Internal nanoparticle structure of temperature-responsive self-assembled PNIPAM-b-PEG-b-PNIPAM triblock copolymers in aqueous solutions: NMR, SANS and light scattering studies

In this study we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solid-like particles and chain network with a mesh size of 1-3 nm are present; nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have non-uniform structure with “frozen” areas interconnected by single chains in Gaussian conformation. SANS data with deuterated “invisible” PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.

An assessment of the latent and sensible heat flux on the simulated regional climate over Southwestern South Atlantic Ocean

A Regional Climate Model (RegCM3) 10-year (1990-1999) simulation over southwestern South Atlantic Ocean (SAO) is evaluated to assess the mean climatology and the simulation errors of turbulent fluxes over the sea. Moreover, the relationship between these fluxes and the rainfall over some cyclogenetic areas is also analyzed. The RegCM3 results are validated using some reanalyses datasets (ERA40, R2, GPCP and WHOI). The summer and winter spatial patterns of latent and sensible heat fluxes simulated by the RegCM3 are in agreement with the reanalyses (WHOI, R2 and ERA40). They show large latent heat fluxes exchange in the subtropical SAO and at higher latitudes in the warm waters of Brazil Current. In particular, the magnitude of RegCM3 latent heat fluxes is similar to the WHOI, which is probably related to two factors: (a) small specific humidity bias, and (b) the RegCM3 flux algorithm. In contrast, the RegCM3 presents large overestimation of sensible heat flux, though it simulates well their spatial pattern. This simulation error is associated with the RegCM3 underestimation of the 2-m air temperature. In southwestern SAO, in three known cyclogenetic areas, the reanalyses and the RegCM3 show the existence of different physical mechanisms that control the annual cycles of latent/sensible heating and rainfall. It is shown that over the eastern coast of Uruguay (35A degrees-43A degrees S) and the southeastern coast of Argentina (44A degrees-52A degrees S) the sea-air moisture and heat exchange play an important role to control the annual cycle of precipitation. This does not happen on the south/southeastern coast of Brazil.

Ground-based detection of sprites and their parent lightning flashes over Africa during the 2006 AMMA campaign

Sprites have been detected in video camera observations from Niger over mesoscale convective systems in Nigeria during the 2006 AMMA (African Monsoon Multidisciplinary Analysis) campaign The parent lightning flashes have been detected by multiple Extremely Low Frequency (ELF) receiving stations worldwide The recorded charge moments of the patent lightning flashes are often in excellent agreement between different receiving sites, and are furthermore consistent with conventional dielectric breakdown in the mesosphere as the origin of the sprites Analysis of the polarization of the horizontal magnetic field at the distant receivers provides evidence that the departure from linear magnetic polarization at ELF is caused primarily by the clay night asymmetry of the Earth-ionosphere cavity Copyright (C) 2009 Royal Meteorological Society

Gradual Decline in Malaria-Specific Memory T Cell Responses Leads to Failure to Maintain Long-Term Protective Immunity to Plasmodium chabaudi AS Despite Persistence of B Cell Memory and Circulating Antibody

The mechanisms responsible for the generation and maintenance of immunological memory to Plasmodium are poorly understood and the reasons why protective immunity in humans is so difficult to achieve and rapidly lost remain a matter for debate. A possible explanation for the difficulty in building up an efficient immune response against this parasite is the massive T cell apoptosis resulting from exposure to high-dose parasite Ag. To determine the immunological mechanisms required for long-term protection against P. chabaudi malaria and the consequences of high and low acute phase parasite loads for acquisition of protective immunity, we performed a detailed analysis of T and B cell compartments over a period of 200 days following untreated and drug-treated infections in female C57BL/6 mice. By comparing several immunological parameters with the capacity to control a secondary parasite challenge, we concluded that loss of full protective immunity is not determined by acute phase parasite load nor by serum levels of specific IgG2a and IgG1. Abs, but appears to be a consequence of the progressive decline in memory T cell response to parasites, which occurs similarly in untreated and drug-treated mice with time after infection. Furthermore, by analyzing adoptive transfer experiments, we confirmed the major role of CD4(+) T cells for guaranteeing long-term full protection against P. chabaudi malaria. The Journal of Immunology, 2008, 181: 8344-8355.

In vitro sensitivity of Leishmania (Viannia) braziliensis and Leishmania (Leishmania) amazonensis Brazilian isolates to meglumine antimoniate and amphotericin B

Resistance of Leishmania parasites to specific chemotherapy has become a well-documented problem in the Indian subcontinent in recent years but only a few studies have focused on the susceptibility of American Leishmania isolates. Our susceptibility assays to meglumine antimoniate were performed against intracellular amastigotes after standardizing an in vitro model of macrophage infection appropriate for Leishmania (Viannia) braziliensis isolates. For the determination of promastigote susceptibility to amphotericin B, we developed a simplified MTT-test. The sensitivity in vitro to meglumine antimoniate and amphotericin B of 13 isolates obtained from Brazilian patients was determined. L. (V.) braziliensis isolates were more susceptible to meglumine antimoniate than Leishmania (Leishmania) amazonensis. EC(50), EC(90) and activity indexes (calculated over the sensitivity of reference strains), suggested that all isolates tested were susceptible in vitro to meglumine antimoniate, and did not show association with the clinical outcomes. Isolates were also uniformly susceptible in vitro to amphotericin B.

The analytic torsion of a cone over an odd dimensional manifold

We study the analytic torsion of a cone over an orientable odd dimensional compact connected Riemannian manifold W. We prove that the logarithm of the analytic torsion of the cone decomposes as the sum of the logarithm of the root of the analytic torsion of the boundary of the cone, plus a topological term, plus a further term that is a rational linear combination of local Riemannian invariants of the boundary. We show that this last term coincides with the anomaly boundary term appearing in the Cheeger Muller theorem [3, 2] for a manifold with boundary, according to Bruning and Ma (2006) [5]. We also prove Poincare duality for the analytic torsion of a cone. (C) 2010 Elsevier B.V. All rights reserved.

Homotopy type of gauge groups of quaternionic line bundles over spheres

Let P be a principal S(3)-bundle over a sphere S(n), with n >= 4. Let G(p) be the gauge group of P. The homotopy type of G(p) when n - 4 was studied by A. Kono in [A. Kono, A note on the homotopy type of certain gauge groups, Proc. Roy. Soc. Edinburgh Sect. A 117 (1991) 295-297]. In this paper we extend his result anti we study the homotopy type of the gauge group of these bundles for all n <= 25. (C) 2008 Elsevier B.V. All rights reserved.

Numerical study of the atmospheric flow over a coastal cliff

This work presents a numerical method suitable for the study of the development of internal boundary layers (IBL) and their characteristics for flows over various types of coastal cliffs. The IBL is an important meteorological occurrence for flows with surface roughness and topographical step changes. A two-dimensional flow program was used for this study. The governing equations were written using the vorticity-velocity formulation. The spatial derivatives were discretized by high-order compact finite differences schemes. The time integration was performed with a low storage fourth-order Runge-Kutta scheme. The coastal cliff (step) was specified through an immersed boundary method. The validation of the code was done by comparison of the results with experimental and observational data. The numerical simulations were carried out for different coastal cliff heights and inclinations. The results show that the predominant factors for the height of the IBL and its characteristics are the upstream velocity, and the height and form (inclination) of the coastal cliff. Copyright (C) 2010 John Wiley & Sons, Ltd.

SU(3) mass-splittings of heavy-baryons in QCD

We extract directly (for the first time) the charmed (C = 1) and bottom (B = -1) heavy-baryons (spin 1/2 and 3/2) mass-splittings due to SU(3) breaking using double ratios of QCD spectral sum rules (QSSR) in full QCD, which are less sensitive to the exact value and definition of the heavy quark mass, to the perturbative radiative corrections and to the QCD continuum contributions than the simple ratios commonly used for determining the heavy baryon masses. Noticing that most of the mass-splittings are mainly controlled by the ratio kappa <(S) over bars >/<(d) over bard > of the condensate, we extract this ratio, by allowing 1 sigma deviation from the observed masses of the Xi(c.b) and of the Omega(c). We obtain: kappa = 0.74(3), which improves the existing estimates: kappa = 0.70(10) from light hadrons. Using this value, we deduce M(Omega b) = 6078.5(27.4) MeV which agrees with the recent CDF data but disagrees by 2.4 sigma with the one from D0. Predictions of the Xi(Q)` and of the spectra of spin 3/2 baryons containing one or two strange quark are given in Table 2. Predictions of the hyperfine splittings Omega(Q)* - Omega(Q) and Xi(Q)* - Xi(Q) are also given in Table 3. Starting for a general choice of the interpolating currents for the spin 1/2 baryons, our analysis favours the optimal value of the mixing angle b similar or equal to (-1/5-0) found from light and non-strange heavy baryons. (C) 2010 Elsevier B.V. All rights reserved.

Catalytic hydrodechlorination of chlorobenzene over supported palladium catalyst in buffered medium

The catalytic hydrodechlorination (HDC) reaction, which is an attractive abatement process for chlorinated organic wastes, was studied over a magnetically recoverable supported Pd(0) catalyst. We investigated the most favorable reaction conditions under which to obtain the highest substrate conversion rates while preserving the catalyst properties and morphology. Sodium hydroxide, triethylamine and buffered solutions were used as proton scavengers in the HDC of chlorobenzene under mild conditions. It was observed that sodium hydroxide caused corrosion of the silica support, triethylamine in 2-propanol preserved the morphology of the catalyst which could be recycled for up to five successive H DC reactions, and aqueous buffer solutions preserved the catalyst morphology and the catalytic activity for up to four successive HDC reactions. The use of buffer solutions to neutralize the HCl formed during the HDC reaction is an interesting, less aggressive, alternative approach to HDC reactions. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and magnetic characterization of TmCo(2)B(2)C

A new quaternary intermetallic borocarbide TmCo(2)B(2)C has been synthesized via rapid-quench of an arc-melted ingot. Elemental and powder-diffraction analyses established its correct stoichiometry and single-phase character. The crystal structure is isomorphous with that of TmNi(2)B(2)C (I4/mmm) and is stable over the studied temperature range. Above 7 K, the paramagnetic state follows modified Curie-Weiss behavior (chi = C/(T - theta) + chi(0)) wherein chi(0) = 0.008(1) emu mol(-1) with the temperature-dependent term reflecting the paramagnetism of the Tm subsystem: mu(eff) = 7.6(2) mu(B) (in agreement with the expected value for a free Tm(3+) ion) and theta = -4.5(3) K. Long-range ferromagnetic order of the Tm sublattice is observed to develop around similar to 1 K. No superconductivity is detected in TmCo(2)B(2)C down to 20 mK, a feature which is consistent with the general trend in the RCo(2)B(2)C series. Finally, the influence of the rapid-quench process on the magnetism (and superconductivity) of TmNi(2)B(2)C will be discussed and compared to that of TmCo(2)B(2)C.

Mass-splittings of doubly heavy baryons in QCD

We consider (for the first time) the ratios of doubly heavy baryon masses (spin 3/2 over spin 1/2 and SU(3) mass-splittings) using double ratios of sum rules (DRSR), which are more accurate than the usual simple ratios often used in the literature for getting the hadron masses. In general, our results agree and compete in precision with potential model predictions. In our approach, the alpha(s) corrections induced by the anomalous dimensions of the correlators are the main sources of the Xi(QQ)*-Xi(QQ) mass-splittings, which seem to indicate a 1/M(Q) behaviour and can only allow the electromagnetic decay Xi(QQ)* -> Xi(QQ) + gamma but not to Xi(QQ) + pi. Our results also show that the SU(3) mass-splittings are (almost) independent of the spin of the baryons and behave approximately like 1/M(Q), which could be understood from the QCD expressions of the corresponding two-point correlator. Our results can improved by including radiative corrections to the SU(3) breaking terms and can be tested, in the near future, at Tevatron and LHCb. (C) 2010 Published by Elsevier B.V.

Degenerate Two-Photon Absorption in All-Trans Retinal: Nonlinear Spectrum and Theoretical Calculations

In this work we investigate the degenerate two-photon absorption spectrum of all-trans retinal ill ethanol employing the Z-scan technique with femtosecond pulses, The two-photon absorption (2PA) spectrum presents a monotonous increase as the excitation wavelength approaches the one-photon absorption band and it peak at 790 nm. We attribute the 2PA hand to the mixing of states (1)B(u)+-like and vertical bar S(1)>, which are strongly allowed by one- and two-photon, respectively. We modeled the 2PA spectrum by using the sum-over-states approach and obtained spectroscopic parameters of the electronic transitions to vertical bar S >, vertical bar S(2)> (""(1)Bu(+)""), vertical bar S(3)>, and vertical bar S(4)> singlet-excited states. The results were compared with theoretical predictions of one- and two-photon transition calculations using the response Functions formalism within the density functional theory framework with the aid of the CAM-B3LYP functional.

HFD groups in the Solovay model

Hajnal and Juhasz proved that under CH there is a hereditarily separable, hereditarily normal topological group without non-trivial convergent sequences that is countably compact and not Lindelof. The example constructed is a topological subgroup H subset of 2(omega 1) that is an HFD with the following property (P) the projection of H onto every partial product 2(I) for I is an element of vertical bar omega(1)vertical bar(omega) is onto. Any such group has the necessary properties. We prove that if kappa is a cardinal of uncountable cofinality, then in the model obtained by forcing over a model of CH with the measure algebra on 2(kappa), there is an HFD topological group in 2(omega 1) which has property (P). Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

The bar-radical of a class of almost alternative baric algebras

In this article we prove that, if (U, ) is a finite dimensional baric algebra of (gamma, delta) type over a field F of characteristic not equal 2,3,5 such that gamma(2) - delta(2) + delta = 1 and 0,1, then rad(U) = R(U)boolean AND(bar(U))(2), where R(U) is the nilradical (maximal nil ideal) of U.