Open Access
Silver nanoparticles loaded electrospun nanofibers for humidity optical fiber sensing
(2012) Urrutia Azcona, Aitor; Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Rodríguez, Yoany; Arregui San Martín, Francisco Javier; Matías Maestro, Ignacio; Ingeniaritza Elektrikoa eta Elektronikoa; Institute of Smart Cities - ISC; Ingeniería Eléctrica y Electrónica
In this work, a new optical device based on silver loaded electrospun nanofibers (ENFs) for measuring Relative Humidity is proposed. Fiber mats composed of poly(acrylic acid) and β-cyclodextrin were deposited onto an optical fiber core by electrospinning. Afterwards the ENFs were submitted to a thermal curing. Then, the ENFs were loaded with Ag nanoparticles (Ag NPs) synthesized using a Ag+ loading step and a further reduction step with dimethylamine borane (DMAB). Several load/reduction cycles were performed. Ag NPs enhance significantly the optical response of the polymer-only fiber mats. The Ag NPs loaded ENF sensor was tested using controlled variations of Relative Humidity (RH). The results showed a very fast response of the absorbance spectra enabling high performance applications such as human breathing monitoring.
Open Access
Self-referenced optical fiber sensor based on LSPR generated by gold and silver nanoparticles embedded in layer-by-layer nanostructured coatings
(MDPI, 2022) Martínez Hernández, María Elena; Goicoechea Fernández, Javier; Rivero Fuente, Pedro J.; Sandúa Fernández, Xabier; Arregui San Martín, Francisco Javier; Ingeniaritza; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren; Institute of Smart Cities - ISC; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería; Ingeniería Eléctrica, Electrónica y de Comunicación
In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon has been designed for the detection of two different chemical species (mercury and hydrogen peroxide) by using Layer-by-Layer Embedding (LbL-E) as a nanofabrication technique. In the first step, silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) have been synthesized by using a chemical protocol as a function of the strict control of three main parameters, which were polyelectrolyte concentration, a loading agent, and a reducing agent. In the second step, their incorporation into nanometric thin films have been demonstrated as a function of the number of bilayers, which shows two well-located absorption peaks associated to their LSPR in the visible region at 420 nm (AgNPs) and 530 nm (AuNPs). Finally, both plasmonic peaks provide a stable real-time reference measurement, which can be extracted from the spectral response of the optical fiber sensor, which shows a specific sensing mechanism as a function of the analyte of study.
Open Access
Effect of both protective and reducing agents in the synthesis of multicolor silver nanoparticles
(Springer, 2013) Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Urrutia Azcona, Aitor; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica y Electrónica; Ingeniaritza Elektrikoa eta Elektronikoa
In this paper, the influence of variable molar ratios between reducing and loading agents (1:100, 1:50, 1:20, 1:10, 1:5, 1:2, 1:1, 2:1) and between protective and loading agents (0.3:1, 0.75:1, 1.5:1, 3:1, 7.5:1, 30:1, 75:1) in the synthesis of silver nanoparticles by chemical reduction has been evaluated to obtain multicolor nanoparticles with a high stability in time. The protective agent poly(acrylic acid, sodium salt) (PAA) and reducing agent dimethylaminoborane (DMAB) play a key role in the formation of the resultant color. Evolution of the optical absorption bands of the silver nanoparticles as a function of PAA and DMAB molar ratios made it possible to confirm the presence of silver nanoparticles or clusters with a specific shape. The results reveal that a wide range of colors (violet, blue, green, brown, yellow, red, orange), sizes (from nanometer to micrometer), and shapes (cubic, rod, triangle, hexagonal, spherical) can be perfectly tuned by means of a fine control of the PAA and DMAB molar concentrations.
Open Access
An optical fiber sensor for Hg2+ detection based on the LSPR of silver and gold nanoparticles embedded in a polymeric matrix as an effective sensing material
(MDPI, 2021-07-07) Martínez Hernández, María Elena; Sandúa Fernández, Xabier; Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In this work, an optical fiber sensor based on the localized surface plasmon resonance (LSPR) phenomenon is presented as a powerful tool for the detection of heavy metals (Hg2+). The resultant sensing film was fabricated using a nanofabrication process, known as layer-by-layer embedding (LbL-E) deposition technique. In this sense, both silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) were synthesized using a synthetic chemical protocol as a function of a strict control of three main parameters: polyelectrolyte concentration, loading agent, and reducing agent. The use of metallic nanostructures as sensing materials is of great interest because well-located absorption peaks associated with their LSPR are obtained at 420 nm (AgNPs) and 530 nm (AuNPs). Both plasmonic peaks provide a stable real-time reference that can be extracted from the spectral response of the optical fiber sensor, giving a reliable monitoring of the Hg2+ concentration.
Open Access
Single-stage in situ synthesis of silver nanoparticles in antibacterial self-assembled overlays
(Springerlink, 2012) Urrutia Azcona, Aitor; Rivero Fuente, Pedro J.; Ruete Ibarrola, Leyre; Goicoechea Fernández, Javier; Matías Maestro, Ignacio; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
In this work, a novel single-stage process for in situ synthesis of Ag nanoparticles (NPs) using the layer-bylayer (LbL) technique is presented. The Ag NPs were formed into nanotextured coatings based on sequentially adsorbed poly(allylamine hydrochloride) (PAH) and SiO2 NPs. Such highly porous surfaces have been used in the fabrication of highly efficient ion release films for applications such as antibacterial coatings. In this approach, the amino groups of the PAH acted as reducing agent and made possible the in situ formation of the Ag NPs. This reduction reaction occurred during the LbL process as the coating was assembled, without any further step after the fabrication and stabilization of the multilayer film. Biamminesilver nitrate was used as the Ag+ ion source during the LbL process and it was successfully reduced to Ag NPs. All coatings were tested with gram-positive and gram-negative bacterial cultures of Escherichia coli, Staphylococcus aureus, and Lactobacillus delbrueckii showing an excellent antimicrobial behavior against these types of bacteria (more than 99.9% of killing efficiency in all cases).
Open Access
An antibacterial submicron fiber mat with in situ synthesized silver nanoparticles
(Wiley, 2012) Rivero Fuente, Pedro J.; Urrutia Azcona, Aitor; Goicoechea Fernández, Javier; Rodríguez, Yoany; Corres Sanz, Jesús María; Arregui San Martín, Francisco Javier; Matías Maestro, Ignacio; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Institute of Smart Cities - ISC; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2
This work presents an alternative approachfor fabricating electrospun submicron highly hydrophilicfiber mats loaded with silver nanoparticles. These fiber matsshow a high efficient antibacterial behavior, very attractivefor applications like wound healing and skin regenerationprocesses. The fabrication method is divided in two steps.First, poly(acrylic acid) (PAA) and b-cyclodextrin (b-CD)submicron fibers were electrospun and further stabilizedusing a thermal treatment, yielding stable hydrogel-likefibers with diameters ranging from 100 nm up to severalmicrons. In the second step, silver ions were loaded into thefibers and then reduced to silver nanoparticles in-situ. Theelectrospinning parameters were adjusted to achieve thedesired properties of the fiber mat (density, size) and after-wards, the characteristics of the silver nanoparticles(amount, size, aggregation) were tuned by controlling thesilver ion loading mechanism. Highly biocide surfaces wereachieved showing more than 99.99% of killing efficiency.The two-step process improves the reproducibility and tun-ability of the fiber mats. To our knowledge, this is the firsttime that stable hydrogel fibers with a highly biocide behav-ior have been fabricated using electrospinning.
Open Access
A comparative study of two different approaches for the incorporation of silver nanoparticles into layer-by-layer films
(Springer, 2014) Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Matías Maestro, Ignacio; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica y Electrónica; Ingeniaritza Elektrikoa eta Elektronikoa; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In this work, a comparative study about the incorporation of silver nanoparticles (AgNPs) into thin films is presented using two alternative methods, the in situ synthesis process and the layer-by-layer embedding deposition technique. The influence of several parameters such as color of the films, thickness evolution, thermal post-treatment, or distribution of the AgNPs along the coatings has been studied. Thermal post-treatment was used to induce the formation of hydrogel-like AgNPs-loaded thin films. Cross-sectional transmission electron microscopy micrographs, atomic force microscopy images, and UV-vis spectra reveal significant differences in the size and distribution of the AgNPs into the films as well as the maximal absorbance and wavelength position of the localized surface plasmon resonance absorption bands before and after thermal post-treatment. This work contributes for
Open Access
Self-referenced optical fiber sensor for hydrogen peroxide detection based on LSPR of metallic nanoparticles in layer-by-layer films
(MDPI, 2019) Goicoechea Fernández, Javier; Rivero Fuente, Pedro J.; Sada Oreja, Samuel; Arregui San Martín, Francisco Javier; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren; Ingeniaritza; Institute of Smart Cities - ISC; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniería; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Intensity-based optical fiber sensors are one of the most studied sensor approaches thanks to their simplicity and low cost. Nevertheless, their main issue is their lack of robustness since any light source fluctuation, or unexpected optical setup variation is directly transferred to the output signal, which, significantly reduces their reliability. In this work, a simple and robust hydrogen peroxide (H2O2) optical fiber sensor is proposed based on the Localized Surface Plasmon Resonance (LSPR) sensitivity of silver and gold metallic nanoparticles. The precise and robust detection of H2O2 concentrations in the ppm range is very interesting for the scientific community, as it is a pathological precursor in a wide variety of damage mechanisms where its presence can be used to diagnose important diseases such as Parkinson's disease, diabetes, asthma, or even Alzheimer's disease). In this work, the sensing principle is based the oxidation of the silver nanoparticles due the action of the hydrogen peroxide, and consequently the reduction of the efficiency of the plasmonic coupling. At the same time, gold nanoparticles show a high chemical stability, and therefore provide a stable LSPR absorption band. This provides a stable real-time reference that can be extracted from the spectral response of the optical fiber sensor, giving a reliable reading of the hydrogen peroxide concentration.
Open Access
Multicolor layer-by-layer films using weak polyelectrolyte assisted synthesis of silver nanoparticles
(Springer, 2013) Rivero Fuente, Pedro J.; Goicoechea Fernández, Javier; Urrutia Azcona, Aitor; Matías Maestro, Ignacio; Arregui San Martín, Francisco Javier; Ingeniería Eléctrica y Electrónica; Ingeniaritza Elektrikoa eta Elektronikoa
In the present study, we show that silver nanoparticles (AgNPs) with different shape, aggregation state and color (violet, green, orange) have been successfully incorporated into polyelectrolyte multilayer thin films using the layerby- layer (LbL) assembly. In order to obtain colored thin films based on AgNPs is necessary to maintain the aggregation state of the nanoparticles, a non-trivial aspect in which this work is focused on. The use of Poly(acrylic acid, sodium salt) (PAA) as a protective agent of the AgNPs is the key element to preserve the aggregation state and makes possible the presence of similar aggregates (shape and size) within the LbLcolored films. This approach based on electrostatic interactions of the polymeric chains and the immobilization of AgNPs with different shape and size into the thin films opens up a new interesting perspective to fabricate multicolornanocomposites based on AgNPs.