Pd2+ fluorescent sensors based on amino and imino derivatives of rhodamine and improvement of water solubility by the formation of inclusion complexes with β-cyclodextrin

Yan Song Zhang, Rathinam Balamurugan, Jian Chin Lin, Sri Fitriyani, Jui Hsiang Liu, Alexander Emelyanenko

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Mono- and bis-rhodamine derivatives appended with amino (RhB1) and imino (BRI) groups, respectively, have been designed as colorimetric and fluorescent sensors for the selective detection of Pd2+. In addition, an attempt has been made to improve the water solubility of the probe by synthesizing inclusion complexes of RhB1 with β-cyclodextrin as the host molecule. The resulting probe, RhB1-CD, exhibited exactly the same physicochemical phenomena as the guest molecule RhB1, indicating that complexation with β-CD improved the water solubility of RhB1 without affecting its sensing ability. With increasing concentrations of Pd2+, the absorption (556 nm) and emission (591 nm) intensities of BRI as well as the absorption intensities of RhB1/RhB1-CD (563 nm) increase, whereas the emission intensities of RhB1/RhB1-CD decrease due to fluorescence quenching. Therefore, BRI can act as an "OFF-ON" fluorescent probe switch in CH3CN/H2O (3:2 v/v) with a detection limit of 1 μM in solution, whereas RhB1 and RhB1-CD act as "ON-OFF" fluorescent probes in EtOH/H2O (1:1 v/v) and water, respectively, with a detection limit of 10 μM. All these probes exhibited high selectivity for Pd2+ and reversibility by treatment with Na2S. In the presence of commonly coexisting metal ions, such as Hg2+, Fe3+, Cu2+ and Al3+, BRI undergoes either catalytic Schiff base hydrolysis or it is unaffected by its affinity to the metal ions. However, Pd2+ can be effectively distinguished by a 12-15 nm bathochromic shift in its emission spectrum when compared with that of other metal ions. A Job's plot revealed that BRI forms 1:2 complexes by a spirolactam ring opening mechanism, whereas RhB1/RhB1-CD form 2:1 complexes by a ring opening mechanism followed by Pd2+-induced dimerization; the proposed binding mechanisms are presented.

Original languageEnglish
Pages (from-to)1536-1544
Number of pages9
JournalAnalyst
Volume142
Issue number9
DOIs
Publication statusPublished - 2017 May 7

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Rhodamines
Cyclodextrins
Solubility
Metal ions
solubility
Metals
probe
Ions
sensor
Derivatives
Fluorescent Dyes
Limit of Detection
Water
Sensors
Chemical Phenomena
Molecules
Dimerization
Schiff Bases
ion
metal

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Biochemistry
  • Environmental Chemistry
  • Spectroscopy
  • Electrochemistry

Cite this

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title = "Pd2+ fluorescent sensors based on amino and imino derivatives of rhodamine and improvement of water solubility by the formation of inclusion complexes with β-cyclodextrin",
abstract = "Mono- and bis-rhodamine derivatives appended with amino (RhB1) and imino (BRI) groups, respectively, have been designed as colorimetric and fluorescent sensors for the selective detection of Pd2+. In addition, an attempt has been made to improve the water solubility of the probe by synthesizing inclusion complexes of RhB1 with β-cyclodextrin as the host molecule. The resulting probe, RhB1-CD, exhibited exactly the same physicochemical phenomena as the guest molecule RhB1, indicating that complexation with β-CD improved the water solubility of RhB1 without affecting its sensing ability. With increasing concentrations of Pd2+, the absorption (556 nm) and emission (591 nm) intensities of BRI as well as the absorption intensities of RhB1/RhB1-CD (563 nm) increase, whereas the emission intensities of RhB1/RhB1-CD decrease due to fluorescence quenching. Therefore, BRI can act as an {"}OFF-ON{"} fluorescent probe switch in CH3CN/H2O (3:2 v/v) with a detection limit of 1 μM in solution, whereas RhB1 and RhB1-CD act as {"}ON-OFF{"} fluorescent probes in EtOH/H2O (1:1 v/v) and water, respectively, with a detection limit of 10 μM. All these probes exhibited high selectivity for Pd2+ and reversibility by treatment with Na2S. In the presence of commonly coexisting metal ions, such as Hg2+, Fe3+, Cu2+ and Al3+, BRI undergoes either catalytic Schiff base hydrolysis or it is unaffected by its affinity to the metal ions. However, Pd2+ can be effectively distinguished by a 12-15 nm bathochromic shift in its emission spectrum when compared with that of other metal ions. A Job's plot revealed that BRI forms 1:2 complexes by a spirolactam ring opening mechanism, whereas RhB1/RhB1-CD form 2:1 complexes by a ring opening mechanism followed by Pd2+-induced dimerization; the proposed binding mechanisms are presented.",
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Pd2+ fluorescent sensors based on amino and imino derivatives of rhodamine and improvement of water solubility by the formation of inclusion complexes with β-cyclodextrin. / Zhang, Yan Song; Balamurugan, Rathinam; Lin, Jian Chin; Fitriyani, Sri; Liu, Jui Hsiang; Emelyanenko, Alexander.

In: Analyst, Vol. 142, No. 9, 07.05.2017, p. 1536-1544.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Pd2+ fluorescent sensors based on amino and imino derivatives of rhodamine and improvement of water solubility by the formation of inclusion complexes with β-cyclodextrin

AU - Zhang, Yan Song

AU - Balamurugan, Rathinam

AU - Lin, Jian Chin

AU - Fitriyani, Sri

AU - Liu, Jui Hsiang

AU - Emelyanenko, Alexander

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N2 - Mono- and bis-rhodamine derivatives appended with amino (RhB1) and imino (BRI) groups, respectively, have been designed as colorimetric and fluorescent sensors for the selective detection of Pd2+. In addition, an attempt has been made to improve the water solubility of the probe by synthesizing inclusion complexes of RhB1 with β-cyclodextrin as the host molecule. The resulting probe, RhB1-CD, exhibited exactly the same physicochemical phenomena as the guest molecule RhB1, indicating that complexation with β-CD improved the water solubility of RhB1 without affecting its sensing ability. With increasing concentrations of Pd2+, the absorption (556 nm) and emission (591 nm) intensities of BRI as well as the absorption intensities of RhB1/RhB1-CD (563 nm) increase, whereas the emission intensities of RhB1/RhB1-CD decrease due to fluorescence quenching. Therefore, BRI can act as an "OFF-ON" fluorescent probe switch in CH3CN/H2O (3:2 v/v) with a detection limit of 1 μM in solution, whereas RhB1 and RhB1-CD act as "ON-OFF" fluorescent probes in EtOH/H2O (1:1 v/v) and water, respectively, with a detection limit of 10 μM. All these probes exhibited high selectivity for Pd2+ and reversibility by treatment with Na2S. In the presence of commonly coexisting metal ions, such as Hg2+, Fe3+, Cu2+ and Al3+, BRI undergoes either catalytic Schiff base hydrolysis or it is unaffected by its affinity to the metal ions. However, Pd2+ can be effectively distinguished by a 12-15 nm bathochromic shift in its emission spectrum when compared with that of other metal ions. A Job's plot revealed that BRI forms 1:2 complexes by a spirolactam ring opening mechanism, whereas RhB1/RhB1-CD form 2:1 complexes by a ring opening mechanism followed by Pd2+-induced dimerization; the proposed binding mechanisms are presented.

AB - Mono- and bis-rhodamine derivatives appended with amino (RhB1) and imino (BRI) groups, respectively, have been designed as colorimetric and fluorescent sensors for the selective detection of Pd2+. In addition, an attempt has been made to improve the water solubility of the probe by synthesizing inclusion complexes of RhB1 with β-cyclodextrin as the host molecule. The resulting probe, RhB1-CD, exhibited exactly the same physicochemical phenomena as the guest molecule RhB1, indicating that complexation with β-CD improved the water solubility of RhB1 without affecting its sensing ability. With increasing concentrations of Pd2+, the absorption (556 nm) and emission (591 nm) intensities of BRI as well as the absorption intensities of RhB1/RhB1-CD (563 nm) increase, whereas the emission intensities of RhB1/RhB1-CD decrease due to fluorescence quenching. Therefore, BRI can act as an "OFF-ON" fluorescent probe switch in CH3CN/H2O (3:2 v/v) with a detection limit of 1 μM in solution, whereas RhB1 and RhB1-CD act as "ON-OFF" fluorescent probes in EtOH/H2O (1:1 v/v) and water, respectively, with a detection limit of 10 μM. All these probes exhibited high selectivity for Pd2+ and reversibility by treatment with Na2S. In the presence of commonly coexisting metal ions, such as Hg2+, Fe3+, Cu2+ and Al3+, BRI undergoes either catalytic Schiff base hydrolysis or it is unaffected by its affinity to the metal ions. However, Pd2+ can be effectively distinguished by a 12-15 nm bathochromic shift in its emission spectrum when compared with that of other metal ions. A Job's plot revealed that BRI forms 1:2 complexes by a spirolactam ring opening mechanism, whereas RhB1/RhB1-CD form 2:1 complexes by a ring opening mechanism followed by Pd2+-induced dimerization; the proposed binding mechanisms are presented.

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