Contributions of Crystalline and Noncrystalline Cellulose Can Occur in the Same Spectral Regions: Evidence Based on Raman and IR and Its Implication for Crystallinity Measurements.

Aggregated states of celluloses remain poorly understood, and therefore, the topic requires careful investigation. In this study, Raman, IR, and X-ray diffraction (XRDs) were used to study cotton microcrystalline cellulose (MCC) and MCC that has been ball-milled to various degrees. Raman and IR spectroscopy methods indicated that when these ball-milled samples were wet with water, most underwent conformational changes at the molecular level. Although formation of cellulose II was observed in longer duration ball-milled samples, the changes primarily gave rise to increased contributions in spectral and diffraction regions typically associated with the contributions of crystalline cellulose I. Moreover, when the wet samples were air-dried at 25 °C, the newly formed cellulose I-like structures partly reverted to the previous form present in the initial dry state. These findings explained for the previously reported XRD and NMR observations, where the addition of water resulted in increased crystallinities of cellulose samples. The implications of these findings to cellulose crystallinity measurements and other situations are discussed.

New cellulose crystallinity estimation method that differentiates between organized and crystalline phases.

A new method is proposed for estimation of cellulose crystallinity (CrI) based on 93 cm-1 Raman band in spectra of cellulose I materials. In this method (93-Raman), CrI was determined based on regression that was developed using the ratios of peak-heights of the 93 and 1096 cm-1 Raman bands (I93/I1096). For calibration purposes, a set of eight samples, all derived from cotton microcrystalline cellulose Whatman CC31 were selected. When the peak intensity ratios (I93/I1096) were plotted against the calculated CrIs of the calibration set samples, the plot showed an excellent linear correlation (R2 = 0.9888). The 93-Raman method was used to estimate crystallinities of a number of cellulose materials including poplar wood samples that were hydrothermally treated at various temperatures. The wood 93-Raman CrI data showed that the method is able to differentiate between organized and crystalline phases of cellulose, a capability lacking in many other CrI estimation methods.

Pulmonary exposure to cellulose nanocrystals caused deleterious effects to reproductive system in male mice.

Over the past several years there has been an increased number of applications of cellulosic materials in many sectors, including the food industry, cosmetics, and pharmaceuticals. However, to date, there are few studies investigating the potential adverse effects of cellulose nanocrystals (CNC). The objective of this study was to determine long-term outcomes on the male reproductive system of mice upon repeated pharyngeal aspiration exposure to CNC. To achieve this, cauda epididymal sperm samples were analyzed for sperm concentration, motility, morphological abnormalities, and DNA damage. Testicular and epididymal oxidative damage was evaluated, as well as histopathology examination of testes. In addition, changes in levels of testosterone in testes and serum and of luteinizing hormone (LH) in serum were determined. Three months after the last administration, CNC exposure significantly altered sperm concentration, motility, cell morphology, and sperm DNA integrity. These parameters correlated with elevated proinflammatory cytokines levels and myeloperoxidase (MPO) activity in testes, as well as oxidative stress in both testes and epididymis. Exposure to CNC also produced damage to testicular structure, as evidenced by presence of interstitial edema, frequent dystrophic seminiferous tubules with arrested spermatogenesis and degenerating spermatocytes, and imbalance in levels of testosterone and LH. Taken together, these results demonstrate that pulmonary exposure to CNC induces sustained adverse effects in spermatocytes/spermatozoa, suggesting male reproductive toxicity.

Gender differences in murine pulmonary responses elicited by cellulose nanocrystals.

BACKGROUND: Cellulose-based materials have been used for centuries to manufacture different goods derived from forestry and agricultural sources. In the growing field of nanocellulose applications, its uniquely engineered properties are instrumental for inventive products coming to competitive markets. Due to their high aspect ratio and stiffness, it is speculated that cellulose nanocrystals (CNC) may cause similar pulmonary toxicity as carbon nanotubes and asbestos, thus posing a potential negative impact on public health and the environment. METHODS: The present study was undertaken to investigate the pulmonary outcomes induced by repeated exposure to respirable CNC. C57BL/6 female and male mice were exposed by pharyngeal aspiration to CNC (40 µg/mouse) 2 times a week for 3 weeks. Several biochemical endpoints and pathophysiological outcomes along with gene expression changes were evaluated and compared in the lungs of male and female mice. RESULTS: Exposure to respirable CNC caused pulmonary inflammation and damage, induced oxidative stress, elevated TGF-ß and collagen levels in lung, and impaired pulmonary functions. Notably, these effects were markedly more pronounced in females compared to male mice. Moreover, sex differences in responses to pulmonary exposure to CNC were also detected at the level of global mRNA expression as well as in inflammatory cytokine/chemokine activity. CONCLUSIONS: Overall, our results indicate that there are considerable differences in responses to respirable CNC based on gender with a higher pulmonary toxicity observed in female mice.

Highly Transparent and Toughened Poly(methyl methacrylate) Nanocomposite Films Containing Networks of Cellulose Nanofibrils.

Cellulose nanofibrils (CNFs) are a class of cellulosic nanomaterials with high aspect ratios that can be extracted from various natural sources. Their highly crystalline structures provide the nanofibrils with excellent mechanical and thermal properties. The main challenges of CNFs in nanocomposite applications are associated with their high hydrophilicity, which makes CNFs incompatible with hydrophobic polymers. In this study, highly transparent and toughened poly(methyl methacrylate) (PMMA) nanocomposite films were prepared using various percentages of CNFs covered with surface carboxylic acid groups (CNF-COOH). The surface groups make the CNFs interfacial interaction with PMMA favorable, which facilitate the homogeneous dispersion of the hydrophilic nanofibrils in the hydrophobic polymer and the formation of a percolated network of nanofibrils. The controlled dispersion results in high transparency of the nanocomposites. Mechanical analysis of the resulting films demonstrated that a low percentage loading of CNF-COOH worked as effective reinforcing agents, yielding more ductile and therefore tougher films than the neat PMMA film. Toughening mechanisms were investigated through coarse-grained simulations, where the results demonstrated that a favorable polymer-nanofibril interface together with percolation of the nanofibrils, both facilitated through hydrogen bonding interactions, contributed to the toughness improvement in these nanocomposites.

Spatially resolved characterization of cellulose nanocrystal-polypropylene composite by confocal Raman microscopy.

Raman spectroscopy was used to analyze cellulose nanocrystal (CNC) -polypropylene (PP) composites and to investigate the spatial distribution of CNCs in extruded composite filaments. Three composites were made from two forms of nanocellulose (CNCs from wood pulp and the nano-scale fraction of microcrystalline cellulose) and two of the three composites investigated used maleated PP as a coupling agent. Raman maps, based on cellulose and PP bands at 1098 and 1460 cm(-1), respectively, obtained at 1 µm spatial resolution showed that the CNCs were aggregated to various degrees in the PP matrix. Of the three composites analyzed, two showed clear existence of phase-separated regions: Raman images with strong PP and absent/weak cellulose or vice versa. For the third composite, the situation was slightly improved but a clear transition interface between the PP-abundant and CNC-abundant regions was observed, indicating that the CNC remained poorly dispersed. The spectroscopic approach to investigating spatial distribution of the composite components was helpful in evaluating CNC dispersion in the composite at the microscopic level, which helped explain the relatively modest reinforcement of PP by the CNCs.