Electroless growth of zinc oxide has been accomplished using palladium catalysts coordinated to pulsed plasma deposited poly(4-vinylpyridine) nanolayers. Four different and concurrent functional properties have been identified, which encompass photoconductivity, superhydrophobicity, photo-switchable wetting, and bacterial killing.

Single-step synthesis of structurally well-defined anhydride containing layers has been accomplished at ambient temperatures by pulsed plasmachemical deposition. High proton conductivity values are attained following hydrolysis of the anhydride centres to carboxylic acid groups.

Attachment of chiral azobenzene chromophores to plasmachemical deposited structurally well-defined nanolayers yields supramolecular chiroptical properties. In the case of (S)-3-methyl-3-amino-1-(4′-cyano-4-azobenzene)pyrrolidine derivatized pulsed plasma poly(glycidyl methacrylate) nanofilms, circular dichroism measurements demonstrate enantiomeric toggling (switching) and longevity of chiroptical performance, which can be attributed to stable supramolecular helical configurations.

Hydrophilic beta-cyclodextrin barrels have been tethered to a hydrophobic pulsed plasma deposited poly(4-vinylbenzyl chloride) linker layer via the Williamson ether synthesis reaction to produce an amphiphilic system that spontaneously undergoes emulsion formation to give rise to a macroporous structure. Utilization of a nonwoven polypropylene scaffold (surface area 0.52 m(2) g(-1)) yields a hierarchical 3-level porous architecture comprising beta-cyclodextrin nanopores (0.78 nm), gradient polyHIPE macroporosity (3-5 mu m), and nonwoven fibres (250 mu m spacing). These high-surface-area functional materials (672 m(2) g(-1)) are shown to readily "capture" probe molecules via host-guest inclusion complex formation with the surface-tethered cyclodextrin barrels. Subsequent "release" is accomplished by altering the pH. The repeat cycling of this "capture and release" behavior has been demonstrated to exceed 90% efficiency in relation to environmentally harmful water pollutant molecules commonly associated with industrial and agricultural effluents.

β-cyclodextrin barrels can be tethered to solid surfaces using the Williamson ether synthesis reaction via an intermediate pulsed plasma deposited poly(4-vinylbenzyl chloride) linker layer. The loading and release of perfume molecules through host-guest inclusion complex formation with surface tethered β-cyclodextrin has been followed by infrared spectroscopy and quartz crystal microbalance measurements. Fragrance release lasts for several months and can be easily recharged.

Surface-tethered bottlebrushes have been prepared by ATRP grafting of the macroinitiator brush backbone onto plasmachemical-deposited poly(vinylbenzyl chloride) initiator nanofilms followed by ATRP growth of the side chains (bristles). The surface density of bottlebrushes can be precisely tailored by varying the plasmachemical deposition parameters employed for producing the poly(vinylbenzyl chloride) initiator nanolayers. Lateral force scanning probe microscopy has shown that poly(glycidyl methacrylate)-graft-poly(sodium styrene sulfonate) bottlebrush-decorated surfaces give rise to an enhancement in lubrication.

Existing methods for fabricating protein arrays and patterns on solid surfaces rely upon multiple-step chemical reaction procedures. A more straightforward approach is described where proteins are written directly onto a protein resistant surface which eliminates the need for back-filling. This is achieved by the spatially controlled delivery of protein-containing activation solutions onto poly(N-acryloylsarcosine methyl ester) protein-resistant surfaces. The surface tethered proteins are shown to retain their biological function whilst the surrounding poly(N-acryloylsarcosine methyl ester) background prohibits non-specific protein binding.

Conventional fog-harvesting mechanisms are effectively pseudo-2D surface phenomena in terms of water droplet-plant interactions. In the case of the Cotula fallax plant, a unique hierarchical 3D arrangement formed by its leaves and the fine hairs covering them has been found to underpin the collection and retention of water droplets on the foliage for extended periods of time. The mechanisms of water capture and release as a function of the surface 3D structure and chemistry have been identified. Of particular note is that water is retained throughout the entirety of the plant and held within the foliage itself (rather than in localized regions). Individual plant hairs form matlike structures capable of supporting water droplets; these hairs wrap around water droplets in a 3D fashion to secure them via a fine nanoscale groove structure that prevents them from easily falling to the ground.

Highly wettable polymer surfaces can be produced by using two consecutive plasma treatment steps corresponding to crosslinking followed by oxidation. Contact angle and XPS measurements indicate that these surfaces are stable towards hydrophobic recovery. Plasma modification of porous polymer sheets using this 2-step approach gives rise to high water absorption capacities.

The impact of picoliter-sized water droplets on superhydrophobic CF(4) plasma fluorinated polybutadiene surfaces is investigated with high-speed imaging. Variation of the surface topography by plasmachemical modification enables the dynamics of wetting to be precisely controlled. Final spreading ratios as low as 0.63 can be achieved. A comparison of the maximum spreading ratio and droplet oscillation frequencies to models described in the literature shows that both are found to be much lower than theoretically predicted.

Patterned polymer brush surfaces have been fabricated using the molecular scratchcard lithography technique, where a functional top nanolayer (acting also as a resist) is selectively removed using a scanning probe tip to expose underlying atom-transfer radical polymerization (ATRP) initiator sites. The lateral spreading of grafted polymer brush patterns across the adjacent functional resist surface can be reversibly actuated via solvent exposure. Effectively, this methodology provides a means for hiding/unveiling functional surfaces on the nanoscale.

A lift-off method for creating multifunctional patterned surfaces has been devised. It entails consecutive pulsed plasmachemical deposition of a reactive bottom layer and a protective top release layer. By way of example, a bottom/top layer combination comprising pulsed plasma deposited poly(glycidyl methacrylate)/poly(pentafluorostyrene) has been shown to display selective adhesive lift-off of the latter. Application of a prepatterned adhesive template yields well-defined arrays of reactive epoxide functionality surrounded by a passive fluoropolymer background or vice versa.

Bromine-containing nanolayers are deposited by pulsed plasma deposition of 2-bromoethylacrylate. Subsequent covalent immobilization of single-strand DNA onto these films is achieved via the reaction with a terminal thiol group linker contained in the oligonucleotide.

We describe microarraying of carbohydrates for protein screening using either disulfide bridge or Schiff base imine immobilization chemistries on plasmachemical deposited functional nanolayers. The commonly observed issue of nonspecific background binding of proteins is overcome by spotting carbohydrates through a protein-resistant overlayer yielding spatially localized interaction with a reactive functional underlayer.

A simple two-step plasmachemical methodology is outlined for the fabrication of microcondensor surfaces. This comprises the creation of a superhydrophobic background followed by pulsed plasma deposition of a hydrophilic polymer array. Microcondensation efficiency has been explored in terms of the chemical nature of the hydrophilic pixels and their dimensions. These results are compared to the hydrophilic-hydrophobic pattern present on the Stenocara beetle's back, which is used by the insect to collect water in the desert. Potential applications include fog harvesting, microfluidics, and biomolecule immobilization.

Plasmachemical nanolayering in combination with localized removal of an upper passivation layer is shown to be a simple route for the fabrication of patterned functional surfaces. Protein and DNA arrays can be prepared utilizing a dual layer structure in which the outer layer is nonbinding, and the exposed underlayer specifically immobilizes the respective biomolecule.

Thiol-terminated single-stranded deoxyribonucleic acids (ssDNA) can be immobilized onto pulsed plasma deposited poly(allylmercaptan) surfaces via disulfide bridge chemistry and are found to readily undergo nucleic acid hybridization. Unlike other methods for oligonucleotide attachment to solid surfaces, this approach is shown to be independent of substrate material or geometry, and amenable to highly efficient rewriting.