Nanoporous titania-coated alumina membranes: sol-gel synthesis and characterisation

In this work, nanoporous titania top layers were deposited by dip-coating process on microporous alpha-alumina substrates using the sol-gel process. The alumina substrates were synthesized by slip casting method using Taguchi optimising approach. The microporous substrate was then used to coat nanoporous titania layers by the sol-gel method. The thickness, pore size, structure and permeability of the membranes were characterised using SEM, XRD, STA and Hg-Porosimetry. The process conditions to achieve defect-free nanoporous titania layers with the average pore size of about 4 nm coated on the microporous alumina substrates with the average pore size of about 270 nm were determined.     

Influence of nanoporesize on platelet adhesion and activation

In this study we have evaluated the influence of biomaterial nano-topography on platelet adhesion and activation. Nano-porous alumina membranes with pore diameters of 20 and 200 nm were incubated with whole blood and platelet rich plasma. Platelet number, adhesion and activation were determined by using a coulter hematology analyzer, scanning electron microscopy, immunocytochemical staining in combination with light microscopy and by enzyme immunoassay. Special attention was paid to cell morphology, microparticle generation, P-selectin expression and beta-TG production. Very few platelets were found on the 200 nm alumina as compared to the 20 nm membrane. The platelets found on the 20 nm membrane showed signs of activation such as spread morphology and protruding filipodia as well as P-selectin expression. However no microparticles were detected on this surface. Despite the fact that very few platelets were found on the 200 nm alumina in contrast to the 20 nm membrane many microparticles were detected on this surface. Interestingly, all microparticles were found inside circular shaped areas of approximately 3 mum in diameter. Since this is the approximate size of a platelet we speculate that this is evidence of transient, non-adherent platelet contact with the surface, which has triggered platelet microparticle generation. To the authors knowledge, this is the first study that demonstrates how nanotexture can influence platelet microparticle generation. The study highlights the importance of understanding molecular and cellular events on nano-level when designing new biomaterials.     

Fabrication of gold nanodot arrays on a transparent substrate as a nanobioplatform for label-free visualization of living cells

Two-dimensional gold (Au) nanodot arrays on a transparent substrate were fabricated for imaging of living cells. A nanoporous alumina mask with large-area coverage capability was prepared by a two-step chemical wet etching process after a second anodization. Highly ordered Au nanodot arrays were formed on indium-tin-oxide (ITO) glass using very thin nanoporous alumina of approximately 200 nm thickness as an evaporation mask. The large-area Au nanodot arrays on ITO glass were modified with RGD peptide (arginine; glycine; aspartic acid) containing a cysteine (Cys) residue and then used to immobilize human cancer HeLa cells, the morphology of which was observed by confocal microscopy. The confocal micrographs of living HeLa cells on Au nanodot arrays revealed enhanced contrast and resolution, which enabled discernment of cytoplasmic organelles more clearly. These results suggest that two-dimensional Au nanodot arrays modified with RGD peptide on ITO glass have potential as a biocompatible nanobioplatform for the label-free visualization and adhesion of living cells.     

Structure-dependent adhesion and friction on highly ordered metallic nanopore membranes

Highly ordered metallic nanopore membranes are fabricated by direct deposition of nickel on typical porous anodic alumina (PAA) templates. The large-area uniform nanopore arrays of the PAA templates are accurately transferred to the metallic nanopore replicas, depending on the thickness of the deposited metal and the pore size of the base template. We demonstrate the ready tunability of the pore size and reproducibility of the metallic nanopore structure in a wide range of pore sizes. The adhesion and friction characteristics of the metallic replicas are studied according to the pore size using atomic force microscopy (AFM). As the pore diameter increases, the friction coefficients increase nonlinearly, and the adhesive forces scarcely change. These characteristics are understood in terms of the structural properties of the replicas, specifically the surface morphology and the real contact area. Initial pore formation from a flat thin film reduces the adhesive force by up to four times.     

Investigation of transmission of 1.7-MeV He+ beams through porous alumina membranes

The process of charged particles transmission through nanoporous alumina membranes with a pore diameter of about 20 nm was studied. A guiding effect was observed for particles passing through dielectric nanocapillaries, which is also typical of glass microcapillaries. The maximum transmission factor measured was 0.625. It was shown in an experiment that Rutherford backscattering is capable of analyzing the quality of the structure of nanoporous membranes.     

Surface modification of nanoporous alumina membranes by plasma polymerization

The deposition of plasma polymer coatings onto porous alumina (PA) membranes was investigated with the aim of adjusting the surface chemistry and the pore size of the membranes. PA membranes from commercial sources with a range of pore diameters (20, 100 and 200?nm) were used and modified by plasma polymerization using n-heptylamine (HA) monomer, which resulted in a chemically reactive polymer surface with amino groups. Heptylamine plasma polymer (HAPP) layers with a thickness less than the pore diameter do not span the pores but reduce their diameter. Accordingly, by adjusting the deposition time and thus the thickness of the plasma polymer coating, it is feasible to produce any desired pore diameter. The structural and chemical properties of modified membranes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and x-ray electron spectroscopy (XPS). The resultant PA membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture, bioreactors, biosensing, drug delivery, and engineering complex composite membranes.     

Gas adsorption gates based on ultrathin composite polymer films

High surface area alumina coatings were prepared on surface acoustic wave (SAW) mass balances. These coatings were fabricated by anodic etching of evaporated aluminum films. The coatings consisted of roughly collinear pores penetrating through the monolithic alumina film. The nanoporous (NP) coatings were characterized by scanning electron microscopy, and the pore number density and diameter were found to be (3.8 +/- 0.5) x 10(3) pores/microm2 and 6.8 +/- 4.8 nm, respectively. The mass of volatile organic compounds that adsorbed onto naked and chemically modified NP alumina coatings was measured using SAW mass balances and compared to the mass absorbed onto SAW devices having planar aluminum coatings. Thirty-four times more heptane adsorbed to the naked NP coating than to the planar coating. The mass loading response was also measured after modification with organic thin films (3-12 nm thick) that spanned the pores of the NP coating. These organic thin films were composed of sixth-generation, amine-terminated poly(amido amine) dendrimers and poly(maleic anhydride)-c-poly(methyl vinyl ether) (Gantrez). The key result of this study is that these organic thin films modulate adsorption of VOCs onto the pore walls of the NP alumina. Specifically, a single 3-nm-thick monolayer of the dendrimer reduces permeability of the VOCs by approximately 17%, whereas a 12-nm-thick G6-NH2/Gantrez composite reduces permeability by 100%. Thus, the polymer composite acts as a nonselective gate that controls access of VOCs to the underlying surface area of the pores.     

Thermal stability and its improvement of the alumina membrane top-layers prepared by sol-gel methods

The thermal stability of unsupported alumina membrane top-layers was studied by determining the pore structure (mainly pore size) change of alumina gels, prepared by sol-gel methods, after sintering at different temperatures ranging from 450 to 1200 °C. The average pore size of the pure alumina membranes and PVA-added membranes increased sharply after sintering at temperatures higher than 1000 °C. Addition of 3% lanthanum, either by mixing lanthanum nitrate in the alumina sol or impregnating lanthanum nitrate into calcined alumina gel, followed by a second heat treatment, can considerably stabilize the pore structure of the alumina membrane top-layers. The pore diameter for the lanthanum-doped membranes was stabilized within 25 nm after sintering at 1200 °C for 30 h, about one-sixth of that for the pure alumina membranes after sintering at 1200 °C for 30 h. The substantial increase in the pore size for the pure alumina membranes at the sintering temperature of 1000 to 1200 °C was accompanied by the phase transformation from -to -alumina. The addition of lanthanum can raise this phase transformation temperature by about 200 °C.     

Surface morphology and adsorbed proteins affect phagocyte responses to nano-porous alumina

This study evaluates human neutrophil responses to aluminum oxide membranes with different pore sizes (20 nm and 200 nm in diameter) uncoated and pre-coated with serum, collagen I, or fibrinogen. The effect of released neutrophil granule components on the survival of osteoblastic cells (MG63) bound to the alumina membranes has also been evaluated. Without protein coatings the 20 nm pore-size membranes prompt higher reactive oxygen species (ROS) production as assessed by luminol-amplified chemiluminescence than the 200 nm pore-size membranes. Such pore-size depending responses were also found on membranes pre-coated with fibrinogen, but not with collagen or serum were in fact a much lower ROS production was observed. In addition, uncoated and fibrinogen-coated membranes prompt stronger release of the granule enzymes, myeloperoxidase and elastase, than collagen or serum-coated alumina. Equally important, we found that surface-mediated phagocyte activation and the subsequent release of granule components had a significant affect on the adhesion, viability and proliferation of osteoblasts. This stresses the importance of studying not only cell/surface interactions but also cell/cell interactions in wound healing and tissue regeneration processes.     

Fabrication of novel porous anodic alumina membranes by two-step hard anodization

Porous anodic alumina (PAA) membranes with highly ordered hexagonal cells and a novel pore structure have been fabricated by two-step hard anodization in a H(2)SO(4)-Al(2)(SO(4))(3)-H(2)O system at 40 and 50?V, giving average cell diameters of 77 and 96?nm, respectively. There are several tiny pores embedded in each big shallow pore on the top of the membranes, and there is only one pore in one cell at their bottom. The cells on both sides of the membranes present almost the same periodic arrangement. In order to explore the formation of the novel pore structure, PAA membranes fabricated at different current densities (30-200?mA?cm(-2)) are obtained by maintaining a constant voltage at 40?V. The experimental results show that the interpore distance is not only dependent on the anodization voltage, but is also influenced by the current density, which means that the pore structure of PAA membranes fabricated by hard anodization can be accurately designed and controlled by adjusting the anodization voltage and current density simultaneously.     

Correlation between structural and optical properties of 30 nm and 60 nm lead sulfide nanowires

PbS nanowires with 30 nm and 60 nm diameter fabricated under the same condition of electrochemical deposition with sulfuric and oxalic anodic alumina membranes (AAM), respectively, have been successfully prepared in order to study their optical properties in relation to their size. Scanning electron microscopy indicates that the 60 nm PbS nanowire arrays have the same shape with the 30 nm. X-ray diffraction result shows that 60 nm PbS nanowires are crystalline and have a highly (200) preferential orientation like 30 nm ones. UV spectrum considers the nanowire size decrease as the absorption peak shifts to the blue. The quantum confinement effects compared between 30 nm and 60 nm PbS nanowire arrays were observed by the measurements of ultraviolet-visible absorption spectroscopy (UV-vis).     

溶胶-凝胶法制备不对称氧化铝膜

以异丙醇铝为原料,过量的水、醇溶剂的存在有利于异丙醇铝水解．适宜的水铝比H₂O／Al^3＋为100：1;醇铝比ROH／Al^3＋为5：1;酸胶溶剂的浓度H^＋／Al^3＋为0．07：1．溶胶的雾化快速胶凝法,大大缩短了凝胶干燥的时间,采用这种方法能容易地制备膜厚均匀、且无龟裂的无机氧化铝膜．适宜的溶胶浓度为0．5～1．4mol AlOOH／L溶胶,喷雾距离＜200mm,膜厚与溶胶浓度、喷雾时间成正比,与喷雾距离的平方成反比．用γ-AlOOH溶胶对基质膜作进一步的修饰制备不对称氧化铝膜时,勃母石溶胶的初始晶粒的大小决定着氧化铝膜的孔径,勃母石溶胶的胶体粒子的直径决定着形成的不对称膜的稳定性．勃母石溶胶的胶体粒子的平均直径与支撑体基质膜表面的最可见孔径相当时,喷涂于基质膜表面的溶胶快速胶凝后,能形成无裂纹和针孔的均匀凝胶膜．以表面最可几孔径为0．1μm的氧化铝膜为基质膜,雾化溶胶胶粒平均直径为100nm左右的勃母石溶胶,喷涂于基质膜表面,快速胶凝后于400℃焙烧形成的支撑γ-Al₂O₃膜孔径为3nm．     

From heterogeneous to homogeneous nucleation of isotactic poly(propylene) confined to nanoporous alumina

The crystallization of highly isotactic polypropylene confined in self-ordered nanoporous alumina is studied by differential scanning calorimetry. A transformation from a predominantly heterogeneous to predominantly homogeneous nucleation takes place if the pore diameter is smaller than 65 nm. Crystallization is suppressed with decreasing pore size, and the absence of nucleation below 20 nm pores indicates the critical nucleus size. The results reported here might enhance the understanding of nanocomposites containing semicrystalline polymers and reveal design criteria for polymeric nanofibers with tailored mechanical and optical properties.     

硼掺杂的γ-A12O3催化膜的制备及其热稳定性的研究

在勃姆石AlOOH溶胶中引入一定量的H2BO3溶液,经不同温度的热处理,制成不同硼掺杂含量的无支撑的γ-A12O3催化膜。用XRD、BET分别对膜的晶相和膜的微孔结构,包括比表面积、孔径和孔容进行了研究,结果发现：随着硼含量的增加,在低温下,膜的比表面积和孔容都不断增加,而对孔径的影响不大;经1200℃处理后,未掺杂硼的膜的比表面积,孔径和孔容分别为5.4m2/g,49nm和0.063cm3/g,而经掺杂16％摩尔硼的膜的比表面积,孔径和孔容分别为35m2/g,13nm和0.225cm3/g,这说明硼的掺杂对γ-A12O3膜的热稳定性有很好的改善作用。     

IR Scattering by Optically Inhomogeneous Nanoporous Anodic Alumina Films

This paper presents results of thermographic studies of nanoporous alumina films having different geometric parameters of their porous layer (thickness and average pore diameter), which were exposed to thermal radiation. The films have been shown to shield thermal radiation. The present results suggest that nanoporous alumina membranes can be used as heat shields for reducing the thermal contrast of an object and the surrounding background in the IR spectral region.     

Helium Ion Microscopy Visualizes Lipid Nanodomains in Mammalian Cells

Cell membranes are composed of 2D bilayers of amphipathic lipids, which allow a lateral movement of the respective membrane components. These components are arranged in an inhomogeneous manner as transient micro‐ and nanodomains, which are believed to be crucially involved in the regulation of signal transduction pathways in mammalian cells. Because of their small size (diameter 10–200 nm), membrane nanodomains cannot be directly imaged using conventional light microscopy. Here, direct visualization of cell membrane nanodomains by helium ion microscopy (HIM) is presented. It is shown that HIM is capable to image biological specimens without any conductive coating and that HIM images clearly allow the identification of nanodomains in the ultrastructure of membranes with 1.5 nm resolution. The shape of these nanodomains is preserved by fixation of the surrounding unsaturated fatty acids while saturated fatty acids inside the nanodomains are selectively removed. Atomic force microscopy, fluorescence microscopy, 3D structured illumination microscopy, and direct stochastic optical reconstruction microscopy provide additional evidence that the structures in the HIM images of cell membranes originate from membrane nanodomains. The nanodomains observed by HIM have an average diameter of 20 nm and are densely arranged with a minimal nearest neighbor distance of ≈15 nm.     

Nanoporous aluminum oxide as a novel support material for enzyme biosensors

To construct novel amperometric sensors for the detection of hydrogen peroxide and pyruvate, peroxidase and pyruvate oxidase were immobilized in self-supporting nanoporous alumina membranes those made by anodic oxidation. Pyruvate oxidase and other enzymes were enclosed in poly(carbamoylsulfonate) hydrogel and sucked into the nanoporous alumina structure before polymerization. The alumina membranes were investigated by scanning electron microscopy before and after the enzyme immobilization. In an amperometric flow detector cell, pyruvate and hydrogen peroxide were detected under flow injection analysis conditions in concentration ranges from 1 microM to 100 microM and 5 microM to 500 microM, respectively. The achieved operational stability showed that alumina membranes can be used to construct enzyme-modified electrodes.     

Synthetic control of large-area,ordered Fe nanotubes and their nanotube-core/alumina-sheath nanocables

Fe nanotubes with different outer diameters (55 nm, 80 nm, 200 nm) have been successfully fabricated into the anodic alumina membranes (AAMs) by direct-current electrochemical deposition technique, and their nanotube-core/alumina-sheath nanocables were further realized with a simple chemical etching method. X-ray diffraction, scanning electron microscopy and transmission electron microscopy analyses show that the Fe nanotube core is single crystalline along [110] crystal direction, and the sheath is an amorphous alumina. Such a new nanostructure may be suitable for two-dimensional ferromagnetic structural materials and the diameter of the nanocables can be modulated by controlling the experimental conditions, and the formation mechanism was explored. Our experimental results provide a useful way for fabricating low-cost and large-scale metal nanocables, which are of important applications in modern nanoelectronics.     

Multifunctional substrates of thin porous alumina for cell biosensors

We have fabricated anodic porous alumina from thin films (100/500 nm) of aluminium deposited on technological substrates of silicon/glass, and investigated the feasibility of this material as a surface for the development of analytical biosensors aiming to assess the status of living cells. To this goal, porous alumina surfaces with fixed pitch and variable pore size were analyzed for various functionalities. Gold coated (about 25 nm) alumina revealed surface enhanced Raman scattering increasing with the decrease in wall thickness, with factor up to values of approximately 10⁴ with respect to the flat gold surface. Bare porous alumina was employed for micro-patterning and observation via fluorescence images of dye molecules, which demonstrated the surface capability for a drug-loading device. NIH-3T3 fibroblast cells were cultured in vitro and examined after 2 days since seeding, and no significant (P > 0.05) differences in their proliferation were observed on porous and non-porous materials. The effect on cell cultures of pore size in the range of 50–130 nm—with pore pitch of about 250 nm—showed no significant differences in cell viability and similar levels in all cases as on a control substrate. Future work will address combination of all above capabilities into a single device.     

Fabrication of metallic nanowire arrays by electrodeposition into nanoporous alumina membranes: effect of barrier layer

Deposition into nanoporous alumina membranes is widely used for nanowire fabrication. Herein using AC electrodeposition ternary Fe–Co–Ni nanowires are fabricated within the nanoscale-pores of alumina membranes. Using an electrodeposition frequency of 1,000 Hz, 15 V_rms, consistently and repeatably yield nanowire arrays over membranes several cm² in extent. Electrochemical Impedance Spectroscopy (EIS) is used to explain the effects of AC electrodeposition frequency. The impedance of the residual alumina barrier layer, separating the underlying aluminum metal and the nanoporous membrane, decreases drastically with electrodeposition frequency facilitating uniform pore-filling of samples several cm² in area. Anodic polarization studies on thin films having alloy compositions identical to the nanowires display excellent corrosion resistance properties.