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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Characterizing ions in solution by NMR methods

Giesecke, Marianne January 2014 (has links)
NMR experiments performed under the effect of electric fields, either continuous or pulsed, can provide quantitative parameters related to ion association and ion transport in solution.  Electrophoretic NMR (eNMR) is based on a diffusion pulse-sequence with electric fields applied in the form of pulses. Magnetic field gradients enable the measurement of the electrophoretic mobility of charged species, a parameter that can be related to ionic association. The effective charge of the tetramethylammonium cation ion in water, dimethylsulphoxide (DMSO), acetonitrile, methanol and ethanol was estimated by eNMR and diffusion measurements and compared to the value predicted by the Debye-Hückel-Onsager limiting law. The difference between the predicted and measured effective charge was attributed to ion pairing which was found to be especially significant in ethanol. The association of a large set of cations to polyethylene oxide (PEO) in methanol, through the ion-dipole interaction, was quantified by eNMR. The trends found were in good agreement with the scarce data from other methods. Significant association was found for cations that have a surface charge density below a critical value. For short PEO chains, the charge per monomer was found to be significantly higher than for longer PEO chains when binding to the same cations. This was attributed to the high entropy cost required to rearrange a long chain in order to optimize the ion-dipole interactions with the cations. Moreover, it was suggested that short PEO chains may exhibit distinct binding modes in the presence of different cations, as supported by diffusion measurements, relaxation measurements and chemical shift data. The protonation state of a uranium (VI)-adenosine monophosphate (AMP) complex in aqueous solution was measured by eNMR in the alkaline pH range. The question whether or not specific oxygens in the ligand were protonated was resolved by considering the possible association of other species present in the solution to the complex. The methodology of eNMR was developed through the introduction of a new pulse-sequence which suppresses artifactual flow effects in highly conductive samples. In another experimental setup, using NMR imaging, a constant current was applied to a lithium ion (Li ion) battery model. Here, 7Li spin-echo imaging was used to probe the spin density in the electrolyte and thus visualize the development of Li+ concentration gradients. The Li+ transport number and salt diffusivity were obtained within an electrochemical transport model. The parameters obtained were in good agreement with data for similar electrolytes. The use of an alternative imaging method based on CTI (Constant Time Imaging) was explored and implemented. / <p>QC 20140825</p>
42

Elaboration, structuration et propriétés rhéologiques de nanocomposites polymères modèles à base de Laponite / Design, structuration and rheological properties of Laponite based polymeric nanocomposites

Abakar Adam, Omar 24 September 2012 (has links)
Ce travail concerne l'étude du comportement rhéologique de nanocomposites modèles à base de Laponite dans du polyoxyde d'éthylène ou des mélanges polyoxyde d'éthylène avec du polyméthacrylate de méthyle. L'influence des paramètres moléculaires, masse molaire de la matrice et mode de protection des particules sur les propriétés rhéologiques a été étudiée. La meilleure dispersion est obtenue à partir d'une solution, la dilution d'un mélange maître conduisant à des matériaux hétérogènes. Les mélanges POE/PMMA sont compatibles à l'état fondu dans toute la gamme de concentrations mais hétérogènes à température ambiante au-dessus de 30% en poids de particules. En diluant un mélange Laponite/PEO dans le PMMA, nous avons montré que ces domaines se concentrent en particules en dessous de 30% de PEO et qu'une cocontinuité de phases PEO contenant les particules et PMMA essentiellement pur est formée au-dessus de 30% de PEO. La présence des particules diminue fortement la cristallinité. / This study concerns model nanocomposites based on Laponite and polyethylene oxide, alone or blended with polymethylmethacrylate. We studied the influence of the parameters on rheological properties of model PEO/Laponite nanocomposites such as matrix molecular weight, preparation method. The best dispersion state of the particles is obtained from solution. Melt dispersion leads to a low frequency modulus which depends on the length and grafting density of the particles. Heterogeneous materials are obtained from melt dispersion of a master batch. PMMA/PEO blends appear to be homogeneous at room temperature only for PEO concentration less than 30wt%. Laponite particles are concentrated in small domains where most of PEO has been extracted. At higher concentrations of PEO, a continuous phase containing PEO and Laponite above percolation concentration is observed, leading to an elastic modulus at low frequency. The presence of Laponite decreases significantly the crystallinity of PEO.
43

Synthesis and characterization of polysulfone/nanoclay/polyethylene oxide composite ultrafiltration membranes. / Síntese e caracterização de membranas compósitas de polisulfona para ultrafiltração modificadas com nanoargila e polióxido de etileno.

Rodrigues, Raphael 15 December 2015 (has links)
Membrane structure modification is a common approach to enhance membrane properties and performance. For example, the addition of dopants to the membrane casting solution has been observed to increase hydrophilicity, alter surface and internal pore structure, increase thermal and mechanical resistance, and impart anti-fouling properties. In this study, it was evaluated how the addition of individual and simultaneous nanoclay and polyethylene oxide (PEO) dopants affected the structure and performance of polysulfone (PSU) ultrafiltration membranes. Membrane performance was evaluated in the cross-flow configuration. The pure water permeability of the neat PSU membrane was 15 L/m².h.bar and at the optimal dosage of the individually doped membranes was 1.5% weight nanoclay to PSU and 5% weight PEO to PSU resulting in permeability of 56 and 237 L/m².h.bar, respectively. Simultaneous doping using the optimal individual weight percentages had a lower effect resulting in a permeability of 192 L/m².h.bar, in contrast the simultaneous addition of 4.5% nanoclay and 5% PEO had a higher effect resulting in a permeability of 319 L/m².h.bar. The control membrane was compared to the referred membranes and with the 4.5% nanoclay membrane (best permeability only when combined with PEO). These membranes were further examined to determine dopant effects on pore microstructure, superficial charge, separation performance, and fouling susceptibility. In general, doping with nanoclay improved membrane thermal/mechanical resistance and permeability with minimal loss in rejection. Doping with PEO resulted in a greater permeability as compared to nanoclay; however, PEO doping decreased rejection, mechanical resistance, and increased irreversible fouling. Thus, both advantageous and disadvantageous effects should be considered when selecting a dopant to optimize membrane performance. / A modificação da estrutura de membranas é uma abordagem utilizada para melhorar as propriedades de membranas e desempenho de um sistema. Por exemplo, a adição de dopantes na solução de síntese da membrana permite aumentar a hidrofilicidade, alterar a estrutura de poros superficiais e internos e conferir propriedades anti-depósitos. Neste estudo, foi avaliada como a adição de óxido de polietileno e de nano-argila afetam a estrutura e desempenho de membranas de ultrafiltração de polisulfona (PSU). O desempenho da membrana foi avaliado na configuração de fluxo paralelo (cross-flow). A permeabilidade média à água pura da membrana de PSU pura foi de 15 L/m2.h.bar. As dosagem ótimas das membranas dopadas individualmente foram de 1,5% em massa de PSU para nano-argila e 5% em massa de PSU para PEO, resultando em permeabilidades médias de 56 e 237 L/m2.h.bar, respectivamente. A dopagem simultânea usando ambas as percentagens individuais ótimas teve um efeito menor do que o esperado, resultando em uma permeabilidade média de 192 L/m2.h.bar. Em contraste, verificou-se que a adição simultânea de 4,5% de nano-argila combinada com 5% de PEO teve um efeito maior do que o uso isolado dos aditivos, resultando em uma permeabilidade média de 319 L/m2.h.bar. Desta forma, a membrana de controle foi comparada com as referidas membranas e com membranas compostas somente por nano-argila a 4,5. Estas membranas foram ainda examinadas em detalhes para determinar os efeitos dos dopantes na microestrutura dos poros, cargas superficiais, desempenho da separação, sensibilidade à formação de depósitos, rugosidade superficial e propriedades térmicas e mecânicas. Verificou-se que a dopagem com nano-argila melhora a resistência térmica e mecânica e a permeabilidade das membranas, com uma perda mínima na rejeição. A dopagem com PEO resultou em um aumento notável de permeabilidade em comparação com a adição individual de nano-argila. No entanto, a capacidade de rejeição e resistência térmica e mecânica destas membranas diminuem e a formação de depósitos irreversíveis aumenta. Desta forma, avalia-se que para a utilização de mais de um tipo de dopante os efeitos vantajosos e desvantajosos devem ser considerados individualmente e em conjunto no esforço de se otimizar o desempenho de sistemas de membranas.
44

Synthesis and characterization of polysulfone/nanoclay/polyethylene oxide composite ultrafiltration membranes. / Síntese e caracterização de membranas compósitas de polisulfona para ultrafiltração modificadas com nanoargila e polióxido de etileno.

Raphael Rodrigues 15 December 2015 (has links)
Membrane structure modification is a common approach to enhance membrane properties and performance. For example, the addition of dopants to the membrane casting solution has been observed to increase hydrophilicity, alter surface and internal pore structure, increase thermal and mechanical resistance, and impart anti-fouling properties. In this study, it was evaluated how the addition of individual and simultaneous nanoclay and polyethylene oxide (PEO) dopants affected the structure and performance of polysulfone (PSU) ultrafiltration membranes. Membrane performance was evaluated in the cross-flow configuration. The pure water permeability of the neat PSU membrane was 15 L/m².h.bar and at the optimal dosage of the individually doped membranes was 1.5% weight nanoclay to PSU and 5% weight PEO to PSU resulting in permeability of 56 and 237 L/m².h.bar, respectively. Simultaneous doping using the optimal individual weight percentages had a lower effect resulting in a permeability of 192 L/m².h.bar, in contrast the simultaneous addition of 4.5% nanoclay and 5% PEO had a higher effect resulting in a permeability of 319 L/m².h.bar. The control membrane was compared to the referred membranes and with the 4.5% nanoclay membrane (best permeability only when combined with PEO). These membranes were further examined to determine dopant effects on pore microstructure, superficial charge, separation performance, and fouling susceptibility. In general, doping with nanoclay improved membrane thermal/mechanical resistance and permeability with minimal loss in rejection. Doping with PEO resulted in a greater permeability as compared to nanoclay; however, PEO doping decreased rejection, mechanical resistance, and increased irreversible fouling. Thus, both advantageous and disadvantageous effects should be considered when selecting a dopant to optimize membrane performance. / A modificação da estrutura de membranas é uma abordagem utilizada para melhorar as propriedades de membranas e desempenho de um sistema. Por exemplo, a adição de dopantes na solução de síntese da membrana permite aumentar a hidrofilicidade, alterar a estrutura de poros superficiais e internos e conferir propriedades anti-depósitos. Neste estudo, foi avaliada como a adição de óxido de polietileno e de nano-argila afetam a estrutura e desempenho de membranas de ultrafiltração de polisulfona (PSU). O desempenho da membrana foi avaliado na configuração de fluxo paralelo (cross-flow). A permeabilidade média à água pura da membrana de PSU pura foi de 15 L/m2.h.bar. As dosagem ótimas das membranas dopadas individualmente foram de 1,5% em massa de PSU para nano-argila e 5% em massa de PSU para PEO, resultando em permeabilidades médias de 56 e 237 L/m2.h.bar, respectivamente. A dopagem simultânea usando ambas as percentagens individuais ótimas teve um efeito menor do que o esperado, resultando em uma permeabilidade média de 192 L/m2.h.bar. Em contraste, verificou-se que a adição simultânea de 4,5% de nano-argila combinada com 5% de PEO teve um efeito maior do que o uso isolado dos aditivos, resultando em uma permeabilidade média de 319 L/m2.h.bar. Desta forma, a membrana de controle foi comparada com as referidas membranas e com membranas compostas somente por nano-argila a 4,5. Estas membranas foram ainda examinadas em detalhes para determinar os efeitos dos dopantes na microestrutura dos poros, cargas superficiais, desempenho da separação, sensibilidade à formação de depósitos, rugosidade superficial e propriedades térmicas e mecânicas. Verificou-se que a dopagem com nano-argila melhora a resistência térmica e mecânica e a permeabilidade das membranas, com uma perda mínima na rejeição. A dopagem com PEO resultou em um aumento notável de permeabilidade em comparação com a adição individual de nano-argila. No entanto, a capacidade de rejeição e resistência térmica e mecânica destas membranas diminuem e a formação de depósitos irreversíveis aumenta. Desta forma, avalia-se que para a utilização de mais de um tipo de dopante os efeitos vantajosos e desvantajosos devem ser considerados individualmente e em conjunto no esforço de se otimizar o desempenho de sistemas de membranas.
45

Retention of protein repulsive character and antimicrobial activity of PEO brush layers following nisin entrapment

Auxier, Julie A. 30 November 2012 (has links)
Nisin, an amphiphilic, antimicrobial peptide, has been shown to integrate into the hydrophobic inner region of poly(ethylene oxide) (PEO) brush layers; however, the presence of integrated nisin may compromise the protein repulsive character of the PEO layer. In particular, the introduction of fibrinogen to nisin-loaded brush layers has been observed to cause changes consistent with partial elution of nisin and/or location of fibrinogen at the interface. Questions surrounding the possibility of fibrinogen adsorption warrant further investigation, as the location of procoagulant proteins at a peptide-loaded PEO layer would significantly reduce the viability of a medical device coating based on such an approach. In this work, the preferential location of fibrinogen at PEO brush layers was investigated by: detection of FITC-labeled fibrinogen after sequential introduction of nisin and labeled fibrinogen; measurement of changes in the zeta potential of PEO coated and uncoated surfaces following nisin, fibrinogen, and/or buffer challenges; and evaluation of adsorption and elution kinetics in label-free, sequential adsorption experiments using optical waveguide lightmode spectroscopy (OWLS). PEO layers were constructed through radiolytic grafting of Pluronic�� F108 or F68 onto silanized silica surfaces producing long-chain or short-chain PEO layers, respectively. Adsorption results indicated that sequential introduction of nisin and fibrinogen to PEO brush layers, based on F108, does not result in fibrinogen adsorption beyond that expected for a nisin-free PEO layer. No evidence of nisin entrapment in fibrinogen-repellent F68 layers was recorded. Low-level fibrinogen adsorption observed at F68 layers following the introduction of nisin was determined to be a result of nisin adsorption at (uncoated) defect regions on the surface. In conclusion, retention of PEO layer capacity for protein repulsion after nisin entrapment is owing to a steric repulsive barrier provided by PEO segments extending beyond the level of entrapped nisin. It was then hypothesized that the immobilized, pendant PEO chains will inhibit exchange of entrapped nisin by competing proteins, and therefore prolong nisin activity retention. In order to evaluate nisin function following its entrapment, the antimicrobial activity of nisin-loaded, F108-coated silica surfaces was evaluated against the Gram-positive indicator strain, Pediococcus pentosaceous. The retained biological activity of these nisin-loaded layers was evaluated after incubation in the presence of bovine serum albumin (BSA), for contact periods up to one week. Surfaces were withdrawn at selected times and placed on plates inoculated with P. pentosaceous to measure kill zone radius in order to quantify nisin activity. In the presence of BSA, F108-coated surfaces retained more antimicrobial activity than the uncoated, hydrophobic surfaces. These results strongly suggest that PEO brush layers may serve as a viable drug storage platform due to the retained non-fouling character after bioactive peptide entrapment and the prolonged peptide activity in the presence of other proteins. / Graduation date: 2013
46

Fosfatação e ligação cruzada de amido de trigo e suas aplicações em filmes compósitos usando poli(óxido de etileno) / Phosphated and cross-linked wheat starches and their application in biocomposites films using polyethylene oxide

Bruni, Graziella Pinheiro 24 November 2016 (has links)
Submitted by Gabriela Lopes (gmachadolopesufpel@gmail.com) on 2017-03-14T15:42:14Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2017-03-17T21:44:15Z (GMT) No. of bitstreams: 2 Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-03-17T21:44:15Z (GMT). No. of bitstreams: 2 Dissertação Graziella Pinheiro Bruni.pdf: 2435737 bytes, checksum: dd5dfba33efd7d9048f7888720783b4a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-11-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A associação entre polímeros naturais e sintéticos para formação de biocompósitos tem sido estudada. A mistura do amido com o poli (óxido de etileno) (PEO) para a formação de biocompósitos é interessante, pois o PEO é biodegradável, apresenta alta viscosidade e biocompatibilidade com matrizes orgânicas. Além disso, o PEO apresenta uma estrutura semicristalina que pode influenciar nas propriedades dos biocompositos. A interação do amido com PEO pode ser influenciada pela estrutura molecular do amido. Com isso, objetivou-se com o presente trabalho desenvolver filmes biocompósitos à base de amidos de trigo nativo, fosfatado ou intercruzado com a adição do PEO. O amido de trigo foi modificado por fosfatação e por ligação cruzada. Os amidos foram avaliados quanto ao teor de fósforo, teor de amilose, poder de intumescimento, solubilidade em água, propriedades térmicas, propriedades de pasta, cristalinidade e morfologia. Os filmes foram elaborados com amido nativo, fosfatado ou de ligação cruzada, e com adição de PEO. Os filmes foram avaliados quanto à morfologia, solubilidade em água, permeabilidade ao vapor de água (PVA), propriedades mecânicas, parâmetros de cor (luminosidade e opacidade), cristalinidade, rugosidade e higroscopicidade. O amido fosfatado, em relação aos demais amidos, apresentou maior teor de fósforo, teor de amilose e maior poder de intumescimento e solubilidade em água. Os filmes, independentemente do tipo de amido, com a adição de PEO quando comparados aos filmes de amidos sem PEO, apresentaram morfologia descontínua, foram mais cristalinos e rugosos e menos hidrofílicos. Os filmes biocompósitos apresentaram características adequadas para aplicação em embalagens flexíveis. / The association between natural and synthetic polymers for the formation of biocomposites has been studied. The mixture of starch with poly (ethylene oxide) (PEO) for the formation of biocomposites is interesting, since the PEO is biodegradable, has high viscosity and biocompatibility with organic matrices. In addition, PEO has a semicrystalline structure that may influence the properties of the biocomposites. The interaction of the starch with PEO can be influenced by the molecular structure of the starch. The aim of this work was to develop biocomposite films based on native wheat starches, phosphated or crosslinked with the addition of PEO. The wheat starch was modified by phosphating and crosslinking. Starches were evaluated for phosphorus content, amylose content, swelling power, water solubility, thermal properties, past properties, crystallinity and morphology. The films were prepared with native, phosphate or crosslinked starch, and with addition of PEO. The films were evaluated for morphology, water solubility, water vapor permeability (WVP), mechanical properties, color parameters (luminosity and opacity), crystallinity, roughness and hygroscopicity. The phosphate starch, in relation to the other starches, presented higher phosphorus content, amylose content, swelling power and water solubility. The films, regardless of the type of starch, with the addition of PEO when compared to the starch films without PEO presented discontinuous morphology, were more crystalline and rough and less hydrophilic. The biocomposite films presented characteristics for possible use in flexible packages.
47

The effect of PEO homopolymers on the behaviours and structural evolution of Pluronic F127 Smart Hydrogels for Controlled Drug Delivery Systems

Shriky, Banah, Mahmoudi, N., Kelly, Adrian L., Isreb, Mohammad, Gough, Timothy D. 06 April 2022 (has links)
Yes / Understanding the structure-property relationships of drug delivery system (DDS) components is critical for their development and the prediction of bodily performance. This study investigates the effects of introducing polyethylene oxide (PEO) homopolymers, over a wide range of molecular weights, into Pluronic injectable smart hydrogel formulations. These smart DDSs promise to enhance patient compliance, reduce adverse effects and dosing frequency. Pharmaceutically, Pluronic systems are attractive due to their unique sol-gel phase transition in the body, biocompatibility, safety and ease of injectability as solutions before transforming into gel matrices at body temperature. This paper presents a systematic and comprehensive evaluation of gelation and the interplay of microscopic and macroscopic properties under both equilibrium and non-equilibrium conditions in controlled environments, as measured by rheology in conjunction with time-resolved Small Angle Neutron Scattering (SANS). The non-equilibrium conditions investigated in this work offer a better understanding of the two polymeric systems’ complex interactions affecting the matrix thermo-rheological behaviour and structure and therefore the future release of an active pharmaceutical ingredient from the injectable DDS.
48

Injection moulded controlled release amorphous solid dispersions: Synchronized drug and polymer release for robust performance

Deshmukh, Shivprasad S., Paradkar, Anant R, Abrahmsén-Alami, S., Govender, R., Viridén, A., Winge, F., Matic, H., Booth, J., Kelly, Adrian L. 26 October 2020 (has links)
Yes / A study has been carried out to investigate controlled release performance of caplet shaped injection moulded (IM) amorphous solid dispersion (ASD) tablets based on the model drug AZD0837 and polyethylene oxide (PEO). The physical/chemical storage stability and release robustness of the IM tablets were characterized and compared to that of conventional extended release (ER) hydrophilic matrix tablets of the same raw materials and compositions manufactured via direct compression (DC). To gain an improved understanding of the release mechanisms, the dissolution of both the polymer and the drug were studied. Under conditions where the amount of dissolution media was limited, the controlled release ASD IM tablets demonstrated complete and synchronized release of both PEO and AZD0837 whereas the release of AZD0837 was found to be slower and incomplete from conventional direct compressed ER hydrophilic matrix tablets. Results clearly indicated that AZD0837 remained amorphous throughout the dissolution process and was maintained in a supersaturated state and hence kept stable with the aid of the polymeric carrier when released in a synchronized manner. In addition, it was found that the IM tablets were robust to variation in hydrodynamics of the environment and PEO molecular weight. / The research was funded by AstraZeneca, Sweden.
49

Cisplatine : une vieille molécule pour de nouveaux défis. : développement d’une prodrogue macromoléculaire multifonctionnelle applicable au traitement local du glioblastome / Cisplatin : an old drug to tackle new challenges : development of a multifunctional macromolecular prodrug for the local treatment of glioblastoma

Lajous, Hélène 22 May 2018 (has links)
Le glioblastome constitue la tumeur primitive maligne la plus fréquente et la plus agressive du système nerveux central, caractérisée par un pronostic sombre. L’infusion locale dans le parenchyme cérébral du cisplatine a présenté des résultats encourageants sur des modèles précliniques. La nanovectorisation permet de concentrer l’efficacité thérapeutique d’agents anticancéreux à leur cible. Leur fonctionnalisation par des unités d’imagerie offre la possibilité de suivre de façon non invasive par imagerie par résonance magnétique (IRM) leur biodistribution au sein du tissu lésé. Dans cette optique, un copolymère tribloc amphiphile biocompatible a été synthétisé par polymérisations par ouverture de cycle successives à partir d’un oxyde de polyéthylène (PEO). Après micellisation dans l’eau, des complexes de gadolinium ont été greffés sur la couronne de PEO et les fonctions carboxylates situées en périphérie du coeur micellaire se sont réticulées sur le cisplatine, conduisant à la formation d’une prodrogue macromoléculaire de taille nanométrique stable dans le temps. Le potentiel de ces nanoparticules bifonctionnelles comme agents de contraste IRM a été exploré à haut champ magnétique. Une telle vectorisation du cisplatine a en outre permis d’augmenter de façon significative l’accumulation du platine dans deux lignées humaines de glioblastome ainsi que la formation d’adduits à l’ADN par rapport à la drogue libre. L’implication de mécanismes biologiques sous-jacents à cette étude pose la question de l’existence d’autres cibles alternatives critiques des dérivés du platine, remettant en cause le paradigme établi depuis un demi-siècle définissant l’ADN comme la cible ultime du cisplatine. / Glioblastoma is the most frequent and aggressive primary malignant tumor of the central nervous system with a gloomy prognosis. Local infusion of cisplatin within the brain parenchyma exhibited promising results in preclinical models. Nanovectorization of anticancer agents even promotes the concentration of their therapeutic efficiency on their target. Anchorage ofimaging moieties on such smart drug delivery systems further enables the non-invasive monitoring of their biodistribution within the damaged tissue by magnetic resonance imaging (MRI). From this perspective, a biocompatible amphiphilic triblock copolymer was synthesized by successive ring-opening polymerizations from a polyethylene oxide (PEO). After micellization in water, gadolinium complexes were grafted to the PEO corona and the carboxylate functions located at the surface of the micelle’s core were able to cross-link with cisplatin. A stable nano-sized macromolecular prodrug was therefore recovered. Relaxomety measurements at a high magnetic field confirmed the intrinsic potential of these hybrid nanoparticles as alternative MRI contrast agents. Besides, cisplatin vectorization allowed for substantially increasing the accumulation of platinum compounds in two human glioblastoma cell lines as well as the subsequent formation of DNA adducts in comparison with the free drug. Biological mechanisms below this study raise the question whether critical alternative targets of platinum derivatives might exist, thus undermining the old-established paradigm that defines DNA as the ultimate target of cisplatin.
50

Colloidal chemical potential in attractive nanoparticle-polymer mixtures: simulation and membrane osmometry

Quant, Carlos Arturo 17 August 2004 (has links)
The potential applications of dispersed and self-assembled nanoparticles depend critically on accurate control and prediction of their phase behavior. The chemical potential is essential in describing the equilibrium distribution of all components present in every phase of a system and is useful as a building block for constructing phase diagrams. Furthermore, the chemical potential is a sensitive indicator of the local environment of a molecule or particle and is defined in a mathematically rigorous manner in both classical and statistical thermodynamics. The goal of this research is to use simulations and experiments to understand how particle size and composition affect the particle chemical potential of attractive nanoparticle-polymer mixtures. The expanded ensemble Monte Carlo (EEMC) simulation method for the calculation of the particle chemical potential for a nanocolloid in a freely adsorbing polymer solution is extended to concentrated polymer mixtures. The dependence of the particle chemical potential and polymer adsorption on the polymer concentration and particle diameter are presented. The perturbed Lennard-Jones chain (PLJC) equation of state (EOS) for polymer chains1 is adapted to calculate the particle chemical potential of nanocolloid-polymer mixtures. The adapted PLJC equation is able to predict the EEMC simulation results of the particle chemical potential by introducing an additional parameter that reduces the effects of polymer adsorption and the effective size of the colloidal particle. Osmotic pressure measurements are used to calculate the chemical potential of nanocolloidal silica in an aqueous poly(ethylene oxide) (PEO) solution at different silica and PEO concentrations. The experimental data was compared with results calculated from Expanded Ensemble Monte Carlo (EEMC) simulations. The results agree qualitatively with the experimentally observed chemical potential trends and illustrate the experimentally-observed dependence of the chemical potential on the composition. Furthermore, as is the case with the EEMC simulations, polymer adsorption was found to play the most significant role in determining the chemical potential trends. The simulation and experimental results illustrate the relative importance of the particles size and composition as well as the polymer concentration on the particle chemical potential. Furthermore, a method for using osmometry to measure chemical potential of nanoparticles in a nanocolloid-mixture is presented that could be combined with simulation and theoretical efforts to develop accurate equations of state and phase behavior predictions. Finally, an equation of state originally developed for polymer liquid-liquid equilibria (LLE) was demonstrated to be effective in predicting nanoparticle chemical potential behavior observed in the EEMC simulations of particle-polymer mixtures.

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