Molecular strategies of the pygmy grasshopper Eucriotettix oculatus adapting to long-term heavy metal pollution.

To study the heavy metal accumulation and its impact on insect exterior and chromosome morphology, and reveal the molecular mechanism of insects adapting to long-term heavy metal compound pollution habitats, this study, in the Diaojiang river basin, which has been polluted by heavy metals(HMs) for nearly a thousand years, two Eucriotettix oculatus populations was collected from mining and non-mining areas. It was found that the contents of 7 heavy metals (As, Cd, Pb, Zn, Cu, Sn, Sb) in E. oculatus of the mining area were higher than that in the non-mining 1-11 times. The analysis of morphology shows that the external morphology, the hind wing type and the chromosomal morphology of E. oculatus are significant differences between the two populations. Based on the heavy metal accumulation，morphological change, and stable population density, it is inferred that the mining area population has been affected by heavy metals and has adapted to the environment of heavy metals pollution. Then, by analyzing the transcriptome of the two populations, it was found that the digestion, immunity, excretion, endocrine, nerve, circulation, reproductive and other systems and lysosomes, endoplasmic reticulum and other cell structure-related gene expression were suppressed. This shows that the functions of the above-mentioned related systems of E. oculatus are inhibited by heavy metal stress. However, it has also been found that through the significant up-regulation of genes related to the above system, such as ATP2B, pepsin A, ubiquitin, AQP1, ACOX, ATPeV0A, SEC61A, CANX, ALDH7A1, DLD, aceE, Hsp40, and catalase, etc., and the down-regulation of MAPK signalling pathway genes, can enhanced nutrient absorption, improve energy metabolism, repair damaged cells and degrade abnormal proteins, maintain the stability of cells and systems, and resist heavy metal damage so that E. oculatus can adapt to the environment of heavy metal pollution for a long time.

Visible light-mediated synthesis of quinazolinones from benzyl bromides and 2-aminobenzamides without using any photocatalyst or additive.

This paper reports a novel method for the visible-light-mediated synthesis of quinazolinones from the reaction of benzyl bromides with 2-aminobenzamides. The reaction proceeded efficiently at room temperature upon irradiation with an 18 W blue light-emitting diode in air without photocatalysts or additives. By varying the solvent type, substrate molar ratio, and reaction time, the optimal reaction conditions, including the use of methanol solvent, room temperature, and reaction time of 28 h, were identified. Under these conditions, various quinazolinones were obtained using 18 substrates, with the highest yield of 93%. To determine the industrial value of the proposed method, a scale-up reaction was performed and 80% product yield was achieved. Mechanistic studies revealed that the reaction likely proceeded via a radical pathway and that the hydrogen bromide by-product generated during the first step of the reaction of benzyl bromide with 2-aminobenzamide promoted the subsequent step.

1,2-Alkynyl Functionalization of Unactivated Alkenes via Diverse Radical-Triggered Functional Group Migration.

We have developed a transition-metal-free radical approach for 1,2-alkynyl functionalization of unactivated alkenes through the combination of 3-exo-dig cyclization with alkynyl migration triggered by in situ-generated diverse radical precursors. This strategy provides a robust toolkit to access a variety of synthetically important α-functionalized alkynyl ketones, simultaneously installing densely functionalized carbonyl, alkynyl, and other various functional groups into the alkenes. The broad substrate scope, which includes distinctly electron-donating or electron-withdrawing alkynyl migrating groups, excellent functional group compatibility, and remarkable selectivity make this protocol practical and attractive.

Surface Engineering in Covalent Organic Polymers for High-Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries are a promising energy storage technology due to their tempting high theoretical capacity and energy density. Nevertheless, the wastage of active materials that originates from the shuttling effect of polysulfides still hinders advancement of Li-S batteries. The effective design of cathode materials is extremely pivotal to solve this thorny problem. Herein, surface engineering in covalent organic polymers (COPs) has been performed to investigate the influence of pore wall polarity on the performance of COP-based cathodes used for Li-S batteries. With the assistance of experimental investigation and theoretical calculations, performance improvement by increasing pore surface polarity and a synergy effect of the polarized functionalities, along with nano-confinement effect of the COPs, are disclosed, to which the improved performance of Li-S batteries including outstanding Coulombic efficiency (99.0 %) and extremely low capacity decay (0.08 % over 425 cycles at 1.0 C) is attributed. This work not only enlightens the designable synthesis and applications of covalent polymers as polar sulfur hosts with high utilization of active materials, but also provides a feasible guide for the design of effective cathode materials for future advanced Li-S batteries.

Brønsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles for construction of cyano-substituted all-carbon quaternary centers.

We report a Brønsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles with 2,2-diarylacetonitriles for efficient construction of cyano-substituted all-carbon quaternary centers with excellent yields. The synthetic utility was demonstrated by the conversion of the cyano-group which enables the divergent preparation of aldehydes, primary amines and amides. Control experiments suggested that this process involves C-H oxidation of 2,2-diarylacetonitriles to in situ generate δ,δ-disubstituted p-quinone methide intermediates. This protocol provides an efficient method for C6 functionalization of 2,3-disubstituted indoles to construct all-carbon quaternary centers.

Metabolite Changes in Orange Dead Leaf Butterfly Kallima inachus during Ontogeny and Diapause.

Holometabolism is a form of insect development which includes four life stages: egg, larva, pupa, and imago (or adult). The developmental change of whole body in metabolite levels of holometabolous insects are usually ignored and lack study. Diapause is an alternative life-history strategy that can occur during the egg, larval, pupal, and adult stages in holometabolous insects. Kallima inachus (Lepidoptera: Nymphalidae) is a holometabolous and adult diapausing butterfly. This study was intended to analyze metabolic changes in K. inachus during ontogeny and diapause through a non-targeted UPLC-MS/MS (ultra-performance liquid chromatograph coupled with tandem mass spectrometry) based metabolomics analysis. A variety of glycerophospholipids (11), amino acid and its derivatives (16), and fatty acyls (nine) are crucial to the stage development of K. inachus. 2-Keto-6-acetamidocaproate, N-phenylacetylglycine, Cinnabarinic acid, 2-(Formylamino) benzoic acid, L-histidine, L-glutamate, and L-glutamine play a potentially important role in transition of successive stages (larva to pupa and pupa to adult). We observed adjustments associated with active metabolism, including an accumulation of glycerophospholipids and carbohydrates and a degradation of lipids, as well as amino acid and its derivatives shifts, suggesting significantly changed in energy utilization and management when entering into adult diapause. Alpha-linolenic acid metabolism and ferroptosis were first found to be associated with diapause in adults through pathway analyses. Our study lays the foundation for a systematic study of the developmental mechanism of holometabolous insects and metabolic basis of adult diapause in butterflies.

Covalent organic framework with sulfonic acid functional groups for visible light-driven CO2 reduction.

In this study, a covalent organic framework (TpPa-SO3H) photocatalyst with sulfonic acid function groups was synthesized using a solvothermal method. The morphologies and structural properties of the as-prepared composites were characterized by X-ray diffraction, infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption-desorption measurements, and field emission scanning electron microscopy. An electrochemical workstation was used to test the photoelectric performance of the materials. The results show that TpPa-SO3H has -SO3H functional groups and high photocatalytic performance for CO2 reduction. After 4 h of visible-light irradiation, the amount of CO produced is 416.61 µmol g-1. In addition, the TpPa-SO3H photocatalyst exhibited chemical stability and reusability. After two testing cycles under visible light irradiation, the amount of CO produced decreased slightly to 415.23 and 409.15 µmol g-1. The XRD spectra of TpPa-SO3H were consistent before and after the cycles. Therefore, TpPa-SO3H exhibited good photocatalytic activity. This is because the introduction of -SO3H narrows the bandgap of TpPa-SO3H, which enhances the visible light response range and greatly promotes the separation of photogenerated electrons.

Cardiovascular Protective Effects of Oral Hypoxia Inducible Factor Prolyl Hydroxylase Inhibitor Roxadustat in the Treatment of Type 4 Cardiorenal-Anemia Syndrome: Protocol of a Randomized Controlled Trial.

Background: Patients with chronic kidney disease (CKD) are at high risk of developing heart failure and anemia, which is defined as type 4 cardiorenal-anemia syndrome (CRAS). CRAS aggravates the deterioration of both kidney and heart function, ultimately resulting in a high mortality. This study aims to examine the efficacy and safety of roxadustat in the treatment of type 4 CRAS. Methods and Design: This study is designed as a randomized, open-label, controlled trial. A total of 68 patients diagnosed with type 4 CRAS will be randomly divided into roxadustat group and erythropoietin with a 1:1 ratio. Participants in the roxadustat group will receive roxadustat with an initial dose of 70 or 100 mg three times a week, and participants in the erythropoietin group will receive subcutaneous injection of erythropoietin for 24 weeks, to maintain a hemoglobin ranging from 100 to 120 g per liter. The primary outcome is the change in heart function, including brain natriuretic peptide (BNP), 6-min walk test (6-WT), and left ventricular ejection fraction (LVEF). Secondary outcomes to be assessed include death, cardiovascular events, hospitalization regarding heart failure, Minnesota Heart Failure Quality of life scale (MLHFQ) score, New York Heart Association (NYHA) cardiac function grade, echocardiographic parameters including left ventricular diastolic diameter and volume (LVDD and LVDV) and ventricular mass (LVM), anemia related parameters, inflammatory parameters, and safety assessments. Conclusion: The findings of this study will provide potential evidence for roxadustat in CRAS management. Trial Registration: Chinese Clinical Trial Registry, ID: ChiCTR2100050031. Registered on 16 August 2021.

Chiral Phosphoric Acid-Catalyzed C6 Functionalization of 2,3-Disubstituted Indoles for Synthesis of Heterotriarylmethanes.

The direct regio- and enantioselective C6 functionalization of 2,3-disubstituted indoles with azadienes has been developed using chiral phosphoric acid as catalyst, providing a convenient approach to synthesize the optically active heterotriarylmethanes with excellent yields, broad substrate scope, and up to 98% ee. Mechanistic studies revealed that N-alkylation of 2,3-disubstituted indoles with azadienes would be reversible, and enantioselective C6 functionalization could be enabled.

Synthesis of Mannich-type derivatives from amides activated by hydrogen bonding with ZnCl2.

The amide group has one of the most significant functionalities found in many natural products. Herein, low-nucleophilic amides are used in a Mannich-type reaction to synthesize N-acyl-protected amine derivatives. A highly efficient synthetic method utilizing simple aldehydes, N-substituted anilines, and amides as substrates was established through a one-pot amide pathway activated by hydrogen bonding between the ZnCl2 and amide under solvent-free conditions. This strategy can be broadly applied to medicinal chemistry. More importantly, compared with the previous Lewis acid catalyzed reaction, we proposed a new application of zinc chloride.

Transformation between 2D covalent organic frameworks with distinct pore hierarchy via exchange of building blocks with different symmetries.

Transformation between 2D covalent organic frameworks (COFs) via exchange of molecular building blocks with different symmetries has been realized, which gives rise to the conversion between 2D COFs with distinct pore hierarchy. This type of monomer replacement has expanded the scope of the building-unit-exchange-based COF-to-COF transformation strategy.

Identification and Expression Profile Analysis of Chemosensory Genes From the Antennal Transcriptome of Bamboo Locust (Ceracris kiangsu).

Studies of chemosensory genes are key to a better understanding of intra- and interspecific communications between insects and their environment and provide opportunities for developing environmentally friendly pesticides to target pest species. The bamboo locust Ceracris kiangsu Tsai (Orthoptera: Acrididae) is one of the most important bamboo leaf-eating insects in southern China. However, the genes underlying olfactory sensation are lacking in the bamboo locust. In this study, the transcriptomes of male and female C. kiangsu antennae were sequenced and analyzed. A total of 125 chemosensory genes, including 91 odorant receptors (ORs), 13 ionotropic receptors (IRs), 13 odorant-binding proteins (OBPs), six chemosensory proteins (CSPs), and two sensory neuron membrane proteins, were identified based on sequence alignment and phylogenetic analyses. The expression patterns of all candidate genes on the antennae of males and females, maxillary palps, tarsi, wings, and thoraxes-abdomens were confirmed by real-time quantitative PCR. The analyses demonstrated that most genes are highly expressed in the antennae, and 35 ORs, 7 IRs, 10 OBPs, and 1 CSP exhibit significantly male-biased expression patterns, indicating their potential functions in mating behavior and the recognition of female sex pheromones. In addition to the antennal-predominant genes, some were abundant in the maxillary palps and some in the non-olfactory tissues, suggesting their different functions in the olfactory system of C. kiangsu. Our research offers an extensive resource for investigating the chemoreception mechanism of C. kiangsu. Further studies of olfactory function will provide comprehensive methods and original strategies for integrated pest management.

A Covalent Organic Framework with Extended π-Conjugated Building Units as a Highly Efficient Recipient for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have recently become a research hotspot because of their tempting theoretical capacity and energy density. Nevertheless, the notorious shuttle of polysulfides hinders the advancement of Li-S batteries. Herein, a two-dimensional covalent organic framework (COF) with extended π-conjugated units has been designed, synthesized, and used as sulfur recipients with 88.4 wt % in loading. The COF offers an elaborate platform for sufficient Li-S redox reactions with almost theoretical capacity release (1617 mA h g-1 at 0.1 C), satisfactory rate capability, and intensively traps polysulfides for a decent Coulombic efficiency (ca. 98.0%) and extremely low capacity decay (0.077% per cycle after 528 cycles at 0.5 C). The structural factors of the COF on the high-performance batteries are revealed by density functional theory calculations to be the high degrees of conjugation and proper interlayer space. This work not only demonstrates the great potential of COFs as highly efficient sulfur recipients but also provides a viable guidance for further design of COF materials to tackle shuttling issues toward active materials in electrochemical energy storage.

The transcriptome analysis of the bamboo grasshopper provides insights into hypothermic stress acclimation.

The bamboo grasshopper, Ceracris kiangsu Tsai, is a pest of bamboos and widely distributed in China from high temperature plains to low temperature plateaus. In this study, high-throughput sequencing was used to analyze the transcriptome of C. kiangsu. Approximately 129,314,084 reads were generated using an Illumina sequencing. De novo assembly yielded 39,013 unigenes with an average length of 987 bp. Based on sequence similarity searches with known proteins, a total of 19,769 (50.67%) unigenes were identified. Of these annotated unigenes, 2114 and 11,412 unigenes were assigned to clusters of orthologous groups and gene ontology, respectively. Furthermore, 2128 simple sequence repeats (SSRs) were identified in the unigenes Differences were observed in gene expression after hypothermic stress, with the most up-regulated genes including heat shock protein genes (Hsps) and genes involved in ATP-binding. The down-regulation of genes involved in the catalytic activity of metabolic mechanisms was also observed. The obtained transcriptome information revealed the ability of C. kiangsu to build cold-tolerance after exposed to a mild low temperature and the transcriptional responses elicited by hypothermic stress.

A gaseous hydrogen chloride chemosensor based on a 2D covalent organic framework.

A tetraphenylethene-based 2D covalent organic framework (COF) has been synthesized. It exhibits a very fast response and high sensitivity to the presence of gaseous HCl by way of distinct changes in fluorescence emission and color, which makes the COF a good chemosensor for spectroscopic and naked-eye detection of gaseous HCl.

Metal-free oxidative trifluoromethylation of indoles with CF3SO2Na on the C2 position.

An efficient method of synthesizing 2-trifluoromethylindoles from indoles with easy-to-handle, cheap and low-toxic CF3SO2Na under metal-free conditions is described, which selectively introduces trifluoromethyl to indoles on the C2 position. The desired product can be obtained in 0.7 g yield. A radical intermediate may be involved in this transformation.

Positive Selection Drove the Adaptation of Mitochondrial Genes to the Demands of Flight and High-Altitude Environments in Grasshoppers.

The molecular evolution of mitochondrial genes responds to changes in energy requirements and to high altitude adaptation in animals, but this has not been fully explored in invertebrates. The evolution of atmospheric oxygen content from high to low necessarily affects the energy requirements of insect movement. We examined 13 mitochondrial protein-coding genes (PCGs) of grasshoppers to test whether the adaptive evolution of genes involved in energy metabolism occurs in changes in atmospheric oxygen content and high altitude adaptation. Our molecular evolutionary analysis of the 13 PCGs in 15 species of flying grasshoppers and 13 related flightless grasshoppers indicated that, similar to previous studies, flightless grasshoppers have experienced relaxed selection. We found evidence of significant positive selection in the genes ATP8, COX3, ND2, ND4, ND4L, ND5, and ND6 in flying lineages. This results suggested that episodic positive selection allowed the mitochondrial genes of flying grasshoppers to adapt to increased energy demands during the continuous reduction of atmospheric oxygen content. Our analysis of five grasshopper endemic to the Tibetan Plateau and 13 non-Tibetan grasshoppers indicated that, due to positive selection, more non-synonymous nucleotide substitutions accumulated in Tibetan grasshoppers than in non-Tibetan grasshoppers. We also found evidence for significant positive selection in the genes ATP6, ND2, ND3, ND4, and ND5 in Tibetan lineages. Our results thus strongly suggest that, in grasshoppers, positive selection drives mitochondrial genes to better adapt both to the energy requirements of flight and to the high altitude of the Tibetan Plateau.

A head transcriptome provides insights into odorant binding proteins of the bamboo grasshopper.

The bamboo grasshopper Ceracris kiangsu is a famous bamboo pest in China. The identification of genes involved in olfactory behavior of C. kiangsu is necessary for better understanding the molecular basis and expression profiles of behavior ecology. However, necessary genomic and transcriptomic data are lacking in the species, limiting control efficiency. The primary objective of this study was to find and describe odorant binding proteins in the head of the bamboo grasshopper. We performed the paired-end sequencing on an Illumina Hiseq2000 following the vendor's recommended protocol. Functional annotation was performed by comparison with public databases. OBP genes were first identified using BLASTN and BLASTX results from our C. kiangsu datebase, which was established from the date of transcriptome sequencing. The gene-specific primers were used to conduct RT-PCR to detect the tissue distribution of OBPs using a SYBR Premix ExTaq kit following the manufacturer's instructions with a real-time thermal cycler. We obtained more than 133 million clean reads derived from the C. Kiangsu heads using the next-generation sequencing, which were assembled into 260,822 unique sequences (average 814 bp). We have detected eight putative odorant binding protein genes (OBPs) of C. kiangsu for the first time, and analyzed the expression profiles of the OBPs in different tissues (head, antenna, mouthpart, body and leg). Our results reveal that the eight OBPs display a clear divergence, strongly indicating that they possessed diverse functions, and thus provides comprehensive sequence analysis for elucidating the molecular basis of OBPs in C. kiangsu. In addition, we find that the relative expression levels of OBP1, OBP2 and OBP8 are significantly higher in the antennae as compared to the other OBP genes, suggesting that these three OBP genes play crucial roles in the locust's odorant discrimination. In general, this is the first study to characterize the complete head transcriptome of C. kiangsu using high-throughput sequencing. The study opens a window for functional characterization of the OBPs of C. kiangsu, with potential for new or refined applications of semiochemicals for control of this notorious pest.

Synthesis of Chiral Pyrazolone and Spiropyrazolone Derivatives through Squaramide-Catalyzed Reaction of Pyrazolin-5-ones with o-Quinone Methides.

A bifunctional squaramide-catalyzed reaction of pyrazolin-5-ones with o-quinone methides in situ generated from 2-(1-tosylalkyl)phenols has been successfully developed, providing a facile access to chiral pyrazolones with high enantioselectivities. In addition, the chiral spiropyrazolones with adjacent tertiary and quaternary stereogenic centers can also be obtained through cascade chlorination/cyclization of the chiral pyrazolones.

The complete mitochondrial genome of the jumping grasshopper Sinopodisma pieli (Orthoptera: Acrididae) and the phylogenetic analysis of Melanoplinae.

In this study, we reported the complete mitochondrial genome (mitogenome) of Sinopodisma pieli by polymerase chain reaction method for the first time, the type species of the genus Sinopodisma. Its mitogenome was a circular DNA molecule of 15,625 bp in length, with 76.0% A+T, and contained 13 protein-coding genes, 22 transfer RNA genes and two ribosomal RNA genes and one A+T control region. The overall base composition of the S. pieli mitogenome was 42.8% for A, 33.2% for T, 13.5% for C, and 10.5% for G, respectively. All 13 mitochondrial PCGs shared the start codon ATN. Twelve of the PCGs ended with termination codon TAA and TAG, while cytochrome coxidase subunit 1 (COI) utilized an incomplete T as terminator codon. All tRNA genes could be folded into the typical cloverleaf secondary structure, except trnS(AGN) lacking of dihydrouridine arm. The sizes of the large and small ribosomal RNA genes were 1379 bp and 794 bp, respectively. The A+T rich region was 798 bp in length and contained 88.5% AT content. A phylogenetic analysis based on 13 PCGs by using Bayesian inference (BI) and maximum likelihood (ML) revealed that Sinopodisma is not monophyletic group. We think that the name and taxonomic status of S. tsinlingensis are right, and it should not be moved into the genus Pedopodisma. These data will provide important information for a better understanding of the population genetics and species identification for Sinopodisma.