Saúl Vallejos

Working with water insoluble organic molecules in aqueous media: fluorene derivative-containing polymers as sensory materials for the colorimetric sensing of cyanide in water

This paper describes a strategy followed to achieve a sensing phenomenon in aqueous media using water-insoluble organic molecules. We have prepared a methacrylamide and a methacrylate with pendant cyanide chemosensors based on a fluorene-derivative motif, and we have fabricated highly hydrophilic membranes by means of copolymerising these hydrophobic monomers with others. Therefore, upon absorption of water in the membranes, solvated ions enter the membrane by a simple diffusion mechanism, reaching the hydrophobic chemosensor motifs and giving rise to a macroscopic sensing phenomenon. In this way, we have prepared solid materials (dense membranes or films) capable of selectively detecting cyanide, with an extremely low detection threshold, in aqueous solution by means of colour changes (naked-eye sensing) (13 ppb). Nevertheless, the key point of this research is the description of the possibilities of anchoring organic insoluble molecules (i.e., drugs, fungicides, bactericides, sensing probes, etc.) to solubilise them in water, or to prepare hydrogels, permitting the use of these molecules in aqueous media or in biological media for medical, biological or biochemical purposes.

Solid Polymer Substrates and Coated Fibers Containing 2,4,6- Trinitrobenzene Motifs as Smart Labels for the Visual Detection of Biogenic Amine Vapors

Attempts to polymerize trinitrobenzene derivatives (TNB) have been fruitless so far. Accordingly, polymers containing TNB have not been exploited in spite of their envisaged potential applications. Here, we describe two ways for preparing polymers with TNB moieties thus overcoming the previously reported polymerization impairments. We also report on the exploitation of the materials, both obtained as tractable transparent films and coated fibers, as smart labels for the visual detection of amine vapors. More precisely, amines in the atmosphere surrounding the sensory materials diffuse into them reacting with the TNB motifs forming highly colored Meisenheimer complexes, giving rise to development of color and to the naked eye sensing phenomenon. This is the case of highly volatile amines, such as trimethylamine, produced in food spoilage, specifically in the deterioration of fish or meat, for which the color development of the smart labels can be used as a visual test for food freshness.

Forced Solid-State Interactions for the Selective “Turn-On” Fluorescence Sensing of Aluminum Ions in Water Using a Sensory Polymer Substrate

Selective and sensitive solid sensory substrates for detecting Al(III) in pure water are reported. The material is a flexible polymer film that can be handled and exhibits gel behavior and membrane performance. The film features a chemically anchored salicylaldehyde benzoylhydrazone derivative as an aluminum ion fluorescence sensor. A novel procedure for measuring Al(III) at the ppb level using a single solution drop in 20 min was developed. In this procedure, a drop was allowed to enter the hydrophilic material for 15 min before a 5 min drying period. The process forced the Al(III) to interact with the sensory motifs within the membrane before measuring the fluorescence of the system. The limit of detection of Al(III) was 22 ppm. Furthermore, a water-soluble sensory polymer containing the same sensory motifs was developed with a limit of detection of Al(III) of 1.5 ppb, which was significantly lower than the Environmental Protection Agency recommendations for drinking water.

An organic/inorganic hybrid membrane as a solid "turn-on" fluorescent chemosensor for coenzyme A (CoA), cysteine (Cys), and glutathione (GSH) in aqueous media.

The preparation of a fluorogenic sensory material for the detection of biomolecules is described. Strategic functionalisation and copolymerisation of a water insoluble organic sensory molecule with hydrophilic comonomers yielded a crosslinked, water-swellable, easy-to-manipulate solid system for water “dip-in” fluorogenic coenzyme A, cysteine, and glutathione detection by means of host-guest interactions. The sensory material was a membrane with gel-like behaviour, which exhibits a change in fluorescence behaviour upon swelling with a water solution of the target molecules. The membrane follows a “turn-on” pattern, which permits the titration of the abovementioned biomolecules. In this way, the water insoluble sensing motif can be exploited in aqueous media. The sensory motif within the membrane is a chemically anchored piperazinedione-derivative with a weakly bound Hg(II). The response is caused by the displacement of the cation from the membrane due to a stronger complexation with the biomolecules, thus releasing the fluorescent sensory moieties within the membrane.

Methacrylate copolymers with pendant piperazinedione-sensing motifs as fluorescent chemosensory materials for the detection of Cr(VI) in aqueous media

A fluorogenic sensory film, or dense membrane, capable of detecting Cr(VI), Fe(III), and Hg(II) in water was prepared. The film was prepared by a bulk radical polymerization of different comonomers, one of which contained a piperazinedione motif as sensory fluorophore. The film exhibited gel-like behavior and was highly tractable, even after being swollen in water. The sensing conditions were chosen to overcome interference from iron and mercury cations, giving rise to a material with a detection limit of 1 ppb for Cr(VI).

Direct visual detection and quantification of mercury in fresh fish meat using facilely prepared polymeric sensory labels

We describe herein the direct visual detection of mercury in fish and water using easily prepared polymeric labels. The polymeric film has chemically anchored dithizone motifs. The sensory film is prepared from a conventional vinyl polymer by straightforward solid-phase reactions. The sensory material is stable under ambient conditions, is reusable and can be handled without care by unskilled persons. Upon contacting fish meal, the sensory film changes colour, allowing for the colourimetric quantification of the mercury content in the fish with the naked eye or using the colour definition of a digital picture. Moreover, the sensory film can also be used to detect mercury in water (limit of detection of 1.60 ppb) and to extract mercury from water media.

A smart material for the in situ detection of mercury in fish.

We have developed a new fluorogenic polymer capable of detecting the presence of mercury contamination in fish samples. The modified polymer emits blue light when irradiated with UV light proportional to the quantity of mercury, as MeHg+ or Hg2+, present in fish. The quantitative relation between the concentration of mercury in fish and the increase of fluorescence in the polymer in contact with fish samples was confirmed, giving rise to quick and reliable results in the measurements of the presence of mercury in fish using a portable fluorogenic polymeric probe.

Surface Coating by Gold Nanoparticles on Functional Polymers: On-Demand Portable Catalysts for Suzuki Reactions

We have developed new functionalized polymers capable of being easily coated by gold nanoparticles, uniformly distributed on the surface of the polymers, by simply adding a gold(III) solution in water to the polymers. The polymer-supported gold nanoparticle material was used as an efficient portable and reusable catalyst for Suzuki reactions in mixed organic-aqueous solvents.

Easy and inexpensive method for the visual and electronic detection of oxidants in air by using vinylic films with embedded aniline

Conventional nonconductive vinylic films with dispersed aniline change their color and become conductive in the presence of specific oxidant gases, namely, chlorine and hydrogen peroxide. The color change arises from the polymerization of the aniline to yield the conjugated polymer polyaniline, which at the same time renders the flexible vinylic films conductive. We present a simple and straightforward method using both colorimetric and electrical responses to detect and quantify the presence of oxidants (Cl2 and H2O2) in the air. Using RGB analysis (red, green and blue parameters defining the colors in digital pictures on a computer display) based on different pictures taken with a smartphone of discs extracted from the films and by measuring the UV-vis spectral variation in the presence of different concentrations of Cl2 and H2O2, we obtained limits of detection and quantification between 15 and 200 ppbv for H2O2 and between 37 and 583 ppbv for Cl2. Additionally, the electrical response was measured using a fabricated device to visually detect the electrical conductivity activation of the sensor in the presence of oxidant atmospheres, detecting a rapid decrease in resistivity (three orders of magnitude) when the polymerization of aniline began, changing the film from non-conductive to conductive.

Molecular Dynamics of Functional Azide-Containing Acrylic Films

A report on the syntheses, thermal, mechanical and dielectric characterizations of two novel polymeric acrylic materials with azide groups in their pendant structures is presented. Having the same general structure, these polymers differ in length of oxyethylene units in the pendant chain [-CONH-CH2CH2-(O-CH2CH2)nN3], where n is 1 (poly(N-(2-(2-azidoethoxy)ethyl)methacrylamide), PAzMa1) or 2 (poly(N-2-(2-(2-azidoethoxy)ethoxy)ethyl)methacrylamide), PAzMa2), leading with changes in their dynamics. As the thermal decomposition of the azide group is observed above 100 °C, dielectric analysis was carried out in the temperature range of −120 °C to 100 °C. Dielectric spectra of both polymers exhibit in the glassy state two relaxations labelled in increasing order of temperature as γ- and β-processes, respectively. At high temperatures and low frequencies, the spectra are dominated by ohmic conductivity and interfacial polarization effects. Both, dipolar and conductive processes were characterized by using different models. Comparison of the dielectric activity obtained for PAzMa1 and PAzMa2 with those reported for crosslinked poly(2-ethoxyethylmethacrylate) (CEOEMA) was performed. The analysis of the length of oxyethylene pendant chain and the effect of the methacrylate or methacrylamide nature on the dynamic mobility was analysed.