Influence of Solvent Polarizability on the Keto-Enol Equilibrium in 4-[5-(naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol

详细信息    查看全文

• 作者：Arkadiusz Matwijczuk ; Andrzej Górecki ; Daniel Kamiński…
• 关键词：1 ; 3 ; 4 ; thiadiazoles ; Intramolecular proton transfer ; Keto ; enol tautomery ; Molecular spectroscopy
• 刊名：Journal of Fluorescence
• 出版年：2015
• 出版时间：November 2015
• 年：2015
• 卷：25
• 期：6
• 页码：1867-1874
• 全文大小：843 KB
• 参考文献：1.Juszczak M, Matysiak J, Brzana W, Niewiadomy A, Rzeski W (2008) Evaluation of the antiproliferative activity of 2-(monohalogenophenylamino)-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazoles. Arzneimittelforschung 58(7):353-57. doi:10.-055/?s-0031-1296519 PubMed
  2.Juszczak M, Matysiak J, Niewiadomy A, Rzeski W (2011) The activity of a new 2-amino-1,3,4-thiadiazole derivative 4ClABT in cancer and normal cells. Folia Histochem Cytobiol 49(3):436-44CrossRef PubMed
  3.Matysiak J, Los R, Malm A, Karpinska MM, Glaszcz U, Rajtar B, Polz-Dacewicz M, Wesolowska-Trojanowska M, Niewiadomy A (2012) Synthesis and antibacterial activity of novel fused 1,3-thiazoles and 1,3-thiazines incorporating a 2,4-dihydroxyphenyl residue. Arch Pharm 345(4):302-13. doi:10.-002/?ardp.-01100251 CrossRef
  4.Matysiak J, Nasulewicz A, Pelczynska M, Switalska M, Jaroszewicz I, Opolski A (2006) Synthesis and antiproliferative activity of some 5-substituted 2-(2,4-dihydroxyphenyl)-1,3,4-thiadiazoles. Eur J Med Chem 41(4):475-82. doi:10.-016/?j.?ejmech.-005.-2.-07 CrossRef PubMed
  5.Skrzypek A, Matysiak J, Karpinska MM, Niewiadomy A (2013) Synthesis and anticholinesterase activities of novel 1,3,4-thiadiazole based compounds. J Enzym Inhib Med Chem 28(4):816-23. doi:10.-109/-4756366.-012.-88041 CrossRef
  6.Skrzypek A, Matysiak J, Niewiadomy A, Bajda M, Szymanski P (2013) Synthesis and biological evaluation of 1,3,4-thiadiazole analogues as novel AChE and BuChE inhibitors. Eur J Med Chem 62:311-19. doi:10.-016/?j.?ejmech.-012.-2.-60 CrossRef PubMed
  7.Gagos M, Matwijczuk A, Kaminski D, Niewiadomy A, Kowalski R, Karwasz GP (2011) Spectroscopic studies of intramolecular proton transfer in 2-(4-fluorophenylamino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole. J Fluoresc 21(1):1-0. doi:10.-007/?s10895-010-0682-5 PubMedCentral CrossRef PubMed
  8.Wang JBR (1996) Tautomeric equilibria of hydroxypyridines in different solvents:an ab initio study. J Phys Chem 100:16141-6146. doi:10.-021/?jp961295z CrossRef
  9.Lu JHB, Yan H (1999) Thermodynamic studies of chemical equilibrium in supercritical carbon. J Supercrit Fluids 5(2):135-43CrossRef
  10.Nihan Yonet NB, Yurtsever M, Yagci Y (2007) Spectroscopic and theoretical investigation of capillary-induced keto–enol tautomerism of phenacyl benzoylpyridinium-type photoinitiators. Polym Int 56:525-31CrossRef
  11.Tong YAA (1996) Spectroscopic studies of the keto end enol tautomers of 1Phenyl-3-methyl-4-benzyl-5-pyrazolone. Microchem J 53:34-1CrossRef
  12.Koll A (2003) Specific features of intramolecular proton transfer reaction in Schiff bases. Int J Mol Sci 4:434-44CrossRef
  13.Rospenk M, Król-Starzomska I, Filarowski A, Koll A (2002) Proton transfer and self-association of sterically modified Schiff bases. Chem Phys 287(1-):113-24
  14.Fujii TKK, Kawauchi O, Tanaka N (1997) Photochromic behavior in the fluorescence spectra of 9-anthrol encapsulated in Si–Al glasses prepared by the sol–gel method. J Phys Chem B 101(50):10631-0637CrossRef
  15.Hoser AA, Kaminski DM, Matwijczuk A, Niewiadomy A, Gagos M, Wozniak K (2013) On polymorphism of 2-(4-fluorophenylamino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole (FABT) DMSO solvates. CrystEngComm 15(10):1978-988. doi:10.-039/?c3ce26778d CrossRef
  16.Kaminski DM, Hoser AA, Gagos M, Matwijczuk A, Arczewska M, Niewiadomy A, Wozniak K (2010) Solvatomorphism of 2-(4-fluorophenylamino)-5-(2,4-dihydroxybenzeno)-1,3,4-thiadiazole chloride. Cryst Growth Des 10(8):3480-488. doi:10.-021/?cg1003319 CrossRef
  17.Murthy ASN, Balasubramanian A, Rao CNR (1962) Spectroscopic study of keto-enol equilibria. Can J Chem 50:2267-271CrossRef
  18.Reichardt C (2003) Solvents and solvent effects in organic chemistry. Wiley-VCH, Weinheim
  19.Lide DR (2007) CRC handbook of chemistry and physics, vol. Taylor and Francis, Boca Raton
  20.Lakowicz J (2006) Principles of fluorescence spectroscopy. Springer, New YorkCrossRef
  21.Kaminski DM, Matwijczuk A, Pociecha D, Gorecka E, Niewiadomy A, Dmowska M, Gagos M (2012) Effect of 2-(4-fluorophenylamino)-5-(2,4-dihydroxyphenyl)-1,3,4-thiadiazole on the molecular organisation and structural properties of the DPPC lipid multibilayers. Biochim Biophys Acta 1818(11):2850-859. doi:10.-016/?j.?bbamem.-012.-7.-13 CrossRef PubMed
  
• 作者单位：Arkadiusz Matwijczuk (1) (4)
  Andrzej Górecki (3)
  Daniel Kamiński (2)
  Beata My?liwa-Kurdziel (4)
  Leszek Fiedor (4)
  Andrzej Niewiadomy (2)
  Grzegorz P. Karwasz (5)
  Mariusz Gago? (6)
  
  1. Department of Biophysics, University of Life Sciences in Lublin, 20-950, Lublin, Poland
  4. Faculty of Biochemistry, Biophysics and Biotechnology, Jagiellonian University, Gronostajowa 7, 30-387, Kraków, Poland
  3. Department of Physical Biochemistry, Faculty of Biochemistry, Biophysics and Biotechnology, Jagiellonian University, Kraków, Poland
  2. Department of Chemistry, University of Life Sciences in Lublin, 20-950, Lublin, Poland
  5. Aleksander Jab?oński Institute of Physics, Nicolaus Copernicus University, 87-100, Toruń, Poland
  6. Department of Cell Biology, Institute of Biology and Biochemistry, Maria Curie-Sk?odowska University, 20-033, Lublin, Poland
  
• 刊物类别：Biomedical and Life Sciences
• 刊物主题：Biomedicine
  Biomedicine
  Biophysics and Biomedical Physics
  Biotechnology
  Biochemistry
  Analytical Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1573-4994

文摘

This work presents spectroscopic studies of the keto–enol equilibrium induced by solvent polarizability in 4-[5-(naphthalen-1-ylmethyl)-1,3,4-thiadiazol-2-yl]benzene-1,3-diol a strong antiproliferative and anticancer thiadiazol derivative. Electronic absorption, steady state and time resolved fluorescence, and infrared spectroscopies were applied to investigate the keto and enol forms of this compound in a series of polar and non-polar solvents. The enol form dominates in polar solvents while, surprisingly, the keto form dominates in non-polar solvents with high average electric dipole polarizability e.g. n-alkenes. The electronic absorption spectrum of this derivative is more dependent on spatially averaged electric dipole polarizability of the solvent than on Kirkwood’s correlation or on Lorenz-Lorenz electric polarizability. By analogy of n-alkanes to the alkyl parts of lipids, one can expect that the transformation of 1,3,4-thiadiazoles to the keto form may be facilitated in the hydrophobic core of the lipid membrane. Such a transition may be of great practical importance for the design of biologically active pharmaceutics, which are able to interact with the hydrophobic regions of cell membranes in a specific manner. Keywords 1,3,4-thiadiazoles Intramolecular proton transfer Keto-enol tautomery Molecular spectroscopy