environmental applications of ft-icr mass spectrometryft-icr mass spectrometry oxidized peptide and...
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Dissertation DefenseJanuary 7, 2010
Environmental Applications of Environmental Applications of FT-ICR Mass Spectrometry
Oxidized Peptide and Metal Sulfide Clusters
Jeffrey M. SpragginsUniversity of DelawareUniversity of DelawareDepartment of Chemistry & BiochemistryAdvisor: Douglas Ridge, Ph.D.
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OverviewESI FT-ICR Mass Spectrometry
Overview
Metal Sulfide ClustersOxidized Peptides
• Johnston Group• Dr. Laskin: PNNL
Luther Group(Marine Studies)
• Energy resolved SID Molecular Capping
Gas Phase
• Energy-resolved SID• Molecular Dynamics
• RRKM Theory
Molecular Capping Agents
Ion-Molecule ReactionsFragmentationMechanisms
Metal Sulfide Metal Sulfide Formation
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ESI FT-ICR Mass Spectrometry
O idi d P tid
ESI FT ICR Mass Spectrometry
Oxidized Peptides
Jeffrey M. Spraggins, Julie A. Lloyd, Murray V. Johnston, Julia Laskin, Douglas P. Rid J A S M Sp (2009) A t d f li tiRidge J.Am. Soc. Mass Spec. (2009), Accepted for puplication.
Julie A. Lloyd, Jeffrey M. Spraggins, Murray V. Johnston, Julia Laskin, J. Am. Soc. Mass Spec. (2006), 17(9), 1289-1298
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Oxidation ReactionOxidation Reaction
AngII + O Tyr*
AngII AngII + 3OO3
( 143 M)
His*
AngII + 4O Tyr* and His*
(~143µM)
g
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Asp-Arg-Val-Tyr-Ile-His-Pro-PheAsp Arg Val Tyr Ile His Pro Phe
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6 T FT-ICR MS: PNNL6 T FT ICR MS: PNNLQuad
Bender
6T Magnet
Lens 4 Lens 5Lens 3
Lens 2
Segmented
SAMSurface
DecelerationLenses
Lens 1
gLenses Trapping
Plates
CollisionalQuadrupole
Resolving Quadrupole
Accumulation Quadrupole
Ion Source
Ion Funnel
Quadrupole20-50 mTorr
Quadrupole5×10-5 Torr
Quadrupole2 mTorr
C d C lli iIon Funnel0.6-0.8 Torr Trapping
PlatesConductance
LimitCollimating
Plate
Laskin J.; Denisov E. V.; Shukla A. K.; Barlow S. E.; Futrell J. H. Analytical chemistry 2002, 74, 3255-61.
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AngII+3O
sity
AngII
Inte
ns
AngII+4O
AngII+O
m/z
m/z(b-d: 43eV SID Spectra)
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Asp-Arg-Val-Tyr-Ile-His-Pro-Phe
y7
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Energy Resolved FECs: AngIIEnergy Resolved FECs: AngIIen
sity
Rel
ativ
e In
teR
Collision Energy (eV)
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Acidic Amino Acids
HN
OH
H2N
O
O
AcidsJ. Laskin
J. Futrell
O
HN
NH2OO
HO
O
N
H2N
HH
J. ut
V. Wysocki
J. Beauchamp
H2N
O
H
O
H2N
HN
O
H2N
NH
O
NH
J p
O
O
Scheme Ia Scheme Ib
O
H2N O
NH
HO
OO
NH
N
H2N
HH
H
O
O
H2N
NH
O
y7
H2NO
H2N
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AngII: charge delocalizationAngII: charge delocalization
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
b4+O4
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Energy Resolved FECs: AngII+OEnergy Resolved FECs: AngII Oen
sity
Rel
ativ
e In
teR
Collision Energy (eV)
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AngII+OOH
HO
OH AngII Ob4 fragmentation pathway
N
O
HN
HO
H
O
N
O
NH
O
ONH
NH
OH
OH
Scheme II
b4+O
ONH
OO
O
OH
HO
NHH
ON
H
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AngII+O: b4 fragmentAngII O: b4 fragment
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Acidic Amino Acids
HN
OH
H2N
O
O
AcidsJ. Laskin
J. Futrell
O
HN
NH2OO
HO
O
N
H2N
HH
J. ut
V. Wysocki
J. Beauchamp
H2N
O
H
O
H2N
HN
O
H2N
NH
O
NH
J p
O
O
Scheme Ia Scheme Ib
O
H2N O
NH
HO
OO
NH
N
H2N
HH
H
O
O
H2N
NH
O
H2NO
H2N
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
-71-45
-71-88
b55
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AngII+3OAngII 3O[MH+3O]+-45 & [MH+3O]+-71
HN
O
NH
O
H
O
HNO
H
H
O
NH
H
O
O
NNH
O
H
O
Scheme III
N
O
HN H
OH
C
O
NH
HOH
N
CO
O
3O +
[MH+3O]+-45
[MH+3O]+-71
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AngII+3OHN
N
O
HN
N
O
AngII 3O[MH+3O]+-88 & b5
fragmentation pathway
HN
O
HN
O
O
HN
O
HN
O
O
H
H
NNH
H
NH
HN O O
O
H
Scheme IV
O
NH
NH
OO
O
H
H
O
NH
O
NH
O
H
Scheme IV
NH
O
H
O
3O + 88
HN H
O
N
H N
O
HNO
O
H2N
O
NH
O
[MH+3O]+-88
N H
O
H2N
O
NH
O
H
b5
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Transition StatesTransition States
RRKM Theory
ve In
tens
ityR
elat
iv
Collision Energy (eV)
[MH+nO]+ DRVYIHPF DRVY*IHPF DRVYIH*PF DRVY*IH*PF [ O] M/Z 1046 1062 1110 1126 E0(eV) 1.14 1.20 1.21 1.24 ΔS‡(cal/mol K) -25.9 -21.6 -17.0 -15.3 Relative E 0 0 06 0 07 0 11 Relative E0 0 0.06 0.07 0.11 A, s-1 5.6x107 4.8x108 4.8x109 1.2x1010
Log (A) 7.7 8.7 9.7 10.1
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Entropic Considerations
ΔS‡(cal/mol K)
Considerations(a) y7 fragment
(b) b4+O fragmentOHO
-25.9 -21.6 -17.0
( ) b4 O ag t
(c) [AngII+3O]-45
N H
O
H
O
N
O
OH
O
H2N
O
HN
O
H
OOHN
H
NH
O
HN
(a) (b) (c)
Side Chain
Backbone
Amide Bond
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ConclusionsConclusionsUnmodified Ang II
Charge-remote selectivity towards y7 fragmentCharge remote selectivity towards y7 fragment
M+O adduct FECs suggest that the b4 pathway is a charge-remote process.
C-term Tyr* - Backbone interaction leads to b4 fragment ion.y 4 g
M+3O product FECs show both charge-remote and charge-directed selective fragmentation channels are opened with the oxidation of the His residue.
Loss of 45m/z and 71m/z driven by strong H-bonding within the His* side chain.His* is thought to compete with Arg for the lone proton leading to the b5 and [MH+3O]+-88 charge-directed fragments.
RRKM results imply destabilization due to entropic effects.
Consistent with proposed fragmentation mechanisms for oxidation products
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The Big PictureThe Big Picture
Structurally characterize peptide degradation by ozone exposure
Contribution to Fundamental MS/MS Literature
Understanding oxidized peptide fragmentation could benefit MS protein g p p f g pstructural research
Method for increasing fragmentation sequence coverage for proteomic studiesstudies
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ESI FT-ICR Mass SpectrometryESI FT ICR Mass Spectrometry
Metal Sulfide Clusters
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+ - +
-Dissolved Ions
Project Goal
Clusters
• Metal Sulfide Precipitation
- Cluster Aggregation†
1(Dissolved PolynuclearMolecular Species)
• Experimental Approach
Capping Agents
Nanoparticles
- Capping Agents
10Nanoparticles
(1-100nm)
- Ion-Molecule Reactions
∞Solid state material
† T. F. Rozan, M. E. Lassman, D. P. Ridge, G. W. Luther. Evidence for iron, copper and zinc complexation as multinuclear
Size (nm)material zinc complexation as multinuclear sulphide clusters in oxic rivers.Nature, 2000, 406, 879-882.
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+ - +
- Project GoalDissolved Ions
Mass SpectrometryClusters
1
UV/VIS SpectroscopyNanoparticles
10Nanoparticles
∞Solid state material Size (nm)material
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7T FT-ICR MS: UD7T FT ICR MS: UD
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ESI of Metal Salt Solutions
Observed Nucleation Processes
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Salt Clusters Observed using ESI FT-ICR MSSalt Clusters Observed using ESI FT ICR MS
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Signal VarianceVariance• [Cd(CH3COO)3]-
• [Cd2(CH3COO)5]-
Sampling was done using separate aliquots for each spectrum and [Cd2(CH3COO)5]
• [Cd3(CH3COO)7]-
• [Cd4(CH3COO)9]-
spectrum and
[ 4( 3 )9]
• [Cd5(CH3COO)11]-
• [Cd6(CH3COO)13]-[ 6( 3 )13]
• [Cd7(CH3COO)15]-
• [Cd8(CH3COO)17]-
A single aliquot was continually injected as spectra were repeatedly [ 8( 3 )17]taken.
0 3 mM cadmium acetate 0.3 mM cadmium acetate water/MeOH solution (1:1)
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Important PointsImportant PointsVariance in signal over time suggests that clusters observed using ESI are forming in solution. observed using ESI are forming in solution.
Results highlight processes taking place in low dielectric g g p g pconstant solvents
Water/MeOH (ε=66†)Hydrothermal Fluids (ε=10-23‡)
†Akerlof G Dielectric Constant of some Organic Solvent-Water Mixtures at various Temperatures J Am Chem Soc †Akerlof, G. Dielectric Constant of some Organic Solvent-Water Mixtures at various Temperatures. J. Am. Chem. Soc. 1932, 54, 4125-4139.‡Weingartner, H.; Franck, E. U. Supercritical Water as a Solvent. Angew Chem Int Ed Engl. 2005, 44, 2672-2692.
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Making Metal Sulfide Clusters
Molecular Capping Agents
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Solution Chemistry: Mononuclear AnionsSolution Chemistry: Mononuclear Anions
A) 3 mM aqueous solution of Cd(NO3)2•4H2O diluted 50/50 with MeOH.
B) 1.5 mM aqueous solution of Cd(NO3)2•4H2O and 2-mercaptopyridine (1:1) diluted 50/50 with MeOH.50/50 with MeOH.
C) H2S(g) bubbled through a 3 mM aqueous solution of Cd(NO3)2•4H2O followed by dditi f 2 t idi addition of 2-mercaptopyridine
(1:1), then diluted 50/50 with MeOH.
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Solution Chemistry: Binuclear AnionsSolution Chemistry: Binuclear Anions
A) 3 mM aqueous solution of Cd(NO3)2•4H2O diluted 50/50 with MeOH.
B) 1.5 mM aqueous solution of Cd(NO3)2•4H2O and 2-mercaptopyridine (1:1) diluted 50/50 with MeOH.50/50 with MeOH.
C) H2S(g) bubbled through a 3 mM aqueous solution of Cd(NO3)2•4H2O followed by dditi f 2 t idi addition of 2-mercaptopyridine
(1:1), then diluted 50/50 with MeOH.
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Solution Chemistry: Trinuclear AnionsSolution Chemistry: Trinuclear Anions
A) 3 mM aqueous solution of Cd(NO3)2•4H2O diluted 50/50 with MeOH.
B) 1.5 mM aqueous solution of Cd(NO3)2•4H2O and 2-mercaptopyridine (1:1) diluted 50/50 with MeOH.50/50 with MeOH.
C) H2S(g) bubbled through a 3 mM aqueous solution of Cd(NO3)2•4H2O followed by dditi f 2 t idi addition of 2-mercaptopyridine
(1:1), then diluted 50/50 with MeOH.
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Important PointsImportant PointsSulfidic clusters are observed when 2-mercaptopyridine is introduced.introduced.
Reactivity with H2S is selective based on cluster size for y 2[Cdx(NO3)2x+1]- species.
Sampling a solution based processGas phase ion-molecule reactions
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Making Metal Sulfide Clusters
Gas Phase Ion-Molecule Reactions
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Cadmium Salt ClustersCadmium Salt ClustersReactive Clusters
[Cd(CH3COO)3]-
[Cd2(CH3COO)5]-
[Cd3(CH3COO)7]-
[Cd4(CH3COO)9]-
[Cd2(CH3COO)3]+
[Cd3(CH3COO)5]+
[Cd4(CH3COO)7]+
Non-Reactive Clusters
[Cd(NO3)3]-
[Cd2(NO3)5]-
[Cd3(NO3)7]-
[Cd4(NO3)9]-
[CdNO3(CH3OH)]+
[CdNO3(CH3OH)(H2O)]+
[CdxCl2x+1]-
[ZnxCl2x+1]-
[Cd4(NO3)9] [ 3( 3 )( 2 )]
[CdCl(CH OH)]+[CdCl(CH3OH)]+
[Cd2Cl3(CH3OH)]+
[ZnCl(CH3OH)]+
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[Cd2(NO3)5]-[Cd2(NO3)5]
H2S
-2H
NO
3{536 m/z}
H2S
-2H
NO
3
[Cd2SH(NO3)4]-[Cd2S(NO3)3]-
{444 m/z} {507 m/z}-HNO3
H2S
HN
O3
[Cd2(SH)2(NO3)3]-
{478 m/z}
H
-2H
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[Cd2(NO3)5]-Cd2S0 [Cd2(NO3)5]
H2S
-2H
NO
3{536 m/z}
H2S
-2H
NO
3
Cd2S0
[Cd2SH(NO3)4]-[Cd2S(NO3)3]-
{444 m/z} {507 m/z}-HNO3
H2S
HN
O3
Cd2S1
[Cd2(SH)2(NO3)3]-
{478 m/z}
H
-2H
Cd2S2
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[Cd2(NO3)5]-
OH
{536 m/z}S0
r = k[Cluster Family][H2S]
d[S0]
dt= -k1[S0]
[Cd2(NO3)4SH]-
H2S
-CH
3CO
O
{507 m/z}S
k1r = k[Cluster Family]
H2S is in excess d[S1] k [S ] k [S ][Cd2S(NO3)3]-
{444 m/z}
2S CO
OH
S1
k
•Pseudo First Order kinetics[ 1]
dt= k1[S0] – k2[S2]
[S ]= [A] e-k1t
[Cd2(NO3)3(SH)2]-
{478 m/z}
H2
-CH
3C
S2
k2
d[S2]
dt= k2[S1]Integrated Rate Equations
[S0]= [A]0 e k1t
[S1]=k1
k2-k1(e-k1t - e-k2t)
k3 = 0
dt
[A]0 k2 k1
(k k )(k k ) (k k )(k k ) (k k )(k k )
e-k1t e-k2t e-k3t
[S2]= k1k2 + +(k2-k1)(k3-k1) (k1-k2)(k3-k2) (k1-k3)(k2-k3)
[ 2] 1 2
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4x10-9 torr[Cd2(NO3)5]- +H2S (g)
[Cd2SH(NO3)4]-
[Cd2S(NO3)3]-
[Cd2(SH)2(NO3)3]-
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[Cd2S0]-
k = 0 084 ± 0 004 s-1
[Cd2(NO3)5]- +H2S
[Cd2S1]-
k1= 0.084 ± 0.004 s
k2= 0.019 ± 0.001s-1
[Cd2SH(NO3)4]-
[Cd2S(NO3)3]-
[Cd2S2]-
2
[Cd2(SH)2(NO3)3]-
H2S: 4x10-9 torr
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[Cd2S0]-
k = 0 084 ± 0 004 s-1
Reaction Efficiency
[Cd2S1]-
k1= 0.084 ± 0.004 s
k2= 0.019 ± 0.001s-1
Efficiency
• Assume fastest RXN is collision rate limited
[Cd2S2]-
2
[Cd(NO3)(CH3OH)]+
k1= 2.85 ± 0.27 s-1
• Capture Collision Theory†
H2S: 4x10-9 torr
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[Cd2S0]-
k = 0 084 ± 0 004 s-1
Reaction Efficiency
[Cd2S1]-
k1= 0.084 ± 0.004 s
k2= 0.019 ± 0.001s-1
Efficiency
• Assume fastest RXN is collision rate limited
[Cd2S2]-
2
[Cd(NO3)(CH3OH)]+
k1= 2.85 ± 0.27 s-1
• Capture Collision Theory†
⎟⎟⎠
⎞⎜⎜⎝
⎛⎟⎠⎞
⎜⎝⎛ μ
=−
−x
921
x1
1x
c PTorr10x4
Da19.29s85.2k
kk
H2S: 4x10-9 torr
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[Cd2S0]-
k = 0 084 ± 0 004 s-1
Reaction Efficiency
[Cd2S1]-
k1= 0.084 ± 0.004 s
k2= 0.019 ± 0.001s-1
k1/kc= 0.031
Efficiency
• Assume fastest RXN is collision rate limited
[Cd2S2]-
2
k2/kc= 0.0069 [Cd(NO3)(CH3OH)]+
k1= 2.85 ± 0.27 s-1
• Capture Collision Theory†
⎟⎟⎠
⎞⎜⎜⎝
⎛⎟⎠⎞
⎜⎝⎛ μ
=−
−x
921
x1
1x
c PTorr10x4
Da19.29s85.2k
kk
H2S: 4x10-9 torr
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Anionic Cadmium ClustersReactant
P (10-9
torr)ΔH
(kcal/mol)k1/kc k2/kc k3/kc k4/kc k5/kc k6/kc k7/kc
[Cd(CH3COO)3]- 4 -6.236082 0 032 0 034 0 023
Anionic Cadmium Clusters
[Cd(CH3COO)3] 4 6.236082 0.032 0.034 0.023
[Cd(CH3COO)3]- 9 -6.236082 0.035 0.042 0.030
[Cd2(CH3COO)5]- 4 0.018 0.015 0.010 0.0020
[Cd2(CH3COO)5]- 9 0.019 0.015 0.0095 0.0034[ 2( 3 )5]
[Cd3(CH3COO)7]- 4 0.015 0.14 0.038 0.011 0.019 0.0073
[Cd3(CH3COO)7]- 9 0.016 0.24 0.061 0.012 0.035 0.0082
[Cd4(CH3COO)9]- 4 0.013 0.034(24) 1.00* 1.00* 1.00* 0.0079 0.0097(15)
[Cd4(CH3COO)9]- 9 0.013 0.042(15) 1.00* 1.00* 1.00* 0.0080 0.015
[Cd(NO3)3]- 4 & 9 9.710921 No RXN
[Cd2(NO3)5]- 4 0 031 0 0069[Cd2(NO3)5] 4 0.031 0.0069
[Cd3(NO3)7]- 4 0.046 0.035 0.00090
[Cd4(NO3)9]- 4 0.0094 0.0090 0.017
[CdCl3]- 4 & 9 8.8245642 No RXN[ 3]
[CdxCl2x+1]- 4 & 9 No RXN
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Anionic Cadmium ClustersReactant
P (10-9
torr)ΔH
(kcal/mol)k1/kc k2/kc k3/kc k4/kc k5/kc k6/kc k7/kc
[Cd(CH3COO)3]- 4 -6.236082 0 032 0 034 0 023
Anionic Cadmium Clusters
[Cd(CH3COO)3] 4 6.236082 0.032 0.034 0.023
[Cd(CH3COO)3]- 9 -6.236082 0.035 0.042 0.030
[Cd2(CH3COO)5]- 4 0.018 0.015 0.010 0.0020
[Cd2(CH3COO)5]- 9 0.019 0.015 0.0095 0.0034
Most Anionic Metal Cluster reactionsare < 5% efficient.[ 2( 3 )5]
[Cd3(CH3COO)7]- 4 0.015 0.14 0.038 0.011 0.019 0.0073
[Cd3(CH3COO)7]- 9 0.016 0.24 0.061 0.012 0.035 0.0082
[Cd4(CH3COO)9]- 4 0.013 0.034(24) 1.00* 1.00* 1.00* 0.0079 0.0097(15)
[Cd4(CH3COO)9]- 9 0.013 0.042(15) 1.00* 1.00* 1.00* 0.0080 0.015
[Cd(NO3)3]- 4 & 9 9.710921 No RXN
[Cd2(NO3)5]- 4 0 031 0 0069[Cd2(NO3)5] 4 0.031 0.0069
[Cd3(NO3)7]- 4 0.046 0.035 0.00090
[Cd4(NO3)9]- 4 0.0094 0.0090 0.017
[CdCl3]- 4 & 9 8.8245642 No RXN[ 3]
[CdxCl2x+1]- 4 & 9 No RXN
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Anionic Cadmium ClustersReactant
P (10-9
torr)ΔH
(kcal/mol)k1/kc k2/kc k3/kc k4/kc k5/kc k6/kc k7/kc
[Cd(CH3COO)3]- 4 -6.236082 0 032 0 034 0 023
Anionic Cadmium Clusters
[Cd(CH3COO)3] 4 6.236082 0.032 0.034 0.023
[Cd(CH3COO)3]- 9 -6.236082 0.035 0.042 0.030
[Cd2(CH3COO)5]- 4 0.018 0.015 0.010 0.0020
[Cd2(CH3COO)5]- 9 0.019 0.015 0.0095 0.0034
The Exception…[ 2( 3 )5]
[Cd3(CH3COO)7]- 4 0.015 0.14 0.038 0.011 0.019 0.0073
[Cd3(CH3COO)7]- 9 0.016 0.24 0.061 0.012 0.035 0.0082
[Cd4(CH3COO)9]- 4 0.013 0.034(24) 1.00* 1.00* 1.00* 0.0079 0.0097(15)
[Cd4(CH3COO)9]- 9 0.013 0.042(15) 1.00* 1.00* 1.00* 0.0080 0.015
[Cd(NO3)3]- 4 & 9 9.710921 No RXN
[Cd2(NO3)5]- 4 0 031 0 0069[Cd2(NO3)5] 4 0.031 0.0069
[Cd3(NO3)7]- 4 0.046 0.035 0.00090
[Cd4(NO3)9]- 4 0.0094 0.0090 0.017
[CdCl3]- 4 & 9 8.8245642 No RXN[ 3]
[CdxCl2x+1]- 4 & 9 No RXN
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[Cd4(CH3COO)9]-
[Cd4(CH3COO)8SH]-
H2S
-2C
H3C
OO
H
H2S
-CH
3CO
OH
[Cd4(CH3COO)7S]-
-CH3COOH{894 m/z}
{980 m/z}
{954 m/z}
[Cd4(CH3COO)7(SH)2]-[Cd4(CH3COO)6S(SH)]-
-CH3COOH
{894 m/z}
H2S
-CH
3CO
OH
{954 m/z}
{868 m/z} {928 m/z}
H2S
-CH
3CO
OH
[Cd4(CH3COO)4S2]-
-CH3COOH{808 m/z}
OH
OH
OH
[Cd4(CH3COO)6(SH)3]-[Cd4(CH3COO)5S(SH)2]-
-CH3COOH
H2S
-CH
3CO
O
{842 m/z} {902 m/z}
H2S
-CH
3CO
O
[Cd4(CH3COO)4S2(SH)]-
-CH3COOH{782 m/z}
H2S
-CH
3CO
O
[Cd4(CH3COO)3S3]-
-CH3COOH{722 m/z}
H2S
3CO
OH
H2S
3CO
OH
H2S
3CO
OH
H2S
3CO
OH
[Cd4(CH3COO)5(SH)4]-[Cd4(CH3COO)4S(SH)3]-
-CH3COOH
-CH
3
{816 m/z} {876 m/z}
-CH
3
[Cd4(CH3COO)3S2(SH)2]-
-CH3COOH{756 m/z}
-CH
3
[Cd4(CH3COO)2S3(SH)]-
-CH3COOH{696 m/z}
-CH
3
H2S
-CH
3CO
OH
H2S
-CH
3CO
OH
H2S
-CH
3CO
OH
H2S
-CH
3CO
OH
[Cd4(CH3COO)4(SH)5]-[Cd4(CH3COO)3S(SH)4]-
-CH3COOH{790 m/z} {850 m/z}
[Cd4(CH3COO)2S2(SH)3]-
-CH3COOH{730 m/z}[Cd4(CH3COO)S3(SH)2]-
-CH3COOH{670 m/z}
[Cd4(CH3COO)3(SH)6]-[Cd4(CH3COO)2S(SH)5]-
H2S
-CH
3CO
OH
H2S
-CH
3CO
OH
[Cd4(CH3COO)S2(SH)4]-
H2S
-CH
3CO
OH
[Cd4S3(SH)3]-
-CH3COOH
H2S
-CH
3CO
OH
-CH3COOH{764 m/z} {824 m/z}-CH3COOH{704 m/z}-CH3COOH
{644 m/z}
[Cd4(CH3COO)2(SH)7]-[Cd4(CH3COO)S(SH)6]-
-CH3COOH
H2S
-CH
3CO
OH
{738 m/z} {798 m/z}
H2S
-CH
3CO
OH
[Cd4S(SH)5]-
-CH3COOH{678 m/z}
H2S
-CH
3CO
OH
HH
[Cd4(CH3COO)(SH)8]-[Cd4S(SH)7]-
-CH3COOH
H2S
-CH
3CO
OH
{712 m/z} {772 m/z}
H2S
-CH
3CO
OH
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[Cd4(CH3COO)9]- +H2S (g)[Cd4S0]-
k1/kc= 0.013
k1/kc= 0.013
[Cd4S(CH3COO)9]-9x10-9 torr[Cd4S1]-
[Cd4S2]-
1 c
k2/kc= 0.034
k2/kc= 0.043
k /k = 1 0*
[Cd4S(CH3COO)9]
[Cd4S2(SH)3(CH3COO)2]-
[Cd4S2(SH)4(CH3COO)]-
[Cd4S3]-k3/kc= 1.0*
k3/kc= 1.0
k4/kc= 1.0*
[ 4 2( )4( 3 )][Cd4S3(SH)3]-
[Cd4S2(SH)5]-
[Cd4S4]-k4/kc= 1.0*
k /k = 1 0*
k5/kc= 1.0*4x10-9 torr
[Cd4S5]-
[Cd S ]-
k5/kc= 1.0*
k6/kc= 0.0079
k6/kc= 0.0080
[Cd4S6]
[Cd4S7]-k7/kc= 0.0097
k7/kc= 0.015
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9x10-9 torr
[Cd4S(CH3COO)9]-
[Cd4(CH3COO)9]- +H2S (g)
[Cd4S2(SH) ]-[Cd4S(CH3COO)9]
[Cd4S2(SH)3(CH3COO)2]-
[Cd4S2(SH)4(CH3COO)]-
[Cd4S2(SH)5]
[ 4 2( )4( 3 )][Cd4S3(SH)3]-
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Anionic Cadmium ClustersReactant
P (10-9
torr)ΔH
(kcal/mol)k1/kc k2/kc k3/kc k4/kc k5/kc k6/kc k7/kc
[Cd(CH3COO)3]- 4 -6.236 0 032 0 034 0 023
Anionic Cadmium Clusters
[Cd(CH3COO)3] 4 6.236 0.032 0.034 0.023
[Cd(CH3COO)3]- 9 -6.236 0.035 0.042 0.030
[Cd2(CH3COO)5]- 4 0.018 0.015 0.010 0.0020
[Cd2(CH3COO)5]- 9 0.019 0.015 0.0095 0.0034[ 2( 3 )5]
[Cd3(CH3COO)7]- 4 0.015 0.14 0.038 0.011 0.019 0.0073
[Cd3(CH3COO)7]- 9 0.016 0.24 0.061 0.012 0.035 0.0082
Calculated reaction enthalpies are consistent with observed reactivity.
[Cd4(CH3COO)9]- 4 0.013 0.034(24) 1.00* 1.00* 1.00* 0.0079 0.0097(15)
[Cd4(CH3COO)9]- 9 0.013 0.042(15) 1.00* 1.00* 1.00* 0.0080 0.015
[Cd(NO3)3]- 4 & 9 9.711 No RXN
[Cd2(NO3)5]- 4 0 031 0 0069[Cd2(NO3)5] 4 0.031 0.0069
[Cd3(NO3)7]- 4 0.046 0.035 0.00090
[Cd4(NO3)9]- 4 0.0094 0.0090 0.017
[CdCl3]- 4 & 9 8.825 No RXN[ 3]
[CdxCl2x+1]- 4 & 9 No RXN
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Cationic Metal Sulfide Clusters
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[Cd4(CH3COO)7]+
+H2S
SH- Substitution
CH3COOH Elimination
H2S Addition
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[Cd4(CH3COO)7]++H2S (g)
[Cd4SH(CH3COO)6]+ [Cd4(SH)2(CH3COO)5]+
9x10-9 torr
[ 4 ( 3 )6]
[Cd4(SH)3(CH3COO)4]+
[Cd4S(SH)(CH3COO)4]+
[Cd4SH(CH3COO)6(H2S)]+
[ 4( )3( 3 )4][Cd4S(SH)2(CH3COO)3]+
[Cd4(SH)2(CH3COO)5(H2S)]+
[Cd4(SH)4(CH3COO)3]+
[Cd4S(SH)3(CH3COO)2]+
[Cd4S(SH)4(CH3COO)]+
[Cd4S(SH)3(CH3COO)2(H2S)]+
[Cd4(SH)3(CH3COO)4(H2S)]+
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[Cd4(CH3COO)7]++H2S (g) 9x10-9 torr
[Cd4(SH)3(CH3COO)4]+
[Cd4S(SH)2(CH3COO)3]+
[Cd4(SH)2(CH3COO)5(H2S)]+
[Cd4SH(CH3COO)6]+
[C 4(S )2(C 3COO)5( 2S)]
[Cd4(SH)2(CH3COO)5]+
[Cd4S(SH)(CH3COO)4]+
[Cd4SH(CH3COO)6(H2S)]+
[Cd4(SH)4(CH3COO)3]+
[Cd4S(SH)3(CH3COO)2]+
[Cd4(SH)3(CH3COO)4(H2S)]+[Cd4(SH)3(CH3COO)4(H2S)]
[Cd4S(SH)4(CH3COO)]+
[Cd4S(SH)3(CH3COO)2(H2S)]+
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.442 Not Obs
[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.183 Not Obs
[CdCl]+ -11.163 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.903 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759478 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066
Cationic Metal Clusters show much higherreaction efficiencies.
[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.441937 Not Obs
[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.182772 Not Obs
[CdCl]+ -11.162765 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.902944 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.442 Not Obs
[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.183 Not Obs
[CdCl]+ -11.163 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.903 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759478 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.441937 Not Obs
Reaction rates vary significantly with successive[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.182772 Not Obs
Reaction rates vary significantly with successivesulfide addition.
[CdCl]+ -11.162765 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.902944 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759478 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066
NO3 > OH > Cl
[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.441937 Not Obs
[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.182772 Not Obs
[CdCl]+ -11.162765 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.902944 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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Cationic Cadmium ClustersReactant
P(10-9 torr)
ΔH (kcal/mol)
k1/kc k2/kc k3/kc k4/kc k5/kc
[Cd(CH3COO)]+ -3.759478 Not Obs
Cationic Cadmium Clusters
[Cd2(CH3COO)3]+ 4 0.77 0.0033 0.0045
[Cd3(CH3COO)5]+ 4 0.923 0.0722 0.0045 0.0013[Cd (CH COO) ]+ 9 0 88 0 073 0 0062 0 0066
Calculated reaction enthalpy is consistent with observed reactivity.[Cd3(CH3COO)5] 9 0.88 0.073 0.0062 0.0066
[Cd4(CH3COO)7]+ 9 0.37 0.54 0.28 0.0029 0.0016
[Cd(NO3)]+ -17.441937 Not Obs
y
[Cd(NO3)(CH3OH)]+ 4 1.00
[Cd(NO3)(CH3OH)(H2O)]+ 4 0.61
[CdOH]+ -27.182772 Not Obs
[CdCl]+ -11.162765 Not Obs
[CdCl(CH3OH)]+ 4 0.16 0.0062
[CdOH(CH3OH)]+ 4 0.77
[ ( 3 )]
[ZnCl]+ -11.902944 Not Obs
[ZnCl(CH3OH)]+ 4 0.037
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ConclusionsConclusionsESI of salt solutions show variation of cluster size vs. time.
Data suggests that both % methanol and concentration play a role.
Solution experiments show successive substitutions of mp for NO3
Treatment with H2S leads to replacement of (NO3)2 with SO4 for larger clusters.
Gas phase ion-molecule reactions between metal salt clusters and H2S result in the formation of a variety of metal sulfide species.
Anionic clusters display < 5% reaction efficiency with the exception of Anionic clusters display < 5% reaction efficiency with the exception of [Cd4(CH3COO)9]-
Cationic metal clusters show higher initial reaction efficiencies which decreases significantly with successive SH- substitutionsignificantly with successive SH substitution.
DFT calculations are consistent with gas phase reactivity (Kaitlin Papson).
Similarities between gas and condensed phases highlighted by salt nucleation in binary solvents, spectator solvent molecules, and similarities in [Cdx(NO3)2x+1]- reactivity.
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Dissolved Ions Project Goal+ - +-
ClustersMass Spectrometry
1
Size (nm)
Nanoparticles Spectroscopy
10
∞Solid state material
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The Big PictureThe Big Picture
Elucidation of initial steps for metal sulfide formation
Gas phase ion-molecule reactions as models for aqueous metal sulfide reactions
The Next Step: high pressure source-side reactions.p g p
Structural characterizationSurface deposition
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Tying it all together….Tying it all together….The technique: FT-ICR MSUnderstanding environmental chemical processesUnderstanding environmental chemical processes
Atmospheric: BiomoleculesAquatic: Inorganic clustersq g
Analytical ChemistryMass Spectrometry
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AcknowledgementsAcknowledgementsDr. RidgeOur Research Group
FundingUD GK 12p
Kaitlin PapsonNick ZeringoUna Kim
UD GK-12NSFDelaware EPSCoRUna Kim
Scott Robinson
C ll b
UD IGERT
CollaboratorsGeorge Luther
Kate MullaughMurray Johnston
Julie LloydJulia Laskin (PNNL)
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Environmental PerspectiveEnvironmental Perspective
Evidence of Salt Nucleation at Hydrothermal SitesSalt deposits†
gyser-like brine discharges†
‘salt diapirs‡’ (dī· ə· pîr)Buoyant/Mobile salt layer piercing the brittle overlying rocky y p g y g
†Hovland, M.; Rueslatten, H. G.; Johnsen, H. K.; Kvamme, B.; Kuznetsova, T. Salt Formation Associated with Sub-Surface Boiling and Supercritical Water. Mar. Pet. Geol. 2006, 23, 855-869.
‡Hovland, M.; Fichler, C.; Rueslatten, H.; Johnsen, H. K. Deep-Rooted Piercement Structures in Deep Sedimentary Basins -Manifestations of Supercritical Water Generation at Depth? J. Geochem. Explor. 2006, 89, 157-160.
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B
+
FT-ICR MS
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B XXXX
qB+ + +f = 2πm
FT-ICR MS
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B XXXX
+ _
+
FT-ICR MS
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Why we care? Past Research
The Instrument Making Clusters
Gas Phase Moving Forward
Fourier Transform
f =qB2πm
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Energy Resolved FECs: AngII+3OEnergy Resolved FECs: AngII 3Oen
sity
Rel
ativ
e In
teR
Collision Energy (eV)
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
-71-45
-71
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[AngII+3O]-45[AngII 3O] 45
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[AngII+3O]-71[AngII 3O] 71
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Asp-Arg-Val-Tyr(+O)-Ile-His(+3O)-Pro-PheAsp Arg Val Tyr( O) Ile His( 3O) Pro Phe
-88
b55
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AngII+3O: b5 fragmentAngII 3O: b5 fragment
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[AngII+3O]+-88 fragment[AngII 3O] 88 fragment
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[AngII+3O]+-88 fragment[AngII 3O] 88 fragment
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RRKM Modeling: Dr. Julia LaskinRRKM Modeling: Dr. Julia Laskin
RTEAek −=TST: Arrhenius Equation
Energy DepositionAek =
Survival CurvesFrequencies
Activation energy RRKM FrequenciesE0 & ΔS‡
Activation Entropy0
[MH+nO]+ DRVYIHPF DRVY*IHPF DRVYIH*PF DRVY*IH*PF M/Z 1046 1062 1110 1126 E0(eV) 1.14 1.20 1.21 1.24 ΔS‡(cal/mol K) -25.9 -21.6 -17.0 -15.3 Relative E0 0 0.06 0.07 0.11 A, s-1 5.6x107 4.8x108 4.8x109 1.2x1010
Log (A) 7.7 8.7 9.7 10.1
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Electrospray MechanismElectrospray Mechanism
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Solution Chemistry: Tetranuclear AnionsSolution Chemistry: Tetranuclear Anions
A) 3 mM aqueous solution of Cd(NO3)2•4H2O diluted 50/50 with MeOH.
B) 1.5 mM aqueous solution of Cd(NO3)2•4H2O and 2-mercaptopyridine (1:1) diluted 50/50 with MeOH.50/50 with MeOH.
C) H2S(g) bubbled through a 3 mM aqueous solution of Cd(NO3)2•4H2O followed by dditi f 2 t idi addition of 2-mercaptopyridine
(1:1), then diluted 50/50 with MeOH.
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Solution Chemistry: Pentanuclear AnionsSolution Chemistry: Pentanuclear Anions
A) 3 mM aqueous solution of Cd(NO3)2•4H2O diluted 50/50 with MeOH.
B) 1.5 mM aqueous solution of Cd(NO3)2•4H2O and 2-mercaptopyridine (1:1) diluted 50/50 with MeOH.50/50 with MeOH.
C) H2S(g) bubbled through a 3 mM aqueous solution of Cd(NO3)2•4H2O followed by dditi f 2 t idi addition of 2-mercaptopyridine
(1:1), then diluted 50/50 with MeOH.
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Bimolecular Rate Constants[Cd(NO3)(CH3OH)]+
k1= 2 85 ± 0 27 s-1• Determine [H2S]k1 2.85 ± 0.27 s• Assume fasted measured k is collision rate limited.
• Capture Collision Theory 4x10-9 Torr
( )2( )220
10.5260.5092
0.9754kk
2
L
<<+
+= ττ
’ d l 21
D T'1
'11.85 ⎟⎠⎞
⎜⎝⎛α
μ=τ
µD’ dipole moment (0.97 D)α' volume polarizability(3.67 Å3)
τ = 2.49 464.1kk
L
=
( )
21'⎟⎞
⎜⎛ α
11310L smoleculecm10x304.8k −−−=
1139L smoleculecm10
'Z342.2k −−−
⎟⎟⎠
⎞⎜⎜⎝
⎛μα
=
µ’ reduced mass (29.193 Da)
L
1139 smoleculecm10x216.1k −−−=
Theoretical collision rateTheoretical collision rate
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Bimolecular Rate Constants[Cd(NO3)(CH3OH)]+
k1= 2 85 ± 0 27 s-1• Determine [H2S]k1 2.85 ± 0.27 s• Assume fasted measured k is collision rate limited.
• Capture Collision Theory 4x10-9 Torr
1139 smoleculecm10x216.1k −−−=Theoretical collision rate
]SH[k
smoleculecm10x216.1k2
1111392
1 == −−−[H2S] = 2.34x109 molecules cm-3
[H2S] = 6.62x10-8 Torr
113 s0.0007 0.0024k −±=Slowest reaction observed
113921 smoleculecm10x12.021.1k −−−±= 113122
3 smoleculecm10x31.003.1k −−−±=1 smoleculecm10x12.021.1k ± 3 smoleculecm10x31.003.1k ±Fastest Slowest
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Reaction Efficiency [Cd(NO3)(CH3OH)]+
111 s0.27 85.2k −±=
113921 smoleculecm10x12.021.1k −−−±=
0.1kk=
⎟⎟⎠
⎞⎜⎜⎝
⎛⎟⎠⎞
⎜⎝⎛ μ
=−
−x
921
x1
1x
c PTorr10x4
Da19.29s85.2k
kk
kc
11392 smoleculecm10x120211k −−−±=
113 s0.0003 0.0024k −±=
113122 smoleculecm10x130031k −−−±=
111 s0.27 85.2k −±=
1 smoleculecm10x12.021.1k ±= 3 smoleculecm10x13.003.1k ±=
1.00.1kk
c
±= 0001.0000896.0kk
c
±=
Fastest Slowest
c c