skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 5:00 PM ET until 11:00 PM ET on Friday, June 21 due to maintenance. We apologize for the inconvenience.

Title: Optimization of film over nanosphere substrate fabrication for SERS sensing of the allergen soybean agglutinin

Metal film over nanosphere (FON) substrates are a mainstay of surface‐enhanced Raman scattering (SERS) measurements because they are inexpensive to fabricate, have predictable enhancement factors, and are relatively robust. This work includes a systematic investigation of how the three major FON fabrication parameters—nanosphere size, deposited metal thickness, and metal choice—impact the resulting localized surface plasmon resonance (LSPR). With these three parameters, it is quite simple to fabricate FONs with an optimal LSPR for SERS experiments with various excitation wavelengths. Some SERS experiments require that the substrates be incubated in organic solvents that have the potential to damage the substrate; as such, this work also explores how solvent incubation impacts the physical and optical properties of the FON substrate. Although no significant increase in physical damage is obvious, the LSPR does shift significantly. Finally, these optimized FONs were employed for the sensing of an important allergen, soybean agglutinin. The FONs were modified with a glycopolymer that has affinity for soybean agglutinin and clear Raman bands demonstrate detection of 10 μg/ml soybean agglutinin. Overall, this work serves the dual purpose of both sharing critical details about FON design and demonstrating detection of an important lectin analyte.

more » « less
Award ID(s):
2011401 1420013
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Raman Spectroscopy
Page Range / eLocation ID:
p. 482-490
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Nanohybrids of graphene and two-dimensional (2D) layered transition metal dichalcogenides (TMD) nanostructures can provide a promising substrate for extraordinary surface-enhanced Raman spectroscopy (SERS) due to the combined electromagnetic enhancement on TMD nanostructures via localized surface plasmonic resonance (LSPR) and chemical enhancement on graphene. In these nanohybrid SERS substrates, the LSPR on TMD nanostructures is affected by the TMD morphology. Herein, we report the first successful growth of MoS2 nanodonuts (N-donuts) on graphene using a vapor transport process on graphene. Using Rhodamine 6G (R6G) as a probe, SERS spectra were compared on MoS2 N-donuts/graphene nanohybrids substrates. A remarkably high R6G SERS sensitivity up to 2 × 10−12 M has been obtained, which can be attributed to the more robust LSPR effect than in other TMD nanostructures such as nanodiscs as suggested by the finite-difference time-domain simulation. This result demonstrates that non-metallic TMD/graphene nanohybrids substrates can have SERS sensitivity up to one order of magnitude higher than that reported on the plasmonic metal nanostructures/2D materials SERS substrates, providing a promising scheme for high-sensitivity, low-cost applications for biosensing. 
    more » « less
  2. Abstract

    In recent years, concerns have been raised regarding the contamination of grapes with pesticide residues. As consumer demand for safer food products grows, regular monitoring of pesticide residues in food has become essential. This study sought to develop a rapid and sensitive technique for detecting two specific pesticides (phosmet and paraquat) present on the grape surface using the surface‐enhanced Raman spectroscopy (SERS) method. Gold nanostars (AuNS) particles were synthesized, featuring spiky tips that act as hot spots for localized surface plasmon resonance, thereby enhancing Raman signals. Additionally, the roughened surface of AuNS increases the surface area, resulting in improved interactions between the substrate and analyte molecules. Prominent Raman peaks of mixed contaminants were acquired and used to characterize and quantify the pesticides. It was observed that the SERS intensity of the Raman peaks changed in proportion to the concentration ratio of phosmet and paraquat. Moreover, AuNS exhibited superior SERS enhancement compared to gold nanoparticles. The results demonstrate that the lowest detectable concentration for both pesticides on grape surfaces is 0.5 mg/kg. These findings suggest that SERS coupled with AuNS constitutes a practical and promising approach for detecting and quantifying trace contaminants in food.

    Practical Application

    This research established a novel surface‐enhanced Raman spectroscopy (SERS) method coupled with a simplified extraction protocol and gold nanostar substrates to detect trace levels of pesticides in fresh produce. The detection limits meet the maximum residue limits set by the EPA. This substrate has great potential for rapid measurements of chemical contaminants in foods.

    more » « less
  3. Abstract

    The impact of tunable morphologies and plasmonic properties of gold nanostars is evaluated for the surface‐enhanced Raman scattering (SERS) detection of uranyl. To do so, gold nanostars are synthesized with varying concentrations of the Good's buffer reagent, 2‐[4‐(2‐hydroxyethyl)‐1‐piperazinyl]propanesulfonic acid (EPPS). EPPS plays three roles including as a reducing agent for nanostar nucleation and growth, as a nanostar‐stabilizing agent for solution phase stability, and as a coordinating ligand for the capture of uranyl. The resulting nanostructures exhibit localized surface plasmon resonance (LSPR) spectra that contain two visible and one near‐infrared plasmonic modes. All three optical features arise from synergistic coupling between the nanostar core and branches. The tunability of these optical resonances is correlated with nanostar morphology through careful transmission electron microscopy (TEM) analysis. As the EPPS concentration used during synthesis increases, both the length and aspect ratio of the branches increase. This causes the two lower energy extinction features to grow in magnitude and become ideal for the SERS detection of uranyl. Finally, uranyl binds to the gold nanostar surface directly and via sulfonate coordination. Changes in the uranyl signal are directly correlated to the plasmonic properties associated with the nanostar branches. Overall, this work highlights the synergistic importance of nanostar morphology and plasmonic properties for the SERS detection of small molecules.

    more » « less
  4. Abstract

    Two‐dimensional transition metal dichalcogenides (TMDs)/graphene van der Waals (vdW) heterostructures integrate the superior light–solid interaction in TMDs and charge mobility in graphene, and therefore are promising for surface‐enhanced Raman spectroscopy (SERS). Herein, a novel TMD (MoS2and WS2) nanodome/graphene vdW heterostructure SERS substrate, on which an extraordinary SERS sensitivity is achieved, is reported. Using fluorescent Rhodamine 6G (R6G) as probe molecules, the SERS sensitivity is in the range of 10−11to 10−12mon the TMD nanodomes/graphene vdW heterostructure substrates using 532 nm Raman excitation, which is comparable to the best sensitivity reported so far using plasmonic metal nanostructures/graphene SERS substrates, and is more than three orders of magnitude higher than that on single‐layer TMD and graphene substrates. Density functional theory simulation reveals enhanced electric dipole moments and dipole–dipole interaction at the TMD/graphene vdW interface, yielding an effective means to facilitate an external electrostatic perturbation on the graphene surface and charge transfer. This not only promotes chemical enhancement on SERS, but also enables electromagnetic enhancement of SERS through the excitation of localized surface plasmonic resonance on the TMD nanodomes. This TMD nanodome/graphene vdW heterostructure is therefore promising for commercial applications in high‐performance optoelectronics and sensing.

    more » « less
  5. Surface-enhanced Raman scattering (SERS), a powerful technique for trace molecular detection, depends on chemical and electromagnetic enhancements. While recent advances in instrumentation and substrate design have expanded the utility, reproducibility, and quantitative capabilities of SERS, some challenges persist. In this review, advances in quantitative SERS detection are discussed as they relate to intermolecular interactions, surface selection rules, and target molecule solubility and accessibility. After a brief introduction to Raman scattering and SERS, impacts of surface selection rules and enhancement mechanisms are discussed as they relate to the observation of activation and deactivation of normal Raman modes in SERS. Next, experimental conditions that can be used to tune molecular affinity to and density near SERS substrates are summarized and considered while tuning these parameters is conveyed. Finally, successful examples of quantitative SERS detection are discussed, and future opportunities are outlined. 
    more » « less