Facile preparation of a CoNiS/CF electrode by SILAR for a high sensitivity non-enzymatic glucose sensor.

The nanomaterials for non-enzymatic electrochemical sensors are usually pre-synthesized and coated onto electrodes by ex situ methods. In this work, amorphous cobalt-nickel sulfide (CoNiS) nanoparticles were facilely prepared on copper foam (CF) by the in situ successive ionic layer adsorption and reaction (SILAR) method, and as-prepared CoNiS/CF was studied as an electrode for non-enzymatic glucose sensing. It was analyzed by field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDAX) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance was investigated by cyclic voltammetry (CV) and chronoamperometry (CA). This binary sulfide electrode showed better performance toward glucose oxidation compared to the corresponding single sulfide and showed a wide linear range of 0.005 to 3.47 mM, a high sensitivity of 2298.7 µA mM-1 cm-2 and a low detection limit of 2.0 µM. The sensor exhibited high sensitivity and good repeatability and stability and was able to detect glucose in an actual sample. This work provides a simple and fast in situ electrode preparation method for a high-sensitivity glucose sensor.

Exploration of cardiopulmonary resuscitation teamwork training for maternal cardiac arrest using the SimMan intelligent simulation platform: A simulation teaching study.

Background and Aims: Maternal cardiac arrest is the most urgent clinical event in obstetrics and can lead to serious consequences, such as maternal or fetal death. Therefore, the training of team cardiopulmonary resuscitation (CPR) skills for obstetricians is essential. The aim of this study was to investigate the effect of applying intelligent simulation to CPR in maternal cardiac arrest teamwork training for obstetricians. Methods: Twenty-four obstetricians who participated in the "Maternal First Aid Workshop," organized by our hospital in 2018, were selected as training participants. The SimMan intelligent comprehensive patient simulator was used to train the CPR team collaboration with first-aid skills. Each team participating in the training was assessed before and after the training using a questionnaire survey. Results: The evaluation of the results after the training showed that all four teams were qualified and that the timing of the cesarean section was 100% correct. The mean score, team collaboration score, and chest compression fraction were significantly higher than before training. Teamwork CPR assessment time, interruption time of chest compressions, and artificial airway establishment time were significantly shorter than before training. The questionnaire survey showed that 95.8% of the physicians reported that the training was rewarding and helpful to their clinical work, and 100% of the physicians believed that obstetricians require similar training. Conclusion: Using the SimMan intelligent comprehensive patient simulator to train obstetricians for CPR of maternal cardiac arrest teamwork first-aid skills can significantly improve the training effect, clinical first-aid skills, and teamwork awareness.

Systematic Analysis of the Relationship Between Elevated Zinc and Epilepsy.

Previous studies have indicated a potential relationship between zinc and epilepsy. The aim of this study is to investigate the causal relationship between zinc, zinc-dependent carbonic anhydrase, and gray matter volume in brain regions enriched with zinc and epilepsy, as well as explore the possible mechanisms by which zinc contributes to epilepsy. First, this study assessed the risk causality between zinc, carbonic anhydrase, and gray matter volume alterations in zinc-enriched brain regions and various subtypes of epilepsy based on Two-sample Mendelian randomization analysis. And then, this study conducted GO/KEGG analysis based on colocalization analysis, MAGMA analysis, lasso regression, random forest model, and XGBoost model. The results of Mendelian randomization analyses showed a causal relationship between zinc, carbonic anhydrase-4, and generalized epilepsy (p = 0.044 , p = 0.010). Additionally, carbonic anhydrase-1 and gray matter volume of the caudate nucleus were found to be associated with epilepsy and focal epilepsy (p = 0.014, p = 0.003 and p = 0.022, p = 0.009). A colocalization relationship was found between epilepsy and focal epilepsy (PP.H4.abf = 97.7e - 2). Meanwhile, the MAGMA analysis indicated that SNPs associated with epilepsy and focal epilepsy were functionally localized to zinc-finger-protein-related genes (p < 1.0e - 5). The genes associated with focal epilepsy were found to have a molecular function of zinc ion binding (FDR = 2.3e - 6). After the onset of epilepsy, the function of the gene whose expression changed in the rats with focal epilepsy was enriched in the biological process of vascular response (FDR = 4.0e - 5). These results revealed mechanism of the increased risk of epilepsy caused by elevated zinc may be related to the increase of zinc ion-dependent carbonic anhydrase or the increase of the volume of zinc-rich caudate gray matter.

The molecular mechanism of action for the potent antitumor component extracted using supercritical fluid extraction from Croton crassifolius root.

ETHNOPHARMACOLOGICAL RELEVANCE: The root of Croton crassifolius has been used as a traditional Chinese medicine (TCM), called Radix Croton Crassifolius, and commonly known as "Ji Gu Xiang" in Chinese. Its medicinal value has been recorded in several medical books or handbooks, such as "Sheng Cao Yao Xing Bei Yao", "Ben Cao Qiu Yuan" and "Zhong Hua Ben Cao". It has been traditional employed for treating sore throat, stomach-ache, rheumatism and cancer. AIM OF THE STUDY: At present, there are limited studies on the evaluation of low-polarity extracts of roots in C. crassifolius. Consequently, the aim of this study was to evaluate the antitumor effect of the low-polarity extract of C. crassifolius root. MATERIALS AND METHODS: Extracts were obtained by supercritical fluid extraction. The extracts were tested for antitumor effects in vitro on several cancer cell lines. A CCK-8 kit was used for further analysis of cell viability. A flow cytometer and propidium iodide staining were used to evaluate the cell cycle and apoptosis. Hoechst staining, JC-1 staining and the fluorescence probe DCFH-DA were used to evaluate apoptotic cells. Molecular mechanisms of action were analyzed by quantitative RT‒PCR and Western blotting. Immunohistochemistry was used for the evaluation of xenograft tumors in male BALB/c mice. Finally, molecular docking was employed to predict the bond between the desired bioactive compound and molecular targets. RESULTS: Eleven diterpenoids were isolated from low-polarity C. crassifolius root extracts. Among the compounds, chettaphanin II showed the strongest activity (IC50 = 8.58 µM) against A549 cells. Evaluation of cell viability and the cell cycle showed that Chettaphanin II reduced A549 cell proliferation and induced G2/M-phase arrest. Chttaphanin II significantly induced apoptosis in A549 cells, which was related to the level of apoptosis-related proteins. The growth of tumor tissue was significantly inhibited by chettaphanin II in experiments performed on naked mice. The antitumor mechanism of chettaphanin II is that it can obstruct the mTOR/PI3K/Akt signaling pathway in A549 cells. Molecular docking established that chettaphanin II could bind to the active sites of Bcl-2 and Bax. CONCLUSIONS: Taken together, the natural diterpenoid chettaphanin II was identified as the major antitumor active component, and its potential for developing anticancer therapies was demonstrated for the first time by antiproliferation evaluation in vitro and in vivo.

A transcribed ultraconserved noncoding RNA, uc.285+, promotes colorectal cancer proliferation through dual targeting of CDC42 by directly binding mRNA and protein.

The transcribed ultraconserved region (T-UCR) belongs to a new type of lncRNAs that are conserved in homologous regions of the rat, mouse and human genomes. A lot of research has reported that differential expression of T-UCRs can influence the development of various cancers, revealing the ability of T-UCRs as new therapeutic targets or potential cancer biomarkers. Most studies on the molecular mechanisms of T-UCRs in cancer have focused on ceRNA regulatory networks and interactions with target proteins, but the present study reveals an innovative dual-targeted regulatory approach in which T-UCRs bind directly to mRNAs and directly to proteins. We screened T-UCRs that may be related to colorectal cancer (CRC) by performing a whole-genome T-UCR gene microarray and further studied the functional mechanism of T-UCR uc.285+ in the development of CRC. Modulation of uc.285+ affected the proliferation of CRC cell lines and influenced the expression of the CDC42 gene. We also found that uc.285+ promoted the proliferation of CRC cells by directly binding to CDC42 mRNA and enhancing its stability while directly binding to CDC42 protein and affecting its stability. In short, our research on the characteristics of cell proliferation found that uc.285+ has a biological function in promoting CRC proliferation. uc.285+ may have considerable potential as a new diagnostic biomarker for CRC.

Prussian Blue Analogue-Derived Co3O4 as Catalysts for Enhanced Selective Oxidation of Cyclohexane Using Molecular Oxygen.

Selective conversion of inert C-H bonds in alkanes into high-value-added functional groups (alcohols, ketones, carboxylic acids, etc.) plays a vital role in establishing a green and sustainable chemical industry. Catalytic selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone) is a typical representative of alkane functionalization. In this work, hollow cage-like Co3O4 (Co3O4-C) and particle Co3O4 (Co3O4-P) were synthesized by calcining two types of Prussian blue analogues (PBAs), which were used to catalyze the selective oxidation of cyclohexane. The Co3O4-C predominantly exposed (311) crystal plane is easier to adsorb cyclohexane than Co3O4-P, which is beneficial to shorten the induction period, accelerate the reaction rate, and improve the conversion. Consequently, Co3O4-C displayed a 10% conversion of cyclohexane within 1 h, and the KA oil selectivity reached 90%. The Co3O4-P exposed (220) crystal plane has a higher molar percentage of oxygen vacancies and more active oxygen species, as well as a strong cyclohexanone adsorption capacity, which is conducive to the deep oxidation of cyclohexanone to adipic acid and other diacid products. The mechanism analysis of cyclohexane oxidation catalyzed by PBA-based Co3O4 shows that it exemplifies the feasibility to tailor the surface of catalysts by modulating the PBAs, which ultimately influences their reaction performance for accelerating the reaction and maintaining high cyclohexane conversion and KA oil selectivity.

Impact of Vitamin C on Inflammatory Response and Myocardial Injury in Sepsis Patients.

Background: Amidst the complexities of sepsis-induced inflammatory responses and myocardial injury, this study investigates the therapeutic potential of vitamin C in mitigating sepsis complications. The findings offer crucial insights into the prospective use of vitamin C, shaping future strategies for enhanced patient care. Objective: To investigate the impact of vitamin C on the inflammatory response and myocardial damage in individuals with sepsis. Methods: A total of 83 sepsis patients treated in our hospital from January 2021 to January 2023 were randomly divided into a control group (n=41, receiving basic treatment) and a study group (n=42, receiving vitamin C in addition to basic treatment). To evaluate the impact of treatment, we compared organ dysfunction, inflammatory response index, myocardial injury index, and morbidity/mortality rates before and after the intervention in both groups. It allowed for a comprehensive analysis of the treatment's effects on these key parameters. Results: After therapy, the study group exhibited lower SOFA ratings compared to the control group (P < .05). Levels of Hypersensitive C-reactive Protein (hs-CRP), Tumor Necrosis Factor (TNF), High Mobility Group Protein B1 (HMGB1), Creatine Kinase Isoenzyme (CK-MB), Troponin I (cTnI), and B-type brain natriuretic peptide (BNP) were significantly lower in the study group than in the control group after treatment (P < .05). The study group also demonstrated a lower morbidity and mortality rate (9.52%) compared to the control group (29.27%) (P < .05). Conclusions: Vitamin C supplementation holds significant therapeutic value, contributing to reduced inflammatory response, myocardial injury, morbidity, and mortality rates in sepsis patients. This intervention enhances clinical efficacy, fostering disease regression.

A divergent intermediate strategy yields biologically diverse pseudo-natural products.

The efficient exploration of biologically relevant chemical space is essential for the discovery of bioactive compounds. A molecular design principle that possesses both biological relevance and structural diversity may more efficiently lead to compound collections that are enriched in diverse bioactivities. Here the diverse pseudo-natural product (PNP) strategy, which combines the biological relevance of the PNP concept with synthetic diversification strategies from diversity-oriented synthesis, is reported. A diverse PNP collection was synthesized from a common divergent intermediate through developed indole dearomatization methodologies to afford three-dimensional molecular frameworks that could be further diversified via intramolecular coupling and/or carbon monoxide insertion. In total, 154 PNPs were synthesized representing eight different classes. Cheminformatic analyses showed that the PNPs are structurally diverse between classes. Biological investigations revealed the extent of diverse bioactivity enrichment of the collection in which four inhibitors of Hedgehog signalling, DNA synthesis, de novo pyrimidine biosynthesis and tubulin polymerization were identified from four different PNP classes.

Toward a remote sensing method based on commercial LiDAR sensors for the measurement of spray drift and potential drift reduction.

Spray drift is inevitable in chemical applications, drawing global attention because of its potential environmental pollution and the risk of exposing bystanders to pesticides. This issue has become more pronounced with a growing consensus on the need for enhanced environmental safeguards in agricultural practices. Traditionally, spray drift measurements, crucial for refining spray techniques, relied on intricate, time-consuming, and labor-intensive sampling methods utilizing passive collectors. In this study, we investigated the feasibility of using close-range remote sensing technology based on Light Detection and Ranging (LiDAR) point clouds to implement drift measurements and drift reduction classification. The results show that LiDAR-based point clouds vividly depict the spatial dispersion and movement of droplets within the vertical plane. The capability of LiDAR to accurately determine drift deposition was demonstrated, evident from the high R2 values of 0.847, 0.748 and 0.860 achieved for indoor, wind tunnel and field environments, respectively. Droplets smaller than 100 µm and with a density below 50 deposits·cm-2·s-1 posed challenges for LiDAR detection. To address these challenges, the use of multichannel LiDAR with higher wavelengths presents a potential solution, warranting further exploration. Furthermore, we found a satisfactory consistency when comparing the drift reduction classification calculated from LiDAR measurements with those obtained though passive collectors, both in indoor tests and the unmanned air-assisted sprayer (UAAS) field test. However, in environments with less dense clouds of larger droplets, a contradiction emerged between higher drift deposition and lower scanned droplet counts, potentially leading to deviations in the calculated drift potential reduction percentage (DPRP). This was exemplified in a field test using an unmanned aerial vehicle sprayer (UAVS). Our findings provide valuable insights into the monitoring and quantification of pesticide drift at close range using LiDAR technology, paving the way for more precise and efficient drift assessment methodologies.

Spraying performance of umbrella wind-field-type atomization and its application to parameter optimization.

BACKGROUND: We designed an umbrella wind-field-type anti-drift spraying device to improve droplet deposit in the fruit tree canopy, reduce spray drift between fruit tree rows, and avoid uneven droplet deposit in the canopy. RESULTS: We used Computational Fluid Dynamics combined with wind field tests to optimize the parameters of the anti-drift spray device, and the results showed that airflow velocity at the outlet of the device after optimization was 24.5 m s-1 , which is 48% higher than that before optimization (16.5 m s-1 ) airflow velocity. We designed wind tunnel tests and field tests to analyze the anti-drift characteristics of the anti-drift spraying device. Wind tunnel test results showed that the side airflow velocity, outlet diameter, spray distance, and spray drift ratio were correlated. The mathematical models established by vertical and horizontal multifactor orthogonal tests were significant (P < 0.05, R2 0.947, 0.878, respectively). The results of the field tests showed that side airflow, velocity spray pressure and outlet diameter had significant effects on the droplet deposit characteristics (in descending order: the side airflow velocity, spray pressure, and outlet diameter). The maximum droplet deposit was 6.34 µL cm-2 when the side airflow velocity was 2 m s-1 , the spray pressure was 0.4 MPa, and the outlet diameter was 70 mm2 . When the side airflow velocity exceeded 2 m s-1 , the outlet diameter and spray pressure had to be reduced to ensure better droplet deposit. CONCLUSION: The results indicated that the umbrella wind field could reduce spray drift and ineffective deposit in off-target areas and provides a reference for the comprehensive analysis of the spray drift deposit law. © 2023 Society of Chemical Industry.

The dynamic recruitment of LAB proteins senses meiotic chromosome axis differentiation in C. elegans.

During meiosis, cohesin and meiosis-specific proteins organize chromatin into an axis-loop architecture, coordinating homologous synapsis, recombination, and ordered chromosome segregation. However, how the meiotic chromosome axis is assembled and differentiated with meiotic progression remains elusive. Here, we explore the dynamic recruitment of two long arms of the bivalent proteins, LAB-1 and LAB-2, in Caenorhabditis elegans. LAB proteins directly interact with the axis core HORMA complexes and weak interactions contribute to their recruitment. LAB proteins phase separate in vitro, and this capacity is promoted by HORMA complexes. During early prophase, synapsis oppositely regulates the axis enrichment of LAB proteins. After the pachytene exit, LAB proteins switch from a reciprocal localization pattern to a colocalization pattern, and the normal dynamic pattern of LAB proteins is altered in meiotic mutants. We propose that LAB recruitment senses axis differentiation, and phase separation of meiotic structures helps subdomain establishment and accurate segregation of the chromosomes.

An Antennae-Enriched Odorant-Binding Protein EonuOBP43 Mediate the Behavioral Response of the Tea Green Leafhopper, Empoasca onukii Matsuda to the Host and Nonhost Volatiles.

Olfaction is crucial for Empoasca onukii Matsuda to recognize odors from the host and nonhost plants, and it has been proposed that odorant binding proteins are directly required for odorant discrimination and represent potential targets of interest for pest control. Here, we cloned EonuOBP43 and expressed the recombinant EonuOBP43 protein. Furthermore, competitive fluorescence binding assays with 19 ligands indicated that terpenoids and alkanes showed a relatively higher than for other classes of chemicals. Additionally, ligand docking and site-directed mutagenesis results revealed that seven hydrophobic residues, including Val-86, Met-89, Phe-90, Ile-104, Ile-105, Leu-130, and Val-134, played a key role in the binding of EonuOBP43 to plant volatiles. In olfactometer tests, E. onukii were significantly attracted to α-farnesene and repelled to ß-caryophyllene, and dsOBP43 treated adult lost response to α-farnesene and ß-caryophyllene. In summary, our results demonstrated that EonuOBP43 may function as a carrier in the process of sensing plant compounds of E. onukii.

Unraveling the Fundamental Mechanism of Interface Conductive Network Influence on the Fast-Charging Performance of SiO-Based Anode for Lithium-Ion Batteries.

HIGHLIGHTS: Influence of interface conductive network on ionic transport and mechanical stability under fast charging is explored for the first time. The mitigation of interface polarization is precisely revealed by the combination of 2D modeling simulation and Cryo-TEM observation, which can be attributed to a higher fraction formation of conductive inorganic species in bilayer SEI, and primarily contributes to a linear decrease in ionic diffusion energy barrier. The improved stress dissipation presented by AFM and Raman shift is critical for the linear reduction in electrode residual stress and thickness swelling. Progress in the fast charging of high-capacity silicon monoxide (SiO)-based anode is currently hindered by insufficient conductivity and notable volume expansion. The construction of an interface conductive network effectively addresses the aforementioned problems; however, the impact of its quality on lithium-ion transfer and structure durability is yet to be explored. Herein, the influence of an interface conductive network on ionic transport and mechanical stability under fast charging is explored for the first time. 2D modeling simulation and Cryo-transmission electron microscopy precisely reveal the mitigation of interface polarization owing to a higher fraction of conductive inorganic species formation in bilayer solid electrolyte interphase is mainly responsible for a linear decrease in ionic diffusion energy barrier. Furthermore, atomic force microscopy and Raman shift exhibit substantial stress dissipation generated by a complete conductive network, which is critical to the linear reduction of electrode residual stress. This study provides insights into the rational design of optimized interface SiO-based anodes with reinforced fast-charging performance.

Anti-infective therapy durations predict psychological stress and laparoscopic surgery quality in pelvic abscess patients.

BACKGROUND: The degree of psychological stress and the difficulty and efficacy of laparoscopic surgery differ in patients with pelvic abscesses after different durations of anti-infection treatment. AIM: To compare and analyse the effects of different durations of anti-infective therapy on patients' preoperative psychological stress level and the clinical efficacy of laparoscopic surgery in patients with pelvic abscesses to offer a reference for the selection of therapy plans. METHODS: A total of 100 patients with pelvic abscesses who were admitted to the Department of Gynecology of Suzhou Ninth Hospital affiliated to Soochow University (Suzhou Ninth People's Hospital) from January 2018 to December 2022 were retrospectively enrolled. According to the different durations of anti-infective therapy, they were divided into Group S (50 patients, received anti-infective therapy for 24-48 h) and Group L (50 patients, received anti-infective therapy for 48-96 h). Baseline data, state-trait anxiety score at admission and before surgery, self-rating anxiety scale (SAS) + self-rating depression scale (SDS) score, surgery time, adhesion grading score, intraoperative blood loss, presence or absence of intraoperative intestinal injury, ureteral injury or bladder injury, postoperative body temperature, length of hospital stay, and presence or absence of recurrence within 3 mo after surgery, chronic pelvic pain, incision infection, dysmenorrhea, menstrual disorder or intestinal obstruction were compared between the S group and the L group. RESULTS: There was no significant difference in the background data between the S group and the L group (P < 0.05). There was no significant difference in the state-trait anxiety score or SAS + SDS score between the S group and the L group on admission (P < 0.05). The state-trait anxiety score and SAS + SDS score of the S group were lower than those of Group L after receiving different durations of anti-infective therapy (P < 0.05). There was no significant difference in the incidence of intestinal, ureteral or bladder injury between the S group and the L group (P < 0.05). The surgery time of Group S was shorter than that of Group L, and the adhesion score and intraoperative blood loss volume were lower than those of Group L (P < 0.05). There was no significant difference in the incidence of incision infection, dysmenorrhea, menstrual disorder or intestinal obstruction between the S group and the L group (P < 0.05). The postoperative body temperature of Group S was lower than that of Group L (P < 0.05), and the hospital stay was shorter than that of Group L (P < 0.05). The incidences of recurrence and chronic pelvic pain within 3 mo after surgery were lower than that of Group L (P < 0.05). CONCLUSION: Twenty-four to forty-eight hours of anti-infective therapy is better than 48-96 h of anti-infective therapy for patients with pelvic abscesses because the degree of psychological stress is lower, which is more conducive to achieving better outcomes after laparoscopic surgery.

Tracing the Bioaccessibility of Per- and Polyfluoroalkyl Substances in Fish during Cooking Treatment.

The effect of cooking on the contents of per- and polyfluoroalkyl substances (PFAS) in foods has been widely studied, but whether cooking-induced structural and chemical modifications in foods affect the oral bioaccessibility of PFAS remains largely unknown. In this study, three kinds of fishes with different fat contents were selected, and the bioaccessibility of PFAS during cooking treatment (steaming and frying) was evaluated using in vitro gastrointestinal simulation with gastric lipase addition. The results showed that related to their molecular structures, the bioaccessibility of an individual PFAS varied greatly, ranging from 26.0 to 108.1%. Cooking can reduce the bioaccessibility of PFAS, and steaming is more effective than oil-frying; one of the possible reasons for this result is that the PFAS is trapped in protein aggregates after heat treatment. Fish lipids and cooking oil ingested with meals exert different effects on the bioaccessibility of PFAS, which may be related to the state of the ingested lipid/oil and the degree of unsaturation of fatty acids. Gastric lipase boosted the release of long-chain PFAS during in vitro digestion, indicating that the degree of lipolysis considerably influences the bioaccessibility of hydrophobic PFAS. Estimated weekly PFAS intakes were recalibrated using bioaccessibility data, enabling more accurate and reliable dietary exposure assessments.

Metasurfaces for generating higher-order Poincaré beams by polarization-selective focusing and overall elimination of co-polarization components.

Focused higher-order Poincaré (HOP) beams are of particular interest because they facilitate understanding the exotic properties of structured light and their applications in classical physics and quantum information. However, generating focused HOP beams using metasurfaces is challenging. In this study, we proposed a metasurface design comprising two sets of metal nanoslits for generating coaxially focused HOP beams. The nanoslits were interleaved on equispaced alternating rings. The initial rings started at the two adjacent Fresnel zones to provide opposite propagation phases for overall elimination of the co-polarization components. With the designed hyperbolic and helical profiles of the geometric phases, the two vortices of the opposite cross-circular-polarizations were formed and selectively focused, realizing HOP beams of improved quality. Simulations and experimental results demonstrated the feasibility of the proposed metasurface design. This study is of significance in the integration of miniaturized optical devices and enriches the application areas of metasurfaces.

Synthetic Matching of Complex Monoterpene Indole Alkaloid Chemical Space.

Monoterpene indole alkaloids (MIAs) are endowed with high structural and spatial complexity and characterized by diverse biological activities. Given this complexity-activity combination in MIAs, rapid and efficient access to chemical matter related to and with complexity similar to these alkaloids would be highly desirable, since such compound classes might display novel bioactivity. We describe the design and synthesis of a pseudo-natural product (pseudo-NP) collection obtained by the unprecedented combination of MIA fragments through complexity-generating transformations, resulting in arrangements not currently accessible by biosynthetic pathways. Cheminformatic analyses revealed that both the pseudo-NPs and the MIAs reside in a unique and common area of chemical space with high spatial complexity-density that is only sparsely populated by other natural products and drugs. Investigation of bioactivity guided by morphological profiling identified pseudo-NPs that inhibit DNA synthesis and modulate tubulin. These results demonstrate that the pseudo-NP collection occupies similar biologically relevant chemical space that Nature has endowed MIAs with.

Characterization of Ionotropic Receptor Gene EonuIR25a in the Tea Green Leafhopper, Empoasca onukii Matsuda.

Ionotropic receptors (IRs) play a central role in detecting chemosensory information from the environment and guiding insect behaviors and are potential target genes for pest control. Empoasca onukii Matsuda is a major pest of the tea plant Camellia sinensis (L.) O. Ktze, and seriously influences tea yields and quality. In this study, the ionotropic receptor gene EonuIR25a in E. onukii was cloned, and the expression pattern of EonuIR25a was detected in various tissues. Behavioral responses of E. onukii to volatile compounds emitted by tea plants were determined using olfactometer bioassay and field trials. To further explore the function of EonuIR25a in olfactory recognition of compounds, RNA interference (RNAi) of EonuIR25a was carried out by ingestion of in vitro synthesized dsRNAs. The coding sequence (CDS) length of EonuIR25a was 1266 bp and it encoded a 48.87 kD protein. EonuIR25a was enriched in the antennae of E. onukii. E. onukii was more significantly attracted by 1-phenylethanol at a concentration of 100 µL/mL. Feeding with dsEonuIR25a significantly downregulated the expression level of EonuIR25a, after 3 h of treatment, which disturbed the behavioral responses of E. onukii to 1-phenylethanol at a concentration of 100 µL/mL. The response rate of E. onukii to 1-phenylethanol was significantly decreased after dsEonuIR25a treatment for 12 h. In summary, the ionotropic receptor gene EonuIR25a was highly expressed in the antennae of E. onukii and was involved in olfactory recognition of the tea plant volatile 1-phenylethanol. The present study may help us to use the ionotropic receptor gene as a target for the behavioral manipulation of E. onukii in the future.

Sulfonium-based precise alkyl transposition reactions.

S-adenosyl-L-methionine (SAM), a sulfonium-based cofactor, plays an important role in numerous biological processes as methyl donor. Inspired by the function of sulfonium motif in this nature's synthetic toolkit, we here present an aryne-activation strategy that the sulfonium intermediates in situ generated from thioethers display unique reactivity toward alkyl group transposition. Experimental and theoretical studies indicate that the reaction occurs in an intermolecular fashion where the TfO--incorporated [K(18-crown-6)] complex acts as a key promoter for this thermodynamically favored process. Next, a series of robust, easy-to-prepare sulfonium salts are designed and developed as electrophilic alkylation reagents accordingly. Both systems feature for broad scope, excellent selectivity, and simple operation. Moreover, we highlight the synthetic value through molecular editing and late-stage modification of complex scaffolds or even active pharmaceutical ingredients.