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Enlightened from our previous work of structural simplification of quinine and innovative application of natural products against phytopathogenic fungi, lead structure 2,8-bis(trifluoromethyl)-4-quinolinol (3) was selected to be a candidate and its diversified design, synthesis, and antifungal evaluation were carried out. All of the synthesized compounds Aa1-Db1 were evaluated for their antifungal activity against four agriculturally important fungi, Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani, and Sclerotinia sclerotiorum. Results showed that compounds Ac3, Ac4, Ac7, Ac9, Ac12, Bb1, Bb10, Bb11, Bb13, Cb1. and Cb3 exhibited a good antifungal effect, especially Ac12 had the most potent activity with EC50 values of 0.52 and 0.50 μg/mL against S. sclerotiorum and B. cinerea, respectively, which were more potent than those of the lead compound 3 (1.72 and 1.89 μg/mL) and commercial fungicides azoxystrobin (both >30 μg/mL) and 8-hydroxyquinoline (2.12 and 5.28 μg/mL). Moreover, compound Ac12 displayed excellent in vivo antifungal activity, which was comparable in activity to the commercial fungicide boscalid. The preliminary mechanism revealed that compound Ac12 might cause an abnormal morphology of cell membranes, an increase in membrane permeability, and release of cellular contents. These results indicated that compound Ac12 displayed superior in vitro and in vivo fungicidal activities and could be a potential fungicidal candidate against plant fungal diseases.

Plant pathogenic fungi seriously affect agricultural production and are difficult to control. The discovery of new leads based on natural products is an important way to innovate fungicides. In this study, 30 natural-product-based magnolol derivatives were synthesized and characterized on the basis of NMR and mass spectroscopy. Bioactivity tests on phytopathogenic fungi (Rhizoctonia solani, Fusarium graminearum, Botrytis cinerea, and Sclerotinia sclerotiorum) in vitro of these compounds were performed systematically. The results showed that 11 compounds were active against four kinds of phytopathogenic fungi with EC50 values in the range of 1.40-20.00 μg/mL, especially compound L5 that exhibited excellent antifungal properties against B. cinerea with an EC50 value of 2.86 μg/mL, approximately 2.8-fold more potent than magnolol (EC50 = 8.13 μg/mL). Moreover, compound L6 showed the highest antifungal activity against F. graminearum and Rhophitulus solani with EC50 values of 4.39 and 1.40 μg/mL, respectively, and compound L7 showed good antifungal activity against S. sclerotiorum. Then, an in vivo experiment of compound L5 against B. cinerea was further investigated in vivo using infected tomatoes (curative effect, 50/200 and 36%/100 μg/mL). The physiological and biochemical studies illustrated that the primary action mechanism of compound L5 on B. cinerea might change the mycelium morphology, increase cell membrane permeability, and destroy the function of mitochondria. Furthermore, structure-activity relationship (SAR) studies revealed that hydroxyl groups play a key role in antifungal activity. To sum up, this study provides a reference for understanding the application of magnolol-based antifungal agents in crop protection.

Rhizoctonia solani causes serious plant diseases. Neocryptolepine presented the significant antifungal activity against R. solani, however the mode of action is unclear. In this paper, we investigated the potential mode of action of neocryptolepine against R. solani integrated the proteomics and transcriptomics. Results showed that after treatment with neocryptolepine, 1012 differentially expressed proteins and 10 920 differentially expressed genes of R. solani were found, most of them were enriched in mitochondrial respiratory chain. It affected oxidative phosphorylation led to the enrichment of ROS and the decrease of MMP, and inhibited complex III activity with the inhibition rate of 63.51% at 10 μg/mL. The mitochondrial structural and function were damaged. Cytochrome b-c1 complex subunit Rieske (UQCRFS1) with the high binding score to neocryptolepine was found as a potential target. In addition, it inhibited the sclerotia formation and presented antifungal efficacy by decreasing the diameter of a wound in potato in a concentration-dependent manner. Above results indicated that neocryptolepine inhibited the complex III activity by binding UQCRFS1 and blocked the ion transfer to cause the death of R. solani mycelia. This study laid the foundation for the future development of neocryptolepine as an alternative biofungicide.

A pyrrolidine-mediated Knoevenagel-type reaction for highly stereoselective construction of novel α-halo-1,3-dienylsulfonyl fluorides was achieved in up to 100% Z-selectivity and high yields at roo...

A clickable connective hub 1-bromo-2-triazolethane-1-sulfonyl fluoride BTESF (1) was developed and successfully applied for the fluorosulfonylvinylation of a host of primary and secondary cyclic or acyclic amines including amino acids and pharmaceuticals. Further antimicrobial experiments revealed that vinyl sulfonyl fluoride functionalized norfloxacin (3ak), ciprofloxacin (3am), and lomefloxacin (3an) exhibited 4-fold improved antimicrobial activity against Gram-positive bacteria compared to their parent drugs.

Humulus lupulus Linn. is a traditional medicinal and edible plant with several biological properties. The aims of this work were: (1) to evaluate the in vitro antifungal activity of H. lupulus ethanolic extract, (2) to study the in vitro and in vivo antifungal activity of isoxanthohumol, an isoprene flavonoid from H. lupulus, against Botrytis cinerea, and (3) to explore the antifungal mechanism of isoxanthohumol on B. cinerea. The present data revealed that the ethanolic extract of H. lupulus exhibited moderate antifungal activity against the five tested phytopathogenic fungi in vitro, and isoxanthohumol showed highly significant antifungal activity against B. cinerea, with an EC50 value of 4.32 µg/mL. Meanwhile, it exhibited moderate to excellent protective and curative efficacies in vivo. The results of morphologic observation, RNA-seq, and physiological indicators revealed that the antifungal mechanism of isoxanthohumol is mainly related to metabolism, it affected the carbohydrate metabolic process, destroyed the tricarboxylic acid (TCA) cycle, and hindered the generation of ATP by inhibiting respiration. Further studies indicated that isoxanthohumol caused membrane lipid peroxidation, thus accelerating the death of B. cinerea. This study demonstrates that isoxanthohumol can be used as a potential botanical fungicide for the management of phytopathogenic fungi.

Summary Taxane-based reagents, such as Taxol, Taxotere, and Abraxane, are popular anti-cancer drugs that can differ in their clinical efficacy. This difference is generally attributed to their active pharmaceutical ingredients. Here, we report a serendipitous discovery that Taxol induces metabolic dysregulation and unfolded protein response. Surprisingly, these effects of Taxol are entirely dependent on its excipient, Cremophor EL (CrEL). We show that CrEL promotes aerobic glycolysis and in turn results in drastic upregulation of angiopoietin like 4 (ANGPTL4), a major regulator of human blood lipid profile. Notably, premedication with dexamethasone further enhances the expression of ANGPTL4. Consistently, we find that the amplitude and frequency of increase in triglycerides is more prominent in Taxol-treated patients with breast cancer. In addition, we find that CrEL activates the unfolded protein response pathway to trigger proinflammatory gene expression and caspase/gasdermin E-dependent pyroptosis. Finally, we discuss the implications of these results in anti-cancer therapies., Graphical abstract, Highlights • Cremophor EL, the excipient of chemotherapy drug Taxol, is biologically active • Cremophor EL promotes aerobic glycolysis in cancer and primary human immune cells • Dexamethasone and Cremophor EL may cause dyslipidemia via ANGPTL4 upregulation • Cremophor EL promotes the unfolded protein response, Biological sciences; Molecular biology; Cell biology; Cancer

The first Cu-catalyzed chemical selective desulfonylation of vinyl sulfonyl fluorides and vinyl sulfonyl compounds to their corresponding olefins was developed using B2pin2–water as the reductant. This protocol featured a wide substrate scope, mild conditions and excellent functional group compatibility.

The sulfur(VI) fluoride exchange reaction (SuFEx), developed by Sharpless and co-workers in 2014, is a new category of click reaction that creates molecular connections with absolute reliability and unprecedented efficiency through a sulfur(VI) hub. Ethenesulfonyl fluoride (ESF), as one of the most important sulfur(VI) hubs, exhibits extraordinary reactivity in SuFEx click chemistry and organic synthesis. This review summarizes the chemical properties and applications of ESF in click chemistry, organic chemistry, materials science, medicinal chemistry and in many other fields related to organic synthesis.1 Introduction2 Chemical Transformations of ESF3 Chemical Transformations of 2-Arylethenesulfonyl Fluorides4 Novel SuFEx Reagents Derived from ESF5 Applications of ESF Derivatives in Medicinal Chemistry6 Applications of ESF Derivatives in Materials Science7 Conclusion

Summary Rh-catalyzed, highly enantioselective (up to 99.8% ee) synthesis of aliphatic sulfonyl fluorides was accomplished. This protocol provides a portal to a class of novel 2-aryl substituted chiral sulfonyl fluorides, which are otherwise extremely difficult to access. This asymmetric synthesis has the feature of mild conditions, excellent functional group compatibility, and wide substrate scope (51 examples) generating a wide array of structurally unique chiral β-arylated sulfonyl fluorides for sulfur(VI) fluoride exchange (SuFEx) click reaction and drug discovery., Graphical Abstract, Highlights • Enantioselective synthesis of di(hetero)arylalkyl sulfonyl fluorides were achieved • These novel SuFEx Clickable molecules will play significant roles for drug discovery • The asymmetric C-C bond construction is a new portal to chiral sulfonyl fluorides • This protocol feathers with mild condition, wide scope, and excellent compatibility, Catalysis; Organic Chemistry; Stereochemistry

We discovered that with the promotion of sulfuryl fluoride, the carbonyl groups of amides performed as nucleophiles while the hydroxyl groups of alcohols were activated to functionalize as electrophiles. This study displayed that the amide C-N bonds could be easily cleaved with delicate nucleophiles to form the ester C-O bonds at room temperature without using transition metals. The broad substrate scope and excellent functional group compatibility were proved with 44 examples in up to 99% yields.

Exclusively regioselective addition of (hetero)aromatic groups to 1,3-dienylsulfonyl fluorides using the Rh(I)/diene catalyst produces a class of (E)-2-aryl-4-(aryl or alkyl)but-3-ene-1-sulfonyl fl...

Isoquinoline alkaloids possess broad pharmacological activities. In this study, the antifungal activity of twelve isoquinoline alkaloids, including berberine (1), jatrorrhizine (2), coptisine (3), corydaline (4), tetrahydroberberine (5), chelidonine (6), dihydrosanguinarine (7), chelerythrine (8), sanguinarine (9), palmatine (10), tetrahydropalmatine (11) and columbamine (12) were evaluated against eight plant pathogenic fungi in vitro. All the tested compounds showed varying degrees of inhibition against the eight tested plant fungi. Among them, sanguinarine exhibited high antifungal activity (EC50 ranging from 6.96–59.36 μg/mL). It displayed the best inhibitory activity against Magnaporthe oryzae (EC50 = 6.96 μg/mL), compared with azoxystrobin (EC50 = 12.04 μg/mL), and significantly suppressed spore germination of M. oryzae with the inhibition rate reaching 100% (50 μg/mL). The optical microscopy and scanning electron microscopy observations revealed that after treating M. oryzae mycelia with sanguinarine at 10 μg/mL, the mycelia appeared curved, collapsed and the cell membrane integrity was eventually damaged. Furthermore, the reactive oxygen species production, mitochondrial membrane potential and nuclear morphometry of mycelia had been changed, and the membrane function and cell proliferation of mycelia were destroyed. These results will enrich our insights into action mechanisms of antifungal activity of sanguinarine against M. oryzae.

A simple, practical and gram-scale process for direct transformation of primary alcohols or silyl ethers to ammonium salts was developed. This method has the feathers of easy work-up (a simple filtration), mild condition, high yield, great practicality and robustness. And the application of the ammonium salts in Suzuki coupling reaction was also accomplished.

At present more than 250 FDA approved chlorine containing drugs were available in the market and many pharmaceutically important drug candidates in pre-clinical trials. Thus, it is quite obvious to expect that in coming decades there will be an even greater number of new chlorine-containing pharmaceuticals in market. Chlorinated compounds represent the family of compounds promising for use in medicinal chemistry. This review describes the recent advances in the synthesis of chlorine containing heterocyclic compounds as diverse biological agents and drugs in the pharmaceutical industries for the inspiration of the discovery and development of more potent and effective chlorinated drugs against numerous death-causing diseases., Graphical abstract Image 1, Highlights • The applications of chlorine in medicinal chemistry is one of the fastest growing hot research areas in the chemistry community. • More than 250 FDA approved chloro-containing drugs are in the market. • This review summarizes nearly 130 FDA approved drugs against diverse biological agents. • Discussions of the SAR of potent drugs were included.

Oxytetracycline is one of the tetracycline antibiotics for feeding pig or cow, tetracycline antibiotics are the most widely used in animals and veterinary medicine as growth promoters and antibacte...

A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.

The protocol for simple, efficient, and mild synthesis of oxazolyl sulfonyl fluorides was developed through Rh2(OAc)4-catalyzed annulation of methyl-2-diazo-2-(fluorosulfonyl)acetate (MDF) or its ethyl ester derivative with nitriles. This practical method provides a general and direct route to a unique class of highly functionalized oxazolyl-decorated sulfonyl fluoride warheads with great potential in medicinal chemistry, chemical biology, and drug discovery.

Magnolia officinalis, as a well-known herb worldwide, has been widely used to treat multiple diseases for a long time. In this study, the petroleum ether extract from M. officinalis showed effective antifungal activity against seven plant pathogens (particularly against R. solani with an inhibition rate of 100.00% at 250 μg/mL). Honokiol and magnolol, isolated by the bioassay-guided method, exhibited greater antifungal activity than tebuconazole (EC50 = 3.07 μg/mL, p ≤ 0.001) against R. solani, which EC50 values were 2.18 μg/mL and 3.48 μg/mL, respectively. We used transcriptomics to explore the mechanism of action of honokiol against R. solani. Results indicated that honokiol may exert antifungal effects by blocking the oxidative phosphorylation metabolic pathway. Further studies indicated that honokiol induced ROS overproduction, disrupted the mitochondrial function, affected respiration, and blocked the TCA cycle, which eventually inhibited ATP production. Besides, honokiol also damaged cell membranes and caused morphological changes. This study demonstrated that the lignans isolated from M. officinalis possess the potential to be developed as botanical fungicides.

Sulfur (SVI) based moieties, especially, the sulfonyl or sulfonamide based analogues have showed a variety of pharmacological properties, and its derivatives propose a high degree of structural diversity that has established useful for the finding of new therapeutic agents. The developments of new less toxic, low cost and highly active sulfonamides containing analogues are hot research topics in medicinal chemistry. Currently, more than 150 FDA approved Sulfur (SVI)-based drugs are available in the market, and they are widely used to treat various types of diseases with therapeutic power. This comprehensive review highlights the recent developments of sulfonyl or sulfonamides based compounds in huge range of therapeutic applications such as antimicrobial, anti-inflammatory, antiviral, anticonvulsant, antitubercular, antidiabetic, antileishmanial, carbonic anhydrase, antimalarial, anticancer and other medicinal agents. We believe that, this review article is useful to inspire new ideas for structural design and developments of less toxic and powerful Sulfur (SVI) based drugs against the numerous death-causing diseases.

The construction of para-amino-arylfluorosulfates was achieved through installation of fluorosulfate (–OSO2F) functionality into aromatic C(sp2)–H bonds by the reaction of N-arylhydroxylamine with sulfuryl fluoride (SO2F2). This method provides a mild process for the preparation of broadly applicable fluorosulfate moieties without the requirement of phenols or transition metals.

Optically actuated silicon structures reveal rapid calcium signal propagation in biofilms., Bacterial response to transient physical stress is critical to their homeostasis and survival in the dynamic natural environment. Because of the lack of biophysical tools capable of delivering precise and localized physical perturbations to a bacterial community, the underlying mechanism of microbial signal transduction has remained unexplored. Here, we developed multiscale and structured silicon (Si) materials as nongenetic optical transducers capable of modulating the activities of both single bacterial cells and biofilms at high spatiotemporal resolution. Upon optical stimulation, we capture a previously unidentified form of rapid, photothermal gradient–dependent, intercellular calcium signaling within the biofilm. We also found an unexpected coupling between calcium dynamics and biofilm mechanics, which could be of importance for biofilm resistance. Our results suggest that functional integration of Si materials and bacteria, and associated control of signal transduction, may lead to hybrid living matter toward future synthetic biology and adaptable materials.

Direct synthesis of alkynes from inexpensive, abundant alcohols was achieved in high yields (greater than 40 examples, up to 95% yield) through a SO2F2-promoted dehydration and dehydrogenation process. This straightforward transformation of sp3-sp3 (C-C) bonds to sp-sp (C≡C) bonds requires only inexpensive and readily available reagents (no transition metals) under mild conditions. The crude alkynes are sufficiently free of impurities to permit direct use in further transformations, as illustrated by regioselective Huisgen alkyne-azide cycloaddition reactions with PhN3 to give 1,4-substituted 1,2,3-traiazoles (16 examples, up to 92% yield) and Sonogashira couplings (10 examples, up to 77% yield).

Regional sources of nitrogen oxides (NOx) in North China during summer were explored using both a Bayesian isotopic mixing model and a positive matrix factorization (PMF) model. Results showed that the nitrogen isotope (δ15N) composition of particulate nitrate (NO3−) varied between −8.9‰ and +14.1‰, while the oxygen isotope (δ18O) composition ranged from +57.4‰ to +93.8‰. Based on results from the Bayesian isotopic mixing model, the contribution of the hydroxyl radical (•OH) NOx conversion pathway showed clear diurnal fluctuation; values were higher during the day (0.53 ± 0.16) and lower overnight (0.42 ± 0.17). Values peaked at 06:00–12:00 and then decreased gradually until 00:00–06:00 the next day. Coal combustion (31.34 ± 9.04%) was the most significant source of NOx followed by biomass burning (25.74 ± 2.58%), mobile sources (23.83 ± 3.66%), and microbial processes (19.09 ± 5.21%). PMF results indicated that the contribution from mobile sources was 19.83%, slightly lower as compared to the Bayesian model (23.83%). The PMF model also reported a lower contribution from coal combustion (28.65%) as compared to the Bayesian model (31.34%); however, the sum of biomass burning and microbial processes in the Bayesian model (44.83%) was lower than the aggregate of secondary inorganic aerosol, sea salt, and soil dust in PMF model (51.52%). Overall, differences between the two models were minor, suggesting that this study provided a reasonable source quantification for NOx in North China during summer.

Elemental carbon (EC), the highly recalcitrant carbonaceous material released exclusively from fossil fuel combustion and biomass burning, is a preferred geochemical agent for evaluating anthropogenic activities. We investigated the spatiotemporal trends of EC and char/soot ratios (char and soot, the two subtypes of EC, differ in formation mechanisms and physicochemical characteristics) in five sediment cores from eastern China marginal seas, spatially spanning from inshore coastal mud areas to offshore remote mud areas. The temporal profiles of EC depositional fluxes closely tracked socioeconomic development in China over the past ∼150 years, with the most pronounced increasing trend beginning in the early 1980s, commensurate with the implementation of national policy of Reform and Open in 1978. The temporal EC profiles in China differed significantly from those in European/American countries, reflecting their different socioeconomic development stages. The spatiotemporal trends of char/soot ratios were also highly informative. Temporally, they decreased from bottom to subsurface layers, indicating the switch of China from an agricultural economy to an industrial economy during the 20th century. Spatially, they decreased from inshore to offshore areas, suggesting the differential transport patterns of EC among these sampling regimes.

Nine antialgal active compounds, (i.e. trehalose (1), twenty-two methyl carbonate (2), (-)-dihydromenisdaurilide (3), 3,7,11,15-tetramethyl-2-hexadecen-1-ol (4), isophytol (5), 8-hexadecenol (6), 17-hydroxyheptadecanoic acid (7), trans-asarone (8) and 2-amino-3-mercaptopropanoic acid (9)) were isolated from Ulva pertusa for the first time by sephadex LH-20 column chromatography, silica gel column chromatography and repeated preparative TLC. Except for compound 4, all compounds represented novel isolated molecules from marine macroalgae. Further, antialgal activities of these compounds against Amphidinium carterae, Heterosigma akashiwo, Karenia mikimitoi, Phaeocystis globosa, Prorocentrum donghaiense and Skeletonema costatum were investigated for the first time. Results showed these nine compounds have selectivity antialgal effects on all test red tide microalgae, and antialgal activities against red tide microalgae obviously enhanced with the increase of concentration of antialgal compounds. Based on this, EC50–96 h values of these nine compounds for six red tide microalgae were obtained for the first time. By analyzing and comparing EC50–96 h values, it has been determined that seven compounds (1, 3, 4, 6, 7, 8 and 9) showed the superior application potential than potassium dichromate or gossonorol and other six compounds as a characteristic antialgal agent against Heterosigma akashiwo, Karenia mikimitoi and Prorocentrum donghaiense. Overall this study has suggested that green algae Ulva pertusa is a new source of bioactive compounds with antialgal activity.

Engineered silicon-based materials can display photoelectric and photo-thermal responses under light illumination, which may lead to further innovations at the silicon–biology interfaces. Silicon nanowires have small radial dimensions, promising as highly localized cellular modulators, however the single crystalline form typically has limited photothermal efficacy due to the poor light absorption and fast heat dissipation. In this work, we report strategies to improve the photothermal response from silicon nanowires by introducing nanoscale textures on the surface and in the bulk. We next demonstrate high-resolution extracellular modulation of calcium dynamics in a number of mammalian cells including glial cells, neurons, and cancer cells. The new materials may be broadly used in probing and modulating electrical and chemical signals at the subcellular length scale, which is currently a challenge in the field of electrophysiology or cellular engineering.

Silicon-based materials have been widely used. However, remotely controlled and interconnect-free silicon configurations have been rarely explored, because of limited fundamental understanding of the complex physicochemical processes that occur at interfaces between silicon and biological materials. Here, we describe rational design principles, guided by biology, for establishing intracellular, intercellular and extracellular silicon-based interfaces, where the silicon and the biological targets have matched properties. We focused on light-induced processes at these interfaces, and developed a set of matrices to quantify and differentiate the capacitive, Faradaic and thermal outputs from about 30 different silicon materials in saline. We show that these interfaces are useful for the light-controlled non-genetic modulation of intracellular calcium dynamics, of cytoskeletal structures and transport, of cellular excitability, of neurotransmitter release from brain slices, and of brain activity in vivo.

Graphene has been combined with molybdenum disulfide (MoS2) to ameliorate the poor cycling stability and rate performance of MoS2 in lithium ion batteries, yet the underlying mechanisms remain less explored. Here, we develop multiscale modeling to investigate the enhanced electrochemical and thermal transport properties of graphene/MoS2 heterostructures (GM-Hs) with a complex morphology. The calculated electronic structures demonstrate the greatly improved electrical conductivity of GM-Hs compared to MoS2. Increasing the graphene layers in GM-Hs not only improves the electrical conductivity but also stabilizes the intercalated Li atoms in GM-Hs. It is also found that GM-Hs with three graphene layers could achieve and maintain a high thermal conductivity of 85.5 W/(m·K) at a large temperature range (100–500 K), nearly 6 times that of pure MoS2 [∼15 W/(m·K)], which may accelerate the heat conduction from electrodes to the ambient. Our quantitative findings may shed light on the enhanced battery performances...

SUMMARY CNS cortical histogenesis depends on polarity signaling pathways that regulate cell adhesion and motility. Here we report that conditional deletion of the Rho GTPase Cdc42 in cerebellar granule cell precursors (GCPs) results in abnormalities in cerebellar foliation revealed by iDISCO clearing methodology, a loss of columnar organization of proliferating GCPs in the external germinal layer (EGL), disordered parallel fiber organization in the molecular layer (ML), and a failure to extend a leading process and form a neuron-glial junction during migration along Bergmann glia (BG). Notably, GCPs lacking Cdc42 had a multi-polar morphology and slowed migration rate. In addition, secondary defects occurred in BG development and organization, especially in the lateral cerebellar hemispheres. By phosphoproteomic analysis, affected Cdc42 targets included regulators of the cytoskeleton, cell adhesion and polarity. Thus, Cdc42 signaling pathways are critical regulators of GCP polarity and the formation of neuron-glial junctions during cerebellar development., Graphical abstract

We have developed a Pd-catalyzed direct dehydroxylative cyanation of phenols by employing an inexpensive food additive, potassium ferrocyanide (K4[Fe(CN)6]), as the cyanating reagent instead of highly toxic cyanide salts. This protocol provides a strategically distinct approach for the preparation of aryl nitriles in a safe, mild, convenient and practical manner.

Large-scale assembly of individual atoms over smooth surfaces is difficult to achieve. A configuration of an atom reservoir, in which individual atoms can be readily extracted, may successfully address this challenge. In this work, we demonstrate that a liquid gold–silicon alloy established in classical vapor–liquid–solid growth can deposit ordered and three-dimensional rings of isolated gold atoms over silicon nanowire sidewalls. We perform ab initio molecular dynamics simulation and unveil a surprising single atomic gold-catalyzed chemical etching of silicon. Experimental verification of this catalytic process in silicon nanowires yields dopant-dependent, massive and ordered 3D grooves with spacing down to ~5 nm. Finally, we use these grooves as self-labeled and ex situ markers to resolve several complex silicon growths, including the formation of nodes, kinks, scale-like interfaces, and curved backbones., Parallel patterning of atoms over a large surface would represent a major advance over current serial methods of single atom manipulation. Here, the authors explore a periodic instability from liquid alloy droplets for high-throughput atom printing.

A tunable nanosphere lithography (NSL) technique is combined with metal-assisted etching of silicon (Si) to fabricate ordered, high-aspect-ratio Si nanowires. Non-close-packed structures are directly prepared via shear-induced ordering of the nanospheres. The spacing between the nanospheres is independent of their diameters and tuned by changing the loading of nanospheres. Nanowires with spacings between 110 and 850 nm are easily achieved with diameters between 100 and 550 nm. By eliminating plasma or heat treatment of the nanospheres, the diameter of the nanowires fabricated is nearly identical to the nanosphere diameter in the suspension. The elimination of this step helps avoid common drawbacks of traditional NSL approaches, leading to the high-fidelity, large-scale fabrication of highly crystalline, nonporous Si nanowires in ordered hexagonal patterns. The ability to simultaneously control the diameter and spacing makes the NSL technique more versatile and expands the range of geometries that can be fabricated by top-down approaches.

Traditional shape memory polymers (SMPs) are mostly thermoresponsive and their applications in nanooptics are hindered by heat-demanding programming and recovery processes. By integrating a polyurethane-based shape memory copolymer with templating nanofabrication, reconfigurable/rewritable macroporous photonic crystals have been demonstrated. This SMP coupled with the unique macroporous structure enables unusual all-room-temperature shape memory cycles. "Cold" programming involving microscopic order-disorder transitions of the templated macropores is achieved by mechanically deforming the macroporous SMP membranes. The rapid recovery of the permanent, highly ordered photonic crystal structure from the temporary, disordered configuration can be triggered by multiple stimuli, including a large variety of vapors and solvents, heat, and microwave radiation. Importantly, the striking chromogenic effects associated with these athermal and thermal processes render a sensitive and noninvasive optical methodology for quantitatively characterizing the intriguing nanoscopic shape memory effects. Some critical parameters/mechanisms that could significantly affect the final performance of SMP-based reconfigurable photonic crystals, including strain recovery ratio, dynamics and reversibility of shape recovery, as well as capillary condensation of vapors in macropores, which plays a crucial role in vapor-triggered recovery, can be evaluated using this new optical technology.

Antibacterial-resistance speaks to an overall alarm, particularly in regards to the flare-up of methicillin-resistance Staphylococcus aureus (MRSA), a classic reason for genuine skin and flimsy tissues diseases. Clinically noteworthy antibacterial-resistance is probably the best challenge of the 21st century. Notwithstanding, new-fangled antibiotics are right now being created at a much more slow pace than our developing requirement for such drugs. The intriguing atomic structure of indole ring makes them appropriate possibility for the drug advancement. In this scaled down survey we abridge novel indole-based derivatives potency against diverse bacterial strains. Specifically, we plot the connection between the different structures of altered indole derivatives along with its antibacterial movement against multidrug-resistance MRSA could be discussed. This prepared information may fill in as a target for the adjustment of accessible molecules to plan new powerful antibacterial agents with lesser side effects.

Aquaporin-2 (AQP2) is a molecular water channel protein responsible for water reabsorption by the kidney collecting ducts. Many water balance disorders are associated with defects in AQP2 gene expression regulated by the peptide hormone vasopressin. Here, we studied roles of Elf3 (E26 transformation-specific (Ets)-related transcription factor 3) in AQP2 gene expression in the collecting duct cells (mpkCCD). Vasopressin increased AQP2 mRNA and protein levels without affecting AQP2 mRNA degradation, indicative of transcriptional regulation. Elf3 knockdown and overexpression, respectively, reduced and increased AQP2 gene expression under basal and vasopressin-stimulated conditions. However, the vasopressin-to-basal ratios of AQP2 gene expression levels remained constant, indicating that Elf3 does not directly mediate vasopressin response but modulates the level of AQP2 gene expression inducible by vasopressin. The Elf3-modulated AQP2 gene expression was associated with AQP2 promoter activity, in line with Elf3’s ability to bind an Ets element in the AQP2 promoter. Mutation in the Ets element reduced both basal and vasopressin-stimulated AQP2 promoter activity, again without affecting vasopressin-to-basal ratios of the AQP2 promoter activity. Lithium chloride reduced both Elf3 and AQP2 mRNA in the mpkCCD cells as well as in mouse kidney inner medulla. We conclude that Elf3 modulates AQP2 promoter activity thereby gauging vasopressin-inducible AQP2 gene expression levels. Our data provide a potential explanation to lithium-induced nephrogenic diabetes insipidus where lithium reduces Elf3 and hence AQP2 abundance.

Inspired by quinine and its analogues, we designed, synthesized, and evaluated two series of quinoline small molecular compounds (a and 2a) and six series of quinoline derivatives (3a-f) for their antifungal activities. The results showed that compounds 3e and 3f series exhibited significant fungicidal activities. Significantly, compounds 3f-4 (EC50 = 0.41 μg/mL) and 3f-28 (EC50 = 0.55 μg/mL) displayed the superior in vitro fungicidal activity and the potent in vivo curative effect against Sclerotinia sclerotiorum. Preliminary mechanism studies showed that compounds 3f-4 and 3f-28 could cause changes in the cell membrane permeability, accumulation of reactive oxygen species, loss of mitochondrial membrane potential, and effective inhibition of germination and formation of S. sclerotiorum sclerotia. These results indicate that compounds 3f-4 and 3f-28 are novel potential fungicidal candidates against S. sclerotiorum derived from natural products.

In this paper, the nitrogen atom was inserted into the anthracycline system of the isocryptolepine nucleus to obtain the “Aza”-type structure benzo[4,5]imidazo[1,2-c] quinazoline. A series of “Aza”-type derivatives were designed, synthesized and evaluated for their antifungal activity against six plant fungi in vitro. Among all derivatives, compounds A-0, B-1 and B-2 showed significant antifungal activity against B. cinerea with the EC50 values of 2.72 μg/mL, 5.90 μg/mL and 4.00 μg/mL, respectively. Compound A-2 had the highest activity against M. oryzae with the EC50 values of 8.81 μg/mL, and compound A-1 demonstrated the most control efficacy against R. solani (EC50, 6.27 μg/mL). Moreover, compound A-0 was selected to investigate the in vivo tests against B. cinerea and the results indicated that the preventative efficacy of it up to 72.80% at 100 μg/mL. Preliminary mechanism studies revealed that after treatment with A-0 at 5 µg/mL, the B. cinerea mycelia appeared curved, collapsed and the cell membrane integrity may be damaged. The reactive oxygen species production, mitochondrial membrane potential and nuclear morphometry of mycelia have been changed, and the membrane function and cell proliferation of mycelia were destroyed. Compounds A-0, A-1, B-1 and B-2 presented weaker toxicities against two cells lines than isocryptolepine. This study lays the foundation for the future development of isocryptolepine derivatives as environmentally friendly and safe agricultural fungicides.

It is highly desired but remains challenging to develop efficient catalysts for CO2 conversion. Herein, N-doped porous carbon-supported ultra-small ZnS (ZnS/NPC‒X) were developed as photothermal catalysts for CO2 conversion by pyrolyzing the protein-Zn(II) network. The optimal catalyst ZnS/NPC‒2 possesses plenty of Lewis acid/base sites, hierarchical porous structure and high photothermal efficiency, jointly affording it high photothermally catalytic performance for CO2 cycloaddition and methylation reactions. This work provides a new strategy to prepare porous carbon-supported catalysts, which can find wide applications in photothermal catalysis.

A sandwich-like 2D-mesoporous-carbon/MoS2 -nanosheet heterostructure is fabricated for the first time. The hybrid structure is composed of three well-stacked monolayers: an ordered-mesoporous-carbon monolayer, a MoS2 monolayer, and a further ordered-mesoporous-carbon monolayer. This unique heterostructure exhibits excellent electrochemical performance as an anode material for lithium-ion batteries.

Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are byproducts generated from the incomplete combustion of organic materials, including fossil fuels and biomass. The similar production processes shared by BC and PAHs provide the possibility to infer the BC sources using the PAHs signatures. This study successfully utilized data sets of BC and PAHs analyzed from the continental shelf surface sediments of the Bohai and Yellow Seas to a standard receptor model of positive matrix factorization (PMF) to apportion the sources of BC in the sediment matrix. Results showed that combustion of fossil fuels (i.e., coal and oil/petroleum) accounted for an average level of 83 ± 5% of the total BC preserved, which was significantly higher than that from the biomass burning (17 ± 5%). The spatial distributions of the fossil BC concentrations and percentages differed significantly from those of the biomass BC, implying their different geochemical behaviors in the continental shelf regimes and further emphasizing the importance to effectively differentiate between fossil BC and biomass BC. In addition to the relative proportions of the BC subtypes (char-BC/soot-BC), the regional-specific hydrodynamic conditions, including the cold cyclonic eddy, resuspension and coastal current, also exerted a significant influence on these spatial variations.

Dechlorane Plus (DP), which has severe effects on marine ecosystems, has been proposed for listing under the Stockholm Convention as a persistent organic pollutant (POPs). This study was the first comprehensive investigation of the concentration and fate of DP in the Bohai Sea (BS) based on determination of river estuary water, river estuary sediment, surface seawater, bottom seawater, and sea sediments samples. The highest water DP levels were found in river estuary in Tianjin in North China due to the huge usage of DP in recent years, and spatial distribution analysis indicates it was mainly affected by regional high urbanization and emission of E-waste. The spatial distribution of DP in the BS was mainly affected by a combination of coastal hydrodynamics and land anthropogenic activities. On the basis of multi-box mass balance, simulations of DP in seawater showed an increase from 2014 to 2025, before leveling off at 184 pg L −1 by a constant DP input to the BS. Riverine discharge almost contributed to the total input (∼99%) and dominated the DP levels in the BS. Degradation of DP accounted for 55.3% and 78.1% of total DP output in seawater and sediment, respectively, indicating that degradation mainly affected decline of DP in the environment.

Developing advanced carbon materials as a metal-free electrocatalyst to replace noble metal-based one for, but not limited to, oxygen reduction reaction (ORR) is of great allure but remains challenging. In this work, carbon dots (CDs) self-decorated, N, S codoped porous carbon (NSPC) was fabricated by alkali-assisted protein decomposition and reconstruction. Specifically, in hot alkaline solution, proteins hydrolyzed into protein fragments, and then part of the fragments formed highly crystalline CDs. After freeze-dried and pyrolyzed, the CDs-containing protein fragments were converted into CDs/NSPC composites. The as-prepared CDs/NSPC possesses rich edge, heteroatom-dopant, high porosity, and smooth electron transfer between CDs and NSPC, synergistically contributing to CDs/NSPC such an outstanding ORR catalytic performance that even outperforms Pt/C. Furthermore, CDs/NSPC was evaluated as an air electrode catalyst for Zn-air batteries with excellent stability and high-power density.