Ce projet contribue à développer la prochaine génération de nano-emballages en utilisant une approche plus sûre et éco-conçue avec des avantages directs à la fois pour l'environnement et la sécurité des consommateurs. Les emballages alimentaires constituent l’un des principaux secteurs d’applications des nanotechnologies avec des enjeux environnementaux prometteurs de substitution des pétro-plastiques par des bio-plastiques et de réduction des pertes et gaspillages alimentaires grâce à des emballages plus performants, de type actifs et intelligents. Dans le cas de matériaux nano-composites (matrice polymérique contenant des nano-particules) destinés au contact alimentaire, le risque majeur en terme de santé humaine est lié à leur impact sur la migration de composés indésirables de l’emballage vers l’aliment (stabilisants UV, antioxydants, plastifiants, etc) qui peuvent avoir des effets néfastes en fonction des doses et durées d’exposition. Ces interactions contenant/contenu sont soumises à une réglementation européenne dont l’objectif est la protection de la santé du consommateur en fixant des limites de migration spécifique pour tous les composés supposés entrer dans la composition des matériaux plastiques dédiés au contact alimentaire. Dans le cas des nanomatériaux, la présence de nanoparticules est susceptible de modifier les interactions entre le polymère et les additifs et par voie de conséquence leurs propriétés de transfert. Ainsi, la formalisation des phénomènes de migration de l’emballage vers l’aliment établie sur des matériaux plastiques ne contenant pas de nanoparticules ne peut pas être directement transposée au nano-matériaux. De plus la présence de ces nanoparticules peut profondément modifier l’éco-toxicité environnementale du système matrice- nanoparticule -additif.La présente étude vise à comprendre et contrôler l’impact des structures nanocomposites (matrice polymérique contenant des nano-particules) sur les propriétés de transport (diffusivité et solubilité) des nanoparticules et des additifs chimiques en condition d’usage. À cet égard, il est nécessaire de combler le déficit de connaissances dans a caractérisation de la structure 3D, des propriétés physico-chimique et des interactions aux interfaces entre nanoparticules et matrice dans les nanomatériaux. Devant la complexité du système étudié, la modélisation est indispensable pour représenter (simplifier sans pour autant perdre trop de connaissances) la structure 3D des nanomatériaux et simuler, reproduire puis prédire, l’évolution de leurs propriétés de transfert en fonction des paramètres structurels et en condition d’usage. La modélisation des transferts est également indispensable pour, dans une approche d’ingénierie inverse, éco-concevoir et dimensionner à façon des nano-emballages sûrs pour l’Homme et l’Environnement. Dans cette optique une démarche de modélisation multi-échelle des relations structure/propriétés de transfert de masse a été mise en place sur des matériaux nanocomposites ciblés choisis pour leur pertinence dans le domaine de l’emballage alimentaire. / The market of nanotechnologies is dominated by the food packaging area which amounts more than 20% of the total nanotechnologies market in 2015. However, the wide-scale use of nanomaterials raises important questions about environmental and safety issues that could hinder their development. In the case of plastics intended to be in contact with food, the risk of contamination concerns not only the nanoparticles but also all the chemical additives added during the material processing. The presence of nanoparticles is susceptible to modify the interactions between polymer and the additives with a possible change in their transport properties and therefore the food contamination.The present work aims at identifying the relationship between the structural characteristic and the transport properties (diffusivity and solubility) of nanoparticles and chemical additives incorporated in nanocomposites. In this regard, it is necessary to fill the gap of knowledge in 3D nanostructure characterization and a multi-scale modeling of mass transfer properties of nanocomposites in real usage conditions.In this way, polyethylene and nanoclay were selected based on the best compromise between real potential applications and the scientific knowledge previously published and eventually the nanocomposites were synthesized with LLDPE, Cloisite20 and a compatibilizer by melt intercalation method.The nanocomposite structure was characterized using TEM, X-ray nanotomography, TGA and XRD then submitted to migration tests undertaken in contact with different food simulants which represent various types of food (aqueous, acid, alcoholic) following the recommendation of the European regulation on the food contact material. To evaluate the positive or adverse effects of the nanomaterials on the contamination of the food by chemical additives which are usually incorporated with the plastic packaging, the virgin polymer and nanocomposite material were spiked with a mixture of the additives exhibiting various volatility, polarity and molecular weight. Then, the transport properties (i.e inertia) of nanocomposite structure was distinctively investigated on kinetic (apparent diffusion coefficient) and thermodynamic (partition coefficient) considerations.The results indicated that nanoclay addition in plastic materials favorably reduced the migration of additives by modifying both their diffusivity in the polymer and their partition between the polymer and the food simulant. However, while the partition coefficient of additives increases in nanocomposite in comparison to pure LLDPE for the samples in contact with all types of food simulants, the reduction of diffusion coefficient is significantly dependent on the nature of the food simulant in contact. Hence, it can be concluded that the major role in the migration of additives is not played by the imposed tortuosity path, but by the factors such as the affinity between the base polymer and simulants as well as the effects of simulants on swelling and crystallinity of the samples. Moreover, the effect of additive-related parameters and the structural parameters were assessed and put in perspective with their impact on the transport properties of nanostructures. Integrating the results of characterization and transfer properties led to an improved understanding of the influence of structure of nanocomposites on their mass transfer properties and therefore on the suitability of using them as food contact materials.

<p>Cellulose nanocrystals (CNCs) and its composite coatings may impart many benefits in packaging, electronic, optical, etc. applications; however, large-scale coating production is a major engineering challenge. To fill this knowledge gap, a potential large-scale manufacturing technique, roll-to-roll reverse gravure processing, has been described in this work for the manufacture of CNC and CNC-poly(vinyl alcohol) (PVA) coatings on a flexible polymer substrate. Various processing parameters which control the coating structure and properties were examined. The most important parameters in controlling liquid transfers were gravure roll, gravure speed, substrate speed, and ink viscosity. After successful fabrication, coating adhesion was investigated with a crosshatch adhesion test. The surface roughness and morphology of the coating samples were characterized by atomic force microscopy and optical profilometer. The Hermans order parameter (S) and coating transparency were measured by UV–Vis spectroscopy. The effect of viscosity on CNC alignment was explained by the variation of shear rate, which was controlled by the micro-gravure rotation. Finally, the CNC alignment effect was investigated for gas barrier and thermal management applications.</p> <p>In packaging applications, cellulose nanomaterials may impart enhanced gas barrier performance due to their high crystallinity and polarity. In this work, low to superior gas barrier pristine nanocellulose films were produced using a shear-coating technique to obtain a range of anisotropic films. Induction of anisotropy in a nanocellulose film can control the overall free volume of the system which effectively controls the gas diffusion path and hence, controlled anisotropy results in tunable barrier properties. The highest anisotropy materials showed a maximum of 900-fold oxygen barrier improvement compared to the isotropic arrangement of nanocellulose film. The Bharadwaj model of nanocomposite permeability was modified for pure nanoparticles, and the CNC data were fitted with good agreement. Overall, the oxygen barrier performance of anisotropic nanocellulose films was 97 and 27 times better than traditional barrier materials such as biaxially oriented poly(ethylene terephthalate) (BoPET) and ethylene vinyl alcohol copolymer (EVOH), respectively, and thus could be utilized for oxygen-sensitive packaging applications. </p> The in-plane thermal conductivity of CNC - PVA composite films containing different PVA molecular weights, CNC loadings and varying order parameters (S) were investigated for potential application in thermal management of flexible electronics. Isotropic CNC - PVA bulk films with 10-50 wt% PVA solid loading showed significant improvement in thermal conductivity compared to either one component system (PVA or CNC). Furthermore, anisotropic composite films exhibited in-plane thermal conductivity as high as ~ 3.45 W m-1 K-1 in the chain direction, which is higher than most polymeric materials used as substrates for flexible electronics. Such an improvement can be attributed to the inclusion of PVA as well as to a high degree of CNC orientation. The theoretical model was used to study the effect of CNC arrangement (both isotropic and anisotropic configurations) and interfacial thermal resistance on the in-plane thermal conductivity of the CNC-PVA composite films. To demonstrate an application for flexible electronics, thermal images of a concentrated heat source on both neat PVA and CNC-PVA composite films were taken that showed the temperature of the resulting hot spot was lower for the composite films at the same power dissipation.

O estufamento de embalagens a vácuo de carnes refrigeradas, também conhecido como blown pack, é atribuído a bactérias psicrófilas e psicrotróficas, dentre as quais fazem parte algumas espécies de clostrídios, enterobactérias e bactérias lácticas. A capacidade desses microrganismos crescer em temperaturas de refrigeração adequadas torna um desafio o seu controle pela indústria. O Brasil é um dos grandes produtores de carne bovina no mundo e apesar da importância que a indústria de carne representa para o país, existem poucos estudos sobre as possíveis causas da deterioração do tipo blown pack. A importância deste trabalho fundamenta-se na escassez de pesquisas sobre esse problema que afeta a indústria de carne. O objetivo dessa pesquisa foi avaliar a presença dos principais microrganismos envolvidos na deterioração tipo blown pack, com ênfase em clostrídios, enterobactérias e bactérias láticas. Assim, o método Terminal- Restriction Fragment Length Polymorphism, disponível no laboratório de Biologia Molecular do CENA-USP, foi empregado por permitir um diagnóstico rápido e preciso para detecção de microrganismos. Foram analisadas 15 amostras de carne bovinas refrigeradas, embaladas a vácuo e estufadas, provenientes de frigoríficos dos estados de São Paulo, Mato Grosso do Sul e Goiás. Os cortes utilizados para as análises foram contrafilé, músculo, alcatra, cupim, picanha e filé de costela. As amostras apresentavam características de deterioração tipo blown pack dentro da data de validade, com períodos armazenamento variando de 30 a 120 dias. Foram identificadas as espécies Clostridium algidicarnis, Clostridium gasigenes, Clostridium putrefaciens, Clostridium frigidicarnis, Lactobacillus sakei, Hafnia alvei e Serratia liquefaciens pela técnica T-RFLP, que se mostrou uma excelente ferramenta de identificação microbiana nas amostras de carne. Devido à alta prevalência de enterobactérias nas amostras de carnes detectadas pela técnica de T-RFLP, foram realizadas análises convencionais com isolamento e identificação de enterobactérias, a fim de confirmar a presença destes microrganismos viáveis e cultiváveis nas amostras. As espécies de enterobactérias cultivadas e identificadas foram H. alvei, Ser. liquefaciens, Citrobacter braakii, Pantoea sp e Yersinia enterocolitica, sendo esta última potencialmente patogênica e de interesse em saúde pública. Observou-se que a H. alvei foi a espécie predominante nas amostras avaliadas, tanto pela técnica de T-RFLP como pelas análises microbiológicas convencionais. Com o objetivo de complementar os resultados, foram realizadas análises convencionais de cultivo visando o isolamento de Clostridium estertheticum e Clostridium gasigenes nas amostras de carne. A técnica de PCR foi empregada com a finalidade de identificação dos isolados obtidos. / The distension of the packaging of vacuum packed chilled meat, also know as blown pack, is assigned to psichrophilic and psychrotrophic bacteria, among which are part some clostridium, enterobacteria and lactic bacteria.The ability of these microorganisms to grow at refrigeration temperatures makes it an appropriate challenge its control by the industry. Brazil is a major producer of beef in the world and despite the importance of the beef industry represents for the country, there are few studies on the possible causes of deterioration of blown pack type. The importance of this work is based on the dearth of research on this problem that affects the meat industry. The aim of this study was to evaluate the presence of the main microorganisms involved in the deterioration blown pack type, with emphasis on clostridia, enterobacteria and lactic bacteria. Thus, the method-Terminal Restriction Fragment Length Polymorphism, available at Molecular biology laboratory of CENA-USP, was used to allow a rapid and accurate diagnosis for the detection of microorganisms. We analyzed 15 samples of beef chilled, vacuum packed wich abundant gas production, refrigerators from the states of São Paulo, Mato Grosso do Sul and Goiás cuts used for the analysis were striploin, shin, rump, hump, cop of rump and cube roll. The samples showing signs of deterioration such blown pack within the shelf life, with storage periods ranging from 30 to 120 days. Were identified Clostridium algidicarnis, Clostridium gasigenes, Clostridium putrefaciens, Clostridium frigidicarnis, Lactobacillus sakei, Hafnia alvei and Serratia liquefaciens by TRFLP technique, which proved an excellent tool for microbial identification in meat samples. The high prevalence of enterobacteria in samples of meat detected by the technique of TRFLP analysis was performed with conventional isolation and identification of enterobacteria, in order to confirm the presence of viable and culturable microorganisms in the samples. The species of enterobacteria were identified and cultivated H. alvei, Ser. liquefaciens, Citrobacter braakii, Pantoea sp. and Yersinia enterocolitica, the latter being potentially pathogenic and interest in public health. It was observed that H. alvei was the predominant species in the samples evaluated by both the T-RFLP technique and by conventional microbiological tests. In order to complement the results were analyzed conventional cultivation and isolation of Clostridium estertheticum and Clostridium gasigenes in meat samples. The PCR technique was employed for the purpose of identification of isolates.

Este trabalho teve como objetivo estabelecer a tecnologia de processamento mínimo de laranja \'Pêra\', visando obtenção de um produto conveniente com qualidade microbiológica e sensorial que atendam às necessidades do consumidor. Primeiramente, visando facilitar o descascamento das laranjas foi estudado o efeito do tratamento hidrotérmico no tempo de descascamento e na qualidade dos frutos minimamente processados armazenados a 6&#176;C. Frutos resfriados a 6&#176;C e imersos em água a 50&#176;C por 8 minutos, foram descascados num tempo 3,2 vezes menor que as laranjas controle. O rendimento em laranjas comercializáveis foi de 95% para laranjas tratadas hidrotermicamente contra 60% para laranjas controle. As laranjas tratadas hidrotermicamente foram preferidas quanto à aparência e não tiveram sua qualidade físicoquímica e sensorial afetada. Em uma segunda etapa, foi determinada a eficácia da sanificação no processamento mínimo das laranjas. Os níveis de contaminação tanto por fungos quanto por bactérias foram baixos, atingindo no máximo 4 x 102 UFC.g-1. Não foram detectados coliformes nem Salmonella. Embora todas as contagens microbianas tenham sido baixas em todos os tratamentos, naqueles nos quais se utilizou sanificação foram encontradas as menores contaminações, mostrando a eficácia da sanificação. Na terceira etapa estudou-se o efeito de níveis de processamento mínimo e de temperaturas de armazenamento na atividade respiratória e na produção etileno das laranjas. O processamento interferiu na atividade respiratória, sendo maior essa influência imediatamente após o descascamento e separação dos segmentos. O processamento mínimo de laranjas nas formas inteiras com ou sem albedo afetou a atividade respiratória somente na primeiras horas após o processamento. Durante todo período de armazenamento a atividade respiratória das laranjas a 1&#176; e 11&#176;C não diferiram entre si, sendo inferior à das laranjas a 21&#176; e 31&#176;C. O etileno foi detectado apenas nos frutos mantidos a 21&#176; e 31&#176;C. O quociente de temperatura foi maior na faixa de 11-21&#176;C. Na quarta etapa foram estudadas tecnologias de embalagem, quanto à eficácia na manutenção da qualidade microbiológica, sensorial e físico-química da laranja \'Pêra\' minimamente processada. A embalagem de PVC foi tão eficiente quanto a embalagem de polipropileno sob atmosfera modificada passiva ou ativa, dentro do período avaliado, permitindo a conservação das laranjas por até 9 dias a 12&#176;C e até 12 dias a 6&#176;C. / The purpose of this work was to establish a minimal processing technology for \'Pera\' orange in order to obtain a suitable product with microbiological and sensory qualities meeting customers&#39; needs. Firstly, in order to make orange peeling easier, it was studied the effect of the hydrothermal treatment on peeling time and quality of minimally processed fruits stored at 6&#176;C. Fruits cooled at 6&#176;C and immersed in water at 50&#176;C for 8 minutes were peeled 3.2 times faster than control oranges. Commercial yield of hydrothermally treated oranges was 95%, while in control oranges it was 60%. Hydrothermally treated oranges showed better appearance with no alterations in their physicochemical and sensory qualities. Secondly, the sanification effectiveness in the minimal processing of oranges was determined. Contamination levels by fungi or bacteria were low, reaching a maximum of 4 x 102 CFU.g-1. No coliforms or Salmonella were detected. Although all microbial counts were low for all treatments, those undergoing sanification showed lower contamination rates, evidencing the sanification effectiveness. A third stage involved the study of the effect of minimal processing and storage temperatures on the respiratory activity and ethylene production in oranges. Processing influenced the respiratory activity especially immediately after peeling and separation of segments. Minimal processing of whole oranges, with or without albedo, affected the respiratory activity only during the first hours after processing. The respiratory activity of oranges at 1&#176; and 11&#176;C did not differ during all storage period and were lower than the respiratory activity of oranges stored at 21&#176; and 31&#176;C. Ethylene was detected only in fruits kept at 21&#176; e 31&#176;C. The temperature quotient was higher for 11-21&#176;C A fourth stage involved the study of packaging technologies in relation to their effectiveness at maintaining microbial, sensory and physicochemical qualities in minimally processed \'Pera\' oranges. PVC film was as effective as the polypropylene one under passive or active modified atmosphere within the period evaluated, with oranges stored at 6&#176; and 12&#176;C showing shelf life of 12 and 9 days, respectively.

Este trabalho teve como objetivo estabelecer a tecnologia de processamento mínimo de laranja \'Pêra\', visando obtenção de um produto conveniente com qualidade microbiológica e sensorial que atendam às necessidades do consumidor. Primeiramente, visando facilitar o descascamento das laranjas foi estudado o efeito do tratamento hidrotérmico no tempo de descascamento e na qualidade dos frutos minimamente processados armazenados a 6&#176;C. Frutos resfriados a 6&#176;C e imersos em água a 50&#176;C por 8 minutos, foram descascados num tempo 3,2 vezes menor que as laranjas controle. O rendimento em laranjas comercializáveis foi de 95% para laranjas tratadas hidrotermicamente contra 60% para laranjas controle. As laranjas tratadas hidrotermicamente foram preferidas quanto à aparência e não tiveram sua qualidade físicoquímica e sensorial afetada. Em uma segunda etapa, foi determinada a eficácia da sanificação no processamento mínimo das laranjas. Os níveis de contaminação tanto por fungos quanto por bactérias foram baixos, atingindo no máximo 4 x 102 UFC.g-1. Não foram detectados coliformes nem Salmonella. Embora todas as contagens microbianas tenham sido baixas em todos os tratamentos, naqueles nos quais se utilizou sanificação foram encontradas as menores contaminações, mostrando a eficácia da sanificação. Na terceira etapa estudou-se o efeito de níveis de processamento mínimo e de temperaturas de armazenamento na atividade respiratória e na produção etileno das laranjas. O processamento interferiu na atividade respiratória, sendo maior essa influência imediatamente após o descascamento e separação dos segmentos. O processamento mínimo de laranjas nas formas inteiras com ou sem albedo afetou a atividade respiratória somente na primeiras horas após o processamento. Durante todo período de armazenamento a atividade respiratória das laranjas a 1&#176; e 11&#176;C não diferiram entre si, sendo inferior à das laranjas a 21&#176; e 31&#176;C. O etileno foi detectado apenas nos frutos mantidos a 21&#176; e 31&#176;C. O quociente de temperatura foi maior na faixa de 11-21&#176;C. Na quarta etapa foram estudadas tecnologias de embalagem, quanto à eficácia na manutenção da qualidade microbiológica, sensorial e físico-química da laranja \'Pêra\' minimamente processada. A embalagem de PVC foi tão eficiente quanto a embalagem de polipropileno sob atmosfera modificada passiva ou ativa, dentro do período avaliado, permitindo a conservação das laranjas por até 9 dias a 12&#176;C e até 12 dias a 6&#176;C. / The purpose of this work was to establish a minimal processing technology for \'Pera\' orange in order to obtain a suitable product with microbiological and sensory qualities meeting customers&#39; needs. Firstly, in order to make orange peeling easier, it was studied the effect of the hydrothermal treatment on peeling time and quality of minimally processed fruits stored at 6&#176;C. Fruits cooled at 6&#176;C and immersed in water at 50&#176;C for 8 minutes were peeled 3.2 times faster than control oranges. Commercial yield of hydrothermally treated oranges was 95%, while in control oranges it was 60%. Hydrothermally treated oranges showed better appearance with no alterations in their physicochemical and sensory qualities. Secondly, the sanification effectiveness in the minimal processing of oranges was determined. Contamination levels by fungi or bacteria were low, reaching a maximum of 4 x 102 CFU.g-1. No coliforms or Salmonella were detected. Although all microbial counts were low for all treatments, those undergoing sanification showed lower contamination rates, evidencing the sanification effectiveness. A third stage involved the study of the effect of minimal processing and storage temperatures on the respiratory activity and ethylene production in oranges. Processing influenced the respiratory activity especially immediately after peeling and separation of segments. Minimal processing of whole oranges, with or without albedo, affected the respiratory activity only during the first hours after processing. The respiratory activity of oranges at 1&#176; and 11&#176;C did not differ during all storage period and were lower than the respiratory activity of oranges stored at 21&#176; and 31&#176;C. Ethylene was detected only in fruits kept at 21&#176; e 31&#176;C. The temperature quotient was higher for 11-21&#176;C A fourth stage involved the study of packaging technologies in relation to their effectiveness at maintaining microbial, sensory and physicochemical qualities in minimally processed \'Pera\' oranges. PVC film was as effective as the polypropylene one under passive or active modified atmosphere within the period evaluated, with oranges stored at 6&#176; and 12&#176;C showing shelf life of 12 and 9 days, respectively.

Thesis (MScFoodSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Fresh ready-to-cook fish fillets are prone to rapid loss of freshness and other quality attributes, as well as accelerated growth of spoilage micro-organisms under sub-optimal storage conditions. Cape hake (Merluccius capensis) is an important seafood in South Africa; however, rapid loss of quality and eventual spoilage is a problem limiting the economic potential. Thus, the aim of this study was to investigate the effects of active (40% CO2 + 30% O2 + 30% N2) and passive (0.039% CO2 + 20.95% O2 + 78% N2) modified atmosphere packaging (MAP) under different storage temperatures (0°C, 4°C, and 8°C) on the quality attributes of Cape hake (Merluccius capensis) fish fillets. This was achieved by investigating the effects of MAP (with or without absorbent pads) and storage temperature on quality attributes (microbial, physicochemical and sensory), changes in composition and concentration of volatile compounds (VOCs) and shelf life of Cape hake fillets. Modified atmosphere packaging, storage temperature and the use of absorbent pads had a significant (p < 0.05) impacts on physicochemical properties of Cape hake fillets during refrigerated storage. Highest storage temperature (8°C) led to accelerated deterioration of packaged Cape hake fillets. Generally, active MAP better maintained the quality attributes of Cape hake than passive MAP at 0°C and 4°C. Headspace gas composition of O2 and CO2 were significantly influenced by the storage time, temperature, MAP conditions and their interactions (p < 0.05). Irrespective of storage temperature, active-MA packaged fillets had lower pH values in comparison to fillets stored under passive-MAP. Drip loss was higher in active-MA fillets packaged without absorbent pad. Passive-MAP fillets did not show any drip loss. Absorbent pad was used to add value to MAP storage as MAP resulted in drip. The use of absorbent pad combined with low storage temperature maintained the firmness of hake fillets, across all temperatures. The interaction of MAP, absorbent pad and storage temperature had a significant effect on the aerobic mesophillic bacteria counts. Based on the aerobic mesophillic bacteria count fillets stored under active-MAP at 0°C (5.2 log cfu/g) was limited to day 12, while the fillet stored under passive-MAP at 0°C (log cfu/g) was limited to greater than day 3. Overall sensory acceptability of fillets decreased with increase in storage temperature across all treatments. Additionally, MAP had a significant (p < 0.05) impact on sensory attributes such as appearance and odour acceptability, with active-MA packaged fillets stored at 0°C having highest overall acceptability. A total of 16 volatiles were identified in Cape hake fillets, including 4 primary VOCs and 12 secondary VOCs. The VOCs associated with spoilage include tri-methylamine (TMA) (ammonia like), esters (sickeningly sweet) and sulphur group (putrid). MAP had a significant (p< 0.05) influence on volatile composition and concentration. Active-MA packaged fillets performed better during storage and had lower TMA value of 0.85% on day 12 in comparison with 7.22% under passive-MAP on day 6 at 0°C. The results obtained demonstrated that changes in volatile compounds were significantly (p< 0.05) influenced by storage duration, temperature and MAP. The development of high levels of VOCs and off-odour corresponded with high aerobic mesophillic bacteria count (≥ 5.5 log cfu/g). Based on these developments the storage life of Cape hake fillets packaged under active-MAP with absorbent pad and stored at 0°C was limited to 12 d, while the passive-MAP (control) fillets stored at 0°C was limited to 3 d. The use of active-MAP, in combination with absorbent pads and 0°C storage in addition to good hygienic practices, was effective in maintaining the postharvest quality of Cape hake fish fillets and led to higher shelf life. / AFRIKAANSE OPSOMMING: Vars, gereed-vir-kook vis filette is geneig om gou hulle varsheid en ander gehalte kenmerke te verloor en die vervoegde groei van mikro-organismes wat bederf tydens stoor veroorsaak, vind plaas. Kaapse stokvis (Merluccius capensis) is in Suid-Afrika ‘n gewilde seekos maar die ekonomiese potensiaal daarvan word deur die feit dat dit so gou in gehalte afneem en bederf, beperk. Dus word daar met hierdie studie gepoog om die effek van aktiewe (40% CO2 + 30% O2 + 30% N2) en passiewe (0.039% CO2 + 20.95% O2 + 78% N2) aangepasde verpakking (MAP) onder verskillende stoortemperature (0°C, 4°C, en 8°C) op die gehalte kenmerke van Kaapse stokvis (Merluccius capensis) filette te ondersoek. Dit is gedoen deur om die effek van MAP (met of sonder kussinkies) en stoortemperatuur op die gehalte kenmerke (mikrobies, fisiochemies en sensories) asook veranderinge in komposisie en konsentrasie van vlugtige samestellings (VOCs) en die raklewe van Kaapse stokvis filette te ondersoek. Aangepasde atmosfeer verpakking, stoortemperatuur en die gebruik van absorberende kussinkies het ‘n groot impak (p < 0.05) op die fisiochemiese kenmerke van Kaapse stokvis tydens stoor in yskaste gehad. Hoë stoortemperature (8°C) het aanleiding gegee tot die vinnige bederf van verpakte Kaapse stokvis filette. Oor die algemeen het aktiewe MAP die gehalte van die Kaapse stokvis filette teen 0°C and 4°C beter bewaar. Die komposisie van O2 en CO2 is heelwat deur stoortyd, temperatuur, MA toestande en die interaksies tussen bogenoemde, beïnvloed (p< 0.05). By alle temperature het aktiewe MA verpakte filette laer pH waardes getoon in vergeleke met filette wat in onder passiewe MA verpak is. Die drupverlies was hoër in aktiewe MA filette verpak sonder absorberende kussinkies. Passiewe MAP filette het nie enige drupverlies getoon nie. Absorberende kussinkies is gebruik om waarde by te voeg tot MAP stoor aaangesien MAP gelei het tot drup. By alle temperature het die gebruik van absorberende kussinkies tesame met lae stoortemperature bygedra tot die behoud van fermheid. Die interaksie van MAP, absorberende kussinkies, en stoortemperatuur het ‘n groot effek gehad op die aerobiese mesofiliese bakterië telling. Weens die aerobiese mesofiliese bakterië telling is stoor van filette onder aktiewe MAP teen 0°C (5.2 log cfu/g) beperk tot dag 12, terwyl filette gestoor onder passiewe MAP teen 0°C ( log cfu/g) beperk is tot dag 3. Oor die algemeen het die sensoriese aanneemlikheid van filette sonder inasgneming van die behandeling, verklein met ‘n toename in stoortemperature. MAP het ook ‘n groot impak op die sensoriese kenmerke soos voorkoms, reuk, en aktiewe MA verpakte fillets gestoor teen 0°C is oor die algemeen die aanneemlikste. ‘n Totaal van 16 vlugtige substanse is in Kaapse stokvis identifiseer. Dit het vier primêre VOCs en 12 sekondêre VOCs ingesluit. Die VOCs wat met bederf assosieer word, sluit tri-metilamien (TMA) (soos ammoniak), esters (soet) en die swael groep (smetterig) in. MAP het ‘n groot (p < 0.05) invloed op die vlugtige komposisie en konsentrasie. Aktiewe MA verpakte filette het beter tydens stoor presteer en het ‘n laer TMA waarde van 0.85% op dag 12 gehad, in vergelyking met 7.22 % onder passiewe MAP op dag 6 teen 0°C. Die resultate toon dat veranderinge in vlugtige samestellings grootliks beïnvloed word (p < 0.05) deur stoortyd, temperature en MAP. Die ontwikkeling van hoë vlakke van VOCs, slegte reuke en verlies aan varsheid gaan tesame met hoë aerobiese mesofiliese bakterië telling (≥ 5.5 log cfu/g). Gegrond op hierdie tellings is die stoorleeftyd van Kaapse stokvis filette beperk tot dag 12, terwyl passiewe MAP (die kontrole) filette gestoor teen 0°C, beperk is tot dag 3. Om op te som, die gebruik van aktiewe MAP tesame met absorberende kussinkies en 0°C stoor asook goeie higiëniese praktyk, kon die na-oes gehalte van Kaapse stokvis filette behou en het gelei tot ‘n langer rakleeftyd.

Scientific research, technological development, and commercialisation are processes through which new technologies continually emerge and enter markets. Nanotechnology is an example of an emergent technology (or rather a suite of technologies) which promises to open up a universe of possibilities for the development of new products and processes. Advocates of the technology argue that nanotechnology has the potential to spur economic development while at the same time offering partial solutions to many of the grand challenges of our times such as alleviating hunger, providing new energy sources, reducing climate change, curing diseases, etc. However, alongside these optimistic views, there are also fears and apprehensions concerning the safe and ethical development of nanotechnologies, including the need to address potential negative impacts on the natural environment and human health and safety. The food and food packaging area has shown itself to be a particularly sensitive sector in this respect where the potential for nanoparticles to enter the human body has enhanced the sensitivity of the industry to public concern. The past has shown that any changes or modifications made to food have resulted in public backlash (e.g. GM foods). Due to this some parts of the food and packaging industry remain cautious about making transparent their use of nanotechnologies in their products and processes. However, simultaneously pressure is mounting from regulatory agencies, and from some activists, to pursue the safe and 'responsible' development of nanotechnologies (whatever that may be) as an ethical obligation. The use of nanotechnologies in food and food packaging has become increasingly complex because of its introduction at various points in the food chain, giving rise to debates as to "who is responsible". As a contribution to the debate on what constitutes the 'responsible' governance of new/emergent technologies, this thesis investigates the governance of nanotechnologies and the idea of 'responsibility' and 'responsible innovation' through the lens of perspectives of different actors within the nanotech food chain. A qualitative research methodology was used where semi-structured interviews were conducted with a heterogeneous group of actors with a particular focus on the food and food packaging sectors. Research in comparative national settings (Canada and India) was conducted on the grounds that regulation of nanotechnologies differs significantly across OECD and non-OECD countries, and where the global debate on nanotechnologies is organised and dominated by OECD countries. Findings from this thesis showed that the set of critical elements, such as health and safety, that are put forward by such OECD countries like Canada for the 'responsible' development of nanotechnologies are not the same as that found in India and are seen to differ. In India, meeting the grand challenges of society such as food security, clean drinking water and alleviating poverty take precedent over other elements, where science, technology (such as nanotechnologies) and innovation are harnessed by entrepreneurs, and small and large firms to solve these national problems. However, while I began the study with the intention of comparing two national territories with different regulatory settings, the study also found a case of collaborative Canada-India transnational research network where 'responsibility' is influenced through certain funding criteria set by the more dominant partner, Canada. This suggests the return of public intervention by dominant OECD countries in pro-actively shaping R&amp;D processes that are influencing the 'responsible' development of nano-products in such emerging markets, where there is a potential for future trade associations.

The contamination of foods with hydrocarbon mixtures migrating from food contact materials (FCM) was first observed for jute and sisal bags treated with batching oil in the 1990s. Since the millennium, the focus has shifted to printing inks and recycled cardboard packaging as most recognized sources for hydrocarbon contamination from FCM. Mineral oil containing printing inks can either release hydrocarbons directly from the printing of folding boxes into food or indirectly entering the recycling chain of cardboard material by printed products, such as newspapers. The contamination of dry foods with mineral oil hydrocarbons (MOH) from recycled fiber packaging has been reported to reach up to 100 mg/kg [1]. Using LC-GC-FID technique the MOH were categorized into mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The molecular mass, which is assumed to be toxicological relevant, is derived from the GC retention times of accumulated MOSH in human tissues and is limited to n C16 to n-C35 [2]. MOSH is the most significant contaminant of the human body reaching 1-10 g per person, which is of particular concern since a formation of microgranulomas (causing inflammatory reactions) in the liver was observed in rats fed with saturated hydrocarbons [3]. Furthermore, some MOAH are assumed to be genotoxic analogous to polycyclic aromatic hydrocarbons [3]. In the latest draft of a German ‘Mineral Oil Regulation’ the following limits for the migration of MOH from recycled fiber are proposed: for MOSH C16-20 4.0 mg/kg, MOSH C21-35 2.0 mg/kg and for MOAH 0.5 mg per kg food [4]. Functional barriers reducing the migration of undesirable compounds from recycled cardboards (such as MOH and other contaminants) could be a part of the solution for this issue. Supporting that approach in this study, the boxes of recycled cardboard featuring a barrier layer on the internal surface or an integrated adsorbent available early in 2014 were investigated for their efficiency in reducing migration of mineral oil hydrocarbons into dry food. A practice-oriented one-year storage test was performed with wheat flakes in seven configurations: a box of virgin fibers, two boxes of unprotected recycled cardboard, three cardboards with barrier layers (a flexo-printed polyacrylate layer, a polyvinyl alcohol coating and a multilayer involving polyester) and a cardboard containing activated carbon. The highest migration of MOH (C16-24) was observed in the boxes of unprotected recycled cardboard (MOSH: 11.4 mg/kg, MOAH: 2.4 mg/kg). Of the three investigated barrier layers only two reduced migration of MOH into food below the limits of the 3rd draft of the German mineral oil ordinance (2014) until the end of shelf life. The cardboard box involving active carbon as adsorbent prevented detectable migration of mineral oil hydrocarbons (<0.1 mg/kg). In the case of virgin fiber, which was virtually free of MOH (<1 mg/kg), migration close to the proposed limits was detected (C16-24, MOSH: 1.5 mg/kg, MOAH: 0.4 mg/kg). Therefore, it has been proven that the transport box (corrugated board) substantially contributed to the transfer of MOH into food. Plastic FCM can also release hydrocarbons, such as polyolefin oligomeric hydrocarbons (POH), into food. These POH are of synthetic nature and are formed during the polymerization process of polyolefins (150 – 3000 mg/kg in granulates of homo/hetero polymers involving ethylene and propylene). This group of synthetic contaminants contain also saturated hydrocarbons (POSH) analogous to mineral oils, but contrary no aromatic hydrocarbons. Further, a significant amount (10 – 50%) of monounsaturated hydrocarbons (POMH) was determined in the oligomeric fraction of polyolefins, which are not detectable in mineral oil products. Therefore, these POMH can be used as a marker for POH migration. A method based on two-dimensional high performance liquid chromatography on-line coupled to gas chromatography (on-line HPLC-HPLC-GC) was developed to enable the separate analysis of saturated, monounsaturated and aromatic hydrocarbons in extracts of packaging materials like polyolefins or paperboard and foods, repectively. It is an extension of the HPLC-GC method for MOSH and MOAH [1] using an additional argentation HPLC column, since normal-phase HPLC on silica gel did not preseparate saturated from monounsaturated hydrocarbons. Further, this method and comprehensive two-dimensional GC (GCxGC) was used to investigate the concentration of different oligomer types in polypropylene (PP) and polyethylene (PE) based sealing layers as well as their corresponding granulates. The analyzed sealing layers contained 180-995 mg/kg POSH and 90-435 mg/kg POMH (C16-35). Only in sealing layers involving low-density PE, oxidized polyolefin oligomers as well as cyclic oligomers (alkylated cyclopentanes and hexanes) have been detected. The transfer of POH (C16-35) from the investigated sealing layers into food can be substantial (>50%) and can reach more than 2 mg per kg food. The level of contamination depends on the oligomer content of the sealing layer, the fat content of the food, the processing temperature and the surface-volume ratio. Hot melt adhesives are widely utilized to glue cardboard boxes used as food packaging material. The analysed raw materials of hot melts mainly consisted of paraffinic waxes, hydrocarbon resins and polyolefins. The hydrocarbon resins, functioning as tackifiers, were the predominant source of hydrocarbons of sufficient volatility to migrate via gaseous phase into dry foods. The 18 hydrocarbon resins analyzed contained 8.2-118 g/kg saturated and up to 59 g/kg aromatic hydrocarbons (C16-24). These synthetic tackfier resins, especially the oligomers ≤C24, have been characterized structurally and migration into food was estimated using a food simulant and by the analysis of real food samples. About 0.5-1.5 % of the potentially migrating substances (C16 24) of a hot melt were found to be transferred into food under storage conditions, which can result in a food contamination of approximately 1 mg/kg food in this case. The order of magnitude depends on the absolute amount of potentially migrating substances from the hot melt, the hot melt surface, contact time, amount and type of foods.

Neste trabalho, ingredientes naturais antimicrobianos foram adicionados em filme biodegradável (biofilme) à base de fécula de mandioca tendo como plastificantes sacarose e açúcar invertido. A seleção dos ingredientes antimicrobianos (cravo em pó, canela em pó, pimenta vermelha em pó, óleo essencial de laranja, café em pó, mel e extrato de própolis) foi conduzida por meio de um delineamento experimental (fatorial fracionado 27-3) e os biofilmes foram analisados quanto às suas propriedades de barreira (permeabilidade ao vapor de água e taxa de permeabilidade ao vapor de água) e propriedades mecânicas (resistência máxima à tração e porcentagem de alongamento na ruptura). Os biofilmes apresentaram valores inferiores aos apresentados pelo biofilme controle quanto às propriedades mecânicas. Em geral, a taxa de permeabilidade ao vapor de água nos biofilmes antimicrobianos manteve-se estatisticamente igual ao do controle. Na segunda etapa do trabalho, a otimização dos ingredientes selecionados foi realizada através de delineamento experimental, com somente adição de cravo e canela em pó, que apresentaram resultados mais promissores na etapa anterior. Foi constatado que a adição de cravo e canela em pó alterou as propriedades mecânicas, porém as alterações foram menos intensas com a adição da canela em pó do que com o cravo em pó, o que pode ser justificado pela diferença de granulometria entre eles. A taxa de permeabilidade diminuiu até certa concentração dos ingredientes (0,34% para a canela em pó e 0,20% para o cravo em pó). O efeito antimicrobiano dos biofilmes foi investigado como embalagem de fatias de pão tipo forma e foi constatado que a atividade de água dos biofilmes aumentou após 7 dias de contato. É provável que os biofilmes tenham se tornado meios propícios para o desenvolvimento de bolores e leveduras visto que estes microrganismos cresceram de forma similar ou mais intensa nas fatias de pão na presença do que na ausência dos biofilmes. A partir dos resultados obtidos, não é possível avaliar de forma clara, o efeito antimicrobiano dos ingredientes incorporados na matriz dos biofilmes contra o crescimento de bolores e leveduras em fatias de pão tipo forma. / In this work, natural antimicrobial ingredients were added to biodegradable film (biofilm) based on cassava starch with sucrose and inverted sugar as plasticizers. The selection of the antimicrobial ingredients (clove powder, cinnamon powder, red pepper powder, orange essencial oil, coffee powder, honey and propolis extract) was carried out applying an experimental design (incomplete factorial 27-3) and the barrier properties (water vapour permeability and water vapour permeability rate) and mechanical properties (tensile strength and elongation at break) of the biofilms were determined. The biofilms presented lower data regarding mechanical properties when compared to biofilm control. In general, the water vapour permeability rate of the antimicrobial biofilms was statistically equal to the control. In the second phase of the work, the optimization of the selected ingredients was carried out applying an experimental design, with the addition of only clove and cinnamon powder due to the fact that they showed the most promissing results at the previous phase. The addition of clove and cinnamon powder modified the mechanical properties but the modifications resulted by the addition of cinnamon powder were less intense tha n the ones resulted by the addition of clove powder, which can be justified by the particle size differences between them. The water vapour permeability rate decreased by specific ingredients concentration (0.34% for the cinnamon in powder and 0.20% for the clove in powder). The biofilms antimicrobial effect was investigated as packaging of pan bread slices and it was verified that the biofilms water activity increased after 7 days of contact. Probably, the biofilms became suitable substrates for yeast and mold development due to the fact that these microorganisms grew equally or more intensely in the pan bread slices when the biofilms were present in comparison to the cases of its absence. According to the results, it is not possible to evaluate clearly the antimicrobial effect of the added ingredients to the biofilm matrix against yeast and mold development in pan bread slices.

Orientador: Benedito Carlos Benedetti / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agrícola / Made available in DSpace on 2018-08-15T21:08:21Z (GMT). No. of bitstreams: 1 Bachelli_MaraLigiaBiazotto_M.pdf: 1116172 bytes, checksum: a831f41eca24b6d23a6b8523017e708e (MD5) Previous issue date: 2010 / Resumo: Este trabalho teve como objetivo avaliar os compostos dióxido de cloro, ácido peracético e ozônio, como agentes sanitizantes alternativos para alface minimamente processada em comparação ao hipoclorito de sódio. O mesmo foi conduzido em duas etapas, sendo adotada em ambas a mesma metodologia para o processamento mínimo, que consistiu em seleção, pré-enxágüe, corte, sanitização e enxágüe, centrifugação e embalagem. Na primeira etapa definiram-se as concentrações mais adequadas de dióxido de sódio, ácido peracético e água ozonizada, para serem utilizadas na segunda etapa. Nesta etapa, comparouse os três tratamentos com o sanitizante hipoclorito de sódio na concentração de 150 mg L-1 e imersão por 15 min., além do tratamento com água potável (controle). Na segunda etapa, dois ensaios foram realizados, um em julho/2009 e outro em outubro/2009, e em ambos a alface minimamente processada foi armazenado a 2+1ºC e as amostras foram submetidas a análises microbiológicas, físico-químicas e sensorial, no dia zero (antes e após sanitização) e aos 3, 6, 9 e 12 dias, além do monitoramento da composição gasosa no interior das embalagens. Na primeira etapa, os melhores resultados foram: solução de dióxido de cloro na concentração de 60 mg L-1 por 10 min. de imersão; solução de ácido peracético com 100 mg L-1 por 15 min. De imersão e água ozonizada na concentração de ozônio de 1,2 mg L-1 com tempo de imersão de 1 min. Na segunda etapa, todos os tratamentos de sanitização reduziram a contagem microbiana em comparação com a matéria-prima antes do processamento. A lavagem com água potável foi capaz de reduzir 1 ciclo logarítmico na contagem total de microrganismos aeróbios mesófilos e psicrotróficos, bolores e leveduras no primeiro ensaio, mas não foi suficiente para a redução de coliformes totais; porém, o mesmo não aconteceu no segundo ensaio. O dióxido de cloro foi o tratamento mais eficiente nos dois ensaios para a redução de coliformes totais passando de >1,1x10³ UFC g-1 (antes do processo) para <3,0 UFC g-1 (após sanitização). O ácido peracético foi o sanitizante que apresentou a maior redução para mesófilos e psicrotróficos no dia zero em relação ao produto antes do processamento, chegando a reduzir até 5 ciclos logarítmicos; porém, na avaliação sensorial no 6º dia o produto foi rejeitado, por apresentar manchas nas folhas e sua impressão global da aparência receber uma nota média muito baixa (3,76). O tratamento com hipoclorito de sódio recebeu a segunda maior média (7,86). O uso de água ozonizada não se mostrou eficiente na redução da carga microbiana, necessitando outros estudos em concentrações diferentes. De acordo com as análises microbiológicas a alface minimamente processada apresentou ausência de E.coli e de Salmonella spp. em todas as amostras. Tomando como base que níveis populacionais maiores que 105 UFC g-1 já são indicadores de final de vida de prateleira, pode-se concluir que, sob refrigeração a 2ºC, a durabilidade da alface minimamente processada foi de seis dias para os tratamentos utilizados / Abstract: This study aimed to evaluate the compounds chlorine dioxide, peracetic acid and ozone as alternative sanitizers for minimally processed lettuce as compared to sodium hypochlorite. The study was conducted in two stages, in both adopted the same methodology for the minimal processing, consisting of selection, pre-rinse, cut, sanitize and rinse, centrifugation and packaging. The first stage outlined the most appropriate concentrations of sodium dioxide, peracetic acid and ozonated water to be used in the second stage. In this step, it was compared the three treatments with sodium hypochlorite sanitizer at a concentration of 150 mg L-1 and immersion for 15 min. In addition to treatment with water (control). In the second stage, two experiments were conducted, one in July/2009 and another in October/2009, and in both the minimally processed lettuce was stored at 2 +1°C and the samples were subjected to microbiological, physicochemical and sensory analysis, in day zero (before and after sanitization) and at 3, 6, 9 and 12 days, in addition to monitoring the gas composition inside the package. In the first stage, the best results were: solution of chlorine dioxide at 60 mg L-1 for 10 min immersion; peracetic acid solution with 100 mg L-1 for 15 min immersion and ozonated water at 1.2 mg L-1 for 1 min immersion. In the second step, all sanitation treatments reduced the microbial count in comparison with the raw material before processing. Rinsing with water was able to reduce 1 log cycle in the total count of aerobic mesophilic and psychrotrophic bacteria, yeasts and molds in the first test, but was not sufficient to reduce total coliform, but it did not happen in the second test. Chlorine dioxide was the most effective treatment in two trials to reduce total coliform passing of> 1.1 x 10 ³ CFU g-1 (before trial) to <3.0 CFU g-1 (after sanitization). Peracetic acid was the sanitizer that showed the greatest reduction in bacteria mesophilic and psychrotrophic bacteria on day zero for the product before processing to reduce reaching 5 log cycles, but the sensory evaluation on the 6th day the product was rejected by presenting spots on the leaves, and overall bad aspect, which caused to receive a very low average score (3.76). Treatment with sodium hypochlorite received the second highest average (7.86). The use of ozonated water was not efficient in reducing microbial load, requiring further studies in different concentrations. According to the microbiological analysis, minimally processed lettuce showed absence of E.coli and Salmonella spp. in all samples. Based on that population levels greater than 105 UFC g-1 are already indicators of the end of shelf life, it can be concluded that, under refrigeration at 2°C, the durability of minimally processed lettuce was six days for all treatments / Mestrado / Tecnologia Pós-Colheita / Mestre em Engenharia Agrícola