institute of organic chemistry and biochemistry as cr, v.v.i. czech university of life sciences...
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Institute of Organic Chemistry and Biochemistry AS CR, v.v.i.
Czech University of Life Sciences Prague
Jana Jaklová Dytrtová, Michal Jakl
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 flow cell
WE
Positive potential – supports the oxidation
AgCyp
MgCyp
CaCypZnCyp Ag
AgAgAg
AgCyp
AgCyp
ESI-MS
RE
AgCyp
AgCyp
Cyp
Spontaneous oxidation
Spontaneous reduction
Ag+/Ag(s) ... 800 mV
2 electrodes connection
Dytrtová et al., IJMS 2013
V
MS
Sample inlet
WE
RE
A
3 electrodes connection
ECMS
V
A
RE
WEAE
inlet
RT: 0,00 - 7,52
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
5,50
5,25
5,16
5,67
5,725,05
5,00 5,36
4,914,77
5,86
5,976,08
4,61
6,22
6,28
4,507,064,30
6,564,13 6,700,65 4,02
3,337,00
3,883,833,662,21
3,102,601,151,04 2,822,411,35 3,46 7,172,991,99
1,541,600,460,07 7,36
NL: 1,61E6
m/z= 691,00-691,20 MS 3_Cela_0,51ml_Cyp_ZE_DP306bAg_vs_AgCl1400mV_-500mV_PA_1400mV_DA120s
RT: 0,00 - 7,29
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
5,685,07
4,98
5,514,234,29
4,43
4,68 4,765,20 5,40
4,514,09 5,79
5,874,04
5,93 6,01
3,98
3,90
6,126,20
6,43
3,763,70
3,62
3,426,54 6,65
7,153,12 6,790,13 6,901,19 2,50 3,312,03 2,592,311,660,58 2,890,21 1,390,52 1,000,88 1,94 2,111,61
NL: 4,65E6
m/z= 691,00-691,20 MS 3_Cela_0,51ml_Cyp_ZE_DP306gAg_vs_AgCl1400mV_-500mV_PA_1400mV_DA120s
2 electrodes connectionAg (W),Ag/AgCl/NH4Cl (Ref)
3 electrodes connectionAg (W),Ag/AgCl/NH4Cl (Ref),Pt (Aux)
intensity 1.4x106intensity 4.6x105
Cyproconazole (10-5 M), 25 mM NH4OAc, EtOH:H2O (1:1)
Zn
Cl
Ag
Cd
NO3
Pb
Ca
Mg
NH4
FA
K
SO4
LMWOAs
Na
PO4
SO3
CO3
SiO4
enzymes
Cyp
Cyp
Cyp
Cyp
Cyp
Cyp
Cyp
Cyp
Ag
Ag
Ag
Ag
AgAg
Cl
OH
NN
N
12
4
No sample pretreatment2 min of analysis
RT: 0.00 - 40.46
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Time (min)
0
10
20
30
40
50
60
70
80
90
100
Re
lativ
e A
bu
nd
an
ce
7.1532.9416.16
12.764.33 31.826.88 24.53 33.267.49 15.044.25 24.8823.5021.297.61 12.21 34.221.10 16.44
16.871.337.92
1.4612.07 34.62
8.22 21.01 26.2116.96
17.16 35.4126.3617.34 35.64
8.6111.93 26.69 31.3917.50 36.08
27.619.31 28.57 37.5819.48
NL:5.99E7
m/z= 690.50-691.50 MS 3_cela_Cyp_poz575a_2000mV_180s
Generation
Eacc: 1000 mV
Acc. time 5 min
100 200 300 400 500 600 700 800 900 10000
2x105
4x105
6x105
100 200 300 400 500 600 700 800 900 10000
1x106
2x106
3x106
4x106
100 200 300 400 500 600 700 800 900 10000
1x1062x106
3x106
4x106
m/z
off-line
[Ag(Cyp)2]+
Inte
nist
y
on-line 1000 mV
[Cu(Cyp)2]+
[CuCl(Cyp)2]+
on-line 800 mV
Benefits of the electrochemical cell prior MS:
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 reactions in situ Unique approach for study of electrochemical reactions
We are able to lend the electrochemical device to your lab for independent tests
Dr. Jana Jaklová Dytrtovádytrtova@uochb.cas.czwww.uochb.cz
Dr. Michal Jakljakl@af.czu.czhome.czu.cz/jakl
Grant Agency of the Czech Republic (project No. 13-21409P)
Ministry of Education of the Czech Republic (S grant)
dytrtova@uochb.cas.cz
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