Project description:Gold nanoparticles possess unique photothermal properties and have gained considerable interest in biomedical research, particularly for photothermal therapy (PTT). This study focuses on evaluating the photothermal properties of gold nanorods (AuNRs) supported on glass substrates upon excitation with near-infrared (NIR) light. Two aspect ratios of AuNRs were electrostatically immobilized onto glass with controlled coverage. In situ X-ray diffraction (XRD) was performed to evaluate the photothermal behavior and morphological changes of the supported AuNRs during NIR laser irradiation. The XRD data sets were corroborated with scanning electron microscopy and Vis-NIR spectroscopy characterization. XRD revealed a linear temperature increase with laser power, aligning with theoretical predictions, and a slope dependent on the AuNR coverage, until the onset of morphology transformations around 120 °C. This study provides valuable insights into the photothermal properties of supported AuNRs, crucial for their application in PTT.
Project description:The growth of gold nanorods can be arrested at intermediate stages by treatment with Na(2)S, providing greater control over their optical resonances. Nanorods prepared by the seeded reduction of AuCl(4) in aqueous cetyltrimethylammonium bromide solutions in the presence of AgNO(3) typically exhibit a gradual blueshift in longitudinal plasmon resonance, over a period of hours to days. This "optical drift" can be greatly reduced by adding millimolar concentrations of Na(2)S to quench nanorod growth, with an optimized sulfur:metal ratio of 4:1. The sulfide-treated nanorods also experience a marked redshift as a function of Na(2)S concentration to produce stable plasmon resonances well into the near-infrared. Sulfide treatment permitted a time-resolved analysis of nanorod growth by transmission electron microscopy, revealing two distinct periods: an initial growth burst (t < 15 min) that generates dumbbell-shaped nanorods with flared ends and a slower phase (t > 30 min) favoring growth around the midsection, leading to nanorods with the more familiar oblate geometry. The blueshift in plasmon resonance that accompanies the dumbbell-to-oblate shape transition correlates more strongly with changes in the length-to-midsection (L/D(1)) ratio rather than the length-to-end width (L/D(2)) ratio, based on the empirical relationship introduced by El-Sayed and co-workers.
Project description:Cu has recently received great interest as a potential candidate for glucose sensing to overcome the problems with noble metals. In this work, reduced graphene oxide-encapsulated Cu nanoparticles (Cu@RGO) have been prepared via an electrostatic self-assembly method. This core/shell composites were found to be more stable than conventional Cu-decorated graphene composites and bare copper nanoparticles in an air atmosphere because the graphene shell can effectively protect the Cu nanoparticles from oxidation. In addition, the obtained Cu@RGO composites also showed an outstanding electrocatalytic activity toward glucose oxidation with a wide linear detection range of 1 μM to 2 mM, low detection limit of 0.34 μM (S/N = 3), and a sensitivity of 150 μA mM-1 cm-2. Moreover, Cu@RGO composites exhibited a satisfactory reproducibility, selectivity, and long effective performance. These excellent properties indicated that Cu@RGO nanoparticles have great potential application in glucose detection.
Project description:Plasmonic gold nanorods play important roles in nowadays state-of-the-art plasmonic sensing techniques. Most of the previous studies and applications focused on gold nanorods with relatively small aspect ratios, where the plasmon wavelengths are smaller than 900 nm. Gold nanorods with large aspect ratios are predicted to exhibit high refractive-index sensitivity (Langmir 2008, 24, 5233⁻5237), which therefore should be promising for the development of high-performance plasmonic chemical- and bio-sensors. In this study, we developed gold nanorods with aspect ratios over 7.9, which exhibit plasmon resonances around 1064 nm. The refractive index (RI) sensitivity of these nanorods have been evaluated by varying their dielectric environment, whereby a sensitivity as high as 473 nm/RIU (refractive index unit) can be obtained. Furthermore, we have demonstrated the large-aspect-ratio nanorods as efficient substrate for surface enhanced Raman spectroscopy (SERS), where an enhancement factor (EF) as high as 9.47 × 10⁸ was measured using 4-methylbenzenethiol (4-MBT) as probe molecule. Finally, a type of flexible SERS substrate is developed by conjugating the gold nanorods with the polystyrene (PS) polymer. The results obtained in our study can benefit the development of plasmonic sensing techniques utilized in the near-infrared spectral region.
Project description:We present a method for producing gold nanorods surrounded by a hollow polymeric shell of polystyrenesulfonate and show that the cavities of such particles can be filled with various organic dyes. The approach consists of covering gold nanorods with silica, followed by its slow hydrolysis in an aqueous medium in the presence of the polymer thin layer permeable for dye molecules. The proposed method enables the yolk-shell nanoparticles to be obtained and loaded with organic dyes without a need to use thermal treatment and/or chemical etching, which makes it suitable for use in the creation of spasers.
Project description:Gold nanorods (GNRs) are valued for their tunable surface plasmon resonance (SPR) and unique optical properties, but precise control over their size and shape remains challenging. Current synthesis techniques often yield polydisperse samples and require high concentrations of cytotoxic surfactants, limiting their biomedical applications. In this study, we introduce a novel electrochemical synthesis method that offers precise control of GNR characteristics by leveraging open circuit potential (OCP) data from colloidal synthesis. This approach involves the electrochemical growth of gold nano-seeds immobilized on fluorine-doped tin oxide (FTO) substrates, using physical vapor deposition (PVD) followed by thermal annealing to generate the Au seeds. This eliminates the need for seed solutions and significantly reduces surfactant usage. By optimizing electrochemical parameters, we produce uniform GNRs up to 700 nm in length, surpassing the typical 100 nm size from traditional methods. These larger GNRs exhibit superior optical and thermal properties, making them ideal for biomedical imaging, photothermal therapy, and applications requiring deeper tissue penetration. Their increased size also enhances stability, biosensing sensitivity, and circulation time, making them suitable for drug delivery and catalysis. This scalable method improves nanorod growth understanding while addressing cytotoxicity concerns.
Project description:Gold nanorods (AuNR) have been intensively used in nanomedicine for cancer diagnostics and therapy, due to their excellent plasmonic photothermal properties. Tuning the size and aspect ratio of AuNR tailors the localized surface plasmon resonance (LSPR) in the NIR spectrum at which biological tissues are transparent, thus enables specific and effective treatment. The AuNR extravasates into tumor interstitium through enhanced permeation and retention (EPR) effect. Efficient AuNR based cancer therapy requires efficient AuNR tumor delivery. However, the size of AuNR can dramatically affect its blood circulation and tumor accumulation. Here we proposed for the first time a systematic framework to investigate the size-dependent kinetics of AuNRs during EPR mediated tumor delivery. By using 64Cu-labeled AuNRs with positron emission tomography (PET) and kinetic modeling, the in vivo uptake and kinetics of 64Cu-AuNR during its blood circulation, tumor accumulation and elimination were studied both in vitro and in vivo. The results of different sized AuNRs were compared and the optimum size of AuNR was suggested for EPR mediated tumor delivery. Our study provides a better understanding of the in vivo behavior of AuNR, which can help future design of nanomaterials for cancer imaging and therapy.
Project description:Chirality plays a key role in modern science and technology. Here, we report a simple and effective sensing platform for visual chiral recognition of enantiomers. In this sensing platform, gold nanorods (AuNRs) prepared through a common synthesis route are used as colorimetric probes for visual recognition of glutamine (Gln) enantiomers. D-Gln could rapidly induce the aggregation of AuNRs, thereby resulting in appreciable blue-to-gray color change of AuNRs solution; however, L-Gln could not induce color change of AuNRs. This distinct color change can be easily distinguished by the naked eyes; as a result, a visual method of chiral recognition was suggested. The method was applied to determine the enantiometric excess of D-Gln through the whole range of -100% ~ 100%. The chiral assay can be performed with a simple UV-vis spectrometer or the naked eyes. Notably, the AuNRs do not need any chiral labeling or modification, and the chiral recognition is based on the inherent chirality of AuNRs. This chiral assay method is simple, sensitive, cheap and easy to operate. This study is the first example using AuNRs for direct visual recognition of enantiomers, and will open new opportunity to construct more chiral recognition methods for some important compounds.
Project description:The emergence of nanoscience and nanotechnology has revitalised research interest in using copper and its derived nanostructures to find exciting and novel applications. In this work, mono- and bimetallic gold and palladium nanoparticles supported on copper oxide nanorods (CuONRs) were prepared and their catalytic performance towards the reduction of H2O2 to form reactive oxygen radical species (ROS) was evaluated. The characterisation using microscopy and spectroscopic techniques confirms the successful synthesis of CuONRs, CuONRs@Au6NPs, CuONRs@Pd6NPs and CuONRs@Au3Pd3NPs. The efficient generation of ROS was confirmed using UV-vis spectroscopy and 1,3-diphenylisobenzofuran (DPBF) as a radical scavenger. The CuONRs possess excellent catalytic reduction activity for H2O2 by generating ROS. However, CuONRs also have lattice oxygens which do not participate in the catalytic reduction step. The lattice oxygens however allowed for the adsorption of gold and palladium nanoparticles (Au6NPs, Pd6NPs and Au3Pd3NPs) and thus enhanced catalytic reduction of H2O2 to produce ROS. The produced ROS was subsequently involved in the catalytic oxidation of a chromogenic substrate (TMB), resulting in blue coloured diimine (TMBDI) complex which was monitored using UV-vis and could also be observed using the naked eye. The catalyst dependence on pH, temperature, and H2O2 concentration towards efficient ROS generation was investigated. The gold and palladium-supported CuONRs nanocatalysts were evaluated for their potential applications in the fabrication of colorimetric biosensors to detect glucose oxidation by glucose oxidase (GOx). Glucose was used as a model analyte. The enzymatic reaction between GOx and β-d-glucose produces H2O2 as a by-product, which is then catalytically converted to ROS by the nanoparticles.
Project description:The immune system may respond to engineered nanomaterials (ENM) through inflammatory reactions. The NLRP3 inflammasome responds to a wide range of ENM, and its activation is associated with various inflammatory diseases. The objective of the study was to compare the effects of gold ENM of different shapes on NLRP3 inflammasome activation and related signalling pathways. Differentiated THP-1 cells (wildtype, ASC- or NLRP3-deficient), were exposed to PEGylated gold nanorods, nanostars, and nanospheres. Exposed cells were subjected to gene expression analysis. Nanorods, but not nanostars or nanospheres, showed NLRP3 inflammasome activation. ASC- or NLRP3-deficient cells did not show this effect. Gold nanorod-induced NLRP3 inflammasome activation was accompanied by downregulated sterol/cholesterol biosynthesis, oxidative phosphorylation, and purinergic receptor signalling. In conclusion, the shape and surface chemistry of gold nanoparticles determine NLRP3 inflammasome activation.