Cellulose Microfibril Aggregates Research Articles

Wood cellulose microfibrils have a 24-chain core-shell nanostructure in seed plants.

Wood cellulose microfibril (CMF) is the most abundant organic substance on Earth but its nanostructure remains poorly understood. There are controversies regarding the glucan chain number (N) of CMFs during initial synthesis and whether they become fused afterward. Here, we combined small-angle X-ray scattering, solid-state nuclear magnetic resonance and X-ray diffraction analyses to resolve CMF nanostructures in native wood. We developed small-angle X-ray scattering measurement methods for the cross-section aspect ratio and area of the crystalline-ordered CMF core, which has a higher scattering length density than the semidisordered shell zone. The 1:1 aspect ratio suggested that CMFs remain mostly segregated, not fused. The area measurement reflected the chain number in the core zone (Ncore). To measure the ratio of ordered cellulose over total cellulose (Roc) by solid-state nuclear magnetic resonance, we developed a method termed global iterative fitting of T1ρ-edited decay (GIFTED), in addition to the conventional proton spin relaxation editing method. Using the formula N = Ncore/Roc, most wood CMFs were found to contain 24 glucan chains, conserved between gymnosperm and angiosperm trees. The average CMF has a crystalline-ordered core of ~2.2 nm diameter and a semidisordered shell of ~0.5 nm thickness. In naturally and artificially aged wood, we observed only CMF aggregation (contact without crystalline continuity) but not fusion (forming a conjoined crystalline unit). This further argued against the existence of partially fused CMFs in new wood, overturning the recently proposed 18-chain fusion hypothesis. Our findings are important for advancing wood structural knowledge and more efficient use of wood resources in sustainable bio-economies.

Estimating cellulose microfibril orientation in the cell wall sublayers of bamboo through dimensional analysis of microfibril aggregates

The mechanical performance and dimensional stability of bamboo is highly dependent on the microfibril orientation in its cell wall sublayers. However, a comprehensive and quantitative description of this orientation at the sublayer scale of cell wall is very challenging to do. Here, we proposed a new approach to quantitatively estimate the cellulose microfibril orientation across the whole cell wall of both fibers and parenchyma cells in bamboo. This new approach is based on the geometrical correlation between the actual and apparent dimensions of cellulose microfibril aggregates, which are respectively determinedly with CP/MAS 13C NMR and high-resolution field emission scanning electron microscopy (FE-SEM). For comparison, the average microfibril angle (MFA) of both fibers and parenchyma cells were also measured using X-ray diffraction (XRD). It was concluded that the cellulose microfibrils in the broad sublayers of the bamboo fibers exhibited a relatively small MFA of about 10°, while those in the narrow sublayers were nearly oriented in the transverse with a MFA of about 80°. For parenchyma cells, the MFA of the broad and narrow sublayers were estimated to be 50–70° and 70–80°, respectively. Modified cell wall structural models for the two types of cells were then proposed.

The Arrangement and Size of Cellulose Microfibril Aggregates in the Cell Walls of Sclerenchyma Fibers and Parenchyma Tissue in Bamboo

Understanding the assembly and spatial arrangement of bamboo cell wall components is crucial for its optimal utilization. Bamboo cell walls consist of aggregates of cellulose microfibrils and matrix. In the present study, the size and arrangement of cellulose microfibril aggregates in the cell walls of sclerenchyma fibers and parenchyma cells in moso bamboo were investigated with NMR and FE-SEM. The NMR measurement showed that the characteristic sizes of the microfibril aggregates of fibers and parenchyma cells were approximately 25.8 nm and 18.8 nm, respectively. Furthermore, high-resolution SEM showed the size of microfibril aggregates varied little across the cell wall of sclerenchyma fiber. However, there were significant size differences between the broad and narrow lamellae both in fiber and parenchyma cells, which is thought to be closely related to the orientation of microfibrils in these layers. The microfibril aggregates in the fibers mainly appear in a random arrangement, although occasionally in a radial or tangential arrangement in individual cell. Parenchyma cells have a relatively thinner cell wall layers, in which microfibril aggregates appear in a concentric lamellar arrangement.

Changes in wheat straw cell walls during ozone pretreatment

Abstract Treatment of plant biomass with ozone is a promising delignification method. It was shown that lignin removal from the cell wall during ozonation was limited by topochemical reactions and toke place in the secondary rather in the primary cell wall. The separation of cellulose microfibrils, the loss of cell wall stiffness and complete removal of intercellular substance during the delignification process were visualized by SEM. The dependence of the average diameter of the cellulose microfibril aggregates in the cell wall of ozonized straw on ozone consumption was studied. Lignin removal caused an increase of size of cellulose microfibrils aggregates. It was demonstrated that there was an optimal degree of delignification, at which cellulose became more accessible to enzymes in the subsequent bioconversion processes. The data on the ozone consumption, residual lignin content, and sugars yield in the enzymatic hydrolysis of ozonized wheat straw were obtained. It was also found that the optimum delignification degree for sugars yield was ≈10% of residual lignin content and optimum ozone consumption was 2 mol·О3/mol C9PPU (phenylpropane structural unit) of lignin in raw straw.

Effect of drying conditions on cellulose microfibril aggregation and “hornification”

Drying of chemical pulps results in a decreased swelling of the fibres, leading to lower density and strength properties of paper sheets. To investigate how variation of pulp pH, drying process temperature, and final moisture content affect this phenomenon, structural studies were performed on a cellulose-rich pulp. Interrupting the drying at moisture contents of around 20%, using drying temperatures of 80 °C and 140 °C, resulted in a more severe degree of hornification than if the pulp was completely dried at the same temperatures. This increased loss of swelling was accompanied by increased cellulose microfibril aggregation. No change of the cellulose microfibril size or of the cellulose crystallinity, as determined by NMR, could be seen. Further, the accessibility of the cellulose microfibril surfaces, including surfaces between microfibrils, was unaffected by the drying. Thus, hornification should not primarily be related to a reduction of accessible cellulosic surfaces.

Functional Specialization of Cellulose Synthase Isoforms in a Moss Shows Parallels with Seed Plants.

The secondary cell walls of tracheary elements and fibers are rich in cellulose microfibrils that are helically oriented and laterally aggregated. Support cells within the leaf midribs of mosses deposit cellulose-rich secondary cell walls, but their biosynthesis and microfibril organization have not been examined. Although the Cellulose Synthase (CESA) gene families of mosses and seed plants diversified independently, CESA knockout analysis in the moss Physcomitrella patens revealed parallels with Arabidopsis (Arabidopsis thaliana) in CESA functional specialization, with roles for both subfunctionalization and neofunctionalization. The similarities include regulatory uncoupling of the CESAs that synthesize primary and secondary cell walls, a requirement for two or more functionally distinct CESA isoforms for secondary cell wall synthesis, interchangeability of some primary and secondary CESAs, and some CESA redundancy. The cellulose-deficient midribs of ppcesa3/8 knockouts provided negative controls for the structural characterization of stereid secondary cell walls in wild type P. patens Sum frequency generation spectra collected from midribs were consistent with cellulose microfibril aggregation, and polarization microscopy revealed helical microfibril orientation only in wild type leaves. Thus, stereid secondary walls are structurally distinct from primary cell walls, and they share structural characteristics with the secondary walls of tracheary elements and fibers. We propose a mechanism for the convergent evolution of secondary walls in which the deposition of aggregated and helically oriented microfibrils is coupled to rapid and highly localized cellulose synthesis enabled by regulatory uncoupling from primary wall synthesis.

Adsorption behaviour of polyphenols on cellulose is affected by processing history

The impacts of hydrothermal, mechanical and drying treatments, as representative food processing methods, on cellulose binding capacity for food polyphenols have been assessed using bacterial cellulose hydrogels as a plant cell wall model system. The results show that boiling and autoclaving exert no significant effects on the binding of polyphenols. In contrast, freeze-drying decreases polyphenol adsorption onto cellulose by an order of magnitude. Rehydration of the freeze-dried cellulose prior to soaking in polyphenol solutions halves this effect. The positive correlation between the polyphenol binding capacity and water content suggests that the swelling ability of cellulose networks contributes to polyphenol-cellulose interactions. Characterisation of the multi-scale structure of cellulose hydrogels by combining SEM, XRD, SAXS and SANS indicates that the polyphenol binding capacity is strongly affected by the degree of cellulose microfibril aggregation and the availability of hydroxyl groups in the cellulose structure. The formation of interfibrillar aggregates, connected by a strong hydrogen bonding network as a result of the freeze-drying process, has been shown to limit solvent accessibility towards the interior of cellulose ribbons upon rehydration of the samples. This structural modification can be linked to the large decrease in the adsorption of polyphenols observed for the freeze-dried rehydrated samples.

Influence of cellulose supramolecular structure on strength properties of chemical pulp

Abstract The industrially produced chemical pulps have lower strength properties than those obtained under laboratory conditions, and this difference is referred to as the strength delivery (SD) problem. In this study, the hypothesis was put forward that the SD could, at least in part, be accounted for by the supramolecular structure of the cellulose microfibrils of the fiber wall. To test the hypothesis, two bleached softwood kraft pulps (BSKP) were manufactured from the same starting material with different degrees of cellulose aggregation, but the pulps were otherwise as similar as possible in other controllable respects. The chemical and physical properties, including the pulp strength, were tested. A selective increase of the degree of cellulose microfibril aggregation resulted in a pulp with a decreased tear index (TI) at a specified tensile index, and this decrease was similar in magnitude to what is typically encountered in SD. Accordingly, the current experimental study succeeded in mimicking the SD problem. The lateral fibril aggregate dimensions (LFAD) seem to play a pivotal role and it can be safely concluded in general that the supramolecular structure of cellulose in the fibers may be an important factor contributing to the SD problem.

Changes in accessibility of cellulose during kraft pulping of wood in deuterium oxide

Fresh birch chips were treated with different concentrations of sodium hydroxide and sodium sulfide in deuterium oxide in typical kraft pulping conditions and the extent of irreversible deuteration of the chips/pulps was followed by Fourier transform infrared (FT-IR) spectroscopy. Water retention values (WRV) of pulps were measured to evaluate accessibility of cellulose. The kraft pulping with deuterium oxide led to significant proton-deuterium exchange that was not reversed when the chips/pulps were washed with water. The deuteration followed a first order dynamics with a maximum obtained in the beginning of delignification stage. Higher dosages of effective alkali resulted in a higher degree of deuteration and lower WRV. An inverse relationship between the extent of deuteration and WRV suggests that both were induced by cellulose microfibril aggregation. Results also indicate that hemicellulose dissolution plays an important role in the induction of cellulose microfibril aggregation, while lignin dissolution has less influence.

Fast and efficient nanoshear hybrid alkaline pretreatment of corn stover for biofuel and materials production

We report a fast and efficient nano-scale shear hybrid alkaline (NSHA) pretreatment method of lignocellulosic biomass. In this work, corn stover was pretreated in a modified Taylor–Couette reactor with alkali (sodium hydroxide) at room temperature for two minutes. Up to 82% of high cellulose content in the remaining solids was achieved with the novel NSHA pretreatment process. Compared with untreated corn stover, an approximately 4-fold increase in enzymatic cellulose conversion and a 5-fold increase in hemicellulose conversion were achieved. Compositional analysis proved significant removals of both lignin and hemicellulose after the NSHA pretreatment. SEM images revealed that the synergistic effect of NSHA pretreatment caused the severe disruption of biomass structure and exposure of cellulose microfibril aggregates in NSHA pretreated corn stover.

Accessibility of cellulose: Structural changes and their reversibility in aqueous media

During various processing treatments, the accessibility of cellulose in cellulosic fibers reduces, which is often interpreted as cellulose microfibril aggregation. This affects the reactivity of cellulose in further processing to novel cellulosic products such as nanocellulose. In this study, the effect of aqueous treatments at elevated temperatures and various pH on accessibility of an oxygen delignified eucalyptus kraft pulp was evaluated by using deuteration combined with Fourier-transform infrared (FT-IR) spectroscopy and water retention value (WRV) test. Acidic treatments reduced WRV and caused irreversible deuteration of the pulp. However, alkaline treatments increased WRV and caused reversible deuteration of the pulp. Both deuteration and reprotonation of the deuterated pulp followed the same slow, first-order dynamics. This led us to propose that incubation of alkaline cellulosic pulp suspensions at elevated temperatures does not only lead to reduction in accessibility but also to a dynamic interconversion between accessible and inaccessible regions.

Small-angle X-ray scattering study on nanostructural changes with water content in red pine, American pine, and white ash

Wood is a highly sophisticated and multihierarchical material. The nanoscale structures in natural cell walls of red pine, American pine, and white ash specimens were investigated using the small-angle X-ray scattering (SAXS) technique. A tangent-by-tangent method was used to analyze the SAXS data. The results demonstrate that the multihierarchical scatterers in the three specimens can be divided into two dominant components, i.e., a sharp component and a wide component. The sharp component mainly corresponds to the contribution of cellulose microfibrils, and its size is almost unaffected by the water content. However, the wide component includes voids or microcracks and cellulose microfibril aggregates; its size changes, reflecting swelling and water accumulation in the voids or microcracks. Because of the different morphological features of the cell walls, softwood (red pine and American pine) displays different tendencies from hardwood (white ash) in terms of changes in the wide component with water content: the average scatterer size of the wide component has an incremental tendency with the water content in softwood, but it has a descending tendency in hardwood. Fractal analysis further revealed that in white ash the surface of scatterers is coarser and the scatterers form more compact nanostructures than in the two pine woods. All this nanostructural information can be used to explain well the difference of swelling behaviors between the two pines and the white ash.

Comparison of the characteristics of cellulose microfibril aggregates of wood, rice straw and potato tuber

The focus of this study has been to isolate cellulose microfibril aggregates by the one-time grinding treatment from wood, rice straw and potato tuber, and to compare their morphological and mechanical properties. Field emission scanning electron microscopy images showed that the diameter range of isolated microfibril aggregates from wood, 12–20 nm, was smaller than those from rice straw and potato tuber, 12–35 nm and 12–55 nm, respectively. These differences were observed even in the purified rice straws and potato tuber before the grinder treatment, but were hardly observed in the purified wood. The results of X-ray analysis and tensile tests indicated that there were no significant differences among the sources in the cellulose crystallinity and Young’s modulus of the isolated microfibril aggregates in the dry state. These results suggest that the inherent characteristics of cellulose microfibril aggregates in the dry state are very similar regardless of plant sources and tissue functions.

Comparison of the characteristics of cellulose microfibril aggregates isolated from fiber and parenchyma cells of Moso bamboo (Phyllostachys pubescens)

This study examined the relationship between the functions of plant cells and the characteristics of cellulose microfibril aggregates in the cell walls. For this purpose, the mature bamboo (Phyllostachys pubescens) culm was separated into fiber and parenchyma cells, and then the morphological and physical properties of the cellulose microfibril aggregates isolated from both cells were compared. SEM observations revealed that both fiber and parenchyma cells consist of similar microfibril aggregates approximately 15–20 nm in width. Moreover, X-ray analysis and the tensile tests of the sheets prepared from the microfibril aggregates showed that the cellulose microfibrils isolated from fiber and parenchyma cells had almost the same cellulose crystallinity and longitudinal Young’s modulus in the dry state. These results suggest that all the cellulose microfibrils synthesized in the same individual exhibit the same characteristics in the dry state regardless of cell function.

Cellulose microfibril aggregates and their size variation with cell wall type

The organization of wood cell wall components involves aggregates of cellulose microfibrils and matrix known as macrofibrils. A combination of field emission electron microscopy and environmental scanning electron microscopy was used to visualise the organization of macrofibrils in different cell wall types comparing normal and reaction wood of radiata pine and poplar as examples of a typical softwood and hardwood. The size of macrofibrils is shown to vary among cell wall types with the smallest structures occurring in the gelatinous layer of tension wood (14 nm) and the largest structures in the S2L layer of compression wood (23 nm). A positive correlation between macrofibril size and degree of lignification is observed, with macrofibrils apparently increasing in size in more highly lignified cell wall types. The fibrillar structure of the secondary wall varies from microfibril-sized structures of 3–4 nm up to large aggregates of 60 nm diameter. The size of macrofibrils also varies slightly among adjacent cells of the same cell wall type. Macrofibrils occur predominantly in a random arrangement, although radial and tangential lamellae may sometimes be seen in individual cells.