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INSTRUMENTO DE ANLISIS Y CLASIFICACIN DE ESPECIES EN SUSPENSIN MEDIANTE IONIZACION SECUNDARIA POR ELECTROSPRAY, ANLISIS DE MOVILIDAD Y MASA INSTRUMENT FOR CLASSIFICATION AND ANALYSIS OF SUSPENDED SPECIES THROUGH SECONDARY ELECTROSPRAY


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SLIDE 1

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 CARBALLIDO1,2, JUAN FERNANDEZ DE LA MORA1,3, GUILLERMO VIDAL DE MIGUEL1,2,4 1Sociedad Europea de Análisis Diferencial de Movilidad,

2Universidad de Valladolid,

3Universidad de Yale, 4ETH Zurich arturo.alvaro@seadm.com

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Aerosol instrumentation

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SLIDE 2

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

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SLIDE 3

Architecture and main elements of the device

Aerosol instrumentation

3 Sample

Sampler

Analyzer Post processing software

Adsorbent

Desorber

LFSESI DMA Triple Quad MS

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SLIDE 4

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

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SLIDE 5

Most relevant technologies used Nanospray, SESI (Secondary Electrospray Ionization).

Aerosol instrumentation

5

  • 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.

  • 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.

Chorro

Cono de Taylor

Pluma Capilar

Department of Electrical Engineering University of South Florida

  • G. Vidal-de-Miguel et al. Anal. Chem.
  • LFSESI. Improving vapor ionization efficiency
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SLIDE 6

Most relevant technologies used Supercritical planar DMA

Aerosol instrumentation

6

  • 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

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SLIDE 7

Most relevant technologies used

Comercial API MS to couple with DMA

Aerosol instrumentation

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  • ¿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.

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SLIDE 8

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

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SLIDE 9

Operation modes

Nano ESI+DMA+MS (Mobility dimension addition to MS)

Aerosol instrumentation

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  • 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 Ionization

DMA

Commercial MS^2

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SLIDE 10

Operation modes

SESI+DMA+MS on-line

Aerosol instrumentation

10

Sample

  • 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

  • Without pre-concentration

LFSESI Ionization

DMA

Commercial MS^2

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SLIDE 11

Operation modes

SESI+DMA+MS off-line for vapours

Aerosol instrumentation

11

  • 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
  • Slow analysis

Sampler

Adsorbent Thermal desorber

LFSESI Ionization

DMA

Commercial MS^2

Sample

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SLIDE 12

Operation modes

SESI+DMA+MS off-line for liquid volatilization

Aerosol instrumentation

12

  • 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

Adsorbent Thermal desorber

LFSESI Ionization

DMA

Commercial MS^2

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SLIDE 13

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

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SLIDE 14

Applications and performance

Explosives detection

Aerosol instrumentation

14

  • 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 & pre-concentration

Sample Analysis

Adsorbed sample

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SLIDE 15

Applications and performance

Atmospheric research: Combustion engines emissions

Aerosol instrumentation

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  • 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.

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SLIDE 16

Applications and performance

Engineering studies: Polymer characterization, pesticides…

Aerosol instrumentation

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  • It is a particular case of the Nano ESI+DMA+MS operation mode.
  • Tandem DMA-MS analysis enables for family compound characterization. It is possible to
  • btain information of the folding or the nature of them. For example in the case of the

polymers

  • When analyzing complex samples, the mass spectra can be simplified my mobility filtering.

For example, looking for pesticides in a complex corn extract sample

Fumonisin analysis in Corn extract m/z–Mobility 2D Spectra

DMA Voltage [kV] m/z

Globular PEG

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SLIDE 17

Applications and performance

Biochemistry and medicine

Aerosol instrumentation

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  • The device may be used for the analysis of biological samples
  • For instance breath analysis in the SESI+DMA+MS on-line operation mode. The temporal

evolution of certain metabolite can be observed through this method. We have also worked on cancer breath bio-markers research.

  • It is also possible to study folding state and collision sections of big bio-molecules such as

Concanavalin protein in the mode the Nano ESI+DMA+MS

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SLIDE 18

Thanks for your attention!

Aerosol instrumentation

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Any questions?

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SLIDE 19

ARTURO ÁLVARO CARBALLIDO1,2, JUAN FERNANDEZ DE LA MORA1,3, GUILLERMO VIDAL DE MIGUEL1,2,4

1Sociedad Europea de Análisis Diferencial de Movilidad, 2Universidad de Valladolid, 3Universidad de Yale, 4ETH Zurich

arturo.alvaro@seadm.com

Aerosol instrumentation

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INSTRUMENTO DE ANÁLISIS Y CLASIFICACIÓN DE ESPECIES EN SUSPENSIÓN MEDIANTE IONIZACIÓN SECUNDARIA POR ELECTROSPRAY, ANÁLISIS DE MOVILIDAD Y MASA INSTRUMENT FOR CLASSIFICATION AND ANALYSIS OF SUSPENDED SPECIES THROUGH SECONDARY ELECTROSPRAY IONIZATION, MASS AND MOBILITY ANALYSIS