A molecular chemodosimeter to probe "closed shell" ions in kidney cells.

Two quinidine-functionalized coumarin molecular probes have been synthesized and have been found to bind metal cations (Cd, Co, Cu, Fe, Hg, Ni, and Zn) with high affinity in organic-aqueous media (DMSO-HEPES). The chemodosimeters coordinate with the Zn ions in a two-to-one ratio (molecular probe : Zn) with a log  of 10.0 M.

The effect of outer-sphere anions on the spectroscopic response of metal-binding chemosensors.

Ion pair receptors typically contain two separate binding sites, for the metal and the anion respectively. Here we report a less synthetically demanding approach, whereby we prepared a family of ion pair sensors based on a rhodamine fluorescent scaffold containing a tunable cation binding motif. When exposed to ion pairs, a competition for the metal ion is established between these ligands and anions.

Structural Features of a Family of Coumarin-Enamine Fluorescent Chemodosimeters for Ion Pairs.

A family of coumarin-enamine chemodosimeters is evaluated for their potential use as fluorescent molecular probes for multiple analytes [cadmium(II), cobalt(II), copper(II), iron(II), nickel(II), lead(II), and zinc(II)], as their chloride and acetate salts. These fluorophores displayed excellent optical spectroscopic modulation when exposed to ion pairs with different Lewis acidic and basic properties in dimethyl sulfoxide (DMSO). The chemodosimeters were designed to undergo excited-state intramolecular proton transfer (ESIPT), which leads to significant Stokes shifts (ca.

Binding of Mono- and Dianions within Silver Thiazolylurea Tweezers and Capsules.

A silver thiazolylurea complex, [Ag(TUTh)], has been used as a host species for geometrically differently shaped mono- and dianions: trigonal planar (NO), tetrahedral (SO), and octahedral (SiF). In the presence of nitrate a 1:1 near-planar tweezer host-guest species is formed, with poor binding in solution despite excellent geometric complementarity being found between the host and the anion in the solid state. In the presence of either SO or SiF a 2:1 host-guest species is formed, whereby the guest is held in a capsulelike arrangement stabilized by an array of eight NH hydrogen-bond donors, as confirmed by X-ray crystallographic studies.

Crystal structure of di-aqua-bis-(7-di-ethyl-amino-3-formyl-2-oxo-2H-chromen-4-olato-κ(2) O (3),O (4))zinc(II) dimethyl sulfoxide disolvate.

The structure of the title coordination complex, [Zn(C14H14NO4)2(H2O)2]·2C2H6OS, shows that the Zn(II) cation adopts an octa-hedral geometry and lies on an inversion center. Two organic ligands occupy the equatorial positions of the coordination sphere, forming a chelate ring motif via the O atom on the formyl group and another O atom of the carbonyl group (a pseudo-β-diketone motif). Two water mol-ecules occupy the remaining coordination sites of the Zn(II) cation in the axial positions.

Small molecule recognition of mephedrone using an anthracene molecular clip.

An anthracene molecular probe has been synthesised and shown to target mephedrone, a stimulant drug from the cathinone class of new psychoactive substances (NPS). A protocol has been developed to detect mephedrone via the probe using NMR spectroscopy in a simulated street sample containing two of the most common cutting agents, benzocaine and caffeine.

A fluorescent dipyrrinone oxime for the detection of pesticides and other organophosphates.

An N,N-carbonyl-bridged dipyrrinone oxime has been synthesized and studied as a potential sensor for organophosphates. The molecular sensor underwent a drastic colorimetric response upon formation of the adduct. The pesticide dimethoate was found to produce the biggest spectral response, with a limit of detection equal to 4.

A pyrene-based fluorescent sensor for Zn2+ ions: a molecular 'butterfly'.

A simple pyrene-based triazole receptor has been synthesised and shown to self-assemble in the presence of ZnCl(2) in an exclusively 2:1 ratio, whereas a mixture of 2:1 and 1:1 ratios are observed for other Zn(2+) salts. The pyrene units are syn in orientation; this is supported by a strong excimer signal observed at 410 nm in the presence of ZnCl(2) in acetonitrile. DFT calculations and 2D NMR support the proposed structure.

Conformational and configurational analysis of an N,N carbonyl dipyrrinone-derived oximate and nitrone by NMR and quantum chemical calculations.

The geometries and relative energies of new N,N carbonyl dipyrrinone-derived oxime molecules (E/Z-s-cis 4a and E/Z-s-cis 4b) have been investigated. The calculated energies, molecular geometries, and (1) H/(13) C NMR chemical shifts agree with experimental data, and the results are presented herein. The E-s-cis conformations of 4a and 4b and the Z-s-cis conformation of 5b were found to be the thermodynamically most stable isomers with the oxime hydrogen atom or the methyl functional group adopting an anti-orientation with respect to the dipyrrinone group.

A lanthanide-based chemosensor for bioavailable Fe3+ using a fluorescent siderophore: an assay displacement approach.

The measurement of trace analytes in aqueous systems has become increasingly important for understanding ocean primary productivity. In oceanography, iron (Fe) is a key element in regulating ocean productivity, microplankton assemblages and has been identified as a causative element in the development of some harmful algal blooms. The chemosenor developed in this study is based on an indicator displacement approach that utilizes time-resolved fluorescence and fluorescence resonance energy transfer as the sensing mechanism to achieve detection of Fe3+ ions as low as 5 nM.

Squaraine dyes in molecular recognition and self-assembly.

Squaraine dye molecules and their derivatives are gaining significant interest in the field of supramolecular chemistry, both in host-guest recognition and self-assembly. The unique structure and properties of squaraine molecules has led to extensive research into their use as sensors. This feature article covers the most recent studies (2004-2009) in the development, characterization, and application of squaraine dye-based molecular sensors, self-assembly, and their use in polymeric materials and biological applications.

A Colorimetric Chemodosimeter for Pd(II): A Method for Detecting Residual Palladium in Cross-Coupling Reactions.

A colorimetric chemodosimeter (SQ1) for the detection of trace palladium salts in cross-coupling reactions mediated by palladium is described. Decolorization of SQ1 is affected by nucleophilic attack of ethanethiol in basic DMSO solutions. Thiol addition is determined to have an equilibrium constant (K(eq)) of 2.

Novel chemiluminescent detection of chemical warfare simulant.

A glow assay technology for the detection of a chemical warfare simulant is presented, which is based on modulating the peroxyoxalate chemiluminescence pathway by way of utilising an oximate super nucleophile that gives an "off-on" glow response.

Detection of chemical warfare simulants by phosphorylation of a coumarin oximate.

The detection of chemical warfare simulants is attained by the PET mechanism that gives an "off-on" fluorescent response with a half-life of approximately 50 ms upon phosphorylation of a reactive oximate functionality; the X-ray crystal structure of the oximate was also obtained and is discussed.

An artificial siderophore for the detection of iron(III).

An artificial siderophore in the form of a squaraine dye (1) has been synthesized. The bidentate ligand chelates to Fe(III) between the deprotonated hydroxyl group on the ortho position of the ring adjacent to the carbonyl group of the cyclobutadiene ring. The optical response is due to a subtle geometry change of 1 on chelation to Fe(III).

Slow anion exchange, conformational equilibria, and fluorescent sensing in venus flytrap aminopyridinium-based anion hosts.

The synthesis, anion binding, and conformational properties of a series of 3-aminopyridinium-based, tripodal, tricationic hosts for anions are described. Slow anion and conformational exchange on the (1)H NMR time scale at low temperature, coupled with NMR titration, results in a high level of understanding of the anion-binding properties of the compounds, particularly with respect to significant conformational change resulting from induced fit complexation. Peak selectivity for halides, particularly Cl(-), is observed.

Anion sensing 'venus flytrap' hosts: a modular approach.

A series of podands based on three hydrogen bonding 'arms' have been prepared and their affinities for simple inorganic anions measured.

Cooperative anion binding and electrochemical sensing by modular podands.

A series of podands based on two or three hydrogen bonding "arms" situated in mutually ortho, meta, or para relationships about an aryl core have been prepared, and their affinities for simple inorganic anions were measured. Of the two-arm hosts the meta compound and to a lesser extent the ortho host exhibit a cooperative anion binding effect. The two arms function essentially independently in the para derivative.