Bacterial nanocellulose (BNC) whose biosynthesis fully conforms to green chemistry principles arouses much interest of specialists in technical chemistry and materials science because of its specific properties, such as nanostructure, purity, thermal stability, reactivity, high crystallinity, etc. The functionalization of the BNC surface remains a priority research area of polymers. The present study was aimed at scaled production of an enlarged BNC sample and at synthesizing cellulose nitrate (CN) therefrom. Cyclic biosynthesis of BNC was run in a semisynthetic glucose medium of 10−72 L in volume by using the Medusomyces gisevii Sa-12 symbiont. The most representative BNC sample weighing 6800 g and having an α-cellulose content of 99% and a polymerization degree of 4000 was nitrated. The nitration of freeze-dried BNC was performed with sulfuric-nitric mixed acid. BNC was examined by scanning electron microscopy (SEM) and infrared spectroscopy (IR), and CN was explored to a fuller extent by SEM, IR, thermogravimetric analysis/differential scanning analysis (TGA/DTA) and 13C nuclear magnetic resonance (NMR) spectroscopy. The three-cycle biosynthesis of BNC with an increasing volume of the nutrient medium from 10 to 72 L was successfully scaled up in nonsterile conditions to afford 9432 g of BNC gel-films. CNs with a nitrogen content of 10.96% and a viscosity of 916 cP were synthesized. It was found by the SEM technique that the CN preserved the 3D reticulate structure of initial BNC fibers a marginal thickening of the nanofibers themselves. Different analytical techniques reliably proved the resultant nitration product to be CN. When dissolved in acetone, the CN was found to form a clear high-viscosity organogel whose further studies will broaden application fields of the modified BNC.
Bacterial nanocellulose (BNC) is a unique product of microbiological synthesis, having a lot of applications among which the most important is biomedicine. Objective complexities in scaling up the biosynthesis of BNC are associated with the nature of microbial producers for which BNC is not the target metabolite, therefore biosynthesis lasts long, with the BNC yield being small. Thus, the BNC scale-up problem has not yet been overcome. Here we performed biosynthesis of three scaled sheets of BNC (each having a surface area of 29,400 cm2, a container volume of 441 L, and a nutrient medium volume of 260 L and characterized them. The static biosynthesis of BNC in a semisynthetic nutrient medium was scaled up using the Medusomyces gisevii Sa-12 symbiotic culture. The experiment was run in duplicate. The BNC pellicle was removed once from the nutrient medium in the first experiment and twice in the second experiment, in which case the inoculum and glucose were not additionally added to the medium. The resultant BNC sheets were characterized by scanning electron microscopy, capillary viscosimetry, infrared spectroscopy, thermomechanical and thermogravimetric analyses. When the nutrient medium was scaled up from 0.1 to 260 L, the elastic modulus of BNC samples increased tenfold and the degree of polymerization 2.5-fold. Besides, we demonstrated that scaled BNC sheets could be removed at least twice from one volume of the nutrient medium, with the yield and quality of BNC remaining the same. Consequently, the world’s largest BNC sheets 210 cm long and 140 cm wide, having a surface area of 29,400 cm2 each (weighing 16.24 to 17.04 kg), have been obtained in which an adult with burns or vast wounds can easily be wrapped. The resultant sheets exhibit a typical architecture of cellulosic fibers that form a spatial 3D structure which refers to individual and extremely important characteristics of BNC. Here we thus demonstrated the scale-up of biosynthesis of BNC with improved properties, and this result was achieved by using the symbiotic culture.
Lignocellulosic biomass is of great interest as an alternative energy resource because it offers a range of merits. Miscanthus × giganteus is a lignocellulosic feedstock of special interest, as it combines a high biomass productivity with a low environmental impact, including CO2 emission control. The chemical composition of lignocellulose determines the application potential for efficient industrial processing. Here, we compiled a sample collection of Miscanthus × giganteus that had been cultivated in different climate regions between 2019 and 2021. The chemical composition was quantified by the conventional wet methods. The findings were compared with each other and with the known data. Starting as soon as the first vegetation year, Miscanthus was shown to feature the following chemical composition: 43.2–55.5% cellulose content, 17.1–25.1% acid-insoluble lignin content, 17.9–22.9% pentosan content, 0.90–2.95% ash content, and 0.3–1.2% extractives. The habitat and the surrounding environment were discovered herein to affect the chemical composition of Miscanthus. The stem part of Miscanthus was found to be richer in cellulose than the leaf (48.4–54.9% vs. 47.2–48.9%, respectively), regardless of the planation age and habitat. The obtained findings broaden the investigative geography of the chemical composition of Miscanthus and corroborate the high value of Miscanthus for industrial conversion thereof into cellulosic products worldwide.
The present paper is a fundamental study on the physicochemical properties and hydrolysis behavior of cellulose samples differing in origin: bacterial, synthetic, and vegetal. Bacterial cellulose was produced by Medusomyces gisevii Sa-12 in an enzymatic hydrolyzate derived from oat-hull pulp. Synthetic cellulose was obtained from an aqueous glucose solution by electropolymerization. Plant-based cellulose was isolated by treatment of Miscanthus sacchariflorus with dilute NaOH and HNO3 solutions. We explored different properties of cellulose samples, such as chemical composition, degree of polymerization (DP), degree of crystallinity (DC), porosity, and reported infrared spectroscopy and scanning electron microscopy results. The hydrolysis behavior was most notable dependent on the origin of cellulose. For the bacterial cellulose sample (2010 DP, 90% DC, 89.4% RS yield), the major property affecting the hydrolysis behavior was its unique nanoscale reticulate structure promoting fast penetration of cellulases into the substrate structure. The study on enzymatic hydrolysis showed that the hydrolysis behavior of synthetic and Miscanthus celluloses was most influenced by the substrate properties such as DP, DC and morphological structure. The yield of reducing sugars (RS) by hydrolysis of synthetic cellulose exhibiting a 3140 DP, 80% DC, and highly depolymerization-resistant fibers was 27%. In contrast, the hydrolysis of Miscanthus-derived cellulose with a 1030 DP, 68% DC, and enzyme-accessible fibers provided the highest RS yield of 90%. The other properties examined herein (absence/presence of non-cellulosic impurities, specific surface, pore volume) had no considerable effect on the bioconversion of the cellulosic substrates.
Carbon neutrality is a requisite for industrial development in modern times. In this paper, we review information on possible applications of polymers from the energy crop Miscanthus in the global industries, and we highlight the life cycle aspects of Miscanthus in detail. We discuss the benefits of Miscanthus cultivation on unoccupied marginal lands as well as the rationale for the capabilities of Miscanthus regarding both soil carbon storage and soil remediation. We also discuss key trends in the processing of Miscanthus biopolymers for applications such as a fuel resources, as part of composite materials, and as feedstock for fractionation in order to extract cellulose, lignin, and other valuable chemicals (hydroxymethylfurfural, furfural, phenols) for the subsequent chemical synthesis of a variety of products. The potentialities of the biotechnological transformation of the Miscanthus biomass into carbohydrate nutrient media and then into the final products of microbiological synthesis are also examined herein.
Scaling biosynthesis of bacterial nanocellulose (BNC) allowed samples of composite paper with an increased proportion of BNC to be obtained. This work aims to study BNC samples and bleached soft wood kraft pulp (BSKP) composite paper with a ratio of components varying across a wide range: 10:90, 30:70, 50:50, 60:40, 70:30, 90:10. The method of paper manufacturing was chosen based on the determinations of strength and deformation properties of composite samples with the BNC:BSKP ratio of 20:80. Surface application of BNT on BSKP handsheet provided for an increase in the strength values (tear resistance – by 37%, burst index – by 17%) and deformation characteristics (tension stiffness – by 66%, fracture work – by 8%, breaking length – by 4%) compared to a reference sample. The formation of composites is confirmed in all samples. Scanning electron spectroscopy revealed that paper composites comprise interlaced micro BSKP and nano BNC fibres. As the proportion of BNC in composites elevated, densification of the structure was observed due to an increased fraction of cross-linked nanosized elements. IR spectroscopy indicated the resemblance of cellulose structure in all samples. It was found that an increase in the degree of polymerisation of composite paper is directly proportional to an increase in the BNC amount in the samples. The filtering ability of composite paper samples against microorganisms in the culture liquid of the Medusomyces gisevii Sa-12 producer was studied. It should be noted that yeast retention is achieved with 70% BNC in the paper composite. The presented properties of the new material determine prospects for its use in filtering microorganisms.
Extended cultivation with multiple removal of BC pellicles is proposed herein as a new biosynthetic process for bacterial cellulose (BC). This method enhances the BC surface area by 5–11 times per unit volume of the growth medium, improving the economic efficiency of biosynthesis. The resultant BC gel-films were thin, transparent, and congruent. The degree of polymerization (DP) and elastic modulus (EM) depended on the number of BC pellicle removals, vessel shape, and volume. The quality of BC from removals II–III to VII was better than from removal I. The process scale-up of 1:40 by volume increased DP by 1.5 times and EM by 5 times. A fact was established that the symbiotic Medusomyces gisevii Sa-12 was adaptable to exhausted growth medium: the medium was able to biosynthesize BC for 60 days, while glucose ran low at 24 days. On extended cultivation, DP and EM were found to decline by 39–64% and 57–65%, respectively. The BC gel-films obtained upon removals I–VI were successfully trialed in experimental tension-free hernioplasty.
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