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P. Turner et al., There is a pressing need for reliable, reproducible and accurate measurements of graphene's properties, through international standards, to facilitate industrial growth. However, trustworthy and verified standards require rigorous metrological studies, determining, quantifying and reducing the sources of measurement uncertainty. Towards this effort, we report the procedure and the results of an international interlaboratory comparison (ILC) study, conducted under Versailles Project on Advanced Materials and Standards. This ILC focusses on the comparability of Raman spectroscopy measurements of chemical vapour deposition (CVD) grown graphene using the same measurement protocol across different institutes and laboratories. With data gathered from 17 participants across academia, industry (including instrument manufacturers) and national metrology institutes, this study investigates the measurement uncertainty contributions from both Raman spectroscopy measurements and data analysis procedures, as well as provides solutions for improved accuracy and precision. While many of the reported Raman metrics were relatively consistent, significant and meaningful outliers occurred due to differences in the instruments and data analysis. These variations resulted in inconsistent reports of peak intensity ratios, peak widths and the coverage of graphene. Due to a lack of relative intensity calibration, the relative difference reported in the 2D- and G peak intensity ratios (${I_{2{\text{D}}}}/{I_{\text{G}}}$) was up to 200%. It was also shown that the standard deviation for ${\Gamma _{2{\text{D}}}}$ values reported by different software packages, was 15× larger for Lorentzian fit functions than for pseudo-Voigt functions. This study has shown that by adopting a relative intensity calibration and consistent peak fitting and data analysis methodologies, these large, and previously unquantified, variations can be significantly reduced, allowing more reproducible and comparable measurements for the graphene community, supporting fundamental research through to the growing graphene industry worldwide. This project and its findings directly underpin the development of the ISO/IEC standard 'DTS 21356-2—Nanotechnologies—Structural Characterisation of CVD-grown Graphene'., PT, KRP, EJL and AJP would like to thank the European Union’s Horizon 2020 research and innovation program under Grant Agreement No. 881603 (Graphene Flagship Core 3) for funding. RA acknowledges funding by the Spanish MICINN (PID2019104739GB/100/AEI/10.13039/501100011033) and by the Government of Aragon (project DGA E13-17R (FEDER, EU)).

Immuno-specific enrichment of extracellular vesicles (EVs) originating from specific cells/tissues is a promising source of information towards improving insights into cellular pathways underpinning various pathologies and developing novel non-invasive diagnostic methods. Enrichment is an important aspect in mass spectrometry-based analyses of EVs. Herein, we report a protocol for immuno-magnetic enrichment of subtype specific EVs and their subsequent processing for mass spectrometry. Specifically, we conjugated placental alkaline phosphatase (PLAP) antibodies to magnetic iron oxide nanowires (NWs) derived from bacterial biofilms and demonstrated the utility of this approach by enriching placental specific EVs (containing PLAP) from cell culture media. We demonstrate efficient PLAP+ve EV enrichment for both NW-PLAP and Dynabeads™-PLAP, with PLAP protein recovery (83.7±8.9% and 83.2±5.9%, respectively), high particle-to-protein ratio (7.5±0.7×109 and 7.1 ± 1.2×109, respectively), and low non-specific binding of non-target EVs (7±3.2% and 5.4±2.2%, respectively). Furthermore, our optimized EV enrichment and processing approach identified 2518 and 2545 protein groups with mass spectrometry for NW-PLAP and Dynabead™-PLAP, respectively, with excellent reproducibility (Pearson correlation 0.986 and 0.988). The proposed immuno-specific EVs enrichment and liquid chromatography-tandem mass spectrometry method using naturally occurring iron oxide magnetic NWs or gold-standard Dynabeads™ enables high-quality EV proteomic studies.

Compounds and composites with high dielectric performance are in high demand in electronic industry due to their ability to store more charge and lower energy dissipation. In this paper we present synthesis of flexible three phase nanocomposite films of graphene/titania/polydimethylsiloxane with reasonably high real part of permittivity and very low imaginary part of permittivity. Dielectric permittivity of polydimethylsiloxane was raised by addition of graphene and rutile titania used as conducting and ceramic additives, respectively added in various weight ratios. Dielectric studies of synthesized three phase graphene/titania/polydimethylsiloxane nanocomposite films with weight/weight of 2:15:20 exhibits dielectric permittivity of 34.8 even at very high frequency of 2 MHz. While loss tangent of the same three phase graphene/titania/polydimethylsiloxane nanocomposite film is as low as 0.01 and its AC conductivity is 4.3 × 10⁻⁵ Sm⁻¹. Complex impedance and complex electric modulus of three phase graphene/titania/polydimethylsiloxane nanocomposite films also confirm its capacitive behaviour. Based on these properties and results we propose that these type of three phase graphene/titania/polydimethylsiloxane nanocomposite films can be used as useful dielectric materials in energy storage devices. Refereed/Peer-reviewed

Refereed/Peer-reviewed Layered vanadate cathodes hold promise for aqueous zinc-ion batteries (AZIBs) owing to their multiple redox reactions as well as large interlayer space for Zn2+ storage. However, they are limited by vanadium dissolution during cycling, in association with severe capacity fade and unsatisfactory cyclic life. To address this challenge, we herein report a pre-inserted dual-cation vanadate (NaxZnyV3O8·nH2O) cathode, which combines the Zn2+-reinforced cathode structure with the Na+-enlarged lattice distance for fast and stable Zn2+ migration. Multiple ex situ analysis found that electrochemically active Zn3(OH)2V2O7·2H2O was generated after discharging, and this corresponds to the efficient suppression of vanadium dissolution by strong ionic bonding. As a result, a certain NaxZnyV3O8·nH2O cathode having a Na+ to Zn2+ ratio of 2:1 retains 99.6% of capacity after 418 cycles at 0.1 A g−1, 90.5% after 6000 cycles at 1.0 A g−1, and 96.7% after 9499 cycles at 10.0 A g−1. Our method paves a way for researchers to develop robust cathode materials for ultra-stable AZIBs.

A new method based on scanning atmospheric plasma for an ultrafast reduction of graphene oxide (GO) and preparation of highly conductive graphene films and patterns is presented. This simple method is shown to provide a direct and scalable fabrication of graphene films on flexible and shaped substrates with a variety of patterns for broad applications. An effective and ultrafast (similar to 60 s) reduction of GO films into highly conductive graphene films at room temperature is demonstrated by this process that is impossible to achieve by conventional wet chemical and thermal reduction process. The software controlled x-y scanning unit allows fabrication of graphene films with variety of patterns on different substrates including glass, plastic, ceramics and metals with complex shapes required for flexible and wearable electronics and devices. Characterization results confirmed that a thin transparent graphene film can be produced with a surface sheets resistance of 22 k Omega/sq at the transparency of 88%, and a thick film (similar to 25 mu m) with a sheet resistance of 186 Omega/sq. A practical application of plasma fabricated graphene films was demonstrated for a supercapacitor devices able to deliver an outstanding volumetric capacitance of 536.55 F/cm(3) at a current density of 1 A/g. (C) 2017 Elsevier Ltd. All rights reserved. Refereed/Peer-reviewed

usc It is a challenge to compound hydrophilic MXene nanosheets with hydrophobic elastomers for various applications such as stretchable devices. In this work, Ti3C2Tx MXene nanosheets of 3.5 ± 1.0 nm in thickness were chemically modified by a facile method to enhance compatibility with a common elastomer, nitrile butadiene rubber (NBR). X-ray photoelectron spectroscopy showed the presence of nitrogen in the MXene through the modification by allylamine, whilst Raman spectroscopy revealed an increase in =O groups, exposing more reactive sites on the nanosheet surface. Fourier transform infrared spectroscopy indicated the disappearance of –C=C bonds in the nanocomposites as well as the breakage of –C≡N bonds, confirming that allylamine bridged MXene nanosheets with the matrix molecules. X-ray diffraction study showed the complete exfoliation of nanosheets in the elastomer matrix at 2.0 vol%, as confirmed by TEM micrographs. At 14.0 vol% MXene, the Young’s modulus, tensile strength and thermal conductivity of NBR were improved by 700, 240 and 440%, respectively. A percolation threshold of electrical conductivity was obtained at 3.9 vol% of MXene while thermal conductivity at 19.6 vol% – 1.01 W·m−1K−1 – outperformed previous elastomer nanocomposites containing boron nitride, zinc oxide, graphene nanoplatelets and alumina. Refereed/Peer-reviewed

Refereed/Peer-reviewed The inconsistent wettability of biological superwetting materials, due to aging, morphological change, structural fragility and biodegradation, limit their practical use for highly demanding applications such as oil-water separation and dye adsorption. Herein, we present a new source of superwetting materials harvested from waste chestnut-shell. The material is in the form of micro-fibres which are intrinsically oleophilic/hydrophobic, chemically stable, lightweight and structurally robust. The harvested microfibres, laying between inner-liner and outer shell of the chestnut, are naturally enriched with aliphatic and aromatic hydrocarbon that results in their high oleophilicity. We demonstrated that these superoleophilic fibre-networks could be used as oil-absorbent exhibiting outstanding absorption efficiency with a maximum capacity of similar to 94% of their own weight. Afterwards, an efficient filtration membrane was engineered using these micro-fibres showing their ability for continuous oil-water separation process for a series of organic solvents (toluene, canola oil, engine oil, hexane, turpentine oil, petrol and olive oil) co-existing with water. Furthermore, the fibres were realized to be capable of adsorbing organic dyes at oil-water interfaces in both static (slow adsorption) and dynamic (instant adsorption) condition suggesting their multifunctionality in wastewater treatments. A small amount of fibres (0.75 g/L) could efficiently remove water miscible dyes of lthodamine-B and Methylene blue with a maximum removal efficiency of 88% and similar to 91%, respectively. These low-cost natural fibres from biowaste with outstanding oil-water separation and organic dye-adsorption capacity have considerable advantages compared to other low-cost materials reported earlier for industrial wastewater-treatment and environmental remediation.

A novel porous 3D-structured carbon composite material with a unique architecture by combining graphene and carbonized metal-organic framework (C-MOF) (HKUST-1) microrods for high performing supercapacitors has been synthesised and characterised. The HKUST-1 microrods were prepared by a new method, converting their diamond-like shape into microrods via mechanical shear mixing in an aqueous solution. Grinding of HKUST-1 and graphene oxide (GO) resulted in the formation of a 3D GO-MOF composite with intercalated HKUST-1 microrods between GO sheets. The composite film was treated by a laser scribing method and created a highly porous, a high surface area (>600 m²/g) and conductive 3D nanostructured composite film (L-rGO-C-MOF) used as electrodes for supercapacitor applications. The prepared film showed a high capacitance of 390 F/g at 5 mV/s, and a cyclic stability of 97.8% at 10 A/g after 5000 cycles. The symmetrical supercapacitor delivered an excellent power density of 8037.5 W/kg with an outstanding energy density of 22.3 Wh/kg confirming a new pathway to design new 3D porous graphene-MOF composites for high-performance energy storage devices. Refereed/Peer-reviewed

In comparison with inorganic and dry polymeric materials, conductive polymer hydrogels are promising soft electrode materials due to their unique solid-liquid interface. Nevertheless, the existing hydrogels lack either excellent electrochemical performance or mechanical resilience. Here we report a strategy to overcome this limitation by integrating two types of conducting polymers – polyaniline and PEDOT – through a molecular bridge provided by phytic acid. The acid replaces some of PSS, promoting transformation of PEDOT chains from the benzoic structure to the quinoid structure. The resulting hydrogel consists of a 3D network of PEDOT sheets where PANi are inlaid; it has highly improved mechanical properties in comparison with PEDOT hydrogel due to molecular interactions between PANi and PEDOT. A flexible solid-state supercapacitor based on PEDOT/PANi hydrogel delivered a high volumetric energy density of 0.25 mWh cm−3 at a power density of 107.14 mW cm−3, surpassing many of previously reported solid-state supercapacitors based on PEDOT and hydrogels of other conducting polymers and graphene oxide. This study represents a new direction for the development of conductive polymer composite hydrogels which combine excellent electrochemical performance with mechanical resilience Refereed/Peer-reviewed

In this report, we employed surface-initiated atom transfer radical polymerisation to graft thermo-responsive copolymers of oligo(ethylene glycol) methacrylates from the surface of diatom biosilica microcapsules. We demonstrate the application of the resulting composites for thermo-responsive drug delivery Refereed/Peer-reviewed

A practical fabrication technique is presented to tackle the trade-off between the water flux and salt rejection of thin film composite (TFC) reverse osmosis (RO) membranes through controlled creation of a thinner active selective polyamide (PA) layer. The new thin film nano-composite (TFNC) RO membranes were synthesized with multifunctional poly tannic acid-functionalized graphene oxide nanosheets (pTA-f-GO) embedded in its PA thin active layer, which is produced through interfacial polymerization. The incorporation of pTA-f-GOL into the fabricated TFNC membranes resulted in a thinner PA layer with lower roughness and higher hydrophilicity compared to pristine membrane. These properties enhanced both the membrane water flux (improved by 40%) and salt rejection (increased by 8%) of the TFNC membrane. Furthermore, the incorporation of biocidal pTA-f-GO nanosheets into the PA active layer contributed to improving the antibacterial properties by 80%, compared to pristine membrane. The fabrication of the pTA-f-GO nanosheets embedded in the PA layer presented in this study is a very practical, scalable and generic process that can potentially be applied in different types of separation membranes resulting in less energy consumption, increased cost-efficiency and improved performance.

Nanoporous alumina (NPA) arrays prepared by electrochemical anodization have been attractive platform for application in molecular separations, biosensing, drug delivery and fuel cells due to their highly ordered pore structures, controllable pore dimensions and unique physical, optical, transport and electrochemical properties. However, there is still a lack of knowledge about the influence of the pore dimensions, shape and surface area on these properties. Hence the aim of this work is to use a focused ion beam (FIB) to mill a barrier layer of NPA to open a either single nanopore, several nanopores and 1 μm and 20 μm square areas of nanopore arrays to explore their electrochemical properties and biosensing performances. The internal surface of opened NPA nanopores was modified by covalent attachment of streptavidin and used for impedance label-free biosensing. The biosensor performance of this antibody modified nanopore biosensing platform was evaluated using various concentrations of biotin as a model analyte. Electrochemical impedance spectrometric (EIS) measurements of pore resistivity were carried out for different patterns of nanopore arrays. The results showed that small areas or number of pores provide better biosensing performance compared to large nanopore arrays. Refereed/Peer-reviewed

Aim: This study aimed to demonstrate radiofrequency (RF)-triggered release of drugs and drug carriers from drug-eluting implants using gold nanoparticles as energy transducers. Materials & methods: Titanium wire with a titania nanotube layer was used as an implant loaded with indomethacin and micelles (tocopheryl PEG succinate) as a drug and drug carrier model. RF signals were generated from a customized RF generator to trigger in vitro release. Results & discussion: Within 2.5 h, 18 mg (92%) of loaded drug and 14 mg (68%) of loaded drug carriers were released using short RF exposure (5 min), compared with 5 mg (31%) of drug and 2 mg (11%) of drug carriers without a RF trigger. Gold nanoparticles can effectively function as RF energy transducers inside titania nanotubes for rapid release of therapeutics at arbitrary times. Conclusion: The results of this study show that RF is a promising strategy for triggered release from implantable drug delivery systems where on-demand delivery of therapeutics is required. Original submitted 19 November 2012; Revised submitted 1 April 2013

Anodic aluminium oxide (AAO) has been investigated and utilized in numerous products for almost a century. But the rapidly increasing interest in nanoscale materials and their outstanding properties has propelled nanoporous AAO to the fore as one of the most popular nanomaterial with applications across a gamut of areas including molecular separation, catalysis, energy generation and storage, electronics and photonics, sensors and biosensors, drug delivery and template synthesis. Material fabrication of AAO is based on facile and inexpensive electrochemical anodization with the self-ordering process of nanopores not requiring any lithography or templating, and the outcome of the process are perfectly ordered and size controlled nanopores with distinctive pore geometries. Recent research on AAO is characterized by a remarkable trajectory of innovation, in particular with regards to control of surface functionality and, concomitantly, to the design of intricate structural features such as modulated, branched, and multilayered pore architectures. This review illuminates research on recent development of AAO focussing on surface and structural engineering, and on emerging applications. Key examples and critical preparative issues and resulting improvements sparking opportunities for further applications in AAO properties are discussed. We conclude this review with an outlook providing a critical perspective on future trends on surface and structural engineering of AAO. Refereed/Peer-reviewed

This work presents the fabrication of gold nanotube membranes (GNT) using gold deposition on porous anodic aluminum oxide (AAO) template and demonstrates the catalytic properties generated by the nanostructured gold surface. AAO membranes were prepared by electrochemical anodization of Al in 0.3 M oxalic acid electrolyte. Electroless gold deposition on AAO was performed via several steps using commercially available gold plating solutions. Scanning electron microscopy (SEM) images confirm that the gold nanotubes formed inside AAO pores have characteristic nanoclustered morphology as a result of the nucleation process during gold deposition. It was found that catalytic properties of GNT membranes depend on the size of gold nanoclusters which can be controlled by pH during nucleation process. The excellent catalytic properties (catalytic rate constant k = 0.132 min−1) of the GNT membranes were demonstrated by testing catalytic conversion of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of NaBH4 as a reductant. The correlation between the size of gold nanoclusters and catalytic activity was verified showing the capability of controlling and further improving catalytic properties of GNT membranes. Refereed/Peer-reviewed

Naturally available and biocompatible materials are potential substitutes for synthetic mesoporous materials as suitable drug carriers for the development of cost-effective drug delivery systems. This work investigates the application of a porous silica material derived from diatoms, also known as diatomaceous earth. The aim is to explore the surface functionalization of diatom microcapsules and their impact on the drug loading and release characteristics of water-insoluble drugs. Indomethacin was used as the model for poorly soluble drug. The surface modification on diatoms was performed with two organosilanes; 3-aminopropyltriethoxy silane and N-(3-(trimethoxysilyl) propyl) ethylene diamine and phosphonic acids (2-carboxyethyl-phosphonic acid and 16-phosphono-hexadecanoic acid) providing organic surface hydrophilic and hydrophobic properties. Extensive characterizations using scanning electron microscopy, X-ray photoelectron spectroscopy and differential scanning calorimetry was performed to confirm covalent grafting of monolayer aminosilane and phosphonic acid on the diatom surfaces. Differences in loading capacity of diatoms (15–24%) and release time (6–15 days) were observed which is due to the presence of different functional groups on the surface. It was found that 2-carboxyethyl-phosphonic acid, 3-aminopropyltriethoxy silane and N-(3-(trimethoxysilyl) propyl) ethylene diamine render diatom surfaces hydrophilic, due to polar carboxyl functional group (COOH) and active amine species (NH and NH2) that favor drug adsorption; better encapsulation efficiency and prolonged release of drugs, over the hydrophobic surface created by 16-phosphono-hexadecanoic acid. This work demonstrates diatom porous silica as a promising drug carrier, with possibility to further improve their performances by tailoring their surface functionalities to achieve the required drug loading and release characteristics for different therapeutic conditions.

Bacterial infection, extensive inflammation and poor osseointegration have been identified as the major reasons for [early] orthopaedic implant failures based on titanium. Creating implants with drug-eluting properties to locally deliver drugs is an appealing way to address some of these problems. To improve properties of titanium for orthopaedic applications, this study explored the modification of titanium surfaces with titaniananotube (TNT) arrays, and approach that combines drug delivery into bone and potentially improved bone integration. A titania layer with an array of nanotube structures (∼120 nm in diameter and 50 μm in length) was synthesized on titanium surfaces by electrochemical anodization and loaded with the water-insoluble anti-inflammatory drug indomethacin. A simple dip-coating process of polymer modification formed thin biocompatible polymer films over the drug-loaded TNTs to create TNTs with predictable drug release characteristics. Two biodegradable and antibacterial polymers, chitosan and poly(lactic-co-glycolic acid), were tested for their ability to extend the drug release time of TNTs and produce favourable bone cell adhesion properties. Dependent on polymer thickness, a significant improvement in the drug release characteristics was demonstrated, with reduced burst release (from 77% to >20%) and extended overall release from 4 days to more than 30 days. Excellent osteoblast adhesion and cell proliferation on polymer-coated TNTs compared with uncoated TNTs were also observed. These results suggest that polymer-modified implants with a TNT layer are capable of delivering a drug to a bone site over an extended period and with predictable kinetics. In addition, favourable bone cell adhesion suggests that such an implant would have good biocompatibility. The described approach is broadly applicable to a wide range of drugs and implants currently used in orthopaedic practice. Refereed/Peer-reviewed

Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions. Refereed/Peer-reviewed

The unique morphologies and properties of the diatom silica shell with its intricate, hierarchically organized three dimensional (3-D) structures with nanoscale dimensions have attracted considerable interest in materials science and nanotechnology in recent years. This review highlights recent emerging applications from diatom nanotechnology research with particular emphasis on applications based on the integration of micro and nanostructures including sensing/biosensing, drug delivery and chemical-free pest control. © 2011 Bentham Science Publishers.

Aim: This study explores the use of natural silica-based porous material from diatoms, known as diatomaceous earth, as a drug carrier of therapeutics for implant- and oral-delivery applications. Materials & Methods: To prove this concept, two drugs models were used and investigated: a hydrophobic (indomethacin) and hydrophilic (gentamicin). Results & Discussion: Results show the effectiveness of diatom microcapsules for drug-delivery application, showing 14–22 wt% drug loading capacity and sustained drug release over 2 weeks. Two steps in the drug release from diatom structures were observed: the first, rapid release (over 6 h is attributed to the surface deposited drug) and the second, slow and sustained release over 2 weeks with zero order kinetics. Conclusion: These results confirm that natural material based on diatom silica can be successfully applied as a drug carrier for both oral and implant drug-delivery applications, offering considerable potential to replace existing synthetic nanomaterials.

In this review article we collect and analyse preparation, chemistry and properties of silica materials relevant for drug delivery applications. We review some of the most relevant milestones in the research of silica materials for implantable, oral, intravenous and dermal drug delivery systems. Preparation, chemistry and drug delivery characteristics of fumed silica nanoparticles (oral and dermal delivery route), silica xerogels (implant delivery), mesoporous silica materials (implant and oral delivery) and mesoporous silica spheres (intravenous delivery) with particular emphasis on their role in anticancer therapy and the design of stimuli responsive drug delivery systems are analysed. Recent progress in the research of silica materials for controlled drug delivery, namely, biocompatibility aspects, research on hybrid materials, anticancer and stimuli-responsive mesoporous silica materials are particularly emphasized. Refereed/Peer-reviewed

Transition metal hexacyanoferrate (MeHCF) have attracted extensive attention because of their outstanding properties including, electrocatalysis, molecular magnetism, biosensing and ion-exchange. This paper describes an approach for fabrication of ordered nanoarrays of Ni hexacyanoferrate (NiHCF) structures with different morphologies such as dots, rods and tubes in order to advance their properties and applications. The method is based on the conversion of Ni into NiHCF nanostructures by electrochemical oxidation in the presence of hexacyanoferrate ions, using nanoporous anodic alumina oxide (AAO) as a template. The structure and morphology of formed Ni and NiHCF nanoarrays were confirmed by scanning electron microscopy (SEM), showing agreement with the pore structures of the AAO template. The electrocatalytic activity of NiHCF nanorod array electrodes showed high catalytic properties for the detection of hydrogen peroxide and the potential to be used as a platform for direct biosensing applications. The ion-exchange ability of fabricated NiHCF nanostructures (nanorods and nanotubes) toward alkali cations such as Na + has been successfully confirmed.

The application of nanotechnology to medicine termed as 'nanomedicine' is recognised as an emerging field with enormous potential for developing new therapeutic concepts. A range of nanoscale materials have been explored in the last few years for drug delivery to address the problems associated with conventional drug therapies such as limited drug solubility, poor biodistribution, lack of selectivity and unfavourable pharmacokinetics. Among them, nanoporous materials with ordered and controlled pore structures, high surface area and pore volume, attracted great attention, particularly for implantable drug delivery systems. This review presents the recent progress in this field focused on electrochemically engineered nanopores/nanotube materials such as nanoporous alumina and nanotubular titania. The basic concept of fabrication of these unique materials using a self-ordering process, description of their structural properties, biocompatibility and recent applications for therapeutic implants is presented.

Diatoms occupy sunlit aquatic environments. From a materialsscientist’s point of view, these unicellular algae are microscopicsilica nanofabrication factories that use two overlapping valvessealed together by girdle bands to encase themselves in a silicafrustule. The frustule is created with 3D precision of tens ofnanometers, in a hierarchical manner, and with multifunctionalproperties (Fig. 1).

The fabrication of three-dimensional (3D) architectures withnanoscale dimensions is still an evolving research area ofnanotechnology. Various methodologies including conven-tional and unconventional fabrications, such as photolitho-graphy, scanning beam lithography, molding, embossing, andimprinting, have been developed in the past decade.

Here, we report on the development of advanced biopolymer-coated drug-releasing implants based on titanium (Ti) featuring titania nanotubes (TNTs) on its surface. These TNT arrays were fabricated on the Ti surface by electrochemical anodization, followed by the loading and release of a model antibiotic drug, gentamicin. The osteoblastic adhesion and antibacterial properties of these TNT–Ti samples are significantly improved by loading antibacterial payloads inside the nanotubes and modifying their surface with two biopolymer coatings (PLGA and chitosan). The improved osteoblast adhesion and antibacterial properties of these drug-releasing TNT–Ti samples are confirmed by the adhesion and proliferation studies of osteoblasts and model Gram-positive bacteria (Staphylococcus epidermidis). The adhesion of these cells on TNT–Ti samples is monitored by fluorescence and scanning electron microscopies. Results reveal the ability of these biopolymer-coated drug-releasing TNT–Ti substrates to promote osteoblast adhesion and proliferation, while effectively preventing bacterial colonization by impeding their proliferation and biofilm formation. The proposed approach could overcome inherent problems associated with bacterial infections on Ti-based implants, simultaneously enabling the development of orthopedic implants with enhanced and synergistic antibacterial functionalities and bone cell promotion.

A simple procedure for fabrication of gold films with nanorod arrays is described. The method is based on thermal evaporation of gold onto a porous alumina (PA) membrane used as a template. The gold films were obtained after removing the template and characterized using scanning electron microscopy, atomic force microscopy and ultraviolet-visible spectrophotometry. The prepared gold films are composed of arrays of sharp (

A new method mapping the defects in self-assembled monolayers (SAMs) is described. The method is based on electrochemical polymerisation of nonconductive tyramine in defect sites of a monolayer and subsequent visualisation of the polymer structures by atomic force microscopy (AFM). SAMs of hexadecanthiol (HDT) on gold prepared by deposition from solution and microcontact printing were used as a model for this study. The method allows easy mapping of defects on monolayers and provides information about their shape, size, size distribution, defect density and spatial distribution. Comparative electrochemical characterisation of defects in SAMs before and after polymerisation shows that polymer growth occurs on the sites of uncovered gold. The approach should be applicable for the characterisation of defects in other types of ultra-thin organic films on conducting surfaces.

Alzheimer's disease (AD) is caused by the accumulation of β-amyloid protein (Aβ) in the brain. The aggregation of β-amyloid protein to higher molecular weight fibrillar forms is also considered to be an important step in the pathogenesis of the disease. the memory problems associated with AD are likely to be caused by changes in synaptic plasticity. Recent studies suggest that Aβ binds to the α7 nicotinic acetylcholine receptor (α7 nAChR), which plays an important role in synaptic plasticity and memory. A loop domain localized towards the C-terminus of the extracellular region of the receptor has been identified as forming part of a putative Aβ-binding site. In cell culture experiments, the binding of Aβ to the α7 nAChR has been found to cause an increase in the level of acetylcholinesterase, which is also increased around amyloid plaques in the AD brain. These studies indicate that the Aβ-binding site on the α7 nAChR receptor is an important new target for therapeutic development in AD.

The reversible cyclic voltammetry of pea plastocyanin ( Pisum sativum ) was studied with a wide range of electrodes: edge-oriented pyrolytic graphite (PGE), glassy carbon (GCE), gold (Au) and platinum (Pt) electrodes. Plastocyanin was coated onto the electrode surface by exploiting the electrostatic interaction between the negatively charged protein and a wide range of positively charged promoters. The effect of the redox response with an extended range of promoters, including poly- l -lysine, polymyxin B, neomycin, tobramycin, geneticin, spermine and spermidine, were included in this study. The resulting cyclic voltammograms reveal that the observed midpoint potential for plastocyanin can be shifted significantly depending on the choice of promoter. The stability of the negatively charged plastocyanin–promoter layer on an electrode was gauged by the rate of bulk diffusion of the protein from the immobilised film into the solution. Reversible cyclic voltammograms were obtained using edge-oriented pyrolytic graphite (PGE) and glassy carbon electrodes (GCE) with all promoters; however, platinum and gold electrodes were unable to sustain a defined redox response. The combination of pyrolytic graphite electrode/poly- l -lysine/plastocyanin was found to be the most stable combination, with a redox response which remained well defined in solution for more than 1 h at pH 7.0. The midpoint potentials obtained in this manner differed between the two graphite electrodes PGE and GCE using poly- l -lysine as the promoter. This effect was in addition to the expected pH dependence of the midpoint potential for plastocyanin and the results indicated that the p K a for plastocyanin on PGE was 4.94 compared to that on GCE of 4.66. It is concluded that both the electrode material and the nature of the promoter can influence the position of the redox potentials for proteins measured in vitro. This study extends the range of biogenic promoters used in combination with electrode materials. Thus, we can begin to develop a more comprehensive understanding of electrode–protein interactions and draw conclusions as to metalloprotein function, in vivo. To support these studies, we have sought information as to the nature of the electrode/promoter/protein interaction using scanning tunneling microscopy (STM) to study both the promoter and the plastocyanin protein on a gold surface.

Three immobilization methods have been used for scanning tunneling microscopy (STM) studies of glucose oxidase (GOD) on gold. They are based on (a) physical adsorption from solution, (b) microcontact printing, and (c) covalent bonding onto self-assembled monolayers (SAMs) of 3-mercaptopropionic acid (MPA). The STM images are used to provide information about the organization of individual GOD molecules and more densely packed monolayers of GOD on electrode surfaces, thus providing information on the role of interfacial structure on biosensor performance. The use of atomically flat gold substrates enables easy distinction of deposited enzyme features from the flat gold substrate. Microcontact printing is found to be a more reliable method than adsorption from solution for preparing individual GOD molecules on the gold surface. STM images of printed samples reveal two different shapes of native GOD molecules. One is a butterfly shape with dimensions of 10 ± 1 nm × 6 ± 1 nm, assigned to the lying position of...

In the quest for solutions to meeting future energy demands, solar fuels play an important role. A particularly promising example is photocatalysis since even incremental improvements in performance in this process are bound to translate into significant cost benefits. Here, we report that semiconducting and high surface area 3D silicon replicas prepared from abundantly available diatom fossils sustain photocurrents and enable solar energy conversion. Refereed/Peer-reviewed

The understanding of the electrochemical properties of nanopores is the key factor for better understanding their performance and applications for nanopore-based sensing devices. In this study, the influence of pore dimensions of nanoporous alumina (NPA) membranes prepared by an anodization process and their electrochemical properties as a sensing platform using impedance spectroscopy was explored. NPA with four different pore diameters (25 nm, 45 nm and 65 nm) and lengths (5 μm to 20 μm) was used and their electrochemical properties were explored using different concentration of electrolyte solution (NaCl) ranging from 1 to 100 μM. Our results show that the impedance and resistance of nanopores are influenced by the concentration and ion species of electrolytes, while the capacitance is independent of them. It was found that nanopore diameters also have a significant influence on impedance due to changes in the thickness of the double layer inside the pores. Refereed/Peer-reviewed

We report the application of diatom as a solid carrier for water insoluble drugs applied in oral drug delivery system based on the self-emulsifying drug delivery system (SEDDS) caprylocaproyl macrogol-8 glycerides/lecithin/propylene glycol/caprylic/capric triglyceride. Diatoms are fossilized skeletons of photosynthetic algae with complex 3-dimensional (3D), porous structure consisting of amorphous silica, obtained by purification of diatomaceous earth. Different solid samples of carbamazepine (CBZ) suspension in SEDDS, called solid self-emulsifying phospholipid suspension (SSEPS), were prepared using two methods: adsorption of CBZ dispersion in SEDDS by gentle mixing with diatoms in mortar with pestle (Method A) or dispersion of diatoms in ethanol solution of CBZ and SEDDS components, followed by ethanol evaporation (Method B). Release rate of CBZ from SSEPS was significantly higher in comparison to pure drug, physical mixture of diatoms and CBZ as well as solid dispersion of pure CBZ and diatoms obtained by ethanol evaporation. The dissolution of CBZ from SSEPS sample prepared using method B was faster than from the sample prepared by the method A. Higher dissolution for sample prepared by the method B can be attributed to the partial adsorption (deeper localization) of liquid material inside the pores of diatoms. Upon storage of the samples under accelerated conditions (40 °C and 70% RH) for 10 weeks no significant changes in CBZ crystallinity and dissolution was in case of SSEPS, contrary to solid dispersion with increased crystallinity, indicating that diatoms with adsorbed liquid CBZ-loaded SEPS can maintain initial CBZ characteristics. Refereed/Peer-reviewed

The influence of the topography of the underlying gold surface on the integrity of self-assembled monolayers (SAMs) of hexadecanethiol (HDT) prepared by solution assembly and microcontact printing was assessed using six different gold substrates. The bare substrates were evaluated for roughness and defects using scanning tunneling microscopy (STM). The structural integrity of self-assembled monolayers on these substrates has been evaluated using both surface methods (STM) and electrochemical measurements. Perhaps not surprisingly, the flattest substrates seem to produce the highest quality monolayer. It is surprising to note, however, that the layer quality is not necessarily traceable to a variation in coverage. Despite both the solution-formed and printed SAMs appearing similar in STM images, electrochemical assessment of the SAM integrity indicated the printed SAMs were inferior, forming a less effective passivating barrier with many more pinholes. The quality of printed SAMs could be improved consider...

The fabrication of enzyme electrodes using self-assembled monolayers (SAMs) has attracted considerable interest because of the spatial control over the enzyme immobilization. A model system of glucose oxidase covalently bound to a gold electrode modified with a SAM of 3-mercaptopropionic acid was investigated with regard to the effect of fabrication variables such as the surface topography of the underlying gold electrode, the conditions during covalent attachment of the enzyme and the buffer used. The resultant monolayer enzyme electrodes have excellent sensitivity and dynamic range which can easily be adjusted by controlling the amount of enzyme immobilized. The major drawback of such electrodes is the response which is limited by the kinetics of the enzyme rather than mass transport of substrates. Approaches to bringing such enzyme electrodes into the mass transport limiting regime by exploiting direct electron transfer between the enzyme and the electrode are outlined.

Background Diatoms are important single-celled autotrophs that dominate most lit aquatic environments and are distinguished by surficial frustules with intricate designs of unknown function. Principal Findings We show that some frustule designs constrain diffusion to positively alter nutrient uptake. In nutrient gradients of 4 to 160 times over, J.G.M., L.S., N.H.V., J.S. and D.L. were supported by the Australian Research Council (ARC) and Flinders University. J.G.M. and L.S. were supported by the Australian Antarctic Division. R.L. was supported by the ARC and the US National Institutes of Health.

Karan Gulati1,2, Moom Sinn Aw1, Dusan Losic1,21Ian Wark Research Institute, The University of South Australia, Adelaide, SA, Australia; 2School of Chemical Engineering, The University of Adelaide, Adelaide, SA, AustraliaAbstract: The blood–brain barrier (BBB) blocks the passage of active molecules from the blood which makes drug delivery to the brain a challenging problem. Oral drug delivery using chemically modified drugs to enhance their transport properties or remove the blocking of drug transport across the BBB is explored as a common approach to address these problems, but with limited success. Local delivery of drugs directly to the brain interstitium using implants such as polymeric wafers, gels, and catheters has been recognized as a promising alternative particularly for the treatment of brain cancer (glioma) and neurodegenerative disorders. The aim of this study was to introduce a new solution by engineering a drug-releasing implant for local drug delivery in the brain, based on titanium (Ti) wires with titania nanotube (TNT) arrays on their surfaces. Drug loading and drug release characteristics of this system were explored using two drugs commonly used in oral brain therapy: dopamine (DOPA), a neurotransmitter agent; and doxorubicin (DOXO), an anticancer drug. Results showed that TNT/Ti wires could provide a considerable amount of drugs (>170 µg to 1000 µg) with desirable release kinetics and controllable release time (1 to several weeks) and proved their feasibility for use as drug-releasing implants for local drug delivery in the brain.Purpose: In this report, a new drug-releasing platform in the form of nanoengineered Ti wires with TNT arrays is proposed as an alternative for local delivery of chemotherapeutics in the brain to bypass the BBB. To prove this concept, drug loading and release characteristics of two drugs important for brain therapy (the neurotransmitter DOPA and the anticancer drug DOXO) were explored.Methods: Titania nanotube arrays on the surface of Ti wires (TNT/Ti) were fabricated using a simple anodization process, followed by separate loading of two drugs (DOPA and DOXO) inside the nanotube structures. The loading and in vitro release characteristics of prepared TNT/Ti implants were examined using thermogravimetric analysis (TGA) UV-Vis spectroscopy.Results: Scanning electron microscopy studies confirmed that well-ordered, vertically aligned, densely packed nanotube arrays with an average diameter of 170 nm and length 70 µm were formed on the surface of TNT/Ti wires. TGA results showed a total drug loading of 170 µg and 1200 µg inside the TNTs for DOPA and DOXO respectively. Two-phase drug release behavior was observed including a fast release (burst) for the first 6 hours and a prolonged slow release phase for 8 days, both with acceptable dosage and desirable release kinetics. The physical, structural, loading and release characteristics of prepared TNT/Ti implants showed several advantages in comparison with existing and clinically proved brain implants.Conclusion: Our results confirmed that TNT/Ti wires can be successfully employed as a suitable platform to release neurotransmitters such as DOPA and anticancer drugs such as DOXO. Hence, they are a feasible alternative as drug-releasing implants for local drug delivery in the brain to combat neurodegenerative disorders or brain tumors.Keywords: titania nanotubes, brain implants, local drug delivery, dopamine, doxorubicinA Letter to the Editor has been received and published for this article.

A multi-drug delivery system with sequential release based on titania nanotube arrays and polymer micelles as drug carriers is presented. Delivery of multiple water insoluble and soluble drugs required for combined local therapy is demonstrated. Refereed/Peer-reviewed

In this report, a label-free reflectometric interference spectroscopy (RIfS) based microchip biosensor for the detection of circulating tumour cells (CTCs) is demonstrated. Highly ordered nanoporous anodic aluminium oxide (AAO) fabricated by electrochemical anodization of aluminium foil was used as the RIfS sensing platform. Biotinylated anti-EpCAM antibody that specifically binds to human cancer cells of epithelial origin such as pancreatic cancer cells (PANC-1) was covalently attached to the AAO surface through multiple surface functionalization steps. Whole blood or phosphate buffer saline spiked with low numbers of pancreatic cancer cells were successfully detected by specially designed microfluidic device incorporating an AAO RIfS sensor, without labour intensive fluorescence labelling and/or pre-enhancement process. Our results show that the developed device is capable of selectively detecting of cancer cells, within a concentrations range of 1000–100,000 cells/mL, with a detection limit of fewer than 1000 cells/mL, a response time of fewer than 5 min and sample volume of 50 μL of. The presented RIfS method shows considerable promise for translation to a rapid and cost-effective point-of-care diagnostic device for the detection of CTCs in patients with metastatic cancer. Refereed/Peer-reviewed

This work presents the use of nanoporous anodic aluminium oxide [AAO] for reflective interferometric sensing of volatile sulphur compounds and hydrogen sulphide [H2S] gas. Detection is based on changes of the interference signal from AAO porous layer as a result of specific adsorption of gas molecules with sulphur functional groups on a gold-coated surface. A nanoporous AAO sensing platform with optimised pore diameters (30 nm) and length (4 µm) was fabricated using a two-step anodization process in 0.3 M oxalic, followed by coating with a thin gold film (8 nm). The AAO is assembled in a specially designed microfluidic chip supported with a miniature fibre optic system that is able to measure changes of reflective interference signal (Fabry-Perrot fringes). When the sensor is exposed to a small concentration of H2S gas, the interference signal showed a concentration-dependent wavelength shifting of the Fabry-Perot interference fringe spectrum, as a result of the adsorption of H2S molecules on the Au surface and changes in the refractive index of the AAO. A practical biomedical application of reflectometric interference spectroscopy [RIfS] Au-AAO sensor for malodour measurement was successfully shown. The RIfS method based on a nanoporous AAO platform is simple, easy to miniaturise, inexpensive and has great potential for development of gas sensing devices for a range of medical and environmental applications.

Bacterial infections present an enormous problem causing human suffering and cost burdens to the healthcare systems worldwide. Herein we present several versatile strategies for controlled release of antibacterial agents which include silver ions as well as traditional antibiotics. At the heart of these release platforms is a thin film deposited by plasma polymerization. The use of plasma polymerization makes these strategies applicable to the surface of many types of medical devices since the technique for deposition of a polymer film from plasma in practically substrate independent. Refereed/Peer-reviewed

Enhanced control over the surface properties of porous materials is of great interest owing to applications as diverse as the detection of chemical and biological species, molecular separation, drug delivery, and catalysis. Recent research has made inroads into this issue, devising experimental strategies towards surface manipulation in porous materials. However, the increasingly stringent device requirements for advanced applications, such as energy storage, controlled release, biochemical gates, nanoreactors, sorption, and high-performance molecular transport and separation, demand the development of multiphasic, responsive, and multifunctional materials. Self-organized nanoporous anodic aluminum oxide (AAO) membranes prepared by electrochemical anodization have become popular materials, attractive for their high surface area (up to 250 mg ), high porosity (10 porescm ), highly ordered and monodisperse pores, tunable thickness and pore dimensions, excellent chemical, thermal, and mechanical stability, biocompatibility, and inexpensive fabrication. A considerable number of studies have been devoted to the development of AAO membranes with complex pore geometries in order to improve the membrane properties for applications in molecular separation and to enable the template synthesis of sophisticated nanostructures with novel architectures and unique optical, magnetic, energy-storage, and electrical properties. Membranes with branched, multilayered, and modulated pore structures have been generated by precise and temporal control over the anodization conditions. In contrast, control at a similar level of complexity over the surface inside the pores of AAOmembrane is currently lacking, despite the fact that the functionality on the pore surface is a key determinant for device performance. In particular, the selectivity and efficiency of molecular transport and separation through AAO membranes are not only effectively modulated by changing the size, but also by the charge and polarity of the porous layer and the engineered affinity towards the species of interest. Several surface-modification techniques have been applied to AAO membranes including silanization, formation of self-assembled monolayers, grafting of polymer brushes, plasma processing, sol–gel modification, metal deposition (chemical vapor deposition, electroless and pulse electrochemical plating), and quantumdot adsorption. However, multifunctional and multilayered surface modification has not been demonstrated until our recent work in which we fabricated AAO membranes with distinctly different internal and external surface functionalities. This study provided a glimpse of the opportunities for controlling the surface properties in porous materials but stopped short of demonstrating truly multilayered surface modifications, tunability, and functional properties. Here, we describe AAO membranes having pores with spatially controlled multilayered surface functionalities, selected self-assembly of gold nanoparticles on amino-functionalized layers, and selective membrane transport. Membranes with layered surface functionalities inside the pore channel were prepared by a series of anodization and silanization cycles with pentafluorophenyldimethylpropylchlorosilane (PFPTES), 3-aminopropyltriethoxysilane (APTES), and N-triethoxysilylpropyl-O-polyethyleneoxide urethane (PEGS), respectively, achieving a range of functionalities and wettabilities. The fabrication approach is shown schematically in Scheme 1. Typically, at least three anodization steps were used. The first anodization was carried out on electropolished aluminum foil for 3 h using a constant voltage of 40 V at a temperature of 1 8C in 0.3m aqueous oxalic acid (C2H2O4). Afterwards, the sacrificial layer was removed by treatment with phosphoric acid/chromium trioxide solution to generate a textured concave pattern on the Al surface, which acted as a template for the subsequent pore formation during the second anodization. Upon completion of this step, the generated porous layer was treated with the first silane. The following third anodization was then performed to generate a virgin porous layer below the first silanized porous layer. We found that silanized surfaces were chemically inert and mechanically stable under anodization conditions. The newly generated pore surfaces were then [*] A. M. M. Jani, Prof. Dr. N. H. Voelcker School of Chemical and Physical Sciences Flinders University Bedford Park 5042 SA (Australia) Fax: (+61)8-8201-2905 E-mail: nico.voelcker@flinders.edu.au Homepage: http://www.voelckerlab.com

Diatom silica microcapsules prepared by purification of diatomaceous earth (DE) were functionalised by dopamine modified iron-oxide nanoparticles, in order to introduce diatoms with magnetic properties. The application of magnetised diatomsas magnetically guided drug delivery microcarriers has been demonstrated. Refereed/Peer-reviewed

Atomic layer deposition (ALD) of SiO 2 onto nanoporous alumina (PA) membranes was investigated with the aim of adjusting the pore size and transport properties. PA membranes from commercial sources with a range of pore diameters (20 nm, 100 nm and 200 nm) were used and modified by atomic layer deposition using tris(tert-butoxy)silanol and water as the precursor couple. By adjusting the number of deposition cycles, the thickness of the conformal silica coating was controlled, reducing the effective pore diameter, and subsequently changing the transport properties of the PA membrane. Silica coated PA membranes with desired pore diameters from

Diatoms are unicellular, eukaryotic, photosynthetic algae that are found in aquatic environments. Diatoms have enormous ecological importance on this planet and display a diversity of patterns and structures at the nano- to millimetre scale. Diatom nanotechnology, a new interdisciplinary area, has spawned collaborations in biology, biochemistry, biotechnology, physics, chemistry, material science and engineering. We survey diatom nanotechnology since 2005, emphasizing recent advances in diatom biomineralization, biophotonics, photoluminescence, microfluidics, compustat domestication, multiscale porosity, silica sequestering of proteins, detection of trace gases, controlled drug delivery and computer design. Diatoms might become the first organisms for which the gap in our knowledge of the relationship between genotype and phenotype is closed.

An electroless gold deposition method was used to fabricate gold nanotubes within the pores of polycarbonate and porous alumina template membranes. This approach provides control over the pore size of the membrane, with pore sizes being reduced to molecular dimensions. The effect of the pore size and surface chemistry on the transport properties of gold nanotube membranes has been explored. By modifying the membrane with a highly hydrophobic thiol, the separation of hydrophobic and hydrophilic molecules was achieved. Refereed/Peer-reviewed

The remarkable electrocatalytic properties and small size of carbon nanotubes make them ideal for achieving direct electron transfer to proteins, important in understanding their redox properties and in the development of biosensors. Here, we report shortened SWNTs can be aligned normal to an electrode by self-assembly and act as molecular wires to allow electrical communication between the underlying electrode and redox proteins covalently attached to the ends of the SWNTs, in this case, microperoxidase MP-11. The efficiency of the electron transfer through the SWNTs is demonstrated by electrodes modified with tubes cut to different lengths having the same electron-transfer rate constant.

Diatom silica microparticles were chemically modified with self-assembled monolayers of 3-mercaptopropyl-trimethoxysilane (MPTMS), 3-aminopropyl-trimethoxysilane (APTES) and n-(2-aminoethyl)-3-aminopropyl-trimethoxysilane (AEAPTMS), and their application for the adsorption of mercury ions (Hg(II)) is demonstrated. Fourier transform infrared spectroscopy and x-ray photoelectron spectroscopy analyses revealed that the functional groups (-SH or -NH2) were successfully grafted onto the diatom silica surface. The kinetics and efficiency of Hg(II) adsorption were markedly improved by the chemical functionalization of diatom microparticles. The relationship among the type of functional groups, pH and adsorption efficiency of mercury ions was established. The Hg(II) adsorption reached equilibrium within 60 min with maximum adsorption capacities of 185.2, 131.7 and 169.5 mg g−1 for particles functionalized with MPTMS, APTES and AEAPTMS, respectively. The adsorption behavior followed a pseudo-second-order reaction model and Langmuirian isotherm. These results show that mercapto- or amino-functionalized diatom microparticles are promising natural, cost-effective and environmentally benign adsorbents suitable for the removal of mercury ions from aqueous solutions. Refereed/Peer-reviewed

Nanoporous alumina (PA) arrays produced by self-ordering growth, using electrochemical anodization, have been extensively explored for potential applications based upon the unique thermal, mechanical and structural properties, and high surface-to-volume ratio of these materials. However, the potential applications and functionality of these materials may be further extended by molecular-level engineering of the surface of the pore rims. In this paper we present a method for the generation of chemical gradients on the surface of PA arrays based upon plasma co-polymerization of two monomers. We further extend these chemical gradients, which are also gradients of surface charge, to those of bound ligands and number density gradients of nanoparticles. The latter represent a highly exotic new class of materials, comprising aligned PA, capped by gold nanoparticles around the rim of the pores. Gradients of chemistry, ligands and nanoparticles generated by our method retain the porous structure of the substrate, which is important in applications that take advantage of the inherent properties of these materials. This method can be readily extended to other porous materials. Refereed/Peer-reviewed