Polyacrylate Microspheres for Tunable Fluorimetric Zinc Ions Sensor

A novel concept of optical fluorimetric sensing using polymeric microspheres is explored on example of zinc ions sensors. The novel approach proposed uses the advantage of concomitant presence in a microsphere of two compounds: a receptor, fluorescently silent complexing ligand and an optical transducer, fluorescent compound. Binding of the analyte by the ligand affects its absorption spectrum, leading to decrease of the free ligand absorption and increase of complex absorption band. The decrease of free ligand absorption exposes emission of the transducer, yielding increase in fluorescence intensity on analyte concentration increase. This approach was verified experimentally using Zn²⁺ as a model analyte, the fluorimetric sensor obtained uses 1-(2-pyridylazo)-2-naphthol (PAN) as analyte sensitive receptor and pyrene as optical transducer. In the absence of zinc ions in the sample emission of pyrene embedded in the spheres was significantly quenched, whereas increase of Zn²⁺ ions concentration in the sample resulted in dependence of fluorescence intensity on logarithm of zinc ions concentration in extraordinary wide range, from 10^–7 to 0.1 M. The response mechanism was explained by surface accumulation of zinc ion–PAN complex on the microsphere/sample solution interface. It was also shown that introduction of cation-exchanging sites to the microspheres significantly alters the responses pattern leading to high sensitivity over relatively limited concentration range (3–4 orders of magnitude). In the latter case the observed responses can be tuned to occur in chosen concentration range, simply by adjusting sample pH

Fate of Poly(3-octylthiophene) Transducer in Solid Contact Ion-Selective Electrodes

An experimental approach allowing visualization and quantification of the underestimated spontaneous process of partition of conducting polymer transducer material to the ion-selective membrane phase is proposed. The approach proposed is based on optical properties of the transducer material applied, using polythiophene as a model system. It is shown that this process occurs not only during the sensor preparation step but also during pretreatment of the sensor before use. As shown, this uncontrolled partition of the transducer to the receptor leads to conducting polymer contents in the membrane phase reaching 0.5% w/w; this process is accompanied by a partial spontaneous change of the oxidation state of polythiophene. The conducting polymer present in the membrane participates to some extent in the overall response of the sensor, which can be observed as a change in the polythiophene optical emission spectra. Fluorescence microscopic images obtained clearly show that the conducting polymer is distributed throughout the membrane thickness, being present also at the membrane/solution interface. The experimental results presented were obtained for K⁺-selective sensors using poly­(3-octylthiophene) as a model transducer; however, the proposed approach is also applicable for other systems

Nanofiber-Supported Palladium NanocubesToward Highly Active and Reusable Catalyst

Electrospun nanofibers were used to support palladium nanocubes, resulting in a highly active, stable, and reusable catalyst. The system proposed herein offers significant advantages compared to catalysts in the form of nanoparticles suspension. The porous, solvent permeable structure of the nanofiber mat ensures uniform and stable time distribution of palladium nanoparticles; preventing coalescence and allowing multiple use of the catalyst. The proposed cross-linked poly(vinyl alcohol) nanofiber mat loaded with Pd nanocubes during the nanofiber preparation step is a macroscopic structure of intrinsically nanostructural character of the catalyst that can be easily transferred between different solutions without compromising its effectiveness in consecutive cycles. Thus, obtained system was characterized with high catalytic activity as tested on a model example of 4-nitrophenol (4-NP) reduction by NaBH4 to 4-aminophenol (4-AP). It is shown that loading nanofibers with Pd nanocubes during electrospinning resulted in a significantly more stable system compared to surface modification of obtained nanofibers with nanocube suspension

Nanoparticles of Fluorescent Conjugated Polymers: Novel Ion-Selective Optodes

A novel type of ion-selective nano-optode is proposed, in which a conjugated polymer is used as optical transducer and nanoprobe material. Thus, contrary to most of the proposed optodes, the response does not require presence of pH-sensitive dye in the sensor. The conjugated polymer nanosensor material is in partially oxidized formit is bearing positive charges and its emission is quenched. The receptor is an optically silent uncharged ionophore selective for the analyte cation. When a binding event occurs, positive charges are formed in the nanosphere, leading to a decrease in the oxidation state of the polymer, in the absence of redox potential change, resulting in increased emission. This general approach herein proposed results in a simple sensor, benefitting from a novel optical transduction mechanism and high lipophilicity of the polymer matrix that results in linear responses over a broad concentration range of analyte. For the model system studied, the linear dependence of emission intensity on the logarithm of analyte (K⁺) concentration was obtained for a broad range from 10^–5 M to 0.1 M

Dithizone Modified Gold Nanoparticles Films for Potentiometric Sensing

For the first time, application of a membrane composed of gold nanoparticles decorated with complexing ligand for potentiometric sensing is shown. Gold nanoparticles drop cast from a solution form a porous structure on a substrate electrode surface. Sample cations can penetrate the gold nanoparticles layer and interact with ligand acting as a charged ionophore, resulting in Nernstian potentiometric responses. Anchoring of complexing ligand on the gold surface abolishes the necessity of ionophore application. Moreover, it opens the possibility of preparation of potentiometric sensors using chelators of significantly different selectivity patterns further enhanced by the absence of polymeric membrane matrix. This was clearly seen, for example, for gold nanoparticles stabilizing the applied ligand–dithizone–thiol conformation leading to a high potentiometric selectivity toward copper ions, much higher than that of ionophores typically used to induce selectivity for polymeric ion-selective membranes