Angular Dependences of Third Harmonic Generation from Microdroplets

We present experimental and theoretical results for the angular dependence of third harmonic generation (THG) of water droplets in the micrometer range (size parameter $62<ka<248$). The THG signal in $p$- and $s$-polarization obtained with ultrashort laser pulses is compared with a recently developed nonlinear extension of classical Mie theory including multipoles of order $l\leq250$. Both theory and experiment yield over a wide range of size parameters remarkably stable intensity maxima close to the forward and backward direction at ``magic angles''. In contrast to linear Mie scattering, both are of comparable intensity.Comment: 4 pages, RevTeX, 3 figures available on request from [email protected], submitted to PR

Der Verbleib kupferbasierter Fungizide in Weinbergböden: Eine Fallstudie der stabilen Kupfer-Isotopenverhältnisse und Elektronenspinresonanz von Calco- und Vertisolen in Soave (Italien)

Kupferbasierte Fungizide sind im Weinbau weit verbreitet und im biologischen Weinbau die einzig erlaubten Pestizide zur Bekämpfung von falschem Mehltau. Durch den intensiven, dauerhaften Gebrauch von Kupfer reichert sich dieser, mit wachsenden ökotoxikologischen Konsequenzen, in Weinbergböden an. In dieser Studie untersuchen wir den Verbleib von Kupfer in einem Calcosol und einem Vertisol aus Soave (Italien). Beide Böden werden seit über 50 Jahren mit Kupfer behandelt. Wir stellen Massenbilanzen auf und nutzen die innovative Kombination aus Messung stabiler Cu-Isotopenverhältnisse und Elektronenspinresonanzspektroskopie (ESR), um Einblicke in die biogeochemischen Mechanismen der Kupferbindung zu erlangen. Die untersuchten Böden weisen hohe exogene Kupfergehalte auf, welche eine Akkumulation der heutigen maximalen Behandlungsmenge über 50 Jahre überschreiten. Dies belegt, dass einmal sehr viel größere Mengen Cu im Weinbau verwendet wurden und dass ein Großteil dieses Kupfers in den jeweiligen Böden verbleibt. In Vertisolen fallen die Cu-Konzentrationen unter dem vertischen Horizont schnell auf die geogene Hintergrundkonzentration, wobei in Calcosolen dieser Abfall progressiver erfolgt. Isotopenverhältnisse unterscheiden sich zwischen den verschieden Bodentypen (δCu-65 zwischen 0.12 und 0.37 ‰), obwohl sie die gleiche Behandlung erfahren haben. Kupferisotope in Oberböden sind schwerer als in Unterböden und Citratextraktionen zeigen, dass mobiles Kupfer isotopisch schwerer ist als der Gesamtgehalt. Die Horizonte des Calcosols sind systematisch leichter als die des Vertisols, was auf unterschiedliche biogeochemische Bindungsmechanismen von Kupfer hinweist. Dies wird durch die ESR-Spektren bestätigt. In Oberböden zeigen sie eine Kupferbindung an organisches Material, wobei es im gesamten Bodenprofil Unterschiede in der Cu-Bindung zwischen den beiden Bodentypen gibt. Wenn jedoch Horizonte des Calcosols mit Säure entkalkt werden, nähren sich deren ESR-Spektren denen der Vertisole an, wohingegen letztere nicht auf eine Säurebehandlung reagieren. Somit wird gezeigt, dass in Calcosolen Karbonate an der Bindung von Kupfer beteiligt sind wobei in Vertisolen der vertische Horizont eine wichtige Rolle spielt. Darüber hinaus wird durch die analoge Variation von ESR-Spektren und Isotopenverhältnissen wird die Anwendbarkeit von Cu-Isotopenanalysen und ESR-Spektroskopie zur Aufklärung von biogeochemischen Prozessen in Böden demonstriert

Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13C and 29Si NMR Enhanced by Dynamic Nuclear Polarization

We show that dynamic nuclear polarization (DNP) can be used to enhance NMR signals of13C and 29Si nuclei located in mesoporous organic/inorganic hybrid materials, at several hundreds of nanometers from stable radicals (TOTAPOL) trapped in the surrounding frozen disordered water. The approach is demonstrated using mesoporous silica nanoparticles (MSN), functionalized with 3-(N-phenylureido)propyl (PUP) groups, filled with the surfactant cetyltrimethylammonium bromide (CTAB). The DNP-enhanced proton magnetization is transported into the mesopores via 1H–1H spin diffusion and transferred to rare spins by cross-polarization, yielding signal enhancements εon/off of around 8. When the CTAB molecules are extracted, so that the radicals can enter the mesopores, the enhancements increase to εon/off ≈ 30 for both nuclei. A quantitative analysis of the signal enhancements in MSN with and without surfactant is based on a one-dimensional proton spin diffusion model. The effect of solvent deuteration is also investigated

Response of the streaks, the active and passive eddies in an unsteady channel flow

International audienceSpanwise space–time correlations of the wall shear stress and the longitudinal velocity fluctuations in the low buffer layer of an unsteady channel flow are reported. The imposed amplitude is 20% of the centerline velocity and the imposed frequency covers a large range going from the quasi-steady limit to the bursting frequency of the corresponding steady flow. The unsteady spanwise correlation coefficient is investigated both through its own modulation characteristics (amplitude and phase shifts) and those of the resulting streak spacing. A good correspondence is found between the modulation of the streak spacing and that of the ejection period. The data is further analyzed by temporal filtering of the wall shear stress and streamwise velocity fluctuations. It is shown that the large outer-layer structures play a “passive” role in the unsteady response of the near wall turbulence. The inner wall eddies, in return, are amply responsible for the unsteady reaction of both the turbulent wall shear stress and the streamwise velocity intensities in the buffer layer

Photoionization of LinHm clusters

Ionization potentials of LinHm clusters have been measured from bare Lin clusters to hydrogen saturated clusters. The evolution of electronic properties with the number of H is discussed. We found that LinHm clusters behave like Lin-m clusters. This similarity may be due to a segregation between a metallic part and an insulator part inside the cluster

Alkylcyanoacrylate drug carriers: I. Physicochemical characterization of nanoparticles with different alkyl chain length

Alkylcyanoacrylate particles were physico-chemically characterized in terms of size, surface charge, zeta potential, interaction with charged serum components and surface hydrophobicity as relevant parameters influencing the in vitro interaction with cells in culture and the in vivo organ distribution and fate after intravenous administration. Methyl-, ethyl-, isobutyl- and isohexyl-cyanoacrylate particles were found to be very similar with regard to these properties. Large differences existed with regard to their degradation behaviour. The type of degradation (surface erosion) was determined by photon correlation spectroscopy, and the degradation velocity was evaluated using a turbidimetric assay. Surface modification of the particles by a polymer coating affected neither the type nor the velocity of the degradation

Titanium(III) sulfate as new negative electrode for sodium-ion batteries

A straightforward synthesis of Ti2(SO4)3 and reversible intercalation of 1.7 sodium ions via a two step process with formation of an intermediate phase was reported. The product was then washed with ethyl acetate and dried at 80°C overnight under vacuum. Electrochemical measurements were carried out in Swagelok cells using sodium metal as counter electrode and Whatman GF/D borosilicate glass fiber soaked in the electrolyte as separator. For the sample manually milled, a pseudo-plateau is observed at ca. 1.5 V vs Na+/Na followed by a sloping region to 1.0 V and another pseudo-plateau at ca. 1.0 V. Ball-milled samples exhibit similar profiles but with substantially enhanced capacity, even above 1.5 V. Upon oxidation, two well-defined plateaus at 1.10 and 1.64 V are observed in all samples. The number of electrons exchanged per mol of Ti2(SO4)3 increases with milling time to reach 3.4, which is above the theoretical expected capacity, but only 1.7 are reversible

Electrochemical reactivity of Li2VOSiO4 toward Li

We report on the chemical/electrochemical reactivity of the insulating layered V-based silicate-phase Li2VOSiO4 toward Li. The silicate phase, made by a ceramic approach and consisting of 5-20 μm agglomerates, exhibits only a slight reactivity with Li in chemical or electrochemical reactions. By ball milling Li2VOSiO4 in the presence of carbon, we succeeded in preparing composites that reversibly react with 0.7 Li+ per unit formula at an average voltage of 3.6 V vs Li+/Li0. This electrochemical reactivity was chemically mimicked using NO2BP4 or Br2 and LiI as oxidizing and reducing agents, respectively. Through a combination of X-rays and HRTEM measurements, we showed that the insertion - deinsertion mechanism is a two-phase process with poor kinetics. The delithiated phase crystallizes in space group P4 (a = 6.206 Å, c = 4.5715Å), whereas the precursor lithiated phase crystallizes in P4/nmm (a = 6.366(9) Å, c = 4.456(6) Å). Because silicates such as phosphates are cheap and can also be made redox-active by carbon coatings, they should not be overlooked as possible electrode candidates in future research. © 2006 American Chemical Society

Series of hydrated heterometallic uranyl-cobalt(II) coordination polymers with aromatic polycarboxylate ligands: Formation of U=O&mdash;Co bonding upon dehydration process

Five new heterometallic UO22+-Co2+ coordination polymers have been obtained by hydrothermal reactions of uranyl nitrate and metallic cobalt with aromatic polycarboxylic acids. Single-crystal X-ray diffraction reveals the formation of four 3D frameworks with the mellitate (noted mel) ligand and one 2D network with the isophthalate (noted iso) ligand. The compounds [(UO2(H2O))2Co(H2O)4(mel)]·4H2O (1), [UO2Co(H2O)4(H2mel)]·2H2O (2), and [(UO2(H2O))2Co(H2O)4(mel)] (4) consist of 3D frameworks built up from the connection of mellitate ligands and mononuclear metallic centers. These three compounds exhibit two types of geometry for the uranyl cation: pentagonal bipyramidal environment for 1 and 4, and hexagonal bipyramidal environment for 2. Using the mellitate ligand, the uranyl dinuclear unit is isolated in the compound [(UO2)2(OH)2(Co(H2O)4)2(mel)]·2H2O (3). Due to their 2D framework and the presence of uncoordinated cobalt(II) cations, the compound [(UO2)(iso)3][Co(H2O)6]·3(H2O) (5) is drastically different than the previous one. The thermal behavior of compounds 1, 2, and 3 has been studied by thermogravimetric analysis, X-ray thermodiffraction, and in situ infrared. By heating, the dehydration of compounds 1 and 2 promotes two structural transitions (1 → 1′ and 2 → 2′). The crystal structures of [(UO2(H2O))2Co(H2O)2(mel)] (1′) and [(UO2)Co(H2mel)] (2′) were determined by single-crystal X-ray diffraction; each of them presents a heterometallic interaction between uranyl bond and the Co(II) center. Due to the rarely reported coordination environment for the cobalt center in compound 2′ (square pyramidal configuration), the magnetic properties and EPR characterizations of the compounds 2 and 2′ were also investigated