Comparative Study of Fluorescence Emission of Fisetin, Luteolin and Quercetin Powders and Solutions: Further Evidence of the ESIPT Process
Abstract
:1. Introduction
2. Materials and Methods
2.1. Experimental Setup
2.2. Computational Details
3. Results and Discussion
3.1. Measured FL Spectra of F, L and QDH Powders and Solutions
3.2. Calculation of Wavelengths of Absorption and Emission for F, L and Q Molecules
3.2.1. Different Configurations of Flavonoid Molecules: New System of Notation and Selection of the Configuration with the Lowest Potential Energy
3.2.2. Tautomeric Forms (Enol and Keto) for F, L and Q Molecules
3.2.3. Molecular Orbital Analysis
3.2.4. Relaxed Scan of the S0 and S1 State Energies as a Function of O3-H3 or O5-H5 Distance. Search for the Potential Energy Minima, Corresponding to Enol and Keto Forms
3.2.5. Absorption and Emission Characteristic Wavelengths of L, F and Q Molecules
4. Conclusions
- To better show the difference between the ESIPT processes involving different protons, F and L molecules were chosen, since only one proton can be transferred in each of them. We also analyzed the ESIPT in the Q molecule, where the transfer for two protons is possible.
- To easily distinguish between different configurations of flavonoid molecules, a new system of notation for all possible configurations of the molecules was developed.
- For several possible configurations of F, L and Q molecules, a search for the configuration with lowest potential energy was performed.
- Analysis of the electron populations of frontier molecular orbitals, HOMO and LUMO, performed for the lowest energy configurations of F, L and Q molecules, indicated that for all three molecules, the keto forms are favored in the first excited state.
- Relaxed scans of potential energy as a function of the distance between the corresponding O and H atoms were performed for the F, L, and Q molecules. It was found that in the Q molecule, the H5 proton transfer dominates, which is probably common for all flavonoid molecules that have both H3 and H5 protons.
- For the lowest energy configurations of the F, L and Q molecules, the characteristic wavelengths of absorption and emission were calculated using density functional theory (DFT), and the polarizable continuum model (PCM) was used to consider the influence of the solvents on the absorption and emission energy.
- The FL spectra of F, L and Q powders and their solutions in methanol and propylene glycol were measured. The calculation results for vacuum agreed well with the experimental FL spectra of powders and solutions with high concentration; and the calculation results for solutions, with those measured for solutions with low concentrations.
- The fact that the differences in the spectral positions of the maxima of the measured FL spectra of F and L powders correspond to the calculated emission wavelengths confirms the effectiveness of the ESIPT model used for the calculations and the accuracy of its predictions.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Appendix A
ES0 (a.u) | ES1 (a.u) | ES1 − ES0 (eV) | λab (nm) | fab | μS0 (D) | ES1* (a.u) | ES0* (a.u) | ES1* − ES0* (eV) | λem (nm) | fem | μS1 (D) | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
S0 Opt | S0 Opt | S1 Opt | S1 Opt | |||||||||
F0000A enol | −1028.61834 | −1028.47404 | 3.9267 | 315.75 | 0.6253 | 5.2699 | −1028.48288 | −1028.60976 | 3.4524 | 359.13 | 0.6719 | 5.6120 |
F0000A keto | −1028.59333 | −1028.49146 | 2.7720 | 447.28 | 0.5319 | 7.5186 | −1028.49710 | −1028.58840 | 2.4843 | 499.08 | 0.5110 | 7.1521 |
F0000S enol | −1028.61943 | −1028.47404 | 3.9563 | 313.38 | 0.6245 | 2.0566 | −1028.48303 | −1028.61063 | 3.4722 | 357.08 | 0.6709 | 1.9217 |
F0000S keto | −1028.59616 | −1028.49317 | 2.8025 | 442.41 | 0.5292 | 4.8021 | −1028.49880 | −1028.59120 | 2.5145 | 493.08 | 0.5154 | 4.3103 |
F0011A enol | −1028.61815 | −1028.47136 | 3.9943 | 310.41 | 0.5901 | 1.0451 | −1028.48044 | −1028.60909 | 3.5006 | 354.19 | 0.6381 | 1.4394 |
F0011A keto | −1028.59368 | −1028.49008 | 2.8189 | 439.84 | 0.5104 | 2.6407 | −1028.49604 | −1028.58849 | 2.5159 | 492.81 | 0.4889 | 2.3030 |
F0011S enol | −1028.61752 | −1028.47003 | 4.0133 | 308.94 | 0.5136 | 5.1418 | −1028.47969 | −1028.60824 | 3.4979 | 354.46 | 0.6264 | 5.6228 |
F0011S keto | −1028.59204 | −1028.48909 | 2.8014 | 442.58 | 0.4885 | 6.7982 | −1028.49523 | −1028.58680 | 2.4918 | 497.58 | 0.4724 | 6.5741 |
F0100S enol | −1028.61944 | −1028.47277 | 3.9911 | 310.65 | 0.6232 | 1.9192 | −1028.48200 | −1028.61049 | 3.4962 | 354.63 | 0.6733 | 2.3551 |
F0100S keto | −1028.59672 | −1028.49262 | 2.8325 | 437.72 | 0.5277 | 3.6813 | −1028.49846 | −1028.59158 | 2.5341 | 489.28 | 0.5148 | 3.1464 |
F0100A enol | −1028.61799 | −1028.47226 | 3.9656 | 312.65 | 0.6195 | 5.7780 | −1028.48149 | −1028.60922 | 3.4756 | 356.73 | 0.6750 | 6.2600 |
F0100A keto | −1028.59346 | −1028.49050 | 2.8017 | 442.53 | 0.5306 | 7.4229 | −1028.49633 | −1028.58836 | 2.5041 | 495.12 | 0.5114 | 7.0050 |
F0111A enol | −1028.61839 | −1028.47031 | 4.0296 | 307.69 | 0.5893 | 3.6960 | −1028.47962 | −1028.60918 | 3.5256 | 351.67 | 0.6422 | 4.0375 |
F0111A keto | −1028.59443 | −1028.48972 | 2.8493 | 435.14 | 0.5096 | 3.0845 | −1028.49586 | −1028.58908 | 2.5368 | 488.75 | 0.4896 | 2.8868 |
F0111S enol | −1028.61745 | −1028.46848 | 4.0535 | 305.87 | 0.5692 | 6.7527 | −1028.47848 | −1028.60794 | 3.5228 | 351.95 | 0.6293 | 7.2079 |
F0111S keto | −1028.59245 | −1028.48836 | 2.8327 | 437.70 | 0.4871 | 7.5223 | −1028.49470 | −1028.58702 | 2.5122 | 493.54 | 0.4716 | 7.2479 |
F0001A enol | −1028.61146 | −1028.46703 | 3.9301 | 315.47 | 0.6180 | 2.6925 | −1028.47576 | −1028.60298 | 3.4618 | 358.16 | 0.6692 | 2.8792 |
F0001A keto | −1028.58676 | −1028.48446 | 2.7836 | 445.41 | 0.5344 | 5.2281 | −1028.49013 | −1028.58186 | 2.4960 | 496.73 | 0.5131 | 4.8196 |
F0001S enol | −1028.61198 | −1028.46658 | 3.9564 | 313.38 | 0.6118 | 4.1028 | −1028.47554 | −1028.60322 | 3.4744 | 356.86 | 0.6616 | 4.3161 |
F0001S keto | −1028.58819 | −1028.48541 | 2.7968 | 443.31 | 0.5191 | 6.5756 | −1028.49112 | −1028.58320 | 2.5056 | 494.82 | 0.5062 | 6.1663 |
F0101A enol | −1028.61125 | −1028.46539 | 3.9689 | 312.39 | 0.6129 | 3.0937 | −1028.47451 | −1028.60259 | 3.4854 | 355.72 | 0.6725 | 3.5565 |
F0101A keto | −1028.58703 | −1028.48364 | 2.8133 | 440.72 | 0.5333 | 4.6620 | −1028.48950 | −1028.58198 | 2.5164 | 492.70 | 0.5139 | 4.1789 |
F0101S enol | −1028.61187 | −1028.46512 | 3.9933 | 310.48 | 0.6083 | 4.6401 | −1028.47438 | −1028.60295 | 3.4987 | 354.37 | 0.6635 | 5.0297 |
F0101S keto | −1028.58864 | −1028.48474 | 2.8272 | 438.54 | 0.5167 | 6.3011 | −1028.49067 | −1028.58347 | 2.5253 | 490.98 | 0.5052 | 5.8538 |
ES0 (a.u) | ES1 (a.u) | ES1 − ES0 (eV) | λab (nm) | fab | μS0 (D) | ES1* (a.u) | ES0* (a.u) | ES1* − ES0* (eV) | λem (nm) | fem | μS1 (D) | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
S0 Opt | S0 Opt | S1 Opt | S1 Opt | |||||||||
L0000A enol | −1028.62994 | −1028.47479 | 4.2217 | 293.68 | 0.4830 | 4.7157 | - | - | - | - | - | - |
L0000A keto | - | - | - | - | - | - | −1028.51678 | −1028.59237 | 2.0570 | 602.7 | 0.0541 | 7.0613 |
L0000S enol | −1028.62961 | −1028.47377 | 4.2405 | 292.38 | 0.4699 | 2.3281 | - | - | - | - | - | - |
L0000S keto | - | - | - | - | - | - | −1028.51661 | −1028.59140 | 2.0351 | 609.2 | 0.0484 | 7.3474 |
L0011A enol | −1028.62926 | −1028.47299 | 4.2522 | 291.58 | 0.3734 | 4.7458 | - | - | - | - | - | - |
L0011A keto | - | - | - | - | - | - | −1028.51660 | −1028.59104 | 2.0256 | 612.0 | 0.3734 | 9.6384 |
L0011S enol | −1028.62931 | −1028.47206 | 4.2790 | 289.76 | 0.3408 | 6.3643 | - | - | - | - | - | - |
L0011S keto | - | - | - | - | - | - | −1028.51635 | −1028.59135 | 2.0407 | 607.5 | 0.0479 | 9.4537 |
L0100S enol | −1028.62875 | −1028.47180 | 4.2706 | 290.32 | 0.4091 | 5.0034 | - | - | - | - | - | - |
L0100S keto | - | - | - | - | - | - | −1028.51536 | −1028.58785 | 1.9727 | 628.5 | 0.0360 | 9.8519 |
L0100A enol | −1028.62870 | −1028.47239 | 4.2534 | 291.50 | 0.3954 | 6.9163 | - | - | - | - | - | - |
L0100A keto | - | - | - | - | - | - | −1028.51520 | −1028.58851 | 1.9948 | 621.5 | 0.0406 | 9.9094 |
L0111A enol | −1028.62853 | −1028.47150 | 4.2730 | 290.16 | 0.0011 | 7.4161 | - | - | - | - | - | - |
L0111A keto | - | - | - | - | - | - | −1028.51556 | −1028.58772 | 1.9636 | 631.4 | 0.0362 | 12.1958 |
L0111S enol | −1028.62830 | −1028.47079 | 4.2859 | 289.28 | 0.0527 | 8.9325 | - | - | - | - | - | - |
L0111S keto | - | - | - | - | - | - | −1028.51500 | −1028.58776 | 1.9798 | 626.2 | 0.0360 | 12.3102 |
L0001A enol | −1028.62277 | −1028.46780 | 4.2169 | 294.02 | 0.4742 | 2.7508 | - | - | - | - | - | - |
L0001A keto | - | - | - | - | - | - | −1028.50962 | −1028.58504 | 2.0522 | 604.1 | 0.0532 | 7.0977 |
L0001S enol | −1028.62256 | −1028.46659 | 4.2443 | 292.12 | 0.4753 | 3.7317 | - | - | - | - | - | - |
L0001S keto | - | - | - | - | - | - | −1028.50938 | −1028.58440 | 2.0415 | 607.3 | 0.0364 | 7.0608 |
L0101A enol | −1028.62165 | −1028.46553 | 4.2484 | 291.84 | 0.3954 | 5.4552 | - | - | - | - | - | - |
L0101A keto | - | - | - | - | - | - | −1028.50814 | −1028.58125 | 1.9895 | 623.1 | 0.0399 | 9.7710 |
L0101S enol | −1028.62160 | −1028.46454 | 4.2738 | 290.11 | 0.3947 | 6.2317 | - | - | - | - | - | - |
L0101S keto | - | - | - | - | - | - | −1028.50806 | −1028.58073 | 1.9775 | 626.9 | 0.0364 | 9.8860 |
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ES0 (a.u) | ES1 (a.u) | ES1 − ES0 (eV) | λab (nm) | fab | μS0 (D) | ES1* (a.u) | ES0* (a.u) | ES1* − ES0* (eV) | λem (nm) | fem | μS1 (D) | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
S0 Opt | S0 Opt | S1 Opt | S1 Opt | |||||||||
Fisetin | ||||||||||||
F0100S enol | −1028.61944 | −1028.47277 | 3.9911 | 310.65 | 0.6232 | 1.92 | −1028.48200 | −1028.61049 | 3.4962 | 354.63 | 0.6733 | 2.35 |
F0100S keto | −1028.59672 | −1028.49262 | 2.8325 | 437.72 | 0.5277 | 3.68 | −1028.49846 | −1028.59158 | 2.5341 | 489.28 | 0.5148 | 3.15 |
F0000S enol | −1028.61943 | −1028.47404 | 3.9563 | 313.38 | 0.6245 | 2.06 | −1028.48303 | −1028.61063 | 3.4722 | 357.08 | 0.6709 | 1.92 |
F0000S keto | −1028.59616 | −1028.49317 | 2.8025 | 442.41 | 0.5292 | 4.80 | −1028.49880 | −1028.59120 | 2.5145 | 493.08 | 0.5154 | 4.31 |
Luteolin | ||||||||||||
L0000A enol | −1028.62994 | −1028.47479 | 4.2217 | 293.68 | 0.4830 | 4.72 | - | - | - | - | - | - |
L0000A keto | - | - | - | - | - | - | −1028.51678 | −1028.59237 | 2.0570 | 602.75 | 0.0541 | 7.06 |
L0101A enol | −1028.62165 | −1028.46553 | 4.2484 | 291.84 | 0.3954 | 5.45 | - | - | - | - | - | - |
L0101A keto | - | - | - | - | - | - | −1028.50814 | −1028.58125 | 1.9895 | 623.19 | 0.0399 | 9.77 |
Quercetin | ||||||||||||
Q00001A enol | −1103.82539 | −1103.68525 | 3.8134 | 325.17 | 0.6137 | 1.24 | −1103.69358 | −1103.81652 | 3.3470 | 370.48 | 0.6121 | 1.77 |
Q00001A keto O3 | - | - | - | - | - | - | −1103.69792 | −1103.78879 | 2.4728 | 501.46 | 0.5086 | 3.32 |
Q00001A keto O5 | - | - | - | - | - | - | −1103.70799 | −1103.78516 | 2.0999 | 590.50 | 0.1009 | 5.12 |
ES0 (a.u) | ES1 (a.u) | ES1 − ES0 (eV) | λab (nm) | fab | μS0 (D) | ES1* (a.u) | ES0* (a.u) | ES1* − ES0* (eV) | λem (nm) | fem | μS1 (D) | |
---|---|---|---|---|---|---|---|---|---|---|---|---|
S0 Opt | S0 Opt | S1 Opt | S1 Opt | |||||||||
METHANOL | ||||||||||||
Fisetin | ||||||||||||
F0100S enol | −1028.63734 | −1028.49589 | 3.8492 | 322.11 | 0.7242 | 3.15 | −1028.50771 | −1028.62438 | 3.1745 | 390.56 | 1.0327 | 4.12 |
F0100S keto | −1028.61643 | −1028.50454 | 3.0445 | 407.24 | 0.6319 | 5.55 | −1028.51289 | −1028.60894 | 2.6135 | 474.40 | 0.8204 | 4.62 |
F0000S enol | −1028.63717 | −1028.49566 | 3.8508 | 321.97 | 0.724 | 2.76 | −1028.50759 | −1028.62445 | 3.1800 | 389.89 | 1.0336 | 2.01 |
F0000S keto | −1028.61600 | −1028.50446 | 3.0351 | 408.50 | 0.6325 | 6.99 | −1028.51285 | −1028.60862 | 2.6062 | 475.73 | 0.8202 | 5.97 |
Luteolin | ||||||||||||
L0000A enol | −1028.64902 | −1028.50110 | 4.0252 | 308.02 | 0.0003 | 6.67 | - | - | - | - | - | - |
L0000A keto | - | - | - | - | - | - | −1028.5402 | −1028.624 | 2.2788 | 544.08 | 0.3191 | 8.77 |
L0101A enol | −1028.64580 | −1028.49820 | 4.0164 | 308.70 | 0.6991 | 7.51 | - | - | - | - | - | - |
L0101A keto | - | - | - | - | - | - | −1028.5356 | −1028.6142 | 2.1388 | 579.69 | 0.3000 | 12.03 |
Quercetin | ||||||||||||
Q00001A enol | −1103.84661 | −1103.70812 | 3.7684 | 329.02 | 0.7071 | 2.03 | −1103.71784 | −1103.83612 | 3.2185 | 385.23 | 1.0064 | 3.11 |
Q00001A keto O3 | −1103.81936 | −1103.70920 | 2.9975 | 413.63 | 0.6337 | 5.75 | −1103.71748 | −1103.81215 | 2.5761 | 481.29 | 0.7960 | 5.05 |
Q00001A keto O5 | - | - | - | - | - | - | −1103.73257 | −1103.81851 | 2.3384 | 530.22 | 0.4758 | 5.75 |
PROPYLENE GLYCOL | ||||||||||||
Fisetin | ||||||||||||
F0100S enol | −1028.63716 | −1028.50829 | 3.5069 | 353.54 | 0.7478 | 3.14 | −1028.50746 | −1028.62550 | 3.2121 | 385.99 | 1.0294 | 4.11 |
F0100S keto | −1028.61623 | −1028.50724 | 2.9657 | 418.06 | 0.651 | 5.53 | −1028.51275 | −1028.60949 | 2.632 | 471.07 | 0.8177 | 4.61 |
F0000S enol | −1028.63699 | −1028.50793 | 3.5120 | 353.03 | 0.7475 | 2.75 | −1028.50734 | −1028.62556 | 3.217 | 385.41 | 1.0302 | 2.01 |
F0000S keto | −1028.61580 | −1028.50714 | 2.9568 | 419.32 | 0.6514 | 6.97 | −1028.51271 | −1028.60915 | 2.6244 | 472.44 | 0.8176 | 5.95 |
Luteolin | ||||||||||||
L0000A enol | −1028.64884 | −1028.51396 | 3.6700 | 337.83 | 0.7272 | 6.65 | - | - | - | - | - | - |
L0000A keto | - | - | - | - | - | - | −1028.54001 | −1028.62368 | 2.2767 | 544.58 | 0.3142 | 8.76 |
L0101A enol | −1028.64502 | −1028.51140 | 3.6360 | 341.00 | 0.7481 | 7.51 | −1028.51463 | −1028.63366 | 3.2389 | 382.80 | 1.0091 | 10.28 |
L0101A keto | - | - | - | - | - | - | −1028.53530 | −1028.61932 | 2.2863 | 542.30 | 0.0688 | 12.03 |
Quercetin | ||||||||||||
Q00001A enol | −1103.84650 | −1103.71263 | 3.6426 | 340.38 | 0.7296 | 2.0305 | −1103.71760 | −1103.83593 | 3.2198 | 385.07 | 1.0030 | 3.10 |
Q00001A keto O3 | −1103.81910 | −1103.71084 | 2.9459 | 420.88 | 0.6532 | 5.7260 | −1103.71727 | −1103.81243 | 2.5892 | 478.85 | 0.7938 | 5.02 |
Q00001A keto O5 | - | - | - | - | - | - | −1103.73235 | −1103.81821 | 2.3365 | 530.64 | 0.4704 | 5.74 |
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Deriabina, A.; Prutskij, T.; Morales Ochoa, H.D.; Delgado Curiel, E.; Palacios Corte, V. Comparative Study of Fluorescence Emission of Fisetin, Luteolin and Quercetin Powders and Solutions: Further Evidence of the ESIPT Process. Biosensors 2024, 14, 413. https://doi.org/10.3390/bios14090413
Deriabina A, Prutskij T, Morales Ochoa HD, Delgado Curiel E, Palacios Corte V. Comparative Study of Fluorescence Emission of Fisetin, Luteolin and Quercetin Powders and Solutions: Further Evidence of the ESIPT Process. Biosensors. 2024; 14(9):413. https://doi.org/10.3390/bios14090413
Chicago/Turabian StyleDeriabina, Alexandra, Tatiana Prutskij, Hector Daniel Morales Ochoa, Esteban Delgado Curiel, and Veranda Palacios Corte. 2024. "Comparative Study of Fluorescence Emission of Fisetin, Luteolin and Quercetin Powders and Solutions: Further Evidence of the ESIPT Process" Biosensors 14, no. 9: 413. https://doi.org/10.3390/bios14090413