Tuning the Acceptor Unit of Push–Pull Porphyrazines for Dye-Sensitized Solar Cells

A family of four push–pull porphyrazines of A₃B type, where each unit A contains two peripheral propyl chains and the unit B is endowed with a carboxylic acid, were prepared. The carboxylic acid was attached to the β-position of the pyrrolic unit, either directly (Pz 10), or through cyanovinyl (Pz 11) and phenyl (Pz 7) groups. The fourth Pz (14) consisted in a pyrazinoporphyrazine wherein the dinitrogenated heterocycle provided intrinsic donor–acceptor character to the macrocycle and contained a carboxyphenyl substituent. The direct attachment of the carboxylic acid functions and their linkers to the porphyrazine core produces stronger perturbation on the electronic properties of the macrocycle, with respect to their connection through fused benzene or pyrazine rings in TT112 and 14, respectively. The HOMO and LUMO energies of the Pzs, which were estimated with DFT calculations, show little variation within the series, except upon introduction of the cyanovinyl spacer, which produces a decrease in both frontier orbital energetic levels. This effective interaction of cyanovinyl substitution with the macrocycle is also evidenced in UV/Vis spectroscopy, where a large splitting of the Q-band indicates strong desymmetrization of the Pz. The performance of the four Pzs as photosensitizers in DSSCs were also investigated.     

Defect assisted subwavelength resolution in III-V semiconductor photonic crystal flat lenses with n = −1

We propose a III-V semiconductor photonic crystal slab designed to operate as a n = −1 superlens at λ₀ = 1.55 μm. The structure consists of air holes arranged in a two-dimensional triangular lattice, of period a, nanopatterned in an InP/InGaAsP/InP slab. Exploiting the second pass-band regime (a/λ₀ ∼ 0.31), subwavelength resolutions as low as 0.38λ₀ for planar lenses have been obtained by the insertion of hexagonal nanocavities within the crystal.     

Polyamine concentration, transglutaminase activity and changes in protein synthesis during cryopreservation of shoot tips of apple variety Annurca

Changes in metabolism and protein expression were analysed during cryopreservation of the ancient apple variety Annurca. Our experiments concerned transglutaminase activity, polyamine levels and protein expression associated with shoot tip dehydration. Cryopreserved shoot tips displayed 72% regrowth after treatment in liquid medium with 0.75 M sucrose for 1 day followed by dehydration to 19% moisture content (fresh weight basis). After dehydration, the concentration of polyamines putrescine and spermidine decreased compared with untreated controls, while spermine concentration remained unaffected. Transglutaminase activity was slightly reduced in treated samples, while post-thaw regrowth enzyme activity approached control values. We also detected significant changes in protein expression profiles and identified six proteins related with stress response or involved in the slowing down of the cell cycle. The relationship between biochemical parameters, protein synthesis and cryotolerance is discussed.     

Effect of high pressure treatment on the characteristics of a model emulsion

The aim of this study was to investigate the use of HP (high pressure) technology as a possible alternative method for decontamination of non-food medium. HP (500?MPa) did not modify significantly the physicochemical characteristics of a model non-food emulsion. A 10?min HP treatment inactivated totally Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans even if all the five microorganisms were inoculated together, regardless of the initial load. No recovery was observed until six months of storage at 25°C.     

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

In the present study, we investigated the oxidation of 2500 ppm of di-n-butyl ether under fuel-rich conditions (φ = 2) at low temperatures (460–780 K), a residence time of 1 s, and 10 atm. The experiments were carried out in a fused silica jet-stirred reactor. Oxidation products were identified and quantified in gas samples by gas chromatography and Fourier transform infrared spectrometry. Samples were also trapped through bubbling in cool acetonitrile for high-pressure liquid chromatography (HPLC) analyses. 2,4-dinitro-phenylhydrazine was used to derivatize carbonyl products and distinguish them from other isomers. HPLC coupled to high resolution mass spectrometry (Orbitrap Q-Exactive^®) allowed for the detection of oxygenated species never observed before, i.e., low-temperature oxidation products (C₈H₁₂O_4,6, C₈H₁₆O_3,5,7, and C₈H₁₈O₂,₅) and species that are more specific products of atmospheric oxidation, i.e., C₁₆H₃₄O₄, C₁₁H₂₄O₃, C₁₁H₂₂O₃, and C₁₀H₂₂O₃. Flow injection analyses indicated the presence of high molecular weight oxygenated products (m/z > 550). These results highlight the strong similitude in terms of classes of oxidation products of combustion and atmospheric oxidation, and through autoxidation processes. A kinetic modeling of the present experiments indicated some discrepancies with the present data.     

Environmental gamma and radon dosimetry in Venezuela

Environmental gamma exposure and radon concentration levels measured in Venezuelan regions are presented. A new generation image analyser was used for particle track counting in CR-39 detectors. Mineral water wells from where water is supplied for massive consumption have an alpha activity around 0.450 Bq L⁻¹ and few of them have concentrations above 50 Bq L⁻¹. Coastal potable water activity is on the average around 5.3 ± 12% Bq L⁻¹. Indoor radon national average is 36 ± 5% Bq m⁻³; in two of the 36 monitored sites, the measured average is above 400 ± 5% Bq m⁻³. In air gamma dose values are between 100 and 144 nGy h⁻¹. In soil, ¹³⁷Cs concentration is around 0.5 and 10 Bq kg⁻¹ at the depth of down to 20 cm. Building materials were included in this study. ⁷Be and ¹³⁷Cs were measured in low concentration in tropical plants on Tepuy-s (sacred mountains in the Amazonas State). Geological active faults were identified by radon concentration measurements using LR-115.     

Supramolecular click chemistry for the self-assembly of a stable Zn(II)-porphyrin-C60 conjugate

Owing to the complementarity between a bis-Zn(II)-porphyrin receptor and a fullerene ligand bearing two pyridine substituents, the substrate can be clicked onto the ditopic receptor, thus leading to a stable non-covalent macrocyclic 1 ratio 1 complex.