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

the role of adenosine monophosphate

Funding Information: The authors acknowledge financial support from the European Innovation Council (Horizon 2020 Project: 965018—BIOCELLPHE), the MCIN/AEI/10.13039/501100011033 (grant PID2019-108954RB-I00), the FSE (“El FSE invierte en tu futuro”), the Xunta de Galicia/FEDER (grant GRC ED431C 2020/09), the European Regional Development Fund (ERDF), and the Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior, FCT-MCTES (grants UIDB/50006/2020, UIDP/50006/2020 and Met4cat, EXPL/QUI-COL/0263/2021). J. F.-L. thanks FCT-UNL for the research contract through the Program DL 57/2016−Norma Transitória. S. N. thanks the FCT-MCTES Portugal for her doctoral grant associated with the Chemistry PhD program (SFRH/BD/144618/2019). C. F.-L. acknowledges Xunta de Galicia for a predoctoral scholarship (Programa de axudas á etapa predoutoral). C. L., A. F. L., S. N and J. F. L thank the financial support of the PROTEOMASS Scientific Society (Portugal) (General Funding Grants 2022-2023) and the Associate Laboratory Research Unit for Green Chemistry-Clean Processes and Technologies - LAQV/REQUIMTE. This work was carried out in part through the use of the INL Advanced Electron Microscopy, Imaging and Spectroscopy Facility and Microscopy Facility at CACTI (Universidade de Vigo). The authors thank Dr. Jamila Djafari for her assistance with the graphical abstract. Publisher Copyright: © 2023 The Royal Society of Chemistry.The seed-mediated growth of gold nanostructures is known to be strongly dependent not only on the gold seed nanocrystal structure but also on the presence of different additives that may influence the morphology, and therefore the crystalline structure of the final nanoparticle. Among the different additives or capping ligands, biomolecules are an interesting family due to their potential biomedical applications such as drug delivery, bioimaging, biosensing, phototherapy, and antimicrobial activities. Here, we develop a seed-mediated strategy for synthesizing uniform Au nanostars with tuneable optical properties which involves adenosine monophosphate (AMP) as a capping ligand. The experimental data reveal the key role of AMP not just providing colloidal stability and directing the reduction of the gold precursor via complexation but also mediating the anisotropic growth of the Au seeds via its selective adsorption on the different crystalline facets of Au nanoparticles. These observations agree with theoretical simulations carried out using molecular dynamics and density functional theory (DFT) calculations. Interestingly, the obtained Au nanostars showed high thermal stability as well as colloidal stability in polar organic solvents, which allowed their direct silica coating via the Stöber method. Importantly, we also explored the mimic enzymatic activity of the resulting gold nanostars and observed a superior catalytic activity compared with other gold nanoparticles reported in the literature.publishersversionpublishe

Bolaform surfactant‐induced Au nanoparticle assemblies for reliable solution‐based surface‐enhanced Raman scattering detection

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGSolution-based surface-enhanced Raman scattering (SERS) detection typically involves the aggregation of citrate-stabilized Au nanoparticles into colloidal assemblies. Although this sensing methodology offers excellent prospects for sensitivity, portability, and speed, it is still challenging to control the assembly process by a salting-out effect, which affects the reproducibility of the assemblies and, therefore, the reliability of the analysis. This work presents an alternative approach that uses a bolaform surfactant, B20, to induce the plasmonic assembly. The decrease of the surface charge and the bridging effect, both promoted by the adsorption of B20, are hypothesized as the key points governing the assembly. Furthermore, molecular dynamic simulations supported the bridging effect of the B20 by showing the preferential bridging of surfactant monomers between two adjacent Au(111) slabs. The colloidal assemblies showed excellent SERS capabilities towards the rapid, on-site detection and quantification of beta-blockers and analgesic drugs in the nanomolar regime, with a portable Raman device. Interestingly, the application of state-of-the-art convolutional neural networks, such as ResNet, allows a 100% accuracy in classifying the concentration of different binary mixtures. Finally, the colloidal approach was successfully implemented in a millifluidic chip allowing the automation of the whole process, as well as improving the performance of the sensor in terms of speed, reliability, and reusability without affecting its sensitivity.MCIN/AEI/10.13039/501100011033 | Ref. PID2019-108954RB-I00MCIN/AEI/10.13039/501100011033 | Ref. PID2019-106960GB-I00MCIN/AEI/10.13039/501100011033 | Ref. BES-2017-08167MEC/AEI | Ref. CTQ2017-84354-PXunta de Galicia | Ref. GRC ED431C 2020/09Xunta de Galicia | Ref. GR 2007/08

Histidine‐mediated synthesis of chiral cobalt oxide nanoparticles for enantiomeric discrimination and quantification

Chiral transition metal oxide nanoparticles (CTMOs) are attracting a lot of attention due to their fascinating properties. Nevertheless, elucidating the chirality induction mechanism often remains a major challenge. Herein, the synthesis of chiral cobalt oxide nanoparticles mediated by histidine (Co3O4@L-His and Co3O4@D-His for nanoparticles synthesized in the presence of L- and D-histidine, respectively) is investigated. Interestingly, these CTMOs exhibit remarkable and tunable chiroptical properties. Their analysis by x-ray photoelectron, Fourier transform infrared, and ultraviolet-visible absorption spectroscopy indicates that the ratio of Co2+/Co3+ and their interactions with the imidazole groups of histidine are behind their chiral properties. In addition, the use of chiral Co3O4 nanoparticles for the development of sensitive, rapid, and enantioselective circular dichroism-based sensors is demonstrated, allowing direct molecular detection and discrimination between cysteine or penicillamine enantiomers. The circular dichroism response of the chiral Co3O4 exhibits a limit of detection and discrimination of cysteine and penicillamine enantiomers as low as 10 µm. Theoretical calculations suggest that the ligand exchange and the coexistence of both species adsorbed on the oxide surface are responsible for the enantiomeric discrimination. This research will enrich the synthetic approaches to obtain CTMOs and enable the extension of the applications and the discovery of new chiroptical properties.National Natural Science Foundation of China | Ref. 22271257Agencia Estatal de Investigación | Ref. PID2019-108954RB-I00Xunta de Galicia | Ref. ED431C 2020/09Universidade de Vigo/CISU

Effect of Gold Nanoparticles on Transport Properties of the Protic Ionic Liquid Propylammonium Nitrate

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUGThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jced.1c00135[Abstract] Here, we analyze the effect of gold-nanoparticle (AuNPs)-doping of the protic ionic liquid (IL) propyl ammonium nitrate (PAN) on some physical properties, such as density, viscosity, and ionic conductivity, in a broad temperature range. This IL was lightly doped with four different AuNPs (concentration of gold lower than 0.2 mM): Au nanospheres of about 15, 60, and 80 nm diameter and Au nanorods of about 40 nm length and 12 nm width. AuNPs were synthesized following a seed growth approach and further functionalized with O-[2-(3-mercapto propionylamino)ethyl] O′-methyl-poly(ethylene glycol) (m-PEG-SH) in order to provide stability to the IL medium. The stability of the AuNPs in PAN was characterized by UV–vis spectroscopy. The results obtained here indicate that their presence produces a strong influence on the measured transport properties of PAN, decreasing viscosity up to 25% and increasing ionic conductivity up to 10% for the smallest AuNPs. Moreover, as temperature increases, the influence of AuNPs produces a decrease in the percentage deviations for viscosity and ionic conductivity. In the case of density, the AuNP-doping produces a mainly unexpected increase only for the sample with the smallest AuNPs, that is practically constant with temperature. When we equalize the AuNP concentration for all sizes and shapes, it is observed that the smallest AuNPs give higher variations in the studied properties than the bigger ones; also, the shape of the rod has an influence on the measured results. In addition, we have applied Walden’s rule to relate the three measured magnitudes, observing that AuNP addition decreases ionicity with respect to the reference sample, which is even more when we added smaller AuNPs. Finally, we explain all data assuming cation solvation of the AuNPs, which creates a local breaking of the pseudolattice structure of the PAN. Comparison with other published data is difficult because the behavior of a nanoparticle solution strongly depends on its particular composition and no data are available, in our knowledge, of any similar mixture to those studied here.The financial support of Ministerio de Economía y Competitividad (MINECO) (MAT2016-77809-R and MAT2017-89239-C2-(1,2)-P); Xunta de Galicia (GRC ED431C 2016/001 and ED431D 2017/06) is also acknowledged. All these research projects were partially supported by FEDERXunta de Galicia; ED431C 2016/001Xunta de Galicia; ED431D 2017/06https://pubs.acs.org/doi/suppl/10.1021/acs.jced.1c00135/suppl_file/je1c00135_si_001.pd

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

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

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

Growth and Branching of Gold nanoparticles Through MesoporousSilica Thin Films

Composite materials made of mesoporous oxide thin films containing metallic nanoparticles are of high interest in various fields, including catalysis, biosensing and non-linear optics. We demonstrate in this work the fabrication of such composite materials containing a sub-monolayer of gold nanoparticles (GNPs) of various shapes covered with mesoporous silica thin films. Additionally, the shape of the GNPs (and thus their optical properties) can be modified in situ through seeded growth and branching. Such growth proceeds upon wetting with HAuCl 4 solution, a surfactant (cetyltrimethylammonium bromide, CTAB) and a mild reducing agent (ascorbic acid, AA). The effect of varying several reaction parameters (time and CTAB and AA concentrations) was evaluated, showing that more anisotropic particles are obtained at longer reaction times, lower CTAB concentration and higher AA concentration. The final shape of the GNPs was also found to depend on their initial shape and size, as well as the pore size of the mesoporous film covering them. Because the growth proceeds through the pores of the film, it may lead to shapes that are not easily obtained in solution, such as particles with branches on one side only. Finally, we have confirmed that no damage was induced to the mesoporous silica structure during the growth process and thus the final particles remain well covered by the thin film, which can eventually be used as a filter between the GNPs and the outer medium.Fil: Angelomé, Paula C.. Universidad de Vigo; EspañaFil: Pastoriza Santos, Isabel. Universidad de Vigo; EspañaFil: Pérez Juste, Jorge. Universidad de Vigo; EspañaFil: Rodríguez-González, Benito. Universidad de Vigo; EspañaFil: Zelcer, Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; ArgentinaFil: Soler Illia, Galo Juan de Avila Arturo. Universidad de Buenos Aires; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Liz Marzán, Luis M.. Universidad de Vigo; Españ