Selective sensing of Fe3+ based on fluorescence quenching by 2,6-bis(benzoxazolyl)pyridine with beta-cyclodextrin in neutral aqueous solution

A selective and sensitive fluorescent chemosensor (BBOZP-CD) for Fe(3+) was composed of water-soluble beta-cyclodextrins and 2,6-bis(benzoxazolyl)pyridine which was synthesized through the reaction of 2,6-pyridinedicarboxylic acid and o-aminophenol catalyzed by polyphosphoric acid under microwave irradiation. The chemosensor BBOZP-CD for metal ions were carefully investigated by fluorescent quenching in present of metal ions. The result showed BBOZP-CD chemosensor was remarkable fluorescence quenching and a highly selectivity and sensitivity for Fe(3+) in neutral aqueous solution, and the other common metal ions did not notably disturb the detection of Fe(3+). Additionally, the effect of pH to the chemosensor for Fe(3+) was also studied. The result indicated the respond signals of BBOZP-CD to Fe(3+) was stable and hardly influenced while the pH value was greater than 3.6.     

Functionalized Fe3O4 nanoparticles for detecting zinc ions in living cells and their cytotoxicity

The zinc tank: A new fluoro-chromogenic chemosensor based on BODIPY-functionalized Fe(3)O(4) nanoparticles (1) has been prepared. Chemoprobe 1 exhibits high selectivity for Zn(2+) over other competing metal ions tested. Moreover, confocal microscopy experiments established that 1 can be used for detecting Zn(2+) levels in living cells (see figure).     

Thiacalix[4]arene based reconfigurable molecular switches: set-reset memorized sequential device

The fluorescent chemosensors 3, 5 and 7 based on thiacalix[4]arene bearing naphthyl groups have been designed and synthesized. The optical chemosensor 3 based on a thiacalix[4]arene of cone conformation behaves as "turn-on" optical chemosensor for Fe(3+) and F(-) ions. However, chemosensors 5 and 7 based on a thiacalix[4]arene of 1,3-alternate conformation demonstrate "turn-on" optical behaviour for Hg(2+), F(-) ions (with receptor 5 as turn-on for K(+) ions also) and "turn-off" behaviour for Fe(3+) ions. The simultaneous presence of Fe(3+) and Hg(2+) or K(+) or F(-) ions results in formulation of reversible "on-off" switches. Various molecular logic gates developed in response to molecular switching between these chemical inputs have been integrated into sequential logic circuits with memory function in a feedback loop which mimics "set-reset" molecular level information processing device.     

Optical chemosensor for Ag+, Fe3+, and cysteine: information processing at molecular level

A thiacalix[4]arene based chemosensor 3 bearing two pyrene groups has been synthesized which demonstrates ratiometric sensing with Ag(+) and fluorescence quenching with Fe(3+) ions in mixed aqueous media. The 'in situ' prepared Ag(+) and Fe(3+) complexes showed high selectivity toward cysteine. The molecular switching between three chemical inputs (Ag(+), Fe(3+), cysteine) results in various molecular logic gates which have been integrated sequentially to generate a sequential information processing device.     

Incorporation of triazole into a quinoline-rhodamine conjugate imparts iron(iii) selective complexation permitting detection at nanomolar levels

Two new rhodamine based probes 1 and 2 for the detection of Fe(3+) were synthesized and their selectivity towards Fe(3+) ions in the presence of other competitive metal ions tested. The probe 1 formed a coloured complex with Fe(3+) as well as Cu(2+) ions and revealed the lack of adequate number of coordination sites for selective complexation with Fe(3+). Incorporation of a triazole unit to the chelating moiety of 1 resulted in the probe 2, that displayed Fe(3+) selective complex formation even in the presence of other competitive metal ions like Li(+), Na(+), K(+), Cu(2+), Mg(2+), Ca(2+), Sr(2+), Cr(3+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). The observed limit of detection of Fe(3+) ions (5 × 10(-8) M) confirmed the very high sensitivity of 2. The excellent stability of 2 in physiological pH conditions, non-interference of amino acids, blood serum and bovine serum albumin (BSA) in the detection process, and the remarkable selectivity for Fe(3+) ions permitted the use of 2 in the imaging of live fibroblast cells treated with Fe(3+) ions.     

Salicylimine-based fluorescent chemosensor for aluminum ions and application to bioimaging

In this study, an assay to quantify the presence of aluminum ions using a salicylimine-based receptor was developed utilizing turn-on fluorescence enhancement. Upon treatment with aluminum ions, the fluorescence of the sensor was enhanced at 510 nm due to formation of a 1:1 complex between the chemosensor and the aluminum ions at room temperature. As the concentration of Al(3+) was increased, the fluorescence gradually increased. Other metal ions, such as Na(+), Ag(+), K(+), Ca(2+), Mg(2+), Hg(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Pb(2+), Cr(3+), Fe(3+), and In(3+), had no such significant effect on the fluorescence. In addition, we show that the probe could be used to map intracellular Al(3+) distribution in live cells by confocal microscopy.     

Rhodamine-based highly sensitive colorimetric off-on fluorescent chemosensor for Hg2+ in aqueous solution and for live cell imaging

A novel rhodamine-based highly sensitive and selective colorimetric off-on fluorescent chemosensor for Hg(2+) ions is designed and prepared by using the well-known thiospirolactam rhodamine chromophore and furfural hydrazone as signal-reporting groups. The photophysical characterization and Hg(2+)-binding properties of sensor RS1 in neutral N, N-dimethylformamide (DMF) aqueous solution are also investigated. The signal change of the chemosensor is based on a specific metal ion induced reversible ring-opening mechanism of the rhodamine spirolactam. The response of the chemosensor for Hg(2+) ions is instantaneous and reversible. And it successfully exhibits a remarkably "turn on" response toward Hg(2+) over other metal ions (even those that exist in high concentration). Moreover, this sensor is applied for in vivo imaging in Rat Schwann cells to confirm that RS1 can be used as a fluorescent probe for monitoring Hg(2+) in living cells with satisfying results, which further demonstrates its value of practical applications in environmental and biological systems.     

Pyrene-linked triazole-modified homooxacalix[3]arene: a unique C3 symmetry ratiometric fluorescent chemosensor for Pb2+

A new type of fluorescent chemosensor based on homooxacalix[3]arene was synthesized. The fluorescent sensor was highly selective for Pb(2+) in comparison with other metal ions tested by enhancement of the monomer emission of pyrene. The C(3) symmetric structure of homooxacalix[3]arene has potential application in the development of a new ratiometric fluorescent chemosensor for heavy metal ions.     

Two-photon excited fluorescent chemosensor for homogeneous determination of copper(II) in aqueous media and complicated biological matrix

In the present work, a two-photon excited fluorescent chemosensor for Cu(2+) was prepared. The probe was constructed on the basis of internal charge transfer (ICT) principle with macrocyclic dioxotetraamine as the Cu(2+) receptor. The good water-solubility of the molecule enabled recognition and assay of Cu(2+) ions in biological media. The photophysical properties of the chemosensor were investigated in detail, exhibiting favorable fluorescence quantum yield and moderate two-photon absorption cross-section. The studies on binding thermodynamics demonstrated the formation of 1?:?1 complex between the chemosensor and Cu(2+) and an association constant of ca. 1.04 × 10(5) M(-1). Due to the rational design of the molecular structure, the sensor was highly specific to Cu(2+), which ensured high selectivity in Cu(2+) determination. Upon Cu(2+) binding, the intramolecular charge-transfer extent within the chromophore was weakened resulting in a remarkable quenching of fluorescence, based on which quantitative determination of Cu(2+) was performed. Good linearity was obtained between the fluorescence quenching value and Cu(2+) concentration ranging from 0.04 to 2.0 μM in aqueous solution. Benefiting from the merits of two-photon excitation, the chemosensor was free of interference from background luminescence in serum. A homogeneous quantitative determination of Cu(2+) was achieved in the serum medium with a linear range of 0.04 to 2.0 μM. Considering the structural flexibility of the sensor, this work also opens up the possibility to construct other two-photon excited chemosensors for direct homogeneous assay of various molecules/ions in complicated biological sample matrices.     

Layer-by-layer assembled Fe3O4@C@CdTe core/shell microspheres as separable luminescent probe for sensitive sensing of Cu2+ ions

A novel multifunctional microsphere with a fluorescent CdTe quantum dots (QDs) shell and a magnetic core (Fe(3)O(4)) has been successfully developed and prepared by a combination of the hydrothermal method and layer-by-layer (LBL) self-assembly technique. The resulting fluorescent Fe(3)O(4)@C@CdTe core/shell microspheres are utilized as a chemosensor for ultrasensitive Cu(2+) ion detection. The fluorescence of the obtained chemosensor could be quenched effectively by Cu(2+) ions. The quenching mechanism was studied and the results showed the existence of both static and dynamic quenching processes. However, static quenching is the more prominent of the two. The modified Stern-Volmer equation showed a good linear response (R(2) = 0.9957) in the range 1-10 μM with a quenching constant (K(sv)) of 4.9 × 10(4) M(-1). Most importantly, magnetic measurements showed that the Fe(3)O(4)@C@CdTe core/shell microspheres were superparamagnetic and they could be separated and collected easily using a commercial magnet in 10 s. These results obtained not only provide a way to solve the embarrassments in practical sensing applications of QDs, but also enable the fabrication of other multifunctional nanostructure-based hybrid nanomaterials.     

A "turn-on" fluorescent Hg2+ chemosensor based on Ferrier carbocyclization

A "turn-on" fluorescent chemosensor with excellent selectivity and satisfactory sensitivity on Hg(2+) detection in 100% water media has been established employing a carbohydrate based Ferrier carbocyclization reaction. The probe has also presented satisfactory results for the imaging of Hg(2+) ions in cells and organisms.     

A squaraine-based colorimetric and "turn on" fluorescent sensor for selective detection of Hg2+ in an aqueous medium

A novel squaraine-based chemosensor SQ-1 has been synthesized, and its sensing behavior toward various metal ions was investigated by UV-vis and fluorescence spectroscopies. In AcOH-H(2)O (40:60, v/v) solution, Hg(2+) ions coordinate with SQ-1 causing a deaggregation which induces a visual color and absorption spectral changes as well as strong fluorescence. In contrast, the addition of other metals (e.g., Pb(2+), Cd(2+), Cu(2+), Zn(2+), Al(3+), Ni(2+), Co(2+), Fe(3+), Ca(2+), K(+), Mg(2+), Na(+), and Ag(+)) does not induce these changes at all. Thus SQ-1 is a specific Hg(2+) sensing agent due to the inducing deaggregation of the dye molecule by Hg(2+).     

Ratiometric sensing of Hg2+ based on the calix[4]arene of partial cone conformation possessing a dansyl moiety

A new fluorescent chemosensor based on the calix[4]arene of partial cone conformation possessing a dansyl moiety has been synthesized. The chemosensor demonstrates selective optical recognition of Hg(2+) and Cu(2+) in two contrasting modes. The receptor exhibited ratiometric sensing of Hg(2+) and "ON-OFF" type of fluorescence behavior in the presence of Cu(2+). The compound behaves as a fluorescent molecular switch upon chemical inputs of Hg(2+) and Cu(2+) ions.     

Poly(amine ester) dendrimer with naphthyl units as a fluorescent chemosensor for Al(III), Cu(II), and Zn(II).

A poly(amine ester) dendrimer with naphthyl units (G1N6) has been synthesized as a fluorescent chemosensor for metal ions. We investigated the metal-ion recognition of G1N6 by adding each of Ag(+), Al(3+), Ba(2+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(3+), Mg(2+), Ni(2+), and Zn(2+) in acetonitrile solution. Large changes were observed in the fluorescence spectra of G1N6 upon the addition of Al(3+), Cu(2+), and Zn(2+).     

Dual-mode unsymmetrical squaraine-based sensor for selective detection of Hg2+ in aqueous media

A novel chemosensor based on unsymmetrical squaraine dye (USQ-1) for the selective detection of Hg(2+) in aqueous media is described. USQ-1 in combination with metal ions shows dual chromogenic and "turn-on" fluorogenic response selectivity toward Hg(2+) as compared to Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+), Al(3+), Cu(2+), Cd(2+), Mn(2+), Fe(3+), Ag(+), Pb(2+), Zn(2+), Ni(2+) and Co(2+) due to the Hg(2+)-induced deaggregation of the dye molecule. A recognition mechanism based on the binding mode is proposed based on the absorption and fluorescence changes, (1)H NMR titration experiments, ESI-MS study, and theoretical calculations.     

Indole-based chemosensor for Hg2+ and Cu2+ ions: applications in molecular switches and live cell imaging

An indole based "ratiometric" and "turn-off" tris(N-methylindolyl)methane based chemosensor depicting a contrasting fluorescent behavior towards Hg(2+) and Cu(2+) ions, exhibited NOR and YES logic functions, and also imaged intracellular Hg(2+) in cervix cancer (HeLa) cells.     

Rhodamine-alginate conjugate as self indicating gel beads for efficient detection and scavenging of Hg2+ and Cr3+ in aqueous media

Effective extraction of Hg(2+) and Cr(3+) ions from aqueous media by novel rhodamine-alginate polymer-based highly fluorogenic, as well as colorimetric, chemosensor beads.     

Efficient immobilization of a cadmium chemosensor in a thin film: generation of a cadmium sensor prototype

[reaction: see text] The development of an ion-selective chemosensor for Cd(2+) allows generation of a "real-time" sensor. Immobilization of the chemosensor on quartz was achieved in a simple monolayer and in a thin film using a polymer intermediary. As intended, the thin film contains much more chemosensor than the monolayer and provides measurable responses to aqueous Cd(2+) concentrations below 1 microM. Alkali and alkaline earth ions do not interfere with Cd(2+) sensing; Zn(2+) and Cu(2+) are potential interferents.     

A sensitive and selective fluorescence sensor for the detection of arsenic(III) in organic media

Arsenic contamination is a leading environmental problem. As such, levels of this toxic metalloid must be constantly monitored by reliable and low-cost methodologies. Because the currently accepted upper limit for arsenic in water is 10 ppb, very sensitive and selective detection strategies must be developed. Herein we describe the synthesis and characterization of a fluorescent chemical probe, namely, ArsenoFluor1, which is the first example of a chemosensor for As(3+) detection in organic solvents at 298 K. AF1 exhibits a 25-fold fluorescence increase in the presence of As(3+) at λ(em) = 496 nm in THF, which is selective for As(3+) over other biologically relevant ions (such as Na(+), Mg(2+), Fe(2+), and Zn(2+)) and displays a sub-ppb detection limit.     

A new "turn-on" naphthalenedimide-based chemosensor for mercury ions with high selectivity: successful utilization of the mechanism of twisted intramolecular charge transfer, near-IR fluorescence, and cell images

For the first time, a new near-IR "turn-on" fluorescent chemosensor with high selectivity for Hg(2+) ions was designed according to the twisted intramolecular charge transfer (TICT) mechanism. The selective fluorescence enhancement effect can be optimized by modulating the solvent systems. And this naphthalenedimide-based sensor with long wavelength absorption and emission can be used to image intracellular Hg(2+) ions in living Hela cells.