A selective emissive chromogenic and fluorogenic seleno-coumarin probe for Cu2+ detection in aprotic media

A. C. Gonçalves, J. Luis Capelo, C. Lodeiro, A. A. Dos Santos

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

A new selenium containing coumarin (compound 7) was designed and synthesized from the amide linkage between coumarin-519 (6) and 2-(butylselanyl)ethanamine (5). The molecular structure of 7 was accurately characterized, and its photophysical properties in acetonitrile, ethanol and chloroform solutions were studied by absorption, stationary and time-resolved fluorescence spectroscopies. Changes in the solvent polarity affected the Stokes shift, quantum yields and lifetime of the excited states. The spectroscopic behavior of compound 7 was evaluated in the presence of different monovalent, divalent and trivalent metallic cations (Na+, K+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, Hg2+, Hg+, Ag+, Al3+, Fe3+, Ga3+ and Cr3+) in acetonitrile solution. Among the tested cations, 7 exhibited high selective interaction with Cu2+, which was evidenced by the not expected absorption hypsocromic shift (usually coumarin-519 gives red-shifted complexes) and intense chelation-enhanced fluorescence quenching (CHEQ). We performed spectrophotometric and spectrofluorimetric titrations of 7 upon addition of Cu2+. From these data, the minimal detectable and quantifiable amounts were calculated and found to be 0.2 and 0.4 μmol L-1 by absorption and 0.6 and 1.0 μmol L-1 by emission, respectively. The 7-Cu2+ compound presented the 1-:-1 stoichiometry and the stability constant values of absorption and emission were found to be log-β = 5.78 and log-β = 6.32 respectively. Taking into account the high selectivity of the 7-Cu2+ compound in organic solvent systems, and considering the role of copper in organic transformations, it can be regarded as a promising fluorescent sensor for studies concerning the determination of oxidation-dependent transient entities in organic reactions like those involving cuprates. Additionally, it can be used for the detection and quantification of this metal cation in vitro in aprotic biological systems.

Original languageEnglish
Pages (from-to)1174-1181
Number of pages8
JournalPhotochemical and Photobiological Sciences
Volume16
Issue number7
DOIs
Publication statusPublished - 1 Jan 2017

Fingerprint

Chromogenics
Cations
probes
cations
acetonitrile
Fluorescence spectroscopy
Quantum yield
Biological systems
Selenium
Chloroform
Chelation
Titration
Excited states
Amides
Stoichiometry
fluorescence
Organic solvents
Molecular structure
chelation
Copper

Keywords

  • ALZHEIMER A-BETA
  • RECOGNITION
  • CHEMISTRY; CU(II)
  • IONS
  • DYES

Cite this

@article{8885dd73844e4cd299a961c30c52a8e4,
title = "A selective emissive chromogenic and fluorogenic seleno-coumarin probe for Cu2+ detection in aprotic media",
abstract = "A new selenium containing coumarin (compound 7) was designed and synthesized from the amide linkage between coumarin-519 (6) and 2-(butylselanyl)ethanamine (5). The molecular structure of 7 was accurately characterized, and its photophysical properties in acetonitrile, ethanol and chloroform solutions were studied by absorption, stationary and time-resolved fluorescence spectroscopies. Changes in the solvent polarity affected the Stokes shift, quantum yields and lifetime of the excited states. The spectroscopic behavior of compound 7 was evaluated in the presence of different monovalent, divalent and trivalent metallic cations (Na+, K+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, Hg2+, Hg+, Ag+, Al3+, Fe3+, Ga3+ and Cr3+) in acetonitrile solution. Among the tested cations, 7 exhibited high selective interaction with Cu2+, which was evidenced by the not expected absorption hypsocromic shift (usually coumarin-519 gives red-shifted complexes) and intense chelation-enhanced fluorescence quenching (CHEQ). We performed spectrophotometric and spectrofluorimetric titrations of 7 upon addition of Cu2+. From these data, the minimal detectable and quantifiable amounts were calculated and found to be 0.2 and 0.4 μmol L-1 by absorption and 0.6 and 1.0 μmol L-1 by emission, respectively. The 7-Cu2+ compound presented the 1-:-1 stoichiometry and the stability constant values of absorption and emission were found to be log-β = 5.78 and log-β = 6.32 respectively. Taking into account the high selectivity of the 7-Cu2+ compound in organic solvent systems, and considering the role of copper in organic transformations, it can be regarded as a promising fluorescent sensor for studies concerning the determination of oxidation-dependent transient entities in organic reactions like those involving cuprates. Additionally, it can be used for the detection and quantification of this metal cation in vitro in aprotic biological systems.",
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A selective emissive chromogenic and fluorogenic seleno-coumarin probe for Cu2+ detection in aprotic media. / Gonçalves, A. C.; Luis Capelo, J.; Lodeiro, C.; Dos Santos, A. A.

In: Photochemical and Photobiological Sciences, Vol. 16, No. 7, 01.01.2017, p. 1174-1181.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A selective emissive chromogenic and fluorogenic seleno-coumarin probe for Cu2+ detection in aprotic media

AU - Gonçalves, A. C.

AU - Luis Capelo, J.

AU - Lodeiro, C.

AU - Dos Santos, A. A.

N1 - sem pdf conforme despacho. Unidade de Ciencias Biomoleculares Aplicadas-UCIBIO/REQUIMTE - FCT/MEC-UID/Multi/04378/2013 ; LAQV/REQUIMTE - UID/QUI/50006/2013 (POCI-01-0145-FEDER-007728).

PY - 2017/1/1

Y1 - 2017/1/1

N2 - A new selenium containing coumarin (compound 7) was designed and synthesized from the amide linkage between coumarin-519 (6) and 2-(butylselanyl)ethanamine (5). The molecular structure of 7 was accurately characterized, and its photophysical properties in acetonitrile, ethanol and chloroform solutions were studied by absorption, stationary and time-resolved fluorescence spectroscopies. Changes in the solvent polarity affected the Stokes shift, quantum yields and lifetime of the excited states. The spectroscopic behavior of compound 7 was evaluated in the presence of different monovalent, divalent and trivalent metallic cations (Na+, K+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, Hg2+, Hg+, Ag+, Al3+, Fe3+, Ga3+ and Cr3+) in acetonitrile solution. Among the tested cations, 7 exhibited high selective interaction with Cu2+, which was evidenced by the not expected absorption hypsocromic shift (usually coumarin-519 gives red-shifted complexes) and intense chelation-enhanced fluorescence quenching (CHEQ). We performed spectrophotometric and spectrofluorimetric titrations of 7 upon addition of Cu2+. From these data, the minimal detectable and quantifiable amounts were calculated and found to be 0.2 and 0.4 μmol L-1 by absorption and 0.6 and 1.0 μmol L-1 by emission, respectively. The 7-Cu2+ compound presented the 1-:-1 stoichiometry and the stability constant values of absorption and emission were found to be log-β = 5.78 and log-β = 6.32 respectively. Taking into account the high selectivity of the 7-Cu2+ compound in organic solvent systems, and considering the role of copper in organic transformations, it can be regarded as a promising fluorescent sensor for studies concerning the determination of oxidation-dependent transient entities in organic reactions like those involving cuprates. Additionally, it can be used for the detection and quantification of this metal cation in vitro in aprotic biological systems.

AB - A new selenium containing coumarin (compound 7) was designed and synthesized from the amide linkage between coumarin-519 (6) and 2-(butylselanyl)ethanamine (5). The molecular structure of 7 was accurately characterized, and its photophysical properties in acetonitrile, ethanol and chloroform solutions were studied by absorption, stationary and time-resolved fluorescence spectroscopies. Changes in the solvent polarity affected the Stokes shift, quantum yields and lifetime of the excited states. The spectroscopic behavior of compound 7 was evaluated in the presence of different monovalent, divalent and trivalent metallic cations (Na+, K+, Ca2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, Hg2+, Hg+, Ag+, Al3+, Fe3+, Ga3+ and Cr3+) in acetonitrile solution. Among the tested cations, 7 exhibited high selective interaction with Cu2+, which was evidenced by the not expected absorption hypsocromic shift (usually coumarin-519 gives red-shifted complexes) and intense chelation-enhanced fluorescence quenching (CHEQ). We performed spectrophotometric and spectrofluorimetric titrations of 7 upon addition of Cu2+. From these data, the minimal detectable and quantifiable amounts were calculated and found to be 0.2 and 0.4 μmol L-1 by absorption and 0.6 and 1.0 μmol L-1 by emission, respectively. The 7-Cu2+ compound presented the 1-:-1 stoichiometry and the stability constant values of absorption and emission were found to be log-β = 5.78 and log-β = 6.32 respectively. Taking into account the high selectivity of the 7-Cu2+ compound in organic solvent systems, and considering the role of copper in organic transformations, it can be regarded as a promising fluorescent sensor for studies concerning the determination of oxidation-dependent transient entities in organic reactions like those involving cuprates. Additionally, it can be used for the detection and quantification of this metal cation in vitro in aprotic biological systems.

KW - ALZHEIMER A-BETA

KW - RECOGNITION

KW - CHEMISTRY; CU(II)

KW - IONS

KW - DYES

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U2 - 10.1039/c7pp00036g

DO - 10.1039/c7pp00036g

M3 - Article

VL - 16

SP - 1174

EP - 1181

JO - Photochemical and Photobiological Sciences

JF - Photochemical and Photobiological Sciences

SN - 1474-905X

IS - 7

ER -