A nanotecnologia é um fenômeno que se aplica a praticamente todos os etores da ciência, sendo que na área cosmética o elevado investimento neste campo tem reforçado a idéia de que os produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A crescente exigência do consumidor e os avanços no conhecimento sobre a obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados como, por exemplo, nanoemulsões, que além da inerente estabilidade, apresentam aspecto sensorial agradável, alta capacidade de espalhabilidade e hidratação. Existem dois métodos de obtenção das nanoemulsões: empregando baixa ou alta energia de emulsificação. O uso de óleos vegetais em produtos cosméticos tem sido intensamente valorizado, baseando-se no conceito de que são seguros e biocompatíveis. Podem ser utilizados em cosméticos com sua funcionalidade potencializada, sendo estes ricos em ácidos graxos essenciais, Ômega 3, Ômega 6, Ômega 9, fitosteróis, vitamina C e polifenóis (antocianinas). Alguns óleos vegetais têm poder antioxidante comprovado, previnem as oxidações biológicas e reduzem a formação de radicais livres responsáveis pelo dano celular, grande vilão do envelhecimento e das doenças crônico-degenerativas, como o câncer. Atualmente é crescente o interesse da pesquisa sobre a atividade de substâncias capazes de proteger a pele contra a radiação ultravioleta de forma eficaz. O metoxicinamato de octila é um filtro solar químico capaz de proteger a pele e conferir um fator de proteção solar ao produto final. Nesse estudo foram desenvolvidas nanoemulsões à base de óleos de oliva e semente de uva aditivadas de metoxicinamato de octila. Após a análise da estabilidade físico-química e caracterização das formulações, foram avaliados o potencial antioxidante das formulações, o efeito de proteção solar do sistema, liberação e permeação do ativo e uma possível irritação ocular das formulações que se mantiveram estáveis. / Nanotechnology is a phenomenon that is applied to mainly all sectors of science. In the cosmetic area the high investment has strengthened the idea that nanotechnology products offer real advantages to consumers. The growing demand of consumers and the advances in the knowledge about production and stability of dispersed systems enable the development of differentiated vehicles such as nano-emulsions, which besides their inherent stability, they have pleasant sensorial aspect, high spread ability and hydration power. There are two methods of nano-emulsions attainment: low or high energy of emulsifying. The use of vegetable oils in cosmetic products has had enormous and growing value, based in the concept that they are safe and biocompatible. They can be used in cosmetics with their functionality improved, being rich in essential fatty acids, Omega 3, Omega 6, Omega 9, phytosterols, vitamin C and polyphenols (anthocyanins). Some vegetable oils have proved antioxidant power, as well as they avoid biological oxidation and decrease the forming of free radicals responsible for cellular damage, which are the causes of aging and disease such as cancer. Nowadays, the interest of research about the activity of substances that protect the skin against ultraviolet irradiation in an efficacious way is growing. Octylmethoxycinnamate is a chemical sunscreen that can protect skin and offers sun protection factor to final product. In this study nano-emulsions were developed using olive oil and grape seed oil added with octylmethoxycinnamate. After the analysis of the physic-chemical stability and formulation characterization, the antioxidant potential of formulations, the effect of sun protection of the system, delivery and permeation of the active agent, and a possible ocular irritation of the stable formulations were evaluated.

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-04-20T14:03:24Z No. of bitstreams: 1 Aline Caye_.pdf: 2351829 bytes, checksum: c279bc104c17316c0cf4d257c01f624d (MD5) / Made available in DSpace on 2018-04-20T14:03:24Z (GMT). No. of bitstreams: 1 Aline Caye_.pdf: 2351829 bytes, checksum: c279bc104c17316c0cf4d257c01f624d (MD5) Previous issue date: 2018-02-23 / BB - Banco do Brasil / Ao introduzir atividades de maior valor agregado ao agronegócio, como é o caso do desenvolvimento do setor produtor de azeite de oliva na agroindústria do Rio Grande do Sul, amplia-se a competitividade desta atividade para a economia do Estado, que não tem tradição na produção de azeite de oliva. Essa possibilidade é uma descoberta relativamente recente, retomada com sucesso em 2003, com o cultivo de mudas de oliva, em Caçapava do Sul/RS, conforme a EMATER/RS-Ascar (2015), e vem sendo considerada um exemplo de agregação de valor e inovação para o agronegócio do RS. A temática abordada neste trabalho refere-se ao desenvolvimento do sistema setorial de inovação de azeite de oliva no Rio Grande do Sul. O objetivo geral do presente trabalho é analisar quais são e como se comportam os elementos e atores que explicam o desenvolvimento desse sistema no RS. A justificativa da pesquisa reside em aplicar um olhar sistêmico no processo de desenvolvimento de um setor produtivo de elevado valor agregado no agronegócio do RS. O recorte teórico de Sistema Setorial de Inovação (SSI) permite a compreensão de elementos que vão além da firma e sua estrutura de mercado. Para apoiar os resultados e análises, buscou-se embasamento teórico em assuntos como inovação, sistema setorial de inovação (SSI), inovação no setor agroalimentar e azeite de oliva. Os procedimentos metodológicos utilizados, para este estudo, caracterizaram-se como exploratórios e descritivos, utilizando como métodos a pesquisa bibliográfica, a pesquisa documental e a pesquisa de campo. A abordagem qualitativa foi utilizada para responder ao problema de pesquisa. A coleta de dados deu-se sob a forma de pesquisa de campo, através de entrevistas com diferentes atores do SSI, e pela pesquisa documental. Entre julho e dezembro de 2017 foram entrevistados vinte e um (21) atores do setor de azeite de oliva. Através destas entrevistas foi possível constatar que o sistema setorial de inovação (SSI) de azeite de oliva no RS constituiu-se com mais vigor recentemente e ainda está em desenvolvimento. O clima e o solo, as condições de manejo do olival, a sanidade da fruta, a colheita precoce, as condições e o tempo de transporte das azeitonas até o lagar e o cuidado no processamento do azeite são diferenciais que garantem qualidade ao azeite gaúcho, comprovada em guias e concursos internacionais. Além desses elementos, a troca de experiências e os fluxos de conhecimentos tecnológicos dos atores também foram e são fundamentais para o desenvolvimento deste SSI. Em geral, os produtores do azeite de oliva do RS não dependem exclusivamente da olivicultura, não fazem financiamentos bancários para adquirir o olival, tampouco, para mantê-lo, e não contratam seguro do olival. Sendo assim, entende-se que o SSI de Azeite de Oliva no RS está em desenvolvimento, com a presença de atores diversos que possuem função distintas, com firmas heterogêneas em tamanho e em possibilidades de produção e inovação. Analisar esse SSI é uma forma de relatar o desenvolvimento de um segmento produtor de um bem de valor agregado no agronegócio do RS, podendo ser considerada uma experiência relevante para analisar o potencial do agronegócio gaúcho e agregar mais valor em seus produtos finais. / By introducing higher added value activities to agribusiness, such as the development of the olive oil producing sector in the Rio Grande do Sul agro-industry, the competitiveness of this activity for the State's economy is broadened, which has no tradition in production of olive oil. This possibility is a relatively recent finding, successfully resumed in 2003, with the cultivation of olive trees in Caçapava do Sul/RS, according to EMATER/RS-Ascar (2015), and has been considered an example of aggregation of value and innovation for agribusiness in RS. The theme addressed in this study refers to the development of the sectorial system of innovation of olive oil in Rio Grande do Sul. The general objective of the present work is to analyze what are and how behave the elements and actors that explain the development of this system in RS. The research's justification lies in applying a systemic perspective to the process of developing a productive sector with high added value in the RS agribusiness. The theoretical section of Sectorial System of Innovation (SSI) allows the understanding of elements that go beyond the firm and its market structure. To support the results and analyzes, it was sought theoretical basis in subjects such as innovation, sectorial system of innovation (SSI), innovation in the agro-food sector and olive oil. The methodological procedures used for this study were characterized as exploratory and descriptive, using methods such as bibliographic research, documentary research and field research. The qualitative approach was used to answer the research problem. Data collection took the form of field research, through interviews with different SSI actors, and through documentary research. Between August and October 2017, twenty-one (21) actors from the olive oil sector were interviewed. Through these interviews it was possible to verify that the sectorial system of innovation (SSI) of olive oil in RS has been more vigorous recently and is still under development. The climate and the soil, olive tree management conditions, fruit sanitation, early harvesting, the conditions and the time of transportation of the olives to the winery and the care in the olive oil processing are differentials that guarantee quality to the gaúcho olive oil, proven in guides and international competitions. Besides these elements, the exchange of experiences and the technological knowledge flows of the actors were also and are fundamental for the development of this SSI. In general, olive oil producers in RS do not depend exclusively on olive cultivation, do not make bank financing to purchase the olive grove, nor to maintain it, and do not hire insurance from the olive grove. Thus, it is understood that SSI of Olive Oil in RS is under development, with the presence of diverse actors that have different functions, with heterogeneous firms in size and in possibilities of production and innovation. Analyzing this SSI is a way of reporting the development of a segment of a added value product in the RS agribusiness, and can be considered a relevant experience to analyze the potential of the gaúcho agribusiness to add more value to its final products.

Diariamente são descartados no mundo toneladas de resíduos do processamento de frutas que poderiam ser aproveitados pelo seu elevado poder nutricional e funcional, que acabam sendo desperdiçados e podem gerar sérios problemas ao meio ambiente. Outro descarte inadequado que agrava esse problema ambiental é o de embalagens plásticas, que quando não submetidas ao processo de reciclagem trazem enormes danos. Por esses fatores, esse estudo teve como objetivo o aproveitamento de subprodutos da indústria de alimentos para o desenvolvimento de farinhas funcionais e aproveitamento dos resíduos da indústria de capsulas nutracêuticas de gelatina e óleo de chia como matriz para as embalagens biodegradáveis ativas. A quitosana também foi utilizada como matriz no desenvolvimento de filmes aplicados como embalagens. Primeiramente foram avaliados quatro resíduos obtidos de diferentes frutas: resíduo do processamento de suco de mirtilo (bagaço), resíduo do processamento de azeite de oliva (bagaço), cascas de mamão e abacaxi. As propriedades físico químicas, funcionais e antioxidantes desses resíduos foram analisadas, sendo que no geral todos demonstraram alto teor de fibras dietéticas. Em relação às propriedades funcionais a farinha de mamão se destacou pelos elevados valores de capacidade de retenção de água e óleo, pela alta solubilidade e maiores teores de carotenoides (15,56 ± 0,35 mg/100g). A farinha de mirtilo foi a que apresentou o maior poder antioxidante pelo método DPPH (4,62 ± 0,18 IC50 em mg de farinha) e maior teor de compostos fenólicos (23,59 ± 0.85 mg/g GAE), além disso exibiu alto teor de antocianinas. Devido a estas propriedades, a farinha e o extrato do resíduo de mirtilo foram incorporados à gelatina do resíduo do processamento de cápsulas nutracêuticas de óleo de chia para o desenvolvimento de filmes biodegradáveis ativos. Os filmes foram avaliados em relação as suas propriedades mecânicas, de barreira ao vapor da água e luz UV, capacidade antioxidante e aplicação como embalagem em produtos alimentícios. Os resultados sugeriram que a adição de fibras promoveu uma diminuição da resistência à tração e aumento na permeabilidade ao vapor da água. No entanto, a adição de fibra também proporcionou um aumento significativo na barreira de luz UV a 500 nm, sendo eficaz na redução da oxidação lipídica de óleo de girassol. Os filmes com adição de extrato não exibiram alteração nas propriedades mecânicas ou de barreira em comparação com a formulação controle. Além disso, estes filmes exibiram capacidade antioxidante estável por 28 dias. Filmes desenvolvidos com a farinha de mamão e resíduos de gelatina apresentaram comportamento similar aos filmes com resíduos de mirtilo, já que a farinha de mamão também alterou algumas propriedades originais do filme como as propriedades mecânicas e de barreira, e agregaram poder antioxidante. Com o objetivo de melhorar essas propriedades foram então desenvolvidas micropartículas de farinha de casca de mamão em spray drying utilizando o resíduo de gelatina como material de parede. Os resultados indicaram que as micropartículas de casca de mamão ao serem adicionadas na gelatina originaram uma matriz de filme mais contínua e homogênea com aumento da resistência à tração e do módulo de Young. Os filmes com micropartículas (7,5%), quando aplicados como material de embalagem para banha de porco, foram os mais eficientes como barreiras ativas (maior atividade antioxidante), pois um menor teor de peróxidos, dienos e trienos conjugados foram quantificados na amostra após 22 dias. A farinha de resíduos da produção de azeite de oliva também foi utilizada para o desenvolvimento de filmes biodegradáveis, porém o biopolimero utilizado foi a quitosana. A incorporação de farinha de resíduo de oliva na matriz de quitosana também causou alterações na morfologia, tornando o filme mais heterogêneo e áspero. Por esse motivo foram testadas a adição de micropartículas de farinha de oliva nos filmes. A adição de 10% de micropartículas de oliva melhorou significativamente a resistência à tração dos filmes sem alterar as suas propriedades originais. A farinha e as micropartículas de oliva aumentaram a capacidade antioxidante dos filmes, esse aumento foi proporcional à concentração de farinha ou micropartículas adicionadas ao filme. Os filmes com 30% de farinha ou micropartículas foram eficazes como embalagem protetora contra a oxidação de nozes durante 31 dias. A partir dos resultados obtidos neste trabalho fica evidenciado a viabilidade do uso de resíduos da indústria de alimentos e resíduos da indústria de cápsulas nutracêuticas para o desenvolvimento de filmes e uso como embalagens biodegradáveis em diferentes produtos. / Every day tons of fruit processing residues are discarded worldwide that could be harnessed for their high nutritional and functional power and that end up being wasted and generating problems for the environment. Another inadequate disposal that aggravates this environmental problem is the plastic packaging, which when not subjected to the recycling process bring huge damages. Due to these factors, this study aims at the utilization of by-products of the food industry for the development of active biodegradable packaging. Firstly, four residues obtained from different fruits, processing residue of blueberry juice (bagasse), processing residue of olive oil (bagasse), peels of papaya and pineapple were evaluated. The physicochemical, functional and antioxidant properties of these residues were analyzed, and in general, all showed high total dietary fiber content. In relation to the functional properties, papaya flour was distinguished by high water and oil retention capacity, high solubility and higher carotenoid content (15.56 ± 0.35 mg / 100g). The blueberry flour had the highest antioxidant power by the DPPH method (4.62 ± 0.18 IC50 in mg of flour) and a higher content of phenolic compounds (23.59 ± 0.85 mg / g GAE), in addition, it exhibited a high content of anthocyanins. Due to these properties, the flour and extract of the blueberry residue were incorporated into the gelatin from the processing residue of chia oleuroceutical capsules for the development of active biodegradable films for packaging. The films were evaluated in relation to their mechanical properties, water vapor barrier, and UV light, antioxidant capacity and application as packaging in food products. The results suggested that fiber addition promoted a decrease in tensile strength and an increase in water vapor permeability. However, the addition of fiber also provided a significant increase in the UV light barrier at 500 nm being effective in reducing the lipid oxidation of sunflower oil. Films with added extract showed no change in mechanical or barrier properties compared to the control formulation. In addition, these films exhibited a stable antioxidant capacity for 28 days. Films developed with papaya flour and gelatin residues showed similar behavior to films with blueberry residues since papaya flour also altered some of the original properties of the film as mechanical and barrier properties, and added antioxidant power. In order to improve these properties microparticles of papaya peel flour were then developed in spray drying using the gelatin residue as the wall material. The results indicated that the microparticles of papaya peel, when added to gelatin, gave a more continuous and homogeneous film matrix increasing tensile strength and Young's modulus. Microparticles films (7.5%), when applied as packaging material for lard, were the most efficient as active barriers (higher antioxidant activity) because a lower peroxide content was quantified in the sample after 22 days. The residue flour from olive oil production was also used for the development of biodegradable films, but the biopolymer used was chitosan. The incorporation of olive residue flour in the chitosan matrix also caused changes in the morphology, making the film more heterogeneous and rough. For this reason, the addition of olive flour microparticles in the films was tested. The addition of 10% of olive microparticles significantly improved the tensile strength of films without altering their original properties. The flour and the microparticles of olive increased the antioxidant capacity of the films; this increase was proportional to the concentration of flour or micro added to the film. Films with 30% flour or microparticles were effective as protective packaging against Walnut oxidation for 31 days. From the results obtained in this work, it is evident the viability of the use of residues from the food and waste industry of the nutraceutical capsule industry for the development of films and use as biodegradable packaging in different products.

A necessidade de um controle de qualidade seguro e confiável em produtos e/ou matérias-primas provenientes das indústrias farmacêuticas e agrícolas torna as análises de seus ativos e constituintes extremamente importantes para os fabricantes, bem como para os usuários desses produtos. Apesar da espectroscopia de Ressonância Magnética Nuclear (RMN) ser uma das mais importantes ferramentas de análise qualitativa, ainda é pouco usada para fins quantitativos. Considerando esses fatos, métodos para análises de produtos farmacêuticos e agrícolas, empregando técnicas de RMN, foram desenvolvidos no presente trabalho. Um método quantitativo de RMN de 1H em alta resolução para análise de paracetamol em diferentes formulações farmacêuticas foi validado de acordo com a Resolução RE nº 899. Neste método foi usado um padrão interno, tornando desnecessária a construção de uma curva analítica. Outros ativos presentes nas formulações também puderam ser quantificados e alguns excipientes, identificados. De acordo com NBR 14029, foram desenvolvidos e validados métodos empregando RMN em alta resolução de 1H e 31P para análise de glifosato em agrotóxicos. Neste caso, foi empregado um padrão externo, o qual possibilitou análises quantitativas sequenciais dos diferentes núcleos sem a necessidade de um novo preparo de amostra. A RMN em alta resolução de 1H também foi avaliada como um método alternativo para a determinação de ácidos graxos em óleos e azeites, dispensando as reações de transesterificações necessárias para as análises cromatográficas. A RMN no domínio do tempo (RMN-DT) foi usada no desenvolvimento de um método para detecção de adulteração de azeites de oliva com óleo de soja. Esse método baseou-se na diferença de viscosidade do azeite e do óleo e possui a grande vantagem de poder ser aplicado em embalagens lacradas. Por fim, diferentes abordagens analíticas empregando a RMN em alta resolução foram feitas para análises do fitoterápico Cardo-Leiteiro (Silybum marianum L. Gaertn., Asteraceae), possibilitando a quantificação simultânea de sete constituintes ativos, incluindo dois pares de diastereoisômeros. Assim, demonstrou-se no presente trabalho o potencial das técnicas de RMN quantitativas, para o controle de qualidade de produtos farmacêuticos e agrícolas, com algumas vantagens sobre os outros métodos analíticos normalmente usados nessas análises. / The need for effective and reliable quality control in products and/or raw materials from pharmaceutical and agricultural industries make analyses of their actives compounds and constituents very important to manufacturers and consumers. Nuclear Magnetic Resonance spectroscopy (NMR) is one of the most important tools for qualitative analysis but it is rarely used as quantitative method. Considering these facts, quantitative NMR methods (qNMR) for analysis of pharmaceutical and agricultural products were developed in this thesis. A high resolution 1H qNMR method for paracetamol, in different pharmaceutical formulations, was validated according to RE Resolution Nº 899. An internal standard was used in this method, therefore, the construction of a calibration curve was unnecessary. Other actives constituents present in the formulations could also be quantified and some excipients, identified. According to NBR 14029, high resolution qNMR 1H and 31P methods were developed and validated for glyphosate. In this case, an external standard was used, which enabled sequential quantitative analyses of different nuclei without the need to prepare a new sample. The high-resolution qNMR 1H was also used as an alternative method for fatty acids determination in oils and olive oils, dispensing transesterifications reactions required for GC analysis. Time domain NMR (TD-NMR) was used to develop a method to detect adulteration of olive oil with soybean oil. This method was based on the viscosity difference between olive oil and soybean oil, and has a great advantage, because it can be applied in sealed packages. Finally, different analytical approaches using high resolution NMR 1H were studied to qualitative and quantitative analysis of milk thistle (Silybum marianum L. Gaertn., Asteraceae), a botanical dietary supplement, enabling the simultaneous quantification of seven active constituents, including two pairs of diastereoisomers. Therefore, it was demonstrated in this thesis the potential of qNMR techniques to quality control of pharmaceutical and agricultural products, with some advantages over other analytical methods, normally used in these analyses.

Les sociétés économiquement développées sont confrontées à la problématique du vieillissement de leur population associée à la recrudescence des pathologies dégénératives. Parmi les manifestations du vieillissement, l'atteinte de l'appareil locomoteur (ostéoporose et sarcopénie) est considérée comme un problème majeur de santé publique. De ce fait, le développement de mesures préventives permettant de préserver la santé des séniors constitue un véritable enjeu de santé publique. La recherche scientifique fournit de nombreuses preuves concernant l'importance de l'alimentation dans la diminution ou l'exacerbation de certaines maladies. Ces observations confirment le vieux concept soutenant que l'adoption d'une alimentation équilibrée permet le maintien d'un état de santé satisfaisant, en particulier avec l'avancée en âge. A ce jour, le potentiel de l'huile d'olive, en tant que telle ou comme vecteur de nutriments lipophiles d'intérêt pour la prévention nutritionnelle de l'ostéoporose et de la sarcopénie, n'a jamais été testé. La prévalence de l'ostéoporose étant très supérieure chez la femme ménopausée qui souffre également d'une perte musculaire accélérée, cette population a été ciblée dans la présente étude. Dans une première étape, des résultats originaux ont été obtenus concernant l'effet de l'ovariectomie sur le métabolisme musculaire. Ainsi, notre travail montre qu'après ablation des ovaires, la synthèse protéique musculaire est réduite, en association avec une diminution d'un marqueur de la protéolyse de ce tissu. Pris dans son ensemble, ces résultats démontrent un ralentissement du renouvellement protéique musculaire suite à l'ovariectomie. En termes de mécanismes mis en jeu, une augmentation de l'infiltration lipidique tissulaire a été observée. En parallèle du ralentissement du renouvellement musculaire après ovariectomie, une augmentation du renouvellement osseux, classiquement décrit dans la littérature, a été mis en évidence. Dans un second temps, l'effet de l'huile d'olive et plus particulièrement des polyphénols présents dans cet aliment en association avec la vitamine D et l'acide ocosahexaénoïque et leur éventuelle synergie a été évalué à l'aide d'un modèle d'ostéoporose post-ménopausique. Des souris ovariectomisées ont été soumises à une des 4 huiles suivantes : huile de maïs, huile d'olive raffinée, huile d'olive extra vierge ou huile de poisson. Pour chaque huile, un groupe supplémentaire de souris ovariectomisées a reçu de l'huile enrichie en vitamine D. Cette étude a permis de mettre en évidence un effet protecteur de l'association de l'huile d'olive extra vierge et de la vitamine D sur la perte osseuse induite par l'ovariectomie chez la souris. En effet, l'accélération du renouvellement osseux consécutive à la carence estrogénique est freinée par cette association de nutriments, qui diminuent également l'expression des marqueurs du stress oxydant et de l'inflammation. Les résultats obtenus sont en cours de validation chez l'Homme grâce à une investigation clinique réalisée chez des femmes ménopausées. Celle-ci a été mise en place au cours de ces travaux de thèse. / Economically developed societies face the problem of an aging population combined with the increase in degenerative diseases. Among the signs of aging, musculoskeletal pathologies (osteoporosis and sarcopenia) are considered major public health problems. Therefore, the development of preventive measures to preserve seniors’ health is a real public health issue. Scientific research provides ample evidence of the importance of diet in diseases reduction or exacerbation. These observations confirm the old concept arguing that the adoption of a balanced diet helps to maintain a healthy life, especially with advancing age. To date, the potential of the olive oil, as such or as a vector of lipophilic nutrients, for the prevention of osteoporosis and sarcopenia, has never been tested. As the prevalence of osteoporosis is much higher in postmenopausal women who also suffer from an accelerated muscle mass loss, this population was targeted in this study. In a first step, original results were obtained regarding the effect of ovariectomy on muscle metabolism. Thus, our work showed that after removal of the ovaries, muscle protein synthesis was reduced in association with a decrease in the expression of a proteolysis marker of this tissue. Taken together, these results suggest a slowing down of muscle protein turnover after ovariectomy. In terms of mechanisms, an increase in lipid tissue infiltration was observed. The slowdown in muscle protein renewal after ovariectomy was associated with an increased bone turnover, classically described in the literature. In a second step, the effect of olive oil and more particularly its polyphenols in combination with vitamin D and docosahexaenoic acid and their possible synergy was assessed using a postmenopausal osteoporosis model. Ovariectomized mice were subjected to one of the following oils: corn oil, refined olive oil, extra virgin olive oil or fish oil. Four additional groups of ovariectomized mice received the oil fortified with vitamin D. This study demonstrated a protective effect of the combination of virgin olive oil and vitamin D on bone loss induced by ovariectomy in mice. Indeed, the acceleration of the bone turnover induced by the estrogen deficiency was inhibited by this combination of nutrients, which also decreased the expression of oxidative stress and inflammation markers. These results are currently being validated in a clinical investigation conducted in postmenopausal women, which has been established during this thesis work.

The issue of food traceability is one that affects a great number of sectors and policy areas. Within the EU, there is increasing demand from consumers, businesses and institutions to have more direct access to information about how food is produced, transformed, and distributed. Currently, however, practices in the industry are very much open to human error. Databases are highly vulnerable to inaccuracies and hacking, as well as deliberate faults caused by corruption or fraudulent conduct. With food traceability being so closely related to trade and public health issues, there is arguably increasing incentive for the EU to seek alternative tools to increase transparency and accountability throughout supply chains. Consequently, this paper will examine a possible alternative to current practices by evaluating the applicability of 'blockchain' technology, namely a system of digitised, decentralised ledgers, which could allow key stakeholders to access information about the provenance of food immediately, comprehensively and securely. The analysis will focus specifically on Extra Virgin Olive Oil (EVOO), one of the most adulterated products in the food industry, identifying gaps and opportunities in current traceability systems. The research question tackled in this paper, therefore, may be formulated as follows: how and to what extent could blockchain technology constitute a sustainable solution for improving the traceability of EVOO within the EU? The paper begins with a brief overview of the issue and an explanation of the research methodology used, followed by an elaboration of key terms and concepts and a detailed explanation of the principles underlying blockchain technology. Subsequently, the key challenges and opportunities associated with blockchain-based traceability systems are examined through a case study, followed by an analysis aimed at assessing the sustainability of blockchain solutions for the EVOO sector. The conclusion, lastly, provides an overview of relevant findings and proposes a final assessment.

The production of olive oil has seen an increase in recent years due to a broader understanding of the health benefits of the Mediterranean Aliment Culture. With this expanding industry we also see an increase in the waste products associated with olive oil production. Given the high polluting content of the waste streams and the economic costs associated with its removal and processing, waste remediation and disposal has become a significant point of interest for both producers and local bodies. In this project, wastes of the olive oil production industry are examined for their use as the raw material for a novel product used in the control of horticulturally important diseases, examining the effect of extraction protocols on the activity of the final product. Active fractions of the olive oil wastes were identified from literature and protocols for their extraction and recovery developed; incorporating both standard solvent extraction and novel ultrasound-assisted extraction. Criteria for the analysis of extract quality were outlined and potential target applications identified. The biophenolic compounds of olive wastes were identified as providing the majority of the active fraction, so protocols were developed for the recovery of these compounds. Standard solvent extraction and ultrasound-assisted extraction were examined for their effectiveness of biophenolic recovery and their effect on product quality. Certain horticulturally important diseases were identified as potential targets, and bioassays undertaken to determine the ability of a crude extract to inhibit and control these diseases. It was found that the action of ultrasound during extraction provides a greater degree of recovery of biophenolic compounds, with minimal loss of product quality; as determined by bioassays and total biophenol determination. This increase in recovery is due primarily to the destruction of cellular material resulting in higher rates and absolute yields of recovery. This work provides evidence of the occurrence of some interesting phenomenon in the recovery of biophenols from olive wastes that deserves further examination. The crude olive leaf extract was shown to have an inhibitory effect on bacteria and effectively no inhibitory effect on fungal species in the total biophenol ranges tested. Erwinia amylovora and Staphylococcus aureus both showed a large susceptibility to the olive leaf extract. Results showed a higher degree of susceptibility of Gram positive bacteria and a potential resistance in soil microbes. For bacterial species, total biophenol concentrations of 0.15 to 3.50 mg GAE/ml provided inhibitory effects, while with the fungal species tested, no inhibitory effects were found at total biophenol concentrations of up to 2.50 mg GAE/ml. Some evidence exists that there is an opportunity for the economic recovery of olive biophenols for use as a novel product, but more work is required to determine specific applications and/or targets of use, as well as optimisation of the extraction and purification protocol. A sample removed from interfering compounds will allow the examination of activity of particular compounds and hence a better understanding of the action of the olive waste extract.

A la primera part d’aquesta tesi doctoral s’ha portat a terme l’anàlisi de composició bàsica de 16 productes flequers i de brioixeria tradicionals de la província de Lleida. Els resultats obtinguts indiquen que existeix una gran variabilitat a la composició nutricional dels productes estudiats, derivada de les matèries primeres utilitzades, de la seva formulació i dels processos d’elaboració. La segona part de la tesi s’ha centrat en la millora de les propietats tecnològiques i dels perfils nutricional i sensorial del pa a través de la incorporació d’oli d’oliva verge com a ingredient. Amb aquesta finalitat s’han estudiat els efectes de l’addició d’oli d’oliva a diferents nivells (0-75%) sobre les propietats fisicoquímiques i reològiques de la massa de pa y els efectes sobre el producte final en termes de volum específic, perfil sensorial i composició nutricional. Els pans elaborats amb 4%, 10% i 20% d’oli d’oliva verge han mostrat bones propietats reològiques; no obstant, únicament els dos primers han estat acceptats sensorialment. La tercera part de la tesi s’ha centrat en millorar el contingut fenòlic del pa elaborat amb un 10% d’oli d’oliva verge, per això ha estat necessari establir el procediment d’extracció i quantificació de compostos fenòlics d’una matriu de pa. A més s’ha estudiat la millor combinació temperatura-temps-format de cocció del producte per a minimitzar la pèrdua de compostos fenòlics i maximitzar la preservació del contingut fenòlic inicial. A partir de l’anàlisi sensorial i de la quantificació de fenols, el pa formulat amb oli d’oliva Arbequina enriquit en compostos fenòlics ha estat l’escollit com a producte finalista. / En la primera parte de esta tesis doctoral se ha llevado a cabo el análisis de composición básica de 16 productos de panadería y bollería tradicionales de la provincia de Lleida. Los resultados obtenidos indican que existe una gran variabilidad en la composición nutricional de los productos estudiados, derivada de las materias primas utilizadas, de su formulación y de los procesos de elaboración. La segunda parte de la tesis se ha centrado en la mejora de las propiedades tecnológicas y de los perfiles nutricional y sensorial del pan a través de la incorporación de aceite de oliva virgen como ingrediente. Con esta finalidad se han estudiado los efectos de la adición de aceite de oliva a distintos niveles (0-75%) sobre las propiedades físico-químicas y reológicas de la masa panaria, y sus efectos sobre el producto final en términos de volumen específico, perfil sensorial y composición nutricional. Los panes elaborados con 4%, 10% y 20% de aceite de oliva virgen han mostrado buenas propiedades reológicas; sin embargo únicamente los dos primeros han sido aceptados sensorialmente. La tercera parte de la tesis se ha centrado en mejorar el contenido fenólico del pan elaborado con un 10% de aceite de oliva virgen, para lo que se ha establecido el procedimiento de extracción y cuantificación de compuestos fenólicos de una matriz panaria. Además se ha estudiado la mejor combinación temperatura-tiempo-formato de cocción del producto para minimizar la pérdida de compuestos fenólicos y maximizar la preservación del contenido fenólico inicial. A partir del análisis sensorial y de la cuantificación de fenoles, el pan formulado con aceite de oliva Arbequina enriquecido en compuestos fenólicos ha sido escogido como el producto finalista. / In the first part of this doctoral thesis the basic composition analysis of 16 baked and pastry traditional products of Lleida province has been carried out. The obtained data indicates that there is a great variability in the nutritional composition of the studied products, which is derived of raw materials used, of their formulation and manufacturing processes. The second part of the thesis has been focused on the improvement of technological properties and of nutritional and sensorial profiles of bread through the addition of virgin olive oil as ingredient. For this purpose the effect of addition of different levels of virgin olive oil (0-75%) on physiochemical and rheological properties of bread dough, and its effects on final product in terms of specific volume, sensory profile and nutritional composition have been studied. Bread made with 4%, 10% and 20% of virgin olive oil showed good rheological properties, but only the first two were considered acceptable from sensory analyses. The third part of the thesis has been focused on improving the phenolic content of the bread made with 10% of virgin olive oil; to achieve it, establishing the phenolic compounds extraction and quantification procedure of a bread matrix has been necessary. Furthermore the best combination temperature-time-format of product baking to minimize the lost of phenolic compounds and maximize the preservation of initial phenolic content has been studied. From sensory analyses and phenolic quantification, the bread formulated with Arbequina olive oil enriched with phenolic compounds has been chosen as finalist product.

La present tesi avalua els efectes de certs factors ambientals sobre la paraoxonasa1 (PON1), enzim antioxidant, possiblement protector enfront les malalties cardiovasculars, a través de dos estudis d'intervenció i un de transversal. En primer lloc, el tractament amb simvastatina dels pacients amb hipercolesterolèmia familiar, que presentaven una activitat paraoxonasa baixa, s'associava a un increment de l'activitat fins a valors similars als d'individus normolipèmics, independentment dels polimorfismes PON1-55 o PON1-192. En segon lloc, l'entrenament físic s'associava a un augment de l'activitat paraoxonasa en els individus QQ i una disminució de la mateixa en els portadors de l'al·lel R pel polimorfisme PON1-192. L'increment de l'activitat paraoxonasa immediatament després de l'exercici físic agut era seguit per una disminució subseqüent de l'activitat. La recuperació dels nivells basals d'activitat paraoxonasa a les 24h de l'exercici físic agut es donava en els individus QQ independentment del seu estat d'entrenament, i en els individus portadors de l'al·lel R només quan estan entrenats. En tercer lloc, el consum elevat d'àcid oleic comportava un augment de la concentració de c-HDL i de l'activitat paraoxonasa en els homes portadors dels genotips QR i RR del polimorfisme PON1-192, respectivament.Paraules claus: paraoxonasa, PON1, genotips, simvastatina, hipercolesterolèmia familiar, interacció gen-dieta, lipoproteïna d'alta densitat (HDL), exercici físic agut, entrenament físic, estrès oxidatiu, àcid oleic, oli d'oliva, peròxids lipídics, malaltia cardiovascular. / The present thesis evaluates some environmental factor effects on paraoxonase1 (PON1), an possibly protective against cardiovascular disease antioxidant enzyme, through two intervention studies and a cross-sectional one. First, treatment with simvastatin of the familial hypercholesterolemic patients, which had low paraoxonase activity, was associated with an increase in the activity to values similar to the normolipemic ones, regardless of the PON1-55 or PON1-192 polymorphisms. Second, Regular exercise was associated with an increase in PON1 activity in QQ subjects and with a decrease in R carriers. Increased PON1 activity immediately after a bout of exercise was subsequently followed by a decrease of activity. The recovery of the basal PON1 activity levels at 24 h was found in QQ subjects regardless of their training status and in trained R carriers, but not in untrained R carriers. Third, high oleic acid intake was associated with increased HDL cholesterol and PON1 activity levels only in men who were QR and RR of the PON1-192 polymorphism, respectively.

Com a busca pela praticidade e rapidez na obtenção dos resultados, torna-se cada vez mais importante a implementação de métodos que possam ponderar se os resultados quantitativos são realmente necessários. Os métodos qualitativos são utilizados como uma triagem que antecedem a quantificação e que permite uma redução tanto de tempo como de custos. Estes métodos têm cada vez mais ganhado importância e o uso instrumental proporcionou novas perspectivas e garantia de uma maior confiabilidade e aplicabilidade. O desenvolvimento de metodologias qualitativas aliando métodos instrumentais e quimiometria podem ser apropriados para autenticação de amostras. Desta forma, associado à espectroscopia na região do ultravioleta e visível (UV-Vis) o método quimiométrico de reconhecimento de padrões supervisionado de mínimos quadrados parciais com análise discriminante (PLS-DA), mostrou ser uma ferramenta capaz de autenticar amostras de óleo de soja transgênica e não transgênica, bem como, a autenticação de azeite de oliva extra virgem de acordo com os percentuais de acidez. Além disso, o método proposto permite uma análise rápida e não destrutiva da amostra. Nos estudos, a autenticação de óleos de sojas transgênicos e não transgênicos pode ser atribuída ao deslocamento batocrômico, provavelmente devido às diferenças no grupo cromóforo presente nas amostras transgênicas e não transgênicas, enquanto que nos azeites extra virgem de diferentes percentuais de acidez a autenticação pode ser atribuída a ocorrência de efeitos hipercrômico e hipocrômico. A espectroscopia na região do UV-Vis permitiu a autenticação geográfica de azeites de oliva da região do Mediterrâneo através do método quimiométrico de análise de componentes independentes (ICA). Por ser um método baseado na independência estatística, diferenças entre as amostras provenientes de diferentes países banhados pelo mar Mediterrâneo puderam ser discriminadas, bem como amostras provenientes de um mesmo país. / The search for practical and quickly results increase the importance of methodologies that can ponder if the quantitative results are really needed. The qualitative methods are used as a prior screening to quantification and allows a reduction of time and costs. These methods have increasingly its importance and the instrumental employ provided new perspectives and ensuring greater reliability and applicability. The development of qualitative methods combining instrumental and chemometric can be appropriate for authentication samples. Thus, coupled with spectroscopy in the ultraviolet and visible region (UV-Vis) the supervised pattern recognition method of partial least squares with discriminant analysis (PLS-DA), showed be a tool to authenticate transgenic and non-transgenic soybean oil samples, as well, extra virgin olive oil according to the acidity percentage. Furthermore, the proposed method promote a rapid and non-destructive analysis of the samples. Authentication studies of transgenic and non transgenic soybeans oils can be attributed to the bathochromic shift, due to differences in the chromophore group present in the transgenic and non transgenic samples, while in the extra virgin olive oils with different acidity percentages the authentication can be attributed to the occurrence of hyperchromic and hypochromic effects. UV-Vis spectroscopy allowed the geographic authentication of extra virgin olive oils from the Mediterranean region through the chemometric method of independent component analysis (ICA). Due the ICA be a method based on statistical independence, differences between samples from different countries around the Mediterranean Sea were authenticated, as well the samples from the same country.