Electronic Supplementary Information. DPT tautomerisation of the wobble guanine thymine DNA base mispair is not mutagenic: QM and QTAIM arguments 1

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1 Electronic Supplementary Information DPT tautomerisation of the wole guanine thymine DNA ase mispair is not mutagenic: QM and QTAIM arguments 1 Ol ha O. Brovarets a,, Roman O. Zhurakivsky a and Dmytro M. Hovorun a,, a Department of Molecular and Quantum Biophysics, Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, 150 Akademika Zaolotnoho Str., Kyiv, Ukraine Department of Molecular Biotechnology and Bioinformatics, Institute of High Technologies, Taras Shevchenko National University of Kyiv, 2-h Akademika Hlushkova Ave., Kyiv, Ukraine Corresponding author. dhovorun@img.org.ua 1 Dedicated to Dr. Viktor I. Danilov ( ), our colleague and collaorator, foundator of the quantum iophysics in Ukraine. S1

2 Tale S1 Electron-topological, structural, virational and energetical characteristics of the intermolecular H-onds revealed in the wg T, wg* T* and TS wg T wg* T* and polar characteristics of the latters otained at the B3LYP/ G(d,p) level of theory in vacuum Complex AH B Н-ond ρ a Δρ 100 ε c d A B d d H B e Δd AH f AH B g Δν h E HB i wg T N3H O N1H O wg* T* O6H N O2H N TS wg T wg* T* O6H N * 7.86 N2H O ** a The electron density at the (3,-1) 2 BCP of the H-ond, a.u. The Laplacian of the electron density at the (3,-1) BCP of the H-ond, a.u. c The ellipticity at the (3,-1) BCP of the H-ond d The distance etween the A (H-ond donor) and B (H-ond acceptor) atoms of the AH B H-ond, Å e The distance etween the H and B atoms of the AH B H-ond, Å f The elongation of the H-ond donating group AH upon the AH B H-onding, Å g The H-ond angle, degree h The redshift of the stretching virational mode ν(ah) of the AH H-onded group, cm -1 i Energy of the H-onds, calculated y Iogansen s [1], Nikolaienko-Bulavin-Hovorun (marked with an asterisk) [2] or Espinose- Molins-Lecomte (marked with a doule asterisk) [3,4] formulas, kcal mol -1 j The dipole moment of the complex, D μ j S2

3 Tale S2 Electron-topological and structural characteristics of the intermolecular H-onds revealed in the 9 key points and polar characteristics of the latters otained at the B3LYP/ G(d,p) level of theory in vacuum along the IRC of the wg T wg* T* tautomerisation via the DPT Complex Key point 1 (-8.63 Bohr): wg T Key point 2 (-1.41 Bohr): Δρ O6 H =0 Key point 3 (-1.29 Bohr): ρ O6-H =ρ H-N3 Key point 4 (-0.98 Bohr): Δρ H N3 =0 Key point 5 (-0.31 Bohr): Δρ H O2 =0 Key point 6 (-0.17 Bohr): ρ N1-H =ρ H-O2 Key point 7 (0.00 Bohr): TS wg T wg* T* Key point 8 (0.18 Bohr): Δρ N1 H =0 Key point 9 (1.17 Bohr): wg* T* AH B Н-ond/A-H-B covalent ond Notes: for footnote definitions see Tale 1. ρ Δρ 100 ε d A B d H B AH B μ N3H O N1H O N3H O N1H O N2H O N3-H-O N1H O N2H O O6H N N1H O N2H O O6H N N1H O N2H O O6H N N1-H-O N2H O O6H N N2H O O6H N O2H N O6H N O2H N S3

4 Tale S3 Energetical and kinetic characteristics of the wg T wg* T* tautomerisation via the DPT otained at the different levels of QM theory for the geometry calculated at the B3LYP/ G(d,p) level of QM theory in vacuo Level of QM theory G a E c d G TS E TS G e E f kcal mol -1 cm -1 τ g MP2/ G(2df,pd) MP2/ G(3df,2pd) MP2/cc-pVTZ MP2/cc-pVQZ a The relative Gis free energy of the wg* T* ase pair ( G wg T =0.00; T= K), kcal mol -1 The relative electronic energy of the wg* T* ase pair ( E wg T =0.00), kcal mol -1 c The Gis free energy of activation for the forward reaction of the wg T wg* T* tautomerisation via the DPT, kcal mol -1 d The activation electronic energy for the forward reaction of the wg T wg* T* tautomerisation, kcal mol -1 e The Gis free energy of activation for the reverse reaction of the wg T wg* T* tautomerisation, kcal mol -1 f The activation electronic energy for the reverse reaction of the wg T wg* T* tautomerisation g The lifetime of the wg* T* ase mispair, s The frequency of the virational mode in the wg* T* ase pair, which ecomes imaginary in the TS wg T wg* T* of the wg T wg* T* DPT tautomerisation, is equal to cm -1 and the zero-point virational energy associated with this normal mode is equal to 2.93 kcal mol -1 or cm -1 (B3LYP/ G(d,p) level of QM theory). The periods T ( , , , , and s, respectively) of all 6 low-frequency intermolecular virations in the wg* T* DNA ase mispair (16.5, 25.6, 60.3, 69.9, 96.0 and cm -1 ) are significantly less than the lifetime of the wg* T* ase mispair. S4

5 Tale S4 Interase interaction energies (in kcal/mol) for the studied ase pairs in vacuum otained at the MP2/ G(2df,pd)//B3LYP/ G(d,p) level of theory a Complex -ΔE int ΣE ΣE HB / ΔE int, HB % c -ΔG int wg T wg* T* a The counterpoise-corrected electronic interaction energy The total energy of the intermolecular H-onds c The counterpoise-corrected Gis free energy of interaction (T= K) S5

6 Key point 1 Key point 2 Key point 3 Key point 4 wg T Δρ O6 H =0 ρ O6-H =ρ H-N3 Δρ H N3 =0 IRC=-8.63 Bohr IRC=-1.41 Bohr IRC=-1.29 Bohr IRC=-0.98 Bohr Key point 5 Key point 6 Key point 7 Key point 8 Key point 9 Δρ H O2 =0 ρ N1-H =ρ H-O2 TS wg T wg* T* Δρ N1 H =0 wg* T* IRC=-0.31 Bohr IRC=-0.17 Bohr IRC=0.00 Bohr IRC=0.18 Bohr IRC=1.17 Bohr Fig. S1 Geometric structures of the 9 key points descriing the evolution of the wg T wg* T* tautomerisation via the DPT along the IRC otained at the B3LYP/ G(d,p) level of theory in vacuo. Coordinates of the 9 key points are presented for each structure. The dotted lines indicate AH B H-onds, while continuous lines show covalent onds (their lengths are presented in angstroms). Caron atoms are in light-lue, nitrogen in dark-lue, hydrogen in grey and oxygen in red. S6

7 a Fig. S2 Profiles of: (a) the electronic energy E and () the first derivative of the electronic energy with respect to the IRC - de/dirc along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. Fig. S3 Profile of the dipole moment μ along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S7

8 a c d Fig. S4 Profiles of: (a) the electron density ρ; () the Laplacian of the electron density Δρ; (c) the ellipticity ε and (d) the energy of the H-ond E HB, estimated y the EML formula [3,4], at the (3,-1) BCPs of the intermolecular covalent and hydrogen onds along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S8

9 a c Fig. S5 Profiles of: (a) the distance d A B etween the electronegative A and B atoms; () the distance d AH/HB etween the hydrogen and electronegative A or B atoms and (c) the angle AH B of the intermolecular covalent and hydrogen onds along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S9

10 a c d Fig. S6 Profiles of: (a) the electron density ρ; () the Laplacian of the electron density Δρ; (c) the ellipticity ε and (d) the energy E HB, estimated y the EML formula [3,4], at the (3,-1) BCP of the third N2H O2 H-ond along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S10

11 a c Fig. S7 Profiles of: (a) the distance d N2 O2 etween the N2 and O2 atoms of the N2H O2 H-ond; () the distances d N2H and d H O2 of the N2H O2 H-ond and (c) the angle N2H O2 of the N2H O2 H-ond along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S11

12 Fig. S8 Profiles of the NBO charges of the hydrogen atoms involved in the N3H I O6/O6H I N3, N1H II O2/O2H II N1 and N2H III O2 H-onds along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. a Fig. S9 Profiles of: (a) the distance R(H-H) etween the glycosidic hydrogens and () the α 1 ( N1H(T)H(G)) and α 2 ( N9H(G)H(T)) glycosidic angles along the IRC of the wg T wg* T* tautomerisation via the DPT otained at the B3LYP/ G(d,p) level of theory in vacuo. S12

13 References. 1. Iogansen A.V. Direct proportionality of the hydrogen onding energy and the intensification of the stretching ν(xh) viration in infrared spectra, Spectrochim. Acta A Mol. Biomol. Spectrosc., 1999, 55, Nikolaienko T.Y., Bulavin L.A., Hovorun D.M. Bridging QTAIM with virational spectroscopy: The energy of intramolecular hydrogen onds in DNA-related iomolecules, Phys. Chem. Chem. Phys., 2012, 14, Espinosa E., Molins E., Lecomte C. Hydrogen ond strengths revealed y topological analyses of experimentally oserved electron densities, Chem. Phys. Lett., 1998, 285, Mata I., Alkorta I., Espinosa E., Molins E. Relationships etween interaction energy, intermolecular distance and electron density properties in hydrogen onded complexes under external electric fields, Chem. Phys. Lett., 2011, 507, S13

PCCP PAPER. Introduction. Ol ha O. Brovarets abc and Dmytro M. Hovorun* abc. View Article Online View Journal

PCCP PAPER. Introduction. Ol ha O. Brovarets abc and Dmytro M. Hovorun* abc. View Article Online View Journal PAPER View Article Online View Journal Cite this: DOI: 10.1039/c3cp52644e Received 25th June 2013, Accepted 20th September 2013 DOI: 10.1039/c3cp52644e www.rsc.org/pccp Atomistic nature of the DPT tautomerisation