Ching Kheng Quah

FRET based ‘red-switch’ for Al3+ over ESIPT based ‘green-switch’ for Zn2+: dual channel detection with live-cell imaging on a dyad platform

Our designed chemosensor, rhodamine-HBT-dyad (RHD), selectively detects two biologically important ions (Al3+ and Zn2+) at two different wavelengths (‘naked-eye’ colors red and green, respectively) through two different mechanisms (i.e. FRET and ESIPT) at ppm level. The sensor can also detect the Al3+ ion through displacement of the Zn2+ ion in vivo.

Nanomolar detection of hypochlorite by a rhodamine-based chiral hydrazide in absolute aqueous media: application in tap water analysis with live-cell imaging.

By employing the oxidation property of hypochlorite (OCl(-)), a novel rhodamine-based hydrazide of the chiral acid ((S)-(-)-2-pyrrolidone-5-carboxylic acid) (RHHP) was designed and synthesized for detection of OCl(-) absolutely in aqueous medium at nanomolar level. The structure of the chiral sensor was also proved by the X-ray crystallography. The bioactivity and the application of the probe for detection of OCl(-) in natural water system have been demonstrated. A plausible mechanism for oxidation of the sensor followed by hydrolysis is also proposed. The sensibility of the receptor toward OCl(-) was studied in absolute aqueous media, and the detection limit of hypochlorite-mediated oxidation to the receptor in nanomolar level makes this platform (RHHP) an ultrasensitive and unique system for OCl(-) oxidation.

Rapid and ratiometric detection of hypochlorite with real application in tap water: molecules to low cost devices (TLC sticks)

We have designed a chemodosimeter DPNO (weak fluorescence) which can be oxidized to HPNO (strong blue fluorescence) by OCl(-) with high selectivity and sensitivity in a ratiometric approach with a noticeably lower detection limit. The sensor could be useful for the detection of hypochlorites in tap water.

Structural Correlation of Some Heterocyclic Chalcone Analogues and Evaluation of Their Antioxidant Potential

A series of six novel heterocyclic chalcone analogues 4(a–f) has been synthesized by condensing 2-acetyl-5-chlorothiophene with benzaldehyde derivatives in methanol at room temperature using a catalytic amount of sodium hydroxide. The newly synthesized compounds are characterized by IR, mass spectra, elemental analysis and melting point. Subsequently; the structures of these compounds were determined using single crystal X-ray diffraction. All the synthesized compounds were screened for their antioxidant potential by employing various in vitro models such as DPPH free radical scavenging assay, ABTS radical scavenging assay, ferric reducing antioxidant power and cupric ion reducing antioxidant capacity. Results reflect the structural impact on the antioxidant ability of the compounds. The IC50 values illustrate the mild to good antioxidant activities of the reported compounds. Among them, 4f with a p-methoxy substituent was found to be more potent as antioxidant agent.

Cd2+ Triggered the FRET “ON”: A New Molecular Switch for the Ratiometric Detection of Cd2+ with Live-Cell Imaging and Bound X-ray Structure

On the basis of the Förster resonance energy transfer mechanism between rhodamine and quinoline-benzothiazole conjugated dyad, a new colorimetric as well as fluorescence ratiometric probe was synthesized for the selective detection of Cd(2+). The complex formation of the probe with Cd(2+) was confirmed through Cd(2+)-bound single-crystal structure. Capability of the probe as imaging agent to detect the cellular uptake of Cd(2+) was demonstrated here using living RAW cells.

A Triphenyl Amine‐Based Solvatofluorochromic Dye for the Selective and Ratiometric Sensing of OCl− in Human Blood Cells

A new visible-light-excitable fluorescence ratiometric probe for OCl(-) has been developed based on a triphenylamine-diamiomaleonitrile (TAM) moiety. The structure of the dye was confirmed by single-crystal X-ray analysis. It behaves as a highly selective and sensitive probe for OCl(-) over other analytes with a fast response time (∼100 s). OCl(-) reacts with the probe leading to the formation of the corresponding aldehyde in a mixed-aqueous system. The detection limit of the probe is in the 10(-8) M range. The probe (TAM) also exhibits solvatofluorochromism. Changing the solvent from non-polar to polar, the emission band of TAM largely red-shifted. Moreover, the probe shows an excellent performance in real-life application in detecting OCl(-) in human blood cells. The experimentally observed changes in the structure and electronic properties of the probe after reaction with OCl(-) were studied by DFT and TDDFT computational calculations.

A rhodamine–quinoline based chemodosimeter capable of recognising endogenous OCl− in human blood cells

A rhodamine–quinoline based chemodosimeter (RHQ) has been designed, synthesized and characterized in this paper. The structure of the sensor is confirmed through single crystal X-ray study. It detects hypochlorite (OCl−) selectively among other analytes studied. It showed colorimetric and orange-red fluorescence “turn-on” upon addition of OCl−. The OCl−-promoted ring opening of the rhodamine spirolactam ring in RHQ evokes a large absorbance as well as fluorescence enhancement in water–acetonitrile (1/1, v/v) medium with no significant response to other competitive analytes. Furthermore, we demonstrate here that RHQ can endogenously detect OCl− in human blood cells (peripheral blood mononuclear cells). It also exhibits excellent performance in the “dip stick” method. The optimized structure of the probe is calculated by density functional theory calculations. Moreover, the limit of detection of the probe is in the 10−8 M range.

Heteroaryl Chalcones: Design, Synthesis, X-ray Crystal Structures and Biological Evaluation

Chalcone derivatives have attracted increasing attention due to their numerous pharmacological activities. Changes in their structures have displayed high degree of diversity that has proven to result in a broad spectrum of biological activities. The present study highlights the synthesis of some halogen substituted chalcones 3(a–i) containing the 5-chlorothiophene moiety, their X-ray crystal structures and the evaluation of possible biological activities such as antibacterial, antifungal and reducing power abilities. The results indicate the tested compounds show a varied range of inhibition values against all the tested microbial strains. Compound 3c with a p-fluoro substituent on the phenyl ring exhibits elevated antimicrobial activity, whereas the compounds 3e and 3f displayed the least antimicrobial activities. The compounds 3d, 3e, 3f and 3i showed good ferric and cupric reducing abilities, and the compounds 3b and 3c showed the weakest reducing power in the series.

ESIPT and CHEF based highly sensitive and selective ratiometric sensor for Al3+ with imaging in human blood cells

Based on excited state intramolecular proton transfer (ESIPT) and chelation enhanced fluorescence (CHEF) mechanisms, a new fluorescence ratiometric probe for Al3+ was designed and synthesized, and its structure was confirmed through single crystal X-ray study. This probe is capable of showing excited state intramolecular proton transfer through two different pathways. The introduction of Al3+ in a mixed aqueous solution with the probe results in an abrupt change in the photophysical properties of the probe. A ratiometric emission profile was observed in the presence of Al3+. Interestingly, the presence of other metal ions (especially trivalent ions, e.g. Fe3+, Cr3+, Ga3+ and In3+) do not perturb the fluorescence intensity of the probe (except Cu2+ and Pb2+, where slight changes were noticed). This indicates that the probe shows high affinity towards Al3+. The ratiometric sensing phenomenon may be explained by the presence of two different mechanisms, namely, excited state intramolecular proton transfer and chelation induced enhanced fluorescence, which are demonstrated by the probe in presence of Al3+ in the excited state. The complexation of the probe with Al3+ inhibits excited state intramolecular proton transfer while the chelation induced enhanced fluorescence mechanism becomes dominant. The probe efficiently detected the cellular uptake of Al3+, which is demonstrated here with human blood-cell imaging. Moreover, the detection limit was found to be 6.72 × 10−8 M.

Single excited state intramolecular proton transfer (ESIPT) chemodosimeter based on rhodol for both Hg2+ and OCl−: ratiometric detection with live-cell imaging

For ratiometric, fluorogenic and “naked eye” detection of the environmentally and biologically important ions Hg2+ and OCl− in one platform, a 2-(2′-hydroxyphenyl)-benzothiazole (HBT) inserted thiolactam containing a new rhodol system, spirothiolactamized benzothiazole substituted N,N-diethylrhodol (STBR), is designed and synthesized. We can detect Hg2+ and OCl− in solutions by a simple, easy-to-synthesize practical ratiometric chemodosimeter with two different modes of reactions with a low detection limit. The observed color in the presence of Hg2+ or OCl− may arise from the reaction of Hg2+ or OCl− with STBR – the thiolactam moiety is broken and it helps to achieve maximum π–π* conjugation which results in a brilliant red fluorescence. From 1H-NMR and ESI-MS data, it is clear that the modes of the reaction for Hg2+ and OCl− are different. Test strips are also prepared to observe color changes. The sensing phenomena are fruitfully applied for live-cell imaging in Saccharomyces cerevisiae cells (from a short to long time range, 0 min to 120 min). The single crystal X-ray structure of the synthesised ESIPT rhodol moiety is also reported.