Synthèse de poly(N-isopropylacrylamide)s modifiés par des groupements cholestérols et leur étude en solutions aqueuses

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Micellar and surface properties of a poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) copolymer in aqueous solution

Critical micelle concentrations (cmc) of aqueous solutions of poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) were determined at several temperatures by surface tensiometry. Below the lower critical solution temperature (LCST), the low Delta(mic) H-0 determined can be assigned to the PMMA block being tightly coiled in the dispersed molecular state, so that the unfavorable interactions of hydrophobic entities with water are minimized. Above the LCST the cmc value was found to increase; an anomalous behavior that can be directly related to the micelle-globule transition of the hydrophilic block. Interestingly, above the LCST the surface tension of relatively concentrated solutions was found to depend weakly on temperature not following the usual strong decrease with temperature expected for aqueous solutions. (C) 2007 Elsevier Inc. All rights reserved.

Thermo-responsive poly(methyl methacrylate)-block-poly(N-isopropylacrylamide) block copolymers synthesized by RAFT polymerization: micellization and gelation

RAFT polymerization was used to prepare PMMA-b-PNIPAM copolymers. Two different chain transfer agents, tBDB and MCPDB, were used to mediate the sequential polymerizations. Micellar solutions and gels were prepared from the resulting copolymers in aqueous solution. When heated above T-c of PNIPAM (about 31 degrees C), DLS revealed that PNIPAM coronas collapsed, resulting in aggregation of the original micelles. The micellar gels underwent syneresis above T-c as water was expelled from the ordered gel structure, the lattice periodicity of which was determined by SANS. A large decrease in lattice spacing was observed above T-c. The gel became more viscoelastic at high temperature, as revealed by shear rheometry which showed a large increase in G".

Rheological and thermal behaviour of poly(N-isopropylacrylamide)/alginate smart polymeric networks

Interpenetrating polymeric networks based on sodium alginate and poly(N-isopropylacrylamide) (PNIPAAm) covalently crosslinked with N,N′-methylenebisacrylamide have been investigated using rheology, thermogravimetry, differential scanning calorimetry, X-ray diffraction measurements and scanning electron microscopy (SEM). An improved elastic response of the samples with a higher PNIPAAm content and increased amount of crosslinking agent was found. The temperature-responsive behaviour of the hydrogel samples was evidenced by viscoelastic measurements performed at various temperatures. It is shown that the properties of these gels can be tuned according to composition, amount of crosslinking agent and temperature changes. X-ray scattering analysis revealed that the hydrophobic groups are locally segregated even in the swollen state whilst cryo-SEM showed the highly heterogeneous nature of the gels.

Multi-responsive hydrogels based on N-isopropylacrylamide and sodium alginate

Hydrogels consisting of sodium alginate and N-isopropylacrylamide covalently crosslinked with N,N′-methylenebisacrylamide were prepared. The mixed-interpenetrated networks obtained were characterized using elemental analysis, Fourier transform infrared and Raman spectroscopy, swelling measurements and environmental scanning electron microscopy. The thermo- and pH-responsive properties of these hydrogels were evidenced by their swelling behaviour, which depended also on the amount of crosslinking agent and hydrogel composition.

Synthesis, characterization and solution properties of amphiphilic N-isopropylacrylamide-poly(ethylene glycol)-dodecyl methacrylate thermosensitive polymers

Terpolymers of N-isopropylacrylamide, dodecyl methacrylate (DOMA) and poly(ethylene glycol) (PEG) methacrylate, were synthesized by random copolymerization, and the composition was controlled to achieve systems having different thermosensitivities. H-1 NMR spectra and gel permeation chromatography (GPC) were employed to characterize the different samples obtained. The solution properties were studied by employing spectrophotometry, fluorescence, and dynamic light scattering techniques. The chemical compositions in the final terpolymers are close to those in the feed. The polymers exhibited cloud point temperatures (T-es) varying from 17 to 52 degrees C. Micropolarity studies using I-1/I-3 ratio of the vibronic bands of pyrene show the formation of amphiphilic aggregates capable of incorporating hydrophobic drugs as the polymer concentration is increased. The critical aggregation concentration (CAC) increases from 3.6 x 10(-3) to 1 x 10(-2) g/l with the PEG content varying from 5 to 35 mol%. Anisotropy measurements confirm the results obtained by pyrene fluorescence and show that the aggregates resulting from intermolecular interactions present different organizations. The hydrodynamic diameters (Dh) of the aggregates determined by dynamic light scattering (DLS) vary from 40 to 150 nm depending on the terpolymer composition. The T-cs and Dh values decreased with the ionic strength, and this behavior was attributed to the dehydration of the polymeric micelles. The capacity of solubilization of the aggregates was evaluated by employing pyrene, and the obtained results confirm the ability to incorporate hydrophobic molecules. (c) 2005 Elsevier B.V All rights reserved.

The Interaction Between N-Isopropylacrylamide-Acrylic Acid-Ethyl Methacrylate Thermosensitive Polymers and Cationic Surfactants

The interaction between cationic surfactants and isopropylacrylamide-acrylic acid-ethyl methacrylate (IPA:AA:EMA) terpolymers has been investigated using steady-state fluorescence and spectrophotometric measurements to assess the effect of the polymer composition on the aggregation process and terpolymers' thermosensitivities. Micropolarity studies using pyrene show that the interaction of cationic surfactants with IPA:AA:EMA terpolymers occurs at surfactant concentrations much smaller than that observed for the pure surfactant in aqueous solution. The critical aggregation concentration (CAC) values decrease with both the hydrocarbon length of the surfactant and the content of ethyl methacrylate. These results were interpreted as a manifestation of the increasing contribution of attractive hydrophobic and electrostatic forces between negatively charged polymer chains and positively charged surfactant molecules. The increase of ethyl methacrylate in the copolymers lowers the CAC due to the larger hydrophobic character of the polymer backbone. The cloud point determination reveals that the lower critical solution temperatures (LCST) depend strongly on the copolymer composition and surfactant nature. The binding of surfactants molecules to the polymer chain screens the electrostatic repulsion between the carboxylic groups inducing a conformational transition and the dehydration of the polymer chain.

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

Solution properties of star and linear poly(N-isopropylacrylamide)

The LCST transitions of novel N-isopropylacrylamide ( NIPAM) star polymers, prepared using the four-armed RAFT agent pentaerythritoltetrakis(3-(S-benzyltrithiocarbonyl) propionate) (PTBTP) and their hydrolyzed linear arms were studied using H-1 NMR, PFG-NMR, and DLS. The aim was to determine the effect of polymer architecture and the presence of end groups derived from RAFT agents on the LCST. The LCST transitions of star PNIPAM were significantly depressed by the presence of the hydrophobic star core and possibly the benzyl end groups. The effect was molecular weight dependent and diminished once the number of repeating units per arm >= 70. The linear PNIPAM exhibited an LCST of 35 degrees C, regardless of molecular weight; the presence of both hydrophilic and hydrophobic end groups after hydrolysis from the star core was suggested to cancel effects on the LCST. A significant decrease in R-H was observed below the LCST for star and linear PNIPAM and was attributed to the formation of n-clusters. Application of a scaling law to the linear PNIPAM data indicated the cluster size n = 6. Tethering to the hydrophobic star core appeared to inhibit n-cluster formation in the lowest molecular weight stars; this may be due to enhanced stretching of the polymer chains, or the presence of larger numbers of n-clusters at temperatures below those measured.

Bile-salt-induced aggregation of poly(N-isopropylacrylamide) and lowering of the lower critical solution temperature in aqueous solutions

The effect of sodium cholate (NaC; concentration 1-16 mM), a biological surfactant, on the aggregation behavior of 1% (w/v, 2.2 × 10(-3) M) poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions was studied as a function of temperature. From turbidity, dynamic light scattering, viscosity, and fluorescence measurements, it was observed that (i) there is NaC-induced nanoscale aggregation of PNIPAM in its sol state and (ii) the lower critical solution temperature corresponding to sol-gel transition shifts to a lower temperature by about 2 °C.

Multifunctional bioactive glass scaffolds coated with layers of poly(d,l-lactide-co-glycolide) and poly(n-isopropylacrylamide-co-acrylic acid) microgels loaded with vancomycin

A new family of multifunctional scaffolds, incorporating selected biopolymer coatings on basic Bioglass® derived foams has been developed. The polymer coatings were investigated as carrier of vancomycin which is a suitable drug to impart antibiotic function to the scaffolds. It has been proved that coating with PLGA (poly(lactic-co-glycolic acid)) with dispersed vancomycin-loaded microgels provides a rapid delivery of drug to give antibacterial effects at the wound site and a further sustained release to aid mid to long-term healing. Furthermore, the microgels also improved the bioactivity of the scaffolds by acting as nucleation sites for the formation of HA crystals in simulated body fluid. © 2013 Elsevier B.V. All rights reserved.

Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.

Development of biocompatible and “smart” porous structures using CO2-assisted processes

Dissertação apresentada para a obtenção do grau de Doutor em Engenharia Química, especialidade Engenharia da Reacção Química, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Development of thermoresponsive (polysulfone/polyacrylonitrile) - based membranes for bioseparation processes

Mestrado integrado em Engenharia Química e Bioquímica

Bioactive beads for local sensing of proteases in 3D engineered tissues

Dissertação para obtenção do Grau de Doutor em Bioengenharia (MIT)