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.

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Due to the limited volumes of conventional sources of cellulose (cotton and wood), research centered on producing the most competitive science-driven products – cellulose nitrates – from new, domestic, easily renewable feedstocks is extremely relevant. The review of scientific literature corroborates the lack of data on the feasibility to obtain cellulose nitrates from Miscanthus, except for the authors’ publications. Here we suggest a tree-like industrial crop, Miscanthus var. KAMIS, growing with an yield of up to 20 t/ha a year on industrial plantations in Kaliningradskaya, Kaluzhskaya and Yaroslavskaya Oblasts and in Primorskiy Krai. A pulp sample derived from Miscanthus var. KAMIS by the nitric-acid process exhibits a high α-cellulose content of 96 % and degree of polymerization of 1350. Under optimum synthesis conditions previously identified for unconventional feedstocks, a cellulose nitrate sample was synthesized by treating the pulp with commercially available mixed acid and had the following functional characteristics: 11.26 % nitrogen content, 52 mPа∙s viscosity, and – 95 % solubility on alcohol-ester mixture. Morphological features of pulp and cellulose nitrate samples were characterized by scanning electron microscopy. IR spectroscopy revealed the presence of functional groups in pulp samples (3411, 2913, 1637, 1429, 1369, 1317, 1161, 700-500 cm-1) and cellulose nitrate samples (2553, 1642, 1276, 830, 746, 680 cm-1), which allow those samples to be identified as cellulose and nitrate cellulose esters, respectively. It was found by scanning electron microscopy that the cellulose nitrate sample matches industrial Colloxylines by the onset temperature of decomposition (199 °С) and specific head of decomposition (8,43 kJ/g). The practical importance of this study is that we experimentally justify the feasibility to utilize the new, unconventional, domestic, easily renewable feedstock, Miscanthus var. KAMIS, as a precursor of high-quality cellulose nitrates

High and unstable prices on such cocoa products as cocoa butter have triggered a search for substitutes. Thus, it is necessary to develop identification methods for chocolate authenticity, since chocolate is one of the most popular confectionery products. The present research employed the methods of thermal and thermomechanical analysis to study samples of chocolate produced in the countries of the Eurasian Economic Community (the Russian Federation, the Republic of Kazakhstan, and the Republic of Belarus) and chocolate bars with cocoa butter substitutes. An analysis of the sucrose – cocoa butter (CB) system revealed that samples with CB = 10–30%, 60%, and 90% demonstrated a single polymorphic modification of glycerides CB α-form with a melting point of 21–23°C. The samples with CB = 0%, 50%, 70%, and 80% showed a more heat-resistant modification (β’-modification) with a maximum melting point of 27.0–27.5°C. In addition, the melting peaks of glycerides were found not constant, which may indicate a eutectic effect in the sucrose – CB system. The samples of chocolate produced in the Russian Federation and the Republic of Kazakhstan passed the tempering stage and demonstrated the most heat-resistant β-modification of CB. However, the samples differed in the melting temperature: T max = 33.9°C for the Russian chocolate and T = 34.8°C for the samples from Kazakhstan (the Rakhat brand). The samples from Belarus did not pass the tempering and were found to contain a thermodynamically unstable CB α-phase (the Kommunarka factory). The samples produced by the Spartak factory (Gomel, the republic of Belarus) contained an additional CB β’-phase. The differential scanning calorimetry (DSC) curves for chocolate bars with CB substitutes differed from the DSC curves for cocoa butter and chocolate samples. The fact can be used for identification. The DSC method can be used to identify the individual characteristics of the producer of chocolate and its analogues since the parameters of the melting curve of the fat phase and the shape of the curve are individual. The thermomagnetic analysis (TMA) method complemented the identification by determining the mass fraction of the liquid phase. Joint application of DSC and TMA methods allowed the authors to evaluate the quality of chocolate, its formulation, as well as to reveal the presence of cocoa products substitutes in the samples as compared to the reference sample.

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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