Is Vitamin A an Antioxidant or a Prooxidant?

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1 Supporting Information Is Vitamin A an Antioxidant or a Prooxidant? Duy Quang Dao 1,*, Thi Chinh Ngo 1, Nguyen Minh Thong 2, Pham Cam Nam 3,* 1 Institute of Research and Development, Duy Tan University, 03 Quang Trung, Danang, , Viet Nam 2 Campus in Kon Tum, The University of Danang, 704 Phan Dinh Phung, Kon Tum, , Viet Nam 3 Department of Chemistry, The University of Da Nang University of Science and Technology, 54 Nguyen Luong Bang, Danang, , Viet Nam. List of supporting information Figure S1: Molecular structure of small species used for validating the computational methods Table S1: Comparisons of experimental and calculated BDE(C C), BDE(C H), BDE(C OH) and BDE(O H) values of small species using different DFT methods at G(2d,2p) basis set. Table S2. Cartesian coordinates of neutral, anion and cation forms of diethyl ether (DEE) in the same solvent optimized at BMK/6-31G level of theory Table S3: Thermochemical properties (BDE, PDE, PA, ETE) of the retinol in the gas phase (GAS), chloroform (CHLO) and diethyl ether (DEE) solvent calculated at (RO)BMK/ G(2d,2p)//BMK/6-31G model chemistries, (unit in kcal/mol). Figure S2. FEDAM of retinol and HOO radical in the gas phase and DEE solvent Table S4. Cartesian coordinates and molecular enthalpies of all transition states of HAT reactions optimized at RO(BMK)/ G(2d,2p)// BMK/6-31G level of theory 1

2 Figure S3. IRC plots for all transition states of HAT reactions of HOO radical with retinol at BMK/6-31G level of theory in the gas phase Table S5. Relative energies (in kcal/mol) of H-atom transfer and radical adduct formation reactions between the vitamin A and HOO radical in the gas phase (GAS) and diethyl ether (DEE) solvent at (RO)BMK/ G(2d,2p)//BMK/6-31G model chemistries. Figure S4. IRC plots for all transition states of RAF reactions of HOO radical with retinol at BMK/6-31G level of theory in the gas phase. 2

3 Validating DFT methods for predicting the BDE of different C C, C H, O H and C OH bonds in vitamin A Different small species which have reasonably similar molecular structure with a part of the vitamin A one are chosen to calculate BDEs of C C, C H, C OH, or O H bonds using the six DFT methods (i.e. M06, BMK, PBE, HSEH1PBE, TSSSTPSS and B3LYP) and the two basic sets (i.e. 6-31G basis set for structural optimization and G(2d,2p) for single point energy calculation). Indeed, a series of different compounds including cyclohexene, methylcyclohexene, cyclohexane, methyl- and ethyl-cyclohexane, and different straight-chain alcohols containing up to 5 carbon atoms is used for this series of calculation (Figure S1). The comparison of the calculated results obtained with the experimental ones allows validating the calculation methods chosen for the present study. Figure S1: Molecular structure of small species used for validating the computational methods 3

4 Table S1: Comparisons of experimental and calculated BDE(C C), BDE(C H), BDE(C OH) and BDE(O H) values of small species using different DFT methods at G(2d,2p) basis set. Molecules Calculated BDE (kcal/mol) M06 BMK PBE HSEH1PBE TPSSTPSS B3LYP Expt. BDE (*) (kcal/mol) CH 3 -OH 93.9 (1.9) 93.7 (1.7) 95.5 (3.5) 90.5 (1.5) 89.4 (2.6) 88.4 (3.6) 92.0±0.17 CH 3 O-H (22.3) (1.0) (3.8) (4.0) (3.7) (2.5) 104.2±0.9 C 2 H 5 -OH 95.1 (1.1) 95.3 (1.3) 95.6 (1.6) 91.3 (2.2) 89.8 (4.2) 89.0 (5.0) 94.0±0.7 C 2 H 5 O-H (18.2) (1.4) 99.8 (4.8) 99.4 (5.2) 99.5 (5.1) (3.2) 104.6±0.8 nc 4 H 9 -OH 95.8 (2.1) 95.7 (2.0) 95.7 (2.0) 91.7 (2.0) 89.6 (4.1) 89.1 (4.6) 93.7±1 nc 4 H 9 O-H (19.8) (1.0) 99.5 (2.4) 99.2 (2.7) 99.3 (2.6) (0.7) 101.9±1 CH 2 CHCH 2 -OH 80.4 (0.4) 81.0 (1.0) 79.9 (0.1) 77.1 (2.9) 74.4 (5.6) 74.0 (6.0) 80.0±1 nc 5 H 11 -OH 95.9 (3.1) 94.7 (1.9) 95.8 (3.0) 91.7 (1.1) 89.8 (3.0) 89.2 (3.6) 92.8±1.5 Cyclohexane-H (17.6) 98.9 (0.6) 94.4 (5.1) 94.8 (4.7) 96.5 (3.0) 96.2 (3.3) (21.0) 85.1 (3.2) 79.4 (2.5) 81.1 (0.8) 81.8 (0.1) 82.0 (0.1) (20.4) 82.5 (3.0) 75.9 (3.6) 77.9 (1.6) 78.6 (0.9) 78.8 (0.7) (1.4) 89.6 (0.5) 86.1 (4.0) 85.6 (4.5) 80.6 (9.5) 81.1 (9.0) 90.1± (1.2) 86.8 (0.6) 81.7 (5.7) 82.0 (5.4) 76.5 (10.9) 77.0 (10.4) 87.4±1.3 (Data in parentheses are experiment-calculated deviation values: BDE= BDE expt - BDE calc ) (*) Luo, Y.-R. Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press,

5 As a result, the calculated BDE values of the small species evaluated in this study are resumed in Table S1. All the BDE values were investigated at restricted open shell level and at the G(2d,2p) basis set. And the values in parentheses consist in the deviation between experimental and calculated data. As can be seen, the BMK method gives a maximal deviation from 0.5 to 3.2 kcal/mol. While, the higher experimented/calculated differences from 0.4 to 22.3 kcal/mol, from 5.6 to 5.7 kcal/mol, and from 0.8 to 5.4 kcal/mol are observed for the M06 method, the PBE method and the HSEH1PBE one, respectively. And the TPSSTPSS and B3LYP level of theory lead to the deviation from 10.6 to 10.9 kcal/mol and from 10.2 to 10.4 kcal/mol, respectively. So, it can be seen that the BMK method provides the best fit between experimental and computational data for the small species chosen. For that reason, this DFT method will be used for further calculations. 5

6 Solvation enthalpy calculations for Diethyl ether solvent Solvation enthalpies of proton and electron in DEE solvent was calculated in proposing that a proton or an electron when surrounded by another solvent molecules will bind to a solvent molecule (DEE sol ) to yield a charged particle DEE or DEE. And these particles are embedded in a dielectric continuum. H +DEE DEE H, H sol (H + ) (R.S1) e +DEE DEE e, H sol (e ) (R.S2) Thus, solvent enthalpies of proton and electron can be provided by the following equations: H H =H DEE H H DEE H H (Eq.S1) H e =H DEE e H DEE H e (Eq.S2) Using (Eq.7) and (Eq.8), the solvation enthalpies of proton and electron in DEE solvent calculated at BMK/ G(2d,2p)//BMK/6-31G model chemistries were equal to and kcal/mol, respectively. Cartesian coordinates of neutral, anion and cation forms of diethyl ether (DEE) molecule in the same solvent optimized at BMK/6-31G level of theory are shown in Table S2 of Supporting information. 6

Table S2. Cartesian coordinates of neutral, anion and cation forms of diethyl ether (DEE) in the same solvent optimized at BMK/6-31G level of theory. Cartesian coordinates 0 1 O 0.00000000 0.

88607600 1.18892300-1.16655200 H 0.88607600-1.18892300-1.16655200 H -0.88607600-1.18892300-1.16655200 H 0.00000000 3.30269400-0.17222400 H 0.00000000-3.30269400-0.17222400 H -0.88619500 2.37125900 1.

137312 (Hartree/Particle) Thermal correction to Energy= 0.144071 Thermal correction to Enthalpy= 0.145015 Thermal correction to Gibbs Free Energy= 0.

7 Table S2. Cartesian coordinates of neutral, anion and cation forms of diethyl ether (DEE) in the same solvent optimized at BMK/6-31G level of theory. Cartesian coordinates 0 1 O C C C C H H H H H H H H H H Frequencies calculation Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Neutral DEE Cartesian coordinates -1 2 O C C C C H H H H H H H H H H Frequencies calculation Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Anion DEE 7

Sum of electronic and zero-point Energies= -233.442399 Sum of electronic and thermal Energies= -233.435629 Sum of electronic and thermal Enthalpies= -233.

8 Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Cartesian coordinates 1 1 O C C C C H H H H H H H H H H H Frequencies calculation Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Cation DEE 8

9 Table S3: Thermochemical properties (BDE, PDE, PA, ETE) of the retinol in the gas phase (GAS), chloroform (CHLO) and diethyl ether (DEE) solvent calculated at (RO)BMK/ G(2d,2p)//BMK/6-31G model chemistries, (unit in kcal/mol). Bonds PA ETE PDE BDE GAS CHLO DEE GAS CHLO DEE GAS CHLO DEE GAS CHLO DEE C4 H C5 H C6 H C7 H C9 H C10 H C11 H C13 H C14 H C15 H C17 H C18 H C19 H C20 H O H

10 Figure S2. FEDAM of retinol and HOO radical in the gas phase and DEE solvent HOO HOO IE (ev) Ret Ret HOO(gas) HOO(dee) Ret(gas) Ret(dee) EA (ev) 10

11 Table S4. Cartesian coordinates and molecular enthalpies of all transition states of HAT reactions optimized at RO(BMK)/ G(2d,2p)// BMK/6-31G level of theory Cartesian coordinates TS (C4-H + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H C H

12 H H C H H H H O H O Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF = Cartesian coordinates TS (C9-H + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H

13 H C H C C H C C H H H H C H H O H C H H H C H H H H O H O Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF = Cartesian coordinates TS (C18-H + HOO ) 0 2 C C C C C

14 C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G 14

15 Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF =

16 Figure S3. IRC plots for all transition states of HAT reactions of HOO radical with retinol at BMK/6-31G level of theory in the gas phase. (C4-H + HOO ) (C9-H + HOO ) (C18-H + HOO ) 16

17 Table S5: Relative energies (in kcal/mol) of H-atom transfer and radical adduct formation reactions between the vitamin A and HOO radical in the gas phase (GAS) and diethyl ether (DEE) solvent at (RO)BMK/ G(2d,2p)//BMK/6-31G model chemistries. Reaction path E, kcal/mol GAS DEE C4H + HOO VTA+OOH Int TS Int Prod C9H + HOO Int TS Int Prod C18H + HOO Int TS Int Prod C2=C3 + HOO Int TS Int TS Int Prod C10=C11 + HOO Int TS Int TS Int Prod C12=C13 + HOO Int TS Int

18 TS Int Prod C14=C15 + HOO Int TS Int TS Int Prod C16=C17 + HOO Int TS Int TS Int Prod

19 Table S6. Cartesian coordinates and molecular enthalpies of all transition states of RAF reactions optimized in the gas phase at RO(BMK)/ G(2d,2p)// BMK/6-31G level of theory Cartesian coordinates TS1 (C2=C3 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H

20 C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS2 (C2=C3 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C

21 C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF = Cartesian coordinates TS1 (C10=C11 + HOO ) 0 2 C C

22 C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O

23 H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS2 (C10=C11 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H

24 H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS1 (C12=C13 + HOO ) 0 2 C C C C C C H H H H H H C H H

25 H C H C H C C C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF=

26 Cartesian coordinates TS2 (C12=C13 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H C H H H

27 C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS1 (C14=C15 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C

28 H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS2(C14=C15 + HOO ) 0 2 C C C C C C H H

29 H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy=

30 Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS1 (C16=C17 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C H C C C H H H C H C C H C C H H H H C H

31 H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF= Cartesian coordinates TS2 (C16=C17 + HOO ) 0 2 C C C C C C H H H H H H C H H H C H C

32 H C C C H H H C H C C H C C H H H H C H H O H C H H H C H H H H O O H Frequencies calculation at BMK/6-31G Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Single point energy calculation at (RO)BMK/ G(2d,2p) HF=

33 Figure S4. IRC plots for all transition states of RAF reactions of HOO radical with retinol at BMK/6-31G level of theory in the gas phase. TS1 TS2 C2=C3 + HOO C10=C11 + HOO C12=C13 + HOO 33

34 C14=C15 + HOO C16=C17 + HOO 34

35 35

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