Near-Field Plasmonics of an Individual Dielectric Nanoparticle above a Metallic Substrate

We simulate and discuss the local electric-field enhancement in a system of a dielectric nanoparticle placed very near to a metallic substrate. We use finite-element numerical simulations in order to understand the field-enhancement mechanism in this dielectric NP-on-mirror system. Under appropriate excitation conditions, the gap between the particle and the substrate becomes a "hot spot", i.e., a region of intense electromagnetic field. We also show how the optical properties of the dielectric NP placed on a metallic substrate affect the plasmonic field enhancement in the nanogap and characterize the confinement in the gap. Our study helps to understand and design systems with dielectric NPs on metallic substrates which can be equally as effective for SERS, fluorescence, and nonlinear phenomena as conventional all plasmonic structures.

Atomistic investigation on the structure-property relationship during thermal spray nanoparticle impact

During thermal spraying, hot particles impact on a colder substrate. This interaction of crystalline copper nanoparticles and copper substrate is modelled, using MD simulation. The quantitative results of the impacts at different velocities and temperatures are evaluated using a newly defined flattening aspect ratio. This ratio between the maximum diameter after the impact and the height of the splat increases with increasing Reynolds numbers until a critical value is reached. At higher Reynolds numbers the flattening aspect ratio decreases again, as the kinetic energy of the particle leads to increasing substrate temperature and, therefore, decreases the substrate resistance. Thus, the particle penetrates into the substrate and deforms less.

Plant extract: A promising biomatrix for ecofriendly, controlled synthesis of silver nanoparticles

Uses of plants extracts are found to be more advantageous over chemical, physical and microbial (bacterial, fungal, algal) methods for silver nanoparticles (AgNPs) synthesis. In phytonanosynthesis, biochemical diversity of plant extract, non-pathogenicity, low cost and flexibility in reaction parameters are accounted for high rate of AgNPs production with different shape, size and applications. At the same time, care has to be taken to select suitable phytofactory for AgNPs synthesis based on certain parameters such as easy availability, large-scale nanosynthesis potential and non-toxic nature of plant extract. This review focuses on synthesis of AgNPs with particular emphasis on biological synthesis using plant extracts. Some points have been given on selection of plant extract for AgNPs synthesis and case studies on AgNPs synthesis using different plant extracts. Reaction parameters contributing to higher yield of nanoparticles are presented here. Synthesis mechanisms and overview of present and future applications of plant-extract-synthesized AgNPs are also discussed here. Limitations associated with use of AgNPs are summarised in the present review.

Dissolving Microneedle Delivery of Nanoparticle Encapsulated Antigen Elicits Efficient Cross-Priming and Th1 Immune Responses by Murine Langerhans Cells

Dendritic cells (DCs) of the skin play an important role in skin-mediated immunity capable of promoting potent immune responses. We availed of polymeric dissolving microneedle (MN) arrays laden with nano-encapsulated antigen to specifically target skin DC networks. This modality of immunization represents an economic, efficient and potent means of antigen delivery directly to skin DCs, which are inefficiently targeted by more conventional immunization routes. Following MN immunization, Langerhans cells (LCs) constituted the major skin DC subset capable of cross-priming antigen-specific CD8(+) T cells ex-vivo. While all DC subsets were equally efficient in priming CD4(+) T cells, LCs were largely responsible for orchestrating the differentiation of CD4(+) IFN-γ and IL-17 producing effectors. Importantly, depletion of LCs prior to immunization had a profound effect on CD8(+) CTL responses in vivo, and vaccinated animals displayed reduced protective anti-tumour and viral immunity. Interestingly, this cross-priming bias was lost following MN immunization with soluble antigen, suggesting that processing and cross-presentation of nano-particulate antigen is favoured by LCs. Therefore, these studies highlight the importance of LCs in skin immunization strategies and that targeting of nano-particulate immunogens through dissolvable polymeric MNs potentially provides a promising technological platform for improved vaccination strategies.Journal of Investigative Dermatology accepted article preview online, 22 September 2014. doi:10.1038/jid.2014.415.

A New Mechanism for Hydroxyl Radical Production in Irradiated Nanoparticle Solutions

The absolute yield of hydroxyl radicals per unit of deposited X-ray energy is determined for the first time for irradiated aqueous solutions containing metal nanoparticles based on a “reference” protocol. Measurements are made as a function of dose rate and nanoparticle concentration. Possible mechanisms for hydroxyl radical production are considered in turn: energy deposition in the nanoparticles followed by its transport into the surrounding environment is unable to account for observed yield whereas energy deposition in the water followed by a catalytic-like reaction at the water-nanoparticle interface can account for the total yield and its dependence on dose rate and nanoparticle concentration. This finding is important because current models used to account for nanoparticle enhancement to radiobiological damage only consider the primary interaction with the nanoparticle, not with the surrounding media. Nothing about the new mechanism appears to be specific to gold, the main requirements being the formation of a structured water layer in the vicinity of the nanoparticle possibly through the interaction of its charge and the water dipoles. The massive hydroxyl radical production is relevant to a number of application fields, particularly nanomedicine since the hydroxyl radical is responsible for the majority of radiation-induced DNA damage.

The interaction of surface plasmon polaritons with a silver film edge

A prism coupling arrangement is used to excite surface plasmons at the surface of a thin silver aim and a photon scanning tunnelling microscope is used to detect the evanescent field above the silver surface. Excitation of the silver/ air mode of interest is performed at lambda(1) = 632 . 8 nm using a tightly focused beam, while the control of the tip is effected by exciting a counter-propagating surface plasmon field at a different wavelength. lambda(2) = 543 . 5 nm, using an unfocused beam covering a macroscopic area. Propagation of the red surface plasmon is evidenced by an exponential tail extending away from the launch site, but this feature is abruptly truncated if the surface plasmon encounters the edge of the silver film - there is no specularly reflected 'beam'. Importantly, the radiative decay of the surface mode at the film edge is observable only at larger tip-sample separations, emphasizing the importance of accessing the mesoscopic regime.

Gold nanoparticle cellular uptake, toxicity and radiosensitisation in hypoxic conditions

Background and purpose: Gold nanoparticles (GNPs) are novel agents that have been shown to cause radiosensitisation in vitro and in vivo. Tumour hypoxia is associated with radiation resistance and reduced survival in cancer patients. The interaction of GNPs with cells in hypoxia is explored.

Materials and methods: GNP uptake, localization, toxicity and radiosensitisation were assessed in vitro under oxic and hypoxic conditions.

Results: GNP cellular uptake was significantly lower under hypoxic than oxic conditions. A significant reduction in cell proliferation in hypoxic MDA-MB-231 breast cancer cells exposed to GNPs was observed. In these cells significant radiosensitisation occurred in normoxia and moderate hypoxia. However, in near anoxia no significant sensitisation occurred.

Conclusions: GNP uptake occurred in hypoxic conditions, causing radiosensitisation in moderate, but not extreme hypoxia in a breast cancer cell line. These findings may be important for the development of GNPs for cancer therapy.

Tunable gold nanoparticles shape and size in reductive and structuring media containing protic ionic liquids

Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV-visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.

Use of water in aiding olefin/paraffin (liquid + liquid) extraction via complexation with a silver bis(trifluoromethylsulfonyl)imide salt

This paper describes the extraction of C₅–C₈ linear α-olefins from olefin/paraffin mixtures of the same carbon number via a reversible complexation with a silver salt (silver bis(trifluoromethylsulfonyl)imide, Ag[Tf₂N]) to form room temperature ionic liquids [Ag(olefin)_x][Tf₂N]. From the experimental (liquid + liquid) equilibrium data for the olefin/paraffin mixtures and Ag[Tf₂N], 1-pentene showed the best separation performance while C₇ and C₈ olefins could only be separated from the corresponding mixtures on addition of water which also improves the selectivity at lower carbon numbers like the C₅ and C₆, for example. Using infrared and Raman spectroscopy of the complex and Ag[Tf₂N] saturated by olefin, the mechanism of the extraction was found to be based on both chemical complexation and the physical solubility of the olefin in the ionic liquid ([Ag(olefin)_x][Tf₂N]). These experiments further support the use of such extraction techniques for the separation of olefins from paraffins.

Preaggregated Ag Nanoparticles in Dry Swellable Gel Films for Off-the-Shelf Surface-Enhanced Raman Spectroscopy

Large, thin (50 mu m) dry polymer sheets containing numerous surface-enhanced Raman spectroscopy (SERS) active Ag nanopartide aggregates have been prepared by drying aqueous mixtures of hydroxyethylcelloulose (HEC) and preaggregated Ag colloid in 10 x 10 cm molds. In these dry films, the particle aggregates are protected from the environment during storage and are easy to handle; for example, they can be cut to size with scissors. When in use, the highly swellable HEC polymer allowed the films to rapidly absorb aqueous analyte solutions while simultaneously releasing the Ag nanoparticle aggregates to interact with the analyte and generate large SERS signals. Either the films could be immersed in the analyte solution or 5 mu L droplets were applied to the surface; in the latter method, the local swelling caused the active area to dome upward, but the swollen film remained physically robust and could be handled as required. Importantly, encapsulation and release did not significantly compromise the SERS performance of the colloid; the signals given by the swollen films were similar to the very high signals obtained from the parent citrate-reduced colloid and were an order of magnitude larger than a commercially available nanoparticle substrate. These "Poly-SERS" films retained 70% of their SERS activity after being stored for 1 year in air. The films were sufficiently homogeneous to give a standard deviation of 3.2% in the absolute signal levels obtained from a test analyte, primarily due to the films' ability to suppress "coffee ring" drying marks, which meant that quantitative analysis without an internal standard was possible. The majority of the work used aqueous thiophenol as the test analyte; however, preliminary studies showed that the Poly-SERS films could also be used with nonaqueous solvents and for a range of other analytes including theophylline, a therapeutic drug, at a concentration as low as 1.0 x 10(-5) mol dm(-3) (1.8 mg/dm(3)), well below the sensitivity required for theophylline monitoring where the target range is 10-20 mg/dm(3).

The role of mitochondrial function in gold nanoparticle mediated radiosensitisation

Gold nanoparticles (GNPs), have been demonstrated as effective preclinical radiosensitising agents in a range of cell models and radiation sources. These studies have also highlighted difficulty in predicted cellular radiobiological responses mediated by GNPs, based on physical assumptions alone, and therefore suggest a significant underlying biological component of response. This study aimed to determine the role of mitochondrial function in GNP radiosensitisation. Using assays of DNA damage and mitochondrial function through levels of oxidation and loss of membrane potential, we demonstrate a potential role of mitochondria as a central biological mechanism of GNP mediated radiosensitisation.

Gold nanoparticle surface functionalization: a necessary requirement in the development of novel nanotherapeutics

With several gold nanoparticle-based therapies currently undergoing clinical trials, these treatments may soon be in the clinic as novel anticancer agents. Gold nanoparticles are the subject of a wide ranging international research effort with preclinical studies underway for multiple applications including photoablation, diagnostic imaging, radiosensitization and multifunctional drug-delivery vehicles. These applications require an increasingly complex level of surface modification in order to achieve efficacy and limit off-target toxicity. This review will discuss the main obstacles in relation to surface functionalization and the chemical approaches commonly utilized. Finally, we review a range of recent preclinical studies that aim to advance gold nanoparticle treatments toward the clinic.

Radiosensitising Nanoparticles as Novel Cancer Therapeutics — Pipe Dream or Realistic Prospect?

The field of high atomic number nanoparticle radiosensitising agents is reviewed. After a brief discussion of the new mode of physicochemical action implied by irradiation of high atomic number nanoparticles embedded in biological systems, a series of exemplars are discussed. Silver-, gadolinium- and gold-based nanoparticles are discussed in order of increasing atomic number with functionalisation strategies being outlined. In vitro and in vivo evidence for radio-enhancement and the mechanisms attributed to the increased biological effect are discussed.

Enhancing Liquid-Phase Olefin-Paraffin Separations Using Novel Silver-Based Ionic Liquids

This paper describes the extraction of C5-C8 linear α-olefins from olefin/paraffin mixtures of the same carbon number using silver(I)/N,N-dimethylbenzamide bis(trifluoromethylsulfonyl)imide ([Ag(DMBA)₂][Tf₂N]) or silver(I)/propylamine bis(trifluoromethylsulfonyl)imide ([Ag(PrNH₂)₂][Tf₂N]) as the extracting agent. The separation performance of the system increased with increasing chain length. [Ag(DMBA)₂][Tf₂N] appeared to outperform [Ag(PrNH₂)₂][Tf₂N] in terms of both selectivity and distribution coefficient. The [Ag(DMBA)₂][Tf₂N] system was successfully modeled using the universal quasi-chemical activity coefficient (UNIQUAC) model. These results support the potential future development of amine/amide-based ligands for producing soluble silver complexes useful for the separation of olefins from paraffins.

HOLOGRAPHIC IMAGES OF IODINE ATOMS ON A SILVER SURFACE FROM ELECTRON-EMISSION PATTERNS

BARTON 1 has suggested that photoelectron interference patterns may be used directly as holograms to obtain atomic-resolution images of surface structures. Bulk structures have been obtained previously by this means from experimental patterns of high-energy Kikuchi(quasi-elastically scattered) and Auger electrons 2,3. Here we test the feasibility of this technique for determination of surface structures using Auger intensity patterns obtained 4,5 from iodine chemisorbed on a pseudomorphic silver monolayer on Pt{111}. By direct numerical holographic inversion, we obtain three-dimensional images which show that iodine adatoms are located in hollows of 3-fold symmetry on the surface. The images yield the site symmetry with good atomic resolution in the surface plane, but suffer from poor resolution along the Ag-I axis. We anticipate that data with better angular resolution obtained at low temperatures would improve the spatial resolution of such images.