Synthesis and characterization of surface-enhanced Raman-scattered gold nanoparticles

In this paper, we report a simple, rapid, and robust method to synthesize surface-enhanced Raman-scattered gold nanoparticles (GNPs) based on green chemistry. Vitis vinifera L. extract was used to synthesize noncytotoxic Raman-active GNPs. These GNPs were characterized by ultraviolet-visible spectroscopy, dynamic light-scattering, Fourier-transform infrared (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The characteristic surface plasmon-resonance band at ~528 nm is indicative of spherical particles, and this was confirmed by TEM. The N–H and C–O stretches in FTIR spectroscopy indicated the presence of protein molecules. The predominant XRD plane at (111) and (200) indicated the crystalline nature and purity of GNPs. GNPs were stable in the buffers used for biological studies, and exhibited no cytotoxicity in noncancerous MIO-M1 (Müller glial) and MDA-MB-453 (breast cancer) cell lines. The GNPs exhibited Raman spectral peaks at 570, 788, and 1,102 cm-1. These new GNPs have potential applications in cancer diagnosis, therapy, and ultrasensitive biomarker detection.

Microcontact deprinting: A technique to pattern gold nanoparticles

A simple and general patterning technique for inorganic nanoparticles (NPs, e.g., gold NPs) is demonstrated, consisting of the selective lift-off of metal precursor loaded block copolymer micelles. The procedure works as follows: first, a topographically micropatterned polystyrene (PS) stamp is placed in contact with a substrate covered with hexagonally arranged micelles. Then the assembly is heated above the glass transition temperature (Tg) of PS, and finally, the PS stamp is peeled off, removing from the substrate the micelles that were in contact with the protrusions of the stamp. As a result, patterns of micelles either exactly identical to the original or with much smaller features down to submicrometer were obtained. In a subsequent step, the organic material can be removed and the metal precursor reduced by plasma treatment, resulting in patterns of NPs. This technique, denoted as “μ-contact deprinting”, provides a fast and inexpensive way to obtain hierarchical patterns of NPs on a wide range of substrates. It is demonstrated that it can even be applied on curved surfaces because of the softness of the PS stamp above its T

Hybrid hierarchical patterns of gold nanoparticles and poly(ethylene glycol) microstructures

Hybrid surface micro-patterns composed of topographic structures of polyethylene glycol (PEG)-hydrogels and hierarchical lines of gold nanoparticles (Au NPs) were fabricated on silicon wafers. Micro-sized lines of Au NPs were first obtained on the surface of a silicon wafer via “micro-contact deprinting”, a method recently developed by our group. Topographic micro-patterns of PEG, of both low and high aspect ratio (AR up to 6), were then aligned on the pre-patterned surface via a procedure adapted from the soft lithographic method MIMIC (Micro-Molding in Capillaries), which is denoted as “adhesive embossing”. The result is a complex surface pattern consisting of alternating flat Au NP lines and thick PEG bars. Such patterns provide novel model surfaces for elucidating the interplay between (bio)chemical and physical cues on cell behavior.

The French consul's wife : memoirs of Céleste de Chabrillan in gold-rush Australia

A former Parisian courtesan, bare-back-rider, and polka dancer, Céleste de Chabrillan scandalized Melbourne when she arrived in 1854. Her vivid account of years spent in diplomatic circles and on the goldfields reveals her great energy and will.

Fabrication of boron nitride nanotube-gold nanoparticle hybrids using pulsed plasma in liquid

Plasma, generated in liquid at atmospheric pressure by a nanosecond pulsed voltage, was used to fabricate hybrid structures from boron nitride nanotubes and gold nanoparticles in deionized water. The pH was greatly reduced, conductivity was significantly increased, and concentrations of reactive oxygen and nitrogen species in the water were increased by the plasma treatment. The treatment reduced the length of the nanotubes, giving more individual cuplike structures, and introduced functional groups onto the surface. Gold nanoparticles were successively assembled onto the functionalized surfaces. The reactive species from the liquid plasma along with the nanosecond pulsed electric field seem to play a role in the shortening and functionalization of the nanotubes and the assembly of gold nanoparticles. The potential for targeted drug delivery was tested in a preliminary investigation using doxorubicin-loaded plasma-treated nanotubes which were effective at killing ∼99% of prostate cancer cells.

Structure of the electrical double layer at aqueous gold and silver interfaces for saline solutions

We report the structure of the electrical double layer, determined from molecular dynamics simulations, for a range of saline solutions (NaCl, KCl, MgCl2 and CaCl2) at both 0.16 and 0.60molkg(-1) on different facets of the gold and silver aqueous interfaces. We consider the Au/Ag(111), native Au/Ag(100) and reconstructed Au(100)(5×1) facets. For a given combination of metallic surface and facet, some variations in density profile are apparent across the different cations in solution, with the corresponding chloride counterion profiles remaining broadly invariant. All density profiles at the higher concentration are predicted to be very similar to their low-concentration counterparts. We find that each electrolyte responds differently to the different metallic surface and facets, particularly those of the divalent metal ions. Our findings reveal marked differences in density profiles between facets for a given metallic interface for both Mg(2+) and Ca(2+), with Na(+) and K(+) showing much less distinction. Mg(2+) was the only ion for which we find evidence of materials-dependent differences in interfacial solution structuring between the Ag and Au.

Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

Structure of arginine overlayers at the aqueous gold interface: implications for nanoparticle assembly.

Adsorption of small biomolecules onto the surface of nanoparticles offers a novel route to generation of nanoparticle assemblies with predictable architectures. Previously, ligand-exchange experiments on citrate-capped gold nanoparticles with the amino acid arginine were reported to support linear nanoparticle assemblies. Here, we use a combination of atomistic modeling with experimental characterization to explore aspects of the assembly hypothesis for these systems. Using molecular simulation, we probe the structural and energetic characteristics of arginine overlayers on the Au(111) surface under aqueous conditions at both low- and high-coverage regimes. In the low-density regime, the arginines lie flat on the surface. At constant composition, these overlayers are found to be lower in energy than the densely packed films, although the latter case appears kinetically stable when arginine is adsorbed via the zwitterion group, exposing the charged guanidinium group to the solvent. Our findings suggest that zwitterion-zwitterion hydrogen bonding at the gold surface and minimization of the electrostatic repulsion between adjacent guanidinium groups play key roles in determining arginine overlayer stability at the aqueous gold interface. Ligand-exchange experiments of citrate-capped gold nanoparticles with arginine derivatives agmatine and N-methyl-l-arginine reveal that modification at the guanidinium group significantly diminishes the propensity for linear assembly of the nanoparticles.

In-situ synthesis of gold nanoparticles for multifunctionalization of silk fabrics

A simple in-situ synthesis route for gold nanoparticles (NPs) was developed to realize multifunctions for silk fabrics. The gold NPs were prepared in a heated solution containing white silk fabric samples. The silk fabrics were colored red and brown by the gold NPs because of their localized surface plasmon resonance (LSPR) property. Gold nanospheres on silk were obtained at a low gold content, and gold nanoplates were synthesized as the gold content increased. The silk fabrics treated with gold NPs showed good light fastness. Moreover, the gold NPs endowed silk fabrics with strong antibacterial activity, excellent UV protection property and enhanced thermal conductivity. © 2013 Elsevier Ltd. All rights reserved.

New gold nanostructures for sensor applications: a review

Gold based structures such as nanoparticles (NPs) and nanowires (NWs) have widely been used as building blocks for sensing devices in chemistry and biochemistry fields because of their unusual optical, electrical and mechanical properties. This article gives a detailed review of the new properties and fabrication methods for gold nanostructures, especially gold nanowires (GNWs), and recent developments for their use in optical and electrochemical sensing tools, such as surface enhanced Raman spectroscopy (SERS). © 2014 by the authors; licensee MDPI, Basel, Switzerland.

Boron nitride nanosheets as improved and reusable substrates for gold nanoparticles enabled surface enhanced Raman spectroscopy.

Atomically thin boron nitride (BN) nanosheets have been found to be excellent substrates for noble metal particles enabled surface enhanced Raman spectroscopy (SERS), thanks to their good adsorption of aromatic molecules, high thermal stability and weak Raman scattering. Faceted gold (Au) nanoparticles have been synthesized on BN nanosheets using a simple but controllable and reproducible sputtering and annealing method. The size and density of the Au particles can be controlled by sputtering time, current and annealing temperature etc. Under the same sputtering and annealing conditions, the Au particles on BN of different thicknesses show various sizes because the surface diffusion coefficients of Au depend on the thickness of BN. Intriguingly, decorated with similar morphology and distribution of Au particles, BN nanosheets exhibit better Raman enhancements than silicon substrates as well as bulk BN crystals. Additionally, BN nanosheets show no noticeable SERS signal and hence cause no interference to the Raman signal of the analyte. The Au/BN substrates can be reused by heating in air to remove the adsorbed analyte without loss of SERS enhancement.

The influence of graphene on the electrical communication through organic layers on graphite and gold electrodes

The influence of graphene on the electrical communication through organic layers fabricated on graphite and gold electrodes is investigated. These layers were prepared by in situ reductive adsorption of 4-aminobenzoic acid in the presence of NaNO2 and HCl to have surface bound carboxylic acid functionalities, followed by covalent attachment of 1-aminopyrene via an amide coupling reaction to have surface bound pyrene groups for graphene immobilization via noncovalent π-π stacking interaction. The coverage of the layers created via reductive adsorption on graphite electrodes was found to be much higher than that on gold electrodes. It was revealed that graphene significantly enhances the electrical communication through the layers on graphite electrodes but on gold electrodes the enhancement effect through the layers was only minor. However, when gold electrodes were modified with a self-assembled monolayer (SAM) of propanethiol the subsequent immobilization of graphene resulted in a significant enhancement of the electrical communication. It is also found that immobilization of graphene could affect the electron transfer between the redox probe, pyrene and the underlying electrodes. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to characterize the graphene sheets. Cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and X-ray photoelectron spectroscopy (XPS) were also used to characterize the stepwise modified electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold and silver mining in the 16th and 17th centuries, land titles and agricultural productivity

Although agricultural productivity is critical for economic development very little is known about the causes of the large dispersion in agricultural productivity across the world. Microeconomic studies increasingly stress the lack of land rights in many poor countries as an important source of low productivity. This paper examines the role played by land titles in explaining differences in agricultural productivity for 93 countries. Using the per capita accumulated value of gold and silver production in the 16th and 17th centuries as instruments for land rights it is shown that enforcement of land titles is a significant source of agricultural productivity inequality across the world.

In situ synthesis of natural rubber latex-supported gold nanoparticles for flexible SERS substrates

Natural rubber latex (NRL) from Hevea brasiliensis was used as a matrix to synthesize gold nanoparticles (AuNPs), leading to an organic-inorganic hybrid latex of NRL-supported AuNPs (AuNPs@NRL). The in situ and environmentally friendly preparation of AuNPs in an NRL matrix was developed by thermal treatment without using any other reducing agents or stabilizers because natural rubber particles and non-rubber components present in serum can serve as supporters for the synthesized AuNPs. As a result, the nanosized and well-dispersed AuNPs not only are decorated on the surface of natural rubber particles, but also can be found in the serum of NRL. The size of the AuNPs presented in NRL matrix can be controlled by adjusting the concentration of NRL. Furthermore, the flexible surface-enhanced Raman scattering (SERS) substrates made from the AuNPs@NRL through vacuum filtration presented good enhancement of the Raman probe molecule of 4-mercaptopyridine and outstanding SERS reproducibility. The capability of synthesizing the bio-supported nanohybrid latex provides a novel green and simple approach for the fabrication of flexible and effective SERS substrates.