Investigation of Gelation Techniques for the Fabrication of Cellulose Aerogels.

Because of the pronounced degradation of the environment, there has been an escalated demand for the fabrication of eco-friendly and highly efficient products derived from renewable sources. Cellulose aerogels have attracted significant interest attributable to their structural characteristics coupled with biodegradability and biocompatibility. The features of the molecular structure of cellulose allow for the use of various methods in the production of gels. For instance, the presence of hydroxyl groups on the cellulose surface allows for chemical crosslinking via etherification reactions. On the other hand, cellulose gel can be procured by modulating the solvent power of the solvent. In this study, we investigate the impact of the gelation methodology on the structural attributes of aerogels. We present methodologies for aerogel synthesis employing three distinct gelation techniques: chemical crosslinking, cryotropic gelation, and CO2-induced gelation. The outcomes encompass data derived from helium pycnometry, Fourier-transform infrared spectroscopy, nitrogen porosimetry, and scanning electron microscopy. The resultant specimens exhibited a mesoporous fibrous structure. It was discerned that specimens generated through cryotropic gelation and CO2-induced gelation manifested higher porosity (93-95%) and specific surface areas (199-413 m2/g) in contrast to those produced via chemical crosslinking (porosity 72-95% and specific surface area 25-133 m2/g). Hence, this research underscores the feasibility of producing cellulose-based aerogels with enhanced characteristics, circumventing the necessity of employing toxic cross-linking agents. The process of gel formation through chemical crosslinking enables the creation of gels with enhanced mechanical properties and a more resilient structure. Two alternative methodologies prove particularly advantageous in applications necessitating biocompatibility and high porosity. Notably, CO2-induced gelation has not been hitherto addressed in the literature as a means to produce cellulose gels. The distinctive feature of this approach resides in the ability to combine the stages of obtaining an aerogel in one apparatus.

Investigation of the 3D Printing Process Utilizing a Heterophase System.

Direct ink writing (DIW) requires careful selection of ink composition with specific rheological properties, and it has limitations, such as the inability to create overhanging parts or branched geometries. This study presents an investigation into enhancing the 3D printing process through the use of a heterophase system, aiming to overcome these limitations. A modification was carried out in the 3D printer construction, involving adjustments to the structural elements responsible for the extrusion device's movement. Additionally, a method for obtaining a heterophase system based on gelatin microparticles was developed to enable the 3D printing process with the upgraded printer. The structure and rheological properties of the heterophase system, varying in gelatin concentration, were thoroughly examined. The material's viscosity ranged from 5.4 to 32.8 kPa·s, exhibiting thixotropic properties, pseudoplastic behavior, and long-term stability at 20 °C. The developed 3D printing technology was successfully implemented using a heterophase system based on different gelatin concentrations. The highest product quality was achieved with a heterophase system consisting of 4.5 wt.% gelatin, which exhibited a viscosity of 22.4 kPa·s, enabling the production of products without spreading or compromising geometrical integrity.

Preparation of Protein Aerogel Particles for the Development of Innovative Drug Delivery Systems.

The research was oriented towards the preparation of aerogel particles based on egg white and whey protein isolate using various dispersion methods: dripping, spraying, and homogenization. Based on the results of analytical studies, the most appropriate samples were selected to obtain aerogels loaded with the drug. The results of the experimental research were used to study methods for obtaining nasal drug delivery systems based on aerogels. Protein aerogels were obtained by thermal gelation followed by supercritical drying. The obtained particles of protein aerogels have a specific surface area of up to 350 m2/g with a pore volume of up to 2.9 cm3/g, as well as a porosity of up to 95%. The results of experimental studies have shown that changing the dispersion method makes it possible to control the structural characteristics of protein aerogel particles. The results of the studies were applied to obtain innovative nasal drug delivery systems for the treatment of socially significant diseases. Analytical studies were conducted to determine the amount and state of adsorbed drugs in protein aerogel particles, as well as in vivo experiments on the distribution of clomipramine in blood plasma and brain tissue of rats to study the pharmacokinetics and bioavailability of the resulting drug-loaded protein aerogel.

Chitosan Aerogel Particles as Nasal Drug Delivery Systems.

The nasal drug delivery route has distinct advantages, such as high bioavailability, a rapid therapeutic effect, non-invasiveness, and ease of administration. This article presents the results of a study of the processes for obtaining chitosan aerogel particles that are promising as nasal or inhalation drug delivery systems. Obtaining chitosan aerogel particles includes the following steps: the preparation of a chitosan solution, gelation, solvent replacement, and supercritical drying. Particles of chitosan gels were obtained by spraying and homogenization. The produced chitosan aerogel particles had specific surface areas of up to 254 m2/g, pore volumes of up to 1.53 cm3/g, and porosities of up to 99%. The aerodynamic diameters of the obtained chitosan aerogel particles were calculated, the values of which ranged from 13 to 59 µm. According to the calculation results, a CS1 sample was used as a matrix for obtaining the pharmaceutical composition "chitosan aerogel-clomipramine". X-ray diffraction (XRD) analysis of the pharmaceutical composition determined the presence of clomipramine, predominantly in an amorphous form. Analysis of the high-performance liquid chromatography (HPLC) data showed that the mass loading of clomipramine was 35%. Experiments in vivo demonstrated the effectiveness of the pharmaceutical composition "chitosan aerogel-clomipramine" as carrier matrices for the targeted delivery of clomipramine by the "Nose-to-brain" mechanism of nasal administration. The maximum concentration of clomipramine in the frontal cortex and hippocampus was reached 30 min after administration.

Extrusion-Based 3D Printing for Highly Porous Alginate Materials Production.

Three-dimensional (3D) printing is a promising technology for solving a wide range of problems: regenerative medicine, tissue engineering, chemistry, etc. One of the potential applications of additive technologies is the production of highly porous structures with complex geometries, while printing is carried out using gel-like materials. However, the implementation of precise gel printing is a difficult task due to the high requirements for "ink". In this paper, we propose the use of gel-like materials based on sodium alginate as "ink" for the implementation of the developed technology of extrusion-based 3D printing. Rheological studies were carried out for the developed alginate ink compositions. The optimal rheological properties are gel-like materials based on 2 wt% sodium alginate and 0.2 wt% calcium chloride. The 3D-printed structures with complex geometry were successfully dried using supercritical drying. The resulting aerogels have a high specific surface area (from 350 to 422 m2/g) and a high pore volume (from 3 to 3.78 cm3/g).

Synthesis and Properties of Silica and Alginate Hybrid Aerogel Particles with Embedded Carbon Nanotubes (CNTs) for Selective Sorption.

The manuscript describes methods for producing hybrid silica microparticles and hybrid alginate beads with carbon nanotube (CNT) contents up to 4.5 and 30 wt.%, respectively. Silica hybrid aerogel microparticles with embedded nanotubes were obtained using a two-stage sol⁻gel method with a gelling process in an oil-emulsion. Alginate hybrid aerogels with embedded nanotubes were obtained using cross-linking reactions. The following methods were used to measure the structural characteristics of obtained materials: nitrogen adsorption porosimetry, scanning electron microscopy (SEM), and others. It is shown that specific surface area and pore volume increase with the increase of CNT content in silica aerogel microparticles. Obtained aerogels were tested as adsorbents for argon⁻oxygen separation. The alginate hybrid aerogel with 30 wt.% CNT content has the best argon adsorption selectivity.