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Nanocrystalline cellulose particles are new class of cellulose materials that can find the wide application in various technical areas, biotechnology and medicine. The nanoparticles are usually made by treatment or initial cellulose samples with concentrated sulfuric acid (SA) at various temperatures and following mechanical or ultrasound disintegration. Unfortunately, conditions of existing methods for preparation of nanocellulose are multifarious and give both crystalline and amorphous nanoparticles. Therefore in this paper the optimal conditions for obtaining just of nanocrystalline cellulose particles (NCP) have been studied. The experiment showed that isolation of NCP is carried out in narrow interval of the acid concentration: from 50 to about 61 wt. %. If concentration of SA is less than 50 wt. % then micro-scale particles are isolated. On the other hand, if concentration of SA is higher than 63 wt. % the cellulose completely dissolves, and as a result instead of nanocrystalline the amorphous particles are formed with decreased yield. In the range of the acid concentration from 55 to 61 wt. %, a low decrystallization of the initial cellulose is taken place that contributes to forming of rod-like nanocrystalline cellulose particles. The following optimal conditions of the acidic treatment for isolation of NCP were proposed: concentration of sulfuric acid 57-60 wt. %, acid to cellulose ratio 8-10, temperature [45][46][47][48][49][50][51][52][53][54][55] o C, time 40-60 min. These optimal conditions in combination with the high-power disintegration permit obtaining the rod-like nanocrystalline cellulose particles (150-200 x 10-20 nm) with the increased yield (70-75%).

The effect of biomass loading from 50 to 200 g/L on enzymatic hydrolysis was studied using switchgrass samples pretreated by dilute acid and hypochlorite-alkaline methods. It was confirmed that an increase of initial loading of the pretreated biomass leads to a decrease of enzymatic digestibility, probably due to difficulty of mass transfer of cellulolytic enzymes in the high-viscous substrate slurry and also because of an inhibiting effect of the formed sugars. An additional sharp problem connected with enzymatic hydrolysis at the high-solids loading is absorption and retention of liquid hydrolysate by residual non-hydrolyzed biomass that causes diminution of the available volume (V a ) of the sugar solution and decreases productivity of the saccharification process. To optimize the high-solids enzymatic hydrolysis, the maximal amount of the formed sugars was determined A m = C m x V a,m , where C m is maximal concentration of the sugar solution and V a,m is maximal available volume. Such an approach makes it possible to find the optimal conditions for the hydrolysis: optimal biomass loading and hydrolysis time. After enzymatic hydrolysis at these optimal conditions, the low-lignified biomass pretreated by hypochlorite-alkaline method displayed much more available volume of sugar solution and higher digestibility characteristics than the cellolignin obtained by acidic pretreatment of the initial biomass sample.

Cellulose has a complex, multi-level supermolecular architecture. This natural polymer is built from superfine fibrils having diameters in the nano scale, and each such nanofibril contains ordered nanocrystallites and low-ordered nano-domains. In this review, the nano-structure of cellulose and its influence on various properties of the polymer is discussed. In particular, the ability of nano-scale crystallites to undergo lateral co-crystallization and aggregation, as well as to undergo phase transformation through dissolution, alkalization, and chemical modification of cellulose has been the subject of investigation. The recent investigations pave the way for development of highly reactive cellulosic materials. Methods for preparation nanofibrillated cellulose and free nano-particles are described. Some application areas of the nanostruc-tured and nano-cellulose are discussed.

BackgroundDuring the process of bioethanol production, cellulose is hydrolyzed into its monomeric soluble units. For efficient hydrolysis, a chemical and/or mechanical pretreatment step is required. Such pretreatment is designed to increase enzymatic digestibility of the cellulose chains inter alia by de-crystallization of the cellulose chains and by removing barriers, such as lignin from the plant cell wall. Biological pretreatment, in which lignin is decomposed or modified by white-rot fungi, has also been considered. One disadvantage in biological pretreatment, however, is the consumption of the cellulose by the fungus. Thus, fungal species that attack lignin with only minimal cellulose loss are advantageous. The secretomes of white-rot fungi contain carbohydrate-active enzymes (CAZymes) including lignin-modifying enzymes. Thus, modification of secretome composition can alter the ratio of lignin/cellulose degradation.ResultsPleurotus ostreatus PC9 was genetically modified to either overexpress or eliminate (by gene replacement) the transcriptional regulator CRE1, known to act as a repressor in the process of carbon catabolite repression. The cre1-overexpressing transformant demonstrated lower secreted cellulolytic activity and slightly increased selectivity (based on the chemical composition of pretreated wheat straw), whereas the knockout transformant demonstrated increased cellulolytic activity and significantly reduced residual cellulose, thereby displaying lower selectivity. Pretreatment of wheat straw using the wild-type PC9 resulted in 2.8-fold higher yields of soluble sugar compared to untreated wheat straw. The overexpression transformant showed similar yields (2.6-fold), but the knockout transformant exhibited lower yields (1.2-fold) of soluble sugar. Based on proteomic secretome analysis, production of numerous CAZymes was affected by modification of the expression level of cre1.ConclusionsThe gene cre1 functions as a regulator for expression of fungal CAZymes active against plant cell wall lignocelluloses, hence altering the substrate preference of the fungi tested. While the cre1 knockout resulted in a less efficient biological pretreatment, i.e., less saccharification of the treated biomass, the converse manipulation of cre1 (overexpression) failed to improve efficiency. Despite the inverse nature of the two genetic alterations, the expected “mirror image” (i.e., opposite regulatory response) was not observed, indicating that the secretion level of CAZymes, was not exclusively dependent on CRE1 activity.Electronic supplementary materialThe online version of this article (10.1186/s13068-018-1209-6) contains supplementary material, which is available to authorized users.

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The effect of the concentration of sulfuric acid (SA) and temperature on structure and properties of cellulose (MCC) had been studied. Investigations showed that solubility of the initial sample at the room temperature increased gradually in the range of the acid concentration from 50 to 60 wt.% SA. When SA concentration reached 65 wt.%, then MCC sample dissolved completely. Cellulose regenerated from 65 wt.% SA had an amorphized structure and was characterized by high enzymatic digestibility. At increased temperature, 45°C, solubility of MCC in SA was raised, while yield and DP decreased. After treatment of MCC with hot 50–60 wt.% SA, the crystallinity degree of the obtained cellulose samples changed slightly, and these samples retained mainly the CI crystalline polymorph. However, when SA concentration reached 65 wt.%, then regenerated cellulose had CII crystalline polymorph, reduced crystallinity degree, and low DP. Using optimal conditions of the acidic treatment (57–60 wt.% SA, T = 45°C; t=1 h) in combination with the high-power disintegration permitted obtaining the CI nanocrystalline cellulose particles (NCP) having sizes 150–200 × 10–20 nm with the heightened yield (65–70%). These NCP can be used, for example, as reinforcing nanofillers for various composites.

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