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

Synthesis of tuneable gold nanostars: the role of adenosine monophosphate

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.Agencia Estatal de Investigación | Ref. PID2019-108954RB-I00Xunta de Galicia | Ref. ED431C 2020/09Fundação para a Ciência e a Tecnologia | Ref. UIDB/50006/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50006/2020Fundação para a Ciência e a Tecnologia | Ref. EXPL/QUI-COL/0263/2021Universidade de Vigo/CISU

2-Hydroxychalcone−β-cyclodextrin conjugate with pH-modulated photoresponsive binding properties

Stimuli-responsive supramolecular receptors are important building blocks for the construction of self-assembled functional materials. We report the design and synthesis of a pH- and light-responsive 2-hydroxychalcone−β-cyclodextrin conjugate (1-Ct) and its characterization by spectroscopic and computational methods. 1-Ct follows the typical reaction network of trans-chalcone-flavylium photoswitches. Upon light irradiation, 1-Ct can be photochemically converted into the cis-chalcone/hemiketal forms (1-Cc/1-B) under neutral pH conditions or to the flavylium cation (1-AH+) at acidic pH values. This stimuli-responsive β-cyclodextrin host, 1-Ct, was found to form stronger intramolecular self-inclusion complexes (Kintra = 14) than 1-AH+ (Kintra = 3) and weaker than 1-Cc/1-B (overall Kintra = 179), allowing control over their stability and binding properties by combinations of pH and light stimuli.Fundação para a Ciência e a Tecnologia | Ref. UIDB/50006/2020Fundação para a Ciência e a Tecnologia| Ref. UIDP/50006/2020Fundação para a Ciência e a Tecnologia | Ref. UIDB/04326/202

Highly porous palladium nanodendrites : wet-chemical synthesis, electron tomography and catalytic activity

A simple procedure to obtain highly porous hydrophilic palladium nanodendrites in one-step is described. The synthetic strategy is based on the thermal reduction of a Pd precursor in the presence of a positively charged polyelectrolyte such as polyethylenimine (PEI). Advanced electron microscopy techniques combined with X-ray diffraction (XRD), thermogravimetry and BET analysis demonstrate the polycrystalline nature of the nanodendrites as well as their high porosity and active surface area, facilitating a better understanding of their unique morphology. Besides, catalytic studies performed using Raman scattering and UV-Vis spectroscopies revealed that the nanodendrites exhibit a superior performance as recyclable catalysts towards hydrogenation reaction compared to other noble metal nanoparticles

Plasmonic MOF thin films with raman standard for fast and ultrasensitive SERS detection of chemical warfare agents in ambient air

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core–shell Au@Ag nanorods individually encapsulated within a ZIF-8 framework (Au@Ag@ZIF-8). While the Au@Ag nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of Au@Ag@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N2, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine

Plasmonic MOF Thin Films with Raman Internal Standard for Fast and Ultrasensitive SERS Detection of Chemical Warfare Agents in Ambient Air

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core–shell Au@Ag nanorods individually encapsulated within a ZIF-8 framework (Au@Ag@ZIF-8). While the Au@Ag nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of Au@Ag@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N2, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine