Copper(II) complexes with unsymmetrical pentadentate ed3a-type diamino-tricarboxylate ligands. Crystal structures, configurational analysis and DFT study of complexes

The O–O–N–N–O-type pentadentate ligands H3ed3a, H3pd3a and H3pd3p (H3ed3a stands ethylenediamine-N,N,N′-triacetic acid; H3pd3a stands 1,3-propanediamine-N,N,N′-triacetic acid and H3pd3p stands 1,3-propanediamine-N,N,N′-tri-3-propionic acid) and the corresponding novel octahedral or square-planar/trigonal-bipyramidal copper(II) complexes have been prepared and characterized. H3ed3a, H3pd3a and H3pd3p ligands coordinate to copper(II) ion via five donor atoms (three deprotonated carboxylate atoms and two amine nitrogens) affording octahedral in case of ed3a3− and intermediate square-pyramidal/trigonal-bipyramidal structure in case of pd3a3− and pd3p3−. A six coordinate, octahedral geometry has been established crystallographically for the [Mg(H2O)6][Cu(ed3a)(H2O)]2 · 2H2O complex and five coordinate square-pyramidal for the [Mg(H2O)5Cu(pd3a)][Cu(pd3a)] · 2H2O. Structural data correlating similar chelate Cu(II) complexes have been used for the better understanding the pathway: octahedral → square-pyramidal ↔ trigonal- bipyramid geometry. An extensive configuration analysis is discussed in relation to information obtained for similar complexes. The infra-red and electronic absorption spectra of the complexes are discussed in comparison with related complexes of known geometries. Molecular mechanics and density functional theory (DFT) programs have been used to model the most stable geometric isomer yielding, at the same time, significant structural data. The results from density functional studies have been compared with X-ray data.

Thinking in three dimensions: Exploring students' geometric thinking and spatial ability with the Geometer's Sketchpad

Current reform initiatives recommend that geometry instruction include the study of three-dimensional geometric objects and provide students with opportunities to use spatial skills in problem-solving tasks. Geometer's Sketchpad (GSP) is a dynamic and interactive computer program that enables the user to investigate and explore geometric concepts and manipulate geometric structures. Research using GSP as an instructional tool has focused primarily on teaching and learning two-dimensional geometry. This study explored the effect of a GSP based instructional environment on students' geometric thinking and three-dimensional spatial ability as they used GSP to learn three-dimensional geometry. For 10 weeks, 18 tenth-grade students from an urban school district used GSP to construct and analyze dynamic, two-dimensional representations of three-dimensional objects in a classroom environment that encouraged exploration, discussion, conjecture, and verification. The data were collected primarily from participant observations and clinical interviews and analyzed using qualitative methods of analysis. In addition, pretest and posttest measures of three-dimensional spatial ability and van Hiele level of geometric thinking were obtained. Spatial ability measures were analyzed using standard t-test analysis. ^ The data from this study indicate that GSP is a viable tool to teach students about three-dimensional geometric objects. A comparison of students' pretest and posttest van Hiele levels showed an improvement in geometric thinking, especially for students on lower levels of the van Hiele theory. Evidence at the p < .05 level indicated that students' spatial ability improved significantly. Specifically, the GSP dynamic, visual environment supported students' visualization and reasoning processes as students attempted to solve challenging tasks about three-dimensional geometric objects. The GSP instructional activities also provided students with an experiential base and an intuitive understanding about three-dimensional objects from which more formal work in geometry could be pursued. This study demonstrates that by designing appropriate GSP based instructional environments, it is possible to help students improve their spatial skills, develop more coherent and accurate intuitions about three-dimensional geometric objects, and progress through the levels of geometric thinking proposed by van Hiele. ^

Characterizing Internet worm spatial-temporal infection structures

Since the Morris worm was released in 1988, Internet worms continue to be one of top security threats. For example, the Conficker worm infected 9 to 15 million machines in early 2009 and shut down the service of some critical government and medical networks. Moreover, it constructed a massive peer-to-peer (P2P) botnet. Botnets are zombie networks controlled by attackers setting out coordinated attacks. In recent years, botnets have become the number one threat to the Internet. The objective of this research is to characterize spatial-temporal infection structures of Internet worms, and apply the observations to study P2P-based botnets formed by worm infection. First, we infer temporal characteristics of the Internet worm infection structure, i.e., the host infection time and the worm infection sequence, and thus pinpoint patient zero or initially infected hosts. Specifically, we apply statistical estimation techniques on Darknet observations. We show analytically and empirically that our proposed estimators can significantly improve the inference accuracy. Second, we reveal two key spatial characteristics of the Internet worm infection structure, i.e., the number of children and the generation of the underlying tree topology formed by worm infection. Specifically, we apply probabilistic modeling methods and a sequential growth model. We show analytically and empirically that the number of children has asymptotically a geometric distribution with parameter 0.5, and the generation follows closely a Poisson distribution. Finally, we evaluate bot detection strategies and effects of user defenses in P2P-based botnets formed by worm infection. Specifically, we apply the observations of the number of children and demonstrate analytically and empirically that targeted detection that focuses on the nodes with the largest number of children is an efficient way to expose bots. However, we also point out that future botnets may self-stop scanning to weaken targeted detection, without greatly slowing down the speed of worm infection. We then extend the worm spatial infection structure and show empirically that user defenses, e.g. , patching or cleaning, can significantly mitigate the robustness and the effectiveness of P2P-based botnets. To counterattack, we evaluate a simple measure by future botnets that enhances topology robustness through worm re-infection.

Mapping Transnational Crime in El Salvador: New Trends and Lessons from Colombia

Since El Salvador’s civil war formally ended in 1992 the small Central American nation has undergone profound social changes and significant reforms. However, few changes have been as important or as devastating as the nation’s emergence as a central hub in the transnational criminal “pipeline” or series of recombinant, overlapping chains of routes and actors that illicit organizations use to traffic in drugs, money weapons, human being, endangered animals and other products. The erasing of the once-clear ideological lines that drove the civil war and the ability of erstwhile enemies to join forces in criminal enterprises in the post-war period is an enduring and dangerous characteristic of El Salvador’s transnational criminal evolution. Trained, elite cadres from both sides, with few legitimate job opportunities, found their skills were marketable in the growing criminal structures. The groups moved from kidnapping and extortion to providing protection services to transnational criminal organizations to becoming integral parts of the organizations themselves. The demand for specialized military and transportation services in El Salvador have exploded as the Mexican DTOs consolidate their hold on the cocaine market and their relationships with the transportista networks, which is still in flux. The value of their services has risen dramatically also because of the fact that multiple Mexican DTOs, at war with each other in Mexico and seeking to physically control the geographic space of the lucrative pipeline routes in from Guatemala to Panama, are eager to increase their military capabilities and intelligence gathering capacities. The emergence of multiple non-state armed groups, often with significant ties to the formal political structure (state) through webs of judicial, legislative and administrative corruption, has some striking parallels to Colombia in the 1980s, where multiple types of violence ultimately challenged the sovereignty of state and left a lasting legacy of embedded corruption within the nation’s political structure. Organized crime in El Salvador is now transnational in nature and more integrated into stronger, more versatile global networks such as the Mexican DTOs. It is a hybrid of both local crime – with gangs vying for control off specific geographic space so they can extract payment for the safe passage of illicit products – and transnational groups that need to use that space to successfully move their products. These symbiotic relationships are both complex and generally transient in nature but growing more consolidated and dangerous.

Morfometria dos forames mandibular, mentual e infraorbital de Lobo-guará Chrysocyon brachyurus, Illiger, 1815 aplicada a bloqueios anestésicos

CHAPTER II - The Chrysocyon brachyurus is the biggest South American canid which has a high frequency of dental injuries, both in wild and captivity. Thus, veterinary procedures are necessary to preserve the feeding capacity of hundreds of captive specimens worldwide. The aim of this study was to study the mandibular morphometry of maned wolf with emphasis on the establishment of anatomic references to the anesthetic blockage of the inferior alveolar and mental nerves. Therefore, 15 measurements in 22 hemimandibles of C. brachyurus adults were taken. For extra-oral technique of blockage of the inferior alveolar nerve at the level of the mandibular foramen, it is stated that the needle should be advanced, close to the medial surface of the mandibular ramus, by 11.4 mm perpendiculary from the palpable concavity. Alternatively, the needle can be introduced for 30.4 mm from the angular process at 20-25 degrees angle with the ventral margin. For blocking only the mentual nerve, it is recommended the introduction of needle for 10 mm, close to the lateral aspect of the mandibular body, at the level of the lower first premolar. The mandibular foramen showed similars position, size and symmetry in the maned wolfs specimens examined. The comparison of the data with those available for other carnivores reflects the necessity for determining these anatomical references specifically for each species.

Finite element model updating of a RC building considering seismic response trends

Peer reviewed

Theoretical Study of Heteroatom Doping in Tuning the Catalytic Activity of Graphene for Triiodide Reduction

Graphene with heteroatom doping has found increasing applications in a broad range of catalytic reactions. However, the doping effects accounting for the enhanced catalytic activity still remain elusive. In this work, taking the triiodide electroreduction reaction as an example, we study systematically the intrinsic activity of graphene and explore the origin of doping-induced activity variation using first-principles calculations, in which two typical N and S dopants are tested. The most common graphene structures, basal plane, armchair edge, and zigzag edge, are considered, and it is found that the former two structures show a weak adsorption ability for the iodine atom (the key intermediate in the triiodide electroreduction reaction), corresponding to a low catalytic activity. Doping either N or S can strengthen the adsorption and thus increase the activity, and the codoping of N and S (NS-G) exhibits a synergistic effect. A detailed investigation into the whole process of the triiodide electroreduction reaction at the CH3CN/NS-G interface is also carried out to verify these activity trends. It is found that the zigzag edges which contain spin electrons show a relatively stronger adsorption strength compared with the basal plane and armchair edge, and initial doping would result in the spin disappearance that evidently weakens the adsorption; with the disappearance of spin, however, further doping can increase the adsorption again, suggesting that the spin electrons may play a preliminary role in affecting the intrinsic activity of graphene. We also analyzed extensively the origin of doping-induced adsorption enhancement of graphene in the absence of spin; it can be rationalized from the electronic and geometric factors. Specifically, N doping can result in a more delocalized “electron-donating area” to enhance I adsorption, while S doping provides a localized structural distortion, which activates the nearest sp2-C into coordinatively unsaturated sp3-C. These results explain well the improved activity of the doping and the synergistic effect of the codoping. The understandings are generalized to provide insight into the enhanced activity of the oxygen reduction reaction on heteroatom doped graphene. This work may be of importance toward the design of high-activity graphene based material.

Sigma models for genuinely non-geometric backgrounds

The existence of genuinely non-geometric backgrounds, i.e. ones without geometric dual, is an important question in string theory. In this paper we examine this question from a sigma model perspective. First we construct a particular class of Courant algebroids as protobialgebroids with all types of geometric and non-geometric fluxes. For such structures we apply the mathematical result that any Courant algebroid gives rise to a 3D topological sigma model of the AKSZ type and we discuss the corresponding 2D field theories. It is found that these models are always geometric, even when both 2-form and 2-vector fields are neither vanishing nor inverse of one another. Taking a further step, we suggest an extended class of 3D sigma models, whose world volume is embedded in phase space, which allow for genuinely non-geometric backgrounds. Adopting the doubled formalism such models can be related to double field theory, albeit from a world sheet perspective.

Isotope and fatty acid trends along continental shelf depth gradients: Inshore versus offshore hydrological influences on benthic trophic functioning

Anthropogenic activities and land-based inputs into the sea may influence the trophic structure and functioning of coastal and continental shelf ecosystems, despite the numerous opportunities and services the latter offer to humans and wildlife. In addition, hydrological structures and physical dynamics potentially influence the sources of organic matter (e.g., terrestrial versus marine, or fresh material versus detrital material) entering marine food webs. Understanding the significance of the processes that influence marine food webs and ecosystems (e.g., terrestrial inputs, physical dynamics) is crucially important because trophic dynamics are a vital part of ecosystem integrity. This can be achieved by identifying organic matter sources that enter food webs along inshore–offshore transects. We hypothesised that regional hydrological structures over wide continental shelves directly control the benthic trophic functioning across the shelf. We investigated this issue along two transects in the northern ecosystem of the Bay of Biscay (north-eastern Atlantic). Carbon and nitrogen stable isotope analysis (SIA) and fatty acid analysis (FAA) were conducted on different complementary ecosystem compartments that include suspended particulate organic matter (POM), sedimentary organic matter (SOM), and benthic consumers such as bivalves, large crustaceans and demersal fish. Samples were collected from inshore shallow waters (at ∼1 m in depth) to more than 200 m in depth on the offshore shelf break. Results indicated strong discrepancies in stable isotope (SI) and fatty acid (FA) compositions in the sampled compartments between inshore and offshore areas, although nitrogen SI (δ15N) and FA trends were similar along both transects. Offshore the influence of a permanently stratified area (described previously as a “cold pool”) was evident in both transects. The influence of this hydrological structure on benthic trophic functioning (i.e., on the food sources available for consumers) was especially apparent across the northern transect, due to unusual carbon isotope compositions (δ13C) in the compartments. At stations under the cold pool, SI and FA organism compositions indicated benthic trophic functioning based on a microbial food web, including a significant contribution of heterotrophic planktonic organisms and/or of SOM, notably in stations under the cold pool. On the contrary, inshore and shelf break areas were characterised by a microalgae-based food web (at least in part for the shelf break area, due to slope current and upwelling that can favour fresh primary production sinking on site). SIA and FAA were relevant and complementary tools, and consumers better medium- to long-term system integrators than POM samples, for depicting the trophic functioning and dynamics along inshore–offshore transects over continental shelves.

Advanced voxel-based CAD modelling for FSI simulations for automotive structures design

Additive Manufacturing (AM) is nowadays considered an important alternative to traditional manufacturing processes. AM technology shows several advantages in literature as design flexibility, and its use increases in automotive, aerospace and biomedical applications. As a systematic literature review suggests, AM is sometimes coupled with voxelization, mainly for representation and simulation purposes. Voxelization can be defined as a volumetric representation technique based on the model’s discretization with hexahedral elements, as occurs with pixels in the 2D image. Voxels are used to simplify geometric representation, store intricated details of the interior and speed-up geometric and algebraic manipulation. Compared to boundary representation used in common CAD software, voxel’s inherent advantages are magnified in specific applications such as lattice or topologically structures for visualization or simulation purposes. Those structures can only be manufactured with AM employment due to their complex topology. After an accurate review of the existent literature, this project aims to exploit the potential of the voxelization algorithm to develop optimized Design for Additive Manufacturing (DfAM) tools. The final aim is to manipulate and support mechanical simulations of lightweight and optimized structures that should be ready to be manufactured with AM with particular attention to automotive applications. A voxel-based methodology is developed for efficient structural simulation of lattice structures. Moreover, thanks to an optimized smoothing algorithm specific for voxel-based geometries, a topological optimized and voxelized structure can be transformed into a surface triangulated mesh file ready for the AM process. Moreover, a modified panel code is developed for simple CFD simulations using the voxels as a discretization unit to understand the fluid-dynamics performances of industrial components for preliminary aerodynamic performance evaluation. The developed design tools and methodologies perfectly fit the automotive industry’s needs to accelerate and increase the efficiency of the design workflow from the conceptual idea to the final product.

Understanding 3D structures from sketches

Sketches are a unique way to communicate: drawing a simple sketch does not require any training, sketches convey information that is hard to describe with words, they are powerful enough to represent almost any concept, and nowadays, it is possible to draw directly from mobile devices. Motivated from the unique characteristics of sketches and fascinated by the human ability to imagine 3D objects from drawings, this thesis focuses on automatically associating geometric information to sketches. The main research directions of the thesis can be summarized as obtaining geometric information from freehand scene sketches to improve 2D sketch-based tasks and investigating Vision-Language models to overcome 3D sketch-based tasks limitations. The first part of the thesis concerns geometric information prediction from scene sketches improving scene sketch to image generation and unlocking new creativity effects. The thesis proceeds showing a study conducted on the Vision-Language models embedding space considering sketches, line renderings and RGB renderings of 3D shape to overcome the use of supervised datasets for 3D sketch-based tasks, that are limited and hard to acquire. Following the obtained observations and results, Vision-Language models are applied to Sketch Based Shape Retrieval without the need of training on supervised datasets. We then analyze the use of Vision-Language models for sketch based 3D reconstruction in an unsupervised manner. In the final chapter we report the results obtained in an additional project carried during the PhD, which has lead to the development of a framework to learn an embedding space of neural networks that can be navigated to get ready-to-use models with desired characteristics.

Assessment Of The Fixation Of Mandibular Symphysis Fractures Using Conical Cannulated Screws: Mechanical And Photoelastic Tests.

The aim of this study was to use mechanical and photoelastic tests to compare the performance of cannulated screws with other fixation methods in mandibular symphysis fractures. Ten polyurethane mandibles were allocated to each group and fixed as follows: group PRP, 2 perpendicular miniplates; group PLL, 1 miniplate and 1 plate, parallel; and group CS, 2 cannulated screws. Vertical linear loading tests were performed. The differences between mean values were analyzed with the Tukey test. The photoelastic test was carried out using a polariscope. The results revealed differences between the CS and PRP groups at 1, 3, 5, and 10 millimeters of displacement. The photoelastic test confirmed higher stress concentration in all groups close to the mandibular base, whereas the CS group showed it throughout the region assessed. Conical cannulated screws performed well in mechanical and photoelastic tests.

Temporomandibular Dysfunction Post-craniotomy: Evaluation Between Pre- And Post-operative Status.

To identify risk factors associated with post-operative temporomandibular joint dysfunction after craniotomy. The study sample included 24 patients, mean age of 37.3 ± 10 years; eligible for surgery for refractory epilepsy, evaluated according to RDC/TMD before and after surgery. The primary predictor was the time after the surgery. The primary outcome variable was maximal mouth opening. Other outcome variables were: disc displacement, bruxism, TMJ sound, TMJ pain, and pain associated to mandibular movements. Data analyses were performed using bivariate and multiple regression methods. The maximal mouth opening was significantly reduced after surgery in all patients (p = 0.03). In the multiple regression model, time of evaluation and pre-operative bruxism were significantly (p < .05) associated with an increased risk for TMD post-surgery. A significant correlation between surgery follow-up time and maximal opening mouth was found. Pre-operative bruxism was associated with increased risk for temporomandibular joint dysfunction after craniotomy.

Focal Osteoporotic Bone Marrow Defect Mimicking A Mandibular Cystic Lesion.

An unusual presentation of a focal osteoporotic bone marrow defect (FOBMD) of the mandible mimicking a cystic lesion is documented. A definitive diagnosis could be established only on the basis of the histopathologic evaluation. A 66-year-old Brazilian woman was referred by her dentist for well-defined radiolucency of the mandibular molar region suggesting a cystic lesion of odontogenic origin. The computed tomography scan confirmed that the lesion did not affect the corticals. The biopsy confirmed the diagnosis of FOBMD. The diagnostic difficulty in the current case is obvious, because FOBMD, usually exhibiting an ill-defined radiolucency, is seldom suspected preoperatively when a differential diagnosis is considered for focal well-defined radiolucent areas in the jaws.

Infratentorial Gray Matter Atrophy And Excess In Primary Craniocervical Dystonia.

Primary craniocervical dystonia (CCD) is generally attributed to functional abnormalities in the cortico-striato-pallido-thalamocortical loops, but cerebellar pathways have also been implicated in neuroimaging studies. Hence, our purpose was to perform a volumetric evaluation of the infratentorial structures in CCD. We compared 35 DYT1/DYT6 negative patients with CCD and 35 healthy controls. Cerebellar volume was evaluated using manual volumetry (DISPLAY software) and infratentorial volume by voxel based morphometry of gray matter (GM) segments derived from T1 weighted 3 T MRI using the SUIT tool (SPM8/Dartel). We used t-tests to compare infratentorial volumes between groups. Cerebellar volume was (1.14 ± 0.17) × 10(2) cm(3) for controls and (1.13 ± 0.14) × 10(2) cm(3) for patients; p = 0.74. VBM demonstrated GM increase in the left I-IV cerebellar lobules and GM decrease in the left lobules VI and Crus I and in the right lobules VI, Crus I and VIIIb. In a secondary analysis, VBM demonstrated GM increase also in the brainstem, mostly in the pons. While gray matter increase is observed in the anterior lobe of the cerebellum and in the brainstem, the atrophy is concentrated in the posterior lobe of the cerebellum, demonstrating a differential pattern of infratentorial involvement in CCD. This study shows subtle structural abnormalities of the cerebellum and brainstem in primary CCD.