矿物的微生物风化地球化学研究－－以磷矿石和方解石为例

微生物与矿物间的相互作用是自然界中广泛发生的一种地质作用，微生物直接参与了自然界的物质循环，微生物对矿物风化作用的过程和机理与矿物种类、菌种及环境条件密切相关。目前还缺乏对矿物风化微观过程及风化过程中微生物生理生化特征的研究资料，随着分子生物学理论与技术的快速发展，用地球化学结合微生物学与分子生物学的理论和方法来综合研究微生物的矿物风化过程已成为可能。从分子水平和微观作用过程研究其风化过程与机理，理解微生物与矿物界面之间的相互作用及其反馈机制，是表生作用过程中生物地球化学的重要研究内容。 选用胶质芽孢杆菌（Bacillus mucilaginosus）、黑曲霉（Aspergillus niger）和青霉（Penicillium sp.），以磷矿石和方解石为例，探讨实验条件下微生物对矿物的风化作用过程与机理。微生物对矿物风化作用具有能耗低、污染小和流程短等特点，充分利用这些特点是解决土壤中无效磷的有效利用、磷矿资源的开发以及减少环境污染等问题的有效途径，对矿产资源的可持续利用和建立健康的生态环境具有十分重要的意义。采用离子色谱、ICP-OES、XRD、TEM、EDS、2-DE、电子探针和MC-ICP-MS等分析测试手段，研究微生物对矿物的风化过程与机理，得到如下结果： (1) 在黑曲霉对磷矿石风化过程中，由黑曲霉生长引发的生物机械破坏作用和生物化学降解作用是对磷矿石风化的主要趋动力，包括菌丝生长对矿物的穿插作用以及机械剥蚀作用；此外，菌体及生物大分子形成生物膜覆盖在矿物表面形成易于发生生化降解的微环境，有机酸络合Ca生成次生矿物草酸钙促进了磷矿石的风化。磷矿石直接与菌体接触所发生的风化作用强于磷矿石装入透析袋中的间接风化作用。 (2) 在胶质芽孢杆菌对磷矿石的风化过程中，菌体及其胞外多糖类物质在矿粉表面形成生物膜、菌体生长、代谢产物及有机物的机械剥蚀破碎作用等是造成矿物风化的重要原因；磷矿石直接与菌体接触进行的风化作用强于磷矿石装入透析袋中的间接风化作用。 (3) 黑曲霉对磷矿石的风化作用强于胶质芽孢杆菌，两者对磷矿石进行风化时，生物物理风化作用是导致矿物风化的主要因素；胶质芽孢杆菌风化磷矿石的过程中没有草酸钙的产生。 (4) 胶质芽孢杆菌对磷矿石的风化过程中，菌体蛋白质的表达发生变化，蛋白质的量与质的变化与磷矿石的风化密切有关。磷矿石的加入导致菌体生理代谢途径改变以适应环境的变化，并分泌相关的蛋白质导致矿物的风化。 (5) 采用Sr同位素示踪研究黑曲霉与青霉对磷灰石和方解石混合物的风化差异。黑曲霉作用混合矿物的初期，培养液pH值相对较低，对其中方解石有风化作用；中后期由于pH值升高，对磷灰石有较强的风化作用,对磷灰石的风化是由黑曲霉产生的大分子有机物对磷灰石中Ca络合的结果。青霉与混合矿物发生相互作用时，在最初的很短时间内青霉对磷灰石有风化作用，但对方解石的风化作用却表现在整个风化作用时间段，相比而言，青霉对磷灰石的风化作用不明显。这种风化差异与真菌的生物学特性有关，并表现为微生物对矿物风化的选择性。 本项研究对进一步认识土壤植被生态系统中的磷循环规律和循环过程中微生物所起的作用，以及用微生物风化作用的方式促进磷矿资源开发利用具有重要理论和实际意义。

Atelier ORIXAS: Projeto Tripartite África/Brasil/França: luta contra a desertificação: promoção da segurança alimentar e redução da pobreza.

No âmbito do Programa de Cooperação Científica Tripartite entre a Agence Inter-établissements de Recherche pourle Développement (AIRD), Agence Panafricaine de la Grande Muraille Verte (APGMV) e o Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), o projeto ORIXAS "Observatórios Regionais Integrados de Regiões Árida, Semiáridas e Sub-úmidas secas" concebido em uma visão transversal, foca principalmente em metodologias e ferramentas para apoiar dispositivos de monitoramento ambiental para ser aplicado nos países inseridos na iniciativa africana Grande Muralha Verde - GMV (Burkina-Faso, Djibouti, Érythrée, Éthiopie, Mali, Mauritanie, Niger, Nigeria, Sénégal, Soudan, Tchad) e tem como objetivo desenvolver abordagens metodológicas e produtos compartilhados para melhorar a avaliação e monitoramento da desertificação e os impactos diretos ou indiretos de iniciativas para lutar contra o desmatamento e desertificação no âmbito da GMV. Esta publicação contempla aspectos metodológicos utilizados pelo projeto "ORIXAS" durante a primeira oficina de trabalho coletivo África-Brasil-França - Atelier (MAISON DE LA TÉLÉDÉTECTION), realizada de 10 a 19 de junho de 2014, em Montpellier França, objetivando informar a forma de execução dos estudos que vêm sendo realizados no escopo do projeto, visando principalmente a luta contra a desertificação, promoção da segurança alimentar e redução da pobreza nos países inseridos na iniciativa africana Grande Muralha Verde - GMV.

Aspergillus e Aspergilose

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Biobased additives as biodegradability enhancers with application in TPU-based footwear components

Among the wide variety of materials employed in the manufacture of shoes, thermoplastic polyurethanes (TPUs) are one of the most widely used. Given its widespread use, and associated waste management problems, the development of more biodegradable and evironmentally compatible solutions is needed. In this work, a polyester-based TPU used in the footwear industry for outsoles production was modified by compounding with lignin, starch and cellulose at content of 4% (w/w). The biodegradability was evaluated by using agar plate tests with the fungi Aspergillus niger ATCC16404, the Gram-negative bacteria Pseudomonas aeruginosa ATCC9027 and an association of both (consortium), and soil tests at 37 °C and 58 °C. The obtained results evidenced a positive effect of the tested biobased additives, the most favourable results being registered with lignin. These results were corroborated by the structural modifications observed by FTIR analysis. Additionally, mechanical tests prove the suitability of using the lignin modified TPUs for footwear outsoles production.

“Green preservatives” – combating fungi in the food industry by applying antifungal lactic acid bacteria

Fungal spoilage is the most common type of microbial spoilage in food leading to significant economical and health problems throughout the world. Fermentation by lactic acid bacteria (LAB) is one of the oldest and most economical methods of producing and preserving food. Thus, LAB can be seen as an interesting tool in the development of novel bio-preservatives for food industry. The overall objective of this study was to demonstrate, that LAB can be used as a natural way to improve the shelf-life and safety of a wide range of food products. In the first part of the thesis, 116 LAB isolates were screened for their antifungal activity against four Aspergillus and Penicillium spp. commonly found in food. Approximately 83% of them showed antifungal activity, but only 1% showed a broad range antifungal activity against all tested fungi. The second approach was to apply LAB antifungal strains in production of food products with extended shelf-life. L. reuteri R29 strain was identified as having strong antifungal activity in vitro, as well as in sourdough bread against Aspergillus niger, Fusarium culmorum and Penicillium expansum. The ability of the strain to produce bread of good quality was also determined using standard baking tests. Another strain, L. amylovorus DSM19280, was also identified as having strong antifungal activity in vitro and in vivo. The strain was used as an adjunct culture in a Cheddar cheese model system and demonstrated the inhibition of P. expansum. Significantly, its presence had no detectable negative impact on cheese quality as determined by analysis of moisture, salt, pH, and primary and secondary proteolysis. L. brevis PS1 a further strain identified during the screening as very antifungal, showed activity in vitro against common Fusarium spp. and was used in the production of a novel functional wortbased alcohol-free beverage. Challenge tests performed with F. culmorum confirmed the effectiveness of the antifungal strain in vivo. The shelf-life of the beverage was extended significantly when compared to not inoculated wort sample. A range of antifungal compounds were identified for the 4 LAB strains, namely L. reuteri ee1p, L. reuteri R29, L. brevis PS1 and L. amylovorous DSM20531. The identification of the compounds was based on liquid chromatography interfaced to the mass spectrometer and PDA detector

Self-organized vegetation patterning as a fingerprint of climate and human impact on semi-arid ecosystems

Spatially periodic vegetation patterns are well known in arid and semi-arid regions around the world. Mathematical models have been developed that attribute this phenomenon to a symmetry-breaking instability. Such models are based on the interplay between competitive and facilitative influences that the vegetation exerts on its own dynamics when it is constrained by arid conditions, but evidence for these predictions is still lacking. Moreover, not all models can account for the development of regularly spaced spots of bare ground in the absence of a soil prepattern. We applied Fourier analysis to high-resolution, remotely sensed data taken at either end of a 40-year interval in southern Niger. Statistical comparisons based on this textural characterization gave us broad-scale evidence that the decrease in rainfall over recent decades in the sub-Saharan Sahel has been accompanied by a detectable shift from homogeneous vegetation cover to spotted patterns marked by a spatial frequency of about 20 cycles km-1. Wood cutting and grazing by domestic animals have led to a much more marked transition in unprotected areas than in a protected reserve. Field measurements demonstrated that the dominant spatial frequency was endogenous rather than reflecting the spatial variation of any pre-existing heterogeneity in soil properties. All these results support the use of models that can account for periodic vegetation patterns without invoking substrate heterogeneity or anisotropy, and provide new elements for further developments, refinements and tests. This study underlines the potential of studying vegetation pattern properties for monitoring climatic and human impacts on the extensive fragile areas bordering hot deserts. Explicit consideration of vegetation self-patterning may also improve our understanding of vegetation and climate interactions in arid areas. © 2006 The Authors.

Interactions spatiales et auto-organisation des végétations semi-arides

Les recherches récapitulées dans cette thèse de doctorat ont porté sur les causes de l’organisation spatiale des végétations périodiques. Ces structures paysagères aux motifs réguliers, tachetés, tigrés ou labyrinthiques, d’échelle décamétrique à hectométrique, couvrant des étendues considérables sur au moins trois continents, constituent un cas d’école dans l’étude des processus endogènes présidant à l’hétérogénéité du couvert végétal. Ces structures prennent place sur un substrat homogène, mis à part la rétroaction du couvert lui-même, et sont marquées par des écotones abrupts et la persistance d’une proportion considérable de sol nu. Plusieurs modèles ont mis en avant l’existence possible d’un phénomène d’auto-organisation du couvert, qui verrait une structure d’ensemble émerger des interactions locales entre individus. Ces modèles se basent sur le jeu simultané de la consommation de la ressource (compétition) et de l’amélioration de l’un ou l’autre des éléments du bilan de la même ressource par le couvert (facilitation). La condition à l’existence d’une structure d’ensemble spatialement périodique et stable réside dans une différence entre la portée de la compétition (plus grande) et celle de la facilitation. L’apparition de ces structures est modulée par le taux de croissance biologique, qui est le reflet des contraintes extérieures telles que l’aridité, le pâturage ou la coupe de bois. Le modus operandi des interactions spatiales supposées entre individus reste largement à préciser.

Nos recherches ont été menées au sud-ouest de la République du Niger, à l’intérieur et dans les environs du parc Régional du W. Trois axes ont été explorés :(i) Une étude de la dépendance spatiale entre la structure de la végétation (biovolumes cartographiés) et les paramètres du milieu abiotique (relief, sol), sur base d’analyses spectrales et cross-spectrales par transformée de Fourier (1D et 2D). (ii) Une étude diachronique (1956, 1975 et 1996) à large échelle (3000 km²) de l’influence de l’aridité et des pressions d’origine anthropique sur l’auto-organisation des végétations périodiques, basée sur la caractérisation de la structure spatiale des paysages sur photos aériennes via la transformée de Fourier en 2D. (iii) Trois études portant sur les interactions spatiales entre individus :En premier lieu, via l’excavation des systèmes racinaires (air pulsé) ;Ensuite, par un suivi spatio-temporel du bilan hydrique du sol (blocs de gypse) ;Enfin, via le marquage de la ressource par du deutérium.

Nous avons ainsi pu établir que les végétations périodiques constituent bien un mode d’auto-organisation pouvant survenir sur substrat homogène et modulé par les contraintes climatiques et anthropiques. Un ajustement rapide entre l’organisation des végétations périodiques et le climat a pu être montrée en zone protégée. La superficie et l’organisation des végétations périodiques y ont tour à tour progressé et régressé en fonction d’épisodes secs ou humides. Par contre, en dehors de l’aire protégée, la possibilité d’une restauration du couvert semble fortement liée au taux d’exploitation des ressources végétales. Ces résultats ont d’importantes implications quant à la compréhension des interactions entre climat et écosystèmes et à l’évaluation de leurs capacités de charge. La caractérisation de la structure spatiale des végétations arides, notamment par la transformée de Fourier d’images HR, devrait être généralisée comme outil de monitoring de l’état de ces écosystèmes. Nos études portant sur les modes d’interactions spatiales ont permis de confirmer l’existence d’une facilitation à courte portée du couvert végétal sur la ressource. Cependant, cette facilitation ne semble pas s’exercer sur le terme du bilan hydrique traditionnellement avancé, à savoir l’infiltration, mais plutôt sur le taux d’évaporation (deux fois moindre à l’ombre des canopées). Ce mécanisme exclut l’existence de transferts diffusifs souterrains entre sols nu et fourrés. Des transferts inverses semblent d’ailleurs montrés par le marquage isotopique. L’étude du bilan hydrique et la cartographie du micro-relief, ainsi que la profondeur fortement réduite de la zone d’exploitation racinaire, jettent de sérieux doutes quant au rôle communément admis des transferts d’eau par ruissellement/diffusion de surface en tant que processus clé dans la compétition à distance entre les plantes. L’alternative réside dans l’existence d’une compétition racinaire de portée supérieure aux canopées. Cette hypothèse trouve une confirmation tant par les rhizosphères excavées, superficielles et étendues, que dans le marquage isotopique, montrant des contaminations d’arbustes situés à plus de 15 m de la zone d’apport. De même, l’étude du bilan hydrique met en évidence les influences simultanées et contradictoires (facilitation/compétition) des ligneux sur l’évapotranspiration.

/

This PhD thesis gathers results of a research dealing with the causes of the spatial organisation of periodic vegetations. These landscape structures, featuring regular spotted, labyrinthine or banded patterns of decametric to hectometric scale, and extending over considerable areas on at least three continents, constitute a perfect study case to approach endogenous processes leading to vegetation heterogeneities. These patterns occur over homogeneous substratum, except for vegetation’s own feedbacks, and are marked by sharp ecotones and the persistence of a considerable amount of bare soil. A number of models suggested a possible case of self-organized patterning, in which the general structure would emerge from local interactions between individuals. Those models rest on the interplay of competitive and facilitative effects, relating to soil water consumption and to soil water budget enhancement by vegetation. A general necessary condition for pattern formation to occur is that negative interactions (competition) have a larger range than positive interactions (facilitation). Moreover, all models agree with the idea that patterning occurs when vegetation growth decreases, for instance as a result of reduced water availability, domestic grazing or wood cutting, therefore viewing patterns as a self-organised response to environmental constraints. However the modus operandi of the spatial interactions between individual plants remains largely to be specified.

We carried out a field research in South-West Niger, within and around the W Regional Park. Three research lines were explored: (i) The study of the spatial dependency between the vegetation pattern (mapped biovolumes) and the factors of the abiotic environment (soil, relief), on the basis of spectral and cross-spectral analyses with Fourier transform (1D and 2D). (ii) A broad scale diachronic study (1956, 1975, 1996) of the influence of aridity and human induced pressures on the vegetation self-patterning, based on the characterisation of patterns on high resolution remote sensing data via 2D Fourier transform. (iii) Three different approaches of the spatial interactions between individuals: via root systems excavation with pulsed air; via the monitoring in space and time of the soil water budget (gypsum blocks method); and via water resource labelling with deuterated water.

We could establish that periodic vegetations are indeed the result of a self-organisation process, occurring in homogeneous substratum conditions and modulated by climate and human constraints. A rapid adjustment between vegetation patterning and climate could be observed in protected zones. The area and patterning of the periodic vegetations successively progressed and regressed, following drier or wetter climate conditions. On the other hand, outside protected areas, the restoration ability of vegetation appeared to depend on the degree of vegetation resource exploitation. These results have important implications regarding the study of vegetation-climate interactions and the evaluation of ecosystems’ carrying capacities. Spatial pattern characterisation in arid vegetations using Fourier transform of HR remote sensing data should be generalised for the monitoring of those ecosystems. Our studies dealing with spatial interaction mechanisms confirmed the existence of a short range facilitation of the cover on water resource. However, this facilitation does not seem to act through the commonly accepted infiltration component, but rather on the evaporative rate (twice less within thickets). This mechanism excludes underground diffusive transfers between bare ground and vegetation. Inverse transfers were even shown by deuterium labelling. Water budget study and micro-elevation mapping, along with consistent soil shallowness, together cast serious doubts on the traditional mechanism of run-off/diffusion of surface water as a key process of the long range competition between plants. An alternative explanation lies in long range root competition. This hypothesis find support as well in the excavated root systems, shallow and wide, as in isotopic labelling, showing contaminations of shrubs located up to 15 m of the irrigated area. Water budget study also evidenced simultaneous contradictory effects (facilitation/competition) of shrubs on evapotranspiration.

Oil on Troubled Waters-Multinational Corporations and Realising Human Rights in the Developing World with Particular Reference to Nigeria

This article examines the current state of tension in the Niger Delta of Nigeria. It locates the current unrest in the continued denial of economic, social and cultural rights to the oil-rich communities in the area. The author argues that this denial happened with the complicity and acquiescence of the international community. The Nigerian government as well as multinational corporations operating in the area have not been responsive to the development needs of the people. The article argues that, although the primary obligation for realising the economic, social and cultural rights of host communities rests on the government, multi-national corporations in developing countries, considering their awesome resources and influence on government policies, should be similarly obligated to respect, promote and protect those rights.

THE IMPACT OF BURNING AND GRAZING OF HEATHLAND PLANTS AND INVERTEBRATES IN COUNTRY ANTRIM

The impact of burning and grazing on plant, ground beetle and spider species was investigated experimentally in stands of varying ages (burnt in 1982 and 1988 and unburnt plots) on an area of heather moorland in County Antrim, north-east Ireland. Burning initiated complex succession pathways which appear to have characteristic plant and invertebrate species associations. Removal of Calluna dominance initiated a period of high plant species diversity. Investigation of initial post-fire regeneration suggested that the frequency of occurrence of plant species changed over time and was affected by grazing. Grouping of species by the position of their renewal bud, i.e. their life-form, did not account for all observed interspecific variation. The dominant species after burning were Eriophorum vaginatum, E. angustifolium and Vaccinium myrtillus. Studies of vegetation canopy structure showed that, even with the exclusion of the main grazing herbivores, Calluna will not re-establish itself as the dominant species until several years after burning. The ground beetle Nebria salina was trapped more often on plots burnt in 1988 than on unburnt plots or those burnt in 1982. In comparison, Pterostichus niger and Carabus granulatus were trapped in greater numbers on plots burnt in 1982 than on unburnt plots and plots burnt in 1988. The large species Carabus problematicus and Carabus glabratus were trapped in greater numbers on unburnt plots. Similarly, more of the spiders Ceratinella brevipes and Centromerita concinna were trapped on the plots burnt in 1982. In comparison, Lepthyphantes zimmermanni and Robertus lividus were trapped more often on unburnt plots than on plots burnt in 1982 and 1988. Results are discussed with respect to the importance of the continuation of traditional heathland management practices.

Coal combustion residues valorisation:Research and development on compressed brick production

This paper presents the results of an experimental investigation on compressive strength of unfired compressed brick obtained with coal combustion residues (CCRs) produced by the Niger Coal Society. Preliminary physical and optical (XRD and SEM) characterisation of coal slag, including lixiviation tests, have been carried out. Cement powder, lateritic clayey soil and sand have been chosen as stabilizing agents for bricks. 12 dosages have been tested and about 300 bricks have been produced with a hand-operated press. Results show uniaxial compressive strengths (UCSs) ranging from 4 MPa to 27 MPa for the highest cement stabilisation ratio. UCS higher than 7.5 MPa have been observed for stabilisation with 20% of laterite +10% cement after 45 days of curing. Obtained bricks showed good mechanical resistance and low weight. No health threat has been detected for the obtained samples. Study developments are oriented towards the analysis of Pozzolanic properties of CCRs, properties of hydrated lime stabilisation, thermal properties and durability assessment.© 2012 Elsevier Ltd. All rights reserved.

Coal Combustion Residuals valorisation through the production of compressed masonry brick

The Niger Coal Society (Societé Nigérienne de Charbon – SONICHAR) produces electricity for local consumption in Tefereyre, 75 km north-west from Agadez, Niger. The coal combustion residuals production is about 150,000 tons per year. In order to reduce this environmental burden and to valorize these by-products, a study focusing on their physical and chemical features as well as on the mechanical resistance of compressed brick has been undertaken. Physical characterization of coal slag, chemical and lixiviation tests have been carried out, assessing the material main parameters, verifying the presence of hazardous composites and elements and comparing the obtained results with the findings of an in-deep literary review. Cement powder has been chosen as stabilizing agent as a preliminary option. Four different dosages have been tested and bricks have been produced with a hand-operated press. Compressive strength has been tested at different days of curing. Results show remarkable uniaxial compressive strengths (UCS) for all the mixes after cure, ranging from 4MPa up to more than 20MPa for the highest stabilization ratio. UCS higher than 5MPa have been observed for 20% and 30% cement stabilization ratios after only 7 days of cure, reaching respectively about 11MPa and 13MPa after 45 days. In conclusion obtained bricks show good mechanical resistance and low weight. No health threat has been detected from the obtained sample. Study developments are oriented towards the feasibility of the utilization of low-cost, locally available stabilization means, notably clay and cohesive soils, and on thermal properties assessment.

Age-related prevalence and met need for correctable and uncorrectable near vision impairment in a multi-country study

Purpose: To estimate the prevalence, potential determinants, and proportion of met need for near vision impairment (NVI) correctable with refraction approximately 2 years after initial examination of a multi-country cohort. Design: Population-based, prospective cohort study. Participants: People aged ≥35 years examined at baseline in semi-rural (Shunyi) and urban (Guangzhou) sites in China; rural sites in Nepal (Kaski), India (Madurai), and Niger (Dosso); a semi-urban site (Durban) in South Africa; and an urban site (Los Angeles) in the United States. Methods: Near visual acuity (NVA) with and without current near correction was measured at 40 cm using a logarithm of the minimum angle of resolution near vision tumbling E chart. Participants with uncorrected binocular NVA ≤20/40 were tested with plus sphere lenses to obtain best-corrected binocular NVA. Main Outcome Measures: Prevalence of total NVI (defined as uncorrected NVA ≤20/40) and NVI correctable and uncorrectable to >20/40, and current spectacle wearing among those with bilateral NVA ≤20/63 improving to >20/40 with near correction (met need). Results: Among 13 671 baseline participants, 10 533 (77.2%) attended the follow-up examination. The prevalence of correctable NVI increased with age from 35 to 50-60 years and then decreased at all sites. Multiple logistic regression modeling suggested that correctable NVI was not associated with gender at any site, whereas more educated persons aged >54 years were associated with a higher prevalence of correctable NVI in Nepal and India. Although near vision spectacles were provided free at baseline, wear among those who could benefit was <40% at all but 2 centers (Guangzhou and Los Angeles). Conclusions: Prevalence of correctable NVI is greatest among persons of working age, and rates of correction are low in many settings, suggesting that strategies targeting the workplace may be needed.

Compósitos de polímeros naturais e nanopartículas metálicas

Esta tese descreve diversas estratégias de preparação assim como a caracterização de nanocompósitos com base em distintos biopolímeros. Em particular foi estudada a incorporação de nanopartículas (NPs) metálicas, nomeadamente de Ag, Cu e Au. Estes nanomateriais apresentam um potencial prático enorme em diversas áreas, no entanto foi investigada especificamente a sua aplicação como materiais antimicrobianos. No primeiro capítulo apresenta-se uma revisão bibliográfica, onde são realçados os principais tópicos discutidos ao longo da tese. Inicialmente apresenta-se uma contextualização deste trabalho sendo seguidamente apresentadas algumas considerações sobre nanocompósitos e o seu impacto tecnológico atual. Em seguida, descrevem-se as vantagens do uso de NPs como cargas nos materiais compósitos especificamente no caso de bionanocompósitos. Foi focado o uso da celulose como matriz uma vez que foi o composto “base” usado neste trabalho. Fez-se a descrição exaustiva das metodologias existentes na literatura para a preparação dos nanocompósitos celulósicos com diferentes NPs metálicas assim como das respetivas aplicações. Dentro das aplicações, foi dado especial destaque às propriedades antimicrobianas dos materiais preparados seja a nível da sua atividade antibacteriana ou antifúngica. Esta introdução privilegia o trabalho relacionado diretamente com os sistemas descritos nos capítulos subsequentes. No segundo capítulo apresentam-se os resultados obtidos para nanocompósitos de prata em matriz celulósica. Através do uso de metodologias, tais como a síntese in situ e a pós-deposição, foram preparados diversos materiais usando dois substratos celulósicos distintos nomeadamente a celulose vegetal e bacteriana. Estes nanocompósitos foram caracterizados em termos da sua morfologia e composição química, verificando-se a importância destas características na sua atividade antibacteriana. Foi verificado que nanocompósitos com teores de Ag de 5 x 10-4 (% m/m) são suficientes para obter atividade antibacteriana. A libertação de Ag(I) foi estudada em alguns destes materiais de modo a tentar perceber o mecanismo subjacente a este tipo de nanocompósitos. No terceiro capítulo é apresentado o estudo de NPs coloidais de Ag e Au como cargas para a preparação de nanocompósitos à base de quitosano nãomodificado e modificado quimicamente (derivado solúvel em água e derivado anfifílico). Foram preparados filmes finos de espessura de 9-14 μm, caracterizando-se as suas propriedades óticas e antibacterianas. As propriedades óticas foram ajustadas, quer pela variação do teor de NPs de Ag (0,3-3,9% m/m) ou pela utilização de amostras de NPs com distribuição de tamanho de partícula distinta. Foi investigada a atividade antibacteriana tanto para bactérias Gram-negativas (Klebsiella pneumoniae e Escherichia coli) como para Gram-positivas (Staphylococcus aureus). Para nanocompósitos preparados com o quitosano não modificado verificou-se uma dependência em função do teor de Ag. No caso do uso de derivados modificados, os materiais preparados mostraram uma eficiência superior, mesmo sem NPs de Ag. No quarto capítulo é apresentada a síntese e caracterização de nanocompósitos de pululano e NPs de Ag. Neste estudo é avaliada a atividade antifúngica dos filmes compósitos preparados contra o Aspergillus niger usando protocolos padrão. Estes materiais foram preparados na forma de filmes (66-74 μm de espessura) por evaporação de solvente da mistura de pululano e coloides de Ag. Foi observado o aumento da inibição do fungo na presença dos nanocompósitos, tendo sido pela primeira vez mostrado o efeito disruptivo destes materiais sobre os esporos do A. niger através da análise das imagens de SEM. Este efeito ocorre na presença dos filmes devido à presença das cargas de NPs de Ag dispersas no pululano. O desenvolvimento de materiais de papel com NPs de Cu é um desafio devido à propensão destas espécies em oxidar sob condições ambiente. No quinto capítulo é descrita pela primeira vez o estudo comparativo do crescimento e estabilidade de NPs de Cu em celulose vegetal e bacteriana. Para além disso foi avaliado o uso de nanoestruturas com diferentes dimensionalidades como cargas, nomeadamente nanoesferas e nanofios. Foi observado que o uso de nanofios aumenta a resistência à oxidação destes nanocompósitos para tempos de exposição ao ar mais prolongados. As matrizes celulósicas apresentam comportamento distinto no crescimento e/ou adsorção das NPs de Cu. A celulose bacteriana foi o substrato mais eficiente para retardar a oxidação das NPs. A atividade antibacteriana destes nanocompósitos foi avaliada. Ao longo desta dissertação são apresentados métodos distintos para a obtenção de nanocompósitos com base em biopolímeros e NPs metálicas. Estes estudos permitiram não só a preparação de novos nanocompósitos mas também compreender e otimizar os mecanismos subjacentes à sua preparação. Ao mesmo tempo, este trabalho contribuiu para a transferência de tecnologia e conhecimento entre a área da Nanotecnologia e a área dos materiais derivados de fontes renováveis. As propriedades apresentadas por estes nanomateriais mostraram a sua possível aplicação como novos materiais antimicrobianos, no entanto é possível antecipar futuras aplicações em outras áreas tecnológicas.

Pesquisa de antifúngicos de origem vegetal

Dissertação mest., Engenharia Biológica, Universidade do Algarve, 2009

Produção de enzimas celulósicas, usando resíduos industriais e seu uso como biocatalisador na produção de biocombustíveis

Dissertação mest., Engenharia Biológica, Universidade do Algarve, 2010