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Owing to their excellent photoelectric properties, donor-acceptor (D-A) type photocatalytic covalent organic frameworks (COFs) have attracted significant research interest in recent years. However, the limited D-A structural units of existing COFs restrict the development of novel and efficient photocatalytic COF materials. To solve this problem, we developed a series of D-A-A-type COFs utilizing a Lewis acid regulation strategy, in which Lewis acids act as the coordination centers, and pyridine and cyano groups act as ligands. Lewis acid sites in COFs serve as electron acceptors, facilitating the separation and transfer of photogenerated electron-hole pairs. This process is crucial for photocatalysis because it significantly increases the efficiency of the catalytic reaction by reducing the recombination rate of charge carriers. The developed Lewis acid-activated D-A-A COFs efficiently catalyzed the hydroxylation of various phenylboronic acid compounds under visible light. The developed catalysts are expected to contribute to increasing the fabrication efficiency of industrially important organic materials.
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This study reports a protocol for the highly regioselective photocatalyzed C-H nitrosylation of imidazo[1,2-a]pyridine scaffolds at the C3 position under a combination of visible-light irradiation and continuous flow without any external photocatalyst. This protocol involves mild and safe conditions and shows good tolerance to air and water along with excellent functional group compatibility and site selectivity, generating various 3-nitrosoimidazo[1,2-a]pyridines in excellent yields under photocatalyst-, oxidant-, and additive-free conditions.Notably, the proposed nitrosylation reaction, which introduces the chromophore NO into imidazo[1,2-a]pyridine scaffolds, occurs efficiently under visible-light irradiation without any additional photocatalyst owing to the intense light-absorption characteristics of the nitrosylation products. This study could guide future studies on the development of green organic-synthesis strategies with a wide variety of potential applications.
RESUMEN
Covalent organic frameworks (COFs) are a novel class of crystalline porous polymers, which possess high porosity, excellent stability, and regular nanochannels. 2D COFs provide a 1D nanochannel to form the proton transport channels. The abovementioned features afford a powerful potential platform for designing materials as proton transportation carriers. Herein, the authors incorporate sulfonic acid groups on the pore walls as proton sources for enhancing proton transport conductivity in the 1D channel. Interestingly, the sulfonic acid COFs (S-COFs) electrolytes being binder free exhibit excellent proton conductivity of ≈1.5 × 10-2 S cm-1 at 25 â and 95% relative humidity (RH), which rank the excellent performance in standard proton-conducting electrolytes. The S-COFs electrolytes keep the high proton conduction over the 24 h. The activation energy is estimated to be as low as 0.17 eV, which is much lower than most reported COFs. This research opens a new window to evolve great potential of structural design for COFs as the high proton-conducting electrolytes.
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Estructuras Metalorgánicas , Electrólitos , Polímeros , Protones , Ácidos SulfónicosRESUMEN
An enantioselective electrophilic α-cyanation of 1-indanone-derived ß-keto esters and ß-keto amides using a hypervalent iodine as the cyanide-transfer reagent was realized. A chiral N,N'-dioxide was used as the efficient bifunctional organocatalyst in the presence of inorganic base, which gave the corresponding α-cyano dicarbonyl compounds in yields of 50-99% with good enantioselectivities (87-97% ee).
RESUMEN
The novel donor-acceptor (D-A) type covalent organic frameworks TATF-COF and TATP-COF, with multiple fluorine groups as electron storage units, were successfully constructed to achieve efficient charge transfer and photocatalytic activity for antibacterial photocatalytic therapy. Fluorine, the most electronegative element, was utilized as an electron-withdrawing substituent for the acceptor, which could unite the donor unit together and efficiently improve the charge transfer from the donor to acceptor. The unique D-A structures of TATF-COF and TATP-COF ensure that they have narrow band gaps, strong photocurrent responses, long fluorescence lifetimes, and good capacity to generate reactive oxygen species (ROS) to realize good antibacterial activity. Meanwhile, the inclusion of multiple hydrophilic fluorine groups means that TATF-COF and TATP-COF are highly water dispersible, which is also beneficial in terms of promoting the generation of adequate quantities of ROS. Hence, in view of their excellent photoelectric properties and good water dispersibility, further investigations were performed, and excellent antibacterial activities in vitro against both gram-negative and gram-positive bacteria were demonstrated for TATF-COF and TATP-COF. In addition, we also showed that they can function as effective antibacterial dental materials.
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Mythimna separata and Mythimna loreyi are global pests of gramineous cereals, heavily controlled with synthetic insecticides. Here, we generated two high-quality chromosome-level genome assemblies for M. separata (688 Mb) and M. loreyi (683 Mb). Our analysis identified Z and W chromosomes, with few genes and abundant transposable elements (TEs) found on the W chromosome. We also observed a recent explosion of long interspersed nuclear elements (LINEs), which contributed to the larger genomes of Mythimna. The two armyworms diverged ~10.5 MYA, with only three chromosomes have intrachromosomal rearrangements. Additionally, we observed a tandem repeat expansion of α-amylase genes in Mythimna, which may promote the digestion of carbohydrates and exacerbate their damage to crops. Furthermore, we inferred the sex pheromone biosynthesis pathway for M. separata, M. loreyi and Spodoptera frugiperda. We discovered that M. loreyi and S. frugiperda synthesized the same major constituents of sex pheromones through different pathways. Specifically, the double bonds in the dominant sex pheromone components of S. frugiperda were generated by Δ9- and Δ11-desaturase, while they were generated by Δ11-desaturase and chain-shortening reactions in M. loreyi. We also identified pheromone receptor (PR) genes and inferred their corresponding components. These findings provide a better understanding of sex pheromone communication and promote the development of a new pest control strategy involving pheromone traps, which are more effective and environmentally friendly than current strategies.
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Mariposas Nocturnas , Atractivos Sexuales , Animales , Atractivos Sexuales/genética , Atractivos Sexuales/metabolismo , Spodoptera/genética , Mariposas Nocturnas/genética , Ácido Graso Desaturasas/genética , Ácido Graso Desaturasas/metabolismo , CromosomasRESUMEN
In this study, two novel fluorine-functionalized crystalline covalent organic frameworks (COFs), namely DF-TAPB-COF and DF-TATB-COF, were synthesized, and their ordered structure, porosity, suitable pore size, and abundant fluorine groups were expected to serve as effective carriers in drug delivery. The excellent cell viability of DF-TAPB-COF and DF-TATB-COF was verified using MTT assays. Both COFs exhibited very high loading capacities in terms of drug loading performance, in particular the drug loading rate of DF-TAPB-COF for 5-fluorouracil (5-FU) was up to 69%. They also exhibited efficient drug release performance in a simulated body fluid environment. Cell endocytosis experiments demonstrated that DF-TAPB-COF and DF-TATB-COF could be effectively endocytosed by cells. Hence, this study offers new insight into the design and development of COF-based drug carrier systems.
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The olfactory system of insects is essential in many crucial behaviors, such as host seeking, mate recognition, and locating oviposition sites. Lepidopteran moths possess two main olfactory organs, including antennae and labial palps. Compared to antennae, the labial palps are relatively specific and worthy of further investigation due to the labial-palp pit organ (LPO), which contains a large number of sensilla located on the tip segment. The fall armyworm, Spodoptera frugiperda, is a worldwide lepidopteran pest, which can damage more than 350 plants and cause significant economic losses. In this study, we surveyed the structure of the labial palps and LPO of S. frugiperda using a super-high magnification lens zoom 3D microscope. Then, the distribution and fine structure of sensilla located in the LPO of S. frugiperda were investigated using scanning electron microscopy. Subsequently, the electrophysiological responses of labial palps to CO2 and 29 plant volatiles were recorded by using electrolabialpalpography. Our results showed the fine structure of labial palps, the LPO, and the sensilla located in the LPO of S. frugiperda. Moreover, we demonstrated that the labial palps are olfactory organs that respond to both CO2 and other volatile compounds. Our work established a foundation for further study of the roles of labial palps in insect olfactory related behaviors. Further investigations on the function of labial palps and their biological roles together with CO2 and volatile compound responses in S. frugiperda are necessary, as they may provide better insect behavioral regulators for controlling this pest.
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The anatomical organization of distinct regions in the insect brain often reflects their functions. In the present study, the brain structure of Apolygus lucorum was examined by using immunolabeling and three-dimensional reconstruction. The results revealed the location and volume of prominent neuropils, such as the antennal lobes (AL), optic lobes (OL), anterior optic tubercles (AOTU), central body (CB), lateral accessory lobes (LAL), mushroom lobes, and distinct tritocerebral neuropils. As expected, this brain is similar to that of other insects. One exception, however, is that the antennal lobes were found to be the most prominent neuropils. Their size relative to the entire brain is the largest among all insect species studied so far. In contrast, the calyx, a region getting direct input from the antennal lobe, has a smaller size relative to the brain than that of other species. These findings may suggest that olfaction plays an essential role for A. lucorum.
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A highly efficient catalytic asymmetric formal [3+2] cycloaddition reaction of 5-alkoxyoxazoles with azodicarboxylate compounds has been realized by a chiral N,N'-dioxide/Co(BF4)2·6H2O complex. A series of poly-substituted 1,2,4-triazolines compounds were obtained in moderate to excellent yields (70-99%) with excellent enantioselectivities (82-98% ee).
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A highly efficient asymmetric Mannich-type reaction between α-tetralone-derived ß-keto esters/amides and 1,3,5-triaryl-1,3,5-triazinanes was realized in the presence of chiral N,N'-dioxide-Ni(ii) or Mg(ii) complex. A variety of optically active ß-amino compounds with all-carbon quaternary stereocenters were obtained in good yields with excellent enantioselectivities. A possible transition state was proposed based on these experiments and previous reports.
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The oriental armyworm, Mythimna separata (Walker), is a polyphagous, migratory pest relying on olfactory cues to find mates, locate nectar, and guide long-distance flight behavior. In the present study, a combination of neuroanatomical techniques were utilized on this species, including backfills, confocal microscopy, and three-dimensional reconstructions, to trace the central projections of sensory neurons from the antenna and the labial pit organ, respectively. As previously shown, the axons of the labial sensory neurons project via the ipsilateral labial nerve and terminate in three main areas of the central nervous system: (1) the labial-palp pit organ glomerulus of each antennal lobe, (2) the gnathal ganglion, and (3) the prothoracic ganglion of the ventral nerve cord. Similarly, the antennal sensory axons project to multiple areas of the central nervous system. The ipsilateral antennal nerve targets mainly the antennal lobe, the antennal mechanosensory and motor center, and the prothoracic and mesothoracic ganglia. Specific staining experiments including dye application to each of the three antennal segments indicate that the antennal lobe receives input from flagellar olfactory neurons exclusively, while the antennal mechanosensory and motor center is innervated by mechanosensory neurons from the whole antenna, comprising the flagellum, pedicle, and scape. The terminals in the mechanosensory and motor center are organized in segregated zones relating to the origin of neurons. The flagellar mechanosensory axons target anterior zones, while the pedicular and scapal axons terminate in posterior zones. In the ventral nerve cord, the processes from the antennal sensory neurons terminate in the motor area of the thoracic ganglia, suggesting a close connection with motor neurons. Taken together, the numerous neuropils innervated by axons both from the antenna and labial palp indicate the multiple roles these sensory organs serve in insect behavior.
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An asymmetric Meerwein-Ponndorf-Verley (MPV) reduction of glyoxylates was for the first time accomplished via an N,N'-dioxide/Y(OTf)3 complex with aluminium alkoxide and molecular sieves (MSs) as crucial additives. A variety of optically active α-hydroxyesters were obtained with excellent results. A possible reaction mechanism was proposed based on the experiments.
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The mirid bug Apolygus lucorum (Meyer-Dür), a polyphagous pest, is dependent on olfactory cues to locate various host plant species and mates. In this study, we traced the projection pathway of the antennal sensory neurons and visualized their projection patterns in the central nervous system of A. lucorum through confocal microscopy and digital reconstructions. We also examined the glomerular organization of the primary olfactory center of the brain, the antennal lobe, and created a three-dimensional model of the glomeruli. We found that the axons of the sensory neurons project into the brain via the ipsilateral antennal nerve, and descend further into the gnathal ganglion, prothoracic ganglion, mesothoracic ganglion, and metathoracic ganglion, and reach as far as to the abdominal ganglion. Such a projection pattern indicates that antennal sensory neurons of A. lucorum may be potentially directly connected to motor neurons. The antennal lobe, however, is the major target area of antennal sensory neurons. The antennal lobe is composed of a large number of glomeruli, i.e. 70-80 glomeruli in one AL of A. lucorum. The results of this study which provide information about the basic anatomical arrangement of the brain olfactory center of A. lucorum, are important for further investigations of chemosensory encoding mechanisms of the mirid bug.
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Heterópteros/anatomía & histología , Animales , Antenas de Artrópodos/anatomía & histología , Antenas de Artrópodos/fisiología , Axones/metabolismo , Sistema Nervioso Central/anatomía & histología , Sistema Nervioso Central/fisiología , Femenino , Imagenología Tridimensional , Inmunohistoquímica , Masculino , Microscopía Confocal , Vías Olfatorias/fisiología , Células Receptoras Sensoriales/fisiologíaRESUMEN
By using immunostaining and three-dimensional reconstruction, the anatomical organization of the antennal lobe glomeruli of the female cotton bollworm Helicoverpa armigera was investigated. Eighty-one glomeruli were identified, 15 of which were not previously discovered. The general anatomical organization of the AL of female is similar to that of male and all glomeruli were classified into four sub-groups, including the female-specific glomerular complex, posterior complex, labial-palp pit organ glomerulus, and ordinary glomeruli. A global-wide comparison on the complete glomerular map of female and male was performed and for the first time the quantitative difference in volume for each individual homologous glomerulus was analyzed. We found that the sexual dimorphism includes not only the sex-specific glomeruli but also some of the other glomeruli. The findings in the present study may provide a reference to examine the antennal-lobe organization more in detail and to identify new glomeruli in other moth species. In addition, the complete identification and global-wide comparison of the sexes provide an important basis for mapping the function of distinct glomeruli and for understanding neural mechanisms underlying sexually dimorphic olfactory behaviors.
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Antenas de Artrópodos/fisiología , Mariposas Nocturnas/fisiología , Vías Olfatorias/fisiología , Animales , Femenino , Masculino , Caracteres SexualesRESUMEN
A highly enantioselective dearomative cascade reaction between 2-isocyanoethylindoles and 3-alkenyl-oxindoles was realized using a chiral N,N'-dioxide-Mg(II) complex catalyst. This reaction provides a straightforward access to polycyclic 3-spirooxindoles bearing cyclopenta[b]indole units with four contiguous stereocenters in excellent yields and moderate to good stereoselectivities via a Michael/Friedel-Crafts/Mannich cascade.
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Alcaloides/síntesis química , Indoles/química , Compuestos Policíclicos/síntesis química , Compuestos de Espiro/síntesis química , Alcaloides/química , Catálisis , Ligandos , Estructura Molecular , Oxindoles , Compuestos de Espiro/química , EstereoisomerismoRESUMEN
A series of tenofovir analogues with potential antiviral and immunobiologically active compounds were synthesized through an asymmetric transfer hydrogenation reaction from achiral purine derivatives. Up to 97% ee and good to excellent yields were achieved under mild conditions through short reaction steps. The present report suggests an efficient process to acquire tenofovir and its analogues.