Divergent Biosynthesis of Bridged Polycyclic Sesquiterpenoids by a Minimal Fungal Biosynthetic Gene Cluster.

The bridged polycyclic sesquiterpenoids derived from sativene, isosativene, and longifolene have unique structures, and many chemical synthesis approaches with at least 10 steps have been reported. However, their biosynthetic pathway remains undescribed. A minimal biosynthetic gene cluster (BGC), named bip, encoding a sesquiterpene cyclase (BipA) and a cytochrome P450 (BipB) is characterized to produce such complex sesquiterpenoids with multiple carbon skeletons based on enzymatic assays, heterologous expression, and precursor experiments. BipA is demonstrated as a versatile cyclase with (-)-sativene as the dominant product and (-)-isosativene and (-)-longifolene as minor ones. BipB is capable of hydroxylating different enantiomeric sesquiterpenes, such as (-)-longifolene and (+)-longifolene, at C-15 and C-14 in turn. The C-15- or both C-15- and C-14-hydroxylated products are then further oxidized by unclustered oxidases, resulting in a structurally diverse array of sesquiterpenoids. Bioinformatic analysis reveals the BipB homologues as a discrete clade of fungal sesquiterpene P450s. These findings elucidate the concise and divergent biosynthesis of such intricate bridged polycyclic sesquiterpenoids, offer valuable biocatalysts for biotransformation, and highlight the distinct biosynthetic strategy employed by nature compared to chemical synthesis.

Backside Coating for Stable Zn Anode with High Utilization Rate.

Stable Zn anodes with high utilization rate are urgently required to promote the specific and volumetric energy densities of Zn-ion batteries for practical applications. Herein, contrary to the widely utilized surface coating on Zn anodes, this work shows that a zinc foil with a backside coated layer delivers much enhanced cycling stability even under high depth of discharge. The backside coating significantly reduces stress concentration, accelerates heat diffusion, and facilitates electron transfer, thus effectively preventing dendrite growth and structural damage at high Zn utilization. As a result, the developed anode can be stably cycled for 334 h at 85.5% Zn utilization, which outperforms bare Zn and previously reported results on surface-coated Zn foils. An NVO-based full cell also shows stable performance with high Zn utilization rate (69.4%), low negative-positive electrodes ratio (1.44), and high specific/volumetric energy densities (155.8 Wh kg-1/178 Wh L-1), which accelerates the progress toward practical zinc-ion batteries.

Engineering High-Tortuosity 3D Gradient Structure and CFD-Assisted Multifield Analysis for Solar Interfacial Evaporation.

Solar interfacial evaporation is a promising method for solving the global shortage of fresh water. While 2D evaporators can efficiently localize solar-converted heat at the thin layer of the water-air interface, 3D solar evaporators can maximize energy reutilization while maintaining effective mass transport ability, few studies are conducted to explore the effect of gradient porosity on evaporation performance. In this study, a multifield assisted strategy based on a gradient 3D structure with high tortuosity is proposed, which creates a thermal field environment for efficient evaporation through high absorption of sunlight and excellent photothermal conversion and uses the gradient structure to optimize the internal pressure field to enhance water evaporation and transport. This hierarchically nanostructured solar absorber, with porosity inhomogeneity-induced pressure gradient and optimized temperature management, is a valuable design idea for manufacturing a more efficient 3D solar evaporator in the field of seawater desalination. Owing to the understanding of optimizing the dimension by various simulation parameters, the evaporation efficiencies of such structures are found to be 165.7%, suppressing the most evaporator. Moreover, it can provide new ideas and references for the fields of mass transfer and thermal management.

Flexible Energy Storage Devices to Power the Future.

The field of flexible electronics is a crucial driver of technological advancement, with a strong connection to human life and a unique role in various areas such as wearable devices and healthcare. Consequently, there is an urgent demand for flexible energy storage devices (FESDs) to cater to the energy storage needs of various forms of flexible products. FESDs can be classified into three categories based on spatial dimension, all of which share the features of excellent electrochemical performance, reliable safety, and superb flexibility. In this review, the application scenarios of FESDs are introduced and the main representative devices applied in disparate fields are summarized first. More specifically, it focuses on three types of FESDs in matched application scenarios from both structural and material aspects. Finally, the challenges that hinder the practical application of FESDs and the views on current barriers are presented.

Genome Mining of Linaridins Provides Insights into the Widely Distributed LinC Oxidoreductases.

Linaridins are a family of underexplored ribosomally synthesized and post-translationally modified peptides despite the prevalence of their biosynthetic gene clusters (BGCs) in microbial genomes, as shown by bioinformatic studies. Our genome mining efforts reveal that 96 putative oxidoreductase genes, namely, LinC, are encoded in linaridin BGCs. We heterologously expressed two such LinC-containing linaridin BGCs, yan and ydn, from Streptomyces yunnanensis and obtained three new linaridins, named yunnanaridins A-C (1-3). Their structures are characterized by Z-configurations of the dehydrobutyrines and the presence of a variety of epimerized amino acid residues. Yunnanaridin A (1) is the sixth member of the family of type-B linaridins, whereas yunnanaridins B (2) and C (3) represent the first examples of expressed type-C linaridins. Interestingly, heterologous expression of the same BGCs with LinC in-frame knockouts produced the same compounds. This work expands the structural diversity of linaridins and provides evidence for the notion that the widespread LinCs may not be involved in linaridin biosynthesis.

Ursane and 24-Noroleanane-Type Triterpenoids with Anti-HIV Activity from the Twigs and Leaves of Antirhea chinensis.

Investigations on the twigs and leaves of Antirhea chinensis have led to the discovery of two undescribed pentacyclic triterpenoids (1 and 2) and nine known analogs. Compounds 1 and 2, each assigned as the ursane and 24-noroleanane-type triterpenoids, featuring similar oxidation pattern of 3ß,6ß,19α-trihydroxy-28-carboxyl. Their structures were elucidated via comprehensive analyses of spectroscopic data. Compound 1 displayed potent anti-HIV activity (EC50 =1.24 µM) and high selectivity index (SI >32.3).

Antimicrobial abietane-type diterpenoids from Torreya grandis.

Twelve undescribed abietane-type diterpenoids, along with ten known analogues were isolated from the twigs and leaves of Torreya grandis var. merrillii Hu. Their structures were characterized by spectroscopic data analyses, single-crystal X-ray diffraction, and ECD spectra. Torgranols A-C possess three different architectures shaped via a common 6,7-seco-procedure and subsequent ring formations. In particular, torgranol A represents the first example of a 6,7-seco-abietane diterpenoid featuring a unique oxygen bridge between C-3 and C-6. The biosynthetic pathways for torgranols A-C were proposed. Some compounds displayed antimicrobial activities against Mycobacterium tuberculosis and/or Staphylococcus aureus.

Lanthipeptides from the Same Core Sequence: Characterization of a Class II Lanthipeptide Synthetase from Microcystis aeruginosa NIES-88.

Class II lanthipeptide synthetases (LanMs) are relatively promiscuous to core peptide variations. Previous studies have shown that different LanMs catalyze identical reactions on the same core sequence fused to their respective cognate leaders. We characterized a new LanM enzyme from Microcystis aeruginosa NIES-88, MalM, and demonstrated that MalM and ProcM exhibited disparate dehydration and cyclization patterns on identical core peptides. Our study provided new insights into the regioselectivity of LanMs and showcased an appropriate strategy for lanthipeptide structural diversity engineering.

Biochemical Reconstitution Reveals the Biosynthetic Timing and Substrate Specificity for Thioamitides.

Thioamitides are apoptosis-inducing ribosomally synthesized and post-translationally modified peptides (RiPPs) with substantial post-translational modifications (PTMs), whose biosynthetic details remain elusive. We reconstituted their key PTMs through in vitro enzymatic reactions and gene coexpressions in E. coli and rigorously demonstrated the order of those modifications. Notably, thioamitide biosynthesis involves N- to C-terminal thioamidations and employs both leader-dependent and leader-independent reactions followed by leader removal by successive degradation. Our study provides a comprehensive overview of thioamitide biosynthesis and lays the foundation for thioamitide engineering in E. coli.

Vulnerability and driving factors of soil inorganic carbon stocks in Chinese croplands.

The long-term stability of soil inorganic carbon (SIC) and its minimum contribution towards global C cycle has been challenged, as recent studies have showed rapid decreases in SIC stocks in intensive agricultural systems. However, the extent of SIC losses and its driving factors remains unclear. Here, we compared changes in SIC density (SICD) in Chinese croplands between the 1980s and 2010s. The SIC contents in 1980s were obtained from second national soil survey (n = 949) and published studies (n = 47). The SIC contents in 2010s were based on resampling of soil profiles from the same locations during 2019 and 2020 (n = 30), as well as data from published studies and national soil survey (n = 903). We found that Chinese croplands have lost 27-38% of SICD from the 0-40 cm soil layer and that the soil pH has decreased by 0.53 units over the past 30 years. These SIC losses increased with the ratio of precipitation (P) to potential evapotranspiration (PET) and most notably with nitrogen (N) fertilization. The SICD decreased greatly in humid and semiarid regions, and these losses were enhanced by high N fertilization rates; however, the SICD increased in very arid regions. This analysis demonstrates that the water balance and N fertilization are major drivers leading to dramatic losses of SICD in croplands and, consequently, to decreases in soil fertility and functions.

Attenuation model of tunnel blast vibration velocity based on the influence of free surface.

In tunnel blasting excavation, it is important to clarify the attenuation law of blast wave propagation and predict the blast vibration velocity effectively to ensure safe tunnel construction and protection design. The effects of the free surface area its quantity on the blast vibration velocity are considered, and free surface parameters are introduced to improve the existing blast vibration velocity prediction formula. Based on the Tianhuan railway Daqianshiling tunnel project, field blast vibration monitoring tests are performed to determine changes in the peak blasting vibration velocity based on the blast distance and free surface area. LS-DYNA is used to establish tunnel blasting excavation models under three operating conditions; subsequently, the attenuation law of blast vibration velocity and changes in the vibration response spectrum are analysed. Results show that the free surface area and number of free surfaces enable the blast vibration velocity to be predicted under various operating conditions: a smaller free surface area results in a narrower frequency band range, whereas more free surfaces result in a narrower frequency band range. The improved blast vibration velocity prediction formula is validated using field and numerical test data. It is indicated that the improved formula is applicable to various tunnelling conditions.

Strategies to mitigate nitrate leaching in vegetable production in China: a meta-analysis.

Nitrate leaching is a main nitrogen (N) loss pathway in vegetable production. Although there are numerous mitigation practices that control nitrate leaching, an integrated assessment of these measures is lacking. Thus, we conducted a meta-analysis to integrate the assessment of strategies for controlling nitrate leaching from vegetable systems in China. The main strategies included improved N fertilizer management (INFM), reduced water management (RWM), comprehensive regulation of N fertilizer and water management (CFWM), and catch crops (CCs). Each mitigation measure decreased nitrate leaching significantly and did not reduce vegetable yields. CFWM reduced nitrate leaching the most at 41% on average, followed by CCs, RWM, and INFM (35%, 24%, and 22%, respectively). The nitrate leaching scaled yields (NLSY, defined as yield divided by the quantity of nitrate leaching) were significantly increased by 87%, 44%, 32%, and 27% for CFWM, CCs, INFM, and RWM, respectively. The efficacies of the strategies were dependent on soil properties. CFWM, INFM, and RWM were more effective in soils with low pH and coarse texture than in other soils. In conclusion, the risk of nitrate leaching from vegetable production systems is high, and INFM and CFWM are suggested to decrease nitrate leaching from vegetable production.

Cytotoxic Tigliane Diterpenoids from Croton damayeshu.

Chemical investigation of an EtOH extract of the twigs and leaves of Croton damayeshu afforded 10 new tigliane diterpenoids, crodamoids A-J (1-10), along with five known compounds. Their structures were elucidated by physical data analysis. Compounds 8, 9, and 15 displayed cytotoxic effects against two human tumor cell lines, A549 and HL-60 (IC50: 0.9-2.4 µM).

1,3-Bis(4-methyl-benz-yl)pyrimidine-2,4(1H,3H)-dione.

In the title mol-ecule, C(20)H(20)N(2)O(2), the central pyrimidine ring forms dihedral angles of 71.9 (1) and 69.8 (1)° with the two benzene rings. In the crystal, weak inter-molecular C-H⋯O hydrogen bonds link mol-ecules into centrosymmetric dimers. The crystal packing exhibits also π-π inter-actions as indicated by short distances of 3.674 (2) Šbetween the centroids of the pyrimidine rings of neighbouring mol-ecules.