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Made available in DSpace on 2017-07-21T18:15:32Z (GMT). No. of bitstreams: 1 DOUGLAS RUNDVALT.pdf: 2542992 bytes, checksum: 4af8944eae7b7b7858a293c2b9d5cc80 (MD5) Previous issue date: 2013-07-02 / The geo-historical importance of the Cold War to the present comes in the form of arms race generating dual technologies under the so-called military-industrial complex. Innovations in the U.S have provided the recovery of economic growth and hegemony in the decades of 1980-90. One of the ramifications of this militaryindustrial complex in the current times deal with the manipulation of biological beings to serve as weapons of war. At the beginning of the century. XXI, are witnessing the creation of a new enemy without a defined territory and no address to attack,international terrorism, elected as justification for continued investment in new military technologies. In this present study we demonstrate these new tactics developed within the National Security, which many private interests converged in the creation of Bioshield. Thence we define this new ramification of the MIC - complex militaryindustrial-biotech (CMIB), enabler of new profits from partnerships between military and civilians, and already tested in the case of global flu like pandemics. / A importância geohistórica da Guerra Fria nos chega até o presente na forma da corrida armamentista geradora de tecnologias duais no âmbito do que se convencionou chamar de complexo industrial-militar (CIM). As inovações no campo militar proporcionaram aos Estados Unidos a retomada do crescimento econômico e da hegemonia nas décadas de 1980-90. Uma das ramificações desse CIM nos tempos atuais lidam com a manipulação de seres biológicos para servirem como armas de guerra. No início do séc. XXI, presenciamos a criação de um novo inimigo sem território definido e sem endereço para atacar, o terrorismo internacional, eleito como justificativa para a continuidade de investimentos em novas tecnologias militares. Neste trabalho demonstramos essas novas táticas desenvolvidas no âmbito da Segurança Nacional, que convergiram diversos interesses privados na criação do Escudo de Biodefesa. Daí que definimos essa nova ramificação do CIM de complexo-industrial-militar-biotecnológico (CIMB), iabilizadora de novos lucros a partir de parcerias entre militares e civis, e já testada no caso das pandemias gripais globais.

Philosophiae Doctor - PhD / Electrochemiluminiscence, (ECL), is an electrochemically-induced process that leads to the generation of measurable luminescent signals at the electrode surface. The luminescent signals occur when electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light. Immobilization of the ECL luminophore on an electrode surface provides enhancement of ECL intensity. This work presents results of the feasibility study focused on the application of novel luminophores for electrochemiluminescence (ECL) sensors. The thesis mainly focuses on studying the ECL of polyanilinorutheniumbipyridyl- imidazo phenanthroline and carboxydifluoroboradiazaindancence luminophores. The influence of the synthetic methods on the electrochemical, structural and photophysical properties of poly(8-anilino-lnaphthalene sulphonic acid) (P ANSA) synthesized by electropolymerization (PANSA) and chemical polymerization (PANSA) were studied. Cyclic voltammetry (CV) data revealed that the electrogenerated PANSA contains species of mixed redox states; with evidence of the presence of penigraniline, emeraldine and leucoemeraldine forms of PANSA. In contrast, the CV of PANSA indicated that it is predominantly in the emeraldine form with a reduction potential at approximately + 0.2 V. The presence of emeraldine moiety in PANSA was confirmed from UV-Vis spectroscopy data. A band gap energy value of 2.5 eV was calculated for the emeraldine in PANSA from the UV data. Comparative study of the charge transfer coefficient, DCT, of the two types of PANSA indicated moderate charge propagation in PANSA (DCT = 1.68 ± 0.1 x 10-8 cm2 s-') which was order of magnitude lower than for PANSA (DCT = 1.68 ± 0.3 x 10-7 cm2 s-'). The differences in the structural properties of the two polymers were reflected in their IR spectra, with evidence of C=C and C=N stretching vibrations observed at 2030, 2158 and 2486 cm-I in PANSA, which are absent in PANSA. The mode of synthesis had a modest impact on the photophysics of the polymers, for example PANSA exhibited a luminescent lifetime of9.00 ± 0.05 ns compared with 11.5 ± 0.07 ns for PANSA. However, time resolved emission anisotropy studies gave a rotational correlation time, p, of 13.8 ± 2.47 ns for PANSA compared to 0.633 ± 0.03 ns for its chemically generated analogue. This suggests a much shorter chain length in the PANSA molecule and higher cross-linking or aggregation in PANSA that can limit incorporation of ruthenium complex on the polymer backbone. As a result, electrochemiluminescent films have been formed by electrodepositing polyaniline, PANI, films in the presence of [Ru(bpY)2PIC]2+; bpy is 2,2'-bipyridyl and PIC is (2,2'-bipyridyl)-2( 4- carboxylphenyl) imidazo [4,5 ][ 1,10] phenanthroline in this work. The homogeneous charge transport diffusion coefficient, DCT, for the Ru2+/3+couple within the PANI film is 2.6 ± 0.9 x 10-10 cm2s-l. The large DCT facilitates a fast regeneration of Ru3+and, coupled to a relatively rigid microenvironment, results in a high ECL intensity in the presence oftripropylamine as co-reactant compared to [Ru(bpY)3f+. Significantly, despite the conducting nature of the polymer backbone, the [Ru(bpy)2PICH2]2+ loaded PANI has the highest efficiency, 1.00%, yet reported for a surface confined ruthenium complex. PANI-Ru complex showed to have many properties that make it an ideal luminophore for sensitive and selective analytical methods; however, it would be useful to have other ECL labels that can span a wide range of wavelengths so that simultaneous determination of several analytes in a single sample can be investigated. In this case, the photophysics, electrochemical and electrochemiluminescent properties of a novel 1,3,5,7 -tetramethyl-8-[ (2-fluorophenyl)-6-methoxy-l ,5-naphthyridine-3-carboxy ]-4,4'difluoroboradiazaindace-ne BODIPY -COOH, dye were demonstrated in this work. The photophysics studies revealed that BODIPY -COOH is highly luminescent: exhibiting sharp absorbance bands, intense emission bands and high emission quantum yield. The quantum yield proved to be solvent dependent and was determined to be 0.88 ± 0.02 and 0.60 ± 0.04 in dimethylsulphoxide (DMSO) and acetonitrile (MeCN), respectively. Electrochemiluminescence (ECL) of BODIPYCOOH in solution was generated in the presence of either benzoyl peroxide (BPO) or hydrogen peroxide. The ECL turn-on potential in the presence of BPO was observed at potentials that are greater than - 1.5 V, and when H202 was used the ECL turn-on potential was significantly fine-tuned to less negative potential of - 0.4 V. Electrochemiluminescent thin films of BODIPY -COOH on Pt electrodes exhibited luminescence properties similar to those of the free dye in solution. However, the solution based approach ECL has its own limitations such as loss of signal due to the diffusion of the ECL reagent out of the detection zone. To overcome loss of signal effects, the introduction of cysteamine and cysteine linkers to the BODIPY dye were employed. It was seen that self-quenching was not sufficient to interfere significantly with the film ECL emission properties and thus the BODIPY thin film can be used in ECL applications. Interestingly, the BODIPY film exhibited the strongest luminescence in water and this is potentially useful in ECL application in biological media.

Les inventions biotechnologiques ont un double visage, une face bienveillante et une face terrifiante, chacune source potentielle de risques majeurs. Comment les contrôler et les réguler ? La recrudescence des catastrophes majeures (crises sanitaires) liées à l’usage de produits biotechnologiques, d’une part, puis l’échec à l’adoption d’un protocole de vérification à la Convention d’interdiction des armes biologiques suivi de l’émergence de nombreuses publications à risques dans le domaine des biotechnologies, d’autre part, démontrent l’omniprésence et la transversalité de cette problématique. Par leur essence duale, les biotechnologies appellent des solutions globales. La voie d’une gestion cohérente semble s’ouvrir au travers d’un corps de règle prenant tous ces paramètres en considération, les risques majeurs. L’avantage de cette législation, si elle admet une modification préalable de la nomenclature des risques majeurs en y intégrant les risques liés aux conflits, reposera sur sa globalité et sur la responsabilisation de tous. Face à une menace biotechnologique qui est perçue comme dominante dans les années à venir, l’émerge d’un ordre public mondial favorable à un accroissement de la responsabilité des Etats à l’égard de la sécurité humaine serait souhaitable. Le but de toute institution étatique étant de garantir à ses ressortissants leur sécurité et leur sûreté quelles que soient les circonstances, cet ordre public pourrait trouver ses bases au sein des réglementations relatives aux droits de l’homme et au droit de l’environnement ; réglementations déjà émancipées de la distinction entre situations de paix, de crises ou de conflits / The biotechnological inventions have a double face, a kindly face and a terrifying face, each potential source of major risks. How to control them and to regulate them? The outbreak of the major disasters (sanitary crisis) bound to biotechnological products, on one hand, the failure to the adoption of a Protocol to the Biological Weapon Convention, followed by the emergence of numerous publications at risks in the field of biotechnology, on the other hand, demonstrate the omnipresence and the transverse character of this problem. By their duality, biotechnologies need global solutions. The way of a coherent management seems to open through a body of rule considering all these parameters, the major risks. The advantage of this legislation, if it admits a preliminary modification of the list of the major risks by integrating the risks connected to the conflicts, will be based on its global aspect and everyone’s responsibility. In front of biotechnological threat, which is perceived as dominant in the years to come, an emergent world law and order favourable to an increase of the responsibility of States towards the human safety would be desirable. The purpose of any state institution is the guarantee of Nationals safety, whatever circumstances are, this law and order could find its bases within the regulations relative to human rights and to environmental law; these regulations are already indifferent to the distinction between situations of peace, crisis or conflicts