Separation of lanthanides and actinides(III) using tridentate benzimidazole, benzoxazole and benzothiazole ligands

The ability of new hydrophobic tridentate ligands based on 2,6-bis(benziinidazol-2-yl)pyridine, 2,6-bis(benzoxazol-2-yl)pyridine and 2,6-bis(benzothiazol-2-yl)pyridine to selectively extract americium(III) from europium(III) was measured. The most promising ligand-2,6-bis(benzoxazol-2-yl)-4-(2-decyl-1-tetradecyloxy)pyridine L-9 was found to give separation factors (SFAm/Eu) of up to 70 when used to extract cations from 0.02-0.10 M HNO3 into TPH in synergy with 2-bromodecanoic acid. Six structures of lanthanide complexes with 2,6-bis(benzoxazol-2-yl)pyridine L-6 were then determined to evaluate the types of species that are likely to be involved in the separation process. Three structural types were observed, namely [LnL(6)(NO3)(3)(H2O)2], 11-coordinate only for La, [LnL(6) (NO3)(3) (CH3CN)], 10-coordinate for Pr, Nd and Eu and [LnL(6) (NO3)(3)(H2O)], L 10-coordinate for Eu and Gd. Quantum Mechanics calculations were carried out on the tridentate ligands to elucidate the conformational preferences of the ligands in the free state and protonated and diprotonated forms and to assess the electronic properties of the ligands for comparison with other terdentate ligands used in lanthanide/actinide separation processes.

Solvent extraction and lanthanide complexation studies with new terdentate ligands containing two 1,3,5-triazine moieties

The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L-5) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D-Am/D-Eu separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO3. Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO3. In order to investigate the possible nature of the extracted species crystal structures of L-5 and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L-4) were also determined. The structure of L-5 shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L-5 is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L-4. The crystal structure of Yb(L-4)(NO3)(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L-4 and L-5 are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L-1) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L-4 and L-5 is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L-1 evolve from the presence of two adjacent nitrogen atoms in the triazine rings.

QSAR studies of multidentate nitrogen ligands used in lanthanide and actinide extraction processes

Quantitative structure activity relationships (QSARs) have been developed to optimise the choice of nitrogen heterocyclic molecules that can be used to separate the minor actinides such as americium(III) from europium(III) in the aqueous PUREX raffinate of nuclear waste. Experimental data on distribution coefficients and separation factors (SFs) for 47 such ligands have been obtained and show SF values ranging from 0.61 to 100. The ligands were divided into a training set of 36 molecules to develop the QSAR and a test set of 11 molecules to validate the QSAR. Over 1500 molecular descriptors were calculated for each heterocycle and the Genetic Algorithm was used to select the most appropriate for use in multiple regression equations. Equations were developed fitting the separation factors to 6-8 molecular descriptors which gave r(2) values of >0.8 for the training set and values of >0.7 for the test set, thus showing good predictive quality. The descriptors used in the equations were primarily electronic and steric. These equations can be used to predict the separation factors of nitrogen heterocycles not yet synthesised and/or tested and hence obtain the most efficient ligands for lanthanide and actinide separation. (C) 2003 Elsevier B.V. All rights reserved.

New bis(triazinyl) pyridines for selective extraction of americium(III)

New hydrophobic, tridentate nitrogen heterocyclic reagents (BATPs) such as 2,6-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[1,2,4]triazin-3-yl) pyridine (1) and 2,6-bis(9,9,10,10-tetramethyl-9,10-dihydro-1,2,4-triaza-anthrane-3-yl) pyridine (2) have been studied. I is resistant to hydrolysis in 3 M nitric acid, whereas 2 is resistant to both acid hydrolysis and radiolysis. The molecules are able to give significantly enhanced separations of americium(III) from an excess of europium(III) in nitric acid. Typically, for 1 D-Am = 500 and SFAm,/Eu = 5000 compared with D-Am = 30 and SFAm /Eu = 400 with the reference molecule 2,6-bis(isopropyl[1,2,4]triazin-3-yl) pyridine (7). In order to increase the stability of 1 and 2, the labile alpha-benzylic hydrogens that are present in 7 have been replaced by alkyl groups. Three molecules of 1 are able to enclose completely the coordination sphere of the M(III) in the crystal structure of [Y(1)(3)][Y(NO3)(5)]center dot NO3 center dot 2.5H(2)O.

The coordination chemistry of 1,2,4-triazinyl bipyridines with lanthanide(III) elements - implications for the partitioning of americium(III)

It has been established that 6-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2'-bipyridines (R,hemi-BTPs) have properties which are intermediate between those of the terpyridines and the bis(1,2,4-triazin-3-yl)pyridines (BTPs). However, they resemble the terpyridines much more closely than the BTPs. It has been shown that Et, hemi-BTP when dissolved in TPH-a dodecane-like solvent-is a selective reagent for the separation of americium(III) from europium(III). Solution NMR in acetonitrile largely confirmed the crystallographic results. There was no evidence for a 1 : 3 complex cation, or for significant differences between metal(III)-N distances for the pyridine and 1,2,4-triazine rings. Intramolecular hydrogen bonding plays a crucial role in the formation of metal coordination spheres, which explains the differences between the terpyridyl, R,hemi-BTPs and the BTPs. Protonation of the R,hemi-BTPs facilitates a conformational change which is necessary for complexation.

Design of a biomimetic skin for an octopus-inspired robot - Part II: Development of the skin artefact

In order to develop skin artefact for an octopus-inspired robot arm, which is designed to be able to elongate 60% of its original length, silicone rubber and knitted nylon sheet were selected to manufacture an artificial skin, due to their higher elastic strain and high flexibility. Tensile and scissors cutting tests were conducted to characterise the matrix and reinforcing materials and the skin artefact. Material properties of the individual and the composite materials were compared with the measured properties of real octopus skin presented in Part I. The Young’s modulus of the skin should be below 20 MPa and the elastic strain range should be over 60%. The fracture toughness should be at least 0.9 kJ·m−2. Tubes made of the skin artefact filled with liquid were tested to study volume change under deformation. Finite element analysis model was developed to simulate the material and arm structure under tensile loading. Results show that the skin artefact developed has similar mechanical properties as the real octopus skin and satisfies all the design specifications of the OCTOPUS robot.

Measurement of intrinsic properties of amyloid fibrils by the peak force QNM method

We report the investigation of the mechanical properties of different types of amyloid fibrils by the peak force quantitative nanomechanical (PF-QNM) technique. We demonstrate that this technique correctly measures the Young’s modulus independent of the polymorphic state and the cross-sectional structural details of the fibrils, and we show that values for amyloid fibrils assembled from heptapeptides, a-synuclein, Ab(1–42), insulin, b-lactoglobulin,lysozyme, ovalbumin, Tau protein and bovine serum albumin all fall in the range of 2–4 GPa.

Developing skin analogues for a robotic octopus

In order to fabricate a biomimetic skin for an octopus inspired robot, a new process was developed based on mechanical properties measured from real octopus skin. Various knitted nylon textiles were tested and the one of 10-denier nylon was chosen as reinforcement. A combination of Ecoflex 0030 and 0010 silicone rubbers was used as matrix of the composite to obtain the right stiffness for the skin-analogue system. The open mould fabrication process developed allows air bubble to escape easily and the artificial skin produced was thin and waterproof. Material properties of the biomimetic skin were characterised using static tensile and instrumented scissors cutting tests. The Young’s moduli of the artificial skin are 0.08 MPa and 0.13 MPa in the longitudinal and transverse directions, which are much lower than those of the octopus skin. The strength and fracture toughness of the artificial skin, on the other hand are higher than those of real octopus skins. Conically-shaped skin prototypes to be used to cover the robotic arm unit were manufactured and tested. The biomimetic skin prototype was stiff enough to maintain it conical shape when filled with water. The driving force for elongation was reduced significantly compared with previous prototypes.

Social connection and practice-dependence: some recent developments in the global justice literature

This review essay discusses two recent attempts to reform the framework in which issues of international and global justice are discussed: Iris Marion Young’s ‘social connection’ model and the practice-dependent approach, here exemplified by Ayelet Banai, Miriam Ronzoni and Christian Schemmel’s edited collection. I argue that while Young’s model may fit some issues of international or global justice, it misconceives the problems that many of them pose. Indeed, its difficulties point precisely in the direction of practice dependence as it is presented by Banai et al. I go on to discuss what seem to be the strengths of that method, and particularly Banai et al.’s defence of it against the common claim that it is biased towards the status quo. I also discuss Andrea Sangiovanni and Kate MacDonald’s contributions to the collection.

Skolmisslyckande - en fråga om vårt samhälles syn på människors värde? : Normer och värderingar i svensk skolmiljö

Denna didaktiskt inriktade C-uppsats i etik tar upp elevers skolmisslyckande satt i förhållande till skolans styrdokument, lärares yrkesetik samt vårt samhälles syn på människors värde. Syftet med uppsatsen är att utifrån Iris Marion Youngs teori kring förtryck samt Harald Ofstads teori kring styrka och svaghet, ur ett etiskt/moraliskt perspektiv, söka efter svar på följande frågeställningar: Kan elever i svensk skola anses vara förtryckta enligt Youngs teori om förtryck? Kan man inom svensk skola finna tendenser till ett sådant förakt för svaghet som Ofstad diskuterar? Vilka bakomliggande strukturella förklaringar kan man utifrån dessa teorier finna till varför vissa lärare i svensk skola medvetet eller omedvetet orsakar vissa elevers känsla av att vara kränkta, misslyckade och osynliggjorda såsom uppsatsens källmaterial påvisar? Metoden består av en etisk analys av kvalitativt empiriskt källmaterial. Källmaterialet, som bygger på delar av en doktorsavhandling i filosofi författad av Carina Henriksson, analyseras med hjälp av analysverktyg skapade utifrån Youngs teori kring förtryck samt Ofstads teori kring styrka och svaghet. Slutsatsen man kan dra utifrån analyserna visar att vissa elever i svensk skola kan anses vara förtryckta samt att man inom svensk skola kan finna tendenser till förakt för svaghet. Analyserna visar även att de bakomliggande strukturella förklaringar man kan finna till detta förtryck samt förakt för svaghet handlar om traditioner som genom historiens gång blivit allmänt vedertagna och därmed normativa, trots att de motsäger de etiska principer vårt samhälle sägs bygga på, principer man kan finna i bland annat skolans värdegrund samt lärares yrkesetiska principer.

Os formados pelas escolas estaduais de ensino médio e a demanda por ensino superior na cidade de São Paulo: uma análise exploratória dos fatores de escolha - 2007 a 2009

Apesar de serem muitas as análises sobre tendências do Ensino Superior no Brasil, sobre o nível de qualidade das instituições ou sobre políticas de cotas sociais ou raciais, são raras as investigações destinadas a melhor compreender a decisão pela busca do Ensino Superior por parte dos concluintes do Ensino Médio público. Trabalhos empíricos desenvolvidos com esse objetivo costumam focalizar indivíduos já em graduação, desconsiderando aqueles que poderiam buscar o Ensino Superior e não o fizeram. Na cidade de São Paulo, esse contingente representa 81% dos 123.000 concluintes do ensino médio, todos os anos. Este trabalho busca explorar fatores que expliquem a decisão pela busca do ensino superior a partir do perfil e grau de envolvimento da família, do desempenho escolar e da condição de trabalho dos componentes de uma amostra com 52 jovens que entre 2007 e 2009 terminaram o ensino médio em escolas estaduais da Capital. A contribuição desta pesquisa decorre da excepcional variedade de dados colecionados desses indivíduos, observados em dois anos distintos: 2007 e 2010, e dados secundários sobre seu histórico escolar e sobre a qualidade das escolas em que estudaram. Este trabalho exploratório foi ainda complementado com estudos de caso de seis indivíduos tomados em amostra, submetidos a uma entrevista em profundidade para observar outras possíveis informações relevantes para compreender a decisão pela busca ou não do ensino superior. Dentre as evidências colhidas, surpreendeu o fato que o desempenho em matemática dos indivíduos e a qualidade da escola onde estudaram não explicaram a busca por formação superior. Renda e escolaridade dos pais mostraram-se menos influentes que a posse de computador no domicílio. Da parte da família, a presença do pai e da mãe (biparentais) e com mais elevadas expectativas de escolarização dos filhos mostraram-se importantes indicadores pela busca de maior escolarização por parte dos filhos.

Terrores e mistérios da adolescência e juventude: uma análise da preferência dos jovens pela história de terror

Dividida em três blocos principais, a presente dissertação pretende apontar as relações entre o gosto da juventude pela história de terror e a Psicologia da Educação.

Anonimato e fama no reality show BBB 3

In the present work we make an incursion about the Reality Show, in a specific study of the program Big Brother 3 (BBB 3) approaching the question of Anonymity and Fame, though of its Narratives Strategic. We search to explain phenomenon of transformations of anonymous people in celebrities, showing all net of relationships established by the participants of BBB 3, during the together in the setting house, stage of the tram that tells the daily one of a group of youngs. Supported in concepts of it and Reality Show, the work is link the theories semiotic of means, proposal for Algirda Julien Greimas. We stand out strategies of the program, showing that they on the basis of structuralize elements fiction that stimulate and seduce the receiving public. How empirical reference, the work bases on the program Big Brother Brazil, shown for the Rede Globo de Televisão opened canal, in period of January 14 to April 01 of 2003. Ahead of the results gotten in analysis, we verify that BBB 3 is a format of reality and fiction. What although to create the effect of a hurt of real everything to show, its reality artificial, built principally for edition of the images

Tecendo os fios de rede: juventude e produção de si em projetos sociais.

The study is about youthful subjectivities in quarters, of the West Zone of Natal-RN, marked for lacks and contingencies that constitute the everyday life of the social existence of its young inhabitants. For this purpose the researchers selected two youth groups: the Association of Youths Constructing Dreams (in the quarter of Felipe Camarão) and Lelo Melodia Crew (Quarter of Guarapes). Both are articulated through the strategy of coalition in regional and national nets. The hypothesis is that inside the groups and nets new youthful citizens arises. That would be a change in the representation of poor youth: from 1980 s street children - young whose social stigma associated poverty and crime to late 1990 s kids of project (pointing their trajectory in social projects) or, in present days, called as young peripherals - for the enrollment in cultural movements, as the hip hop movement - These new young citizens are contributing to new social imagery significations on poor youths. The methodology encloses: a) focal group; b) participant research analyzing the making arts (ways to think, social daily practices, actions engaged in a diversity plans) of youth groups; c) life stories of some of the youngs produced in workshops; d) not structuralized interviews. d) several documents of the groups; e) local and national surveys. Results emphasize a feeling of opening to a project of autonomy in relation to a social system that leaves them in a situation of social precariousness. Conclusion remarks that such practices of the youthful groups through the art, leisure, sport and culture unfold politics effect so that can point innovative forms of politics participation on the part of this specific segment of poor youths of Brasilian country, although conflicts and paradoxes crosses individual citizens, youth groups and youth nets.

O emprego juvenil no limiar do século XXI :estudo a partir da RAIS e dos programas de inserção de jovens no mercado de trabalho de Natal/RN

This study received the title THE JUVENILE EMPLOYMENT IN THE THRESHOLD OF THE XXI CENTURY: study starting from RAIS and of the programs of youths' insert in the labor market of Natal/RN . It presents as main objective to investigate, starting from the officials data of the Ministério do trabalho e emprego - MTE and of the federal and state government programs, the evolution of the formal employment for youths and the difficulties that leads the success of the returned initiatives the youths' insert in the formal market of work in Brazil and in Rio Grande do Norte, in the period from 2000 to 2004. To accomplish the research, it prioritizes the study of the evolution of the formal employment starting from the data of the MTE as form of diagnosing the formal market of the juvenile work. Search a descriptive way to identify the first results of the programs Primeiro Emprego- PPE (federal) and Primeira Chance - PPC (state), to interpret and to identify the existent gaps among the proposal initial of those programs and the first results obtained in the city of Natal. The research has character no-probability and it applies closed questionnaires for youths assisted by the programs. Were interviewed the local representatives of PPE and PPC, besides representatives of the organized civil society all through open structured interview, covering a total of 103 interviews. The results demonstrated that while PPC (state) obtained success inserting youngs, the PPE (federal) just got to insert 1,5% of the amount subsidized by the state program in Natal. That situation demonstrates a clear preference of the companies for PPC (state), in detriment of the federal program