Individual Gold Nanoparticles Research Articles

Single-Nanoparticle-Based Nanomachining for Fabrication of a Uniform Nanochannel Sensor.

The structure of nanomaterials and nanodevices determines their functionality and applications. A single uniform nanochannel with a high aspect ratio is an attractive structure due to its unique rigid structures, easy preparation, and diverse pore structures and it holds significant promising importance in fields such as nanopore sensing and nanomanufacturing. Although the metal-nanoparticle-assistant silicon etching technique can produce uniform nanochannels, however, the fabrication of single through nanochannels remains a challenge thus far. A simple and versatile strategy is developed that allows for the retention of individual gold nanoparticle on a substrate, enabling single-nanoparticle nanomachining. This method involves three steps: the formation of a carbon protective layer on individual nanoparticles via electron-beam irradiation, selective removal of unprotected nanoparticles using a corrosive agent, and subsequent elimination of the carbon layer. This enables the fabrication of a single submillimeter-long uniform through nanochannel in the silicon wafer, which can be employed for nanopore sensing and shape-based nanoparticle distinguishing. The developed method can also facilitate single-nanoparticle studies and nanomachining for a broad application in materials science, electronics, micro/nano-optics, and catalysis.

Faraday rotation enhancement for colloidal spherical Au and Ag nanoparticles and their mixtures

So far, magnetooptical (MO) properties of silver nanoparticles (AgNPs) have been studied only by magnetic circular dichroism (MCD) spectroscopy at the surface plasmon resonance (SPR) band. However, direct knowledge of the Faraday rotation effect (FR) is very important in fundamental research and applications. In the present work, we study an enhancement of FR of individual gold nanoparticles (AuNPs) and AgNPs and their mixture of colloidal aqueous suspension. The Au and Ag spherical NPs were synthesized independently as colloids in an aqueous suspension and then such mixtures were studied (AgNPs were also studied as a suspension in hexane). The noble metal NPs were characterized by TEM, UV–Vis, and refraction methods. The enhancement of FR of individual NPs was observed and it is consistent with available MCD results. For the mixtures, observed changes of magnitude of FR is small, and coupling of both SPR is rather weak. The obtained FR spectra associated with SPR band have been successfully converted to MCD spectra using the Kramers-Kronig transformation. Calculated MCD spectra are consisted with that obtained by direct measurements.

Three-dimensional photoinduced force microscopy reveals artifacts from photothermal tip vibrations

Photoinduced force microscopy (PiFM) is a technique for nanoscale characterization of optically active materials. For correct data analysis, it is important to understand and recognize potential artifacts. In this study, we provide a Fourier-based framework for the different origins of the photoinduced force, including the photothermal motion of the atomic force microscopy (AFM) tip in PiFM measurements. We use individual gold nanoparticles as a model system to explore such tip-related phenomena and to demonstrate the benefits of three-dimensional analysis of the photoinduced force. Comparison of the in-phase heterodyne PiFM signal and the derivative of the tip–sample interaction, ∂⟨kts⟩/∂zc, directly reveals a photothermal origin for the PiFM signal in our experiments. Furthermore, we observe a lateral photothermal vibration of the tip apex induced by tip asymmetry. This lateral vibration emphasizes the importance of considering the motion of the AFM tip during data analysis. The improved lateral resolution conferred by ∂⟨kts⟩/∂zc can lead to misinterpretation. Our findings highlight that meticulous data analysis is required to ensure the correct interpretation of PiFM data.

Enhancement of cellular uptake by increasing the number of encapsulated gold nanoparticles in polymeric micelles

We apply a combination of polycaprolactone (PCL)-thiol ligand functionalization with flow-controlled microfluidic block copolymer self-assembly to produce biocompatible gold nanoparticle (GNP)-loaded micellar polymer nanoparticles (GNP-PNPs) in which GNPs are encapsulated within PCL cores surrounded by an external layer of poly(ethylene glycol) (PEG). By varying both the relative amount of block copolymer and the microfluidic flow rate, a series of GNP-PNPs are produced in which the mean number of GNPs per PNP in the < 50-nm fraction (Zave,d< 50 nm) varies between 0.1 and 1.9 while the external PEG surface is constant. Zave,d< 50 nm values are determined by statistical analysis of TEM images and compared with the results of cell uptake experiments on MDA-MB-231 cancer cells. For Zave,d< 50 nm ≤ 1 (including a control sample of individual GNPs also with a PEG surface layer), cell uptake is relatively constant, but increases sharply for Zave,d< 50 nm > 1, with a factor of 7 enhancement as Zave,d< 50 nm increases from 1 to ∼2. Enabled by the shear processing control provided by the microfluidic chip, these results provide the first evidence that cellular uptake can be enhanced specifically by increasing the number of GNPs per vector, with other parameters, including polymeric material, internal structure, and external surface chemistry, held constant. They also demonstrate a versatile platform for packaging GNPs in biocompatible polymeric carriers with flow-controlled formulation optimization for various therapeutic and diagnostic applications.

Reversible Regulation of Long-Distance Charge Transport in DNA Nanowires by Dynamically Controlling Steric Conformation.

Understanding of DNA-mediated charge transport (CT) is significant for exploring circuits at the molecular scale. However, the fabrication of robust DNA wires remains challenging due to the persistence length and natural flexibility of DNA molecules. Moreover, CT regulation in DNA wires often relies on predesigned sequences, which limit their application and scalability. Here, we addressed these issues by preparing self-assembled DNA nanowires with lengths of 30-120 nm using structural DNA nanotechnology. We employed these nanowires to plug individual gold nanoparticles into a circuit and measured the transport current in nanowires with an optical imaging technique. Contrary to the reported cases with shallow or no length dependence, a fair current attenuation was observed with increasing nanowire length, which experimentally confirmed the prediction of the incoherent hopping model. We also reported a mechanism for the reversible CT regulation in DNA nanowires, which involves dynamic transitions in the steric conformation.

Background-free four-wave mixing microscopy of small gold nanoparticles inside a multi-cellular organ

The ability to detect small metallic nanoparticles by optical microscopy inside environmentally relevant species may have a wide impact for ecotoxicology studies. Here, we demonstrate four-wave mixing microscopy on individual small gold nanoparticles inside the hepatopancreas of Oniscus Asellus, a terrestrial isopod, which ingests metals found in the soil. After the exposure to food containing 10 nm radius gold nanoparticles, hepatopancreas tubules were collected, and nanoparticles were imaged by four-wave mixing microscopy with high contrast, locating them with sub-cellular resolution in the volume, despite the significant light scattering from these multi-cellular organs. Notably, the ultrafast dynamics of the four-wave-mixing non-linearity of gold nanoparticles resonantly excited and probed at their localized surface plasmon allows them to be distinguished from other metal deposits in the hepatopancreas, which manifest as a long-lived photothermal contrast. Our findings bring unexpected insight into the location of gold nanoparticles in relation to the cell types forming the hepatopancreas. Considering its simplicity, volumetric imaging capabilities, specificity, and compatibility with living cell studies, four-wave mixing microscopy holds great potential to investigate the fate of metal nanoparticles inside biological systems.

Correlative light-electron microscopy using small gold nanoparticles as single probes

Correlative light-electron microscopy (CLEM) requires the availability of robust probes which are visible both in light and electron microscopy. Here we demonstrate a CLEM approach using small gold nanoparticles as a single probe. Individual gold nanoparticles bound to the epidermal growth factor protein were located with nanometric precision background-free in human cancer cells by light microscopy using resonant four-wave mixing (FWM), and were correlatively mapped with high accuracy to the corresponding transmission electron microscopy images. We used nanoparticles of 10 nm and 5 nm radius, and show a correlation accuracy below 60 nm over an area larger than 10 µm size, without the need for additional fiducial markers. Correlation accuracy was improved to below 40 nm by reducing systematic errors, while the localisation precision is below 10 nm. Polarisation-resolved FWM correlates with nanoparticle shapes, promising for multiplexing by shape recognition in future applications. Owing to the photostability of gold nanoparticles and the applicability of FWM microscopy to living cells, FWM-CLEM opens up a powerful alternative to fluorescence-based methods.

Localized Spontaneous Chiroptical Response in Disordered Plasmonic Nanoaggregates

Metamaterials exhibiting orders-of-magnitude enhanced artificial chiroptical response than natural counterparts have been intensely investigated. The underlying principle of these chiral responses heavily hinges on an elaborate nanostructure fabrication to generate either intrinsic geometry chirality or handedness-dependent mode interference. Here, we unveil that localized spontaneous chiroptical response can be leveraged by plasmonic nanoaggregates with a disordered coupling effect. The near-field coupling among disordered individual gold nanoparticles leads to localized hot spots that are sensitive to the handedness of light. As a consequence, the nearby nanoparticles showcase near-unity circular dichroism in linear absorption to left- and right-circularly polarized light. It directly leads to a subsequent selective photothermal deformation of plasmonic nanoparticles, which produces prominent nonlinear circular dichroism in two-photon fluorescence by circular polarization beams. Such localized spontaneous chirality is then experimentally evidenced by nanoscale multiplexing watermarks in polychromatic beams with left- and right-circular polarizations. Our results might open a new strategy to tailor the chiroptical response in disordered photonic systems and facilitate the study of chiral light–matter interactions at the deep-subwavelength regime.

Fluorescence ratio immunoassay for fumonisin B1 based on the oxidase characteristics of the growth of monodispersed 2-D MnO2 nanosheet on an individual gold nanoparticle (AuNP@MnO2).

Fumonisin B1 (FB1) is one of the important mycotoxins posing health risks in the area of food safety. Asensitive fluorescence ratio immunoassay has been establishedfor FB1 based on the growth of monodispersed 2-D MnO2 nanosheet on an individual gold nanoparticle (AuNP@MnO2). FB1 competed with the coated FB1-BSA to bind the FB1 monoclonal antibody. After awashing step, alkaline phosphatase-labeled goat anti-mouse IgG (ALP-IgG) with high catalytic activity was combined with FB1 monoclonal antibody. ALP reacts with ascorbic acid 2-phosphate (AAP) to produce ascorbic acid (AA), which decomposes AuNP@MnO2 to dehydroascorbic acid (DHAA). O-Phenylenediamine dihydrochloride (OPD) is oxidized to yellow-fluorescent substrate of 2,3-diaminophenazine (DAP) (excitation, 423 nm; emission, 570 nm) by AuNP@MnO2. Meanwhile, OPD can also be reduced to blue fluorescent substrate of OPDred (excitation, 350 nm; emission, 430 nm) by DHAA. The content of FB1 can be determined by fluorescence ratio of blue/yellow. The limit of detection (LOD) of the fluorescence ratio immunoassay for FB1 was 0.06 ng mL-1, and the linear range was from 0.25 to 60.00 ng mL-1. The effectiveness of the assay was verified in real maize samples, and satisfactory recoveries were attained. The correlation coefficient of these results between the fluorescence ratio immunoassay and commercial ELISA kit was 0.9999. This method provides a sensitive and selective tool for the detection of FB1 in maize samples.

Charge transfer effect: a new assignment of the abnormal optical absorption band of gold nanoparticles

As a significant accompanying phenomenon of surface-enhanced Raman scattering (SERS), the addition of foreign molecules to colloidal gold or silver nanoparticles results in a new abnormal optical absorption (AOA) band, which usually appears in the long-wavelength region. The assignment of this AOA band has long been debated as an important issue that is desired to be addressed in the SERS field, which is crucial for a clear understanding of the SERS enhancement mechanism and beneficial to surface plasmonics. In this study, both the calculated and measured optical absorptions of gold nanoparticle monomers and dimers as well as their interactions with adsorbed molecules, showed that the AOA band in the long-wavelength region which was assigned to the characteristic longitudinal localized surface plasmon resonance (LSPR) effect of gold nanoparticle chain aggregates in conventional SERS electromagnetic theory, should be attributed to the charge-transfer resonance absorption from gold nanoparticles to adsorbed molecules. This was further confirmed by the corresponding SERS effects. As the excitation wavelength at 785 nm was resonant with the broad AOA band centered at 750 nm, the SERS peaks of the adsorbed pyridine molecules could be dramatically enhanced due to the charge-transfer resonance effect. In contrast, under an excitation wavelength of 532 nm, the SERS peaks appeared very weak, although the excitation wavelength was resonant with the LSPR absorption band of the individual gold nanoparticles.

Real-Time Interfacial Nanothermometry Using DNA-PAINT Microscopy.

Biofunctionalized nanoparticles are increasingly used in biomedical applications including sensing, targeted delivery, and hyperthermia. However, laser excitation and associated heating of the nanomaterials may alter the structure and interactions of the conjugated biomolecules. Currently no method exists that directly monitors the local temperature near the material's interface where the conjugated biomolecules are. Here, a nanothermometer is reported based on DNA-mediated points accumulation for imaging nanoscale topography (DNA-PAINT) microscopy. The temperature dependent kinetics of repeated and reversible DNA interactions provide a direct readout of the local interfacial temperature. The accuracy and precision of the method is demonstrated by measuring the interfacial temperature of many individual gold nanoparticles in parallel, with a precision of 1 K. In agreement with numerical models, large particle-to-particle differences in the interfacial temperature are found due to underlying differences in optical and thermal properties. In addition, the reversible DNA interactions enable the tracking of interfacial temperature in real-time with intervals of a few minutes. This method does not require prior knowledge of the optical and thermal properties of the sample, and therefore opens the window to understanding and controlling interfacial heating in a wide range ofnanomaterials.

Design of a Signal-Amplified Aptamer-Based Lateral Flow Test Strip for the Rapid Detection of Ochratoxin A in Red Wine.

In order to improve the weak optical performance of gold nanoparticles and realize the signal amplification of lateral flow chromatography test strips, individual gold nanoparticles (AuNPs) were aggregated into gold nanoparticle aggregates through functional groups around polyamidoamine (PAMAM) dendrimers. A signal-amplified aptamer-based lateral flow chromatography test strip was constructed for the rapid determination of ochratoxin A (OTA). Under optimal conditions, the visual detection limit of this test strip was 0.4 ng mL−1 and the semi-quantitative limit of detection (LOD) was 0.04 ng mL−1. Compared with other traditional aptamer lateral flow chromatography test strips, its sensitivity was improved about five times. The whole test could be completed within 15 min. The aptamer-based strip was applied to the detection of OTA in red wine; the average recoveries ranged from 93% to 105.8% with the relative standard deviation (RSD) varying from 3% to 8%, indicating that the test strip may be a potentially effective tool for the on-site detection of OTA.

&lt;i&gt;Cocculus hirsutus&lt;/i&gt; Leaf Assisted Green Synthesis of Ag-Au Bimetallic Nanoparticles and their Antioxidant Properties

Bimetallic nanoparticles (BMNPs) of silver and gold are synthesized by eco- friendly green chemical procedure using leaf extract of Cocculus hirsutus. Under the experimental condition most individual silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) are spherical whereas silver-gold bimetallic nanoparticles (Ag-Au BMNPs) found cloudy and lost their individual shape. Ag-Au BMNPs formed by the co-reduction of Au(III) and Ag(I) ions in aqueous leaves extract solution where the extract act as both reducing and capping agent. NPs were characterized with the help of UV-Vis absorption spectroscopy, high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) analysis. UV-Vis spectroscopy exhibit surface plasmon absorption maxima at 435 and 540 nm for AgNPs and AuNPs respectively whereas surface plasmon resonance (SPR) maxima for Au-Ag bimetallic appeared in between the peaks corresponding to pure silver and gold at the same reaction conditions. X-ray diffraction analysis confirmed that crystalline nanoparticles (NPs) are face centered cubic structure. The synthesized bimetallic nanocomposites show stronger scavenging ability, around 67% and 75% on hydroxyl radical and superoxide radicals at the concentration of 400 µg/ml respectively, compared to the mono metallic AgNPs and AuNPs, indicating stronger antioxidant properties of Ag-Au BMNPs.

Label-free detection of single nanoparticles with disordered nanoisland surface plasmon sensor

We report sensing of single nanoparticles using disordered metallic nanoisland substrates supporting surface plasmon polaritons (SPPs). Speckle patterns arising from leakage radiation of elastically scattered SPPs provide a unique fingerprint of the scattering microstructure at the sensor surface. Experimental measurements of the speckle decorrelation are presented and shown to enable detection of sorption of individual gold nanoparticles and polystyrene beads. Our approach is verified through bright-field and fluorescence imaging of particles adhering to the nanoisland substrate.

Gold nanoparticles enhance antibody effect through direct cancer cell cytotoxicity by differential regulation of phagocytosis

Ramucirumab is the first FDA-approved monotherapy for advanced gastric cancer. In this study, Ramucirumab (Ab) is attached to gold nanoparticles to enhance uptake efficiency. Gold nanoparticles can induce direct cytotoxic effects to cancer cells in the presence of Ab, while individual Ab or gold nanoparticles don’t have such an effective anticancer effect even at extremely high concentrations. Proteomic and transcriptomic analyses reveal this direct cytotoxicity is derived predominantly from Ab-mediated phagocytosis. High affinity immunoglobulin gamma Fc receptor I shows differential up-regulation in gastric cancer cells treated by these nanodrugs compared with Ab, especially for Ab with gold nanorods. Simplified and powerful designs of smart nanoparticles are highly desired for clinical application. The enhancement of Ab accumulation with a simple composition, combined with direct cytotoxic effects specific to cancer cells brought improved therapeutic effects in vivo compared with Ab, which can promote further clinical application of gold nanomaterials in the diagnosis and therapeutics of gastric cancer.

Additive Manufacturing of Gold Nanostructures Using Nonlinear Photoreduction under Controlled Ionic Diffusion.

Multiphoton photoreduction of photosensitive metallic precursors via direct laser writing (DLW) is a promising technique for the synthesis of metallic structures onto solid substrates at the sub-micron scale. DLW triggered by a two photon absorption process is done using a femtosecond NIR laser (λ = 780 nm), tetrachloroauric acid (HAuCl4) as a gold precursor, and isinglass as a natural hydrogel matrix. The presence of a polymeric, transparent matrix avoids unwanted diffusive processes acting as a network for the metallic nanoparticles. After the writing process, a bath in deionized water removes the gold precursor ions and eliminates the polymer matrix. Different aspects underlying the growth of the gold nanostructures (AuNSs) are here investigated to achieve full control on the size and density of the AuNSs. Writing parameters (laser power, exposure time, and scanning speed) are optimized to control the patterns and the AuNSs size. The influence of a second bath containing Au3+ to further control the size and density of the AuNSs is also investigated, observing that these AuNSs are composed of individual gold nanoparticles (AuNPs) that grow individually. A fine-tuning of these parameters leads to an important improvement of the created structures’ quality, with a fine control on size and density of AuNSs.

A compact photonic resonator absorption microscope for point of care digital resolution nucleic acid molecular diagnostics.

Rapid, sensitive, and selective detection of nucleic acid biomarkers for health diagnostic applications becomes feasible for point of care scenarios when the detection instrument is inexpensive, simple, and robust. Here, we report the design, implementation, and characterization of a point of care instrument for photonic resonator absorption microscopy (PRAM) that takes advantage of resonant optical coupling between plasmonic gold nanoparticle tags and a photonic crystal (PC) surface. Matching the PC resonant wavelength to the gold nanoparticle's surface plasmon wavelength generates localized and efficient quenching of the PC resonant reflection intensity, resulting in the ability to clearly detect and count individual gold nanoparticles when they are captured on the PC surface. Surface-captured nanoparticles are observed by illuminating the PC at normal incidence with polarized light from a low-intensity red LED, and recording of PC reflected intensity on an inexpensive CMOS image sensor. A contrast limited adaptive histogram equalization (CLAHE) image processing algorithm was applied to derive counts of captured nanoparticles. The instrument is utilized in the context of an activate capture + digital counting (AC + DC) assay for a specific miRNA sequence, using nucleic acid toehold probes applied to gold nano-urchin (AuNU) nanoparticles to achieve 160 aM detection limits in a 30 min. assay.

Вивчення нанорозмірних плівок золота методом скануючої тунельної мікроскопії

It was shown that despite the difference in the morphology of thin gold films obtained by different methods and on different substrates, the films mainly consist of spherical nanoparticles. The linear dimensions of individual surface objects were determined using the example of a gold film on mica. Analysis of the surface morphology showed that its structural formations are evenly distributed and have sizes from 250 nm to 500 nm. Upon receipt of gold nanofilms by magnetron sputtering on a glass substrate, the size of individual gold nanoparticles ranges from 20 nm to 80 nm. When ion spraying on a substrate of polished monocrystalline silicon, the size of individual gold nanoparticles ranges from 2 nm to 10 nm. The union of individual nanoparticles into large elongated nanoobjects up to 20-40 nm in size is observed. Thus, having the opportunity to compare data on the mode of vacuum deposition (substrate temperature, beam density, deposition time, etc.), as well as surface relief, you can develop technologies for obtaining a surface with a given set of properties, as well as develop new methods of gold deposition on different surfaces. The obtained results are very important for application in biology and medicine. They make it possible to create different types of sensors and diagnostic tests.

Water Decomposition Occurring During Laser Breakdown of Aqueous Solutions Containing Individual Gold, Zirconium, Molybdenum, Iron or Nickel Nanoparticles

Generation rates of hydrogen peroxide (H2O2), hydroxyl radicals (•OH), molecular hydrogen (H2), and molecular oxygen (O2) forming during the optical breakdown of aqueous colloidal solutions containing Au, Mo, Zr, Fe, and Ni nanoparticles have been studied. It is shown that the processes occurring during the dissociation of water molecules under the influence of laser breakdown plasma and leading to the formation of various chemical products depend on the material of the nanoparticles present in the colloid. It was found that the highest rates of generation of water decomposition products are observed in aqueous colloidal solutions of Fe and Ni nanoparticles. The use of Au nanoparticles leads to the lowest generation rate. In general, the materials from which the nanoparticles are made, depending on the efficiency of the formation of water decomposition products, are arranged as follows: Ni&amp;gt; Fe&amp;gt; Mo&amp;gt; Zr&amp;gt; Au.

Optical characterization and tunable antibacterial properties of gold nanoparticles with common proteins

The interaction of three proteins, viz. Bovine Serum Albumin (BSA), Human Serum Albumin (HSA) and Hen Egg White Lysozyme (HEWL) with gold nanoparticles (GNPs) is investigated using surface plasmon resonance (SPR) spectroscopy, fluorescence spectroscopy and circular dichroism (CD). Size and morphology of the samples was established using Transmission Electron Microscopy (TEM) and stability studies was established using zeta potential analysis. The stability of protein-GNP complex was found to be greater than that of individual protein as well as individual GNPs. Also HEWL-GNP complex was more stable compared to the other protein complexes. Absorbance of proteins increases with increase in gold nanoparticle concentration due to the extension of peptide strands of protein and decrease in hydrophobicity of gold nanoparticles. A ground state complex is also formed which is evident from the moderate shift observed in the absorbance peaks. Apparent association constant was also determined from the absorption spectra and was found to be maximum for HEWL and minimum for HSA. Gold nanoparticles were found to act as quenchers and reduced the protein fluorescence intensity. Binding constant and number of binding sites were found to be maximum for HEWL and minimum for HSA. The temperature dependent fluorescence studies were also performed to calculate the thermodynamic parameters and to determine the nature of interaction between the proteins and gold nanoparticles. The circular dichroism studies elucidate the reason behind the maximum binding for HEWL and minimum binding for HSA. TGA analysis determined the thermal stability of the samples. Fluorescence lifetime studies indicate static quenching of proteins. Antibacterial activity of protein-gold nanoparticles was studied against four pathogens, viz. Bacillus pumilus, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus. HEWL exhibits a tunable antimicrobial activity against Pseudomonas aeruginosa due to the maximum binding of HEWL with gold nanoparticles. The study proposes a novel method for adjusting the antibacterial activity of HEWL against Pseudomonas aeruginosa when the resistance of this pathogen is a major issue in the chemotherapy of many infectious diseases. Thus the combination therapy of protein-gold nanoparticles could prove to be a new approach in medical field in the near future.