Segmented-Block Poly(ether amide)s Containing Flexible Polydisperse Polyethyleneoxide Sequences and Rigid Aromatic Amide Moieties.

We describe the synthesis and characterization of three novel aromatic diamines containing oxyethylene sequences of different lengths. These diamines were polymerized using the low-temperature solution polycondensation method with isophthaloyl chloride (IPC), terepthaloyl chloride (TPC), [1,1'-biphenyl]-4,4'-dicarbonyl dichloride (BDC), and 4,4'-oxybis(benzoyl chloride) (OBE), obtaining twelve poly(ether amide)s with short segments of polydisperse polyethyleneoxide (PEO) sequences in the polymer backbone. These polymers show reasonably high molecular mass materials (Mw > 12,000), and the relationship between their structure and properties has been carefully studied. Compared with conventional polyamides containing monodisperse PEO sequences, the polydispersity of the PEO segments within the structural units exerts a significant influence on the crystallinity, flexibility, solubility, and the thermal properties of the polymers. For instance, the all-para oriented polyamides (TPCP-A), with an average number of 8.2 ethylenoxide units per structural unit can be transformed conventionally (Tm = 259 °C) in comparison with thermally untransformable polymer with 2 ethylenoxide units (Tm = 425 °C).

A simple one-pot determination of both total phenolic content and antioxidant activity of honey by polymer chemosensors.

We have developed a new method for the rapid (2 h) and inexpensive (materials cost < 0.02 €/sample) "2-in-1" determination of the total phenolic content (TPC) and the antioxidant activity (AOX) in honey samples. The method is based on hydrophilic colorimetric films with diazonium groups, which react with phenols rendering highly colored azo groups. The TPC of the sample is correlated to its trolox equivalent antioxidant capacity (TEAC). The intensity of the color allows us to determine both TPC and TEAC of the sample by the analysis of a picture taken with a smartphone that is analysed by the use of the color-definition-parameters (RGB). The controlled light conditions and the systematic use of the same camera avoid the periodical calibration of the system improving the efficiency of the method. Thus, it is a simple method carried out by non-specialized personnel and it involves much lower money and time investment compared to traditional methods.

Heteroaromatic Polyamides with Improved Thermal and Mechanical Properties.

We prepared high-performance aromatic copolyamides, containing bithiazole and thiazolo-thiazole groups in their main chain, from aromatic diamines and isophthaloyl chloride, to further improve the prominent thermal behavior and exceptional mechanical properties of commercial aramid fibers. The introduction of these groups leads to aramids with improved strength and moduli compared to commercial meta-oriented aromatic polyamides, together with an increase of their thermal performance. Moreover, their solubility, water uptake, and optical properties were evaluated in this work.

Polymer films containing chemically anchored diazonium salts with long-term stability as colorimetric sensors.

We have prepared polymeric films as easy-to-handle sensory materials for the colorimetric detection and quantification of phenol derivatives (phenols) in water. Phenols in water resources result from their presence in pesticides and fungicides, among other goods, and are harmful ecotoxins. Colorless polymeric films with pendant diazonium groups attached to the acrylic polymer structure were designed and prepared for use as sensory matrices to detect phenol-derived species in water. Upon dipping the sensory films into aqueous media, the material swells, and if phenols are present, they react with the diazonium groups of the polymer to render a highly colored azo group, giving rise to the recognition phenomenon. The color development can be visually followed for a qualitative determination of phenols. Additionally, quantitative analysis can be performed by two different techniques: a) by using a UV-vis spectrophotometer (limit of detection of 0.12 ppm for 2-phenylphenol) and/or b) by using a smartphone with subsequent RGB analysis (limit of detection of 30 ppb for 2-phenylphenol).

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.

Sensory Polymeric Foams as a Tool for Improving Sensing Performance of Sensory Polymers.

Microcellular sensory polymers prepared from solid sensory polymeric films were tested in an aqueous Hg(II) detection process to analyze their sensory behavior. First, solid acrylic-based polymeric films of 100 µm thickness were obtained via radical copolymerization process. Secondly, dithizone sensoring motifs were anchored in a simple five-step route, obtaining handleable colorimetric sensory films. To create the microporous structure, films were foamed in a ScCO2 batch process, carried out at 350 bar and 60 °C, resulting in homogeneous morphologies with cell sizes around 5 µm. The comparative behavior of the solid and foamed sensory films was tested in the detection of mercury in pure water media at 2.2 pH, resulting in a reduction of the response time (RT) around 25% and limits of detection and quantification (LOD and LOQ) four times lower when using foamed films, due to the increase of the specific surface associated to the microcellular structure.

Polymeric chemosensor for the detection and quantification of chloride in human sweat. Application to the diagnosis of cystic fibrosis.

We have developed a new extremely hydrophilic polymeric film suitable for the detection and quantification of chloride in human sweat directly on the skin. The film, or membrane, has chemically anchored 6-methoxyquinoline groups as chloride responsive fluorescent motifs. We have prepared the sensory material from a standard vinyl copolymer, by a convenient and easy solid-phase reaction. The sensory material has a water swelling percentage of 700%, facilitating an immediate detection of chloride, is reusable for at least 6 cycles and can be handled without care by unskilled persons. The initially high fluorescence of the material decreases in the presence of chloride, allowing the quantification of chloride concentration by using the colour definition of a digital picture or a fluorimeter. The suitability of the material to perform quantitative chloride analysis of human sweat by putting it in contact with the skin offers promise for its application in the sweat test used for the diagnosis of cystic fibrosis (CF).

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 ß-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.

Solvent-Free Off-On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials.

A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses.

Functional Aromatic Polyamides.

We describe herein the state of the art following the last 8 years of research into aromatic polyamides, wholly aromatic polyamides or aramids. These polymers belong to the family of high performance materials because of their exceptional thermal and mechanical behavior. Commercially, they have been transformed into fibers mainly for production of advanced composites, paper, and cut and fire protective garments. Huge research efforts have been carried out to take advantage of the mentioned characteristics in advanced fields related to transport applications, optically active materials, electroactive materials, smart materials, or materials with even better mechanical and thermal behavior.

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.

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.

Acrylic Polymers with Pendant Phenylboronic Acid Moieties as "Turn-Off" and "Turn-On" Fluorescence Solid Sensors for Detection of Dopamine, Glucose, and Fructose in Water.

We report herein a fluorescence polymer membrane as a film-shaped solid sensory kit for the detection and quantification in water of saccharides, namely, fructose and glucose, and dopamine. The sensory motifs are phenylboronic acids, which are chemically incorporated in the polymer network in the radically initiated bulk polymerization process. The sensory membrane is fluorescent. The interaction of the sensory motifs with dopamine "turn-off" the fluorescence due to a dynamic quenching, while stable complexes are formed with saccharides giving rise to a fluorescence "turn-on". The variation of the fluorescence intensity and the wavelength of the maxima permitted the titration of the species with a detection limit of 3-4 × 10-4 M. The hydrophilic membrane allowed for the detection in water in spite of the lack of solubility in this medium of the sensory phenylboronic acid derivative monomer.

Water-soluble polymers, solid polymer membranes, and coated fibres as smart sensory materials for the naked eye detection and quantification of TNT in aqueous media.

This study developed sensory polymeric materials for the colorimetric sensing of TNT in aqueous media. Solid films and coated fabrics permitted the detection of TNT, through colour change, and its quantification, by taking a picture of the materials and processing their RGB parameters to define the evolved colour.

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).

Putting to work organic sensing 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. A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with a fluorene derivative.