A Quantum-Chemical Study of Tautomeric Equilibria of Fluorescein Dyes in DMSO

Lebed, Alexander V.; Biryukov, A. V.; Mchedlov‐Petrossyan, Nikolay O.

doi:10.1007/s10593-014-1481-8

Cited by 12 publications

(23 citation statements)

References 35 publications

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“…Such dramatic destabilization of the dipolar tautomer is in line with behavior of the parent compound fluorescein [6,7,27-29,58,59,64,65]. The zwitterionic tautomer of sulfonefluorescein, however, predominates in any solvent, owing to the weak basicity of the SO 3 À group; recently it was confirmed by quantum-chemical calculations [31].…”

Section: Microscopic Dissociation Constantsmentioning

confidence: 69%

“…The above-mentioned regularities of tautomerism of fluorescein dyes have been recently corroborated by quantum-chemical calculations [31].…”

Section: Introductionmentioning

confidence: 67%

“…Some data on ethers and esters of fluorescein dyes are available in the literature [25][26][27][28][29][30][31][32][33][34][35][36][37]; Amat-Guerri et al studied the ethers of eosin and rose bengal B and thus estimated the fractions of the lactonic monoanions of these dyes [37].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ionization and tautomerism of methyl fluorescein and related dyes

Mchedlov‐Petrossyan

Cheipesh

Shekhovtsov

et al. 2015

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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Section: Microscopic Dissociation Constantsmentioning

confidence: 69%

“…The above-mentioned regularities of tautomerism of fluorescein dyes have been recently corroborated by quantum-chemical calculations [31].…”

Section: Introductionmentioning

confidence: 67%

See 1 more Smart Citation

Ionization and tautomerism of methyl fluorescein and related dyes

Mchedlov‐Petrossyan

Cheipesh

Shekhovtsov

et al. 2015

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…Quantum‐chemical calculations give support to such an ionisation scheme, valid both in water and DMSO. It is also demonstrated that structure 5 is improbable for the unsubstituted fluorescein, to some extent admissible for eosin (X = Y = Br), and predominating for TNF as estimated for vacuum, DMSO and water, as shown by ab initio quantum‐chemical calculations, such as B3LYP/6‐31++G* * and polarized continuum model (PCM) .…”

Section: Introductionmentioning

confidence: 71%

The molecular structure of anionic species of 2,4,5,7‐tetranitrofluorescein as studied by electrospray ionisation, nuclear magnetic resonance and X‐ray techniques

Mchedlov‐Petrossyan

Steinbach

Vodolazkaya

et al. 2018

Coloration Technology

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Among the fluorescein dyes, the behaviour of their nitro derivatives in solution is most unusual, and yet at the same time rarely studied. In this study, their 13 C nuclear magnetic resonance and electrospray spectra are reported, which confirm, in concert with their ultraviolet-visible spectra, the molecular structures of the neutral and ionic species of 2,4,5,7-tetranitrofluorescein observed in different solvents and at various pH values. A peculiar property of this dye consists in its lactonisation of the double-charged anion, contrary to the wellknown coloured and fluorescent dianions of fluorescein, eosin, etc. Also, this dianion-lactone exhibits high ability for opening the pyran ring. This cleavage takes place at much lower pH values as compared with those for fluorescein and its halogen derivatives. The ruptured species can be formed as either lactone or carbinol; the latter appears as a result of the nucleophilic attack of a HO À on the central carbon atom. The corresponding molecular structures are identified via the electrospray method and X-ray analysis. The behaviour of some other nitrofluoresceins in alkaline media is also considered. Coloration TechnologySociety of Dyers and Colourists † Just now, an article "Syntheses of novel acid-base indicators by nitration of phenolphthalein and fluorescein" by Y. Negishi,

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“…Accordingly, new works appear on the protolytic and spectral properties of both previously known [28][29][30][31][32] and new [25,[33][34][35] or previously little studied [36][37][38][39][40][41][42] fluorescein compounds, including data analysis in the gas phase [43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Protolytic Equilibria in Organized Solutions: Ionization and Tautomerism of Fluorescein Dyes and Related Indicators in Cetyltrimethylammonium Chloride Micellar Solutions at High Ionic Strength of the Bulk Phase

Mchedlov‐Petrossyan

Vodolazkaya

2021

Liquids

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Ionic equilibrium of 22 hydroxyxanthenes, including halogen and nitro derivatives of fluorescein, and their thio- and aza analogues, were studied spectrophotometrically in micellar solutions of cetyltrimethylammonium chloride at ionic strength of the bulk phase 4.0 M KCl. This micellar pseudophase is characterized by the electrostatic surface potential of +(15–16) mV and the ETN value of 0.623. In the case of dyes bearing the COOH group, colorless lactone is the predominant tautomer of the molecular form H2R. A new classification of fluoresceins is developed. The dyes were divided into four groups based on the nature of tautomerism of the anions. In the case of the fluorescein type, the monoanions HR− exist predominantly as “carboxylate” tautomers, with ionized carboxylic and non–ionized hydroxylic group. For the dyes of the eosin type, the situation is opposite, while for the intervening type of compounds, the concentrations of the two tautomers are comparable. Dyes capable of forming lactone anions HR− were classified as the fourth type. For some of them, even the dianion R2− exists as a lactone. The relationship between the stepwise ionization constants, Ka1/Ka2, varies from 1.3 to 1.07 × 105 and is determined by the state of tautomeric equilibrium of molecules and ions.

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A Quantum-Chemical Study of Tautomeric Equilibria of Fluorescein Dyes in DMSO

Cited by 12 publications

References 35 publications

Ionization and tautomerism of methyl fluorescein and related dyes

Ionization and tautomerism of methyl fluorescein and related dyes

The molecular structure of anionic species of 2,4,5,7‐tetranitrofluorescein as studied by electrospray ionisation, nuclear magnetic resonance and X‐ray techniques

Protolytic Equilibria in Organized Solutions: Ionization and Tautomerism of Fluorescein Dyes and Related Indicators in Cetyltrimethylammonium Chloride Micellar Solutions at High Ionic Strength of the Bulk Phase

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