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Electrochemistry upfront MS 1 ROXY - EC/LC upfront MS With ReactorCell for Generating Redox metabolites Cleavage of proteins/peptides Signal enhancement.

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Presentation on theme: "Electrochemistry upfront MS 1 ROXY - EC/LC upfront MS With ReactorCell for Generating Redox metabolites Cleavage of proteins/peptides Signal enhancement."— Presentation transcript:

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2 Electrochemistry upfront MS 1

3 ROXY - EC/LC upfront MS With ReactorCell for Generating Redox metabolites Cleavage of proteins/peptides Signal enhancement in MS Oxidative stress Metabolism 2

4 Why Electrochemistry / MS? Mimics Natures Redox Reactions In Drug Development and Proteomics Fast & Clean Complementary to existing methods 3

5 Why Electrochemistry / MS? Mimics Natures Redox Reactions Drug development Immediate results, minutes vs weeks No by products, no cleanup No biohazard No rodents Proteomics No enzymes, clean without by products 4

6 Electrochemistry / MS Mimicking natures redox reactions Fast alternative for laborious, time consuming procedures 5

7 Electrochemistry / MS Mimicking natures redox reactions Fast alternative for laborious, time consuming procedures 6 MSEC

8 Modes of operation On-line EC/MS On-line EC/LC/MS - Pre injection - Post column Off-line EC/MS 7

9 Electrochemical Reaction 8 ΔEΔE

10 Facilitates the EC reaction 9 Role of electrode potential E E (mV) Signal (%) no reaction formation of oxidation or reduction products A B

11 Facilitates the EC reaction 10 Role of electrode potential E E (mV) Signal (%) 2000 formation of secondary products A B C B C B: instable intermediate

12 How to Find Optimum Δ E ? Traditional Electrochemistry: Voltammogram On-line EC/ESI-MS: MS Voltammogram 11 oxidative degradation of the substrate oxidation products

13 Typical Reactions Catalyzed by Cytochrome P450Simulated by EC Allylic and aliphatic hydroxylation Possible at high potentials (only with ROXY) Benzylic hydroxylation Possible Desalkylation of amines Possible Desalkylation of ethers and thioethers Ethers: Possible Tioethers: not mimicked Hydroxylation of aromatics Possible Epoxide formation Possible Oxidation of heteroatoms (N, S) Possible Adapted from W. Lohmann et al. LC/GC Jan R-CH 2 -CH 3 R-CH-CH 3 OH N-CH 2 -R NH + R- CHO R-O-CH 2 -R R-OH + RCHO O C=C R C R R HOOH R C NH R R C + N R O-O- R R H

14 Proteomics Electrochemical cleavage (oxidation) of proteins/peptides enzymatic digestion by electro-chemical cell no enzymes, no non-specific cleavage, no auto-digestion, etc. 13

15 Electrochemistry in Proteomics 14

16 Electrochemistry in Proteomics 15

17 Electrochemistry in Proteomics 16

18 Conclusion EC/MS Many application areas Time and cost savings... Fast and clean 17

19 Conclusion EC/MS Mimics Natures Redox Reactions Drug development Immediate results, minutes vs weeks No by products, no cleanup No biohazard No rodents Proteomics No enzymes, clean without by products 18

20 Thank you!


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