17 Search Results

The coexistence of rigid and mobile molecules or molecular segments abounds in biomolecular assemblies. Examples include the carbohydrate-rich cell walls of plants and intrinsically disordered proteins that contain rigid β-sheet cores. In solid-state nuclear magnetic resonance (NMR) spectroscopy, dipolar polarization transfer experiments are well suited for detecting rigid components, whereas scalar-coupling experiments are well suited for detecting highly mobile components. However, few NMR methods are available to detect the segments that undergo intermediate-amplitude fast motion. Here, we introduce two NMR experiments, a two-dimensional T_2H-filtered CP-hCH correlation and a three-dimensional J-INADEQUATE CCH correlation, to observe this intermediate-amplitude motion. Both experiments involvemore » ¹H detection under fast magic-angle spinning (MAS). By combining ¹H transverse relaxation (T_2H) filters with dipolar polarization transfer, we suppress the signals of both highly rigid and highly mobile species, thus revealing the signals of intermediate mobile species. ¹H detection under fast MAS is crucial for distinguishing the different motional amplitudes. Here, we demonstrate these techniques on several plant cell wall samples and show that they allow the selective detection and resolution of certain hemicellulose and pectin signals, which are usually masked by the signals of the rigid cellulose and the highly dynamic pectins in purely dipolar and scalar NMR spectra.« less

Summary The Poaceae family of plants provides cereal crops that are critical for human and animal nutrition, and also, they are an important source of biomass. Interacting plant cell wall components give rise to recalcitrance to digestion; thus, understanding the wall molecular architecture is important to improve biomass properties. Xylan is the main hemicellulose in grass cell walls. Recently, we reported structural variation in grass xylans, suggesting functional specialisation and distinct interactions with cellulose and lignin. Here, we investigated the functions of these xylans by perturbing the biosynthesis of specific xylan types. We generated CRISPR/Cas9 knockout mutants in Brachypodium distachyonmore » XAX1 and GUX2 genes involved in xylan substitution. Using carbohydrate gel electrophoresis, we identified biochemical changes in different xylan types. Saccharification, cryo‐SEM, subcritical water extraction and ssNMR were used to study wall architecture. Bd XAX1A and Bd GUX2 enzymes modify different types of grass xylan. Brachypodium mutant walls are likely more porous, suggesting the xylan substitutions directed by both Bd XAX1A and GUX2 enzymes influence xylan‐xylan and/or xylan–lignin interactions. Since xylan substitutions influence wall architecture and digestibility, our findings open new avenues to improve cereals for food and to use grass biomass for feed and the production of bioenergy and biomaterials.« less

Polysaccharide methylation, especially that of pectin, is a common and important feature of land plant cell walls. Polysaccharide methylation takes place in the Golgi apparatus and therefore relies on the import of S-adenosyl methionine (SAM) from the cytosol into the Golgi. However, so far, no Golgi SAM transporter has been identified in plants. Here we studied major facilitator superfamily members in Arabidopsis that we identified as putative Golgi SAM transporters (GoSAMTs). Knockout of the two most highly expressed GoSAMTs led to a strong reduction in Golgi-synthesized polysaccharide methylation. Furthermore, solid-state NMR experiments revealed that reduced methylation changed cell wall polysaccharidemore » conformations, interactions and mobilities. Notably, NMR revealed the existence of pectin ‘egg-box’ structures in intact cell walls and showed that their formation is enhanced by reduced methyl esterification. Here, these changes in wall architecture were linked to substantial growth and developmental phenotypes. In particular, anisotropic growth was strongly impaired in the double mutant. The identification of putative transporters involved in import of SAM into the Golgi lumen in plants provides new insights into the paramount importance of polysaccharide methylation for plant cell wall structure and function.« less

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samplesmore » have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.« less

Plant cell walls consist of a mixture of polysaccharides that render the cell wall a strong and dynamic material. Understanding the molecular structure and dynamics of wall polysaccharides is important for understanding and improving the properties of this energy-rich biomaterial. So far, solid-state NMR studies of cell wall structure and dynamics have solely relied on ¹³C chemical shifts measured from 2D and 3D correlation experiments. To increase the spectral resolution, sensitivity and upper limit of measurable distances, it is of interest to explore ¹H chemical shifts and ¹H-detected NMR experiments for analyzing cell walls. Here we demonstrate 2D and 3Dmore » ¹H–¹³C correlation experiments at both moderate and fast MAS frequencies of 10–50 kHz to resolve and assign ¹H chemical shifts of matrix polysaccharides in Arabidopsis primary cell walls. Here, both ¹³C-detected and ¹H-detected experiments are implemented and are shown to provide useful and complementary information. Using the assigned ¹H chemical shifts, we measured long-range correlations between matrix polysaccharides and cellulose using ¹H–¹H instead of ¹³C–¹³C spin diffusion, and the 2D experiments can be conducted with either ¹³C or ¹H detection.« less

van der Waals (vdW) layered compounds provided a fruitful research platform for the realization of superconductivity. However, a vdW layered superconductor with a high transition temperature (T_c) at ambient conditions is still rare. Here, using variable-composition evolutionary structure predictions, we systematically explored the stable compounds in the P-S system up to 20 GPa. Opposed to the complex stoichiometries at ambient conditions, only one compound, PS₂, is predicted to be thermodynamically stable above 8 GPa. Strikingly, PS₂ is a vdW layered material isostructural to 3R–MoS₂ exhibiting a predicted T_c of around 11 K at ambient pressure, both in the bulk andmore » the monolayer form. PS₂ has been successfully synthesized via high-pressure experiments following the theoretical predictions. Furthermore, this enables replacing transition metals with group V elements in transition-metal dichalcogenides and paves the way in the search for vdW layered materials with superior properties.« less

Sporopollenin is a ubiquitous and extremely chemically inert biopolymer that constitutes the outer wall of all land-plant spores and pollen grains. Sporopollenin protects the vulnerable plant gametes against a wide range of environmental assaults, and is considered as a prerequisite for the migration of early plants onto land2. Despite its importance, the chemical structure of plant sporopollenin has remained elusive1. Using a newly developed thioacidolysis degradative method together with state-of-the-art solid-state NMR techniques, we determined the detailed molecular structure of pine sporopollenin. We show here that pine sporopollenin is primarily composed of aliphatic-polyketide-derived polyvinyl alcohol units and 7-O-p-coumaroylated C16 aliphaticmore » units, crosslinked through a distinctive dioxane moiety featuring an acetal. Naringenin was also identified as a minor component of pine sporopollenin. This discovery answers the long-standing question about the chemical makeup of plant sporopollenin, laying the foundation for future explorations of sporopollenin biosynthesis and for design of new biomimetic polymers with desirable inert properties.« less