The large-area low-cost rough plasmonic crystal (r-PC) SERS substrates introduced herein outperform smooth counterparts and rough films both in magnitude of the Enhancement Factor (EF) and in the number of vibrational peaks displayed in the Raman spectrum. In r-PCs, photonic modes launched by the lattice excite more intense and abundant localized resonances in the sharp edges and gaps present in the rough metal surface. 2D r-PCs are fabricated by nanoimprinting a nanocrystalline titania paste followed by silver coating, resulting in a highly reproducible rough photonic architecture. The SERS performance of these architectures is tested via detection of two molecules; Benzenethiol and 4-Mercaptopyridine. The resulting EFs exceed 10 7 in the case of Benzenethiol and 10 10 when using 4-Mercaptopyridine. The simple fabrication strategy and the high performance exhibited by these nanoimprinted substrates, place rough plasmonic architectures as one of the most promising candidates for inexpensive and efficient mass-produced SERS substrates.
A cost-effective label-free optical biosensor based on gold-coated self-ordered nanoporous anodic alumina bilayers is presented. The structure is formed by two uniform nanoporous layers of different porosity (i.e., a top layer with large pores and a bottom layer with smaller pores). Each layer presents uniform pore size, regular pore distribution, and regular diameter along its pore length. To increase and improve the output sensing signals, a thin gold layer on the top surface was deposited. The gold layer increases the refractive index contrast between the nanoporous alumina layer and the analytical aqueous solution, and it results in a greater contrast in the interferometric spectrum and a higher sensitivity of the structure. From this structurally engineered architecture, the resulting reflectivity spectrum shows a complex series of Fabry-Pérot interference fringes, which was analyzed by the reflective interferometric Fourier transform spectroscopy (RIFTS) method. To determine the performance of this structure for biosensing applications, we tested bovine serum albumin (BSA) as the target protein. The results show a significant enhancement of the RIFTS peak intensity and position when a gold layer is on the top surface.
Herein, we present a smart enzymatic sensor based on nanoporous anodic alumina (NAA) and its photoluminescence (PL) in the UV−visible range. The asproduced structure of NAA is functionalized and activated in order to perform the enzyme immobilization in a controlled manner. The whole process is monitored through the PL spectrum and each stage is characterized by an exclusive barcode, which is associated with the PL oscillations. This characteristic property allows us to calculate the change in the effective optical thickness that takes place after each stage. This makes it possible to accurately detect and quantify the immobilized enzyme within the NAA structure. Finally, the NAA geometry (i.e., the pore length and its diameter) is optimized to improve the enzyme immobilization and its detection inside the pores. This enzymatic sensor can give quick and accurate measurements of enzyme levels, what is crucial in clinical enzymology to prevent and detect diseases at their primary stage.
A rugate filter based on nanoporous anodic alumina was fabricated using an innovative sinusoidal current profile with small current variation. The resulting structure consisted of highly parallel pores with modulations of the pore diameter along the pore axis and with no branching. The effect of the period time and the pore widening post-treatment was studied. From reflectance measurements, it was seen that the position of the reflection band can be tuned by adjusting the period time and the width by pore-widening post-treatments. We tested one of the rugate filters by infiltrating the structure with EtOH and water in order to evaluate its sensing capabilities. This method allows the fabrication of complex in-depth modulated nanoporous anodic alumina structures that open up the possibility of new kinds of alumina-based optical sensing devices.
Modifying the diameter of the pores in nanoporous anodic alumina opens new possibilities in the application of this material. In this work, we review the different nanoengineering methods by classifying them into two kinds: in situ and ex situ. Ex situ methods imply the interruption of the anodization process and the addition of intermediate steps, while in situ methods aim at realizing the in-depth pore modulation by continuous changes in the anodization conditions. Ex situ methods permit a greater versatility in the pore geometry, while in situ methods are simpler and adequate for repeated cycles. As an example of ex situ methods, we analyze the effect of changing drastically one of the anodization parameters (anodization voltage, electrolyte composition or concentration). We also introduce in situ methods to obtain distributed Bragg reflectors or rugate filters in nanoporous anodic alumina with cyclic anodization voltage or current. This nanopore engineering permits us to propose new applications in the field of biosensing: using the unique reflectance or photoluminescence properties of the material to obtain photonic barcodes, applying a gold-coated double-layer nanoporous alumina to design a self-referencing protein sensor or giving a proof-of-concept of the refractive index sensing capabilities of nanoporous rugate filters.
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