Preparation of liposomes containing small gold nanoparticles using electrostatic interactions.

The development of liposome-nanoparticle colloid systems offers a versatile approach towards the manufacture of multifunctional therapeutic platforms. A strategy to encapsulate small metallic nanoparticles (<4nm) within multilamellar vesicles, effected by exploiting electrostatic interactions was investigated. Two liposome-gold nanoparticle (lipo-GNP) systems were prepared by the reverse-phase evaporation method employing cationic or anionic surface functionalised particles in combination with oppositely charged lipid compositions with subsequent post-formulation PEGylation. Structural characterisation using electron microscopy and elemental analysis revealed a regular distribution of GNPs between adjacent lipid bilayers of intact liposomes. Nanoparticle encapsulation efficacy of the two lipo-GNP systems was revealed to be significantly different (p=0.03), evaluated by comparing the ratio of measured lipid to gold concentration (loading content) determined by a colorimetric assay and atomic emission spectroscopy, respectively. It was concluded that the developed synthetic strategy is an effective approach for the preparation of liposome-nanoparticle colloids with potential to control the relative concentration of encapsulated particles to lipids by providing favourable electrostatic interactions.

Carbon-cryogel hierarchical composites as effective and scalable filters for removal of trace organic pollutants from water.

Effective technologies are required to remove organic micropollutants from large fluid volumes to overcome present and future challenges in water and effluent treatment. A novel hierarchical composite filter material for rapid and effective removal of polar organic contaminants from water was developed. The composite is fabricated from phenolic resin-derived carbon microbeads with controllable porous structure and specific surface area embedded in a monolithic, flow permeable, poly(vinyl alcohol) cryogel. The bead-embedded monolithic composite filter retains the bulk of the high adsorptive capacity of the carbon microbeads while improving pore diffusion rates of organic pollutants. Water spiked with organic contaminants, both at environmentally relevant concentrations and at high levels of contamination, was used to determine the purification limits of the filter. Flow through tests using water spiked with the pesticides atrazine (32 mg/L) and malathion (16 mg/L) indicated maximum adsorptive capacities of 641 and 591 mg pollutant/g carbon, respectively. Over 400 bed volumes of water contaminated with 32 mg atrazine/L, and over 27,400 bed volumes of water contaminated with 2 µg atrazine/L, were treated before pesticide guideline values of 0.1 µg/L were exceeded. High adsorptive capacity was maintained when using water with high total organic carbon (TOC) levels and high salinity. The toxicity of water filtrates was tested in vitro with human epithelial cells with no evidence of cytotoxicity after initial washing.

Repairing Peripheral Nerves: Is there a Role for Carbon Nanotubes?

Peripheral nerve injury continues to be a major global health problem that can result in debilitating neurological deficits and neuropathic pain. Current state-of-the-art treatment involves reforming the damaged nerve pathway using a nerve autograft. Engineered nerve repair conduits can provide an alternative to the nerve autograft avoiding the inevitable tissue damage caused at the graft donor site. Commercially available nerve repair conduits are currently only considered suitable for repairing small nerve lesions; the design and performance of engineered conduits requires significant improvements to enable their use for repairing larger nerve defects. Carbon nanotubes (CNTs) are an emerging novel material for biomedical applications currently being developed for a range of therapeutic technologies including scaffolds for engineering and interfacing with neurological tissues. CNTs possess a unique set of physicochemical properties that could be useful within nerve repair conduits. This progress report aims to evaluate and consolidate the current literature pertinent to CNTs as a biomaterial for supporting peripheral nerve regeneration. The report is presented in the context of the state-of-the-art in nerve repair conduit design; outlining how CNTs may enhance the performance of next generation peripheral nerve repair conduits.

Bacteriophage-nanocomposites: an easy and reproducible method for the construction, handling, storage and transport of conjugates for deployment of bacteriophages active against Pseudomonas aeruginosa.

The purpose of this work was proof of concept to develop a novel, cost effective protocol for the binding of bacteriophages to a surface without loss of function, after storage in various media. The technology platform involved covalently bonding bacteriophage 13 (a Pseudomonas aeruginosa bacteriophage) to two magnetised multiwalled carbon nanotube scaffolds using a series of buffers; bacteriophage-nanotube (B-N) conjugates were efficacious after storage at 20 °C for six weeks. B-N conjugates were added to human cell culture in vitro for 9 days without causing necrosis and apoptosis. B-N conjugates were frozen (-20 °C) in cell culture media for several weeks, after which recovery from the human cell culture medium was possible using a simple magnetic separation technique. The retention of viral infective potential was demonstrated by subsequent spread plating onto lawns of susceptible P. aeruginosa. Analysis of the human cell culture medium revealed the production of interleukins by the human fibroblasts upon exposure to the bacteriophage. One day after exposure, IL-8 levels transitorily increased between 60 and 100 pg/mL, but this level was not found on any subsequent days, suggesting an initial but not long lasting response. This paper outlines the development of a method to deliver antimicrobial activity to a surface that is small enough to be combined with other materials. To our knowledge at time of publication, this is the first report of magnetically coupled bacteriophages specific to human pathogens which can be recovered from test systems, and could represent a novel means to conditionally deploy antibacterial agents into living eukaryotic systems without the risks of some antibiotic therapies.

Chemical control of graphene architecture: tailoring shape and properties.

Single layer graphene and graphene oxide feature useful and occasionally unique properties by virtue of their two-dimensional structure. Given that there is a strong correlation between graphene architecture and its conductive, mechanical, chemical, and sorptive properties, which lead to useful technologies, the ability to systematically deform graphene into three-dimensional structures, therefore, provides a controllable, scalable route toward tailoring such properties in the final system. However, the advent of chemical methods to control graphene architecture is still coming to fruition and requires focused attention. The flexibility of the graphene system and the direct and indirect methods available to induce morphology changes of graphene sheets are first discussed in this review. Focus is then given toward chemical reactions that influence the shape of presynthesized graphene and graphene oxide sheets, from which a toolbox can be extrapolated and used in controlling the spatial arrangement of graphene sheets within composite materials and ultimately tailoring graphene-based device performance. Finally, the properties of three-dimensionally controlled graphene-based systems are highlighted for their use as batteries, strengthening additives, gas or liquid sorbents, chemical reactor platforms, and supercapacitors.

Phenolic carbon tailored for the removal of polar organic contaminants from water: a solution to the metaldehyde problem?

Current water treatment technologies are inefficient at treating water contaminated with metaldehyde, an 8-member cyclic tetramer of acetaldehyde widely used as a molluscicide in large-scale agriculture and in gardens, and which has been frequently observed to breach European regulatory limits in the UK due to its high solubility and frequent use. Here, we examine the controls on metaldehyde adsorption onto activated phenolic carbon, namely the influence of activation degree, pore size distribution, particle size, point of zero charge and surface functionalisation, by synthesising "tailored" carbons from phenolic resin. Metaldehyde adsorption has been found to be independent of specific surface area (SBET), which is highly unusual for an adsorption process, and is favoured in carbons with (a) high microporosity with narrow pore size distribution, (b) presence of mesopores which allow efficient diffusive transport, and (c) an absence of negatively charged functional groups. The maximum adsorption capacity of the phenolic resin-derived carbons, tested at an elevated (i.e. exceeding environmental levels) water concentration of 64 mg metaldehyde/L, was 76 mg metaldehyde/g carbon compared with 13 mg metaldehyde/g carbon in industrial granular activated carbon (GAC). The phenolic resin-derived carbons and GAC showed similar adsorption kinetics with maximum metaldehyde uptake occurring within 30 min under batch adsorption conditions, although adsorption isotherms indicate much stronger adsorption of metaldehyde on the phenolic resin-derived carbons. Adsorption efficiency for metaldehyde was maintained even in the presence of high background concentrations of organic matter and inorganic salts, indicating the potential utility of these "designer" carbons in waste and/or drinking water treatment.

Synthesis and application of hydride silica composites for rapid and facile removal of aqueous mercury.

The adsorption of ionic mercury(II) from aqueous solution on functionalized hydride silicon materials was investigated. The adsorbents were prepared by modification of mesoporous silica C-120 with triethoxysilane or by converting alkoxysilane into siloxanes by reaction with acetic acid. Mercury adsorption isotherms at 208C are reported, and maximum mercury loadings were determined by Langmuir fitting. Adsorbents exhibited efficient and rapid removal of ionic mercury from aqueous solution, with a maximum mercury loading of approximately 0.22 and 0.43 mmol of Hg g1 of silica C-120 and polyhedraloligomeric silsesquioxane (POSS) xerogel, respectively. Adsorption efficiency remained almost constant from pH 2.7 to 7. These inexpensive adsorbents exhibiting rapid assembly, low pH sensitivity, and high reactivity and capacity, are potential candidates as effective materials for mercury decontamination in natural waters and industrial effluents.

Buckycolumn electrodes: a practical and improved alternative to conventional materials utilised for biological electrochemical monitoring.

Here we report the use of buckycolumn (BC) carbon nanotube materials as electrochemical sensors for measurement of key biological molecules. The BC electrode was able to conduct stable long-term measurements of dopamine compared to the more commonly used electrode materials for bioanalysis.

In vitro biocompatibility of multiwalled carbon nanotubes with sensory neurons.

Multiwalled carbon nanotubes (MWCNTs) possess unique properties rendering them a potentially useful biomaterial for neurobiological applications such as providing nanoscale contact-guidance cues for directing axon growth within peripheral nerve repair scaffolds. The in vitro biocompatibility of MWCNTs with postnatal mouse spinal sensory neurons was assessed for this application. Cell culture medium conditioned with MWCNTs was not significantly toxic to dissociated cultures of postnatal mouse dorsal root ganglia (DRG) neurons. However, exposure of DRG neurons to MWCNTs dispersed in culture medium resulted in a time- and dose-dependent reduction in neuronal viability. At 250 µg mL⁻¹, dispersed MWCNTs caused significant neuronal death and unusual neurite morphologies illustrated by immunofluorescent labelling of the cytoskeletal protein beta (III) tubulin, however, at a dose of 5 µg mL⁻¹ MWCNTs were nontoxic over a 14-day period. DRG neurons grown on fabricated MWCNT substrates produced neurite outgrowths with abnormal morphologies that were significantly inferior in length to neurons grown on the control substrate laminin. This evidence demonstrates that to be utilized as a biomaterial in tissue scaffolds for nerve repair, MWCNTs will require robust surface modification to enhance biocompatibility and growth promoting properties.

Driving forces of conformational changes in single-layer graphene oxide.

The extensive oxygen-group functionality of single-layer graphene oxide proffers useful anchor sites for chemical functionalization in the controlled formation of graphene architecture and composites. However, the physicochemical environment of graphene oxide and its single-atom thickness facilitate its ability to undergo conformational changes due to responses to its environment, whether pH, salinity, or temperature. Here, we report experimental and molecular simulations confirming the conformational changes of single-layer graphene oxide sheets from the wet or dry state. MD, PM6, and ab initio simulations of dry SLG and dry and wetted SLGO and electron microscopy imaging show marked differences in the properties of the materials that can explain variations in previously observed results for the pH dependent behavior of SLGO and electrical conductivity of chemically modified graphene-polymer composites. Understanding the physicochemical responses of graphene and graphene oxide architecture and performing selected chemistry will ultimately facilitate greater tunability of their performance.

Hyperstoichiometric interaction between silver and mercury at the nanoscale.

Breaking through the stoichiometry barrier: as the diameter of silver particles is decreased below a critical size of 32 nm, the molar ratio of aqueous Hg(II) to Ag(0) drastically increases beyond the conventional Hg/Ag ratio of 0.5:1, leading to hyperstoichiometry with a maximum ratio of 1.125:1. Therein, around 99% of the initial silver is retained to rapidly form a solid amalgam with reduced mercury.

pH-driven physicochemical conformational changes of single-layer graphene oxide.

Single-layer graphene oxides (SLGOs) undergo morphological changes depending on the pH of the system and may account for restricted chemical reactivity. Herein, SLGO may also capture nanoparticles through layering and enveloping when the pH is changed, demonstrating potential usefulness in drug delivery or waste material capture.

High efficiency removal of dissolved As(III) using iron nanoparticle-embedded macroporous polymer composites.

Novel nanocomposite materials where iron nanoparticles are embedded into the walls of a macroporous polymer were produced and their efficiency for the removal of As(III) from aqueous media was studied. Nanocomposite gels containing α-Fe(2)O(3) and Fe(3)O(4) nanoparticles were prepared by cryopolymerisation resulting in a monolithic structure with large interconnected pores up to 100 µm in diameter and possessing a high permeability (ca. 3 × 10(-3) ms(-1)). The nanocomposite devices showed excellent capability for the removal of trace concentrations of As(III) from solution, with a total capacity of up to 3mg As/g of nanoparticles. The leaching of iron was minimal and the device could operate in a pH range 3-9 without diminishing removal efficiency. The effect of competing ions such as SO(4)(2-) and PO(4)(3-) was negligible. The macroporous composites can be easily configured into a variety of shapes and structures and the polymer matrix can be selected from a variety of monomers, offering high potential as flexible metal cation remediation devices.

Morphological and chemical features of nano and macroscale carbons affecting hydrogen peroxide decomposition in aqueous media.

Chemical and structural factors of carbon materials affect their activity in adsorption and surface reactions in aqueous media. Decomposition of hydrogen peroxide studied is a probe reaction for exploring parameters of carbons that might be involved, such as specific surface area, nitrogen and oxygen doping and conformational changes. To date, a detailed comparison of the behavior of carbon nanoscale (Carbon Nanotubes, CNT, Single Layer Graphene Oxide, SLGO) with macroscale (Activated carbons, AC) materials in this reaction has not been forthcoming. Herein, we demonstrate that on their first cycle, ACs in doped and undoped forms outperform all nanoscale carbons tested in the H(2)O(2) decomposition. Among the nanocarbons, nitrogen-doped CNT exhibited the highest activity in this reaction. However, subsequent recycling of each carbon, without chemical regeneration between uses, reveals SLGO exhibits greater reaction rate stability over an extended number of cycles (n>8) than other carbons including nitrogen-doped CNT and ACs. The effects of pH, temperature and concentration on the reaction were analyzed. Quantum-chemical modeling and reaction kinetics analysis reveal key processes likely involved in hydrogen peroxide decomposition and show evidence that the reaction rate is linked to active sites with N-and O-containing functionalities.

Real-time imaging of complex nanoscale mechanical responses of carbon nanotubes in highly compressible porous monoliths.

A facile and rapid assembly of powdered carbon nanotubes (CNTs) into compressible, porous, macroscale monoliths is reported. Despite a Poisson's ratio just above zero, we found that the sample under compression inside a scanning electron microscope (SEM) revealed CNT regions behaving in auxetic and vortex-like rotational modes as well as standard collapse responses. This method is crucial in understanding the macroscale behaviour based on the accumulation of nanoscale responses to an applied force.

Use of iron-based technologies in contaminated land and groundwater remediation: a review.

Reactions involving iron play a major role in the environmental cycling of a wide range of important organic, inorganic and radioactive contaminants. Consequently, a range of environmental clean-up technologies have been proposed or developed which utilise iron chemistry to remediate contaminated land and surface and subsurface waters, e.g. the use of injected zero zero-valent iron nanoparticles to remediate organic contaminant plumes; the generation of iron oxyhydroxide-based substrates for arsenic removal from contaminated waters; etc. This paper reviews some of the latest iron-based technologies in contaminated land and groundwater remediation, their current state of development, and their potential applications and limitations.

Neurite outgrowths of neurons with neurotrophin-coated carbon nanotubes.

Multiwalled carbon nanotubes (CNTs) coated with neurotrophin were used to regulate the differentiation and survival of neurons. Neurotrophin (nerve growth factor [NGF] or brain-derived neurotrophic factor [BDNF]) was covalently bound to CNTs modified by amino groups using a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) reagent. The CNTs coated with NGF or BDNF promoted the neurite outgrowths of neurons in the same manner as soluble NGF and soluble BDNF. By enzyme-linked immunosorbent assay (ELISA), we demonstrated that neurotrophin-coated CNTs carry neurotrophin. These results suggest that neurotrophin-coated CNTs have biological activity and stimulate the neurite outgrowths of neurons.

Polyurea-functionalized multiwalled carbon nanotubes: synthesis, morphology, and Raman spectroscopy.

An in situ polycondensation approach was applied to functionalize multiwalled carbon nanotubes (MWNTs), resulting in various linear or hyperbranched polycondensed polymers [e.g., polyureas, polyurethanes, and poly(urea-urethane)-bonded carbon nanotubes]. The quantity of the grafted polymer can be easily controlled by the feed ratio of monomers. As a typical example, the polyurea-functionalized MWNTs were measured and characterized in detail. The oxidized MWNTs (MWNT-COOH) were converted into acyl chloride-functionalized MWNTs (MWNT-COCl) by reaction with neat thionyl chloride (SOCl2). MWNT-COCl was reacted with excess 1,6-diaminohexane, affording amino-functionalized MWNTs (MWNT-NH2). In the presence of MWNT-NH2, the polyurea was covalently coated onto the surfaces of the nanotube by in situ polycondensation of diisocyanate [e.g., 4,4'-methylenebis(phenylisocyanate)] and 1,6-diaminohexane, followed by the removal of free polymer via repeated filtering and solvent washing. The coated polyurea content can be controlled to some extent by adjusting the feed ratio of the isocyanato and amino groups. The structure and morphology of the resulting nanocomposites were characterized by FTIR, NMR, Raman, confocal Raman, TEM, EDS, and SEM measurements. The polyurea-coated MWNTs showed interesting self-assembled flat- or flowerlike morphologies in the solid state. The signals corresponding to that of the D and G bands of the carbon nanotubes were strongly attenuated after polyurea was chemically tethered to the MWNT surfaces. Comparative experiments showed that the grafted polymer species and structures have a strong effect on the Raman signals of polymer-functionalized MWNTs.