Mechanistic Pathways for the Reaction of Quercetin with Hydroperoxy Radical

Mechanistic pathways for the reaction of quercetin with hydroperoxy radical

Zoran S. Marković 1 , Jasmina M. Dimitrić Marković 2* Ćemal B. Doličanin 1

2* Faculty of Physical Chemistry University of Belgrade Studentski trg 12-16, 11000 Belgrade, Republic of Serbia,

Fax: (+)+ 381 11 187 133, Phone: (+)+ 381 11 333 6624

e-mail:

Supporting Information

Table 1. Some selected structural parameters: bond lengths, bond angles, and torisioal angles

Bond length (Å) / Q / 3OH / 5OH / 7OH / 3’OH / 4’OH / exp
O1-C2 / 1.367 / 1.352 / 1.372 / 1.359 / 1.367 / 1.371 / 1.371
C2-C3 / 1.360 / 1.440 / 1.358 / 1.368 / 1.359 / 1.368 / 1.362
C3-C4 / 1.450 / 1.515 / 1.473 / 1.445 / 1.458 / 1.460 / 1.431
C4-C10 / 1.433 / 1.443 / 1.452 / 1.440 / 1.431 / 1.429 / 1.423
C5-C10 / 1.418 / 1.422 / 1.470 / 1.444 / 1.422 / 1.422 / 1.418
C5-C6 / 1.385 / 1.388 / 1.451 / 1.365 / 1.383 / 1.383 / 1.365
C6-C7 / 1.401 / 1.393 / 1.388 / 1.445 / 1.399 / 1.399 / 1.396
C7-C8 / 1.391 / 1.400 / 1.390 / 1.451 / 1.394 / 1.395 / 1.386
C8-C9 / 1.387 / 1.382 / 1.421 / 1.383 / 1.388 / 1.387 / 1.381
C9-C10 / 1.402 / 1.398 / 1.379 / 1.400 / 1.401 / 1.401 / 1.390
C9-O1 / 1.354 / 1.365 / 1.344 / 1.357 / 1.354 / 1.353 / 1.368
C2-C1’ / 1.467 / 1.446 / 1.467 / 1.464 / 1.470 / 1.452 / 1.469
C1’-C2’ / 1.404 / 1.413 / 1.404 / 1.406 / 1.378 / 1.407 / 1.398
C2’-C3’ / 1.383 / 1.378 / 1.383 / 1.382 / 1.435 / 1.377 / 1.383
C3’-C4’ / 1.399 / 1.403 / 1.399 / 1.401 / 1.459 / 1.466 / 1.392
C4’-C5’ / 1.386 / 1.388 / 1.386 / 1.386 / 1.388 / 1.442 / 1.378
C5’-C6’ / 1.392 / 1.389 / 1.392 / 1.391 / 1.386 / 1.363 / 1.380
C6’-C1’ / 1.401 / 1.409 / 1.401 / 1.402 / 1.432 / 1.435 / 1.398
C3-O3 / 1.354 / 1.236 / 1.344 / 1.348 / 1.351 / 1.344 / 1.358
C4=O4 / 1.252 / 1.230 / 1.229 / 1.250 / 1.249 / 1.249 / 1.269
C5-O5 / 1.337 / 1.332 / 1.237 / 1.340 / 1.337 / 1.336 / 1.352
C7-O7 / 1.355 / 1.353 / 1.357 / 1.250 / 1.353 / 1.352 / 1.359
C3’-O3’ / 1.359 / 1.358 / 1.359 / 1.357 / 1.252 / 1.331 / 1.373
C4’-O4’ / 1.369 / 1.364 / 1.369 / 1.366 / 1.326 / 1.245 / 1.374
O3-H3 / 0.974 / 0.980 / 0.975 / 0.975 / 0.976 / 0.906
O5-H5 / 0.983 / 0.986 / 0.980 / 0.980 / 0.980 / 0.948
O7-H7 / 0.962 / 0.962 / 0.962 / 0.962 / 0.962 / 0.914
O3’-H3’ / 0.965 / 0.965 / 0.965 / 0.965 / 0.976
O4’-H4’ / 0.961 / 0.962 / 0.962 / 0.962 / 0.977
H3---O4 / 2.032 / 1.942 / 2.019 / 2.013 / 1.998
H5---O4 / 1.771 / 1.731 / 1.774 / 1.798 / 1.802
H3’---O4’ / 2.146 / 2.146 / 2.146 / 2.148 / 2.046
H4’---O3’ / 2.050
Bond angle(º)
O1-C2-C3 / 119.8 / 120.6 / 118.5 / 119.2 / 119.7 / 119.1 / 120.7
C2-C3-C4 / 121.2 / 117.6 / 122.7 / 121.7 / 121.1 / 121.2 / 120.8
C2-C3-O3 / 123.7 / 123.2 / 123.7 / 123.3 / 124.2 / 124.3 / 121.7
C3-O3-H3 / 105.1 / 104.1 / 105.4 / 105.3 / 105.3 / 110.3
C3-C4-O4 / 118.9 / 119.9 / 117.2 / 118.7 / 118.3 / 118.1 / 120.5
C3-C4-C10 / 116.7 / 116.8 / 115.1 / 116.7 / 116.8 / 116.9 / 116.8
C4-C10-C9 / 119.3 / 120.4 / 118.3 / 118.4 / 119.1 / 119.1 / 120.4
C10-C9-O1 / 120.4 / 121.2 / 123.3 / 121.2 / 120.7 / 129.9 / 120.1
C10-C5-O5 / 120.6 / 120.4 / 122.8 / 119.4 / 120.4 / 120.4 / 118.8
C5-O5-H5 / 108.2 / 108.0 / 109.1 / 108.7 / 108.9 / 101.9
C10-C5-C6 / 119.9 / 120.4 / 117.7 / 120.1 / 120.0 / 120.0 / 121.5
C5-C6-C7 / 119.3 / 119.1 / 121.6 / 120.1 / 119.2 / 119.2 / 119.1
C6-C7-C8 / 122.4 / 122.2 / 120.1 / 119.0 / 122.5 / 122.4 / 122.1
C6-C7-O7 / 121.0 / 116.7 / 117.6 / 122.0 / 116.2 / 116.2 / 120.1
C7-C8-C9 / 117.4 / 117.6 / 119.7 / 119.1 / 117.5 / 117.5 / 117.2
C8-C9-C10 / 122.3 / 122.7 / 123.2 / 121.6 / 122.2 / 122.1 / 123.0
C1’-C2’-C3’ / 120.4 / 120.6 / 120.5 / 120.5 / 120.8 / 119.4 / 120.3
C3’-C4’-C5’ / 120.2 / 120.3 / 120.1 / 120.2 / 121.0 / 116.6 / 120.2
C4’-C5’-C6’ / 120.3 / 120.4 / 120.4 / 120.3 / 119.2 / 120.8 / 119.9
C5’-C6’-C1’ / 119.9 / 119.9 / 119.9 / 119.9 / 121.8 / 121.1 / 120.6
C6’-C1’-C2’ / 119.4 / 119.0 / 119.2 / 119.4 / 119.5 / 120.1 / 119.0
C6’-C1’-C2 / 121.7 / 122.2 / 121.7 / 121.9 / 121.1 / 121.2 / 121.5
C4’-O4’-H4’ / 110.9 / 111.2 / 111.0 / 111.2 / 105.9 / 101.8
C3’-O3’-H3’ / 108.9 / 109.1 / 108.8 / 109.1 / 105.9 / 112.6
Torsional angle (º)
O1-C2-C1’-C2’ / 10.4 / 0.0 / 0.0 / -14.8 / 0.0 / 0.0 / 8.0

Table 2. Some NBO charges and spin densities for the reactants, transition states, and products

Reactants / TS / Products
Nat. charg. / Spin dens. / Nat. charg. / Spin dens. / Nat. char. / Spin dens.
QO4’H4’ / 0 / 0.00 / QO4’ / -0.28 / 0.46 / QO4’ / 0 / 1
H4’ / 0.52 / -0.03
OOH / 0 / 1.00 / OOH / -0.24 / 0.57 / HOOH / 0 / 0
QO3’ / -0.27 / 0.47 / QO3’ / 0 / 1
H3’ / 0.52 / -0.03
OOH / -0.25 / 0.56 / HOOH / 0 / 0
QO3 / -0.17 / 0.49 / QO3 / 0 / 1
H3 / 0.52 / -0.03
OOH / -0.35 / 0.54 / HOOH / 0 / 0
QO5 / -0.27 / 0.56 / QO5 / 0 / 1
H5 / 0.53 / -0.02
OOH / -0.26 / 0.46 / HOOH / 0 / 0
QO7 / -0.25 / 0.54 / QO7 / 0 / 1
H7 / 0.52 / -0.03
OOH / -0.27 / 0.49 / HOOH / 0 / 0

Table 3. Some selected NBO orbital occupancies and orbital energies

NBO / Quercetin / Transition / Products
Occ. / Ener / Occ. / Ener / Occ. / Ener
BD1 C4'O4' / 1.99 / 1.99 / -1.074 / 1.99 / -1.171
BD2 C4'O4' / 1.74 / -0.531 / 1.92 / -0.479
BD1* C4'O4' / 0.03 / 0.471 / 0.01 / 0.622
BD2* C4'O4' / 0.79 / -0.095 / 0.35 / -0.010
BD H4'O4' / 1.99 / -0.879
BD H4'O1 / 1.7 / -0.570
BD *H4'O1 / 0.29 / 0.259
BD1 C3'O3' / 1.99 / -1.090 / 1.99 / -1.160
BD2 C3'O3' / 1.76 / -0.494 / 1.90 / -0.481
BD1* C3'O3' / 0.01 / 0.506 / 0.01 / 0.607
BD2 *C3'O3' / 0.70 / -0.073 / 0.40 / -0.026
BD H3'O3' / 1.99 / -0.853
BD H3'O1 / 1.76 / -0.640
BD *H3'O1 / 0.23 / 0.335
BD1 C3O3 / 1.99 / -1.090 / 1.99 / -1.174
BD2 C3O3 / 1.78 / -0.508 / 1.91 / -0.479
BD1* C3O3 / 0.01 / 0.503 / 0.01 / 0.634
BD2* C3O3 / 0.78 / -0.091 / 0.35 / -0.016
BD H3O3 / 1.99 / -0.850
BDH3O1 / 1.73 / -0.601
BD*H3O1 / 0.27 / 0.301
BD1 C5O5 / 1.99 / -1.048 / 1.99 / -1.120 / 1.99 / -1.175
BD2 C5O5 / 1.82 / -0.484 / 1.89 / -0.471
BD1* C5O5 / 0.01 / 0.546 / 0.01 / 0.638
BD2* C5O5 / 0.54 / -0.029 / 0.27 / 0.015
BD H5O5 / 1.99 / -0.860
BD H5O1 / 1.83 / -0.712
BD* H5O1 / 0.19 / 0.403
BD1 C7O7 / 2 / -1.053 / 1.99 / -1.093 / 2 / -1.160
BD2 C7O7 / 1.75 / -0.498 / 1.84 / -0.474
BD1* C7O7 / 0.02 / 0.503 / 0.01 / 0.616
BD2* C7O7 / 0.63 / -0.057 / 0.32 / -0.004
BD H7O7 / 1.99 / -0.868
BD H7O1 / 1.77 / -0.640
BD* H7O1 / 0.23
HOO
BD1 OO1 / 2 / -1.049
BD2 OO1
Lp1 O / 2 / -0.836
Lp2 O / 1.74 / -0.508
Lp3 O
Lp1 O1 / 2 / -0.836
Lp2 O1 / 1.98 / -0.515
Lp3 O1 / 1.25 / -0.496
BD OH / 2 / -0.904

The geometries for all transition states in Cartesians coordinates.

TS3

0 2

C -2.34088400 0.04861500 -0.20723000

C -1.57635800 -1.10275600 0.02328500

C -3.75482700 -0.07030200 -0.17853800

C -4.34348400 -1.30460500 0.05997700

C -2.13840500 -2.34055600 0.26978800

C -1.69154400 1.30739800 -0.45623000

C -3.53183400 -2.42040100 0.27956400

C 3.79905500 -1.55699200 -0.10322100

C 4.64665800 -0.45497900 0.07911500

C 0.45576000 0.10964100 -0.22036100

C 4.12579200 0.82946900 0.15448300

C 2.43673700 -1.35945200 -0.20732800

C 2.75701900 1.03582600 0.04027200

C 1.90083800 -0.05985200 -0.14647500

C -0.22443800 1.28080800 -0.55280900

H -5.02320200 -3.59966900 0.51282000

H -1.52916700 -3.21252400 0.45564400

H -5.42381700 -1.37507200 0.07476500

H 6.50171600 0.03927600 0.29619300

H 5.27061400 -2.76741800 -0.08930600

H 2.35905400 2.03536000 0.10823800

H 1.80049300 -2.22232600 -0.34293500

H 0.29264300 3.24915900 -0.32542300

H 4.78948600 1.67291000 0.30796400

O 5.97418500 -0.75548200 0.17249400

O 4.31037400 -2.81231000 -0.17564600

O -0.21601800 -1.03209100 0.03992400

O -4.06162600 -3.64134300 0.52086900

O 0.40928800 2.32607200 -1.01216000

O -2.32391300 2.37897500 -0.57973500

O -0.64111500 3.27292400 1.45018200

H -1.47834500 3.30453500 0.94424700

O 0.23851400 3.95012600 0.66358200

O -4.53176000 0.99436200 -0.38341500

H -3.94341500 1.77472500 -0.51671300

TS3'

0 2

C -2.85005400 -0.39738200 0.07100600

C -2.00202900 0.68590100 -0.20235400

C -4.24432900 -0.15910900 0.17867000

C -4.74055400 1.12297500 0.01050600

C -2.47863200 1.97551500 -0.37426900

C -2.28756900 -1.70427100 0.23608100

C -3.85291500 2.17105100 -0.26445500

C 3.39165700 0.67014500 -0.57894700

C 4.16661400 -0.51889700 -0.67057500

C 3.54249900 -1.76276400 -0.59522500

C 2.00216700 0.58163000 -0.41000900

C 2.17135900 -1.83336800 -0.42387100

C 1.37946500 -0.66100300 -0.33016000

C -0.07703900 -0.72621500 -0.16970700

C -0.84393900 -1.81614100 0.09904100

H -5.25521600 3.47420200 -0.34798900

H -1.81503300 2.79974700 -0.58921700

H -5.80699500 1.28958500 0.09490200

H 5.70856500 0.52019900 -0.88929300

H 4.25797900 2.19869500 0.34688400

H 1.69757900 -2.80058500 -0.36720000

H 1.43884800 1.50295500 -0.35893900

H -1.12491100 -3.62294700 0.45580100

H 4.14377900 -2.65868100 -0.66957800

O 5.48622500 -0.42383500 -0.83896000

O 4.03192800 1.82715200 -0.67960700

O -0.66383300 0.50042800 -0.31149100

O -4.29778500 3.43726100 -0.43868200

O -0.34898800 -3.06232500 0.27324400

O -2.94631100 -2.73555700 0.49008300

O -5.08843500 -1.16178500 0.44195100

H -4.56886300 -1.99010800 0.53129600

O 4.41566500 2.24648200 1.61534100

O 4.20857600 0.94750100 1.95744400

H 3.28773100 0.91595200 2.26436000

TS4'

0 2

C 3.10462400 -0.54884000 0.04450800

C 2.42352500 0.67670700 -0.00577900

C 4.52114400 -0.53814300 0.12791100

C 5.20151200 0.66758300 0.15274900

C 3.08632800 1.89326300 0.01820100

C 2.35586200 -1.76743700 0.01153900

C 4.47630900 1.86500100 0.09684100

C -2.88277300 1.52208500 -0.12485600

C -3.85161800 0.50446000 -0.35066400

C 0.30470600 -0.42247600 -0.12475700

C -3.42353400 -0.82895800 -0.49354400

C -1.53809600 1.21217600 -0.06267800

C -2.08276300 -1.14193500 -0.41088300

C -1.12328900 -0.12253300 -0.19890900

C 0.90755400 -1.64505600 -0.08054000

H 6.05725300 2.94465500 0.16964100

H 2.55029800 2.82953200 -0.02474100

H 6.28242300 0.66071700 0.21511100

H -5.77449000 0.15496200 0.10529400

H -4.27124500 2.78354100 -0.04343000

H -1.76590400 -2.16577600 -0.52180200

H -0.82743200 2.00752200 0.10428400

H 0.93262400 -3.50461700 -0.04938500

H -4.16749000 -1.59562900 -0.66766100

O -5.10829000 0.88924000 -0.42294500

O -3.30366200 2.79010300 0.02319600

O 1.07251700 0.70905100 -0.08441800

O 5.10370700 3.06384900 0.11710500

O 0.24282200 -2.81730000 -0.10234600

O 2.85446800 -2.91276400 0.05838600

O -7.66893000 -0.62243300 0.32473500

H -8.26208800 -0.43327200 1.06582700

O -6.42670800 -0.56732900 0.89068600

O 5.20870100 -1.68326600 0.18278300

H 4.57211000 -2.43022300 0.15458400

TS5

0 2

C 1.95709900 0.02211400 -0.30177700

C 1.05209700 1.07545000 -0.13146200

C 3.35556600 0.36019100 -0.46617800

C 3.74508600 1.71410000 -0.33473900

C 1.44734000 2.40904500 -0.02181300

C 1.42832100 -1.31824800 -0.33846100

C 2.80546700 2.71189400 -0.11282100

C -4.31525900 0.92436000 0.33691000

C -5.08302600 -0.20860900 0.04020800

C -0.83844100 -0.36722300 -0.19051000

C -4.46458000 -1.39277700 -0.32998100

C -2.93688100 0.85891400 0.25894700

C -3.07704500 -1.46617300 -0.40806400

C -2.30112200 -0.33772200 -0.11250800

C -0.02003900 -1.44592200 -0.34299800

H 4.09711400 4.12690200 -0.06543400

H 0.71335700 3.18854900 0.12358600

H 4.79895800 1.93460600 -0.45106200

H -6.90365000 -0.85530600 -0.04893600

H -5.87215600 1.95433900 0.71373300

H -2.60954000 -2.39238900 -0.69917400

H -2.37063400 1.74803900 0.49442100

H 0.32834100 -3.26539100 -0.46381400

H -5.06521400 -2.26528200 -0.56207200

O -6.43576500 -0.03826700 0.14702100

O -4.91606100 2.08567100 0.70280700

O -0.28118200 0.86835300 -0.06292300

O 3.14344200 4.01750600 0.00671300

O -0.47548700 -2.71245100 -0.43340100

O 2.08917700 -2.37884200 -0.34008100

O 3.79096600 -2.05811100 1.68570700

H 3.12019000 -2.40722600 1.05174300

O 4.92100800 -1.97315700 0.92356700

O 4.24211100 -0.50631800 -0.80416000

H 4.61007400 -1.43828100 0.03649300

TS7

0 2

C 1.83822700 1.09432600 -0.23196900

C 1.24375500 -0.16328100 -0.38325000

C 3.25915900 1.21820100 -0.34715600

C 4.02628700 0.10319100 -0.59765800

C 1.99765200 -1.29977100 -0.63585000

C 0.99454200 2.22958900 0.03415200

C 3.40402200 -1.16056100 -0.74679900

C -3.97968300 -1.45892900 -0.25694400

C -4.99354200 -0.56943700 0.11999900

C -0.94159100 0.72119400 -0.03105500

C -4.68449600 0.74165000 0.44699800

C -2.66854800 -1.02479300 -0.30401000

C -3.36628300 1.18563100 0.40162400

C -2.34504900 0.30309900 0.02456800

C -0.42798700 1.97592900 0.12777900

H 4.48669800 -2.67737500 0.04032900

H 1.53777000 -2.26853800 -0.77138600

H 5.10101900 0.18026500 -0.68134000

H -6.90385800 -0.43564800 0.38830500

H -5.22924200 -2.87655000 -0.49707600

H -3.14241500 2.20741500 0.66020400

H -1.90782400 -1.73157300 -0.60087100

H -0.56069300 3.80972500 0.42799400

H -5.47400900 1.42430000 0.74090400

O -6.25435600 -1.09732500 0.13321700

O -4.27652500 -2.74435100 -0.57712700

O -0.09860700 -0.31922300 -0.28143900

O 4.11947900 -2.22846400 -0.99469300

O -1.18747400 3.06598900 0.37013600

O 1.40945300 3.39887300 0.18342600

O 3.64260800 -2.16374800 1.77614400

H 2.87641000 -2.73292500 1.94850800

O 4.54610400 -2.99663000 1.18113800

O 3.84057300 2.41474700 -0.20904700

H 3.14731600 3.08573000 -0.03218300

1