A combination of experimental and TD-DFT investigations on the fluorescent detection of sulfite and bisulfite ions in aqueous solution via nucleophilic addition reaction

Nandhini, C.; Kumar, Pramod; Shanmugapriya, R.; Vennila, K.N.; Al‐Sehemi, Abdullah G.; Pannipara, Mehboobali; Elango, Kuppanagounder P.

doi:10.1016/j.jphotochem.2021.113668

Cited by 7 publications

(3 citation statements)

References 35 publications

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“…The discrepancies in the theoretical evaluation and the experimental results could be due to errors in TD-DFT calculations and inadequacy of the basis sets, which leads to either overestimation or underestimation of the excited-state energy. It may also be because of the facts that the transition energies are not only regulated by electronic transfers between the frontier orbitals. − …”

Section: Results and Discussionmentioning

confidence: 99%

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

Panda,

Sahu,

Goswami

et al. 2023

ACS Appl. Bio Mater.

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The present investigation highlights a rhodamine-Band coumarin-based efficient probe that selectively detects Ga 3+ over other metal ions. The active pocket of the ligand for trapping the metal ions and the binding stoichiometry of its Ga 3+ complex were discovered by single-crystal X-ray diffraction (SC-XRD) analysis. This binding stoichiometry was further confirmed in the solution state by mass spectrometry and Job's plot. The detection limit was found to be at the nanomolar level. Pyrophosphate being a well-known quencher could easily quench the fluorescence intensity of the RC in the presence of Ga 3+ and reversibly recognize Ga 3+ in the solution. The spiro ring opening of the ligand after Ga 3+ insertion is proposed to be the principal mechanism for the turn-on fluorescence response. This ring opening was confirmed by SC-XRD data and nuclear magnetic resonance (NMR) titration experiments. Both ground-and excited-state calculations of the ligand and complex have been carried out to obtain information about their energy levels and to obtain the theoretical electronic spectra. Furthermore, the live-cell imaging of the probe only and the probe after the addition of Ga 3+ have been carried out in HaCaT cells and satisfactory responses were observed. Interestingly, with the help of this probe, Ga 3+ can be tracked inside the intracellular organelle such as lysosomes along with other regions of the cell. The article highlights a rhodamine−coumarin-based probe for the detection of Ga 3+ over other metal ions with a nanomolar level detection limit. Structural characterization of the ligand and its Ga 3+ complex was investigated by SC-XRD. Density functional theory (DFT) and time-dependent DFT (TD-DFT) studies were carried out to explore the excited-state energies and electronic spectra. The application of the probe for the detection of Ga 3+ in live cells has been explored, and positive responses were observed.

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Section: Results and Discussionmentioning

confidence: 99%

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

Panda,

Sahu,

Goswami

et al. 2023

ACS Appl. Bio Mater.

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“…To get a better insight into the proposed mechanism of detection of Al(III) by RS5, geometries of RS5 and its Al(III) complex were optimized in the ground (S 0 ) and excited (S 1 ) states by DFT and TD-DFT methods using B3LYP/6-311G basis set in DMSO as described by us earlier [28][29][30]. The vertical excitation energies of ten low lying states, corresponding oscillator strengths and transition compositions along with CI coefficients of free RS5 and its Al(III) complex in DMSO solvent are collected in tables 1 and 2, respectively.…”

Section: Theoretical Studiesmentioning

confidence: 99%

A highly selective and sensitive ratiometric fluorescent probe for quantitative detection of Al(III) in different natural matrices

Shanmugapriya¹,

Saravanakumar²,

Nandhini³

et al. 2022

Methods Appl. Fluoresc.

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Highly selective and sensitive assay of Al(III) using ratiometric fluorescence enhancement is reported in an aqueous solution. The probe (named as RS5) exhibits a red-shift of 54 nm upon binding with Al(III) ion. The significant enhancement response of RS5 at 481 nm is attributed to the formation of a 1:1 complex between the probe and Al(III), wherein RS5 acts as a tridentate NNN-donor ligand. The complexation process is ascertained by 1H, 13C and 27Al NMR and HR-MS spectral techniques. The binding constant of the complex is determined to be 1.3x105 M-1. The ratiometric change in fluorescence upon complexation with Al(III) is ascribed to increase in intramolecular charge transfer (ICT) transition along with chelation enhanced fluorescence (CHEF) processes. The probe can be applied for monitoring Al(III) in a pH range of 6 – 8. The limit of detection (LOD) of RS5 for the examination of Al(III) is found to be 0.3 µM. With an aim to understand the sensing behaviour of RS5, the optical properties of the probe and its Al(III) complex are investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. The probe is successfully employed for the determination of Al(III), with very high recovery percentages, in natural matrices like deep well water, tap water, drinking water, pond water, river water, bovine serum albumin (BSA) solution and blood serum.

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“…To date, the existing conventional methods to detect bisulte/sultes include ion chromatography, 10,11 spectroscopy, [12][13][14][15] electrochemistry, 16,17 and iodometric titration. 18 However, the main disadvantage of these methods is that the majority of them require miscellaneous sample pretreatment and the use of relatively multiple reagents.…”

Section: Introductionmentioning

confidence: 99%

A bis-chalcone based colorimetric probe for the selective detection of bisulfite/sulfite anions: exploring surfactant promoted Michael addition of anions to α, β-unsaturated ketones

2023

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A combination of experimental and TD-DFT investigations on the fluorescent detection of sulfite and bisulfite ions in aqueous solution via nucleophilic addition reaction

Cited by 7 publications

References 35 publications

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

A highly selective and sensitive ratiometric fluorescent probe for quantitative detection of Al(III) in different natural matrices

A bis-chalcone based colorimetric probe for the selective detection of bisulfite/sulfite anions: exploring surfactant promoted Michael addition of anions to α, β-unsaturated ketones

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A combination of experimental and TD-DFT investigations on the fluorescent detection of sulfite and bisulfite ions in aqueous solution via nucleophilic addition reaction

Cited by 7 publications

References 35 publications

Robust Optical Detection of Ga3+ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

Robust Optical Detection of Ga3+ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

A highly selective and sensitive ratiometric fluorescent probe for quantitative detection of Al(III) in different natural matrices

A bis-chalcone based colorimetric probe for the selective detection of bisulfite/sulfite anions: exploring surfactant promoted Michael addition of anions to α, β-unsaturated ketones

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Product

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About

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications

Robust Optical Detection of Ga³⁺ by a Rhodamine- and Coumarin-Based Proficient Probe: Theoretical Investigations and Biological Applications