Supportting Information for
A density functional theory study for the role of end groups on the antioxidative potency of carotenoids
Fu-Xing Liao, Ching-Han Hu*
Department of Chemistry, National Changhua University of Education, Changhua 50058, Taiwan
Email :
Fax: 886-4-7211190
Supporting Information:
(1) Tables s1-s3: Reaction energetics, <S2> expectation values and magnitude of the imaginary frequencies of the transition states computed at B3LYP/6-31G(d) level.
(2) Figures s1-s4: Structures of transition states not illustrated in the manuscript.
Table s1. Reaction Enthalpies and Free Energies (in kcal/mol, at 298 K) Involved in the Hydrogen Abstractions of CARs by MeOO. ; the Results were Obtained Using B3LYP/6-31G(d).a
MeOO. + CAR → MeOOH + CAR(-H).
β-CAR(C4) / 8.09 / 7.85 / -8.34 / 20.16 / -11.64 / 0.8664 / 1.277 / 1628
LYC (C4) / 7.87 / 7.89 / -8.95 / 17.78 / -9.69 / 0.9421 / 1.267 / 1532
ZEA (C4) / 11.16 / 8.31 / -7.33 / 20.29 / -7.51 / 0.8642 / 1.305 / 1807
AST (C3) / 9.62 / 7.19 / -8.92 / 20.00 / -7.26 / 0.7582 / 1.311 / 1670
CAN (C18) / 13.10 / 10.06 / -2.70 / 21.06 / -2.54 / 0.8454 / 1.323 / 1822
DHIR (C3O) / -1.20 / -3.52 / -7.16 / 6.24 / -6.87 / 0.8156 / 1.121 / 1468
DHIRQ(C17) / 13.06 / 9.00 / -4.13 / 20.59 / -4.34 / 1.0451 / 1.318 / 1870
LAH (C11) / 11.76 / 9.64 / -6.51 / 18.52 / -7.63 / 0.7690 / 1.281 / 1634
a <S2>, RC-H, and nimag are the <S2> expectation value, C–H distance (in angstroms) and magnitude of the imaginary frequency (in i cm-1) of the TSs, respectively.
Table s2. Reaction Enthalpies and Free Energies (in kcal/mol, at 298 K) Involved in the Addition of MeOO. to CARs; the Results were Obtained Using B3LYP/6-31G(d).a
MeOO. + CAR → MeOO–CAR.
β-CAR(C5) / 6.26 / 6.10 / -20.09 / 17.21 / -9.46 / 0.9457 / 2.109 / 414
LYC (C5) / 3.83 / 2.71 / -20.59 / 16.40 / -7.55 / 1.0544 / 2.218 / 307
ZEA (C5) / 7.93 / 7.79 / -19.40 / 21.08 / -6.30 / 0.9522 / 2.129 / 403
AST(C7) / 5.11 / 4.68 / -17.08 / 16.48 / -6.15 / 0.9960 / 2.077 / 445
CAN (C7) / 5.03 / 4.54 / -16.28 / 16.44 / -4.93 / 1.0061 / 2.068 / 459
DHIR (C7) / 3.66 / 3.28 / -17.85 / 15.01 / -5.95 / 0.9928 / 2.114 / 421
DHIRQ(C6) / 6.03 / 4.20 / -16.93 / 15.16 / -6.67 / 1.2933 / 2.111 / 366
a <S2>, RC-H, and nimag are the <S2> expectation value, C–H distance (in angstroms) and magnitude of the imaginary frequency (in i cm-1) of the TSs, respectively.
Table s3. Reaction Enthalpies and Free Energies (in kcal/mol, at 298 K) Involved in the Addition of O2 to CAR(-H). and MeOO-CAR. ; the Results were Obtained Using B3LYP/6-31G(d).a
O2 + CAR(-H).→ CAR(-H)–OO.
β-CAR(-H). (C4,C4) / 7.34 / 6.78 / -3.89 / 17.61 / 8.57 / 1.1563 / 2.105 / 352
LYC(-H). (C4,C4) / 7.10 / 6.95 / -1.91 / 18.45 / 10.25 / 1.1346 / 2.065 / 366
ZEA(-H). (C4,C4) / 7.82 / 8.64 / -1.36 / 20.33 / 11.37 / 1.1404 / 2.097 / 362
AST(-H). (,C3C3) / 0.25 / 0.75 / -9.70 / 10.46 / 2.25 / 1.3128 / 2.318 / 130
CAN(-H). (C18,C18) / 6.25 / 7.45 / -6.29 / 18.38 / 4.26 / 1.3258 / 2.111 / 359
DHIR(-H). (C3O,C7’) / 10.57 / 11.77 / 6.51 / 21.99 / 16.30 / 1.0158 / 1.980 / 433
DHIRQ(-H). (C17,C17) / 7.79 / 8.68 / -3.51 / 19.31 / 8.48 / 1.5437 / 2.053 / 421
LA. (C11,C13) / -0.24 / 0.41 / -11.58 / 10.63 / -0.19 / 1.1755 / 2.159 / 272
O2 + MeOO–CAR.→ MeOO–CAR–OO.
MeOO–β-CAR. (C5,C5’) / 13.13 / 10.89 / 6.35 / 26.51 / 20.06 / 1.1406 / 1.979 / 428
MeOO–LYC. (C5,C5’) / 7.53 / 6.32 / 0.66 / 19.84 / 6.66 / 1.1078 / 2.065 / 353
MeOO–ZEA. (C5,C5’) / 11.00 / 12.12 / 2.76 / 24.17 / 15.55 / 1.1007 / 2.076 / 373
MeOO–AST. (C7,C5’) / 15.21 / 16.57 / 12.13 / 28.53 / 24.40 / 0.8425 / 1.883 / 354
MeOO–CAN. (C7,C5’) / 15.09 / 16.45 / 12.49 / 28.40 / 25.51 / 0.9249 / 1.939 / 409
MeOO–DHIR. (C7,C7’) / 8.57 / 9.76 / 4.23 / 20.79 / 13.95 / 0.9915 / 1.992 / 419
MeOO–DHIRQ. (C6,C6’) / 12.91 / 13.95 / 10.09 / 26.51 / 20.67 / 0.7778 / 1.825 / 199
a <S2>, RC-H, and nimag are the <S2> expectation value, C–H distance (in angstroms) and magnitude of the imaginary frequency (in i cm-1) of the TSs, respectively.
DHIR (Ci)
DHIRQ (C2h)
DHIRQ (C2)
Figure s1. Optimized structures and selected geometrical parameters (bond lengths in Å and bond angles in degrees) for the symmetric isomers of DHIR and DHIRQ.
MeOO. + ZEA(C4) → MeOOH + ZEA(-H).
MeOO. + CAN(C18) → MeOOH + CAN(-H).
Figure s2. Optimized structures and selected geometrical parameters for the TSs involved in the HAs of CARs. The positions of reactions are specified in the parentheses.
MeOO. + ZEA (C5) → MeOO–ZEA.
MeOO. + CAN (C7) → MeOO–CAN.
Figure s3. Optimized structures and selected geometrical parameters for the TSs involved in the MeOO. addition to the CARs. The positions of reactions are specified in the parentheses.
ZEA(-H). (C4,C4) + O2 → ZEA(-H)–OO.
CAN(-H). (C18,C18) + O2 → CAN(-H)–OO.
MeOO–ZEA. (C5,C5’) + O2 → MeOO–ZEA–OO.
MeOO–CAN. (C7,C5’) + O2 → MeOO–CAN–OO.
Figure s4. Optimized structures and selected geometrical parameters for the TSs involved in the O2 addition to CAR(-H). and MeOO-CAR.. The positions of HA or peroxide addition, and of O2 additions are specified in the parentheses.