Chapter 1: Supramolecular gels and their applications Gels are viscoelastic materials composed of a solid-like three dimensional fibrillar network that is embedded in a liquid. Supramolecular gels belong to a class of gels which are derived from low molecular weight compounds (typically < 1000). A variety of non-covalent interactions like H-bonding, π-π stacking, donor-acceptor, metal coordination, solvophobic and van der Waals interactions are involved in the formation of the self-assembled fibrous networks (SAFIN’s) in these gels. These non-covalent interactions are weak in nature and as a result, these gels can be reverted back to sol by heating and this process is reversible. These gels are further classified as hydrogels, organogels and aero/xerogels depending on the medium they encompass. Although low molecular weight gelators were known in the early part of the 20th century, it is only in the last two decades that this field has generated widespread interest among scientists. In the 90s, the investigations on these kinds of gels mainly focused on designing new gelator molecules. However, during the last decade, the research interest in this field has shifted more towards designing functional gels. Such gels Scheme 1. Various applications of functional supramolecular gels have been extensively utilized in the templated synthesis of inorganic nanomaterials, in making hybrid materials, as synthetic light harvesting systems, as sensors, in the field of biomaterials such as drug delivery, screening of enzyme inhibitors and tissue engineering and also in the field of organic optoelectronics. In this chapter a few selected examples from each of these fields are highlighted. Chapter 2: Charge transfer induced organogels from 2,3dialkoxyanthracenes and 2,4,7-trinitrofluorenone 2,3-Di-n-alkoxyanthracenes formed charge transfer (CT) interaction promoted organogels in the presence of electron acceptor 2,4,7-trinitrofluorenone (TNF). These dialkoxyanthracences (in the absence of TNF) have been reported previously to form gels in a variety of organic solvents. The gelation property was found to be dependent on the chain length and the derivatives with C6-C16 chains were found to be gelators. On the other hand derivatives with C5-C1 chains were found to be non-gelators. It was found that TNF not only modulated the gelation property of the efficient organogelators, it also transformed the weak and non-gelators into efficient gelators. This charge transfer induced gelation was observed for the derivatives with C10-C4 chains in alcoholic and hydrocarbon solvents whereas the shorter chain derivatives C3-C1 did not form gels. Several other alkoxy and dialkoxy derivatives with substituents in other positions did not show gelation in the presence of TNF. These results suggested that two structural aspects are necessary for these derivatives to form CT gels- the alkoxy chain length and the position of the alkoxy substituents. The thermal stability of all these gels was found to be maximum with a 1:1 stoichiometry of the donor and the acceptor. The common observation, the intensification of color in going from the sol to the gel phase, supported the crucial role of the charge transfer interaction behind the formation of these gels. The rheological characterization of the gels demonstrated that they Figure 1. Chemical structures of 2,3-dialkoxyanthracenes and TNF (middle) and a fluorescence confocal microscopy image (left) and a photograph (right) of DDOA-TNF gel. behaved like viscoelastic soft solids. Chapter 3: A new class of perfluorinated derivatives of bile acids: Synthesis and gelation properties A new class of bile acid based gelators was designed by connecting the side chains of the facially amphiphilic bile acid with perfluoroalkyl chains of different lengths through two different ester linkages-–O-(CO)-and –(CO)-OCH2-. All these three structural aspects i.e. the bile acid moiety, the fluoroalkyl chain length and the spacer were found to influence the gelation properties of the derivatives. Depending on them, there was a variation in terms of the nature of the solvent gelated, the CGCs, the mechanical properties of the gels, etc among the derivatives. The deoxycholic and lithocholic derivatives with the spacer –O-(CO)-formed gels in aromatic hydrocarbons and also in DMSO depending on the fluoroalkyl chain length. The mechanical properties of the gels formed in DMSO were found to be dependent on the bile acid moiety and the fluoroalkyl chain length. In general, the deoxy analogues showed higher elasticity, stiffness and yield stress values for their gels than the litho derivatives. The perfluorinated derivatives having the spacer –(CO)-OCH2-showed gelation properties in organic-aqueous media and in DMSO. Interestingly, organogelation was observed in the deoxy and lithocholic derivatives from both spacer series whereas in the literature most of the bile acid based organogelators are derived from cholic acid. (b) (c) Figure 2. (a) Perfluorinated derivatives of bile acids, (b) photographs of a few DMSO gels and (c) TEM image of a xerogel of a deoxy derivative Chapter 4: Composite aerogels and organogels from 2,3didecyloxyanthracene and bile-perfluoro derivatives Aerogels are unique materials among solids. They have extremely low densities (up to 95% of their volume is air), large pores and high inner surface area. As a result aerogels have very interesting physical properties such as extremely low thermal conductivity, low sound velocity and high optical transparency. There are only a few reports of aerogel formation by low molecular weight gelators. We have investigated the aerogel formation ability of three long 7 chain perfluoroalkyl esters (two deoxycholic and one lithocholic derivative, chart 1) in supercritical CO2. A deoxy derivative, formed aerogel in sc-CO2. When mixed with DDOA (which has been reported previously to form good aerogels in sc-CO2), the perfluoro compound formed aerogels of better quality. The mixed aerogels were characterized by the presence of very large fibers in the micron range (as observed in the aerogel formed by only the fluoro derivative) as well as fibers of smaller size observed in pure DDOA aerogel. We also investigated the behavior of the composite systems in organic solvents. It was found that in DMSO, another deoxy derivative, Figure 3. SEM images of a mixed aerogel of DDOA-DC23C13F27 (left) and a mixed organogel (DMSO) of DDOA-DC23C11F23 (right). DC23C11F23 formed gels with higher thermal stability and improved mechanical properties compared to the native gels of the perfluoro compound or DDOA. Chapter 5: Hydrogels from lanthanide(III) cholates: Tunable, multiple color luminescence from hydrogels and xerogels In this chapter, facile hydrogel formation by several lanthanide cholates is reported. When sodium cholate was added to aqueous solutions of Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III) and Yb(III) and sonicated, the mixtures formed gels within a few seconds. The gels thus obtained were transparent/translucent and thermoirreversible. Rheological measurements showed that all of them could be classified as viscoelastic soft solids. A naphthalene derivative, 2,3-dihyroxynaphthalene was found to sensitize Tb(III) emission very efficiently in its cholate gel when doped in micromolar concentrations. The importance of the gel matrix behind sensitization of Tb(III) was demonstrated by the inefficiency of the same sensitizer DHN in an SDS micellar solution. In mixed gels of Tb(III)-Eu(III) doped with DHN, a energy transfer pathway was found to occur from the sensitized Tb(III) to Eu(III). By a simple tuning of the ratio of these two lanthanide ions, multiple color emissive gels could be made.The emissive properties of the hydrogels were retained in the xerogels and the suspensions of these xerogels in n-hexane were used for making luminescent coatings on glass surface. Figure 4. Tunable, multi-color luminescent hydrogels and xerogels of lanthanide cholates

Les films minces d'hydrogels que nous étudions sont des réseaux chimiques de polymères greffés par liaison covalente sur des substrats solides. Ces revêtements versatiles permettent le contrôle des propriétés interfaciales tel que les propriétés stimulables, le mouillage ou les propriétés mécaniques. Ici, nous nous intéressons aux films minces d'hydrogels stimulables (par la température, la lumière ou le champ électrique).La synthèse des films de gels greffés suit une stratégie simple basée sur la chimie click thiol-ène. Les films sont fabriqués en déposant les polymères stimulables fonctionnalisés par des groupes diène en présence de réticulants dithiols sur des surfaces modifiées thiol. Cette stratégie permet d'obtenir des films d'hydrogels sur une large gamme d'épaisseur avec les propriétés stimulables visées. Nous nous intéressons à la structure des films d'hydrogels greffés de poly(N-isopropylacrylamide) aux propriétés thermo-stimulables. Nous étudions l'effet du confinement et des contraintes dues au greffage sur la surface sur la transition de phase gonflement/dégonflement des gels avec deux approches : le gonflement unilatéral (perpendiculaire à la surface) par ellipsométrie et réflectivité de neutrons, et la topographie (dans le plan) de la surface libre du gel par AFM. Nous développons également de nouveaux films d'hydrogels avec des réseaux d'architectures ciblées. En s'inspirant de l'architecture des gels macroscopiques, nous élaborons diverses architectures : films de gels multicouches, films de réseaux interpénétrés et films de gels hybrides. / Thin films of hydrogels we study are chemical polymer networks covalently grafted on solid substrates. These versatile coatings allow the control of various interfacial properties such as responsive properties, wetting or mechanical properties. Here, thin films of stimuli-responsive hydrogels (with temperature, light or electric field) are the point of interest. The surface-attached gel films are synthesized by following a straightforward strategy based on thiol-ene click chemistry. The formation of the films is achieved by adding bifunctional thiol molecules as cross-linkers to the ene-reactive polymers on thiol-modified surfaces. This strategy allows us to obtain hydrogel films with a wide range of thickness and with the desired properties. We study the structure of surface-attached poly(N-isopropylacrylamide) gel films which show thermo-responsive properties. We determine the effect of confinement and constraints due to the surface-attachment on the swelling/collapse phase transition of hydrogels with two approaches: the one-dimension swelling normal to the surface using ellipsometry and neutron reflectivity and the in-plane observation of the free surface of the gel using AFM. New and complex hydrogel films are also developed by targeting the architecture of the polymer networks. Inspired from macroscopic hydrogels architecture, we design various architectures: multilayer gel films, interpenetrating networks (IPN) gel films and hybrid gel films.

Les hydrogels injectables et auto-réparants suscitent un intérêt particulier dans les domaines de l'ingénierie tissulaire et de la médecine régénératrice. En raison de la nature dynamique de leurs réticulations, ces gels peuvent être pré-formés dans des seringues, extrudés sous cisaillement et s’auto-réparer spontanément après arrêt de la déformation mécanique. Au vu du potentiel que peuvent offrir les polymères fonctionnalisés par des acides boroniques pour la fabrication de gels covalents réversibles, nous avons développé des hydrogels injectables d’acide hyaluronique (HA) réticulés par des liaisons esters boronates pour des applications esthétiques et biomédicales. Pour élaborer de tels gels avec des propriétés optimisées, nous avons exploré l’effet de la nature du dérivé d’acide boronique ainsi que du motif saccharidique greffés sur le HA sur les propriétés rhéologiques dynamiques des gels. Parmi les différents dérivés d'acide boronique, le benzoboroxole (BOR) a été choisi en plus de l'acide phénylboronique (PBA) pour complexer différents motifs saccharidiques greffés sur le HA. Comparé au PBA, le dérivé BOR est, en effet, capable de se complexer de manière plus efficace à pH neutre et avec une plus grande variété de composés saccharidiques, en particulier les glycopyranosides. Cette étude a démontré que les propriétés rhéologiques dynamiques des assemblages de HA formés par complexation des unités de BOR ou PBA avec les différents sucres sont étroitement liées à la dynamique des échanges moléculaires et à la thermodynamique des pontages. En outre, nous avons également établi pour la première fois la possibilité d’obtenir des hydrogels de HA auto-réticulants à pH physiologique via des interactions multivalentes entre les unités de BOR greffées sur le HA et des groupements diols se répétant sur la chaîne polysaccharidique. Outre le BOR, la capacité de son homologue cyclique à six chaînons, la benzoxaborine, et d’un nouveau dérivé original similaire à ce composé a été explorée en tant que nouveaux sites de complexation de saccharides pour la formation de réseaux de HA réversibles. Compte-tenu des propriétés injectables, d'auto-réparation et de réponse à différents stimuli démontrées par ces nouveaux hydrogels de HA, ces biomatériaux apparaissent comme des candidats prometteurs pour de nombreuses applications innovantes dans le domaine biomédical, notamment pour l'ingénierie tissulaire et la thérapie cellulaire. / Injectable and self-healing hydrogels have recently drawn great attention in the fields of tissue engineering and regenerative medicine. Such gels can be pre-formed into syringes, be extruded under shear stress and show rapid recovery when the applied stress is removed due to the dynamic nature of their crosslinks. Given the exciting potential benefit of using boronic acid-containing polymers to construct dynamic covalent hydrogels, we explored this attractive strategy to design injectable boronate-crosslinked hydrogels based on hyaluronic acid (HA) for aesthetic and other biomedical applications. To design hydrogels with optimized properties, we investigated the effect of the nature of the boronic acid moiety as well as the sugar molecule grafted onto the HA backbone on the gel properties. Among arylboronic acid derivatives, benzoboroxole (BOR) was selected in addition to phenylboronic acid (PBA) as the binding site for sugar moieties grafted on HA. This choice was based on the efficient binding capability of BOR at neutral pH compared to PBA, and on its ability to complex glycopyranosides. With this study, we demonstrated that the dynamic rheological properties of the HA networks based on BOR- or PBA-saccharide complexation are closely linked to the molecular exchange dynamics and thermodynamics of the small molecule crosslinkers. Besides, we also established for the first time the feasibility of self-crosslinking HA hydrogels with extremely slow dynamics at physiological pH through multivalent interactions between BOR derivatives grafted on HA and diols from the polysaccharide chains. Finally, in addition to BOR, we demonstrated the unprecedented capacity of its six-membered ring homologue, benzoxaborin, and a new original benzoxaborin-like derivative as new carbohydrate binding sites for the formation of reversible HA networks. Taking into account the injectable, self-healing and stimuli-responsive properties showed by these new HA hydrogels, these biomaterials appear as promising injectable scaffolds for many innovative applications in the biomedical field, including in tissue engineering and cell therapy.

No / The aim of this study was to develop a synthetic hydrogel to act as a corneal substitute capable of selectively supporting the adhesion and proliferation of limbal epithelial cells (LECs) while inhibiting growth of limbal fibroblasts. Deficiency of LECs causes conjunctival epithelial cells to move over the cornea, producing a thick scar pannus. Unilateral defects can be treated using LEC cultured from the unaffected eye, transplanting them to the affected cornea after scar tissue is removed. The underlying wound bed is often damaged, however, hence the need to develop a corneal inlay to aid in corneal re-epithelialization. Transparent epoxy-functional polymethacrylate networks were synthesized using a combination of glycerol monomethacrylate, ethylene glycol dimethacrylate, lauryl methacrylate and glycidyl methacrylate that produced two different bulk hydrogel compositions with different equilibrium water contents (EWCs): Base 1 and Base 2, EWC=55% and 35%, respectively. Two sets of amine-functional hydrogels were produced following reaction of the epoxide groups with excesses of either ammonia, 1,2-diamino ethane, 1,3-diamino propane, 1,4-diamino butane or 1,6-diamino hexane. Neither series of hydrogels supported the proliferation of limbal fibroblasts irrespective of amine functionalization but they both supported the adhesion and proliferation of limbal epithelial cells, particularly when functionalized with 1,4-diamino butane. With Base 1 hydrogels (less so with Base 2) a vigorous epithelial outgrowth was seen from small limbal explants and a confluent epithelial layer was achieved in vitro within 6days. The data support the development of hydrogels specific for epithelial formation.

No description available.

Este trabalho teve como principal objetivo produzir membranas porosas de carboximetilquitosana e hidrogéis de quitosana com propriedades físico-químicas e mecânicas adequadas para aplicações em Engenharia de Tecidos. Para isso, quitosanas com diferentes graus de acetilação (4,0%&lt;GA&lt;40%) e de elevada massa molar média viscosimétrica (Mv&gt;750.000 g.mol-1) foram produzidas através da aplicação de processos consecutivos de desacetilação assistida por irradiação de ultrassom de alta intensidade (DAIUS) à beta-quitina extraída de gládios de lulas Doryteuthis spp. A carboximetilação de quitosana extensivamente desacetilada (Qs-3; GA=4%) foi realizada pela reação com ácido monocloroacético em meio isopropanol/solução aquosa de NaOH, gerando a amostra CMQs-0 (GS&asymp;0,98; Mv&asymp;190.000 g.mol-1). A irradiação de ultrassom de alta intensidade foi empregada para tratar solução aquosa de CMQs-0 durante 1 h e 3 h, resultando nas amostras CMQs-1 (Mv&asymp;94.000 g.mol-1) e CMQs-3 (Mv&asymp;43.000 g.mol-1), respectivamente. Para a produção de membranas reticuladas, genipina foi adicionada em diferentes concentrações (1,0x10-4 mol.L-1, 3,0x10-4 mol.L-1 ou 5,0x10-4 mol.L-1) às soluções aquosas das CMQs, que foram vertidas em placas de Petri e a reação de reticulação procedeu por 24 h. Em seguida, as membranas reticuladas (M-CMQs) foram liofilizadas, neutralizadas, lavadas e liofilizadas novamente, resultando em nove amostras, que foram caracterizadas quanto ao grau médio de reticulação (GR), grau médio de hidratação (GH), morfologia, propriedades mecânicas e quanto à susceptibilidade à degradação por lisozima. O grau médio de reticulação (GR) foi tanto maior quanto maior a concentração de genipina empregada na reação, variando de GR&asymp;3,3% (M-CMQs-01) a GR&asymp;17,8% (M-CMQs-35). As análises de MEV revelaram que as membranas reticuladas M-CMQs são estruturas porosas que apresentam maior densidade de poros aparentes quanto maiores os valores de Mve GR. Entretanto, as membranas preparadas a partir de CMQs de elevada massa molar (Mv&gt;94.000 g.mol-1) e pouco reticuladas (GR&lt;10%), apresentaram propriedades mecânicas superiores em termos de resistência máxima à tração (&gt;170 kPa) e elongação máxima à ruptura (&gt;40%). Por outro lado, as membranas mais susceptíveis à degradação enzimática foram aquelas preparadas a partir de CMQs de baixa massa molar (Mv&asymp;43.000 g.mol-1) e que exibiram baixos graus de reticulação (GR&lt;11%). Hidrogéis estáveis de quitosana sem o uso de qualquer agente de reticulação externo foram produzidos a partir da gelificação de soluções aquosas de quitosana com solução de NaOH ou vapor de NH3. Os hidrogéis produzidos a partir de soluções de quitosana de elevada massa molar média ponderal (Mw&asymp;640.000 g.mol-1) e extensivamente desacetilada (DA&asymp;2,8%) em concentrações poliméricas acima 2,0%, exibiram melhores propriedades mecânicas com o aumento da concentração polimérica, devido à formação de numerosos emaranhamentos físicos das cadeias poliméricas em solução. Os resultados mostram que as propriedades físico-químicas e mecânicas dos hidrogéis de quitosana podem ser controladas variando a concentração do polímero e o processo de gelificação. A avaliação biológica de tais hidrogéis para a regeneração de miocárdio infartado de ratos revelou que os hidrogéis de quitosana preparados a partir de soluções de polímero a 1,5% foram perfeitamente incorporados sobre a superfície do epicárdio do coração e apresentaram degradação parcial acompanhada por infiltração de células mononucleares. / The aim of this study was to produce and characterize porous membranes of carboxymethylchitosan and chitosan-based hydrogel with physicochemical and mechanical properties appropriate for applications in tissue engineering. For this, chitosans with different degrees of acetylation (4,0%&lt;GA&lt;40%) and high viscosity average molecular weight (Mv&gt;750.000 g.mol-1) were produced by application of consecutive processes of ultrasound-assisted deacetylation (USAD) of the beta-chitin extracted from squid pens (Doryteuthis spp.). The carboxymethylation of extensively deacetylated chitosan (Qs-3; DA=4%) was carried out by reaction with monochloroacetic acid in isopropanol/aqueous NaOH, producing CMQs-0 sample (GS&asymp;0,98; Mv&asymp;190.000 g.mol-1). The ultrasonic irradiation was employed to depolymerize the CMQs-0 samples by irradiation for 1 h and 3 h, resulting in CMQs-1 samples (Mv&asymp;94.000 g.mol-1) and CMQs-3 (Mv&asymp;43.000 g.mol-1), respectively. For the production of crosslinked membranes, genipin was added at different concentrations (1,0x10-4 mol.L-1, 3,0x10-4 mol.L-1 ou 5,0x10-4 mol.L-1) in the aqueous solutions of CMQs, which were poured into Petri dishes and the crosslinking reaction proceeded for 24 h. Then, the crosslinked membranes (M-CMQs) were lyophilized, neutralized, washed, and lyophilized again resulting in nine samples which were characterized by crosslinking degree (CrD), swelling ration (SR), morphology, mechanical properties and the susceptibility to enzymatic degradation by lysozyme. The crosslinking degree (CrD) increased with increasing concentration of genipin used in the reaction, varying from CrD&asymp;3.3% (M-CMQs-01) to CrD&asymp;17.8% (M-CMQs-35). The SEM analysis showed that the crosslinked membranes M-CMQs are porous structures that have a higher apparent pores density with increasing values of Mv and CrD. However, the membranes prepared from high molecular weight CMQs (Mv&gt;94.000 g.mol-1) and low crosslinked (GR&lt;10%) showed superior mechanical properties in terms of ultimate tensile strength (&gt;170 kPa) and maximum elongation at break (&gt;40%). However, the more susceptible membrane to enzymatic degradation was prepared from low molecular weight CMQs (Mv&asymp;43.000 g.mol-1) and low cross-linking degrees (GR&lt;11%). Stable chitosan hydrogels without any external crosslinking agent was successfully achieved by inducing the gelation of a viscous chitosan solution with aqueous NaOH or gaseous NH3. The hydrogels produced from high molecular weight (Mw&asymp;640.000 g.mol-1) and extensively deacetylated chitosan (DA&asymp;2,8%) at polymer concentrations above &asymp;2.0% exhibited improved mechanical properties due to the increase of the chain entanglements and intermolecular junctions. The results also show that the physicochemical and mechanical properties of chitosan hydrogels can be controlled by varying their polymer concentration and by controlling the gelation kinetics, i.e. by using different gelation routes. The biological evaluation of such hydrogels for regeneration of infarcted myocardium revealed that chitosan hydrogels prepared from 1.5% polymer solutions was perfectly incorporated onto the epicardial surface of the heart and presented partial degradation accompanied by mononuclear cell infiltration.

A fibroína de seda é uma proteína sintetizada pela espécie Bombyx mori, popularmente conhecida como bicho-da-seda. O casulo de Bombyx mori é composto por fibras de fibroína e pela sericina, responsável por unir os fios de fibroína. A fibroína é um polímero natural bastante versátil e pode ser processada de maneira a formar materiais como filmes, microesferas e hidrogéis. Os hidrogéis são redes tridimensionais formadas por macromoléculas e capazes de absorver grande quantidade de água sem perder sua integridade estrutural. Devido à características como biocompatibilidade, elevado teor de água e boas propriedades de difusão de oxigênio e nutrientes, os hidrogéis são amplamente utilizados em pesquisa biomédica. A fibroína é biodegradável, termicamente estável, altamente cristalina, flexível, resistente à tração, além de insolúvel em água e na maioria dos solventes orgânicos. A fibroína derivada das sedas Frison Extra e Meada 21 Denier foi separada da sericina pelo processo de degomagem, onde as fibras de seda foram imersas em soluções alcalinas e submetidas à aquecimento com posterior remoção de sericina. Os fios de fibroína foram dispersos nas soluções de CaCl2:H2O, LiCl:H2O e LiCl:EtOH:H2O. Diferenças nos tempos de dispersão para amostras distintas degomadas ou não foram observadas, bem como para cada um dos sistemas salino/solvente empregados. Após o processo de dispersão da fibroína as dispersões obtidas foram caracterizadas quanto à textura e reologia. As amostras não degomadas apresentaram maior firmeza e aumento do módulo elástico G\'. Algumas amostras contendo sericina ou etanol apresentaram comportamento newtoniano. Em uma segunda etapa, as amostras foram dialisadas para a produção do hidrogel e em seguida liofilizadas. Não houveram diferenças entre os tempos de gelificação para amostras distintas. Finalmente objetivou-se a caracterização dos hidrogéis obtidos por meio de ensaios termogravimétricos, difratométricos, espectrofotométricos e microscópicos. Todos os hidrogéis de fibroína de seda apresentaram alta resistência térmica, com presença predominante da conformação em folha-&#946; da fibroína. Morfologicamente, os hidrogéis obtidos a partir de dispersões em LiCl:EtOH:H2O e CaCl2:EtOH:H2O apresentaram aspecto de rede enovelada, enquanto que os hidrogéis oriundos de dispersões em LiCl:H2O apresentaram estrutura lamelar. / The silk fibroin is a protein synthesized by Bombyx mori species, popularly known as silkworm silk. The Bombyx mori cocoon is composed of fibroin fibers and the sericin protein, which is responsible for joining the fibroin yarns. The fibroin is a quite versatile natural polymer and can be processed to form materials such as films, microspheres and hydrogels. Hydrogels are three-dimensional networks formed by macromolecules and capable of absorbing large quantities of water without losing their structural integrity. Due to biocompatibility, ability to mimic biological tissues, high water content and good diffusion properties of oxygen and nutrients, hydrogels are widely used in biomedical research. The fibroin is biodegradable, thermally stable, highly crystalline, flexible and tensile resistant. Besides, it is insoluble in water and in most organic solvents. The fibroin from Frison Extra and Meada 21 Denier silks was separated from the sericin by the degumming process, whereby the silk fibers were immersed in alkaline solutions and subjected to heating with subsequent dissolution and removal of sericin. Fibroin yarns were dispersed in various solutions: CaCl2:H2O; LiCl:H2O; and LiCl:EtOH:H2O. It was observed that according to the fibroin type and solvent solution used the time to achieve dispersion varied. Texture and rheology were determined for every sample after dispersion. All non-degummed samples had shown increased firmness and elastic module G\'. It was observed that the samples presented a wide behavior range, some that contained sericin or ethanol presented Newtonian behavior. Subsequently the samples were dialyzed to obtain the hydrogels and lyophilized. All samples (with exception of two) have formed hydrogels in a 24 hours period. The lyophilized hydrogels were analyzed by thermogravimetry, diffractometry, spectrophotometry and microscopy. All silk fibroin hydrogels presented high thermic resistance with &#946;-sheet predominance. Morphologically, all hydrogels obtained from LiCl:EtOH:H2O and CaCl2:EtOH:H2O solutions had shown entangled aspect wile hydrogels from LiCl:H2O solutions had shown lamellar structures.

O açaí (Euterpe oleracea) é uma palmeira nativa do Brasil, distribuída por toda a bacia amazônica. Rico em ácidos graxos essenciais (principalmente o ácido oleico e o ácido linoleico), o óleo de açaí previne condições anormais da pele, como dermatites, escamações e ressecamento, e auxilia no processo de regeneração do tecido epitelial. Conhecendo-se os benefícios dos hidrogéis como curativos, esse trabalho objetivou desenvolver hidrogéis de poli(N-vinil-2- pirrolidona) (PVP) como um sistema de liberação de óleo de açaí para uso tópico em desordens cutâneas. Desconhecendo-se o comportamento do óleo de açaí frente à radiação, foi avaliada a composição de ácidos graxos do óleo antes e após ser submetido à radiação. Duas diferentes matrizes de hidrogel de PVP foram avaliadas quanto às suas características físicas e químicas por meio de ensaios de intumescimento, fração gel, propriedades mecânicas e citotoxicidade in vitro. As duas matrizes foram consideradas adequadas para serem utilizadas como sistema de liberação. Os dispositivos foram obtidos pela incorporação do óleo de açaí nas matrizes de hidrogel de PVP e submetidos aos ensaios de intumescimento, fração gel, propriedades mecânicas e citotoxicidade in vitro, além dos ensaios de caracterização por microscopia eletrônica de varredura e irritação cutânea primária in vivo. Os dois dispositivos de hidrogel de PVP foram submetidos ao ensaio de cinética de liberação por 24 h e o óleo de açaí liberado foi quantificado por cromatografia a gás acoplada a espectrometria de massas, e se mostraram satisfatórios para compor um sistema de liberação de ativos. / Acaí (Euterpe oleracea) is a native palm of Brazil, distributed for the entire Amazonian basin. Rich in essentials fatty acids (mainly oleic acid and linoleic acid), acaí oil prevents abnormal conditions of the skin, as dermatitis and drying, and assists in the regeneration of the epidermis. The benefits of the hydrogels are known as dressings. The purpose of this study was to develop devices for controlled release of acaí oil on poly (N-vynil-2-pyrrolidone) (PVP) hydrogels. The behavior of the acai oil front to the radiation was evaluated by the composition of fatty acids of the oil before and after irradiation. Two different matrices of PVP hydrogel were evaluated physically and chemically through assays of swelling, gel fraction, mechanical proprieties and in vitro cytotoxicity. Both matrices were considered adjusted to be used as an active release system. The devices were obtained by acai oil immobilization in PVP hydrogel matrices, were also characterized through assays of sweeling, gel fraction, mechanical proprieties and in vitro cytotoxicity. Moreover, they were characterized by assays of scanning electron microscopy and in vivo primary cutaneous irritation. Both devices were submitted to assay of active release kinetics, and the acai oil was quantified by gas chromatography coupled with mass spectrometry. The devices showed to be satisfactory to compose a release system of actives.

O açaí (Euterpe oleracea) é uma palmeira nativa do Brasil, distribuída por toda a bacia amazônica. Rico em ácidos graxos essenciais (principalmente o ácido oleico e o ácido linoleico), o óleo de açaí previne condições anormais da pele, como dermatites, escamações e ressecamento, e auxilia no processo de regeneração do tecido epitelial. Conhecendo-se os benefícios dos hidrogéis como curativos, esse trabalho objetivou desenvolver hidrogéis de poli(N-vinil-2- pirrolidona) (PVP) como um sistema de liberação de óleo de açaí para uso tópico em desordens cutâneas. Desconhecendo-se o comportamento do óleo de açaí frente à radiação, foi avaliada a composição de ácidos graxos do óleo antes e após ser submetido à radiação. Duas diferentes matrizes de hidrogel de PVP foram avaliadas quanto às suas características físicas e químicas por meio de ensaios de intumescimento, fração gel, propriedades mecânicas e citotoxicidade in vitro. As duas matrizes foram consideradas adequadas para serem utilizadas como sistema de liberação. Os dispositivos foram obtidos pela incorporação do óleo de açaí nas matrizes de hidrogel de PVP e submetidos aos ensaios de intumescimento, fração gel, propriedades mecânicas e citotoxicidade in vitro, além dos ensaios de caracterização por microscopia eletrônica de varredura e irritação cutânea primária in vivo. Os dois dispositivos de hidrogel de PVP foram submetidos ao ensaio de cinética de liberação por 24 h e o óleo de açaí liberado foi quantificado por cromatografia a gás acoplada a espectrometria de massas, e se mostraram satisfatórios para compor um sistema de liberação de ativos. / Acaí (Euterpe oleracea) is a native palm of Brazil, distributed for the entire Amazonian basin. Rich in essentials fatty acids (mainly oleic acid and linoleic acid), acaí oil prevents abnormal conditions of the skin, as dermatitis and drying, and assists in the regeneration of the epidermis. The benefits of the hydrogels are known as dressings. The purpose of this study was to develop devices for controlled release of acaí oil on poly (N-vynil-2-pyrrolidone) (PVP) hydrogels. The behavior of the acai oil front to the radiation was evaluated by the composition of fatty acids of the oil before and after irradiation. Two different matrices of PVP hydrogel were evaluated physically and chemically through assays of swelling, gel fraction, mechanical proprieties and in vitro cytotoxicity. Both matrices were considered adjusted to be used as an active release system. The devices were obtained by acai oil immobilization in PVP hydrogel matrices, were also characterized through assays of sweeling, gel fraction, mechanical proprieties and in vitro cytotoxicity. Moreover, they were characterized by assays of scanning electron microscopy and in vivo primary cutaneous irritation. Both devices were submitted to assay of active release kinetics, and the acai oil was quantified by gas chromatography coupled with mass spectrometry. The devices showed to be satisfactory to compose a release system of actives.

"Cellulose nanocrystals, one of the most abundant materials in nature, have attracted great attention in the biomedical community due to qualities such as supreme mechanical properties, biodegradability, biocompatibility and low density. In this research, we are interested in developing a bio-inspired material-by-design approach for cellulose-based composites with tailored interfaces and programmed microstructures that could provide an outstanding strength-to-weight ratio. After a preliminary study on some of the existing biomaterials, we have focused our research on studying the nanostructure and nanomechanics of the bamboo fiber, a cellulose-based biocomposite, designed by nature with remarkable strength-to-weight ratio (higher than steel and concrete). We have utilized atomistic simulations to investigate the mechanical properties and mechanisms of interactions between cellulose nanofibrils and the bamboo fiber matrix which is an intertwined hemicellulose and lignin called lignin-carbohydrate complex (LCC). Our results suggest that the molecular origin of the rigidity of bamboo fibers comes from the carbon-carbon or carbon-oxygen covalent bonds in the main chain of cellulose. In the matrix of bamboo fiber, hemicellulose exhibits larger elastic modulus and glass transition temperature than lignin whereas lignin shows greater tendency to adhere to cellulose nanofibrils. Consequently, the role of hemicellulose is found to enhance the thermodynamic properties and transverse rigidity of the matrix by forming dense hydrogen bond networks, and lignin is found to provide the strength of bamboo fibers by creating strong van der Waals forces between nanofibrils and the matrix. Our results show that the amorphous region of cellulose nanofibrils is the weakest interface in bamboo microfibrils. We also found out that water molecules enhance the mechanical properties of lignin (up to 10%) by filling voids in the system and creating hydrogen bond bridges between polymer chains. For hemicellulose, however, the effect is always regressive due to the destructive effect of water molecules on the hydrogen bond in hemicellulose dense structure. Therefore, the porous structure of lignin supports the matrix to have higher rigidity in the presence of water molecules. "