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
Synthesis of SERS-active core–satellite nanoparticles using heterobifunctional PEG linkers
Surface-enhanced Raman scattering (SERS) is a sensitive analytical technique capable of magnifying the vibrational intensity of molecules adsorbed onto the surface of metallic nanostructures. Various solution-based SERS-active metallic nanostructures have been designed to generate substantial SERS signal enhancements. However, most of these SERS substrates rely on the chemical aggregation of metallic nanostructures to create strong signals. While this can induce high SERS intensities through plasmonic coupling, most chemically aggregated assemblies suffer from poor signal reproducibility and reduced long-term stability. To overcome these issues, here we report for the first time the synthesis of gold core–satellite nanoparticles (CSNPs) for robust SERS signal generation. The novel CSNP assemblies consist of a 30 nm spherical gold core linked to 18 nm satellite particles via linear heterobifunctional thiol–amine terminated PEG chains. We explore the effects that the varying chain lengths have on SERS hot-spot generation, signal reproducibility and long-term activity. The chain length was varied by using PEGs with different molecular weights (1000 Da, 2000 Da, and 3500 Da). The CSNPs were characterized via UV-Vis spectrophotometry, transmission electron microscopy (TEM), ζ -potential measurements, and lastly SERS measurements. The versatility of the synthesized SERS-active CSNPs was revealed through characterization of optical stability and SERS enhancement at 0, 1, 3, 5, 7 and 14 days.
more »
« less
- Award ID(s):
- 2022805
- PAR ID:
- 10353584
- Date Published:
- Journal Name:
- Nanoscale Advances
- Volume:
- 4
- Issue:
- 1
- ISSN:
- 2516-0230
- Page Range / eLocation ID:
- 258 to 267
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Metallic nanostructures supporting surface plasmon modes can concentrate optical fields, and enhance luminescence processes from the metal surface at plasmonic hotspots. Such nanoplasmonic metal luminescence contributes to the spectral background in surface-enhanced Raman spectroscopy (SERS) measurements and is helpful in bioimaging, nano-thermometry, and chemical reaction monitoring applications. Despite increasing interest in nanoplasmonic metal luminescence, little attention has been paid to investigating its dependence on voltage modulation. Also, the hyphenated electrochemical surface-enhanced Raman spectroscopy (EC-SERS) technique typically ignores voltage-dependent spectral background information associated with nanoplasmonic metal luminescence due to limited mechanistic understanding and poor measurement reproducibility. Here, we report a combined experiment and theory study on dynamic voltage-modulated nanoplasmonic metal luminescence from hotspots at the electrode-electrolyte interface using multiresonant nanolaminate nano-optoelectrode arrays. Our EC-SERS measurements under 785 nm laser excitation demonstrate that short-wavenumber nanoplasmonic metal luminescence associated with plasmon-enhanced electronic Raman scattering (PE-ERS) exhibits a negative voltage modulation slope (up to ≈30 % V-1) in physiological ionic solutions. Furthermore, we have developed a phenomenological model to intuitively capture plasmonic, electronic, and ionic characteristics at the metal-electrolyte interface to understand the observed dependence of the PE-ERS voltage modulation slope on voltage polarization and ionic strength. The current work represents a critical step toward the general application of nanoplasmonic metal luminescence signals in optical voltage biosensing, hybrid optical-electrical signal transduction, and interfacial electrochemical monitoring.more » « less
-
GenX, the trade name of hexafluoropropylene oxide dimer acid (HFPO-DA) and its ammonium salt, is a short-chain PFAS that has emerged as a substitute for the legacy PFAS perfluorooctanoic acid (PFOA). However, GenX has turned out to be more toxic than people originally thought. In order to monitor and regulate water quality according to recently issued drinking water standards for GenX, rapid and ultrasensitive detection of GenX is urgently needed. For the first time, this study reports ultrasensitive (as low as 1 part per billion (ppb)) and fast detection (in minutes) of GenX in water via surface-enhanced Raman spectroscopy (SERS) using a hierarchical nanofibrous SERS substrate, which was prepared by assembling ~60 nm Ag nanoparticles on electrospun nylon-6 nanofibers through a “hot start” method. The findings in this research highlight the potential of the engineered hierarchical nanofibrous SERS substrate for enhanced detection of short-chain PFASs in water, contributing to the improvement of environmental monitoring and management strategies for PFASs.more » « less
-
Recently, surface-enhanced Raman scattering (SERS) joined other optical methods in making novel anticounterfeiting materials due to the fact that abundant molecular fingerprints in Raman spectra can be less susceptible to fraud. Using these molecular features, it is critical to make novel nanostructures with increased SERS enhancement and stability. Herein, we synthesized star-shaped gold nanoparticles as SERS substrates and applied various Raman probes with these gold nanostars to make SERS tags. The encoded molecular information was successfully decoded using principal component analysis (PCA). These colloidal tags can be further stabilized when embedded in a polymer matrix. We made a prototype ballpoint pen that can do simple writing with these secret SERS inks.more » « less
-
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
An official website of the United States government

