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Methusalem, Advisory Board Meeting, June 24, 2013
Kinetic modeling usingchemo-informatics: Genesys
1http://www.lct.ugent.be
LaboratoryLaboratoryLaboratoryLaboratory forforforfor
Chemical Chemical Chemical Chemical TechnologyTechnologyTechnologyTechnology
Nick Vandewiele, Kevin Van Geem, Marie-Françoise Reyniers, Guy B. Marin
Methusalem, Advisory Board Meeting, June 24, 2013
Kinetic models grow larger and larger
2T.F. Lu, C.K. Law / Progress in Energy and Combustion Science 35 (2009) 192–215
Methusalem, Advisory Board Meeting, June 24, 2013
Genesys: computer generated kinetic models
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Initial
reactants
Mechanism Kinetic model
Automatic calculation of :
• Species thermochemistry
• Elementary reaction kinetics Vandewiele et al. Chem. Eng. J. (2012)
http://www.lct.ugent.be/
Methusalem, Advisory Board Meeting, June 24, 2013
Reaction network generation
k6
k15
k1 k2
k3
k4
k5
k7
k8
k9
k10k11
k12
k13
k14
Molecules Unique Representation
Thermo-dynamics
Reactionfamilies
Reaction Identification
Kinetic Parameters
Reactionrules
Kinetic model enlargement
Termination criterion
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Methusalem, Advisory Board Meeting, June 24, 2013
• Graph theory and algorithms can be applied: main
methods for chemistry apps:
• Sub-graph matching ~ functional group query
• Equivalence test ~ structure database query
Graph representation of molecules
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InChI=1S/C2H4O2/c1-2(3)4/h1H3,(H,3,4)
Defining sub-molecular patterns:
SMARTS (SMILES Arbitrary Target Specification)
CHCH
CH
H
CH3
CH3
Methusalem, Advisory Board Meeting, June 24, 2013
Andrew Dalke’s EuroQSAR 2008 Poster
(http://www.dalkescientific.com/)
Don’t re-invent the wheel: chemo-informatics
6Multiple ligands alignment within 3D field potential from Qmol LLC.
Methusalem, Advisory Board Meeting, June 24, 2013
Genesys: integration of CDK
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Methusalem, Advisory Board Meeting, June 24, 2013
Reaction families in Genesys
• Add chemistry you know that is relevant;
• Constrain reaction families as much as possible
CC
CHC
R
R
R
R
R
RC
CC
C
R
R
R
R
R
R
H+
CC
CC
R
H
R
R
R
RC
CC
C
R
R
R
R
R
H+
C C C
C R
R
R
R H
H+C C C C
R
RR
R
CC
CH
R
R
R
R
CH+C
CC
R
R
R
R
Single bond between radical C and H-bearing
C
sp² C’s in double bond, not sp
Radical C not part of ring
E.g. “C-H β scission in presence of double
bond in γ position”
C
R
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Methusalem, Advisory Board Meeting, June 24, 2013
Defining reaction families: pattern, recipe, constraints
C=C-C(H)-[C;v3]A [C;v3]-C(H)-C=CB H-C([C;v3])-C=CC C(C=C)(H)-[C;v3]
CC
CC
H
Center A
Center B
Center C
CHCH
CH
H
CH3
CH3
Submolecular pattern :
Reactive center:
Molecule Constraints:
MINIMUM Carbon COUNT 5MAXIMUM Carbon COUNT 10TOTAL NUMBER OF SINGLE ELECTRONS 1
RECIPE:
(1) BREAK BOND B,C
(2) INCREASE BOND A,C
(3) LOSE RADICAL A
(4) GAIN RADICAL B
SMARTS:
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Methusalem, Advisory Board Meeting, June 24, 2013
THERMOCHEMISTRY
ESTIMATION
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Ideal gas TD Properties: Benson Additivity
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Methusalem, Advisory Board Meeting, June 24, 2013
Nature of GAVs, ca. 1000 unique groups
Filling the Benson Database
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Sabbe et al. J. Phys. Chem. A 2008, 112, 12235–12251
Sabbe et al. J. Phys. Chem. A 2005, 109, 7466-7480
Methusalem, Advisory Board Meeting, June 24, 2013
NETWORK GENERATION
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Methusalem, Advisory Board Meeting, June 24, 2013
Network generation: HMPA
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HMPA
P N
C
H
P NH
CH2H
P NP
N
OO
P N
C
O
H
P NH
C
OH
C
N
N
CR
R
P
N
C
P
C
N
O
O
PH
NN
CH2
O
C
N
N
PH
O
Define reaction families
Generated species
Methusalem, Advisory Board Meeting, June 24, 2013
BUILDING KINETIC MODELS
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Methusalem, Advisory Board Meeting, June 24, 2013
Building kinetic models: Kinetic group additivity
Saeys et al. 2004, AIChE J.
GAV Library
* Ci-(H)2(C) -1.161 -3.6
* Ci-(C)2(H) -0.884 -8.3
* Ci-(C)3 -0.342 -14.7
* Ci,d-(H) +0.407 -10.6
* Ci,d-(C) -0.009 -14.6
* ...
SMARTS C1 log(A) Ea
GAV Library
* Si-(H) +0.101 -20.2
* Si-(Cd) -0.273 +26.6
* Si-(CS) -0.788 +22.0
* Si-(Cd) +0.566 +35.1
* Si-(Cb) +0.406 +24.3
* ...
SMARTS S1 log(A) Ea
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Sabbe et al. ChemPhysChem 2008, 9, 124 – 140
Methusalem, Advisory Board Meeting, June 24, 2013
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Chemistry knowledge:
A.G. Vandeputte, The thermochemistry and Decomposition Mechanism of
Organosulfur and Organophosphorus Compounds, 2012 (Ph.D)
Kinetic data:
Hydrocarbon reaction families:
Additions and β-scissions: Sabbe et al. ChemPhysChem 2008, 9, 124 – 140
Hydrogen abstractions: Sabbe et al. PCCP, 2010, 12, 1278–1298
Sulfur reaction families:
Hydrogen abstractions : Vandeputte et al. PCCP, 2012;14(37):12773-93
Homolytic substitutions: Vandeputte et al. 2012 (Ph.D)
Generated model:
3612 reactions
151 species
Alkylsulfide thermal decomposition
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Ethyl-methyl-sulfide pyrolysis: validation
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EMS pyrolysis: quantitative analysis
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EMS conversion: 14%
Temperature: 1013K
Residence time: 0.2s
Methusalem, Advisory Board Meeting, June 24, 2013
Conclusion
• Genesys: automatic reaction network generation framework for quantitative models
– Integrated with open-source chemo-informatics library (CDK)
– Generally applicable:
• Support for many elements
• Support for many chemistries
– Quantitative structure – property relationships easily
implementable
• Ideal Gas TD Properties
• Kinetic expressions for elementary reactions
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Methusalem, Advisory Board Meeting, June 24, 2013
Acknowledgments
LCT @ UGent:
• Steven Pyl, Carl Schietekat, Thomas Dijkmans, Ruben De Bruycker
• Aäron Vandeputte, Maarten Sabbe, Ruben Van de Vijver
Funding:
• Long Term Structural Methusalem Funding by the Flemish
Government
• Fund for Scientific Research - Flanders21
Methusalem, Advisory Board Meeting, June 24, 2013
THANK YOU!
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