Substrate Range and Genetic Analysis of Acinetobacter Vanillate Demethylase

An Acinetobacter sp. genetic screen was used to probe structure-function relationships in vanillate demethylase, a two-component monooxygenase. Mutants with null, leaky, and heat-sensitive phenotypes were isolated. Missense mutations tended to be clustered in specific regions, most of which make known contributions to catalytic activity. The vanillate analogs m-anisate, m-toluate, and 4-hydroxy-3,5-dimethylbenzoate are substrates of the enzyme and weakly inhibit the metabolism of vanillate by wild-type Acinetobacter bacteria. PCR mutagenesis of vanAB, followed by selection for strains unable to metabolize vanillate, yielded mutant organisms in which vanillate metabolism is more strongly inhibited by the vanillate analogs. Thus, the procedure opens for investigation amino acid residues that may contribute to the binding of either vanillate or its chemical analogs to wild-type and mutant vanillate demethylases. Selection of phenotypic revertants following PCR mutagenesis gave an indication of the extent to which amino acid substitutions can be tolerated at specified positions. In some cases, only true reversion to the original amino acid was observed. In other examples, a range of amino acid substitutions was tolerated. In one instance, phenotypic reversion failed to produce a protein with the original wild-type sequence. In this example, constraints favoring certain nucleotide substitutions appear to be imposed at the DNA level

UV Surface Environment of Earth-like Planets Orbiting FGKM Stars Through Geological Evolution

The UV environment of a host star affects the photochemistry in the atmosphere, and ultimately the surface UV environment for terrestrial planets and therefore the conditions for the origin and evolution of life. We model the surface UV radiation environment for Earth-sized planets orbiting FGKM stars at the 1AU equivalent distance for Earth through its geological evolution. We explore four different types of atmospheres corresponding to an early Earth atmosphere at 3.9 Gyr ago and three atmospheres covering the rise of oxygen to present day levels at 2.0 Gyr ago, 0.8 Gyr ago and modern Earth (Following Kaltenegger et al. 2007). In addition to calculating the UV flux on the surface of the planet, we model the biologically effective irradiance, using DNA damage as a proxy for biological damage. We find that a pre-biotic Earth (3.9 Gyr ago) orbiting an F0V star receives 6 times the biologically effective radiation as around the early Sun and 3520 times the modern Earth-Sun levels. A pre-biotic Earth orbiting GJ 581 (M3.5V) receives 300 times less biologically effective radiation, about 2 times modern Earth-Sun levels. The UV fluxes calculated here provide a grid of model UV environments during the evolution of an Earth-like planet orbiting a range of stars. These models can be used as inputs into photo-biological experiments and for pre-biotic chemistry and early life evolution experiments.Comment: 10 pages, 5 figure

Effect of UV Radiation on the Spectral Fingerprints of Earth-like Planets Orbiting M dwarfs

We model the atmospheres and spectra of Earth-like planets orbiting the entire grid of M dwarfs for active and inactive stellar models with $T_{eff}$ = 2300K to $T_{eff}$ = 3800K and for six observed MUSCLES M dwarfs with UV radiation data. We set the Earth-like planets at the 1AU equivalent distance and show spectra from the VIS to IR (0.4$\mu$m - 20$\mu$m) to compare detectability of features in different wavelength ranges with JWST and other future ground- and spaced-based missions to characterize exo-Earths. We focus on the effect of UV activity levels on detectable atmospheric features that indicate habitability on Earth, namely: H$_2$O, O$_3$, CH$_4$, N$_2$O and CH$_3$Cl. To observe signatures of life - O$_2$/O$_3$ in combination with reducing species like CH$_4$, we find that early and active M dwarfs are the best targets of the M star grid for future telescopes. The O$_2$ spectral feature at 0.76$\mu$m is increasingly difficult to detect in reflected light of later M dwarfs due to low stellar flux in that wavelength region. N$_2$O, another biosignature detectable in the IR, builds up to observable concentrations in our planetary models around M dwarfs with low UV flux. CH$_3$Cl could become detectable, depending on the depth of the overlapping N$_2$O feature. We present a spectral database of Earth-like planets around cool stars for directly imaged planets as a framework for interpreting future lightcurves, direct imaging, and secondary eclipse measurements of the atmospheres of terrestrial planets in the HZ to design and assess future telescope capabilities.Comment: in press, ApJ (submitted August 18, 2014), 16 pages, 12 figure

Investigation of acceptor levels and hole scattering mechanisms in p-gallium selenide by means of transport measurements under pressure

The effect of pressure on acceptor levels and hole scattering mechanisms in p-GaSe is investigated through Hall effect and resistivity measurements under quasi-hydrostatic conditions up to 4 GPa. The pressure dependence of the hole concentration is interpreted through a carrier statistics equation with a single (nitrogen) or double (tin) acceptor whose ionization energies decrease under pressure due to the dielectric constant increase. The pressure effect on the hole mobility is also accounted for by considering the pressure dependencies of both the phonon frequencies and the hole-phonon coupling constants involved in the scattering rates.Comment: 13 pages, Latex, 4 ps figures. to appear in High Pressure Research 69 (1997

The connection between entropy and the absorption spectra of Schwarzschild black holes for light and massless scalar fields

We present heuristic arguments suggesting that if EM waves with wavelengths somewhat larger than the Schwarzschild radius of a black hole were fully absorbed by it, the second law of thermodynamics would be violated, under the Bekenstein interpretation of the area of a black hole as a measure of its entropy. Thus, entropy considerations make the well known fact that large wavelengths are only marginally absorbed by black holes, a natural consequence of thermodynamics. We also study numerically the ingoing radial propagation of a scalar field wave in a Schwarzschild metric, relaxing the standard assumption which leads to the eikonal equation, that the wave has zero spatial extent. We find that if these waves have wavelengths larger that the Schwarzschild radius, they are very substantially reflected, fully to numerical accuracy. Interestingly, this critical wavelength approximately coincides with the one derived from entropy considerations of the EM field, and is consistent with well known limit results of scattering in the Schwarzschild metric. The propagation speed is also calculated and seen to differ from the value $c$, for wavelengths larger than $R_{s}$, in the vicinity of $R_{s}$. As in all classical wave phenomena, whenever the wavelength is larger or comparable to the physical size of elements in the system, in this case changes in the metric, the zero extent 'particle' description fails, and the wave nature becomes apparent.Comment: 14 Pages, 4 figures. Accepted for publication in the Journal Entrop

Organic ambipolar semiconductors for TFT applications

In the last years we have devoted some effort to the search of new high-mobility semiconductors with ambipolar performances, good processability and environmental stability. Our approach, which is one of the most widely used, consists in the combination of donor and acceptor moieties in the conjugated skeleton, which allows fine tuning of the frontier molecular orbitals. For OTFT applications, low-lying HOMOs are essential to resist air oxidation and thus increase device stability. However, if the HOMO energy is too low, the resulting barrier to hole injection may compromise the transistor performance. Thus, a delicate balance between these two effects is needed. In particular, we have combined naphthaleneimide-derived moieties as electron accepting groups with electron-rich oligothiophene fragments. In these materials, we have found that the presence of ambipolar transport in these planar molecules can be understood on the basis of three interrelated properties: (i) the absence of skeletal distortions allows closer intermolecular pi-pi stacking and enhanced intramolecular pi-conjugation, (ii) increased pi-conjugation raises the HOMO energy, which approaches the Fermi level of common used electrodes; and (iii) more planar structures translate into lower Marcus reorganization energies. However, one of the limitations of these types of semiconductors is the presence of a molecular dipole moment, which forces the molecules to pack with pairwise intermolecular interactions orienting the naphthaleneimide cores in opposite directions, decreasing in some cases molecular orbitals overlapping. In recent contributions, we have devoted our efforts to analyze the effect of molecular interactions, through chemical modifications in order to induce parallel and antiparallel molecular packing, on the electronic properties of ambipolar semiconductors.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Neurotrophins Role in Depression Neurobiology: A Review of Basic and Clinical Evidence

Depression is a neuropsychiatric disorder affecting a huge percentage of the active population especially in developed countries. Research has devoted much of its attention to this problematic and many drugs have been developed and are currently prescribed to treat this pathology. Yet, many patients are refractory to the available therapeutic drugs, which mainly act by increasing the levels of the monoamines serotonin and noradrenaline in the synaptic cleft. Even in the cases antidepressants are effective, it is usually observed a delay of a few weeks between the onset of treatment and remission of the clinical symptoms. Additionally, many of these patients who show remission with antidepressant therapy present a relapse of depression upon treatment cessation. Thus research has focused on other possible molecular targets, besides monoamines, underlying depression. Both basic and clinical evidence indicates that depression is associated with several structural and neurochemical changes where the levels of neurotrophins, particularly of brain-derived neurotrophic factor (BDNF), are altered. Antidepressants, as well as other therapeutic strategies, seem to restore these levels. Neuronal atrophy, mostly detected in limbic structures that regulate mood and cognition, like the hippocampus, is observed in depressed patients and in animal behavioural paradigms for depression. Moreover, chronic antidepressant treatment enhances adult hippocampal neurogenesis, supporting the notion that this event underlies antidepressants effects. Here we review some of the preclinical and clinical studies, aimed at disclosing the role of neurotrophins in the pathophysiological mechanisms of depression and the mode of action of antidepressants, which favour the neurotrophic/neurogenic hypothesis

Understanding organic materials performance in field-effect transistors

Comunicación oralIn the last years, much of our effort has been devoted to the search and study of new high-mobility semiconductors for organic thin film transistors. The approach used for the materials design has been two-fold: (i) the combination of donor and acceptor moieties in the pi-conjugated skeleton, which allows fine tuning of the frontier molecular orbitals, being this necessary for achieving electron/hole or ambipolar transport and ambient stability; and (ii) rational selection of the type and positioning of specific solubilizing substituents ensuring processability, which is essential to make these materials scalable to industry. However, material processability should be attained minimizing a negative effect on charge transport. Therefore, proper energy levels, planar molecular conformations, close intermolecular pi-pi stacking and adequate thin film crystallinity need to be maintained upon alkyl substitution. In this communication, several examples of molecular and polymeric materials are shown. A rational design, guided by experimental and theoretical evidences, has prompted modifications on their conjugated skeletons, donor/acceptor subunits ratio and/or selection of proper alkyl solubilizing chains, which induce noticeable changes in their electronic performances. The main aim of these studies is the basic understanding of charge transport in organic materials. For this end, we will use Raman spectroscopy and DFT quantum-chemical calculations as important tools for materials characterization.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Echo Emission From Dust Scattering and X-Ray Afterglows of Gamma-Ray Bursts

We investigate the effect of X-ray echo emission in gamma-ray bursts (GRBs). We find that the echo emission can provide an alternative way of understanding X-ray shallow decays and jet breaks. In particular, a shallow decay followed by a "normal" decay and a further rapid decay of X-ray afterglows can be together explained as being due to the echo from prompt X-ray emission scattered by dust grains in a massive wind bubble around a GRB progenitor. We also introduce an extra temporal break in the X-ray echo emission. By fitting the afterglow light curves, we can measure the locations of the massive wind bubbles, which will bring us closer to finding the mass loss rate, wind velocity, and the age of the progenitors prior to the GRB explosions.Comment: 25 pages, 3 figures, 2 tables. Accepted for publication in Ap