Nanoporous Alumina Membranes Research Articles

NK-lysin antimicrobial peptide-functionalized nanoporous alumina membranes as biosensors for label-free bacterial endotoxin detection

We report an NK-lysin peptide-functionalized nanoporous anodized aluminum oxide (NAAO) based biosensor to detect bacterial endotoxin. Bovine NK-lysin-derived peptides show antimicrobial activity against bacterial pathogens, and bactericidal activity is primarily due to the membranolysis activity. Antimicrobial activity of NK-lysin NK2A was confirmed against a Gram-negative Mannheimia haemolytica and a Gram-positive Staphylococcus aureus. Electron microscopic examination showed the localization of NK2A conjugated silver nanoparticles, but not unconjugated silver nanoparticles used as control, to the bacterial outer membrane and cell wall. NK2A functionalized NAAO membranes were used in a previously developed four-electrode electrochemical configuration to detect the presence of Gram-negative bacterial lipopolysaccharides (LPS) and Gram-positive bacterial lipoteichoic acid (LTA) molecules. NK2A-functionalized NAAO biosensor could detect LPS with a detection limit of 10 ng/mL within an appreciable signal/noise ratio. Biosensors functionalized with a scrambled amino acid version of NK2A (Sc-NK2A) that lacks antimicrobial activity could not detect the presence of LPS. However, both NK2A and Sc-NK2A functionalized biosensors showed sensing signals with Gram-positive bacterial lipoteichoic acids. These results suggest that the specific binding of NK2A-LPS on the NAAO membrane surface is responsible for the observed biosensor signals. These findings suggest that NK2A-functionalized biosensors can be used for rapid and sensitive label-free LPS detection.

Nanoporous Membranes for the Filtration of Proteins from Biological Fluids: Biocompatibility Tests on Cell Cultures and Suggested Applications for the Treatment of Alzheimer's Disease.

Background: Alzheimer’s disease has a significant epidemiological and socioeconomic impact, and, unfortunately, the extensive research focused on potential curative therapies has not yet proven to be successful. However, in recent years, important steps have been made in the development and functionalization of nanoporous alumina membranes, which might be of great interest for medical use, including the treatment of neurodegenerative diseases. In this context, the aim of this article is to present the synthesis and biocompatibility testing of a special filtrating nano-membrane, which is planned to be used in an experimental device for Alzheimer’s disease treatment. Methods: Firstly, the alumina nanoporous membrane was synthesized via the two-step anodizing process in oxalic acid-based electrolytes and functionalized via the atomic layer deposition technique. Subsequently, quality control tests (spectrophotometry and potential measurements), toxicity, and biocompatibility tests (cell viability assays) were conducted. Results: The proposed alumina nanoporous membrane proved to be efficient for amyloid-beta filtration according to the permeability studies conducted for 72 h. The proposed membrane has proven to be fully compatible with the tested cell cultures. Conclusions: The proposed alumina nanoporous membrane model is safe and could be incorporated into implantable devices for further in vivo experiments and might be an efficient therapeutic approach for Alzheimer’s disease.

A Micropowered Chemoresistive Sensor Based on a Thin Alumina Nanoporous Membrane and SnxBikMoyOz Nanocomposite.

This work presents and discusses the design of an efficient gas sensor, as well as the technological process of its fabrication. The optimal dimensions of the different sensor elements including their deformation were determined considering the geometric modeling and the calculated moduli of the elasticity and thermal conductivity coefficients. Multicomponent SnxBikMoyOz thin films were prepared by ionic layering on an anodic alumina membrane and were used as gas-sensitive layers in the sensor design. The resistance of the SnxBikMoyOz nanostructured film at temperatures up to 150 °C exceeded 106 Ohm but decreased to 104 Ohm at 550 °C in air. The sensitivity of the SnxBikMoyOz composite to concentrations of 5 and 40 ppm H2 at 250 °C (10 mW) was determined to be 0.22 and 0.40, respectively.

Structural Engineering of the Barrier Oxide Layer of Nanoporous Anodic Alumina for Iontronic Sensing.

The hemispherical barrier oxide layer (BOL) closing the bottom tips of hexagonally distributed arrays of cylindrical nanochannels in nanoporous anodic alumina (NAA) membranes is structurally engineered by anodizing aluminum substrates in three distinct acid electrolytes at their corresponding self-ordering anodizing potentials. These nanochannels display a characteristic ionic current rectification (ICR) signal between high and low ionic conduction states, which is determined by the thickness and chemical composition of the BOL and the pH of the ionic electrolyte solution. The rectification efficiency of the ionic current associated with the flow of ions across the anodic BOL increases with its thickness, under optimal pH conditions. The inner surface of the nanopores in NAA membranes was chemically modified with thiol-terminated functional molecules. The resultant NAA-based iontronic system provides a model platform to selectively detect gold metal ions (Au3+) by harnessing dynamic ICR signal shifts as the core sensing principle. The sensitivity of the system is proportional to the thickness of the barrier oxide layer, where NAA membranes produced in phosphoric acid at 195 V with a BOL thickness of 232 ± 6 nm achieve the highest sensitivity and low limit of detection in the sub-picomolar range. This study provides exciting opportunities to engineer NAA structures with tailorable ICR signals for specific applications across iontronic sensing and other nanofluidic disciplines.

Production of nanoporous alumina membranes modified with multi‐walled carbon nanotube, polyacrylamide and polystyrene and use in wastewater treatment

AbstractIn this study, the nanofiltration materials having high selectivity, high filtration and mechanical resistance have been developed for the removal of organic contaminants in wastewater. Al2O3‐NP membranes were modified with multi‐walled carbon nanotube (MWCNT), polyacrylamide‐MWCNT (PA‐MWCNT) and polystyrene‐MWCNT (PS‐MWCNT) to provide better performance in the treatment of wastewater. The evaluation of the separation performance of the prepared membranes was carried out at 25°C using a vacuum filtration unit. Congo red (CR) and methylene blue (MB) dyes were selected as model pollutants. The results showed that the flux value was higher in the unmodified membrane, and the Al2O3‐NP membrane modified with MWCNT exhibited high removal efficiency among the modified membranes.

Electrical monitoring of infection biomarkers in chronic wounds using nanochannels

Chronic wounds represent an important healthcare challenge in developed countries, being wound infection a serious complication with significant impact on patients’ life conditions. However, there is a lack of methods allowing an early diagnosis of infection and a right decision making for a correct treatment. In this context, we propose a novel methodology for the electrical monitoring of infection biomarkers in chronic wound exudates, using nanoporous alumina membranes. Lysozyme, an enzyme produced by the human immune system indicating wound infection, is selected as a model compound to prove the concept. Peptidoglycan, a component of the bacterial layer and the native substrate of lysozyme, is immobilized on the inner walls of the nanochannels, blocking them both sterically and electrostatically. The steric blocking is dependent on the pore size (20–100 nm) and the peptidoglycan concentration, whereas the electrostatic blocking depends on the pH. The proposed analytical method is based on the electrical monitoring of the steric/electrostatic nanochannels unblocking upon the specific degradation of peptidoglycan by lysozyme, allowing to detect the infection biomarker at 280 ng/mL levels, which are below those expected in wounds. The low protein adsorption rate and thus outstanding filtering properties of the nanoporous alumina membranes allowed us to discriminate wound exudates from patients with both sterile and infected ulcers without any sample pre-treatment usually indispensable in most diagnostic devices for analysis of physiological fluids.Although size and charge effects in nanochannels have been previously approached for biosensing purposes, as far as we know, the use of nanoporous membranes for monitoring enzymatic cleavage processes, leading to analytical systems for the specific detection of the enzymes has not been deeply explored so far. Compared with previously reported methods, our methodology presents the advantages of no need of neither bioreceptors (antibodies or aptamers) nor competitive assays, low matrix effects and quantitative and rapid analysis at the point-of-care, being also of potential application for the determination of other protease biomarkers.

Development of Carbon Nanotubes (CNTs) Membrane from Waste Plastic: Towards Waste to Wealth for Water Treatment

Plastic, a non-biodegradable material has always been a concern to the environment and people. This single-use item generates waste to landfills and it persists for centuries once disposed. The urge of transforming such material into a highly valuable product has sought attention from many researchers. This study emphasizes on a nanotechnological approach to synthesize vertically-aligned carbon nanotubes (CNTs) on a substrate template using commercially available plastic bags as carbon precursor. CNTs are grown inside a hexagonally arranged nanoporous anodic alumina membranes (NAAMs). CNTs are liberated by wet chemical etching to dissolve the alumina matrix. The resulting CNTs are used as adsorption media filters for water treatment purpose. The high adsorption affinity towards heavy metals, organic matters and microbes, ability to antifouling and self-cleaning function have made CNTs a better choice over others. This article briefly discusses the catalyst-free synthesis, growth mechanism, characterization and functionalization of CNTs for water treatment application.

Fabrication of nanostructured Pt electrodes templated by nanoporous anodic alumina for electrochemical sensors

Although platinum electrodes are widely used in electrochemical sensors their functionality can be affected by formed components of complex biological fluids. We demonstrated a simple approach to the formation of Pt nanopillars sandwiched between W metal layers and nanoporous anodic alumina membranes, by anodization of W/Al bilayers and substitution of WO3 nanopillars formed by the local anodization of W under the nanopores with Pt. By exploiting the Pourbaix corrosion diagram of W, we could find conditions that allow the selective dissolution of WO3 in pH = 7.4 buffer solution and formation of Pt nanopillars inside the nanoporous aluminum membrane via electroless deposition.

Features of colloidal silica deposits dip coated onto porous alumina membranes from aqueous suspensions

The present work is directed towards understanding the development of coating morphologies and the accompanying hydrodynamics of suspension flows during dip coating on porous substrates. Colloidal silica particles are deposited from aqueous suspension onto nanoporous alumina membranes. The choice of colloidal silica as the model system is motivated by its popularity in fabrication of antireflection coatings, and as nanostructured material templates for electrochemical and catalytic applications. Nanoporous alumina as substrate is notable for its chemical and thermal stability, and its ability to form self-organized pore structures. The objective here is to characterize the dependence of coating morphologies on membrane pore size, wettability, dip coating speed, and size of colloidal particles in suspension. A coating regime map is formulated based on different morphologies obtained for coatings deposited under different operating parameter spaces. The map indicates existence of two perceptibly distinct regimes which emanate from particle-induced interfacial deformation of the meniscus: Scarcely populated particulate deposition regime and densely packed coating regime having significant amount of particle deposition. The experimental results are analysed and explained using numerical results from earlier mathematical models in literature which cater to modified Landau-Levich formulation for porous substrates, as well as the hydrodynamics of colloidal assembly on moving substrates.

Cylindrical nanowire arrays: From advanced fabrication to static and microwave magnetic properties

This article reviews information on arrays of cylindrical magnetic nanowires grown electrochemically inside ordered nanoporous alumina membranes, summarizing some of the most relevant aspects about the advanced synthesis of nanowires and their overall static and microwave magnetic properties. The electrochemical details for the preparation of templates with well-defined hexagonal ordering are addressed focusing on the different anodization methods including mild, hard, pulsed or anodization of aluminum rods. A section follows on the growth of metallic nanowires, either as single element (i.e., Fe, Ni, Co), alloys (i.e., CoFe, CoNi, FeNi) or modulated in composition (i.e., Ferromagnetic/Metal). The static magnetic properties as anisotropy, coercivity and magnetostatic interactions are overviewed with particular emphasis on the influence of magnetocrystalline anisotropy and on the temperature dependence of those properties. The last section is devoted to the ferromagnetic resonance of nanowire arrays of different composition. The dependence of microwave absorption on the orientation of applied field is also a useful tool to determine the magnetic anisotropy parameters and the significance of magnetostatic interactions. The magnetization easy axis can be switched from the nanowire direction to the plane of the membrane as the nanowire filling factor increases or at a compensation temperature, in both cases it derives from the energetic balance of anisotropy and magnetostatic interactions among nanowires. A final subsection is devoted to the spin waves resonance spectra, and the perspectives of applications making use of microwave properties. We expect the article can be useful for researchers interested on the topic and provide a wide overview on the matter to those starting a new research line.

Electrochemical sensing at nanoporous film‐coated electrodes

AbstractIn this paper, we highlight the uniqueness of nanoporous film‐coated electrodes as electrochemical sensing platforms. Specifically, we focus on discussing electrodes coated with insulator‐based monolithic films comprising vertically‐oriented, rigid cylindrical nanopores of uniform diameters (2–200 nm). The electrode coating results in the formation of an array of recessed nanodisk electrodes, and thus we named them recessed nanodisk‐array electrodes (RNEs). We first summarize the properties of nanoporous films commonly used for RNE fabrication, including nanoporous anodic alumina membranes, track‐etched polymer membranes, block copolymer‐derived nanoporous films, and mesoporous silica films. Subsequently, we discuss representative works that take advantage of the uniform size/shape of the nanopores for enhancing electrochemical detection selectivity and sensitivity. RNE‐based sensors measure faradaic currents from redox‐active analytes or exogenously‐added electroactive species that penetrate through the nanopores, or those from redox‐active moieties tethered to the surface of the nanopores or underlying electrodes. The enhanced detection selectivity of these sensors is attributed to the preferential partitioning of analytes into the nanopores or steric/electrostatic exclusion of interfering species. In particular, the uniform sizes/shapes of RNE nanopores play key roles in their higher molecular sieving selectivity and also in the better control of the detection selectivity based on electrostatic/chemical interactions. The detection sensitivity of RNE‐based sensors can be improved by tailoring the chemical environments of the nanopores for analyte preconcentration or for steric/electrostatic manipulation of the dynamics of redox‐tagged binding moieties. These unique characteristics of RNEs, in addition to the mitigation of electrode fouling by the nanoporous films, will enable the development of pretreatment‐free electrochemical sensors for complex matrix solutions.

Nanoporous Alumina Membranes for Sugar Industry: An Investigation of Sintering Parameters Influence onUltrafiltration Performance

Ultrafiltration membranes offer a progressive and efficient means to filter out various process fluids. The prime factor influencing ultrafiltration to a great extent is the porosity of the membranes employed. Regarding membrane development, alumina membranes are extensively studied due to their uniform porosity and mechanical strength. The present research work is specifically aimed towards the investigation of nanoporous alumina membranes, as a function of sintering parameters, on ultrafiltration performance. Alumina membranes are fabricated by sintering at various temperatures ranging from 1200–1300 °C for different holding times between 5–15 h. The morphological analysis, conducted using Scanning electron microscopy (SEM), revealed a homogeneous distribution of pores throughout the surface and cross-section of the membranes developed. It was observed that an increase in the sintering temperature and time resulted in a gradual decrease in the average pore size. A sample with an optimal pore size of 73.65 nm achieved after sintering at 1250 °C for 15 h, was used for the evaluation of ultrafiltration performance. However, the best mechanical strength and highest stress-bearing ability were exhibited by the sample sintered at 1300 °C for 5 h, whereas the sample sintered at 1250 °C for 5 h displayed the highest strain in terms of compression. The selected alumina membrane sample demonstrated excellent performance in the ultrafiltration of sugarcane juice, compared to the other process liquids.

Influence of Pore-Size/Porosity on Ion Transport and Static BSA Fouling for TiO2-Covered Nanoporous Alumina Membranes

The influence of geometrical parameters (pore radii and porosity) on ion transport through two almost ideal nanoporous alumina membranes (NPAMs) coated with a thin TiO2 layer by the atomic layer deposition technique (Sf-NPAM/TiO2 and Ox-NPAM/TiO2 samples) was analyzed by membrane potential and electrochemical impedance spectroscopy measurements. The results showed the significant effect of pore radii (10 nm for Sf-NPAM/TiO2 and 13 nm for Ox-NPAM/TiO2) when compared with porosity (9% and 6%, respectively). Both electrochemical techniques were also used for estimation of protein (bovine serum albumin or BSA) static fouling, and the results seem to indicate deposition of a BSA layer on the Sf-NPAM/TiO2 fouled membrane surface but pore-wall deposition in the case of the fouled Ox-NPAM/TiO2 sample. Moreover, a typical and simple optical technique such as light transmission/reflection (wavelength ranging between 0 and 2000 nm) was also used for membrane analysis, showing only slight transmittance differences in the visible region when both clean membranes were compared. However, a rather significant transmittance reduction (~18%) was observed for the fouled Sf-NPAM/TiO2 sample compared to the fouled Ox-NPAM/TiO2 sample, and was associated with BSA deposition on the membrane surface, thus supporting the electrochemical analysis results.

Optimization of High-Density Fe-Au Nano-Arrays for Surface-Enhanced Raman Spectroscopy of Biological Samples.

The method of realizing nanostructures using porous alumina templates has attracted interest due to the precise geometry and cheap cost of nanofabrication. In this work, nanoporous alumina membranes were utilized to realize a forest of nanowires, providing a bottom-up nanofabrication method suitable for surface-enhanced Raman spectroscopy (SERS). Gold and iron were electroplated through the straight channels of the membrane. The resulting nanowires are, indeed, made of an active element for plasmonic resonance and SERS as the hexagonal distribution of the nanowires and the extreme high density of the nanowires allows to excite the plasmon and detect the Raman signal. The method to reduce the distance between pores and, consequently, the distance of the nanowires after electrodeposition is optimized here. Indeed, it has been predicted that the light intensity enhancement factor is up to 1012 when the gap is small than 10 nm. Measurements of Raman signal of thiol groups drying on the gold nanowires show that the performance of the device is improved. As the thiol group can be linked to proteins, the device has the potential of a biosensor for the detection of a few biomolecules. To assess the performance of the device and demonstrate its ability to analyze biological solutions, we used it as SERS substrates to examine solutions of IgG in low abundance ranges. The results of the test indicate that the sensor can convincingly detect biomolecules in physiologically relevant ranges.

On the temperature dependent magnetization in dual-phase Co nanowires confinedly electrodeposited inside nanoporous alumina membrane

The present paper reports the temperature dependent magnetization in dual-phase Co nanowires electrodeposited inside nanoporous alumina membrane. The Co nanowires were grown inside the nanochannels of the alumina membrane using an acidic sulphate bath (pH 3). Phase analysis, in combination with magnetic measurements, confirmed the mixed-phase structures as hcp and fcc-Co. The dominant fcc-Co phase appears with a minor hcp-Co phase having major c-axis orientation perpendicular to the nanowire axis. The role of phase structures and the interplay of magnetic anisotropies have been discussed to understand the temperature dependent magnetization of these dual-phase Co nanowires embedded inside alumina membrane. The temperature dependent reorientation of easy magnetization axis and the resulting magnetic properties could be ascribed to the magneto-structural coupling for such confinedly grown Co nanowires.

Morphological features and dewetting behaviour of thin polymer films coated on porous substrates

Abstract Polymer thin films coated onto non-wetting substrates tend to become unstable and dewet when heated above the glass transition temperatures. Such dynamics are relevant to applications like organic microelectronics and lithography that require non-continuous and arrayed thin polymer films. In several situations, the substrate of interest has finite permeability due to its porous surface, as in paper, fabric, or sandstones, which may modify the hydrodynamics of a liquid film. In the present work, we report model experiments of thin polystyrene films dewetting nanoporous alumina membranes of different pore sizes. Polystyrene films are prepared by spin coating a toluene-based solution, and heated above the glass transition temperature to initiate dewetting. The effect of annealing time on morphologies of the film is studied. During annealing, the film dewets the porous substrate. However, as pores become saturated, excess polymer self-organizes into a uniform coating. The dynamics of liquid film dewetting near permeable substrates are explained from a fluid mechanical perspective through numerical simulations.

A Sensitive FRET Biosensor Based on Carbon Dots-Modified Nanoporous Membrane for 8-hydroxy-2'-Deoxyguanosine (8-OHdG) Detection with Au@ZIF-8 Nanoparticles as Signal Quenchers.

A sensitive fluorescence resonance energy transfer (FRET) biosensor is proposed to detect 8-hydroxy-2′-deoxyguanosine (8-OHdG), which is a typical DNA oxidation damage product excreted in human urine. The FRET biosensor was based on carbon dots (CDs)-modified nanoporous alumina membrane with CDs as fluorescence donors. Gold nanoparticles were encapsulated in zeolitic imidazolate framework-8 to form Au@ZIF-8 nanoparticles as signal quenchers. CDs and Au@ZIF-8 nanoparticles were biofunctionalized by 8-OHdG antibody. The capture of 8-OHdG on the membrane substrates can bring Au@ZIF-8 nanoparticles closely to CDs. With 350 nm excitation, the fluorescence of CDs was quenched by Au@ZIF-8 nanoparticles and FRET effect occurred. The quenching efficiency was analyzed. The limit of detection (LOD) was 0.31 nM. Interference experiments of the FRET biosensor showed good specificity for 8-OHdG detection. The biosensor could detect urinary 8-OHdG sensitively and selectively with simple sample pretreatment processes. It shows applicability for detecting biomarkers of DNA damage in urine or other biological fluids.

Controllable Reduction of Anionic Contamination in Degradable Amorphous Anodic Alumina Nanoporous Membranes

A controlled approach to an impurity-free composition of porous anodic alumina (PAA) membranes with maintenance of a well-ordered architecture is needed for further progress in numerous subactiviti...

Enhancement the perpendicular magnetic anisotropy of nanopatterned hard/soft bilayer magnetic antidot arrays for spintronic application

Development of perpendicular magnetic anisotropy thin films is a requisite for many applications. In this work, we have illustrated the enhancement of the PMA of Hard (Co)/Soft (Permalloy, Py) ferromagnetic bilayers by depositing them onto nanoporous anodic alumina membranes with different hole diameters varying in the range between 30 nm and 95 nm. A dramatic change in the hysteresis loops behaviour with hole size, D, and magnetic surface cover ratio parameters has been observed: (1) for samples with small antidot hole diameters, the in-plane (INP) hysteresis loops show single-step magnetic behaviour; (2) for D = 75 nm, the hysteresis loops of Co/Py and Py samples exhibit a multistep magnetic behaviour; (3) a decreasing coercivity in the INP hysteresis loops for antidot arrays samples with D> 75 nm has been detected as a consequence of the reduction of the INP magnetic anisotropy and the rising of the out-of-plane component. A crossover of the magnetic anisotropy from the INP to out-of-plane for bilayer antidot samples has been observed for Co/Py ferromagnetic bilayers, favoured by the interfacial exchange coupling between the two ferromagnetic materials. These findings can be of high interest for the development of novel magnetic sensors and for perpendicular-magnetic recording patterned media based on template-assisted deposition techniques.

Enhanced in-plane magnetic anisotropy in thermally treated arrays of Co-Pt nanowires

Ordered arrays of CoxPt100-x cylindrical nanowires (NWs) with x = 90, 80, 70 were synthesized by template-assisted electrodeposition using nanoporous alumina membranes of 55 nm pore diameter. The obtained NWs alloys crystallize in hcp and/or fcc structures, depending on the composition and thermal treatment, resulting in different magnetic behaviors. The magnetic anisotropy was studied as a function of composition and crystalline structure in as-deposited and annealed samples. An enhanced coercivity was obtained for the Co70Pt30 NWs array, in which in-plane anisotropy (e.g., perpendicular to the NWs axis) was found. These characteristics have not been reported for NWs of this kind. A simplified model of effective anisotropy including shape, magnetostatic interaction and magnetocrystalline contributions is presented, which appropriately describes the magnetic behavior of the CoxPt100-x NWs arrays before and after annealing.