Localized Surface Plasmon Resonance Shift Research Articles

Colorimetric sensing of lead ion using gold nanorod with enhanced sensitivity via catalytic etching

AbstractLead, a prevalent heavy metal, poses significant risks to human health through various exposure pathways. Herein, we propose an extremely sensitive assay toward lead ion (Pb2+) using gold nanorods (GNRs) as probes based on its catalytic activity on etching gold in the presence of 2‐mercaptoethanol and sodium thiosulfate. In the presence of Pb2+, etching predominantly occurs at the two ends of GNRs, leading to the reduction of aspect ratio and the corresponding blueshift of the localized surface plasmon resonance (LSPR). With increasing Pb2+ concentration over the range of 0–50 μM, the color of GNR solution lightens, ultimately becoming colorless. The wavelength shift (Δλ) of LSPR is highly dependent on Pb2+ concentration, with a linear regression equation of Δλ = 10.05ln[Pb2+] + 9.59 and an R2 = 0.995. The assay demonstrates high selectivity for Pb2+ over other potentially interfering ions such as Cu2+ because of its special catalytic activity in the etching of GNRs and the complexing ability of 2‐mercaptoethanol and sodium thiosulfate. Validation of the assay was accomplished by analyzing several forest‐derived food samples, affirming the accuracy in real‐world scenarios. The assay we developed holds promise for many applications in environmental protection and food safety.

Enhanced cysteine sensor based on modified gold nanoparticles with synergistic role of pH-responsive poly (N,N-dimethylaminoethyl methacrylate)

The development of a highly sensitive and easy-to-prepare sensor for the detection of cysteine (Cys) is of great importance. Gold nanoparticles (AuNPs) have been frequently utilized as a Cys sensor owing to high affinity of the thiol group to gold. However, the presence of additional materials, such as stabilizers, can impact the sensitivity of this sensor. Herein, pH-sensitive gold nanoparticles (Au-PDA) were synthesized using poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) for the purpose of Cys detection based on the aggregation size-dependent optical property of gold nanoparticles. Detection of cysteine was also followed by UV–Vis analysis, showing a decrease in intensity of localized surface plasmon resonance (LSPR) peak, a red shift from 525 to 550 nm as well as the appearance of a new peek at 650 nm. To enhance sensor performance, systematic investigations were conducted to optimize sensing conditions, focusing on pH, gold concentration, and ionic strength of the medium. Remarkably, the proposed sensor exhibited excellent selectivity towards Cys compared to other amino acids. The sensitivity of the sensor was evaluated using two methods: changes in the absorption intensity and the LSPR shift. The pH-sensitivity of PDMAEME led to a significant improvement in sensing parameters through a synergistic effect on the Au-Cys interaction, leading to a remarkably low LOD of 0.0004 nM, which is the lowest ever reported LOD for detection of Cys. Finally, practical application of the proposed sensor was validated in human blood serum.

Ultrasensitive Dual-Mode Visual/Photoelectrochemical Bioassay for Antibiotic Resistance Genes through Incorporating Rolling Circle Amplicons into a Tailored Nanoassembly.

As emerging contaminants in the environment, antibiotic resistance genes (ARGs) have aroused a global health crisis and posed a serious threat to ecological safety and human health. Thus, efficient and accurate onsite detection of ARGs is crucial for environmental surveillance. Here, we presented a colorimetric-photoelectrochemical (PEC) dual-mode bioassay for simultaneous detection of multiple ARGs by smartly incorporating rolling circle amplification (RCA) into a stimuli-responsive DNA nanoassembly, using the tetracycline resistance genes tetA and tetC as models. The tailored DNA nanoassembly containing RCA amplicons hybridized with specific signal probes: CuO nanoflowers-anchored signal DNA1 and HgO nanoparticles-anchored signal DNA2, respectively. Upon exposure to an acidic stimulus, numerous Cu2+ and Hg2+ were released, serving as the reporting agent of colorimetric/PEC dual-mode assay. The released Cu2+ and Hg2+ induced localized surface plasmon resonance shifts in Au nanorods and triangular Ag nanoplates through an etching process, respectively, enabling visual analysis of ARGs with distinguishing color changes. Meanwhile, numerous Cu2+ and Hg2+ triggered the amplified PEC variations via reacting with the photoactive layers of CuS/CdS and ZnS, respectively. Thus, a rapid and ultrasensitive colorimetric/PEC dual-mode detection of multiple ARGs was achieved with the detection limit down to 17.2 aM. Furthermore, such dual-mode bioassay could discriminate single-base mismatch and successfully determine ARGs in E. coli plasmids and sludge samples, holding great promise for point-of-care genetic diagnostics.

Resonance Quantization in the Absorption Spectra of Concentric Double Gold Nanoshells: A Numerical Study

AbstractConcentric double metallic shells (CDMSs) are strong candidates for photothermal-based therapy, wherein they utilize their tuned plasmon resonance in the near-infrared region via particle coupling factor fitting. Tuning the resonance of CDMSs to the desired near-infrared region is crucial considering the shift caused by variations in their design parameters. In this study, we investigated the effects of these parameters using full-wave electromagnetic analysis to highlight the dominant factors affecting the resonance shift in the absorption spectra of CDMSs. With systematic variations, our simulation data outlined the direct influence of the outer and inner nanoshells’ (NS2 and NS1) aspect ratios r2 and r1, respectively, on the coupling factor (rT) aptitude for resonance tuning. For example, a CDMS with r2 = r1 = 0.8 shows coupling manifestation between NS2 and NS1 with rT as low as 0.2. However, we need the value of rT to be at least 0.6 for a CDMS with r2 = r1 = 0.4. Moreover, the dominant factors of the localized surface plasmon resonance shifts were determined by examining the mismatched parameter values of the same particle and found them to be related to NS2. We demonstrated how these factors are related to the complexity of localized surface plasmon resonance peak shifting and splitting in the absorption spectra of CDMSs. Our findings are expected to greatly improve the design of nanoparticles to optimize their responses in photothermal-based applications.

Machine Learning Color Feature Analysis of a High Throughput Nanoparticle Conjugate Sensing Assay.

Plasmonic nanoparticles are finding applications within the single molecule sensing field in a "dimer" format, where interaction of the target with hairpin DNA causes a decrease in the interparticle distance, leading to a localized surface plasmon resonance shift. While this shift may be detected using spectroscopy, achieving statistical relevance requires the measurement of thousands of nanoparticle dimers and the timescales required for spectroscopic analysis are incompatible with point-of-care devices. However, using dark-field imaging of the dimer structures, simultaneous digital analysis of the plasmonic resonance shift after target interaction of thousands of dimer structures may be achieved in minutes. The main challenge of this digital analysis on the single-molecule scale was the occurrence of false signals caused by non-specifically bound clusters of nanoparticles. This effect may be reduced by digitally separating dimers from other nanoconjugate types. Variation in image intensity was observed to have a discernible impact on the color analysis of the nanoconjugate constructs and thus the accuracy of the digital separation. Color spaces wherein intensity may be uncoupled from the color information (hue, saturation, and value (HSV) and luminance, a* vector, and b* vector (LAB) were contrasted to a color space which cannot uncouple intensity (RGB) to train a classifier algorithm. Each classifier algorithm was validated to determine which color space produced the most accurate digital separation of the nanoconjugate types. The LAB-based learning classifier demonstrated the highest accuracy for digitally separating nanoparticles. Using this classifier, nanoparticle conjugates were monitored for their plasmonic color shift after interaction with a synthetic RNA target, resulting in a platform with a highly accurate yes/no response with a true positive rate of 88% and a true negative rate of 100%. The sensor response of tested single stranded RNA (ssRNA) samples was well above control responses for target concentrations in the range of 10 aM-1 pM.

Highly Responsive Plasmon Modulation in Dopant-Segregated Nanocrystals.

Electron transfer to and from metal oxide nanocrystals (NCs) modulates their infrared localized surface plasmon resonance (LSPR), revealing fundamental aspects of their photophysics and enabling dynamic optical applications. We synthesized and chemically reduced dopant-segregated Sn-doped In2O3 NCs, investigating the influence of radial dopant segregation on LSPR modulation and near-field enhancement (NFE). We found that core-doped NCs show large LSPR shifts and NFE change during chemical titration, enabling broadband modulation in LSPR energy of over 1000 cm-1 and of peak extinction over 300%. Simulations reveal that the evolution of the LSPR spectra during chemical reduction results from raising the surface Fermi level and increasing the donor defect density in the shell region. These results establish dopant segregation as a useful strategy to engineer the dynamic optical modulation in plasmonic semiconductor NC heterostructures going beyond what is possible with conventional plasmonic metals.

Localized surface plasmon resonance shift of biosynthesized and functionalized quasi-spherical gold nanoparticle systems.

Rapid and more environment-friendly means of gold nanoparticle synthesis is necessary in many applications, as in ion detection. Leaf extracts have become effective and economical reducing agents for gold nanoparticle formation, however, effects of extract combinations have not been thoroughly investigated. With the exploitation of combined extract effects, gold nanoparticles were synthesized then functionalized and investigated to produce selected nanoparticle systems which are capable of detecting aqueous lead(ii) ions with minimum detection limits of 10-11 ppm. The measured localized surface plasmon resonance absorption peaks of the gold nanoparticles were 541-800 nm for the synthesis and 549 nm for the functionalization. The diameters of different gold nanoparticle systems were 17-37 nm. These were mostly quasi-spherical in morphology with some rod-, triangular-, and hexagonal plate-like particles. The biosynthesis used polyphenols and acids present in the extracts in the reduction of gold ions into gold nanoparticles, and in the nanoparticle capping and stabilization. Functionalization replaced the capping compounds with alliin, S-allylcysteine, allicin, and ajoene. Gold nanoparticle stability in aqueous systems was verified for two weeks up to five months. The investigations concluded the practicability of the gold nanoparticles in lead(ii) ion detection with selectivity initially verified for other divalent cations.

Quantitative Mid‐Infrared Plasmonic Biosensing on Scalable Graphene Nanostructures

AbstractGraphene nanostructures, exhibiting tunable and nanoscale‐confined mid‐infrared (mid‐IR) plasmons, prevail as a powerful spectroscopic platform for novel surface‐enhanced molecular identification. Particularly, graphene shows exciting opportunities for biosensing applications due to its versatile functionalization methods with different biomolecular building blocks (e.g., enzymes, proteins, and DNA). Here, a quantitative bioassay based on the mid‐IR localized surface plasmon resonance (LSPR) modulation in functionalized graphene nanostructures is demonstrated. Specifically, vitamin B12 (vB12) using the specific recognition elements on modified graphene nanoribbons (i.e., pyrene linkers via π − π stacking + anti‐vB12 antibody fragments via amide bond) is detected. Different concentrations of vB12 spotted on an arrayed panel of a single chip are quantified by the graphene LSPR shifts, where a limit of detection (LOD) of 53.5 ng mL−1 is obtained. The upscaling potential of the bioassay using large area nanostructured graphene films produced by nanoimprinting 2D hole arrays is illustrated. The integration of quantitative bioassay with scalable graphene nanostructures shows promising routes of graphene‐based mid‐IR platforms toward prospective industrial applications.

Fabrication and evaluation of optical nanobiosensor based on localized surface plasmon resonance (LSPR) of gold nanorod for detection of CRP

C-reactive protein (CRP) is a plasma protein that is one of the most expressed proteins in acute phase inflammation cases. It is a well-known biomarker for inflammatory disorders. There is a significant correlation between increasing CRP concentration and the risk of being exposed to cardiovascular diseases (CVD) and sepsis; thus, monitoring and quantifying CRP levels in a simple, inexpensive, and quick manner can improve clinical diagnostics and help prevent major inflammatory conditions. Here a nanobiosensor was developed, benefiting from the LSPR property of gold-nanorod (GNR) to measure CRP concentration. Nanorods were fabricated using One-pot synthesis by trimethyl ammonium bromide (CTAB) as a surfactant. This method provides the advantage of both step and time reduction in synthesis and decreases the contamination probability of nanorods as the products. The nanorods were characterized using TEM with an average size of (24 ± 1 nm) × (5 ± 1 nm) and a typical aspect ratio of ∼4.9. The surface of the rods was modified with a specific aptamer for the target protein, and the LSPR shifts due to the gold nanorod's refractive index change as the result of protein interaction with the biosensor investigated using a 100–900 nm UV absorption device. The results indicated that the nanobiosensor could respond to different CRP concentrations within 30 min. The selectivity test has shown nonresponsive results of nanobiosensor to BSA and TNF-α proteins which are used to evaluate the biosensor behavior in non-target proteins. The detection limit was evaluated at 2 nM, and the sensor's linear response ranged between 2 - 20 nM.

Gold Nanostar-Based Sensitive Catechol Plasmonic Colorimetric Sensing Platform with Ultra-Wide Detection Range

High sensitivity and a wide detection range are always the pursuit of sensor design. In this work, gold nanostars (Au NSs) featuring the shape of sea urchins with an absorption peak at the near infrared region (822 nm) were prepared. We proposed a Au NSs-based plasmonic colorimetric sensing platform for ultrasensitive catechol (CC) detection with a wide detection range from 3.33 nM to 107 μM and a limit of detection (LOD) at 1 nM. The target analyte, CC, was used to reduce silver ions (Ag+) to form silver (Ag) coating on the surface of Au NSs, which caused a blue-shift in the localized surface plasmon resonance (LSPR) of Au NSs. With the gradual increase in CC concentration, the Ag coating on the surface was gradually nucleated, and the LSPR blue-shift carried on. This strategy yields a wide LSPR shift by as much as 276 nm for plasmonic effects, enabling an ultra-wide range and the ultrasensitive detection of CC. This work will facilitate the research of target-mediated LSPR sensors and their wide application in environmental monitoring, food safety, and disease diagnosis.

Plasmon effect on Pd/Au for optical sensing

In this study, gold nanoislands thin films were fabricated by pulsed laser deposition (PLD) method on quartz substrates at different substrate temperatures of 25, 300, 450, and 600 °C. A thin (4-5 nm) Pd film, as hydrogen catalyst over-layer, was sputter deposited on Au films. PLD at 25 and 300 °C led to semi-continuous surface morphology consisting of very fine-grained aggregates, and at 450 and 600 °C to spherical Au NPs. UV-Vis spectrometry showed localized surface plasmon resonance (LSPR) absorption at 732, 606, 586, and 560 nm for room temperature (R.T.), 300, 450, and 600 °C, respectively. FESEM revealed that hydrogen (10%) exposure induces surface stress leading to Au nanoislands separation. UV-Vis spectrophotometry showed a spectral blue-shift for the LSPR peak attributed to the plasmon coupling effect. Results showed that at various hydrogen concentration of 0 to 10%, films deposited at R.T. provides the most LSPR shift. Overall, we showed that plasmon coupling of PLD derived gold thin films is a suitable tool for accurate detection of hydrogen gas.

How to Use Localized Surface Plasmon for Monitoring the Adsorption of Thiol Molecules on Gold Nanoparticles?

The functionalization of spherical gold nanoparticles (AuNPs) in solution with thiol molecules is essential for further developing their applications. AuNPs exhibit a clear localized surface plasmon resonance (LSPR) at 520 nm in water for 20 nm size nanoparticles, which is extremely sensitive to the local surface chemistry. In this study, we revisit the use of UV-visible spectroscopy for monitoring the LSPR peak and investigate the progressive reaction of thiol molecules on 22 nm gold nanoparticles. FTIR spectroscopy and TEM are used for confirming the nature of ligands and the nanoparticle diameter. Two thiols are studied: 11-mercaptoundecanoic acid (MUDA) and 16-mercaptohexadecanoic acid (MHDA). Surface saturation is detected after adding 20 nmol of thiols into 1.3 × 10−3 nmol of AuNPs, corresponding approximately to 15,000 molecules per AuNPs (which is equivalent to 10.0 molecules per nm2). Saturation corresponds to an LSPR shift of 2.7 nm and 3.9 nm for MUDA and MHDA, respectively. This LSPR shift is analyzed with an easy-to-use analytical model that accurately predicts the wavelength shift. The case of dodecanehtiol (DDT) where the LSPR shift is 15.6 nm is also quickly commented. An insight into the kinetics of the functionalization is obtained by monitoring the reaction for a low thiol concentration, and the reaction appears to be completed in less than one hour.

Design of Gelatin-Capped Plasmonic-Diatomite Nanoparticles with Enhanced Galunisertib Loading Capacity for Drug Delivery Applications.

Inorganic diatomite nanoparticles (DNPs) have gained increasing interest as drug delivery systems due to their porous structure, long half-life, thermal and chemical stability. Gold nanoparticles (AuNPs) provide DNPs with intriguing optical features that can be engineered and optimized for sensing and drug delivery applications. In this work, we combine DNPs with gelatin stabilized AuNPs for the development of an optical platform for Galunisertib delivery. To improve the DNP loading capacity, the hybrid platform is capped with gelatin shells of increasing thicknesses. Here, for the first time, full optical modeling of the hybrid system is proposed to monitor both the gelatin generation, degradation, and consequent Galunisertib release by simple spectroscopic measurements. Indeed, the shell thickness is optically estimated as a function of the polymer concentration by exploiting the localized surface plasmon resonance shifts of AuNPs. We simultaneously prove the enhancement of the drug loading capacity of DNPs and that the theoretical modeling represents an efficient predictive tool to design polymer-coated nanocarriers.

Nontrivial, Unconventional Electrochromic Behaviors of Plasmonic Nanocubes.

Plasmonic electrochromism, a change in the localized surface plasmon resonance (LSPR) with an applied electric potential, has been attracting increasing attention for the development of spectroscopic tools or optoelectronic systems. There is a consensus on the mechanism of plasmonic electrochromism based on the classical capacitor and the Drude model. However, the electrochromic behaviors of metallic nanoparticles in narrow optical windows have been demonstrated only with small monotonic LSPR shifts, which limits the use of the electrochromism. Here, we observed three distinct electrochromic behaviors of gold nanocubes with a wide potential range through in situ dark-field electrospectroscopy. Interestingly, the nanocubes show a faster frequency shift under the highly negative potential, and this opens the possibility of largely tunable electrochromic LSPR shifts. The reversibility of the electrochemical switching with these cubes are also shown. We attribute this unexpected change beyond classical understandings to the material-specific quantum mechanical electronic structures of the plasmonic materials.

Plasmonic gel films for time-lapse LSPR detection of hydrogen peroxide secreted from living cells

In this paper, we developed a low-cost and easy-to-fabricate hydrogel-based localized surface plasmon resonance (LSPR) substrate for sensitive, consistent, specific, and time-lapse detection of hydrogen peroxide (H2O2) secreted from living cells in cell culture medium. The uniform and reproducible LSPR substrate was made from agarose, gold nanorods (AuNRs), horseradish peroxidase (HRP), and 3-amino-9-ethylcarbazole (AEC). In H2O2 sensing, insoluble precipitates were generated in the gel film by an HRP-catalyzed reaction in the presence H2O2, and the precipitates near the AuNRs caused a LSPR shift of the substrate, which could be used for H2O2 quantification. Using the developed substrate, we showed that a H2O2 concentration as low as 0.5 μM could be detected in complete cell culture medium within 30 min with good reproducibility. In addition, we demonstrated time-lapse detection of H2O2 secreted from living cells after the cells were stimulated by ascorbic acid. The results indicated that the agarose gel of the substrate provided the filtration capability and the improved stability of the AuNRs allowing detection of H2O2 in cell culture medium without tedious sample preparation procedures. Moreover, the HRP-catalyzed reaction-based LSPR biosensing offered good selectivity for H2O2 detection and possessed great potential for various in vitro cell studies.

Detection of Chemotherapeutic Drug 6-Mercaptopurine Through Manipulating Localized Surface Plasmon Resonance Absorption of Silver Nanoplates

A new colorimetric method for the detection of chemotherapeutic drug 6-mercaptopurine (6-MP) is developed based on controlling localized surface plasmon resonance (LSPR) of triangular silver nanoplates (AgNPs). The triangular AgNPs can be etched by trace amount of Cl− and transformed to a disc-like shape, accompanied by a blueshift of the corresponding LSPR absorption band. With the protective effect of 6-MP, the AgNPs are hardly or partly to be etched by Cl−, resulting in a reversed shift of LSPR. Based on a linear relationship between LSPR wavelength change and the concentration of 6-MP, a fast, visual and selective method for 6-MP assay is established. This method has been successfully applied to the detection of 6-MP in tablets.

Localized surface plasmon resonance shift and its application in scanning near-field optical microscopy

Quantifiable information on refractive index changes due to surface chemistry, structure, and topography is accessibleviaplasmon-enhanced nanoscale imaging.

Multilayered Nanostructure for Inducing a Large and Tunable Optical Field

Objective: The localized surface plasmon resonance (LSPR) and field enhancement of multilayered nanostructure over single and dimer configuration is studied using finite difference time domain (FDTD) method. Experimental: In multilayered nanostructure, there exist concentric nanoshells and metallic core which are separated by a dielectric layer. Strong couplings between the core and nanoshell plasmon resonance modes show a shift in LSPR and enhancement in field around nanostructure. The calculation of the electric field enhancement shows a sharp increase in the electric field on the surface of inner core i.e., inside the dielectric layer of Metal-Dielectric-Metal (MDM) structure whereas smaller enhancement on the outer layer of MDM structure is observed. Results: The Au-Air-Au mono MDM nanostructure shows strong near-field enhancement as compared to bare nanosphere in the infrared region, which have potential applications in surfaceenhanced spectroscopy, whereas Al-Air-Al and Ag-Air-Ag shows potential towards lower wavelength region. On coupling the MDM nanostructure forming a dimer configuration the field enhancement factor increases to 10^8. Conclusion: As compared to other nanostructures, MDM nanostructure provides both strong field enhancement and wide wavelength tunability therefore promising for surface enhanced Raman spectroscopy (SERS) applications.

A multicolor colorimetric assay for sensitive detection of sulfide ions based on anti-etching of triangular gold nanoplates

This study presents a viable colorimetric assay for sensitive sensing of sulfide ions (S2−) using triangular gold nanoplates (AuNPLs) as nanoprobes. The sensing mechanism is based on regulating the etching process of AuNPLs upon the addition of different concentration of S2−. In the presence of Cu2+ and I−, the AuNPLs would be etched by triiodide ions (I3−) produced from the redox reaction between Cu2+ and I−, resulting in the transformation of the shape of AuNPLs from triangular into sphere and blue shifted localized surface plasmon resonance (LSPR). However, in the presence of S2−, a preferential reaction between Cu2+ and S2− occurred, and the inhibition of the formation of I3− prevented the AuNPLs from being etched. Correspondingly, a red shift of LSPR can be observed with an increase of the concentration of S2−, accompanying a readily distinguishable color transition that goes from pink to purplish red, purple, bluish purple and blue. The color alterations allow for a visual estimation of the concentrations of S2−, and the lowest visual concentration through naked-eyes was 0.1 μM. A good linear relationship (R2 = 0.997) between the peak shifts and the concentration of S2− was obtained in the range of 0.02–1.5 μM, and the limit of detection (3 s/k) by UV–vis spectroscopy was as low as 16 nM. The as-established assay displayed excellent selectivity, which was successfully applied for analysis of S2− in environmental water samples.

Nanoplasmonics in High Pressure Environment

An explosion in the interest for nanoplasmonics has occurred in order to realize optical devices, biosensors, and photovoltaic devices. The plasmonic nanostructures are used for enhancing and confining the electric field. In the specific case of biosensing, this electric field confinement can induce the enhancement of the Raman signal of different molecules, or the localized surface plasmon resonance shift after the detection of analytes on plasmonic nanostructures. A major part of studies concerning to plasmonic modes and their application to sensing of analytes is realized in ambient environment. However, over the past decade, an emerging subject of nanoplasmonics has appeared, which is nanoplasmonics in high pressure environment. In last five years (2015–2020), the latest advances in this emerging field and its application to sensing were carried out. This short review is focused on the pressure effect on localized surface plasmon resonance of gold nanosystems, the supercrystal formation of plasmonic nanoparticles stimulated by high pressure, and the detection of molecules and phase transitions with plasmonic nanostructures in high pressure environment.