Nanomaterials have attracted considerable attention during the past decades due to their unique and fascinating properties. However, this class of materials is not an invention of modern age. People have been using nanomaterials for centuries, although unwittingly. Probably the most famous example for the usage of nanomaterials in ancient times is the Lycurgus Cup, a Roman glass cage cup created in the 4th century which changes the colour of its glass from green to ruby depending on the illumination conditions. The foundation for the development of the field of nanotechnology was laid by the speech of Feynman “There is plenty of room at the bottom” in 1959, in which he spoke about the principles of miniaturisation as low as to the atomic level. Today, modern nanotechnology made it its business to purposefully develop and synthesise nanomaterials as well as to face their applications in various fields, such as microelectronics, catalysis or biomedicine. However, the term “nanomaterials” does not solely involve the nanoparticulate units itself, but also their arrangement into two- or three-dimensional structures. Thereby, the maintenance of the nanoscale properties is one of the main challenges. This task was focussed by this work implied the preparation and macroscale arrangement of fluorescent QDs while preserving their optical properties. The main achievement of this work was the development of a novel aerogel material with non-quenching PL behaviour by using silica coated QDs as nanoparticulate building units. In comparison to other monolithic silica-QD structures or aerogels from pure QDs, a defined and controllable distance between the fluorescent QDs is provided in these structures by the silica shell. The spacing was shown to efficiently disable energy transfers so that no spectral shifts, lifetime shortening or PL QY losses are observed during the colloid to gel transition. The silica shell, established by a standard reverse microemulsion approach, was found to exhibit a certain porosity, which was proven by gas adsorption measurements. Existing cavities in the micro- and mesoporous range were found to allow small species such as metal ions to pass through the shell and interact with the QD core causing a detectable change of the PL intensity, which makes these materials suitable for future sensing applications. The gel preparation was based on a metal ion assisted complexation approach, which requires tetrazole functionalisation of the nanoparticulate building units. A major development in this work that permitted this gelation approach for silica-QDs was the development of a novel tetrazole-silane ligand. TMSPAMTz was specifically designed to bind to the silica surface of silica-QDs in aqueous solution and was prepared by a covalent coupling of an alkyl chained silane with a 5-subsituted tetrazole ring. Network formation is subsequently achieved by the interconnection of negatively charged tetrazole rings with metal ions, which allows for a broad spectrum of aerogel materials from different NP species as well as their mixtures as long as tetrazole capping is provided. Considering this diversity and the disabling of energy transfers, straightforward colour tuning was demonstrated herein by mixing differently emitting silica-QD species which gives great prospects for lighting applications. Furthermore, the possibility of plasmon enhanced emission was presented for mixed Au NP/silica-QD gels. With respect to future sensing applications, thin porous films from silica-QDs gels were prepared, which showed a promising concentration dependant PL quenching for the model analyst hydrogen peroxide. However, the film reproducibility of the applied drop-cast coating method was insufficient. As a suggestion to this, a LbL method was presented, wherein a gel is subsequently grown with the metal ion assisted complexation approach. In addition to the tetrazole ligands on the NP surface, tetrazole-silane ligands were used in this approach to functionalise the glass substrate surface. By this, homogeneous gel films of distinct thickness can be grown while the use of organic polymers can be completely avoided. Besides the preparation of NP assemblies, standard Cd-based QD materials as well as Au NPs of different sizes and shape, recent progresses in the synthesis of InP-based QDs were presented in this work. A thorough investigation and understanding of the growth influencing parameters allowed for the establishment of preparation routes for In(Zn)P/GaP/ZnS core/shell/shell QDs with emission wavelengths tuneable within a large range from 500 to 650 nm, narrow peak widths of 45 to 70 nm and PL QYs up to 60%. Successful incorporation of these QDs into salt matrices was further demonstrated. The resulting composite materials are very photostable and suitable as colour conversion materials for solid state lighting, as was clearly pointed out by a self-prepared WLED that met the standard commercial LEDs.

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Tesis por compendio / [ES] El objetivo de esta tesis doctoral ha sido el diseño y caracterización estructural de estructuras tipo gel basadas de polisacáridos extraídos de biomasa acuática con interés para aplicaciones relacionadas con la alimentación. Las propiedades de los polisacáridos extraídos de algas y plantas acuáticas son adecuadas para producir diferentes estructuras tipo gel basadas en la formación de redes reticuladas, como hidrogeles, aerogeles y emulsion-gels. En la primera parte de esta tesis se investigaron los diferentes mecanismos de gelificación de polisacáridos sulfatados, así como los parámetros que afectan a la estructura y las propiedades funcionales de los hidrogeles obtenidos. En base a los resultados, se evaluó la potencial aplicación de los hidrogeles y aerogeles de agar y k-carragenato para encapsular una proteína alimentaria modelo como la caseína, explorando así el efecto protector contra la hidrólisis enzimática tras digestiones gastrointestinales simuladas. En la segunda parte de esta tesis, se desarrollaron estructuras de aerogeles mediante la valorización de una fuente de biomasa residual infrautilizada, como es el Arundo donax. Con esta biomasa se generaron fracciones celulósicas con diferentes grados de purificación y extractos bioactivos solubles en agua, que posteriormente se utilizaron para producir aerogeles bioactivos híbridos. La estructura altamente porosa y la elevada capacidad de sorción de los aerogeles los convierten en excelentes candidatos para la sustitución de las almohadillas absorbentes para mantener la calidad de los productos cárnicos envasados. Los emulsion-gels son reconocidos por su gran potencial como ingredientes funcionales en la industria alimentaria como modificadores de textura y como sustitutos de grasas sólidas. Además, pueden utilizarse como vehículo para la liberación controlada de compuestos bioactivos liposolubles. Así, en la última parte de esta tesis, se investigó la naturaleza de las interacciones entre los componentes en las formulaciones de emulsion-gels basadas en polisacáridos y se relacionó con su estructura y comportamiento mecánico y reológico. Después de estudiar el mecanismo de gelificación de los emulsion-gels de carragenato, estos sistemas se adaptaron y utilizaron para dos diferentes aplicaciones relevantes para los sectores de alimentación y biomedicina. En primer lugar, se produjeron y evaluaron estructuras gelificadas a partir de emulsion-gels de agar y k-carragenato y aerogeles cargados de aceite como encapsulantes de un bioactivo lipofílico como la curcumina. Los resultados mostraron que el tipo de polisacárido y el estado físico de las redes del gel tenían un impacto en la estructura de los productos de la digestión. Por otro lado, se evaluó el potencial de los emulsion-gels basados en polisacáridos sulfatados (k-carragenato y agar) para la producción de un material capaz de simular tejido graso. Los resultados evidencian que los emulsions-gels de agar son adecuadas para producir materiales que simulan las propiedades dieléctricas para imitar tejidos de bajo y alto contenido en agua. / [CA] L'objectiu d'aquesta tesi doctoral ha sigut, el disseny i caracterització estructural d'estructures tipus gel, basades en polisacàrids extrets de biomassa aquàtica amb interès per a aplicacions relacionades amb l'alimentació. Les propietats dels polisacàrids extrets d'algues i plantes aquàtiques, són adequades per a produir diferents estructures tipus gel basades en la formació de xarxes reticulades, com a hidrogels, aerogels i emulsió-gels. En la primera part d'aquesta tesi es van investigar els diferents mecanismes de gelificació de polisacàrids sulfatats, així com els paràmetres que afecten l'estructura i les propietats funcionals dels hidrogels obtinguts. Sobre la base dels resultats, es va avaluar la potencial aplicació dels hidrogels i aerogels d'agar i k-carraguenina per a encapsular una proteïna alimentària model com la caseïna, explorant així l'efecte protector contra la hidròlisi enzimàtica després de digestions gastrointestinals simulades. A la segona part d'aquesta tesi, es van desenvolupar estructures d' aerogels mitjançant la valorització d'una font de biomassa residual infrautilitzada, com és el Arundo donax. Amb aquesta biomassa es van generar fraccions cel·lulòsiques amb diferents graus de purificació i extractes bioactius solubles en aigua, que posteriorment es van utilitzar per a produir aerogels bioactius híbrids. L'estructura altament porosa i l'elevada capacitat de sorció dels aerogels els converteixen en excel·lents candidats per a la substitució dels coixinets absorbents per a mantenir la qualitat dels productes carnis envasats. Els emulsió-gels són reconeguts pel seu gran potencial com a ingredients funcionals en la indústria alimentària com a modificadors de textura i com a substituts de greixos sòlids. A més, poden utilitzar-se com a vehicle per a l'alliberament controlat de compostos bioactius liposolubles. Així, a l'última part d'aquesta tesi, es va investigar la naturalesa de les interaccions entre els components dins les formulacions d' emulsió-gels basades en polisacàrids i es va relacionar amb la seua estructura i comportament mecànic i reològic. Després d'estudiar el mecanisme de gelificació dels emulsió-gels de carraguenina, aquests sistemes es van adaptar i es van utilitzar per a dues aplicacions diferents, rellevants per als sectors de l' alimentació i la biomedicina. En primer lloc, es van produir i van avaluar estructures gelificades a partir de emulsió-gels d'agar i k-carraguenina i aerogels carregats d'oli com a encapsulants d'un bioactiu lipofílic com la curcumina. Els resultats van mostrar que el tipus de polisacàrid i l'estat físic de les xarxes del gel tenien un impacte en l'estructura dels productes de la digestió. D'altra banda, es va avaluar el potencial dels emulsió-gels basats en polisacàrids sulfatats (k-carraguenina i agar) per a la producció d'un material capaç de simular teixit gras. Els resultats evidencien que els emulsió-gels d'agar són adequats per a produir materials que simulen les propietats dielèctriques podentimitar teixits de baix i alt contingut en aigua. / [EN] The aim of this doctoral thesis was to design and characterize the structure of gel-like structures based on polysaccharides extracted from aquatic biomass, with interest for food-related applications. The properties of polysaccharides extracted from seaweeds and aquatic plants make them suitable to produce a range of gel-like structures based on the formation of interconnected networks, such as hydrogels, aerogels and emulsion-gels. In the first part of this thesis, the different gelation mechanism of sulphated polysaccharides and the parameters affecting the structure and functional properties of the obtained hydrogels were investigated. Based on the results, the potential application of agar and k-carrageenan hydrogels and aerogels to encapsulate a model food protein such as casein was evaluated, thus exploring the protective effect against the enzymatic hydrolysis upon simulated gastrointestinal digestions. In the second part of this thesis, aerogel structures were developed by valorising an underutilized waste biomass source such as Arundo donax. This biomass was used to generate cellulosic fractions with different purification degrees and water-soluble bioactive extracts, which were subsequently used to produce hybrid bioactive aerogels. The highly porous structure and high sorption capacity of aerogels make them excellent candidates for the replacement of absorbent pads to maintain the quality of packaged meat products. Emulsion-gels are recognized for their great potential as functional ingredients in the food industry to modify texture and for solid fat replacement. Moreover, they can be used as a delivery vehicle for the controlled release of fat-soluble bioactive compounds. Thus, in the last part, the nature of interactions between the components in polysaccharide-based emulsion-gel formulations was investigated and related to their structure and mechanical and rheological behavior. After studying the gelation mechanism of carrageenan emulsion-gels, these systems were adapted and used for two different applications relevant to the food and biomedicine sectors. Firstly, oil-filled gel-like structures from agar and k-carrageenan emulsion-gels and oil-filled aerogels were produced and evaluated as carriers of a lipophilic bioactive such as curcumin. The results showed that the polysaccharide type and the physical state of the gel network had an impact on the structure of the digestion products. On the other hand, the potential of emulsion-gels based on sulphated polysaccharides (k-carrageenan and agar) for the production of tissue mimicking phantoms was evaluated. The results evidence that the agar emulsion-gels are suitable to produce materials simulating the dielectric properties to mimic low- and high-water content tissues. / Synchrotron experiments were performed at NCD beamline at ALBA Synchrotron with the collaboration of ALBA staff (2018022638 project). This work was financially supported by the grant RTI2018-094268-B-C22 (MCIU/AEI/FEDER, UE). Part of this work was supported by the COST Action ES1408 European network for algal-bioproducts (EUALGAE). Cynthia Fontes-Candia is recipient of a pre-doctoral grant from CONACYT (MEX/Ref. 306680). The projects RTI2018-094268-B-C22 and RTI2018-094408-J-I00 were funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. This work has also received financial support from project PID2019-107663RB-I00 from the Spanish Ministry of Science and Innovation (MICINN). Cynthia Fontes-Candia is recipient of a pre-doctoral grant from CONACYT (MEX/Ref. 306680). Marta Martinez-Sanz is recipient of a Juan de la Cierva (IJCI-2015-23389) contract from the Spanish Ministry of Economy, Industry and Competitiveness. / Fontes Candia, C. (2022). Development and Characterization of Gel-Like Structures from Aquatic Biomass for Food Applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/181564 / Compendio

L'étude de la fusion par confinement inertiel du mélange deutérium + tritium (DT) est une problématique depuis longtemps abordée par le CEA. Les expérimentations liées à cette thématique, effectuées prochainement au sein du laser mégajoule (LMJ), nécessitent l'utilisation de matériaux aux propriétés particulières. Cela concerne entre autres les mousses de polymères (aérogels organiques) composant les cibles de pré-ignition. De tels matériaux doivent notamment associer une importante porosité à une forte teneur métallique (1% atomique de Ti), tout en étant compatible avec les procédés de préparation utilisés. Dans ce contexte, un nouveau complexe polymérisable de titane a été préparé et caractérisé par plusieurs techniques d'analyses. Ce monomère dispose d'une forte teneur métallique tout en présentant une bonne stabilité vis-à-vis l'air et l'humidité. Sa copolymérisation radicalaire selon différentes conditions suivie d'un séchage en condition supercritique a permis l'obtention d'une série d'aérogels organiques. Les caractérisations chimiques (RMN, infrarouge et analyses élémentaires) ainsi que les caractérisations structurales (MEB-EDS, MET, mesure des isothermes d'adsorption/désorption de l'azote et SAXS) de ces polymères ont permis de valider les critères mentionnés dans notre cahier des charges. En outre, ces données ont permis de déterminer les mécanismes de formation de la nanostructure des mousses. / Inertial Confinement Fusion (ICF) is a technique widely studied by the French atomic commission (CEA). Experiments will be performed within the Laser Megajoule (LMJ). They require innovative materials like organic aerogels that constitute laser targets. Such polymeric material must provide both a high porosity and a significant titanium percentage (1 atom %). Moreover, the monomers developed must be compatible with the synthesis procedure already in use. According to these specifications, a new polymerizable titanium complex was synthesized and fully characterized. This air and moisture-stable monomer provides a high metal percentage. Its free-radical cross-linked copolymerization affords several titanium-containing polymers. These gels were dried under supercritical conditions and organic aerogels were obtained. The chemical compositions of these materials were investigated by NMR, IR and elemental analysis while their structure was characterized by MEB-EDS, MET, N2 adsorption/desorption isotherms measurements and SAXS. The data collected fit the specification requirements. Moreover, the mechanisms responsible of the foam nanostructure formation were discussed.

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd–Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd–Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd–Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd–Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd–Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd–Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd–Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

Ce travail de recherche présente la préparation et la caractérisation de matériaux monolithiques hautement poreux dérivés majoritairement de ressources naturelles. L'objectif était de préparer de nouveaux gels biosourcés jusqu'à 91%, de proposer des alternatives au séchage supercritique au CO2, et d'étudier quelques propriétés d'intérêt de tels gels après séchage, non seulement à l'état organique mais, dans certains cas, après pyrolyse pour obtenir des gels de carbone. A ces fins, le tannin et le soja ont été testés comme précurseurs, à différentes concentrations et différents pH, et trois voies de séchages ont été utilisées : supercritique, lyophilisation et séchage évaporatif. Les gels obtenus ont été caractérisés en termes de densité, porosité, distributions de tailles de pores et surfaces spécifiques, qu'ils soient sous forme organique ou carbonée selon l'application envisagée ou le type de porosité attendue. Leurs propriétés mécaniques et thermiques ont aussi été mesurées. La très large gamme de textures poreuses obtenues a permis de proposer des applications en tant qu'isolants thermiques, supports de catalyseur, ou électrodes de condensateur électrochimiques, selon les cas / This manuscript presents the preparation and the characterization of highly porous monolithic materials mainly derived from natural resources. The objectives were to: (i) develop new gels, biosourced up to the 91% level; (ii) suggest alternatives to supercritical drying in CO2, and (iii) investigate properties of interest for such gels in the organic state and, in some cases, after pyrolysis for obtaining carbon gels. For those purposes, tannin and soy flour were tested as precursors, at different concentrations and different pH, and three ways of drying were used: supercritical drying, freeze drying and evaporative drying. The obtained gels were characterized in terms of density, porosity, pore size distributions and specific surface area, whether in organic or in carbon form, depending on the intended application or expected type of porosity. Mechanical and thermal properties were also measured. The obtained broad range of porous textures allowed suggesting applications such as thermal insulators, catalyst supports or electrodes for electrochemical capacitors

Aus CdTe- und Edelmetallnanopartikeln werden 3-dimensionale Netzwerkstrukturen aufgebaut, welche durch einen überkritischen Trocknungsprozess zu hochporösen, weitverzweigten Halbleiter-Metall-Nanokompositen, sogenannten Aerogelen, umgewandelt werden. Zunächst werden Thiol-stabilisierte CdTe- und Edelmetallnanopartikel im wässrigen Milieu hergestellt und deren Morphologie und optischen Eigenschaften umfangreich mittels UV-Vis-Spektroskopie, Fluoreszenzspektroskopie und -lebensdauermessung, ICP-OES, TEM, STEM-EDX und AFM charakterisiert. Als Metallkomponente kamen Gold-, Palladium- sowie bimetallisch gemischte Gold-Palladium-Nanopartikel zum Einsatz. Die Gelierung der Nanopartikellösungen erfolgt durch Vermischen der Kolloide und anschließender kontrollierter Destabilisierung mithilfe einer Xe-Dampflampe oder der Zugabe von Wasserstoffperoxid. Neben einer mechanistischen Beschreibung der Gelbildungsmethoden wurden die resultierenden Hydrogele und die aus der überkritischen Trocknung erhaltenen Aerogele bezüglich Zusammensetzung, Morphologie und optischen Eigenschaften mithilfe von TEM und REM jeweils gekoppelt mit EDX-Analyse, Stickstoff-Porosimetrie, diffuser Reflexionsspektroskopie, Fluoreszenzspektroskopie und Fluoreszenzlebensdauermessungen untersucht. Weiterhin wird die UV-Vis-Spektroskopie als Methode zur Konzentrationsbestimmung von Gold in Lösungen kolloidaler Gold-Nanopartikel validiert. Dabei wird die Absorption der Kolloide bei einer Wellenlänge von 400 nm als Maß verwendet. Die NP-Lösungen werden anhand der Parameter Partikelgröße, Oberflächenfunktionalität und der Oxidationsstufe des enthaltenen Goldes variiert. / 3-dimensional network structures are formed combining CdTe and noble metal nanoparticles. A supercritical drying process allows production of highly porous and widely branched semiconductor-metal nanohybrids, so-called aerogels. Primarily, thiol-capped CdTe and noble metal nanoparticles are synthesized in aqueous media and their morphology and optical properties are studied extensively using UV-Vis and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, ICP-OES, TEM, STEM-EDX and AFM. The metal entity involves gold and palladium nanoparticles as well as bimetallic mixed Au/Pd nanoparticles. After mixing of the different colloids gelation is induced by a controlled destabilization process using a Xenon lamp irradiation or the addition of hydrogen peroxide. Gelation techniques are described mechanistically. Resulting hydrogels and aerogels which are obtained by supercritical drying approach are characterized concerning composition, morphology and optical properties using TEM and SEM each coupled with EDX, nitrogen porosimetry, diffuse reflection spectroscopy, fluorescence spectroscopy and time-resolved fluorescence spectroscopy. Moreover, the UV-Vis spectroscopy is validated as a method to determine the gold concentration in gold nanoparticle solutions using the colloids absorbance at 400 nm as a measure. Gold nanoparticle solutions are varied concerning the parameters particle size, surface functionality and oxidation state of contained gold.

Aerogéis de hidroxipropil metilcelulose (HPMC) com diferentes graus de substituição por grupos metila (DS) e hidroxipropila (MS) foram preparados por liofilização utilizando diferentes ácidos como agentes de reticulação, a saber: ácido cítrico, ácido oxálico e ácido tereftálico. Nanocristais de celulose bacteriana (BCN) neutros e negativamente carregados foram utilizados como carga de reforço nas concentrações de 5% (m/m) e 15% (m/m) em relação à massa da matriz. Os resultados indicaram que HPMCs com menores valores de DS e maiores valores de MS resultam em aerogéis com maior eficiência na reticulação. Além disso, agentes de reticulação insolúveis em água minimizaram a capacidade de reticulação, enquanto agentes de reticulação com uma maior quantidade de grupos funcionais ácidos aumentaram a probabilidade e a eficiência da reação de reticulação das cadeias de HPMC. Os aerogéis apresentaram alta estabilidade em água, solventes orgânicos e meio ácido, além de apresentar resiliência quanto à deformação em meio aquoso. Os aerogéis apresentaram porosidade de ~98%, densidade média variando de 0,021 à 0,026 (± 0,002) g.cm-3, módulo de Young variando de 101 à 150 (± 19) kPa e capacidade média de absorção de água de 18 g de água/g de aerogel. A adição de carga de reforço resultou em um aumento de até 13% na densidade aparente do aerogel e um aumento médio de 20% no módulo de Young dos materiais. A morfologia dos poros dos aerogéis sintetizados é irregular, com ampla faixa de distribuição de tamanho de poros, podendo variar cerca de 5 µm a 500 µm. Nos aerogéis reforçados, as BCNs encontram-se preferencialmente no interior das paredes dos aerogéis, onde o reforço mecânico é mais eficiente. Isotermas de adsorção de 17α-etinilestradiol (EE) foram realizadas, resultando em capacidades de remoção de até 90%, com possibilidade de reciclo. As isotermas indicam que a matriz HPMC J5MS possui maior afinidade para adsorção de EE e que a adição de BCNs aumenta a afinidade das moléculas pelo substrato. As isotermas foram melhor ajustadas com o modelo de Freundlich, indicando que a adição de 5% de BCNs aumenta a capacidade de adsorção do aerogel, enquanto a adição de 15% de BCNs provoca uma diminuição nesta propriedade. / Aerogels of Hydroxypropyl methylcellulose (HPMC), with different degrees of substitution for methyl groups (MS) and hydroxypropyl groups (DS) were prepared by freeze-drying. The HPMCs were combined with three organic acids as crosslinking agents: citric acid, oxalic acid and terephthalic acid. Bacterial cellulose nanocrystals (BCN) neutral and negatively charged were used as reinforcement particles from 5% to 15% m/m in relation to the polymer mass. The results indicated that HPMC with lower DS and higher MS levels result in aerogels with higher crosslink efficiency. Besides that, crosslinking agents that are water insoluble minimized the crosslinking capacity, while crosslinking agents with more functional acid groups presented higher probability and efficiency in the crosslinking reaction. The aerogels presented high stability in water, organic solvents and acid media, and presented mechanical resilience in aqueous media. The resulting aerogels presented porosity of ~98%, average density of 0.021 to 0.026 (± 0.002) g.cm-3, Young modulus of 101 to 150 (± 19) kPa and an average capacity of water absorption of 18 g of water/g of aerogel. The addition of reinforcement particles resulted in an increase in density up to 13% and an average increase in the Young modulus of 20%. The morphology of the aerogels was irregular, with a wide pore size distribution, varying between de 5 µm a 500 µm. In the reinforced aerogels, the BCNs were found preferably inside the aerogels walls, were the mechanical reinforcement is more efficient. Adsorption isotherms of 17 ethinyl estradiol (EE) revealed removal capacity up to 90% and possibility of adsorbent recycling. The isotherms indicated that the HPMC J5MS has higher affinity for EE molecules and that the use of BCNs increases aerogels affinity. The isotherms were well fitted with the Freundlich model, indicating that the addition of 5% BCN increases the adsorption capacity of the aerogels, while the addition of 15 % BCN results in a decrease in this property.

Aerogéis de hidroxipropil metilcelulose (HPMC) com diferentes graus de substituição por grupos metila (DS) e hidroxipropila (MS) foram preparados por liofilização utilizando diferentes ácidos como agentes de reticulação, a saber: ácido cítrico, ácido oxálico e ácido tereftálico. Nanocristais de celulose bacteriana (BCN) neutros e negativamente carregados foram utilizados como carga de reforço nas concentrações de 5% (m/m) e 15% (m/m) em relação à massa da matriz. Os resultados indicaram que HPMCs com menores valores de DS e maiores valores de MS resultam em aerogéis com maior eficiência na reticulação. Além disso, agentes de reticulação insolúveis em água minimizaram a capacidade de reticulação, enquanto agentes de reticulação com uma maior quantidade de grupos funcionais ácidos aumentaram a probabilidade e a eficiência da reação de reticulação das cadeias de HPMC. Os aerogéis apresentaram alta estabilidade em água, solventes orgânicos e meio ácido, além de apresentar resiliência quanto à deformação em meio aquoso. Os aerogéis apresentaram porosidade de ~98%, densidade média variando de 0,021 à 0,026 (± 0,002) g.cm-3, módulo de Young variando de 101 à 150 (± 19) kPa e capacidade média de absorção de água de 18 g de água/g de aerogel. A adição de carga de reforço resultou em um aumento de até 13% na densidade aparente do aerogel e um aumento médio de 20% no módulo de Young dos materiais. A morfologia dos poros dos aerogéis sintetizados é irregular, com ampla faixa de distribuição de tamanho de poros, podendo variar cerca de 5 µm a 500 µm. Nos aerogéis reforçados, as BCNs encontram-se preferencialmente no interior das paredes dos aerogéis, onde o reforço mecânico é mais eficiente. Isotermas de adsorção de 17α-etinilestradiol (EE) foram realizadas, resultando em capacidades de remoção de até 90%, com possibilidade de reciclo. As isotermas indicam que a matriz HPMC J5MS possui maior afinidade para adsorção de EE e que a adição de BCNs aumenta a afinidade das moléculas pelo substrato. As isotermas foram melhor ajustadas com o modelo de Freundlich, indicando que a adição de 5% de BCNs aumenta a capacidade de adsorção do aerogel, enquanto a adição de 15% de BCNs provoca uma diminuição nesta propriedade. / Aerogels of Hydroxypropyl methylcellulose (HPMC), with different degrees of substitution for methyl groups (MS) and hydroxypropyl groups (DS) were prepared by freeze-drying. The HPMCs were combined with three organic acids as crosslinking agents: citric acid, oxalic acid and terephthalic acid. Bacterial cellulose nanocrystals (BCN) neutral and negatively charged were used as reinforcement particles from 5% to 15% m/m in relation to the polymer mass. The results indicated that HPMC with lower DS and higher MS levels result in aerogels with higher crosslink efficiency. Besides that, crosslinking agents that are water insoluble minimized the crosslinking capacity, while crosslinking agents with more functional acid groups presented higher probability and efficiency in the crosslinking reaction. The aerogels presented high stability in water, organic solvents and acid media, and presented mechanical resilience in aqueous media. The resulting aerogels presented porosity of ~98%, average density of 0.021 to 0.026 (± 0.002) g.cm-3, Young modulus of 101 to 150 (± 19) kPa and an average capacity of water absorption of 18 g of water/g of aerogel. The addition of reinforcement particles resulted in an increase in density up to 13% and an average increase in the Young modulus of 20%. The morphology of the aerogels was irregular, with a wide pore size distribution, varying between de 5 µm a 500 µm. In the reinforced aerogels, the BCNs were found preferably inside the aerogels walls, were the mechanical reinforcement is more efficient. Adsorption isotherms of 17 ethinyl estradiol (EE) revealed removal capacity up to 90% and possibility of adsorbent recycling. The isotherms indicated that the HPMC J5MS has higher affinity for EE molecules and that the use of BCNs increases aerogels affinity. The isotherms were well fitted with the Freundlich model, indicating that the addition of 5% BCN increases the adsorption capacity of the aerogels, while the addition of 15 % BCN results in a decrease in this property.