Raman Spectroscopy on Plasmonic Materials: Recent Advances and Applications in Molecular detection

Plasmonic Enhancement of the electric field is the basis of the Surface-enhanced Raman Scattering technique (SERS). This technique is based on the localization of light in the nanoscale occurring in plasmonic materials and provides the best conditions for molecular detection, even single-molecule detection. This can only be achieved by the use of spectroscopy in the nanoscale. The building of functional nanostructured devices to obtain sensitive and selective platforms, with specific applications in molecular detection, biodiagnosis and Cultural Heritage is presented. Plasmonic effects are highly activated in nanostructures substrates containing tips or in interparticle gaps. The nanofabrication of metal nanoparticles with special morphology, such as nanostars is presented here for the specific case of silver. The functionalization with bifunctional molecules gives rise to highly active gaps that can be employed in the molecular detection of pollutants. Another important application of these nanostructured platforms is the functionalization with biological molecules for bioanalytical applications and the detection of colorants with interest for the Cultural Heritage.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Recent Advances in Plasmonic-Enhanced Raman Scattering: Applications in Molecular Detection and Cultural Heritage

Università, Ca' Foscari, Venezia, 28 Mar 2019. -- Seminari

Solution SERS of an insoluble synthetic organic pigment-quinacridone quinone-employing calixarenes as dispersive cavitands

3 páginas, 5 figuras.A possibility of getting SERS spectra of insoluble aromatic compounds in colloidal silver solutions is described. The method tested for the organic pigment quinacridone quinone consists of dispersing it in calix[n]arenes. The potentials of such cavitands, both as dispersing and as silver functionalization agents, is reported as a function of the substitution in their lower rim and their cavity size.This work has been financially supported by the Ministerio de Ciencia e Innovacio´n of Spain (Projects FIS2007-63065 and CONSOLIDER CSD2007-0058/TCP) and the Comunidad de Madrid (MICROSERES II Project S2009/TIC1476).Peer reviewe

Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity

9 pas.; 7 figs.; 2 tabs.This journal is © The Royal Society of Chemistry. Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.This work has been supported by the Spanish Ministerio de Economía y Competitividad (MINECO, grant FIS2014-52212- R). A. G.-L. acknowledges CSIC and FSE 2007–2013 for a JAE-CSIC predoctoral grant.Peer Reviewe

Aplicaciones de la espectroscopía SERS (Surface-Enhanced Raman Scattering) a la detección de pigmentos orgánicos naturales en objetos del Patrimonio Cultural

16 páginas, 17 figuras.La espectroscopía Raman, cuyas prestaciones se han visto considerablemente mejoradas en los últimos 15 años debido a la introducción de técnicas de microscopía (que han sido posibles gracias a importantes avances tecnológicos en filtros ópticos y detectores de alta sensibilidad), se ha convertido en una técnica de identificación molecular de gran utilidad en el campo del Patrimonio Cultural [1]. Al igual que la más conocida espectroscopía Infrarroja, la espectroscopía Raman proporciona información sobre los compuestos moleculares presentes en la muestra bajo estudio, ampliando por ello la información acerca de la presencia de elementos químicos que suministran otras técnicas espectroscópicas tales como XRF, SEM - EDX, PIXE y LIBS utilizadas habitualmente en el análisis de objetos artísticos [2]. Hoy en día podemos encontrar la técnica de microscopía Raman en los departamentos de Conservación y Restauración de los más importantes Museos y Bibliotecas de todo el mundo, utilizándose como técnica no destructiva (incluso in situ) para diagnóstico de diferentes materiales que van desde los pigmentos inorgánicos hasta los biomateriales, en objetos artísticos tan diferentes como manuscritos, pinturas, textiles, cerámicas, vidrios, esculturas, monumentos, e incluso momias o cañones hundidos. La información que se obtiene puede resultar decisiva para la datación y autenticación de las obras artísticas, y ayuda a determinar los cambios físicos y/o químicos que han contribuido a su deterioro a través de la identificación de los productos de degradación de los materiales originales.Agradecemos al MICINN (Proyectos FIS2007-63065 y CONSOLIDER CSD 2007- 0058) y a la Comunidad de Madrid (MICROSERES, S2009TIC-1476) por la financiación parcial de los trabajos aquí expuestos. Agradecemos también el apoyo recibido de la Red Temática de Patrimonio Histórico y Cultural (CSIC). MVC y EdP agradecen al CSIC y al FSE 2007-2013 la concesión de sus respectivos Contratos post- y predoctoral.Peer reviewe

Adsorption of Polyethyleneimine on Silver Nanoparticles and Its Interaction with a Plasmid DNA: A Surface-Enhanced Raman Scattering Study

Raman spectroscopy is applied in this work to study the adsorption of poly(ethyleneimine) (PEI) on Ag nanoparticles obtained by reduction with citrate, as well as to the study of the interaction between PEI and a plasmid. The surface-enhanced Raman spectroscopy (SERS) affords important information about the interaction and orientation of the polymer on the particles. In particular we have found that this polymer interacts with the surface through their amino groups in an interaction which also involves a change in the protonation state of amino groups as well as an increase of the chain order. This interaction implies a charge-transfer effect as deduced from the strong resonant effect in Raman spectra obtained at different excitation wavelengths. The complex formed by PEI and a plasmid, obtained by encoding the HBV (hepatitis B virus) genome inside the EcoRI restriction site of pGEM vector, was also studied by SERS. The interaction between both polymers leads to a conformational change affecting both macromolecules that can be detected by Raman at different excitation wavelengths. PEI undergoes a change to a more disordered structure as well as an increase of the number of protonated amino groups. The plasmid undergoes a structural change from A-DNA structure to B-DNA, along with a change in the superhelicity resulting in a more lineal structure when the plasmid interacts with PEI.Peer reviewe

Femtosecond laser-controlled self-assembly of amorphous-crystalline nanogratings in silicon

8 págs.; 5 figs.; 1 tab.Self-assembly (SA) of molecular units to form regular, periodic extended structures is a powerful bottom-up technique for nanopatterning, inspired by nature. SA can be triggered in all classes of solid materials, for instance, by femtosecond laser pulses leading to the formation of laser-induced periodic surface structures (LIPSS) with a period slightly shorter than the laser wavelength. This approach, though, typically involves considerable material ablation, which leads to an unwanted increase of the surface roughness. We present a new strategy to fabricate high-precision nanograting structures in silicon, consisting of alternating amorphous and crystalline lines, with almost no material removal. The strategy can be applied to static irradiation experiments and can be extended into one and two dimensions by scanning the laser beam over the sample surface. We demonstrate that lines and areas with parallel nanofringe patterns can be written by an adequate choice of spot size, repetition rate and scan velocity, keeping a constant effective pulse number (N ) per area for a given laser wavelength. A deviation from this pulse number leads either to inhomogeneous or ablative structures. Furthermore, we demonstrate that this approach can be used with different laser systems having widely different wavelengths (1030 nm, 800 nm, 400 nm), pulse durations (370 fs, 100 fs) and repetition rates (500 kHz, 100 Hz, single pulse) and that the grating period can also be tuned by changing the angle of laser beam incidence. The grating structures can be erased by irradiation with a single nanosecond laser pulse, triggering recrystallization of the amorphous stripes. Given the large differences in electrical conductivity between the two phases, our structures could find new applications in nanoelectronics.This work has been supported by the LiNaBioFluid project of the H2020 program of the European Commission (FETOPEN- 665337) as well as by the Spanish TEC2014-52642-C2- 1-R. MG-L and JH-R acknowledge the grants respectively awarded by the Spanish Ministry of Education and the Spanish Ministry of Economy and Competiveness.Peer Reviewe

Por una praxis educativa bi/pluri/multi/lingüe en Colombia

En esta nota de política exponemos las complejidades relacionadas con la diversidad lingüística en Colombia, destacando las relaciones asimétricas de poder que perviven entre diferentes grupos lingüísti- cos y examinando las diferentes interpretaciones del plurilingüismo y el multilingüismo. Señalamos que las nociones tradicionales de bi-, multi- y plurilingüismo han sido desafiadas en los últimos años, y, en cambio, abogamos por perspectivas contemporáneas que re- conocen el uso de múltiples lenguas o formas de hablar por parte de individuos y comunidades como una práctica social compleja que está influenciada por factores sociohistóricos y culturales. Finalmente, formulamos recomendaciones con implicaciones políticas desde una perspectiva de pluriversalidad, que reconoce y abraza la diversidad lingüística como un recurso para crear una sociedad más justa, democrática, intercultural e inclusiva