Simple, Robust, and Plasticizer-Free Iodide-Selective Sensor Based on Copolymerized Triazole-Based Ionic Liquid.

Novel solid-contact iodide-selective electrodes based on covalently attached 1,2,3 triazole ionic liquid (IL) were prepared and investigated in this study. Triazole-based IL moieties were synthesized using click chemistry and were further copolymerized with lauryl methacrylate via a simple one-step free radical polymerization to produce a "self-plasticized" copolymer. The mechanical properties of the copolymer are suitable for the fabrication of plasticizer-free ion-selective membrane electrodes. We demonstrate that covalently attached IL moieties provide adequate functionality to the ion-selective membrane, thus achieving a very simple, one-component sensing membrane. We also demonstrate that the presence of iodide as the counterion in the triazole moiety has direct influence on the membrane's functionality. Potentiometric experiments revealed that each electrode displays high selectivity toward iodide anions over a number of inorganic anions. Moreover, the inherent presence of the iodide in the membrane reduces the need for conditioning. The nonconditioned electrodes show strikingly similar response characteristics compared to the conditioned ones. The electrodes exhibited a near Nernstian behavior with a slope of -56.1 mV per decade across a large concentration range with lower detection limits found at approximately 6.3 × 10(-8) M or 8 ppb. These all-solid-state sensors were utilized for the selective potentiometric determination of iodide ions in artificial urine samples in the nanomolar concentration range.

Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers.

The applicability of ion exchange membranes is mainly defined by their permselectivity towards specific ions. For instance, the needed selectivity can be sought by modifying some of the components required for the preparation of such membranes. In this study, a new class of materials -trihexyl(tetradecyl)phosphonium based ionic liquids (ILs) were used to modify the properties of ion exchange membranes. We determined selectivity coefficients for iodide as model ion utilizing six phosphonium-based ILs and compared the selectivity with two classical plasticizers. The dielectric properties of membranes plasticized with ionic liquids and their response characteristics towards ten different anions were investigated using potentiometric and impedance measurements. In this large set of data, deviations of obtained selectivity coefficients from the well-established Hofmeister series were observed on many occasions thus indicating a multitude of applications for these ion-exchanging systems.

Pencil and Gold Electrode Materials for the Electrochemical Study and Analysis of Dinitrotoluene.

The aim of our work was to investigate practical and robust methods for the electrochemical analysis of DNT. Using gold WEs, we differentiated between the nitro substituents in 2,4- and 2,6-DNT in organic electrolyte systems. Switching to an aqueous electrolyte (2 M H2SO4), a limit of detection (LOD) of 0.158 ppm (0.87 µM) and a limit of quantitation (LOQ) of 0.48 ppm (2.64 µM) were observed for 2,4-DNT. Subsequent simplification to wooden craft pencils as WEs in aqueous 2 M H2SO4 electrolyte achieved a LOD of 4.8 ppm (26.48 µM) and a LOQ of 14.6 ppm (80.54 µM) for 2,4-DNT. Alongside this easily renewable WE choice, 2 M H2SO4 was found to improve the solubility of DNT in aqueous media and has not been previously reported as an electrolyte in DNT electroanalysis. On testing a range of pencil grades from 4H to 8B, it was found that 4B gave the best sensitivity. The work serves as a preliminary study into materials that, through their simplicity and availability, may be suitable for the development of a robust and portable instrumental method through the electrochemical work presented here.

Molecular memory with downstream logic processing exemplified by switchable and self-indicating guest capture and release.

Molecular-logic based computation (MLBC) has grown by accumulating many examples of combinational logic gates and a few sequential variants. In spite of many inspirations being available in biology, there are virtually no examples of MLBC in chemistry where sequential and combinational operations are integrated. Here we report a simple alcohol-ketone redox interconversion which switches a macrocycle between a large or small cavity, with erect aromatic walls which create a deep hydrophobic space or with collapsed walls respectively. Small aromatic guests can be captured or released in an all or none manner upon chemical command. During capture, the fluorescence of the alcohol macrocycle is quenched via fluorescent photoinduced electron transfer switching, meaning that its occupancy state is self-indicated. This represents a chemically-driven RS Flip-Flop, one of whose outputs is fed into an INHIBIT gate. Processing of outputs from memory stores is seen in the injection of packaged neurotransmitters into synaptic clefts for onward neural signalling. Overall, capture-release phenomena from discrete supermolecules now have a Boolean basis.

5',6-Dichloro-1',3',3'-trimethyl-spiro-[2H-1-benzopyran-2,2'-indoline].

In the crystal structure of the title compound, C(19)H(17)Cl(2)NO, the indoline and benzopyran ring systems are approximately perpendicular to each other. The indoline ring is in an envelope conformation with the spiro C atom as the flap. The N atom of the indoline ring forms a pyramidal environment, the sum of the angles at this atom being 352.46°.

Wearable technology for bio-chemical analysis of body fluids during exercise.

This paper details the development of a textile based fluid handling system with integrated wireless biochemical sensors. Such research represents a new advancement in the area of wearable technologies. The system contains pH, sodium and conductivity sensors. It has been demonstrated during on-body trials that the pH sensor has close agreement with measurements obtained using a reference pH probe. Initial investigations into the sodium and conductivity sensors have shown their suitability for integration into the wearable system. It is thought that applications exist in personal health and sports performance and training.

Chloride selective calix[4]arene optical sensor combining urea functionality with pyrene excimer transduction.

A neutral 2-site chloride selective compound has been developed (3), based on a 1,3-alternate tetrasubstituted calix[4]arene providing a preorganized supramolecular scaffold. The resultant supramolecular cavity is among the first to combine urea functional groups bridged with single methylene spacers to pyrene moieties. It combines a naturally and synthetically proven H-bonding system with the elegant ratiometric fluorescent signaling properties of an intramolecular pyrene excimer system, triggered by conformational changes upon anion coordination. The excimer emission of 3 is quenched, with a simultaneous rise in the monomer emission solely by the chloride anion among a wide variety of anions tested. 3 has an association constant of 2.4 x 10(4) M(-1) with chloride. The suitability and advantages of ratiometric optical sensor compounds like 3 for use in practical sensor devices is discussed. 3 has an LOD of 8 x 10(-6) M with chloride in acetonitrile-chloroform (95:5 v/v). A dynamic fluorescence study revealed a response time of < 3 s. A recently developed and simple HPLC-based purification method complimented conventional organic work up methods to yield pure product.