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.

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.

Role of Spectral Resonance Features and Surface Chemistry in the Optical Sensitivity of Light-Confining Nanoporous Photonic Crystals.

Nanoporous anodic alumina optical microcavities (NAA-µQVs) with spectrally tunable resonance band and surface chemistry are used as model light-confining photonic crystal (PC) platforms to elucidate the combined effect of spectral light confinement features and surface chemistry on optical sensitivity. These model nanoporous PCs show well-resolved, spectrally tunable resonance bands (RBs), the central wavelength of which is engineered from ∼400 to 800 nm by the period of the input anodization profile. The optical sensitivity of the as-produced (hydrophilic) and dichlorodimethylsilane-functionalized (hydrophobic) NAA-µQVs is studied by monitoring dynamic spectral shifts of their RB upon infiltration with organic- and aqueous-based analytical solutions of equally varying refractive index, from 1.333 to 1.345 RIU. Our findings demonstrate that hydrophilic NAA-µQVs show ∼81 and 35% superior sensitivity to their hydrophobic counterparts for organic- and aqueous-based analytical solutions, respectively. Interestingly, the sensitivity of hydrophilic NAA-µQVs per unit of spectral shift is more than 3-fold higher in organic than in aqueous matrices upon equal change of refractive index, with values of 0.347 ± 0.002 and 0.109 ± 0.001 (nm RIU-1) nm-1, respectively. Conversely, hydrophobic NAA-µQVs are found to be slightly more sensitive toward changes of refractive index in aqueous medium, with sensitivities of 0.072 ± 0.002 and 0.066 ± 0.006 (nm RIU-1) nm-1 in water- and organic-based analytical solutions, respectively. Our advances provide insights into critical factors determining optical sensitivity in light-confining nanoporous PC structures, with implications across optical sensing applications, and other photonic technologies.

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.

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.

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.