Generation of Tamm Plasmon Resonances for Light Confinement Applications in Narrowband Gradient-Index Filters Based on Nanoporous Anodic Alumina.

Gold-coated gradient-index filters based on nanoporous anodic alumina (Au-coated NAA-GIFs) were used as model platforms to elucidate how Tamm plasmons can be tailored by engineering the geometric features of the plasmonic and photonic components of these hybrid structures. NAA-GIFs with well-resolved, intense photonic stopbands at two positions of the visible spectrum were fabricated through sinusoidal pulse anodization. These model photonic crystals were used to assess how the quality of Tamm plasmon resonances can be enhanced by tuning the features of the dielectric mirror and the thickness of the porous gold coating layer. It is found that the highest value of the quality factor of Tamm resonance (Q Tamm = 237) is obtained for 11 nm of gold on a dielectric mirror with low porosity corresponding to the resonant spectral position of λTamm of ∼698 nm. Our analysis indicates that Tamm resonances in as-produced Au-coated NAA-GIFs are weak due to the constrained range of wavelengths (narrow bands) at which these photonic crystal structures reflect light. However, after broadening of their photonic stopband upon pore widening, Tamm resonances become better resolved, with higher intensity. It is also observed that the quality of light confinement worsens progressively with the thickness of the porous gold coating layer after a critical value. In contrast to conventional surface plasmon resonance systems, this hybrid Tamm porous system does not require complex coupling systems and provides a nanoporous structure that can be readily tailored for a range of photonic technologies such as sensing and lasing.

Compact formulation of the transparent-absorbing isotropic interface electromagnetic problem.

A complete formulation of the electromagnetic problem corresponding to the light incidence from a transparent to an absorbing medium (isotropic materials) is developed. According to the standard separation in s and p polarization cases, we explicitly obtain all the relevant formulas that relate the polarization and Poynting vectors of the reflected and transmitted beams with the incident ones. Overall, the procedure is compact since it is short and complete.

Real-Time Monitoring of Doxorubicin Release from Hybrid Nanoporous Anodic Alumina Structures.

This work demonstrates an advanced approach to fabricate Hybrid nanoporous anodic alumina gradient-index filters (Hy-NAA-GIFs) through a heterogeneous anodization process combining sinusoidal current-density anodization and constant potential anodization. As a result, the hybrid structure obtained reveals a single photonic stopband (PSB), which falls within the absorption region of the drug molecule and the intensity of the spectrum that are far from such absorption range. The prepared structures were loaded with the doxorubicin (DOX) drug through the drop-casting method, which allows for evaluating the maximum reflectance of the relative height of the PSB with the average reflectance of the spectrum intensity. Thereafter, this property has been applied in a flow cell setup connected to a reflectance spectrophotometer where different drug-loaded samples were placed to study the behavior and kinetics of the drug release in real-time by varying two parameters, i.e., different pore length and flow rates. As such, obtained results were analyzed with a model that includes a sum of two inverted exponential decay functions with two different characteristic time releases. Overall, this study opens up several possibilities for the Hy-NAA-GIFs to study the drug kinetics from nanoporous structures.

Optical Platform to Analyze a Model Drug-Loading and Releasing Profile Based on Nanoporous Anodic Alumina Gradient Index Filters.

In this work, a methodology that exploits the optical properties of the nanoporous anodic alumina gradient index filters (NAA-GIFs) has been developed and applied to evaluate in real time the release dynamics of a cargo molecule, acting as a model drug, filling the pores. NAA-GIFs with two photonic stopbands (PSBs) were prepared with one of its stop bands in the same absorption wavelength range of the cargo molecule, whereas the second stopband away from this absorption range. Numerical simulation and experiments confirm that the relative height of the high reflectance bands in the reflectance spectra of NAA-GIFs filled with the drug can be related to the relative amount of drug filling the pores. This property has been applied in a flow cell setup to measure in real-time the release dynamics of NAA-GIFs with the inner pore surface modified by layer-by-layer deposition of polyelectrolytes and loaded with the cargo molecule. The methodology developed in this work acts as a tool for the study of drug delivery from porous nanostructures.

Advances in Optical Biosensors and Sensors Using Nanoporous Anodic Alumina.

This review paper focuses on recent progress in optical biosensors using self-ordered nanoporous anodic alumina. We present the fabrication of self-ordered nanoporous anodic alumina, surface functionalization, and optical sensor applications. We show that self-ordered nanoporous anodic alumina has good potential for use in the fabrication of antibody-based (immunosensor), aptamer-based (aptasensor), gene-based (genosensor), peptide-based, and enzyme-based optical biosensors. The fabricated optical biosensors presented high sensitivity and selectivity. In addition, we also showed that the performance of the biosensors and the self-ordered nanoporous anodic alumina can be used for assessing biomolecules, heavy ions, and gas molecules.

Tunable Nanoporous Anodic Alumina Photonic Crystals by Gaussian Pulse Anodization.

This study presents a Gaussian pulse anodization approach to generate nanoporous photonic crystals with highly tunable and controllable optical properties across the visible-NIR spectrum. Nanoporous anodic alumina Gaussian photonic crystals (NAA-GPCs) are fabricated in oxalic acid electrolyte by Gaussian pulse anodization, a novel form of pulse-like anodization. The effect of the Gaussian pulse width in the anodization profile on the optical properties of these photonic crystals is assessed by systematically varying this fabrication parameter from 5 to 60 s. The optical features of the characteristic photonic stopband (PSB) of NAA-GPCs-the position of the central wavelength, full width at half-maximum, and intensity-are found to be highly dependent on the Gaussian pulse width, the angle of incidence of incoming photons, and the nanopore diameter of NAA-GPCs. The effective medium of NAA-GPCs is assessed by monitoring spectral shifts in their characteristic PSB upon infiltration of their nanoporous structure with analytical solutions of d-glucose of varying concentration (0.0125-1 M). Experimental results are validated and mechanistically described by theoretical simulations, using the Looyenga-Landau-Lifshitz effective medium approximation model. Our findings demonstrate that Gaussian pulse anodization is an effective nanofabrication approach to producing highly sensitive NAA-based PC structures with versatile and tunable PSBs across the spectral regions. The findings provide new exiting opportunities to integrate these unique PC structures into photonic sensors and other platform materials for light-based technologies.

An optical biosensor for the determination of cathepsin B as a cancer-associated enzyme using nanoporous anodic alumina modified with human serum albumin-thionine.

An interferometric reflectance spectroscopy-based biosensor for the determination of cathepsin B (Cat B) as a cancer-related enzyme has been fabricated. For this purpose, the nanoporous anodic alumina (NAA) was fabricated electrochemically. The NAA was then modified with the amino-silane coupling agent. After that, human serum albumin (HSA) was immobilized into the NAA pores by using glutaraldehyde as a cross-linking agent. Subsequently, the carboxylic group of HSA was activated with N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS) to attach to thionine (TH) as a photoprobe to fabricate the labeled HSA (HSA-TH). HSA-TH plays a significant role in this sensor to determine cathepsin B as a model analyte for the development of the interferometric reflectance spectroscopy-based biosensor for the measurement of protease. The attached TH adsorbed the illuminated white light on NAA modified with HSA-TH. Therefore, the intensity of the reflected light to the charge-coupled device (CCD) detector decreased in the wavelength range 450-1050 nm. In the presence of Cat B, HAS-TH cleaved into short peptide fragments and washed away by flow cell system. Since TH was removed from NAA, the intensity of the reflected light increased. The peak area has a logarithmic relationship with the concentration of Cat B in the range 0.5 to 64.0 nM. The limit of detection of the biosensor sensor was 0.08 nM. The optical sensor was used for the determination of Cat B in a human serum sample. Graphical abstract Schematic presentation of biosensor for the determination of the cathepsin B which is based on nanoporous anodic alumina modified with HSA-thionine. The principle response of the optical biosensor is based on detecting changes in the intensity of the reflected light after cleaving the immobilized HSA-thionine by cathepsin B into short peptide fragments.

Remote biosensor for the determination of trypsin by using nanoporous anodic alumina as a three-dimensional nanostructured material.

The determination of trypsin in the human real sample is a routine medical investigation to assess the pancreatic disease. Herein, we fabricated an interferometric reflectance spectroscopy based biosensor for the determination trypsin. For this purpose, urease and fluorescein 5(6)-isothiocyanate (FLITC) were immobilized on the nanoporous anodic alumina (NAA). The operation principle of the proposed biosensor is based on the change in the pH of the solution during the reaction of urease and urea and therefore change in the light-absorbing ability of FLITC in the presence of trypsin. The reaction of the urease enzyme with urea increased the pH of the solution because of producing ammonia. This increase in the pH of solution increased the light-absorbing ability of the immobilized FLITC on NAA and therefore the intensity of the reflected light from the NAA to the charge-coupled device detector decreased. In the presence of trypsin, the catalytic activity of immobilized urease on NAA decreased. This decrease in the activity of urease enzyme consequent on the decrease in the amount of the generated ammonia. Therefore, the immobilized FLITC on the NAA did not absorb more light and consciously, the intensity of the light reflected light into the detector increased. The proposed biosensor exhibited a good response to the concentration of trypsin in the range of 0.25-20 µg.mL-1 with the limit of detection of 0.06 µg.mL-1.

Highly sensitive IRS based biosensor for the determination of cytochrome c as a cancer marker by using nanoporous anodic alumina modified with trypsin.

The determination of cytochrome c in the human serum sample is a regular medical investigation performed to assess cancer diseases. Herein, we used interferometric reflectance spectroscopy (IRS) based biosensor for the determination of cytochrome c. For this purpose first, the nanoporous anodic alumina (NAA) was fabricated. Then, the NAA pore walls were functionalized with 3-aminopropyl trimethoxy silane (NAA-NH2). Subsequently, the trypsin enzyme was immobilized on the NAA pore walls. The sensing principle of proposed IRS sensor to cytochrome c is based on a change in the intensity of the reflected light to a charge-coupled device (CCD) detector after digesting of cytochrome c by immobilized trypsin enzymes on NAA-NH2 into the heme-peptide fragment. The heme-peptide fragment then oxidized 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) to green color ABTS·- anion radical in the presence of hydrogen peroxide. The generated green color ABTS·- anion radical solution adsorbed the white light and therefore the intensity of the reflected light from NAA to the CCD decreased. The decrease in the intensity of the white light had a logarithmic relationship with the concentration of the cytochrome c in the range of 1-100 nM. The limit of detections (LOD) for cytochrome c was 0.5 nM. The proposed biosensor exhibited high selectivity, sensitivity, and good stability.

Aptamer-Based Nanoporous Anodic Alumina Interferometric Biosensor for Real-Time Thrombin Detection.

Aptamer biosensors are one of the most powerful techniques in biosensing. Achieving the best platform to use in aptamer biosensors typically includes crucial chemical modifications that enable aptamer immobilization on the surface in the most efficient manner. These chemical modifications must be well defined. In this work we propose nanoporous anodic alumina (NAA) chemically modified with streptavidin as a platform for aptamer immobilization. The immobilization of biotinylated thrombin binding aptamer (TBA) was monitored in real time by means of reflective interferometric spectroscopy (RIfS). The study has permitted to characterize in real time the path to immobilize TBA on the inner pore walls of NAA. Furthermore, this study provides an accurate label-free method to detect thrombin in real-time with high affinity and specificity.

Highly sensitive aptasensor based on interferometric reflectance spectroscopy for the determination of amyloid ß as an Alzheimer's disease biomarkers using nanoporous anodic alumina.

It is well known that Alzheimer's disease is one of the global challenges for the 21st century. Therefore, it is urgent to develop a reliable biosensor for the detection of this disease. Here in, we have developed for the first time, an aptasensor based on interferometric reflectance spectroscopy (IRS) for the determination of amyloid ß (Aß) oligomers that is an Alzheimer's disease biomarker. For this purpose, the nanoporous anodic alumina (NAA) was first fabricated. After that, the pore walls of the NAA were modified with (3-aminopropyl) trimethoxysilane (NAA-NH2). The amino-terminal aptamers probe were then attached to the pore walls of the NAA-NH2 by using glutaraldehyde (GA) as the cross-linking agent. Subsequently, methylene blue (MB) was immobilized into the aptamer as the photo-probe, generating the MB/G-quadruplex complex. Since MB has a high absorption coefficient, the intensity of the reflected white light to the charge-coupled device (CCD) detector decreased. In the presence of the Aß oligomers that have high affinity to the immobilized aptamer, the MB/quadruplex complex broke and MB washed away from the aptasensor. Therefore, the intensity of the reflected white light to the CCD detector increased. The increased signal intensity of the aptasensor has a logarithmic relationship with the concentration of Aß oligomers. The proposed aptasensor exhibited a good response to the concentration of Aß oligomers in the range of 0.5-50.0 µg × mL-1. The experimental detection limit was of 0.02 µg × mL-1 (at 3σ/S). The proposed optical aptasensor exhibited good selectivity, linear range, and stability.

Real-Time Monitoring of Biotinylated Molecules Detection Dynamics in Nanoporous Anodic Alumina for Bio-Sensing.

The chemical modification, or functionalization, of the surfaces of nanomaterials is a key step to achieve biosensors with the best sensitivity and selectivity. The surface modification of biosensors usually comprises several modification steps that have to be optimized. Real-time monitoring of all the reactions taking place during such modification steps can be a highly helpful tool for optimization. In this work, we propose nanoporous anodic alumina (NAA) functionalized with the streptavidin-biotin complex as a platform towards label-free biosensors. Using reflective interferometric spectroscopy (RIfS), the streptavidin-biotin complex formation, using biotinylated thrombin as a molecule model, was monitored in real-time. The study compared the performance of different NAA pore sizes in order to achieve the highest response. Furthermore, the optimal streptavidin concentration that enabled the efficient detection of the biotinylated thrombin attachment was estimated. Finally, the ability of the NAA-RIfS system to quantify the concentration of biotinylated thrombin was evaluated. This study provides an optimized characterization method to monitor the chemical reactions that take place during the biotinylated molecules attachment within the NAA pores.

A photoelectrochemical sandwich immunoassay for protein S100ß, a biomarker for Alzheimer's disease, using an ITO electrode modified with a reduced graphene oxide-gold conjugate and CdS-labeled secondary antibody.

A sandwich-type photoelectrochemical immunoassay is described for the protein S100ß which is an Alzheimer's disease biomarker found in the astrocytes of the brain. Antibody against S100ß (anti-S100ß) was labeled with CdS quantum dots and then acted as a secondary antibody. The labeled antibody was characterized by FTIR, ultraviolet-visible and fluorescence spectroscopy. An indium-tin oxide (ITO) electrode was modified with a nanocomposite prepared from reduced graphene oxide and gold nanoparticles. Then, a sol-gel film containing isocyanate functional groups (-N=C=O) was cast on the surface of the electrode. The NCO group reacts with amino groups of the labeled antibody to covalently bind them to the surface. The S100ß was bound by the primary immobilized antibody on the rGO-Au/ITO electrode and then sandwiched with the labeled secondary antibody. Cyclic voltammetry and electrochemical impedance spectroscopy were applied to confirm the stepwise changes in the electrochemical properties of the electrode surface. The photoelectrochemical immunoassay, typically operated at a potential of +0.2 V (vs. Ag|AgClsat) gives a signal that is related to the logarithm of the S100ß concentration in the range from 0.25 to 10 ng·mL-1 with a lower detection limit of 0.15 pg·mL-1. The method was successfully applied to the determination of S100ß in human serum samples. Graphical abstract Schematic presentation of an immunosensor which is based on an indium tin oxide modified with reduced graphene oxide decorated with gold nanocomposite and antibody. The immunosensor was applied for the determination of S100ß biomarker by using in the labeled antibody.

Stacked Nanoporous Anodic Alumina Gradient-Index Filters with Tunable Multispectral Photonic Stopbands as Sensing Platforms.

This study presents the development and optical engineering of stacked nanoporous anodic alumina gradient-index (NAA-GIFs) filters with tunable multispectral photonic stopbands for sensing applications. The structure of these photonic crystals (PC) is formed by stacked layers of NAA produced with sinusoidally modified effective medium. The progressive modification of the sinusoidal period during the anodization process enables the generation and precise tuning of the characteristic photonic stopbands (PSB) (i.e., one per sinusoidal period in the anodization profile) of these PC structures. Four types of NAA-GIFs featuring three distinctive PSBs positioned within the visible spectral region are developed. The sensitivity of the effective medium of these NAA-GIFs is systematically assessed by measuring spectral shifts in the characteristic PSBs upon infiltration of their nanoporous structure with analytical solutions of d-glucose with several concentrations (0.025-1 M). This study provides new insights into the intrinsic relationship between the nanoporous architecture of these PCs and their optical properties, generating opportunities to fabricate advanced optical sensing systems for high-throughput and multiplexed detection of analytes in a single sensing platform.

Nanoporous Anodic Alumina Surface Modification by Electrostatic, Covalent, and Immune Complexation Binding Investigated by Capillary Filling.

The fluid imbibition-coupled laser interferometry (FICLI) technique has been applied to detect and quantify surface changes and pore dimension variations in nanoporous anodic alumina (NAA) structures. FICLI is a noninvasive optical technique that permits the determination of the NAA average pore radius with high accuracy. In this work, the technique is applied after each step of different surface modification paths of the NAA pores: (i) electrostatic immobilization of bovine serum albumin (BSA), (ii) covalent attachment of streptavidin via (3-aminipropyl)-triethoxysilane and glutaraldehyde grafting, and (iii) immune complexation. Results show that BSA attachment can be detected as a reduction in estimated radius from FICLI with high accuracy and reproducibility. In the case of the covalent attachment of streptavidin, FICLI is able to recognize a multilayer formation of the silane and the protein. For immune complexation, the technique is able to detect different antibody-antigen bindings and distinguish different dynamics among different immune species.

Impact of inkjet printed ZnO electron transport layer on the characteristics of polymer solar cells.

In this paper, we demonstrate that zinc oxide (ZnO) layers deposited by inkjet printing (IJP) can be successfully applied to the low-temperature fabrication of efficient inverted polymer solar cells (i-PSCs). The effects of ZnO layers deposited by IJP as electron transport layer (ETL) on the performance of i-PSCs based on PTB7-Th:PC70BM active layers are investigated. The morphology of the ZnO-IJP layers was analysed by AFM, and compared to that of ZnO layers deposited by different techniques. The study shows that the morphology of the ZnO underlayer has a dramatic effect on the band structure and non-geminate recombination kinetics of the active layer deposited on top of it. Charge carrier and transient photovoltage measurements show that non-geminate recombination is governed by deep trap states in devices made from ZnO-IJP while trapping is less significant for other types of ZnO. The power conversion efficiency of the devices made from ZnO-IJP is mostly limited by their slightly lower J SC, resulting from non-optimum photon conversion efficiency in the visible part of the solar spectrum. Despite these minor limitations their J-V characteristics compare very favourably with that of devices made from ZnO layer deposited using different techniques.

3D Nanoporous Anodic Alumina Structures for Sustained Drug Release.

The use of nanoporous anodic alumina (NAA) for the development of drug delivery systems has gained much attention in recent years. The release of drugs loaded inside NAA pores is complex and depends on the morphology of the pores. In this study, NAA, with different three-dimensional (3D) pore structures (cylindrical pores with several pore diameters, multilayered nanofunnels, and multilayered inverted funnels) were fabricated, and their respective drug delivery rates were studied and modeled using doxorubicin as a model drug. The obtained results reveal optimal modeling of all 3D pore structures, differentiating two drug release stages. Thus, an initial short-term and a sustained long-term release were successfully modeled by the Higuchi and the Korsmeyer-Peppas equations, respectively. This study demonstrates the influence of pore geometries on drug release rates, and further presents a sustained long-term drug release that exceeds 60 days without an undesired initial burst.

Degradation Analysis of Encapsulated and Nonencapsulated TiO2/PTB7:PC70BM/V2O5 Solar Cells under Ambient Conditions via Impedance Spectroscopy.

Inverted organic cells are promising devices for sustainable and low-cost future electric generation. In this work, we present the degradation mechanisms studied in ITO/TiO2/PTB7:PC70BM/V2O5/Ag inverted organic solar cells (iOSCs) by impedance spectroscopy (IS). Measurements were performed on encapsulated (controlled environment) and nonencapsulated (ambient condition) cells following their temporal evolution under AM1.5 illumination for several voltage biases. From the impedance spectra, analyzed in terms of resistive/capacitive equivalent circuits, we were able to identify that the most sensitive layers inside of the device are contact layers. According with presented, IS technique is useful for determining the materials that have more influence on the degradation of organic solar cells. We demonstrate that IS is a powerful technique to identify the limiting mechanisms and to establish the limiting materials inside of the iOSCs.

Optical Monitoring of the Capillary Filling Dynamics Variation in Nanoporous Anodic Alumina toward Sensing Applications.

Fluid imbibition-coupled laser interferometry (FICLI) is a technique in which the kinetics of a fluid infiltrating a nanoporous anodic alumina (NAA) membrane is monitored by the interference of a laser beam at the membrane top and bottom surfaces. Further processing of the measured data results in an estimate of the pore radius. In this work, we study the accuracy of FICLI in the detection of small changes in pore radius, and we evaluate the possibility of using such detection as a sensing paradigm. The accuracy is estimated by measuring samples with increasing pore radius, obtained by successive wet etching steps, and repeatability is evaluated by using different liquids. For decreasing pore radius, samples obtained by the successive deposition of polyelectrolyte double layers are used. With the aim of evaluating the possibility of the FICLI method to sense biological binding events, BSA attachment detection is demonstrated by applying FICLI to samples before and after immobilization of the protein. Results show that the technique permits an accurate estimation of the pore radius, the pore-etching rate (with a radius variation of retch,DI = 1.05 nm/min ± 0.11 nm/min), and the polyelectrolyte double layer thickness (with a radius variation of rPAH/PSS = 3.2 nm ± 0.2 nm per polyelectrolyte double layer). Furthermore, the pore radius reduction measured after BSA immobilization (dBSA = 4.9 nm ± 1.1 nm) is in good agreement with the protein size, as reported in the literature. With these results, we provide a sound basis for the applicability of FICLI as a sensitive technique for the characterization of NAA pore radius modifications.

Nanoporous Anodic Alumina 3D FDTD Modelling for a Broad Range of Inter-pore Distances.

The capability of the finite difference time domain (FDTD) method for the numerical modelling of the optical properties of nanoporous anodic alumina (NAA) in a broad range of inter-pore distances is evaluated. FDTD permits taking into account in the same numerical framework all the structural features of NAA, such as the texturization of the interfaces or the incorporation of electrolyte anions in the aluminium oxide host. The evaluation is carried out by comparing reflectance measurements from two samples with two very different inter-pore distances with the simulation results. Results show that considering the texturization is crucial to obtain good agreement with the measurements. On the other hand, including the anionic layer in the model leads to a second-order contribution to the reflectance spectrum.