Metal island coated polymer sensor for direct determination of the volume effect of chaotropic agents

A new optical sensor is presented, based on the analyte reaction resulting in swelling and shrinking of a thin polymer layer. Changing the concentration of ions in a new bisazide photo-cross-linked poly(vinylpyrrolidone) polymer results in a concentration-dependent volume change of the hydrated gel. The volume response of the sensor induced by different ions is fully reversible over more than 250 cycles. The response of the device depends on the type, the charge and the concentration of the ions. The sensor material is part of an optical thin film system which transforms the variations in volume of the polymer into spectral information. The steady state of the sensor response is obtained within 60 s. The response time is mainly limited by the pump rate, the back pressure and the total volume of the system but not by the swelling of the sensor polymer. A comparative study of ion effects has demonstrated a fundamental correlation of the polymer swelling properties with the Hofmeister series of chaotropic agents. Thus it is concluded that the photopolymer, which is solubilized in aqueous solutions by the interaction of its amide structure with the solvent, behaves like the backbone amide structure of proteins.     

Luminescent dendrimers as ligands for metal ions

Suitably designed luminescent dendrimers can play a role of ligands for luminescent and non-luminescent metal ions. This combination leads to species capable of exhibiting interesting and unusual properties, including (i) shielding excited states from quenching processes, (ii) light harvesting, (iii) conversion of incident UV light into visible or infrared emission, and (iv) metal ions sensing with signal amplification.     

Potentiometric pH response of membranes prepared with various aminated-poly (vinyl chloride) products

The preparation and potentiometric pH response properties of membranes formulated with various aminated-poly(vinyl chloride) (PVC-NH₂) products are described. Products containing secondary and/or primary amino functional groups are obtained by modifying PVC with mono- and/or diamines, respectively. Blank membranes prepared with either type of aminated-polymer exhibit nearly Nernstian potentiometric pH responses over different pH ranges. In general, membranes based on diamino products exhibit pH response over a wider range (5–10.5) than membranes formulated with monoamino products (<8.0). These potentiometric results are used to estimate the basicity of the various primary and secondary amino sites in the membrane phases.Dedicated to Professer W. Simon on the occasion of his 60th birthday     

Synthesis and fluorescence ion-sensory properties of the first dehydropyridoannulene-type cyclophane with enforced exotopic metal ion binding sites

The new twistophane 4 has been synthesised, which comprises a conjugated dehydropyridoannulene-type macrocyclic scaffold with outwardly projecting nitrogen-donor sites for the purpose of metal ion coordination. The macrocyclíc structure of 4 was assigned by using spectroscopic methods, and shown to exist in a twisted and chiral ground state conformation by semi-empirical theoretical calculations. A detailed spectroscopic investigation into the metal ion binding properties of 4 and precursor 11 revealed that they functioned as selective complexants, affording a fluorescence quenching output response characteristic of Pd(II) and Hg(II) ions. Furthermore, 4 also signalled the presence of Fe(II), Co(II), Ni(II) and Ag(I) ions by the precipitation of coordination polymers, and exhibited reversible proton-triggered fluorescence quenching behaviour. Macrocycle 4 thus represents a unique type of molecular sensory platform, which may find a wealth of potential applications such as the detection of heavy-metal pollutants, as well as for the fabrication of proton-switchable materials and coordination polymers with novel electronic and magnetic properties.     

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade^?1 in the concentration range of 10^?1–10^?5 mole L^?1, a detection limit of 1×10^?5 mole L^?1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. , benzoate, I^?, SCN^?). Selectivity was confirmed by calculating the formation constant (K_β) using sandwich membrane method, where K_β for TUD1‐salicylate is 10^0.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (β_HRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of β_HRS, and the shortest lengths of the four N?H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®.     

Analytical assays based on detecting conformational changes of single molecules.

One common strategy for the detection of biomolecules is labeling either the target itself or an antibody that binds to it. Herein, a different approach, based on detecting the conformational change of a probe molecule induced by binding of the target is discussed. That is, what is being detected is not the presence of the target or the probe, but the conformational change of the probe. Recently, a single-molecule sensor has been developed that exploits this mechanism to detect hybridization of a single DNA oligomer to a DNA probe, as well as specific binding of a single protein to a DNA probe. Biomolecular recognition often involves large conformational changes of the molecules involved, and therefore this strategy may be applicable to other assays.     

Optical sensors for determination of heavy metal ions

A review is given on optical means for single shot testing (probing) as well as continuous monitoring (sensing) of heavy metal ions (HMs). Following an introduction into indicator based approaches, we discuss the types of indicator dyes and polymeric supports used, as well as existing sensing schemes for HMs. The wealth of information is compiled in the form of tables and critically reviewed. Notwithstanding the tremendous work performed so far, it is obvious that still severe limitations do exist in terms of selectivity, limits of detection, dynamic ranges, applicability to specific problems, and reversibility. On the other hand, such sensors have found — and will find — their application whenever rapid and cost-effective testing is required, where personnel is scarce or unskilled, and in field tests. Despite their limitations, the number of such sensors (and of irreversible probes) for HMs is likely to increase in future.     

Chemical Sensors for Electronic Nose Systems

Chemical sensors have been widely used for the analysis of volatile organic compounds. Employing chemical sensors in an array format with pattern recognition provides a higher degree of selectivity and reversibility leading to an extensive range of applications. When such systems are used for odour analysis they are termed electronic noses. Application of electronic noses ranges from the food industry, medical industry to environmental monitoring and process control. Many types of different gas sensors have been employed in the array. These include conducting polymers, metal oxide semiconductors, piezoelectric, optical fluorescence and amperometric gas sensors The transducer principle of these sensors is varied and is discussed in detail within this review. Examples of the current trends in sensor array technology as well as the applications to which the sensor-based noses have been applied are also discussed.     

A tetra-coordinate nickel(II) complex as neutral carrier for nitrate-selective PVC membrane electrode

The potentiometric response properties and applications of a tetra-coordinate nickel(II) complex with relatively high selectivity toward nitrate ion are described. The nickel(II) complex of 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene was used as a neutral carrier into plasticized poly(vinyl chloride) (PVC) membrane. The influence of several variables was investigated in order to optimize the potentiometric response and selectivity of the electrode. The resulting membrane electrode incorporating 31.0% PVC, 61.0% dioctyl phthalate (DOP) as plasticizer, 3% methyltrioctylammonium chloride (MTOAC) as a cationic additive and 5% carrier (all w/w) demonstrates a Nernstian response slope of −59.6 mV per decade over the concentration range of 5×10⁻⁶-1×10⁻¹ M NO₃⁻. The electrode exhibits a fast response time (≤10 s), a detection limit of 2.5×10⁻⁶ M, and can be used over a wide pH range of 4-12. The electrode shows improved selectivity in comparison to most of the previously reported nitrate-selective electrodes. It was successfully applied to the determination of nitrate ion in natural water samples.     

A novel blue fluorescent chemosensor for metal cations and protons,based on 1,8‐naphthalimide and its copolymer with styrene

A new blue emitting 2‐allyl‐6‐(2‐dimethylaminoethyloxy)‐benzo[de]isoquinoline‐1,3‐dione, bearing an allylic group has been designed and synthesized. Bulk radical copolymerization has been carried out in order to prepare a fluorescent copolymer, based on styrene. The main photophysical characteristics of the monomeric and polymeric fluorophores have been investigated both in the absence and presence of metal cations and protons. It has been found that the monomeric naphthalimide can be used as a sensor for protons and Zn²⁺, Ni²⁺, Ce³⁺, Cu²⁺, Co²⁺, Ag⁺ cations. The polymeric fluorophore has been shown to be a selective chemosensor for Cu²⁺ cations. Copyright © 2006 John Wiley & Sons, Ltd.