Post-synthetic modification of metal–organic frameworks

Post-synthetic modification (PSM) of metal-organic frameworks encompassing the chemical transformation of the linker present is a promising new route for engineering optical centres and tuning the light emission properties of materials, both in the visible and in the near infrared (NIR) spectral regions. Here, PSM of isoreticular metal-organic framework-3 (IRMOF-3) with ethyl oxalyl monochloride, ethyl acetoacetate, pentane-2,4-dione, 3-(2- hydroxyphenyl)-3-oxopropanal, 2-chloroacetic acid, glyoxylic acid, methyl vinyl ketone and diethyl (ethoxymethylene)malonate followed by chelation of trivalent lanthanide ions afforded intriguing near infrared (Nd3+) and visible (Eu3+, Tb3+) light emitters. IRMOF-3 was used as a case in point due to both its highly porous crystalline structure and the presence of non-coordinating amino groups on the benzenedicarboxylate (bdc) linker amenable to modification. The materials were characterised by elemental analysis, powder X-ray diffraction, optical, scanning and transmission electron microscopy, Fourier transform infrared spectroscopy, and liquid and solid-state nuclear magnetic resonance. The solid-state luminescence properties of Ln-modified-IRMOF-3 were investigated at room temperature. The presence of the bdc aromatic ring, β– diketonate and oxalate enhanced the Ln3+ sensitization via ligand-to-metal energy transfer (anthena effect). As far as photocalysis is concerned, we have synthesized metal−organic frameworks (Cr-MIL-125-AC, Ag-MIL-125-AC) by a green method (solid–vapors reactions). The resulting functionalized materials show a photocatalytic activity for methylene blue degradation up to 6.52 times larger than that of the commercial photocatalyst hombikat UV-100. These findings open the door for further research for improving the photocatalytic performance of metal-organic frameworks.

Planning and design in postindustrial land transformation: east bank Arade river, Lagoa - case study

Tese de dout., Ciências e Tecnologias do Ambiente (Planeamento Urbano), Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2011

La transformation des pratiques professionnelles chez les enseignants du secondaire : analyse des effets de la participation aux cercles d'apprentissage et d'inclusion

Cette recherche poursuit l'objectif général d'analyser la transformation des pratiques professionnelles des enseignants du secondaire à l'égard des élèves en difficulté intégrés en classe régulière suite à leur participation au dispositif des cercles d'apprentissage et d'inclusion (CAI). La problématique met en évidence les changements de paradigmes associés aux multiples réformes du système de l'éducation et les difficultés auxquelles sont confrontés les enseignants depuis l'instauration de la nouvelle Politique de l'adaptation scolaire au Québec. Les nouvelles visées ministérielles prônent désormais une éducation de qualité pour tous. La notion d'équité est à la base des actions qui doivent guider les pratiques de l'école inclusive. Cependant, les écrits sur le sujet soulignent le manque de connaissances des enseignants pour adapter leurs pratiques professionnelles aux élèves en difficulté intégrés dans leur classe (Gaudreau, Legault, Brodeur, Hurteau, Dunberry, Séguin, Legendre, 2008; MacKay, 2006). Ces auteurs suggèrent à cet égard, la nécessité d'implanter dans les milieux des dispositifs de formation continue axés sur l'acquisition de connaissances quant aux processus d'apprentissage des élèves, aux pratiques pédagogiques différenciées et aux stratégies favorables aux apprentissages. La méthodologie utilisée s'inscrit dans une démarche de co-construction des savoirs. (Desmarais, Boyer et Dupont, 2005) avec des enseignants désireux de travailler sur l'amélioration de leurs pratiques professionnelles à l'égard des élèves en difficulté intégrés en classe régulière au secondaire. Ainsi, des groupes de réflexions portant sur l'analyse de l'expérience vécue par les enseignants ont permis d'offrir un accompagnement et un cadre défini pour la collecte de données (Boudreault et Kalubi, 2006). Des entrevues semi-dirigées ont complété notre collecte de données à la fin du projet afin de préciser et de nuancer les propos recueillis lors des groupes de réflexion. Les résultats obtenus nous ont permis d'identifier certaines conditions à mettre en place dans l'accompagnement des enseignants en exercice et de mieux comprendre les difficultés relatives à un tel dispositif.

Study of sewage sludge aimed at agricultural soil amendment by thermogravimetric analysis and fourier-transform infrared spectroscopy

Thermal degradation and gaseous products evolving from the pyrolysis of sewage sludge, aimed at agricultural soil amendment, were investigated using Thermogravimetric Analysis in conjunction with Fourier Transform Infrared Analysis (TG-FTIR). The materials were studied in temperatures ranging from 30 to 800 ºC. Furthermore infrared spectra of sewage sludge samples were performed as a complementary technique. In parallel the sewage sludge was spiked with ibuprofen in order to test whether the mentioned techniques are able to detect the drug. Thermal analysis showed the range of 200-400ºC as the most characteristic for weight loss, corresponding with the organic matter volatilization, while the range of 500-800ºC was also characteristic and due to the volatilization of carbonates. On the other hand, ibuprofen-spiking tests identified at temperature range (150-250ºC) where the compound totally volatilizes, therefore, in this work, the detection of ibuprofen by TGA was established for concentrations higher than 0.5 g/kg sludge, concentration 102 times higher than the concentrations measured by other authors in regular sewage sludge (Martín, et al., 2010). A correlation has been found between the ibuprofen concentrations in the sludge and the intensity of the absorption bands, both for FT-IR spectra at the maximum emission temperature for ibuprofen (232ºC) as for the FT-IR spectra of the non-pyrolyzed samples.

Die Bedeutung der neoliberalen Transformation des Arbeitsmarktes für das gegenwärtige Hochschulstudium

Vortrag an der Fakultät V der Fachhochschule Hannover am Mittwoch, den 19. Oktober 2011.

La cornée humaine, un modèle évitant la transformation tumorale induite par les rayons ultraviolets : étude comparant la fréquence d’induction de dommages à l’ADN, leur l’efficacité de réparation ainsi que la sensibilité à la mort cellulaire induite par les rayons ultraviolets entre la cornée et l’épiderme

Bien qu’ils soient exposés tous deux aux rayons ultraviolets (UVR) solaires, cette exposition génotoxique n’entraîne pas les mêmes conséquences dans l’oeil et la peau. Le rôle des rayons UV dans l’induction et la progression des cancers cutanés est bien démontré. Ces rayons génotoxiques sont absorbés par l’ADN. Ils y induisent ainsi des changements conformationnels pouvant mener à la formation de différents dommages. On retrouve de façon prédominante la liaison de pyrimidines adjacentes en dimères cyclobutyliques de pyrimidines (CPD). Ceux-ci causent les mutations signatures responsables des cancers de la peau induits par les UVR. Cependant, aucune évidence ne démontre l’existence de cancer induit par les UVR dans la cornée. Nous avons donc tenté de découvrir les mécanismes permettant à la cornée d’éviter la transformation tumorale induite par les UVR. L’irradiation d’yeux de lapins aux rayons UVB a permis de prouver la capacité de ces rayons à induire la formation de CPD, et ce, de la cornée jusqu’au cristallin. Par la suite, l’irradiation d’yeux humains aux trois types de rayons UV (UVA, B et C) a permis d’y établir leur patron d’induction de CPD. Nous avons ainsi démontré que l’épithélium cornéen est particulièrement sensible à l’induction de CPD, tous types de rayons UV confondus. Enfin, la comparaison de la quantité de dommages présents dans des échantillons de peaux et de cornées irradiées à la même dose d’UVB a permis de démontrer que l’épithélium cornéen est 3.4 fois plus sensible à l’induction de CPD que l’épiderme. Nous avons par la suite étudié les mécanismes de réponse à ce stress. L’analyse de la viabilité cellulaire à la suite d’irradiations à différentes doses d’UVB a révélé que les cellules de la cornée et de la peau ont la même sensibilité à la mort cellulaire induite par les UVR. Nous avons alors analysé la vitesse de réparation des dommages induits par les UVR. Nos résultats démontrent que les CPD sont réparés 4 fois plus rapidement dans les cellules de la cornée que de la peau. L’analyse des protéines de reconnaissance des dommages a révélé que les cellules de la cornée possèdent plus de protéines DDB2 que les cellules de la peau, et ce, surtout liées à la chromatine. Nous avons alors tenté d’identifier la cause de cette accumulation. Nos analyses révèlent que la cornée possède une moins grande quantité d’ARNm DDB2, mais que la demi-vie de la protéine y est plus longue. Enfin, nos résultats suggèrent que l’accumulation de DDB2 dans les cellules de la cornée est entre autres due à une demi-vie plus longue de la protéine. Cette forte présence de DDB2 dans les cellules de la cornée permettrait un meilleur balayage de l’ADN, faciliterait de ce fait la détection de CPD ainsi que leur réparation et contribuerait donc à la capacité de la cornée à éviter la transformation tumorale induite par les UVR.

New synthetic methodologies for the transformation of biomass derived intermediates to valuable molecules

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

Questioning the Universality of Institutional Transformation Theories in Spatial Planning: Shopping Mall Developments in Palermo

Theories about institutional transformation in spatial planning, although mainly based on the Anglo-Saxon context, have assumed a dominant role in planning research and theory as means to understand the transformations that have been restructuring planning systems in recent decades in the Western world and beyond. The article, looking at transformations of planning practice through the lenses of the concept of planning cultures, debates the utility of building ‘universal’ theories for spatial planning and advocates for the need for a de-provincialization of planning theories. This is done through a case-study approach applied to the history of the transformation of the retail system in a context characterized by the specificities of the Italian planning context and Southern European cities, namely: the planning processes for, and power relationships underlying, the first shopping malls opened in Palermo, Italy, since 2009 — some decades later than most of Western cities.

Transformation or bureaucratisation?: the changing role of community representation in local strategic partnerships in England

The debate about the need to build social capital and to engage local communities in public policy has become a central issue in many advanced liberal societies and developing countries. In many countries new forms of governance have emerged out of a growing realisation that representative democracy by itself is no longer sufficient. One of the most significant public policy trends in the UK has been the involvement of community organisations and their members in the delivery of national policy, mediated through local systems of governance and management. One such policy area is urban regeneration. Central government now requires local authorities in England to set up Local Strategic Partnerships (LSPs) to bring together stakeholders who can prepare Community Strategies and deliver social and economic programmes which target areas of deprivation. This paper reviews the key institutional processes which must be addressed, such as representation, accountability and transformation.

The challenge and response to global tourism in the post-modern era: the commodification, reconfiguration and mutual transformation of Habana Vieja, Cuba

There is a growing literature on the symbolic and cultural meanings of tourism and the ways in which cities are increasingly competing for tourists through the promotion of cultural assets and different forms of spectacle in the `tourist bubble'. To date, research on the role and impact of tourism in cities has largely been confined to those in Western, post-industrial economies. This paper examines the growth of cultural tourism in the central area of Havana, Cuba, and explores the range of unique, devolved, state-owned enterprises that are attempting to use tourism as a funding mechanism to achieve improvements in the social and cultural fabric of the city for the benefit of residents. The paper concludes with an assessment of the implications of this example for our understanding of how the pressures for restructuring and commodification can be moderated at the city level. Copyright 2008 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.

An extensible complex fast Fourier transform processor chip for real-time spectrum analysis and measurement

This paper describes in detail the design of a CMOS custom fast Fourier transform (FFT) processor for computing a 256-point complex FFT. The FFT is well-suited for real-time spectrum analysis in instrumentation and measurement applications. The FFT butterfly processor reported here consists of one parallel-parallel multiplier and two adders. It is capable of computing one butterfly computation every 100 ns thus it can compute a 256-point complex FFT in 102.4 μs excluding data input and output processes.

The transformation of landscape as as aesthetic idear

The present study seeks to thoroughly investigate and delineate the concept alongside the transformation of landscape as an aesthetic idea. On the one side it runs that nature perceived as landscape remains nothing else but granted, evident or 'natural'. On yet another side, and to some fairly significant extend, this thesis identifies landscape as a sheer idea and concept that is shaped and (re-)mediated in an ongoing process. The thesis examines the role of the observer and brings into agreement that every landscape is a produce of creative mental processes. In brief outline, this approach provides a framework for identifying landscape as being inextricably linked with media from the very beginning of their social and cultural inception. As glowing examples for the paradigmatic shift of the classical subjective vision model culminating in the emergence of a new prototype, the camera obscura, together with the panorama, fortify the prevailing argument that the mode of human sense perception is organised and determined by earlier acquainted recognitions. In this matter, as each and every medium strive after accomplishment, then this accomplishment is substantially determined by overwhelming historic, as well as thriving cultural circumstances. In conclusive terms, this study seeks to show how landscape counts as content of a representation, while simultaneously being a very own medium that specifically carries social, geological as well as historic knowledge. In fact, modern vision shall therefore never be bound to any single format or process, rather it will have to always undergo procedures aiming at reshaping the perceivable. Landscape is playing out its major characteristic, specifically that of being, in essence, a purely intellectual, virtual and synthetic product

A Novel Sub-Nyquist Fourier Transform Estimator Based on Alias-free Hybrid Stratified Sampling

This paper introduces a novel method of estimating theFourier transform of deterministic continuous-time signals from a finite number N of their nonuniformly spaced measurements. These samples, located at a mixture of deterministic and random time instants, are collected at sub-Nyquist rates since no constraints are imposed on either the bandwidth or the spectral support of the processed signal. It is shown that the proposed estimation approach converges uniformly for all frequencies at the rate N^−5 or faster. This implies that it significantly outperforms its alias-free-sampling-based predecessors, namely stratified and antithetical stratified estimates, which are shown to uniformly convergence at a rate of N^−1. Simulations are presented to demonstrate the superior performance and low complexity of the introduced technique.

Sociological Knowledge and Transformation at ‘Diversity University’, UK

This chapter is based on a case study of one UK university sociology department and shows how sociology knowledge can transform the lives of ‘non-traditional’ students. The research from which the case is drawn focused on four departments teaching sociology-related subjects in universities positioned differently in UK league tables. It explored the question of the relationship between university reputation, pedagogic quality and curriculum knowledge, challenging taken-for-granted judgements about ‘quality’ and in conceptualising ‘just’ university pedagogy by taking Basil Bernstein’s ideas about how ‘powerful’ knowledge is distributed in society to illuminate pedagogy and curriculum. The project took the view that ‘power’ lies in the acquisition of specific (inter)disciplinary knowledges which allows the formation of disciplinary identities by way of developing the means to think about and act in the world in specific ways. We chose to focus on sociology because (1) university sociology is taken up by all socio-economic classes in the UK and is increasingly taught in courses in which the discipline is applied to practice; (2) it is a discipline that historically pursues social and moral ambition which assists exploration of the contribution of pedagogic quality to individuals and society beyond economic goals; (3) the researchers teach and research sociology or sociology of education - an understanding of the subjects under discussion is essential to make judgements about quality. ‘Diversity’ was one of four case study universities. It ranks low in university league tables; is located in a large, multi-cultural English inner city; and, its students are likely to come from lower socio-economic and/or ethnic minority groups, as well as being the first in their families to attend university. To make a case for transformative teaching at Diversity, the chapter draws on longitudinal interviews with students, interviews with tutors, curriculum documents, recordings of teaching, examples of student work, and a survey. It establishes what we can learn from the case of sociology at Diversity, arguing that equality, quality and transformation for individuals and society are served by a university curriculum which is research led and challenging combined with pedagogical practices which give access to difficult-to-acquire and powerful knowledge.