INSTRUMENTO DE ANÁLISIS Y CLASIFICACIÓN DE ESPECIES EN SUSPENSIÓN MEDIANTE IONIZACION SECUNDARIA POR ELECTROSPRAY, ANÁLISIS DE MOVILIDAD Y MASA INSTRUMENT FOR CLASSIFICATION AND ANALYSIS OF SUSPENDED SPECIES THROUGH SECONDARY ELECTROSPRAY IONIZATION, MASS AND MOBILITY ANALYSIS ARTURO ÁLVARO CARBALLIDO 1,2 , JUAN FERNANDEZ DE LA MORA 1,3 , GUILLERMO VIDAL DE MIGUEL 1,2,4 1 Sociedad Europea de Análisis Diferencial de Movilidad, 2 Universidad de Valladolid, 3 Universidad de Yale, 4 ETH Zurich arturo.alvaro@seadm.com Aerosol instrumentation 1
Index • Architecture and main elements of the device • Most relevant technologies used • Nanospray, SESI. • DMA • Commercial API-MS to couple with DMA • Operation modes • Nano ESI+DMA+MS • SESI+DMA+MS on-line • SESI+DMA+MS off-line for vapours • SESI+DMA+MS off-line for liquid volatilization • Applications and performance • Explosives detection • Atmospheric research: Combustion engines emissions • Engineering studies: Polymer characterization, pesticides… • Biochemistry and medicine Aerosol instrumentation 2
Architecture and main elements of the device Sample Analyzer Post processing software Sampler Adsorbent Desorber LFSESI DMA Triple Quad MS Aerosol instrumentation 3
Index • Architecture and main elements of the device • Most relevant technologies used • Nanospray, SESI. • DMA • Commercial API-MS to couple with DMA • Operation modes • Nano ESI+DMA+MS • SESI+DMA+MS on-line • SESI+DMA+MS off-line for vapours • SESI+DMA+MS off-line for liquid volatilization • Applications and performance • Explosives detection • Atmospheric research: Combustion engines emissions • Engineering studies: Polymer characterization, pesticides… • Biochemistry and medicine Aerosol instrumentation 4
Most relevant technologies used Nanospray, SESI (Secondary Electrospray Ionization). • Nanospay: – The sample must be electrically conductive. It is sprayed at low flow. Capillary of 20-50 ID – It is a soft ionization technique. It ionizes with low or no fragmentation. – Multi-charge states are common, which is good for large biological molecules. – Smaller drop size than ES. High ionization efficiency and sample use. (Improved ionization patented). • Secondary Electrospray Ionization (SESI): – The gaseous sample, or vaporized liquid gets in touch with a blank nanospray “charger solution” – There is a charge transfer process from the “charger” to the sample. – It allows selective ionization adjusting the ionization potential of the charger. Capilar Chorro Pluma Cono de Taylor Department of Electrical Engineering G. Vidal-de-Miguel et al. Anal. Chem. LFSESI. Improving vapor ionization efficiency University of South Florida • Our patented low flow SESI with an impact region enables more than tenfold increase over the theoretical ionization limit for vapors by charge transfer from ions, while also suppressing vapor dilution effects of the counterflow gas jet protecting the MS from entry of vapors and particles. Aerosol instrumentation 5
Most relevant technologies used Supercritical planar DMA • Operation: HV DC + high speed drift flow • Characteristic: – Real mobility/size analysis – Continuous analysis for a fixed mobility with ≈50% transmission – Analysis time of 0.1s. Mobility switches in 50ms. (With the MS HV source). – Resolution of 40-70 FWMH depending in the ion size. – The flow remains Laminar at Reynolds numbers (Re) far above 10 000 Aerosol instrumentation 6
Most relevant technologies used Comercial API MS to couple with DMA • ¿Why a commercial MS? Reliability and updated technology • Advantages of a DMA - triple quadrupole MS system: More sensitivity. The best choice for ion monitoring. • Advantages of a DMA - Q-Tof / Trap MS system: Mass resolution. The best choice for wide 2D mass-mobility sweeps. • ¿Which model? (API required) • Shimadzu LCMS 2010 de. • ABSciex TOF Qstar • ABSciex Qtrap 3200, 4500 & 5500 • ABSciex Triple Quad 5000 & 5500 • …Thermo AB Sciex Corp. Aerosol instrumentation 7
Index • Architecture and main elements of the device • Most relevant technologies used • Nanospray, SESI. • DMA • Commercial API-MS to couple with DMA • Operation modes • Nano ESI+DMA+MS • SESI+DMA+MS on-line • SESI+DMA+MS off-line for vapours • SESI+DMA+MS off-line for liquid volatilization • Applications and performance • Explosives detection • Atmospheric research: Combustion engines emissions • Engineering studies: Polymer characterization, pesticides… • Biochemistry and medicine Aerosol instrumentation 8
Operation modes Nano ESI+DMA+MS (Mobility dimension addition to MS) • Ionization source: Nano ESI. (Improved ionization patented). • Main analysis modes: The ones of the MS + mobility dimension • Type of samples: Liquid. Low flow (≈2µl/min) + Liquid samples at low flow with low fragmentation (Nano ESI mode) +Continuous analysis +Permits mobility sweep. Mobility dimension added to an existing MS - Ionization only for liquids at low flow LFSESI DMA Commercial MS^2 Ionization Aerosol instrumentation 9
Operation modes SESI+DMA+MS on-line • Ionization source: SESI* (improved ionization patented) or APCI (corona discharge) • Main analysis modes: The ones of the MS + mobility dimension • Type of samples: Vapors. Direct vapor ionization* and analysis without pre-concentration * Vapors are ionized through secondary electrospray mechanism. There is a charge transfer process from the “charger” to the sample. +Gaseous samples without pre-concentration +Continuous analysis +Permits mobility sweep LFSESI DMA Commercial MS^2 - Without pre-concentration Ionization Sample Aerosol instrumentation 10
Operation modes SESI+DMA+MS off-line for vapours • Ionization source: SESI (improved ionization patented) or APCI (corona discharge) • Main analysis modes: The ones of the MS + mobility dimension + pre-concentration and desorption parameters • Type of samples: Vapors. Adsorbent pre-concentration + thermal desorption + Vapor ionization. +Pre-concentrated gaseous samples. Direct ionization of Vapors. +Permits on-site sampling +The lowest detection limits are achieved on this mode - Intermittent signal Thermal LFSESI Sampler DMA Adsorbent Commercial MS^2 desorber Ionization - Slow analysis Sample Aerosol instrumentation 11
Operation modes SESI+DMA+MS off-line for liquid volatilization • Ionization source: SESI (improved ionization patented) or APCI (corona discharge) • Main analysis modes: The ones of the MS + mobility dimension • Type of samples: Liquid. A small liquid sample is vaporized in the desorber and ionized through secondary electrospray mechanism +Liquid samples. Very low quantities(2µl) +Fast analysis - Intermitent signal Thermal LFSESI DMA Adsorbent Commercial MS^2 desorber Ionization Aerosol instrumentation 12
Index • Architecture and main elements of the device • Most relevant technologies used • Nanospray, SESI. • DMA • Commercial API-MS to couple with DMA • Operation modes • Nano ESI+DMA+MS • SESI+DMA+MS on-line • SESI+DMA+MS off-line for vapours • SESI+DMA+MS off-line for liquid volatilization • Applications and performance • Explosives detection • Atmospheric research: Combustion engines emissions • Engineering studies: Polymer characterization, pesticides… • Biochemistry and medicine Aerosol instrumentation 13
Applications and performance Explosives detection • It is a particular case of the SESI+DMA+MS off-line for vapors operation mode • The samples are taken directly from cargo containers or tracks • It is possible to detect a fraction of 1 ppq of explosives in ambient air in a few minutes • By selecting an appropriate charger solution (HCl in negative mode) the ionization through SESI is favorable to explosives because of their polarity and ionization energy. 1/700 ionization efficiencies are reached for explosives without fragmentation and with low interfering substances ionization. • Main isomeric interfering substances can be separated in mobility thanks to the DMA Sample collection & Sample Analysis pre-concentration Adsorbed sample Aerosol instrumentation 14
Applications and performance Atmospheric research: Combustion engines emissions • It is a particular case of the SESI+DMA+MS off-line or the on-line for vapors operation mode • It was discovered that exhaust fumes produced interferences in explosives mass channels • Many explosives are nitrated organic compounds, so there are many common features between the study of atmospheric chemistry of nitric acid and organic vapors and our own explosive studies. Notice however that the sensitivity and selectivity of our instrument is vastly better than previously available for atmospheric studies • There was found a wide range of substances coming as product of the combustion engines • In the particular case of isomeric interfering substances on explosive mass channels, most of the molecules can be separated from real explosives in mobility. Even the ones with higher intensities. Aerosol instrumentation 15
Recommend
More recommend
