Bacterial cellulose nanocrystals (BCNCs) are biocompatible cellulose nanomaterials that can host guest nanoparticles to form hybrid nanocomposites with a wide range of applications. Herein, we report the synthesis of a hybrid nanocomposite that consists of plasmonic gold nanoparticles (AuNPs) and superparamagnetic iron oxide (Fe 3 O 4 ) nanoparticles supported on BCNCs. As a proof of concept, the hybrid nanocomposites were employed to isolate and detect malachite green isothiocyanate (MGITC) via magnetic separation and surface-enhanced Raman scattering (SERS). Different initial gold precursor (Au 3+ ) concentrations altered the size and morphology of the AuNPs formed on the nanocomposites. The use of 5 and 10 mM Au 3+ led to a heterogenous mix of spherical and nanoplate AuNPs with increased SERS enhancements, as compared to the more uniform AuNPs formed using 1 mM Au 3+ . Rapid and sensitive detection of MGITC at concentrations as low as 10 −10 M was achieved. The SERS intensity of the normalized Raman peak at 1175 cm −1 exhibited a log-linear relationship for MGITC concentrations between 2 × 10 −10 and 2 × 10 −5 M for Au@Fe 3 O 4 @BCNCs. These results suggest the potential of these hybrid nanocomposites for application in a broad range of analyte detection strategies.
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Highly porous gold supraparticles as surface-enhanced Raman spectroscopy (SERS) substrates for sensitive detection of environmental contaminants
Surface-enhanced Raman spectroscopy (SERS) has great potential as an analytical technique for environmental analyses. In this study, we fabricated highly porous gold (Au) supraparticles ( i.e. , ∼100 μm diameter agglomerates of primary nano-sized particles) and evaluated their applicability as SERS substrates for the sensitive detection of environmental contaminants. Facile supraparticle fabrication was achieved by evaporating a droplet containing an Au and polystyrene (PS) nanoparticle mixture on a superamphiphobic nanofilament substrate. Porous Au supraparticles were obtained through the removal of the PS phase by calcination at 500 °C. The porosity of the Au supraparticles was readily adjusted by varying the volumetric ratios of Au and PS nanoparticles. Six environmental contaminants (malachite green isothiocyanate, rhodamine B, benzenethiol, atrazine, adenine, and gene segment) were successfully adsorbed to the porous Au supraparticles, and their distinct SERS spectra were obtained. The observed linear dependence of the characteristic Raman peak intensity for each environmental contaminant on its aqueous concentration reveals the quantitative SERS detection capability by porous Au supraparticles. The limit of detection (LOD) for the six environmental contaminants ranged from ∼10 nM to ∼10 μM, which depends on analyte affinity to the porous Au supraparticles and analyte intrinsic Raman cross-sections. The porous Au supraparticles enabled multiplex SERS detection and maintained comparable SERS detection sensitivity in wastewater influent. Overall, we envision that the Au supraparticles can potentially serve as practical and sensitive SERS devices for environmental analysis applications.
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- NSF-PAR ID:
- 10386284
- Date Published:
- Journal Name:
- RSC Advances
- Volume:
- 12
- Issue:
- 51
- ISSN:
- 2046-2069
- Page Range / eLocation ID:
- 32803 to 32812
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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.
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Rapid and cost-effective detection of antibiotics in wastewater and through wastewater treatment processes is an important first step in developing effective strategies for their removal. Surface-enhanced Raman scattering (SERS) has the potential for label-free, real-time sensing of antibiotic contamination in the environment. This study reports the testing of two gold nanostructures as SERS substrates for the label-free detection of quinoline, a small-molecular-weight antibiotic that is commonly found in wastewater. The results showed that the self-assembled SERS substrate was able to quantify quinoline spiked in wastewater with a lower limit of detection (LoD) of 5.01 ppb. The SERStrate (commercially available SERS substrate with gold nanopillars) had a similar sensitivity for quinoline quantification in pure water (LoD of 1.15 ppb) but did not perform well for quinoline quantification in wastewater (LoD of 97.5 ppm) due to interferences from non-target molecules in the wastewater. Models constructed based on machine learning algorithms could improve the separation and identification of quinoline Raman spectra from those of interference molecules to some degree, but the selectivity of SERS intensification was more critical to achieve the identification and quantification of the target analyte. The results of this study are a proof-of-concept for SERS applications in label-free sensing of environmental contaminants. Further research is warranted to transform the concept into a practical technology for environmental monitoring.more » « less
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Abstract Surface‐enhanced Raman scattering (SERS) sensing in microfluidic devices, namely optofluidic‐SERS, suffers an intrinsic tradeoff between mass transport and hot spot density, both of which are required for ultrasensitive detection. To overcome this compromise, photonic crystal‐enhanced plasmonic mesocapsules are synthesized, utilizing diatom biosilica decorated with in‐situ growth silver nanoparticles (Ag NPs). In the optofluidic‐SERS testing of this study, 100× higher enhancement factors and more than 1,000× better detection limit are achieved compared with traditional colloidal Ag NPs, the improvement of which is attributed to unique properties of the mesocapsules. First, the porous diatom biosilica frustules serve as carrier capsules for high density Ag NPs that form high density plasmonic hot‐spots. Second, the submicron‐pores embedded in the frustule walls not only create a large surface‐to‐volume ratio allowing for effective analyte capture, but also enhance the local optical field through the photonic crystal effect. Last, the mesocapsules provide effective mixing with analytes as they are flowing inside the microfluidic channel. The reported mesocapsules achieve single molecule detection of Rhodamine 6G in microfluidic devices and are further utilized to detect 1 × 10−9
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Abstract Nanostructured molecular semiconductor films are promising Surface-Enhanced Raman Spectroscopy (SERS) platforms for both fundamental and technological research. Here, we report that a nanostructured film of the small molecule
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2ra06248h
