Plasmonic Gold Research Articles

Python-assisted detection and photothermal inactivation of Salmonella typhimurium and Staphylococcus aureus on a background-free SERS chip

In this study, a background-free surface-enhanced Raman scattering (SERS) chip with a sandwich configuration was fabricated to enable reliable detection and photothermal inactivation of multiple bacteria. The SERS chip consists of a graphene-coated, phenylboronic-modified plasmonic gold substrate (pAu/G/PBA), and two aptamer-functionalized core (gold)-shell (Prussian blue/Poly-L-lysine and 4-mercaptobenzonitrile/polydopamine) SERS tags (Au@PB@PLL@Apt and Au@MB@PDA@Apt). The detection signals rely on the characteristic and nonoverlapping Raman bands of the SERS tags within the Raman-silent region (1800-2800 cm−1), where no background signals from the sample matrix are observed, leading to improved detection sensitivity and accuracy. Considering the relatively large size of bacteria (e.g., micron level), a rapid Raman mapping technique was chosen over conventional point-scan methods to achieve more reliable quantitative analysis of bacteria. This technique involves collecting and analyzing intensity signals of SERS tags from all the scattering points with an average ensemble effect, which is facilitated by the use of Python. As a proof-of-concept, model bacterium of Salmonella typhimurium and Staphylococcus aureus were successfully detected using the SERS chip with a dynamic range of 10–107 CFU/mL. Additionally, the SERS chip demonstrated successful detection of these bacteria in whole blood samples. Moreover, the photothermal effect of pAu/G led to efficient bacteria elimination, achieving approximately 100% eradication. This study integrated a background-free SERS chip with a Python-assisted rapid Raman mapping technique, resulting in a reliable, rapid and accurate method for detecting and eliminating multiple bacteria, which may provide a promising alternative for multiple screening of bacteria in real samples.

Sensitization Strategies of Lateral Flow Immunochromatography for Gold Modified Nanomaterials in Biosensor Development.

Gold nanomaterials have become very attractive nanomaterials for biomedical research due to their unique physical and chemical properties, including size dependent optical, magnetic and catalytic properties, surface plasmon resonance (SPR), biological affinity and structural suitability. The performance of biosensing and biodiagnosis can be significantly improved in sensitivity, specificity, speed, contrast, resolution and so on by utilizing multiple optical properties of different gold nanostructures. Lateral flow immunochromatographic assay (LFIA) based on gold nanoparticles (GNPs) has the advantages of simple, fast operation, stable technology, and low cost, making it one of the most widely used in vitro diagnostics (IVDs). However, the traditional colloidal gold (CG)-based LFIA can only achieve qualitative or semi-quantitative detection, and its low detection sensitivity cannot meet the current detection needs. Due to the strong dependence of the optical properties of gold nanomaterials on their shape and surface properties, gold-based nanomaterial modification has brought new possibilities to the IVDs: people have attempted to change the morphology and size of gold nanomaterials themselves or hybrid with other elements for application in LFIA. In this paper, many well-designed plasmonic gold nanostructures for further improving the sensitivity and signal output stability of LFIA have been summarized. In addition, some opportunities and challenges that gold-based LFIA may encounter at present or in the future are also mentioned in this paper. In summary, this paper will demonstrate some feasible strategies for the manufacture of potential gold-based nanobiosensors of post of care testing (POCT) for faster detection and more accurate disease diagnosis.

Enhancing in vitro photothermal therapy using plasmonic gold nanorod decorated multiwalled carbon nanotubes.

Photothermal therapy (PTT) is a promising approach for cancer treatment that selectively heats malignant cells while sparing healthy cells. Here, the light-to-heat conversion efficiency of multiwalled carbon nanotubes (MWCNTs) within the near-infrared biological transmission window is enhanced by decorating them with plasmonic gold nanorods (GNRs). The results reveal a significant photothermal enhancement of hybrid MWCNTs-GNRs compared to bare MWCNTs, displaying a 4.9 enhancement factor per unit mass. The enhanced plasmonic PTT properties of MWCNTs-GNRs are also investigated in vitro using PC3 prostate cancer cell lines, demonstrating a potent ablation efficiency. These findings advance innovative hybrid plasmonic nanostructures for clinical applications.

Photochemical decoration of gold nanoparticles on MoS2 nanoflowers grafted onto the flexible carbon cloth as a recyclable SERS sensor for the detection of antibiotic residues on curved surfaces

Surface-enhanced Raman spectroscopy (SERS)-based flexible substrate has recently been demonstrated to be effective in detecting molecules on curved surfaces, however a suitable method for fabricating the flexible SERS substrate still remains a hurdle. In this paper, we fabricated a flexible SERS substrate by anchoring the plasmonic gold nanoparticles (Au-NPs) onto the hydrothermally grown flower-like molybdenum disulfide (MoS2) grafted onto carbon cloth (CC) via a facile photoreduction route. Benefitting from the abundant hotspots generation of the Au-NPs and photo-induced charge-transfer ability of MoS2, the constructed Au-NPs/MoS2/CC substrate exhibit a superior SERS sensing ability, excellent SERS enhancement factor, high flexibility and mechanical stability towards the nitrofurantoin (NFT) with an ultra-low detection limit of 10−11 M. As a trial for practical applications, the flexible substrate was used to detect NFT (10−4 M) in the curved surfaces of meat samples via swab technique. The ability of the flexible Au-NPs/MoS2/CC substrate to sustain the robust Raman signals of NFT even after recycling up to 4 cycles validated its reusability. The proposed flexible SERS substrate with reusable capability indicates its great potential in practical applications for the detection of target molecules on the curved surfaces.

Broadband Near-Infrared Photothermal Response of Tissue-Mimicking Phantoms Embedded with Plasmonic Gold Nanorod Aggregates: Implications for the Non-invasive Eradication of Malignant Tumors

Broadband Near-Infrared Photothermal Response of Tissue-Mimicking Phantoms Embedded with Plasmonic Gold Nanorod Aggregates: Implications for the Non-invasive Eradication of Malignant Tumors

Single-electron transfer reactions on surface-modified gold plasmons

Photoredox catalysis's relevance in organic synthesis research and innovation will increase in the coming decades. However, the processes rely almost exclusively on expensive noble metal complexes, most notably iridium complexes, to absorb light and transfer a single charge to a substrate or a catalyst to initiate cascade transformations. Light-triggered plasmon resonances generate a non-Fermi-Dirac energy distribution with many hot carriers that decay in ∼1 ps. Their ultrafast relaxation makes performing single electron transfer (SET) transformations challenging. Herein, a novel photosystem is proposed based on surface-modified gold nanoparticles (aka plasmon "molecularization"), which improved charge separation and, more importantly, enabled SET reactions, expanding the portfolio of photocatalysts available for photoredox catalysis. The photosystem was made into an electrode, permitting its use in photoelectrochemical arrangements that leverage electro- and photo-chemical approaches' benefits and chemical engineering solutions, helping the synthetic chemistry efforts towards greener synthesis and synthesis of more complex structures on a scale.

Light blocking and phase modulation based on thermo-plasmonic hotspots in WS2 monolayer

Here we demonstrate light blocking and phase modulation in nano-plasmonic donate shape rings based on the thermo-plasmonic effect in these structures. For this purpose, we use a laser writing system to fabricate nanohole arrays and cover them with plasmonic gold thin film via a sputtering machine. The chemical vapor deposition method is also used to produce a WS2 layer, which is suitable for light blocking and phase modulation due to the nonlinearity of this two-dimensional material. After theoretically and experimentally evaluating the plasmonic donate-shaped substrate, we use the ellipsometric method to characterize the optical modes of the samples and record the switching manner and light-blocking phenomena under the probe laser excitation set to 980 nm. Our results show phase modulation based on the thermo-plasmonic effect of nano gap in donated double rings and light blocking by thermal expansion of the WS2 layer, which can open new insight into plasmon and two-dimensional material-based devices.

UV‐to‐NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation

AbstractPhotocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR‐absorbing upconversion nanoparticles (UCNP) with UV‐Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C−C coupling to fabricate a UC−POP nanocomposite. The light‐harvesting ability of UC−POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC−POP. A three‐times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC−POP, subsequently boosting the photocatalytic activity of UC−POP−Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC−POP−Au compared to POP and UC−POP due to the facile electron‐hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting.

UV-to-NIR Harvesting Conjugated Porous Polymer Nanocomposite: Upconversion and Plasmon Expedited Thioether Photooxidation.

Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR-absorbing upconversion nanoparticles (UCNP) with UV-Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C-C coupling to fabricate a UC-POP nanocomposite. The light-harvesting ability of UC-POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC-POP. A three-times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC-POP, subsequently boosting the photocatalytic activity of UC-POP-Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC-POP-Au compared to POP and UC-POP due to the facile electron-hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting.

Interband- and Intraband-Induced Hot Electron Transfer in Plasmonic Gold–Cerium Oxide Core–Shell Nanoparticles

Interband- and Intraband-Induced Hot Electron Transfer in Plasmonic Gold–Cerium Oxide Core–Shell Nanoparticles

Publisher's Note: “Highly efficient and stable near-infrared photo sensor based on multilayer MoS2/p-Si integrated with plasmonic gold nanoparticles” [Appl. Phys. Lett. 123, 061104 (2023)

Publisher's Note: “Highly efficient and stable near-infrared photo sensor based on multilayer MoS2/p-Si integrated with plasmonic gold nanoparticles” [Appl. Phys. Lett. <b>123</b>, 061104 (2023)

Catalytic activity-modulated etching of plasmonic gold nanorods enabled ultra-sensitive colorimetric strategy for Early-Stage cancer diagnosis

While the aberrant low expression of metallothioneins (MTs) in tissue has been recognized as an effective indicator to spot the occurrence of early-stage malignant tumors, the ultra-sensitive detection of MTs at a low concentration (<10 nM) remains to be developed. Here, a facile multicolor colorimetric visualization strategy is introduced to detect MTs at an extremely low concentration down to 28 pM, enabled by the catalytic activity-modulated etching of plasmonic gold nanorods (CAEPAu). The catalytic reduction is inhibited by covering the nanospheres with highly specific protein corona recognizing MTs, thus facilitating a customized etching of nanorods (NRs) into nanospheres to present color correspondingly. The CAEPAu assay detects MTs in 35 min, significantly faster than the existing method (∼3 h). We demonstrate to use CAEPAu assay to precisely detect and distinguish MTs in four tumor cells, clinic blood samples and other proteins.

One-Stop Plasmonic Nanocube-Excited SERS Immunoassay Platform of Multiple Cardiac Biomarkers for Rapid Screening and Progressive Tracing of Acute Myocardial Infarction.

Rapid and precise acute myocardial infarction (AMI) diagnosis is essential for preventing patient death. In addition, the complementary roles of creatine kinase muscle brain (CK-MB) and cardiac troponin I (cTnI) cardiac biomarkers in the early and late stages of AMI demand their simultaneous detection, which is difficult to implement using conventional fluorescence and electrochemical technologies. Here, a nanotechnology-based one-stop immuno-surface-enhanced Raman scattering (SERS) detection platform is reported for multiple cardiac indicators for the rapid screening and progressive tracing of AMI events. Optimal SERS is achieved using optical property-based, excitation wavelength-optimized, and high-yield anisotropic plasmonic gold nanocubes. Optimal immunoassay reaction efficiencies are achieved by increasing immobilized antibodies. Multiple simultaneous detection strategies are implemented by incorporating two different Raman reports with narrow wavenumbers corresponding to two indicators and by establishing a computational SERS mapping process to accurately detect their concentrations, irrespective of multiple enzymes in the human serum. The SERS platform precisely estimated AMI onset and progressive timing in human serum and made rapid AMI identification feasible using a portable Raman spectrometer. This integrated platform is hypothesized to significantly contribute to emergency medicine and forensic science by providing timely treatment and observation.

Feasibility of NAD(P)/NAD(P)H as redox agents in enzymatic plasmonic gold nanostar assays for galactose quantification.

Plasmonic colorimetric sensors have emerged as powerful analytical tools in biochemistry due to their localized surface plasmon resonance extinction in the visible range. Here, we describe the feasibility of NAD(P)/NAD(P)H as redox agents in enzymatic plasmonic gold nanostar (AuNS) assays for galactose quantification using three model enzymes, GalDH, AR and GalOx, immobilized separately on polyvinylpyrrolidone-capped AuNS scaffolds. These highly specific, sensitive and selective bioassays induce the transformation of AuNS into quasi-spherical nanoparticles during the biorecognition of galactose in water and synthetic blood matrices. As a result, using our inexpensive and simple AuNS plasmon bioassays, the presence of galactose may be detected spectrophotometrically and by the naked eye.

Rapid ultra-sensitive nucleic acid detection using plasmonic fiber-optic spectral combs and gold nanoparticle-tagged targets

Nucleic acid (NA) is a widely-used biomarker for viruses. Accurate quantification of NA can provide a reliable basis for point-of-care diagnosis and treatment. Here, we propose a tilted fiber Bragg grating (TFBG)-based plasmonic fiber-optic spectral comb for fast response and ultralow limit NA detection. The TFBG is coated with a gold film which enables excitation of surface plasmon resonance (SPR), and single-stranded probe NAs with known base sequences are assembled on the gold film. To enhance sensitivity of refractive index (RI) for sensing a chosen combination of probe and target NAs around the TFBG surface, gold nanoparticles (AuNPs) are bonded to the target NA molecules as “RI-labels”. The NA combination-induced aggregation of AuNPs induces significant spectral responses in the TFBG that would be below the detection threshold for the NAs in the absence of the AuNPs. The proposed TFBG-SPR NA sensor shows a fast response time of 30 s and an ultra-wide NA detection range from 1 × 10−18 mol/L to 1 × 10−7 mol/L. In the NA concentration range of 1 × 10−12 mol/L (1 pM) to 105 pM, an ultra-high sensitivity of 1.534 dB/lg(pM) is obtained. The sensor achieves an ultra-low limit of detection down to 1.0 × 10−18 mol/L (1 aM), which is more than an order of magnitude lower than the previous reports. The proposed sensor not only shows potentials in practical applications of NA detection, but also provides a new way for TFBG-SPR biochemical sensors to achieve higher RI sensitivity.

Plasmon-Enhanced Perovskite Solar Cells Based on Inkjet-Printed Au Nanoparticles Embedded into TiO2 Microdot Arrays.

The exceptional property of plasmonic materials to localize light into sub-wavelength regimes has significant importance in various applications, especially in photovoltaics. In this study, we report the localized surface plasmon-enhanced perovskite solar cell (PSC) performance of plasmonic gold nanoparticles (AuNPs) embedded into a titanium oxide (TiO2) microdot array (MDA), which was deposited using the inkjet printing technique. The X-ray (XRD) analysis of MAPI (methyl ammonium lead iodide) perovskite films deposited on glass substrates with and without MDA revealed no destructive effect of MDA on the perovskite structure. Moreover, a 12% increase in the crystallite size of perovskite with MDA was registered. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) techniques revealed the morphology of the TiO2_MDA and TiO2-AuNPs_MDA. The finite-difference time-domain (FDTD) simulation was employed to evaluate the absorption cross-sections and local field enhancement of AuNPs in the TiO2 and TiO2/MAPI surrounding media. Reflectance UV-Vis spectra of the samples comprising glass/TiO2 ETL/TiO2_MDA (ETL-an electron transport layer) with and without AuNPs in TiO2_MDA were studied, and the band gap (Eg) values of MAPI have been calculated using the Kubelka-Munk equation. The MDA introduction did not influence the band gap value, which remained at ~1.6 eV for all the samples. The photovoltaic performance of the fabricated PSC with and without MDA and the corresponding key parameters of the solar cells have also been studied and discussed in detail. The findings indicated a significant power conversion efficiency improvement of over 47% in the PSCs with the introduction of the TiO2-AuNPs_MDA on the ETL/MAPI interface compared to the reference device. Our study demonstrates the significant enhancement achieved in halide PSC by utilizing AuNPs within a TiO2_MDA. This approach holds great promise for advancing the efficiency and performance of photovoltaic devices.

Space-Confined Electrochemical Aptasensing with Conductive Hydrogels for Enhanced Applicability to Aflatoxin B1 Detection.

Aflatoxin B1 (AFB1) contamination has received considerable attention for the serious harm it causes and its wide distribution. Hence, its efficient monitoring is of great importance. Herein, a space-confined electrochemical aptasensor for AFB1 detection is developed using a conductive hydrogel. Plasmonic gold nanoparticles (AuNPs) and methylene blue-embedded double-stranded DNA (MB-dsDNA) were integrated into the conductive Au-hydrogel by ultraviolet (UV) polymerization. Specific recognition of AFB1 by the aptamer released MB from MB-dsDNA in the matrix. The free DNA migrated to the outer layer due to electrostatic repulsion during the Au-hydrogel formation. The electrochemical aptasensor based on this Au-hydrogel offered a twofold enlarged oxidation current of MB (IMB) compared with that recorded in the homogeneous solution for AFB1 detection. Upon light illumination, this IMB was further enlarged by the local surface plasmon resonance (LSPR) of the AuNPs. Ultimately, the Au-hydrogel-based electrochemical aptasensor provided a detection limit of 0.0008 ng mL-1 and a linear range of 0.001-1000 ng mL-1 under illumination for AFB1 detection. The Au-hydrogel allowed for space-confined aptasensing, favorable conductivity, and LSPR enhancement for better sensitivity. It significantly enhanced the applicability of the electrochemical aptasensor by avoiding complicated electrode fabrication and signal loss in a bulk homogeneous solution.

Smaller Gold Nanoparticles Release DNA More Efficiently During fs Laser Pulsed Optical Heating.

This work investigates the effect of plasmonic gold nanoparticle (AuNP) size on the rate of thermal release of single-stranded oligonucleotides under femtosecond (fs)-pulsed laser irradiation sources. Contrary to the theoretical predictions that larger AuNPs (50-60nm diameter) would produce the most solution heating and fastest DNA release, it is found that smaller AuNP diameters (25nm) lead to faster dsDNA denaturation rates. Controlling for the pulse energy fluence, AuNP concentration, DNA loading density, and the distance from the AuNP surface finds the same result. These results imply that the solution temperature increases around the AuNP during fs laser pulse optical heating may not be the only significant influence on dsDNA denaturation, suggesting that direct energy transfer from the AuNP to the DNA (phonon-phonon coupling), which is increased as AuNPs decrease in size, may play a significant role.

Transport and Interfacial Injection of d-Band Hot Holes Control Plasmonic Chemistry.

Harnessing nonequilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field with the potential to control photochemical reactions, particularly for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot-carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence among plasmon excitation, hot-carrier generation, transport, and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiency at the solid/liquid interface. Measuring the internal quantum efficiency of ultrathin (14-33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is limited by hot hole collection at the metal/electrolyte interface. Our solid- and liquid-state experimental approach, combined with ab initio simulations, demonstrates more efficient collection of high-energy d-band holes traveling in the [111] orientation, enhancing oxidation reactions on {111} surfaces. These findings establish new guidelines for optimizing plasmonic photocatalytic systems and optoelectronic devices.

Multi-Modal Laser-Fabricated Nanocomposites with Non-Invasive Tracking Modality and Tuned Plasmonic Properties

Ultrapure composite nanostructures combining semiconductor and metallic elements as a result of ultrafast laser processing are important materials for applications in fields where high chemical purity is a crucial point. Such nanocrystals have already demonstrated prospects in plasmonic biosensing by detecting different analytes like dyes and bacteria. However, the structure of the nanocomposites, as well as the control of their properties, are still very challenging due to the significant lack of research in this area. In this paper, the synthesis of silicon–gold nanoparticles was performed using various approaches such as the direct ablation of (i) a gold target immersed in a colloidal solution of silicon nanoparticles and (ii) a silicon wafer immersed in a colloidal solution of plasmonic nanoparticles. The formed nanostructures combine both plasmonic (gold) and paramagnetic (silicon) modalities observed by absorbance and electron paramagnetic resonance spectroscopies, respectively. A significant narrowing of the size distributions of both types of two-element nanocrystals as compared to single-element ones is shown to be independent of the laser fluence. The impact of the laser ablation time on the chemical stability and the concentration of nanoparticles influencing their both optical properties and electrical conductivity was studied. The obtained results are important from a fundamental point of view for a better understanding of the laser-assisted synthesis of semiconductor–metallic nanocomposites and control of their properties for further applications.