S1 Supporting Information Long-Range Electron ... - Caltech Authors
Supporting Information Long-Range Electron Tunneling Jay R. Winkler* and Harry B. Gray* Beckman Institute California Institute of Technology 1200 E. California Boulevard Pasadena, CA 91125 Email: [email protected], [email protected]
S1
Semiclassical ET theory predicts that reactants will have identical configurations at the transition state for an electron-exchange reaction. For the electron exchange reaction between Fc and Fc+ in the gas phase, this configuration is defined as Q‡ (Figure S1). The energy required to reach this 2
λ1 = 12 k (Q − Qo )
configuration is equal to λ1+λ2, where and where k is an arbitrary force constant. The
[
]
λ 2 = 12 k Q − (Q + δQ ) , 2
transition state configuration (Q‡) corresponds to a Q ‡ = Qo + 12 δ Q
minimum value of λ1+λ2, found by differentiation:
Figure S1. Gas-phase potential energy surfaces for Fc and Fc++e− illustrating the vertical ionization energy (IE)v and electron affinity (EA)v. The electron-transfer transition state configuration is Q‡.
The ionization energy at Q‡ is given by:
[
]
2
(
)
2
IE (Q‡ ) = E 00 + 12 k Q ‡ − (Qo + δQ ) − 12 k Q‡ − Qo .
Simplification gives the following result: IE (Q ‡ ) = E00 Hence, the Fc ionization energy at the electron-exchange transition state is best approximated by the adiabatic ionization energy.
S2
Oxidoreductases – 6557 sequences
Transferases – 8355 sequences
Hydrolases – 6077 sequences
Lyases – 188 sequences
Isomerases – 145 sequences
Ligases – 338 sequences
Figure S2. Amino-acid occurrence frequencies in enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S3
Oxidoreductases – 6557 sequences
Transferases – 8355 sequences
Hydrolases – 6077 sequences
Lyases – 188 sequences
Isomerases – 145 sequences
Ligases – 338 sequences
Figure S3. Amino-acid occurrence frequencies in enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S4
Oxidoreductases – 30,851 sequences
Transferases – 81,134 sequences
Hydrolases – 55,666 sequences
Lyases – 22,864 sequences
Isomerases – 13,922 sequences
Ligases – 30,175 sequences
Figure S4. Amino-acid occurrence frequencies in enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S5
Oxidoreductases – 30,851 sequences
Transferases – 81,134 sequences
Hydrolases – 55,666 sequences
Lyases – 22,864 sequences
Isomerases – 13,922 sequences
Ligases – 30,175 sequences
Figure S5. Amino-acid occurrence frequencies in enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S6
Cytochrome P450 Family with transmembrane segments – 350 sequences
Figure S6. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S7
Cytochrome P450 Family with transmembrane segments – 350 sequences
Figure S7. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S8
Cytochrome P450 Family without transmembrane segments – 625 sequences
Figure S8. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S9
Cytochrome P450 Family without transmembrane segments – 625 sequences
Figure S9. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S10
O2- and H2O2-reactive enzymes with transmembrane segments – 1648 sequences
Figure S10. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S11
O2- and H2O2-reactive enzymes with transmembrane segments – 1648 sequences
Figure S11. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S12
O2- and H2O2-reactive enzymes without transmembrane segments – 5501 sequences
Figure S12. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S13
O2- and H2O2-reactive enzymes without transmembrane segments – 5501 sequences
Figure S13. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S14
S1
Semiclassical ET theory predicts that reactants will have identical configurations at the transition state for an electron-exchange reaction. For the electron exchange reaction between Fc and Fc+ in the gas phase, this configuration is defined as Q‡ (Figure S1). The energy required to reach this 2
λ1 = 12 k (Q − Qo )
configuration is equal to λ1+λ2, where and where k is an arbitrary force constant. The
[
]
λ 2 = 12 k Q − (Q + δQ ) , 2
transition state configuration (Q‡) corresponds to a Q ‡ = Qo + 12 δ Q
minimum value of λ1+λ2, found by differentiation:
Figure S1. Gas-phase potential energy surfaces for Fc and Fc++e− illustrating the vertical ionization energy (IE)v and electron affinity (EA)v. The electron-transfer transition state configuration is Q‡.
The ionization energy at Q‡ is given by:
[
]
2
(
)
2
IE (Q‡ ) = E 00 + 12 k Q ‡ − (Qo + δQ ) − 12 k Q‡ − Qo .
Simplification gives the following result: IE (Q ‡ ) = E00 Hence, the Fc ionization energy at the electron-exchange transition state is best approximated by the adiabatic ionization energy.
S2
Oxidoreductases – 6557 sequences
Transferases – 8355 sequences
Hydrolases – 6077 sequences
Lyases – 188 sequences
Isomerases – 145 sequences
Ligases – 338 sequences
Figure S2. Amino-acid occurrence frequencies in enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S3
Oxidoreductases – 6557 sequences
Transferases – 8355 sequences
Hydrolases – 6077 sequences
Lyases – 188 sequences
Isomerases – 145 sequences
Ligases – 338 sequences
Figure S3. Amino-acid occurrence frequencies in enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S4
Oxidoreductases – 30,851 sequences
Transferases – 81,134 sequences
Hydrolases – 55,666 sequences
Lyases – 22,864 sequences
Isomerases – 13,922 sequences
Ligases – 30,175 sequences
Figure S4. Amino-acid occurrence frequencies in enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S5
Oxidoreductases – 30,851 sequences
Transferases – 81,134 sequences
Hydrolases – 55,666 sequences
Lyases – 22,864 sequences
Isomerases – 13,922 sequences
Ligases – 30,175 sequences
Figure S5. Amino-acid occurrence frequencies in enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S6
Cytochrome P450 Family with transmembrane segments – 350 sequences
Figure S6. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S7
Cytochrome P450 Family with transmembrane segments – 350 sequences
Figure S7. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S8
Cytochrome P450 Family without transmembrane segments – 625 sequences
Figure S8. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S9
Cytochrome P450 Family without transmembrane segments – 625 sequences
Figure S9. Amino-acid occurrence frequencies in the primary sequences of the cytochrome P450 family of enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S10
O2- and H2O2-reactive enzymes with transmembrane segments – 1648 sequences
Figure S10. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes with transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S11
O2- and H2O2-reactive enzymes with transmembrane segments – 1648 sequences
Figure S11. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes with transmembrane segments relative to the average frequencies of enzymes with transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S12
O2- and H2O2-reactive enzymes without transmembrane segments – 5501 sequences
Figure S12. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes without transmembrane segments relative to the average frequencies in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S13
O2- and H2O2-reactive enzymes without transmembrane segments – 5501 sequences
Figure S13. Amino-acid occurrence frequencies in the primary sequences of O2- and H2O2-reactive enzymes without transmembrane segments relative to the average frequencies of enzymes without transmembrane segments in the Enzyme Data Bank of the Swiss Institute of Bioinformatics (http://www.uniprot.org/).
S14
