Polydiacetylene rhodamine-based colorimetric chemosensor for Au3+ detection.

A novel platform of a polydiacetylene combined with rhodamine B (PDA-Rho) colorimetric chemosensor array was prepared from a diacetylene monomer and rhodamine B derivative. Rhodamine B derivative as the ion-recognition element was embedded in the polydiacetylene matrix. To fabricate chemosensor, diacetylene monomer connected rhodamine B derivatives (DA-Rho) was coated onto a filter paper surface via drop-casting technique and transformed to polydiacetylene by polymerisation through ultraviolet (UV) irradiation. From the result, PDA-Rhoen exhibited high sensitivity and selectivity for Au3+ and could be monitored directly by naked eyes providing a fast, portable and easy-to-use as a molecular device in the real system. The DFT calculation results showed a stable complex between PDA-Rho and Au3+. We believe that, this method offers a sensitive and accurate process for Au3+ ion detection in real environmental and biological applications.

An ultra-low detection limit gold(III) probe based on rhodamine-covalent hydrogel sensor.

A highly sensitive and selective optical chemosensor (Arg-Rhoen) for determination of Au3+ was prepared by covalent immobilization of rhodamine ethylenediamine on agarose gel. Spectrophotometric studies of complex formation, chemical structures and purity of the hydrogel sensor were carried out using TGA, NMR, TEM, and IR. The complexation study results indicated that this probe can selectively detect Au3+ via a metal ion chelation-induced ring-opening reaction, and then caused a remarkable colour change from colourless to pink and a strong fluorescence enhancement. Theoretical DFT calculation results suggested that the hydrogel sensor Arg-Rhoen formed stable complexes with Au3+ through a large number of cation-dipole interactions. Reusability has been established by repeatedly dipping and rinsing the hydrogel in aqueous Au3+ and EDTA in basic solutions. We believe that this approach may provide an easily measurable and inherently sensitive method for Au3+ detection in environmental and biological applications.

A colorimetric paper-based optode sensor for highly sensitive and selective determination of thiocyanate in urine sample using cobalt porphyrin derivative.

In this work, a highly sensitive colorimetric paper-based optode for the determination of thiocyanate in urine samples was developed for the first time. The cocktail solution of the optode was composed of 5,10,15,20-tetrakis(4-octyloxyphenyl)porphyrin cobalt(II) complex (L), tridodecylmethylammonium chloride (TDMACl), 2-nitrophenyl octyl ether, and polyvinyl chloride as an ionophore, an ion exchanger, a plasticizer, and a polymer, respectively. The paper-based optode responded to thiocyanate by increasing the blue component in the RGB index and a visible change, with the naked-eye, of the optode color from pink to green was observed. From the central composite design, the optimized conditions that yielded the highest sensitivity were 4.70 mmol/kg TDMACl and 13.75 mmol/kg L. The developed optode sensor was highly selective and responded to thiocyanate over other anions, with a working range of 0.001-5 mM and with a coefficient of determination (R2) of 0.9915. The limits of detection using naked-eye and camera were determined to be 50.0 µM and 1.26 µM, respectively. In addition, the LOD and LOQ estimated from the standard deviation of the blank were 0.65 and 1.87 µM, respectively. Furthermore, this sensor was successfully applied to the detection of thiocyanate in urine samples from non-smokers and smokers. The results were in good agreement with the standard ion chromatography (IC) technique. This developed paper-based optode sensor was simple, low-cost, portable, and easy to use as a sensing device without any complicated instrument.

Gold sensing with rhodamine immobilized hydrogel-based colorimetric sensor.

A highly sensitive and selective optical membrane for determination of Au3+ was synthesized by immobilization of a rhodamine derivative on agarose hydrogel. The sensing dye was synthesized by solvatochromism of rhodamine B via rhodamine lactone-zwitterion equilibrium. UV-vis spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were employed to confirm that the rhodamine-lactone (RhoL) was incorporated into the agarose hydrogel. The results showed that the sensor was highly selective for recognizing Au3+ over other metal ions in real systems. In addition, DFT calculation results suggested that the membrane sensor formed stable complexes with Au3+ through a large number of cation-dipole and ion-ion interactions. In addition, according to changes in signaling upon adding various Au3+ concentration, the limit of detection of Arg-RhoL for Au3+ is calculated to be 5 µM. This approach may provide an easily measurable and inherently sensitive method for Au3+ ion detection in environmental and biological applications.

Azocalix[4]arene strapped calix[4]pyrrole: a confirmable fluoride sensor.

A new chromogenic fluoride sensor based on 1,3-di-p-nitrophenylazocalix[4]arene-calix[4]pyrrole (1) was designed and synthesized. The color of the solution of probe 1 changed upon the addition of any F(-), CH(3)CO(2)(-), PhCO(2)(-), and H(2)PO(4)(-) ions. However, from these ions the highly specific sensing of F(-) is achieved by the addition of Ca(2+) which leads to a color change from light sky blue (of 1·F(-)) back to the original light orange color of 1.

Facile synthesis of rhodamine-based highly sensitive and fast responsive colorimetric and off-on fluorescent reversible chemosensors for Hg2+: preparation of a fluorescent thin film sensor.

Fluorescence-active chemosensors (L1-L4), comprising a rhodamine scaffold and a pseudo azacrown cation-binding subunit, have been proposed and characterized as a fluorescent chemosensor for Hg(2+). An on-off type fluorescent enhancement was observed by the formation of the ring-opened amide form of the rhodamine moiety, which was induced by the interactions between Hg(2+) and the chemosensor. Upon the addition of Hg(2+), an overall emission change of 350-fold was observed, and the selectivity was calculated to be 300 times higher than Cu(2+) for receptors L2-L4. A polymeric thin film can be obtained by doping poly(methyl methacrylate) or PMMA with chemosensor L2. Such a thin film sensor can be used to detect Hg(2+) with high sensitivity and can be recovered using diluted NaOH.

Conformation-selective synthesis and binding properties of N-benzylhexahomotriaza-p-chlorocalix[3]trinaphthylamide.

N-benzylhexahomotriaza-p-chlorocalix[3]trinaphthylamide in partial cone conformation was selectively synthesized by appropriately controlling the steric effect during the amidation reactions of N-benzylhexahomotriaza-p-chlorocalix[3]tri(ethyl acetate) in cone or partial cone conformations with use of 1-aminomethylnaphthalene. The conformation was confirmed by (1)H, (13)C, and 2D NMR and X-ray single-crystal analysis. Analyses of the complexes revealed that recognition is strongly affected by Cd(2+), Pb(2+), and F(-) ions.

Self-assembly and electrochemical oxidation of polyamidoamine-carbazole dendron surfmer complexes: nanoring formation.

We report a detailed and quantitative study on the supramolecular complexation of amine-functionalized polyamidoamine (PAMAM) dendrimer G(4)-NH(2) with carboxylic acid terminal dendrons containing peripheral electroactive carbazole groups of different generations (G(0)COOH, G(1)COOH, and G(2)COOH). While the focus is on a detailed understanding and mechanism of complex formation, subsequent electrochemical oxidation of the dendron surfmers resulted in the formation of nanoring structures electrodeposited on the conducting substrate. Complexation was confirmed by NMR, UV-vis, and IR measurements. Critical micelle concentration (CMC), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) studies revealed that the ringlike structures were formed during the equilibrium-decomplexation stage and that the electrochemical process did not destroy the complex but rather stabilized it. The different generations of the dendrons provided various structures and complex formation efficacy. This type of template polymerization combined with electrochemically anodic oxidation has not been previously reported.

Novel C3v-symmetrical N7-Hexahomotriazacalix[3]cryptand: a highly efficient receptor for halide anions.

[structure: see text] We report the synthesis of a novel C(3)(v)()-symmetrical N(7)-hexahomotriazacalix[3]cryptand (1). Compound 1 was shown to be in a fixed cone conformation by (1)H NMR spectroscopy and X-ray single-crystal structure determination. Complexation studies showed that 1 is a selective receptor for halide ions. The effects of zinc metal cation on the receptor (1-Zn(2+)) upon anion recognition are also shown.