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Polyaniline as electrolyte in polymer electrolyte membrane fuel cellsTreptow, Florian January 2005 (has links)
The applications of polyaniline (PAni) for use as electrolyte in Polymer-Electrolyte-Membrane Fuel Cells (PEMFC) were investigated. P Ani was dissolved in N-methyl pyrrolidone (NMP), cast as Emeraldine Base membranes (EB) and then doped with halide acids. The proton conductivity was measured according to Hittorf. The chloride ion distribution within the membrane was evaluated using energy-dispersive-X-ray analysis (EDX) and photometric analysers and the diffusion coefficient was calculated. The specific resistance was determined using conventional 4-point measurement. Halide doped membranes were found to be proton conducting, however, during cell operation halide removal occurred causing a rapid decline in the cell performance. The maximum power density achieved was O.3m W·cm-2 for a 70J.1m thick membrane saturate with chloride between 3,5 and 4,5mgchloride per gPAni. Composite membranes with phosphotungstic acid (PWA), antimonic acid (AA) and zirconium phosphate (ZP) were developed and also tested in a standard measuring fuel cell. While membranes produced via ion exchange (ZP) showed the same result like halide doped ones, AA composite membranes showed a stable voltage and current results. The highest measured outcome of 373.3mW·cm-2 was found with a PWA membrane, produced through dispersing 3g of phosphotungstic acid in 300ml of a 1% polyanilinelNMP solution. It was also observed, that the higher power density was obtained from the fuel cell which uses the lower-loaded membrane. It is clear that a positive effect on the cell performance is given by the addition of phosphotungstic acid to the polyaniline membrane. Therefore, the saturation of PW A have to be taken into account to not lower the power density.
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The effect of selected natural oils on the permeation of flurbiprofen through human skinCowley, Amé January 2012 (has links)
In pharmaceutical sciences, topical delivery is a transport process of an active pharmaceutical ingredient (API) from a formulated dosage form to the target site of action. For most topical delivery systems, the skin surface, or the specific skin layers, such as the outermost layer of the stratum corneum, the lipids amid the corneocytes within the stratum corneum, the corneocytes themselves, the epidermis, dermis, Langerhans cells, Merckle cells or the appendageal structures can be the target delivery location. When an API is delivered to the skin, it has to firstly diffuse from the formulation in which it is applied, to the skin surface. From there the API may partition into the stratum corneum, permeate across the stratum corneum and partition into the viable epidermis, from where it may partition further into the dermis and permeate across the dermis into the bloodstream (Wiechers, 2008:1-3, 7).
With respect to the barrier function of the skin, the intercellular spaces within the stratum corneum contain lipids and its main purpose is to operate as a barrier to water-loss and to provide an imperative diffusional barrier to the absorption of APIs. This resistance is comprised of a complex interaction of lipids that creates a hydrophilic and lipophilic penetration pathway. The fundamental aspect underlying the impermeability of the skin, therefore, is the lipophilic nature of the stratum corneum (Bouwstra et al., 2003:4; Franz & Lehman, 2000:25; Walker & Smith, 1996:296).
A common approach for the promotion of poorly penetrating APIs in transdermal delivery is the incorporation of chemical penetration enhancers in delivery systems, in order to promote the partitioning of an API into the stratum corneum. These chemicals are also referred to as accelerants, promoters and absorption promoters. Penetration enhancers are added to topical formulations and usually also partition into the stratum corneum, where they temporarily and reversibly disrupt its fundamental diffusional barrier properties, hence facilitating the absorption of an API through the skin (Büyüktimkin et al., 1997:358-359; Sinha & Kaur, 2000:1131; Walker & Smith, 1996:296). The mechanisms for the enhancement of diffusion of the API should therefore increase the solubility and partitioning of the drug from the formulation into the skin. It should further increase the solubility of the API within the skin and promote its permeability and diffusion coefficient (Rajadhyaksha et al., 1997:489).
Fatty acids are recognised to effectively enhance the penetration of transdermally delivered hydrophilic and lipophilic APIs. Many penetration enhancers contain saturated and unsaturated hydrocarbon chains, and a popular fatty acid that has been used in this regard is oleic acid (Williams & Barry, 2004:609-610). It is believed that fatty acids disrupt the lipid organisation of the intercellular lipids within the stratum corneum to cause fluidisation of these bilayers, making the stratum corneum more permeable to APIs. Excipients with polar (hydrophilic) head groups and long hydrophobic chains i.e. fatty acids, can penetrate into the intercellular lipids of the stratum corneum and disrupt these endogenous lipid components, thereby increasing diffusion of an API within the skin (Barry, 2006:9-10; Hadgraft & Finnin, 2006:367-368; Kanikkannan et al., 2006:18; Williams & Barry, 2004:610).
Natural oils are widely used in topical formulations and were an obvious choice in this study. Oils are liquids at room temperature, whereas fats are in solid form. They are relatively easy to obtain from both plants and animals. The main constituents of fats and oils are triglycerides comprising of fatty acids and a glycerol. Oils control the evaporation of moisture from the skin, spread easily and evenly and are partly metabolised in the skin to release valuable fatty acids (Fang et al., 2004:170,173; Lautenschläger, 2004:46; Mitsui, 1997:121-122).
The focus of this study was not formulation per se, but included the formulation of avocado-, grapeseed-, emu-, crocodile, olive and coconut oil into semisolid emulgel- and two foam formulations. This was done in order to investigate the penetration enhancing properties of their fatty acid content on flurbiprofen which was chosen as the marker API. The emulgels containing the natural oils were compared to the same emulgel formulation containing liquid paraffin, and a hydrogel without the inclusion of an oil.
Six natural oils were analysed by gas chromatography (GC) in order to quantify their fatty acid compositions, whilst also providing qualitative information by indicating the retention times of the materials with an alkyl chain composition (Mitsui, 1997:260). Data obtained with the GC indicated that olive- (76%), avocado- (68%), emu- (46%) and crocodile oil (40%) presented with high levels of oleic acid, also known as a mono-unsaturated fatty acid (MUFA). Lower levels of oleic acid were observed within grapeseed- (27%) and coconut oil (8%). The only oil demonstrating high levels of the poly-unsaturated fatty acid (PUFA), linoleic acid, was grapeseed oil (61%), whereas the remainder of the oils showed levels below 24%. Contrary, coconut oil seemed to have been the only oil high in saturated fatty acids (SFAs) and consisted of a lauric acid content of 52% and medium levels of myristic acid (21%). Average levels of palmitic acid (SFA) were found in crocodile- (21%) and in emu oil (21%), both of animal origin, whereas avocado-, grapeseed-, olive- and coconut oils from plants presented with levels below 15%. Stearic acid was also present in levels below 10% in all of these oils, with the oils of animal origin portraying the highest values.
A method was developed and validated to determine the concentration of the marker flurbiprofen after diffusion from the formulations into the skin, as well as concentrations of the marker that diffused through the skin, by means of high performance liquid chromatography (HPLC). Franz cell membrane diffusion studies were conducted prior to the skin diffusion studies in order to verify the actual release of the marker from the semisolid formulations.
Skin diffusion experiments were performed using dermatomed excised, human skin to which the six emulgel formulations, containing the natural oils, were applied. A comparative study was performed utilising liquid paraffin and a hydrogel, in order to compare the diffusion of the marker, flurbiprofen, into and through the skin. The two oil emulgel formulations that had indicated the best flux values were subsequently formulated into foam preparations in order to compare the penetration enhancement properties on flurbiprofen of these two oils in a foam preparation, to those in the equivalent emulgels. The data generated for all ten the formulations were compared, and the formulations that yielded the best results with regards to median flux values and the flurbiprofen concentrations within the stratum corneum-epidermis and epidermis-dermis, were identified.
Application of the liquid paraffin emulgel (21.29 μg/ml) depicted the highest average concentration of the diffused lipophilic flurbiprofen within the stratum corneum-epidermis, followed by the olive oil foam (21.47 μg/ml), olive oil emulgel (17.82 μg/ml) and grapeseed oil emulgel (17.78 μg/ml). Very similar concentrations for the marker were demonstrated by the hydrogel (16.73 μg/ml) and crocodile oil emulgel (14.89 μg/ml), whereas a lower concentration was shown for coconut oil emulgel (7.18 μg/ml). The remainder of the formulations yielded concentrations below 3%, i.e. the avocado oil emulgel (2.72 μg/ml), the coconut oil foam (1.57 μg/ml) and finally the emu oil emulgel (1.25 μg/ml).
The penetration of the marker, flurbiprofen, being trapped within the skin seemed to have been enhanced more by the oleic acid (UFA) containing emulgels and foam, especially. This was followed by oils containing high linoleic acid values, which indicated that the more kinked shaped the fatty acids, the more difficult it became to insert themselves within the lipid structures of the stratum corneum, with a resulting accumulation of the marker (Fang et al., 2003:318-319). It therefore seemed that those oils that predominantly consisted of unsaturated fatty acids (UFAs) (grapeseed-, crocodile- and olive oils) seemed to have increased the concentration of the diffused marker more significantly than those oils containing an almost even combination of MUFAs and PUFAs (avocado oil), or those mainly consisting of SFAs (coconut oil).
Average concentrations of the diffused flurbiprofen found in the epidermis-dermis region of the skin for all of the formulations demonstrated low concentrations, ranging between 0.97 - 5.39 μg/ml, with the exception of the emu oil emulgel that presented with a higher concentration of 16.15 μg/ml. The reason for the high accumulation of the marker might have been as a result of epidermal proliferation, with subsequent accumulation of the marker within the epidermis-dermis due to high oleic- and linoleic acid values, as well as small amounts of palmitoleic acid present within this oil (Katsuta et al., 2005:1011).
The resistance of the epidermis-dermis region to the general permeation of flurbiprofen might have been caused by its lipophilic nature, resulting in a reduced solubility within the hydrophilic environment of this region (Hadgraft, 1999:5).
Median results from the skin diffusion studies demonstrated that the hydrogel (23.79 μg/cm2.h) had the highest flux, followed by the olive oil- (17.99 μg/cm2.h), liquid paraffin- (15.70 μg/cm2.h), coconut oil- (13.16 μg/cm2.h), grapeseed oil- (11.85 μg/cm2.h), avocado oil- (8.31 μg/cm2.h), crocodile oil- (6.68 μg/cm2.h) and emu oil emulgels (4.41 μg/cm2.h).
The fact that the hydrogel presented a higher flux value for the marker could have been as a result of its high water content that had caused hydration of the skin. Hydration opens up the dense lipid structures inside of the stratum corneum, due to swelling of the corneocytes, with a subsequent increase in the marker‘s flux (Benson, 2005:28; Ranade & Hollinger, 2004:213). The high flux value of flurbiprofen with the liquid paraffin emulgel might also have resulted from the fact that it occluded the skin, which increased the hydration of the stratum corneum, with a subsequent increase in the flux (Mitsui, 1997:124; Thomas & Finnin, 2004:699).
Results from the skin diffusion studies could be explained by the fact that the fatty acids differ in their hydrocarbon chain by (1) the length of the chain, and (2) the position- and number of the double bonds (Babu et al., 2006:144). It is suggested that fatty acids with hydrocarbon (lipophilic) chains between C12 to C14 (also present within coconut oil) have an optimal balance of the partition coefficient and its affinity for the skin (Ogiso & Shintani, 1990:1067). It appears as though the branched UFAs, especially oleic acid, present in high quantities in olive oil, were more powerful enhancers of the diffusion of the marker, flurbiprofen (Chi et al., 1995:270).
Foam formulations were manufactured with the olive- and coconut oil emulgels that had demonstrated the best median flux values of flurbiprofen from the natural oil emulgel formulations. These formulated foams, however, did not significantly increased flux values for flurbiprofen through the skin, but only achieved values of 5.56 μg/cm2.h for the olive oil foam and 4.36 μg/cm2.h for the coconut oil foam formulations. The low flux values could have been attributed to the nature of the formulation itself, which was filled with trapped air that could have resulted in the formulation not making optimal direct contact with the available skin surface.
Throughout this study, it became evident that olive oil, predominantly consisting of oleic acid (UFA), was most effective in enhancing the flux of the lipophilic marker, flurbiprofen, through the skin, closely followed by coconut oil consisting of SFAs, with lauric- and myristic acid as its main constituents. Better enhancement effects were observed with those oils containing high amounts of oleic acid (MUFA), than oils consisting of almost equal amounts of both PUFAs and MUFAs (avocado-, emu- and crocodile oil), or oils mainly consisting of PUFAs (grapeseed oil) as its main components, but their effect was not more significant than the oil containing SFAs (coconut oil) as its key components. / Thesis (MSc (Pharmaceutics))--North-West University, Potchefstroom Campus, 2013.
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The effect of selected natural oils on the permeation of flurbiprofen through human skinCowley, Amé January 2012 (has links)
In pharmaceutical sciences, topical delivery is a transport process of an active pharmaceutical ingredient (API) from a formulated dosage form to the target site of action. For most topical delivery systems, the skin surface, or the specific skin layers, such as the outermost layer of the stratum corneum, the lipids amid the corneocytes within the stratum corneum, the corneocytes themselves, the epidermis, dermis, Langerhans cells, Merckle cells or the appendageal structures can be the target delivery location. When an API is delivered to the skin, it has to firstly diffuse from the formulation in which it is applied, to the skin surface. From there the API may partition into the stratum corneum, permeate across the stratum corneum and partition into the viable epidermis, from where it may partition further into the dermis and permeate across the dermis into the bloodstream (Wiechers, 2008:1-3, 7).
With respect to the barrier function of the skin, the intercellular spaces within the stratum corneum contain lipids and its main purpose is to operate as a barrier to water-loss and to provide an imperative diffusional barrier to the absorption of APIs. This resistance is comprised of a complex interaction of lipids that creates a hydrophilic and lipophilic penetration pathway. The fundamental aspect underlying the impermeability of the skin, therefore, is the lipophilic nature of the stratum corneum (Bouwstra et al., 2003:4; Franz & Lehman, 2000:25; Walker & Smith, 1996:296).
A common approach for the promotion of poorly penetrating APIs in transdermal delivery is the incorporation of chemical penetration enhancers in delivery systems, in order to promote the partitioning of an API into the stratum corneum. These chemicals are also referred to as accelerants, promoters and absorption promoters. Penetration enhancers are added to topical formulations and usually also partition into the stratum corneum, where they temporarily and reversibly disrupt its fundamental diffusional barrier properties, hence facilitating the absorption of an API through the skin (Büyüktimkin et al., 1997:358-359; Sinha & Kaur, 2000:1131; Walker & Smith, 1996:296). The mechanisms for the enhancement of diffusion of the API should therefore increase the solubility and partitioning of the drug from the formulation into the skin. It should further increase the solubility of the API within the skin and promote its permeability and diffusion coefficient (Rajadhyaksha et al., 1997:489).
Fatty acids are recognised to effectively enhance the penetration of transdermally delivered hydrophilic and lipophilic APIs. Many penetration enhancers contain saturated and unsaturated hydrocarbon chains, and a popular fatty acid that has been used in this regard is oleic acid (Williams & Barry, 2004:609-610). It is believed that fatty acids disrupt the lipid organisation of the intercellular lipids within the stratum corneum to cause fluidisation of these bilayers, making the stratum corneum more permeable to APIs. Excipients with polar (hydrophilic) head groups and long hydrophobic chains i.e. fatty acids, can penetrate into the intercellular lipids of the stratum corneum and disrupt these endogenous lipid components, thereby increasing diffusion of an API within the skin (Barry, 2006:9-10; Hadgraft & Finnin, 2006:367-368; Kanikkannan et al., 2006:18; Williams & Barry, 2004:610).
Natural oils are widely used in topical formulations and were an obvious choice in this study. Oils are liquids at room temperature, whereas fats are in solid form. They are relatively easy to obtain from both plants and animals. The main constituents of fats and oils are triglycerides comprising of fatty acids and a glycerol. Oils control the evaporation of moisture from the skin, spread easily and evenly and are partly metabolised in the skin to release valuable fatty acids (Fang et al., 2004:170,173; Lautenschläger, 2004:46; Mitsui, 1997:121-122).
The focus of this study was not formulation per se, but included the formulation of avocado-, grapeseed-, emu-, crocodile, olive and coconut oil into semisolid emulgel- and two foam formulations. This was done in order to investigate the penetration enhancing properties of their fatty acid content on flurbiprofen which was chosen as the marker API. The emulgels containing the natural oils were compared to the same emulgel formulation containing liquid paraffin, and a hydrogel without the inclusion of an oil.
Six natural oils were analysed by gas chromatography (GC) in order to quantify their fatty acid compositions, whilst also providing qualitative information by indicating the retention times of the materials with an alkyl chain composition (Mitsui, 1997:260). Data obtained with the GC indicated that olive- (76%), avocado- (68%), emu- (46%) and crocodile oil (40%) presented with high levels of oleic acid, also known as a mono-unsaturated fatty acid (MUFA). Lower levels of oleic acid were observed within grapeseed- (27%) and coconut oil (8%). The only oil demonstrating high levels of the poly-unsaturated fatty acid (PUFA), linoleic acid, was grapeseed oil (61%), whereas the remainder of the oils showed levels below 24%. Contrary, coconut oil seemed to have been the only oil high in saturated fatty acids (SFAs) and consisted of a lauric acid content of 52% and medium levels of myristic acid (21%). Average levels of palmitic acid (SFA) were found in crocodile- (21%) and in emu oil (21%), both of animal origin, whereas avocado-, grapeseed-, olive- and coconut oils from plants presented with levels below 15%. Stearic acid was also present in levels below 10% in all of these oils, with the oils of animal origin portraying the highest values.
A method was developed and validated to determine the concentration of the marker flurbiprofen after diffusion from the formulations into the skin, as well as concentrations of the marker that diffused through the skin, by means of high performance liquid chromatography (HPLC). Franz cell membrane diffusion studies were conducted prior to the skin diffusion studies in order to verify the actual release of the marker from the semisolid formulations.
Skin diffusion experiments were performed using dermatomed excised, human skin to which the six emulgel formulations, containing the natural oils, were applied. A comparative study was performed utilising liquid paraffin and a hydrogel, in order to compare the diffusion of the marker, flurbiprofen, into and through the skin. The two oil emulgel formulations that had indicated the best flux values were subsequently formulated into foam preparations in order to compare the penetration enhancement properties on flurbiprofen of these two oils in a foam preparation, to those in the equivalent emulgels. The data generated for all ten the formulations were compared, and the formulations that yielded the best results with regards to median flux values and the flurbiprofen concentrations within the stratum corneum-epidermis and epidermis-dermis, were identified.
Application of the liquid paraffin emulgel (21.29 μg/ml) depicted the highest average concentration of the diffused lipophilic flurbiprofen within the stratum corneum-epidermis, followed by the olive oil foam (21.47 μg/ml), olive oil emulgel (17.82 μg/ml) and grapeseed oil emulgel (17.78 μg/ml). Very similar concentrations for the marker were demonstrated by the hydrogel (16.73 μg/ml) and crocodile oil emulgel (14.89 μg/ml), whereas a lower concentration was shown for coconut oil emulgel (7.18 μg/ml). The remainder of the formulations yielded concentrations below 3%, i.e. the avocado oil emulgel (2.72 μg/ml), the coconut oil foam (1.57 μg/ml) and finally the emu oil emulgel (1.25 μg/ml).
The penetration of the marker, flurbiprofen, being trapped within the skin seemed to have been enhanced more by the oleic acid (UFA) containing emulgels and foam, especially. This was followed by oils containing high linoleic acid values, which indicated that the more kinked shaped the fatty acids, the more difficult it became to insert themselves within the lipid structures of the stratum corneum, with a resulting accumulation of the marker (Fang et al., 2003:318-319). It therefore seemed that those oils that predominantly consisted of unsaturated fatty acids (UFAs) (grapeseed-, crocodile- and olive oils) seemed to have increased the concentration of the diffused marker more significantly than those oils containing an almost even combination of MUFAs and PUFAs (avocado oil), or those mainly consisting of SFAs (coconut oil).
Average concentrations of the diffused flurbiprofen found in the epidermis-dermis region of the skin for all of the formulations demonstrated low concentrations, ranging between 0.97 - 5.39 μg/ml, with the exception of the emu oil emulgel that presented with a higher concentration of 16.15 μg/ml. The reason for the high accumulation of the marker might have been as a result of epidermal proliferation, with subsequent accumulation of the marker within the epidermis-dermis due to high oleic- and linoleic acid values, as well as small amounts of palmitoleic acid present within this oil (Katsuta et al., 2005:1011).
The resistance of the epidermis-dermis region to the general permeation of flurbiprofen might have been caused by its lipophilic nature, resulting in a reduced solubility within the hydrophilic environment of this region (Hadgraft, 1999:5).
Median results from the skin diffusion studies demonstrated that the hydrogel (23.79 μg/cm2.h) had the highest flux, followed by the olive oil- (17.99 μg/cm2.h), liquid paraffin- (15.70 μg/cm2.h), coconut oil- (13.16 μg/cm2.h), grapeseed oil- (11.85 μg/cm2.h), avocado oil- (8.31 μg/cm2.h), crocodile oil- (6.68 μg/cm2.h) and emu oil emulgels (4.41 μg/cm2.h).
The fact that the hydrogel presented a higher flux value for the marker could have been as a result of its high water content that had caused hydration of the skin. Hydration opens up the dense lipid structures inside of the stratum corneum, due to swelling of the corneocytes, with a subsequent increase in the marker‘s flux (Benson, 2005:28; Ranade & Hollinger, 2004:213). The high flux value of flurbiprofen with the liquid paraffin emulgel might also have resulted from the fact that it occluded the skin, which increased the hydration of the stratum corneum, with a subsequent increase in the flux (Mitsui, 1997:124; Thomas & Finnin, 2004:699).
Results from the skin diffusion studies could be explained by the fact that the fatty acids differ in their hydrocarbon chain by (1) the length of the chain, and (2) the position- and number of the double bonds (Babu et al., 2006:144). It is suggested that fatty acids with hydrocarbon (lipophilic) chains between C12 to C14 (also present within coconut oil) have an optimal balance of the partition coefficient and its affinity for the skin (Ogiso & Shintani, 1990:1067). It appears as though the branched UFAs, especially oleic acid, present in high quantities in olive oil, were more powerful enhancers of the diffusion of the marker, flurbiprofen (Chi et al., 1995:270).
Foam formulations were manufactured with the olive- and coconut oil emulgels that had demonstrated the best median flux values of flurbiprofen from the natural oil emulgel formulations. These formulated foams, however, did not significantly increased flux values for flurbiprofen through the skin, but only achieved values of 5.56 μg/cm2.h for the olive oil foam and 4.36 μg/cm2.h for the coconut oil foam formulations. The low flux values could have been attributed to the nature of the formulation itself, which was filled with trapped air that could have resulted in the formulation not making optimal direct contact with the available skin surface.
Throughout this study, it became evident that olive oil, predominantly consisting of oleic acid (UFA), was most effective in enhancing the flux of the lipophilic marker, flurbiprofen, through the skin, closely followed by coconut oil consisting of SFAs, with lauric- and myristic acid as its main constituents. Better enhancement effects were observed with those oils containing high amounts of oleic acid (MUFA), than oils consisting of almost equal amounts of both PUFAs and MUFAs (avocado-, emu- and crocodile oil), or oils mainly consisting of PUFAs (grapeseed oil) as its main components, but their effect was not more significant than the oil containing SFAs (coconut oil) as its key components. / Thesis (MSc (Pharmaceutics))--North-West University, Potchefstroom Campus, 2013.
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Diffusion dans un hydrogel : applications aux biocapteurs et optimisation de la technique de spectroscopie par corrélation de fluorescence (FCS)Gendron, Pierre-Olivier January 2008 (has links)
Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.
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Diffusion dans un hydrogel : applications aux biocapteurs et optimisation de la technique de spectroscopie par corrélation de fluorescence (FCS)Gendron, Pierre-Olivier January 2008 (has links)
Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal
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