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
Nanophotonic resonators can confine light to deep-subwavelength volumes with highly enhanced near-field intensity and therefore are widely used for surface-enhanced infrared absorption spectroscopy in various molecular sensing applications. The enhanced signal is mainly contributed by molecules in photonic hot spots, which are regions of a nanophotonic structure with high-field intensity. Therefore, delivery of the majority of, if not all, analyte molecules to hot spots is crucial for fully utilizing the sensing capability of an optical sensor. However, for most optical sensors, simple and straightforward methods of introducing an aqueous analyte to the device, such as applying droplets or spin-coating, cannot achieve targeted delivery of analyte molecules to hot spots. Instead, analyte molecules are usually distributed across the entire device surface, so the majority of the molecules do not experience enhanced field intensity. Here, we present a nanophotonic sensor design with passive molecule trapping functionality. When an analyte solution droplet is introduced to the sensor surface and gradually evaporates, the device structure can effectively trap most precipitated analyte molecules in its hot spots, significantly enhancing the sensor spectral response and sensitivity performance. Specifically, our sensors produce a reflection change of a few percentage points in response to trace amounts of the amino-acid proline or glucose precipitate with a picogram-level mass, which is significantly less than the mass of a molecular monolayer covering the same measurement area. The demonstrated strategy for designing optical sensor structures may also be applied to sensing nano-particles such as exosomes, viruses, and quantum dots.
more » « less- NSF-PAR ID:
- 10208725
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Light: Science & Applications
- Volume:
- 10
- Issue:
- 1
- ISSN:
- 2047-7538
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The enormous increase of Raman signal in the vicinity of metal nanoparticles allows surface‐enhanced Raman spectroscopy (SERS) to be employed for label‐free detection of substances at extremely low concentrations. However, the ultimate potential of label‐free SERS to identify pharmaceutical compounds at low concentrations, especially in relation to biofluid sensing, is far from being fully realized. Opioids are a particular challenge for rapid clinical identification because their molecular structural similarities prevent their differentiation with immunolabeling approaches. In this paper, a new method called quantitative label‐free SERS (QLF‐SERS) which involves the formation of halide‐conjugated gold nanoclusters trapping the analyte of interest near the SERS hot spots is reported, and it is demonstrated that it yields a 105fold improvement in the detection limit over previously reported results for the entire class of clinically relevant opioids and their metabolites. Measurements of opioid concentrations in multicomponent mixtures are also demonstrated. QLF‐SERS has comparable detection limits as currently existing laboratory urine drug testing techniques but is significantly faster and inexpensive and, therefore, can be easily adapted as part of a rapid clinical laboratory routine.
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