A new half-condensed Schiff base platform: structures and sensing of Zn2+ and H2PO4- ions in an aqueous medium.

A newly designed and synthesized half-condensed organic moiety 2-hydroxy-5-methyl-3-[(2-phenylamino-phenylimino)-methyl]-benzaldehyde (HL') and a Zn2L4 complex sequentially detect Zn2+ and H2PO4- ions as low as 1.13 nM and1.23 µM, respectively. HL' and a dinuclear Zn(ii) complex of in situ generated L- in a solution formulated as Zn2L4 under investigation were characterized by physicochemical and spectroscopic studies along with detailed structural analyses by single-crystal X-ray crystallography. The selectivity and sensitivity of HL' towards Zn2+ ions and of the Zn2L4 complex towards H2PO4- ions are based on CHEF and via displacement pathways, respectively. Dual sensing of Zn2+ ions and H2PO4-ions in an aqueous medium via "Green-Blue-Green" emission with the reversible transformation of in situ formed HL' to HL was established by detailed electronic absorption and emission spectroscopic studies. This non-cytotoxic probe (HL', i.e. produced HL in solution) and Zn2L4 complexes are able to monitor the subcellular distribution changes of Zn2+ and H2PO4- ions, respectively, by fluorescence microscopy using the human semen sample.

Bilirubin Quantification in Human Blood Serum by Deoxygenation Reaction Switch-Triggered Fluorescent Probe.

A coumarin-based fluorescent compound, bilirubin fluorescent probe N-oxide (BFPNox), was successfully designed and synthesized for highly selective and sensitive detection of free bilirubin with short response time. The fluorescence "turn-on" response of the probe is based on the in situ generated Fe2+-mediated deoxygenation reaction of N-oxide from the diethylarylamine group of the probe, where the group attached to the coumarin π-conjugated system is responsible for the fluorescence quenching state of the probe, BFPNox. Here, the reaction of the added Fe3+ ions with bilirubin produces Fe2+ ions in situ in aqueous buffer. Fluorescence enhancement of BFPNox was achieved by more than 12-fold when a double equivalent of bilirubin solution was added in reaction buffer at pH 7.2 (50 mM HEPES, 5% DMSO) at 25 °C under excitation at 400 nm. It detected free bilirubin as low as 76 nM in an aqueous system without any interference of metal ions, anions, and other important biomolecules with a linear concentration range of 0-10 µM (R2 = 0.991). The probe was also employed in the estimation of free bilirubin in human serum specimens to verify the efficacy of this probe. With these, it is revealed that this probe is a good candidate to be used as a powerful diagnostic tool for the assessment of free bilirubin with significant accuracy and reliability.

A Lysosome-Targetable Fluorescence Sensor for Ultrasensitive Detection of Hg2+ in Living Cells and Real Samples.

A new lysosome-targetable fluorescence sensor, Lyso-HGP, was designed and synthesized based on 4-methyl-2,6-diformylphenol as a fluorophore. Lyso-HGP displays highly sensitive fluorescent detection of Hg2+ in HEPES buffer solution (10 mM, DMSO 1%) of pH 7.0 at 37 °C due to the formation of highly fluorescent formyl-functionalized derivative Lyso-HGP-CHO. The sensor triggered a "turn-on" fluorescence response to Hg2+ with a simultaneous increase of fluorescence intensity by 180-fold just after 10 min. The response is very selective over a variety of biologically relevant cations, anions, molecules, and competitive toxic heavy metal cations. The limit of detection (LOD) was calculated as low as 6.82 nM. So, it can be utilized to detect this toxic heavy metal in biology and environmental samples in an aqueous buffer medium. Also, the sensor is able to monitor the subcellular distribution of Hg2+ specifically localized in the lysosome's compartment in the MCF7 human breast cancer cell line by fluorescence microscopy.

Highly Sensitive Ratiometric Chemosensor and Biomarker for Cyanide Ions in the Aqueous Medium.

A newly designed cyanide-selective chemosensor based on chromone containing benzothiazole groups [3-(2,3-dihydro-benzothiazol-2-yl)-chromen-4-one (DBTC)] was synthesized and structurally characterized by physico-chemical, spectroscopic, and single-crystal X-ray diffraction analyses. The compound DBTC can detect cyanide anions based on nucleophilic addition as low as 5.76 nM in dimethyl sulfoxide-N-(2-hydroxyethyl)piperazine-N'-ethanesulfonic acid buffer (20 mM, pH 7.4) (v/v = 1:3). The binding mode between receptor DBTC and cyanide nucleophile has also been demonstrated by experimental studies using various spectroscopic tools and theoretical studies, and the experimental work has also been verified by characterizing one supporting compound of similar probable structure of the final product formed between DBTC and cyanide ion (DBTC-CN compound) by single-crystal X-ray analysis for detailed structural analyses. In theoretical study, density functional theory procedures have been used to calculate the molecular structure and the calculation of the Fukui function for evaluation of the electrophilic properties of each individual acceptor atom. Furthermore, the efficacy of the probe (DBTC) to detect the distribution of CN- ions in living cells has been checked by acquiring the fluorescence image using a confocal microscope. Notably, the paper strips with DBTC were prepared, and these could serve as efficient and suitable CN- test kits successfully.

A New Lysosome-Targetable Turn-On Fluorogenic Probe for Carbon Monoxide Imaging in Living Cells.

A lysosome-targetable fluorogenic probe, LysoFP-NO2, was designed and synthesized based on a naphthalimide fluorophore that can detect selectively carbon monoxide (CO) in HEPES buffer (pH 7.4, 37 °C) through the transformation of the nitro group into an amino-functionalized system in the presence of CO. LysoFP-NO2 triggered a "turn-on" fluorescence response to CO with a simultaneous increase of fluorescence intensity by more than 75 times. The response is selective over a variety of relevant reactive nitrogen, oxygen, and sulfur species. Also, the probe is an efficient candidate for monitoring changes in intracellular CO in living cells (MCF7), and the fluorescence signals specifically localize in the lysosome compartment.

A fluorescent probe for the selective detection of creatinine in aqueous buffer applicable to human blood serum.

A naphthalimide-based fluorescence light-up probe, FCP-Pd, has been designed and synthesized for selective detection and quantitation of creatinine in PBS buffer of pH 7.2 at 37 °C with a 'turn-on' response over a variety of interfering metal ions and/or anions and several biologically significant species. This probe is highly effective in estimating creatinine in human blood serum, which confirms the reliability and accuracy of this new system to be applied in clinical and toxicological analysis.

A new fluorogenic probe for the selective detection of carbon monoxide in aqueous medium based on Pd(0) mediated reaction.

A coumarin-based fluorogenic probe, PCO-1, senses carbon monoxide (CO) selectively in HEPES buffer at pH 8.0 through the intramolecular cyclization-elimination pathway based on Pd(0) mediated reaction. The probe exhibits a 'turn-on' response of CO over a variety of relevant reactive oxygen, nitrogen and sulfur species.

Effect of metal oxidation state on FRET: a Cu(I) silent but selectively Cu(II) responsive fluorescent reporter and its bioimaging applications.

Copper(II) and copper(I) complexes of a newly designed and crystallographically characterized Schiff base (HL) derived from rhodamine hydrazide and cinnamaldehyde were isolated in pure form formulated as [Cu(L)(NO3)] (L-Cu) (1) and [Cu(HL)(CH3CN)(H2O)]ClO4 (HL-Cu) (2), and characterized by physicochemical and spectroscopic tools. Interestingly, complex 1 but not 2 offers red fluorescence in solution state, and eventually HL behaves as a Cu(II) ions selective FRET based fluorosensor in HEPES buffer (1 mM, acetonitrile-water: 1/5, v/v) at 25 °C at biological pH with almost no interference of other competitive ions. The dependency of the FRET process on the +2 oxidation state of copper has been nicely supported by exhaustive experimental studies comprising electronic, fluorimetric, NMR titration, and theoretical calculations. The sensing ability of HL has been evaluated by the LOD value towards Cu(II) ions (83.7 nM) and short responsive time (5-10 s). Even the discrimination of copper(I) and copper(II) has also been done using only UV-Vis spectroscopic study. The efficacy of this bio-friendly probe has been determined by employing HL to detect the intercellular distribution of Cu(II) ions in HeLa cells by developing image under fluorescence microscope.

Selective and sensitive turn-on chemosensor for arsenite ion at the ppb level in aqueous media applicable in cell staining.

A newly designed and structurally characterized cell permeable diformyl-p-cresol based receptor (HL) selectively senses the AsO3(3-) ion up to ca. 4.1 ppb in aqueous media over the other competitive ions at biological pH through an intermolecular H-bonding induced CHEF (chelation-enhanced fluorescence) process, established by detailed experimental and theoretical studies. This biofriendly probe is highly competent in recognizing the existence of AsO3(3-) ions in a living organism by developing an image under a fluorescence microscope and useful to estimate the amount of arsenite ions in various water samples.

A napthelene-pyrazol conjugate: Al(III) ion-selective blue shifting chemosensor applicable as biomarker in aqueous solution.

A newly synthesized and crystalographically characterized napthelene­pyrazol conjugate, 1-[(5-phenyl-1H-pyrazole-3-ylimino)-methyl]-naphthalen-2-ol (HL) behaves as an Al(III) ion-selective chemosensor through internal charge transfer (ICT)-chelation-enhanced fluorescence (CHEF) processes in 100 mM HEPES buffer (water­DMSO 5:1, v/v) at biological pH with almost no interference of other competitive ions. This mechanism is readily studied from electronic, fluorimetric and (1)H NMR titration. The probe (HL) behaved as a highly selective fluorescent sensor for Al(III) ions as low as 31.78 nM within a very short response time (15­20 s). The sensor (HL), which has no cytotoxicity, is also efficient in detecting the distribution of Al(III) ions in HeLa cells via image development under fluorescence microscope.