Hyaluronic Acid Aerogels Made Via Freeze-Thaw-Induced Gelation.

The biodegradability, biocompatibility, and bioactivity of hyaluronic acid (HA), a natural polysaccharide, combined with the low density, high porosity, and high specific surface area of aerogels attract interest for biomedical applications such as wound dressings. In this work, physically cross-linked HA aerogels were prepared via the freeze-thaw (FT) induced gelation method, solvent exchange, and drying with supercritical CO2. The morphology and properties of HA aerogels (volume shrinkage, density, and specific surface area) were investigated as a function of several process parameters: HA concentration, solution pH, number of FT cycles, and type of nonsolvent used during solvent exchange. We demonstrate that the HA solution pH plays a key role in the aerogel formation, as not all conditions result in materials with high specific surface area. HA aerogels were of low density (<0.2 g/cm3), high specific surface area (up to 600 m2/g), and high porosity (≥90%). Scanning electron microscopy pictures revealed that HA aerogels present a porous structure with meso- and small macropores. The results show that HA aerogels are promising biomaterials with tunable properties and internal structure that offer high potential as, e.g., wound dressings.

Release Kinetics of Dexamethasone Phosphate from Porous Chitosan: Comparison of Aerogels and Cryogels.

Porous chitosan materials as potential wound dressings were prepared via dissolution of chitosan, nonsolvent-induced phase separation in NaOH-water, formation of a hydrogel, and either freeze-drying or supercritical CO2 drying, leading to "cryogels" and "aerogels", respectively. The hydrophilic drug dexamethasone sodium phosphate was loaded by impregnation of chitosan hydrogel, and the release from cryogel or aerogel was monitored at two pH values relevant for wound healing. The goal was to compare the drug-loading efficiency and release behavior from aerogels and cryogels as a function of the drying method, the materials' physicochemical properties (density, morphology), and the pH of the release medium. Cryogels exhibited a higher loading efficiency and a faster release in comparison with aerogels. A higher sample density and lower pH value of the release medium resulted in a more sustained release in the case of aerogels. In contrast, for cryogels, the density and pH of the release medium did not noticeably influence release kinetics. The Korsmeyer-Peppas model showed the best fit to describe the release from the porous chitosan materials into the different media.

Crosslinker-Free Hyaluronic Acid Aerogels.

Aerogels based on hyaluronic acid (HA) were prepared without any chemical crosslinking by polymer dissolution, network formation via nonsolvent-induced phase separation, and supercritical CO2 drying. The influence of solution pH, concentration of HA, and type of nonsolvent on network volume shrinkage, aerogel density, morphology, and specific surface area was investigated. A marked dependence of aerogel properties on solution pH was observed: aerogels with the highest specific surface area, 510 m2/g, and the lowest density, 0.057 g/cm3, were obtained when the HA solution was at its isoelectric point (pH 2.5). This work reports the first results ever on neat HA aerogels and constitutes the background for their use as advanced materials for biomedical applications.

Cellulose Aerogel Microparticles via Emulsion-Coagulation Technique.

Cellulose aerogel microparticles were made via emulsification/nonsolvent induced phase separation/drying with supercritical CO2. Cellulose was dissolved in NaOH-based solvent with and without additives in order to control solution gelation. Two emulsions, cellulose solution/oil and cellulose nonsolvent/oil, were mixed to start nonsolvent induced phase separation (or coagulation) of cellulose inside each cellulose droplet leading to the formation of so-called microgels. Different options of triggering coagulation were tested, by coalescence of droplets of cellulose solution and cellulose nonsolvent and by diffusion of nonsolvent partly soluble in the oil, accompanied by coalescence. The second option was found to be the most efficient for stabilization of the shape of coagulated cellulose microgels. The influence of gelation on particle formation and aerogel properties was investigated. The aerogel particles' diameter was around a few tens of microns, and the specific surface area was 250-350 m2/g.

Mechanical properties of cellulose aerogels and cryogels.

Highly porous and lightweight cellulose materials were prepared via dissolution-coagulation and different drying routes. Cellulose of three different molecular weights was dissolved in an ionic liquid/dimethyl sulfoxide mixture. Drying was performed either with supercritical CO2 resulting in "aerogels", or via freeze-drying resulting in "cryogels". The influence of cellulose molecular weight, concentration and drying method on the morphology, density, porosity and specific surface area was determined. The mechanical properties of cellulose cryogels and aerogels under uniaxial compression were studied in detail and analyzed in the view of existing models developed for porous materials. It was demonstrated that the Poisson's ratio of cellulose aerogels is not equal to zero, contrary to what is usually reported in the literature, but decreases with an increase in density. Compressive modulus and yield stress of cryogels turned out to be higher than those of aerogels taken at the same density. This was interpreted by the different morphology of the porous materials studied.

An Opinion Paper on Aerogels for Biomedical and Environmental Applications.

Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be assessed for other technology sectors. Based on current efforts to address the material supply chain by a circular economy approach and longevity as well as quality of life with biotechnological methods, environmental and life science applications are two emerging market opportunities where the use of aerogels needs to be further explored and evaluated in a multidisciplinary approach. In this opinion paper, the relevance of the topic is put into context and the corresponding current research efforts on aerogel technology are outlined. Furthermore, key challenges to be solved in order to create materials by design, reproducible process technology and society-centered solutions specifically for the two abovementioned technology sectors are analyzed. Overall, advances in aerogel technology can yield innovative and integrated solutions for environmental and life sciences which in turn can help improve both the welfare of population and to move towards cleaner and smarter supply chain solutions.

Starch Aerogels: A Member of the Family of Thermal Superinsulating Materials.

Starch aerogels were prepared via dissolution in water (thermomechanical treatment), retrogradation, solvent exchange, and drying with supercritical CO2. Amylose content in starches was varied from 0 to 100%. The aerogels' bulk density, morphology, specific surface area, thermal conductivity, and mechanical properties under compression were investigated. Pea starch aerogels had one of the highest specific surface area and lowest density and thermal conductivity (0.021-0.023 W/m·K), with the latter indicating that a new thermal superinsulation material was obtained. A detailed study of the influence of processing parameters on pea starch aerogels properties showed the importance of retrogradation time which decreases specific surface area and increases mechanical properties and thermal conductivity. Finally, a comparison of starch aerogel thermal conductivity with that of other bioaerogels is performed.

Strong, Thermally Superinsulating Biopolymer-Silica Aerogel Hybrids by Cogelation of Silicic Acid with Pectin.

Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica-biopolymer hybrids are a promising alternative. A one-pot process to monolithic, superinsulating pectin-silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed "neck-free" nanoscale network structure with thicker struts. Such a design is superior to "neck-limited", classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica-biopolymer nanocomposite aerogels.

Diffusion of 1-ethyl-3-methyl-imidazolium acetate in glucose, cellobiose, and cellulose solutions.

Solutions of glucose, cellobiose and microcrystalline cellulose in the ionic liquid 1-ethyl-3-methyl-imidazolium ([C2mim][OAc]) have been examined using pulsed-field gradient (1)H NMR. Diffusion coefficients of the cation and anion across the temperature range 20-70 °C have been determined for a range of concentrations (0-15% w/w) of each carbohydrate in [C2mim][OAc]. These systems behave as an "ideal mixture" of free ions and ions that are associated with the carbohydrate molecules. The molar ratio of carbohydrate OH groups to ionic liquid molecules, α, is the key parameter in determining the diffusion coefficients of the ions. Master curves for the diffusion coefficients of cation, anion and their activation energies are generated upon which all our data collapses when plotted against α. Diffusion coefficients are found to follow an Arrhenius type behavior and the difference in translational activation energy between free and associated ions is determined to be 9.3 ± 0.9 kJ/mol.

Aeropectin: fully biomass-based mechanically strong and thermal superinsulating aerogel.

Monolithic pectin aerogels, aeropectins, were prepared via dissolution-gelation-coagulation and subsequent drying with supercritical CO2. Aeropectin had pore sizes that varied from mesopores to small macropores and compression moduli in the range from 4 to 18 MPa. Aeropectins show plastic deformation up to 60% strain before the pore walls collapse. Pectin aerogels have a thermal conductivity below that of air in ambient conditions, making them new thermal superinsulating fully biomass-based materials. The contribution of gas and solid conduction plus radiative heat transfer were determined and discussed.

Creating and exploring carboxymethyl cellulose aerogels as drug delivery devices.

Carboxymethyl cellulose (CMC) is a well-known cellulose derivative used in biomedical applications due to its biocompatibility and biodegradability. In this work, novel porous CMC materials, aerogels, were prepared and tested as a drug delivery device. CMC aerogels were made from CMC solutions, followed by non-solvent induced phase separation and drying with supercritical CO2. The influence of CMC characteristics and of processing conditions on aerogels' density, specific surface area, morphology and drug release properties were investigated. Freeze-drying of CMC solutions was also used as an alternative process to compare the properties of the as-obtained "cryogels" with those of aerogels. Aerogels were nanostructured materials with bulk density below 0.25 g/cm3 and high specific surface area up to 143 m2/g. Freeze drying yields highly macroporous materials with low specific surface areas (around 5-18 m2/g) and very low density, 0.01 - 0.07g/cm3. Swelling and dissolution of aerogels and cryogels in water and in a simulated wound exudate (SWE) were evaluated. The drug was loaded in aerogels and cryogels, and release kinetics in SWE was investigated. Drug diffusion coefficients were correlated with material solubility, morphology, density, degree of substitution and drying methods, demonstrating tuneability of new materials' properties in view of their use as delivery matrices.

Hydrophobic Modification of Pectin Aerogels via Chemical Vapor Deposition.

Pectin aerogels, with very low density (around 0.1 g cm-3) and high specific surface area (up to 600 m2 g-1), are excellent thermal insulation materials since their thermal conductivity is below that of air at ambient conditions (0.025 W m-1 K-1). However, due to their intrinsic hydrophilicity, pectin aerogels collapse when in contact with water vapor, losing superinsulating properties. In this work, first, pectin aerogels were made, and the influence of the different process parameters on the materials' structure and properties were studied. All neat pectin aerogels had a low density (0.04-0.11 g cm-1), high specific surface area (308-567 m2 g-1), and very low thermal conductivity (0.015-0.023 W m-1 K-1). Then, pectin aerogels were hydrophobized via the chemical vapor deposition of methyltrimethoxysilane using different reaction durations (2 to 24 h). The influence of hydrophobization on material properties, especially on thermal conductivity, was recorded by conditioning in a climate chamber (25 °C, 80% relative humidity). Hydrophobization resulted in the increase in thermal conductivity compared to that of neat pectin aerogels. MTMS deposition for 16 h was efficient for hydrophobizing pectin aerogels in moist environment (contact angle 115°) and stabilizing material properties with no fluctuation in thermal conductivity (0.030 W m-1 K-1) and density for the testing period of 8 months.

The European Polysaccharide Network of Excellence (EPNOE) research roadmap 2040: Advanced strategies for exploiting the vast potential of polysaccharides as renewable bioresources.

Polysaccharides are among the most abundant bioresources on earth and consequently need to play a pivotal role when addressing existential scientific challenges like climate change and the shift from fossil-based to sustainable biobased materials. The Research Roadmap 2040 of the European Polysaccharide Network of Excellence (EPNOE) provides an expert's view on how future research and development strategies need to evolve to fully exploit the vast potential of polysaccharides as renewable bioresources. It is addressed to academic researchers, companies, as well as policymakers and covers five strategic areas that are of great importance in the context of polysaccharide related research: (I) Materials & Engineering, (II) Food & Nutrition, (III) Biomedical Applications, (IV) Chemistry, Biology & Physics, and (V) Skills & Education. Each section summarizes the state of research, identifies challenges that are currently faced, project achievements and developments that are expected in the upcoming 20 years, and finally provides outlines on how future research activities need to evolve.

Tuning bio-aerogel properties for controlling drug delivery. Part 2: Cellulose-pectin composite aerogels.

The release of the model drug theophylline from cellulose-pectin composite aerogels was investigated. Cellulose and pectin formed an interpenetrated network, and the goal was to study and understand the influence of each component and its solubility in simulated gastric and intestinal fluids on the kinetics of release. Cellulose was dissolved, coagulated in water, followed by impregnation with pectin solution, crosslinking of pectin with calcium (in some cases this step was omitted), solvent exchange and supercritical CO2 drying. Theophylline was loaded via impregnation and its release into simulated gastric fluid was monitored for 1 h followed by release into simulated intestinal fluid. The properties of the composite aerogels were varied via the cellulose and pectin concentrations as well as the calcium content in the precursor solutions. The release kinetics was correlated with aerogel specific surface area, bulk density as well as network swelling and erosion. The Korsmeyer-Peppas model was employed to identify the dominant release mechanisms during the various stages of the release.

Tuning the properties of porous chitosan: Aerogels and cryogels.

Highly porous chitosan-based materials were prepared via dissolution, non-solvent induced phase separation and drying using different methods. The goal was to tune the morphology and properties of chitosan porous materials by varying process parameters. Chitosan concentration, concentration of sodium hydroxide in the coagulation bath and aging time were varied. Drying was performed via freeze-drying leading to "cryogels" or via drying with supercritical CO2 leading to "aerogels". Cryogels were of lower density than aerogels (0.03-0.12 g/cm3vs 0.07-0.26 g/cm3, respectively) and had a lower specific surface area (50-70 vs 200-270 m2/g, respectively). The absorption of simulated wound exudate by chitosan aerogels and cryogels was studied in view of their potential applications as wound dressing. Higher absorption was obtained for cryogels (530-1500%) as compared to aerogels (200-610%).

Tailoring the morphology and properties of starch aerogels and cryogels via starch source and process parameter.

Porous starch materials with various morphology and properties were made via starch dissolution, retrogradation and drying either with supercritical CO2 ("aerogels") or lyophilisation ("cryogels"). Their properties were correlated with the rheological response of retrograded starch gels and crystallinity of aerogels and cryogels. All starch cryogels possess very low density (0.07 - 0.16 g/cm3), very large macropores and low specific surface area (around 3-13 m2/g). Their morphology is mainly the replica of sublimated ice crystals. The properties of starch aerogels strongly depend on starch source: the lowest density (around 0.1 g/cm3) and highest specific surface area (170-250 m2/g) was recorded for pea starch aerogels and the highest density (0.3-0.6 g/cm3) and lowest specific surface area (7-90 m2/g) for waxy maize starch aerogels. The morphology and properties of starch aerogels are interpreted by amylose and amylopectin evolution during retrogradation.

Polysaccharide-based aerogels for thermal insulation and superinsulation: An overview.

To reduce energy losses due to the insufficient thermal insulation is one of the current "hot" topics. Various commercial porous materials are used with the best conductivity around 0.03-0.04 W/(m·K). Aerogels are the only known materials with "intrinsic" thermal superinsulating properties, i.e. with thermal conductivity below that of air in ambient conditions (0.025 W/(m·K)). The classical thermal superinsulating aerogels are based on silica and some synthetic polymers, with conductivity 0.014-0.018 W/(m·K). Aerogels based on natural polymers are new materials created at the beginning of the 21st century. Can bio-aerogels possess thermal superinsulating properties? What are the bottlenecks in the development of bio-aerogels as new high-performance thermal insulationing materials? We try to answer these questions by analyzing thermal conductivity of bio-aerogels reported in literature.

Tuning bio-aerogel properties for controlling theophylline delivery. Part 1: Pectin aerogels.

A comprehensive study of release kinetics of a hydrophilic drug from bio-aerogels based on pectin was performed. Pectin aerogels were made by polymer dissolution, gelation (in some cases this step was omitted), solvent exchange and drying with supercritical CO2. Theophylline was loaded and its release was studied in the simulated gastric fluid during 1 h followed by the release in the simulated intestinal fluid. Pectin concentration, initial solution pH and concentration of calcium were varied to tune the properties of aerogel. The kinetics of theophylline release was monitored and correlated with aerogel density, specific surface area, and aerogel swelling and erosion. Various kinetic models were tested to identify the main physical mechanisms governing the release.

Influence of cellulose on ion diffusivity in 1-ethyl-3-methyl-imidazolium acetate cellulose solutions.

Solutions of microcrystalline cellulose in 1-ethyl-3-methyl-imidazolium acetate have been investigated using pulsed-field gradient (1)H NMR. In all cases the geometrically larger cation was found to diffuse faster than the smaller anion. Arrhenius temperature analysis has been applied to the ion diffusivities giving activation energies. The diffusion and published viscosity data for these solutions were shown to follow the Stokes-Einstein relationship, giving hydrodynamic radii of 1.6 Š(cation) and 1.8 Š(anion). Theories for obstruction, free-volume and hydrodynamic effects on solvent diffusion have been applied. The Mackie-Meares and Maxwell-Fricke obstruction models provided a correct trend only when assuming a certain fraction of ions are bound to the polymer. From this fraction it was shown that the maximum dissolvable cellulose concentration is ∼27% w/w, which is consistent with the highest known prepared concentration of cellulose in this ionic liquid. The Phillies' hydrodynamic model is found to give the best description for the cellulose concentration dependence of the ion diffusivities.

Unidirectional All-Cellulose Composites from Flax via Controlled Impregnation with Ionic Liquid.

Mechanically strong all-cellulose composites are very attractive in the terms of fully bio-based and bio-degradable materials. Unidirectional flax-based all-cellulose composites are prepared via facile room-temperature impregnation with an ionic liquid, 1-ethyl-3-methyl imidazolium acetate. To determine the optimal processing conditions, the kinetics of flax dissolution in this solvent is first studied using optical microscopy. Composite morphology, crystallinity, density, the volume fraction of cellulose II and tensile properties are investigated, indicating that flax dissolution should be within certain limits. On the one hand, the amount of cellulose II formed through dissolution and coagulation should be high enough to "fuse" flax fibers, resulting in a density increase. On the other hand, only the surface layer of the fibers should be dissolved to maintain the strength provided by the inner secondary layer and avoid a detrimental decrease in crystallinity. The highest Young's modulus and strength, 10.1 GPa and 151.3 MPa, respectively, are obtained with a crystallinity of 43% and 20 vol% of cellulose II.