Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

A Study of Single Stage Semi‐Dry Anaerobic Digestion of Organic Fraction of Municipal Solid Waste

Solid waste generation is a natural consequence of human activity and is increasing along with population growth, urbanization and industrialization. Improper disposal of the huge amount of solid waste seriously affects the environment and contributes to climate change by the release of greenhouse gases. Practicing anaerobic digestion (AD) for the organic fraction of municipal solid waste (OFMSW) can reduce emissions to environment and thereby alleviate the environmental problems together with production of biogas, an energy source, and digestate, a soil amendment. The amenability of substrate for biogasification varies from substrate to substrate and different environmental and operating conditions such as pH, temperature, type and quality of substrate, mixing, retention time etc. Therefore, the purpose of this research work is to develop feasible semi-dry anaerobic digestion process for the treatment of OFMSW from Kerala, India for potential energy recovery and sustainable waste management. This study was carried out in three phases in order to reach the research purpose. In the first phase, batch study of anaerobic digestion of OFMSW was carried out for 100 days at 32°C (mesophilic digestion) for varying substrate concentrations. The aim of this study was to obtain the optimal conditions for biogas production using response surface methodology (RSM). The parameters studied were initial pH, substrate concentration and total organic carbon (TOC). The experimental results showed that the linear model terms of initial pH and substrate concentration and the quadratic model terms of the substrate concentration and TOC had significant individual effect (p < 0.05) on biogas yield. However, there was no interactive effect between these variables (p > 0.05). The optimum conditions for maximizing the biogas yield were a substrate concentration of 99 g/l, an initial pH of 6.5 and TOC of 20.32 g/l. AD of OFMSW with optimized substrate concentration of 99 g/l [Total Solid (TS)-10.5%] is a semi-dry digestion system .Under the optimized condition, the maximum biogas yield was 53.4 L/kg VS (volatile solid).. In the second phase, semi-dry anaerobic digestion of organic solid wastes was conducted for 45 days in a lab-scale batch experiment for substrate concentration of 100 g/l (TS-11.2%) for investigating the start-up performances under thermophilic condition (50°C). The performance of the reactor was evaluated by measuring the daily biogas production and calculating the degradation of total solids and the total volatile solids. The biogas yield at the end of the digestion was 52.9 L/kg VS for the substrate concentration of 100 g/l. About 66.7% of volatile solid degradation was obtained during the digestion. A first order model based on the availability of substrate as the limiting factor was used to perform the kinetic studies of batch anaerobic digestion system. The value of reaction rate constant, k, obtained was 0.0249 day-1. A laboratory bench scale reactor with a capacity of 36.8 litres was designed and fabricated to carry out the continuous anaerobic digestion of OFMSW in the third phase. The purpose of this study was to evaluate the performance of the digester at total solid concentration of 12% (semi-dry) under mesophlic condition (32°C). The digester was operated with different organic loading rates (OLRs) and constant retention time. The performance of the reactor was evaluated using parameters such as pH, volatile fatty acid (VFA), alkalinity, chemical oxygen demand (COD), TOC and ammonia-N as well as biogas yield. During the reactor’s start-up period, the process is stable and there is no inhibition occurred and the average biogas production was 14.7 L/day. The reactor was fed in continuous mode with different OLRs (3.1,4.2 and 5.65 kg VS/m3/d) at constant retention time of 30 days. The highest volatile solid degradation of 65.9%, with specific biogas production of 368 L/kg VS fed was achieved with OLR of 3.1 kg VS/m3/d. Modelling and simulation of anaerobic digestion of OFMSW in continuous operation is done using adapted Anaerobic Digestion Model No 1 (ADM1).The proposed model, which has 34 dynamic state variables, considers both biochemical and physicochemical processes and contains several inhibition factors including three gas components. The number of processes considered is 28. The model is implemented in Matlab® version 7.11.0.584(R2010b). The model based on adapted ADM1 was tested to simulate the behaviour of a bioreactor for the mesophilic anaerobic digestion of OFMSW at OLR of 3.1 kg VS/m3/d. ADM1 showed acceptable simulating results.

Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation

A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions

A novel copper(I) complex that is a monomeric single helix in solid state but a dimeric double helix in solution

Single helical [(CuL)-L-I]ClO4.12CH(2)Cl(2) (L=1:2 condensate of benzil dihydrazone and 2-acetylpyridine) unfolds and coils up in CH2Cl2 solution to generate double helical [(Cu2L2)-L-I](2+).

A fluxional (CuN2O2)-N-I core: binding of a keto oxygen atom to Cu-I and Ag-I

[Cu(2-acetylpyridine)(2)]ClO4 (1), characterised here, has a novel Cu'N202 core in the solid state. Variable-temperature H-1 NMR studies show that the two chelate rings open up in solution at room temperature and the keto oxygen atoms dangle freely. As the temperature is lowered, the 0 atoms tend to bind to the metal atom. The corresponding silver(I) complex, [Ag(2-acetylpyridine)2]ClO4 (4), characterised by single-crystal X-ray crystallography, has an (AgN2)-N-I core in the solid state as well as in solution. Thus, while 1 is fluxional, 4 is not. In cyclic voltammetry, complex 1 displays a quasireversible Cu-II/I couple with a half-wave potential of 0.40 V vs. SCE. Complex I is easily oxidised by air and H2O2 in methanol to give rise to a dinuclear copper(II) complex where the ligand framework is not simple acetylpyridine. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Nanozipper formation in the solid state from a self-assembling tripeptide with a single tryptophan residue

The self-assembly of a terminally protected tripeptide Boc-gamma-Abu(1)-Ala(2)-Trp(3)-OMe (gamma-Abu = gamma-aminobutyric acid) I results in the formation of a nanostructured supramolecular zipper through various non-covalent interactions in the crystal in which the indole side-chain of the Trp(3) residue plays a key role via N-H...pi interactions. (c) 2006 Published by Elsevier Ltd.

Resting-state functional connectivity following a single dose treatment with CB1 neutral antagonist tetrahydrocannabivarin (THCv) in healthy volunteers

BACKGROUND: The cannabinoid cannabinoid type 1 (CB1) neutral antagonist tetrahydrocannabivarin (THCv) has been suggested as a possible treatment for obesity, but without the depressogenic side-effects of inverse antagonists such as Rimonabant. However, how THCv might affect the resting state functional connectivity of the human brain is as yet unknown. METHOD: We examined the effects of a single 10mg oral dose of THCv and placebo in 20 healthy volunteers in a randomized, within-subject, double-blind design. Using resting state functional magnetic resonance imaging and seed-based connectivity analyses, we selected the amygdala, insula, orbitofrontal cortex, and dorsal medial prefrontal cortex (dmPFC) as regions of interest. Mood and subjective experience were also measured before and after drug administration using self-report scales. RESULTS: Our results revealed, as expected, no significant differences in the subjective experience with a single dose of THCv. However, we found reduced resting state functional connectivity between the amygdala seed region and the default mode network and increased resting state functional connectivity between the amygdala seed region and the dorsal anterior cingulate cortex and between the dmPFC seed region and the inferior frontal gyrus/medial frontal gyrus. We also found a positive correlation under placebo for the amygdala-precuneus connectivity with the body mass index, although this correlation was not apparent under THCv. CONCLUSION: Our findings are the first to show that treatment with the CB1 neutral antagonist THCv decreases resting state functional connectivity in the default mode network and increases connectivity in the cognitive control network and dorsal visual stream network. This effect profile suggests possible therapeutic activity of THCv for obesity, where functional connectivity has been found to be altered in these regions.

Towards coherent optical control of a single hole spin: Rabi rotation of a trion conditional on the spin state of the hole

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Distribution of Rhodophyta in streams from São Paulo State, southeastern Brazil

Distribution of Rhodophyta was investigated in 172 stream segments, which were sampled from May to October in 1992-1993 and 1996-1997 in six natural regions (parts of biomes or geological areas) of São Paulo State, southeastern Brazil. Red algae occurred in 60.5 % of stream segments sampled, a high frequency in comparison with other major surveys in the world (18-65 %). 17 species of freshwater red algae were found, of which the most widespread was Batrachospermum delicatulum occurring in 17 sites of five regions. The proportion of morphological types was as follows: gelatinous filaments (62.5 %), free filaments (19 %), tufts (12.5 %) and crusts (6 %); all but free filaments can be considered as having mechanisms to tolerate stress provoked by current velocity. No significant difference was found between the frequency distributions of variables measured for all streams and for those with red algae. Rhodophyta occurred under the following conditions (means): temperature (19.0 degrees C), current velocity (48 cm s(-1)), specific conductance (74 mu S cm(-1)), turbidity (8 NTU), oxygen (67.3 %) and pH (6.9 +/- 0.7). on the basis of species composition among the regions, the following patterns were evident: 1) the number of red algal species per region ranged from 1 to 10; 2) the highest proportion of sites with red algae (65-73 %) was found in hard water regions and in Atlantic rainforest, whereas the lowest (50 %) was found in tropical rainforest; 3) more than half of the species were exclusive from a single region, whereas the higher proportion of exclusive species was in the subtropical rainforest (50 %). No combination of stream variables was clearly associated with the occurrence of red algae for the regions as a whole. Species composition for streams and rivers of São Paulo State revealed higher similarities with other tropical regions and had few species in common with freshwater red algal floras of other continents.

Role of oxygen vacancies in the magnetic and dielectric properties of the high-dielectric-constant system CaCu3Ti4O12: An electron-spin resonance study

We report experiments of electron spin resonance (ESR) of Cu2+ in polycrystalline samples of CaCu3Ti4O12 post-annealed in different atmospheres. After being synthesized by solid state reaction, pellets of CaCu3Ti4O12 were annealed for 24 h at 1000 degrees C under air, Ar or O-2. Our temperature dependent ESR data revealed for all samples nearly temperature independent g value (2.15(1)) and linewidth for T > T-N approximate to 25 K. However, the values of ESR linewidth are strongly affected by the oxygen content in the sample. For instance, argon post-annealed samples show a much larger linewidth than the O-2 or air post-annealed samples. We attribute this broadening to an increase of the dipolar homogeneous broadening of the Cu2+ ESR lines due to the presence of oxygen vacancies which induce an S=1/2 spin inside the TiO6 octahedra. Correlation between a systematic dependence of the ESR linewidth on the oxygen content and the high dielectric constant of these materials is addressed. Also, ESR, magnetic susceptibility, and specific heat data for a single crystal of CaCu3Ti4O12 and for polycrystals of CdCu3Ti4O12 are reported.

The Bauru Group: A continental Cretaceous unit in Brazil - Concepts based on micropaleontological, oxygen isotope and stratigraphical data

The integration of outcrop and subsurface information, including micropaleontological data, facies and sequence stratigraphic studies, and oxygen isotope analysis, allow us to present a new stratigraphic model for the Cretaceous continental deposits of the Bauru Group, Brazil. Thirty-eight fossil taxa were recovered from these deposits, including 29 species of ostracodes and 9 species of charophytes. Seven of these ostracode species and three subspecies are new and formally described here. The associations of Chara barbosai - Ilyocypris cf. riograndensis, found in the Adamantina Formation, and Amblyochara sp. - Neuquenocypris minor mineira nov. subsp., found in the Marília Formation. Ponte Alta Member, represent two distinct groups that are respectively Turonian-Santonian and Maastrichtian (probably Late Maastrichtian) in age. Therefore, a hiatus, encompassing more than 11 Ma, separates those two formations. From bottom to top, four depositional cycles were recognized in the Bauru Group in western São Paulo: cycles 1 and 2 belong to Caiuá Formation (fluvio-lacustrine and lacustrine deposits in the Presidente Prudente region), cycle 3 to the Santo Anastácio and lower Adamantina Formation (respectively fluvial and lacustrine deposits), and cycle 4 to the upper Adamantina Formation (fluvio-lacustrine facies). An erosional unconformity separates the Caiuá and Santo Anastácio Formations (between cycles 2 and 3). The Marília Formation is a distinct unit from the underlying succession; it does not occur in western São Paulo, but is found in restricted areas of São Paulo, Minas Gerais, Mato Grosso do Sul and Goiás States. During the deposition of the Bauru Group (Aptian? to Maastrichtian) the climate was hot and arid-semiarid. Shallow lakes underwent fluctuations in expansion (wet phases) and contraction (dry phases), as well as variations in salinity. During the deposition of the Adamantina Formation (Turonian-Santonian) there were long, dry periods that caused segmentation of large lakes (due to topographic irregularities in the basaltic substrate) and sometimes exposures of the lake floors; when flooded these lake floors were colonized by extensive meadows of single species of charophytes. Small ephemeral ponds, that were hydrochemically unstable and colonized by multiple species of charophytes, were the depositional sites for the marls and mudstones of Ponte Alta Member (Maastrichtian, Late Maastrichtian?). Our micropaleontological age control, combined with the Late Cretaceous ages of volcanic ashes found in the southeastern Brazil coastal basins, and the stratigraphic position of analcimites from the Jaboticabal-SP region, suggest a Late Coniacian-Santonian age for important magmatic events occurred in the interior of Brazil (north-central São Paulo State, Triângulo Mineiro, and southwestern Goiás State).

Using state-space techniques to represent frequency dependent single-phase lines directly in time domain

This paper proposes to use a state-space technique to represent a frequency dependent line for simulating electromagnetic transients directly in time domain. The distributed nature of the line is represented by a multiple 1t section network made up of the lumped parameters and the frequency dependence of the per unit longitudinal parameters is matched by using a rational function. The rational function is represented by its equivalent circuit with passive elements. This passive circuit is then inserted in each 1t circuit of the cascade that represents the line. Because the system is very sparse, it is possible to use a sparsity technique to store only nonzero elements of this matrix for saving space and running time. The model was used to simulate the energization process of a 10 km length single-phase line. ©2008 IEEE.

Integrated single-stage converters with Tri-state modulation suitable for photovoltaic systems

The aim of this work is to present two topological simplified converters named Tri-state Boost and Tri-state Buck-Boost integrated single-phase inverters. An important operation capability can be achieved for these converters using a Tri-state Modulation control scheme. This is the inductive power decoupling and the independent input output control. These features are directly related with the photovoltaic micro-converter needs, improving efficiency, cost and mainly lifetime. These features for the proposed modulation are confirmed through experimental results. © 2011 IEEE.

Tri-state single-phase integrated inverters with input to output power decoupling control

Researches on control for power electronics have looked for original solutions in order to advance renewable resources feasibility, specially the photovoltaic (PV). In this context, for PV renewable energy source the usage of compact, high efficiency, low cost and reliable converters are very attractive. In this context, two improved simplified converters, namely Tri-state Boost and Tri-state Buck-Boost integrated single-phase inverters, are achieved with the presented Tri-state modulation and control schemes, which guarantees the input to output power decoupling control. This feature enhances the field of single-phase PV inverters once the energy storage is mainly inductive. The main features of the proposal are confirmed with some simulations and experimental results. © 2012 IEEE.