Study on the structure and vibrational spectra of efavirenz conformers using DFT: Comparison to experimental data

Efavirenz, (S)-6-chloro-4-(cyclopropylethynyl)-1,4-dihydro-4-(trifluoromethyl)-2H-3 ,1-benzoxazin-2-one, is an anti HIV agent belonging to the class of the non-nucleoside inhibitors of the HIV-1 virus reverse transcriptase. A systematic quantum chemical study of the possible conformations, their relative stabilities and vibrational spectra of efavirenz has been reported. Structural and spectral characteristics of efavirenz have been studied by vibrational spectroscopy and quantum chemical methods. Density functional theory (DFT) calculations for potential energy curve, optimized geometries and vibrational spectra have been carried out using 6-311++G(d,p) basis sets and B3LYP functionals. Based on these results, we have discussed the correlation between the vibrational modes and the crystalline structure of the most stable form of efavirenz. A complete analysis of the experimental infrared and Raman spectra has been reported on the basis of wavenumber of the vibrational bands and potential energy distribution. The infrared and the Raman spectra of the molecule based on OFT calculations show reasonable agreement with the experimental results. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. (C) 2011 Elsevier B.V. All rights reserved.

Intermolecular charge transfer and vibrational analysis of hydrogen bonding in acetazolamide

In the present work the structural and spectral characteristics of acetazolamide have been studied by methods of infrared, Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) employing B3LYP with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. Based on these results, we have discussed the correlation between the vibrational modes and the structure of the dimers of acetazolamide. The calculated vibrational spectra of three dimers of acetazolamide have been compared with observed spectra, and the assignment of observed bands was carried out using potential energy distribution. The observed spectra agree well with the values computed from the OFT. A comparison of observed and calculated vibrational spectra clearly shows the effect of hydrogen bonding. The frequency shifts observed for the different dimers are in accord with the hydrogen bonding in acetazolamide. Natural bond orbital (NBO) analyses reflect the charge transfer interaction in the individual hydrogen bond units and the stability of different dimers of acetazolamide. (C) 2012 Elsevier B.V. All rights reserved.

A Smooth Discretization Bridging Finite Element and Mesh-free Methods Using Polynomial Reproducing Simplex Splines

This work sets forth a `hybrid' discretization scheme utilizing bivariate simplex splines as kernels in a polynomial reproducing scheme constructed over a conventional Finite Element Method (FEM)-like domain discretization based on Delaunay triangulation. Careful construction of the simplex spline knotset ensures the success of the polynomial reproduction procedure at all points in the domain of interest, a significant advancement over its precursor, the DMS-FEM. The shape functions in the proposed method inherit the global continuity (Cp-1) and local supports of the simplex splines of degree p. In the proposed scheme, the triangles comprising the domain discretization also serve as background cells for numerical integration which here are near-aligned to the supports of the shape functions (and their intersections), thus considerably ameliorating an oft-cited source of inaccuracy in the numerical integration of mesh-free (MF) schemes. Numerical experiments show the proposed method requires lower order quadrature rules for accurate evaluation of integrals in the Galerkin weak form. Numerical demonstrations of optimal convergence rates for a few test cases are given and the method is also implemented to compute crack-tip fields in a gradient-enhanced elasticity model.

傅立叶分解法荧光层析成像

本文提出一种基于结构光照明和傅立叶分解方法的荧光层析成像技术，该技术首先将激发光的强度沿着光轴方向调制成余弦函数，然后用此激发光对样品作传统的二维扫描，在每一个扫描位置余弦函数的频率在一定的范围内扫描，同时一一对应地记录下所发出的荧光强度。只要对所纪录的荧光序列做一个简单的傅立叶变换，即可以得到此位置样品沿着光轴方向的荧光团分布。这样通过一个传统的二维扫描，就可以得到一个三维的阳样品分布。

Assessment of the Distribution and Abundance of Coastal Sharks in the U.S. Gulf of Mexico and Eastern Seaboard, 1995 and 1996

During 1995 and 1996, the National Marine Fisheries Service (NMFS), conducted pilot studies to develop survey methodology and a sampling strategy for assessment of coastal shark populations in the Gulf of Mexico and western North Atlantic. Longline gear similar to that used in the commercial shark fishery was deployed at randomly selected stations within three depth strata per 60 nautical mile gridf rom Brownsville, Tex. to Cape Ann, Mass. The survey methodology and gear design used in these surveys proved effective for capturing many of the small and large coastal sharks regulated under the auspices of the 1993 Fisheries Management Plan (FMP) for Sharks oft he Atlantic Ocean. Shark catch rates, species composition, and relative abundance documented in these pilot surveys were similar to those reported from observer programs monitoring commercial activities. During 78 survey days, 269 bottom longline sets were completed with 879 sharks captured.

Untrawlable Bottom in Shrimp Statistical Zones of the Northwest Gulf of Mexico

The Gulf of Mexico Fisheries Management Council tasked the National Marine Fisheries Service with determining the extent, if any, of loss oft rawlable bottom in the Gulf of Mexico based upon fishing industry concerns. There are approximately 31 million hectares in the 21 shrimp statistical zones in the Gulf, approximately 23 million hectares of waters that are <35 fathoms (where most shrimp trawling effort occurs), and approximately 11 million hectares in zones 10-21, <35f athoms, which were examined. There are 31,338 known hangs, snags, artificial reefs, hazards to navigation, oil rigs, and similar obstructions which cause trawling to be unfeasible in these zones. There are several refuge (i.e. untrawlable) areas associated with the Alabama Artificial Reefs. Conservatively assuming 1 hectare for each known obstruction, coupled with the known area of each refuge, the estimate of total untrawlable bottom in zones 10-21 less than 35 fathoms in the Gulf is 185,953 hectares, or roughly 1.7% of this total trawlable area. Sensitivity analysis demonstrated the robustness of this assumption, with a range of 0.3-4.3% possible. In specific shrimp zones, untrawlable area is much less than 1% except in zones 10 (26%) and 11(2.5%), both of which possess a refuge. Other than the implementation periods of these refugia, no temporal trends were detectable with respect to the amount of untrawlable bottom.

Observations of the 1992 U.S. Pelagic Pair Trawl Fishery in the Northwest Atlantic

Pelagic pair trawling for tuna, Thunnus spp., and swordfish, Xiphias gladius, was introduced in U.S. Northwest Atlantic waters in 1991. During autumn (October-November) of 1992 under the authority oft he Federal Atlantic Swordfish Regulations, the National Marine Fisheries Service placed observers aboard pelagic pair trawl vessels to document the catch, bycatch, discard, and gear used in this new fishery. The fishery is conducted primarily at night along shelf-edge waters from June to November. In late 1991, revised regulations restricted swordfish to bycatch in this fishery resulting in pelagic pair trawl vessels targeting tuna throughout 1992. Analyses of 1992 data indicate that albacore, T. alalunga, was the predominant species caught, although yellowfin tuna, T. albaeares, and bigeye tuna, T. obesus, were the preferred target species. Bycatch also included swordfish, large sharks, pelagic rays and other pelagic fishes, other tunas, and marine mammals.

Friction of sliding surfaces carrying adsorbed lubricant layers

In concentrated contacts the behaviour of lubricants is much modified by the high local pressures: changes can arise both from molecular ordering within the very thin film lubricant layers present at the interface as well as from the deposition on the component surfaces of more solid-like polymeric boundary layers. These 'third bodies' separating the solid surfaces may have rheological or mechanical properties very different from those observed in the bulk. Classical elasto-hydrodynamic theory considers the entrapped lubricant to exhibit a piezo-viscous behaviour while the conventional picture of more solid boundary lubricant layers views their shear strength r as being linearly dependent on local pressure p, so that T = TO + ap where TO and a are constants. If TO is relatively small, then the coefficient of friction \i = T Ip ~ a and so Amonton's laws are recovered. However, the properties of adsorbed or deposited surface films, or indeed other third bodies such as debris layers, may be more complex than this. A preliminary study has looked quantitatively at the influence of the pressure dependence of the shear strength of any surface layer on the overall friction coefficient of a contact which is made up of an array of asperities whose height varies in a Gaussian manner. Individual contact points may be elastic or plastic. The analysis results in plots of coefficient of friction versus the service or load parameter PIH&NRa where P is the nominal pressure on the contact, HS the hardness of the deforming surface, N the asperity density, R the mean radius of curvature of the asperities, and a is the standard deviation of their height distribution. In principle, any variation oft withp can be incorporated into the model; however, in this initial study we have used data on colloidal suspensions from the group at the Ecole Centrale de Lyon as well as examining the effect of functional relationships of somewhat greater complexity than a simple linear form. Results of the analysis indicate that variations in fj. are possible as the load is varied which depend on the statistical spread of behaviour at individual asperity contacts. The value of this analysis is that it attempts to combine the behaviour of films on the molecular scale with the topography of real engineering surfaces and so give an indication of the effects at the full-size or macro-scale that can be achieved by chemical or molecular surface engineering.

Lares de Infância e Juventude

Dissertação de Mestrado apresentada à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Serviço Social.

Just how controversial is evidential holism?

This paper is an examination of evidential holism, a prominent position in epistemology and the philosophy of science which claims that experiments only ever confirm or refute entire theories. The position is historically associated with W.V. Quine, and it is at once both popular and notorious, as well as being largely under-described. But even though there’s no univocal statement of what holism is or what it does, philosophers have nevertheless made substantial assumptions about its content and its truth. Moreover they have drawn controversial and important conclusions from these assumptions. In this paper I distinguish three types of evidential holism and argue that the most oft-cited and controversial thesis is entirely unmotivated. The other two theses are much overlooked, but are well-motivated and free from controversial implications.

Cracks and Fissures: Gower's Poetics on the Edge

This essay examines Gower's oft-discussed flexible or situational ethics with a focus on the way in which he positions his poems, especially the Confessio Amantis between several different elements. His multi-linguality has concerned readers for a long time, as have his idea of the "middle weie" and, more recently, the way in which he does not offer an overall fixed moral sense but rather focuses on the contradictions inherent in the human condition. The central thesis of the essay is that Gower uses all of these elements to create a poetic that is placed on the edge rather than in a commonplace centre. It is here that we can see cracks and fissures emerge in Gower's work, and it is here that we can begin to better understand his poetics.

A novel GUCY2D mutation, V933A, causes central areolar choroidal dystrophy

Purpose: To identify the genetic cause of central areolar choroidal dystrophy (CACD) in a large Northern Irish family.
Methods: We previously reported linkage of the locus for CACD in this family to an interval of approximately 5 cM on chromosome 17p13 flanked by polymorphic markers D17S1810 and CHLC GATA7B03. We undertook sequence capture, massively-parallel sequencing and computational alignment, base-calling and annotation to identify a causative mutation. Conventional sequencing was used to confirm the results.
Results: Deep sequencing identified a single-base substitution in guanylate cyclase 2D, membrane (retina-specific) (GUCY2D). The novel mutation segregated with the disease phenotype and resulted in substitution of valine by alanine at position 933, within the catalytic domain of the protein. It altered a motif that is strongly conserved in a large number of distantly related proteins across several species, and was predicted to have a damaging effect on protein activity.
Conclusion: Mutations in GUCY2D have previously been associated with dominant cone rod dystrophies (CORD6) and recessive forms of Leber's congenital amaurosis (LCA). This is the first report of GUCY2D mutation causing CACD and adds to our understanding of genotype-phenotype correlation in this heterogeneous group of choroidoretinal dystrophies.

Origin of extraordinarily high catalytic activity of Co3O4 and its morphological chemistry for CO oxidation at low temperature

Understanding and then designing efficient catalysts for CO oxidation at low temperature is one of the hottest topics in heterogeneous catalysis. Among the existing catalysts. Co3O4 is one of the most interesting systems: Morphology-controlled Co3O4 exhibits exceedingly high activity. In this study, by virtue of extensive density functional theory (OFT) calculations, the favored reaction mechanism in the system is identified. Through careful analyses on the energetics of elementary reactions on Co3O4(1 1 0)-A, Co3O4(1 1 0)-B, Co3O4(1 1 1) and Co3O4(1 0 0), which are the commonly exposed surfaces of Co3O4, we find the following regarding the relation between the activity and structure: (i) Co3+ is the active site rather than Co2+: and (ii) the three-coordinated surface oxygen bonded with three Co3+ may be slightly more reactive than the other two kinds of lattice oxygen, that is, the two-coordinated 0 bonded with one Co2+ and one Co3+ and the three-coordinated 0 bonded with one Co2+ and two Co3+. Following the results from Co3O4, we also extend the investigation to MnO2(1 1 0), Fe3O4(1 1 0), CuO(1 1 0) and CuO(1 1 1), which are the common metal oxide surfaces, aiming to understand the oxides in general. Three properties, such as the CO adsorption strength, the barrier of CO reacting with lattice 0 and the redox capacity, are identified to be the determining factors that can significantly affect the activity of oxides. Among these oxides, Co3O4 is found to be the most active one, stratifying all the three requirements. A new scheme to decompose barriers is introduced to understand the activity difference between lattice O-3c and O-2c on (1 1 0)-B surface. By utilizing the scheme, we demonstrate that the origin of activity variance lies in the geometric structures. (C) 2012 Elsevier Inc. All rights reserved.

In Deutschland mehr Vorbehalte gegenüber älteren Arbeitnehmern: ein deutsch-britischer Vergleich

Infolge steigender Lebenserwartung sowie sinkender Geburtenraten wird das Durchschnittsalter der Bevölkerung in den meisten Industrienationen in den kommenden 50 Jahren stark ansteigen. Zur gleichen Zeit scheidet nach wie vor die Mehrzahl älterer Arbeitnehmer vor Erreichen der gesetzlichen Altersgrenze aus dem Arbeitsmarkt aus. Dies hat sowohl negative Auswirkungen auf die Finanzierbarkeit sozialer Sicherungssysteme als auch langfristig auf die Verfügbarkeit qualifizierter Arbeitnehmer am Arbeitsmarkt. Nationale Regierungen verfolgen daher gegenwärtig verschiedene Maßnahmen mit dem Ziel, die Arbeitsmarktbeteiligung älterer Arbeitnehmer zu erhöhen (OECD 2006). Diese Maßnahmen werden jedoch zum Teil durch die Strategien des betrieblichen Personalmanagements konterkariert, die oft noch jugendzentristisch ausgeprägt sind und ältere Mitarbeiter bei Einstellung, Beförderung, Weiterbildung sowie bei Arbeitsplatz- und Arbeitszeitgestaltung direkt oder indirekt benachteiligen (Bellmann et al. 2003).

Soziale Gruppenarbeit als Alternative zur geschlossenen Unterbringung strafunmündiger Kinder

Wenn 12- bis 13-jährige Kinder mit diversen von ihnen begangenen Straftaten die Öffentlichkeit in Aufruhr versetzen, wird - besonders nach schweren Fällen - oft eine härtere Gangart gefordert. Doch längst nicht so viele Kinder, wie die Medien uns weis machen wollen, sind delinquent. Und anstatt zu fragen, ob und wie man problematischen Kindern und Jugendlichen bereits zu Beginn ihrer Jugendhilfekarrieren sinnvoll helfen kann, diskutiert die Politik über geschlossene Unterbringung und andere Formen strengerer Settings von sogenannten "Monsterkids". In dieser Diplomarbeit wird soziale Gruppenarbeit als Alternative diskutiert.