SUPPLEMENTARY INFORMATION
For JASMS manuscript:
Bipolar Mass Spectrometry of Labile Co-ordination Complexes,
Redox Active Inorganic Compounds and Proteins Using a Glass
Nebulizer for Sonic-Spray Ionization
M. M. Antonakis,† A. Tsirigotaki,† K. Kanaki,† C. J. Milios‡ and Spiros A. Pergantis*,†
†
Environmental Chemical Processing Laboratory and ‡Division of Inorganic Chemistry,
Department of Chemistry, University of Crete, Voutes Campus, Heraklion 71003, Greece
Supplementary Information Content:
Figure S1. Modified Meinhard® pneumatic glass nebulizer used for V-EASI-MS: (1)
fused silica capillary located at glass nebulizer tip; (2) nut and PEEK sleeve used to
secure fused silica capillary in place; (3) fused silica capillary going to sample; (4) 40-60
psi N2 gas line.
Figure S2. (a) Meinhard® V-EASI source coupled to mass spectrometer (LCQ,
Thermo). Inset shows top view of fused silica capillary coming out of the back of
nebulizer and going into sample tube; and (b) close-up of V-EASI nebulizer next to mass
spectrometer entrance.
Figure S3. ES mass spectrum acquired from the analysis of 100 µg mL-1 cytochrome c
in 80% DMSO, at 300 oC heated inlet capillary and source induced dissociation potential
of 15 V.
Figure S4. Negative ion mass spectrometric analysis of the [Cu6Dy] complex in
acetonitrile solution, using V-EASI-MS with a heated ion transfer capillary at 205 oC and
sid voltage at 15 V (a), and using ES-MS with a heated ion transfer capillary at 205 oC
and sid voltage at 10 V (b).
Figure S5. Time course stability of Se(IV) species of selenous acid in solution as
screened by negative ion V-EASI-MS analysis. Expected peak for the oxidized analyte
[Μ+Ο–Η]- is at m/z 145.
Figure S6. Negative ion mass spectra for arsenite using V-EASI-MS (a), and ES-MS at
4 kV spray voltage (b).
Figure S7. Negative ion mass spectrum obtained using a dual V-EASI nebulizer
configuration for the separate aspiration of [Cu6Tb] in acetonitrile and STFA in
acetonitrile/water. Numbers in green correspond to STFA ions, whereas numbers in blue
correspond to [Cu6Tb] complex ions. Masses in boxes represent bracketing masses for
potential accurate mass measurements.
Figure S2. Modified Meinhard® pneumatic glass nebulizer used for V-EASI-MS: (1) fused
silica capillary located at glass nebulizer tip; (2) nut and PEEK sleeve used to secure
fused silica capillary in place; (3) fused silica capillary going to sample; (4) 40-60 psi N2
gas line.
a
b
Figure S2. (a) Meinhard® V-EASI source coupled to mass spectrometer (LCQ,
Thermo). Inset shows top view of fused silica capillary coming out of the back of
nebulizer and going into sample tube; and (b) close-up of V-EASI nebulizer next
to mass spectrometer entrance.
CYT_100ppm _80% DMSO #2-25 RT: 0.07-0.97 AV: 24 NL: 5.56E4
T: + p ESI s id=20.00 Full m s [ 100.00-2000.00]
1767.1
100
95
90
85
80
75
70
1546.5
Relative Abundance
65
60
55
50
45
40
1125.1
35
1375.0
30
1237.5
25
1031.5
20
1551.3
15
1772.7
10
5
0
200
400
600
800
1000
1200
1400
1600
1800
2000
m /z
Figure S3. ESI (a) and SSI (b) mass spectra acquired from the analysis of 100
µg mL-1 cytochrome c in 80% DMSO, at 300 oC heated inlet capillary and source
induced dissociation potential of 15-20 V,
[Μ+NO3]100
a
1630.6
2.43E4
Relative Abundance
50
1718.4
1547.7
0
100
1898.9
1553.1
1.83E4
b
1372.5
1613.5
50
1902.7
824.5
1657.1 1840.3
188.9
339.1
408.5
557.6
981.1
692.4
1066.7
1163.9
1511.2
1739.5
1926.9
1280.3
0
200
400
600
800
1000
1200
1400
1600
1800
2000
m/z
Figure S4. Negative ion mass spectrometric analysis of the [Cu 6Dy] complex in
acetonitrile solution, using V-EASI-MS with a heated ion transfer capillary at 205
oC and sid voltage at 15 V (a), and using ES-MS with a heated ion transfer
capillary at 205 oC and sid voltage at 10 V (b).
[M-H2O]-
t=0days
t=3days
e
c
a
d
n
u
b
A
Relative Abundance
[M-H]-
tiv
la
e
R
t=14days
m/z
Figure S5. Time course stability of Se(IV) species of selenous acid in solution as
screened by negative ion V-EASI-MS analysis. Expected peak for the oxidized analyte
[Μ+Ο–Η]- is at m/z 145.
[M-H]Relative Abundance
100
107.1
4.22e2
a
As(III)
60
141,0
20
100
3.61e2
123.1
107.1
60
b
[M-H+O]As(V)
As(III)
20
80
85
90
95
100 105 110 115 120 125 130 135 140 145 150 155 160
m/z
Figure S6. Negative ion mass spectra for arsenite using V-EASI-MS (a), and ESMS at 4 kV spray voltage (b).
792.80
100
[M+NO3]1628.33
1200.60
80
1064.60
1608.5
1336.60
928.73
60
1666.5
1472.47
656.87
1744.40
40
289.00
520.87
1880.40
20
248.87
195.07
1948.47
384.87
0
200
400
600
800
1000
1200
1400
1600
1800
2000
m/z
Figure S7. Negative ion mass spectrum obtained using a dual V-EASI nebulizer
configuration for the separate aspiration of [Cu6Tb] in acetonitrile and STFA in
acetonitrile/water. Numbers in green correspond to STFA ions, whereas numbers
in blue correspond to [Cu6Tb] complex ions. Masses in boxes represent
bracketing masses for potential accurate mass measurements.