1. Electrochemistry upfront MS
Panacea:
an ancient Greek goddess of healing.
an answer or solution for all problems or difficulties. 1

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

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

4. 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

5. Electrochemistry / MS Mimicking nature’s redox reactions
Fast alternative for laborious, time consuming procedures

6. Electrochemistry / MS Mimicking nature’s redox reactions
Fast alternative for laborious, time consuming procedures EC MS

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

8. Electrochemical Reaction
Oxidation of a dihydroxyphenyl derivate to 1,2 benzoquinone derivate, by dehydration

9. Role of electrode potential E
Facilitates the EC reaction 20 40 60 80
100
400
800
1200
1600
E (mV)
Signal (%)
formation of oxidation or reduction products
no reaction
A  B

10. Role of electrode potential E
Facilitates the EC reaction
formation of secondary products 20 40 60 80
100
400
800
1200
1600
E (mV)
Signal (%)
2000 B C
A  B  C
B: instable intermediate

11. oxidative degradation of the substrate
How to Find Optimum ΔE ?
Traditional Electrochemistry: Voltammogram
On-line EC/ESI-MS: “MS Voltammogram”
180
200
220
240
260
280
300
320
340
360
380
400
1000
2000
3000
4000
5000
1500
2500
intensity [-]
m/z
E [mV]
oxidative degradation of the substrate
oxidation products

12. Typical Reactions Catalyzed by Cytochrome P450
Simulated by EC
Allylic and aliphatic hydroxylation
Possible at high potentials
(only with ROXY)
Benzylic
hydroxylation
Possible
Desalkylation of amines
Desalkylation of ethers and thioethers
Ethers: Possible
Tioethers: not mimicked
Hydroxylation of aromatics
Epoxide formation
Oxidation of heteroatoms (N, S)
R-CH2-CH R-CH-CH3 OH
N-CH2-R NH + R-CHO
R-O-CH2-R R-OH + RCHO O
C=C R
C C HO
R C NH R R C+ N R O- H
Adapted from W. Lohmann et al. LC/GC Jan. 2010 12

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

14. Electrochemistry in Proteomics

15. Electrochemistry in Proteomics

16. Electrochemistry in Proteomics

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

18. 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

19. Thank you!