Ésteres produzidos por via biotecnológica são considerados e classificados como naturais e sua demanda tem aumentado. Várias leveduras podem produzir ésteres e seu método de seleção é altamente importante para inúmeros tipos de indústrias. Trinta e quatro cepas de leveduras, isoladas de vinhos tintos em barris de carvalho elaborados na Serra Gaúcha e de queijos artesanais do Sul do Brasil, foram utilizadas neste trabalho. Cada cepa foi inoculada na superfície de meio sólido inclinado rico em glicose e nitrogênio, diretamente no frasco utilizado para a microextração em fase sólida (SPME) seguida pela injeção num cromatógrafo gasoso com detecção por espectrometria de massas (GC/MS) e quantificação utilizando detector de ionização de chama (GC-FID). O método foi desenvolvido e validado, sendo que a fibra DVB/PDMS/CAR, temperatura de extração de 80˚C e 20 minutos de aquecimento da amostra antes da extração foram as condições ótimas estabelecidas. A metodologia de superfície e resposta foi usada para a otimização da produção de acetato de etila pela levedura Zygosaccharomyces bailii BCV 08, e um planejamento fatorial 22 foi aplicado para determinar as melhores condições de temperatura de cultivo (X1, 20 até 36 ˚C) e agitação (X2, 0 a 200 rev/min). Os melhores resultados foram obtidos com a temperatura de 28 ˚C e 0 rev/min, onde houve um aumento de 60% na produção de acetato de etila. Foram avaliados os efeitos das fontes de carbono (glicose e frutose) e do mosto de uva sobre a produção de acetato de etila. A máxima concentração de acetato de etila produzida foi de 71,11 mg/L, utilizando o mosto de uva como meio. Experimentos utilizando biorreatores de 4L levaram à produção máxima de 133,74 mg/L de acetato de etila, 14,57 mg/L de hexanoato de etila, 4.093,74 mg/L de octanoato de etila e 3.775,28 mg/L de decanoato de etila. / Esters produced by biotechnological means are legally labeled as natural and there is an increasing demand for these products. Several yeasts can accumulate esters, and their selection is highly interesting for many industries. Thirty-four yeast strains isolated from red wine oak barrels of Serra Gaúcha winemaking region and from homemade cheeses of Southern Brazil were used in this research. The yeasts were inoculated in agar slants of a solid medium rich in glucose and nitrogen, directly inside the extraction transparent glass vials, using a headspace solid phase microextraction (SPME) method followed by injection of gas chromatography with mass spectrometric detection (GC/MS), and quantification by flame ionization detector (GC/FID). The analytical method was developed and validated, and the DVB/PDMS/CAR fiber, extraction temperature of 80˚C, and 20 minutes of sample heating time volatilization prior to the extraction step were the best conditions. A response surface methodology was used to optimize the production of ethyl acetate by Zygosaccharomyces bailii BCV 08, which was selected, and a 22 full factorial central composite design was applied to determine the best conditions for the cultivation temperature (X1, 20 to 36 ˚C) and stirring speed (X2, 0 to 200 rev/min). The best results were found with temperature of 28 ˚C and medium agitation of 0 rev/min, with a 60% increase in ethyl acetate production. We evaluated the effect of the carbon sources (glucose and fructose) and grape must on ethyl acetate formation; the maximal yield was reached with grape must and the highest concentration of ethyl acetate produced was 71.11 mg/L. Employing experiments on bioreactors of 4L, it was possible to improve the esters production by this yeast; a maximal production of 133.74 mg/L of ethyl acetate, 14.57 mg/L of ethyl hexanoate, 4093.74 mg/L of ethyl octanoate, and 3775.28 mg/L of ethyl decanoate was reached.

<p align=\"justify\">As propriedades de fluorescência da 2,4-(1H,3H)-quinazolinediona, produto da reação entre o íon cianato e o ácido 2-aminobenzóico possibilitaram o desenvolvimento de um método simples, sensíveis, seletivo e reprodutível para a análise de íons cianato em meio aquo etanólico. O método foi aplicado a análises de íons cianato em diferentes frações do destilado de cana e os dados sugerem uma forte correlação entre a presença de ureia no vinho, e as concentrações de íons cianato e de carbamato de etila (CE) no destilado. A citrulina apresenta-se também como uma fonte de íons cianato, tendo como um de seus produtos o CE na presença do etanol. Acompanhando-se no destilado recém-obtido as variações nas concentrações de íons cianato e de carbamato de etila em função do tempo, observa-se que à medida que diminui a concentração de íons cianato há um aumento na concentração de carbamato de etila. Foram estudados os aspectos cinéticos e termodinâmicos da formação de CE por meio da reação entre íons cianato e o etanol. Os valores das constantes de velocidade para o consumo do íon cianato e para a de formação de CE são de (8&sbquo;0 &plusmn; 0&sbquo;4) &times; 10-5 e de (8&sbquo;90 &plusmn; 0&sbquo;4) &times; 10-5 s-1, respectivamente, a 25 &deg;C em solução etanólica 48% (v&frasl;v) com pH 4&sbquo;5. Nas condições experimentais, as constantes de velocidade são independentes das concentrações de etanol e dos íons cianato, porém são dependentes da acidez pH e apresentam os valores dos parâmetros de ativação de &Delta;H&#8225; &#61; 19&sbquo;4 &plusmn; 1 kcal&frasl;mol, &Delta;S&#8225; &#61; -12&sbquo;1 &plusmn; 1 cal&frasl;K e &Delta;G&#8225; &#61; 23&sbquo;0 &plusmn; 1 kcal&frasl;mol. Cálculos computacionais empregando-se teoria do funcional de densidade (DFT) sugerem que os valores calculados de &Delta;H&#8225;1 &Delta;S&#8225;1 e &Delta;G&#8225;1 estão de acordo com os obtidos experimentalmente e condizem com o mecanismo proposto. Observa-se que íons de Cu(II) catalisam a oxidação de íons cianeto à cianato promovendo a formação de CE. Além disso, íons de Cu(II) pode se coordenar com alguns precursores de CE. / <p align=\"justify\">Based on the fluorescence properties of 2,4-(1H,3H)-quinazolinedione, a product of the reaction between cyanate and 2-aminobenzoic acid, a simple, sensitive, selective, and reproducible method for the cyanate analysis in aqueous ethanolic media is proposed. The method was applied to cyanate analysis in different fractions of sugarcane distillate and the data strongly suggest a correlation between the presence of urea in wine, and cyanate and ethyl carbamate (EC) concentrations in the spirit. Citrulline also presents itself as a cyanate source, having EC as one of its products in the presence of ethanol. Monitoring changes in cyanate and EC concentrations as function of the time in freshly distilled sugar cane spirit, it was observed that as the cyanate concentration decreases, the EC concentration increases. Thermodynamic and kinetic aspects of EC formation through the reaction between cyanate and ethanol were investigated. The rate constant values for cyanate ion decay and EC formation are (8.0 &plusmn; 0.4) &times; 10-5 s-1 and (8.90 &plusmn; 0.4) &times; 10-5 s-1, respectively, at 25 &deg;C in 48% ethanolic solution at pH 4.5. Under the investigated experimental conditions, the rate constants are independent of the ethanol and cyanate concentrations but increase as the temperature increases &Delta;H&#8225; &#61; 19.4 &plusmn; 1 kcal&frasl;mol, &Delta;S&#8225; &#61; -12.1 &plusmn; 1 cal&frasl;K and &Delta;G&#8225; &#61; 23.0 &plusmn; 1 kcal&frasl;mol) and decrease as pH solution increases. According to molecular modeling (DFT) that was performed to analyze the reaction mechanism, Isocyanic acid is the active EC precursor. The calculated &Delta;H&#8225;1 &Delta;S&#8225;1 and &Delta;G&#8225;1 values are in very good agreement with the experimental ones. The copper effect on EC formation reaction was also studied. Copper acts on the cyanide oxidation reaction and could coordinate with some EC precursors.

Today’s market offers an ever-increasing range of cellulose pulps (derivative pulps) made fromvarious wood types through different delignification processes. Each pulp segment has its uniquecharacteristics, which makes it difficult for the producer of cellulose derivatives to choose the mostsuitable pulp for optimum processability and product quality. The objective of this study was toimprove knowledge of cellulose pulps and to describe how different pulp properties affectprocessability and quality in the production of viscose dope and cellulose ethers.Ten pulp samples were investigated, originating from both sulfite and sulfate processes, with highand low viscosities and with softwood and hardwood as raw material. The pulps were analyzed fortheir properties and then processed to viscose dope and a cellulose ether in two separate pilotfacilities. The intermediates in the viscose process as well as the quality of the viscose dope andcellulose ether were analyzed and the results correlated to pulp properties.Multivariate regression methods were applied to investigate the dominating physical and chemicalproperties of each pulp and pulp segment, and to study the use of spectroscopic analyses inpredicting pulp origin, concentration and composition of hemicelluloses as well as the content ofreducing end groups in cellulose. For the production of viscose dope, the models presented showedthe most important pulp properties for good cellulose reactivity and viscose filterability. In addition,the properties affecting gel formation, flocculation, degree of substitution and clarity in theproduction of cellulose ether were highlighted. The study also emphasized the need to supplementthe use of conventional analyses on pulps and viscose intermediates with other analytical methods,such as molecular weight distribution and carbohydrate analysis, to better predict the quality ofboth viscose dope and viscose fiber.The results of the present study could be useful to predict the origin and properties of new pulps, toreplace or supplement otherwise expensive pulp analyses, and to assess the impact of pulpproperties on the production of cellulose derivatives without extensive pilot-scale trials.

While all women hope to deliver a healthy baby, approximately 3-5% babies are affected by birth defects. Birth defects can occur naturally or be induced by teratogens. Alcohol is a known teratogen that causes fetal alcohol spectrum disorder (FASD), the most commonly known cause of neurobehavioural and neurodevelopmental deficits. Individuals affected with FASD are likely to be involved with or require additional assistance from healthcare, education, social services, and justice sectors. Due to this immense burden, effective prevention of FASD can have a major public impact. Prevention of FASD can occur at different levels: primary prevention (preventing alcohol-induced birth defects from occurring in the first place); secondary prevention (preventing alcohol-induced birth defects from developing or progressing); tertiary prevention (improving the outcome of individuals affected with FASD); and quaternary prevention (preventing another child from being affected with FASD). The objective of this thesis was to explore a multilevel birth defect and FASD prevention strategy. Primary prevention by was investigated by maternal multivitamin supplementation to optimize fetal growing conditions, as alcoholics are commonly deficient in nutrients. A meta-analysis of maternal multivitamin supplementation demonstrated a decreased risk for certain congenital anomalies and pediatric cancers. Secondary prevention was investigated by a randomized double-blinded placebo-controlled evaluating the ability of high doses of antioxidants (vitamin C and vitamin E) to mitigate the effects of prenatal alcohol exposure. The study was ceased due to safety concerns regarding high doses of vitamin C and vitamin E in preeclamptic studies. Tertiary prevention was investigated by anonymous meconium screening of babies of Grey-Bruce, Ontario residents delivering at or transferred to St. Joseph’s Health Care in London, Ontario. A 30% prevalence of fatty acid ethyl esters (FAEE) positive meconium was observed at this high-risk unit. Meconium screening is also a means of quaternary prevention since positive screens also identify mothers who were unable to stop consuming alcohol after 13 weeks of pregnancy, and therefore are at risk of delivering another child who is prenatally exposed to alcohol. The identification and engagement of these mothers into treatment programs constitutes primary prevention of FASD in subsequent pregnancies.

While all women hope to deliver a healthy baby, approximately 3-5% babies are affected by birth defects. Birth defects can occur naturally or be induced by teratogens. Alcohol is a known teratogen that causes fetal alcohol spectrum disorder (FASD), the most commonly known cause of neurobehavioural and neurodevelopmental deficits. Individuals affected with FASD are likely to be involved with or require additional assistance from healthcare, education, social services, and justice sectors. Due to this immense burden, effective prevention of FASD can have a major public impact. Prevention of FASD can occur at different levels: primary prevention (preventing alcohol-induced birth defects from occurring in the first place); secondary prevention (preventing alcohol-induced birth defects from developing or progressing); tertiary prevention (improving the outcome of individuals affected with FASD); and quaternary prevention (preventing another child from being affected with FASD). The objective of this thesis was to explore a multilevel birth defect and FASD prevention strategy. Primary prevention by was investigated by maternal multivitamin supplementation to optimize fetal growing conditions, as alcoholics are commonly deficient in nutrients. A meta-analysis of maternal multivitamin supplementation demonstrated a decreased risk for certain congenital anomalies and pediatric cancers. Secondary prevention was investigated by a randomized double-blinded placebo-controlled evaluating the ability of high doses of antioxidants (vitamin C and vitamin E) to mitigate the effects of prenatal alcohol exposure. The study was ceased due to safety concerns regarding high doses of vitamin C and vitamin E in preeclamptic studies. Tertiary prevention was investigated by anonymous meconium screening of babies of Grey-Bruce, Ontario residents delivering at or transferred to St. Joseph’s Health Care in London, Ontario. A 30% prevalence of fatty acid ethyl esters (FAEE) positive meconium was observed at this high-risk unit. Meconium screening is also a means of quaternary prevention since positive screens also identify mothers who were unable to stop consuming alcohol after 13 weeks of pregnancy, and therefore are at risk of delivering another child who is prenatally exposed to alcohol. The identification and engagement of these mothers into treatment programs constitutes primary prevention of FASD in subsequent pregnancies.

Magnetic particles have attracted increasing attention in fields ranging from separation processes to electromagnetic information storage an medical application. Various approaches for their synthesis have been developed and studied to satisfy the criteria of production. Improvement and optimization of size, stability, and functionality is of vital importance in biological applications. The main aspect of project, initially, was to study the application of aqueous functionalized magnetic nanoparticles coupled with high gradient magnetic separation technique for the removal of trace residue of organic contaminants from drinking water. However, the importance of synthesizing stable ferrofluid for this purpose became clear later and took precedence over the initial objective. Different approaches were adopted, such as the incorporation of poly(ethylene glycol) methacrylate, ethylenediamine, and chitosan, to enhance the stability of magnetic particles. However, these surface modifications had unfavorable effect on the stability of initial particles. In accord with the initial objective of the project, the possibility of utilization of β-cyclodextrin, as organic pollutant entrapment agent, was investigated in preliminary studies conducted on its interaction with a model compound, procaine hydrochloride. The outcomes of these experiments suggest its potential as a biocompatible removal agent for the elimination of organic pollutant in drinking water system, or other applications that require selective separation of organic compounds.

In this study, WO3 and NiO thin films were deposited on the ITO/Glass substrates by radio frequency (RF) magnetron sputtering, respectively. The physical and electrochromic properties of thin films were investigated. On the other hand, the lithium perchlorate (LiClO4) powder was dispersed in propylene carbonate (PC) solvent to complete 1 M electrolyte. Then, as the 4.5 wt.% of ethyl cellulose and 8 wt.% ethylene carbonate (EC) were added to this electrolyte under stirring, a gel polymer electrolyte (GPE) was formed. Finally, the WO3 and NiO thin films obtained with the optimal deposition parameters were combined with the GPE to set up a complementary electrochromic device (CECD). The effects of the various coloring voltages on the electrochromic properties of CECD are investigated. The memory effect, energy-saving efficient, response time and switch lifetime of CECD are also estimated and discussed. Experimental results reveal that the amorphous thin films can be obtained with the RF power of 100 W and oxygen concentration of 60% at room temperature (RT). The thicknesses of WO3 and NiO films were approximately 530 nm and 180 nm, respectively. The stoichiometric of thin films were 2.99 for O/W ratio and 1.01 for O/Ni ratio. The GPE [(1 M LiClO4+PC)+ethyl cellulose(4.5 wt.%)+EC(8 wt.%)] exhibits a viscosity coefficient of 100 mPa∙s, a maximum ion conductivity (£m) of 7.17 mS/cm, a minimum activation energy (Ea) of 0.033 eV and a average visible transmittance of 82% at RT. The optimal electrochromic CECD (Glass/ITO/WO3/GPE/NiO/ITO/Glass) biased with a coloring/bleaching voltage of ¡Ó2.2 V revealed a transmittance variation (£GT%) of 54.53%, an optical density change (£GOD) of 0.790, an intercalation charge (Q) of 6.28 mC/cm2 and a coloration efficiency (£b) of 125.21 cm2/C at a wavelength (£f) of 550 nm. The chromaticity coordinates of CECD were x=0.289 and y=0.365 under the colored state. In addition, the energy-saving efficient of CECD was 15.19 W/V-m2 over the wavelength range between 380 nm and 780 nm. Also, it presented an open-circuit memory effect that the colored transmittance (£f at 550 nm) was 18.9% in 24 h. The total response time of the CECD was about 4 s for coloring and bleaching steps. After the repeated switch of 1,000 times, the £GT% of CECD was 43.57%. In this study, WO3 and NiO thin films with good adhesion, amorphous, and nearly stoichiometric were successfully deposited by RF sputter. Furthermore, high £m and high transmittance of GPE can be prepared easily and inexpensively. Our results demonstrated that the CECD exhibited the advantages of low applied voltage, high £b, fast response time and long-term memory characteristics.

ªí­±¤Æ¾Ç»â°ì¤¤¡A¬ã¨s¹L´çª÷Äݳ洹ªí­±¤W§lªþºA¤A°ò(C2H5)¤§¤ÏÀ³¡A¤w¦³¬Û·í¦hªº³ø¾É¡C¨ä¦@ÃѬ°£]-H®ø¥h(£]-elimination)§Î¦¨¤A²m(C2H4)²æªþ¬O¥D­n¤ÏÀ³¸ô®|¡C¥»¬ã¨s«h¥H¤£¦Pµ{«×¬t¨ú¥Nªº¤A°ò(ethyl)¡GCF3CF2-¡BCHF2CF2-¡BCF3CHF-¡BCF3CH2-¤ÎCH3CH2-§@¬°¹ï·Ó¡A§lªþ¦bCu(100)³æ´¹­±¤W¥Hµ{·Å¤ÏÀ³/²æªþ(TPR/D)¹êÅç±´°Q¤ÏÀ³¾÷ºc¡Aµ²ªGÅã¥Ü«e¨âºØ¼Ë«~¥ý¶i¦æ£\-F®ø¥h§Î¦¨Ethylideneªí­±¤¤¶¡Åé¡A«eªÌ¦A¦Û¨­°¸¦X©ó350K¥Í¦¨CF3-CF=CF-CF3¡A¦Ó«áªÌ°¸¦X©ó300K¥Í¦¨CHF2-CF=CF-CHF2¡C«á¤TºØ¼Ë«~«hµo¥Í£]®ø¥hª½±µ²£¥ÍCHF=CF2(310K)¡BCH2=CF2(225K)©MCH2=CH2(250K)¡C¥Ñ©ó­n¶i¦æ¸û§C·Å¤§£]®ø¥h¤ÏÀ³®É¡A¹L´çºA§e¥­­±¤ÎEclipsedºc«¬(¦p¥k¹Ï)¡CÂǥѦ¹¬Ý¥X«e¨âºØ¼Ë«~¤§£]¸ô®|¹L´çºA¬O¨ã¦³¨â¹ïF-F¤¬¥¸§@¥Î¡A³o¨Ï±o¹L´çºA¸û¤£Ã­©w¡A¯à»Ùª@°ª¾É­P¤ÏÀ³¸ô®|Â੹¬Û¹ï¯à»Ù¥i¯à¸û§C¤§£\®ø¥h¡C«á¤TºØ¼Ë«~¦æ£]®ø¥h¤§¹L´çºA¦]¦³¸û¤ÖF-F±Æ¥¸¡A©Ò¥H¦æ£]®ø¥h¤ÏÀ³¡C¨Ï¥Î¼ÒÀÀ­pºâªºµ²ªG¤]Åã¥Ü¡A·í©Mª÷ÄÝÁäµ²ªº£\ºÒ¤W¨ã¬t¨ú¥N®É°£³y¦¨ªºÁä¯àÅܱj¡A¥ç·|³y¦¨¦b¹L´çºA¦b¶i¦æª÷ÄÝ-ºÒÁäÂ_µõ®É¯à»Ù¤É°ª¦Ó¶}±Ò¬Û¹ï¯à»Ù¥i¯à¸û§C¤§£\®ø¥h³q¹D¡C¬ã¨sµ²ªG©Ò¤Ï¬M¤A°ò¤W¬t¨ú¥N¦ì¸m¤Îµ{«×¤£¦P©Ò³y¦¨ªº¤ÏÀ³¸ô®|ªº¿ï¾Ü©Ê¡A§¡¥i¥Ñ¤W­z¹L´çºA¤©¥H¦X²zªº¸ÑÄÀ¡C

The esterification of lactic acid with ethanol over Lewatit S 100, strong cation ion exchange resin catalyst, was studied in counter current vapor-liquid contactor type differential reactor by feeding ethanol and lactic acid solution as vapor and liquid phases, respectively. The ethanol vapor phase was diluted by dry air and the water removal was achieved by the mass transfer of water from liquid to vapor phase. Effect of ethanol to lactic acid feed molar ratio and vapor flow rate on fractional conversion and water removal efficiency were tested at 40-70&deg / C of column temperature range. It was observed that Lewatit S 100 was adequate catalyst for esterification of lactic acid with ethanol. Increase in ethanol to lactic acid feed molar ratio enhanced both lactic acid conversion and water removal by upper product stream. However, lactic acid conversion was suppressed by the increase of inlet vapor flow rate because of the decrease in ethanol concentration in gas phase which affected both esterification reaction rate and mass transfer rate. The reaction temperature is the other important parameter that affects the mass transfer of ethanol from vapor to liquid phase. Although reaction rate and equilibrium conversion values were promoted by temperature, the lower solubility of ethanol in liquid phase limited the fractional conversion while promoted the water mass transfer from liquid to vapor phase. The optimized vapor phase velocity and temperature can yield higher conversions than the equilibrium conversion at the same temperature and initial composition. Therefore, low pressure organic acids such as lactic acid can be successfully esterified by using counter current V-L contactor type reactors and by using integrated reaction and separation units.

Performance studies on the treatment of VOCs in air streams by a pilot-scale regenerative catalytic oxidizer (RCO) and a full-scale regenerative thermal oxidizer (RTO) were conducted. The pilot-scale RCO was constructed with two 20-cm x 200-cm (inside diameter x packing height) regenerative beds packed with gravel (average particle size = 1.25 cm) used as the thermal regenerative solid material. Experimental results indicate that destruction efficiencies of 97 and 90%, respectively, were obtained for methyl ethyl ketone and toluene at a superficial gas velocity of 0.372 m/s (evaluated at 25¢J) and a maximum bed temperature of 400¢J. It was estimated that an electrical thermal energy of approximately 84 kWh was required for treating 1,000 m3 of the waste air stream by the RCO. The full-scale RTO was constructed with two regenerative beds of 100-cm square x 200-cm height packed with the gravel used in the RCO. A paint solvent containing methyl ethyl ketone, ethyl benzene, xylenes, and ethyl acetate was used for the target VOCs. Experimental results indicate that, at a superficial gas velocity of 0.372 m/s (evaluated at 25¢J), VOC destruction efficiencies of 84, 92, 95 and 98% were obtained for the beds at temperature ranges of 200-300, 300-500, 400-700, and 500-700¢J. These conditions corresponded to empty gas retention times of 1.07, 0.85, 0.41, and 0.39s, respectively, for the cited temperature ranges. Finally, it was estimated that electrical watts of approximately 0.10, 0.45, 1.78, 2.43 kWh were required for treating 1,000 m3 of the waste air stream, respectively, at bed temperature ranges of 200-300, 300-500, 400-700, and 500-700¢J.