Studies on Rare-Earth/Iron and Actinide/Iron Multilayers

Hyperfine Interactions - Multilayers of Ce/Fe and U/Fe were fabricated by sputtering and studied by X-ray diffraction and reflectivity, Mössbauer spectroscopy and polarised neutron...     

Y-shaped two-photon absorbing molecules with an imidazole-thiazole core

Two new classes of two-photon absorbing Y-shaped molecules have been developed to possess an imidazole-thiazole core and a stilbene-type conjugation pathway with either nitro or sulfonyl as terminal electron-accepting group.     

Experimental observation of light-induced solitary waves of analyte bands in capillary electrophoresis.

The phenomenon of electrophoresis in free solution has been studied theoretically down to the molecular level for decades. In addition, intermolecular photo-induced proton transfer reactions, which occur in a wide class of molecules (phenols and aminoarenes) as well as proteins (green fluorescent protein), were also studied extensively. However, the study of the effect of light-induced electrophoretic mobility changes of the analytes in electrophoresis was begun only recently. In the present work, capillary zone electrophoresis was chosen as the environment to measure the magnitude of these electrophoretic mobility shifts induced by light. Background electrolytes (running electrolytes) with high refractive indices were developed, allowing the capillary to work like an optical fiber. The experimental conditions for obtaining stable coupling and guided laser light along the liquid core are discussed. Experimental evidence of band compression is observed, leading to a solitary wave behavior of the analyte band (2-naphthol). These solitary waves result from competition between thermal diffusion (dispersion mechanism) and a nonlinear (band compression) effect due to the combined electrophoresis phenomenon and absorption of guided light by the molecules of the band (which are subjected to a "reversible intermolecular proton transfer reaction" as one of their decay routes). The possibilities of applying this effect to different methods and techniques are also discussed.     

Phytochemical Investigation and Biological Activities of Lantana rhodesiensis

Lantana rhodesiensis Moldenke is a plant widely used to treat diseases, such as rheumatism, diabetes, and malaria in traditional medicine. To better understand the traditional uses of this plant, a phytochemical study was undertaken, revealing a higher proportion of polyphenols, including flavonoids in L. rhodesiensis leaf extract and moderate proportion in stem and root extracts. The antioxidant activity of the extracts was also determined using three different assays: the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging activity, the FRAP method (Ferric-reducing antioxidant power) and the β-carotene bleaching test. The anti-malarial activity of each extract was also evaluated using asexual erythrocyte stages of Plasmodium falciparum, chloroquine-sensitive strain 3D7. The results showed that the leaf extract exhibited higher antioxidant and anti-malarial activities in comparison with the stem and root extracts, probably due to the presence of higher quantities of polyphenols including flavonoids in the leaves. A positive linear correlation was established between the phenolic compound content (total polyphenols including flavonoids and tannins; and total flavonoids) and the antioxidant activity of all extracts. Furthermore, four flavones were isolated from leaf dichloromethane and ethyl acetate fractions: a new flavone named rhodescine (5,6,3′,5′-tetrahydroxy-7,4′-dimethoxyflavone) (1), 5-hydroxy-6,7,3′,4′,5′-pentamethoxyflavone (2), 5-hydroxy-6,7,3′,4′-tetramethoxyflavone (3), and 5,6,3′-trihydroxy-7,4′-dimethoxyflavone (4). Their structures were elucidated by ¹H, ¹³CNMR, COSY, HSQC, HMBC, and MS-EI spectral methods. Aside from compound 2, all other molecules were described for the first time in this plant species.     

Theoretical and Experimental Analysis of Protoporphyrin IX Photodegradation Using Multi-Wavelength Light Sources

Photodynamic procedures have been used in many applications, ranging from cancer treatment to microorganism inactivation. Photodynamic reactions start with the activation of a photosensitizing molecule with light, leading to the production of cytotoxic molecules that promote cell death. However, establishing the correct light and photosensitizer dosimetry for a broadband light source remains challenging. In this study, we proposed a theoretical mathematical model for the photodegradation of protoporphyrin IX (PpIX), when irradiated by multi-wavelength light sources. The theoretical model predicts the experimental photobleaching (temporal change in PpIX concentration) of PpIX for different light sources. We showed that photobleaching occurs independently of the light source wavelengths but instead depends only on the number of absorbed photons. The model presented here can be used as an important mathematical approach to better understand current photodynamic therapy protocols and help achieve optimization of the doses delivered.     

Demonstration of high efficiency third harmonic conversion of high power Nd-glass laser radiation

We report on efficient conversion from 1.054 μm to 0.35 μm by third harmonic generation in two Type II KDP crystals. Energy conversion efficiencies of up to 80% have been measured under conditions applicable to large glass laser systems. A new tripling scheme used for these experiments requires a minimum of optical components and is insensitive to exact crystal alignment and laser beam divergence. A convenient scaling law allows tripling optimization for many different laser conditions.     

Two-photon induced anisotropy in PMMA film doped with Disperse Red 13

In this paper we present optical anisotropy induced by 150-fs laser pulses operating at 775 nm in poly(methyl methacrylate) (PMMA) films doped with Disperse Red 13 (DR13). Two-photon absorption of DR13 induces reversible birefringence in the sample, a feature associated with the molecular orientation caused by isomerization of the azochromophores. No irreversible anisotropy, associated with photobleaching of the chromophore was observed. The slope of 2 obtained for the induced birefringence as a function of the excitation irradiance corroborates the two-photon nature of the process.     

The role of cloud tracking and passive microwave techniques in the short-term prediction of flood hazard on a regional scale

The role of remote sensing in enhancing the monitoring capabilities and the short-term prediction of the risk of flooding on a regional scale is addressed in this paper by means of the application of storm identification and cloud tracking techniques to a few case studies where cluster analysis based on infrared satellite imagery is used as the primary source of information. Polar satellite sensors, which provide passive microwave images, were also proposed in the literature for application in flood forecasting operational problems, though the accuracy of passive microwave techniques is only acceptable when rainfall estimates are integrated over quite large spatial and temporal scales. Climatological studies are well suited to make use of such data while the measure of instantaneous rainfall is still lacking of an adequate validation. A theoretical and numerical framework for the assessment of the reliability of passive microwave estimates of instantaneous rainfall within the typical resolution scales of polar satellite sensors is provided in the paper.

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Sommario Il ruolo delle tecniche di monitoraggio da sensori remoti nell'incrementare le potenzialità di previsione a breve termine del rischio di inondazione a scala regionale è analizzato nel presente lavoro attraverso l'applicazione di tecniche di identificazione ed inseguimento dei corpi nuvolosi ad alcuni casi di studio in cui le immagini satellitarie nella banda dell'infrarosso termico sono utilizzate come principale strumento di monitoraggio. In letteratura viene inoltre proposta l'utilizzazione, in applicazioni operative di previsione delle inondazioni, di sensori alle microonde passive montati su satelliti ad orbita polare: l'accuratezza di tali tecniche è tuttavia accettabile solo quando le stime di precipitazione vengono integrate su ampie scale spaziali e temporali. Mentre l'uso di tali tecniche per studi climatologici è di notevole utilità, la misura della precipitazione alle piccole scale spazio-temporali necessita ancora di un adeguato processo di validazione. Nel presente lavoro viene proposto un approccio teorico per la stima dell'affidabilità di tali stime di precipitazione alle scale tipiche della risoluzione spaziale del sensore.

     

Electrochemical, EPR and computational results on [Fe2Cp2(CO)2]-based complexes with a bridging hydrocarbyl ligand

The dimetallacyclopentenone complexes [Fe₂Cp₂(CO)(μ−CO){μ−η¹:η³−C_αHC_β(R)C(O)}] (R = CH₂OH, 1a; R = CMe₂OH, 1b; R = Ph, 1c) were prepared by photolytic reaction of [Fe₂Cp₂(CO)₄] with alkyne according to the literature procedure. The X-ray and the electrochemical characterization of 1c are presented. The μ-allenyl compound [Fe₂Cp₂(CO)₂(μ−CO){μ−η¹:η²_α,β−C_αHC_βCMe₂][BF₄] ([2][BF₄]), obtained by reaction of 1b with HBF₄, underwent monoelectron reduction to give a radical species which was detected by EPR at room temperature. The EPR signal has been assigned to [Fe₂Cp₂(CO)₂(μ−CO){μ−η¹:η²_α,β-C_αHC_βCMe₂}], [2]^•. The molecular structures of [2]⁺ and [2]^• were optimized by DFT calculations. The unpaired electron in [2]^• is localized mainly at the metal centers and, coherently, [2]^• does not undergo carbon-carbon dimerization, by contrast with what previously observed for the μ-vinyl radical complex [Fe₂Cp₂(CO)₂(μ−CO){μ−η¹:η²-CHCH(Ph)}]^•, [3]^•. Electron spin density distributions similar to the one of [2]^• were found for the μ-allenyl radical complexes [Fe₂Cp₂(CO)₂(μ-CO){μ-η¹:η²_α,β-C_αHC_βC(R¹)(R²)}]^• (R¹ = R² = H, [4]^•; R¹ = H, R² = Ph, [5]^•; R¹ = R² = Ph, [6]^•).     

Transmission d'images et d'hologrammes par une nappe de fibres optiques au moyen d'un codage chromatique

A new method of addition of 2-D complex optical signals is proposed. The addition is performed by suitably matched spatial filtering. For that purpose the effect of compacting of periodic objects images is employed.