Colloidal Synthesis of Gold Semishells

This work describes a novel and scalable colloid chemistry strategy to fabricate gold semishells based on the selective growth of gold on Janus silica particles (500 nm in diameter) partly functionalized with amino groups. The modulation of the geometry of the Janus silica particles allows us to tune the final morphology of the gold semishells. This method also provides a route to fabricating hollow gold semishells through etching of the silica cores with hydrofluoric acid. The optical properties were characterized by visible near-infrared (vis-NIR) spectroscopy and compared with simulations performed using the boundary element method (BEM). These revealed that the main optical features are located beyond the NIR region because of the large core size

Achieving accurate FTIR measurements on high performance bandpass filters

The sources of ordinate error in FTIR spectrometers are reviewed with reference to measuring small out-of-band features in the spectra of bandpass filters. Procedures for identifying instrumental artefacts are described. It is shown that features well below 0.01%T can be measured reliably

Osteogenic effects of simvastatin-loaded mesoporous titania thin films

The use of statins in the field of bone regeneration is under current investigation due to the existing demand for non-toxic anabolic agents capable of enhancing bone formation in cases of substantial loss. Simvastatin, a coenzyme currently prescribed in clinics to inhibit cholesterol biosynthesis, has been proven to promote osteogenic differentiation by stimulating bone formation and inhibiting osteoclasts activity. We present the loading of simvastatin in mesoporous TiO2 thin films toward combining the pro-osteogenic properties of this molecule with the demonstrated bioactivity of titania. TiO2 thin films processing and characterization were carried out, as well as evaluation of MC3T3-E1 pre-osteoblasts viability when directly incubated with different concentrations of simvastatin, followed by the analysis of osteogenic activity promoted by simvastatin upon loading in the thin films. The accessible porosity of 36% quantified on the 95 ± 5 nm thick mesoporous thin films, together with pore diameters of 5.5 nm, necks between pores of 2.8 nm and interpore distances of 12 ± 2 nm allow the loading of the simvastatin molecule, as confirmed by FTIR spectroscopy. Simvastatin was found to promote MC3T3-E1 pre-osteoblasts viability at concentrations ≤0.01 g l−1, with a cytotoxicity threshold of 0.05 g l−1. We additionally found that film loadings with 0.001 g l−1 simvastatin promotes statistically higher MC3T3-E1 pre-osteoblast proliferation whereas a higher concentration of 0.01 g l−1 leads to statistically higher osteogenic activity (ALP synthesis), after 21 days of incubation, as compared to unloaded films. These results demonstrate the potential of simvastatin local administration based on bioactive mesoporous thin films to promote pro-osteogenic properties. By focusing this strategy on the coating of metallic prostheses, the supply of simvastatin to the target tissue can be favored and risks of systemic side effects will be reduced while enhancing the osteointegration of the implants.Fil: Lopez Alvarez, Miriam. Universidad de Vigo; EspañaFil: López Puente, Vanesa. Universidad de Vigo; EspañaFil: Rodriguez Valencia, Cosme. Universidad de Vigo; EspañaFil: Angelome, Paula Cecilia. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Liz Marzan, Luis M. Ikerbasque; EspañaFil: Serra, Julia. Universidad de Vigo; EspañaFil: Pastoriza Santos, Isabel. Universidad de Vigo; EspañaFil: Gonzalez, Pio. Universidad de Vigo; Españ

Electron beam excitation of plasmonic modes in gold dimers

We report on the first realization of hyperspectral imaging for visualization and excitation of plasmon modes in dimers of 100 nm gold decahedra by a scanning electron beam

SERS-based molecularly imprinted plasmonic sensor for highly sensitive PAH detection

A novel hybrid plasmonic platform based on the synergetic combination of a molecularly imprinted polymer (MIP) thin film with Au nanoparticle (NPs) assemblies, noted as Au@MIP, was developed for surface-enhanced Raman scattering (SERS) spectroscopy recognition of polycyclic aromatic hydrocarbons (PAHs). While the MIP trapped the PAH close to the Au surface, the plasmonic NPs enhanced the molecule's Raman signal. The Au@MIP fabrication comprises a two-step procedure, first, the layer-by-layer deposition of Au NPs on glass and their further coating with a uniform MIP thin film. Profilometry analysis demonstrated that the thickness and homogeneity of the MIP film could be finely tailored by tuning different parameters such as prepolymerization time or spin-coating rate. Two different PAH molecules, pyrene or fluoranthene, were used as templates for the fabrication of pyrene- or fluoranthene-based Au@MIP substrates. The use of pyrene or fluoranthene, as the template molecule to fabricate the Au@MIP thin films, enabled its ultradetection in the nM regime with a 100-fold improvement compared with the nonimprinted plasmonic sensors (Au@NIPs). The SERS data analysis allowed to estimate the binding constant of the template molecule to the MIP. The selectivity of both pyrene- and fluoranthene-based Au@MIPs was analyzed against three PAHs of different sizes. The results displayed the important role of the template molecule used for the Au@MIPs fabrication in the selectivity of the system. Finally, the practical applicability of pyrene-based Au@MIPs was shown by performing the detection of pyrene in two real samples: creek water and seawater. The design and optimization of this type of plasmonic platform will pave the way for the detection of other relevant (bio)molecules in a broad range of fields such as environmental control, food safety, or biomedicine.Fil: Castro-Grijalba, Alexander. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de San Luis. Facultad de Ciencias de la Salud. Laboratorio de Quimica Analitica Ambiental.; Argentina. Universidad de Vigo; EspañaFil: Montes-García, Verónica. Universidad de Vigo; EspañaFil: Cordero-Ferradás, María José. Universidad de Vigo; EspañaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Pérez-Juste, Jorge. Universidad de Vigo; EspañaFil: Pastoriza-Santos, Isabel. Universidad de Vigo; Españ

Biogenic synthesis of metal nanoparticles using a biosurfactant extracted from corn and their antimicrobial properties

A new and promising biosurfactant extracted from corn steep liquor has been used for the green synthesis of gold and silver nanoparticles (NPs) in a one-step procedure induced by temperature. Most of the biosurfactants proposed in the literature are produced by pathogenic microorganisms; whereas the biosurfactant used in the current work was extracted from a liquid stream, fermented spontaneously by lactic acid bacteria, which are generally recognized as safe (GRAS) microorganisms. The reduction of a gold precursor in the presence of a biosurfactant gives rise to a mixture of nanospheres and nanoplates with distinct optical features. Moreover, the growth of nanoplates can be promoted by increasing the reaction temperature to 60 °C. In the case of silver, the biosurfactant just induces the formation of pseudo-spherical NPs. The biosurfactant plays a key role in the reduction of the metal precursor, as well as in the stabilization of the resulting NPs. Furthermore, the antimicrobial activity of the resulting silver colloids has been analyzed against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. The biosurfactant stabilized NPs slightly increased the inhibition of E. coli in comparison with citrate stabilized Ag NPs. The use of this biosurfactant extracted from corn steep liquor for the synthesis of metal NPs contributes to enhancing the application of green technologies and increasing the utilization of clean, non-toxic and environmentally safe production processes. Therefore, it can help to reduce environmental impact, minimize waste and increase energy efficiency in the field of nanomaterials.This work was supported by the Spanish MINECO (MAT2013-45168-R and MAT2016-77809-R) and Fundación Ramón Areces. Also, Xanel Vecino gratefully acknowledges her post-doctoral grant (SFRH/BPD/101476/2014) supported by the Portuguese Foundation for Science and Technology (FCT, Portugal).info:eu-repo/semantics/publishedVersio

Using Surface Enhanced Raman Scattering to Analyze the Interactions of Protein Receptors with Bacterial Quorum Sensing Modulators

Many members of the LuxR family of quorum sensing (QS) transcriptional activators, including LasR of Pseudomonas aeruginosa, are believed to require appropriate acyl-homoserine lactone (acyl-HSL) ligands to fold into an active conformation. The failure to purify ligand-free LuxR homologues in nonaggregated form at the high concentrations required for their structural characterization has limited the understanding of the mechanisms by which QS receptors are activated. Surface-enhanced Raman scattering (SERS) is a vibrational spectroscopy technique that can be applied to study proteins at extremely low concentrations in their active state. The high sensitivity of SERS has allowed us to detect molecular interactions between the ligand-binding domain of LasR (LasRLBD) as a soluble apoprotein and modulators of P. aeruginosa QS. We found that QS activators and inhibitors produce differential SERS fingerprints in LasRLBD, and in combination with molecular docking analysis provide insight into the relevant interaction mechanism. This study reveals signal-specific structural changes in LasR upon ligand binding, thereby confirming the applicability of SERS to analyze ligand-induced conformational changes in proteinsS

Tunable narrowband Excitonic Optical Tamm States enabled by a metal-free all-organic structure

Optical Tamm States (OTS) are confined optical modes that can occur at the interface between two highly reflective structures. However, due to the strong reflectance required, their implemen-tation with highly processable and metal-free flexible materials has proven challenging. Herein, we develop the first structure supporting OTS based only on organic polymeric materials, demon-strating a photonic platform based on non-critical, widely available, and easily processable mate-rials. The structures fabricated present large areas and consist of a narrowband multi-layered polymeric Distributed Bragg Reflector (DBR) followed by a thin film of J-aggregate molecular exci-tonic material that can act as a highly reflective surface within a narrowband range. We take ad-vantage of the narrowband spectral response of the DBR and of the reflective molecular layer to tune the OTS band by varying the periodicity of the multilayer, opening the door for the fabrica-tion of OTS structures based on lightweight integrable excitonic devices with cost-effective proce-dures.Comment: 15 pages, 8 (3+5) figures, supplementary information include

Plasmonic supercrystals

For decades, plasmonic nanoparticles have been extensively studied due to their extraordinary properties, related to localized surface plasmon resonances. A milestone in the field has been the development of the so-called seed-mediated growth method, a synthetic route that provided access to an extraordinary diversity of metal nanoparticles with tailored size, geometry and composition. Such a morphological control came along with an exquisite definition of the optical response of plasmonic nanoparticles, thereby increasing their prospects for implementation in various fields. The susceptibility of surface plasmons to respond to small changes in the surrounding medium or to perturb (enhance/quench) optical processes in nearby molecules, has been exploited for a wide range of applications, from biomedicine to energy harvesting. However, the possibilities offered by plasmonic nanoparticles can be expanded even further by their careful assembly into either disordered or ordered structures, in 2D and 3D. The assembly of plasmonic nanoparticles gives rise to coupling/hybridization effects, which are strongly dependent on interparticle spacing and orientation, generating extremely high electric fields (hot spots), confined at interparticle gaps. Thus, the use of plasmonic nanoparticle assemblies as optical sensors have led to improving the limits of detection for a wide variety of (bio)molecules and ions. Importantly, in the case of highly ordered plasmonic arrays, other novel and unique optical effects can be generated. Indeed, new functional materials have been developed via the assembly of nanoparticles into highly ordered architectures, ranging from thin films (2D) to colloidal crystals or supercrystals (3D). The progress in the design and fabrication of 3D supercrystals could pave the way toward next generation plasmonic sensors, photocatalysts, optomagnetic components, metamaterials, etc. In this Account, we summarize selected recent advancements in the field of highly ordered 3D plasmonic superlattices. We first analyze their fascinating optical properties for various systems with increasing degrees of complexity, from an individual metal nanoparticle through particle clusters with low coordination numbers to disordered self-assembled structures and finally to supercrystals. We then describe recent progress in the fabrication of 3D plasmonic supercrystals, focusing on specific strategies but without delving into the forces governing the self-assembly process. In the last section, we provide an overview of the potential applications of plasmonic supercrystals, with a particular emphasis on those related to surface-enhanced Raman scattering (SERS) sensing, followed by a brief highlight of the main conclusions and remaining challenges.Agencia Estatal de Investigación | Ref. MAT2017-86659-RMinisterio de Economía, Industria y Competitividad | Ref. MAT2016-77809-

Integrating plasmonic supercrystals in microfluidics for ultrasensitive, label-free, and selective surface-enhanced raman spectroscopy detection

Surface-enhanced Raman spectroscopy (SERS) microfluidic chips for label-free and ultrasensitive detection are fabricated by integrating a plasmonic supercrystal within microfluidic channels. This plasmonic platform allows the uniform infiltration of the analytes within the supercrystal, reaching the so-called hot spots. Moreover, state-of-the-art simulations performed using large-scale supercrystal models demonstrate that the excellent SERS response is due to the hierarchical nanoparticle organization, the interparticle separation (IPS), and the presence of supercrystal defects. Proof-of-concept experiments confirm the outstanding performance of the microfluidic chips for the ultradetection of (bio)molecules with no metal affinity. In fact, a limit of detection (LOD) as low as 10–19 M was reached for crystal violet. The SERS microfluidic chips show excellent sensitivity in the direct analysis of pyocyanin secreted by Pseudomonas aeruginosa grown in a liquid culture medium. Finally, the further integration of a silica-based column in the plasmonic microchip provides charge-selective SERS capabilities as demonstrated for a mixture of positively and negatively charged molecules.Agencia Estatal de Investigación | Ref. TEC2017-85376-C2-1-RAgencia Estatal de Investigación | Ref. TEC2017-85376-C2-2-RXunta de Galicia | Ref. GRC ED431C 2016−486 048Gobierno de Extremadura | Ref. IB18073Agencia Estatal de Investigación | Ref. IJCI-2016-2910