Facile Photochemical Syntheses of Conjoined Nanotwin Gold-Silver Particles within a Biologically-Benign Chitosan Polymer.
ABSTRACT: A simple photochemical method for making conjoined bi-metallic gold-silver (Au/Ag) nanotwins, a new breed of nanoparticles (NPs), is developed. To the best of our knowledge, the photochemical method resulted in distinct, conjoined, bimetallic nanotwins that are different from any well-established alloyed or core-shell nanostructures in the literature. The conjoined Au-Ag NPs possessed surface plasmon resonance (SPR) properties of both metals. The bimetallic nanostructures possessing distinctive optical properties of both metals were obtained using Au NPs as seeds in the first step, followed by the addition of a silver precursor as feed in the second step during a photochemical irradiation process. In the first step, small, isotropic or large, anisotropic Au NPs are generated by photoinduced reduction within a biocompatible chitosan (CS) polymer. In the second step, a silver precursor (AgNO₃) is added as the feed to the AuNPs seed, followed by irradiation of the solution in the ice-bath. The entire photochemical irradiation process resulting in the formation of bimetallic Au-AgNPs did not involve any other reducing agents or stabilizing agents other than the CS polymer stabilizer. The small, conjoined Au-Ag bi-metallic NPs exhibited SPR with peak maxima centering at ~400 nm and ~550 nm, whereas the large conjoined nanoparticles exhibited SPR with peak maxima centering at ~400 nm, 550 nm, and 680 nm, characteristic of both gold and silver surface plasmons in solution. The tunability in the SPR and size of the bimetallic NPs were obtained by varying the reaction time and other reaction parameters, resulting in average sizes between 30 and 100 nm. The SPR, size, distribution, and elemental composition of the bi-metallic NPs were characterized using UV-Vis absorption, electron microscopy, and energy dispersive X-ray spectroscopy (EDS) studies.
Project description:Plant extract of Pulicaria undulata (L.) was used as both reducing agent and stabilizing ligand for the rapid and green synthesis of gold (Au), silver (Ag), and gold-silver (Au-Ag) bimetallic (phase segregated/alloy) nanoparticles (NPs). These nanoparticles with different morphologies were prepared in two hours by stirring corresponding metal precursors in the aqueous solution of the plant extracts at ambient temperature. To infer the role of concentration of plant extract on the composition and morphology of NPs, we designed two different sets of experiments, namely (i) low concentration (LC) and (ii) high concentration (HC) of plant extract. In the case of using low concentration of the plant extract, irregular shaped Au, Ag, or phase segregated Au-Ag bimetallic NPs were obtained, whereas the use of higher concentrations of the plant extract resulted in the formation of spherical Au, Ag, and Au-Ag alloy NPs. The as-prepared Au, Ag, and Au-Ag bimetallic NPs showed morphology and composition dependent catalytic activity for the reduction of 4-nitrophenol (4-NPh) to 4-aminophenol (4-APh) in the presence of NaBH4. The bimetallic Au-Ag alloy NPs showed the highest catalytic activity compared to all other NPs.
Project description:In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible.
Project description:Advances in nanotechnology provide opportunities for the prevention and treatment of periodontal disease. While physicochemical properties of Ag containing nanoparticles (NPs) are known to influence the magnitude of their toxicity, it is thought that nanosilver can be made less toxic to eukaryotes by passivation of the NPs with a benign metal. Moreover, the addition of other noble metals to silver nanoparticles, in the alloy formulation, is known to alter the silver dissolution behavior. Thus, we synthesized glutathione capped Ag/Au alloy bimetallic nanoparticles (NPs) via the galvanic replacement reaction between maltose coated Ag NPs and chloroauric acid (HAuCl4) in 5% aqueous triblock F127 copolymer solution. We then compared the antibacterial activity of the Ag/Au NPs to pure Ag NPs on Porphyromonas gingivalis W83, a key pathogen in the development of periodontal disease. Only partially oxidized glutathione capped Ag and Ag/Au (Au:Ag?0.2) NPs inhibited the planktonic growth of P. gingivalis W83. This effect was enhanced in the presence of hydrogen peroxide, which simulates the oxidative stress environment in the periodontal pocket during chronic inflammation.
Project description:Precise control of alloying sites has long been a challenging pursuit, yet little has been achieved for the atomic-level manipulation of metallic nanomaterials. Here we describe utilization of a surface motif exchange (SME) reaction to selectively replace the surface motifs of parent [Ag<sub>44</sub>(SR)<sub>30</sub>]<sup>4-</sup> (SR?=?thiolate) nanoparticles (NPs), leading to bimetallic NPs with well-defined molecular formula and atomically-controlled alloying sites in protecting shell. A systematic mass (and tandem mass) spectrometry analysis suggests that the SME reaction is an atomically precise displacement of SR-Ag(I)-SR-protecting modules of Ag NPs by the incoming SR-Au(I)-SR modules, giving rise to a core-shell [Ag<sub>32</sub>@Au<sub>12</sub>(SR)<sub>30</sub>]<sup>4-</sup>. Theoretical calculation suggests that the thermodynamically less favorable core-shell Ag@Au nanostructure is kinetically stabilized by the intermediate Ag<sub>20</sub> shell, preventing inward diffusion of the surface Au atoms. The delicate SME reaction opens a door to precisely control the alloying sites in the protecting shell of bimetallic NPs with broad utility.
Project description:In this report, we demonstrate a rapid, simple, and green method for synthesizing silver-gold (Ag-Au) bimetallic nanoparticles (BNPs). We used a novel modification to the galvanic replacement reaction by suspending maltose coated silver nanoparticles (NPs) in ? 2% aqueous solution of EO100PO65EO100 (Pluronic F127) prior to HAuCl4 addition. The Pluronic F127 stabilizes the BNPs, imparts biocompatibility, and mitigates the toxicity issues associated with other surfactant stabilizers. BNPs with higher Au:Ag ratios and, subsequently, different morphologies were successfully synthesized by increasing the concentration of gold salt added to the Ag NP seeds. These BNPs have enhanced catalytic activities than typically reported for monometallic Au or Ag NPs (? 2-10 fold) of comparable sizes in the sodium borohydride reduction of 4-nitrophenol. The 4-nitrophenol reduction rates were highest for partially hollow BNP morphologies.
Project description:BACKGROUND: Nanoparticles (NPs) have gained significance in medical fields due to their high surface-area-to-volume ratio. In this study, we synthesized NPs from a medicinally important plant - Plumbago zeylanica. MATERIALS AND METHODS: Aqueous root extract of P. zeylanica (PZRE) was analyzed for the presence of flavonoids, sugars, and organic acids using high-performance thin-layer chromatography (HPTLC), gas chromatography-time of flight-mass spectrometry (GC-TOF-MS), and biochemical methods. The silver NPs (AgNPs), gold NPs (AuNPs), and bimetallic NPs (AgAuNPs) were synthesized from root extract and characterized using ultraviolet-visible spectra, X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The effects of these NPs on Acinetobacter baumannii, Staphylococcus aureus, and Escherichia coli biofilms were studied using quantitative biofilm inhibition and disruption assays, as well as using fluorescence, scanning electron microscopy, and atomic force microscopy. RESULTS: PZRE showed the presence of phenolics, such as plumbagin, and flavonoids, in addition to citric acid, sucrose, glucose, fructose, and starch, using HPTLC, GC-TOF-MS, and quantitative analysis. Bioreduction of silver nitrate (AgNO?) and chloroauric acid (HAuCl?) were confirmed at absorbances of 440 nm (AgNPs), 570 nm (AuNPs), and 540 nm (AgAuNPs), respectively. The maximum rate of synthesis at 50°C was achieved with 5 mM AgNO? within 4.5 hours for AgNPs; and with 0.7 mM HAuCl4 within 5 hours for AuNPs. The synthesis of AgAuNPs, which completed within 90 minutes with 0.7 mM AgNO? and HAuCl?, was found to be the fastest. Fourier-transform infrared spectroscopy confirmed bioreduction, while EDS and XRD patterns confirmed purity and the crystalline nature of the NPs, respectively. TEM micrographs and DLS showed about 60 nm monodispersed Ag nanospheres, 20-30 nm Au nanospheres adhering to form Au nanotriangles, and about 90 nm hexagonal blunt-ended AgAuNPs. These NPs also showed antimicrobial and antibiofilm activity against E. coli, A. baumannii, S. aureus, and a mixed culture of A. baumannii and S. aureus. AgNPs inhibited biofilm in the range of 96%-99% and AgAuNPs from 93% to 98% in single-culture biofilms. AuNPs also showed biofilm inhibition, with the highest of 98% in S. aureus. AgNPs also showed good biofilm disruption, with the highest of 88% in A. baumannii. CONCLUSION: This is the first report on rapid and efficient synthesis of AgNPs, AuNPs and AgAuNPs from P. zeylanica and their effect on quantitative inhibition and disruption of bacterial biofilms.
Project description:Nanosensors based on flexible polymers have emerged as powerful tools for next generation smart devices in the recent years. Here, we report a facile protocol to fabricate an immunosensor supported by a thermally resistant flexible polymer substrate (polyarylene ether nitrile, PEN). The immunosensor is a localized surface plasmon resonance (LSPR) optical sensor for in-vitro protein detection based on anti-body coated gold-silver bimetallic nanoparticles (Au-Ag NPs) immobilized on a PEN substrate. Plasmonic spectroscopy and morphological characterization show that the Au-Ag NPs essentially exhibit a more uniform size distribution and higher quality factors than those from single-component Au NPs. Furthermore, it should be noted that the robust PEN substrate in this nanosensor acts a flexible substrate to support Au-Ag NPs and immobilize the nanoparticles via quick thermal annealing at 290 °C. Thanks to these merits, a prostate-specific antigen (PSA) concentration as low as 1 ng/mL can be specifically discriminated via the prepared PEN/Au-Au NPs, which confirms that the protocol reported in this work can be readily adapted for the construction of various flexible immunosensors for different applications.
Project description:Metallic and dielectric nanoparticles (NPs) have synergistic electromagnetic properties but their positioning into morphologically defined hybrid arrays with novel optical properties still poses significant challenges. A template-guided self-assembly strategy is introduced for the positioning of metallic and dielectric NPs at pre-defined lattice sites. The chemical assembly approach facilitates the fabrication of clusters of metallic NPs with interparticle separations of only a few nanometers in a landscape of dielectric NPs positioned hundreds of nanometers apart. This approach is used to generate two-dimensional interdigitated arrays of 250 nm diameter TiO2 NPs and clusters of electromagnetically strongly coupled 60 nm Au NPs. The morphologydependent near- and far-field responses of the resulting multiscale optoplasmonic arrays are analyzed in detail. Elastic and inelastic scattering spectroscopy in combination with electromagnetic simulations reveal that optoplasmonic arrays sustain delocalized photonic-plasmonic modes that achieve a cascaded E-field enhancement in the gap junctions of the Au NP clusters and simultaneously increase the E-field intensity throughout the entire array.
Project description:Metallic nanoparticles (NPs) have received recently considerable interest of photonic and photovoltaic communities. In this work, we report the optoelectronic properties of gold NPs (Au-NPs) obtained by depositing very thin gold layers on glass substrates through thermal evaporation electron-beam assisted process. The effect of mass thickness of the layer was evaluated. The polycrystalline Au-NPs, with grain sizes of 14 and 19 nm tend to be elongated in one direction as the mass thickness increase. A 2 nm layer deposited at 250°C led to the formation of Au-NPs with 10-20 nm average size, obtained by SEM images, while for a 5 nm layer the wide size elongates from 25 to 150 nm with a mean at 75 nm. In the near infrared region was observed an absorption enhancement of amorphous silicon films deposited onto the Au-NPs layers with a corresponding increase in the PL peak for the same wavelength region.
Project description:Production and use of metallic nanoparticles have increased dramatically over the past few years and design of nanomaterials has been developed to minimize their toxic potencies. Traditional chemical methods of production are potentially harmful to the environment and greener methods for synthesis are being developed in order to address this. Thus far phytosynthesis have been found to yield nanomaterials of lesser toxicities, compared to materials synthesized by use of chemical methods. In this study nanoparticles were synthesized from an extract of leaves of golden rod (Solidago canadensis). Silver (Ag), gold (Au) and Ag-Au bimetallic nanoparticles (BNPs), synthesized by use of this "green" method, were evaluated for cytotoxic potency. Cytotoxicity of nanomaterials to H4IIE-luc (rat hepatoma) cells and HuTu-80 (human intestinal) cells were determined by use of the xCELLigence real time cell analyzer. Greatest concentrations (50 µg/mL) of Ag and Ag-Au bimetallic were toxic to both H4IIE-luc and HuTu-80 cells but Au nanoparticles were not toxic. BNPs exhibited the greatest toxic potency to these two types of cells and since AuNPs caused no toxicity; the Au functional portion of the bimetallic material could be assisting in uptake of particles across the cell membrane thereby increasing the toxicity.