Global change progressively increases foliar nitrogen-phosphorus ratios in China's subtropical forests.

Globally increased nitrogen (N) to phosphorus (P) ratios (N/P) affect the structure and functioning of terrestrial ecosystems, but few studies have addressed the variation of foliar N/P over time in subtropical forests. Foliar N/P indicates N versus P limitation in terrestrial ecosystems. Quantifying long-term dynamics of foliar N/P and their potential drivers is crucial for predicting nutrient status and functioning in forest ecosystems under global change. We detected temporal trends of foliar N/P, quantitatively estimated their potential drivers and their interaction between plant types (evergreen vs. deciduous and trees vs. shrubs), using 1811 herbarium specimens of 12 widely distributed species collected during 1920-2010 across China's subtropical forests. We found significant decreases in foliar P concentrations (23.1%) and increases in foliar N/P (21.2%). Foliar N/P increased more in evergreen species (22.9%) than in deciduous species (16.9%). Changes in atmospheric CO2 concentrations ( P CO 2 $$ {\mathrm{P}}_{{\mathrm{CO}}_2} $$ ), atmospheric N deposition and mean annual temperature (MAT) dominantly contributed to the increased foliar N/P of evergreen species, while P CO 2 $$ {\mathrm{P}}_{{\mathrm{CO}}_2} $$ , MAT, and vapor pressure deficit, to that of deciduous species. Under future Shared Socioeconomic Pathway (SSP) scenarios, increasing MAT and P CO 2 $$ {\mathrm{P}}_{{\mathrm{CO}}_2} $$ would continuously increase more foliar N/P in deciduous species than in evergreen species, with more 12.9%, 17.7%, and 19.4% versus 6.1%, 7.9%, and 8.9% of magnitudes under the scenarios of SSP1-2.6, SSP3-7.0, and SSP5-8.5, respectively. The results suggest that global change has intensified and will progressively aggravate N-P imbalance, further altering community composition and ecosystem functioning of subtropical forests.

Emerging roles of the epitranscriptome in parasitic protozoan biology and pathogenesis.

RNA modifications (epitranscriptome) - such as N6-methyladenosine (m6A), 5-methylcytosine (m5C), and pseudouridine (Ψ) - modulate RNA processing, stability, interaction, and translation, thereby playing critical roles in the development, replication, virulence, metabolism, and life cycle adaptations of parasitic protozoa. Here, we summarize potential homologs of the major human RNA modification regulatory factors in parasites, outline current knowledge on how RNA modifications affect parasitic protozoa, highlight the regulation of RNA modifications and their crosstalk, and discuss current progress in exploring RNA modifications as potential drug targets. This review contributes to our understanding of epitranscriptomic regulation of parasitic protozoa biology and pathogenesis and provides new perspectives for the treatment of parasitic diseases.

Synergistic Effect of Salt and Anionic Surfactants on Interfacial Tension Reduction: Insights from Molecular Dynamics Simulations.

Surfactants are commonly utilized in chemical flooding processes alongside salt to effectively decrease interfacial tension (IFT). However, the underlying microscopic mechanism for the synergistic effect of salt and surfactants on oil displacement remains ambiguous. Herein, the structure and properties of the interface between water and n-dodecane are studied by means of molecular dynamics simulations, considering three types of anionic surfactants and two types of salts. As the salt concentration (ρsalt) increases, the IFT first decreases to a minimum value, followed by a subsequent increase to higher values. The salt ions reduce the IFT only at low ρsalt due to the salt screening effect and ion bridging effect, both of which contribute to a decrease in the nearest head-to-head distance of surfactants. By incorporating salt doping, the IFTs can be reduced by at most 5%. Notably, the IFTs of different surfactants are mainly determined by the hydrogen bond interactions between oxygen atoms in the headgroup and water molecules. The presence of a greater number of oxygen atoms corresponds to lower IFT values. Specifically, for alkyl ethoxylate sulfate, the ethoxy groups play a crucial role in reducing the IFTs. This study provides valuable insights into formulating anionic surfactants that are applicable to oil recovery processes in petroleum reservoirs using saline water.

Research on the Prediction Method of Braking Rotation Angle for Remote-Controlled Excavator.

To calculate, analyze, and predict the rotation angle during the deceleration and braking process of large remote-controlled excavators, this article established a spatial coordinate system based on a simplified model of a hydraulic excavator's upper structure. Using the D-H parameter method, a mathematical model of the working device's center of gravity and its rotational inertia was established. Based on the characteristics of the excavator's hydraulic system and the relationship between brake torque variations, a prediction model was developed to forecast the stopping position (brake rotary angle) of the excavator's bucket after braking. Subsequently, the predicted results were validated using simulation and compared with existing experimental data to assess the accuracy of the model. The findings demonstrate that the predictive model exhibited high precision with minimal error. The utilization of this model enabled effective forecasting of the excavator's braking position changes, providing a theoretical foundation for the intelligent remote control of excavators.

Hybridization chain reaction cascaded amplification platform for sensitive detection of pathogen.

Rapid, sensitive, and accurate identification of pathogens is vital for preventing and controlling fish disease, reducing economic losses in aquaculture, and interrupting the spread of food-borne diseases in human populations. Herein, we proposed a hybridization chain reaction (HCR) cascaded dual-signal amplification platform for the ultrasensitive and specific detection of pathogenic microorganisms. A couple of specific primers for target bacterial 16S rRNAs were used to obtain amplified target single-stranded DNAs (AT-ssDNA). Then, AT-ssDNA initiated HCR amplification along with the opening of fluorophore (FAM) and a quencher (BHQ1) labeled hairpin reporter probe (H1), and the FAM fluorescence signal recovered. The proposed strategy could achieve a detection limit down to 0.31 CFU/mL for Staphylococcus aureus (S. aureus), 0.49 CFU/mL for Escherichia coli (E. coli) in buffer, and a linear range from 1 to 1 × 106 CFU/mL for S. aureus, 1 to 1 × 107 CFU/mL for E. coli. Furthermore, this platform enabled sensitive and precise detection of pathogenic microorganisms in complex samples such as fish blood and different organ tissues (large intestine, gallbladder, heart, liver, ren, gill, skin), which shows great potential in disease prevention and control in aquatic products.

Increase in leaf organic acids to enhance adaptability of dominant plant species in karst habitats.

Estimation of leaf nutrient composition of dominant plant species from contrasting habitats (i.e., karst and nonkarst forests) provides an opportunity to understand how plants are adapted to karst habitats from the perspective of leaf traits. Here, we measured leaf traits-specific leaf area (SLA), concentrations of total carbon ([TC]), nitrogen ([TN]), phosphorus ([TP]), calcium ([Ca]), magnesium ([Mg]), manganese ([Mn]), minerals ([Min]), soluble sugars, soluble phenolics, lipids, and organic acids ([OA])-and calculated water-use efficiency (WUE), construction costs (CC), and N/P ratios, and searched for correlations between these traits of 18 abundant plant species in karst and nonkarst forests in southwestern China. Variation in leaf traits within and across the abundant species was both divergent and convergent. Leaf [TC], [Ca], [Min], [OA], and CC were habitat-dependent, while the others were not habitat- but species-specific. The correlations among [TN], [TP], SLA, [TC], CC, [Min], WUE, [OA], and CC were habitat-independent, and inherently associated with plant growth and carbon allocation; those between [CC] and [Lip], between [Ca] and [Mg], and between [Mg] and [WUE] were habitat-dependent. Habitat significantly affected leaf [Ca] and thus indirectly affected leaf [OA], [Min], and CC. Our results indicate that plants may regulate leaf [Ca] to moderate levels via adjusting leaf [OA] under both high and low soil Ca availability, and offer new insights into the abundance of common plant species in contrasting habitats.

Electrochemically Enabled C-Terminal Peptide Modifications.

Modified peptides serve as promising therapeutic leads, valuable tools for chemical biology, and diverse functional materials. Synthetic strategies which enable the direct modification of native peptide sequences are particularly attractive for the rapid generation of designer peptides. This chapter details an operationally simple electrochemical approach to the modification of the peptide C-terminus, which proceeds via direct anodic oxidation of C-terminal peptide carboxylic acids. Electrochemical decarboxylation affords a key N,O-acetal intermediate, which can be engaged with various nucleophiles. Herein, step-by-step protocols for C-terminal arylation and sulfonylation are presented to highlight the utility of the method for the preparation of valuable functionalized peptides.

An Electrochemical Approach to Designer Peptide α-Amides Inspired by α-Amidating Monooxygenase Enzymes.

Designer C-terminal peptide amides are accessed in an efficient and epimerization-free approach by pairing an electrochemical oxidative decarboxylation with a tandem hydrolysis/reduction pathway. Resembling Nature's dual enzymatic approach to bioactive primary α-amides, this method delivers secondary and tertiary amides bearing high-value functional motifs, including isotope labels and handles for bioconjugation. The protocol leverages the inherent reactivity of C-terminal carboxylates, is compatible with the vast majority of proteinogenic functional groups, and proceeds in the absence of epimerization, thus addressing major limitations associated with conventional coupling-based approaches. The utility of the method is exemplified through the synthesis of natural product acidiphilamide A via a key diastereoselective reduction, as well as bioactive peptides and associated analogues, including an anti-HIV lead peptide and blockbuster cancer therapeutic leuprolide.

V6 O13-δ @C Nanoscrolls with Expanded Distances between Adjacent Shells as a High-Performance Cathode for a Knittable Zinc-Ion Battery.

Herein, the defective vanadate oxide (V6 O13-δ )/C (denoted as DVOC) nanoscrolls with large distance between adjacent shells are constructed as a cathode material for ZIBs. By simultaneously enlarging the distance between adjacent shells and engineering the defective structure for oxide crystal, the DVOC nanoscrolls achieve fast kinetics, high reversibility and good energy storage capability. The formation process of DVOC nanoscrolls is investigated and a self-assembling-rolling sequential mechanism is disclosed. Moreover, the fiber-shaped flexible ZIBs are fabricated based on the DVOC cathode. Their admirable volumetric energy density, good high rate capability and excellent cycling stability demonstrate the superiority of the unique structure. Therefore, this work not only introduces a new strategy to improve the properties of vanadium oxides but also provide a new strategy for the design of knittable power sources for flexible electronics.

Total synthesis of biseokeaniamides A-C and late-stage electrochemically-enabled peptide analogue synthesis.

The first total synthesis of cytotoxic cyanobacterial peptide natural products biseokeaniamides A-C is reported employing a robust solid-phase approach to peptide backbone construction followed by coupling of a key thiazole building block. To rapidly access natural product analogues, we have optimized an operationally simple electrochemical oxidative decarboxylation-nucleophilic addition pathway which exploits the reactivity of native C-terminal peptide carboxylates and abrogates the need for building block syntheses. Electrochemically-generated N,O-acetal intermediates are engaged with electron-rich aromatics and organometallic reagents to forge modified amino acids and peptides. The value of this late-stage modification method is highlighted by the expedient and divergent production of bioactive peptide analogues, including compounds which exhibit enhanced cytotoxicity relative to the biseokeaniamide natural products.

Ionothermal Synthesis of Germanosilicate Zeolites Constructed with Double-Four-Ring Structure-Building Units in the Presence of Organic Base.

The crystallization chemistry of silica-based zeolites in ionic liquids remains highly puzzling and interesting in the field of zeolite science. Herein, we report the successful ionothermal synthesis of germanosilicate zeolites. The ionothermal templating effect with respect to the structure, alkalinity and concentration of organic additives was comparatively studied. The results showed that a small amount of organic base could effectively aid the dissolution of silica source and facilitate the crystallization of germanosilicate zeolites with ionic liquid as template. Remarkably, STW and IRR structures constructed with double-four-ring (D4R) structure-building units were ionothermally prepared using 1-ethyl/butyl-3-methyl imidazolium and 1-benzyl-3-methyl imidazolium ionic liquids as template, respectively. Ionothermal synthesis tailored with organic base showed suitable chemistry for the formation of germanium-containing siliceous D4R units. This finding will be helpful for the rational exploration of novel extra-large-pore zeolitic structures.

Building C(sp3)-rich complexity by combining cycloaddition and C-C cross-coupling reactions.

Prized for their ability to rapidly generate chemical complexity by building new ring systems and stereocentres1, cycloaddition reactions have featured in numerous total syntheses2 and are a key component in the education of chemistry students3. Similarly, carbon-carbon (C-C) cross-coupling methods are integral to synthesis because of their programmability, modularity and reliability4. Within the area of drug discovery, an overreliance on cross-coupling has led to a disproportionate representation of flat architectures that are rich in carbon atoms with orbitals hybridized in an sp2 manner5. Despite the ability of cycloadditions to introduce multiple carbon sp3 centres in a single step, they are less used6. This is probably because of their lack of modularity, stemming from the idiosyncratic steric and electronic rules for each specific type of cycloaddition. Here we demonstrate a strategy for combining the optimal features of these two chemical transformations into one simple sequence, to enable the modular, enantioselective, scalable and programmable preparation of useful building blocks, natural products and lead scaffolds for drug discovery.

Reverse Screening Methods to Search for the Protein Targets of Chemopreventive Compounds.

This article is a systematic review of reverse screening methods used to search for the protein targets of chemopreventive compounds or drugs. Typical chemopreventive compounds include components of traditional Chinese medicine, natural compounds and Food and Drug Administration (FDA)-approved drugs. Such compounds are somewhat selective but are predisposed to bind multiple protein targets distributed throughout diverse signaling pathways in human cells. In contrast to conventional virtual screening, which identifies the ligands of a targeted protein from a compound database, reverse screening is used to identify the potential targets or unintended targets of a given compound from a large number of receptors by examining their known ligands or crystal structures. This method, also known as in silico or computational target fishing, is highly valuable for discovering the target receptors of query molecules from terrestrial or marine natural products, exploring the molecular mechanisms of chemopreventive compounds, finding alternative indications of existing drugs by drug repositioning, and detecting adverse drug reactions and drug toxicity. Reverse screening can be divided into three major groups: shape screening, pharmacophore screening and reverse docking. Several large software packages, such as Schrödinger and Discovery Studio; typical software/network services such as ChemMapper, PharmMapper, idTarget, and INVDOCK; and practical databases of known target ligands and receptor crystal structures, such as ChEMBL, BindingDB, and the Protein Data Bank (PDB), are available for use in these computational methods. Different programs, online services and databases have different applications and constraints. Here, we conducted a systematic analysis and multilevel classification of the computational programs, online services and compound libraries available for shape screening, pharmacophore screening and reverse docking to enable non-specialist users to quickly learn and grasp the types of calculations used in protein target fishing. In addition, we review the main features of these methods, programs and databases and provide a variety of examples illustrating the application of one or a combination of reverse screening methods for accurate target prediction.

Divergent Synthesis of Pyrone Diterpenes via Radical Cross Coupling.

A divergent strategy for assembling pyrone diterpenes is presented. Capitalizing on the unique stereo- and chemoselectivity features of radical-based chemistry, the core decalin of these structures is efficiently forged using an electrochemically assisted oxidative radical polycyclization while key peripheral substituents are appended using decarboxylative radical cross couplings. In this way, access to four natural products (subglutinols A/B, higginsianin A, and sesquicillin A) is achieved in a concise and stereocontrolled fashion that is modular and amenable to future medicinal chemistry explorations.

Co-Structure-Directing Effect in Ionothermal Synthesis of Extra-Large-Pore Aluminophosphate Zeotype with -CLO Topology.

The ionothermal synthesis of extra-large-pore aluminophosphate zeotype with -CLO topological structure, DNL-1, was studied by using 1,6-hexanediamine and several quaternary ammonium compounds with different types of cations and anions as co-structure-directing agents (co-SDAs). The phase selectivity and crystallization process were investigated, and results showed that the crystallization of the -CLO and LTA structures correlated with the alkalinity and concentration, rather than with the structure of the co-SDA. By combining solid/solution 13 C NMR spectroscopy and other characterizations on DNL-1 obtained with different co-SDAs, it was demonstrated that the ionic-liquid cation was unalterably occluded in the structure, whereas occlusion of the co-SDA cation was not imperative. A plausible crystallization pathway was accordingly deduced, in which alkaline co-SDA, which acted as an acidity regulator in the ionothermal system, could facilitate the formation of the double-four-ring (d4r) unit (Al4 P4 O20 ), and influence their subsequent assembly mode around ionic-liquid cations, and thus, direct the crystallization of -CLO and LTA structures at different concentrations of co-SDA.

Amide-Ligand-Controlled Highly para-Selective Arylation of Monosubstituted Simple Arenes with Arylboronic Acids.

Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.

Effect of acoustic parameters on the cavitation behavior of SonoVue microbubbles induced by pulsed ultrasound.

SonoVue microbubbles could serve as artificial nuclei for ultrasound-triggered stable and inertial cavitation, resulting in beneficial biological effects for future therapeutic applications. To optimize and control the use of the cavitation of SonoVue bubbles in therapy while ensuring safety, it is important to comprehensively understand the relationship between the acoustic parameters and the cavitation behavior of the SonoVue bubbles. An agarose-gel tissue phantom was fabricated to hold the SonoVue bubble suspension. 1-MHz transmitting transducer calibrated by a hydrophone was used to trigger the cavitation of SonoVue bubbles under different ultrasonic parameters (i.e., peak rarefactional pressure (PRP), pulse repetition frequency (PRF), and pulse duration (PD)). Another 7.5-MHz focused transducer was employed to passively receive acoustic signals from the exposed bubbles. The ultraharmonics and broadband intensities in the acoustic emission spectra were measured to quantify the extent of stable and inertial cavitation of SonoVue bubbles, respectively. We found that the onset of both stable and inertial cavitation exhibited a strong dependence on the PRP and PD and a relatively weak dependence on the PRF. Approximate 0.25MPa PRP with more than 20µs PD was considered to be necessary for ultraharmonics emission of SonoVue bubbles, and obvious broadband signals started to appear when the PRP exceeded 0.40MPa. Moreover, the doses of stable and inertial cavitation varied with the PRP. The stable cavitation dose initially increased with increasing PRP, and then decreased rapidly after 0.5MPa. By contrast, the inertial cavitation dose continuously increased with increasing PRP. Finally, the doses of both stable and inertial cavitation were positively correlated with PRF and PD. These results could provide instructive information for optimizing future therapeutic applications of SonoVue bubbles.

Iron-Catalyzed Regioselective Transfer Hydrogenative Couplings of Unactivated Aldehydes with Simple Alkenes.

An FeBr3 -catalyzed reductive coupling of various aldehydes with alkenes that proceeds through a direct hydride transfer pathway has been developed. With (i) PrOH as the hydrogen donor under mild conditions, previously challenging coupling reactions of unactivated alkyl and aryl aldehydes with simple alkenes, such as styrene derivatives and α-olefins, proceeded smoothly to furnish a diverse range of functionalized alcohols with complete linear regioselectivity.