The plant cell wall is a dynamic network of several biopolymers and structural proteins including cellulose, pectin, hemicellulose and lignin. Cellulose is one of the main load bearing components of this complex, heterogeneous structure, and in this way, is an important regulator of cell wall growth and mechanics. Glucan chains of cellulose aggregate via hydrogen bonds and van der Waals forces to form long thread-like crystalline structures called cellulose microfibrils. The shape, size, and crystallinity of these microfibrils are important structural parameters that influence mechanical properties of the cell wall and these parameters are likely important determinants of cell wall digestibility for biofuel conversion. Cellulose–cellulose and cellulose-matrix interactions also contribute to the regulation of the mechanics and growth of the cell wall. As a consequence, much emphasis has been placed on extracting valuable structural details about cell wall components from several techniques, either individually or in combination, including diffraction/scattering, microscopy, and spectroscopy. In this review, we describe efforts to characterize the organization of cellulose in plant cell walls. X-ray scattering reveals the size and orientation of microfibrils; diffraction reveals unit lattice parameters and crystallinity. The presence of different cell wall components, their physical and chemical states, and their alignment and orientation have been identified by Infrared, Raman, Nuclear Magnetic Resonance, and Sum Frequency Generation spectroscopy. Direct visualization of cell wall components, their network-like structure, and interactions between different components has also been made possible through a host of microscopic imaging techniques including scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. This review highlights advantages and limitations of different analytical techniques for characterizing cellulose structure and its interaction with other wall polymers. We also delineate emerging opportunities for future developments of structural characterization tools and multi-modal analyses of cellulose and plant cell walls. Ultimately, elucidation of the structure of plant cell walls across multiple length scales will be imperative for establishing structure-property relationships to link cell wall structure to control of growth and mechanics.
Cellulose microfibrils are crucial for many of the remarkable mechanical properties of primary cell walls. Nevertheless, many structural features of cellulose microfibril organization in cell walls are not yet fully described. Microscopy techniques provide direct visualization of cell wall organization, and quantification of some aspects of wall microstructure is possible through image processing. Complementary to microscopy techniques, scattering yields structural information in reciprocal space over large sample areas. Using the onion epidermal wall as a model system, we introduce resonant soft X-ray scattering (RSoXS) to directly quantify the average interfibril spacing. Tuning the X-ray energy to the calcium L-edge enhances the contrast between cellulose and pectin due to the localization of calcium ions to homogalacturonan in the pectin matrix. As a consequence, RSoXS profiles reveal an average center-to-center distance between cellulose microfibrils or microfibril bundles of about 20 nm.
Cellulose, the most abundant biopolymer on earth, is a versatile, energy rich material found in the cell walls of plants, bacteria, algae, and tunicates. It is well established that cellulose is crystalline, although the orientational order of cellulose crystallites normal to the plane of the cell wall has not been characterized. A preferred orientational alignment of cellulose crystals could be an important determinant of the mechanical properties of the cell wall and of cellulose-cellulose and cellulose-matrix interactions. Here, the crystalline structures of cellulose in primary cell walls of onion (Allium cepa), the model eudicot Arabidopsis (Arabidopsis thaliana), and moss (Physcomitrella patens) were examined through grazing incidence wide angle X-ray scattering (GIWAXS). We find that GIWAXS can decouple diffraction from cellulose and epicuticular wax crystals in cell walls. Pole figures constructed from a combination of GIWAXS and X-ray rocking scans reveal that cellulose crystals have a preferred crystallographic orientation with the (200) and (110)/($$1\bar 10$$ 1 1 ¯ 0 ) planes preferentially stacked parallel to the cell wall. This orientational ordering of cellulose crystals, termed texturing in materials science, represents a previously unreported measure of cellulose organization and contradicts the predominant hypothesis of twisting of microfibrils in plant primary cell walls.
Starchy food items such as rice and potato with high carbohydrate content raise blood sugar. Hence, consuming low glycaemic foods is one tool to keep diabetes under control. In this study, potato and brown rice (Njavara rice) starches were subjected to hydrothermal treatments: heat moisture treatment (HMT) and annealing (ANN) to develop starch-based food products fit for consumption by diabetic patients. The effects of hydrothermal treatments on physicochemical properties and in-vitro enzymatic digestion of starch were determined. It was observed that hydrothermal treatments decreased the swelling power (SP)% and increased the water solubility (WS)% of the native starches. Native potato starch (PSN) showed a high SP of 80.33%, while annealed potato starch (PANN) and heat moisture treated potato starch (PHMT) showed SP reduced to 65.33% and 51.66%, respectively. Similarly, the SP % reduced from 64.33% in native brown rice (BRN) to 44.66% in annealed brown rice (BRANN) and 38.33% in heat moisture treated brown rice (BRHMT). WS % increased from 32.86% in PSN to 36.66% in PANN and 40.66% in PHMT. In BRN, the WS % increased from 14.0% to 14.66% in BRANN and 18.33% in BRHMT. Amylose content increased from 13.23% and 14.56% in PSN and BRN to 16.14% in PANN 17.99% in PHMT, 17.33% in BRANN, and 18.98% in BRHMT. The PSN crystallinity index reduced from 33.49 to 30.50% in PANN and 32.60% in PHMT. At 12 h of enzymatic digestion, it was found that the degree of hydrolysis (DoH) of PHMT (31.66%) and PANN (36.82%) reduced when compared to PSN (41.09%). Similarly, BRHMT exhibited the lowest DoH at 12 h compared to BRANN (29.24%) and BRN (35.48%). This study highlights the importance of hydrothermal treatments on starch in developing low glycaemic index commercial starch-based food products.
Cellulose obtained from plants is a bio‐polysaccharide and the most abundant organic polymer on earth that has immense household and industrial applications. Hence, the characterization of cellulose is important for determining its appropriate applications. In this article, we review the characterization of cellulose morphology, surface topography using microscopic techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Other physicochemical characteristics like crystallinity, chemical composition, and thermal properties are studied using techniques including X‐ray diffraction, Fourier transform infrared, Raman spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This review may contribute to the development of using cellulose as a low‐cost raw material with anticipated physicochemical properties. Highlights Morphology and surface topography of cellulose structure is characterized using microscopy techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Analytical techniques used for physicochemical characterization of cellulose include X‐ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and thermogravimetric analysis.
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