A Telechelic Fluorescent Indicator Based on Polymer Conformational Change for Free Copper(II) Ions
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PROVIDER: S-EPMC10708570 | biostudies-literature | 2023 Nov
REPOSITORIES: biostudies-literature
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Project description:Heavy metal ions, i.e., copper(II) (Cu(II)), are harmful to the environment and our health. The current research established an eco-friendly and efficient metal-sensitive indicator, which can identify Cu(II) ions in both liquid and solid forms, by utilizing anthocyanin extract obtained from jambolao fruit (Syzgium cumini) that is incorporated within bacterial cellulose nanofibers (BCNF).The CIE Lab color parameters demonstrated that Cu(II) binding causes a sensible change in color. It was observed that the visible color altered with an increase in the Cu(II) concentration. The bacterial cellulose nanofibers that were altered with anthocyanin were analyzed using ATR-FTIR and FESEM. The sensor's selectivity was tested by using a range of metal ions such as lead (Pb2+), cobalt (Co2+), cadmium (Cd2+), nickel (Ni2+), aluminium (Al3+), barium (Ba2+), manganese (Mn2+), zinc (Zn2+), mercury (Hg2+) and sodium (Na+). The findings demonstrated that the suggested sensor showed excellent selectivity toward Cu(II) ion. Cu(II) can be accurately identified using the sensing technique, with detection limits ranging from 10-400 ppm and 50-500 ppm for liquid and solid samples, respectively, and through observation with naked eye. The fabricated green metallochromic sensor is promising to be a simple, cheap, mobile and easily operable for the real-time and on-site detection of Cu(II) ion.
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Project description:Copper deficiency can adversely impact health, and using copper cookware can help supplement copper ions. In this study, we have developed a fluorescent Cu(II) sensor using an efficient DNAzyme, a novel cofactor 2-mercaptoethanol and an optimized fluorophore. This sensor has demonstrated high sensitivity, with a linear detection range of 30 nM-50 μM and a detection limit of 3.4 nM. Furthermore, it has shown high selectivity for Cu(II) ions and possesses excellent anti-interference ability against 10,000-fold excess of Ca(II) and Mg(II), etc. These features allow the sensor suitable for quantitatively detecting Cu(II) in a copper pot, where a maximum Cu(II) concentration of 40.0 μM was achieved upon the addition of pickled cucumber. Our findings suggest that acidic conditions are beneficial for increasing Cu(II) content in the cooking medium. This provides a scientific basis for using copper cookware as a means to increase dietary copper intake.
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Project description:A novel spirobifluorene derivative bearing two bissulfonamido groups is successfully synthesized by Sonogashira coupling. This compound exhibits a strong fluorescence quenching by Cu(II) ion in a 50% mixture between acetonitrile and 20 mM pH 7.0 N-(2-hydroxyethyl)piperazine-N'-ethanesulfonic acid (HEPES) buffer with a detection limit of 98.2 nM. However, this sensor also shows ratiometric signal shifts from blue to yellow in the presence of Zn(II), Pb(II), and Hg(II) ions. The static quenching mechanism is verified by the signal reversibility using ethylenediaminetetraacetic acid (EDTA) and the Stern-Volmer plots at varying temperatures. The Cu(II)-spirobifluorene complex shows a highly selective fluorescence enhancement upon the addition of CN- ion with the detection limit of 390 nM. The application of this complex for quantitative analysis of spiked CN- ion in real water samples resulted in good recoveries.
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Project description:Herein, we have investigated principally with the use of UV and fluorescence (steady-state and time-resolved) spectroscopy the interactions between selected pentapeptides with tyrosine residue (EYHHQ, EHYHQ, EHHQY, and KYHHE) and various metal ions (Cu2+, Mn2+, Co2+, Ni2+, Zn2+, Cr3+, Cd2+, Ag+, Pb2+, Sr2+, Ba2+, Ca2+, Mg2+, Al3+, Fe2+, and Ga3+) in order to establish the relationship between the position of a tyrosine residue in the peptide sequence and the metal ion-binding properties. Among the peptides studied, EHYHQ was evaluated as an efficient and selective ligand for developing a chemosensor for the detection of copper(II) ions. While significant fluorescence emission quenching was observed for that peptide in the presence of Cu2+ cations, other metal cations used at the same and at considerably higher concentrations caused a negligible change of the fluorescence emission spectrum, indicating a high selectivity of EHYHQ for Cu2+ ions. Under optimum conditions, fluorescence intensity was inversely proportional to the concentration of Cu2+ ions. The limit of detection of Cu2+ ions with the use of EHYHQ was determined at the level of 26.6 nM. The binding stoichiometry of the complexes of the studied peptides with Cu2+ ions was evaluated spectrophotometrically and fluorimetrically (as in the case of EHYHQ confirmed by mass spectrometry) and found to be 1:2 (Cu2+-peptide) for all the investigated systems. Furthermore, the stability constant (K) values of these complexes were determined. The reversibility of the proposed Cu2+ ions sensor was confirmed, the pH range where the sensor acts was determined, while its analytical performance was compared with some other reported recently fluorescent sensors. The mechanism of the interactions between EHYHQ and Cu2+ was proposed on the basis of NMR spectroscopy investigations.
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Project description:A label free fluorescent peptide probe (HDSGWEVHH) was used for Cu2+ and S2- determination in aqueous solution. Our results demonstrated that HDSGWEVHH is highly selective and sensitive for monitoring free Cu2+ concentration via quenching of the probe fluorescence upon Cu2+ binding. The mechanism of the complexation is investigated with Cyclic Voltammetry (CV), 1H nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) spectroscopy and computational techniques. Theoretical calculation results indicated the binding ratio of the probe to Cu2+ is 2 : 1 and the binding constant was obtained as 1.72 × 10 8 M-1. Cu2+ concentration can be detected with the detection limit of 16 nM. Free Cu2+ concentration released from the metallothionein-Cu complex at different pH values was detected. Cu2+ concentration in real water and tea samples was also detected, and the results were consistent with the ones monitored by atomic absorption spectrometer. Because of the exceedingly small K sp value of CuS (1.27 × 10-36), S2- can sequester Cu2+ from HDSGWEVHH to restore the tryptophan (W) fluorescence. Thus the HDSGWEVHH-Cu2+ complex can also be used for S2- detection. The S2- concentrations can be monitored with a detection limit of 19 nM. The assay is also amenable to measurement of S2- concentration in pure water samples. Thus the probe designed herein is sensitive, label free, low cost, and environmentally friendly for Cu2+ and S2- determination in aqueous solutions.
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Project description:Two new coumarin-based "turn-off" fluorescent probes, (E)-3-((3,4-dihydroxybenzylidene)amino)-7-hydroxy-2H-chromen-2-one (BS1) and (E)-3-((2,4-dihydroxybenzylidene)amino)-7-hydroxy-2H-chromen-2-one (BS2), were synthesized and their detection of copper(II) and iron(III) ions was studied. Results show that both compounds are highly selective for Cu²⁺ and Fe³⁺ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3) and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II) or iron(III) ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10⁻⁵ M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu²⁺ and Fe³⁺ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.
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Project description:The title compound, C40H64O12, crystallizes in a pseudomerohedrally twinned primitive monoclinic cell with similar contributions of the two twin components. There are two symmetry-independent half-molecules of nonactin in the asymmetric unit. Each molecule has a pseudo-S4 symmetry and resides on a crystallographic twofold axis; the axes pass through the molecular center of mass and are perpendicular to the plane of the macrocycle. The literature description of the room-temperature structure of nonactin as an order-disorder structure in an orthorhombic unit cell is corrected. We report a low-temperature high-precision ordered structure of ;free' nonactin that allowed for the first time precise determination of its bond distances and angles. It possesses an unfolded and more planar geometry than its complexes with encapsulated Na+, K+, Cs+, Ca2+ or NH4+ cations that exhibit more isometric overall conformations.
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Project description:We have recently described a cryptand structure, FCryp-1, with appropriate properties for an indicator of intracellular free Na+ concentration using the 19F-n.m.r. chemical shift of the incorporated 5FBAPTA [1,2-bis-(2-amino-5-fluorophenoxy)ethane-NNN'N'-tetra-acetic acid] reporter group to measure the free cytosolic Na+ concentration [( Na+]i) [Smith, Morris, Hesketh and Metcalfe (1986) Biochim. Biophys. Acta 889, 82-83]. FCryp-1 carries four carboxylate groups to confer aqueous solubility and the indicator is membrane-permeant when the carboxyls are esterified with acetoxymethyl ester groups. Here we describe the synthesis of FCryp-2 to provide a fluorescent indicator of [Na+]i. FCryp-2 retains the parent tribenzo (2:2:1) cryptand structure of FCryp-1, in which the benzenoid ring at C-21 in FCryp-1 is replaced by an indole derivative which acts as the fluorophor in FCryp-2. With excitation at 340 nm, FCryp-2 gives an emission maximum at 460 nm in the absence of Na+ which shifts to 395 nm when FCryp-2 is saturated with Na+, with an isosbestic point at 455 nm. The apparent dissociation constant of FCryp-2 in a buffer solution of 100 mM-KCl/20 mM-KH2PO4/K2HPO4, pH 7.0, at 37 degrees C is 6.0 mM and the free Na+ concentration can be measured either from the calibrated fluorescence intensity at 395 nm, which increases 25-fold when Na+ is bound to FCryp-2, or from the ratio of fluorescence intensities at 395 nm and 455 nm. The measurement of free [Na+] by either method is unaffected by K+, Ca2+ or Mg2+ in the normal intracellular concentration ranges. Free [Na+] measurements by the ratio method are unaffected by pH from 6.6 to 7.6.
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