Spelling suggestions: "subject:"water solubility"" "subject:"later solubility""
11 |
AN EXPERIMENTAL AND THEORETICAL INVESTIGATION ON THE KINETICS OF WATER EXSOLUTION IN HIGH SILICATE MELTSNicholis, Mikes G. 11 October 2001 (has links)
No description available.
|
12 |
Simple Descriptors for Modeling the Solubility of Gases, Alcohols, and Halogenated Hydrocarbons in WaterSidigu, Sule 18 December 2007 (has links)
No description available.
|
13 |
A Membrane Separation Process for Biodiesel PurificationSaleh, Jehad 02 February 2011 (has links)
In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content.
First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME.
Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface.
Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance.
A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size.
Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures.
In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.
|
14 |
A Membrane Separation Process for Biodiesel PurificationSaleh, Jehad 02 February 2011 (has links)
In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content.
First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME.
Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface.
Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance.
A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size.
Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures.
In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.
|
15 |
A Membrane Separation Process for Biodiesel PurificationSaleh, Jehad 02 February 2011 (has links)
In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content.
First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME.
Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface.
Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance.
A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size.
Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures.
In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.
|
16 |
Chemické modifikace hydrogelů z přírodního polysacharidu / Chemical modifications of hydrogels from natural polysaccharidePoštulková, Hana January 2014 (has links)
V teoretické části práce by shrnuty chemické a fyzikální vlastnosti, chemická struktura a využití přírodního polysacharidu gum karaya. Hlavním cíle diplomové práce byla alkalická modifikace původní nerozpustné gum karayi na rozpustný produkt, který může být v budoucnu využit pro další aplikace například v medicíně. Nerozpustnost gum karayi je způsobena přítomností acetylových skupin a vícemocných iontů ve struktuře polysacharidu. Byly zkoumány optimální podmínky pro modifikační proces. Pro modifikaci byl použit hydroxid sodný, draselný nebo amonný a čas modifikace od 1 minuty po 24 hodin pro roztok originální gum karayi s koncentrací od 0,1 do 3 %. Pro určení chemického složení originálního a modifikovaných vzorků byla využita FTIR. Bylo prokázáno, že vzorky A2, B1 - 7, C1 - 8 a E1 - 2 byly zcela deacetylovány, protože pás pro acetylovou skupinu nebyl v FTIR spektrech pozorován. Odstranění acetylových skupin alkalickou modifikací bylo taktéž potvrzeno 13C CP MAS NMR. Pomocí XRD byl prokázán amorfní charakter originálního vzorku. Množství vlhkosti a teplotní stabilita vzorků byly zkoumána pomocí TGA. Bylo zjištěno, že termální stability originální gum karayi je vyšší než u modifikovaných vzorků. Termální stabilita modifikovaných vzorků byla ovlivněna reakčními parametry. Entalpické změny vzorků byly studovány pomocí DSC, nicméně nebyly pozorovány žádné významné rozdíly mezi modifikovanými vzorky a originální gum karayou. Prvkové složení bylo určeno pomocí ICP-OES a byla potvrzena přítomnost vápníku, draslíku a hořčíku ve struktuře polysacharidu. Molekulová hmotnost modifikovaných vzorků byla měřena pomocí GPC a byla stanovena na 8 milionů g·mol-1. Reologické měření roztoků gum karayi bylo provedeno pro určení lineární viskoelastické oblasti. Dále byl sledován efekt NaCl na viskozitu originálního vzorku. Viskozita klesala s vyšším množstvím NaCl. Pokles viskozity originálního vzorku je způsoben výměnou vápenatých iontů za sodné, což vede k uvolnění fyzikálně vázané struktury a tím k vyšší rozpustnosti vzorku ve vodě.
|
17 |
A Membrane Separation Process for Biodiesel PurificationSaleh, Jehad January 2011 (has links)
In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content.
First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME.
Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface.
Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance.
A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size.
Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures.
In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.
|
18 |
Modelos de predição do coeficiente de sorção no solo de pesticidas não iônicos: diferentes algoritmos de logP e uma abordagem alternativa de logS.Reis, Ralpho Rinaldo dos 17 May 2013 (has links)
Made available in DSpace on 2017-05-12T14:46:52Z (GMT). No. of bitstreams: 1
Ralpho.pdf: 2205542 bytes, checksum: 37ae4ee862cc62b72b5ed65409967739 (MD5)
Previous issue date: 2013-05-17 / Collecting data on pesticide effects on the environment and several ecosystems is a slow
and costly process. Therefore, significant research efforts have been focused on developing
mathematical models to predict physical, chemical or biological properties of environmental
interest. The soil sorption coefficient normalized to organic carbon content (Koc) is a
physicochemical key parameter used in environmental risk assessments of substances
released into the environment. Thus, several logKoc prediction models that use hydrophobic
parameter (logP) or the logarithm of water solubility (logS) as descriptor have been reported
in the last decades. Mostly, due to the lack of reliable experimental values of logP or logS,
algorithms are used to calculate such properties. Despite the availability and easiness to
access several algorithms for this purpose, scientific studies do not describe the procedure
adopted to choose the algorithm used in quantitative structure-property relationship (QSPR)
studies. Furthermore, the strong correlation between logP and logS prevents their application
in the same mathematical equation obtained by multiple linear regression method. Since the
sorption process of a chemical compound in soil is related both to its water solubility and its
water/organic matter partition, it is expected models that are able to combine these two
properties will can record more realistic results. This doctoral dissertation consists of two
scientific papers. In the first one, a study was carried out to check the influence of choosing
logP algorithm on logKoc modeling. Models were constructed to relate logKoc with logP
according to different freeware algorithms. All models were assessed based on their statistic
qualities and predictive power. The obtained results clearly showed that an arbitrary choice
of the algorithm may not result in the best prediction model. On the other hand, a good
choice can lead to obtaining simple models with statistic qualities and predictive power
comparable to more complex models. The second paper aims at proposing an alternative
approach for logKoc modeling, using simple descriptor of solubility, here referred as logarithm
of corrected solubility by octanol/water partition (logSP). Thus, models were built with this
descriptor and also with logP and logS conventional descriptors, which are isolated or
associated with other explicative variables of easy physicochemical interpretation. The
obtained models were validated and compared to other models previously published. The
results showed that the use of logSP descriptor to replace the conventional ones led to
obtaining simple models with statistic qualities and predictive power that are higher than
other more complex models already found in literature. / A coleta de dados relativos aos danos causados pelos pesticidas sobre o meio ambiente e
seus ecossistemas é lenta e onerosa. Desta maneira, grandes incentivos têm sido
destinados às pesquisas que visam à construção de modelos matemáticos para predição de
propriedades físicas, químicas ou biológicas de interesse ambiental. O coeficiente de sorção
no solo normalizado para o conteúdo de carbono orgânico (Koc) é um importante parâmetro
físico-químico utilizado nas avaliações de riscos ambientais das substâncias lançadas no
meio ambiente. Assim, vários modelos para predição de logKoc, utilizando o parâmetro
hidrofóbico (logP) ou o logaritmo da solubilidade em água (logS) como descritores, têm sido
publicados nas últimas décadas. Muitas vezes, em virtude da ausência de valores
experimentais confiáveis de logP ou logS, são usados algoritmos para o cálculo dessas
propriedades. Apesar da disponibilidade e facilidade de acesso a diversos algoritmos para
tal finalidade, os artigos científicos não descrevem o procedimento adotado para escolha do
algoritmo usado nos estudos QSPR. Além disto, a forte correlação entre logP e logS impede
que sejam usados em uma mesma equação obtida por regressão linear múltipla. Como o
processo de sorção de um composto químico no solo está relacionado tanto com sua
solubilidade em água como com sua partição água/matéria orgânica, espera-se que
modelos que sejam capazes de combinar essas duas informações possam gerar resultados
mais realistas. Este trabalho de tese é constituído de dois artigos. No primeiro artigo, foi feito
um estudo para verificar a influência da escolha do algoritmo de logP na modelagem de
logKoc. Foram construídos modelos que relacionam logKoc com logP a partir de diferentes
algoritmos livres disponíveis. Todos os modelos foram avaliados quanto às suas qualidades
estatísticas e poder de predição. Os resultados obtidos mostraram claramente que uma
escolha arbitrária deste algoritmo pode não levar ao melhor modelo de predição. Por outro
lado, uma boa escolha pode conduzir à obtenção de modelos simples com qualidades
estatísticas e poder de predição comparáveis a de modelos mais complexos. No segundo
artigo, o objetivo foi a proposição de uma abordagem alternativa para a modelagem de
logKoc, utilizando um descritor simples de solubilidade, aqui designado como logaritmo da
solubilidade corrigida pela partição octanol/água (logSP). Assim, foram construídos modelos
com tal descritor e também com os descritores convencionais logP e logS, isolados ou
associados com outras variáveis explicativas de fácil interpretação físico-química. Os
modelos obtidos foram validados e comparados com outros modelos publicados
anteriormente. Os resultados mostraram que o uso do descritor logSp em substituição aos
descritores convencionais conduziu à obtenção de modelos simples com qualidades
estatísticas e poder de predição superiores a de outros modelos mais complexos
encontrados na literatura.
|
19 |
Modelos de predição do coeficiente de sorção no solo de pesticidas não iônicos: diferentes algoritmos de logP e uma abordagem alternativa de logS.Reis, Ralpho Rinaldo dos 17 May 2013 (has links)
Made available in DSpace on 2017-07-10T19:23:40Z (GMT). No. of bitstreams: 1
Ralpho.pdf: 2205542 bytes, checksum: 37ae4ee862cc62b72b5ed65409967739 (MD5)
Previous issue date: 2013-05-17 / Collecting data on pesticide effects on the environment and several ecosystems is a slow
and costly process. Therefore, significant research efforts have been focused on developing
mathematical models to predict physical, chemical or biological properties of environmental
interest. The soil sorption coefficient normalized to organic carbon content (Koc) is a
physicochemical key parameter used in environmental risk assessments of substances
released into the environment. Thus, several logKoc prediction models that use hydrophobic
parameter (logP) or the logarithm of water solubility (logS) as descriptor have been reported
in the last decades. Mostly, due to the lack of reliable experimental values of logP or logS,
algorithms are used to calculate such properties. Despite the availability and easiness to
access several algorithms for this purpose, scientific studies do not describe the procedure
adopted to choose the algorithm used in quantitative structure-property relationship (QSPR)
studies. Furthermore, the strong correlation between logP and logS prevents their application
in the same mathematical equation obtained by multiple linear regression method. Since the
sorption process of a chemical compound in soil is related both to its water solubility and its
water/organic matter partition, it is expected models that are able to combine these two
properties will can record more realistic results. This doctoral dissertation consists of two
scientific papers. In the first one, a study was carried out to check the influence of choosing
logP algorithm on logKoc modeling. Models were constructed to relate logKoc with logP
according to different freeware algorithms. All models were assessed based on their statistic
qualities and predictive power. The obtained results clearly showed that an arbitrary choice
of the algorithm may not result in the best prediction model. On the other hand, a good
choice can lead to obtaining simple models with statistic qualities and predictive power
comparable to more complex models. The second paper aims at proposing an alternative
approach for logKoc modeling, using simple descriptor of solubility, here referred as logarithm
of corrected solubility by octanol/water partition (logSP). Thus, models were built with this
descriptor and also with logP and logS conventional descriptors, which are isolated or
associated with other explicative variables of easy physicochemical interpretation. The
obtained models were validated and compared to other models previously published. The
results showed that the use of logSP descriptor to replace the conventional ones led to
obtaining simple models with statistic qualities and predictive power that are higher than
other more complex models already found in literature. / A coleta de dados relativos aos danos causados pelos pesticidas sobre o meio ambiente e
seus ecossistemas é lenta e onerosa. Desta maneira, grandes incentivos têm sido
destinados às pesquisas que visam à construção de modelos matemáticos para predição de
propriedades físicas, químicas ou biológicas de interesse ambiental. O coeficiente de sorção
no solo normalizado para o conteúdo de carbono orgânico (Koc) é um importante parâmetro
físico-químico utilizado nas avaliações de riscos ambientais das substâncias lançadas no
meio ambiente. Assim, vários modelos para predição de logKoc, utilizando o parâmetro
hidrofóbico (logP) ou o logaritmo da solubilidade em água (logS) como descritores, têm sido
publicados nas últimas décadas. Muitas vezes, em virtude da ausência de valores
experimentais confiáveis de logP ou logS, são usados algoritmos para o cálculo dessas
propriedades. Apesar da disponibilidade e facilidade de acesso a diversos algoritmos para
tal finalidade, os artigos científicos não descrevem o procedimento adotado para escolha do
algoritmo usado nos estudos QSPR. Além disto, a forte correlação entre logP e logS impede
que sejam usados em uma mesma equação obtida por regressão linear múltipla. Como o
processo de sorção de um composto químico no solo está relacionado tanto com sua
solubilidade em água como com sua partição água/matéria orgânica, espera-se que
modelos que sejam capazes de combinar essas duas informações possam gerar resultados
mais realistas. Este trabalho de tese é constituído de dois artigos. No primeiro artigo, foi feito
um estudo para verificar a influência da escolha do algoritmo de logP na modelagem de
logKoc. Foram construídos modelos que relacionam logKoc com logP a partir de diferentes
algoritmos livres disponíveis. Todos os modelos foram avaliados quanto às suas qualidades
estatísticas e poder de predição. Os resultados obtidos mostraram claramente que uma
escolha arbitrária deste algoritmo pode não levar ao melhor modelo de predição. Por outro
lado, uma boa escolha pode conduzir à obtenção de modelos simples com qualidades
estatísticas e poder de predição comparáveis a de modelos mais complexos. No segundo
artigo, o objetivo foi a proposição de uma abordagem alternativa para a modelagem de
logKoc, utilizando um descritor simples de solubilidade, aqui designado como logaritmo da
solubilidade corrigida pela partição octanol/água (logSP). Assim, foram construídos modelos
com tal descritor e também com os descritores convencionais logP e logS, isolados ou
associados com outras variáveis explicativas de fácil interpretação físico-química. Os
modelos obtidos foram validados e comparados com outros modelos publicados
anteriormente. Os resultados mostraram que o uso do descritor logSp em substituição aos
descritores convencionais conduziu à obtenção de modelos simples com qualidades
estatísticas e poder de predição superiores a de outros modelos mais complexos
encontrados na literatura.
|
20 |
Coordination des métaux post-transitionnels de la période 6 par des porphyrines à acide(s) carboxylique(s) suspendu(s) : vers l’alpha-radio-immunothérapie et de nouveaux commutateurs moléculaires / Coordination of the period 6 post-transition metals by overhanging carboxylic acid porphyrins : towards alpha-radio-immunotherapy and new molecular switchesNdoyom, Victoria 21 September 2015 (has links)
Ce manuscrit traite de la complexation des métaux post-transitionnels de la période 6 par des porphyrines comportant une ou deux anses à acide(s) carboxylique(s) suspendu(s). Celles-ci possèdent des cinétiques rapides d'insertion du Bi permettant d'envisager, de par la complexation et la vectorisation du 213Bi, une application en α-radio-immunothérapie (α-RIT). Dans ce but, trois porphyrines à anse(s) ont été élaborées et le meilleur taux d'insertion du 213Bi a été obtenu avec la porphyrine bis-anse bis-acide grâce à un processus sans précédent de transmétallation Pb«froid»213Bi, il atteint les 80% et est comparable à celui obtenu avec le CHX-DTPA, meilleur chélate du 213Bi. S'agissant de la vectorisation du 213Bi, deux porphyrines bifonctionnelles ont été préparées et les tests de couplage sur anticorps ont montré la formation d'agrégats en raison de leur faible hydrosolubilité. Par ailleurs, une porphyrine hydrosoluble mono-anse monoacide a été synthétisée, mais en absence d'une deuxième anse à acide carboxylique l'insertion du 213Bi reste faible (< 10%). Ce travail permet de conclure que pour atteindre notre objectif d'α-RIT, il faudra élaborer une porphyrine hydrosoluble comportant deux anses à acide carboxylique. Les deux autres parties sont plus fondamentales, d'abord l'accès à un commutateur moléculaire grâce à une double translocation d'ions métalliques au sein de complexes bimétalliques de thallium, déclenchée par un processus d'oxydoréduction TlI↔TlIII. En effet, au sein de nos complexes bimétalliques, deux modes de coordination coexistent, l'un avec un métal M lié à la porphyrine «out of plane» OOP et l'autre avec un métal M' lié à l'anse «hanging atop» HAT. Nous visons un état dans lequel le TlIII serait OOP et le deuxième métal M HAT et un second avec le TlI HAT et M OOP. Les études de coordination du thallium par une porphyrine bis-anse bis-acide ont mis en évidence la formation du 1er exemple de complexe à valence mixte TlIII/TlI par photo-oxydation ou par réduction du HgII. De plus, les deux états du commutateur moléculaire visé ont été obtenus indépendamment : TlIII OOP/PbII HAT et TlI HAT/ PbII OOP. L'utilisation du deuxième phénomène redox pourra permettre le passage de l'un à l'autre constituant un premier pas vers un commutateur moléculaire. Finalement, nous visons de nouveaux complexes supramoléculaires de coordination à partir de sous-unités bimétalliques dont l'assemblage métal-dirigé via l'anse sera modulé par la nature des métaux sur la porphyrine. Trois nouvelles porphyrines ont été synthétisées avec une ou deux anses à acide carboxylique suspendu dont la position α est substituée par une seconde fonction acide carboxylique ou par une fonction cyano. La métallation de celles-ci par le PbII, le HgII ou le CdII a été étudiée et deuxstructures RX de complexes dinucléaires de CdII et de PbII ont été obtenues avec une porphyrine bis-anse bis-cyano. Elles montrent l'influence de la nature du métal sur l'orientation des groupements coordinants. / This manuscript is related to the complexation of the period 6 main group and late transition metals by porphyrins bearing one or two straps with overhanging carboxylic acid. These porphyrins possess fast metal ion insertion rate allowing us to consider, through 213Bi-α-emitter complexation and vectorization, an application in α-radio-immunotherapy (α-RIT). For that purpose, we designed 3 strapped-porphyrins with one or 2 overhanging carboxylic acid. The best 213Bi insertion rate of 80% was obtained with the bis-acid bis-strapped porphyrin thanks to an unprecedented transmetallation “cold” Pb213Bi process; which is close to that of the CHX-DTPA, best known 213Bi chelate. Regarding 213Bi vectorization, 2 BFC porphyrins were synthetized and immunoconjugation experiments proved aggregate formation due to their poor water-solubility. Furthermore, a water-soluble mono-acid and mono-strapped porphyrin was realised but without the 2nd carboxylic acid the 213Bi insertion was very low (<10%). This work provided the conclusion that to achieve the α-RIT objective we have to design a new porphyrin water-soluble with 2 straps bearing one overhanging carboxylic acid. The 2 last chapters are related to fundamental applications, Firstly, a molecular switch through thallium heterobimetallic complexes in which a double translocation of metallic ions will take place thanks to Tl(I)↔Tl(III) redox process. In fact, in our heterobimetallic porphyrin complexes 2 coordination modes can coexist, one M metal is out of the porphyrin plane (OOP) while the other M’ metal is bound to the strap and hanging atop the porphyrin (HAT). So, we considered a state in which the Tl(III) will be OOP while the other metal M will be HAT and in the 2nd the Tl(I) will be HAT and the M metal will be OOP. Thallium coordination studies were implemented with a bis-acid bis-strapped porphyrin and they evidenced the sunlight-driven and redox-driven formation the 1st example of a mixed-valence Tl(III)/Tl(I) porphyrin complex. Moreover, 2 states of the targeted molecular switch have been independently obtained the OOP Tl(III)/HAT Pb(II), and the HAT Tl(I)/OOP Pb(II). Using the 2nd phenomenon, we can consider obtaining transition between those 2 complexes to move towards an eventual molecular switch. Finally, we aim new supramolecular coordination complexes from bimetallic and dynamic porphyrin sous-units of which the metal-directed self-assembly through the strap could be modulated by the nature of metals bound to the porphyrin. 3 new porphyrins were designed with strap(s) bearing overhanging carboxylic acid of which α-position is occupied by either one other carboxylic acid or a cyano group. Metalation studies of those porphyrins was performed with Pb(II), Bi(III), Hg(II) or Cd(II) and 2 Xray structures of binuclear complexes of Cd(II) and Pb(II) was obtained with a bis-cyanoacid bis-strapped porphyrin. They proved the influence of the metallic ion nature on the coordinating group orientation.
|
Page generated in 0.0814 seconds