Rosalesvognsen3457

Engineered bacteria are promising bioagents to synthesize antitumor drugs at tumor sites with the advantages of avoiding drug leakage and degradation during delivery. Here, we report an optically controlled material-assisted microbial system by biosynthesizing gold nanoparticles (AuNPs) on the surface of Shewanella algae K3259 (S. algae) to obtain Bac@Au. Leveraging the dual directional electron transport mechanism of S. algae, the hybrid biosystem enhances in situ synthesis of antineoplastic tetrodotoxin (TTX) for a promising antitumor effect. Because of tumor hypoxia-targeting feature of facultative anaerobic S. algae, Bac@Au selectively target and colonize at tumor. Upon light irradiation, photoelectrons produced by AuNPs deposited on bacterial surface are transferred into bacterial cytoplasm and participate in accelerated cell metabolism to increase the production of TTX for antitumor therapy. The optically controlled material-assisted microbial system enhances the efficiency of bacterial drug synthesis in situ and provides an antitumor strategy that could broaden conventional therapy boundaries.The anti-Kasha process provides the possibility of using high-energy excited states to develop novel applications. Our previous research (Nature communications, 2020, 11, 793) has demonstrated a dual-emission anti-Kasha-active fluorophore for bioimaging application, which exhibits near-infrared emissions from the S1 state and visible anti-Kasha emissions from the S2 state. Here, we applied tunable blue-side femtosecond stimulated Raman spectroscopy (FSRS) and transient absorption spectroscopy, assisted by quantum calculations, to reveal the anti-Kasha dual emission mechanism, in which the emergence of two fluorescing states is due to the retardation of internal conversion from the S2 state to the S1 state. It has been demonstrated that the facts of anti-Kasha high-energy emission are commonly attributed to a large energy gap between the two excited states, leading to a decrease in the internal conversion rate due to a poor Franck-Condon factor. In this study, analysis of the calculation and FSRS experimental results provide us further insight into the dual-emission anti-Kasha mechanism, where the observation of hydrogen out-of-plane Raman modes from FSRS suggested that, in addition to the energy-gap law, the initial photoinduced molecular conformational change plays a key role in influencing the rate of internal conversion.Herein, access to axially and centrally chiral sulfinamides via asymmetric allylic alkylation was reported. A series of sulfinamides were obtained with good outcomes (up to 99% yield, >191 dr, and 982 er). click here The synthetic utility of the reaction was demonstrated by scaled-up synthesis, product transformation, and application as a catalyst in asymmetric catalysis.2D/layered semiconductors are of interest for fundamental studies and for applications in optoelectronics and photonics. Work to date focused on extended crystals, produced by exfoliation or growth and investigated by diffraction-limited spectroscopy. Processes such as vapor-liquid-solid (VLS) growth carry potential for mass-producing nanostructured van der Waals semiconductors with exceptionally high crystal quality and optoelectronic/photonic properties at least on par with those of extended flakes. Here, we demonstrate the synthesis, structure, morphology, and optoelectronics/photonics of GaSe van der Waals nanoribbons obtained by Au- and Ag-catalyzed VLS growth. Although all GaSe ribbons are high-quality basal-plane oriented single crystals, those grown at lower temperatures stand out with their remarkably uniform morphology and low edge roughness. Photoluminescence spectroscopy shows intense, narrow light emission at the GaSe bandgap energy. Nanophotonic experiments demonstrate traveling waveguide modes at visible/near-infrared energies and illustrate approaches for locally exciting and probing such photonic modes by cathodoluminescence in transmission electron microscopy.A site-specific oxidation of (sp3)C-C(sp3) and (sp3)C-H bonds in aryl alkanes by the use of NaNO2/HCl was explored. The method is chemical-oxidant-free, transition-metal-free, uses water as the solvent, and proceeds under mild conditions, making it valuable and attractive to synthetic organic chemistry.Using grazing incidence X-rays and X-ray photoelectron spectroscopy during the mass transfer limited catalytic oxidation of CO, the long-range surface structure of Pd(100) was investigated. Under the reaction conditions of 504 O2 to CO, 300 mbar pressure, and temperatures between 200 and 450 °C, the surface structure resulting from oxidation and the subsequent oxide reduction was elucidated. The reduction cycle was halted, and while under reaction conditions, angle-dependent X-ray photoelectron spectroscopy close to the critical angle of Pd and modeling of the data was performed. Two proposed models for the system were compared. The suggestion with the metallic islands formed on top of the oxide island was shown to be consistent with the data.Various nanofillers have been adopted to enhance the thermal conductivity of polymer nanocomposites. While it is widely believed that the contact thermal resistance between adjacent nanofillers can play an important role in limiting thermal conductivity enhancement of composite materials, lack of direct experimental data poses a significant challenge to perceiving the effects of these contacts. This study reports on direct measurements of thermal transport through contacts between silver nanowires (AgNWs) with a poly(vinylpyrrolidone) (PVP) interlayer. The results indicate that a PVP layer as thin as 4 nm can increase the total thermal resistance of the contact by up to an order of magnitude, when compared to bare AgNWs, even with a larger contact area. On the other hand, the thermal boundary resistance for PVP/silver interfaces could be significantly lower than that between polymer-carbon nanotubes (CNTs). Analyses based on these understandings further show why AgNWs could be more effective nanofillers than CNTs.Harmful algal blooms (HABs) are symptomatic of ecosystem imbalance, leading to major worldwide marine natural disasters, and seriously threaten the human health. Some HAB algae's exceptional genome size prohibited the genomic investigations on molecular mechanisms, for example, Prorocentrum. This study performed translatome sequencing (RNC-seq) for Prorocentrum donghaiense to assemble the translatome reference sequences on appropriate cost to enable the global molecular study at translatome and proteome levels. By analyzing the translatome and proteome of P. donghaiense in phosphor-rich, phosphor-deficient, and phosphor-restored media, we found massive up-regulation of energy and material production pathways in phosphor-rich conditions that enables autoactivation of translation, which is the key to its exponential growth in HABs. To break down the autoactivation, we demonstrated that mild translation delay using very low concentrations of cycloheximide efficiently controls the blooming without harming other aquatic organisms and humans. Our result provides a novel hint for controlling HABs and demonstrated the RNC-seq as an economic strategy on investigating functions of organisms with large and unknown genomes.O-Phenyloximes tethered to alkenes undergo 5-exo-trig iminyl radical cyclizations upon microwave irradiation. Trapping of the resulting cyclic radicals results in C-C, C-N, C-O, C-S, or C-X bond formation. Allylic sulfides undergo a tandem cyclization-thiyl radical β-elimination, affording terminal alkenes. The cyclizations exhibit a broad scope, and in some cases they are highly diastereoselective. The pyrroline adducts are versatile intermediates that can be transformed into a range of different species.A Rh(III)-catalyzed Csp2-Csp3 σ-bond carbenoid functionalization of α-(2-indolyl)alcohols with acceptor/acceptor diazo compounds has been developed. This transformation provides an efficient strategy to assemble stable C2-enolated indole skeletons via Csp2-Csp3 σ-bond cleavage.A new asymmetric catalytic conjugate reduction of yne-allenones to synthesize enantioenriched cyclobuta[a]naphthalen-4(2H)-ones has been established that uses copper-bisphosphine complexes as catalysts and gives excellent regio- and enantioselectivities (≥99% ee) in most cases. This protocol tolerates a broad scope of substrates, exhibits high compatibility with various substituents, and gives excellent stereoselectivity, providing a catalytic and efficient entry to fabrication of synthetically important chiral 6-6-4 tricarbocyclic scaffolds.A unique strategy for the attainment of a discotic nematic (ND) mesophase is reported consisting of a central benzene core to which are attached two 4-alkylphenyl and two 4-pentylbiphenyl moieties diagonally via alkynyl linkers. The rotational nature and incompatibility of unequal phenylethynyl units led to the disruption of π-π interactions within cores that aids to the realization of ND phase and favors high solid-state emission. When used in OLEDs, compounds act as an efficient solid-state pure deep-blue emitter with Commission Internationale de L'Eclairage (CIEx,y) coordinates of (0.16, 0.07).The cyclocondensation of cross-conjugated enynones, dienynones, and trienynones (easily available due to low-cost starting compounds) with arylhydrazines leads to the regioselective synthesis of pyrazole derivatives (dihetaryl-substituted ethens, buta-1,3-diens, and hexa-1,3,5-triens) or results in 4,5-dihydro-1H-pyrazoles in good yield. The reaction path is controlled by the character of the substituent in enynone the pyrazoles are obtained from the reaction of substrates that contain five-membered heteroaromatic substituents with arylhydrazines, and the 4,5-dihydro-1H-pyrazoles are obtained from the reaction of 1,5-diphenylpent-1-en-4-yn-3-one with arylhydrazines consistently. Despite the presence of a substituent, cyclocondensation of 2-hydrazinylpyridine with all of examined cross-conjugated enynones leads to the formation of pyrazoles. The reaction does not require special conditions (temperature, catalyst, inert atmosphere). The cyclocondensation pathways are determined by the electronic effect of an electron-rich five-membered heteroaromatic ring in the substrate. The synthesis allows use of various substituents and functional groups in enynone and hydrazine. The present method features high yields and simplicity of the product purification. The obtained pyrazoles possess fluorescent properties with a quantum yield up to 31%.A highly enantioselective synthesis of chiral heterobicyclic spiroketals is reported via a "one-pot" cyclopropanation-rearrangement (CP-RA) cascade reaction that is sequentially catalyzed by a chiral Rh(II) catalyst and tetrabutylammonium fluoride (TBAF). Exocyclic vinyl substrates form spirocyclopropanes with tert-butyldimethylsilyl-protected enoldiazoacetates in excellent yields and with excellent enantioselectivities when catalyzed by chiral dirhodium(II) carboxylates, and following desilylation with simultaneous rearrangement in the presence of TBAF, they give (S)-spiroketals in high yields with excellent chirality retention (>95% ee).