Environmental Degradation of Pharmaceuticals and Pollutants using EC/MS ASMS 2015 St. Louis, MO, USA

Principle of EC upfront MS Potential (∆E) is the driving force of the reaction ∆E (Potential) Reduction Oxidation

Antec’s Electrochemical Flow (Through) Cells ChipCell™ Nanoflow applications 50-1000 nL/min ReactorCell™ Universal starter cell 1 -20 µL/min µ-PrepCell™ High yield cell 20 – 200 µL/min

Why Coupling EC with MS? EC cell oxidation or reduction MS for direct identification incl. unstable & short-lived components Electrochemically induced reactions show excellent agreement with Nature’s REDOX reactions, e.g., enzymatic, aquatic, microbial, chemical, ROS, UV light, etc., Reactions are instantaneously  very fast, no isolation from biological matrix, etc.

MS Voltammogram – Quick Assessment of Oxidation Products Amiodarone

Application Areas Electrochemistry/MS Electrochemistry upfront MS Disulfide bond reduction Peptide bond cleavage Desalting DNA damage Signal enhancement in MS Skin sensitization Pollutants Metabolite synthesis Drug metabolism Drug ̶ protein binding Oxidative tagging of proteins Purposeful degradation Combining electrochemistry (EC) with MS and LC/MS has shown great potential for the investigation of drug metabolism. The oxidation of target compounds occurs in the electrochemical cell within seconds and the similarity between reactions catalyzed by cytochrome P450 in nature and simulated in the electrochemical cell is high . Recently, the use of on-line EC/LC/MS has been extended towards new applications such as:

Instrumental Set-up

ROXY™ Product Line • ROXY™ Potentiostat*) dual cell control, +/- 4.9 V ROXY™ EC System*) all parts included for direct on-line EC/MS ROXY™ EC/LC System*) electrochemical cell integrated in autosampler**) for non-compromised EC, LC and MS *) all instruments are fully compatible with any MS **) Intl. Patent Application PCT/NL2010/050309

MS Voltammogram Boscalid (Pesticide) Synonim: PESTANAL® (Sigma Aldrich)

Boscalid Degradation Electrochemical oxidation of pesticides …simulation of pesticide meta-bolism (phase I &II) minutes vs. weeks excellent agreement with in vivo data Electrochemical degradation scheme of boscalid W. Lohmann, J .Am Soc Mass Spectrom, 20, 2009, 138 10

Environmental persistence EC starting voltage (mV) Persistence in Environment, Stability in EC? Compound Environmental persistence EC starting voltage (mV) Sulfadizine Medium 1100 Metabenzthiazuron Stable 1800 Ethidimurin -1420 Ibuprofen 1200 17ß-estradiol Unstable 300 Clotrimazol 1750 PCB31 Very Stable 4500 Tetracene 1600 => QSAR modeling…

Stability and Structure Compound Structure EC starting voltage (mV) Naphthalene 340 Anthracene 930 Phenanthren 600 Benzo[a]anthracene 750 Tetracene 1600 Chrysene 1300

Environmental Pollutants