RESUMEN
Fe(II) and Ni(II) paraCEST contrast agents containing the di-pyridine macrocyclic ligand 2,2',2â³-(3,7,10-triaza-1,5(2,6)-dipyridinacycloundecaphane-3,7,10-triyl)triacetamide (DETA) are reported here. Both [Fe(DETA)]2+ and [Ni(DETA)]2+ complexes were structurally characterized. Crystallographic data revealed the seven-coordinated distorted pentagonal bipyramidal geometry of the [Fe(DETA)]·(BF4)2·MeCN complex with five coordinated nitrogen atoms from the macrocyclic ring and two coordinated oxygen atoms from two amide pendant arms. The [Ni(DETA)]·Cl2·2H2O complex was six-coordinated in nature with a distorted octahedral geometry. Four coordinated nitrogen atoms were from the macrocyclic ring, and two coordinated oxygen atoms were from two amide pendant arms. [Fe(DETA)]2+ exhibited well-resolved sharp proton resonances, whereas very broad proton resonances were observed in the case of [Ni(DETA)]2+ due to the long electronic relaxation times. The CEST peaks for the [Fe(DETA)]2+ complex showed one highly downfield-shifted and intense peak at 84 ppm with another shifted but less intense peak at 28 ppm with good CEST contrast efficiency at body temperature, whereas [Ni(DETA)]2+ showed only one highly shifted intense peak at 78 ppm from the bulk water protons. Potentiometric titrations were performed to determine the protonation constants of the ligand and the thermodynamic stability constant of the [M(DETA)]2+ (M = Fe, Co, Ni, Cu, Zn) species at 25.0 °C and I = 0.15 mol·L-1 NaClO4. Metal exchange studies confirmed the stability of the complexes in acidic medium in the presence of physiologically relevant anions and an equimolar concentration of Zn(II) ions.
Asunto(s)
Medios de Contraste , Protones , Ligandos , Medios de Contraste/química , Estructura Molecular , DEET , Cristalografía por Rayos X , Piridinas/química , Amidas/química , Compuestos Ferrosos/química , Oxígeno , Nitrógeno , AguaRESUMEN
This study highlights the successful synthesis of a potential ligand, 2,2',2'',2'''-((pyridine-2,6-diylbis(methylene))bis(azanetriyl))tetraacetamide (PATA), along with its corresponding Co(II) and Ni(II) complexes for paraCEST-based agents. X-ray diffraction data confirmed that both the complexes are six coordinated with distorted octahedral geometries, but only the [Co(PATA)]2+ complex has a good structural feature to show paraCEST activity. After a thorough characterization of the ligand and both of its complexes, various studies, including solution-state magnetic properties, redox properties, temperature, and pH variation studies, were carried out. [Co(PATA)]2+ remained inert in the presence of competing ions, under acidic conditions, at high temperatures, and in the physiological pH range. The paraCEST response of [Co(PATA)]2+ has been measured in the presence of HEPES buffer medium, and a high paraCEST feature was discovered at both 37 and 25 °C. The pH variation paraCEST studies were carried out and the exchange rate constant of the probe at 37 and 25 °C was also determined. However, due to the fast exchange of water protons, the [Ni(PATA)(OH2)]2+ complex remained inactive in the CEST process.
RESUMEN
Co(II) and Ni(II) complexes of two tri-pyridine-based ligands with two hydroxy and two amide exchangeable protons (TDTA) and with six amide exchangeable protons (TMTP) were investigated for application as paraCEST-based magnetic resonance imaging (MRI) contrast agents. The two hydroxy groups present in the TDTA ligand were found to be passive while the amide group was active towards the CEST process. In the case of the Co(II) and Ni(II) complexes of the TMTP ligand, all three coordinated amide groups participated in the exchange process, and excellent CEST signals were observed. The X-ray structure of the four complexes revealed the seven-coordinate geometry of Co(II) complexes and the six-coordinate geometry of Ni(II) complexes. The presence of amide protons and hydroxy protons in the complexes was detected by the NMR method. The stability of the complexes in solution at high temperatures, in different pH ranges and acidic conditions, in the presence of competing cations, and biologically relevant anions was investigated. Potentiometric titrations were carried out to determine the ligand's protonation constants and the complexes' thermodynamic stability constant at 25.0 °C and I = 0.15 mol L-1 NaClO4. ParaCEST studies of [Co(TMTP)]2+ and [Ni(TMTP)]2+ at variable pH and variable pulse power are highlighted.
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The present investigation highlights a rhodamine-B- and coumarin-based efficient probe that selectively detects Ga3+ over other metal ions. The active pocket of the ligand for trapping the metal ions and the binding stoichiometry of its Ga3+ 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 Ga3+ and reversibly recognize Ga3+ in the solution. The spiro ring opening of the ligand after Ga3+ 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 Ga3+ have been carried out in HaCaT cells and satisfactory responses were observed. Interestingly, with the help of this probe, Ga3+ 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 Ga3+ over other metal ions with a nanomolar level detection limit. Structural characterization of the ligand and its Ga3+ 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 Ga3+ in live cells has been explored, and positive responses were observed.
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Cumarinas , Colorantes Fluorescentes , Colorantes Fluorescentes/química , Ligandos , Rodaminas/química , Iones/análisisRESUMEN
The present investigation highlights a quinoline-based small molecule probe (DEQ) for the detection of Cd2+ among other metal ions in near-aqueous media. The probe DEQ and its Cd2+ complex (DEQ-Cd) have been synthesized and characterized by all possible spectroscopic methods. The weakly emissive DEQ showed its strong emission in the presence of Cd2+, which is attributed to the photoinduced electron transfer (PET) along with the chelation-enhanced fluorescence (CHEF) mechanism. The 1:1 binding mode between ligand and Cd2+ is confirmed by single crystal XRD analysis, which is further supported by Job's plot and HRMS. The detection limit of the probe to recognize Cd2+ was found to be as low as 89 nM. Furthermore, DEQ can act as a reversible fluorescence probe with the off-on-off mechanism by the alternative addition of Cd2+ and EDTA. DFT and TD-DFT studies exposed the proposed mechanism after Cd2+ insertion and the obtained results for electronic spectra are in line with the experimental results. The response towards pH was quite interesting and allowed us to study its application in live cell imaging. With all the positive results, the proposed ligand DEQ can be used as a potential probe for the detection of Cd2+ in real-life applications.
Asunto(s)
Cadmio , Sondas Moleculares , Cadmio/análisis , Espectrometría de Fluorescencia/métodos , Ligandos , Colorantes Fluorescentes/química , Imagen Óptica/métodosRESUMEN
For the last couple of decades, azabenzene-based ligands have drawn much attention from inorganic chemists due to their ability to coordinate with different metal ions to form supramolecular clusters. These azabenzenes are weak σ donors and strong π acceptors and electron-deficient. Metallogrid complexes and non-grid oligomers are well-defined supramolecular clusters, formed by appropriate chelating ligands, and can show interesting optical, magnetic, and electronic properties. Self-assembly of [n × n] metallogrid complexes is dominated by the entropic factor while the formation of oligonuclear metal ion complexes is dominated by other effects like CFSE, electrostatic factors, ligand conformational characters, etc. Herein, the present article gives an overview of six-membered heterocyclic azine-based ligands and their potential for different metal ions to form polynuclear complexes. Moreover, their temperature-dependent magnetic properties and SCO phenomena are well described and tabulated.
RESUMEN
Fe(iii) is a common pollutant released into our ecosystem from various industrial and anthropogenic activities which when in excess interferes with human health. A plethora of sensors based on various designs and working principles are being continuously synthesized and improvised for its facile detection. In the present review, we have provided a brief overview of the developments made in the field of metal organic framework (MOF) based optical sensors for Fe3+. MOFs have exponentially emerged in the field of research due to their high porosity, modular construction and easy tunability. These inorganic-organic hybrid porous materials are being essentially promoted as optical sensors because of their unique photophysical properties and potential sensing applications.