Surface-enhanced Raman Scattering Signal Enhancement Research Articles

Surface-Enhanced Raman Scattering Based on Sb2S3 Microstructures via Femtosecond Laser Direct Writing.

The noble-metal-free surface-enhanced Raman scattering (SERS) substrates have gained significant attention due to their abundant sources, signal uniformity, biocompatibility, and chemical stability. However, the lack of controllable synthesis and fabrication methods for high-SERS-activity noble-metal-free substrates hinders their practical applications. In this study, we demonstrate the use of a femtosecond laser direct writing technique to precisely manipulate and modify microstructures, resulting in enhanced SERS signals from Sb2S3 nonmetal-oxide semiconductor materials. Compared with unpatterned Sb2S3 samples, the Sb2S3 microstructures exhibited up to a 16-fold increase in Raman scattering intensity. Interestingly, our results indicate that the femtosecond laser can induce a transformation in the crystalline state of Sb2S3 and significantly enhance the Raman spectrum signal within the Sb2S3 microstructures. This enhancement is also highly dependent on the period and depth of the microstructures, possibly due to the cavity effects, resulting in a stronger local field enhancement.

Dual-Modal Colorimetric and Surface-Enhanced Raman Scattering (SERS)-Based Lateral Flow Immunoassay for Ultrasensitive Detection of SARS-CoV-2 Using a Plasmonic Gold Nanocrown.

The 2019 coronavirus disease (COVID-19) outbreak created an unprecedented need for rapid, sensitive, and cost-effective point-of-care diagnostic tests to prevent and mitigate the spread of the SARS-CoV-2 virus. Herein, we demonstrated an advanced lateral flow immunoassay (LFIA) platform with dual-functional [colorimetric and surface-enhanced Raman scattering (SERS)] detection of the spike 1 (S1) protein of SARS-CoV-2. The nanosensor was integrated with a specially designed core-gap-shell morphology consisting of a gold shell decorated with external nanospheres, a structure referred to as gold nanocrown (GNC), labeled with a Raman reporter molecule 1,3,3,1',3',3'-hexamethyl-2,2'-indotricarbocyanine iodide (HITC) to produce a strong colorimetric signal as well as an enhanced SERS signal. Among the different plasmonics-active GNC nanostructures, the GNC-2 morphology, which has a shell decorated with an optimum number and size of nanospheres, produces an intense dark-blue colorimetric signal and ultrahigh SERS signal. The limit of detection (LOD) of the S1 protein via colorimetric detection LFIA was determined to be 91.24 pg/mL. On the other hand, the LOD for the SERS LFIA method was more than three orders of magnitude lower at 57.21 fg/mL. Furthermore, we analyzed the performance of the GNC-2 nanosensor for directly analyzing the S1 protein spiked in saliva samples without any sample pretreatment and achieving the LOD as low as 39.65 fg/mL using SERS-based plasmonics-enhanced LFIA, indicating ultrahigh detection sensitivity. Overall, our GNC nanosensor showed excellent sensitivity, reproducibility, and rapid detection of the SARS-CoV-2 S1 protein, demonstrating excellent potential as a promising point-of-care platform for the early detection of respiratory virus infections.

A mesoporous gold biosensor to investigate immune checkpoint protein heterogeneity in single lung cancer cells

Immune checkpoint proteins (ICPs) play a major role in a patient's immune response against cancer. Tumour cells usually express those proteins to communicate with immune cells as a process of escaping the anti-cancer immune response. Detecting the major functional immune checkpoint proteins present on cancer cells (such as circulating tumor cells or CTCs) and examining the heterogeneity in their expression at the single-cell level could play a crucial role in both cancer diagnosis and the monitoring of therapy. In this study, we develop a mesoporous gold biosensor to precisely assess ICP heterogeneity in individual cancer cells within a lung cancer model. The platform utilizes a nanostructured mesoporous gold surface to capture CTCs and a Surface Enhanced Raman Scattering (SERS) readout to identify and monitor the expression of key ICP proteins (PD-L1, B7H4, CD276, CD80) in lung cancer cells. The homogeneous and abundant pores in mesoporous 3D gold nanostructures enable increased antibody loading on-chip and an enhanced SERS signal, which are key to our single cell capture, and accurate analysis of ICPs in cancer cells with high sensitivity. Our lung cancer cell line model data showed that our method can detect single cells and analyse the expression of four lung cancer associated ICPs on individual cell surfaces during treatment. To show the potential of our mesoporous gold biosensor in analysing clinical samples, we tested 9 longitudinal Peripheral Blood Mononuclear Cells (PBMC) samples from lung cancer patient before and after therapy. Our mesoporous biosensor successfully captured single CTCs and found that the expression of ICPs in CTCs is highly heterogeneous in both pre-treatment and treated PBMC samples isolated from lung cancer patient blood. We suggest that our findings will help clinicians in selecting the most appropriate therapy for patients.

Influence of sandwich-type DNA construction strategy and plasmonic metal on signal generated by SERS DNA sensors

The DNA biosensors are powerful tools in the gene mutation or pathogens detection. That is why there are a lot of DNA detection strategies and methods. Here we present the insight on a slightly overlooked DNA detection technique, surface-enhanced Raman scattering (SERS). The present work is a summary of the influence of the plasmonic metal of the SERS substrate and strategy of the sandwich-type biosensor construction, simply the placement of the Raman reporter and mismatches, on the SERS signal enhancement. We found that, although in general there is an increase in the intensity of the SERS signal when the distance between the Raman scatterer and the SERS-active surface decreases, for this type of DNA SERS sensor a greater intensity of the measured Raman signal is usually observed when the Raman reporter is farther away from the plasmonic substrate. This is probably caused by a significant change in the hybridisation efficiency for the different structures of the sensor analysed due to some steric hindrances.

Ultrasensitive detection of crystal violet using a molybdenum sulfide-silver nanostructure-based sensing platform: roles of the adsorbing semiconductor in SERS signal enhancement.

Crystal violet (CV) is an organic dye that is stabilized by the extensive resonance delocalization of electrons over three electron-donating amine groups. This prevents the molecule from being linked to a metal surface, and therefore, reduces the sensitivity of surface-enhanced Raman scattering (SERS) sensors for this toxic dye. In this work, we improved the sensing performance of a silver-based SERS sensor for CV detection by modifying the active substrate. Molybdenum sulfide (MoS2) nanosheets were employed as a scaffold for anchoring electrochemically synthesized silver nanoparticles (e-AgNPs) through a single step of ultrasonication, leading to the formation of MoS2/Ag nanocomposites. As an excellent adsorbent, MoS2 promoted the adsorption of CV onto the surface of the substrate, allowing more CV molecules to be able to experience the SERS effect originating from the e-AgNPs. Hence, the SERS signal of CV was significantly enhanced. In addition, the effects of the MoS2 content of the nanocomposites on their SERS performance were also taken into account. Using MoS2/Ag with the most optimal MoS2 content of 10%, the SERS sensor exhibited the best enhancement of the SERS signal of CV with an impressive detection limit of 1.17 × 10-11 M in standard water and 10-9 M in tap water thanks to an enhancement factor of 2.9 × 106, which was 11.2 times higher than that using pure e-AgNPs.

Ag-Decorated Si Microspheres Produced by Laser Ablation in Liquid: All-in-One Temperature-Feedback SERS-Based Platform for Nanosensing.

Combination of dissimilar materials such as noble metals and common semiconductors within unified nanomaterials holds promise for optoelectronics, catalysis and optical sensing. Meanwhile, difficulty of obtaining such hybrid nanomaterials using common lithography-based techniques stimulates an active search for advanced, inexpensive, and straightforward fabrication methods. Here, we report one-pot one-step synthesis of Ag-decorated Si microspheres via nanosecond laser ablation of monocrystalline silicon in isopropanol containing AgNO3. Laser ablation of bulk silicon creates the suspension of the Si microspheres that host further preferential growth of Ag nanoclusters on their surface upon thermal-induced decomposition of AgNO3 species by subsequently incident laser pulses. The amount of the AgNO3 in the working solution controls the density, morphology, and arrangement of the Ag nanoclusters allowing them to achieve strong and uniform decoration of the Si microsphere surface. Such unique morphology makes Ag-decorated Si microspheres promising for molecular identification based on the surface-enhanced Raman scattering (SERS) effect. In particular, the designed single-particles sensing platform was shown to offer temperature-feedback modality as well as SERS signal enhancement up to 106, allowing reliable detection of the adsorbed molecules and tracing their plasmon-driven catalytic transformations. Considering the ability to control the decoration degree of Si microspheres by Ag nanoclusters via amount of the AgNO3, the developed one-pot easy-to-implement PLAL synthesis holds promise for gram-scale production of high-quality hybrid nanomaterial for various nanophotonics and sensing applications.

Zinc oxide nanostructures for fluorescence and Raman signal enhancement: a review.

Since the initial discovery of surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF), these techniques have shown huge potential for applications in biomedicine, biotechnology, and optical sensors. Both methods rely on the high electromagnetic fields created at locations on the surface of plasmonic metal nanoparticles, depending on the geometry of the nanoparticles, their surface features, and the specific location of analyte molecules. Lately, ZnO-based nanostructures have been exploited especially as SERS substrates showing high enhancement factors and increased charge transfer effect. Additionally, applications focused on enhancing the fluorescence of analyte molecules as well as on tuning the photoluminescence properties of ZnO nanostructures through combination with metal nanoparticles. This review covers the major recent results of ZnO-based nanostructures used for fluorescence and Raman signal enhancement. The broad range of ZnO and ZnO–metal nanostructures synthesis methods are discussed, highlighting low-cost methods and the recyclability of ZnO-based nanosubstrates. Also, the SERS signal enhancement by ZnO-based nanostructures and the influences of lattice defects on the SERS signal are described. The photoluminescence enhancement of ZnO in the presence of noble metal nanoparticles and the molecular fluorescence enhancement in the presence of ZnO alone and in combination with metal nanoparticles are also reviewed.

Impact of silver nanoparticles size on SERS for detection and identification of filamentous fungi

Using the proper size of nanoparticles as an active substrate, Surface-enhanced Raman scattering (SERS) can provide a reliable technique for detecting and identifying fungi, including Alternaria alternata, Aspergillus flavus, Fusarium verticilliodes, and Aspergillus parasiticus that have been associated to biodeterioration and biodegradation of cultural heritage materials. In this research spherical silver nanoparticles (AgNPs) of average size of 10, 30 and 60 nm were synthesized using the wet chemical method with good yield and their size and shape distributions were examined using small-angle X-ray scattering (SAXS). The protocol for fungi sample preparation proved to be critical for producing high-quality and reproducible SERS spectra. We found that the effect of AgNPs on SERS signal enhancement is size dependent under the same experimental conditions; the SERS intensity of fungal strains using 60 nm achieved up to 2.3x105 enhancement, about twice as intense as those produced with 30 nm, and 10 nm produced a minor broad weak peak barely discernible around 1400 cm−1, similar to the NR spectra profile in the 550–1700 cm−1 spectral region, and the SERS signals using 60 nm showed high reproducibility, with less than 20% variance. Furthermore, we used principal component analysis (PCA) to statistically classify the SERS spectrum into four separate clusters with 99 percent variability so that the four fungal strains could be clearly detected and identified. The SERS technique, in combination with the PCA developed in this study, provides a simple, rapid, accurate, and cost-effective analytical tool for detecting and identifying filamentous fungal strains.

Influence of two-dimensional molybdenum disulfide on the surface enhanced Raman scattering effect in a silver nanocavity

Surface-enhanced Raman scattering (SERS) is commonly associated with metal nanostructures. However, recently large Raman enhancement has also been reported for two-dimensional (2D) semiconductors. In the present work, we exam systematically the influence of thin 2D molybdenum disulfide (MoS2) films on the SERS properties of a typical silver (Ag) nanocavity formed by a single Ag nanoparticle (NP) and a flat Ag surface. The dependence of the localized electric field, Raman enhancement and spatial resolution on the NP-MoS2 film distance, the thickness of MoS2 film, as well as the NP radius were quantitatively calculated and analyzed. The results show that the presence of MoS2 film could efficiently enhance the plasmonic coupling between the NP and the substrate, leading to more significant SERS enhancement. Thinner MoS2 film and shorter NP-film distance will further improve the localized plasmonic enhancement. The calculated Raman enhancement factor reaches 9.1 ×1010 with monolayer MoS2 film under the 660-nm excitation. We also show that the spatial resolution for Raman spectroscopy could be significantly improved by reducing the NP radius, and the maximum resolutions is 4.5 nm at the radius size of 20 nm. Our results offer a theoretical guidance for better understanding the SERS properties of the novel 2D material and its further applications.

Clusters-based silver nanorings: An active substrate for surface-enhanced Raman scattering

Plasmonic nanostructures, particularly irregular surfaces of ring-like silver (Ag) nanostructures are promising candidates in surface-enhanced Raman scattering (SERS) spectroscopy. In this work, clusters-based Ag nanorings have been fabricated and characterized as SERS-active substrates. The rim of the as-fabricated Ag nanorings was found neither discontinuous nor linear aggregation of nanoparticles. High-resolution field emission scanning electron microscopy (FESEM) revealed that the individual constituent clusters were different from each other, particularly in terms of size and shape in addition to the cases how such clusters were emerged as the edge of the nanoring. Considering the dimensions of the clusters and the arrangement of such clusters as nanorings, it was speculated that the local electromagnetic (EM) near-field distributions would excel and thus enhanced SERS signals would be achieved. Indeed, the inherent features of the nanorings facilitated to achieve SERS enhancement factors as high as 2.1 × 104. SERS-activity of as-fabricated Ag nanorings was confirmed using Rhodamine 6G (R6G) as Raman-active dyes and the enhancement was compared to those obtained from R6G adsorbed on Ag-ZnO/Glass and ZnO/Glass. To the best of our knowledge, this is the first attempt to explore the impact of localized EM near-field within the segments of nanorings through SERS spectroscopy. A model was designed resembling the nanorings under this investigation to simulate EM near-field distributions by finite difference time domain (FDTD) analysis. The dimensions of the model geometry were chosen according to the observations achieved by FESEM. To simplify the simulations, nanoobjects were considered spherical and organized in a periodic fashion, although the constituent clusters of Ag nanorings were found irregular in shape and arrangement. Since EM near-field distribution highly depends on interparticle gaps, three scenarios were implemented, such as, small gap in between two adjacent nanoobjects and adjacent nanoobjects in touch and overlapped. Each configuration was simulated and EM near-field distribution was extracted for s-, p- and 450 of incident polarizations followed by a plausible correlation to SERS enhancements. Such correlated investigations as well as clusters-based Ag nanorings not only inspire the ones to look for cost-effective SERS-active substrate, but also understand the underlying EM mechanism in SERS enhancements.

Design criteria to fabricate plasmonic gold nanomaterials for surface-enhanced Raman scattering (SERS)-based biosensing

The discovery of noble metal plasmonic nanoparticles (PNPs) has introduced surface-enhanced Raman scattering (SERS) as a highly sensitive and specific bioanalytical technique with greater potential in point-of-need disease diagnosis. This Tutorial provides an overview of the principles governing a gold PNP-based biosensor design for sensitive and reliable SERS-based detection of disease biomarkers. First, we will highlight the optical transducer properties of PNPs, the principles of SERS, the benefits of SERS detection, and the modes of SERS for biomarker detection. The analytical performance (sensitivity and specificity) and the reliability (accuracy and reproducibility) of a SERS biosensor are mainly dictated by (i) the chemical and optical transducer properties of PNPs, (ii) the functional nano interface, where the interaction(s) between PNPs and target biomolecules take place, and (iii) SERS data acquisition and evaluation metrics. Maintaining a balance between SERS signal enhancement and reproducibility is critical for advancing the field deployment of SERS technologies. However, the reproducibility of SERS biosensors is often overlooked in lieu of the assay sensitivity. Consequently, next, we will discuss the systematic optimization strategies for fabricating gold PNPs as SERS substrates and designing their functional interface to design SERS biosensors with sufficient sensitivity, specificity, and reproducibility. We will highlight the choice of PNPs and their integration into biosensing platforms depending on the mode of SERS detection. Last, we will discuss the SERS data acquisition and performance evaluation as an integral part of the SERS biosensors development workflow.

Au@ZIF-8 SERS paper for food spoilage detection

Putrescine and cadaverine are important volatile indicators for the evaluation of food spoilage. In this study, a metal-organic framework (MOF)-coated surface-enhanced Raman scattering (SERS) paper platform for the detection of putrescine and cadaverine is developed. Au@ zeolite imidazolate framework-8 (ZIF-8) SERS paper is fabricated by the coating of ZIF-8 layer on a Au nanoparticle-impregnated paper that is prepared by dry plasma reduction. The Au@ZIF-8 SERS paper is characterized by scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray diffraction, and N2 sorption isotherm. The ZIF-8 layer enables the accumulation of gaseous molecules and also provides enhancement of SERS signals. The fluorescence, SERS, and simulation results prove the improved detection ability of the Au@ZIF-8 platform for the volatile molecules. For the selective detection of putrescine and cadaverine, the Au@ZIF-8 SERS paper is functionalized with 4-mercatobenzaldehyde (4-MBA). The 4-MBA molecule acts as a Raman reporter and also a specific receptor for the volatile amine molecules. Using the intensity ratiometric detection of 4-MBA-functionalized Au@ZIF-8 SERS paper, putrescine and cadaverine are quantitatively detected with detection limits of 76.99 and 115.88 parts per billion, respectively. Furthermore, the detection of volatile amine molecules released from spoiled salmon, chicken, beef, and pork samples is demonstrated. It is anticipated that the MOF-coated SERS paper platforms will be applicable not only in food safety but other applications including disease diagnosis and environmental monitoring.

Improved surface-enhanced Raman scattering (SERS) sensitivity to molybdenum oxide nanosheets via the lightning rod effect with application in detecting methylene blue

MoO2 nanomaterials show a superior surface-enhanced Raman scattering (SERS) property due to their high concentration of free electrons and low resistivity. However, the physical process of semiconductor-based SERS is still elusive because there are many factors that affect the local electromagnetic field intensity and the subsequent Raman intensity of the molecules in close proximity to the semiconductor nanomaterials. Herein, we investigate the important contribution of surface morphology to molybdenum oxide SERS. The MoO3/MoO2 nanosheets (NSs) are synthesized by oxidizing MoO2 NS, and the surface roughness of MoO3 can be controlled through adjusting the oxidization time. Compared with the MoO2 NS before oxidization, the MoO3/MoO2 NSs exhibit a much stronger SERS signal, which favors their application as a SERS substrate to detect trace amounts of methylene blue molecules. The minimum detectable concentration is up to 10−9 M and the maximum enhancement factor is about 1.4 × 105. Meanwhile, excellent signal reproducibility is also observed using the MoO3/MoO2 NSs as the SERS substrate. A simulated electric field distribution shows that a stronger electric field enhancement is formed due to the lightning rod effect in the gap of corrugated MoO3 NSs. These results demonstrate that the surface topography of molybdenum oxide may play a more important role than their oxidation state in SERS signal enhancement.

Dual platform based sandwich assay surface-enhanced Raman scattering DNA biosensor for the sensitive detection of food adulteration.

Surface enhanced Raman scattering (SERS) DNA biosensing is an ultrasensitive, selective, and rapid detection technique with the ability to produce molecule-specific distinct fingerprint spectra. It supersedes the long amplicon based PCR assays, the fluorescence and spectroscopic techniques with their quenching and narrow spectral bandwidth, and the electrochemical detection techniques using multiplexing. However, the performance of the SERS DNA biosensor relies on the DNA probe length, platform composition, both the presence and position of Raman tags and the chosen sensing strategy. In this context, we herein report a SERS biosensor based on dual nanoplatforms with a uniquely designed Raman tag (ATTO Rho6G) intercalated short-length DNA probe for the sensitive detection of the pig species Sus scrofa. In the design of the signal probe (SP), a Raman tag was incorporated adjacent to the spacer arm, followed by a terminal thiol modifier, which consequently had a strong influence on the SERS signal enhancement. The detection strategy involves the probe-target DNA hybridization mediated coupling of the two platforms, i.e., the graphene oxide-gold nanorod (GO-AuNR) functionalized capture probe (CP) and SP-conjugated gold nanoparticles (AuNPs), consequently enhancing the SERS intensity by both the electromagnetic hot spots generated at the junctions or interstices of the two platforms and the chemical enhancement between the AuNPs and the adsorbed intercalated Raman tag. This dual platform based SERS DNA biosensor exhibited outstanding sensitivity in detecting pork DNA with a limit of detection (LOD) of 100 aM validated with DNA extracted from a pork sample (LOD 1 fM). Moreover, the fabricated SERS biosensor showed outstanding selectivity and specificity for differentiating the DNA sequences of six closely related non-target species from the target DNA sequences with single and three nucleotide base-mismatches. Therefore, the developed short-length DNA linked dual platform based SERS biosensor could replace the less sensitive traditional methods of pork DNA detection and be adopted as a universal detection approach for the qualitative and quantitative detection of DNA from any source.

Dumbbell-Like Silica Coated Gold Nanorods and Their Plasmonic Properties.

Silica coated gold nanorods (GNRs@SiO2) with dumbbell-like morphology allowing dual functionalization in an individual nanostructure have attracted great attention for applications such as sensing and biological imaging. We report a detailed study on the feasibility of controlling the morphology of silica coating on GNRs. The morphology of the silica shell can be either cylindrical or dumbbell shaped. With constant GNR concentration, the ratio of hexadecyltrimethylammonium bromide (CTAB) and tetraethylorthosilicate (TEOS) concentrations is the key to determine the amount of available TEOS for silica deposition on the GNR since the TEOS will diffuse toward the surface of GNRs. The effect of morphologies on surface-enhanced Raman scattering (SERS) performance was also investigated, and we found that the dumbbell morphology of silica coated gold nanorods has the most significant SERS enhancement. Our study is significant in terms of the capability to control the dumbbell morphology of silica coated gold nanorods, which can eventually broaden the application of these plasmonic nanomaterials.

Selective synthesis of three-dimensional ZnO@Ag/SiO2@Ag nanorod arrays as surface-enhanced Raman scattering substrates with tunable interior dielectric layer**Project supported by the Fund from the Science and Technology Department of Jilin Province, China (Grant No. 20170520108JH), the Beihua University Youth Nurtural Fund, China (Grant No. 2017QNJJL15), the Beihua University PhD Research Start-up Fund, China (Grant No. 202116140), and the Undergraduate Innovation Project,

We describe the synthesis of three-dimensional (3D) multilayer ZnO@Ag/SiO2@Ag nanorod arrays by the physico–chemical method. The surface-enhanced Raman scattering (SERS) performance of the 3D multilayer ZnO@Ag/SiO2@Ag nanorod arrays is studied by varying the thickness of dielectric layer SiO2 and outer-layer noble Ag. The 3D ZnO@Ag/SiO2@Ag nanorod arrays create a huge number of SERS “hot spots” that mainly contribute to the high SERS sensitivity. The great enhancement of SERS results from the electron transfer between ZnO and Ag and different electromagnetic enhancements of Ag nanoparticles (NPs) with different thicknesses. Through the finite-difference time-domain (FDTD) theoretical simulation, the enhancement of SERS signal can be ascribed to a strong electric field enhancement produced in the 3D framework. The simplicity and generality of our method offer great advantages for further understanding the SERS mechanism induced by the surface plasmon resonance (SPR) effect.

Surface-Enhanced Raman Scattering-Fluorescence Dual-Mode Nanosensors for Quantitative Detection of Cytochrome c in Living Cells.

During apoptosis process, the release of cytochrome c (Cyt c) is considered to be a key factor in the intrinsic pathway and is often defined as no regression point. Quantitative detection of intracellular Cyt c remains a challenge. Herein, we have developed surface-enhanced Raman scattering (SERS)-fluorescence dual-mode nanosensors for the quantitative assay of Cyt c in living cells. Dual signal detection was achieved by constructing gold nanotriangles (AuNTs) nanosensors capable of specifically recognizing Cyt c. The nanosensors were prepared by modifying the aptamer of Cyt c on AuNTs and connecting the complementary strands modified with Cy5. The AuNTs provided both enhanced SERS signals and fluorescence quenching effects. Once cells were induced by external stimulus (such as toxins) to release Cyt c, Cyt c would specifically bind to its aptamer, and the complementary strands modified with Cy5 would detach which would result in weakened SERS signal and recovery of fluorescence signal. The experimental results showed that the nanosensors not only had excellent selectivity and sensitivity but also realized real-time monitoring of Cyt c translocation event from mitochondria to cytoplasm. The SERS and fluorescence intensity showed good linear relationship with Cyt c concentration ranging from 0.044 to 9.95 μM and achieved a minimum limit of detection (LOD) of 0.02 μM in living cells. The accuracy of intracellular Cyt c quantitative results was more than 90% compared with the ELISA results.

Quantitative and Specific Detection of Exosomal miRNAs for Accurate Diagnosis of Breast Cancer Using a Surface-Enhanced Raman Scattering Sensor Based on Plasmonic Head-Flocked Gold Nanopillars.

MicroRNAs in exosomes (exosomal miRNAs) have attracted increased attention as cancer biomarkers for early diagnosis and prognosis owing to their stability in body fluids. Since strong association exists between exosomal miRNA expression levels and breast cancer, the development of effective methods that can monitor exosomal miRNA expression both over broad concentration ranges and in ultralow amounts is critical. Here, a surface-enhanced Raman scattering (SERS)-based sensing platform is developed for the quantitative determination of exosomal miRNAs. Ultrasensitive exosomal miRNA detection with single-nucleotide specificity is obtained from enhanced SERS signals from a uniform plasmonic head-flocked gold nanopillar substrate, which generates multiple hotspots and enables hybridization between short oligonucleotides, i.e., miRNAs and locked nucleic acid probes. The proposed SERS sensor shows an extremely low detection limit without any amplification process, a wide dynamic range (1 am to 100 nm), multiplex sensing capability and sound miRNA recovery in serum. Furthermore, this sensor allows reliable observation of exosomal miRNA expression patterns from breast cancer cell lines and can discriminate breast cancer subtype based on the difference between these patterns. The results suggest that this sensor can be used for universal cancer diagnosis and further biomedical applications through the quantitative measurement of exosomal miRNAs in bodily fluids.

Detection of Saturated Fatty Acids Associated with a Self-Healing Synthetic Biological Membrane Using Fiber-Enhanced Surface Enhanced Raman Scattering.

The Synthetic Biological Membrane (SBM) project at NASA Ames developed a portable, self-repairing wastewater purification system. The self-repair process relies upon secreted fatty acids from a genetically engineered organism. However, solubilized fatty acids are difficult to detect using conventional methods. Surface-enhanced Raman scattering (SERS) was used to successfully detect solubilized fatty acids with the following limits of detection: 10-9, 10-8, 10-9, and 10-6 M for decanoic acid, myristic acid, palmitic acid, and stearic acid, respectively. Additionally, hollow core photonic crystal fiber (HCPCF) was applied as the sampling device together with SERS to develop in situ surveillance of the production of fatty acids. Using SERS + HCPCF yielded an 18-fold enhancement in SERS signal for the CH2 twist peak at 1295 cm-1 as compared to SERS alone. The results will help the SBM project to integrate a self-healing wastewater purification membrane into future water recycling systems.

Detection of Saturated Fatty Acids Associated with a Self-Healing Synthetic Biological Membrane Using Fiber-Enhanced Surface Enhanced Raman Scattering.

The Synthetic Biological Membrane (SBM) project at NASA Ames developed a portable, self-repairing wastewater purification system. The self-repair process relies upon secreted fatty acids from a genetically engineered organism. However, solubilized fatty acids are difficult to detect using conventional methods. Surface-enhanced Raman scattering (SERS) was used to successfully detect solubilized fatty acids with the following limits of detection: 10-9 M, 10-8 M, 10-9 M, and 10-6 M for decanoic acid, myristic acid, palmitic acid, and stearic acid, respectively. Additionally, hollow core photonic crystal fiber (HCPCF) was applied as the sampling device together with SERS to develop in situ surveillance of the production of fatty acids. Using SERS + HCPCF yielded an 18 fold enhancement in SERS signal for the CH2 twist peak at 1295 cm-1 as compared to SERS alone. The results will help the SBM project to integrate a self-healing wastewater purification membrane into future water recycling systems.