Electronic Structure and Spectro-Structural Correlations of Fe(III)Zn(II) Biomimetics for Purple Acid Phosphatases: Relevance to DNA Cleavage and Cytotoxic Activity

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(II)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(mu-OH)Zn(II)(L-H)](CIO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression align ad along the mu-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. Tie effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic struck ral information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2)<- Br <- H <- CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter a. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating CH3 groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

A concepção de Realeza Católica Visigoda e as ideias políticas de Isidoro de Sevilha

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The carbon footprint of ECLAC subregional headquarters for the Caribbean: Moving towards a climate neutral strategy

.--I. Introduction.--II. Methodology for estimating greenhouse gas emissions.--III. The carbon footprint of ECLAC- Port-of-Spain.--IV. Reducing greenhouse gas emissions: next steps

Brazilian adaptation of the Woodcock-Johnson III cognitive tests

An adaptation of the standard battery of Woodcock-Johnson III Tests of Cognitive Abilities (WJ-III) for Brazilian children and youth was investigated. The sample was composed of 1094 students (54 percent girls), ages 7-17, living in Sao Paulo state (91 percent). Items from Brazilian school books as well as from the WJ-III Spanish version (Bateria-R) were added to comprehension-knowledge tests. Brazilian words were adapted to the auditory tests according to syllabic division and stressed syllables. Items were examined through IRT and age differences through analysis of variance. Results indicated the need to remove items from all WJ-III subtests with the exception of the visual learning test. Analysis of Variance indicated significant age differences (p <= 0.001) for all tests. Thus, the importance of a Brazilian adaptation for the WJ-III was confirmed.

Synthesis and characterization of a diruthenium(II,III)-ketoprofen compound and study of the in vitro effects on CRC cells in comparison to the naproxen and ibuprofen derivatives

A new diruthenium(II,III) complex, of formula [Ru2Cl(ket)(4)], Ruket, containing the non-steroidal anti-inflammatory drug ketoprofen was synthesized and mainly characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis-IR electronic spectroscopy and FTIR and Raman vibrational spectroscopies. The four drug-carboxylato bridging ligands stabilize a Ru-2(II,III) mixed valent core in a paddlewheel type structure as confirmed by ESI mass spectra, electronic and vibrational spectroscopies and magnetic measurements. Ruket and the analogous compounds containing ibuprofen, Ruibp, and naproxen, Runpx, were tested for the biological effects in the human colon carcinoma cells HT-29 and Caco-2 expressing high and low levels of COX-2 respectively. All compounds only weakly affected the proliferation of the colorectal cancer cells HT-29 and Caco-2, and similarly only partially inhibited the production/activity of MMP-2 and MMP-9 by HT-29 cells, suggesting that COX-2 inhibition by these drugs can only partially be involved in the pharmacological effects of these derivatives. (c) 2012 Elsevier Ltd. All rights reserved.

Córdoban Discourses: A Drama of Interreligious Dialogue

SETTING: Cordoba, Spain, 1135 CE, 29th year of the reign of ‘Ali “amir al-muslimin,” second king of the Berber Almoravid dynasty, rulers of Moorish Spain from 1071 to 1147. Cordoba, the capital of Andalus and the center of the Almoravid holdings in Spain, is a bustling cosmopolitan center, a crossroads for Europe and the Middle East, and the meeting-point of three religious traditions. Most significantly, Cordoba at this time is the hub of European intellectual activity. From the square—itself impressively large and surrounded by a massive collonade, the regularity and ordered beauty of which typifies the Moorish taste for symmetry (so beloved of M.C. Escher)—can be seen the huge Cordoban mosque, erected in the 8th-century by Khalif Abd-er-Rahman I to the glory of Allah, oft forgiving, most merciful. It is the second largest building in Islam, and the bastion of the still entrenched but soon to fade Muslim presence in western Europe. SCENE: Three figures sit upon stone benches beneath the westernmost colonnade of the Cordoban mosque, involved in an animated, though friendly discussion on matters of faith and reason, knowledge and God, language and logic. The host is none other than Jehudah Halevi, and his esteemed guests Master Peter Abelard and the venerable Råmånuja, whose obviously advanced age belies his youthful voice, gleaming eye, quick hands, and general exuberance. It is autumn, early evening…

Clinical Use of Quantitative Computed Tomography–Based Advanced Techniques in the Management of Osteoporosis in Adults: the 2015 ISCD Official Positions—Part III

The International Society for Clinical Densitometry (ISCD) has developed new official positions for the clinical use of computed tomography (CT) scans acquired without a calibration phantom, for example, CT scans obtained for other diagnosis such as colonography. This also addresses techniques suggested for opportunistic screening of osteoporosis. The ISCD task force for quantitative CT reviewed the evidence for clinical applications of these new techniques and presented a report with recommendations at the 2015 ISCD Position Development Conference. Here we discuss the agreed upon ISCD official positions with supporting medical evidence, rationale, controversy, and suggestions for further study. Advanced techniques summarized as statistical parameter mapping methods were also reviewed. Their future use is promising but the clinical application is premature. The clinical use of QCT of the hip is addressed in part I and of finite element analysis of the hip and spine in part II.

Collecting the Painted Netherlands: The Art Collection of Ernest of Austria in Brussels

The (art) collection of Archduke Ernest of Austria (1553-1595) is widely unknown when it comes to early-modern Habsburg collections. Ernest, younger brother of Emperor Rudolf II (b. 1552) and educated at the Madrid court, was appointed Governor-General of the Netherlands by King Philip II of Spain, his uncle, in summer 1593. Ernest relocated his court from Vienna to Brussels in early 1594 and was welcomed there with lavish festivities: the traditional Blijde Inkomst, Joyous Entry, of the new sovereign. Unfortunately, the archduke died in February 1595 after residing in Brussels for a mere thirteen months. This investigation aims to shed new light on the archduke and his short-lived collecting ambitions in the Low Countries, taking into account that he had the mercantile and artistic metropolis Antwerp in his immediate reach. I argue, that his collecting ambitions can be traced back to one specific occasion: Ernest’s Joyous Entry into Antwerp in June 1594. There the archduke received a series of six paintings of Pieter Bruegel the Elder (1525/30-1569) known as The Months (painted in 1565), hanging today in separate locations in Vienna, New York and Prague. These works of art triggered Ernest’s collecting ambitions and prompted him to focus mainly on works of art and artefacts manufactured at or traded within the Netherlands during the last eight months of his lifetime. Additionally, it will be shown that the archduke was inspired by the paintings’ motifs and therefore concentrated on acquiring works of art depicting nature and landscape scenes from the 1560s and 1590s. On the basis of the archduke’s recently published account book (Kassabuch) and of the partially published inventory of his belongings, it becomes clear that Ernest of Austria must be seen in line with the better-known Habsburg collectors and that his specific collection of “the painted Netherlands” can be linked directly to his self-fashioning as a rightful sovereign of the Low Countries.

Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.

An educational initiative between the Universidad Politécnica de Madrid and Spanish Young Generation in Nuclear (Jóvenes Nucleares): The Seminar of Nuclear Safety in Advanced Reactors

Jóvenes Nucleares (Spanish Young Generation in Nuclear, JJNN) is a non-profit organization and a commission of the Spanish Nuclear Society (SNE). The Universidad Politécnica de Madrid (Technical University of Madrid, UPM) is one of the most prestigious technical universities of Spain, and has a very strong curriculum in nuclear engineering training and research. Finishing 2009, JJNN and the UPM started to plan a new and first-of-a-kind Seminar in Nuclear Safety focused on the Advanced Reactors (Generation III, III+ and IV). The scope was to make a general description of the safety in the new reactors, comparing them with the built Generation II reactors from a technical point of view but simple and without the need of strong background in nuclear engineering to try to be interesting for the most number of people possible.

Impact of the Economic Recession on Toll Highway Concessions in Spain

After joining the European Union in 1986, Spain experienced steady economic growth that enabled the country to grow at a greater pace than other European countries. During this period, the government of Spain opted for major investments in public infrastructure by taking advantage both of the funding provided by the European Union and of several types of public-private-partnership (PPP) approaches. Within this framework, the government of Spain between 1996 and 2004 procured a series of toll highway concessions. These concessions entered into operation a few years before the global economic recession made itself felt in Spain. The concession contracts signed between the government and some private consortia allocated most of the risks (expropriation, construction, and traffic) to the private sector. In this paper the impact that the economic recession has had on the business performance of the concessionaires is assessed, and the effectiveness of the measures adopted by the government to help the concessionaire to avoid bankruptcy is analyzed. It was found that some of the guarantees offered by the legal framework to the concessionaires in case of bankruptcy are prompting an outcome that could negatively affect the users. In addition to that, some suggestions as to how to better allocate risk in toll highway concessions in the future are provided.

Information as a Key Tool for Rural Development. 25 Years of Experience in Spain

The lack of useful information has become a major obstacle that hinders the participation of the members of the community in the development process because they can not accurately perceive how their individual and/or collective action can influence their environment, and because of the lack of elements that support the decision-making processes. This article addresses these issues from the work carried out by the Association Instituto de Desarrollo Comunitario de Cuenca (IDC Cuenca) in the rural areas of this province of Spain for 25 years. The results show how the application of methodologies for the transmission of information tailored to each group of recipients in some aspects, enhances the participation of individuals.

Extreme pointer years in tree-ring records of central Spain as evidence of climatic events and the eruption of the Huaynaputina Volcano (Peru, 1600 AD)

The study of pointer years of numerous tree-ring chronologies of the central Iberian Peninsula (Sierra de Guadarrama) could provide complementary information about climate variability over the last 405 yr. In total, 64 pointer years have been identified: 30 negative (representing minimum growths) and 34 positive (representing maximum growths), the most significant of these being 1601, 1963 and 1996 for the negative ones, and 1734 and 1737 for the positive ones. Given that summer precipitation was found to be the most limiting factor for the growth of Pinus in the Sierra de Guadarrama in the second half of the 20th century, it is also an explanatory factor in almost 50% of the extreme growths. Furthermore, these pointer years and intervals are not evenly distributed throughout time. Both in the first half of the 17th and in the second half of 20th, they were more frequent and more extreme and these periods are the most notable for the frequency of negative pointer years in Central Spain. The interval 1600–1602 is of special significance, being one of the most unfavourable for tree growth in the centre of Spain, with 1601 representing the minimum index in the regional chronology. We infer that this special minimum annual increase was the effect of the eruption of Huaynaputina, which occurred in Peru at the beginning of 1600 AD. This is the first time that the effects of this eruption in the tree-ring records of Southern Europe have been demonstrated.

Seismic vulnerability analysis of wide-beam buildings in Spain

A number of short-to-mid height RC buildings with wide beams have been constructed in moderate-seismicity areas of Spain. The seismic behavior in the direction of the wide beams appears to be deficient because of low lateral strength, low ductility of the wide beams, big strut compressive forces inside the column-beam connections, and unreliable contribution of the spandrel zones of the wide beams. In the orthogonal direction, the behavior is worse since only the joists and the façade beams contribute to the lateral resistance. The objective is to assess the seismic capability of these structures; further research will involve proposing retrofit strategies. The research approach consists of selecting a number of representative buildings and evaluating their vulnerability by code-type, push-over and dynamic analyses. The cooperation of the masonry infill walls is accounted for. The main conclusion is that the seismic behavior of these buildings is inadequate in most of the situations.

GIS analysis for the study of rural depopulation: the Kingdom of Valencia (Tomas Lopez 1789)

One of the more aspects that have shaped the landscape is the human impact. The human impact has the clearest indicator of the density of settlements in a particular geographic region. In this paper we study all settlements shown on the map of the Kingdom of Valencia, Spain Geographic Atlas (AGE) of Tomas Lopez (1788), and their correspondence with the current ones. To meet this goal we have developed a specific methodology, the systematic study of all existing settlements in historical cartography. This will determine which have disappeared and which have been renamed. The material used has been the historical cartography of Tomas Lopez, part of the AGE (1789), the Kingdom of Valencia (1789), sheets numbers (78, 79, 80 and 81); Current mapping of the provinces of Alicante, Valencia, Castellon, Teruel, Tattagona and Cuenca; As main software ArcGis V.9.3. The steps followed in the methodology are as follows: 1. Check the scale of the maps. Analyze the possible use of a spherical earth model. 2. Geo-reference of maps with latitude and longitude framework. Move the historical longitude origin to the origin longitude of modern cartography. 3 Digitize of all population settlements or cities. 4 Identify historic settlements or cities corresponding with current ones. 5. If the maps have the same orientation and scale, replace the coordinate transformation of historical settlements with a new one, by a translation in latitude and longitude equal to the calculated mean value of all ancient map points corresponding to the new. 6. Calculation of absolute accuracy of the two maps, i.e. the linear distance between the points of both maps. 7 draw in the GIS, the settlements without correspondence, in the current coordinates, and with a circle of mean error of the sheet, in order to locate their current location. If there are actual settlements exist within this circle, they are candidates to be the searched settlements. We analyzed more than 2000 settlements represented in the Atlas of Tomas Lopez of the Kingdom of Valencia (1789), of which almost 14.5% have no correspondence with the existing settlements. The rural landscape evolution of the Valencia, oldest kingdom of Valencia, one can say that can be severely affected by the anthropization suffered in the period from 1789 to the present, since 70% of existing settlements actually have appeared after Tomas Lopez¿s cartography, dated on 1789