1. Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Czech University of Life Sciences Prague Jana Jaklová Dytrtová, Michal Jakl

2.  Limits of ESI-MS analysis  Problematic detection of samples in mixtures (blood, plasma, soil solution, etc.)  Poorly polarizable chemicals are invisible  HPLC/GC-MS analysis  Separation of chemicals from mixtures, but…  Loss of samples in columns  Time and money consuming process  Problematic for hydrophobic (poorly ionizable) analytes

4. Cationization or oxidation/reduction of compounds poorly ionizable by MS Electrochemical separation of chemicals bounded to sample matrix Study of in situ mechanisms of electrochemical reactions Electrochemical flow cell

5. WE Positive potential – supports the oxidation AgCyp MgCyp CaCyp ZnCyp Ag AgCyp ESI-MS RE AgCyp Cyp Spontaneous oxidation Spontaneous reduction Ag + /Ag(s)... 800 mV

7. 2 electrodes connection Dytrtová et al., IJMS 2013 V MS Sample inlet WE RE A

8. 3 electrodes connection EC MS V A RE WE AE inlet

9. 2 electrodes connection Ag (W), Ag/AgCl/NH 4 Cl (Ref) 3 electrodes connection Ag (W), Ag/AgCl/NH 4 Cl (Ref), Pt (Aux) intensity 1.4x10 6 intensity 4.6x10 5 Cyproconazole (10 -5 M), 25 mM NH 4 OAc, EtOH:H 2 O (1:1)

11. Zn Cl Ag Cd NO 3 Pb Ca Mg NH 4 FA K SO 4 LMWOAs Na PO 4 SO 3 CO 3 SiO 4 enzymes Cyp Ag Ag Ag Ag Ag Ag

12. No sample pretreatment 2 min of analysis

13. Generation E acc : 1000 mV Acc. time 5 min

15. Fast No sample pre-treatment CheapVersatileLow sample amount Benefits of the electrochemical cell prior MS:

16.  Possible applications  Separation and analysis of compounds in mixtures  Pesticides and specific contaminants in soil solutions  Organic compounds in waste water  Drug candidates or metabolites in blood or plasma  MS analysis of poorly polarizable chemicals, e.g:  Lipopeptides  Complex aromatic compounds (e.g. helicene structures)  Study of basic electrochemical reactions in situ  Unique approach for study of electrochemical reactions  We are able to lend the electrochemical device to your lab for independent tests

18. Dr. Jana Jaklová Dytrtová dytrtova@uochb.cas.cz www.uochb.cz Dr. Michal Jakl jakl@af.czu.cz home.czu.cz/jakl

19. Grant Agency of the Czech Republic (project No. 13-21409P) Ministry of Education of the Czech Republic (S grant) dytrtova@uochb.cas.cz