Journal of the Serbian Chemical Society 2024 Volume 89, Issue 2, Pages: 195-213
https://doi.org/10.2298/JSC230512087H
Full text (
2974 KB)
The non-ideality in binary aqueous systems contributed to the different abilities of solvent entities incorporated in the solvation shell of methylene blue
Hemdan Sokaina S. 
(Department of Chemistry, Faculty of Science and Art El Marj, Benghazi University, El Marj, Libya), [email protected]
Alnajjar Radwan (Department of Chemistry, Faculty of Science, Benghazi University, Benghazi, Libya + PharmD, Faculty of Pharmacy, Libyan International Medical University, Benghazi, Libya)
The solvatochromic properties of methylene blue (MB) were investigated in neat water, methanol, ethanol, propanol, dioxane and their corresponding aqueous mixtures. The correlation of the empirical solvent polarity scale (ET) values of MB with solvent composition was analysed using the solvent exchange model of Bosch and Roses to explain the preferential solvation of the probe thiazine dye in the binary mixed solvents. Non-linear solvatochromism of MB was observed in aqueous mixtures of methanol, ethanol, propanol and dioxane. The influence of the composition of the solvating shell in preferential solvation of the solute dye was investigated in terms of both solvent–solvent and solute–solvent interactions, and the local mole fraction of each solvent composition in the cybotactic region of the probe was also calculated. Effective mole fraction variation can provide important physicochemical insights into the microscopic and molecular interactions between MB species and solvent components. The results showed that the MB solvation shell was thoroughly saturated with the solvent complex S12 for dioxane more than ethanol and propanol mixtures, and opposite trends for methanol mixtures, whereas the solvent complex S12 could not incorporate into the MB solvation shell. Data from the binary systems were analysed with KAT parameters using a dual model of basicity and polarity. The results showed that the polarity was better suited for spectral shift in aqueous methanol and ethanol solutions, while the basicity was better for aqueous propanol and dioxane solutions.
Keywords: thiazine dye, preferential solvation, aqueous-solvent aggregates, KAT scale
Show references
C. Reichardt, T. Welton, Solvents and Solvent Effects in Organic Chemistry. Wiley-VCH, Weinheim, 2011 (http://dx.doi.org/10.1002/9783527632220)
A. M. Al-Jebaly, S. S. Hemdan, F. K. Ali, J. Sci. Hum. Studies 39 (2017) 1 (http://dx.doi.org/10.37376/1571-000-039-003)
N. Elmsheeti, S. Hemdan, A. Sammour, R. Alnajjar, Chem. Data Collect. 28 (2020) 100465 (https://doi.org/10.1016/j.cdc.2020.100465)
M. S. Masoud, R. I. M. Elsamra, S. S. Hemdan, J. Serb. Chem. Soc. 82 (2017) 856 (http://dx.doi.org/10.2298/JSC170204032M)
A. M. Al-Jebaly, S. S. Hemdan, F. K. Ali, J. Natur. Sci., Life Appl. Sci. 1 (2017) 33 (http://dx.doi.org/10.26389/AJSRP.A071217)
S. Hemdan, A. Al Jebaly, F. Ali, Acad. J. Res. Sci. Pub. 2 (2021) 28 (http://dx.doi.org/10.52132/Ajrsp.e.2021.242)
J. Catalán, C. Dıaz, F. Garcıa-Blanco, J. Org. Chem. 65 (2000) 9226 (http://dx.doi.org/10.1021/jo001008u)
D. C. Da Silva, I. Ricken, M. A. D. R. Silva, V. G. Machado, J. Phys. Org. Chem. 15 (2002) 420 (http://dx.doi.org/10.1002/poc.519)
S. S. Hemdan, J. Solution Chem. (2023) (http://dx.doi.org/10.1007/s10953-023-01301-3)
R. I. Stock, L. G. Nandi, C. R. Nicoleti, A. D. S. Schramm, S. L. Meller, R. S. Heying, D. F. Coimbra, K. F. Andriani,G. F. Caramori, A. J. Bortoluzzi, V.G. Machado, J. Org. Chem. 80 (2015) 7971 (http://dx.doi.org/10.1021/acs.joc.5b00983)
A. Farajtabar, F. Jaberi, F. Gharib, Spectrochim. Acta A 83 (2011) 213 (http://dx.doi.org/10.1016/j.saa.2011.08.020)
O. A. El Seoud, Pure Appl. Chem. 79 (2007) 1135 (http://dx.doi.org/10.1351/pac200779061135)
A. Ben-Naim, J. Phys. Chem. 93 (1989) 3809 (http://dx.doi.org/10.1021/j100346a086)
Y. Marcus, J. Chem. Soc. Faraday Trans. 1 84 (1988) 1465 (http://dx.doi.org/10.1039/F19888401465)
P. Suppan, J. Chem. Soc. Faraday Trans. 1 83 (1987) 495 (http://dx.doi.org/10.1039/F19878300495)
F. Gharib, A. Shamel, F. Jaberi, A. Farajtabar, J Solution Chem. 42 (2013) 1083 (http://dx.doi.org/10.1007/s10953-013-0007-9)
R. D. Skwierczynski, K. A. Connors, J. Chem. Soc. Perkin Trans. 2 (1994) 467 (http://dx.doi.org/10.1039/P29940000467)
S. S. Hemdan, A. M. Algebali, F. K. Ali, J. Chem. Technol. Metall. 58 (2023) 125 (https://journal.uctm.edu/node/j2023-1/JCTM_2023_58_15_22-77_pp125-142.pdf)
J. P. Perdew, Phys. Rev., B 34 (1986) 7406 (https://dx.doi.org/10.1103/PhysRevB.33.8822)
T. Yanai, D. P. Tew, N. C. Handy, Chem. Phys. Lett. 393 (2004) 51 (https://dx.doi.org/10.1016/j.cplett.2004.06.011)
J. Chai, M. Head-Gordon Phys. Chem. Chem. Phys. 10 (2008) 6615 (https://dx.doi.org/10.1039/B810189B)
A. Austin, G. A. Petersson M. J. Frisch, F. J. Dobek, G. Scalmani, K. Throssell, J. Chem. Theory Comput. 8 (2012) 4989 (https://dx.doi.org/10.1021/ct300778e)
M. Walker, A. J. A. Harvey, A. Sen, C. E. H. Dessent, J. Phys. Chem., A 117 (2013) 12590 (https://dx.doi.org/10.1021/jp408166m)
Y. Takano, K. N. Houk, J. Chem. Theory Comput. 1 (2005) 70 (https://dx.doi.org/10.1021/ct049977a)
N. Elmsheeti, S. Hemdan, A. Sammour, R. Alnajjar, Chem. Data Collect. 28 (2020) 100465 (https://dx.doi.org/10.1016/j.cdc.2020.100465)
Gaussian 16, revision C. 01., 2016
Sabirov V. Kh. Vahobjon CCDC 2223592: Experimental Crystal Structure Determination, 2022 (https://doi.org/10.5517/ccdc.csd.cc2dmtsn)
S. S. Hemdan, J. Fluoresc. (2023) (http://dx.doi.org/10.1007/s10895-023-03234-y)
H. C. Boroujeni, F. Gharib, J. Solution Chem. 45 (2016) 95 (https://doi.org/10.1007/s10953-015-0425-y)
X. Chen, A. Farajtabar, W. Jia, H.Zhao, J. Chem. Thermodyn. 138 (2019) 179 (https://doi.org/10.1016/j.jct.2019.06.019)
T. Bevilaqua, T. F. Goncalves, C. G. Venturini, V. G. Machado, Spectochim. Acta, A 65 (2006) 535 (http://dx.doi.org/10.1016/j.saa.2005.12.005)
M. Rosés, C. Ràfols, J. Ortega, E. Bosch, J. Chem. Soc. Perkin Trans. 2 (1995) 1607 (http://dx.doi.org/10.1039/P29950001607)
R.W. Taft, J.L.M. Abboud, M.J. Kamlet, J. Org. Chem. 49 (1984) 2001 (http://dx.doi.org/10.1021/jo00185a034)
X. Yao , R. Fang, H. Zhao , A.Farajtabar, A. Jouyban ,W.E. Acree Jr, J. Mol. Liq. 349 (2022) 118515 (http://dx.doi.org/10.1016/j.molliq.2022.118515).