A Highly Selective and Sensitive Fluorescent Turn-Off Probe for Cu2+ Based on a Guanidine Derivative.
ABSTRACT: A new highly selective and sensitive fluorescent probe for Cu2+, N-n-butyl-4-(1'-cyclooctene-1',3',6'-triazole)-1,8-naphthalimide (L), was synthesized and evaluated. The structure of compound L was characterized via IR, ¹H-NMR, 13C-NMR and HRMS. The fluorescent probe was quenched by Cu2+ with a 1:1 binding ratio and behaved as a "turn-off" sensor. An efficient and sensitive spectrofluorometric method was developed for detecting and estimating trace levels of Cu2+ in EtOH/H?O. The ligand exhibited excitation and emission maxima at 447 and 518 nm, respectively. The equilibrium binding constant of the ligand with Cu2+ was 1.57 × 10? M-1, as calculated using the Stern.
Project description:The fluorescent probe L, based on naphthalimide-modified coumarin, was designed, synthesized, and characterized, which could recognize Cu2+ from other cations selectively and sensitively in HEPES buffer (10 mM, Ph = 7. 4)/CH3CN (1:4, V/V). When the probe L interacted with Cu2+, the color and the fluorescent intensity changed obviously and it provided the naked-eye detection for Cu2+. The recognition mode between them was achieved by Job's plot, IR, MS, SEM, and 1HNMR. In addition, test strips made from L could still interact with Cu2+ in tap water effectively. The limit of detection (LOD) of L was 3.5 × 10-6 M. Additionally, the density functional theory (DFT) calculation method was used to analyze the action mechanism of L toward Cu2+. Importantly, the fluorescent probe L could demonstrate favorable selectivity toward Cu2+ in Caenorhabditis elegans. Thus, L was considered to have some potential for application in bioimaging.
Project description:A new fluorescent chemosensor for copper (II) and subsequent anion sensing was designed and fully characterized. The sensor consisted of a 1,8-naphthalimide core, bearing two terminal dipicolylamine (DPA) receptor units for binding metal cations, and an ethoxyethanol moiety for enhanced water solubility. The DPA units are connected to position 4 of the fluorophore via a triazine-ethylenediamine spacer. Fluorescence titration studies of the chemosensor revealed a high selectivity for Cu2+ over other divalent ions, the emissions were strongly quenched upon binding, and a stability constant of 5.52 log units was obtained. Given the distance from DPA chelating units and the fluorophore, quenching from the Cu2+ complexation suggests an electron transfer or an electronic energy transfer mechanism. Furthermore, the Cu2+-sensor complex proved to be capable of sensing anionic phosphate derivatives through the displacement of the Cu2+ cation, which translated into a full recovery of the luminescence from the naphthalimide. Super-resolution fluorescence microscopy studies performed in HeLa cells showed there was a high intracellular uptake of the chemosensor. Incubation in Cu2+ spiked media revealed a strong fluorescent signal from mitochondria and cell membranes, which is consistent with a high concentration of ATP at these intracellular sites.
Project description:A novel fluorescent Probe 1, based on phenanthro-imidazole has been developed as an efficient chemosensor for the trace detection of copper ions (Cu2+). Probe 1 demonstrated sensitive fluorescence quenching upon binding with Cu2+ through 1:1 stoichiometric chelation. The detection limit for Cu2+ ions was projected through linear quenching fitting to be as low as 2.77 × 10-8 M (or 1.77 ppb). The sensing response was highly selective towards Cu2+ with minimal influence from other common metal ions, facilitating the practical application of Probe 1 in trace detection.
Project description:A novel coumarin derivative (5) was synthesized and used as a colorimetric and fluorescent probe for selective detection of Cu2+ ions in the presence of other metal ions, with the detection limits of 5.7 and 4.0 ppb, respectively. Cu2+ ion reacts with probe 5 to form a 1:1 stoichiometry complex, resulting in a remarkable redshift of absorption maximum from 460 to 510 nm, as well as almost completely quenching fluorescence intensity of probe 5 at the wavelength of 536 nm. These changes can be distinctly observed by naked eyes. In addition, the working pH range of probe 5 is wide and suitable for physiological conditions, thus probe 5 may be used for detection of Cu2+ ions in living cells. The stable structures of probe 5 and its 1:1 complex with Cu2+ ion were optimized at the PBE0/6-31+G(d) level of theory. The presence and characteristics of bonds in compounds were studied through atoms in a molecule and natural bond orbital analysis. The formation of the complex led to a strong transfer of electron density from probe 5 as a ligand to Cu2+ ion, resulting in breaking the ?-electron conjugated system, which is the cause of fluorescence quenching and color change of 5-Cu2+ complex.
Project description:A series of multifunctional compounds (MFCs) 1a-1d based on 1,8-naphthalimide moiety were designed and synthesized. Due to the good fluorescence property and nucleic acid binding ability of 1,8-naphthalimide, these MFCs were applied in Cu2+ ion recognition, lysosome staining as well as RNA delivery. It was found that these MFCs exhibited highly selective fluorescence turn-off for Cu2+ in aqueous solution. The fluorescence emission of 1a-1d was quenched by a factor of 116-, 20-, 12-, and 14-fold in the presence of Cu2+ ions, respectively. Most importantly, 1a-Cu and 1b-Cu could be used as imaging reagents for detection of lysosome in live human cervical cancer cells (HeLa) using fluorescence microscopy. Furthermore, in order to evaluate the RNA delivery ability of 1a-1d, cellular uptake experiments were performed in HeLa, HepG2, U2Os, and MC3T3-E1 cell lines. The results showed that all the materials could deliver Cy5-labled RNA into the targeted cells. Among them, compound 1d modified with long hydrophobic chain exhibited the best RNA delivery efficiency in the four tested cell lines, and the performance was far better than lipofectamine 2000 and 25 kDa PEI, indicating the potential application in non-viral vectors.
Project description:A novel conjugated polymer (PDBDBM) was developed by the polymerization of 1,4-dioctyloxy-2,5-diethynylbenzene with 1,3-bis(4-bromophenyl)propane-1,3-dione based on Pd-catalyzed Sonogashira-coupling reaction. The obtained polymer PDBDBM exhibited bright green photoluminescence under UV irradiation. According to the metal ion titration experiments, PDBDBM showed high sensitivity and selectivity for detection of Cu2+ and Fe3+ over other metal ions. The fluorescent detection limits of PDBDBM were calculated to be 5 nM for Cu2+ and 0.4 μM for Fe3+ and the Stern⁻Volmer quenching constant for Cu2+ and Fe3+ were found to be 1.28 × 10⁸ M-1 and 2.40 × 10⁴ M-1, respectively. These results indicated that the polymer can be used as a potential probe for Cu2+ and Fe3+ detection.
Project description:The detection of pyrophosphatase (PPase) activity is of great significance in diagnosing diseases and understanding the function of PPase-related biological events. This study constructed a turn off-on-off fluorescent system for PPase activity assay based on PPase-regulated competitive coordination of Cu2+ between a water-soluble fluorescent probe 6,7-dihydroxycoumarin (DHC) and pyrophosphate (PPi). The probe DHC can coordinate with Cu2+ and consequently display on-off type fluorescence response. Furthermore, the in situ formed nonfluorescent Cu2+-DHC complex can act as an effective off-on type fluorescent probe for sensing PPi due to the higher coordination reactivity between Cu2+ and PPi than that between Cu2+ and DHC. The subsequent addition of PPase to the mixture containing Cu2+, DHC, and PPi leads to the fluorescence requenching of the system again (an off state) because PPase catalyzes the hydrolysis of PPi into orthophosphate in the reaction system. Under the optimum conditions, the decrease of the fluorescence intensity of DHC-Cu2+-PPi system was linear with the increase of the PPase activity in the range from 0.1 to 0.3?U. The detection limit was down to 0.028?U PPase (S/N = 3). Moreover, the as-established system was also applied to evaluate PPase inhibitor. This study offers a simple yet effective method for the detection of PPase activity.
Project description:A new dansyl-based chemosensor (2-(4-((5-(dimethylamino)naphthalen-1-yl)sulfonyl)piperazin-1-yl)-N-(quinolin-8-yl)acetamide) (DC) for detecting Cu2+ was synthesized and characterized. DC showed great selectivity to Cu2+ by a fluorescent "on-off" detection method. Job plot, ESI-mass spectroscopy, and 1H NMR titration suggested a 1 to 1 binding mode between DC and Cu2+. The detection limit was determined to be 43 nM, which is greatly below the WHO guidelines. In addition, DC can be applied to real samples and zebrafish imaging. The fluorescence quenching mechanism was proposed as the enhancement of intramolecular charge transfer with calculations.
Project description:A novel ruthenium(II) polypyridyl complex bearing 1,8-naphthyridine was successfully designed and synthesized. This complex was fully characterized by EI-HRMS, NMR, and elemental analyses. The recognition properties of the complex for various metal ions were investigated. The results suggested that the complex displayed high selectivity and sensitivity for Cu2+ and Fe3+ ions with good anti-interference in the CH3CN/H2O (1:1, v/v) solution. The fluorescent chemosensor showed obvious fluorescence quenching when the Cu2+ and Fe3+ ions were added. The detection limits of Cu2+ and Fe3+ were 39.9 nmol/L and 6.68 nmol/L, respectively. This study suggested that this Ru(II) polypyridyl complex can be used as a high selectivity and sensitivity fluorescent chemosensor for Cu2+ and Fe3+ ions.
Project description:A series of fluorescent coumarin derivatives 2a-e were systematically designed, synthesized and studied for their Cu2+ sensing performance in aqueous media. The sensitivities and selectivities of the on-to-off fluorescent Cu2+ sensing signal were in direct correlation with the relative arrangements of the heteroatoms within the coordinating moieties of these coumarins. Probes 2b and 2d exhibited Cu2+ concentration dependent and selective fluorescence quenching, with linear ranges of 0-80 ?M and 0-10 ?M, and limits of detection of 0.14 ?M and 0.38 ?M, respectively. Structural changes of 2b upon Cu2+ coordination were followed by fluorescence titration, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), mass spectrometry, and single crystal X-ray diffraction on the isolated Cu2+-coumarin complex. The results revealed a 1:1 stoichiometry between 2b and Cu2+, and that the essential structural features for Cu2+-selective coordination are the coumarin C=O and a three-bond distance between the amide NH and heterocyclic N. Probe 2b was also used to determine copper (II) levels in aqueous soil extracts, with recovery rates over 80% when compared to the standard soil analysis method: inductively coupled plasma-mass spectrometry (ICP-MS).