A MIP-based low-cost electrochemical sensor for 2-furaldehyde detection in beverages.

There is an increasing interest in determining the concentration of furanic compounds naturally formed in food aqueous matrices, by in situ, fast and low-cost methods. A sensor presenting such characteristics is here proposed, and characterized. It is based on a molecularly imprinted polymer (MIP) as a receptor with electrochemical transduction on a screen printed cell (SPC). The molecularly imprinted polymer has been developed for a particular furanic derivative, 2-furaldehyde (2-FAL). The detection bases on the reduction of 2-FAL selectively adsorbed on the polymer layer in contact with the working electrode. The polymer layer is simply formed by in situ polymerization, directly over the SPC and it was characterized by IR, SEM and electrochemical methods. Even if based on an easy and fast preparation procedure, the layer sufficiently adheres to the cell surface giving a reusable sensor. Square wave voltammetry (SWV) was applied as the signal acquisition method. The sensor performance in aqueous solution (NaCl 0.1 M) was tested, obtaining that the dose-response curve is fitted by the Langmuir adsorption isotherm. The sensitivity, and so the limit of detection, were noticeably improved by a chemometric approach based on the Design of experiment method. (optimized conditions: Estep = 0.03 V, Epulse = 0.066 V, f = 31 s-1). In water solution at pH around neutrality the dynamic range was from about 50 µM to 20 mM. Similar results were obtained for a white wine containing 12% ethanol, which has been considered as a typical example of beverage possibly containing furhaldehydes. The higher limit of quantification can be modulated by the amount of MIP deposited, while the lower detection limit by the conditions of the electrochemical measurement.

Voltammetric platform for detection of 2,4,6-trinitrotoluene based on a molecularly imprinted polymer.

New methods for determination of explosive substances as, for example, 2,4,6-trinitrotoluene (TNT), in a rapid way and at low cost are highly required. An electrochemical platform has been here developed with good characteristics of low dimension, fast response, low cost, and high selectivity. It is based on a commercially available screen printed cell with graphite ink working and auxiliary electrodes and a silver ink quasi-reference electrode. The whole cell is covered with a thick layer of cation exchanging acrylic polymer molecularly imprinted with 2,4,6-trinitrotoluene. The polymeric layer acts at the same time as electrolytic medium and selective receptor. It has been demonstrated that, in this medium, 2,4,6-trinitrotoluene is electroactive at graphite electrode, being reduced by a non-reversible reaction. The peak current (differential pulse voltammogram) is proportional to TNT concentration with limit of detection for TNT around 5 × 10(-7) M and linearity range up to 2 × 10(-5) M. The selectivity for TNT relative to other reducible compounds as, for example, nitroaromatic derivatives, and to other possible interfering substances, as negatively charged ions, is good. Measurements can be performed in not de-aerated solution and in small volumes (20 µl), so that the proposed platform is very promising for in situ determinations.

Potentiometric sensor for atrazine based on a molecular imprinted membrane.

A molecular imprinted polymer (MIP) membrane for atrazine, not containing macropores, was synthesized and implemented in a potentiometric sensor. It is expected to work like a solid ISE (where the specific carrier are the imprinted sites) the specific carrier being the imprinted site. The active ion is the protonated atrazine, positively charged. To form this species the determination is carried out in acidic solution at pH lower than 1.8, in which atrazine is prevalently monoprotonated. At these conditions the membrane potential increases with atrazine concentration over a wide concentration range (3 x 10(-5) to 1 x 10(-3)M). The slope of the function E versus logc is about 25 mV/decade, showing that the atrazine form sorbed on MIP is the biprotonated one. The detection limit is determined by the relatively high concentration of atrazine released by the membrane in the sample solution at the considered conditions. It seems to be independent of the atrazine concentration in the internal solution of the sensor, but it depends on the acidity of the solution. The response time is less than 10s and the sensor can be used for more than 2 months without any divergence.

Aluminium speciation in natural water by sorption on a complexing resin.

Very stable aluminium complexes may be present in natural waters, which can be detected only using appropriate methods. One of them is the resin titration based on the sorption of aluminium on a strongly sorbing resin, Chelex 100. It was here used to detect strong aluminium complexes, and to characterize them by determining their concentration, and the corresponding stability constant. High and low salinity waters were sampled in different sites in the North of Italy. In all the samples aluminium complexes with high stability constant, up to 10(17.4) M(-1) in the less acidic solution, were detected. The stability constant depends mainly on the solution acidity, increasing with increasing pH up to 7. The concentration of the ligands responsible for the strong complexation is similar to that of aluminium (from 0.5 to 1.5 microM), or somewhat lower in the case of estuarine and sea waters. A small fraction of aluminium (from 0% to 2%) in freshwaters, higher in estuarine and sea waters (14% and 10%, respectively), is present in weakly bound forms which could also be the hydrolysis products. The conditional constants of the strong complexes were determined for the different samples examined. They were found to be slightly lower in the case of the high salinity waters, in which a value of 10(16.1) M(-1) at pH 7.5 was obtained. This is probably due to the higher ionic strength in marine water, which strongly influences the complexation of trivalent metal ions, as seen for example also in the hydrolysis. It could be deduced that similar substances, but at different concentration, would be responsible for the aluminium complexation in the sea and freshwaters here examined. They could be natural organics like fulvic substances, or better some particular complexing sites in this substances with very high affinity for aluminium.

Investigation on sorption equilibria of Mn(II), Cu(II) and Cd(II) on a carboxylic resin by the Gibbs-Donnan model.

Sorption mechanism of bivalent metal ions on a weak cationic resin containing the carboxylic group is studied. The Gibbs-Donnan model is used to describe and then to predict the sorption through the determination of the intrinsic complexation constants. These quantities characterize the sorption being independent of experimental conditions. They are determined according to a well established procedure and using a recently proposed iterative method for calculation of counter ion concentration in the resin phase. Sorption mechanisms are also studied adding appropriate soluble ligands whose complexing properties are exactly known to the solution containing the resin and the metal ion. Competing with the resin for the complexation of the metal, they shift the sorption curve to higher pH and often this allows detecting other complexes between the metal and the resin. In this way for Mn(II), besides the 1:1 complex formed in the more acidic solution, with logbeta(110)=-4.55, the complex ML(2), characterized by logbeta(120)=-9.80, is found; for Cd(II), besides the ML complex, with logbeta(110)=-3.01, at pH higher than 7, the specie MLOH with logbeta(11-1)=-8.28. For Cu(II) the complex ML(2) is detected, confirming previous findings, with logbeta(120)=-7.24. In the presence of two different ligands, sulphosalicylic and malonic acid, a different complex, ML(2)OH, is identified, with the same intrinsic complexation constant for the two ligands, logbeta(12-1)=-13.35. As expected from the model, the intrinsic complexation constants, especially for the 1:1 complex, are in a good agreement with the complexation constants of acetic acid.

Sorption of proton and heavy metal ions on a macroporous chelating resin with an iminodiacetate active group as a function of temperature.

A macroporous resin containing iminodiacetic groups (Lewatit) was investigated for its sorption properties towards proton and nickel(II) and cadmium(II). Different compositions of the aqueous phase, and different temperatures were examined. The stoichiometry, the exchange coefficients and the intrinsic constants of the sorption equilibria were obtained from the experimental data by using the Gibbs-Donnan model for the ion exchange resin. The intrinsic constants were found to be independent of the composition of the solution, so that they were used for characterizing the sorption equilibria. While the first intrinsic protonation constant of the active groups in the resin was found to depend on the temperature, the second one was independent. The sorption equilibrium of nickel in the resin was different from that of cadmium, being ascribable respectively to the formation of the complexes NiL and Cd(HL)(2). inside the resin. Their intrinsic complexation constants were found to be 10(-1.84) and 10(-3.64) at 25 degrees C. Compared to those of another resin with the same active groups, but not macroporous, they are higher. The dependence of the intrinsic constant on the temperature was also different for the two metals, allowing to evaluate a DeltaH degrees of +30.9 and of +13.7 kJ mol(-1) respectively. When a comparison is possible, these values are near to those in aqueous solution for the complexation with ligands of similar structure. These results can be used to achieve metal ion separation based on temperature variations.

Sorption of protons and metal ions from aqueous solutions by a strong-base anion-exchange resin loaded with sulphonated azo-dyes.

Two sulphonated azo-dyes, which bear a nitrogen donor atom in the diazo group and are known to complex many heavy metal ions in aqueous solution, have been found to be sorbed by a strong-base anion-exchange resin (Dowex 1-X8) simply by ion-exchange. The resin containing the dyes behaves like a chelating resin, able to sorb copper(II) and nickel(II) from aqueous solution, if the proper conditions are chosen. The acidity, ionic composition and volume of the aqueous solution, and the amount and nature of the sorbed ligand are the factors which determine the fraction of metal ion sorbed when the batch technique is used. The experimental results are interpreted by using a model of the resin based on the Donnan equilibrium concept, which allows prediction of the sorption conditions on the basis of some independently determined quantities, such as the protonation and complex formation constants in aqueous solution, and the activity of the counter-ion in the resin phase. The exchange of protons between the resin and the aqueous solution can also be explained with this model.