supporting information: figure legend figure s1 cid ... · figure s1 200 250 300 350 400 450 500...
TRANSCRIPT
Supporting Information:
Figure Legend
Figure S1
CID spectrum of [RGYGGGG+H]+
Figure S2
CID spectra of the radical cations in Table 1.a)-d) [R(G)m–2YG]•+
(m=2-5); e)-g)
[R(G)m–2FG]•+
(m=3-5)
Figure S3
CID spectra of a)-f) [K(G)n-2Y(G)7-n]•+
and g)-l) [K(G)n-2F(G)7-n]•+
(n = 2 – 5).
Formation of [bn – H]•+
and yn+ ions.
Figure S4
Potential energy surface for the formation of [b2 – H]•+
ion from [R•FG]
+. Upper
numbers are enthalpies at 0 K, and lower italicized numbers are free energies at 298 K.
All numbers (in kcal mol–1
) are relative to the enthalpy of [R•FG]
+-1. Selected bond
lengths are in Å.
Figure S5
The transition states for the formation of [b2 – H]•+
from [RFG]•+
and [KFG]•+
through
the pathway of side-chain attack. Upper numbers are enthalpies at 0 K, and lower
italicized numbers are free energies at 298 K. All numbers (in kcal mol–1
) are relative
to the enthalpy of [R•FG]
+-1. Selected bond lengths are in Å.
Figure S6
Low-energy structures and potential energy surface for the interconversion of KFG
radical cations. Upper numbers are enthalpies at 0 K, and lower italicized numbers are
free energies at 298 K. All numbers (in kcal mol-1
) are relative to the enthalpy of
[K•FG]
+-1. Selected bond lengths are in Å.
Figure S7
Potential energy surface for the formation of a2+ ion from [K
•FG]
+. Upper numbers
are enthalpies at 0 K, and lower italicized numbers are free energies at 298 K. All
numbers (in kcal mol–1
) are relative to the enthalpy of [K•FG]
+-1. Selected bond
lengths are in Å
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
Figure S1
200 250 300 350 400 450 500 550 600 650
m/z
0
10
20
30
40
50
60
70
80
90
100
Rela
tive
Ab
un
da
nce
606.2
623.2
548.3467.1197.0 434.2 491.2377.1
[RGYGGGG+H]+
[M-H2O]+
y6+ b5
+b3
+[b2-NH3]+ b6
+
b4+
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
M•+
a2+
200 300 400m/z
0
20
40
60
80
100292.1
288.0
393.9
[M-106]•+
M=RYG
150 250 350 450m/z
0
20
40
60
80
100345.1
451.2349.2
M=RGYG
[M-106]•+
a3+ M•+
[M-106]•+
200 300 400 500m/z
0
20
40
60
80
100406.3
402.1
508.4
a4+
M=RGGYG
M•+
M•+
250 350 450 550m/z
0
20
40
60
80
100 463.3
459.2
565.1
[M-106]•+
a5+
M=RGGGYG
150 250 350 450m/z
0
20
40
60
80
100333.1
435.1
M•+
a3+
M=RGFG
200 300 400 500m/z
0
20
40
60
80
100492.3
390.2
M=RGGFG
M•+
a4+
250 350 450 550m/z
0
20
40
60
80
100447.3
549.3393.9
M=RGGGFG
a5+
y5+
M•+
Rel
ativ
e A
bu
nd
ance
a)
b)
c)
d)
e)
f)
g)
Figure S2Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
Figure S3
a7+
M•+
M•+
M•+
M•+
M•+
M•+
y6+
a4+
a5+
a6+
m/z
451.1
435.1
274.8
550
550m/z
451.1
394.1246.9
550m/z
451.0
393.9362.1
550m/z
451.1
419.3393.9
550m/z
451.1
476.2
394.0
550m/z
451.1
394.2533.4
y6+
[b2-H]•+[z6+H]•+
y6+
y5+
y4+
y6+
y5+
y6+
y5+
y5+
y6+
y5+
578.0
578.0
578.0
578.0
578.0
578.0
g)
h)
i)
j)
k)
l)
a6+
a4+
a5+
600m/z
467.1
291.0
488.1
600m/z
467.1
410.0
378.1 488.1
600m/z
467.0
435.3 488.2
y6+
[M-106]•+[b2-H]•+
y6+
y6+
y5+
[M-106]•+
y6+
[M-106]•+
600m/z
467.1
488.1410.0 492.2
y5+
[M-106]•+
y6+
y6+
[M-106]•+
594.0
594.0
594.0
594.0
600m/z
467.0
488.1
410.1
y5+
594.0
a)
b)
c)
d)
e)
f)
0
100
80
60
40
20
0
100
80
60
40
20
a3+
600m/z
467.0
488.1410.0
321.1
[M-106]•+y5
+
594.0
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
M•+
M•+
M•+
M•+
M•+
M•+
Re
lati
ve A
bu
nd
ance
M = KYGGGGG
M = KGYGGGG
M = KGGYGGG
M = KGGGYGG
M = KGGGGYG
M = KGGGGGY
M = KFGGGGG
M = KGFGGGG
M = KGGFGGG
M = KGGGFGG
M = KGGGGFG
M = KGGGGGF
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
1.748
1.869
+ •1.064
1.653
•
+
1.070
Figure S4
TS( [RFG]+-2
→[b-y]COM1)
[b-y]COM1
[b2-H]+
+ Glycine
+26.5
23.3
39.8
39.1
17.9
16.8
35.3
20.9
1.775
1.974
1.544 +
1.618•+
1.092
[RFG]+-2
[RFG]+-1
TS( [RFG]+-1
→ [RFG]+-2)
0.0
0.0
26.9
26.6
+
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
Figure S5
2.042
1.896
TS ( side-chain attack to form [b2-H]•+ from [KFG]•+)
57.2
55.4
+
+
2.049
1.641
49.2
52.2
TS ( side-chain attack to form [b2-H]•+ from [RFG]•+)
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
+
1.374
1.376
Figure S6
[KFG]+-1
[KF G]+-1
[KFG]+-1
25.2
22.5
0.0
0.0
10.7
8.0
TS([KFG]+
→[K FG]+)
TS([KFG]+
→ [KFG]+)
29.5
26.4
34.2
32.2
+
35.3
33.0
+
1.192
TS([KFG]+
→[KFG]+)
1.645
2.344
1.474
1.102
1.830
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011
Figure S7
+
•
1.327
1.191
+a2
+
[a-x]COM2
[KFG]+-2
TS([KFG]+-2→
[a-x]COM2)
28.1
19.9
2.342
•
•
1.472
2.1181.100
1.480+
1.499+
21.6
20.5
36.5
33.1
35.9
20.0
+ x radical
+
1.102 1.093
Supplementary Material (ESI) for PCCPThis journal is © the Owner Societies 2011