Wide-angle X-ray scattering studies on contemporary and ancient bast fibres used in textiles - ultrastructural studies on stinging nettle

Stinging nettle (Urtica dioica) is a potential source material for industrial applications. However, systematic research on the ultrastructural properties of nettle fibres is lacking. Determining the ultrastructure of nettle and the other bast fibres also provides new insights into the studies of archaeological fibres and their usage. In this study, the nanostructure of modern and ancient nettle samples was studied using wide-angle X-ray scattering (WAXS) and compared to other bast fibres. The culturo-historical fibre samples consisted of nettle, flax, and hemp from White Karelian textiles collected 1894 as well as of 800-900-year-old archaeological textile fragments from Ravattula Ristimaki burial site, Finland. Using WAXS, the average cellulose crystallite widths, relative crystallinities and orientational order (including microfibril angle for the modern fibres) were determined and compared. The results also revealed the suitability of the WAXS analysis for fibre identification. The crystallite widths were of the similar size for all modern fibres (3.4-4.8 nm). Subtle differences in the relative crystallinities in descending order (from flax to nettle, and finally hemp) were observed. Also, subtle differences in the mean MFAs were observed (10 +/- 1 degrees for flax, 12 +/- 1 degrees for nettle, and 14 +/- 1 degrees for hemp). For the culturo-historical fibres, the values for crystallite widths and relative crystallinities were larger compared to the corresponding modern references. In addition, features due to the presence of non-cellulosic, crystalline substances (e.g., calcium oxalates) were detected in the WAXS patterns of all the modern nettle fibres. These features could potentially be used as a tool for identification purposes.Peer reviewe

Spatially-localized bench-top X-ray scattering reveals tissue-specific microfibril orientation in Moso bamboo

Background : Biological materials have a complex, hierarchical structure, with vital structural features present at all size scales, from the nanoscale to the macroscale. A method that can connect information at multiple length scales has great potential to reveal novel information. This article presents one such method with an application to the bamboo culm wall. Moso (Phyllostachys edulis) bamboo is a commercially important bamboo species. At the cellular level, bamboo culm wall consists of vascular bundles embedded in a parenchyma cell tissue matrix. The microfibril angle (MFA) in the bamboo cell wall is related to its macroscopic longitudinal stiffness and strength and can be determined at the nanoscale with wide-angle X-ray scattering (WAXS). Combining WAXS with X-ray microtomography (XMT) allows tissue-specific study of the bamboo culm without invasive chemical treatment. Results : The scattering contribution of the fiber and parenchyma cells were separated with spatially-localized WAXS. The fiber component was dominated by a high degree of orientation corresponding to small MFAs (mean MFA 11 degrees). The parenchyma component showed significantly lower degree of orientation with a maximum at larger angles (mean MFA 65 degrees). The fiber ratio, the volume of cell wall in the fibers relative to the overall volume of cell wall, was determined by fitting the scattering intensities with these two components. The fiber ratio was also determined from the XMT data and similar fiber ratios were obtained from the two methods, one connected to the cellular level and one to the nanoscale. X-ray diffraction tomography was also done to study the differences in microfibril orientation between fibers and the parenchyma and further connect the microscale to the nanoscale. Conclusions : The spatially-localized WAXS yields biologically relevant, tissue-specific information. With the custommade bench-top set-up presented, diffraction contrast information can be obtained from plant tissue (1) from regions-of-interest, (2) as a function of distance (line scan), or (3) with two-dimensional or three-dimensional tomography. This nanoscale information is connected to the cellular level features.Peer reviewe

Near-infrared analysis of nanofibrillated cellulose aerogel manufacturing

Biomaterial aerogel fabrication by freeze-drying must be further improved to reduce the costs of lengthy freeze-drying cycles and to avoid the formation of spongy cryogels and collapse of the aerogel structures. Residual water content is a critical quality attribute of the freeze-dried product, which can be monitored in-line with near-infrared (NIR) spectroscopy. Predictive models of NIR have not been previously applied for biomaterials and the models were mostly focused on the prediction of only one formulation at a time. We recorded NIR spectra of different nanofibrillated cellulose (NFC) hydrogel formulations during the secondary drying and set up a partial least square regression model to predict their residual water contents. The model can be generalized to measure residual water of formulations with different NFC concentrations and the excipients, and the NFC fiber concentrations and excipients can be separated with the principal component analysis. Our results provide valuable information about the freeze-drying of biomaterials and aerogel fabrication, and how NIR spectroscopy can be utilized in the optimization of residual water content.Peer reviewe

Molecular Insights on Successful Reconstitution of Freeze-Dried Nanofibrillated Cellulose Hydrogel

The diversity and safety of nanofibrillated cellulose (NFC) hydrogels have gained a vast amount of interest at the pharmaceutical site in recent years. Moreover, this biomaterial has a high potential to be utilized as a protective matrix during the freeze-drying of heat-sensitive pharmaceuticals and biologics to increase their properties for long-term storing at room temperature and transportation. Since freeze-drying and subsequent reconstitution have not been optimized for this biomaterial, we must find a wider understanding of the process itself as well as the molecular level interactions between the NFC hydrogel and the most suitable lyoprotectants. Herein we optimized the reconstitution of the freeze-dried NFC hydrogel by considering critical quality attributes required to ensure the success of the process and gained insights of the obtained experimental data by simulating the effects of the used lyoprotectants on water and NFC. We discovered the correlation between the measured characteristics and molecular dynamics simulations and obtained successful freeze-drying and subsequent reconstitution of NFC hydrogel with the presence of 300 mM of sucrose. These findings demonstrated the possibility of using the simulations together with the experimental measurements to obtain a more comprehensive way to design a successful freeze-drying process, which could be utilized in future pharmaceutical applications.Peer reviewe