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Lignification of cell wall appositions is a conserved basal defense mechanism in the plant innate immune response. However, the genetic pathway controlling defense-induced lignification remains unknown. Here, we demonstrate the Arabidopsis thaliana SG2-type R2R3-MYB transcription factor MYB15 as a regulator of defense-induced lignification and basal immunity. Loss of MYB15 reduces the content but not the composition of defense-induced lignin, whereas constitutive expression of MYB15 increases lignin content independently of immune activation. Comparative transcriptional and metabolomics analyses implicate MYB15 as necessary for the defense-induced synthesis of guaiacyl lignin and the basal synthesis of the coumarin metabolite scopoletin. MYB15 directly binds to the secondary wall MYB-responsive element consensus sequence, which encompasses the AC elements, to drive lignification. The myb15 and lignin biosynthetic mutants show increased susceptibility to the bacterial pathogen Pseudomonas syringae, consistent with defense-induced lignin having a major role in basal immunity. A scopoletin biosynthetic mutant also shows increased susceptibility independently of immune activation, consistent with a role in preformed defense. Our results support a role for phenylalanine-derived small molecules in preformed and inducible Arabidopsis defense, a role previously dominated by tryptophan-derived small molecules. Understanding the regulatory network linking lignin biosynthesis to plant growth and defense will help lignin engineering efforts to improve the production of biofuels and aromatic industrial products as well as increase disease resistance in energy and agricultural crops.

Diosgenin is a spiroketal steroidal natural product extracted from plants and used as the single most important precursor for the world steroid hormone industry. The sporadic occurrences of diosgenin in distantly related plants imply possible independent biosynthetic origins. The characteristic 5,6-spiroketal moiety in diosgenin is reminiscent of the spiroketal moiety present in anthelmintic avermectins isolated from actinomycete bacteria. How plants gained the ability to biosynthesize spiroketal natural products is unknown. Here, we report the diosgenin-biosynthetic pathways in himalayan paris ( Paris polyphylla ), a monocot medicinal plant with hemostatic and antibacterial properties, and fenugreek ( Trigonella foenum–graecum ), an eudicot culinary herb plant commonly used as a galactagogue. Both plants have independently recruited pairs of cytochromes P450 that catalyze oxidative 5,6-spiroketalization of cholesterol to produce diosgenin, with evolutionary progenitors traced to conserved phytohormone metabolism. This study paves the way for engineering the production of diosgenin and derived analogs in heterologous hosts. Diosgenin is a spiroketal natural product that is used as a precursor in the industrial synthesis of steroids. Here, the authors identified key cytochrome P450 enzymes responsible for the conversion of cholesterol to diosgenin from two phylogenetical distinct diosgenin-producing plant species.

Intrinsic antiferromagnetism in van der Waals (vdW) monolayer (ML) crystals enriches our understanding of two-dimensional (2D) magnetic orders and presents several advantages over ferromagnetism in spintronic applications. However, studies of 2D intrinsic antiferromagnetism are sparse, owing to the lack of net magnetisation. Here, by combining spin-polarised scanning tunnelling microscopy and first-principles calculations, we investigate the magnetism of vdW ML CrTe 2 , which has been successfully grown through molecular-beam epitaxy. We observe a stable antiferromagnetic (AFM) order at the atomic scale in the ML crystal, whose bulk is ferromagnetic, and correlate its imaged zigzag spin texture with the atomic lattice structure. The AFM order exhibits an intriguing noncollinear spin reorientation under magnetic fields, consistent with its calculated moderate magnetic anisotropy. The findings of this study demonstrate the intricacy of 2D vdW magnetic materials and pave the way for their in-depth analysis. In two dimensions magnetic order without magnetic anisotropy is forbidden, making 2D magnetic systems a rich playground for interesting physics. Here, Xian et al. fabricate monolayers of CrTe2, and demonstrate antiferromagnetic ordering, with spin reorientation at finite magnetic fields.

Plant halogenated natural products are rare and harbor various interesting bioactivities, yet the biochemical basis for the involved halogenation chemistry is unknown. While a handful of Fe(II)- and 2-oxoglutarate-dependent halogenases (2ODHs) have been found to catalyze regioselective halogenation of unactivated C–H bonds in bacteria, they remain uncharacterized in the plant kingdom. Here, we report the discovery of dechloroacutumine halogenase (DAH) from Menispermaceae plants known to produce the tetracyclic chloroalkaloid (−)-acutumine. DAH is a 2ODH of plant origin and catalyzes the terminal chlorination step in the biosynthesis of (−)-acutumine. Phylogenetic analyses reveal that DAH evolved independently in Menispermaceae plants and in bacteria, illustrating an exemplary case of parallel evolution in specialized metabolism across domains of life. We show that at the presence of azide anion, DAH also exhibits promiscuous azidation activity against dechloroacutumine. This study opens avenues for expanding plant chemodiversity through halogenation and azidation biochemistry. Halogenated plant natural products are rare and plant halogenation enzymes are thus far unknown. Here Kim et al. identify a dechloroacutumine halogenase from Common Moonseed that catalyzes the final chlorination step in the biosynthesis of acutumine, a chloroalkaloid with selective cytotoxicity to cultured T cells.

Sporopollenin is a ubiquitous and extremely chemically inert biopolymer that constitutes the outer wall of all land-plant spores and pollen grains 1 . Sporopollenin protects the vulnerable plant gametes against a wide range of environmental assaults, and is considered a prerequisite for the migration of early plants onto land 2 . Despite its importance, the chemical structure of plant sporopollenin has remained elusive 1 . 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 that pine sporopollenin is primarily composed of aliphatic-polyketide-derived polyvinyl alcohol units and 7- O - p -coumaroylated C16 aliphatic 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 make-up of plant sporopollenin, laying the foundation for future investigations of sporopollenin biosynthesis and for the design of new biomimetic polymers with desirable inert properties. A distinct feature of pollen gains is their resistant outer wall, called the exine, which is mainly composed of sporopollenin, the toughest biopolymer known to date despite an unknown detailed structure. Now, a structural model of pine sporopollenin is revealed by the application of new degradation chemistry and solid-state NMR spectroscopy.

Topological states emerge at the boundary of solids as a consequence of the nontrivial topology of the bulk. Recently, theory predicts a topological edge state on single layer transition metal dichalcogenides with 1 T ’ structure. However, its existence still lacks experimental proof. Here, we report the direct observations of the topological states at the step edge of WTe 2 by spectroscopic-imaging scanning tunneling microscopy. A one-dimensional electronic state residing at the step edge of WTe 2 is observed, which exhibits remarkable robustness against edge imperfections. First principles calculations rigorously verify the edge state has a topological origin, and its topological nature is unaffected by the presence of the substrate. Our study supports the existence of topological edge states in 1 T ’-WTe 2 , which may envision in-depth study of its topological physics and device applications. Two-dimensional topological insulators support edge conduction electrons but its realization in real materials is rare. Here, Peng et al. report the direct observation of topological states at the step edge of WTe 2 .

The natural product icariin inhibits human phosphodiesterase-5 (PDE5) and represents a unique pharmacophore for treating erectile dysfunction, pulmonary hypertension, and other diseases. In this study, we explore the available icariin-derived chemical scaffolds through medicinal chemistry to develop novel icariin PDE5 inhibitors with improved potency and specificity. We synthesized six novel semi-synthetic icariin analogs as well as three naturally occurring icariin analogs, and characterized the structure-activity relationship in the context of human PDE5 inhibition using in vitro enzyme inhibition and kinetics assays and molecular modeling. Mammalian-cell-based assays and in vitro enzyme inhibition assays against human PDE6C further helped to identify the most potent and selective icariin analogs. Our results reveal the synergistic contribution of functional groups at the C3 and C7 positions of the icariin backbone towards PDE5 inhibition. Whereas a hydrophobic and flexible alkanol group at the C7 position is sufficient to enhance icariin analog potency, combining this group with a hydrophilic sugar group at the C3 position leads to further enhancement of potency and promotes specificity towards PDE5 versus PDE6C. In particular, compounds 3 and 7 exhibit Ki values of 0.036 ± 0.005 μM and 0.036 ± 0.007 μM towards PDE5 respectively, which are approaching those of commercial PDE5 inhibitors, and can effectively reduce GMP levels in cultured human BJ-hTERT cells. This study identifies novel icariin analogs as potent and selective PDE5 inhibitors poised to become lead compounds for further pharmaceutical development.

Polarons are entities of excess electrons dressed with local response of lattices, whose atomic-scale characterization is essential for understanding the many body physics arising from the electron-lattice entanglement, yet difficult to achieve. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we show the visualization and manipulation of single polarons in monolayer CoCl 2 , that are grown on HOPG substrate via molecular beam epitaxy. Two types of polarons are identified, both inducing upward local band bending, but exhibiting distinct appearances, lattice occupations and polaronic states. First principles calculations unveil origin of polarons that are stabilized by cooperative electron-electron and electron-phonon interactions. Both types of polarons can be created, moved, erased, and moreover interconverted individually by the STM tip, as driven by tip electric field and inelastic electron tunneling effect. This finding identifies the rich category of polarons in CoCl 2 and their feasibility of precise control unprecedently, which can be generalized to other transition metal halides. Using scanning tunnelling microscopy (STM) and spectroscopy, the authors show the visualization and manipulation of single polarons in monolayer CoCl 2 . Polarons can be created, moved, erased, and interconverted individually by the STM tip.

To solve the power supply problem of battery-limited Internet of Things devices (IoDs) and the spectrum scarcity problem, simultaneous wireless information and power transfer (SWIPT) and cognitive radio (CR) technology were integrated into the Internet of Things (IoT) network to build a cognitive radio IoT (CRIoT) with SWIPT. In this network, secondary users (SUs) could adaptively switch between spectrum sensing, SWIPT, and information transmission to improve the total throughput. To solve the complicated multi-dimensional resource allocation problem in CRIoT with SWIPT, we propose a multi-dimensional resource allocation algorithm for maximizing the total throughput. Three-dimensional resources were jointly optimized, which are time resource (the duration of each process), power resource (the transmit power and the power splitting ratio of each node), and spectrum resource, under some constraints, such as maximum transmit power constraint and maximum permissible interference constraint. To solve this intractable mixed-integer nonlinear program (MINLP) problem, firstly, the sensing task assignment for cooperative spectrum sensing (CSS) was obtained by using a greedy sensing algorithm. Secondly, the original problem was transformed into a convex problem via some transformations with fixed-power splitting ratio and time switching. The Lagrange dual method and subgradient method were adopted to obtain the optimal power and channel allocation. Then, a one-dimensional search algorithm was used to obtain the optimal power splitting ratio and the time switching ratio. Finally, a heuristic algorithm was adopted to obtain the optimal sensing duration. The simulation results show that the proposed algorithm can achieve higher total system throughput than other benchmark algorithms, such as a greedy algorithm, an average algorithm, and the Kuhn–Munkres (KM) algorithm.

Simultaneous Wireless Information and Power Transfer (SWIPT) integrated with non-orthogonal multiple access (NOMA) offers a promising solution for energy-efficient Internet of Things (IoT) applications in the context of increasingly scarce spectrum resources. This paper addresses the energy efficiency (EE) maximization problem in a downlink cooperative SWIPT-NOMA network, where user cooperation is employed to mitigate the near-far effect and enhance network performance. We formulate the EE optimization problem for a multi-user scenario by jointly optimizing the transmission time, the power allocation ratio, and the transmission power of the near user in the cooperative SWIPT-NOMA network, and we propose a cooperative SWIPT-NOMA energy efficiency allocation algorithm. Firstly, the fractional programming problem for EE maximization is transformed into a more tractable form using the Dinkelbach method. Subsequently, the resource allocation variables are iteratively updated via variable substitution, successive convex approximation, and the Lagrangian dual method until the algorithm converges. Extensive simulations are conducted to evaluate the performance of the proposed algorithm under various conditions and to compare it with existing schemes. The proposed algorithm enhances network energy efficiency while ensuring user throughput, providing a more efficient resource allocation solution for wireless communication networks.