Orientador: Rubens Maciel Filho / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T08:38:40Z (GMT). No. of bitstreams: 1 Bonon_AndersonDeJesus_M.pdf: 18231652 bytes, checksum: 5f90aa98f05330f8a92f9b1163036e84 (MD5) Previous issue date: 2012 / Resumo: Uma das olefinas de fontes renováveis de maior importância no Brasil é o Limoneno, terpeno que compõe cerca de 90% do óleo da casca da laranja. O Brasil é o maior produtor mundial de laranja, com uma produção, entre 2010-2011, de cerca de 15,33 milhões de toneladas do fruto, dos quais 89% da produção são destinadas à produção de suco, sendo a casca e o óleo fixo, resíduos do processo. A parte volátil do óleo é constituída majoritariamente de (R)-limoneno (90 %). Terpenos como o limoneno, podem ser submetidos a reações de oxidação catalítica nos quais os epóxidos são os principais produtos, e podem ser utilizados como precursores para uma ampla variedade de produtos como fármacos, fragrâncias e na fabricação de biopolímeros e resinas. Mediante ao exposto, este trabalho tem por objetivo o estudo da epoxidação de limoneno para a obtenção de epóxidos que possam ser utilizados como monômeros para a síntese de biomateriais para a construção de dispositivos médicos, sendo que avaliou-se sistemas epoxidativos contenho metiltrioxorênio, montmorilonita e alumina. O sistema mais promissor, utilizando H2O2 como oxidante, ?-Al2O3 como catalisador em acetato de etila, foi avaliado em condições reacionais brandas, a 80 °C em pressão atmosférica, caracterizando um sistema verde. As variações na concentração inicial de reagentes a fim de entender o sistema foram estudadas, o que direcionou o estudo para sua otimização via planejamento de experimentos, sendo atingida uma conversão de 100 % em 10 h de reação. A obtenção de limoneno por evaporação de passo curto do óleo de laranja também foi estudada e otimizada, chegando-se à pureza de 99,6 %. O ensaio nas condições ótimas de reação com o limoneno obtido do óleo de laranja mostrou-se idêntico ao limoneno comercial. Os resultados obtidos demonstram a eficácia tanto do processo de obtenção do limoneno, como do sistema reacional com uma produção limpa, uma característica imprescindível para biofabricação / Abstract: One of the most important olefins from a renewable source of in Brazil is limonene. The orange peel oil is about 90% limonene. Brazil is the largest producer of orange in the world wild, with a 2010-2011 production about 15.33 million tons of fruit. About 89% of the fruits are intended for the production of juice, which peel and fixed oil are residue from the process. The volatile oil portion is composed predominantly of (R)-limonene. Terpenes such as limonene, may be subjected to catalytic oxidation reactions where the epoxides are the main products, and can be used as precursors for a wide variety of products such as pharmaceuticals, fragrances and the manufacture of biopolymers and resins. By the above, this work is dedicated to study the epoxidation of limonene in order to obtaining epoxides that may be used as monomers for the synthesis of biomaterials with chemical quality to medical devices manufacturing. Thus, some systems like methyltrioxorhenium, montmorillonite and alumina were tested. The most promissory system, using H2O2 as oxidant, ?-Al2O3 as catalyst and ethyl acetate as solvent, was evaluated in mild reaction conditions, at 80 °C at atmospheric pressure, featuring a green system. It was carried out the initial concentration of the substrate, oxidant and catalyst variation studies in order to understand the system, which directed for the optimization by experimental design. It was achieved a 100% of conversion in 10 hours of reaction. It was also studied the limonene purification by short path evaporation of the orange oil. It was achieved a limonene with 99.6 % of purity. The optimum reaction conditions were performed with limonene obtained from orange oil, the comparative result showed and an identical behavior between the commercial and the distillated limonene. These results demonstrate the effectiveness of both the process, the limonene obtainment and the reaction system with a clean and no toxic production, an essential feature for biofabrication / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

d-Limonene (Lim) was used in various polymer formulations to achieve a more sustainable polymerization. Lim is a renewable and essentially non-toxic compound, derived from citrus fruit peels, that may replace some of the many toxic and fossil-based chemicals used in polymer synthesis. Bulk free-radical polymerizations of n-butyl acrylate (BA) with Lim were performed to investigate Lim co-polymerization kinetics and estimate the monomer reactivity ratios, important parameters in the prediction of copolymer composition. Kinetic modeling of the BA/Lim copolymerization was performed with PREDICI simulation software. The model supports the presence of a significant degradative chain transfer reaction due to Lim. This reaction mechanism is due to the presence of allylic hydrogen in Lim. Nonetheless, relatively high molecular weight polymers were produced. It was concluded that Lim behaves more like a chain transfer agent than a co-monomer. Terpolymerizations of BA, butyl methacrylate (BMA) with Lim were then performed. In order to predict the terpolymer composition, the monomer reactivity ratios for BA/BMA were estimated. By applying the three pairs of co-monomer reactivity ratios to the integrated Mayo-Lewis equation, terpolymer compositions were ably predicted up to high monomer conversion levels. Lim was then used as a chain transfer agent to prepare core-shell latex-based pressure sensitive adhesives (PSA) comprising BA and styrene via seeded semi-batch emulsion polymerization. By varying the concentration of Lim and divinylbenzene crosslinker, the core polymer microstructure was modified to yield different molecular weights and degrees of crosslinking. The core latex was then used as a seed to prepare core-shell latexes. By changing the Lim concentration during the shell-stage polymerization, the molecular weight of shell polymer was also modified. The latexes were characterized for their microstructure and were cast as films for PSA performance evaluation. The PSA performance was shown to be highly related to the polymer microstructure. Tack and peel strength showed a decrease with increasing Lim concentration. Shear strength went through a maximum with a core Lim concentration increase from 0 to 5 phm.

No description available.

Ozone (O₃) and terpenoids react to produce secondary organic aerosol (SOA). This work explored novel ways that these reactions form SOA indoors, with five investigations, in two categories: investigations of (i) the impacts of particle controls on indoor SOA formation, and (ii) two fundamental aspects of indoor SOA formation. For category (i), two investigations examined the particle control devices of ion generators, which are air purifiers that are ineffective at removing particles and emit ozone during operation. With a terpenoid source present (an air freshener), ion generators acted as steady-state SOA generators, both in a 15 m³ chamber and 27 m³ room. The final investigation in category (i) modeled how heating, ventilating, and air-conditioning (HVAC) systems influence SOA formation. Influential HVAC parameters were flow rates, particle filtration, and indoor temperature for residential and commercial models, as well as ozone removal by particle-laden filters for the commercial model. For category (ii), the first investigation measured SOA formation from ozone reactions with single terpenoids and terpenoid mixtures in a 90 L Teflon-film chamber, at low and high ozone concentrations. For low ozone, experiments with only d-limonene yielded the largest SOA number formation, relative to other mixtures, some of which had three times the effective amount of reactive terpenoids. This trend was not observed for high ozone experiments, and these results imply that ozone-limited reactions with d-limonene form byproducts with high nucleation potential. The second investigation in category (ii) explored SOA formation from ozone reactions with surface-adsorbed terpenoids. A model framework was developed to describe SOA formation due to ozone/terpenoid surface reactions, and experiments in a 283 L chamber determined the SOA yield for ozone/d-limonene surface reactions. The observed molar yields were 0.14–0.16 over a range of relative humidities, and lower relative humidity led to higher SOA number formation from surface reactions. Building materials on which ozone/d-limonene surface reactions are predicted to lead to substantial SOA formation are those with initially low surface reactivity, such as glass, sealed materials, or metals. The results from category (ii) suggest significant, previously unexplored mechanisms of SOA number formation indoors. / text

Unstable oil markets with rising environmental concerns have revived widespread interest in production of fuel ethanol from renewable materials. Cellulosic materials are abundant and prominent feedstocks for cheap ethanol production. However, due to recalcitrant structure of these materials, pretreatment is a prerequisite. Depending on the biomass, pretreatment and hydrolysis conditions, a number of degradation products and/or toxic components may be released that show strong inhibitory effects on the fermenting microorganisms. This thesis deals with application of encapsulation technology to ferment the highly toxic hydrolyzates without further pretreatment. Free cells could not tolerate presence of 5 g/l furfural in defined medium, and inhibitors in wood and peel hydrolyzates in batch mode of operation and fermentation failed. Continuous cultivation of wood hydrolyzate was only successful at 0.1 h−1 and the majority of cells lost their viability after 5 retention times. Encapsulated cell system could successfully ferment the synthetic medium containing 5 g/l furfural during sequential batch cultivations with ethanol yield of 0.41-0.42 g/g. Cultivation of undetoxified hydrolyzates was also carried out, where glucose and mannose were converted within 10 h without significant lag phase. However, a gradual decrease in cell activity was observed in sequential batches. Continuous cultivation was more successful, and wood hydrolyzate was fermented to ethanol by encapsulated S. cerevisiae at dilution rates up to 0.5 h−1. More than 75% of the encapsulated cells were viable in the worst conditions. Ethanol was produced with yield 0.44 g/g and specific productivity 0.14–0.17 g/g•h at all dilution rates. Contrary to wood hydrolyzate, where there is no preference for permeation of sugars or inhibitors through the capsules’ membrane, encapsulation technology was applied to eliminate inhibition of limonene in fermentation of orange wastes to ethanol. The capsules’ membrane, of hydrophilic nature, is practically impermeable to hydrophobic compounds such as limonene while allowing penetration of nutrients and products. While presence of 0.1% v/v limonene in the medium results in strong inhibition or even failure of cultivation with free cells, using this technique allowed fermentation of a medium containing 1.5% v/v limonene. The impact of encapsulation on the anaerobic growth pattern, morphological and physiological changes of S. cerevisiae over long-term application was investigated. The growth rate, total RNA and protein content of the encapsulated cells decreased gradually over repeated batch cultivations, while stored carbohydrates content increased. Within 20 batch cultivations, total RNA and protein content of encapsulated cells decreased by 39% and 24%, whereas glycogen and trehalose content increased by factors of 4.5 and 4, respectively. / <p>Akademisk avhandling som för avläggande av teknologie doktorsexamen vid Chalmers tekniska högskola försvaras vid offentlig disputation den 18 april 2008.</p>

Master of Science / Department of Animal Sciences and Industry / Evan C. Titgemeyer / Seven ruminally cannulated heifers approximately 225 kg initial BW were used in a 7 × 4 Youden square design to determine the effects of different levels of limonene on ruminal Fusobacterium necrophorum populations. Treatments included: 1) control, 2) limonene at10 mg/kg diet DM, 3) limonene at 20 mg/kg diet DM, 4) limonene at 40 mg/kg diet DM, 5) limonene at 80 mg/kg diet DM, 6) CRINA-L (a blend of essential oil components) at 180 mg/kg diet DM, 7) tylosin at 12 mg/kg diet DM. Each period included 11 d with 10 d washouts between periods. Samples were collected on d 0 (before treatment initiation), 4, 7, and 10 for measuring F. necrophorum by most probable number (MPN) method using selective culture medium. Results indicate that CRINA-L (P = 0.52) and tylosin (P = 0.19) did not affect ruminal F. necrophorum populations. Limonene linearly decreased (P = 0.03) F. necrophorum populations, and the optimal dietary concentration for limonene was 40 mg/kg DM. Limonene did not affect ruminal degradation rate of lysine, NH3 concentration, or VFA profiles in ruminal fluid. Limonene was useful for reducing ruminal concentrations of F. necrophorum. It may have potential to control liver abscesses, although further research will be needed to assess the effect of limonene under feedlot conditions.

Poly(vinyl alcohol) and polyethylene polymer systems werebuilt in order to study their transport properties (diffusion).First a verification of the AMBER force field was conducted fora poly(vinyl alcohol) system built from a chain with 145repeating units. NPT-molecular dynamics simulations attemperatures between 400 and 527 K were performed. The resultsof the simulations were compared withpressure-volume-temperature data, solubility parameter, X-rayscattering pattern and data for the characteristic ratio. Thefractional free volume distribution was computed and thediffusion characteristics of water in the polymer werestudied. Further another poly(vinyl alcohol) system, with 600repeating units, was used to study oxygen diffusion in dry andwet poly(vinyl alcohol). In these systems the focus was toinvestigate the oxygen paths relative to the backbone and alsothe effect of water on the diffusion coefficients. Jump mapsand correlation function between the velocity of the oxygen wascalculated. The water has a huge impact on the oxygen diffusionand the preferred paths. A larger molecule (limonene) was studied in a polyethylenematrix consisting of 6000 anisotropic united atoms. A 100 nslong trajectory was recorded and also shortertrajectories atdifferent temperatures, which gave the temperature dependenceof the diffusion coefficients. Correlation functions for thelimonene molecule shows that it rotates and tumbles when movingthru the matrix. The main results from the molecular dynamics simulationsshowed that diffusion of larger molecules are possible and alsothat molecular dynamics simulations can predict plasticizationeffects. A new fast experimental method for determining diffusioncoefficients with non iso thermal thermogravimetry weredeveloped. The advantage is that the experiments only takesminutes instead of days with a small effect on theaccuracy.

<p>Poly(vinyl alcohol) and polyethylene polymer systems werebuilt in order to study their transport properties (diffusion).First a verification of the AMBER force field was conducted fora poly(vinyl alcohol) system built from a chain with 145repeating units. NPT-molecular dynamics simulations attemperatures between 400 and 527 K were performed. The resultsof the simulations were compared withpressure-volume-temperature data, solubility parameter, X-rayscattering pattern and data for the characteristic ratio. Thefractional free volume distribution was computed and thediffusion characteristics of water in the polymer werestudied.</p><p>Further another poly(vinyl alcohol) system, with 600repeating units, was used to study oxygen diffusion in dry andwet poly(vinyl alcohol). In these systems the focus was toinvestigate the oxygen paths relative to the backbone and alsothe effect of water on the diffusion coefficients. Jump mapsand correlation function between the velocity of the oxygen wascalculated. The water has a huge impact on the oxygen diffusionand the preferred paths.</p><p>A larger molecule (limonene) was studied in a polyethylenematrix consisting of 6000 anisotropic united atoms. A 100 nslong trajectory was recorded and also shortertrajectories atdifferent temperatures, which gave the temperature dependenceof the diffusion coefficients. Correlation functions for thelimonene molecule shows that it rotates and tumbles when movingthru the matrix.</p><p>The main results from the molecular dynamics simulationsshowed that diffusion of larger molecules are possible and alsothat molecular dynamics simulations can predict plasticizationeffects.</p><p>A new fast experimental method for determining diffusioncoefficients with non iso thermal thermogravimetry weredeveloped. The advantage is that the experiments only takesminutes instead of days with a small effect on theaccuracy.</p>

Anyžinis lofantas (Agastache foeniculum (Pursh) Kuntze) – tai vaistinis, prieskoninis daugiametis augalas. Vienas iš notrelinių šeimos dekoratyvus, daugiametis žolinis augalas, kilęs iš Šiaurės Amerikos. Lietuvoje kol kas dar mažai paplitęs. Auginamas botanikos soduose ir darželiuose, vertinamas kaip labai kvapnus, medingas ir vaistinis augalas. Anyžinis lofantas dirvai mažai reiklus, turi gerai išvystytą šaknų sistemą, todėl nebijo sausros. Geriau auga derlingesnėje žemėje, nepiktžolėtose priesmėlio arba lengvo priemolio dirvose, atviroje, saulėtoje vietoje. Žydi nuo birželio vidurio iki spalio mėnesio. Žiedai – ryškiai violetiniai arba melsvi. Agastache foeniculum paruoštas VDU Kauno Botanikos sode, 2010 metais masinio žydėjimo metu. Sausoje žaliavoje yra 1,71-2,10 % eterinio aliejaus, kurio svarbiausios dalys yra D-limonenas ir estragolis. Nupjauta žolė džiovinama paskleista plonu sluoksniu gerai vėdinamoje arba 35°C temperatūros patalpoje. Išdžiovinta žolė atskiriama nuo stambesnių stiebų ir laikoma sudėta į medžiaginius maišus. Tinkamai išdžiovinta žolė yra 12 - 14 % drėgnumo. Džiovinimas – vienas svarbiausių etapų, kuris labiausiai įtakoja galutinę vaistinės žaliavos kokybę. Šiame darbe – buvo identifikuoti Agastache foeniculum eterinių aliejų komponentai: D- limonenas, estragolis, kariofilenas. Vaistinio anyžinio lofanto eterinių aliejų ekstraktai ruošti naudojant superkritinio skysčio CO2 ekstrakciją. Jų analizė atlikta dujų chromatografu– masių spektrometrijos... [toliau žr. visą tekstą] / Blue giant hyssop (Agastache foeniculum (Pursh Kuntze) is medicinal perennial plant. This ornamental plant is native to North America. In Lithuania is not yet widely spread. It is cultivated in botanical gardens and is valuable because is a fragrant, melliferous medicinal plant. Blue giant hyssop is not strict for soil and has a well developed system of the roots, so it is resistant to drought. This plant prefers a good soil and sunny places. It blooms from the middle of June to October. The flowers are violet or royal-blue. Agastache foeniculum raw material was prepared in Kaunas botanical garden of VMU during flowering season in 2010. In dry raw material is about 1.71 – 2.10  of essential oils, the basic components are D-limonene and estragol. The grass after cutting was spread in a thin layer in well ventilated room or in the room at 35 C temperature. The dried grass was separated from stems and stored in huckaback bags. The well dried grass has about of 12-14  moisture. The drying is one of the most important periods which influence the final quality of drug raw material. In this work the components of essential oils of Agastache foeniculum have been identified. The extracts of volatile oils of Agastache foeniculum were prepared by supercritical CO2 extraction. After the analysis the relative quantities of essential oils components as well as composition have been evaluated by gas chromatography-mass spectrometry detector. Investigations have showed that the... [to full text]

Made available in DSpace on 2015-05-14T12:59:43Z (GMT). No. of bitstreams: 1 ArquivoTotal.pdf: 1079470 bytes, checksum: 8e1fcb4be2280e060a888b32dd42ae68 (MD5) Previous issue date: 2012-11-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Medicinal plants are widely used by human to treat their ailments since the dawn of civilization. Among the most diverse plant species have attracted some interest from researchers, as is the case of "Aromatic Plants" whose activity has been attributed to essential oils. The R-(+)-limonene is a monoterpene found in several species of herbs. Studies have shown that this compound has several pharmacological activities among them, gastroprotective and antitumor. The present study aims to investigate the anxiolytic effect and inhalation toxicity in two phases: psychopharmacological and toxicological evaluation. Initially, a case of inhalation has been standardized to obtain concentration values ideal for application of the substance. After this, it was evaluated the anxiolytic activity of R-(+)-limonene in the elevated plus maze (EPM). Results showed that the substance does not have anxiolytic effects at the concentrations and at times determined. Then the animals were exposed to a daily the substance, being evaluated psychopharmacological activity through the LCE, and toxicity through biochemical and hematologic tests. The results of the EPM showed a characteristic anxiogenic possibly related to irritation that limonene causes olfactory pathways. In hematological examinations, there was a decrease in hematocrit and red blood cell hemolysis caused by continuous use of R (+) limonene inhalation. The high values of MCV, MCH and MCHC suggest changes in metabolism in the hippocampus antagonize the anxiolytic effect of the test substance. In biochemical tests there was an increase in blood glucose, creatinine, AST and lactate dehydrogenase. Increased AST is suggestive of hemolytic anemia, whereas the increase of lactate dehydrogenase is suggestive of folate deficiency or vitamin B12. Therefore, the R (+) limonene in exposure performed with cytotoxic characteristics at a concentration of 5% when administered daily for 30 days. / As plantas medicinais são largamente utilizadas pelo homem no tratamento dos seus males desde os primórdios da civilização. Entre as mais diversas espécies vegetais algumas têm despertado interesse dos pesquisadores, como é o caso das Plantas Aromáticas cuja atividade tem sido atribuída aos óleos essenciais. O R-(+)-limoneno é um monoterpeno encontrado em várias espécies de plantas aromáticas. Estudos demonstraram que esse composto apresenta atividades farmacológicas (ansiolítica, gastroprotetora, antitumorais) possuindo um baixo perfil de toxicidade. O presente estudo tem como objetivo investigar o efeito ansiolítico e a toxicidade por via inalatória. Para tanto, uma caixa de inalação foi padronizada afim de obter valores de concentrações ideais para aplicação da substância. Após, foi avaliado a atividade ansiolítica do R-(+)-limoneno no labirinto em cruz elevado (LCE). Resultados mostraram que a substancia não possui efeitos ansiolíticas para as concentrações e tempos determinados. Em seguida, os animais foram expostos a uma exposição diária (30 dias) à substância sendo avaliados a atividade psicofarmacológica, através do LCE, e a toxicidade, através de exames bioquímicos e hematológicos. Os resultados do LCE mostraram uma característica ansiogênica possivelmente relacionada à irritação que o limoneno causa nas vias olfatórias. Nos exames hematológicos houve uma diminuição no eritrócitos e hematócrito devido a hemólise causada por uso contínuo de R-(+)-limoneno por via inalatória. Os valores elevados de VCM, HCM e CHCM sugerem alterações no metabolismo no hipocampo antagonizando o efeito ansiolítico da substância em estudo. Nos exames bioquímicos houve um aumento na glicemia, creatinina, AST e lacato desidrogenase. O aumento da AST é sugestivo de anemia hemolítica; já o aumento do lactato desidrogenase é sugestivo para deficiência de folatos ou vitamina B12. Portanto, o R-(+)-limoneno em exposição prolongada se apresentou com características tóxicas em uma concentração de 5%.