-assisted nanofabrication. In the template-embedded array (type I) an Au nanorod fills up the AAO pore, while in the annularly spaced array (type II) an Au nanorod keeps approximately 20 nm away from the pore wall. The strongest SERS effect was observed for both types of substrates with an Au nanorod diameter of approximately 66 nm. With respect to the bare AAO template, the NaOH-etched (unetched) type I substrate with the 66 nm Au nanorod showed 115-fold (63-fold) enhancement in Raman scattering, corresponding to a SERS enhancement factor of 10(7)-10(9). For the unetched and ordered Au naonorod arrays, the SERS-active sites localized around the rod end, whereas for the NaOH-etched and partially aggregated Au nanorods, hot spots for SERS were found in the interstices between rod tips. The type II substrate allowed the effect of rod length on the SERS response to be investigated, and the SERS response was observed to vary very little with the rod length increase (250-1000 nm), indicating that majority of the signal originates at the rod end. A comparison between the analytes all-trans-beta-carotene and pyridine suggests that, for both types of substrates, the electromagnetic enhancement is predominant over the chemical enhancement. This work demonstrates that the unetched type I substrate is highly SERS effective, for which the fabrication protocol is advantageous in its simplicity and reproducibility.

Nanosensors Based on Viologen Functionalized Silver Nanoparticles: Few Molecules Surface-Enhanced Raman Spectroscopy Detection of Polycyclic Aromatic Hydrocarbons in Interparticle Hot Spots

The functionalization of silver nanoparticles (Ag NPs) by viologen dications (VGDs) is reported in this work as well as their applications in the surface-enhanced Raman scattering (SERS) detection of polycyclic aromatic hydrocarbons (PAHs). VGDs are able to form intermolecular cavities at interparticle junctions (SERS hot spots) where the analyte can be allocated. This leads to a giant intensification of the Raman emission of the target molecule. This effect was applied in the detection of PAHs, one of the most widespread and dangerous group of pollutants existing in the atmosphere and waters. A comparison between sensing-systems based on different VGDs (lucigenin, diquat, and paraquat) was done for the detection of two PAHs (pyrene and benzo[c]phenanthrene). The functionalization with lucigenin (LG) provided the most powerful and stable VGD-NPs sensor, which allowed the SERS detection of pyrene (PYR) down to 10(-9) M in the macro setup and in the zeptomole range for spectra obtained by single NPs aggregates (micro setup). Besides, SERS spectra afforded important structural information about the interaction mechanism of VGD and PAHs, revealing the formation of a CT complex between the VGD and PYR and changes in the host conformation. The position of the nu(Ag-Cl) band and the plasmon resonance contribution assigned to Ag dimers were also used as spectral markers to monitor the host-guest interaction.