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This study explores the use of an electrochemical cell for accurate detection of cyproconazole in samples like blood, plasma, and soil solution by combining electrochemical separation with mass spectrometry, addressing the limitations of HPLC/GC-MS analysis. The innovative method involves in situ generation of silver cations for efficient separation and analysis without sample pretreatment, offering a time-efficient and cost-effective solution for detecting poorly polarizable chemicals. The technology shows promise in various applications like pesticides analysis in soil, organic compounds in wastewater, and drug metabolites in biological samples.
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Detection of cyproconazole using silver affinity electrochemical separation electrospray ionization mass spectrometry Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Czech University of Life Sciences Prague Jana Jaklová Dytrtová, Michal Jakl
Definition of the problem • 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
Electrochemical cell prior MS detection… Itcansolvetheproblem! Electrochemical flow cell
Me-AES separation Positive potential – supports the oxidation Spontaneous oxidation WE ESI-MS Ag+/Ag(s) ... 800 mV Ag Ag MgCyp ZnCyp Ag AgCyp AgCyp Ag CaCyp AgCyp AgCyp AgCyp Cyp RE Spontaneous reduction
1stelectrochemicalcell construction 2 electrodes connection RE V Sample inlet MS A WE Dytrtová et al., IJMS 2013
2ndelectrochemicalcell construction A 3 electrodes connection V RE inlet WE AE MS EC
1st vs 2nd intensity 4.6x105 intensity 1.4x106 2 electrodes connection Ag (W), Ag/AgCl/NH4Cl (Ref) 3 electrodes connection Ag (W), Ag/AgCl/NH4Cl (Ref), Pt (Aux) Cyproconazole (10-5 M), 25 mM NH4OAc, EtOH:H2O (1:1)
Cyproconazoleseparationfromsoilsolution matrix usingin situgeneratedAgcations Cyp Cyp LMWOAs Ca Zn PO4 Ag Cyp Cd Cyp Cyp K SiO4 Pb SO3 Cyp Cl SO4 NH4 Ag FA enzymes Ag NO3 Ag Cyp CO3 Cyp Na Ag Mg Ag Ag
Cyproconazole separation from soil solution matrix using in situ generated Ag cations No sample pretreatment 2 min of analysis
Cyproconazole separation from soil solution matrix using in situ generated Ag cations Generation Eacc: 1000 mV Acc. time5 min
An alternative method to HPLC? Benefits of the electrochemical cell prior MS:
Development and IP status • 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 reactionsin situ • Unique approach for study of electrochemical reactions • We areable to lend the electrochemical device to your lab for independent tests
Contacts Dr. Jana Jaklová Dytrtová dytrtova@uochb.cas.cz www.uochb.cz Dr. Michal Jakl jakl@af.czu.cz home.czu.cz/jakl
Thank you! Grant Agency of the Czech Republic (project No. 13-21409P) Ministry of Education of the Czech Republic (S grant) dytrtova@uochb.cas.cz