Efeito do substituinte “-F” nas propriedades electrónicas e estruturais de fluoroquinolonas

Este estudo incide sobre as características que a presença do ião flúor em moléculas concede. Mais concretamente em fluoroquinolonas, antibióticos que cada vez são mais utilizados. Fez-se uma analise de vários parâmetros para obtermos informação sobre a interação fármaco-receptor nas fluoroquinolonas. Sendo para isso utilizadas técnicas de caracterização química computacional para conseguirmos caracterizar eletronicamente e estruturalmente (3D) as fluoroquinolonas em complemento aos métodos semi-empíricos utilizados inicialmente. Como é sabido, a especificidade e a afinidade para o sitio alvo, é essencial para eficácia de um fármaco. As fluoroquinolonas sofreram um grande desenvolvimento desde a primeira quinolona sintetizada em 1958, sendo que desde ai foram sintetizadas inúmeros derivados da mesma. Este facto deve-se a serem facilmente manipuladas, derivando fármacos altamente potentes, espectro alargado, factores farmacocinéticos optimizados e efeitos adversos reduzidos. A grande alteração farmacológica para o aumento do interesse neste grupo, foi a substituição em C6 de um átomo de flúor em vez de um de hidrogénio. Para obtermos as informações sobre a influência do ião flúor sobre as propriedades estruturais e electrónicas das fluoroquinolonas, foi feita uma comparação entre a fluoroquinolona com flúor em C6 e com hidrogénio em C6. As quatro fluoroquinolonas presentes neste estudo foram: ciprofloxacina, moxiflocacina, sparfloxacina e pefloxacina. As informações foram obtidas por programas informáticos de mecânica quântica e molecular. Concluiu-se que a presença de substituinte flúor não modificava de forma significativa a geometria das moléculas mas sim a distribuição da carga no carbono vicinal e nos átomos em posição alfa, beta e gama relativamente a este. Esta modificação da distribuição electrónica pode condicionar a ligação do fármaco ao receptor, modificando a sua actividade farmacológica.

An Analysis of the Implementation and Perceived Effectiveness of the SchoolMAX Family Portal

ABSTRACT Title of Document: AN ANALYSIS OF THE IMPLEMENTATION AND PERCEIVED EFFECTIVENESS OF THE SCHOOLMAX FAMILY PORTAL Warren Wesley Watts, Doctor of Education, 2015 Directed By: Margaret J. McLaughlin, Ph.D. Department of Counseling, Higher Education and Special Education School districts have spent millions of dollars implementing student information systems that offer family portals with web-based access to parents and students. One of the main purposes of these systems is to improve school-to-home communication. Research has shown that when school-to-home communication is implemented effectively, parent involvement improves and student achievement increases (Epstein, 2001). The purpose of the study was to (a) understand why parents used or refrained from using the family portal and (b) determine what barriers to use might exist. To this end, this descriptive study identified the information parent users accessed in the SchoolMAX family portal, determined how frequently parents accessed the portal, and ascertained whether parents perceived an increase in communication with their children about academic matters after they began accessing the portal. Finally, the study sought to identify whether barriers existed that prevented parents from using the family portal. The inquiry employed three data sources to answer the aforementioned queries. These sources included (a) a survey sent electronically to 19,108 parents who registered online for the SchoolMAX family portal; (b) SchoolMAX portal usage data from the student information system for system usage between January 1, 2015 and June 30, 2015; and (c) a paper survey sent to 691 parents of students that had never used the SchoolMAX family portal in one elementary school, one middle school and one high school that were representative of other schools in the district. Survey results indicated that parents at all grade levels used the family portal. Usage data also confirmed that approximately 19% of the students had parents who monitored their progress through the family portal. Usage data also showed that parents were monitoring approximately 25% of students in secondary schools (6th – 12th grade) and 16% of students in elementary schools. Of the wide menu of resources available through the SchoolMAX family portal, parents used three areas most frequently: attendance, daily grades, and report cards. Approximately 70% of parents responded that their communication had improved with their children about academic matters since they started using the SchoolMAX family portal, and 90% of parents responded that the SchoolMAX family portal was an effective or somewhat effective tool. Parents also expressed interest in the addition of additional information to the SchoolMAX family portal. Specifically, the top three additions parents wanted to see included homework assignments, high stakes test scores, and graduation requirements. Parents also reported that 92% of them spoke to their children at least 2 to 3 times per week about academics. Due to the low response rate of the parent non-user survey, potential barriers to using the SchoolMAX family portal could not be addressed in this study. However, this issue may be a useful research topic in a future study. Keywords: school to home communication, student information systems, family portal, parent portal

The Development of an On-line Submission and Peer Review System

Online submission and peer review is emerging as the next step forward for many journal publishers in an ever increasing drive to take advantage of technological improvements in transferring data electronically over the internet. The Electronic Submission and PEer REview (ESPERE) project was initiated in 1996 as an electronic Libraries (eLib) initiative of the Higher Education Funding Council for England (HEFCE). Subsequently the project continued as a self-funding group composed of a consortium of learned society and commercial journal publishers intent on utilising the changes in technology to improve the services they provide to their authors as well as cutting their costs and increasing efficiencies.

Linking electronic journals - Lessons from the Open Journal project

The Open Journal project has completed its three year period of funding by the UK Electronic Libraries (eLib) programme (Rusbridge 1998). During that time, the number of journals that are available electronically leapt from a few tens to a few thousand. Some of these journals are now developing the sort of features the project has been advocating, in particular the use of links within journals, between different primary journals, with secondary journals data, and to non-journal sources. Assessing the achievements of the project and considering some of the difficulties it faced, we report on the different approaches to linking that the project developed, and summarise the important user responses that indicate what works and what does not. Looking ahead, there are signs of change, not just to simple linking within journals but to schemes in which links are the basis of "distributed" journals, where information may be shared and documents built from different sources. The significance has yet to be appreciated, but this would be a major change from printed journals. If projects such as this and others have provided the initial impetus, the motivation for distributed journals comes, perhaps surprisingly, from within certain parts of the industry, as the paper shows.

CD-ROM Acrobat Journals Using Networks

The available technologies for publishing journals electronically are surveyed. They range from abstract representations, such as SGML, concerned largely with the structure of the document, to formats such as PostScript which faithfully model the layout and the appearance. The issues are discussed in the context of choosing a format for electronically publishing the journal: Electronic Publishing -- Origination, Dissemination and Design. PostScript is neither widely enough available nor standardised enough to be suitable; a bitmapped pages approach suffers from being resolution-dependent in terms of the visual quality achievable. Reasons are put forward for the final choice of Adobe s new PDF document standard for creating electronic versions of the journal.

Move, for string quartet, piano, percussion and electronics

MOVE is a composition for string quartet, piano, percussion and electronics of approximately 15-16 minutes duration in three movements. The work incorporates electronic samples either synthesized electronically by the composer or recorded from acoustic instruments. The work aims to use electronic sounds as an expansion of the tonal palette of the chamber group (rather like an extended percussion setup) as opposed to a dominating sonic feature of the music. This is done by limiting the use of electronics to specific sections of the work, and by prioritizing blend and sonic coherence in the synthesized samples. The work uses fixed electronics in such a way that allows for tempo variations in the music. Generally, a difficulty arises in that fixed “tape” parts don’t allow tempo variations; while truly “live” software algorithms sacrifice rhythmic accuracy. Sample pads, such as the Roland SPD-SX, provide an elegant solution. The latency of such a device is close enough to zero that individual samples can be triggered in real time at a range of tempi. The percussion setup in this work (vibraphone and sample pad) allows one player to cover both parts, eliminating the need for an external musician to trigger the electronics. Compositionally, momentum is used as a constructing principle. The first movement makes prominent use of ostinato and shifting meter. The second is a set of variations on a repeated harmonic pattern, with a polymetric middle section. The third is a type of passacaglia, wherein the bassline is not introduced right away, but becomes more significant later in the movement. Given the importance of visual presentation in the Internet age, the final goal of the project was to shoot HD video of a studio performance of the work for publication online. The composer recorded audio and video in two separate sessions and edited the production using Logic X and Adobe Premiere Pro. The final video presentation can be seen at geoffsheil.com/move.

Electronic Technology in NL Schools: An Environmental Scan, 2015-16

This study was designed to obtain information on the prevalence of electronic technology—in terms of availability and use—in classrooms in Newfoundland and Labrador. An online survey was developed and delivered electronically to a randomly chosen sample of 800 k-12 educators in Newfoundland & Labrador’s English School District during Winter, 2016. In total, 377 surveys were completed. Among other things, the findings showed that SMART Boards and iPads were receiving significant usage while the usage of computer labs and of various social media tools was not particularly high.

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.

Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.

Efeitos do exercício moderado prévio com oclusão vascular sobre a cinética da oferta e utilização do oxigênio em um exercício subsequente de alta intensidade

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Educação Física, Programa de Pós-Graduação Stricto-Sensu em Educação Física, 2015.

Genetic information and the workplace /

"January 20, 1997."

Design of a variable width pulse generator feasible for manual or automatic control

A variable width pulse generator featuring more than 4-V peak amplitude and less than 10-ns FWHM is described. In this design the width of the pulses is controlled by means of the control signal slope. Thus, a variable transition time control circuit (TTCC) is also developed, based on the charge and discharge of a capacitor by means of two tunable current sources. Additionally, it is possible to activate/deactivate the pulses when required, therefore allowing the creation of any desired pulse pattern. Furthermore, the implementation presented here can be electronically controlled. In conclusion, due to its versatility, compactness and low cost it can be used in a wide variety of applications.

Fictitious capital and the elusive quest in understanding its implications : illusions and paradoxes

This paper deals with the interaction between fictitious capital and the neoliberal model of growth and distribution, inspired by the classical economic tradition. Our renewed interest in this literature has a close connection with the recent international crisis in the capitalist economy. However, this discussion takes as its point of departure the fact that standard economic theory teaches that financial capital, in this world of increasing globalization, leads to new investment opportunities which improve levels of growth, employment, income distribution, and equilibrium. Accordingly, it is said that such financial resources expand the welfare of people and countries worldwide. Here we examine some illusions and paradoxes of such a paradigm. We show some theoretical and empirical consequences of this vision, which are quite different and have harmful constraints.

A diffuse reflectance comparative study of benzil inclusion within p-tert-butylcalix[n]arenes (n=4, 6, and 8) and silicalite

Diffuse reflectance and laser-induced techniques were used to access photochemical and photophysical processes of benzil in solid supports, namely p-tert-butylcalix[n]arenes with n = 4, 6, and 8. A comparative study was performed using these results and those obtained with another electronically inert support, silicalite, which is a hydrophobic zeolite. In the latter substrate, ground-state benzil has the two carbonyl groups in an s-trans planar conformation while in the calixarenes a distribution of conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. In all substrates, room-temperature phosphorescence was obtained in air-equilibrated samples. The decay times vary greatly and the largest lifetime was obtained for benzil/p-tert-butylcalix[6]arene, showing that this host cavity well accommodates benzil, enhancing its room-temperature phosphorescence. p-tert-Butylcalix[6] and [8]arene molecules provide larger hydrophobic cavities than silicalite, and inclusion complexes are formed with these hosts and benzil as guest; p-tert-butylcalix[4]arene does not include benzil. This probe is deposited outside the calix[41 cavity, in the form of microcrystals. Triplet-triplet absorption of benzil was detected in all cases and is predominant in the silicalite channel inclusion case. Benzil ketyl radical formation occurs with inclusion in calix[6]arene and calix[8]arene. In the three cases, benzoyl radical was detected at long times (in the millisecond time scale). Product analysis and identification clearly show that the main detected degradation photoproducts in all substrates are benzoyl radical derivatives. Calix[6] and [8]arenes are able to supply hydrogen atoms that allow also another reaction, the reduction to benzoin through benzil ketyl radical formation.

Comparison of fracture rates between indigenous and non-indigenous populations: a systematic review protocol

INTRODUCTION: Over recent years, there has been concerted effort to 'close the gap' in the disproportionately reduced life expectancy and increased morbidity experienced by indigenous compared to non-indigenous persons. Specific to musculoskeletal health, some data suggest that indigenous peoples have a higher risk of sustaining a fracture compared to non-indigenous peoples. This creates an imperative to identify factors that could explain differences in fracture rates. This protocol presents our aim to conduct a systematic review, first, to determine whether differences in fracture rates exist for indigenous versus non-indigenous persons and, second, to identify any risk factors that might explain these differences.

METHODS AND ANALYSIS: We will conduct a systematic search of PubMed, OVID, MEDLINE, CINAHL and EMBASE to identify articles that compare all-cause fracture rates at any skeletal site between indigenous and non-indigenous persons of any age. Eligibility of studies will be determined by 2 independent reviewers. Studies will be assessed for methodological quality using a previously published process. We will conduct a meta-analysis and use established statistical methods to identify and control for heterogeneity where appropriate. Should heterogeneity prevents numerical syntheses, we will undertake a best-evidence analysis to determine the level of evidence for differences in fracture between indigenous and non-indigenous persons.

ETHICS AND DISSEMINATION: This systematic review will use published data; thus, ethical permissions are not required. In addition to peer-reviewed publication, findings will be presented at (inter)national conferences, disseminated electronically and in print, and will be made available to key country-specific decision-makers with authority for indigenous health.