Thesis (Ph. D.)--Open University. BLDSC no. DX213530.

Birks' unjust enrichment formula was intended to provide a common descriptive structure to all the instances where there was recovery. He did not, however, engage in an analysis of the various reasons why courts awarded restitution. My thesis seeks to fill this gap. I argue that without such an account Birks work is incomplete. According to Birks, for example, money and services both amounted to enrichments and so should be considered together. But there are some differences and similarities between money and services. In order to be able to group them together Birks needs to be able to say that the reasons for giving recovery in money and service cases are similar enough that they can be grouped together. The same goes for all the unjust factors. The point is, the generalisation that Birks sought to do, can only properly be done if one is attuned to the reasons why recovery is granted in each of those cases. If the reasons are similar then the generalisation makes sense. But if they are not then it does not make sense to so generalise. The argument of the thesis is that there three relevant principles to justifying unjust enrichment: the Property Principle, the Benefit-Burden Principle and the Autonomy Principle. The Property Principle states that one should not have property belonging to another. The Benefit-Burden Principle states that if one takes a benefit then one must bear the associated burdens; to put it more colloquially: you have to take the rough with the smooth. These first two principles provide reasons for considering a situation to be defective and the last principle provides a constraint for the operation of the first two. It is there to ensure that the imposition of liability will not unduly affect the autonomy of the defendant. Based on that the thesis proposes that the scope of the unjust enrichment formula be trimmed down to only cover defective transfers of money and other assets. For the other cases, a different analytical structure is needed. This is because the reasons for recovery in those cases are different.

Memoria (licenciado en ciencias jurídicas y sociales) / No autorizada por el autor para ser publicada a texto completo / De las materias que forman la base indispensable del derecho privado, el enriquecimiento injusto* es la única que ha evadido la gran racionalización alcanzada por los escritores de libros de estudio desde mediados del siglo XIX, tanto en Inglaterra como en Estados Unidos. En vez de eso, sus fragmentos, vagamente nombrados, fueron agrupados bajo los márgenes de los contratos y de los trusts. -* La consecuencia es que incluso a comienzos del siglo XXI, el enriquecimiento injusto sigue siendo desconocido para la mayoría de los abogados del common law.* No habrá jugado un rol autónomo en su formación intelectual. Su nombre moderno, adaptado de sus equivalentes civiles, es levemente desconcertante. La desconfianza hacia lo desconocido, por lo tanto, está compuesta por una instintiva aversión ante indicios de una doctrina revolucionaria. En realidad, no tiene tendencias de ese tipo. Ciertamente, el abandono lo ha vuelto engorroso y desordenado, pero el ejemplo de las jurisdicciones civiles continentales muestra que no es disruptivo por naturaleza.

Time-resolved fluorescence was applied to linear and branched pyrene-labelled macromolecules to study their internal dynamics. The linear macromolecules consisted of two series of pyrene-labelled poly(N-isopropylacrylamide)s where the polymer was either end-labelled (Py2-PNIPAM-Y where Y represents the molecular weight of the polymer and equals 6, 8, 14, 25, and 45 kDa) or randomly labelled (Py-PNIPAM-X% where X represents the pyrene content and is equal to 0.1, 2, 3, 4, 5, and 6 mol%) with pyrene. Four dendrimer generations based on a bis(hydroxymethyl)propionic acid backbone represented the branched macromolecules where the terminal sites were labelled with pyrene (PyX-GY-COOH where X represents the number of pyrene units incorporated into the Y`th generation dendrimer). A polystyrene-dendrimer hybrid was also synthesized (PyX-GY-PS). The fluorescence decays of the Py2-PNIPAM-Y and Py-PNIPAM-X% samples were acquired in solvents of varying viscosity and were analyzed with the Birks Scheme and the Fluorescence Blob Model (FBM) to yield the excimer formation rate constants and , respectively. The two parameters showed the same trends with varying viscosity, implying that the same information concerning chain dynamics is obtained from the randomly and end-labelled PNIPAM samples. The fluorescence decays of the Py2-PNIPAM-Y samples were acquired in ethanol and in water to determine how pyrene solubility affects the behavior of the polymers in solution, as probed by time-resolved fluorescence. It was found that the decreased pyrene solubility in water led to large amounts of intra- and intermolecular pyrene aggregation. Finally, the pyrene-labelled dendrimers were studied in tetrahydrofuran (THF) to probe the mobility of the chain ends as a function of generation number. The average rate of excimer formation, , obtained from the Model-Free analysis of the fluorescence decays in THF, increased linearly with generation number. This finding, combined with molecular mechanics optimizations, led to the conclusion that excimer formation was greatly enhanced due to the branched nature of the dendrimer molecule. Together, these studies illustrate three different applications of the use of time-resolved fluorescence to characterize the internal dynamics of pyrene-labelled macromolecules.

A series of pyrene end-labeled monodisperse poly(ethylene oxide)s (PEO(X)-Py2 where X represents the number average molecular weight (Mn) of the PEOs and equals 2, 5, 10 and 16.5 K) and one pyrene mono-labeled PEO (PEO(2K)-Py1) were synthesized and characterized in solution using fluorescence. First, the end-to-end cyclization (EEC) of PEO(X)-Py2 was investigated in seven organic solvents with viscosities (η) ranging from 0.32 to 1.92 mPa•s. The classical Birks scheme was used to globally fit the pyrene monomer and excimer fluorescence decays. The fraction of pyrenes that did not form excimer (ffree) was found to increase with increasing η and Mn. This result was contrary to the assumptions made by Birks’ scheme. To account for this, ffree was assumed to represent the fraction of PEO chains other than the monolabeled polymer impurities that cannot accomplish EEC. A fluorescence blob model (FBM) was applied to handle this assumption in the process of excimer formation for the PEO(X)-Py2 samples in solution. The radius of a blob, Rblob, in organic solvents was determined according to the results retrieved from the FBM. To quantitatively account for the existence of pyrene impurity in pyrene-labeled macromolecules, known amounts of PEO(2K)-Py1 were added into a PEO(2K)-Py2 solution and the fluorescence decays were fitted globally according to the Birks scheme and “model free” (MF) analysis to verify the validation of the MF analysis. The MF analysis was then applied to determine the amounts of 1-pyrenebutyric acid (PyBA) that had been added to a solution of pyrene end-labeled fourth generation dendritic hybrid (Py16-G4-PS). The results demonstrated that the contribution from unwanted fluorescent species could be isolated and quantitatively accounted for by fitting the fluorescence decays of the pyrene monomer and excimer globally with the MF analysis. Since the PEO(X)-Py2 samples form hydrophobic pyrene aggregates in aqueous solution, a sequential model (SM) was proposed to characterize the pyrene excimer formation of PEO(X)-Py2 in water at different polymer concentration (CP). The capture distance over which the pyrenyl end-groups experience hydrophobic forces in water was determined by assuming that the end-to-end distances of the PEO(X)-Py2 samples adopt a Gaussian distribution and that the fraction of pyrenes that are aggregated (fE0) determined by the sequential model corresponds to the fraction of PEO(X)-Py2 chains whose end-to-end distance is smaller than the hydrophobic capture distance. Since a surfactant can interact with a hydrophobically modified water-soluble polymer in aqueous solution, the interactions taking place between PEO(X)-Py2 and sodium dodecyl sulfate (SDS) were investigated at a low PEO(X)-Py2 concentration. The pyrene monomer and excimer fluorescence decays of the PEO(X)-Py2 and SDS solutions were acquired at various SDS concentrations and globally fitted according to the MF analysis to retrieve the parameters that described the kinetics of pyrene excimer formation. At high SDS concentrations above the critical micelle concentration (CMC), the pyrene end-groups of the short-chain samples (PEO(2K)-Py2 and PEO(5K)-Py2) were incorporated inside the same micelle and excimer was formed intramolecularly, while most pyrene groups of the long-chain samples (PEO(10K)-Py2 and PEO(16.5K)-Py2) were isolated into different micelles. Lastly, both the rheological properties and fluorescence behavior of a pyrene-labeled hydrophobically-modified alkali-swellable emulsion (Py-HASE) polymer in basic aqueous solution with SDS were studied. Furthermore, a joint experimental setup that combined a rheometer and a steady-state fluorometer was applied to investigate at the molecular level the effect that a shearing force had on the polymeric network. However, despite the dramatic decrease in solution viscosity with increasing shear rate, no change in the fluorescence spectra was detected, suggesting that changes in the polymeric network that affected the balance of intra- versus intermolecular pyrene associations did not impact the process of excimer formation. Together the experiments described in this thesis represent the broadest set of examples found in the scientific literature where information on the dynamics and level of association of pyrene-labeled polymers has been retrieved through the quantitative analysis of the fluorescence decays acquired with pyrene-labeled polymers in solution.

Time-resolved fluorescence was applied to linear and branched pyrene-labelled macromolecules to study their internal dynamics. The linear macromolecules consisted of two series of pyrene-labelled poly(N-isopropylacrylamide)s where the polymer was either end-labelled (Py2-PNIPAM-Y where Y represents the molecular weight of the polymer and equals 6, 8, 14, 25, and 45 kDa) or randomly labelled (Py-PNIPAM-X% where X represents the pyrene content and is equal to 0.1, 2, 3, 4, 5, and 6 mol%) with pyrene. Four dendrimer generations based on a bis(hydroxymethyl)propionic acid backbone represented the branched macromolecules where the terminal sites were labelled with pyrene (PyX-GY-COOH where X represents the number of pyrene units incorporated into the Y`th generation dendrimer). A polystyrene-dendrimer hybrid was also synthesized (PyX-GY-PS). The fluorescence decays of the Py2-PNIPAM-Y and Py-PNIPAM-X% samples were acquired in solvents of varying viscosity and were analyzed with the Birks Scheme and the Fluorescence Blob Model (FBM) to yield the excimer formation rate constants and , respectively. The two parameters showed the same trends with varying viscosity, implying that the same information concerning chain dynamics is obtained from the randomly and end-labelled PNIPAM samples. The fluorescence decays of the Py2-PNIPAM-Y samples were acquired in ethanol and in water to determine how pyrene solubility affects the behavior of the polymers in solution, as probed by time-resolved fluorescence. It was found that the decreased pyrene solubility in water led to large amounts of intra- and intermolecular pyrene aggregation. Finally, the pyrene-labelled dendrimers were studied in tetrahydrofuran (THF) to probe the mobility of the chain ends as a function of generation number. The average rate of excimer formation, , obtained from the Model-Free analysis of the fluorescence decays in THF, increased linearly with generation number. This finding, combined with molecular mechanics optimizations, led to the conclusion that excimer formation was greatly enhanced due to the branched nature of the dendrimer molecule. Together, these studies illustrate three different applications of the use of time-resolved fluorescence to characterize the internal dynamics of pyrene-labelled macromolecules.

A series of pyrene end-labeled monodisperse poly(ethylene oxide)s (PEO(X)-Py2 where X represents the number average molecular weight (Mn) of the PEOs and equals 2, 5, 10 and 16.5 K) and one pyrene mono-labeled PEO (PEO(2K)-Py1) were synthesized and characterized in solution using fluorescence. First, the end-to-end cyclization (EEC) of PEO(X)-Py2 was investigated in seven organic solvents with viscosities (η) ranging from 0.32 to 1.92 mPa•s. The classical Birks scheme was used to globally fit the pyrene monomer and excimer fluorescence decays. The fraction of pyrenes that did not form excimer (ffree) was found to increase with increasing η and Mn. This result was contrary to the assumptions made by Birks’ scheme. To account for this, ffree was assumed to represent the fraction of PEO chains other than the monolabeled polymer impurities that cannot accomplish EEC. A fluorescence blob model (FBM) was applied to handle this assumption in the process of excimer formation for the PEO(X)-Py2 samples in solution. The radius of a blob, Rblob, in organic solvents was determined according to the results retrieved from the FBM. To quantitatively account for the existence of pyrene impurity in pyrene-labeled macromolecules, known amounts of PEO(2K)-Py1 were added into a PEO(2K)-Py2 solution and the fluorescence decays were fitted globally according to the Birks scheme and “model free” (MF) analysis to verify the validation of the MF analysis. The MF analysis was then applied to determine the amounts of 1-pyrenebutyric acid (PyBA) that had been added to a solution of pyrene end-labeled fourth generation dendritic hybrid (Py16-G4-PS). The results demonstrated that the contribution from unwanted fluorescent species could be isolated and quantitatively accounted for by fitting the fluorescence decays of the pyrene monomer and excimer globally with the MF analysis. Since the PEO(X)-Py2 samples form hydrophobic pyrene aggregates in aqueous solution, a sequential model (SM) was proposed to characterize the pyrene excimer formation of PEO(X)-Py2 in water at different polymer concentration (CP). The capture distance over which the pyrenyl end-groups experience hydrophobic forces in water was determined by assuming that the end-to-end distances of the PEO(X)-Py2 samples adopt a Gaussian distribution and that the fraction of pyrenes that are aggregated (fE0) determined by the sequential model corresponds to the fraction of PEO(X)-Py2 chains whose end-to-end distance is smaller than the hydrophobic capture distance. Since a surfactant can interact with a hydrophobically modified water-soluble polymer in aqueous solution, the interactions taking place between PEO(X)-Py2 and sodium dodecyl sulfate (SDS) were investigated at a low PEO(X)-Py2 concentration. The pyrene monomer and excimer fluorescence decays of the PEO(X)-Py2 and SDS solutions were acquired at various SDS concentrations and globally fitted according to the MF analysis to retrieve the parameters that described the kinetics of pyrene excimer formation. At high SDS concentrations above the critical micelle concentration (CMC), the pyrene end-groups of the short-chain samples (PEO(2K)-Py2 and PEO(5K)-Py2) were incorporated inside the same micelle and excimer was formed intramolecularly, while most pyrene groups of the long-chain samples (PEO(10K)-Py2 and PEO(16.5K)-Py2) were isolated into different micelles. Lastly, both the rheological properties and fluorescence behavior of a pyrene-labeled hydrophobically-modified alkali-swellable emulsion (Py-HASE) polymer in basic aqueous solution with SDS were studied. Furthermore, a joint experimental setup that combined a rheometer and a steady-state fluorometer was applied to investigate at the molecular level the effect that a shearing force had on the polymeric network. However, despite the dramatic decrease in solution viscosity with increasing shear rate, no change in the fluorescence spectra was detected, suggesting that changes in the polymeric network that affected the balance of intra- versus intermolecular pyrene associations did not impact the process of excimer formation. Together the experiments described in this thesis represent the broadest set of examples found in the scientific literature where information on the dynamics and level of association of pyrene-labeled polymers has been retrieved through the quantitative analysis of the fluorescence decays acquired with pyrene-labeled polymers in solution.

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