Layer-by-Layer Biopolymer Assembly for the In Situ Fabrication of AuNP Plasmonic Paper-A SERS Substrate for Food Adulteration Detection.

Here, we introduce an environmentally friendly approach to fabricate a simple and cost-effective plasmonic paper for detecting food additives using surface-enhanced Raman spectroscopy (SERS). The plasmonic paper is fabricated by in situ growth of gold nanoparticles (AuNPs) on filter paper (FP). To facilitate this green fabrication process, we applied a double-layered coating of biopolymers, chitosan (CS) and alginate (ALG), onto the FP using a layer-by-layer (LbL) assembly through electrostatic interactions. Compared to single-layer biopolymer coatings, double-layered biopolymer-coated paper, ALG/CS/FP, significantly improves the reduction properties. Consequently, effective in situ growth of AuNPs can be achieved as seen in high density of AuNP formation on the substrate. The resulting plasmonic paper provides high SERS performance with an enhancement factor (EF) of 5.7 × 1010 and a low limit of detection (LOD) as low as 1.37 × 10-12 M 4-mercaptobenzoic acid (4-MBA). Furthermore, it exhibits spot-to-spot reproducibility with a relative standard deviation (RSD) of 8.2% for SERS analysis and long-term stability over 50 days. This paper-based SERS substrate is applied for melamine (MEL) detection with a low detection limit of 0.2 ppb, which is sufficient for monitoring MEL contamination in milk based on food regulations. Additionally, we demonstrate a simultaneous detection of ß-agonists, including ractopamine (RAC) and salbutamol (SAL), exhibiting the multiplexing capability and versatility of the plasmonic paper in food contaminant analysis. The development of this simple plasmonic paper through the LbL biopolymer assembly not only paves the way for novel SERS substrate fabrication but also broadens the application of SERS technology in food contaminant monitoring.

Tunable surface plasmon resonance enhanced fluorescence via the stretching of a gold quantum dot-coated aluminum-coated elastomeric grating substrate.

In this study, the surface plasmon resonance (SPR)-enhanced fluorescence properties of gold quantum dots (AuQDs) on an aluminum (Al)-coated polydimethylsiloxane (PDMS) grating substrate were investigated by changing the grating pitch via mechanical stretching. The SPR-excitation wavelength of the AuQDs/Al-coated PDMS-grating substrate was tuned by changing the incident light angle from 5° to 60° and stretching it from 0 to 1.0 mm. In addition, the SPR-enhanced fluorescence tuning ability was studied using an AuQD/Al-coated PDMS-grating film by stretching the substrate. The SPR-enhanced fluorescence (SPF) of the AuQDs on the Al-grating was observed using a violet laser as the excitation source at 405 nm with p-polarization. The wavelengths of the SPR excitation, corresponding to the SP-dispersion mode of +1, were shifted to a longer wavelength upon stretching the grating substrate from 0 to 1.0 mm. By stretching the AuQDs/Al-grating PDMS substrate, the SPR-enhanced fluorescence intensity increased at fixed incident angles of 15° and 35°, whereas the SPR-enhanced fluorescence intensity decreased at 40°. Moreover, the SPF could be tuned to exhibit different properties in tunable optical sensors.

Plasmonic photothermal properties of silver nanoparticle grating films.

The plasmon-induced photothermal effect offers effective light-to-heat conversion systems. In this study, we fabricate plasmonic photothermal silver nanoparticle (AgNP) grating films to produce highly effective plasmon-induced heat generation films. AgNP films provide effective heat generation by localized surface plasmon excitation in the void of the AgNP films. The heat generated at a AgNP film by irradiation of solar light is 3.4 times higher than that generated at the reference flat evaporated-Ag film. Furthermore, simultaneous excitation of localized surface plasmons and propagating surface plasmons is confirmed to be obtained on AgNP grating films by finite-difference time-domain simulation and reflectivity measurements. The AgNP grating film is created by the nanoimprinting technique. The grating structure on AgNPs further enhances electric field intensity in the large area of the film, which results in higher heat generation. Thus, 5.4 times higher heat generation is achieved compared with that of the reference flat evaporated-Ag film.

The effect of gold quantum dots/grating-coupled surface plasmons in inverted organic solar cells.

We studied the effect of gold quantum dots (AuQDs)/grating-coupled surface plasmon resonance (GC-SPR) in inverted organic solar cells (OSCs). AuQDs are located within a GC-SPR evanescent field in inverted OSCs, indicating an interaction between GC-SPR and AuQDs' quantum effects, subsequently giving rise to improvement in the performance of inverted OSCs. The fabricated solar cell device comprises an ITO/TiO2/P3HT : PCBM/PEDOT : PSS : AuQD/silver grating structure. The AuQDs were loaded into a hole transport layer (PEDOT : PSS) of the inverted OSCs to increase absorption in the near-ultraviolet (UV) light region and to emit visible light into the neighbouring photoactive layer, thereby achieving light-harvesting improvement of the device. The grating structures were fabricated on P3HT:PCBM layers using a nanoimprinting technique to induce GC-SPR within the inverted OSCs. The AuQDs incorporated within the strongly enhanced GC-SPR evanescent electric field on metallic nanostructures in the inverted OSCs improved the short-circuit current and the efficiency of photovoltaic devices. In comparison with the reference OSC and OSCs with only green AuQDs or only metallic grating, the developed device indicates enhancement of up to 16% power conversion efficiency. This indicates that our light management approach allows for greater light utilization of the OSCs because of the synergistic effect of G-AuQDs and GC-SPR.

Dual-mode surface plasmon resonance sensor chip using a grating 3D-printed prism.

The method for fabricating a grating prism surface plasmon resonance (SPR) sensor chip was developed. The grating prism was 3D-printed by a stereolithography 3D printer and subsequently created a grating pattern by soft lithography. A gold film was thermally evaporated on the grating prism. Moreover, a liquid cell was 3D-printed and assembled into a gold-coated grating prism. To make the sensor chip compact and practical, a compatible prism holder was 3D-printed by a fused deposition model 3D printer. The SPR sensor chip was mounted on the rotation stage and the SPR spectrum was recorded by spectrometer. The SPR excitation of the sensor chip can be extended to the near-infrared region by creating a grating pattern on the prism surface. A gold-coated grating prism exhibited dual modes of SPR excitations, namely, prism-coupling SPR (PC-SPR) and grating-coupling SPR (GC-SPR). The dual-mode SPR excitation was observed at the incident angles of 45°-80°. When the incident angle increased, the SPR excitation of the PC-SPR mode exhibited a blue shift in the wavelength region of 480-690 nm, whereas the GC-SPR mode exhibited a red shift in the wavelength region of 670-770 nm. The surface plasmon (SP) dispersion obtained from the dual-mode SPR configuration confirmed observable PC-SPR (which corresponded to + SP0 of the gold-resin interface) and GC-SPR (which corresponded to -SP+1 of the gold-air interface), which could be excited from the developed substrate. The refractive index sensitivities of the PC-SPR and GC-SPR modes were 2924.4 and 414.9 nm RIU-1, respectively. The SPR excitations of the sensor chip exhibited a simultaneous shift when the local refractive index of the materials adjacent to the gold-coated grating prism surface was changed, especially the material that had overlapping light absorption at the SPR excitation wavelength. Using this fabrication process, the prism is designed and then printed; moreover, the grating pattern on the prism surface can be employed to tune the SPR excitation wavelength of the sensor chip for the versatility and broad perspective of the optical sensing-based SPR.

Colorimetric Detection Based on Localized Surface Plasmon Resonance for Determination of Chemicals in Urine.

Colorimetric sensors based on localized surface plasmon resonance (LSPR) have attracted much attention for biosensor and chemical sensor applications. The unique optical effect of LSPR is based on the nanostructure of noble metals (e.g., Au, Ag, and Al) and the refractive index of the environment surrounding these metal nanomaterials. When either the structure or the environment of these nanomaterials is changed, their optical properties change and can be observed by spectroscopic techniques or the naked eye. Colorimetric-probe-based LSPR provides a simple, rapid, real-time, nonlabelled, sensitive biochemical detection and can be used for point-of-care testing as well as rapid screening for the diagnosis of various diseases. Gold and silver nanoparticles, which are the two most widely used plasmonic nanomaterials, demonstrate strong and sensitive LSPR signals that can be used for the selective detection of several chemicals in biochemical compounds provided by the human body (e.g., urine and blood). This information can be used for the diagnosis of several human health conditions. This paper provides information regarding colorimetric probes based on LSPR for the detection of three major chemicals in human urine: creatinine, albumin, and glucose. In addition, the mechanisms of selective detection and quantitative analysis of these chemicals using metal nanoparticles are discussed along with colorimetric-detection-based LSPR for many other specific chemicals that can be detected in urine, such as catecholamine neurotransmitters, thymine, and various medicines. Furthermore, issues regarding the use of portable platforms for health monitoring with colorimetric detection based on LSPR are discussed.

Colorimetric Determination of Urinary Creatinine in Proteinuria Patients by Chromaticity Analysis of Gold Nanoparticle Colloidal Solutions.

Several scientific works have reported the use of colloidal gold nanoparticle (AuNP) solutions as a colorimetric probe for creatinine detection. Nonetheless, urinary protein is one of the primary chemical components that can interfere with creatinine detection. In this work, we developed a colorimetric probe using AuNP colloidal solution to detect creatinine in the urine of proteinuria patients. A microchamber array was prepared to minimize the sample volume and was used to simultaneously perform spectral recording and image acquisition of several samples. The analyzed volume for each sample was 15 µL. A camera coupled with liquid crystal tunable filters was used to record hyperspectral images, and the signals were then converted to localized surface plasmon resonance (LSPR) spectra. Color changes in the AuNP colloidal solution in the presence of varying concentrations of creatinine and human serum albumin (HSA) indicated different features and could be detected by a hyperspectral imaging technique. The relevant concentration ranges of creatinine and HSA were 5 - 200 and 50 - 250 mg dL-1, respectively. Furthermore, a smartphone camera was adopted to record a color mapping image of the AuNP colloidal solution in the presence of creatinine and HSA at these concentration ranges. Contour plots of red and blue chromaticity levels from color mappings were produced, and 2D fitting equations obtained from these contour plots were adopted to determine the creatinine concentration in the urine of proteinuria patients. This practical technique can be used for screening and can be further developed as a household biosensing device for urinalysis.

Enhancement of organic solar cell performance by incorporating gold quantum dots (AuQDs) on a plasmonic grating.

The incorporation of metallic nanoobjects into devices allows to increase light harvesting, which increases the device performance. In this study, we used a combination of gold quantum dots and grating-coupled surface plasmon resonance (GCSPR) to improve the performance of organic solar cells (OSCs) with a poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PCBM) photoactive layer. Gold quantum dots with a green fluorescent color (green-AuQD) were loaded into a hole transport layer (HTL) aiming to harvest photons in the UV region and emit visible light into the neighboring photoactive layer. Meanwhile, plasmonic grating structures, which were created on the photoactive layer surfaces via the nanoimprinting technique, provided an enhancement effect through light scattering and GCSPR. Thus, an excellent enhancement of OSC efficiency with a significant increase in short circuit photocurrent (J SC) and power conversion efficiency (PCE) in comparison to that of the reference cell was achieved. The fabricated device provides a J SC value as high as 8.41 mA cm-2 (a 14.11% enhancement) and a PCE value of 3.91% (a 19.57% enhancement). The systematic study clearly reveals that the remarkable enhancement of OSC efficiency is achieved by incorporating both AuQD and plasmonic grating.

Fabrication of Miniature Surface Plasmon Resonance Sensor Chips by Using Confined Sessile Drop Technique.

In this study, we demonstrate a simple and efficient method to fabricate miniature surface plasmon resonance (SPR) sensor chips by using confined sessile drop technique. A liquid optical adhesive (NOA 61) was dropped on the circular flat surface of cylindrical substrates made of poly(dimethylsiloxane) (PDMS). The formation of hemispherical optical prisms was accomplished by taking advantage of the sharp edges of cylindrical PDMS substrates that prevented the overflow of liquid NOA 61 at the edge of substrates. The size of the hemispherical optical prisms can be controlled by changing the diameter of the cylindrical PDMS substrates. After UV curing, the SPR sensor chips were obtained by the deposition of 3 nm thick chromium and 47 nm thick gold on the flat side of the prisms. The fabricated miniature SPR sensor chips were then mounted on a three-dimensional-printed flow cell to complete the microfluidic SPR sensor module. The miniature SPR sensor chips provided a comparable sensitivity to the conventional high-refractive-index glass SPR chips. To demonstrate the detection capability of nanometer-sized materials, we applied the miniature microfluidic SPR system for monitoring the deposition of layer-by-layer ultrathin films of poly(diallyldimethylammonium chloride)/poly(sodium 4-styrenesulfonate) and for detecting human immunoglobulin G.

Plasmonic-Enhanced Photocurrent Generation of Organic Photovoltaics Induced by 1D Grating and 2D Crossed Grating Structures.

In this work, plasmonic-enhanced photocurrent generation in organic photovoltaic (OPV) devices is demonstrated. One-dimensional (1D) and two-dimensional (2D) crossed grating structures are created on the active-layer surface composed of a blend of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PC61BM) via a nanoimprinting technique using a template of a Blu-ray disc recordable (BD-R) grating structure. After formation of aluminum back electrodes, the grating-coupled surface plasmon (GCSPR) and light scattering observed in the devices with grating structures provide a 12.3% and 11.0% enhancement of the photocurrent for the devices with 1D grating and 2D crossed grating structures, respectively. The OPV devices with the 2D crossed grating show a plasmonic-enhanced photocurrent under irradiation with light with all polarization directions, whereas those with the 1D grating provide plasmonic enhancement only under illumination with p-polarized light.

Investigation of a gold quantum dot/plasmonic gold nanoparticle system for improvement of organic solar cells.

Light management allows enhancement of light harvesting in organic solar cells (OSCs). In this paper, we describe the investigation of OSCs enhanced by the synergistic effect of gold quantum dots (AuQDs) and localized surface plasmons, obtained by blending a AuQD layer and plasmonic gold nanoparticles (AuNPs) in a hole-transport layer (HTL). Different AuQDs emitting blue, green, and red fluorescence were examined in this study. The OSCs were demonstrated to comprise an ITO-coated glass substrate/AuQDs/PEDOT:PSS:AuNPs/P3HT:PCBM/Al structure. The UV-visible spectra, current density versus voltage characteristics, impedance spectra, and incident photon-to-current efficiency of the fabricated devices were evaluated. The results showed an enhancement of photovoltaic efficiency achieved as a result of the increase in short-circuit current density (J sc) and power conversion efficiency (PCE) in comparison with those of the reference OSCs. The best synergistic effect was found with OSCs consisting of a green-emitting AuQD layer and a HTL containing AuNPs, resulting in the highest improvement in PCE of 13.0%. This indicated that the increase in light harvesting in the developed devices was induced by extended light absorption in the UV region resulting from absorption by the AuQD layer and emission of visible fluorescence from the AuQD layer to the photoactive layers. Moreover, the localized surface plasmon effect of AuNPs, which also contributed to an increase in light trapping in the proposed OSCs, was enhanced by the effect of the AuQDs.

Optical Sensing Platform for the Colorimetric Determination of Silver Nanoprisms and Its Application for Hydrogen Peroxide and Glucose Detections Using a Mobile Device Camera.

Silver nanoprisms (AgNPrs) have a unique localized surface plasmon resonance, resulting in strong absorption and scattering within the visible light region. In this work, we propose image acquisition from colloidal solutions of AgNPrs using a combination of transmitted and scattered light. The developed measurement technique could be carried out by separately recording transmitted and scattering images of the solutions, using a mobile device camera prior to a calculation of the empirical absorption value (IA). The IA value of green for AgNPrs solutions was found to be in agreement with the absorption spectra obtained using a conventional spectroscopic technique. This technique was utilized for the quantifications of hydrogen peroxide and glucose. Good linearities between ΔIA and those typical analytes were observed. The limit of detection for the typical biosensor of glucose was 19.8 µM. As such, we expect the methodology herein developed for hydrogen peroxide and glucose determinations by means of monitoring the color change of transmitted and scatting images from solutions to contribute to the development of simple, rapid, and reliable detection systems to be further applied to biochemical analysis and clinical diagnosis, as well as to household biosensor applications.

Transmission surface plasmon resonance techniques and their potential biosensor applications.

Transmission surface plasmon resonance (TSPR) is an unusual extraordinary optical transmission that is more transparent at certain wavelengths than expected by classical theory. The three main plasmonic structures that providing this phenomenon are nanohole arrays, diffraction gratings, and nanoslit arrays. This extraordinary optical transmission phenomenon is produced as a result of surface plasmon excitations. The shifting in TSPR responses upon changing of dielectric environment at the surface of a metallic film was observed. After TSPR was discovered from metallic nanohole arrays in 1998, the number of papers about this topic rapidly increased. In the 20 years since, TSPR has been utilized to improve the detection limits, sensitivity, selectivity, and dynamic range of biosensing devices, resulting in them having greater potential for commercialization. This review gives a broad overview of the TSPR phenomenon, the development of this technique, and the typical experimental setups used to acquire TSPR signals; it also describes how they are applied in the field of research into biosensors.

Palladium Nanoparticles Immobilized on Individual Calcium Carbonate Plates Derived from Mussel Shell Waste: An Ecofriendly Catalyst for the Copper-Free Sonogashira Coupling Reaction.

The conversion of waste into high-value materials is considered an important sustainability strategy in modern chemical industries. A large volume of shell waste is generated globally from mussel cultivation. In this work, mussel shell waste (Perna viridis) is transformed into individual calcium carbonate plates (ICCPs) and is applied as a support for a heterogeneous catalyst. Palladium nanoparticles (3-6 nm) are deposited with an even dispersion on the ICCP surface, as demonstrated by X-ray diffraction and scanning electron microscopy. Using this system, Sonogashira cross-coupling reactions between aryl iodides and terminal acetylenes were accomplished in high yields with the use of 1 % Pd/ICCP in the presence of potassium carbonate without the use of any copper metal or external ligand. The Pd/ICCP catalyst could also be reused up to three times and activity over 90 % was maintained with negligible Pd-metal leaching. This work demonstrates that mussel shell waste can be used as an inexpensive and effective support for metal catalysts in coupling reactions, as demonstrated by the successful performance of the Pd-catalyzed, copper-free Sonogashira cross-coupling process.

Inverted organic solar cells enhanced by grating-coupled surface plasmons and waveguide modes.

In this study, we demonstrate improved photovoltaic properties in inverted organic thin-film solar cells by simultaneous excitation of grating-coupled surface plasmons and grating-coupled waveguide modes on gold grating surfaces. The cell consists of a glass-ITO substrate/titanium dioxide/poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)/gold structure. The grating structures were fabricated on P3HT:PCBM layers using a nanoimprinting technique with a PDMS stamp. The grating-structured PDMS stamps were fabricated using a DVD-R grating template with a grating pitch, Λ, of 740 nm. Reflectivity measurements made using p-polarized light clearly indicate 2 types of excitation modes, i.e., surface plasmons and waveguide modes, while s-polarized light produces only waveguide modes. Incident photon-to-current efficiency measurements exhibited increased photocurrent wavelengths corresponding to the wavelengths of surface plasmon excitations and waveguide mode excitations. Through the simultaneous excitation of surface plasmons and waveguide modes, short-circuit photocurrents in the grating-structured cells exhibited an improvement of up to 11% in the solar cells, leading to an efficiency increase of 16%.

Selective colors reflection from stratified aragonite calcium carbonate plates of mollusk shells.

An interaction between the incident light and the structural architecture within the shell of Asian green mussel (Perna viridis) induces observable pearlescent colors. In this paper, we investigate the influence of the structural architecture on the expressed colors. After a removal of the organic binder, small flakes from crushed shells show vivid rainbow reflection under an optical microscope. An individual flake expresses vivid color under a bright-field illumination while become transparent under a dark-field illumination. The expressed colors of the aragonite flakes are directly associated with its structural architecture. The flakes with aragonite thickness of 256, 310, and 353 nm, respectively, appear blue, green, and red under an optical microscope. The spectral simulation corroborates the experimentally observed optical effects as the flakes with thicker aragonite layers selectively reflected color with longer wavelengths. Flakes with multiple aragonite thicknesses expressed multi-color as the upper aragonite layers allow reflected colors from the lower layers to be observed.

Development of coated-wire silver ion selective electrodes on paper using conductive films of silver nanoparticles.

Films of silver nanoparticles are used for the first time as an electrical conductor and ion-to-electron transducer to fabricate coated-wire ion selective electrodes (ISEs) on paper. The film of nano silver ink (nano silver film), synthesized from the reduction of AgNO3 by NaBH4, was screen printed on paper. Transmission electron microscopy showed that the synthesized silver nanoparticles (AgNPs) possessed a spherical shape with diameter ca. 5 nm. Energy-dispersive X-ray spectroscopy supported the purity and good stability of the synthesized AgNPs. Nano silver films were sintered at room temperature, 100 °C and 200 °C. Upon increasing the sintering temperature, atomic force microscopy showed that the size of AgNPs of nano silver films increased, but the sheet resistivity decreased. Silver ISEs were then fabricated from nano silver films and o-NPOE-plasticized polymeric membranes containing benzothiazolyl calix[4]arene () as ionophore and KTpClPB as anionic site. The performance of the developed Ag-ISEs was investigated by potentiometric measurements, potentiometric water layer tests, current reversal chronopotentiometry and electrochemical impedance spectroscopy. The coated-wire electrode fabricated from the nano silver film sintering at room temperature showed the best characteristics of Ag-ISEs giving a near Nernstian response slope of 59.7 ± 1.0 mV per decade, 10(-6) to 10(-2) M linear range, detection limit of 4.5 × 10(-7) M, long-term potential stability and good reversibility.

Chemometric analysis of spectroscopic data on shape evolution of silver nanoparticles induced by hydrogen peroxide.

The study on the shape evolution of metal nanoparticles (MNPs) is crucial to gain an understanding on controlling the shape and size of metal nanostructures. In this work, a detailed study on shape evolution of silver (Ag) nanospheres to nanoplates induced by hydrogen peroxide (H2O2) was performed. According to the growth mechanism of Ag nanoplates, the spectrophotometric method combined with chemometric analysis has potential to reveal the structural evolution process as observed by surface plasmon resonance phenomena. The extinction spectra of the evolving nanostructures were analyzed by factor analysis and error indicator functions. Five major components attributed to the different particle shapes and sizes were theoretically predicted. Furthermore, the concentration profiles and pure spectra of these components were resolved using multivariate curve resolution-alternative least squares (MCR-ALS) analysis. The evolution profiles show that the spherical Ag particles systematically evolved into plate structures of different sizes. Larger nanoplates were obtained when higher concentrations of H2O2 were employed. An evidence of nanoplate disintegration was observed when a large amount of H2O2 was employed. The predicted structural morphologies of each component given by chemometric calculation were in excellent agreement with those observed by transmission electron microscope (TEM) images.