The role of water in solvating the hydrogen-bonding center of 2-(2′-hydroxyphenyl)benzoxazole

Osama K. Abou-Zied*

*المؤلف المقابل لهذا العمل

نتاج البحث: المساهمة في مجلةمراجعة النظراء

55 اقتباسات (Scopus)

ملخص

2-(2′-Hydroxyphenyl)benzoxazole (HBO) has been useful as a probe to study tautomerization in DNA. In order to clarify the role of water in solvating the hydrogen-bonding center of HBO, we examine here the effect of water on the ground- and excited-state properties of HBO by steady state absorption and fluorescence spectroscopy, and by ab initio calculations. The study was carried out in solvents of varying polarity and hydrogen-bonding capability and in binary mixtures of 1,4-dioxane/water and methanol/water. HBO exists in three equilibrium structures in its ground state which are solvent-dependent, solvated and closed syn-enols and anti-enol. Only closed syn-enol is able to undergo tautomerization in the excited state to form syn-keto tautomer. Fluorescence due to solvated HBO was observed at 370 nm. The intensity change in the fluorescence peak at 370 nm as a function of water content in the binary solvents was quantitatively analyzed. Two water molecules were found to solvate the hydrogen-bonding center of the syn-enol tautomer in the ground state. The ground-state structures of the syn-enol tautomer with one to four water molecules were calculated by performing ab initio calculations at the MP2/6-31G(d) level and it was found that only two water molecules interact with the hydrogen-bonding center of HBO, confirming the above results. As water content increased in the binary mixtures, the keto tautomer fluorescence shifted to the blue and increased in intensity. This change was attributed to the formation of an anion species in the excited state which is stabilized in high polar binary mixtures. This result was confirmed by measuring the fluorescence in aqueous solution of pH 13. At high water contents, the behavior of the binary mixtures approaches that of pure water in which HBO undergoes water-assisted tautomerization to give the syn-keto tautomer.

اللغة الأصليةEnglish
الصفحات (من إلى)1-10
عدد الصفحات10
دوريةChemical Physics
مستوى الصوت337
رقم الإصدار1-3
المعرِّفات الرقمية للأشياء
حالة النشرPublished - أغسطس 16 2007

ASJC Scopus subject areas

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