The overarching goal of this research was to investigate the differences in the physicochemical and functional properties of protein isolates produced from seven different faba bean genotypes (CDC Fatima, Taboar, SSNS-1, FB9-4, FB18-20, Snowbird and CDC Snowdrop) grown at different locations in Canada (Saskatchewan, Alberta and Manitoba) in 2011 and 2012. The protein isolates were prepared by alkaline extraction (pH 9.5) followed by isoelectric precipitation at pH 4.5. The isolates had an average protein content of ~94% and average protein and isolate yields of ~77% and ~25%, respectively. The physicochemical properties assessed in this study included surface charge/zeta potential (ZP), surface hydrophobicity (SH), and surface and interfacial tension (ST and IT). The functional properties tested included foaming capacity (FC) and foam stability (FS), emulsion capacity (EC) and creaming stability (CS), emulsion activity index (EAI) and emulsion stability index (ESI), oil holding capacity (OHC), and protein solubility. The findings indicated that all physicochemical properties for all isolates were independent of genotype. Overall, an average ZP of + 22.1 mV, SH of 47.2 arbitrary units, and ST and IT of 65.0 mN/m and 10.7 mN/m, respectively, were observed. However, with the exception of ZP considerable differences were observed due to the effect of environment. The ratio of the major globulin protein fractions [legumin:vicilin (L/V)] was found to shift during processing, from 3.8 (range: 3.4-4.6) in the flour to 4.5 (range 4.0-4.9) in the isolates. The L/V ratio for faba bean flour and isolate samples was also found to be independent of genotype. For all genotypes, with the exception of the zero-tannin varieties (Snowbird and CDC Snowdrop), the L/V ratio was affected by the environment. Similar to the physicochemical properties, all functional attributes were found to be independent of genotype. However, environmental effects were observed for all functional properties with the exception of EAI and ESI. Average values for FC of 162.0%, for FS of 65.0%, for EC of 184.0 g/g, for CS of 94.0%, for OHC of 5.7 g/g, for EAI of 13.0 m2/g, for ESI of 10.7 min and for solubility of 81.0% were reported. Zeta potential was observed to be positively correlated with CS (r = 0.46; p<0.05) and FS (r = 0.54; p<0.01), whereas SH and L/V ratio were not. The L/V ratio in the isolate, however, was correlated positively with SH (r = 0.40; p<0.05) and negatively with ZP (r = -0.39; p<0.05). Moreover, the solubility of faba bean isolates was found to be positively correlated with ZP (r = 0.44; p<0.05) and negatively correlated with both IT (r = -0.38; p<0.05) and OHC (r = -0.38; p<0.05). The functional properties of some commercial protein isolates (soy, pea, whey, egg and wheat) were evaluated for comparative purposes. The OHC of the faba bean isolate was found to be higher than that of any of the commercial isolates. With the exception of CS (soy and pea) and FC (egg), all of the emulsifying (EC, EAI and ESI) and foaming (FC and FS) properties of the faba bean protein isolates were comparable to those of soy, pea and egg isolates. In contrast, values for most of the other functional properties were greater for faba bean isolates than for the pea and wheat isolates, but lower than for the whey isolate. For example, the solubility of the protein isolates was observed to decrease in the following order: whey (89.0%) = egg (88.1%) > faba bean (81.0%) > soybean (30.5%) > pea (20.1%) > wheat (10.7%).

The UPPER (Unified Physicochemical Property Estimation Relationships) model uses additive and non-additive parameters to estimate 21 biologically and environmentally important physicochemical properties of organic compounds. Thermodynamically sound relationships are used to predict boiling and melting points, aqueous and octanol solubilities, vapor pressure and the air-octanol, air-water and octanol-water partition coefficients. These properties determine the distribution and fate of organic compounds in biological and environmental systems. The model has been validated on a data set of 2000 hydrocarbons and polyhalogenated hydrocarbons, provides a simple and accurate method to predict the properties studied.

The overall goal of this research was to investigate the effect of seed tempering moisture and micronization temperature on the physicochemical properties of chickpea flour and its subsequent performance as a binder in a model low-fat pork bologna product. This work was divided into three studies. In the first study, the effect of seed tempering moisture (untempered (7% moisture) or tempered to 15 or 22% moisture) and surface micronization temperature (115, 130, 150 or 165oC) and on the physical, chemical and functional properties of chickpea flour were investigated. Chickpea flour became darker as seed moisture or micronization temperature increased. Increasing the micronization temperature at 22% seed moisture increased starch gelatinization from 8.2 to 34.0%. The lipoxygenase activity of chickpea flour also was reduced by micronization of seed. Lipoxygenase activity in flour from non-micronized seed and flour from seed micronized at 115oC without tempering was determined to be 1.98×105 and 1.12×105 units/g of protein, respectively, with no activity found in any other treatments. There was an increase in the water holding (WHC) and oil absorption capacity (OAC) of flour when chickpea seed was tempered to 22% moisture before micronization. Flour from untempered seed and from seed tempered to 15% moisture exhibited small increases in WHC as micronization temperature increased. Micronization had no effect on the OAC of untempered flours, whereas OAC decreased in flour from seed tempered to 15% moisture at higher micronization temperatures. Rapid visco-analysis (RVA) revealed that peak viscosity and final viscosity of all flours from tempered seed decreased with increasing micronization temperature, whereas the trend for both peak viscosity and final viscosity was in the opposite direction with untempered seed. The effect of seed tempering moisture and micronization temperature on the performance of chickpea flour as a binder in a low-fat, comminuted meat product (i.e., low-fat bologna) was investigated in study 2. Both the textural and sensory properties (trained sensory panel, n=12) of the bologna (10% fat) were explored. In study 3, a consumer panel was performed with 101 untrained participants evaluating selected formulations in order to better understand consumer purchasing behaviour as it relates to comminuted meat products containing a pulse-based binder. Bologna containing flour from micronized chickpea was more yellow in colour (CIE system, trained panel and consumer panel evaluation) compared to those with added wheat flour or no binder. There was no effect of tempering or micronization conditions on cook loss or expressible moisture of bologna containing chickpea flour, whereas bologna produced with wheat flour had the greatest WHC among all bologna treatments. Texture profile analysis (TPA) showed that the addition of chickpea flour from seed tempered to 15% or 22% seed moisture and micronized to 115, 130 or 150oC or flour from untempered seed micronized to 130 or 150oC led to an increase in hardness to a level similar to that of bologna containing wheat flour; sensory evaluation by the trained panel did not produce a similar result. A difference in flavour intensity was not found among all bolognas containing chickpea flour during sensory evaluation. Bologna produced with chickpea flour from seed micronized to 150oC and from seed tempered to 22% moisture and micronized to 115oC was comparable to bologna containing wheat flour with respect to overall texture, overall juiciness and flavour acceptability. These results demonstrated that selection of appropriate seed tempering conditions and micronization temperatures is important with respect to the utilization of chickpea flour as a binder in low-fat bologna.

The physicochemical properties of a drug affect to a large extent its subsequent biological absorption and bioavailability profile. Considerable pharmaceutical interest is therefore directed torwards the improvement of drug dissolution characteristics of drugs with low aqueous solubility. This thesis has considered the controlled modification of drug dissolution profiles by means of incorporating low concentrations of hydrophilic polymers by different processes into a host drug substance. In order to examine this approach and its potential use, the physicochemical, solid state, stability and tableting properties of a poorly aqueous soluble drug, phenylbutazone, in alternative polymorphic form and containing low levels of two hydrophilic polymers - hydroxypropyl methylcellulose (H.P.M.C.) and the surfactant poloxamer 188 - prepared by both conventional crystallisation and spray drying are reported. As an integral nart of the work attempts were mado to identify the different polymorphic forms of phenylbutazone. The δ-form, the commercially available stable form and the α and β metastable forms (nomenclature after Muller, 1978) were isolated. The α form was found to be unstable on storage. A 2 fold increase in intrinsic dissolution rate was observed for the metastable β-polymorph compared with the stable δ-polymorphic form. The effect of crystallisation rate on the formation of polymorphs of phenylbutazone was studied using a mini-spray dryer, and slower rates of crystallisation were found to favour polymorph formation. The hydrophilic polymers, H.P.M.C. and poloxamer 188, were incorporated by conventional crystallisation and spray drying into the drug crystal. Samples were subjected to a series of tests including differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, and intrinsic dissolution and solubility. When prepared by conventional crystallisation H.P.M.C. was found to form a "high energy" complex with phenylbutazone which melted 10°C lower than the parent drug. When prepared by spray drying H.P.M.C. inhibited the formation of the metastable β-polymorph of phenylbutazone. A 2 fold increase in intrinsic dissolution rate was observed for crystallised and spray dried samples containing 2% w/w or more added polymer. Poloxamer 188 did not form a complex with phenylbutazone and unlike H.P.M.C. did not inhibit the formation of the β-polymorph. For both crystallised and spray dried samples a 3 fold increase in dissolution rate was obtained at polymer levels of 1% w/w or above. The increase in dissolution has been attributed to facilitated wetting by lowering of interfacial tension rather than through the formation of micelles. The stability of selected phenylbutazone:polymer samples was tested at elevated temperatures. The stability was found to be affected both by the method of sample preparation and the type of additive. Large breakdowns occurring by a hydrolytic effect were identified for the crystallised phenylbutazone samples containing poloxamer 188. The effects on compaction of phenylbutazone in alternative form and presence of polymeric additives were studied by compressing samples of similar particle sizes of phenylbutazone as supplied (δ-form), samples of spray dried phenylbutazone (β-form) and samples containing different concentrations of H.P.M.C. prepared both by conventional crystallisation and spray drying. Compaction data were analysed according to the Heckel relationship and by force transmission ratio as well as from the tensile strengths of prepared tablets. The presence of H.P.M.C. up to 5% w/w concentration in phenylbutazone did not change the mean yield pressure for the crystallised or spray dried samples, although a difference in mean value was observed between the crystallised and spray dried materials, 93.22 MPa and 147.02 MPa respectively. Force transmission was found to be improved for samples containing H.P.M.C. prepared by both techniques and in general, the tablet tensile strengths for crystallised samples containing H.P.M.C. were approximately three times greater than for spray dried samples at equivalent tablet porosity. Differences are attributed to variation in solid state and particulate properties between samples.

Resumo: Em função da crescente importância do material carbono vítreo em áreas estratégicas, devido às suas características intrínsecas, tais como menor massa específica e bons valores de condutividades térmica e elétrica, tem se observado vários estudos na busca de novos precursores poliméricos, assim como no ajuste mais sistemático de seu processamento. Nesse sentido, este trabalho tem como objetivo o estabelecimento de rotas de síntese de resinas furfurílica e fenol-furfurílica e suas dopagens com partículas de cobre, visando o processamento de eletrodos de carbono vítreo reticulado (CVR). Neste contexto foram sintetizadas diferentes formulações de resinas furfurílica e fenol-furfurílica a partir da variação dos monômeros - álcool furfurílico, fenol e formaldeído, respectivamente. A confirmação do sucesso das sínteses foi realizada por análises de espectroscopia de infravermelho com transformada de Fourier, cromatografia gasosa, análises térmicas por calorimetria exploratória diferencial e medidas dos teores de carbono fixo, que mostram resultados entre 27 e 45% em carbono. Em seguida, estas amostras foram dopadas com um colóide contendo as partículas de cobre. As resinas, com e sem dopagem, foram catalisadas, impregnadas em espumas de poliuretano (PU) e carbonizadas, obtendo-se assim, o CVR. Análises por microscopias óptica e eletrônica de varredura mostram a homogeneidade na impregnação das espumas de PU e a textura uniforme das amostras de CVR. Os resultados de resistência à compressão apresentam os melhores valores para o CVR resultante da carbonização com a resina furfurílica ácida (0,55 MPa). / Abstract: Due to the growing importance of glassy carbon material in strategic areas, due to its intrinsic characteristics, such as lower density and good thermal and electrical conductivities values, has been observed several studies looking for new polymeric precursors and tighter processing parameters. In this way, this study aims on the establishment of synthesis routes of furfuryl and phenol-furfuryl alcohol resins and their doping with cupper particles, in order to produce reticulated glassy carbon (RGC) electrodes. Inside of this context were synthesized different formulations of furfuryl and phenol-furfuryl alcohol resins by the monomers variation - furfuryl alcohol, phenol and formaldehyde, respectively. The success confirmation of the synthesis has been done by using FT-IR spectroscopy, gas chromatography, thermal analyses by differential scanning calorimetry (DSC) and carbon yield content measurements that present results between 27 and 45% of carbon. After this, the specimens were doped with a colloid contend the copper particles. The doped and non doped resins were catalyzed, impregnated in polyuretane (PU) foams and carbonized, in order to obtain the reticulated glassy carbon. Optical and Scanning Electron Microscopy analysis show the homogeneity of PU foams impregnation and uniform texture of RGC specimens. Compression results present the best values for RGC resulting from the carbonization with furfuryl alcohol acid resin (0,55 MPa). / Orientador: Edson Cochieri Botelho / Coorientadora: Mirabel Cerqueira Rezende / Banca: Choyu Otani / Banca: Pedro Carlos de Oliveira / Mestre

Foram avaliadas algumas propriedades físico-químicas, como o pH, liberação de íons cálcio, tempo de presa, solubilidade e radiopacidade de 3 cimentos a base do agregado de trióxido mineral, clínquer do cimento Portland e um epóxico experimental. Foram avaliados os cimentos MTA Angelus branco, MTA Bio, cimentos experimentais, MTA fotopolimerizável e Sealepox RP e o Clínquer de cimento Portland acrescido de 20% de óxido de bismuto e 5% de sulfato de cálcio. Para as avaliações do pH e da liberação de íons cálcio foram utilizados tubos de polietileno com 1,0 mm de diâmetro interno e 10,0 mm de comprimento, com apenas uma das extremidades aberta. Esses tubos foram preenchidos com os cimentos e imediatamente imersos em tubos de ensaio contendo 10 mL de água deionizada, onde permaneceram durante todo o período experimental. Realizaram-se avaliações nos períodos de 3, 24, 72 e 168 horas, sempre se renovando a água deionizada ao final de cada período. Os ensaios de tempo de presa, solubilidade e radiopacidade, foram realizados conforme a norma #57 da ADA. Em relação ao tempo de presa, também foi utilizada a agulha de Gilmore de 453,6 g, para a presa final, conforme recomenda a norma #C266-03 da ASTM. Os resultados demonstraram que todos os cimentos apresentaram pH alcalino e liberaram íons cálcio em todos os períodos, com tendência de redução nos períodos finais. Quanto aos tempos de presa, os cimentos MTA Angelus branco e o cimento experimental MTA Bio apresentaram os menores tempos. Já o Clínquer apresentou valores intermediários, e o Sealepox RP, apresentou os tempos mais longos. O cimento MTA fotopolimerizável, por suas características próprias, não foi submetido a esse teste. Em relação ao ensaio de solubilidade, o cimento que mais se aproximou das recomendações da ADA, foi o Sealepox RP, com valores próximos a 1%, enquanto que os cimentos MTA Angelus branco, MTA Bio e o Clínquer acrescido ao radiopacificador e sulfato de cálcio apresentaram valores maiores. O MTA fotopolimerizável apresentou valores menores. Em relação à radiopacidade, a maioria dos cimentos estudados apresentou valores superiores à da dentina, com resultados semelhantes entre si, com exceção do MTA fotopolimerizável, que apresentou valor próximo ao da dentina. / Some properties had been evaluated physicochemical, such as pH, release of calcium ions, setting time, solubility and radiopacity of 3 retrograde filling the base of the aggregate of mineral trioxide, to clínquer of the Portland cement and an experimental epoxy sealer. Experimental cements MTA white Angelus, MTA Bio, light-curing MTA and Sealepox RP and the Clínquer of cement Portland increased of 20% of bismuth oxide and 5% of calcium sulphate had been evaluated. For the evaluations of pH and the release of calcium ions had been used polyethylene pipes with 1,0 mm of internal diameter and 10,0 mm of length, with only one of the extremities open. These pipes had been filled with cements and immediately immersed in pipes of 10 assay I contend mL of distilled water, where they had remained all during the experimental period. Evaluations in the periods of 3, 24, 72 and 168 hours, always if renewing the distilled water to the end of each period. The assays of setting time, solubility and radiopacity, had been carried through in agreement the norm #57 of the ADA. In relation to the setting time, also g was used the needle of Gilmore of 453,6, for the final canine tooth, as it recommends to the norm #C266-03 of the ASTM. The results had demonstrated that all the cements had presented pH alkaline and had liberated calcium ions in all the periods, with trend of reduction in the final periods. How much to the setting time, cements MTA white Angelus and experimental cement MTA Bio had presented the lesser times. Already the Clínquer presented intermediate values, and Sealepox RP, presented the times longest. Light-curing cement MTA, by its proper characteristics, was not submitted to this test. In relation to the solubility assay, the cement that more was come close to the recommendations of the ADA, was Sealepox RP, with next values 1%, whereas cements MTA white Angelus, MTA Bio and the Clínquer increased to the bismuth oxide and calcium sulphate had presented bigger values. The light-curing MTA presented less resulted . In relation to the radiopacity, the majority of studied cements presented more values to the one of the dentine, with similar results between itself, exception of the light-curing MTA, that presented value next to the one to the dentine.

京都大学 / 0048 / 新制・課程博士 / 博士(薬科学) / 甲第21345号 / 薬科博第95号 / 新制||薬科||10(附属図書館) / 京都大学大学院薬学研究科薬科学専攻 / (主査)教授 髙倉 喜信, 教授 小野 正博, 教授 山下 富義 / 学位規則第4条第1項該当 / Doctor of Pharmaceutical Sciences / Kyoto University / DFAM

No description available.

Yes / Lipid membrane-water partitions (e.g., immobilized artificial membrane systems where the lipid membrane is a neutral phospholipid monolayer bound to gel beads) were compared to various organic solvent-water partitions using linear free energy relationships. To this end, we also measured the retention factors of 36 compounds (including neutral and ionic species) from water to liposomes made up of 3-sn-phosphatidylcholine and 3-sn-phosphatidyl-l-serine (80:20, mol/mol), employing liposome electrokinetic chromatography in this work. The results show that lipid membranes exhibit a considerably different chemical environment from those of organic solvents. For both neutral species and ionic species, partitions into the more polar hydroxylic solvents are chemically closer to partition into the lipid membrane as compared to partitions into the less polar hydroxylic solvents and into aprotic solvents. This means that solutes partition into the polar parts of lipid membranes, regardless of whether they are charged or not. In addition, cerasome (i.e., liposome composed mainly of stratum corneum lipids) was compared with regular phospholipid liposomes as a possible model for human stratum corneum in partitions. It was found that the cerasome-water partition exhibits a better chemical similarity to skin permeation. This is probably due to the unique structures of ceramides that occur in cerasome and in the stratum corneum lipid domain. We further show that membranes in membrane-water partitions exhibit very different properties.

The physicochemical properties of a drug affect to a large extent its subsequent biological absorption and bioavailability profile. Considerable pharmaceutical interest is therefore directed torwards the improvement of drug dissolution characteristics of drugs with low aqueous solubility. This thesis has considered the controlled modification of drug dissolution profiles by means of incorporating low concentrations of hydrophilic polymers by different processes into a host drug substance. In order to examine this approach and its potential use, the physicochemical, solid state, stability and tableting properties of a poorly aqueous soluble drug, phenylbutazone, in alternative polymorphic form and containing low levels of two hydrophilic polymers - hydroxypropyl methylcellulose (H. P. M. C. ) and the surfactant poloxamer 188 - prepared by both conventional crystallisation and spray drying are reported. As an integral nart of the work attempts were mado to identify the different polymorphic forms of phenylbutazone. The 6-form, the cammerdiallý 4- available stable ýorm and the a and s metastable forr. s (nomenclature after Huller, 1978).. were isolated. The a form was found to be unstable on storage. A .7 fold increase in intrinsic dissolution rate was observed for the metastable s-polymorph compared with the stable 6-polymorphic form. The effect of crystallisation rate on the formation of polymorphs of phenylbutazone was studied using a mini-spray dryer, and slower rates of crystallisation were found to favour polymorph formation. The hydrophilic polymers, H. P. M. C. and poloxamer 188 were incorporated by conventional crystallisation and spray drying into the drug crystal. Samples were subjected to a series of tests including differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, and intrinsic dissolution and solubility. When prepared by conventional crystallisation H. P. M. C. was f8und to form a "high energy" complex with phenylbutazone which melted 10 C lower than the parent drug. When prepared by spray drying H. P. M. C. inhibited the formation of the metastable a-polymorph of phenylbutazone. A2 fold increase in intrinsic dissolution rate was observed for crystallised and spray dried samples containing 2% w/w or more added polymer. Poloxamer 188 did not form a complex witý phenylbutazone and unlike H. P. M. C. did not inhibit thejgr gation of the a-polymorph. For both crystallised and spray fo0ld increase in dissolution rate was obtained at polymer levels oý 1% w/w or above. The increase in dissolution has been attributed to facilitated wetting by lowering of interfacial tension rather than through the formation of micelles. The stability of-selected phenylbutazone: polymer samples was tested at elevated temperatures. The stability was found to be affected both by the method of sample preparation and the type of additive. Large breakdowns occurring by a hydrolytic effect were identified for the crystallised phenylbutazone samples containing poloxamer 188. The effects on compact. ion of phenylbu. tazone in alternative form and presence of polymeric additives were studied by compressing samples of similar particle sizes of phenylbutazone as supplied (67form), samples of spray dried phenylbutazone (a-form) and samples containing different concentrations of H. P. M. C. prepared both by conventional crystallisation and spray drying. Compaction data were analysed according to the Heckel relationship and by force transmission ratio as well as from the tensile strengths of prepared tablets. The presence of H. P. M. C. up to 5% w/w concentration in phenylbutazone did not change the mean yield pressure for the crystallised or spray dried samples, although a difference in mean value was observed between the crystallised and spray dried materials, 93.22 MPa and 147.02 MPa respectively. Force transmission was found to be improved for samples containing H. P. M. C. prepared by both techniques and in general, the tablet tensile strengths for crystallised samples containing H. P. M. C. were approximately three times greater than for spray dried samples at equivalent tablet porosity. Differences are attributed to variation in solid state and particulate properties between samples. / Saudi Arabian Government