Discovery of the High-Affinity Aptamer for Candidalysin Using a Dual-Mode Colorimetric-SERS Platform.

Localized surface plasmon resonance phenomenon in Ag/Au-WO3-x nanocomposite thin films

LSPR based uric acid sensor using graphene oxide and gold nanoparticles functionalized tapered fiber

3 - Sensing based on localized surface plasmon resonance in metallic nanoparticles

This work presents a comprehensive review on gas sensors based on localized surface plasmon resonance (LSPR) phenomenon, including the theory of LSPR, the synthesis of nanoparticle-embedded oxide thin films, and strategies to enhance the sensitivity of these optical sensors, supported by simulations of the electromagnetic properties. The LSPR phenomenon is known to be responsible for the unique colour effects observed in the ancient Roman Lycurgus Cup and at the windows of the medieval cathedrals. In both cases, the optical effects result from the interaction of the visible light (scattering and absorption) with the conduction band electrons of noble metal nanoparticles (gold, silver, and gold–silver alloys). These nanoparticles are dispersed in a dielectric matrix with a relatively high refractive index in order to push the resonance to the visible spectral range. At the same time, they have to be located at the surface to make LSPR sensitive to changes in the local dielectric environment, the property that is very attractive for sensing applications. Hence, an overview of gas sensors is presented, including electronic-nose systems, followed by a description of the surface plasmons that arise in noble metal thin films and nanoparticles. Afterwards, metal oxides are explored as robust and sensitive materials to host nanoparticles, followed by preparation methods of nanocomposite plasmonic thin films with sustainable techniques. Finally, several optical properties simulation methods are described, and the optical LSPR sensitivity of gold nanoparticles with different shapes, sensing volumes, and surroundings is calculated using the discrete dipole approximation method.

Nowadays there is an increasing request to realize green, eco-friendly, and biodegradable electronic devices for biosensor implementation. In this context, we have conceived and realized a green sensor based on localized surface plasmon resonance (LSPR) phenomenon in a thin-slab waveguide of bacterial cellulose (BC). These LSPR sensors can be obtained simply by gold sputtering on the slab BC waveguides. The performances have been studied investigating the presence of ionic liquids (ILs) inside and in absence of ILs with various thicknesses of the BC substrate. Depending of the thickness of the BC layer, the ILs effect on the LSPR can be constructive or destructive. In this work, we present a study of the sensor performances, in terms of bulk sensitivity and resolution by changing the aforementioned parameters. Analyses in terms of BC geometry are pursued in order to improve the interaction between the light and the LSPR phenomenon. The experimental setup used for this kind of extrinsic optical fiber LSPR sensor is based on two optical fibers used to connect a white light source and a spectrometer with the green LSPR sensor chip. Results evince the suitability of the proposed approach in order to realize sensors and biosensors with several intriguing properties and features. In fact, these LSPR platforms could be used to realize disposable biosensors, when a specific bioreceptor is covalently bonded to the gold.

Plasmonic nanosensors for pharmaceutical and biomedical analysis

Synthesis of colloidal silver nanoparticles has been successfully conducted through the chemical reduction technique. The synthesis used AgNO3, NaOH, and alginate as the precursor, accelerator reagent, and reducing agent and stabilizer, respectively. The effects of heating temperature, reaction time, accelerator concentration, and precursor concentration were investigated according to the localized surface plasmon resonance (LSPR) phenomenon using a UV-Vis spectrophotometer. The nanoparticle size distribution was observed via a Particle Size Analyzer (PSA). The stability of silver nanoparticles was studied for 8 weeks based on the LSPR phenomenon. Then, their antibacterial performance toward S. Aureus ATCC 25923 and E. Coli ATCC 25922 was examined. The results showed the absorbance intensities representing the number of silver nanoparticles formed were influenced by temperature, reaction time, NaOH concentration, and AgNO3 concentration. At 50°C heating, the optimum synthesis of silver nanoparticles was achieved at 50 min with a NaOH concentration of 0.013M. The higher AgNO3 concentration resulted in a greater concentration of silver nanoparticles produced. From the PSA characterization, the average particle sizes for the samples were 1.82 nm and 1.30 nm for AgNO3 concentrations (% w/w; AgNO3/Alginate) of 1.6% and 2.4%, respectively. Based on the LSPR phenomenon, colloidal silver nanoparticles were stable in storage for 8 weeks at room temperature. The increase in the concentration of silver nanoparticles within colloidal could enhance antibacterial performance against S. Aureus and E. Coli. Accordingly, silver nanoparticles synthesized with alginate as a stabilizer have the potential as an antibacterial compound for medical applications.

A large number of deaths from cancer can be attributed to the lack of effective early-stage diagnostic techniques. Thus, accurate and effective early diagnosis is a major research goal worldwide. With the unique phenomenon of localized surface plasmon resonance (LSPR), plasmonic nanomaterials have attracted considerable attention for applications in surface-enhanced Raman scattering (SERS) and metal-enhanced fluorescence (MEF). Both SERS and MEF are ultra-sensitive methods for the detection and identification of early tumor at molecular level. To combine the merits of the fast and accurate imaging of MEF and the stable and clear imaging of SERS, we propose a novel dual functional imaging nanoprobe based on gold nanoparticles and gold nanocluster composites (denoted AuNPC-RGD). The gold nanoparticles are used as LSPR substrates to realized enhancement of Raman or fluorescence signal, while the gold nanoclusters serve as a fluorophore for MEF imaging, and exhibit better biocompatibility and stability. Furthermore, target molecule of cyclic Arg-Gly-Asp (cRGD) is incorporated into the composite to improve delivery efficiency, selectivity and imaging accuracy. These integrated properties endow AuNPC-RGD composites with outstanding biocompatibility and excellent imaging abilities, which could be used to achieve accurate and effective diagnosis for early cancer.

Interacting with light, plasmonic materials generate electric fields induced by localized surface plasmon resonance (LSPR) phenomenon. Electric field generated by plasmonic materials can induce optical phenomena such as light scattering, light emissive recombination and surface-enhanced Raman scattering (SERS). These phenomena grant versatile functionalities to plasmonic materials which can be applied to various devices such as photovoltaics, light emitting diode, meta material, SERS and so on. Amplifying electric field of plasmonic materials can improve the optical phenomenon and applications. Injecting external carriers into plasmonic materials can be good solution to improve electric field generation. In this research, we used incident light to generate photo-carrier and designed the band structure of the materials to extract photo-carrier into the plasmonic materials. We fabricated the substrate consisting of lead sulfide quantum dot/zinc oxide/plasmonic structure. The bottom quantum dot (QD) layer absorbs light and transfer photo-carrier to zinc oxide and plasmonic structure. For the photo-active material, we selected lead sulfide quantum dot (QD) because the band gap of the QD is conveniently tunable by controlling the size of QD. We synthesized the QD with the band gap around 1.3eV to optimize the light absorption ranging from 400nm to 900nm. Upper ZnO layer forms p-n junction with QD and selectively transports electron to top plasmonic materials. To verify the enhancement of electric field in photo-carrier injected plasmonic structure (PCIPS) substrate, we applied PCIPS substrate to SERS device. We measured 4 different molecules and the SERS signals enhanced from 3 to 7 times. Kelvin probe force microcopy (KPFM) measurement showed the change in surface potential of the substrate with and without light incidence. Our device showed great potential in SERS application because the device showed meaningful improvement in SERS signal simply using incident laser used to detect molecules. Figure 1

In this study, we found that the large area of electromagnetic field hot zone induced through magnetic dipole resonance of metal-free structures can greatly enhance Raman scattering signals. The magnetic resonant nanocavities, based on high-refractive-index silicon nanoparticles (SiNPs), were designed to resonate at the wavelength of the excitation laser of the Raman system. The well-dispersed SiNPs that were not closely packed displayed significant magnetic dipole resonance and gave a Raman enhancement per unit volume of 59 347. The hot zones of intense electric field were generated not only within the nonmetallic NPs but also around them, even within the underlying substrate. We observed experimentally that gallium nitride (GaN) and silicon carbide (SiC) surfaces presenting very few SiNPs (coverage: <0.3%) could display significantly enhanced (>50%) Raman signals. In contrast, the Raman signals of the underlying substrates were not enhanced by gold nanoparticles (AuNPs), even though these NPs displayed a localized surface plasmon resonance (LSPR) phenomenon. A comparison of the areas of the electric field hot zones (E2 > 10) generated by SiNPs undergoing magnetic dipole resonance with the electric field hot spots (E2 > 10) generated by AuNPs undergoing LSPR revealed that the former was approximately 70 times that of the latter. More noteworthily, the electromagnetic field hot zone generated from the SiNP is able to extend into the surrounding and underlying media. Relative to metallic NPs undergoing LSPR, these nonmetallic NPs displaying magnetic dipole resonance were more effective at enhancing the Raman scattering signals from analytes that were underlying, or even far away from, them. This application of magnetic dipole resonance in metal-free structures appears to have great potential for use in developing next-generation techniques for Raman enhancement.

Preparation of silver-alginate nanocomposite films as an antibacterial material has been carried out through the casting method of colloidal nanocomposite silver-alginate. Colloidal was made by chemical reduction of AgNO3 precursor salts using microwave irradiation with alginate as a stabilizer and reducing agent and NaOH as an accelerator. The appearance of a brownish yellow color, due to the addition of variation of AgNO3, and the localized surface plasmon resonance (LSPR) phenomenon were identified by UV-Vis spectrophotometer, indicating that silver nanoparticles have been formed. The properties of obtained silver nanoparticles was then examined. The shape and size distribution of silver particles were determined based on the image on transmission electron microscopy (TEM), chemical properties (FTIR), mechanical, crystallinity (XRD), and surface morphology (SEM). Testing of antibacterial activity was performed on silver-alginate nanocomposite films using the diffusion method for gram-positive (S. aureus and MRSA) and gram-negative (E. coli and ESBL) bacteria. The results showed that based on the UV-Vis spectrophotometer characterization results, the LSPR phenomenon appeared at the absorption peak of 401.01–409.00 nm, denoting silver nanoparticles with a spherical shape of 3–22 nm have been formed. Further, the presence of silver nanoparticles affected the mechanical properties of the film, where the tensile strength of the film tended to decrease with the increase in the silver nanoparticles concentration while the crystallinity increased. Next, based on the SEM results the nanocomposite films of silver-alginate had a rough and porous structure. The nanocomposite film had antibacterial activity against E. coli, S. aureus, ESBL, and MRSA. The antibacterial activity film was affected by the concentration of silver nanoparticles.

Preface to the special issue dedicated to Professor Richard P. Van Duyne (1945–2019)

Surface-enhanced Raman spectroscopy (SERS) is a surface analytical technique, which enhances the Raman signal based on the localized surface plasmon resonance (LSPR) phenomenon. It has been successfully used for single molecule (SM) detection and has extended SERS to numerous applications in biomolecular detection. However, SM detection by SERS is still challenging especially with traditional SERS substrates and detection methods. In addition, the fundamental understanding of the SERS enhancement mechanism is still elusive. Furthermore, the application of SERS in biological field is still in the early stage. To address these challenges, there are two main aspects of SERS studied in my dissertation: (a) fundamental aspects through systematic experimental studies combined with simulations, which focus on SM detection, Raman enhancement mechanisms, and (b) the development and optimization of the SERS-based nanoprobe for biomarkers detection from fluidic devices to a single cell. In my dissertation, the following studies have been investigated. First, the sensitivity of a home-made SERS instrument was tested. SM detection was realized by utilizing a highly curved nanoelectrode (NE) to limit the number of attached nanoparticle (NP), which will allow us to have even a single NP on NE (NPoNE) junction in the SERS detection area. The molecule number in a single NPoNE junction which contributes to SERS can be hundreds or even SM. In this first study, we also conducted a correlation study between electrochemical current and SERS to monitor the dynamic formation of the plasmonic junctions. Second, we investigate electromagnetic and chemical enhancement factor tuning by the electrode potential with the assistant of Au@Ag core-shell NPs. The electrode potential induced electromagnetic enhancement (EME) tuning in the Au@Ag NPoNE structure has been confirmed by 3D Finite-difference time-domain (FDTD) simulations. Last is the design of a SERS-based nanoprobe for biomarkers detection and the effort towards single cell analysis. Finally, several SERS-active substrates were examined for biomarkers (H+, glucose, and H2O2) detection, including gold NPs (AuNPs) colloid and AuNPs decorated glass nanopipette. In summary, my dissertation presents the fabrication and development of gold tip nanoelectrode for chemical detection, which can achieve SM sensitivity. SM SERS can be used to improve the fundamental understanding and provide more in-depth insight into mechanisms of SERS and the chemical behaviors of SM on surfaces and in plasmonic cavities. Second, the fabrication and optimization of SERS-active, flexible nanopipette for biological applications. The flexible nanopipette probe provides a platform for reliable detection and quantitative analysis of biomarkers

In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon has been designed for the detection of two different chemical species (mercury and hydrogen peroxide) by using Layer-by-Layer Embedding (LbL-E) as a nanofabrication technique. In the first step, silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) have been synthesized by using a chemical protocol as a function of the strict control of three main parameters, which were polyelectrolyte concentration, a loading agent, and a reducing agent. In the second step, their incorporation into nanometric thin films have been demonstrated as a function of the number of bilayers, which shows two well-located absorption peaks associated to their LSPR in the visible region at 420 nm (AgNPs) and 530 nm (AuNPs). Finally, both plasmonic peaks provide a stable real-time reference measurement, which can be extracted from the spectral response of the optical fiber sensor, which shows a specific sensing mechanism as a function of the analyte of study.

Ensuring consistently high quality and safety is paramount to food producers and consumers alike. Wet chemistry and microbiological methods provide accurate results, but those methods are not conducive to rapid, onsite testing needs. Hence, many efforts have focused on rapid testing for food quality and safety, including the development of various biosensors. Herein, we focus on a group of biosensors, which provide visually recognizable colorimetric signals within minutes and can be used onsite. Although there are different ways to achieve visual color-change signals, we restrict our focus on sensors that exploit the localized surface plasmon resonance (LSPR) phenomenon of metal nanoparticles, primarily gold and silver nanoparticles. The typical approach in the design of LSPR biosensors is to conjugate biorecognition ligands on the surface of metal nanoparticles and allow the ligands to specifically recognize and bind the target analyte. This ligand-target binding reaction leads to a change in color of the test sample and a concomitant shift in the ultraviolet-visual absorption peak. Various designs applying this and other signal generation schemes are reviewed with an emphasis on those applied for evaluating factors that compromise the quality and safety of food and agricultural products. The LSPR-based colorimetric biosensing platform is a promising technology for enhancing food quality and safety. Aided by the advances in nanotechnology, this sensing technique lends itself easily for further development on field-deployable platforms such as smartphones for onsite and end-user applications.