Single step synthesis of Schottky-like hybrid graphene - titania interfaces for efficient photocatalysis.

The development of 2D nanomaterial coatings across metal surfaces is a challenge due to the mismatch between the metal microstructure and the nanoscale materials. The naturally occurring thin oxidative layer present across all metal surfaces, may lead to low adherence and connectivity. In this paper, graphene/titania/Titanium hybrid films were for the first time fabricated by a single step chemical vapour deposition process across Titanium foils. The presence of graphene as a dopant was found to enhance the photocatalytic performance of the final products, applied to the degradation of organic molecules and to lead to Schottky-like junction formation at the metal/oxide interface. These Schottky junctions, where vacancies are present across the titania material due to the graphene doping and where Ti3+ ions are predominantly located, yield enhanced catalytic performance. The highest degradation rate was found to be 9.66 × 10-6 min-1, achieved by the sample grown at 700 °C for 5 min, which was 62% higher than the sample just treated at that temperature without graphene growth. This work provides evidence that graphene may be grown across pure Titanium metal and opens new avenues in biomedical devices design, tribological or separation applications.

Delivery of Abscisic Acid to Plants Using Glutathione Responsive Mesoporous Silica Nanoparticles.

An intracellular glutathione (GSH) responsive phytochemical delivery system based on thiol gated mesoporous silica nanoparticles (MSNs) was developed and tested on the model plant Arabidopsis thaliana. In the present study, monodispersed MSNs with particle diameters of ~20 nm and pore sizes of ~2.87 nm were synthesized and modified. Abscisic acid (ABA), a key phytohormone, was entrapped in the mesopores of MSNs and then the pore entrances of MSNs were covered with decanethiol gatekeepers through GSH-cleavable disulfide linkages. An in vitro release test of ABA from decanethiol gated MSNs proved that there was efficient loading and entrapment of phytochemicals in the absence of a GSH redox trigger. Most importantly, in planta experiments demonstrated that GSH-mediated release of ABA from the pores of MSNs significantly reduced the leaf stomatal aperture and inhibited water loss of treated plants. Moreover, compared with the usage of free ABA, the controlled release of the encapsulated phytohormone from MSNs markedly prolonged the expression of the ABA inducible marker gene (AtGALK2) and finally, improved the drought resistance ability of Arabidopsis seedlings under drought stress. Therefore, the concept of using short-chain molecules as gatekeepers to encapsulate biomolecules in MSNs was demonstrated. The application of MSNs with redox-responsive gatekeepers has been shown in this study to be a potential and efficient technique to deliver phytochemicals into plants and release them in a controllable fashion.

Tailored Mesoporous Silica Nanoparticles for Controlled Drug Delivery: Platform Fabrication, Targeted Delivery, and Computational Design and Analysis.

Mesoporous silica nanoparticles (MSNs) are exceptionally promising drug carriers for controlled drug delivery systems because their morphology, pore structure, pore volume and pore size can be well tailored to obtain certain drug release profiles. Moreover, they possess the ability to specifically transport and deliver anti-cancer drugs when targeting molecules are properly grafted onto their surface. MSNs based drug delivery systems have the potential to revolutionize cancer therapy. This review provides a comprehensive overview of the fabrication, modification of MSNs and their applications in tumour-targeted delivery. In addition, the characterization and analysis of MSNs with computer aided strategies were described. The existing issues and future prospective concerning the applications of MSNs as drug carriers for controlled drug delivery systems were discussed.

Modified iron phosphate/polyvinyl alcohol composite film for controlled-release fertilisers.

Traditional soluble phosphorous (P) fertilisers can be easily leached to pollute water systems, resulting in water eutrophication, a major environmental problem from the oversupply of unused nutrients. One innovative solution is to control the release of P upon demands of the plants. This study established a new concept of controlled-release P fertiliser via incorporation of ferric phosphate (FePO4) as a P source in polyvinyl alcohol (PVA) films, which can immobilise the FePO4 particles and stimuli-responsively accelerate their release rate in the presence of citric acid. More importantly, FePO4 used in this work originated from steelmaking slag as a potential waste reuse. Due to the low solubility of FePO4, diethylamine was introduced to modify FePO4 particles to facilitate the release of P before incorporating with PVA. The effects of diethylamine modification and the properties of FePO4/PVA films were systematically investigated through microscopic and spectroscopic methods. The release of P from particles and films was examined in both deionised water and citric acid solution for 30 days. The results showed a tenfold increase of the release rate of modified FePO4/PVA in citric acid solution compared with that in deionised water, and also a doubled release rate of the modified FePO4/PVA compared to that of FePO4/PVA in citric acid. The improved performance suggests that PVA can maintain the phosphorous content with exposure to water and expedite release in citric acid upon the demand of plants. This composite film offers a new opportunity for the application of insoluble phosphate as a phosphorous fertiliser.

Inorganic Nanoparticles/Metal Organic Framework Hybrid Membrane Reactors for Efficient Photocatalytic Conversion of CO2.

Photocatalytic conversion of carbon dioxide (CO2) to useful products has potential to address the adverse environmental impact of global warming. However, most photocatalysts used to date exhibit limited catalytic performance, due to poor CO2 adsorption capacity, inability to efficiently generate photoexcited electrons, and/or poor transfer of the photogenerated electrons to CO2 molecules adsorbed on the catalyst surface. The integration of inorganic semiconductor nanoparticles across metal organic framework (MOF) materials has potential to yield new hybrid materials, combining the high CO2 adsorption capacity of MOF and the ability of the semiconductor nanoparticles to generate photoexcited electrons. Herein, controlled encapsulation of TiO2 and Cu-TiO2 nanoparticles within zeolitic imidazolate framework (ZIF-8) membranes was successfully accomplished, using rapid thermal deposition (RTD), and their photocatalytic efficiency toward CO2 conversion was investigated under UV irradiation. Methanol and carbon monoxide (CO) were found to be the only products of the CO2 reduction, with yields strongly dependent upon the content and composition of the dopant semiconductor particles. CuTiO2 nanoparticle doped membranes exhibited the best photocatalytic performance, with 7 µg of the semiconductor nanoparticle enhancing CO yield of the pristine ZIF-8 membrane by 233%, and methanol yield by 70%. This work opens new routes for the fabrication of hybrid membranes containing inorganic nanoparticles and MOFs, with potential application not only in catalysis but also in electrochemical, separation, and sensing applications.

Plasmonic substrates for surface enhanced Raman scattering.

As an advanced analytical tool, surface-enhanced Raman scattering (SERS) has broad applications in identification of colorants in paints and glazes, hazard detection to ensure food safety, biomedicine and diagnosis, environmental monitoring, detection of explosives and forensic science. In this review, main types of plasmonic substrates, which include solid substrate with metallic nanostructures and chemically synthesized noble metal colloids, and their fabrication methods are reviewed. The design principles for fabrication of ultrasensitive plasmonic substrates for SERS are presented on the basis of published literature. Finally, various applications of SERS substrates are described, indicating the potential of this technique in practical applications. As an ultrasensitive detection method, SERS is at the core of a rapidly expanding research field.

Silver metal nano-matrixes as high efficiency and versatile catalytic reactors for environmental remediation.

Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications.

Superhydrophobic and Superoleophilic Micro-Wrinkled Reduced Graphene Oxide as a Highly Portable and Recyclable Oil Sorbent.

The potential of superhydrophobic and superoleophilic microwrinkled reduced graphene oxide (MWrGO) structures is here demonstrated for oil spill cleanup. The impact of the thickness of MWrGO films on the sorption performance of three different oils was investigated. Water contact angles across the MWrGO surfaces were found to exceed 150°, while oil could be easily absorbed by the microwrinkled structures of MWrGO within seconds after contact. Although the oil surface diffusion rate was not found to be dependent on the thickness of the graphene oxide films, the oil sorption capacity was the largest with the thinner MWrGO films due to the high surface area resulting from their fine surface texture. Furthermore, the composite films can be repeatedly used for at least 20 oil sorption-removal cycles without any notable loss in selectivity and uptake capacity. These MWrGO/elastomer composite films could be applied as a potential candidate material for future oil spill cleanup.

Mesoporous silica nanoparticles enhance seedling growth and photosynthesis in wheat and lupin.

The application of mesoporous silica nanoparticles (MSNs) as a smart delivery system to agricultural crops is gaining attention but the release of nanoparticles into the environment may pose a potential threat to biological systems. We investigated the effects of MSNs on the growth and development of wheat and lupin plants grown under controlled conditions. We report a dramatic increase in the growth of wheat and lupin plants exposed to MSNs. We also found that, in leaves, MSNs localised to chloroplasts and that photosynthetic activity was significantly increased. In addition, absorption and cellular distribution of MSNs by the two plant species following root uptake were observed using scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS). Following uptake of MSNs at 500 and 1000 mg L(-1), there was enhancement of seed germination, increased plant biomass, total protein and chlorophyll content. Treatment of both species with MSNs at the highest concentration (2000 mg L(-1)) did not result in oxidative stress or cell membrane damage. These findings show that MSNs can be used as novel delivery systems in plants and that over the range of concentrations tested, MSNs do not have any negative impacts on plant growth or development.

A New Insight into Growth Mechanism and Kinetics of Mesoporous Silica Nanoparticles by in Situ Small Angle X-ray Scattering.

The growth mechanism and kinetics of mesoporous silica nanoparticles (MSNs) were investigated for the first time by using a synchrotron time-resolved small-angle X-ray scattering (SAXS) analysis. The synchrotron SAXS offers unsurpassed time resolution and the ability to detect structural changes of nanometer sized objects, which are beneficial for the understanding of the growth mechanism of small MSNs (∼20 nm). The Porod invariant was used to quantify the conversion of tetraethyl orthosilicate (TEOS) in silica during MSN formation, and the growth kinetics were investigated at different solution pH and temperature through calculating the scattering invariant as a function of reaction time. The growth of MSNs was found to be accelerated at high temperature and high pH, resulting in a higher rate of silica formation. Modeling SAXS data of micelles, where a well-defined electrostatic interaction is assumed, determines the size and shape of hexadecyltrimethylammonium bromide (CTAB) micelles before and after the addition of TEOS. The results suggested that the micelle size increases and the micelle shape changes from ellipsoid to spherical, which might be attributed to the solubilization of TEOS in the hydrophobic core of CTAB micelles. A new "swelling-shrinking" mechanism is proposed. The mechanism provides new insights into understanding MSN growth for the formation of functional mesoporous materials exhibiting controlled morphologies. The SAXS analyses were correlated to the structure of CTAB micelles and chemical reaction of TEOS. This study has provided critical information to an understanding of the growth kinetics and mechanism of MSNs.

Functionalized mesoporous silica nanoparticles with redox-responsive short-chain gatekeepers for agrochemical delivery.

The controlled release of salicylic acid (SA), a key phytohormone, was mediated by using a novel decanethiol gatekeeper system grafted onto mesoporous silica nanoparticles (MSNs). The decanethiol was conjugated only to the external surfaces of the MSNs through glutathione (GSH)-cleavable disulfide linkages and the introduction of a process to assemble gatekeepers only on the outer surface so that the mesopore area can be maintained for high cargo loading. Raman and nitrogen sorption isotherm analyses confirmed the successful linkage of decanethiol to the surface of MSNs. The in vitro release of SA from decanethiol gated MSNs indicated that the release rate of SA in an environment with a certain amount of GSH was significantly higher than that without GSH. More importantly, in planta experiments showed the release of SA from decanethiol gated MSNs by GSH induced sustained expression of the plant defense gene PR-1 up to 7 days after introduction, while free SA caused an early peak in PR-1 expression which steadily decreased after 3 days. This study demonstrates the redox-responsive release of a phytohormone in vitro and also indicates the potential use of MSNs in planta as a controlled agrochemical delivery system.

Uptake and cellular distribution, in four plant species, of fluorescently labeled mesoporous silica nanoparticles.

KEY MESSAGE: We report the uptake of MSNs into the roots and their movement to the aerial parts of four plant species and their quantification using fluorescence, TEM and proton-induced x - ray emission (micro - PIXE) elemental analysis. Monodispersed mesoporous silica nanoparticles (MSNs) of optimal size and configuration were synthesized for uptake by plant organs, tissues and cells. These monodispersed nanoparticles have a size of 20 nm with interconnected pores with an approximate diameter of 2.58 nm. There were no negative effects of MSNs on seed germination or when transported to different organs of the four plant species tested in this study. Most importantly, for the first time, a combination of confocal laser scanning microscopy, transmission electron microscopy and proton-induced X-ray emission (micro-PIXE) elemental analysis allowed the location and quantification MSNs in tissues and in cellular and sub-cellular locations. Our results show that MSNs penetrated into the roots via symplastic and apoplastic pathways and then via the conducting tissues of the xylem to the aerial parts of the plants including the stems and leaves. The translocation and widescale distribution of MSNs in plants will enable them to be used as a new delivery means for the transport of different sized biomolecules into plants.