José V. Ros-Lis

A selective chromogenic reagent for cyanide determination

A chromogenic reagent for cyanide determination in water based on the reaction of this anion with a squaraine derivative functionalized with ether chains has been developed.

Finely Tuned Temperature-Controlled Cargo Release Using Paraffin-Capped Mesoporous Silica Nanoparticles†

Financial support from the Spanish Government (projects MAT2009-14564-C04-01 and SAF2010-15512) and the Generalitat Valenciana (projects PROMETEO/2009/016 and PROMETEO/2010/005) is gratefully acknowledged. L. M. thanks the Generalitat Valenciana for a VALi + d postdoctoral contract. We thank UPV electron microscopy and CIPF confocal microscopy services for technical support.

A Mesoporous 3D Hybrid Material with Dual Functionality for Hg2+ Detection and Adsorption

Dual-function hybrid material U1 was designed for simultaneous chromofluorogenic detection and removal of Hg(2+) in an aqueous environment. Mesoporous material UVM-7 (MCM41 type) with homogeneously distributed pores of about 2-3 nm in size, a large specific surface area exceeding 1000 m(2) g(-1), and nanoscale particles was used as an inorganic support. The mesoporous solid is decorated with thiol groups that were treated with squaraine dye III to give a 2,4-bis(4-dialkylaminophenyl)-3-hydroxy-4-alkylsulfanylcyclobut-2-enone (APC) derivative that is covalently anchored to the inorganic silica matrix. The solid was characterised by various techniques including X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and nitrogen adsorption. This hybrid solid is the chemodosimeter for Hg(2+) detection. Hg(2+) reacts with the APC fragment in U1 with release of the squaraine dye into the solution, which turns deep blue and fluoresces strongly. Naked-eye Hg(2+) detection is thus accomplished in an easy-to-use procedure. In contrast, U1 remains silent in the presence of other thiophilic transition metal ions, alkali and alkaline earth metal ions, or anions ubiquitously present in water such as chloride, carbonate, sulfate, and phosphate. Material U1 acts not only as chemodosimeter that signals the presence of Hg(2+) down to parts-per-billion concentrations, but at the same time is also an excellent adsorbent for the removal of mercury cations from aqueous solutions. The amount of adsorbed mercury ranges from 0.7 to 1.7 mmol g(-1), depending on the degree of functionalisation. In addition, hybrid material U1 can be regenerated for both sensing and removal purposes. As far as we know, U1 is the first example of a promising new class of polyfunctional hybrid supports that can be used as both remediation and alarm systems by selective signalling and removal of target species of environmental importance. Model compounds based on silica gel (G1), fumed silica (F1), and micrometre-sized MCM-41 scaffolds (M1) were also prepared and studied for comparative purposes.

Synthesis and study of the use of heterocyclic thiosemicarbazones as signaling scaffolding for the recognition of anions.

A family of heterocyclic thiosemicarbazone dyes (1-9) linked to different furan, thiazole, (bi)thiophene, and arylthiophene pi-conjugated bridges were synthesized in good yields, and their response toward anions was studied. Acetonitrile solutions of 1-9 show bands in the 326-407 region that are modulated by the electron-donor or -acceptor strength of the heterocyclic systems appended to the phenylthiosemicarbazone moiety. Anions of different shape such as fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate, cyanide, and thiocyanate were employed for the recognition studies. From these anions, only fluoride, cyanide, acetate, and dihydrogen phosphate displayed sensing features. Two different effects were observed, (i) a low bathochromic shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the growth of a new red-shifted band with a concomitant change of the solution from yellow or pale yellow to orange-red due to deprotonation. The extent of each process is a balance between the acidity tendency of the thioureido-NH donors modulated by the donor or acceptor groups in the structure of the receptors and the basicity of the anions. Fluorescence studies were also in agreement with the different effects observed on the UV/vis titrations. Stability constants for the two processes (complex formation + deprotonation) for selected receptors and the anions fluoride and acetate were determined spectrophotometrically using the program HYPERQUAD. Semiempirical calculations to evaluate the hydrogen-donating ability of the dyes and (1)H NMR titrations experiments with fluoride were carried out. A prospective electrochemical characterization of compound 3 in the presence of anions was also performed.

Subphthalocyanines as fluoro-chromogenic probes for anions and their application to the highly selective and sensitive cyanide detection.

The use of a subphthalocyanine derivative as a selective chromo-fluorogenic reporter for the anion cyanide in mixed aqueous solutions is reported.

Synthesis and evaluation of thiosemicarbazones functionalized with furyl moieties as new chemosensors for anion recognition

A family of heterocyclic thiosemicarbazone dyes (3a-f and 4) containing furyl groups was synthesized in good yields, characterized and their response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of 3a-f and 4 showed absorption bands in the 335-396 nm range which are modulated by the electron donor or acceptor strength of the heterocyclic systems appended to the thiosemicarbazone moiety. Fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulphate, nitrate, acetate and cyanide anions were used in recognition studies. From these anions, only sensing features were seen for fluoride, cyanide, acetate and dihydrogen phosphate. Two clearly different chromo-fluorogenic behaviours were observed: (i) a small shift of the absorption band due to the coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation. For the latter effect, a change in the colour of solution from pale yellow to purple was observed. Fluorescence studies were also in agreement with the different effects observed in the UV/Vis titrations. In this case, hydrogen bonding interactions were visible through the enhancement of the emission band, whereas deprotonation induced the appearance of a new red-shifted emission. Logarithms of stability constants for the two processes (complex formation + deprotonation) for receptors in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec V1.1.18 program. Semi-empirical calculations to evaluate the hydrogen-donating ability of the receptors and a prospective electrochemical characterization of compound in the presence of fluoride were also performed.

Evaluation of sea bream (Sparus aurata) shelf life using an optoelectronic nose.

A new optoelectronic nose for the shelf-life assessment of fresh sea bream in cold storage has been developed. The chromogenic array used eight sensing materials (based on aluminium oxide and silica gel) containing pH indicators, Lewis acids and an oxidation-reduction indicator. The colour changes of the sensor array were characteristic of sea bream spoilage. Colour modulations were measured on day 0 and for the samples held in cold storage for 2, 4, 7, 9 and 11 days. Determination of moisture content, pH, total volatile basic nitrogen (TVB-N), drip loss, ATP-related compounds and K(1)-value and microbial (mesophilic bacteria and Enterobacteriaceae) analyses were carried out on the same days. The changes in the chromogenic arrays data were processed by statistical analysis (PCA). Moreover, PLS statistical studies allowed the creation of models to correlate the chromogenic data with concentrations of mesophilic and Enterobacteriaceae. The results suggest the feasibility of this system to help develop optoelectronic noses for fish freshness monitoring.

Chromogenic silica nanoparticles for the colorimetric sensing of long-chain carboxylates

Silica nanoparticles functionalized with chromogenic spirobenzopyran and thiourea subunits show selective colour changes in the presence of certain long-chain carboxylates.

Squaraine “ships” in the Y zeolite “bottle”: a chromogenic sensing material for the detection of volatile amines and thiols

The inclusion of squaraine (SQ) dye I into the supercages of zeolite Y (structure code FAU) with a SiO2/Al2O3 ratio of 30 (Z30) through a two-step ship-in-the-bottle approach is reported, resulting in the squaraine-containing hybrid material Z30-SQ. Attempts to use the same synthetic procedure on sodium and ammonium Y zeolites were unsuccessful, stressing the importance of the presence of Bronsted acid centres in the Z30 zeolite. The reflectance spectra of Z30-SQ show a maximum in the typical squaraine monomer region at 618 nm and a shoulder at 570 nm. Spectral analyses revealed that the major species are SQ dimers and (tightly adsorbed) SQ monomers and SQ aggregates are only formed to a minor degree. The emission spectrum of Z30-SQ shows a single band at 669 nm. The sensory performance of this material was tested in the presence of volatile propylamine and propylthiol and other volatile organic compounds (acetone, ethanol, dichloromethane, hexane, acetonitrile, ethyl acetate, ethyl ether and acetic acid). The blue Z30-SQ material reacts with the thiol and amine derivatives, resulting in the bleaching of the solid and disappearance of the absorption band in the visible region, but does not undergo spectroscopic changes in the presence of other volatile organic compounds (VOCs). Whereas the reaction with propylamine is irreversible, a partial reversibility was found in the presence of the thiol. Theoretical investigations of the reactivity of I with several VOC molecules at the semi-empirical level reproduced well the experimentally observed reactivity.

Development of a colorimetric sensor array for squid spoilage assessment

The aim of this work was to develop and evaluate a rapid, easy-to-use optoelectronic system for the shelf-life assessment of squid in cold storage. For this purpose, an optoelectronic nose was designed, which consisted of an array containing six sensing materials prepared by combining different dyes and two inorganic supports (aluminium oxide and silica gel). Samples were packaged with the colorimetric array and kept in cold storage for 12 days. Squid spoilage was monitored simultaneously by the colorimetric array and by the physico-chemical and microbial analyses during storage. Samples exceeded the acceptability limits for microbial counts on the third day. PCA analysis carried out with CIELab showed that the colorimetric array was able to discriminate between fresh squid fit for consumption and spoiled squid. The statistical models obtained by PLS, with the optoelectronic nose, successfully predicted CO2 and O2 content in the headspace as well as microbial growth.