Highly stable 3,4,9,10-perylenediimide radical anions immobilized in robust zirconium phosphonate self-assembled films

Self-assembled thin films of 3,4,9,10-perylenediimides (PDIs) containing up to 50 PDI layers were grown on quartz slides using the zirconium phosphonate technique. When the films were immersed in aqueous solutions of the sodium dithionite reducing agent, in situ reduction of the dye was observed, generating a purple film containing PDI radical anions. The PDI radical anions formed within the films were rather stable, persisting for several minutes in the presence of atmospheric oxygen. Atomic force microscopy (AFM) images showed that the film surface was rather smooth and pinhole-free.     

A new reagent for direct difluoromethylation

Molecular scaffolds containing alkylfluorine substituents are desired in many areas of chemical research from materials to pharmaceuticals. Herein, we report the invention of a new reagent (Zn(SO(2)CF(2)H)(2), DFMS) for the innate difluoromethylation of organic substrates via a radical process. This mild, operationally simple, chemoselective, and scalable difluoromethylation method is compatible with a range of nitrogen-containing heteroarene substrates of varying complexity as well as select classes of conjugated π-systems and thiols. Regiochemical comparisons suggest that the CF(2)H radical generated from the new reagent possesses nucleophilic character.     

Structural aspects of the Eberth-Katschenko layer of Bufo ictericus integument: histochemical characterization and biochemical analysis of the cutaneous calcium (Amphibian, Bufonidae)

Anuran, such as Brazilian toad Bufo ictericus Spix, 1824, possess a calcified dermal layer called the Eberth-Katschenko (EK) layer located between the stratum spongiosum and the stratum compactum. It has been regarded as a protective barrier against desiccation or involved in storage and mobilization of calcium, or a barrier for the interchange of substances between the animal's internal and external environment. The B. ictericus integument was removed from the ventral and dorsal regions and examined by light microscopy, using histochemical techniques, and also submitted to biochemical calcium analysis. The intermediate layer is strongly basophilic and metachromatic. In the EK layer Alcian blue at different critical electrolytic concentration revealed hyaluronic acid, which coexists with the dermal calcium. We conclude that the EK layer of B. ictericus is a discontinuous layer and is formed of hyaluronic acid and a sulfated GAG different from chondroitin sulfate, heparin and heparan sulfate or keratan sulfate. The amount of cutaneous calcium is independent of region and sex. GAGs may play an important role in dermal hydric balance, protecting the animal against desiccation, and hyaluronic acid is probably able to anchor dermal calcium. Thus, all compounds of the EK layer are essential for integument integrity and functionality.     

Bose-Einstein correlations for pions produced inp p collisions at 360 GeV/c

Zeitschrift für Physik C Particles and Fields - Correlations among identically charged pions were measured for pions produced inp p collisions at 360 GeV/c using the EHS spectrometer. The...     

Study on the formation during the production of lead-free piezoceramics at the morphotropic phase boundary

Because of the environmental concerns, the manufacture of ceramics based on lead titanate zirconate [Pb(Zr_1−xTi_x)O₃−PZT] has been condemned because of the lead toxicity. In this context, the electromechanical properties of sodium, potassium and lithium niobate [(Na_0.5−x/2K_0.5−x/2Li_x)NbO₃−NKLN] at the morphotropic phase boundary granted these materials the position of most suitable candidate to replace PZT. However, the production of these ceramics is rather critical mainly because of a natural tendency of forming secondary phases. To help with the studies of the synthesis of this lead-free piezoceramic, this work presents an evaluation of the crystallization of the (Na_0.47K_0.47Li_0.06)NbO₃ phase by solid-state reactions. TG-DTA, XRD, dilatometric and ferroelectric hysteresis analyses indicated that a secondary phase (K₃Li₂Nb₅O₁₅) crystallizes at temperatures above 850 C and also during the sintering of the powders compacts at 1080 C. To prevent the formation of this phase, the addition of Na₂Nb₂O₆.nH₂O microfibers obtained through a microwave hydrothermal synthesis was performed in the sintering process. After to this addition, the suppression of the K₃Li₂Nb₅O₁₅ phase occurred and an increase of the NKLN electrical properties was then obtained.     

Thermal diffusivity and nuclear spin relaxation: a continuous wave free precession NMR study

Continuous wave free precession (CWFP) nuclear magnetic resonance is capable of yielding quantitative and easily obtainable information concerning the kinetics of processes that change the relaxation rates of the nuclear spins through the action of some external agent. In the present application, heat flow from a natural rubber sample to a liquid nitrogen thermal bath caused a large temperature gradient leading to a non-equilibrium temperature distribution. The ensuing local changes in the relaxation rates could be monitored by the decay of the CWFP signals and, from the decays, it was possible to ascertain the prevalence of a diffusive process and to obtain an average value for the thermal diffusivity.     

Experimental generation and characterization of Devil’s vortex-lenses

We propose the first experimental approach for both generation and characterization of high quality Devil’s vortex-lenses. These new type of lenses, able to produce a sequence of optical vortices, are addressed onto a programmable spatial light modulator (SLM) operating in phase-only modulation. The static aberrations arising by the lack of flatness of the SLM display are characterized and mostly compensated by using a Shack–Hartmann wavefront sensor. The analysis of the residual aberrations and their effect on the vortex-lens performance are studied.     

Field performance of an all-semiconductor laser coherent Doppler lidar

We implement and test what, to our knowledge, is the first deployable coherent Doppler lidar (CDL) system based on a compact, inexpensive all-semiconductor laser (SL). To demonstrate the field performance of our SL-CDL remote sensor, we compare a 36 h time series of averaged radial wind speeds measured by our instrument at an 80 m distance to those simultaneously obtained from an industry-standard sonic anemometer (SA). An excellent degree of correlation (R2=0.994 and slope=0.996) is achieved from a linear regression analysis of the CDL versus SA wind speed data. The lidar system is capable of providing high data availability, ranging from 85% to 100% even under varying outdoor (temperature and humidity) conditions during the test period. We also show the use of our SL-CDL for monitoring the dependence of aerosol backscatter on relative humidity. This work points to the feasibility of a more general class of low-cost, portable remote sensors based on all-SL emitters for applications that require demanding laser stability and coherence.     

Photophysical properties of a series of 4‐aryl substituted 1,4‐dihydropyridines

In this article, a series of Hantzsch 1,4‐dihydropyridines with different substituted aryl groups were synthesized and its spectral data obtained by UV–Vis absorption and fluorescence emission spectroscopies in solution. The dihydropyridines present absorption located around 350 nm and fluorescence emission in the blue–green region. A higher Stokes’ shift could be observed for the derivative 3b because of an intramolecular charge transfer in the excited state from the dimethylaniline to the dihydropyridine chromophores, which was corroborated by a linear relation of the fluorescence maxima (ν_max) versus the solvent polarity function (Δf) from the Lippert–Mataga correlation. A comparison between the experimental data and time‐dependent density functional theory‐polarizable continuum model calculations of the vertical transitions was performed to help on the elucidation of the photophysics of these compounds. For these calculations, the S₀ and S₁ states were optimized using Becke, three‐parameter, Lee–Yang–Parr/6‐31 G* and Configuration Interaction Singles/6‐31 G*, respectively. The predicted absorption maxima are in good agreement with the experimental; however, the theoretical fluorescence emission maxima do not match the experimental, which means that the excited specie cannot be related to neither a locally excited state nor to an aromatized structure. Copyright © 2012 John Wiley & Sons, Ltd.     

The radiative return at small angles: virtual corrections

Virtual corrections for electron-positron annihilation into one real and one off-shell photon of invariant mass are evaluated. Special attention is paid to those configurations where the real photon is collinear with the beam direction. This calculation is an important ingredient of a Monte Carlo program, which simulates events with tagged photons from initial-state radiation, including NLO corrections. Received: 24 April 2002 / Published online: 12 July 2002