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Enriching the library of chiral plasmonic nanoparticles that can be chemically mass-produced will greatly facilitate the applications of chiral plasmonics in areas ranging from constructing optical metamaterials to sensing chiral molecules and activating immune cells. Here we report on a halide-assisted differential growth strategy that can direct the anisotropic growth of chiral Au nanoparticles with tunable sizes and diverse morphologies. Anisotropic Au nanodisks are employed as seeds to yield triskelion-shaped chiral nanoparticles with threefold rotational symmetry and high dissymmetry factors. The averaged scattering g-factors of the L- and D-nanotriskelions are as large as 0.57 and - 0.49 at 650 nm, respectively. The Au nanotriskelions have been applied in chiral optical switching devices and chiral nanoemitters. We also demonstrate that the manipulation of the directional growth rate enables the generation of a variety of chiral morphologies in the presence of homochiral ligands., (© 2023. The Author(s).)

Background: CRISPR-Cas12a has been integrated with nanomaterial-based optical techniques, such as surface-enhanced Raman scattering (SERS), to formulate a powerful amplification-free nucleic acid detection system. However, nanomaterials impose steric hindrance to limit the accessibility of CRISPR-Cas12a to the narrow gaps (SERS hot spots) among nanoparticles (NPs) for producing a significant change in signals after nucleic acid detection. Methods: To overcome this restriction, we specifically design chimeric DNA/RNA hairpins (displacers) that can be destabilized by activated CRISPR-Cas12a in the presence of target DNA, liberating excessive RNA that can disintegrate a core-satellite nanocluster via toehold-mediated strand displacement for orchestrating a promising "on-off" nucleic acid biosensor. The core-satellite nanocluster comprises a large gold nanoparticle (AuNP) core surrounded by small AuNPs with Raman tags via DNA hybridization as an ultrabright Raman reporter, and its disassembly leads to a drastic decrease of SERS intensity as signal readouts. We further introduce a magnetic core to the large AuNPs that can facilitate their separation from the disassembled nanostructures to suppress the background for improving detection sensitivity. Results: As a proof-of-concept study, our findings showed that the application of displacers was more effective in decreasing the SERS intensity of the system and attained a better limit of detection (LOD, 10 aM) than that by directly using activated CRISPR-Cas12a, with high selectivity and stability for nucleic acid detection. Introducing magnetic-responsive functionality to our system further improves the LOD to 1 aM. Conclusion: Our work not only offers a platform to sensitively and selectively probe nucleic acids without pre-amplification but also provides new insights into the design of the CRISPR-Cas12a/SERS integrated system to resolve the steric hindrance of nanomaterials for constructing biosensors., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)

Caspase-3 and hydrogen peroxide (H 2 O 2 ) are closely associated with numerous diseases, both of them are vital in different physiological and pathological conditions. They are closely related and also can act independently. The selective and accurate determination of caspase-3 and H 2 O 2 simultaneously to determine their state of being in different situations is of great significance for further study of their molecular mechanisms and the elucidation of their biological functions. In our latest research, a AuNPL-crown nanoprobe was obtained by attaching (4-aminosulfonylphenyl) boronic acid (4-APBA) and peptide-FITC (NH 2 -Asp-Glu-Val-Asp (DEVD)-FITC) to gold nanoplates (AuNPLs). The fabricated AuNPL-crown nanoprobe was used for dual-channel and real-time tracking of the dynamic changes in caspase-3 and H 2 O 2 based on fluorescence resonance energy transfer (FRET)/surface-enhanced Raman spectroscopy (SERS) technology. The AuNPL-crown nanoprobe not only provides synergy but can also achieve noninterference, making the results more reliable and repeatable. This study simultaneously traced the dynamic changes of caspase-3 and H 2 O 2 on a single probe, which provides a potential new platform for the analysis of caspase-3 and H 2 O 2 in the biological environment with high accuracy, sensitivity, convenience, and efficiency. In summary, we develop a new strategy for the simultaneous detection of different substances on a single probe., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A nanoprobe based on polydopamine-coated gold nanobipyramids surface modified with molecules of a phenylboronic acid-substituted distyryl boron dipyrromethene has been fabricated and characterised using various physical and spectroscopic methods. It serves as an ultrasensitive sensor for sialic acids on the surface of cancer cells based on its dual surface-enhanced Raman scattering and fluorescence response. This biomarker can also trigger the photodynamic activity of these nanobipyramids, effectively eradicating the cancer cells mainly through apoptosis as shown by various bioassays.

Plasmonic nanochains, derived from the one-dimensional assembly of individual plasmonic nanoparticles (NPs), remain infrequently explored in biological investigations due to their limited colloidal stability, ineffective cellular uptake, and susceptibility to intracellular disassembly. We report the synthesis of polydopamine (PDA)-coated plasmonic "nanoworms" (NWs) by sonicating citrate-capped gold (Cit-Au) NPs in a concentrated dopamine (DA) solution under alkaline conditions. DA mediates the assembly of Cit-Au NPs into Au NWs within 1 min, and subsequent self-polymerization of DA for 60 min enables the growth of an outer conformal PDA shell that imparts stability to the inner Au NW structure in solution, yielding "core-shell" Au@PDA NWs with predominantly 4-5 Au cores per worm. Our method supports the preparation of monometallic Au@PDA NWs with different core sizes and bimetallic PDA-coated NWs with Au and silver cores. The protonated primary amine and catechol groups of DA, with their ability to interact with Cit anions via hydrogen bonding and electrostatic attraction, are critical to assembly. When compared to unassembled PDA-coated Au NPs, our Au@PDA NWs scatter visible light and absorb near-infrared light more intensely and enter HeLa cancer cells more abundantly. Au@PDA NWs cross the cell membrane as intact entities primarily via macropinocytosis, mostly retain their inner NW structure and outer PDA shell inside the cell for 24 h, and do not induce noticeable cytotoxicity. We showcase three intracellular applications of Au@PDA NWs, including label-free dark-field scattering cell imaging, delivery of water-insoluble cargos without pronounced localization in acidic compartments, and photothermal killing of cancer cells.

Recent years have witnessed significant progress in the field of two-photon-activated photodynamic therapy (TP-PDT). However, traditional photosensitizer (PS)-based TP-PDT remains a critical challenge in clinics due to its low two-photon absorption cross sections. Here, we propose that the therapeutic activity of the current photosensitizer, sulfonated Al-phthalocyanine (AlPcS), can be efficiently excited via plasmonic-resonance energy transfer from the two-photon excited gold nanobipyramids (GBPs) and further generates cytotoxic singlet oxygen for cancer eradication. GBPs possess large two-photon absorption cross sections, excellent photostability, and biocompatibility, which can be used for a high two-photon light-harvesting material in biomedical applications. We compared the in vitro and in vivo capabilities of AlPcS-loaded GBPs as a TP-PDT agent for theranostic applications by benchmarking them against those of the extensively studied gold nanospheres (GNS) and nanorods (GNR). Although all these Au nanostructures could cause enhanced PS two-photon excitation fluorescence and improved singlet oxygen generation capability via the plasmonic resonance-energy transfer process, GBP-AlPcS exhibited the highest two-photon efficiency for photodynamic therapy. Remarkably, in vivo experiment results clearly indicated that the GBP-AlPcS caused efficient suppression of tumor growth and minimal adverse effects on orthotopic A549 human lung tumor xenografts. The system presents great efficiency in improving the treatment depth and precision of traditional photodynamic therapy.

A biosensor based on a combination of cytochrome c (Cyt c ), electrochemical reduced graphene oxides (ERGO), and gold nanoparticles (AuNPs) on a glassy carbon electrode (GCE) was fabricated. The proposed biosensor electrode was denoted as GCE/ERGO-Nafion/AuNPs/Cyt c /Nafion, where ERGO-Nafion was deposited by dropping graphene oxides-Nafion mixed droplet first and following electrochemical reduction, AuNPs were directly deposited on the surface of the ERGO-Nafion modified electrode by electrochemical reduction, and other components were deposited by the dropping-dry method. The effect of the deposition amount of AuNPs on direct electrochemistry of Cyt c in the proposed electrode was investigated. The hydrogen peroxide was taken to evaluate the performance of the proposed biosensor. The results showed that the biosensor has great analytical performance, including a high sensitivity, a wide linear range, a low detection limit, and good stability, reproducibility, and reliability.

Prostate-specific antigen (PSA) is an intercellular glycoprotein produced primarily by the prostate gland, which is commonly chosen as the initial target for the early diagnosis of prostate cancer. In this work, we demonstrate a simple yet sensitive sandwich-type single-particle enumeration (SPE) immunoassay for the quantitative detection of PSA in a flow chamber. The design is based on the luminescence resonance energy transfer (LRET) between upconversion nanoparticles (UCNPs) and gold nanoparticles (GNPs). The carboxyl group-functionalized UCNPs are conjugated with anti-PSA detection antibodies (Ab 1 ) and serve as the luminescence energy donor, while GNPs are modified with anti-PSA capture antibodies (Ab 2 ) and act as the energy acceptor. In the presence of target antigen (i.e., PSA), the specific immnuoreaction brings the donor and acceptor into close proximity, resulting in quenched luminescence. Through statistical counting of the target-dependent fluorescent particles on the glass slide surface, the quantity of antigens in the solution is accurately determined. The dynamic range for PSA detection in Tris-buffered saline (TBS) is 0-500 pM and the limit-of-detection (LOD) is 1.0 pM, which is much lower than the cutoff level in patients' serum samples. In the serum sample assay, comparable LOD was also achieved (i.e., 2.3 pM). As a consequence, this method will find promising applications for the selective detection of cancer biomarkers in clinical diagnosis.

Integration of semiconductors with noble metals to form heteronanostructures can give rise to many interesting plasmonic and electronic properties. A number of such heteronanostructures have been demonstrated comprising noble metals and n-type semiconductors, such as TiO2 , ZnO, SnO2 , Fe3 O4 , and CuO. In contrast, reports on heteronanostructures made of noble metals and p-type semiconductors are scarce. Cu2 O is an unintentional p-type semiconductor with unique properties. Here, the uniform coating of Cu2 O on two types of Au nanorods and systematic studies of the plasmonic properties of the resultant core-shell heteronanostructures are reported. One type of Au nanorods is prepared by seed-mediated growth, and the other is obtained by oxidation of the as-prepared Au nanorods. The (Au nanorod)@Cu2 O nanostructures produced from the as-prepared nanorods exhibit two transverse plasmon peaks, whereas those derived from the oxidized nanorods display only one transverse plasmon peak. Through electrodynamic simulations the additional transverse plasmon peak is found to originate from a discontinuous gap formed at the side of the as-prepared nanorods. The existence of the gap is verified and its formation mechanism is unraveled with additional experiments. The results will be useful for designing metal-semiconductor heteronanostructures with desired plasmonic properties and therefore also for exploring plasmon-enhanced applications in photocatalysis, solar-energy harvesting, and biotechnologies., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidal noble metal nanocrystals are promising for a large number of optical and biotechnological applications. Many practical applications require the formation of large-area, high-density, and uniformly distributed metal nanocrystal arrays on various substrates, to overcome the limitations brought by the instability of colloidal metal nanocrystal solutions and the high cost of single-particle spectroscopy characterizations. A method is developed for directly depositing colloidal metal nanocrystals, including Au nanospheres, Au nanorods, Au nanobipyramids, and (Au core)/(Ag shell) nanorods, from their solutions onto different substrates. The resultant nanocrystal arrays are relatively uniform and dense, with the peak extinction value of a single layer reaching 0.3. Their areas are up to 10 cm by 10 cm and can be further increased if larger-size containers are utilized. The refractive index sensitivities are studied for Au nanorod arrays supported on glass slides, mesoporous silica and titania films, and capped with different molecules. Au nanorods deposited on mesoporous titania films are found to exhibit the highest index sensitivities, comparable to those of the same nanorod sample in solutions. It is expected that this approach will greatly facilitate plasmonic applications that require large-area arrays of noble metal nanocrystals., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The optotransfection of cells based on a femtosecond laser has attracted much attention owing to its high transfection efficiency and high cell viability since its first report by Konig. However, the low throughput in the original method also limits its use in practical applications. Gold nanoparticles (GNPs) have been reported to function as local receivers of light to relax the requirement of accurate optical alignment for the optotransfection of single cells. However, the visible light used in such work is not suitable for penetrating deep tissues in certain applications. In this study, we employed gold nanorods (GNRs) and an infrared femtosecond laser at the wavelength of 980 nm to realize optotransfection of cells with GFP. It was found that the surface coating of GNRs exhibited a significant effect on the process of cell permeabilization.

Gold nanorods exhibit rich colours owing to the nearly linear dependence of the longitudinal plasmon resonance wavelength on the length-to-diameter aspect ratio. This property of Au nanorods has been utilized in this work for dyeing fabrics. Au nanorods of different aspect ratios were deposited on both cotton and silk fabrics by immersing them in Au nanorod solutions. The coating of Au nanorods makes the fabrics exhibit a broad range of colours varying from brownish red through green to purplish red, which are essentially determined by the longitudinal plasmon wavelength of the deposited Au nanorods. The colorimetric values of the coated fabrics were carefully measured for examining the colouring effects. The nanorod-coated cotton fabrics were found to be commercially acceptable in washing fastness to laundering tests and colour fastness to dry cleaning tests. Moreover, the nanorod-coated cotton and silk fabrics show significant improvements on both UV-protection and antibacterial functions. Our study therefore points out a promising approach for the use of noble metal nanocrystals as dyeing materials for textile applications on the basis of their inherent localized plasmon resonance properties.

Understanding the electromagnetic interactions between plasmonic noble metal nanocrystals and different substrates is very important because a number of plasmon-based devices and applications, such as chemical and biological sensing, metamaterials, subwavelength waveguides, plasmon-enhanced photovoltaic cells, plasmon-enhanced spectroscopy, and photoswitches, require the attachment of metal nanocrystals onto various substrates. In this study, we focused on the effect of the dielectric properties of substrates on the far-field scattering patterns of supported Au nanorods. Seven types of substrates, including metals, semiconductors, and insulators, were examined. The far-field scattering patterns from individual Au nanorods were found to exhibit a doughnut shape when the modulus of the dielectric constant of the substrate is above ∼7, while they appear as solid bright spots when the modulus is below ∼7. This finding was validated by numerical electrodynamic calculations. Moreover, the doughnut-shaped scattering patterns are very sensitive to the spacing between the nanorod and substrate. For the nanorods supported on silicon wafers, when the spacing is increased above ∼14 nm, the scattering patterns change from the doughnut shape to the solid bright spot. These results will be useful for the understanding of the plasmonic properties of noble metal nanocrystals supported on substrates and the development of a number of plasmon-based optical and optoelectronic devices at different size scales.

Bifunctional heterostructures composed of gold nanorods and hematite nanoparticle aggregates are prepared facilely through the hydrothermal decomposition of ferric acetylacetonate on the surface of the nanorods. The gold nanorod in the heterostructure is partially coated with the hematite nanoparticle aggregates. The hematite coating is porous. These heterostructures exhibit both plasmonic and superparamagnetic properties. They are well-dispersed in aqueous solutions. Such heterostructures will be potentially useful for many biotechnological applications., (© 2011 American Chemical Society)

Localized surface plasmon resonances of noble metal nanocrystals are powerful in enhancing a variety of linear and nonlinear optical signals and photorelated processes. Here we demonstrate the plasmonic enhancement of the light scattering from hollow mesoporous silica microspheres by attaching a dense layer of gold nanocrystals onto the outer surface of the microspheres. The attachment of gold nanocrystals induces both the shift and intensity increase in the resonant scattering peaks of the microspheres. The spectral region of the resonant scattering enhancement can be controlled by using gold nanocrystals with different plasmon resonance wavelengths. The spectral region of the enhancement is independent of the microsphere diameter. The scattering enhancement factor ranges from 20 to 130, depending on the plasmonic properties and surface coverage of the attached gold nanocrystals. The systematic evolution of the scattering spectra of the individual microspheres is also revealed by chemically etching away the attached gold nanocrystals gradually.

Plasmon-based photothermal therapy is one of the most intriguing applications of noble metal nanostructures. The photothermal conversion efficiency is an essential parameter in practically realizing this application. The effects of the plasmon resonance wavelength, particle volume, shell coating, and assembly on the photothermal conversion efficiencies of Au nanocrystals are systematically studied by directly measuring the temperature of Au nanocrystal solutions with a thermocouple and analyzed on the basis of energy balance. The temperature of Au nanocrystal solutions reaches the maximum at ∼75 °C when the plasmon resonance wavelength of Au nanocrystals is equal to the illumination laser wavelength. For Au nanocrystals with similar shapes, the larger the nanocrystal, the smaller the photothermal conversion efficiency becomes. The photothermal conversion can also be controlled by shell coating and assembly through the change in the plasmon resonance energy of Au nanocrystals. Moreover, coating Au nanocrystals with semiconductor materials that have band gap energies smaller than the illumination laser energy can improve the photothermal conversion efficiency owing to the presence of an additional light absorption channel.

It is known that universality and controllability over nanocrystal orientation must be accomplished to facilitate the potential applications of metal nanocrystals in the areas of photonics, electronics, and optics. The facile fabrication of linear chains of Au nanorods and bifurcated junctions of nanorods/nanospheres is achieved via the crosslinking of H-type tetrakis(4-sulfonatophenyl)porphyrin aggregates in solution. The tuning of the plasmon coupling between the Au nanocrystals is demonstrated by varying the porphyrin concentration and thus the interparticle gap distances. Finite-difference time-domain calculations show that the red shift of the plasmon band exhibits a nearly exponential decay with increasing interparticle gap distances, thus giving rise to a "plasmon ruler equation." The gap distances determined according to this equation agree well with the experimental observations and further confirm the porphyrin-directed assembly process. The interaction mechanism between the Au nanorods and porphyrins is further investigated by a biological procedure using the dark-field light scattering technique.

Core-shell Au nanorod-AgAuS nanostructures were hydrothermally prepared from Au nanorods and metal thiobenzoates and then transformed into Au nanoparticle-decorated sulfide nanostructures.

The effects of various factors on the resonance coupling between elongated Au nanocrystals and organic dyes have been systematically investigated through the preparation of hybrid nanostructures between Au nanocrystals and the electrostatically adsorbed dye molecules. A nanocrystal sample is chosen for each dye to match the longitudinal plasmon resonance wavelength with the absorption peak wavelength of the dye as close as possible so that the resonance coupling strength can be maximized. The resonance coupling strength is found to approximately increase as the molecular volume-normalized absorptivity is increased. It is mainly determined by the plasmon resonance energy of the Au nanocrystals instead of their shapes and sizes. Moreover, the resonance coupling can be reversibly controlled if the dye in the hybrid nanostructures is pH-sensitive. The coupling can also be weakened in the presence of metal ions. These results will be highly useful for designing resonance coupling-based sensing devices and for plasmon-enhanced spectroscopy.

Gold nanocubes demonstrate unique optical properties of the high photoluminescence (PL) quantum yield and a remarkably enhanced extinction band at 544 nm. The 4 x 10(-2) PL yield, which is about 200 times higher than that of gold nanorods, allows gold nanocubes to be successfully used in cell imaging of human liver cancer cells (QGY) and human embryo kidney cells (293T) with a common method of single-photon excitation. The high extinction coefficients of gold nanocubes also facilitate them carrying out the photothermal therapy of QGY and 293T cells, showing similar photokilling efficiency as compared to gold nanorods.

Strong plasmonic-molecular resonance coupling occurs between noble metal nanocrystals and organic adsorbates when the plasmonic resonance is degenerate with the molecular one. This interaction forms the basis for many fundamental studies and practical applications. We describe here the first direct measurement of the resonance coupling on single gold nanorods. The dark-field scattering technique is employed. The nanorods are embedded in hydrogel to facilitate uniform dye adsorption. The adsorbed dye molecules exhibit both monomer and H-aggregate absorption bands. The same gold nanorods are measured before and after the dye adsorption. Both strong and weak coupling are investigated by selecting nanorods with different longitudinal plasmon bands. Excellent agreement between the experiments and an analytic theory is obtained. The resonance coupling reveals a unique three-band structure. The tunability of the coupling on individual nanorods is further demonstrated by photodecomposing the adsorbed dye molecules.

Multiple Fano resonances (mFRs) are arising as a promising optical platform to achieve precise sensing and detection. However, experimentally achieving mFRs by simple structures has remained challenging, which impedes the widespread applications of mFRs. Herein a simple structure composed of a single colloidal metal nanoparticle and a transition metal dichalcogenide flake to simultaneously achieve up to 8 FRs in experiments is demonstrated. Combining theoretical and experimental techniques, that an out‐of‐plane plasmon mode of the metal nanoparticle interferes with the Fabry–Pérot cavity modes from the WS2 flake to form mFRs in the visible region is proved. The simplicity and generality of the method further allow us to systematically study the tunability of the mFRs, in terms of the peak/dip positions and the number of FRs, by changing the structural parameters, which include the thickness of the WS2 flake, size and shape of the plasmonic nanoparticle. In addition, the quality of the mFRs is proved to be adjustable by tuning the reflectivity of the substrate in the system. The highest quality factor and spectral contrast of the achieved resonances are up to ≈180 and ≈0.95, respectively. The simple structure and high‐quality optical modes will prosper applications in precise sensing and light modulation. [ABSTRACT FROM AUTHOR]