1. Pulsed Glow Discharge Mass Spectrometry: An Ionization Source for Aerosol Analysis and Laser Sampling Farzad Fani-Pakdel Qualifying Examination University of Florida - Department of Chemistry Division of Analytical Chemistry

2. Outline Introduction Aerosols Aerosols characterization Glow discharge Research objective Experimental Instrumental set-up Particle introduction into system Preliminary Results Laser Sampling Importance and application Cathode design

3. Aerosols Suspension of fine solid or liquid particles (~3 nm -100  m) in a gas. Biological Aerosols: Viruses: 0.01 - 0.3 micron Bacteria: 0.5 – 10 micron Pollen: 5-100 micron Allergy and sickness Contagious diseases Biological warfare Examples: Atmospheric Aerosols: Dust Fog Haze Smoke Sea spray particles Air pollution (Acidic rain) Atmospheric reactions Material transfer War generated particles Significance:

4. Chemical Characterization of Aerosols hv Nano device Sampling Spectroscopy: non-destructive, surface only Nano sensors: non-destructive, selective, surface only Mass spectrometry: destructive, core and surface both possible Importance: chemical contamination or bio hazard in core Ionization

5. Ideal Ionization Technique Soft ionization provides surface information, at the molecular level CI ICP Intense ionization Provides surface and bulk Information, at atomic level A moderate ionization like EI will result in fragmentation Pulsed glow discharge is an ionization source capable of ionization at all these levels at the same time.

6. Glow Discharge Ionization Source + - Anode (+) Cathode (-) e Negative Glow Ar Ar+ Ar Ar+ Ar * e Penning ionization by meta-stable argon, Electron ionization e CuCu +

7. time V Pulsed Glow Discharge High energy electrons (ICP) Pre-peak Fragmentation Plateau Penning ionization Soft, ( CI ) After peak

8. Schematics of a Glow Discharge -Time of Flight Instrument Majidi, et al., Anal. Chem., 2003, 75, 1983-1996

9. Research Objectives: Application of pulsed GD - TOF Mass Spectrometry for characterization of different particles bulk vs. surface chemical analysis CdSe / ZnS nano particles Gold nano particles with hydrocarbon chains MgCl2, NaCl mixed nano particles Silica nano particles with peptides on surface

10. Experimental Setup TOF GD Figure is modified from the original: Eric Oxley, Ph.D. Dissertation, Department of Chemistry, University of Florida, 2002.

11. Glow Discharge Source Cathode O-ring Eric Oxley, Ph.D. Dissertation, Department of Chemistry, University of Florida, 2002.

12. Particle Introduction 1

13. Particle Introduction 2

14. Particle Introduction 3

15. Particle Introduction 2; Cathode Design Anode Insulator Cathode base Scale in inches

16. Tap water DI water Na-Mg solution Preliminary Results To examine the sample introduction design, a sodium chloride-magnesium nitrate solution(1000ppm of each) was nebulized to produce particles of about 100nm size

17. Laser Sampling: Introduction of particles /atoms into discharge by laser pulse from the sample’s back side. Synchronized sample introduction is possible Study of non-conductive thin films also possible, surface analysis of thin films (brain slice) Sampling yield improves Back side sampling (LIFT or LIBA) has the advantage of sampling directionality

18. Laser Laser Induced Back Ablation mirror Lenz Sample on a quartz window

19. Laser Pulsed Laser Induced Forward Transfer

20. Summary Glow discharge time of flight mass spectrometry can be used for surface and core chemical characterization of particles Cathode of the source needs to be modified for sample introduction An orifice in the cathode seems to be a proper way of particle introduction Laser sampling can be used for synchronized introduction of particles and also analysis of thin films (useful for non-conductive samples)

21. References: 1.Eric Oxley, “The Microsecond Pulsed Glow Discharge: Developments in Time of Flight Mass Spectrometry and Atomic Emission Spectrometry.”, Ph.D. Dissertation, Department of Chemistry, University of Florida, 2002. 2.W.W. Harrison, C. Yang and E. Oxley, Anal. Chem., 2001, 73, 480A-487A 3.C.L. Lewis, M.A. Moser, D.E. Dale, Jr., W. Hang, C. Hassel, F.L. King and V. Majidi, Anal. Chem., 2003, 75, 1983-1996 4.A. B. Bullock, P. R. Bolton, Appl. Phys., 1999, 85, No. 1, 460-465

22. Acknowledgments: Dr Omenetto Dr Harrison Dr Igor Gornushkin Dr Winefordner Dr Smith Dr Kevin Turnery Committee members Winefordner-Omenetto- Smith group Friends from Yost / Martin group Machine shop Electronic Shop