Nanoporous Alumina Membranes Research Articles

Nanomonitor Technology for Glycosylation Analysis

AbstractChanges in protein glycosylation have great potential as markers for the early diagnosis of cancer and other diseases. The current analytical tools for the analysis of glycan structures need expensive instrumentation, advanced expertise, is time consuming and therefore not practical for routine screening of glycan biomarkers from human samples in a clinical setting.We are developing a novel ultrasensitive diagnostic platform called ‘NanoMonitor’ to enable rapid label-free glycosylation analysis. The technology is based on electrochemical impedance spectroscopy where capacitance changes are measured at the electrical double layer interface as a result of interaction of two molecules.The NanoMonitor platform consists of a printed circuit board with array of electrodes forming multiple sensor spots. Each sensor spot is overlaid with a nanoporous alumina membrane that forms a high density of nanowells. Lectins, proteins that bind to and recognize specific glycan structures, are conjugated to the surface of nanowells. When specific glycoproteins from a test sample bind to lectins in the nanowells, it produces a perturbation to the electrical double layer at the solid/liquid interface at the base of each nanowell. This perturbation results in a change in the impedance of the double layer which is dominated by the capacitance changes within the electrical double layer.The nanoscale confinement or crowding of biological macromolecules within the nanowells is likely to enhance signals from the interaction of glycoproteins with the lectins leading to a high sensitivity of detection with the NanoMonitor as compared to other electrochemical techniques.Using a panel of lectins, we were able to detect subtle changes in the glycosylation of fetuin protein as well as differentiate glycoproteins from normal versus cancerous cells. Our results indicate that NanoMonitor can be used as a cost-effective miniature electronic biosensor for the detection of glycan biomarkers.

Synthesis and characterization of quantum dot–polymer composites

In this study, we demonstrate a facile and simple synthesis of quantum dot (QD)-polymer composites. Highly fluorescent semiconducting CdSe/ZnS quantum dots were embedded in different commercially available polymers using one easy step. QD-polymer composite nanoparticles were also synthesized using template-assisted synthesis. In particular, we self-assembled lamellar micelles inside nanoporous alumina membranes which were used for the synthesis of mesoporous silica hollow nanotubes and solid nanorods. We observed that the addition of excess free octadecylamine (ODA) in the QD-silica solution resulted in gelation. The gelation time was found to be dependent on free ODA concentration. Similarly, the emission of QD-polymer composites was also found to be dependent on free ODA concentration. Highly purified QDs provided polymer composites that have a much lower emission compared to unpurified nanocomposites. This was attributed to passivation of the QD surfaces by amine, which reduced the surface defects and non-radiative pathways for excited QDs. Finally, highly fluorescent QD-polymer patterns were demonstrated on glass substrates which retained their emission in both polar and non-polar solvents.

FePd melt-spun ribbons and nanowires: Fabrication and magneto-structural properties

Fe–30%Pd alloys in ribbon and nanowire geometry have been prepared. Ribbon samples were produced by the melt-spinning technique in the Ar environment. FePd nanowires, having about 35 nm in diameter, 105 nm inter-nanowires distance and around 4 μm in length, were synthesized into nanoporous anodic alumina membranes as templates. Energy dispersive X-ray microanalysis of ribbons shows an average atomic composition of Fe (73.2%) and Pd (26.8%). The X-ray diffraction at RT analysis was performed on both surfaces, free and wheel side, of the melt-spun ribbon. It shows the coexistence of two phases: fct and bct FePd, but with differences between both surfaces consisting the existence of Fe oxides (Fe 2O 3 and Fe 3O 4) and a textured 200 reflection in the free side. Heating and cooling thermomagnetic curves exhibit a reversible behaviour from RT to 720 K, but around 770 K a clear irreversible transformation takes place.

Laterally Controlled Template Electrodeposition of Polyaniline

AbstractPolyaniline (PANi) was electrodeposited in gold‐coated nanoporous alumina membranes (NAMs) by anodic polymerization of aniline. PANi deposition was followed by cathodic deposition of Ag or Cu, to form a layer of PANi–metal segmented nanowires in the NAM. The compact PANi nanowires fill the entire pore volume, providing a sharp transition from the polymer to the metal segment. The deposited metal layer enables SEM visualization of the PANi nanowire length in the membrane. Deposition of Cu on PANi nanowires occurs at potentials where the PANi is in its reduced leucoemeraldine state, with no evidence for penetration of the metal into the polymer matrix. The mechanism of metal ion reduction on the nonconducting polymer wires is not yet clear. Free‐standing segmented PANi–Ag and PANi–Cu nanowires obtained by membrane dissolution show a sharp heterojunction between the polymer and metal phases and are mechanically stable.Aniline electropolymerization in the insulating NAM under a lateral potential gradient generated a thickness gradient of the PANi deposit, revealed by subsequent Cu deposition. The potential‐dependent length of the PANi nanowires follows the PANi conductivity pattern, reaching a maximum in the region of stability of the conducting emeraldine phase. The results demonstrate the possibility of obtaining nonlinear graded materials using electrochemical systems showing a complex current–voltage behavior.

On the growth mechanism of nickel and cobalt nanowires and comparison of their magnetic properties

Magnetic nanowires (NWs) are ideal materials for the fabrication of various multifunctional nanostructures which can be manipulated by an external magnetic field. Highly crystalline and textured nanowires of nickel (Ni NWs) and cobalt (Co NWs) with high aspect ratio (∼330) and high coercivity have been synthesized by electrodeposition using nickel sulphate hexahydrate (NiSO4·6H2O) and cobalt sulphate heptahydrate (CoSO4·7H2O) respectively on nanoporous alumina membranes. They exhibit a preferential growth along 〈110〉. A general mobility assisted growth mechanism for the formation of Ni and Co NWs is proposed. The role of the hydration layer on the resulting one-dimensional geometry in the case of potentiostatic electrodeposition is verified. A very high interwire interaction resulting from magnetostatic dipolar interactions between the nanowires is observed. An unusual low-temperature magnetisation switching for field parallel to the wire axis is evident from the peculiar high field M(T) curve.

Magnetic Properties of Electrodeposited FeGa/CoFeB Multilayered Films and Nanowire Arrays

Results concerning the preparation and magnetic characterization of electrochemically deposited [Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">80</sub> Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">20</sub> /Co <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">75</sub> Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">10</sub> B <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">15</sub> ] <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">n</sub> multilayered films and nanowire arrays are reported for the first time. The deposition bath consisted in a single mixed solution of FeSO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> middot7H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O, Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (SO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> middotH <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O, CoSO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> middot7H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O, C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">10</sub> BN, and H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> BO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> . The layers have been deposited successively by changing the electrodeposition potential. The composition and thickness of the different layers were tailored through optimizing deposition parameters such as buffer additives and applied voltage. Two hundred sequences multilayered nanowires were electrodeposited into commercially available nanoporous alumina membranes with pore diameters of 100 nm and lengths of 50 mum. Multilayered films 4-5 mu m thick have been obtained by electrodepositing 50 consecutive sequences of FeGa and CoFeB. The multilayered structures consisting FeGa magnetostrictive alloy and CoFeB amorphous magnetic material are magnetically soft (H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">c</sub> does not exceed 1.6 kA/m).

Preparation and Characterization of Nanoporous Alumina Membrane Made by Two-Step Anodization

he preparation of different pore diameter and thickness nanoporous alumina membranes by two-step anodic oxidation, and the corrosion resistance and mechanical properties of the alumina membrane were investigated. In order to show the infection of pore diameter and thickness on these properties, the dynamic polarization and nano indentation method were mentioned, at the same time hemolytic test was performed for testing biocompatibility of the membrane.

Polarization-dependent fluorescence of proteins bound to nanopore-confined lipid bilayers

Lipid bilayers are essential structural component of biological membranes of all the living species: from viruses and bacteria to plants and humans. Biophysical and biochemical properties of such membranes are important for understanding physical mechanisms responsible for drug targeting. Binding events between proteins and the membrane may be ascertained by introducing fluorescence markers (chromophores) to the proteins. Here we describe a novel biosensing platform designed to enhance signals of these fluorescence markers. Nanoporous aluminum oxide membranes with and without gold (Au) surface coating have been employed for optical detection of bound conjugated streptavidin to biotinylated lipid bilayers-a model system that mimics protein docking to the membrane surface. Unexpectedly, it was found that fluorescence signals from such structures vary when pumped with E-polarized and H-polarized incident optical beams. The origin of the observed polarization-dependent effects and the implications for enhanced fluorescence detection in a biochip format are being discussed.

Mechanical and biological properties of nanoporous carbon membranes

Implantable blood glucose sensors have inadequate membrane–tissue interfaces for long term use. Biofouling and inflammation processes restrict biosensor membrane stability. An ideal biosensor membrane material must prevent protein adsorption and exhibit cell compatibility. In addition, a membrane must exhibit high porosity and low thickness in order to allow the biosensor to respond to analyte fluctuations. In this study, the structural, mechanical and biological properties of nanoporous alumina membranes coated with diamond-like carbon thin films were examined using scanning probe microscopy, nanoindentation and MTT viability assay. We anticipate that this novel membrane material could find use in immunoisolation devices, kidney dialysis membranes and other medical devices encountering biocompatibility issues that limit in vivo function.

Nanomonitors: Electrical Immunoassays for Protein Biomarker Profiling

The objective of this research is to develop a 'point-of-care' device for early disease diagnosis through protein biomarker characterization. Here, we present label-free, high sensitivity detection of proteins with the use of electrical immunoassays that we call nanomonitors. The basis of the detection principle lies in the formation of an electrical double layer and its perturbations caused by proteins trapped in a nanoporous alumina membrane over a microelectrode array platform. High sensitivity and rapid detection of study protein biomarkers for cardiovascular diseases, C-reactive protein (CRP) and myeloperoxidase (MPO) in pure and clinical samples through label-free electrical detection were achieved. CRP and MPO were detected in pure solutions with a lower detection limit of 200 pg/ml and 500 pg/ml, respectively. These two study proteins were also detected from multiplexed samples containing a mixture of both proteins as well as human serum samples. The performance parameters of the nanomonitors, such as speed of detection on the order of minutes, volume of reagents of a few microliters and low cost per assay are comparable to traditional assay methods, such as ELISA. In addition, nanomonitors also provide the advantages of being a label-free technique with large linear dynamic range of detection and a significant reduction in the size of assay, thus making it an ideal candidate for a clinical diagnostic 'lab-on-a-chip' device for protein biomarker profiling and hence early disease diagnosis.

THE EFFECT OF ALUMINUM ELECTROPOLISHING ON NANO-PORES ARRANGEMENT IN ANODIC ALUMINA MEMBRANES

Surface conditions of aluminum can influence the final arrangement of nano-pores in fabrication of ordered nanoporous anodic alumina membranes (AAMs). This study is mainly focused on the different applied voltages of aluminum electropolishing by keeping all the other parameters constant. After heat treatment (stress relieving and annealing at 500°C) of pure aluminum sheets, the samples were electropolished at different voltages (10-60V) to obtain desirable surface smoothness, while the temperature of the container was kept constant. The current-time curves were recorded during electropolishing process. The surface roughness obtained in each applied voltage was examined using optical microscope and atomic force microscope (AFM). The process was followed by two-step anodization in order to reach ordered nano-pores. Finally, the influence of surface roughness on regularity of nano-pores was observed using scanning electron microscope (SEM). The SEM images were analyzed to investigate the morphology and the degree of self ordering of pores of the samples by using a new designed analytical method aiming MATLAB and fast Fourier transform (FFT) technique. It was concluded that the electropolishing voltage and the resulted surface roughness and also formed defects can competitively affect the arrangement of membrane's nano-pores. A desired smoothness obtained from electropolishing voltage of 30V. Also 40V provided the best order with respect to the other voltages.

A polyethylene glycol (PEG) microfluidic chip with nanostructures for bacteria rapid patterning and detection

This paper presents a new poly(ethylene glycol) (PEG) hydrogel based microchip with patterned nanoporous aluminum oxide membrane (AOM) for bacteria fast patterning and detection with low frequency impedance spectrum. The PEG hydrogel micropatterns on the saline-modified nanoporous alumina surface created controlled spatial distribution of hydrophobic and hydrophilic regions. For bacteria patterning and sensing purpose, 20 × 20 microwell arrays were fabricated. These microwell arrays were composed of hydrophilic PEG sidewalls and hydrophobic silane-modified AOM bottom. In the surrounded areas of the microwells where PEG was UV polymerized, solid hydrogel was covalently bonded with silane-modified membrane and this close covering prevented electrolyte flow through the portions underneath the membrane. Anti- E. coli antibody was added and washed to form the patterns in the microwells for bacteria capturing. Then, the target bacteria E. coli O157:H7 was successfully patterned and captured inside the microwells. For the control experiment, the non-target bacteria Staphylococcus was not observed on both PEG and AOM surfaces. The followed impedance experiments showed that this nanohole based electrochemical micro-system could detect this specific bacteria binding in the frequency domain less than 100 Hz with a low bacteria concentration of 10 2 CFU/ml. The bacteria concentration effect on the impedance amplitude was also explored.

Quantum dot nanocolumn photodetectors for light detection in the infrared

Colloidal quantum dots absorbing in the infrared are filled into nanoporous alumina membranes to form narrow columns with aspect ratios of 300:1. The columns define the charge carrier path vertical through the ordered pore structure of the membrane. Electrical transport and photocurrent of various quantum dot column photodetectors based on two different nanomaterials, namely, HgTe and PbS quantum dots, with different quantum dot sizes are investigated. Photocurrents up to long wavelengths of 3μm are demonstrated.

Nondestructive Replication of Self-Ordered Nanoporous Alumina Membranes via Cross-Linked Polyacrylate Nanofiber Arrays

Ordered nanofiber arrays are a promising material platform for artificial adhesive structures, tissue engineering, wound dressing, sensor arrays, and self-cleaning surfaces. Their production via self-ordered porous alumina hard templates serving as shape-defining molds is well-established. However, their release requires the destruction of the hard templates, the fabrication of which is costly and time-consuming, by wet-chemical etching steps with acids or bases. We report the nondestructive mechanical extraction of arrays of cross-linked polyacrylate nanofibers from thus recyclable self-ordered nanoporous alumina hard templates. Silica replicas of the latter were synthesized using the extricated nanofiber arrays as secondary molds that could be mechanically detached from the molded material. The approach reported here, which can be combined with microstructuring, may pave the way for the high-throughput production of both functional nanofiber arrays and ordered nanoporous membranes consisting of a broad range of material systems.

Surface modification of nanoporous alumina membranes by plasma polymerization

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

Characterization of the electrophoretic mobility of gold nanoparticles with different sizes using the nanoporous alumina membrane system

This work presents a new analytical system to study the electrophoretic mobility of gold nanoparticles with different sizes, in which the platinum-coated alumina membranes are used as the separator due to the high pore densities, rigid support structure, chemical and thermal stability. It is shown that the electrophoretic mobility of gold nanoparticles is dependent on the nature of mobile phase and interfacial properties of alumina channels. The transport performance of nanoparticles are improved with the addition of sodium dodecyl sulfate (SDS) into the mobile phase, because SDS not only decreases the physical adsorption of gold nanoparticles on the nano-channel wall of alumina membrane, but also reduces the thickness of the electric double layer (decreasing the apparent size of particles). When the alumina membranes were modified with 6-aminohexanoic acid, it was further confirmed that the physical adsorption played a key role for the electrophoretic mobility of gold nanoparticles. Under optimized conditions, the mobility of gold nanoparticles had a fairly linear dependence on particle size (R2 > 0.99), reiterating that our membrane system was also capable of characterizing gold nanoparticles in nanometer-size regimes.

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.

The temperature dependence of hysteretic processes in Co nanowires arrays

In this paper, the temperature dependence of the hysteretic processes of Co nanowires, squarelly ordered in an array prepared by electrodeposition in nanopores of alumina membranes was analyzed. Both the magnetostatic interactions induced in the nanowires arrays and the thermal stresses (radial, azimuthal and axial stresses), which appear during the cooling of the system (nanowire and alumina template) from room temperature to 3K was evaluated. The analysis of thermal induced stresses provides useful informations concerning the magnetic anisotropy in the Co nanowires. The temperature dependence of the remanent magnetization and coercitive field as an effect of the induced thermal stresses and magnetostatic interactions between nanowires was studied.

Structural engineering of nanoporous anodic aluminium oxide by pulse anodization of aluminium

Nanoporous anodic aluminium oxide has traditionally been made in one of two ways: mild anodization or hard anodization. The first method produces self-ordered pore structures, but it is slow and only works for a narrow range of processing conditions; the second method, which is widely used in the aluminium industry, is faster, but it produces films with disordered pore structures. Here we report a novel approach termed "pulse anodization" that combines the advantages of the mild and hard anodization processes. By designing the pulse sequences it is possible to control both the composition and pore structure of the anodic aluminium oxide films while maintaining high throughput. We use pulse anodization to delaminate a single as-prepared anodic film into a stack of well-defined nanoporous alumina membrane sheets, and also to fabricate novel three-dimensional nanostructures.

Ordered magnetic nanohole and antidot arrays prepared through replication from anodic alumina templates

Highly ordered arrays of Ni nanoholes and Fe 20Ni 80 antidots have been prepared, respectively, by replica/antireplica processing and sputtering techniques using nanoporous alumina membranes as templates. Geometrical characteristics as nanohole/antidot diameter, interpore distance and the overall hexagonal symmetry of arrays are controlled through the original templates. Experimental data on their hysteresis and magnetic domain structure have been taken by vibrating sample magnetometry and magnetic force microscopy, respectively. An analysis of the magnetization process, resulting magnetic anisotropy and magnetic domain structure is summarized considering the influence of those geometry aspects. In particular, the hexagonal symmetry and the density of nanohole/antidots determine the overall magnetic behavior, which is of interest in future high-density magnetic storage systems.