Imidazole-based ionogel as room temperature benzene and formaldehyde sensor.

A room temperature benzene and formaldehyde gas sensor system with an ionogel as sensing material is presented. The sensing layer is fabricated employing poly(N-isopropylacrylamide) polymerized in the presence of 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid onto gold interdigitated electrodes. When the ionogel is exposed to increasing formaldehyde concentrations employing N2 as a carrier gas, a more stable response is observed in comparison to the bare ionic liquid, but no difference in sensitivity occurs. On the other hand, when air is used as carrier gas the sensitivity of the system towards formaldehyde is decreased by one order of magnitude. At room temperature, the proposed sensor exhibited in air higher sensitivities to benzene, at concentrations ranging between 4 and 20 ppm resulting, in a limit of detection of 47 ppb, which is below the standard permitted concentrations. The selectivity of the IL towards HCHO and C6H6 is demonstrated by the absence of response when another IL is employed. Humidity from the ambient air slightly affects the resistance of the system proving the protective role of the polymeric matrix. Furthermore, the gas sensor system showed fast response/recovery times considering the thickness of the material, suggesting that ionogel materials can be used as novel and highly efficient volatile organic compounds sensors operating at room temperature.Graphical abstract.

Engineered protein-based functional nanopatterned materials for bio-optical devices.

The development of new active biocompatible materials and devices is a current need for their implementation in multiple fields, including the fabrication of implantable devices for biomedical applications and sustainable devices for bio-optics and bio-optoelectronics. This paper describes a simple strategy to use designed proteins to develop protein-based functional materials. Using simple proteins as self-assembling building blocks as a platform for the fabrication of new optically active materials takes previous work one step further towards the design of materials with defined structures and functions using naturally occurring protein materials, such as silk. The proposed fabrication strategy generates thin and flexible nanopatterned protein films by letting the engineered protein elements self-assemble over the surface of an elastomeric stamp with nanoscale features. These nanopatterned protein films are easily transferred onto 3D objects (flat and curved) by moisture-induced adhesion. Additionally, flexible nanopatterned protein films are prepared by incorporating a thin polymeric layer as a back support. Finally, taking advantage of the tunability of the selected protein scaffold, the flexible protein-based surfaces are endowed with optical functions, achieving efficient lasing features. As such, this work enables the simple and cost-effective production of flexible and nanostructured, protein-based, optically active biomaterials and devices over large areas toward emerging applications.

Quantum dot/cyclodextrin supramolecular systems based on efficient molecular recognition and their use for sensing.

A supramolecular system based on ketoprofen functionalised CdSe/ZnS nanoparticles and pyrene-modified ß-CD was prepared and successfully used for molecular sensing of different analytes. In addition, a strategy for the individual recovery of all the components of the sensing assay is reported.

Triplet exciplexes as energy transfer photosensitisers.

Experimental evidence is provided for the occurrence of triplet-triplet energy transfer from benzoylthiophene-indole exciplexes to naphthalenes with a remarkable stereodifferentiation; chiral recognition is also observed in the decay of the generated naphthalene triplets.

Photoreaction between benzoylthiophenes and N-BOC-tryptophan methyl ester.

Drug-induced photoallergy requires as the first step formation of covalent drug-protein photoadducts. One of the key amino acids involved in this process is tryptophan (Trp). In this context, several diaryl ketones, including 2-benzoylthiophene (BT), [2-(5-benzoyl-5-thienyl)]-2-methylpropanoic methyl ester (TPA methyl ester) and 4-(2-thienylcarbonyl)phenyl]-2-methylpropanoic methyl ester (SUP methyl ester) have been irradiated in the presence of N-BOC-(L)-tryptophan methyl ester. Laser flash photolysis has allowed to detect three neutral radicals (ketyl, indolyl and skatolyl radicals) resulting from formal hydrogen-atom abstraction. This correlates well with the isolation of homodimers, as well as with cross-coupling products, in the preparative irradiation. The main cross-coupling products were in all cases lactones arising from the reaction of the Trp-derived skatolyl radicals with the corresponding ketyl radicals. These lactones were obtained as the (4R) stereoisomers with remarkable diasteroselectivity. No coupling products through the phenyl p-position of BT or TPA methyl ester were found. By contrast, ketone homodimers and cross-coupling products arising from reaction through the thienyl 5-position were obtained when using BT and SUP methyl ester; this is very interesting, because stable LAT-derived products are difficult to isolate.

Stereodifferentiation in the formation and decay of the encounter complex in bimolecular electron transfer with photoactivated acceptors.

Experimental evidence has been obtained for the involvement of encounter complexes between both enantiomers of a pi,pi* triplet excited ketone and a chiral phenol or indole. Determination of the pre-equilibrium constants (K(EC)) and the intrinsic decay rate constants (kd) indicates a significant stereodifferentiation in both steps of the quenching process.

Steady-state and time-resolved studies on the formation of skatolyl radicals photosensitized by 2-benzoylthiophene.

Quenching of the excited triplet state of 2-benzoylthiophene (BT) by 3-methylindole (CH3InH) leads to several neutral radicals resulting from formal hydrogen-atom abstraction. The transient absorption spectra of the BT ketyl radical (BTH) and the N-centered (CH3In) radical are directly detected by laser flash photolysis. From the differences between the spectra in the presence and the absence of oxygen, the C-centered skatolyl radical (CH2InH) is also observed. Accordingly, product studies demonstrate the formation of homodimers as well as cross-coupling products. They include BTH dimers (BTH-BTH, two stereoisomers), indolyl dimers (three different products) and products derived from reaction of skatolyl and BT ketyl radicals.