Plasmonic MOF Thin Films with Raman Internal Standard for Fast and Ultrasensitive SERS Detection of Chemical Warfare Agents in Ambient Air
| Autor: | Jesus Santamaria, Ignacio Pérez-Juste, Reyes Mallada, M.A. Urbiztondo, Isabel Pastoriza-Santos, Marta Lafuente, Sarah De Marchi, Maria Pilar Pina |
|---|---|
| Přispěvatelé: | European Commission, Agencia Estatal de Investigación (España), Ministerio de Ciencia, Innovación y Universidades (España), Ministerio de Economía y Competitividad (España), Xunta de Galicia, Gobierno de Aragón, Instituto de Salud Carlos III |
| Rok vydání: | 2021 |
| Předmět: |
Materials science
Silver Nanoparticle Metal Nanoparticles Bioengineering Nanotechnology 02 engineering and technology 01 natural sciences Toxic gases symbols.namesake chemistry.chemical_compound Adsorption ZIF8 Surface-enhanced Raman scattering (SERS) Chemical Warfare Agents Thin film Instrumentation Core-shell Fluid Flow and Transfer Processes Detection limit Process Chemistry and Technology Dimethyl methylphosphonate 010401 analytical chemistry Reproducibility of Results 021001 nanoscience & nanotechnology 0104 chemical sciences DFT and Monte Carlo simulations Ultratrace detection chemistry symbols Nanorod Gold 0210 nano-technology Raman spectroscopy Raman scattering |
| Zdroj: | ACS Sensors Digital.CSIC. Repositorio Institucional del CSIC instname Zaguán. Repositorio Digital de la Universidad de Zaragoza |
| ISSN: | 2379-3694 |
| Popis: | 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. The authors are grateful for financial support from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 883390 (H2020-SU-SECU-2019 SERSing Project), Spanish State Research Agency (CTQ2016-79419-R, MAT2016-77809-R, PID2019-108660RB-I00 and PID2019-108954RB-I00), Gobierno de Aragón (T57-17R p, Feder 2014-2020 “Construyendo Europa desde Aragón”), Xunta de Galicia (GRC ED431C 2016-048, FEDER 1014-2020), and CIBER-BNN (initiative funded by the VI National R&D&i Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions, and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund). |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|