Superhydrophobicity from the Inside.

The nature of trapped air on submersed ultra-water-repellent interfaces has been investigated. These gaseous layers (plastrons) can last from hours to, in some examples such as the Salvinia molesta fern, months. The interface of submerged superhydrophobic surfaces with carefully controlled micropatterned surface roughness has been probed using synchrotron-based high-resolution X-ray phase tomography. This technique looks in situ, through the aqueous/gas interface in three dimensions. Long-term plastron stability appears to correlate with the appearance of scattered microdroplets <20 µm in diameter that are sandwiched within the 30 µm thick gaseous interfacial layer. These microdroplets are centered on defects or damaged sections within the substrate surface approximately 20-50 µm apart. Such irregularities represent heterogeneous micro/nano-hierarchical structures with varying surface structures and chemistry. The stability of microdroplets is governed by a combination of electrostatic repulsion, contact angle limitations, and a saturated vapor pressure, the latter of which reduces the rate of diffusion of gas out of the air layer, thus increasing underwater longevity. Homogenous surfaces exhibiting purely nano- or micro-regularity do not support such microdroplets, and, as a consequence, plastrons can disappear in <20 h compared with >160 h for surfaces with scattered microdroplets. Such behavior may be a requirement for long-term nonwetting in any system.

Transparent Aluminium Oxide Coatings of Polymer Brushes.

A novel method for the preparation of transparent Al2O3 coatings of polymers is presented. An environmental-friendly sol-gel method is employed, which implies mild conditions and low costs. A thermoresponsive brush is chosen as a model surface. X-ray photoelectron spectroscopy is used to characterize the samples during the conversion of the precursor Al(OH)3 into oxide and to prove the mildness of the protocol. The study evidences a relation between lateral homogeneity of alumina and the wettability of the polymer surface by the precursor solution, while morphology and elasticity are dominated by the polymer properties. The study of the swelling behavior of the underneath brush reveals the absence of water uptake, proving the impermeability of the alumina layer. The broad chemical and structural variety of polymers, combined with the robustness of transparent alumina films, makes these composites promising as biomedical implants, protective sheets and components for electric and optical devices.

Marine antifouling from thin air.

The dynamic relationship between the settlement behaviour of marine biota (cells, spores, larvae) and the longevity of an entrapped air layer (plastron) on submersed superhydrophobic surfaces was systematically investigated. Plastron lifetime decreased with increasing hydrophobic polymer loadings, and was correlated with the settlement rate of a range of fouling species of varying length scale, motility and hydrophobic/hydrophilic surface preference. The results show that the level of fouling on immersed superhydrophobic surfaces was greater when plastron lifetimes were minimal, regardless of the length scale, motility and the surface preference of the organisms. This is the first direct demonstration of the broad-spectrum attachment-inhibiting properties of a plastron on an immersed superhydrophobic surface.

The relationship between nanobubbles and the hydrophobic force.

The formation of nanobubbles on hydrophobic self-assembled monolayers has been examined in a binary ethanol/water titration using small angle X-ray scattering (SAXS) and atomic force microscopy (AFM). The AFM data demonstrates a localized force effect attributed to nanobubbles on an immersed hydrophobic surface. This evidence is arguably compromised by the possibility that the AFM tip actually nucleates nanobubbles. As a complementary noninvasive technique, SAXS has been used to investigate the interfacial region of the immersed hydrophobic surface. SAXS measurements reveal an electron density depletion layer at the hydrophobic interface, with changing air solubility in the immersing liquid, due to the formation of nanobubbles.

Continuous Flow Copper Laser Ablation Synthesis of Copper(I and II) Oxide Nanoparticles in Water.

Copper(I) oxide (Cu2O) nanoparticles (NPs) are selectively prepared in high yields under continuous flow in a vortex fluidic device (VFD), involving irradiation of a copper rod using a pulsed laser operating at 1064 nm and 600 mJ. The plasma plume generated inside a glass tube (20 mm O.D.), which is rapidly rotating (7.5 k rpm), reacts with the enclosed air in the microfluidic platform, with then high mass transfer of material into the dynamic thin film of water passing up the tube. The average size of the generated Cu2ONPs is 14 nm, and they are converted to copper(II) oxide (CuO) nanoparticles with an average diameter of 11 nm by heating the as-prepared solution of Cu2ONPs in air at 50 °C for 10 h.

Chemoselective and Continuous Flow Hydrogenations in Thin Films Using a Palladium Nanoparticle Catalyst Embedded in Cellulose Paper.

Cellulose immobilized palladium (0) nanoparticles (PdNPs) were prepared for the use in scalable catalytic reactions in flow. Preparation of the catalyst is remarkably simple and fast, where a palladium acetate solution is drop-casted onto cellulose paper and then exposed to 1 atm of hydrogen for a mere 90 s to produce embedded Pd(0) nanoparticles. This catalyst system is efficient in the hydrogenation of alkenes, nitroarenes, ketones, and enamides, with products formed in high yields, under ambient pressure and temperature. The system is also effective for transfer hydrogenation using ammonium formate as an alternative hydrogen source. A high catalyst stability and reusability are demonstrated along with the chemoselective and scalable synthesis of industrially important fine chemicals, including the biobased molecule cyrene.

Vortex fluidic mediated transformation of graphite into highly conducting graphene scrolls.

Two-dimensional graphene has remarkable properties that are revolutionary in many applications. Scrolling monolayer graphene with precise tunability would create further potential for niche applications but this has proved challenging. We have now established the ability to fabricate monolayer graphene scrolls in high yield directly from graphite flakes under non-equilibrium conditions at room temperature in dynamic thin films of liquid. Using conductive atomic force microscopy we demonstrate that the graphene scrolls form highly conducting electrical contacts to highly oriented pyrolytic graphite (HOPG). These highly conducting graphite-graphene contacts are attractive for the fabrication of interconnects in microcircuits and align with the increasing interest in building all sp2-carbon circuits. Above a temperature of 450 °C the scrolls unravel into buckled graphene sheets, and this process is understood on a theoretical basis. These findings augur well for new applications, in particular for incorporating the scrolls into miniaturized electronic devices.

Continuous flow synthesis of phosphate binding h-BN@magnetite hybrid material.

Hexagonal boron nitride (h-BN) is rendered magnetically responsive in aqueous media by binding superparamagnetic magnetite nanoparticles 8.5-18.5 nm in diameter on the surface. The composite material was generated under continuous flow in water in a dynamic thin film in a vortex fluidic device (VFD) with the source of iron generated by laser ablation of a pure iron metal target in the air above the liquid using a Nd:YAG pulsed laser operating at 1064 nm and 360 mJ. Optimum operating parameters of the VFD were a rotational speed of 7.5k rpm for the 20 mm OD (17.5 mm ID) borosilicate glass tube inclined at 45 degrees, with a h-BN concentration at 0.1 mg mL-1, delivered at 1.0 mL min-1 using a magnetically stirred syringe to keep the h-BN uniformly dispersed in water prior to injection into the base of the rapidly rotating tube. The resulting composite material, containing 5.75% weight of iron, exhibited high phosphate ion adsorption capacity, up to 171.2 mg PO4 3- per gram Fe, which was preserved on recycling the material five times.

Structure and Chemical Organization in Damselfly Calopteryx haemorrhoidalis Wings: A Spatially Resolved FTIR and XRF Analysis with Synchrotron Radiation.

Insects represent the majority of known animal species and exploit a variety of fascinating nanotechnological concepts. We investigated the wings of the damselfly Calopteryx haemorrhoidalis, whose males have dark pigmented wings and females have slightly pigmented wings. We used scanning electron microscopy (SEM) and nanoscale synchrotron X-ray fluorescence (XRF) microscopy analysis for characterizing the nanostructure and the elemental distribution of the wings, respectively. The spatially resolved distribution of the organic constituents was examined by synchrotron Fourier transform infrared (s-FTIR) microspectroscopy and subsequently analyzed using hierarchical cluster analysis. The chemical distribution across the wing was rather uniform with no evidence of melanin in female wings, but with a high content of melanin in male wings. Our data revealed a fiber-like structure of the hairs and confirmed the presence of voids close to its base connecting the hairs to the damselfly wings. Within these voids, all detected elements were found to be locally depleted. Structure and elemental contents varied between wing membranes, hairs and veins. The elemental distribution across the membrane was rather uniform, with higher Ca, Cu and Zn levels in the male damselfly wing membranes.

Growth mechanism of textured MgO thin films via SSCVD.

Magnesium oxide thin films have been deposited with use of single source chemical vapor deposition (SSCVD). The resultant films were examined by using transmission electron microscopy, X-ray texture analysis, and pole figure analysis. Due to the nature of the chemical reactions occurring at the surface during SSCVD growth, which result in a high growth rate/low flux environment, films of (111) orientation have been achieved without an amorphous underlayer, an unusual result for films of this orientation. Moreover the films have a strong degree of biaxial texturing in the x-y plane as found with X-ray texture analysis. These findings have important implications for buffer layers in perovskite thin film devices. The mechanism producing these structures has been revealed by using TEM and is discussed here.

The nature of inherent bactericidal activity: insights from the nanotopology of three species of dragonfly.

While insect wings are widely recognised as multi-functional, recent work showed that this extends to extensive bactericidal activity brought about by cell deformation and lysis on the wing nanotopology. We now quantitatively show that subtle changes to this topography result in substantial changes in bactericidal activity that are able to span an order of magnitude. Notably, the chemical composition of the lipid nanopillars was seen by XPS and synchrotron FTIR microspectroscopy to be similar across these activity differences. Modelling the interaction between bacterial cells and the wing surface lipids of 3 species of dragonflies, that inhabit similar environments, but with distinctly different behavioural repertoires, provided the relationship between surface structure and antibacterial functionality. In doing so, these principal behavioural patterns correlated with the demands for antimicrobial efficiency dictated by differences in their foraging strategies. This work now reveals a new feature in the design elegance of natural multi-functional surfaces as well providing insights into the bactericidal mechanism underlying inherently antimicrobial materials, while suggesting that nanotopology is related to the evolutionary development of a species through the demands of its behavioural repertoire. The underlying relationship between the processes of wetting, adhesion and capillarity of the lipid nanopillars and bactericidal efficiency suggests new prospects for purely mechano-responsive antibacterial surfaces.

Influence of oxygen on the crystalline-amorphous transition in gallium nitride films.

Oxygen is a common impurity in nitride-based materials that affects the properties of technologically important materials such as gallium nitride semiconductors. In this work, the influence of oxygen on the structural evolution of GaN films is investigated using near-edge X-ray absorption fine structure (NEXAFS). The combined spectra of Ga L3-edge, N K-edge, and O K-edge indicate that the gallium coordination, formed by a mixture of oxide and nitride bonds, is directly dependent on the concentration of oxygen in the films. Below 24 atom % oxygen, gallium atoms are tetrahedrally coordinated within the films, while at higher concentrations the octahedral environment persists.

Interactions of sodium montmorillonite with poly(acrylic acid).

The chemical-structural modifications of the natural clay sodium montmorillonite during interaction with poly(acrylic acid) were studied mainly by X-ray photoemission spectroscopy. Samples of modified montmorillonite were prepared from the reaction of sodium montmorillonite ( approximately 0.5 g) and an aqueous solution of poly(acrylic acid) (pH approximately 1.8, 50 g) at varying temperatures. X-ray diffraction indicated that the montmorillonite interlayer space ( approximately 13 A), formed by regular stacking of the silicate layers (dimension approximately 1x1000 nm), expanded to approximately 16 A as the reaction was carried out at room temperature and at 30 degrees C. At 60 degrees C, the interlayer space further expanded to approximately 20 A. The results of X-ray photoemission spectroscopy indicated that poly(acrylic acid) molecules exchange sodium ions on the surface of the silicate layers. These combined results allowed development of a reaction model that explains the dependency of the interlayer expansion with temperature. Information concerning the surface chemical reactions and systematic increases in the interlayer distances is particularly useful if montmorillonite and poly(acrylic acid) are to be used for formation of nanocomposite materials.

Selective 1,3-complexation of p-(t)Bu-calix[4]arene by [TiCp(2)Me(2)].

Reaction of p-(t)Bu-calix[4]arene with dimethyl titanocene results in high yield selective 1,3-dimetallation of the calixarene in the cone conformation by selective cleavage of one methyl group.

Selective synthesis of conformationally restricted mono-cyclopentadienyl titanium(IV) complexes of p-tBu-calix[6]arene.

Reaction of p-'Bu-calix[6]arene with potassium metal in methanol followed by [TiCp2Cl2] affords novel mononuclear and binuclear monocyclopentadienyl titanium(IV) complexes, both having the same inverted double cone conformation with a Cp in one of the cavities, in both complexes.

Titanocene dichloride route to a tetranuclear oxo-bridged monocyclopentadienyl titanium(IV) calix[4]arene complex.

Lithiation of p-tBu-calix[4]arene followed by reaction with titanocene dichloride affords a novel tetranuclear titanium(IV) monocyclopentadienyl complex, wherein a single calix[4]arene in a cone conformation provides O-phenoxy coordination to four titanium atoms, with additional mu-oxo bridging between titanium centres in an eight membered ring.

2:1 Ba/Ti(IV) heterobimetallic complex based on two calix[6]arenes.

Reaction of p-Bu(t)-calix[6]arene with barium metal in methanol then [Ti(OPr(i))4] affords a heterobimetallic complex with a central Ti(IV) attached to two calix[6]arenes in the 1,3-alternate conformation, each with an endo-barium sharing common phenolate groups with the titanium centre.

Mechanical stability of surface architecture--consequences for superhydrophobicity.

Wet chemistry methods such as sol-gel provide a facile means of preparing coatings with controlled surface chemistry and architecture. The manipulation of colloidal "building blocks," film constituents, and reaction conditions makes it a promising method for simple, scalable, and routine production of superhydrophobic coatings. Despite all of this, the practical application of superhydrophobic coatings remains limited by low mechanical durability. The translation of chemistry to mechanical strength within superhydrophobic films is severely hindered by the requisite physical structure. More specifically, porosity and the surface architecture of roughness in sol-gel-derived films contribute significantly to poor mechanical properties. These physical effects emphasize that collective structure and chemistry-based strategies are required. This challenge is not unique to superhydrophobics, and there are many principles that can be drawn upon to greatly improve performance. The delicate interplay between chemistry and physical structure has been highlighted through theory and characterization of porous and rough interfaces within and outside the framework of superhydrophobics. Insights can further be drawn from biology. Nature's capacity for self-repair remains extremely challenging to mimic in materials. However, nature does demonstrate strategies for structuring nano- and microbuilding blocks to achieve generally mutually exclusive properties. Difficulties with characterization and example mechanical characterization methods have also been emphasized.

Toward superhydrophobic and durable coatings: effect of needle vs crater surface architecture.

Practical application of sol-gel derived superhydrophobic films is limited by the fragility of "needlelike" surface roughness. An efficient one step procedure is developed to prepare robust thin films with "craterlike" surface roughness from a methyltrimethoxysilane matrix and polymer sphere templates. The films could be readily spray coated to produce roughened surface textures, which are governed by template concentration and geometry. The effect of this on the wettability and robustness of thin films was examined in detail, revealing a rapid trade-off between the two characteristics due to variations in coating porosity.

Molecular organization of the nanoscale surface structures of the dragonfly Hemianax papuensis wing epicuticle.

The molecular organization of the epicuticle (the outermost layer) of insect wings is vital in the formation of the nanoscale surface patterns that are responsible for bestowing remarkable functional properties. Using a combination of spectroscopic and chromatographic techniques, including Synchrotron-sourced Fourier-transform infrared microspectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS) depth profiling and gas chromatography-mass spectrometry (GCMS), we have identified the chemical components that constitute the nanoscale structures on the surface of the wings of the dragonfly, Hemianax papuensis. The major components were identified to be fatty acids, predominantly hexadecanoic acid and octadecanoic acid, and n-alkanes with even numbered carbon chains ranging from C14 to C30. The data obtained from XPS depth profiling, in conjunction with that obtained from GCMS analyses, enabled the location of particular classes of compounds to different regions within the epicuticle. Hexadecanoic acid was found to be a major component of the outer region of the epicuticle, which forms the surface nanostructures, and was also detected in deeper layers along with octadecanoic acid. Aliphatic compounds were detected throughout the epicuticle, and these appeared to form a third discrete layer that was separate from both the inner and outer epicuticles, which has never previously been reported.