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Developing new membrane morphologies and modifying the existing membrane materials are required to obtain membranes with improved gas separation performances. The incorporation of zeolites and low molecular-weight additives (LMWA) into polymers are investigated as alternatives to modify the permselective properties of polymer membranes. In this study, these two alternatives were applied together to improve the separation performance of a polymeric membrane. The polycarbonate (PC) chain characteristics was altered by incorporating p-nitroaniline (pNA) as a LMWA and the PC membrane morphology was modified by introducing zeolite 4A particles as fillers. For this purpose, pure PC and PC/pNA dense homogenous membranes, and PC/zeolite 4A and PC/pNA/zeolite 4A mixed matrix membranes (MMM) were prepared by solvent-evaporation method using dichloromethane as the solvent. The pNA and zeolite 4A concentrations in the casting solutions were changed between 1-5% (w/w) and 5-30% (w/w), respectively. Membranes were characterized by SEM, DSC, and single gas permeability measurements of N2, H2, O2, CH4 and CO2. They were also tested for their binary gas separation performances with CO2/CH4, CO2/N2 and H2/CH4 mixtures at different feed gas compositions. DSC analysis of the membranes showed that, incorporation of zeolite 4A particles into PC/pNA increased the glass transition temperatures, Tg, but incorporation of them to pure PC had no effect on the Tg, suggesting that pNA was a necessary agent for interaction between zeolite 4A and PC matrix. The ideal selectivities increased in the order of pure PC, PC/zeolite 4A MMMs and PC/pNA/zeolite 4A MMMs despite a loss in the permeabilities with respect to pure PC. A significant improvement was achieved in selectivities when the PC/pNA/zeolite 4A MMMs were prepared with pNA concentrations of 1 % and 2 % (w/w) and with a zeolite loading of 20 % (w/w). The H2/CH4 and CO2/CH4 selectivities of PC/pNA (1%)/zeolite 4A (20%) membrane were 121.3 and 51.8, respectively, which were three times higher than those of pure PC membrane. Binary gas separation performance of the membranes showed that separation selectivities of pure PC and PC/pNA homogenous membranes were nearly the same as the ideal selectivities regardless of the feed gas composition. On the other hand, for PC/zeolite 4A and PC/pNA/zeolite 4A MMMs, the separation selectivities were always lower than the respective ideal selectivities for all binary gas mixtures, and demonstrated a strong feed composition dependency indicating the importance of gas-membrane matrix interactions in MMMs. For CO2/CH4 binary gas mixture, when the CO2 concentration in the feed increased to 50 %, the selectivities decreased from 31.9 to 23.2 and 48.5 to 22.2 for PC/zeolite 4A (20%) and PC/pNA (2%)/zeolite 4A (20%) MMMs, respectively. In conclusion, high performance PC based MMMs were prepared by blending PC with small amounts of pNA and introducing zeolite 4A particles. The prepared membranes showed promising results to separate industrially important gas mixtures depending on the feed gas compositions.

Os ácidos linoléicos conjugados (CLA) são potentes anticarcinogênicos em animais de laboratório e inibidores da lipogênese na glândula mamária, fígado e tecido adiposo. No primeiro experimento, foram determinados os teores de CLA de alimentos e o consumo total de CLA em dietas brasileiras. Amostras de leite foram coletadas em rebanhos Holandeses (B. taurus) e Gir (B. indicus) em dois períodos (Águas x Seca). Carne bovina foi coletada de animais terminados em: 1) Pastagem suplementada com concentrado; 2) Dietas com alto volumoso e 3) Dietas com alto concentrado. Amostras de carne suína e de frango foram adquiridas em Piracicaba-SP. Dietas humanas foram amostradas no restaurante da ESALQ. Leite de Holandês nas Águas apresentaram as médias mais elevadas (15,8 ± 2,9 mg/g gordura). Os teores no período da Seca foram significativamente mais baixos, com média de 5,1 mg/g gordura. Houve menor variação entre épocas para B. indicus, (Águas, 9,7 e Seca, 8,0 mg/g gordura). O teor de CLA na carne bovina foi afetado pelo sistema de produção com valores de 2,8 ±0,5; 4,7 ± 1,5 e 9,9 ± 2,4 mg/g gordura, respectivamente, para os animais a pasto, com alto volumoso e alto concentrado. Carne de monogástricos apresentaram os menores valores (frango, 1,0 e suínos, 0,2 mg/g gordura). O experimento 2 estudou os efeitos da suplementação de CLA na produção e composição do leite em 30 vacas cruzadas pastejando estrela africana (Cynodon nlenfuensis var. nlenfuensis). O suplemento (4kg/dia) foi formulado para prover 115% das exigências de proteína metabolizável, sendo fornecidos 150g/cab/dia de Megalac â (Controle) ou 150g/cab/dia de sais de cálcio de CLA (CLA-60, Church & Dwight, Princeton, NJ) da 4 a a 11 a semana de lactação (período de tratamento). Os efeitos residuais foram avaliados entre a 12 a e a 15 a semana (período residual). O tratamento com CLA aumentou a produção de leite (P=0.056) e reduziu o teor de gordura de 2,86 para 2,05% (P<0,01) e a produção de gordura de 437 para 349 g/dia (P<0,01). Houve aumento de 10% no teor de proteína (2,78 para 3,05%; P<0,01) e de 19% na produção (422 para 504 g/dia; P<0.01). A densidade energética do leite foi reduzida (P<0.01) pelo CLA, sendo que o volume de leite aumentou, consequentemente as exigências de energia líquida de lactação foram reduzidas por unidade de leite produzido. A produção do leite e o teor e produção de proteína do leite dos animais tratados mantiveram-se mais elevados no período residual. O CLA reduziu os teores de ácidos graxos (AG) de cadeia curta e a proporção de AG saturados. O tratamento com CLA aumentou o teor de CLA em 30% (P<0.01) e do isômero t10,c12, em 88%. Os resultados do experimento. 1 demonstram que, se o CLA tem efeito protetivo contra câncer sugerido pelos estudos epidemiológicos disponíveis, o enriquecimento de CLA na dieta seria desejável. A suplementação com CLA aumentou a produção de leite, alterou sua composição, e reduziu as exigências nutricionais por unidade de leite, permitindo aumentos de volume de leite e de quantidade de proteína, particularmente em ambientes onde o aporte de energia é restrito. / Conjugated linoleic acids (CLA) are potent anticarcinogenics in animal models and inhibitors of fatty acid synthesis in mammary gland, kidney and adipose tissue. In experiment 1, CLA content of some foods and total intake in Brazilian diets were determined. Milk samples were collected from Holstein herds (B. taurus) and Gir (B. indicus) herds in two seasons (Rainy x Dry). Beef samples were collected from animals finished on: 1) Pasture plus supplement; 2) High roughage feedlot diets 3) High concentrate feedlot diets. Pork and broiler samples were purchased in Piracicaba-SP. Human diets were collected at the university restaurant (ESALQ). Holstein milk at the Rainy season presented the highest values (15.8 ± 2.9 mg/g fat). At the dry season values were much lower averaging 5.1 mg/g fat. For B. indicus there was less variation between seasons, (Rainy, 9,7 and Dry, 8,0 mg/g fat). Beef samples CLA content were affected by the production system and values were 2.8 ±0.5; 4.7 ± 1.5 e 9.9 ± 2.,4 mg/g fat, respectively, for pasture animals, the high roughage and high concentrate. Monogastrics had the lowest values (broiler, 1,0 and pork, 0,2 mg/g fat). Experiment 2 studied the CLA supplementation effects on milk production and composition using 30 crossbred cows grazing stargrass (Cynodon nlenfuensis var. nlenfuensis). The supplement (4kg/dia) was formulated to provide 115% of the metabolizable protein requirements. The control treatment was 150g/cab/dia de Megalac â (Control) and the treatment were 150g/cab/day CLA calcium salts (CLA-60, Church & Dwight, Princeton, NJ) from week 4 to week 11 (treatment period). Residual effects were evaluated between week 12 and week 15 (residual period). CLA treatment increased milk production (P=0.056) and reduced fat content from 2.86 to 2.05% (P<0,01) and fat production from 437 to 349 g/day (P<0,01). Milk protein increased by 10% (2.,78 to 3.05%; P<0.01) and 19% in production (422 to 504 g/day; P<0.01). Milk energy concentration was decreased (P<0.01) by CLA, while milk volume increased, consequently the net energy of lactation was reduced by kilos of milk produced. Milk production and protein production and content, for the treated cows, kept higher in the residual period. CLA reduced short chain fatty acids (FA) and the proportion of saturated FA. CLA treatment increased CLA content by 30% (P<0.01) and for t10,c12, by 88%. Experiment 1 results showed that, if CLA has protective against cancer suggested by the available epidemiological studies, than CLA enrichment should be desirable. CLA supplementation with CLA increased milk volume production, altered it’s composition, and reduced the energy requirements in relation to milk unity produced, allowing higher milk volumes, higher protein produced, particularly in environments where energy is restricted.

Os ácidos linoléicos conjugados (CLA) são potentes anticarcinogênicos em animais de laboratório e inibidores da lipogênese na glândula mamária, fígado e tecido adiposo. No primeiro experimento, foram determinados os teores de CLA de alimentos e o consumo total de CLA em dietas brasileiras. Amostras de leite foram coletadas em rebanhos Holandeses (B. taurus) e Gir (B. indicus) em dois períodos (Águas x Seca). Carne bovina foi coletada de animais terminados em: 1) Pastagem suplementada com concentrado; 2) Dietas com alto volumoso e 3) Dietas com alto concentrado. Amostras de carne suína e de frango foram adquiridas em Piracicaba-SP. Dietas humanas foram amostradas no restaurante da ESALQ. Leite de Holandês nas Águas apresentaram as médias mais elevadas (15,8 ± 2,9 mg/g gordura). Os teores no período da Seca foram significativamente mais baixos, com média de 5,1 mg/g gordura. Houve menor variação entre épocas para B. indicus, (Águas, 9,7 e Seca, 8,0 mg/g gordura). O teor de CLA na carne bovina foi afetado pelo sistema de produção com valores de 2,8 ±0,5; 4,7 ± 1,5 e 9,9 ± 2,4 mg/g gordura, respectivamente, para os animais a pasto, com alto volumoso e alto concentrado. Carne de monogástricos apresentaram os menores valores (frango, 1,0 e suínos, 0,2 mg/g gordura). O experimento 2 estudou os efeitos da suplementação de CLA na produção e composição do leite em 30 vacas cruzadas pastejando estrela africana (Cynodon nlenfuensis var. nlenfuensis). O suplemento (4kg/dia) foi formulado para prover 115% das exigências de proteína metabolizável, sendo fornecidos 150g/cab/dia de Megalac â (Controle) ou 150g/cab/dia de sais de cálcio de CLA (CLA-60, Church & Dwight, Princeton, NJ) da 4 a a 11 a semana de lactação (período de tratamento). Os efeitos residuais foram avaliados entre a 12 a e a 15 a semana (período residual). O tratamento com CLA aumentou a produção de leite (P=0.056) e reduziu o teor de gordura de 2,86 para 2,05% (P<0,01) e a produção de gordura de 437 para 349 g/dia (P<0,01). Houve aumento de 10% no teor de proteína (2,78 para 3,05%; P<0,01) e de 19% na produção (422 para 504 g/dia; P<0.01). A densidade energética do leite foi reduzida (P<0.01) pelo CLA, sendo que o volume de leite aumentou, consequentemente as exigências de energia líquida de lactação foram reduzidas por unidade de leite produzido. A produção do leite e o teor e produção de proteína do leite dos animais tratados mantiveram-se mais elevados no período residual. O CLA reduziu os teores de ácidos graxos (AG) de cadeia curta e a proporção de AG saturados. O tratamento com CLA aumentou o teor de CLA em 30% (P<0.01) e do isômero t10,c12, em 88%. Os resultados do experimento. 1 demonstram que, se o CLA tem efeito protetivo contra câncer sugerido pelos estudos epidemiológicos disponíveis, o enriquecimento de CLA na dieta seria desejável. A suplementação com CLA aumentou a produção de leite, alterou sua composição, e reduziu as exigências nutricionais por unidade de leite, permitindo aumentos de volume de leite e de quantidade de proteína, particularmente em ambientes onde o aporte de energia é restrito. / Conjugated linoleic acids (CLA) are potent anticarcinogenics in animal models and inhibitors of fatty acid synthesis in mammary gland, kidney and adipose tissue. In experiment 1, CLA content of some foods and total intake in Brazilian diets were determined. Milk samples were collected from Holstein herds (B. taurus) and Gir (B. indicus) herds in two seasons (Rainy x Dry). Beef samples were collected from animals finished on: 1) Pasture plus supplement; 2) High roughage feedlot diets 3) High concentrate feedlot diets. Pork and broiler samples were purchased in Piracicaba-SP. Human diets were collected at the university restaurant (ESALQ). Holstein milk at the Rainy season presented the highest values (15.8 ± 2.9 mg/g fat). At the dry season values were much lower averaging 5.1 mg/g fat. For B. indicus there was less variation between seasons, (Rainy, 9,7 and Dry, 8,0 mg/g fat). Beef samples CLA content were affected by the production system and values were 2.8 ±0.5; 4.7 ± 1.5 e 9.9 ± 2.,4 mg/g fat, respectively, for pasture animals, the high roughage and high concentrate. Monogastrics had the lowest values (broiler, 1,0 and pork, 0,2 mg/g fat). Experiment 2 studied the CLA supplementation effects on milk production and composition using 30 crossbred cows grazing stargrass (Cynodon nlenfuensis var. nlenfuensis). The supplement (4kg/dia) was formulated to provide 115% of the metabolizable protein requirements. The control treatment was 150g/cab/dia de Megalac â (Control) and the treatment were 150g/cab/day CLA calcium salts (CLA-60, Church & Dwight, Princeton, NJ) from week 4 to week 11 (treatment period). Residual effects were evaluated between week 12 and week 15 (residual period). CLA treatment increased milk production (P=0.056) and reduced fat content from 2.86 to 2.05% (P<0,01) and fat production from 437 to 349 g/day (P<0,01). Milk protein increased by 10% (2.,78 to 3.05%; P<0.01) and 19% in production (422 to 504 g/day; P<0.01). Milk energy concentration was decreased (P<0.01) by CLA, while milk volume increased, consequently the net energy of lactation was reduced by kilos of milk produced. Milk production and protein production and content, for the treated cows, kept higher in the residual period. CLA reduced short chain fatty acids (FA) and the proportion of saturated FA. CLA treatment increased CLA content by 30% (P<0.01) and for t10,c12, by 88%. Experiment 1 results showed that, if CLA has protective against cancer suggested by the available epidemiological studies, than CLA enrichment should be desirable. CLA supplementation with CLA increased milk volume production, altered it’s composition, and reduced the energy requirements in relation to milk unity produced, allowing higher milk volumes, higher protein produced, particularly in environments where energy is restricted.