High-density Hot Spots Research Articles

Raspberry-Like Plasmonic Nanoaggregates with Programmable Hierarchical Structures for Reproducible SERS Detection of Wastewater Pollutants and Biomarkers.

Conventional solid-based SERS substrates often face challenges with inconsistent sample distribution, while liquid-based SERS substrates are prone to aggregation and precipitation, resulting in irreproducible signals in both cases. In this study, we tackled this dilemma by designing and synthesizing raspberry-like plasmonic nanoaggregates that exhibit a high density of hotspots and are colloidally stable at the same time. In particular, the nanoaggregates consist of a core made of functionalized polystyrene (PS) microspheres, which act as a template for rapid self-assembly of Au@Ag core-shell nanoparticles to form raspberry-like hierarchical nanoaggregates within 5 min of mixing. The optimized nanoaggregates can be used as reproducible and stable SERS substrates for a range of wastewater pollutants (e.g., rhodamine 6G (R6G) and malachite green (MG)) and nucleobases (e.g., adenine and uracil), with the detection limits as low as 1 × 10-10, 1 × 10-16, 3 × 10-8, and 3 × 10-7 M, respectively. Additionally, the trace detection of adenine in clinical urine samples has been successfully demonstrated. Our modular assembly approach opens up new possibilities in SERS substrate design and advanced trace-chemical detection technologies.

Marangoni flow-guided molecular accumulation for sensitive and rapid SERS detection of phthalates

Public attention has been emerging for the prevention and assessment of healthcare risks from phthalate esters (PAEs) in daily life. For the effective detection of small environmentally hazardous materials, we suggest two major points: i) the formation of high-density hotspots and ii) the delivery of molecules to the activated plasmonic regions. In this study, we developed a method for laser-induced Marangoni flow in cotton fabric (CF) nanopillars (NPs) deposited with Au (Au/CFNPs) for the detection of PAEs by surface-enhanced Raman spectroscopy (SERS). We optimized the performance of the Au/CFNP platforms by adjusting both the maskless plasma etching time and the Au deposition thickness. Narrow (∼8 nm) and populated hotspots were achieved at an Ar plasma treatment time of 30 s and a Au thickness of 150 nm. The molecular behaviors were observed via real-time monitoring of SERS signals. Under continuous laser illumination, Marangoni radial convection flow became predominant over the outward capillary force, resulting in molecular accumulation in the detection areas. For small probe dyes and PAEs, the maximum intensities were achieved within 80 s after the injection of analytes and their signal fluctuations were estimated to have a relative standard deviation of < 10 %, which indicated sensitive and reproducible sensing. The prediction of PAEs extracted from the actual samples was investigated on the basis of a model used to quantitatively fit reference samples and the results were compared with those obtained by high-performance liquid chromatography. The results demonstrated that the combination of densified hotspots on three-dimensional porous substrates and laser-induced Marangoni flow is highly desirable for on-site early screening assays for low-quantity harmful materials present in surrounding environments.

Direct Writing of SERS Substrates Using Femtosecond Laser Pulses.

Achieving a high-density, repeatable, and uniform distribution of "hotspots" across the entire surface-enhanced Raman scattering (SERS) substrate is a current challenge in facilitating the efficient preparation of large-area SERS substrates. In this study, we aim to produce homogeneous surface-enhanced Raman scattering (SERS) substrates based on the strong interaction between femtosecond laser pulses and a thin film of colloidal gold nanoparticles (AuNPs). The SERS substrate we obtained consists of irregularly shaped and sharp-edged gold nanoparticle aggregates with specially extruding features; meanwhile, a large number of three-dimensional AuNP stacks are produced. The advantages of such configurations lie in the production of a high density of hotspots, which can significantly improve the SERS performance. When the laser fluence is 5.6 mJ/cm2, the substrate exhibits the best SERS enhancement effect, and a strong SERS signal can still be observed when testing the concentration of R6G at 10-8 mol/L. The enhancement factor of such SERS substrates prepared using femtosecond laser direct writing is increased by 3 orders of magnitude compared to the conventional furnace annealing process. Furthermore, the relative standard deviation for the intensities of the SERS signals was measured to be 5.1% over an area of 50 × 50 μm2, indicating a highly homogeneous SERS performance and excellent potential for practical applications.

In-situ growth of silver nanoparticles on 3D cellulose nanofibrous network for SERS sensing of pesticide residues on uneven surfaces

In this work, 3D nanofibrous network of bacterial nanocellulose (BNC) was employed as matrix template material in a composite system. The plasmonic silver nanoparticles (AgNPs) were in-situ grown onto the nanofibrous network of BNC to form AgNPs@BNC composite nanofibers. Flexible 3D SERS substrates of BNC nanofibrous network with various AgNPs loadings were manufactured by a simple and rapid vacuum-filtration route. Silver nanoparticles were uniformly and firmly embedded into nanocellulose supporting substrate to form 3D high-density SERS hot spots, resulting in a significant enhancement of electromagnetic field. In addition, the hydrophilic BNC demonstrates exceptional adsorption and permeation characteristics, allowing for the capture of target molecules in hotspot regions to amplify detection sensitivity. Consequently, the AgNPs decorated BNC SERS substrate achieves a notable detection sensitivity of 10−14 M, prominent signal homogeneity (RSD=7.3 %) and remarkable storage stability (over a month) for malachite green molecules. A lowest distinguishable level of 10−9 M for carbendazim molecules is also achieved. Moreover, carbendazim residues on uneven fruit surfaces can be directly and rapidly recognized by flexible AgNPs@BNC SERS sensor using a facile adhere-and-read method.

Flexible Multicavity SERS Substrate Based on Ag Nanoparticle-Decorated Aluminum Hydrous Oxide Nanoflake Array for Highly Sensitive In Situ Detection.

Flexible surface-enhanced Raman scattering (SERS) substrates are very promising to meet the needs for real-time and on-field detection in practical applications. However, high-performance flexible SERS substrates often suffer from complexity and high cost in fabrication, limiting their widespread applications. Herein, we developed a facile method to fabricate a flexible multicavity SERS substrate composed of a silver nanoparticle (AgNP)-decorated aluminum hydrous oxide nanoflake array (NFA) grown on a polydimethylsiloxane (PDMS) membrane. Strong plasmon couplings promoted by multiple nanocavities afford high-density hotspots within such a flexible AgNPs@NFA/PDMS film, boosting high SERS sensitivity with an enhancement factor (EF) of ∼1.54 × 109, and a limit of detection (LOD) of ∼7.4 × 10-13 M for rhodamine 6G (R6G) molecules. Furthermore, benefiting from the high sensitivity, high mechanical stability, and transparency of this substrate, in situ SERS detections of trace thiram and crystal violet (CV) molecules on the surface of cherry tomatoes and fish have been realized, with LODs much lower than the maximum allowable limit in food, demonstrating the great potential of such a flexible substrate in food safety monitoring. More importantly, the preparation processes are very simple and environmentally friendly, and the techniques involved are completely compatible with well-established silicon device technologies. Therefore, large-area fabrication with low cost can be readily realized, enabling the extensive applications of SERS sensors in daily life.

Large-area Ag “sesame cake-like” arrays with high-density hotspots for efficient SERS analysis

Nanogap-rich plasmonic metal nanostructures have attracted great attention in surface enhanced Raman scattering (SERS) applications due to their prominent performances. Herein, utilizing enhanced surface diffusion of Ag atoms on a low energy surface, a facile fabrication strategy is developed to construct a large-area Ag “sesame cake-like” (ASCL) array by combining the ultra-thin alumina mask (UTAM) and vapor deposition technique. Owing to the multiple plasmonic coupling effects, the proposed ASCL array possesses enormous hotspots responsible for remarkable sensitivity with an enhancement factor of 4.9 × 106, excellent reproducibility with a relative standard deviation (RSD) smaller than 7.12 % and obvious polarization independent in SERS analysis, which are confirmed by numerical simulations. In addition, the possibility to be fabricated on the flexible substrate makes the ASCL array substrate well meet the increasing demands for practical applications in the fields of food safety, health and environment monitoring.

Fabrication of SERS composite substrates using Ag nanotriangles-modified SiO2 photonic crystal and the application of malachite green detection

A novel surface-enhanced Raman scattering (SERS) composite substrates on the basis of Ag triangular nanoplates(Ag TNPs)-modified SiO2 photonic crystals (PC) is fabricated and applied to the SERS detection of malachite green (MG). It consists of uniformly arranged Ag TNP@SiO2, a new PC. Notably, Ag TNP are uniformly aligned on the SiO2 surface, forming a three-dimensional high-density hotspot nanostructure. With the tip “hot spots” of Ag TNPs, Bragg diffraction of SiO2 and coupling enhancement between Ag TNPs and SiO2, the SERS enhancement of this composite substrates was multiplied. The effect on the SERS of Ag TNP@SiO2 composite substrate was systematically optimized by tuning Ag TNP size, size of SiO2 microspheres, coverage of Ag TNPs on SiO2 and fabrication method of Ag TNPs and PC. Moreover, the uniform of SERS composite substrates and Raman signal was dramatically increased by the method of vertical deposition. Eventually, the SERS composite substrates were employed in MG detection. Its broad detection range of 1 pM–1 μM and low limit of detection (LOD) of 0.49 pM indicated acceptable sensitivity and repeatability. This work illustrates the promising applicability in food safety analysis based on SERS composite substrates composed by Ag TNP@SiO2 with numerous SERS enhancements and excellent stability.

Regenerated SERS substrate based on Ag/AuNPs-TiO2-oxidized carbon cloth for detection of imidacloprid

Imidacloprid (IMI) are widely used in modern tea industry for pest control, but IMI residues pose a great threat to human health. Herein, we propose a regeneration metal-semiconductor SERS substrate for IMI detection. We fabricated the SERS sensor through the in-situ growth of a nano-heterostructure incorporating a semiconductor (TiO2) and plasmonic metals (Au, Ag) on oxidized carbon cloth (OCC). Leveraging the high-density hot spots, the formed Ag/AuNPs-TiO2-OCC substrate exhibits higher enhancement factors (1.92 × 108) and uniformity (RSD = 7.68%). As for the detection of IMI on the substrate, the limit of detection was lowered to 4.1 × 10−6 μg/mL. With a hydrophobic structure, the Ag/AuNPs-TiO2-OCC possessed excellent self-cleaning performance addressing the limitation of single-use associated with traditional SERS substrates, as well as the degradation capability of the substrate under ultraviolet (UV) light. Accordingly, Ag/AuNPs-TiO2-OCC showcases outstanding SERS sensing and regenerating properties, making it poised for extensive application in the field of food safety assurance.

Metamaterial absorbers with Au nanoctahedrons hybrid Ag nanowires for highly efficient UV–Vis absorption and SERS sensing

Herein, a class of functional metamaterial absorbers (MAs) was developed: chemically synthesized Au nanoctahedrons randomly arranged on Ag nanowires (NWs) to form 3D-stacked hybrid structures that is capable of effective absorption of UV–Vis light, and exhibiting surface-enhanced Raman scattering (SERS) sensing performance. Interestingly, these MAs were constructed using a simple functional-group binding and droplet-evaporation self-assembly strategy. Experimental results show that well-designed MAs, with appropriate surface coverage (15–25 %) of Au nanoctahedrons on Ag NWs exhibit a measured average absorptance above 95 % across the 200 to 800 nm wavelength range. Additionally, the proposed MAs demonstrate a SERS enhancement factor of 1.5–2.2 × 109, which is much higher than that of individual Ag NWs or Au nanoctahedrons. The limit of detection for 4-mercaptopyridine molecules was found to be ∼10−11 mol/L. It is inferred that the multiple plasmonic resonances and coupling derived from the hybridization of Au nanoctahedrons and Ag NWs are vital in achieving broadband and high absorbance of UV–Vis spectrum, and the produced conspicuous E-field enhancements with high-density hotspots greatly enhance the SERS-sensing performance. These findings suggest the potential of such functional MAs as promising candidates for optical devices aimed at solar-energy harvesting or trace-substance detection.

Ag Nanoparticles@Au Nanograting Array as a 3D Flexible and Effective Surface-Enhanced Raman Scattering Substrate.

Surface-enhanced Raman scattering (SERS) is a powerful analytical technique for chemical identification, but it remains a great challenge to realize the large-scale and well-controlled fabrication of sensitive and repeatable SERS substrates. Here, we report a facile strategy to fabricate centimeter-sized periodic Au nanograting (Au-NG) decorated with well-arranged Ag nanoparticles (Ag-NPs) (denoted as Ag-NPs@Au-NG) as a three-dimensional (3D) flexible hybrid SERS substrate with high sensitivity and good reproducibility. The Au-NG patterns with periodic ridges and grooves are fabricated through nanoimprint lithography by employing a low-cost digital versatile disc (DVD) as a master mold, and the Ag-NPs are assembled by a well-controlled interface self-assembly method without any coupling agents. Multiple coupling electromagnetic field effects are created at the nanogaps between the Ag-NPs and Au-NG patterns, leading to high-density and uniform hot spots throughout the substrate. As a result, the Ag-NPs@Au-NG arrays demonstrate an ultrahigh SERS sensitivity as low as 10-13 M for rhodamine 6G with a high average enhancement factor (EF) of 1.85 × 108 and good signal reproducibility. For practical applications, toxic organic pollutants including crystal violet, thiram, and melamine have been successfully detected with high sensitivity at a low detection limit, showing a good perspective in the rapid detection of toxic organic pollutants.

Cotton swabs wrapped with three-dimensional silver nanoflowers as SERS substrates for the determination of food colorant carmine on irregular surfaces.

A lightweight, portable, low-cost, and accessible cotton swab was employed as surface enhanced Raman spectroscopy (SERS) matrix template. The silver nanoflowers were in situ grown on the surface of cotton swabs to form three-dimensional Ag nanoflower@cotton swabs (AgNF@CS) SERS substrate with high-density and multi-level hot spots. The SERS performance of AgNFs@CS substrates with various reaction time was systematically studied. The optimal AgNF-120@CS SERS substrate exhibits superior detection sensitivity of 10-10M for methylene blue, good signal reproducibility, high enhancement factor of 1.4 × 107, and excellent storage stability (over 30days). Moreover, the AgNF-120@CS SERS substrate also exhibits prominent detection sensitivity of 10-8M for food colorant of carmine. Besides, the portable AgNF-120@CS SERS substrate is also capable of detecting food colorant residues on irregular food surfaces.

A Three-Dimensional Hydrophobic Surface-Enhanced Raman Scattering Sensor via a Silver-Coated Polytetrafluoroethylene Membrane for the Direct Trace Detection of Molecules in Water.

We report a three-dimensional (3D) SERS substrate consisting of a silver nanoparticle (AgNP) coating on the skeleton-fiber surfaces of a polytetrafluoroethylene (PTFE) membrane. Simple thermal evaporation was employed to deposit Ag onto the PTFE membrane to produce grape-shaped AgNPs. The 3D-distributed AgNPs exhibit not only strong localized surface plasmon resonance (LSPR) but also strong hydrophobic performance. High-density hotspots via silver nano-grape structures and nanogaps, the large 3D interaction volume, and the large total surface area, in combination with the hydrophobic enrichment of the specimen, facilitate high-sensitivity sensing performance of such a SERS substrate for the direct detection of low-concentration molecules in water. An enhancement factor of up to 1.97 × 1010 was achieved in the direct detection of R6G molecules in water with a concentration of 10-13 mol/L. The lowest detection limit of 100 ppt was reached in the detection of melamine in water. Such a SERS sensor may have potential applications in food-safety control, environmental water pollution monitoring, and biomedical analysis.

Ag supraparticles with 3D hot spots to actively capture molecules for sensitive detection by surface enhanced Raman spectroscopy.

To achieve highly sensitive detection using surface-enhanced Raman spectroscopy (SERS), it is imperative to fabricate a substrate with a high density of hot spots and facilitate the entry of target molecules into these hot spot regions. However, steric hindrance arising from the presence of surfactants and ligands on the SERS substrate may impede the access of target molecules to the hot spots. Here, we fabricate non-close-packed three-dimensional (3D) supraparticles with high-density hot spots to actively capture molecules. The formation of 3D supraparticles is attributed to the minimization of free energy during the gradual contraction of the droplet. The numerous capillaries present in non-close-packed supraparticles induce the movement of target molecules into the hot spot region through capillary force along with the solution. The results demonstrate that the SERS enhancement effect of 3D supraparticles is at least one order of magnitude higher than that of multi-layered nanoparticle structures formed under natural drying conditions. In addition, the SERS performance of 3D supraparticles is evaluated with diverse target molecules, including antimicrobial agents and drugs. Hence, this work provides a new idea for the preparation of non-close-packed substrates for SERS sensitive detection.

Formation of fast-ignition hotspots and propagartion of burning waves in pre-compressed isochoric plasmas

The formation and evolution of hotspots is important for achieving ignition and high energy gain in inertial fusion process. However, most of relevant studies are carried out on pre-compressed plasmas with an isobaric configuration, the evolution of the hotspot in a plasma with an isochoric configuration is rarely studied. In this paper, a semi-analytical model is developed to describe the evolution of the hotspot boundary and propagation of fusion burning waves for a high-density pre-compressed plasma with an isochoric configuration in the double-cone ignition scheme. For the shock wave, the strong shock wave approximation and the quasi-isobaric approximation are reasonable. The quasi-isobaric approximation shows that as the plasma density behind the shock wave increases, the plasma temperature decreases. Because of these, the range of &lt;inline-formula&gt;&lt;tex-math id="M4"&gt;\begin{document}$ {\mathrm{\alpha }} $\end{document}&lt;/tex-math&gt;&lt;alternatives&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M4.jpg"/&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M4.png"/&gt;&lt;/alternatives&gt;&lt;/inline-formula&gt;-particles decreases rapidly behind the shock wave, forming an &lt;inline-formula&gt;&lt;tex-math id="M5"&gt;\begin{document}$ {\mathrm{\alpha }} $\end{document}&lt;/tex-math&gt;&lt;alternatives&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M5.jpg"/&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M5.png"/&gt;&lt;/alternatives&gt;&lt;/inline-formula&gt;-particle absorption peak. Therefore, considering that the hotspot is the main region where &lt;inline-formula&gt;&lt;tex-math id="M6"&gt;\begin{document}$ {\mathrm{\alpha }} $\end{document}&lt;/tex-math&gt;&lt;alternatives&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M6.jpg"/&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M6.png"/&gt;&lt;/alternatives&gt;&lt;/inline-formula&gt;-particles are produced and deposited, the position of the shock peak can be used to identify the boundary of the hotspot in a high-density plasma with an isochoric configuration. It also shows that a “self-regulating burning process” exists in the burning process of the isochoric hotspot, most of &lt;inline-formula&gt;&lt;tex-math id="M7"&gt;\begin{document}$ {\mathrm{\alpha }} $\end{document}&lt;/tex-math&gt;&lt;alternatives&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M7.jpg"/&gt;&lt;graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="5-20231474_M7.png"/&gt;&lt;/alternatives&gt;&lt;/inline-formula&gt;-particles are deposited in the stable region and behind the shock, and finally, transport through the shock peak and heat the cold fuel, resulting in the temperature rising. In the high-density hotspots of plasma with an isochoric configuration, the deposition of α-particles behaves as an obvious non-uniform distribution effect. By analyzing the non-uniform deposition of α-particles, the deposition rate of α-particles at the edge of spherical uniform hotspot is calculated, then the temperature and density evolution of the isochoric hotspot can be well described. The model can be used to estimate the Lawson parameter of the hotspots at the end of the early stage of ignition. It is found that a lower fast electron energy is more beneficial to ignition and high gain operation of fusion plasma. It is also shown that the high density of the hotspots in the isochoric plasma will lead to a higher fusion burning rate, which can offset the negative influence of the shock wave and even achieve higher energy gain. The semi-analytical model is verified by the hydrodynamic simulations of O-SUKI-N.

Rapid population decline in McKay’s Bunting, an Alaskan endemic, highlights the species’ current status relative to international standards for vulnerable species

Abstract The McKay’s Bunting (Plectrophenax hyperboreus) is endemic to Alaska, breeds solely on the remote and uninhabited St. Matthew and Hall islands (332 km2) in the central Bering Sea, and is designated as a species of high conservation concern due to its small population size and restricted range. A previous hypothesized population estimate (~2,800 to 6,000 individuals) was greatly increased (~31,200 individuals) after systematic surveys of the species’ entire breeding range in 2003, establishing McKay’s Bunting as one of the rarest passerines in North America. In 2018, we replicated the 2003 surveys and used density surface models to estimate breeding season densities, distributions, and population change over the intervening time period. Our results indicate that the McKay’s Bunting population declined by 38% (95% CI: 27 to 48%) from ~31,560 to 19,481 individuals since 2003. Spatial model predictions showed no areas with an increase of birds on either St. Matthew or Hall islands but revealed declines across 13% (42 km2) of St. Matthew Island. Declines disproportionately occurred both in marginal habitats with reduced rocky nesting substrate and in high-density hotspots along the coast of St. Matthew Island. The total area occupied by breeding adults decreased by 8%, and high-density hotspots shifted inland from the coast of St. Matthew Island to higher elevations on both islands, the latter potentially responses to exceptionally warm weather and reduced spring snow cover in 2018. Additionally, we observed low numbers of predators and interspecific competitors in 2018, suggesting that these did not cause the decline. Our findings indicate that McKay’s Bunting meets international standards for elevating its conservation status from Least Concern to Endangered based on the International Union for Conservation of Nature Red List of Threatened Species ranking criteria. Additional population monitoring and studies to identify the causal mechanisms of the recent population decline of this rare species could assist future population assessments.

An Ultralow‐Cost, Durable, Flexible Substrate for Ultrabroadband Surface‐Enhanced Raman Spectroscopy

Flexible devices have recently seen notable advancements for use in various areas. Surface‐enhanced Raman spectroscopy (SERS) has emerged as a transformative technology in this space. However, practical applications of flexible SERS substrates are often restricted to labs, hindered by challenges such as inconsistent reproducibility, limited scalability (&lt;10 mm2), short lifespan (&lt;1 day), narrowband response (&lt;100 nm), and especially high costs (&gt;10 dollars mm−2). Addressing these barriers, an ultralow‐cost (≈10 cents mm−2), highly durable, flexible substrate that boasts exceptional SERS performance is studied. This highly scalable, adhesive, ultrathin nanomesh, crafted from a 3D network of silver‐deposited PVA nanofibers, ensures a high density of hotspots and consistent measurements (&lt;20% CV). Its protective PVA layer keeps the silver unoxidized for sustained usage (&gt;1 month). Remarkably versatile, this substrate works across a range of excitation laser wavelengths in both the visible and near‐infrared regions, including 488, 532, 633, and 785 nm. Furthermore, the substrate has shown its efficacy in analyzing residual pesticides on fruits for food safety testing and human biofluids (sweat and urine) for health monitoring. This innovation paves the way for transitioning SERS applications from labs to industrial settings.

Ultra-sensitive SERS detection of Aβ 1–42 for Alzheimer's disease using graphene oxide/gold nanohybrids

Alzheimer's disease (AD) is an irreversible neurodegenerative brain disorder and the most common cause of dementia with significant social and economic impact. Despite the severity and prevalence of AD, early diagnosis of AD remains quite challenging. One of the important markers of neuropathology in AD patients is the aggregation of Aβ1–42 monomers into oligomers, which then become fibrils and eventually form beta-amyloid plaques. Herein, a highly sensitive surface-enhanced Raman spectroscopy (SERS) method based on graphene oxide/gold nanoparticles (GO/Au NPs) for the detection of Aβ 1–42 is proposed. Specifically, Au NPs were deposited on the GO surface by in situ reduction to form high-density hot spots for SERS. The limits of detection are 0.0232 ng mL-1 and 0.0192 ng mL-1 for Aβ1–42 monomer and fibrils. In addition, support vector machine (SVM) and one-dimensional convolutional neural network (1DCNN) algorithm were used to identify samples with different fibrils degrees. SERS is expected to be used for label-free diagnosis and early detection of AD, which has exciting potential for biomedical detection.

Three-Phase Catassembly of 10 nm Au Nanoparticles for Sensitive and Stable Surface-Enhanced Raman Scattering Detection.

Interfacial self-assembly with the advantage of providing large-area, high-density plasmonic hot spots is conducive to achieving high sensitivity and stable surface-enhanced Raman scattering (SERS) sensing. However, rapid and simple assembly of highly repeatable large-scale multilayers with small nanoparticles remains a challenge. Here, we proposed a catassembly approach, where the "catassembly" means the increase in the rate and control of nanoparticle assembly dynamics. The catassembly approach was dropping heated Au sols onto oil chloroform (CHCl3), which triggers a rapid assembly of plasmonic multilayers within 15 s at the oil-water-air (O/W/A) interface. A mixture of heated sol and CHCl3 constructs a continuous liquid-air interfacial tension gradient; thus, the plasmonic multilayer film can form rapidly without adding functional ligands. Also, the dynamic assembly process of the three-phase catassembly ranging from cluster to interfacial film formation was observed through experimental characterization and COMSOL simulation. Importantly, the plasmonic multilayers of 10 nm Au NPs for SERS sensing demonstrated high sensitivity with the 1 nM level for crystal violet molecules and excellent stability with an RSD of about 10.0%, which is comparable to the detection level of 50 nm Au NPs with layer-by-layer assembly, as well as breaking the traditional and intrinsic understanding of small particles of plasmon properties. These plasmonic multilayers of 10 nm Au NPs through the three-phase catassembly method illustrate high SERS sensitivity and stability, paving the way for small-nanoparticle SERS sensing applications.

Increasing hotspots density for high-sensitivity SERS detection by assembling array of Ag nanocubes

Trace analysis has great promise in the fields of disease diagnosis and environment protection. Surface-enhanced Raman scattering (SERS) has wide range of utilization due to its reliable fingerprint detection. However, the sensitivity of SERS still needs to be enhanced. Raman scattering of target molecules around hotspots, the area with extremely strong electromagnetic field, can be highly amplified. Therefore, to increase the density of hotspots is one of the major approaches for enhancing the detection sensitivity of target molecules. In this paper, an ordered array of Ag nanocubes was assembled on a thiol modified silicon substrate as a SERS substrate, which provided high-density hotspots. The detection sensitivity is demonstrated by the limit of detection, which is down to 10-6nM with Rhodamine 6G as probe molecule. The wide linear range (10-7-10-13M) and low relative standard deviation (<6.48%) indicate the good reproducibility of the substrate. Furthermore, the substrate can be used for the detection of dye molecules in lake water. This method provides an approach for increasing hotspots of SERS substrate, which could be a promising method to achieve good reproducibility and high sensitivity.

Multi-dimensional plasmonic coupling system for efficient enrichment and ultrasensitive label-free SERS detection of bilirubin based on graphene oxide-Au nanostars and Au@Ag nanoparticles

Rapid and sensitive detection of free bilirubin (BR) is essential for early diagnosis of jaundice and other hepatobiliary diseases. Inspired by sandwich immunoassay strategy, a multi-dimensional plasmonic coupling SERS platform composed of graphene oxide-Au nanostars nanocomposites (GANS NCs) and Au@Ag nanoparticles (NPs) was designed for label-free detection of BR. Specifically, GANS NCs were first prepared, and their excellent SERS activity was ascribed to synergistic enhancement effect of electromagnetic enhancement and chemical enhancement. Furthermore, SERS spectroscopy was used to monitor the adsorption process of BR. Subsequently, secondary reinforcing Au@Ag NPs were directly added, ultimately resulting in a multi-dimensional plasmonic coupling effect. The SERS enhancing mechanism of coupled system was discussed through electromagnetic field simulations. Interestingly, the high-density hotspots generated by strong plasmonic coupling in GANS-Au@Ag substrate could lead to more extraordinary SERS enhancing behavior compared to GANS NCs. Sensing efficiency of the SERS platform was examined by BR with a detection limit down to 10−11 M. Besides, GANS-Au@Ag NCs performed high uniformity and reproducibility. This work not only opens up a new avenue for construction of multi-dimensional plasmonic coupling system, but also offers a new biosensing technology for label-free diagnosis of BR-related diseases, thereby expecting to be applied in clinical diagnosis.