Aromatization of natural products by a specialized detoxification enzyme.

In plants, lineage-specific metabolites can be created by activities derived from the catalytic promiscuity of ancestral proteins, although examples of recruiting detoxification systems to biosynthetic pathways are scarce. The ubiquitous glyoxalase (GLX) system scavenges the cytotoxic methylglyoxal, in which GLXI isomerizes the α-hydroxy carbonyl in the methylglyoxal-glutathione adduct for subsequent hydrolysis. We show that GLXIs across kingdoms are more promiscuous than recognized previously and can act as aromatases without cofactors. In cotton, a specialized GLXI variant, SPG, has lost its GSH-binding sites and organelle-targeting signal, and evolved to aromatize cyclic sesquiterpenes bearing α-hydroxyketones to synthesize defense compounds in the cytosol. Notably, SPG is able to transform acetylated deoxynivalenol, the prevalent mycotoxin contaminating cereals and foods. We propose that detoxification enzymes are a valuable source of new catalytic functions and SPG, a standalone enzyme catalyzing complex reactions, has potential for toxin degradation, crop engineering and design of novel aromatics.

An effector from cotton bollworm oral secretion impairs host plant defense signaling.

Insects have evolved effectors to conquer plant defense. Most known insect effectors are isolated from sucking insects, and examples from chewing insects are limited. Moreover, the targets of insect effectors in host plants remain unknown. Here, we address a chewing insect effector and its working mechanism. Cotton bollworm (Helicoverpa armigera) is a lepidopteran insect widely existing in nature and severely affecting crop productivity. We isolated an effector named HARP1 from H. armigera oral secretion (OS). HARP1 was released from larvae to plant leaves during feeding and entered into the plant cells through wounding sites. Expression of HARP1 in Arabidopsis mitigated the global expression of wounding and jasmonate (JA) responsive genes and rendered the plants more susceptible to insect feeding. HARP1 directly interacted with JASMONATE-ZIM-domain (JAZ) repressors to prevent the COI1-mediated JAZ degradation, thus blocking JA signaling transduction. HARP1-like proteins have conserved function as effectors in noctuidae, and these types of effectors might contribute to insect adaptation to host plants during coevolution.

Functional analysis of CYP71AV1 reveals the evolutionary landscape of artemisinin biosynthesis.

Artemisinin biosynthesis, unique to Artemisia annua, is suggested to have evolved from the ancestral costunolide biosynthetic pathway commonly found in the Asteraceae family. However, the evolutionary landscape of this process is not fully understood. The first oxidase in artemisinin biosynthesis, CYP71AV1, also known as amorpha-4,11-diene oxidase (AMO), has specialized from ancestral germacrene A oxidases (GAOs). Unlike GAO, which exhibits catalytic promiscuity toward amorpha-4,11-diene, the natural substrate of AMO, AMO has lost its ancestral activity on germacrene A. Previous studies have suggested that the loss of the GAO copy in A. annua is responsible for the abolishment of the costunolide pathway. In the genome of A. annua, there are two copies of AMO, each of which has been reported to be responsible for the different product profiles of high- and low-artemisinin production chemotypes. Through analysis of their tissue-specific expression and comparison of their sequences with those of other GAOs, it was discovered that one copy of AMO (AMOHAP) exhibits a different transcript compared to the reported artemisinin biosynthetic genes and shows more sequence similarity to other GAOs in the catalytic regions. Furthermore, in a subsequent in vitro enzymatic assay, the recombinant protein of AMOHAP unequivocally demonstrated GAO activity. This result clearly indicates that AMOHAP is a GAO rather than an AMO and that its promiscuous activity on amorpha-4,11-diene has led to its misidentification as an AMO in previous studies. In addition, the divergent expression pattern of AMOHAP compared to that of the upstream germacrene A synthase may have contributed to the abolishment of costunolide biosynthesis in A. annua. Our findings reveal a complex evolutionary landscape in which the emergence of a new metabolic pathway replaces an ancestral one.

[Spatial Correlation of Land Use Carbon Budget Based on Social Network Analysis： A Case Study of Chongqing Metropolitan Area].

Clarifying the temporal and spatial changes in the carbon budget in the Chongqing metropolitan area and exploring the spatial correlation of land use carbon budget are of great significance for realizing the regional "double carbon" goal. Using 21 districts and counties in Chongqing metropolitan area as the research scale, the IPCC inventory method, carbon emission coefficient method, Gini coefficient, gravity model, and social network analysis were used to estimate the net carbon emissions from land use in Chongqing metropolitan area from 2000 to 2020, and the spatial correlation of the carbon budget was obtained. The results revealed that： ① In the past 20 years, the carbon budget of the Chongqing metropolitan area showed an overall upward trend, with an average annual growth rate of 2.83%, and the spatial distribution was "higher in the north and south, higher in the east and west, and lower in the middle." ② During the past 20 years, the spatial difference of net carbon emissions in the Chongqing metropolitan area became highly average, and the overall Gini coefficient decreased by 11.42%, whereas the intra-group difference was the largest in key development zones. ③ In the past 20 years, the overall structure of the spatial correlation network of land use carbon budget in the Chongqing metropolitan area has become stable and complex, and the network density and network correlation number have increased by 0.43 and 180, respectively, the network correlation degree has increased to 1, and the network health degree has improved. ④ In the individual network structure of land use carbon budget in the Chongqing metropolitan area, the degree centrality of each district and county has increased, and the increase in the central urban area was the most significant, with an increase of 81, whereas the decline in intermediate centrality and proximity centrality has promoted the regional coordinated development and integration process in the metropolitan area. ⑤ In the past 20 years, the density of net carbon emissions in the Chongqing metropolitan area has increased as a whole, with the density of the core area increasing by 0.35 and the density of the core-edge area increasing by 0.34. By exploring the change and spatial correlation of land use carbon budget in the Chongqing metropolitan area, this study clarified the spatial distribution difference of carbon budget and provided support for regional green development.

Endocytosis-mediated entry of a caterpillar effector into plants is countered by Jasmonate.

Insects and pathogens release effectors into plant cells to weaken the host defense or immune response. While the imports of some bacterial and fungal effectors into plants have been previously characterized, the mechanisms of how caterpillar effectors enter plant cells remain a mystery. Using live cell imaging and real-time protein tracking, we show that HARP1, an effector from the oral secretions of cotton bollworm (Helicoverpa armigera), enters plant cells via protein-mediated endocytosis. The entry of HARP1 into a plant cell depends on its interaction with vesicle trafficking components including CTL1, PATL2, and TET8. The plant defense hormone jasmonate (JA) restricts HARP1 import by inhibiting endocytosis and HARP1 loading into endosomes. Combined with the previous report that HARP1 inhibits JA signaling output in host plants, it unveils that the effector and JA establish a defense and counter-defense loop reflecting the robust arms race between plants and insects.

Repopulating Kupffer cells originate directly from hematopoietic stem cells.

BACKGROUND: Kupffer cells (KCs) originate from yolk-sac progenitors before birth. Throughout adulthood, they self-maintain independently from the input of circulating monocytes (MOs) at a steady state and are replenished within 2 weeks after having been depleted, but the origin of repopulating KCs in adults remains unclear. The current paradigm dictates that repopulating KCs originate from preexisting KCs or monocytes, but there remains a lack of fate-mapping evidence. METHODS: We first traced the fate of preexisting KCs and that of monocytic cells with tissue-resident macrophage-specific and monocytic cell-specific fate-mapping mouse models, respectively. Secondly, we performed genetic lineage tracing to determine the type of progenitor cells involved in response to KC-depletion in mice. Finally, we traced the fate of hematopoietic stem cells (HSCs) in an HSC-specific fate-mapping mouse model, in the context of chronic liver inflammation induced by repeated carbon tetrachloride treatment. RESULTS: By using fate-mapping mouse models, we found no evidence that repopulating KCs originate from preexisting KCs or MOs and found that in response to KC-depletion, HSCs proliferated in the bone marrow, mobilized into the blood, adoptively transferred into the liver and differentiated into KCs. Then, in the chronic liver inflammation context, we confirmed that repopulating KCs originated directly from HSCs. CONCLUSION: Taken together, these findings provided in vivo fate-mapping evidence that repopulating KCs originate directly from HSCs, which presents a completely novel understanding of the cellular origin of repopulating KCs and shedding light on the divergent roles of KCs in liver homeostasis and diseases.

Dirigent gene editing of gossypol enantiomers for toxicity-depleted cotton seeds.

Axial chirality of biaryls can generate varied bioactivities. Gossypol is a binaphthyl compound made by cotton plants. Of its two axially chiral isomers, (-)-gossypol is the bioactive form in mammals and has antispermatogenic activity, and its accumulation in cotton seeds poses health concerns. Here we identified two extracellular dirigent proteins (DIRs) from Gossypium hirsutum, GhDIR5 and GhDIR6, which impart the hemigossypol oxidative coupling into (-)- and (+)-gossypol, respectively. To reduce cotton seed toxicity, we disrupted GhDIR5 by genome editing, which eliminated (-)-gossypol but had no effects on other phytoalexins, including (+)-gossypol, that provide pest resistance. Reciprocal mutagenesis identified three residues responsible for enantioselectivity. The (-)-gossypol-forming DIRs emerged later than their enantiocomplementary counterparts, from tandem gene duplications that occurred shortly after the cotton genus diverged. Our study offers insight into how plants control enantiomeric ratios and how to selectively modify the chemical spectra of cotton plants and thereby improve crop quality.

Spindle-like MIL101(Fe) decorated with Bi2O3 nanoparticles for enhanced degradation of chlortetracycline under visible-light irradiation.

Improving the photocatalytic performance of metal-organic frameworks (MOFs) is an important way to expand its potential applications. In this work, zero-dimensional (0D) Bi2O3 nanoparticles were anchored to the surface of tridimensional (3D) MIL101(Fe) by a facile solvothermal method to obtain a novel 0D/3D heterojunction Bi2O3/MIL101(Fe) (BOM). The morphology and optical properties of the as-prepared Bi2O3/MIL101(Fe) composite were characterized. The photocatalytic activity of the synthesized samples was evaluated by degrading chlortetracycline (CTC) under visible-light irradiation. The obtained BOM-20 composite (20 wt % Bi2O3/MIL101(Fe)) exhibits the highest photocatalytic activity with CTC degradation efficiency of 88.2% within 120 min. The degradation rate constant of BOM-20 toward CTC is 0.01348 min-1, which is 5.9 and 4.3 times higher than that of pristine Bi2O3 and MIL101(Fe), respectively. The enhanced photocatalytic activity is attributed to the formation of a Z-scheme heterojunction between Bi2O3 and MIL101(Fe), which is conducive to the rapid separation of photogenerated carriers and the enhancement of photogenerated electron and hole redox capacity. The intermediate products were analyzed by liquid chromatography-mass spectrometry (LC-MS), and a possible photocatalytic degradation path of CTC was proposed. This work provides a new perspective for the preparation of efficient MOF-based photocatalysts.

Facile and rapid synthesis of a novel spindle-like heterojunction BiVO4 showing enhanced visible-light-driven photoactivity.

A spindle-like monoclinic-tetragonal heterojunction BiVO4 was successfully synthesized by a pressure-controllable microwave method. The as-prepared BiVO4 samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy, transient photocurrent responses and electrochemical impedance spectroscopy (EIS). The visible-light-driven photocatalytic activity of the BiVO4 samples was evaluated for the degradation of Rhodamine B (RhB) and tetracycline (TC). The synthesis process needs microwave irradiation for only 10 min without the addition of any auxiliary reagent, pH adjustment, and calcination. The as-prepared spindle-like monoclinic-tetragonal heterojunction BiVO4 exhibits excellent photocatalytic activity for the degradation of both RhB and TC. The photocatalytic degradation rates of RhB and TC over spindle-like BiVO4 are 1.77 and 1.64 times higher, respectively, than that measured over monoclinic BiVO4. The enhanced photocatalytic activity is mainly attributed to the fact that the existence of a heterojunction effectively promotes the separation of photo-generated carriers and extends the visible-light absorption of BiVO4.

Jasmonate response decay and defense metabolite accumulation contributes to age-regulated dynamics of plant insect resistance.

Immunity deteriorates with age in animals but comparatively little is known about the temporal regulation of plant resistance to herbivores. The phytohormone jasmonate (JA) is a key regulator of plant insect defense. Here, we show that the JA response decays progressively in Arabidopsis. We show that this decay is regulated by the miR156-targeted SQUAMOSA PROMOTER BINDING PROTEIN-LIKE9 (SPL9) group of proteins, which can interact with JA ZIM-domain (JAZ) proteins, including JAZ3. As SPL9 levels gradually increase, JAZ3 accumulates and the JA response is attenuated. We provide evidence that this pathway contributes to insect resistance in young plants. Interestingly however, despite the decay in JA response, older plants are still comparatively more resistant to both the lepidopteran generalist Helicoverpa armigera and the specialist Plutella xylostella, along with increased accumulation of glucosinolates. We propose a model whereby constitutive accumulation of defense compounds plays a role in compensating for age-related JA-response attenuation during plant maturation.

A simple and controllable graphene-templated approach to synthesise 2D silica-based nanomaterials using water-in-oil microemulsions.

Using the versatility of silica chemistry, we describe herein a simple and controllable approach to synthesise two-dimensional (2D) silica-based nanomaterials: the diversity and utility of the resulting structures offer excellent platforms for many potential applications.