The photophysical properties of 5-arylvinyl-5'-methyl-2,2'-bipyridyls (AVMBs, 1-9, 11) and their zinc complexes were studied. Similar 2,2'-bipyridyl-based ligands have been applied as optical sensors for metal ions and sensitizers for solar energy conversion. The goal of this investigation is to reveal the factors that determine the emission band shift and fluorescence quantum yield change of the title ligand system upon zinc binding. The outcome of this study will not only advance the fundamental understanding of the coordination-driven photophysical processes embodied in the AVMB platform but facilitate the rational design of fluorescent probes for metal ions, particularly zinc. The AVMB ligands were synthesized using the Horner-Wadsworth-Emmons reaction. AVMBs containing electron-donating aryl groups show absorption and emission in the visible region, which can be assigned to charge-transfer transitions as supported by solvent-dependency and computational studies. The binding between AVMB ligands and zinc ion in acetonitrile was studied using isothermal titration calorimetry (ITC). A multicomponent equilibrium model is suggested that explains the multiple transitions evidenced in fluorescence titration isotherms. Coordination to zinc ion stabilizes the charge-transfer excited state of an AVMB ligand with an electron-donating aryl substituent, consequently results in bathochromic shifts in both absorption and emission. However, unlike the emission band shift, the fluorescence quantum yield change upon zinc complex formation does not have an intuitive correlation with the electronic nature of the aryl group. Lifetime measurements using the Time-Correlated Single Photon Counting method enabled the determination of nonradiative and radiative decay rate constants. Both rates of an AVMB ligand decrease upon zinc binding. The collective effect gives rise to the change in fluorescence quantum yield with the apparent lack of correlation with the electronic property of the aryl group.
2-(2'-Hydroxyphenyl)benzoxazole (HBO) is known for undergoing intramolecular proton transfer in the excited state to result in the emission of its tautomer. A minor long-wavelength absorption band in the range 370-420 nm has been reported in highly polar solvents such as dimethylsulfoxide (DMSO). However, the nature of this species has not been entirely clarified. In this work, we provide evidence that this long-wavelength absorption band might have been caused by base or metal salt impurities that are introduced into the spectral sample during solvent transport using glass Pasteur pipettes. The contamination by base or metal salt could be avoided by using borosilicate glass syringes or nonglass pipettes in sample handling. Quantum chemical calculations conclude that solvent-mediated deprotonation is too energetically costly to occur without the aid of a base of an adequate strength. In the presence of such a base, the deprotonation of HBO and its effect on emission are investigated in dichloromethane and DMSO, the latter of which facilitates deprotonation much more readily than the former. Finally, the absorption and emission spectra of HBO in 13 solvents are reported, from which it is concluded that ESIPT is hindered in polar solvents that are also strong hydrogen bond acceptors.
The discovery of polonium (Po) was first published in July, 1898 by P. Curie and M. Curie. It was the first element to be discovered by the radiochemical method. Polonium can be considered as a famous but neglected element: only a few studies of polonium chemistry have been published, mostly between 1950 and 1990. The recent (2006) event in which (210)Po evidently was used as a poison to kill A. Litvinenko has raised new interest in polonium. 2011 being the 100th anniversary of the Marie Curie Nobel Prize in Chemistry, the aim of this review is to look at the several aspects of polonium linked to its chemical properties and its radiotoxicity, including (i) its radiochemistry and interaction with matter; (ii) its main sources and uses; (iii) its physicochemical properties; (iv) its main analytical methods; (v) its background exposure risk in water, food, and other environmental media; (vi) its biokinetics and distribution following inhalation, ingestion, and wound contamination; (vii) its dosimetry; and (viii) treatments available (decorporation) in case of internal contamination.
Excitation-dependent multiple fluorescence of a 2-(2′hydroxyphenyl)benzoxazole (HBO) derivative ( 1) is described. Compound 1 contains the structure of a charge-transfer (CT) 4hydroxyphenylvinylenebipy fluorophore and an excited-state intramolecular proton transfer capable (ESIPT-capable) HBO component that intersect at the hydroxyphenyl moiety. Therefore, both CT and ESIPT pathways, while spatially mostly separated, are available to the excited state of 1. The ESIPT process offers two emissive isomeric structures (enol and keto) of 1 in the excited state, while the susceptibility of 1 to a base adds another option to tune the composite emission color. In addition to the ground-state acid−base equilibrium that can be harnessed for the control of emission color by excitation energy, compound 1 exhibits excitation-dependent emission that is attributed to solventaffected ground-state structural changes. Therefore, depending on the medium and excitation wavelength, the emission from the enol, keto, and anion forms could occur simultaneously, which are in the color ranges of blue, green, and orange/red, respectively. A composite color of white with CIE coordinates of (0.33, 0.33) can be materialized through judicious choices of medium and excitation wavelength.
Sequential fluorescence enhancement and fluorescence resonance energy transfer over a zinc ion gradient have been engineered in a two-fluorophore heteroditopic ligand platform. This is the first report that the strategies of metal-coordination modulated photoinduced electron transfer (PET), internal charge transfer (ICT), and fluorescence resonance energy transfer (FRET) are integrated in one synthetic fluoroionophore. Comparing to the previously reported single-fluorophore heteroditopic ligands (L.
The recent advances in the development of fluorescent heteroditopic ligands of metal ions are reviewed. The scientific endeavour in this area is fuelled partly by the need for sensing technologies that are (1) targeting substances over large concentration ranges and (2) capable of analysing multiple analytes simultaneously. These objectives are largely not attainable using monotopic coordination platforms. The investigations of the fluorescent heteroditopic ligands of metal ions have revealed surprisingly intricate interplays between metal coordination at two different sites and the photophysical states that are accessible through those systems. The chemical complexity of fluorescent heteroditopic ligands of metal ions warrants further investigations on the fundamental science front in order to fully acquire their potential for meeting our practical needs.
Dedicated to Prof. Adoración Gómez-Quiroga, cancer survivor and outstanding medicinal inorganic chemist.Triple negative breast cancer (TNBC) is one of the breast cancers with poorer prognosis and survival rates. TNBC has a disproportionally high incidence and mortality in women of African descent. We report on the evaluation of Ru-IM (1), a watersoluble organometallic ruthenium compound, in TNBC cell lines derived from patients of European (MDA-MB-231) and African (HCC-1806) ancestry (including IC 50 values, cellular and organelle uptake, cell death pathways, cell cycle, effects on migration, invasion, and angiogenesis, a preliminary proteomic analysis, and an NCI 60 cell-line panel screen). 1 was previously found highly efficacious in MDA-MB-231 cells and xenografts, with little systemic toxicity and preferential accumulation in the tumor. We observe a similar profile for this compound in the two cell lines studied, which includes high cytotoxicity, apoptotic behavior and potential antimetastatic and antiangiogenic properties. Cytokine M-CSF, involved in the PI3/AKT pathway, shows protein expression inhibition with exposure to 1. We also demonstrate a p53 independent mechanism of action.
Identification of stable HOPO–UO22+–fetuin ternary complexes after a chromatographic separation process.
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