Supporting Information for:
A mechanistic study of the H/D exchange reactions of
protonated arginine and arginine-containing di- and tri-peptides
Yiqun Huang, Joe A. Marini, John A. McLean, Shane E. Tichy, David H. Russell*
The complete list of authors of reference 43 the representative collision cross
section profiles for singly charged GGR, GRG, RGG, GR, RG and the
corresponding methyl esters (Figures S1-S2); the temporal plots for product ions
of H/D exchange reactions for [M + H]+ ions of arginine methyl ester, GR, RG,
GRG and RGG (Figures S3-S7); the potential energy surfaces for H/D exchange
reaction of all protonated arginine-containing di- and tri-peptides with ND3
(Figures S8-S12).
S1
Reference 43: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M.A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J.
A., Jr.; Stratmann,R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.;
Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.;
Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.;
Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.;
Morokuma, K.; Salvador, P.; Dannenberg, J. J.; Malick, D. K.; Rabuck,
A. D.; Raghavachari, K.;Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.;
Baboul, A. G.; Stefanov, B.B.; Liu, G.; Liashenko, A.; Piskorz, P.;
Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; AlLaham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P.
M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez,
C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc.,
Pittsburgh, PA, 2001.
S2
Figure S1. (A) Representative collision cross section profiles for singlycharged GGR (top), GRG (middle), and RGG (bottom), respectively. (B)
Representative collision cross section profiles for the corresponding
methyl esters GGROMe (top), GRGOMe (middle), and RGGOMe
(bottom), respectively. Grey bars indicate ±1σ (n = 10) for the average
apex in the collision cross section profile, which is indicated by a dashedline.
S3
Figure S2. (A) Representative collision cross-section profiles for singly-charged
GR (top) and RG (bottom). (B) Representative collision cross-section profiles for
the corresponding methyl esters GROMe (top) and RGOMe (bottom). Grey bars
indicate ± 1 σ (n = 10) for the average apex in the collision cross-section profile,
which is indicated by a dashed-line
S4
Figure S3. A plot of relative abundance of protonated arginine methyl ester verus
H/D exchange time when reacted with ND3.
S5
Figure S4. A plot of relative abundance of protonated GR verus H/D
exchange time when reacted with ND3. The inset region contains an
expanded region between 0 and 20 seconds reaction time.
S6
Figure S5. A plot of relative abundance of protonated RG verus H/D
exchange time when reacted with ND3. The inset region contains an
expanded region between 0 and 20 seconds reaction time.
S7
Figure S6. A plot of relative abundance of protonated GRG verus H/D
exchange time when reacted with ND3. The inset figure contains an
expanded region between 0 and 40 seconds reaction time.
S8
Figure S7. The relative abundance of protonated RGG verus H/D exchange
time when reacted with ND3. The inset figure contains an expanded region
between 0 and 40 seconds reaction time.
S9
ND3
1
7 (0.1)
1 (0.0)
6 (-4.5)
5 (-8.0)
4 (-14.3)
2 (-16.0)
3 (-15.2)
Figure S8. The potential energy surface for H/D exchange of protonated GGR
with ND3, as calculated at the B3LYP/6-31G(d.p)//HF/3-21G(d,p) level of
theory. The numbers in brackets are in kcal/mol.
S10
ND3
1 (0.0)
1 (0.0)
4 (-5.6)
3 (-5.9)
5 (-5.7)
6 (-6.3)
7 (-5.9)
2 (-6.9)
Figure S9. The potential energy surface for H/D exchange of protonated GRG
with ND3, as calculated at the B3LYP/6-31G(d.p)//HF/3-21G(d,p) level of
theory. The numbers in brackets are in kcal/mol.
S11
ND3
5 ( 4.6 )
4 (-0 .1 0 )
6 (2 .8 )
1 (0 .0 )
7 (2 .8 )
1 ( 0.0 )
2 (-3 .3)
3 (- 1. 5)
Figure S10. The potential energy surface for H/D exchange of protonated
RGG with ND3, as calculated at the B3LYP/6-31G(d.p)//HF/3-21G(d,p) level
of theory. The numbers in brackets are in kcal/mol.
S12
ND3
N D 2H
1 (0.0)
1 (0.0)
4 (-6.3)
(-6 .3)
2 (-7.3)
3 (-6.4)
3 (-6.5)
2 (-7.3)
Figure S11. The potential energy surface for H/D exchange of protonated GR
with ND3, as calculated at the B3LYP/6-31G(d.p)//HF/3-21G(d,p) level of
theory. The numbers in brackets are in kcal/mol.
S13
ND 3
N D 2H
1 ( 0 .0 )
1 (0 .0 )
2 (- 9 .9 )
3 ( - 5 .8 . )
3 (- 5 .8 )
2 (-9 . 9 )
4 *
(
*
)
Figure S12. The potential energy surface for H/D exchange of protonated RG
with ND3, as calculated at B3LYP/6-31G(d.p)//HF/3-21G(d,p) level of theory.
The numbers given in brackets are in kcal/mol. The * for structure 4 indicates
that the geometry of the intermediate cannot be optimized at HF/3-21G(d,p)
level of theory, and it is assumed that the structure of this ion has an energy
lower than that of TS3.
S14