Hybrid Photonic Antennae Based on Mesoporous Silica Frameworks

This contribution describes design, preparation and physico-chemical characterization of a new photo-stable hybrid antenna based on mesoporous SBA-15 silica. Concepts of host-guest chemistry are applied in such a way that one or more photoactive guest molecules are incorporated into the silica channels and on the outer surface, acting as energy harvesting and transferring units. The presented composite system be-haves as efficient Förster resonance energy transfer (FRET) pair and shows high photoluminescence and stability towards photodegradation, representing an important step forward in the search for new efficient materials with opto-electronic applications. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3549

Hybrid Photonic Antennae Based on Mesoporous Silica Frameworks

This contribution describes design, preparation and physico-chemical characterization of a new photo-stable hybrid antenna based on mesoporous SBA-15 silica. Concepts of host-guest chemistry are applied in such a way that one or more photoactive guest molecules are incorporated into the silica channels and on the outer surface, acting as energy harvesting and transferring units. The presented composite system be-haves as efficient Förster resonance energy transfer (FRET) pair and shows high photoluminescence and stability towards photodegradation, representing an important step forward in the search for new efficient materials with opto-electronic applications. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3549

Water diffusion modulates the cest effect on Tb(III)-mesoporous silica probes

The anchoring of lanthanide(III) chelates on the surface of mesoporous silica nanoparticles (MSNs) allowed their investigation as magnetic resonance imaging (MRI) and chemical exchange saturation transfer (CEST) contrast agents. Since their efficiency is strongly related to the interaction occurring between Ln-chelates and \u201cbulk\u201d water, an estimation of the water diffusion inside MSNs channels is very relevant. Herein, a method based on the exploitation of the CEST properties of TbDO3A-MSNs was applied to evaluate the effect of water diffusion inside MSN channels. Two MSNs, namely MCM-41 and SBA-15, with different pores size distributions were functionalized with TbDO3A-like chelates and polyethylene glycol (PEG) molecules and characterized by HR-TEM microscopy, IR spectroscopy, N2 physisorption, and thermogravimetric analysis (TGA). The different distribution of Tb-complexes in the two systems, mainly on the external surface in case of MCM-41 or inside the internal pores for SBA-15, resulted in variable CEST efficiency. Since water molecules diffuse slowly inside silica channels, the CEST effect of the LnDO3A-SBA-15 system was found to be one order of magnitude lower than in the case of TbDO3A-MCM-41. The latter system reaches an excellent sensitivity of ca. 55 \ub1 5 \ub5M, which is useful for future theranostic or imaging applications

Surprising Complexity of the [Gd(AAZTA)(H2O)2]- Chelate Revealed by NMR in the Frequency and Time Domains

Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]- (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]- complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal-water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]-, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series

Bifunctional Paramagnetic and Luminescent Clays Obtained by Incorporation of Gd3+and Eu3+Ions in the Saponite Framework

A novel bifunctional saponite clay incorporating gadolinium (Gd3+) and europium (Eu3+) in the inorganic framework was prepared by one-pot hydrothermal synthesis. The material exhibited interesting luminescent and paramagnetic features derived from the co-presence of the lanthanide ions in equivalent structural positions. Relaxometry and photoluminescence spectroscopy shed light on the chemical environment surrounding the metal sites, the emission properties of Eu3+, and the dynamics of interactions between Gd3+ and the inner-sphere water placed in the saponite gallery. The optical and paramagnetic properties of this solid make it an attractive nanoplatform for bimodal diagnostic applications

Can Eucalyptus plantations influence the distribution range of mesocarnivores?

Context The expansion of exotic plantations can impose conservation challenges on wildlife, and the Iberian Peninsula has one of the widest planted areas of exotic Eucalyptus sp. in Europe. Since mesocarnivores are pivotal elements of ecosystems’ functioning and Eucalyptus have been modifying the Portuguese landscape context in the last half century, it is crucial to understand how these systems may affect carnivores’ range. Objectives We aim to identify the drivers of five mesocarnivores’ distribution in Portugal (e.g., land-cover, ecogeographic predictors, mammal prey availability) and understand the influence of Eucalyptus plantations in their distribution range. Methods Using generalized linear models, we modelled the distribution range of mesocarnivores. The initial dataset was randomly split for model training and validation, and the multicollinearity between the predictors was tested. Then, we examined the potential relationship between the Eucalyptus plantations area and the predicted probability presence of each species. Results We detected species-specific patterns explained by different drivers, including climatic, land cover and mammal prey related ones. Furthermore, in areas of Eucalyptus plantations, the probability of occurrence of most Portuguese mesocarnivores is lower: red fox,stone marten,European badger, and Egyptian mongoose. Conclusions Managers must take action to adapt their management to promote native forest patches within plantation, and allow the development of some understory within stands, to improve this plantation’s permeability to mesocarnivores. This will increase the spatial heterogeneity and enhance resource availability, reducing the constraints that plantations might have on the range of mesocarnivores in Portugal.info:eu-repo/semantics/publishedVersio

Resonant Inelastic X-ray Scattering of Methyl Chloride at the Chlorine K Edge

We present a combined experimental and theoretical study of isolated CH3Cl molecules using resonant inelastic x-ray scattering (RIXS). The high-resolution spectra allow extraction of information about nuclear dynamics in the core-excited molecule. Polarization-resolved RIXS spectra exhibit linear dichroism in the spin-orbit intensities, a result interpreted as due to chemical environment and singlet-triplet exchange in the molecular core levels. From analysis of the polarization-resolved data, Cl 2px, y and 2pz electronic populations can be determined

tungsten oxide a catalyst worth studying for the abatement and decontamination of chemical warfare agents

AbstractTungsten(VI) oxide, WO3, was studied and used as a heterogeneous catalyst for the liquid-phase oxidative abatement and solid-phase decontamination of simulants of chemical warfare agents, CWAs. The catalytic performance of WO3 was compared to the one of a soluble W-containing model catalyst, W(IV)-heptaisobutyl polyhedral oligomeric silsesquioxane, W-POSS. In liquid-phase abatement tests, WO3 promoted a complete degradation of the toxic agent simulant within 24 h, in the presence of aqueous hydrogen peroxide, at room temperature. In solid-phase decontamination tests, when WO3 was mixed with sodium perborate as a solid oxidant, it was also tested in the decontamination of a cotton textile support from organosulfide and organophosphonate agents (simulants of blistering and nerve CWAs, respectively), showing promising performances comparable to, or sometimes better than, a nanostructured TiO2 catalyst, taken as a reference material. The environmental impact of the WO3 catalyst was assessed on biolumi..

Cationic double K-hole pre-edge states of CS2 and SF6

Recent advances in X-ray instrumentation have made it possible to measure the spectra of an essentially unexplored class of electronic states associated with double inner-shell vacancies. Using the technique of single electron spectroscopy, spectra of states in CS2 and SF6 with a double hole in the K-shell and one electron exited to a normally unoccupied orbital have been obtained. The spectra are interpreted with the aid of a high-level theoretical model giving excellent agreement with the experiment. The results shed new light on the important distinction between direct and conjugate shake-up in a molecular context. In particular, systematic similarities and differences between pre-edge states near single core holes investigated in X-ray absorption spectra and the corresponding states near double core holes studied here are brought out

Aneurysm permeability following coil embolization: packing density and coil distribution

BACKGROUND: Rates of durable aneurysm occlusion following coil embolization vary widely, and a better understanding of coil mass mechanics is desired. The goal of this study is to evaluate the impact of packing density and coil uniformity on aneurysm permeability. METHODS: Aneurysm models were coiled using either Guglielmi detachable coils or Target coils. The permeability was assessed by taking the ratio of microspheres passing through the coil mass to those in the working fluid. Aneurysms containing coil masses were sectioned for image analysis to determine surface area fraction and coil uniformity. RESULTS: All aneurysms were coiled to a packing density of at least 27%. Packing density, surface area fraction of the dome and neck, and uniformity of the dome were significantly correlated (p \u3c 0.05). Hence, multivariate principal components-based partial least squares regression models were used to predict permeability. Similar loading vectors were obtained for packing and uniformity measures. Coil mass permeability was modeled better with the inclusion of packing and uniformity measures of the dome (r(2)=0.73) than with packing density alone (r(2)=0.45). The analysis indicates the importance of including a uniformity measure for coil distribution in the dome along with packing measures. CONCLUSIONS: A densely packed aneurysm with a high degree of coil mass uniformity will reduce permeability