- Electrochemical
derivatisation
- Down to
1 µl cell volume
- Easy change
of working electrodes
Electrochemical derivatisation for
ECD
The DECADE II with dual cell control (DCC) can be equipped with an
additional flow cell, such as a reactor cell for µ-bore LC-EC. The
Flexcell is positioned between the chromatographic column and
the detection flow cell. A potential is applied that converts the
analyte of interest into an electroactive species that can be detected
by the detection flow cell.
This approach is usually applied to obtain a better selectivity or
sensitivity, and is only applicable for analytes with reversible electrochemical
reaction properties. An example is the pre-reduction followed by oxidative
detection of vitamin K (Antec Leyden's application note 218-005).

Fig. 1. Vitamin K. A post column Flexcell is used at -500
mV for reductive conversion of the hydroxyquinone moiety, followed
by oxidative amperometric detection in a second flow cell at +300
mV (vs Ag/AgCl).
Read more: about the Flexcell the
most versatile flow cell for LC-EC.
Electrochemical derivatisation for MS
Already in the early nineties reports appeared describing the use
of HPLC in combination with electrochemical detection and mass spectrometry
[1]. More recently a combination of LC-EC-MS was used for determination
of ferrocene-labelled alcohols and phenols [2]. After LC separation
the derivatives were oxidised and the charged ferrocinium products
were detected using thermospray MS.
In another publication the electrochemical cleavage of peptides has
been described [3]. In this method cleavage is specifically for tyrosine
and tryptophan which makes the method an inter-esting alternative
to enzymatic digestion.
Requirements for low flow rate in LC-MS make the Flexcell particularly
suitable for µ-bore LC-EC-MS.

Fig. 3. Electrochemical reactor on-line with thermospray MS.
Flexcell
The thin-layer Flexcell with an internal cell volume of about
1 µL is particularly suitable for electrochemical derivatisations
in series with other detectors. Because the efficiency of electrochemical
conversion increases with lower flow rates, this cell is particularly
useful in combination with µ-bore LC.
Another major advantage is that the cell can easily be serviced and
change of working electrodes is possible within a minute.
References
1. H.D. Dewald, S.A. Worst ,J.A. Butcher, E.F. Saulinskas, Electroanalysis
3 (1991) 777
2. G. Diehl, A.Liesener, U. Karst, Analyst 126 (2001) 288
3. H.P. Permentier, J.U. Jurva, M.B. Barroso, R. Bischoff, A.P. Bruins,
in: Proceedings of the 50th ASMS Conference on Mass Spectrometry and
Allied Topics, 2002, poster TPA 002
Ordering information
The Flexcell is available with glassy carbon (GC), gold (Au), platinum
(Pt), copper (Cu) or silver (Ag) as working electrode materials.
|
Part no. |
Description |
| 102.4305 |
Flexcell GC HyREF |
| 102.4325 |
Flexcell Au HyREF |
| 102.4100 |
Flexcell GC ISAAC (incl. Au
with HyREF) |
The working electrode discs are also separately available:
|
Part no. |
Description |
| 100.5007 |
Flexcell WE disc GC |
| 100.5022 |
Flexcell WE disc Pt |
| 100.5027 |
Flexcell WE disc Au |
| 100.5032 |
Flexcell WE disc Ag |
| 100.5037 |
Flexcell WE disc Cu |
|