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A novel Schiff base fluorescent probe for rare earth ion Lu3+ is reported. Emission intensity of the probe is intrinsically non-fluorescent, which is due to isomerization of the C=N bond in the excited-state proton transfer (ESPT) of phenolic protons of the salicylic amide moiety. In the presence of Lu3+, fluorescence intensifies significantly due to inhibition of the C=N isomerization and ESPT. The Schiff base is characterized by high sensitivity and selectivity towards Lu3+. The fluorescence turn-on mechanism of Lu[L]2 system is proposed.

Graphdiyne quantum dots (GDQDs) have attracted increasing attentions due to its unique electronic, optical, and electrochemical properties. However, the low conductivity and quantum yield of GDQDs limit their application. Here, nitrogen-doped graphdiyne dots (N-GDQDs) are firstly synthesized by a simple, friendly and one-step hydrothermal method. The N-GDQDs show a maximum emission at 410 nm under the excitation wavelength of 319 nm. The doping N modifies the surface defect of N-GDQDs and further greatly improves their quantum yield (from 14.6% to 48.6%). In addition, the doping N induces a strong electron transport ability and good conductivity of N-GDQDs. Subsequently, the prepared N-GDQDs are used for constructing an optical-electrochemical nanosensor for sensitive and selective detection of dopamine (DA). DA can quench the fluorescence of N-GDQDs by forming a ground-state non-fluorescent complex between phenoxy anions (in PBS solution) in DA and pyridinic N sites of N-GDQDs, which leads to a highly sensitive and selective detection of DA with a limit of detection (LOD) of 0.14 μM and a linear range of 0.32–500 μM. In the electrochemical detection, DA can be oxidized to DA-quinone under the electric field through N-GDQDs/GCE, which shows a big affinity to N-GDQDs. The LOD for DA is 0.02 μM with a linear range of 0.05–240 μM. Finally, the spiked application for DA detection in human serum samples is investigated, the results show that the method has high accuracy. Our work provides a new carbon quantum dots based sensing platform, which shows great potential in practical application.

The stoichiometry of protein complexes is precisely regulated in cells and is fundamental to protein function. Singe-molecule fluorescence imaging based photobleaching event counting is a new approach for protein stoichiometry determination under physiological conditions. Due to the interference of the high noise level and photoblinking events, accurately extracting real bleaching steps from single-molecule fluorescence traces is still a challenging task. Here, we develop a novel method of using convolutional and long-short-term memory deep learning neural network (CLDNN) for photobleaching event counting. We design the convolutional layers to accurately extract features of steplike photobleaching drops and long-short-term memory (LSTM) recurrent layers to distinguish between photobleaching and photoblinking events. Compared with traditional algorithms, CLDNN shows higher accuracy with at least 2 orders of magnitude improvement of efficiency, and it does not require user-specified parameters. We have verified our CLDNN method using experimental data from imaging of single dye-labeled molecules in vitro and epidermal growth factor receptors (EGFR) on cells. Our CLDNN method is expected to provide a new strategy to stoichiometry study and time series analysis in chemistry.

We report a sensitive sensing strategy based on metal-enhanced fluorescence (MEF) and hybridization chain reaction (HCR). Hg2+ aptamers were immobilized on magnetic nanoparticles (NPs) and HCR process happened without Hg2+, forming long DNA chains and allowing fluorescent indicator (SYBR Green) intercalated in the double helix. After magnetic separation from test solution, positively charged Ag@SiO2 NPs were added, they were electrostatically absorbed on negatively charged DNA chains, acting as “smart dust” to enhance fluorescence signal. This design was used for Hg2+ detection and it showed high sensitivity with a limit of detection down to 25 pM. This method also exhibited good selectivity over other metal ions and was successfully applied in real water sample analyses.

A Schiff base derivative, N-(3-methoxy-4-hydroxybenzylidene)salicyloylhydrazone (L), shows high selectivity to Lu3+ not only in abiotic systems but also in living cells with fluorescence. The presence of PVP can increase the fluorescence intensity. The fluorescence enhancement is presumably due to a combinational effect of intramolecular charge transfer (ICT) and excited-state intra/intermolecular proton transfer (ESPT) during the chelation of L to Lu3+ in a 2 : 1 complex mode.

A series of high brightness orange-red phosphors β-Ca2-xP2O7:xEu3+ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) were synthesized via solid state reaction in air atmosphere. The phase, morphology, photoluminescence properties and fluorescent thermal stability of the obtained phosphors were investigated. The chromaticity coordinates of the samples were calculated and located in the orange-red region. The intense emissions at 585, 591 nm (5D0 → 7F1), 610 nm (5D0 → 7F2) were observed under NUV excitation. Furthermore, the ratio of the emission of 5D0 → 7F2 transition to that of 5D0 → 7F1 transition changed dramatically with varied Eu3+ concentration, indicating the existence of the site symmetry transformation of Eu3+ luminescence center in the matrix. The phosphors performed excellent properties at 423 K with temperature quenching at 473–573 K, and may be potential orange-red phosphor in lighting field.

Here we describe a new BODIPY-based membrane probe (1) that provides an alternative to dialkylcarbocyanine dyes, such as DiI-C18, that can be excited in the blue spectral region. Compound 1 has unbranched octadecyl chains at the 3,5-positions and a meso-amino function. In organic solvents, the absorption and emission maxima of 1 are determined mainly by solvent acidity and dipolarity. The fluorescence quantum yield is high and reaches 0.93 in 2-propanol. The fluorescence decays are well fitted with a single-exponential in pure solvents and in small and giant unilamellar vesicles (GUV) with a lifetime of ca. 4 ns. Probe 1 partitions in the same lipid phase as DiI-C18(5) for lipid mixtures containing sphingomyelin and for binary mixtures of dipalmitoylphosphatidylcholine (DPPC) and dioleoylphosphatidylcholine (DOPC). The lipid phase has no effect on the fluorescence lifetime but influences the fluorescence anisotropy. The translational diffusion coefficients of 1 in GUVs and OLN-93 cells are of the same order as those reported for DiI-C18. The directions of the absorption and emission transition dipole moments of 1 are calculated to be parallel. This is reflected in the high steady-state fluorescence anisotropy of 1 in high ordered lipid phases. Molecular dynamic simulations of 1 in a model of the DOPC bilayer indicate that the average angle of the transition moments with respect to membrane normal is ca. 70°, which is comparable with the value reported for DiI-C18.

A sensitive “on-off” fluorescent protocol for thrombin detection is demonstrated. Firstly, thrombin aptamers which hybridize with labeled help DNA were immobilized on the surface of Ag@SiO2 nanoparticles (NPs). The silver core causes the label Cy5 to display strong metal-enhanced fluorescence. On addition of thrombin and graphene oxide (GO), thrombin (with its high affinity for the aptamers) displaces the Cy5-labeled help DNA which then binds to the surface of GO via π-stacking, causing fluorescence quenching of Cy5. The findings were used to design a thrombin assay that has a 0.05 nM detection limit and excellent selectivity. It was applied to the quantification of thrombin in spiked serum samples where is showed recoveries ranging from 97 % to 107 %, with relative standard deviations between 2.2 and 4.5 %.

A biosensing platform using Ag@SiO2-DNA-fluorophore nanostructure was designed for metal ions and small organic molecules detection. DNA hybridization occurred in the presence of the targets through the formation of base–target–base complex; accordingly, the fluorophore (Cy3) was brought to the surface of Ag@SiO2 core/shell nanostructures. Through controlling the thickness of the silica shell on the Ag nanoparticle, the fluorescence of Cy3 could be enhanced by the surface plasmon resonance of Ag nanoparticle for up to 2.5 folds. This metal-enhanced fluorescence (MEF) sensor provided high sensitivity and selectivity for the detection of Hg2+, Ag+, and coralyne. It may be developed as a new class of MEF biosensors for other metal ions and organic molecules analysis.

Malignant tumor incidences have been rapidly rising recently and are becoming a serious threat to human health. Herein, a multifunctional cancer targeted theranostic nanoplatform is developed by in situ growth of iron oxide magnetic nanoparticles on carbon nanoparticles, and then loaded with fluorescent dye indocyanine green (ICG@MCNPs). The loading of ICG on the nanoplatform significantly improves its photostability, and hence facilitates long-term near-infrared fluorescence (NIRF) imaging and efficient photothermal therapy (PTT) of tumor. The in vivo NIRF imaging reveals that ICG@MCNPs can be targeted to the tumor site. Moreover, in vivo magnetic resonance imaging also confirmed the efficient accumulation of ICG@MCNPs in the tumor site. Inspiringly, the subsequent PTT of tumor-bearing mice is achieved, as evidenced by the complete ablation of the tumor and the recovery of the physiological indexes to normal levels. Benefitting from its low-cost, simple preparation, and excellent dual-modal imaging and therapy, the ICG@MCNPs-based theranostic nanoplatform holds great promise in tumor-targeted nanomedicine.

The UV-vis electronic absorption and fluorescence emission properties of 8-halogenated (Cl, Br, I) difluoroboron dipyrrin (or 8-haloBODIPY) dyes and their 8-(C, N, O, S) substituted analogues are reported. The nature of the meso-substituent has a significant influence on the spectral band positions, the fluorescence quantum yields, and lifetimes. As a function of the solvent, the spectral maxima of all the investigated dyes are located within a limited wavelength range. The spectra of 8-haloBODIPYs display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. Conversely, fluorophores with 8-phenylamino (7), 8-benzylamino (8), 8-methoxy (9), and 8-phenoxy (10) groups emit in the blue range of the visible spectrum and generally have larger Stokes shifts than common BODIPYs, whereas 8-(2-phenylethynyl)BODIPY (6) has red-shifted spectra compared to ordinary BODIPY dyes. Fluorescence lifetimes for 6, 8, and 10 have been measured for a large set of solvents and the solvent effect on their absorption and emission maxima has been analyzed using the generalized Catalán solvent scales. Restricted rotation about the C8-N bond in 7 and 8 has been observed via temperature dependent (1)H NMR spectroscopy, whereas for 10 the rotation about the C8-O bond is not hindered. The crystal structure of 8 demonstrates that the short C8-N bond has a significant double character and that this N atom exhibits a trigonal planar geometry. The crystal structure of 10 shows a short C8-O bond and an intramolecular C-H···π interaction. Quantum-chemical calculations have been performed to assess the effect of the meso-substituent on the spectroscopic properties.

Six conformationally restricted BODIPY dyes with fused carbocycles were synthesized to study the effect of conformational mobility on their visible electronic absorption and fluorescence properties. The symmetrically disubstituted compounds (2, 6) have bathochromically shifted absorption and fluorescence spectral maxima compared to those of the respective asymmetrically monosubstituted dyes (1, 5). Fusion of conjugation extending rings to the α,β-positions of the BODIPY core is an especially effective method for the construction of boron dipyrromethene dyes absorbing and emitting at longer wavelengths. The fluorescence quantum yields Φ of dyes 1-6 are high (0.7 ≤ Φ ≤ 1.0). The experimental results are backed up by quantum chemical calculations of the lowest electronic excitations in 1, 2, 5, 6, and corresponding dyes of related chemical structure but without conformational restriction. The effect of the molecular structure on the visible absorption and fluorescence emission properties of 1-6 has been examined as a function of solvent by means of the recent, generalized treatment of the solvent effect, proposed by Catalán (J. Phys. Chem. B 2009, 113, 5951-5960). Solvent polarizability is the primary factor responsible for the small solvent-dependent shifts of the visible absorption and fluorescence emission bands of these dyes.

A new single molecule multianalyte sensor, vanillic aldehyde rhodamine 6G hydrazone has been designed for the selective detection of Cu 2+ and Hg 2+ ions. UV/Vis spectroscopy indicates that the sensor is a good chromogenic chemosensor for Cu 2+ in 1:99 (v/v) ethanol–water media. Whereas, other ions, such as Li + , Na + , Mg 2+ , K + , Ca 2+ , Cr 3+ , Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Zn 2+ , Ag + , Cd 2+ , Ba 2+ , Hg 2+ and Pb 2+ failed to generate a distinct response. Fluorescence spectral data reveals that the sensor is an excellent fluorescent chemosensor for Hg 2+ in aqueous ethanol solution and with no fluorescent response toward other ions. The spectroscopic behavior of the sensor in living cells indicated that it can be used for the detection of Cu 2+ and Hg 2+ in environmental and biological systems. Mechanisms for the high selectivity of the sensor to Cu 2+ and Hg 2+ are discussed.

In a study of the spectroscopic behavior of two Schiff base derivatives, salicylaldehyde salicylhydrazone (1) and salicylaldehyde benzoylhydrazone (2), Schiff base 1 has high selectivity for Zn(2+) ion not only in abiotic systems but also in living cells. The ion selectivity of 1 for Zn(2+) can be switched for Mg(2+) by swapping the solvent from ethanol-water to DMF (N,N-dimethylformamide)-water mixtures. Imine 2 is a good fluorescent probe for Zn(2+) in ethanol-water media. Many other ions tested, such as Li(+), Na(+), Al(3+), K(+), Ca(2+), Cr(3+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Sn(2+), Ba(2+), Hg(2+), and Pb(2+), failed to induce any spectral change in various solvents. The selectivity mechanism of 1 and 2 for metal ions is based on a combinational effect of proton transfer (ESPT), C═N isomerization, and chelation-enhanced fluorescence (CHEF). The coordination modes of the complexes were investigated.

A Schiff-based fluorescence probe benzene-1,2-dicarbaldehyde bis-benzoyl hydrazide (L) was designed and synthesized. Its sensing behavior toward metal ions has been investigated by absorption and fluorescence spectroscopy. Indicator L showed high selectivity to Zn2+ in various solvents, whereas other metal ions failed to induce response. Especially Cd2+, which has similar chemical properties with Zn2+, can be distinguished from Zn2+ obviously. (C) 2010 Elsevier B.V. All rights reserved.

Staphylococcus aureus accessory gene regulator (agr) locus controls the expression of virulence factors through a classical two-component signal transduction system that consists of a receptor histidine protein kinase AgrC and a cytoplasmic response regulator AgrA. An autoinducing peptide (AIP) encoded by agr locus activates AgrC, which transduces extracellular signals into the cytoplasm. Despite extensive investigations to identify AgrC–AIP interaction sites, precise signal recognition mechanisms remain unknown. This study aims to clarify the membrane topology of AgrC by applying the green fluorescent protein (GFP) fusion technique and the substituted cysteine accessibility method (SCAM). However, our findings were inconsistent with profile obtained previously by alkaline phosphatase. We report the topology of AgrC shows seven transmembrane segments, a periplasmic N-terminus, and a cytoplasmic C-terminus.

The steady-state, UV-vis electronic absorption and fluorescence emission properties of a large set of 3-aryl and 3,5-diaryl substituted difluoroboron dipyrromethene dyes obtained via direct, palladium-catalyzed C-H (het)arylation of the BODIPY core are reported. The spectra display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. As a function of the solvent, the spectral maxima are located within a very narrow wavelength range and are slightly red-shifted with increasing solvent polarizability, which is shown to be the crucial parameter influencing the wavelength position of the maxima. The extended π-conjugation in the 3,5-diaryl products always leads to bathochromically shifted absorption and emission spectra compared to those of the 3-aryl analogues. The derivative with a 3-mesityl substituent has blue-shifted spectra in comparison to its 3-phenyl substituted analogue, reflecting the diminished π-conjugation in the former due to steric strain. The nature of the meso-aryl has only a small effect on the spectral positions but affects the fluorescence quantum yield Φ. The majority of the dyes have high Φ (>0.85), except the compounds with meso-phenyl and meso-(p-nitrophenyl) substituents. Quantum-chemical calculations were performed to evaluate the differences in spectroscopic properties upon substitution of the BODIPY core and to compare them with the corresponding experimental results. ispartof: Photochemical & Photobiological Sciences vol:12 issue:5 pages:835-847 ispartof: location:England status: published

Oxidative stress is a crucial factor inducing cardiomyocyte apoptosis due to cardiac hypertrophy. Additional evidence has revealed that H2S plays an antioxidant role and is cytoprotective. Hence, we aimed to elucidate whether H2S prevents cardiomyocyte apoptosis due to cardiac hypertrophy via its antioxidant function. The cardiac hypertrophy model was obtained by injecting a high dose of isoproterenol (ISO) subcutaneously, and the hemodynamic parameters were measured in groups that received either ISO or ISO with the treatment of NaHS. TUNEL (terminal deoxynucleotidyl transferase mediated dUTP nick-end labeling) and EM (electron microscopy) experiments were performed to determine the occurrence of apoptosis in heart tissues. The expression of caspase-3 protein in the cytoplasm and NADPH oxidase 4 (NOX4), and cytochrome c (cyt c) proteins in the mitochondria were analyzed using Western blotting. In contrast, to determine whether ISO-induced apoptosis in the cultured cardiomyocytes may be related to oxidative stress, JC-1 and MitoSOX assays were performed to detect the mitochondrial membrane potential and reactive oxygen species (ROS) production in the mitochondria. Exogenous H2S was found to ameliorate cardiac function. The histological observations obtained from TUNEL and EM demonstrated that treatment with NaHS inhibited the occurrence of cardiac apoptosis and improved cardiac structure. Moreover, H2S reduced the expression of the cleaved caspase-3, NOX4 and the leakage of cyt c from the mitochondria to the cytoplasm. We also observed that exogenous H2S could maintain the mitochondrial membrane potential and reduce ROS production in the mitochondria. Therefore, H2S reduces oxidative stress due to cardiac hypertrophy through the cardiac mitochondrial pathway.

A highly fluorescent chemosensor based on 1,8-naphthyridine with high sensitivity and selectivity toward Ni(2+)/Cu(2+) over other cations both in aqueous solution over a wide pH range (4-10) and in cellular environments was developed. Counteranions such as acetate, sulfate, nitrate, and perchlorate have no influence on the detection of such metal ions. Ethylenediamine showed high selectivity toward the in situ-prepared Cu(2+) complex over the Ni(2+) complex, which can be applied to distinguish Ni(2+) and Cu(2+). The Ni(2+)-induced fluorescence on-off mechanism was revealed to be mediated by intramolecular charge transfer from the metal to the ligand, while that by Cu(2+) involves intramolecular charge transfer from the ligand to the metal, as confirmed by picosecond time-resolved fluorescence spectroscopy and time-dependent density functional theory calculations.

The synthesis and evaluation of a novel Schiff-base fluorescent probe L for detection of Al(3+) are described. The structure of L was determined by X-ray and other spectroscopic data. The fluorescent spectra changes and microscopy images show that indicator L is highly selective for Al(3+) not only in abiotic systems but also in living cells. Other metal ions failed to respond. The new probe could be used as an efficient tool for Al(3+) monitoring in the environment and biological systems.

Two novel Schiff-based fluorescent probes 1 and 2 for Zn2+ ion were developed. The spectroscopic behavior toward metal ions has been investigated by the absorption and fluorescence method. Both of the two probes were found to show good selectivity to Zn2+ ion over other metal ions in ethanol–water solution, such as Li+, Na+, Mg2+, Al3+, K+, Ca2+, Ba2+, Cr3+, Mn2+, Cu2+, Co2+, Ni2+, Fe3+, Hg2+, Ag+, Cd2+ and Pb2+. The selectivity mechanism of 1 and 2 to metal ions is based on a combinational effect of proton transfer (ESPT), CN isomerization and chelation-enhanced fluorescence (CHEF). pH response experiments show that the probes can be used to indicate pH values under certain conditions.

An "off-on" Zn(2+) and "on-off" Cu(2+) fluorescent chemosensor C was designed and synthesized. The binding of C and Zn(2+)/Cu(2+) is chemically reversible by the addition of EDTA disodium solution; moreover, the fluorescence emission signal of ZnC decreased with the addition of Cu(2+), demonstrating that ZnC could detect Cu(2+)via metal displacement.