Silver nanoparticles prepared by gamma irradiation across metal-organic framework templates

In this study, we demonstrate for the first time the successful fabrication of well-dispersed ultrafine silver nanoparticles inside metal-organic frameworks through a single step gamma irradiation at room temperature. HKUST-1 crystals are soaked in silver nitrate aqueous solution and irradiated with a Cobalt 60 source across a range of irradiation doses to synthesize highly uniformly distributed silver nano-particles. The average size of the silver nanoparticles across the Ag@HKUST-1 materials is found to vary between 1.4 and 3 nm for dose exposures between 1 and 200 kGy, respectively. The Ag@HKUST-1 hybrid crystals exhibit strong surface plasmon resonance and are highly durable and efficient catalytic materials for the reduction of 4-nitrophenol to 4-aminophenol (up to 14.46 × 10-3 s-1 for 1 kGy Ag@HKUST-1). The crystals can be easily recycled for at least five successive cycles of reaction with a conversion efficiency higher than 99.9%. The gamma irradiation is demonstrated to be an effective and environmental friendly process for the synthesis of nano-particles across confined metal-organic frameworks at room temperature with potential applications in environmental science.

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.

Sunlight-driven synthesis of anisotropic silver nanoparticles

Photoinduced shape conversion of silver nanoparticles was realized using sunlight. The silver seeds were transformed to silver nanoprisms under sunlight when the concentration of citrate was low (≤5.0×10-4M). Nevertheless, sunlight converted the obtained silver nanoprisms to silver nanodecahedrons when the concentration of citrate in reaction system was increased. It was found that the ultraviolet light from sunlight played a vital role in the shape conversion from nanoprism to nanodecahedron. Lighting power density did not influence the shape conversion except for reaction rate. Besides, the silver nanodecahedrons were synthesized in the mixed solution of AgNO3 and citrate in absence of silver seeds through irradiation by simulated sunlight. The mechanism on the sunlight induced synthesis of silver nanoparticles was discussed. Anisotropic silver nanoparticles including nanoprisms and nanodecahedrons were obtained through controlling the citrate concentration and irradiation time by sunlight from green light source.

Functional application of noble metal nanoparticles in situ synthesized on ramie fibers

Different functions were imparted to ramie fibers through treatment with noble metal nanoparticles including silver and gold nanoparticles. The in situ synthesis of silver and gold nanoparticles was achieved by heating in the presence of ramie fibers in the corresponding solutions of precursors. The unique optical property of synthesized noble metal nanoparticles, i.e., localized surface plasmon resonance, endowed ramie fibers with bright colors. Color strength (K/S) of fibers increased with heating temperature. Silver nanoparticles were obtained in alkaline solution, while acidic condition was conducive to gold nanoparticles. The optical properties of treated ramie fibers were investigated using UV-vis absorption spectroscopy. Scanning electron microscopy (SEM) was employed to observe the morphologies of silver and gold nanoparticles in situ synthesized on fibers. The ramie fibers treated with noble metal nanoparticles showed remarkable catalytic activity for reduction of 4-nitrophenol (4-NP) by sodium borohydride. Moreover, the silver nanoparticle treatment showed significant antibacterial property on ramie fibers.

Facet selectivity in gold binding peptides: exploiting interfacial water structure

Peptide sequences that can discriminate between gold facets under aqueous conditions offer a promising route to control the growth and organisation of biomimetically-synthesised gold nanoparticles. Knowledge of the interplay between sequence, conformations and interfacial properties is essential for predictable manipulation of these biointerfaces, but the structural connections between a given peptide sequence and its binding affinity remain unclear, impeding practical advances in the field. These structural insights, at atomic-scale resolution, are not easily accessed with experimental approaches, but can be delivered via molecular simulation. A current unmet challenge lies in forging links between predicted adsorption free energies derived from enhanced sampling simulations with the conformational ensemble of the peptide and the water structure at the surface. To meet this challenge, here we use an in situ combination of Replica Exchange with Solute Tempering with Metadynamics simulations to predict the adsorption free energy of a gold-binding peptide sequence, AuBP1, at the aqueous Au(111), Au(100)(1 × 1) and Au(100)(5 × 1) interfaces. We find adsorption to the Au(111) surface is stronger than to Au(100), irrespective of the reconstruction status of the latter. Our predicted free energies agree with experiment, and correlate with trends in interfacial water structuring. For gold, surface hydration is predicted as a chief determining factor in peptide-surface recognition. Our findings can be used to suggest how shaped seed-nanocrystals of Au, in partnership with AuBP1, could be used to control AuNP nanoparticle morphology.

Use of optical interferometry to measure gold nanoparticle adsorption on silica

Adsorption of metal nanoparticles is at the heart of many chemical and biosensor techniques, but there are few approaches that can provide quantitative characterisation of individual nanoparticle films fabricated at different times and/or under different conditions. Using synthesised gold nanoparticles (Au NPs) as a model, the nanoparticle films were investigated using an optical interferometry technique known as fringes of equal chromatic order (FECO), which was further systematically validated against both in situ quartz crystal microbalance (QCM) and ex situ atomic force microscopy (AFM) measurements. The results indicate that the FECO wavelengths has a quantifiable red shift with increasing particle densities, making it possible to quantify the degree of surface coverage via the analysis of the fringe shift at a fixed fringe order. Moreover, the calculated formula between the FECO shifts and the surface coverage allows quantitative analysis of the whole adsorption kinetics investigated. Particularly, the as-proposed FECO technique can successfully monitor the Au NP adsorption in situ, which could be a new versatile technology platform for “online” monitoring method, for example in biosensor applications using Au NP-tagged analytes.

Single-walled carbon nanotubes with DNA recognition

Two methods for attaching DNA to oxidized single-walled carbon nanotubes either in organic solvent or aqueous solution are described. The sites of DNA attachment to the nanotubes have been verified by binding gold nanoparticles modified with DNA of complementary sequence to the DNA-modified nanotubes, and imaging with TEM. The gold nanoparticles appear on the tips of the nanotubes, and at isolated positions (defects) on the sidewalls. The methods provide versatility for the modification of nanotubes with DNA for their directed assembly, or for their composites with gold nanoparticles, into nanoscale devices.

Cancer-cell microsurgery using nonlinear optical endomicroscopy

Near-infrared laser-based microsurgery is promising for noninvasive cancer treatment. To make it a safe technique, a therapeutic process should be controllable and energy efficient, which requires the cancer cells to be identifiable and observable. In this work, for the first time we use a miniaturized nonlinear optical endomicroscope to achieve microtreatment of cancer cells labeled with gold nanorods. Due to the high two-photon-excited photoluminescence of gold nanorods, HeLa cells inside a tissue phantom up to 250 μm deep can be imaged by the nonlinear optical endomicroscope. This facilitates microsurgery of selected cancer cells by inducing instant damage through the necrosis process, or by stopping cell proliferation through the apoptosis process. The results indicate that a combination of nonlinear endomicroscopy with gold nanoparticles is potentially viable for minimally invasive cancer treatment.

Azide photochemistry for facile modification of graphitic surfaces : preparation of DNA-coated carbon nanotubes for biosensing

A facile, two-step method for chemically attaching single-stranded DNA to graphitic surfaces, represented here by carbon nanotubes, is reported. In the first step, an azide-containing compound, N-5-azido-nitrobenzoyloxy succinimide (ANB-NOS), is used to form photo-adducts on the graphitic surfaces in a solid-state photochemical reaction, resulting in active ester groups being oriented for the subsequent reactions. In the second step, pre-synthesized DNA strands bearing a terminal amine group are coupled in an aqueous solution with the active esters on the photo-adducts. The versatility of the method is demonstrated by attaching pre-synthesized DNA to surfaces of carbon nanotubes in two platforms—as vertically-aligned multi-walled carbon nanotubes on a solid support and as tangled single-walled carbon nanotubes in mats. The reaction products at various stages were characterized by x-ray photoelectron spectroscopy. Two different assays were used to check that the DNA strands attached to the carbon nanotubes were able to bind their partner strands with complementary base sequences. The first assay, using partner DNA strands tethered to gold nanoparticles, enabled the sites of DNA attachment to the carbon nanotubes to be identified in TEM images. The second assay, using radioactively labelled partner DNA strands, quantified the density of functional DNA strands attached to the carbon nanotubes. The diversity of potential applications for these DNA-modified carbon-nanotube platforms is exemplified here by the successful use of a DNA-modified single-walled carbon-nanotube mat as an electrode for the specific detection of metal ions.

Electrical Stimulation of Myoblast Proliferation and Differentiation on Aligned Nanostructured Conductive Polymer Platforms

In this study, nanostructured conductive platforms synthesized from aligned multiwalled carbon nanotubes and polypyrrole are investigated as myo-regenerative scaffolds. Myotube formation follows a linear path on the platforms coinciding with extent of nanotopography. In addition, electrical stimulation enhances myo-nuclear number and differentiation. These studies demonstrate that conductive polymer platforms can be used to influence muscle cell behaviour through nanostructure and electrical stimulation.

Cellulose nanofibre textured SERS substrate

Poor reproducibility limits the wide uptake of low-cost surface enhanced Raman spectroscopy (SERS) substrates. This study reports a relatively low-cost and reproducible cellulose nanofibre (CNF) textured SERS substrate. Utilizing a layer of CNFs deposited onto glass slides, nanoscale roughness was achieved, which facilitated effective aggregation of gold nanoparticles (AuNPs) to form a novel CNF textured SERS substrate. This substrate meets the critical roughness requirements to control the distribution of AuNPs to provide 'hot spots' for SERS detection, offering significant signal enhancement. The reproducibility and accuracy of low-cost cellulosic SERS substrates were significantly improved on a model SERS molecule of 4-aminothiophenol.

Structure and properties of citrate overlayers adsorbed at the aqueous Au(111) interface.

One of the most common means of gold nanoparticle (AuNP) biofunctionalization involves the manipulation of precursor citrate-capped AuNPs via ligand displacement. However, the molecular-level structural characteristics of the citrate overlayer adsorbed at the aqueous Au interface at neutral pH remain largely unknown. Access to atomistic-scale details of these interfaces will contribute much needed insight into how AuNPs can be manipulated and exploited in aqueous solution. Here, the structures of such citrate overlayers adsorbed at the aqueous Au(111) interface at pH 7 are predicted and characterized using atomistic molecular dynamics simulations, for a range of citrate surface densities. We find that the overlayers are disordered in the surface density range considered, and that many of their key characteristics are invariant with surface density. In particular, we predict the overlayers to have 3-D, rather than 2-D, morphologies, with the anions closest to the gold surface being oriented with their carboxylate groups pointing away from the surface. We predict both striped and island morphologies for our overlayers, depending on the citrate surface density, and in all cases we find bare patches of the gold surface are present. Our simulations suggest that both citrate-gold adsorption and citrate-counterion pairing contribute to the stability of these citrate overlayer morphologies. We also calculate the free energy of adsorption at the aqueous Au(111) interface of a single citrate molecule, and compare this with the corresponding value for a single arginine molecule. These findings enable us to predict the conditions under which ligand displacement of surface-adsorbed citrate by arginine may take place. Our findings represent the first steps toward elucidating a more elaborate, detailed atomistic-scale model relating to the biofunctionalization of citrate-capped AuNPs.

Facile synthesis of silver submicrospheres and their applications

Uniform silver submicrospheres were synthesized under ambient conditions, through reduction of silver nitrate using ascorbic acid as a reducing agent and Tween 20 as a stabilizer. The silver submicroparticles exhibited strong catalytic activity for the reduction of 4-nitrophenol by sodium borohydride (NaBH4). Significantly, the aggregates of a few silver submicroparticles can be used as surface-enhanced Raman scattering (SERS) substrate to improve markedly the Raman signal of crystal violet. The morphologies of silver submicroparticles can be controlled by changing reaction conditions. The formation process of silver submicroparticles was monitored by time-resolved extinction spectroscopy. The influences of concentrations and molar ratios of reaction reagents on the formation of silver submicroparticles are discussed.

Attenuated total reflectance fourier transform infrared spectroscopy: an analytical technique to understand therapeutic responses at the molecular level

Rapid monitoring of the response to treatment in cancer patients is essential to predict the outcome of the therapeutic regimen early in the course of the treatment. The conventional methods are laborious, time-consuming, subjective and lack the ability to study different biomolecules and their interactions, simultaneously. Since; mechanisms of cancer and its response to therapy is dependent on molecular interactions and not on single biomolecules, an assay capable of studying molecular interactions as a whole, is preferred. Fourier Transform Infrared (FTIR) spectroscopy has become a popular technique in the field of cancer therapy with an ability to elucidate molecular interactions. The aim of this study, was to explore the utility of the FTIR technique along with multivariate analysis to understand whether the method has the resolution to identify the differences in the mechanism of therapeutic response. Towards achieving the aim, we utilized the mouse xenograft model of retinoblastoma and nanoparticle mediated targeted therapy. The results indicate that the mechanism underlying the response differed between the treated and untreated group which can be elucidated by unique spectral signatures generated by each group. The study establishes the efficiency of non-invasive, label-free and rapid FTIR method in assessing the interactions of nanoparticles with cellular macromolecules towards monitoring the response to cancer therapeutics.

Sunlight-induced coloration of silk

Silk fabrics were colored by gold nanoparticles (NPs) that were in situ synthesized through the induction of sunlight. Owing to the localized surface plasmon resonance (LSPR) of gold NPs, the treated silk fabrics presented vivid colors. The photo-induced synthesis of gold NPs was also realized on wet silk through adsorbing gold ions out of solution, which provides a water-saving coloration method for textiles. Besides, the patterning of silk was feasible using this simple sunlight-induced coloration approach. The key factors of coloration including gold ion concentration, pH value, and irradiation time were investigated. Moreover, it was demonstrated that either ultraviolet (UV) light or visible light could induce the generation of gold NPs on silk fabrics. The silk fabrics with gold NPs exhibited high light resistance including great UV-blocking property and excellent fastness to sunlight.