Using the time-dependent density functional theory at the X3LYP/6-31++G(d,p)/SMD level, the vibronic absorption spectrum of the thiazine dye Azure A (AA) in an aqueous solution was calculated. This study is a logical continuation of the previously published work [L.O. Kostjukova et al. Int. J. Quantum Chem. (2021) e26662], in which the water environment of AA was set implicitly in the continuum approximation using the SMD model. In the present work, we used a combined setting of the aqueous environment: three water molecules were explicitly described, forming strong hydrogen bonds with a dye molecule; the rest of the aqueous medium was set implicitly, also by the SMD method. This approach was used to elucidate the effect of site-specific interactions with a solvent on both the ground and excited states of the dye molecule and on the transition between them (solvatochromism). The reverse effect of excitation of the AA molecule on its nearest hydration shell was also of interest. Calculations have shown that there is an increase in these H-bonds upon photoexcitation of the dye. In this case, the maximum of the vibronic absorption spectrum AA undergoes a bathochromic shift by 15 nm. These results were analyzed from the point of view of the solvatochromic theory. Frontier molecular orbitals, between which an electronic transition occurs, and maps of the distribution of electron density and electrostatic potential of the ground and excited states of the "AA+3H2O" system have been built. The photoinduced polarization of the dye molecule was analyzed.
azure A, aqueous solution, excited state, vibronic absorption spectrum, solvatochromism, hydrogen bond, time-dependent density functional theory
1. Moreira L.M., Lyon J.P., Tursi S.M.S., Trajano I., Felipe M.P., Costa M.S., Rodrigues M.R., Codognoto L., de Oliveira H.P.M. Azure dyes as new photosensitizer prototypes to application in photodynamic therapy against Candida spp. Spectroscopy, 2010, vol. 24, pp. 621-628.
2. Francisco C.M.L., Goncalves J.M.L.A., Brum B.S., Santos T.P.C., Lino-dos-Santos-Franco A., Silva D.F.T., Pavani C. The photodynamic e ciency of phenothiazinium dyes is aggregation dependent. New J. Chem., 2017, vol. 41, pp. 14438-14443.
3. Marshall P.N. The composition of stains produced by the oxidation of Methylene Blue. Histochem. J., 1976, vol. 8, pp. 431-442.
4. Li N., Yuan R., Chai Y., Chen S., An H., Li W. New Antibody Immobilization Strategy Based on Gold Nanoparticles and Azure I/Multi-Walled Carbon Nanotube Composite Membranes for an Amperometric Enzyme Immunosensor. J. Phys. Chem. C, 2007, vol. 111, pp. 8443-8450.
5. Gomez-Anquela C., Garcia-Mendiola T., Abad J.M., Pita M., Pariente F., Lorenzo E. Scaffold electrodes based on thioctic acid-capped gold nanoparticles coordinated Alcohol Dehydrogenase and Azure A lms for high performance biosensor. Bioelectrochemistry, 2015, vol. 106, pp. 335-342.
6. Orak I., Toprak M., Turut A. Illumination impact on the electrical characterizations of an Al/Azure A/p-Si heterojunction. Phys. Scr., 2014, vol. 89, p. 115810.
7. Jana A.K., Bhowmik B.B. Enhancement in power output of solar cells consisting of mixed dyes. J. Photochem. Photobiol. A, 1999, vol. 122, pp. 53-56.
8. You Y., Gao S., Xu B., Li G., Cao R. Self-assembly of polyoxometalate-azure A multilayer lms and their photocatalytic properties for degradation of methyl orange under visible light irradiation. J. Colloid Interface Sci., 2010, vol. 350, pp. 562-567.
9. Jiao Q., Liu Q. A mathematical model for interaction of spectroscopic probe with polysaccharides - the binding interaction between azure A and heparin. Spectrosc. Lett., 1998, vol. 31, pp. 1353-1365.
10. Thuy L.P., Nyhan W.L. A new quantitative assay for glycosaminoglycans. Clin. Chim. Acta, 1992, vol. 212, pp. 17-26.
11. Templeton D.M. General occurrence of isosbestic points in the metachromatic dye complexes of sulphated glycosaminoglycans.Int. J. Biol. Macromol., 1988, vol. 10, pp. 131-136.
12. Young M.D., Phillips G.O., Balazs E.A. Polyanions and their complexes. I. Thermodynamic studies of heparin-azure A complexes in solution. Biochim. Biophys. Acta, 1967, vol. 141, pp. 374-381.
13. Liu Q., Jiao Q.C., Liu Z.L., Chen H. The interaction of polysaccharides with a spectroscopic probe: the anion effect on the binding site of heparin. Spectrosc. Lett., 2001, vol. 34, pp. 25-34.
14. Zvyagin A.I., Smirnov M.S., Ovchinnikov O.V. Enhancement of nonlinear optical response of Methylene blue and Azure A during association with colloidal CdS quantum dots. Optik, 2020, vol. 218, p. 165122.
15. Rajan D., Ilanchelian M. Exploring the interaction of Azure dyes with t-RNA by hybrid spectroscopic and computational approaches and its applications toward human lung cancer cell line.Int. J. Biol. Macromol., 2018, vol. 113, pp. 1052-1061.
16. Paul P., Mati S.S., Bhattacharya S.C., Kumar G.S. Exploring the interaction of phenothiazinium dyes methylene blue, new methylene blue, azure A and azure B with tRNAPhe: spectroscopic, thermodynamic, voltammetric and molecular modeling approach. Phys. Chem. Chem. Phys., 2017, vol. 19, pp. 6636-6653.
17. Paul P., Kumar G.S. Photophysical and calorimetric investigation on the structural reorganization of poly(A) by phenothiazinium dyes azure A and azure B. Photochem. Photobiol. Sci., 2014, vol. 13, pp. 1192-1202.
18. Khan A.Y., Kumar G.S. Spectroscopic studies on the binding interaction of phenothiazinium dyes, azure A and azure B to double stranded RNA polynucleotides. Spectrochim. Acta A, 2016, vol. 152, pp. 417-425.
19. Klein F., Szirmai J.A. Quantitative studies on the interaction of azure A with deoxyribonucleic acid and deoxyribonucleoprotein. Biochim. Biophys. Acta, 1963, vol. 72, pp. 48-61.
20. Paul P., Kumar G.S. Spectroscopic studies on the binding interaction of phenothiazinium dyes toluidine blue O, azure A and azure B to DNA. Spectrochim. Acta A, 2013, vol. 107, pp. 303-310.
21. Paul P., Kumar G.S. Thermodynamics of the DNA binding of phenothiazinium dyes toluidine blue O, azure A and azure B. J. Chem. Thermodynamics, 2013, vol. 64, pp. 50-57.
22. Das S., Islam M., Jana G.C., Patra A., Jha P.K., Hossain M. Molecular binding of toxic phenothiazinium derivatives, azures to bovine serum albumin: A comparative spectroscopic, calorimetric, and in silico study. J. Mol. Recogn., 2017, vol. 30, e2609.
23. Czimerova A., Ceklovsky A., Bujdak J.Interaction of montmorillonite with phenothiazine dyes and pyronin in aqueous dispersions: A visible spectroscopy study. Cent. Eur. J. Chem., 2009, vol. 7, pp. 343-353.
24. Maafi M., Laassis B., Aaron J.-J., Photochemically Induced Fluorescence Investigation of β-Cyclodextrin: Azure A Inclusion Complex and Determination of Analytical Parameters. J. Incl. Phenom. Mol. Recogn. Chem., 1995, vol. 22, pp. 235-247.
25. Bhowmik B.B., Mukhopadhyay M. Spectral and photophysical studies of thiazine dyes in Triton X-100. Colloid Polym. Sci., 1988, vol. 266, pp. 672-676.
26. den Tonkelaar W.A.M., Bergshoeff G. Use of azure A instead of methylene blue for determination of anionic detergents in drinking and surface waters. Water Res., 1969, vol. 3, pp. 31-38.
27. Narband N., Uppal M., Dunnill C.W., Hyett G., Wilson M., Parkin I.P. The interaction between gold nanoparticles and cationic and anionic dyes: enhanced UV-visible absorption. Phys. Chem. Chem. Phys., 2009, vol. 11, pp. 10513-10518.
28. Yu M.-E., Cheong B.-S., Cho H.-G. SERS Spectroscopy and DFT Studies of Thionine and its Derivatives Adsorbed on Silver Colloids: Which N Atom is Used for Coordination of a Phenothiazine-Based Natural Dye to Electron-De cient Metal Surface? Bull. Korean Chem. Soc., 2017, vol. 38, pp. 928-934.
29. Ghanadzadeh Gilani A., Ghorbanpour T., Salmanpour M. Additive effect on the dimer formation of thiazine dyes. J. Mol Liquids, 2013, vol. 177, pp. 273-282.
30. Ghanadzadeh Gilani A., Dezhampanah H., Poormohammadi-Ahandani Z. A comparative spectroscopic study of thiourea effect on the photophysical and molecular association behavior of various phenothiazine dyes. Spectrochim. Acta A, 2017, vol. 179, pp. 132-143.
31. Chakraborty A., Ali M., Saha S.K. Molecular interaction of organic dyes in bulk and con ned media. Spectrochim. Acta A, 2010, vol. 75, pp. 1577-1583.
32. Kalyoncu E., Alanyalioglu M. Chronoamperometric and morphological investigation of nucleation and growth mechanism of poly(azure A) thin films. J. Electroanal. Chem., 2011, vol. 660, pp. 133-139.
33. Marban G., Vu T.T., Valdes-Solis T. A simple visible spectrum deconvolution technique to prevent the artefact induced by the hypsochromic shift from masking the concentration of methylene blue in photodegradation experiments. Appl. Catalysis A, 2011, vol. 402, pp. 218-223.
34. Aarthi T., Narahari P., Madras G. Photocatalytic degradation of Azure and Sudan dyes using nano TiO2. J. Hazard. Mater., 2007, vol. 149, pp. 725-734.
35. Mills A., Hazafy D., Parkinson J., Tuttle T., Hutchings M.G. Effect of alkali on methylene blue (C.I. Basic Blue 9) and other thiazine dyes. Dyes Pigments, 2011, vol. 88, pp. 149-155.
36. Wang X.-L., Sun R., Zhu W.-J., Sha X.-L., Ge J.-F. Reversible Absorption and Emission Responses of Nile Blue and Azure A Derivatives in Extreme Acidic and Basic Conditions. J. Fluoresc., 2017, vol. 27, pp. 819-827.
37. Ghanadzadeh Gilani A., Salmanpour M., Ghorbanpour T. Solvatochromism, dichroism and excited state dipole moment of azure A and methylene blue. J. Mol. Liquids, 2013, vol. 179, pp. 118-123.
38. Bertolotti S.G., Previtali C.M. The excited states quenching of phenothiazine dyes by p-benzoquinones in polar solvents. Dyes Pigments, 1999, vol. 41, pp. 55-61.
39. Havelcova M., Kubat P., Nemcova I. Photophysical properties of thiazine dyes in aqueous solution and in micelles. Dyes Pigments, 2000, vol. 44, pp. 49-54.
40. Parkanyi C., Boniface C. A quantitative study of the effect of solvent on the electronic absorptlon and fluorescence spectra of substituted phenothiazines: evaluation of their ground and excited singlet-state dipole moments. Spectrochim. Acta, 1993, vol. 49A, pp. 1715-1725.
41. Agrisuelas J., Gimenez-Romero D., Garcia-Jareno J.J., Vicente F. Vis/NIR spectroelectrochemical analysis of poly-(Azure A) on ITO electrode. Electrochem.Commun., 2006, vol. 8, pp. 549-553.
42. Snehalatha M., Hubert Joe I., Ravikumar C., Jayakumar V.S. Azure A chloride: computational and spectroscopic study. J. Raman Spectrosc., 2009, vol. 40, pp. 176-182.
43. Shahab S., Filippovich L., Kumar R., Darroudi M., Borzehandani M.Y., Gomar M., Hajikolaee F.H. Photochromic properties of the molecule Azure A chloride in polyvinyl alcohol matrix. J. Mol. Structure, 2015, vol. 1101, pp. 109-115.
44. Jacquemin D., Bremond E., Planchat A., Ciofini I., Adamo C. TD-DFT vibronic couplings in anthraquinones: from basis set and functional benchmarks to applications for industrial dyes. J. Chem. Theory Comput., 2011, vol. 7, pp. 1882-1892.
45. Adamo C., Jacquemin D. The calculations of excited-state properties with Time-Dependent Density Functional Theory. Chem. Soc. Rev., 2013, vol. 42, pp. 845-856.
46. Jacquemin D., Bremond E., Ciofini I., Adamo C. Impact of Vibronic Couplings on Perceived Colors: Two Anthraquinones as a Working Example. J. Phys. Chem. Lett., 2012, vol. 3, pp. 468-471.
47. Lopez G.V., Chang C.-H., Johnson P.M., Hall G.E., Sears T.J., Markiewicz B., Milan M., Teslja A. What Is the Best DFT Functional for Vibronic Calculations? A Comparison of the Calculated Vibronic Structure of the S1-S0 Transition of Phenylacetylene with Cavity Ringdown Band Intensities. J. Phys. Chem. A, 2012, vol. 116, pp. 6750-6578.
48. Kostjukova L.O., Leontieva S.V., Kostjukov V.V. TD-DFT absorption spectrum of Azure A in aqueous solution: vibronic transitions and electronic properties.Int. J. Quantum Chem., 2021, e26662.
49. Marenich A.V., Cramer C.J., Truhlar D.G., Universal solvation model based on solute electron density and a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B, 2009, vol. 113, pp. 6378-6396.
50. Fleming S., Mills A., Tuttle T. Predicting the UV-vis spectra of oxazine dyes. Beilstein J. Org. Chem., 2011, vol. 7, pp. 432-441.
51. Xu X., Goddard W.A. The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties. Proc. Natl. Acad. Sci. USA, 2004, vol. 101, pp. 2673-2677.
52. Zhao G.J., Han K.L. Effects of hydrogen bonding on tuning photochemistry: Concerted hydrogen-bond strengthening and weakening. ChemPhysChem, 2008, vol. 9, pp. 1842-1846.
53. Qin Z., Lib X., Zhou M. A Theoretical Study on Hydrogen-Bonded Complex of Proflavine Cation and Water: The Site-dependent Feature of Hydrogen Bond Strengthening and Weakening. J. Chin. Chem. Soc., 2014, vol. 61, pp. 1199-1204.
54. Condon E.U. Nuclear motions associated with electron transitions in diatomic molecules. Phys. Rev., 1928, vol. 32, pp. 858-872.
55. Baiardi A., Bloino J., Barone V. General Time Dependent Approach to Vibronic Spectroscopy Including Franck-Condon, Herzberg-Teller, and Duschinsky E ects. J. Chem. Theory Comput., 2013, vol. 9, pp. 4097-4115.
56. Herzberg G., Teller E. Schwingungsstruktur der Elektronenubergange bei mehratomigen Molekulen. Z. Phys. Chem., Abt. B, 1933, vol. 21, pp. 410-446.
57. Santoro F., Lami A., Improta R., Bloino J., Barone V. Effective method for the computation of optical spectra of large molecules at finite temperature including the Duschinsky and Herzberg-Teller effect: The Qx band of porphyrin as a case study. J. Chem. Phys., 2008, vol. 128, p. 224311.
58. Duschinsky F. The importance of the electron spectrum in multi atomic molecules. Concerning the Franck-Condon principle. Acta Physicochim., URSS, 1937, vol. 7, p. 551.
