Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

English compound and non-compound processing in bilingual and multilingual speakers: effects of dominance and sequential multilingualism

This article reports on a study investigating the relative influence of the first and dominant language on L2 and L3 morpho-lexical processing. A lexical decision task compared the responses to English NV-er compounds (e.g., taxi driver) and non-compounds provided by a group of native speakers and three groups of learners at various levels of English proficiency: L1 Spanish-L2 English sequential bilinguals and two groups of early Spanish-Basque bilinguals with English as their L3. Crucially, the two trilingual groups differed in their first and dominant language (i.e., L1 Spanish-L2 Basque vs. L1 Basque-L2 Spanish). Our materials exploit an (a)symmetry between these languages: while Basque and English pattern together in the basic structure of (productive) NV-er compounds, Spanish presents a construction that differs in directionality as well as inflection of the verbal element (V[3SG] + N). Results show between and within group differences in accuracy and response times that may be ascribable to two factors besides proficiency: the number of languages spoken by a given participant and their dominant language. An examination of response bias reveals an influence of the participants' first and dominant language on the processing of NV-er compounds. Our data suggest that morphological information in the nonnative lexicon may extend beyond morphemic structure and that, similarly to bilingualism, there are costs to sequential multilingualism in lexical retrieval.

Experimental paracoccidioidomycosis: alternative therapy with ajoene, compound from Allium sativum, associated with sulfamethoxazole/trimethoprim

Ajoene has been described as an antithrombotic, anti-tumour, antifungal, antiparasitic and antibacterial agent. This study deals with the efficacy of ajoene to treat mice intratracheally infected with Paracoccidioides brasiliensis. The results indicate that ajoene therapy is effective in association with antifungal drugs (sulfametoxazol/trimethoprim), showing a positive additive effect. Ajoene-treated mice developed Th1-type cytokine responses producing higher levels of IFN-gamma and IL-12 when compared to the infected but untreated members of the control group. Antifungal activity of ajoene involves a direct effect on fungi and a protective pro-inflammatory immune response. Reduction of fungal load is additive to chemotherapy and therefore the combined treatment is mostly effective against experimental paracoccidioidomycosis.

Semilinear parabolic problems in thin domains with a highly oscillatory boundary

In this paper, we study the behavior of the solutions of nonlinear parabolic problems posed in a domain that degenerates into a line segment (thin domain) which has an oscillating boundary. We combine methods from linear homogenization theory for reticulated structures and from the theory on nonlinear dynamics of dissipative systems to obtain the limit problem for the elliptic and parabolic problems and analyze the convergence properties of the solutions and attractors of the evolutionary equations. (C) 2011 Elsevier Ltd. All rights reserved.

Continuity of attractors for parabolic problems with localized large diffusion

In this paper we study the continuity of asymptotics of semilinear parabolic problems of the form u(t) - div(p(x)del u) + lambda u =f(u) in a bounded smooth domain ohm subset of R `` with Dirichlet boundary conditions when the diffusion coefficient p becomes large in a subregion ohm(0) which is interior to the physical domain ohm. We prove, under suitable assumptions, that the family of attractors behave upper and lower semicontinuously as the diffusion blows up in ohm(0). (c) 2006 Elsevier Ltd. All rights reserved.

Hyperfine interaction studies with (181)Ta and (111)Cd probes in the compound Ti(2)Ag

By using the time-differential perturbed angular correlation technique, the electric field gradients (EFG) at (181)Hf/(181)Ta and (111)In/(111)Cd probe sites in the MoSi(2)-type compound Ti(2)Ag have been measured as a function of temperature in the range from 24 to 1073 K. Ab initio EFG calculations have been performed within the framework of density functional theory using the full-potential augmented plane wave + local orbitals method as implemented in the WIEN2k package. These calculations allowed assignments of the probe lattice sites. For Ta, a single well-defined EFG with very weak temperature dependence was established and attributed to the [4(e)4mm] Ti site. For (111)Cd probes, two of the three measured EFGs are well defined and correlated with substitutional lattice sites, i.e. both the [4(e)4mm] Ti site and the [2(a)4/mmm] Ag site.

Structural and magnetic properties and hyperfine interaction in La(3.5)Ru(4)O(13) compound

Structural, magnetic and hyperfine interaction measurements have been carried out on the novel compound La(3.5)Ru(4)O(13) prepared under two different atmospheres (air and oxygen flow). This compound is formed in the orthorhombic structure (space group Pmmm, # 47). The coexistence of the triple-layered perovskite-type planes (quasi-2D structure) and the rutile-like slabs (1D structure) leads to interesting magnetic and electronic properties in this compound. The magnetic susceptibility of this system shows a peak at T similar to 47 K associated with antiferromagnetic interactions. The Curie-Weiss behaviour of the susceptibility provides an effective magnetic moment consistent with Ru ions in low-spin state. Perturbed angular correlation measurements carried out with (111)Cd probe in the temperature range 10-60 K reveal only quadrupole interactions and indicate the occurrence of structural distortions for T<40K. (C) 2009 Elsevier B.V. All rights reserved.

The Granada ignimbrite: A compound pyroclastic unit and its relationship with Upper Miocene caldera volcanism in the northern Puna

The Granada ignimbrite, an Upper Miocene volcanic unit from the northern Puna, previously has been interpreted as an extensive ignimbrite (>2300 km(2)) associated with eruptions from the Vilama caldera (trap-door event). On the basis of new data, we revise its correlation and redefine the unit as a compound, high aspect ratio ignimbrite, erupted at approximately 9.8 Ma. Calculated volumes (similar to 100 km(3)) are only moderate in comparison with other large volume (>1000 km(3)) ignimbrites that erupted approximately 2-6 m.y. later in the region (e.g. Vilama, Panizos, Atana). Six new volcanic units are recognized from sequences previously correlated with Granada (only one sourced from the same center). Consequently, the area ascribed to the Granada ignimbrite is substantially reduced (630 km(2)), and links to the Vilama caldera are not supported. Transport directions suggest the volcanic source for the Granada ignimbrite corresponds to vents buried under younger (>= 7.9-5 Ma) volcanic rocks of the Abra Granada volcanic complex. Episodes of caldera collapse at some stage of eruption are likely, though their nature and timing cannot be defined from available data. The eruption of the Granada ignimbrite marks the onset of a phase of large volume (caldera-sourced) volcanism in the northern Puna. (C) 2007 Elsevier Ltd. All rights reserved.

Generalized solutions of a nonlinear parabolic equation with generalized functions as initial data

In [H. Brezis, A. Friedman, Nonlinear parabolic equations involving measures as initial conditions, J. Math. Pure Appl. (9) (1983) 73-97.] Brezis and Friedman prove that certain nonlinear parabolic equations, with the delta-measure as initial data, have no solution. However in [J.F. Colombeau, M. Langlais, Generalized solutions of nonlinear parabolic equations with distributions as initial conditions, J. Math. Anal. Appl (1990) 186-196.] Colombeau and Langlais prove that these equations have a unique solution even if the delta-measure is substituted by any Colombeau generalized function of compact support. Here we generalize Colombeau and Langlais` result proving that we may take any generalized function as the initial data. Our approach relies on recent algebraic and topological developments of the theory of Colombeau generalized functions and results from [J. Aragona, Colombeau generalized functions on quasi-regular sets, Publ. Math. Debrecen (2006) 371-399.]. (C) 2009 Elsevier Ltd. All rights reserved.

A compound class of Weibull and power series distributions

In this paper we introduce the Weibull power series (WPS) class of distributions which is obtained by compounding Weibull and power series distributions where the compounding procedure follows same way that was previously carried out by Adamidis and Loukas (1998) This new class of distributions has as a particular case the two-parameter exponential power series (EPS) class of distributions (Chahkandi and Gawk 2009) which contains several lifetime models such as exponential geometric (Adamidis and Loukas 1998) exponential Poisson (Kus 2007) and exponential logarithmic (Tahmasbi and Rezaei 2008) distributions The hazard function of our class can be increasing decreasing and upside down bathtub shaped among others while the hazard function of an EPS distribution is only decreasing We obtain several properties of the WPS distributions such as moments order statistics estimation by maximum likelihood and inference for a large sample Furthermore the EM algorithm is also used to determine the maximum likelihood estimates of the parameters and we discuss maximum entropy characterizations under suitable constraints Special distributions are studied in some detail Applications to two real data sets are given to show the flexibility and potentiality of the new class of distributions (C) 2010 Elsevier B V All rights reserved

Horseradish peroxidase compound I as a tool to investigate reactive protein-cysteine residues: from quantification to kinetics

Proteins containing reactive cysteine residues (protein-Cys) are receiving increased attention as mediators of hydrogen peroxide signaling. These proteins are mainly identified by mining the thiol proteomes of oxidized protein-Cys in cells and tissues. However, it is difficult to determine if oxidation occurs through a direct reaction with hydrogen peroxide or by thiol-disulfide exchange reactions. Kinetic studies with purified proteins provide invaluable information about the reactivity of protein-Cys residues with hydrogen peroxide. Previously, we showed that the characteristic UV-Vis spectrum of horseradish peroxidase compound I, produced from the oxidation of horseradish peroxidase by hydrogen peroxide, is a simple, reliable, and useful tool to determine the second-order rate constant of the reaction of reactive protein-Cys with hydrogen peroxide and peroxynitrite. Here, the method is fully described and extended to quantify reactive protein-Cys residues and micromolar concentrations of hydrogen peroxide. Members of the peroxiredoxin family were selected for the demonstration and validation of this methodology. In particular, we determined the pK(a) of the peroxidatic thiol of rPrx6 (5.2) and the second-order rate constant of its reactions with hydrogen peroxide ((3.4 +/- 0.2) x 10(7) M(-1) s(-1)) and peroxynitrite ((3.7 +/- 0.4) x 10(5) M(-1) s(-1)) at pH 7.4 and 25 degrees C. (C) 2011 Elsevier Inc. All rights reserved.

Bcl-2 expression and apoptosis induction in human HL60 leukaemic cells treated with a novel organotellurium(IV) compound RT-04

Organotellurium(]V) compounds have been reported to have multiple biological activities including cysteine protease-inhibitory activity, mainly cathepsin B. As cathepsin B is a highly predictive indicator for prognosis and diagnosis of cancer, a possible antitumor potential for these new compounds is expected. In this work, it was investigated the effectiveness of organotellurium(IV) RT-04 to produce lethal effects in the human promyelocytic leukaemia cell line HL60. Using the MTT tetrazolium reduction test, and trypan blue exclusion assay, the IC50 for the compound after 24 h incubation was 6.8 and 0.35 mu M, respectively. Moreover, the compound was found to trigger apoptosis in HL60 cells, inducing DNA fragmentation and caspase-3, -6, and -9 activations. The apoptsosis-induced by RT-04 is probably related to the diminished Bcl-2 expression, observed by RT-PCR, in HL60-treated cells. In vivo studies demonstrated that the RT-04 treatment (2.76 mg/kg given for three consecutive days) produces no significant toxic effects for bone marrow and spleen CFU-GM. However, higher doses (5.0 and 10 mg/kg) produced a dose-dependent reduction in the number of CFU-GM of RT-04-treated mice. These results suggest that RT-04 is able to induce apoptosis in HL60 cells by Bcl-2 expression down-modulation. Further studies are necessary to better clarify the effects of this compound on bone marrow normal cells. (C) 2008 Elsevier Ltd. All rights reserved.

Expression Profile of Rat Hippocampal Neurons Treated with the Neuroprotective Compound 2,4-Dinitrophenol: Up-Regulation of cAMP Signaling Genes

2,4-Dinitrophenol (DNP) is classically known as a mitochondrial uncoupler and, at high concentrations, is toxic to a variety of cells. However, it has recently been shown that, at subtoxic concentrations, DNP protects neurons against a variety of insults and promotes neuronal differentiation and neuritogenesis. The molecular and cellular mechanisms underlying the beneficial neuroactive properties of DNP are still largely unknown. We have now used DNA microarray analysis to investigate changes in gene expression in rat hippocampal neurons in culture treated with low micromolar concentrations of DNP. Under conditions that did not affect neuronal viability, high-energy phosphate levels or mitochondrial oxygen consumption, DNP induced up-regulation of 275 genes and down-regulation of 231 genes. Significantly, several up-regulated genes were linked to intracellular cAMP signaling, known to be involved in neurite outgrowth, synaptic plasticity, and neuronal survival. Differential expression of specific genes was validated by quantitative RT-PCR using independent samples. Results shed light on molecular mechanisms underlying neuroprotection by DNP and point to possible targets for development of novel therapeutics for neurodegenerative disorders.

LASER-TESTING RIG : Measurement System for evaluation of Shape of concentrating reflector for solar collector Absolicon X10

This Thesis project is a part of the all-round automation of production of concentrating solar PV/T systems Absolicon X10. ABSOLICON Solar Concentrator AB has been invented and started production of the prospective solar concentrated system Absolicon X10. The aims of this Thesis project are designing, assembling, calibrating and putting in operation the automatic measurement system intended to evaluate the shape of concentrating parabolic reflectors.On the basis of the requirements of the company administration and needs of real production process the operation conditions for the Laser testing rig were formulated. The basic concept to use laser radiation was defined.At the first step, the complex design of the whole system was made and division on the parts was defined. After the preliminary conducted simulations the function and operation conditions of the all parts were formulated.At the next steps, the detailed design of all the parts was conducted. Most components were ordered from respective companies. Some of the mechanical components were made in the workshop of the company. All parts of the Laser-testing rig were assembled and tested. Software part, which controls the Laser-testing rig work, was created on the LabVIEW basis. To tune and test software part the special simulator was designed and assembled.When all parts were assembled in the complete system, the Laser-testing rig was tested, calibrated and tuned.In the workshop of Absolicon AB, the trial measurements were conducted and Laser-testing rig was installed in the production line at the plant in Soleftea.

Universal Experimental Measurement System «Sun-Walker» : Automotive measurement system for the evaluation of the solar irradiation distribution for the tests of the solar concentrated systems.

This Thesis project is a part of the research conducted in Solar industry. ABSOLICON Solar Concentrator AB has invented and started production of the prospective solar concentrated system Absolicon X10. The aims of this Thesis project are designing, assembling, calibrating and putting in operation the automatic measurement system intended to evaluate distribution of density of solar radiation in the focal line of the concentrated parabolic reflectors and to measure radiation from the artificial source of light being a calibration-testing tool.On the basis of the requirements of the company’s administration and needs of designing the concentrated reflectors the operation conditions for the Sun-Walker were formulated. As the first step, the complex design of the whole system was made and division on the parts was specified. After the preliminary conducted simulation of the functions and operation conditions of the all parts were formulated.As the next steps, the detailed design of all the parts was made. Most components were ordered from respective companies. Some of the mechanical components were made in the workshop of the company. All parts of the Sun-Walker were assembled and tested. The software part, which controls the Sun-Walker work and conducts measurements of solar irradiation, was created on the LabVIEW basis. To tune and test the software part, the special simulator was designed and assembled.When all parts were assembled in the complete system, the Sun-Walker was tested, calibrated and tuned.