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Based on this actuator, a set of biomimetic soft micro-robots were developed, demonstrating a series of motions, such as grabbing, crawling, and jumping. This strategy of stimuli-responsive micro-actuator preparation can benefit the hydrogel-elastomer hybrid micro-robot designs for applications ranging from self-locomotive robots in environmental monitoring to drug delivery in biomedical engineering.The catalytic behaviors or properties of bimetallic catalysts are highly dependent on the surface composition, but it has been a grand challenge to acquire such information. In this work, we employ Pd@PtnL core-shell nanocrystals with an octahedral shape and tunable Pt shell thickness as a model system to elucidate their surface compositions using catalytic reactions based upon the selective hydrogenation of butadiene and acetylene. Our results indicate that the surface of the core-shell nanocrystals changed from Pt-rich to Pd-rich when they were subjected to calcination under oxygen, a critical step involved in the preparation of many industrial catalysts. The inside-out migration can be attributed to both atomic interdiffusion and the oxidation of Pd atoms during the calcination process. The changes in surface composition were further confirmed using infrared and X-ray photoelectron spectroscopy. This work offers insightful guidance for the development and optimization of bimetallic catalysts toward various reactions.An expeditious green method for the synthesis of diverse valued substituted pyrroles through a Paal-Knorr condensation reaction, using a variety of amines and 2,5-hexanedione/2,5-dimethoxytetrahydrofuran in the presence of a low melting mixture of N,N'-dimethylurea and L-(+)-tartaric acid (which acts as a dual catalyst/solvent system), has fruitfully been revealed. Herein, we have disclosed the applicability of this simple yet effective strategy for the generation of mono- and dipyrroles in good to excellent yields. Moreover, C3-symmetric tripyrrolo-truxene derivatives have also been assembled by means of cyclotrimerization, Paal-Knorr and Clauson-Kaas reactions as crucial steps. Interestingly, the melting mixture was recovered and reused with only a gradual decrease in the catalytic activity (over four cycles) without any significant drop in the yield of the product. This particular methodology is simple, rapid, environmental friendly, and high yielding for the generation of a variety of pyrroles. To the best of our knowledge, the present work reveals the fastest greener method reported up to this date for the construction of substituted pyrroles by utilizing the Paal-Knorr synthetic protocol, achieving impressive yields under operationally simple reaction conditions without involving any precarious/dangerous catalysts or unsafe volatile organic solvents.The iridium/f-diaphos L1, L5 or L12 catalyzed asymmetric hydrogenation of 2-imidazolyl aryl/alkyl ketones to afford two enantiomers of the desired chiral alcohols with high conversions (up to 99% yield) and moderate to excellent enantioselectivities (61% - >99% ee) was realized for the first time. This protocol could be easily conducted on a gram-scale with a TON of 9700.A palladium-catalyzed intramolecular cyclization of Ugi-adducts via a cascade dearomatization/aza-Michael addition process has been developed. Diverse plicamine analogues are constructed in a rapid, highly efficient and step-economical manner, through the combination of an Ugi-4CR and a palladium-catalyzed dearomatization. The synthetic utility of this approach is illustrated by further functional group transformations.We herein present the synthesis of diversely functionalized pyrimidine fused thiazolino-2-pyridones via K2S2O8-mediated oxidative coupling of 6-amino-7-(aminomethyl)-thiazolino-2-pyridones with aldehydes. The developed protocol is mild, has wide substrate scope, and does not require transition metal catalyst or base. Some of the synthesized compounds have an ability to inhibit the formation of Amyloid-β fibrils associated with Alzheimer's disease, while others bind to mature amyloid-β and α-synuclein fibrils.The exploration of MXenes, especially nitride MXenes, in the field of theranostic nanomedicine is still in its infancy. Here, towards synergistic chemo-photothermal oncotherapy, we demonstrate the first kind of 2D titanium nitride (Ti2N) MXene-based nanosystem (Ti2N@oSi) for dual-strategy synergistic oncotherapy. The unique structure of Ti2N nanosheets endows the drug carriers with an ultrahigh loading capacity of 796.3% and an excellent NIR photothermal conversion efficiency of 41.6% for chemo-photothermal therapy. After being coated with a biodegradable organosilica shell, the Ti2N@oSi nanocarriers show excellent characteristics of tumor targeting, pH/glutathione/photothermal-responsive drug release and dual-drug combination chemotherapy. Both in vitro and in vivo therapeutic evaluations demonstrate the pronounced tumor growth inhibition effect and superior biocompatibility of Ti2N@oSi nanocarriers. The excellent drug loading ability, photothermal conversion ability and surface modifiability of Ti2N open up new opportunities for tumor microenvironment-targeted synergistic oncotherapy. This work is supposed to broaden the application of MXenes in nanomedicine and, particularly, provide the first sight to the biomedical application of nitride MXenes.We used dispersion-corrected density-functional theory to perform an in silico search over a series of primary alkylamines, including linear, branched, and cyclic molecules, to identify capping molecules for shape-selective Cu nanocrystal synthesis. We identify several attributes associated with successful capping agents. Generally, molecules with good geometric matching to the Cu surfaces possessed the strongest molecule-surface chemical bonds. However, non-bonding van der Waals interactions and molecular packing constraints can play a more significant role in determining the overall binding energy, the surface coverage, and the likely efficacy of the capping molecule. Though nearly all the molecules exhibited stronger binding to Cu(100) than to Cu(111), all predicted Wulff shapes are primarily 111-faceted, based on ab initio thermodynamics calculations. From predicted capping-molecule densities on Cu(100) and Cu(111) for various solution environments, we identified several candidate molecules to produce 100- or 111-faceted nanocrystals with kinetic shapes, based on synthesis conditions used to grow Cu nanowires with ethylenediamine capping agent. Our study reveals the complexity of capping-molecule binding and important considerations that go into the selection of a successful capping agent.This communication describes a novel water-soluble membrane prepared from chitosan intended for SARS-CoV-2 viral nucleic acid collection and detection. The CSH membrane formed from nanofibers shows promising potential in the quantitative determination of the SARS-CoV-2 viral nucleic acids at a concentration of 102 copies per L in air. The sponge-like structure which allows gas to pass through for collection of viral nucleic acids potentially provides simple, fast, and reliable sampling as well as detection of various types of airborne viruses.As important artificial photosynthesis, the construction of core-shell heterojunction materials is considered to be one of the effective strategies for designing highly active photocatalysts. Here, the Step-scheme (S-scheme) heterojunction photocatalyst is firmly grown by in situ phosphating. The calcination method uses MoO3 nanoparticles as the substrate, and the surface of MoO3 is phosphatized and etched gradually from the outside to the inside using the phosphine gas. The introduced phosphorus atoms can replace MoO3 oxygen atoms to form Mo-P bonds to generate molybdenum phosphide. The interface interaction dominated by chemical bonds has a stronger interface interaction force, which can promote the interface charge transfer leading to optimizing the MoP@MoO3 core-shell composite material, adjusting the quality of sodium hypophosphite, and phosphating MoO3 to varying degrees, producing the best hydrogen production H2 evolution rate is 10 000.02 μmol h-1 g-1. Density functional theory (DFT) calculations and a series of experiments were used to determine the S-scheme charge transfer mechanism in MoP@MoO3. This design provides a new idea for the introduction of surface-active sites and the construction of mixed anion photocatalysts. At the same time, a new design scheme is provided for the in situ construction of S-scheme interface heterojunction materials.We synthesized new oxygen-evolving molecular Ru(II) catalysts with one or two carbazole moieties on the axial pyridyl ligands, namely [Ru(bda)(cbz-py)(py)] and [Ru(bda)(cbz-py)2] [C1 and C2; bdaH2 = 2,2'-bipyridyl-6,6'-dicarboxylic acid, py = pyridine, and cbz-py = 9-(pyridin-4-yl)-9H-carbazole] to investigate the effect of cbz modification on the photophysical and catalytic properties of the well-known molecular catalyst [Ru(bda)(py)2] (C0). The initial oxygen-evolving catalytic activities of C1 and C2 were higher than that of C0 in both a chemical reaction driven by the strong oxidant (NH4)2[Ce(NO3)6] (CAN = ceric ammonium nitrate) and photochemical oxidation using a [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) photosensitizer with Na2S2O8 as the sacrificial oxidant. The higher activities were ascribed to the electron-withdrawing cbz groups, which promoted the radical coupling reaction to form a RuIV-O-O-RuIV species. A unique oxygen-evolution rate change behaviour was observed for both C1 and C2 in the presence of a large excess of CAN, suggesting the competitive oxidation of the cbz moiety during the chemical oxygen evolution reaction. This work suggests that the cbz modification of an oxygen evolution molecular catalyst is a promising approach for integrating the hole accumulator near the oxygen evolution catalytic centre.Reactions of five-membered zirconacycloalkynes and zirconacyloallenes (1-zirconacyclopent-3-ynes and 1-zirconacyclopenta-2,3-dienes) with an excess of Cp2Zr(H)Cl, known as the Schwartz reagent, were studied. Both reactions gave five-membered zirconacycloalkenes, 1-zirconacyclopent-3-enes without subsequent work-up such as protonolysis and hydrogenolysis. The product was identical to the zirconocene-diene complex that was prepared from Cp2Zr(n-Bu)2 (Negishi reagent) and the corresponding 1,4-disubstituted 1,3-dienes. Veliparib purchase These results indicate that formal hydrogenation by metal hydride took place. The use of diisobutylaluminum hydride or 9-borabicyclo[3.3.1]nonane also gave the same product, albeit in lower yields. The reactions starting from deuterated compounds suggested that double hydrozirconation followed by elimination of a dinuclear zirconium complex resulted in the hydrogenated products.The origin, tissue concentration, and health risk of polycyclic aromatic hydrocarbons (PAHs) contaminants in three economically important species of seafood, including catfish (Chrysichthys nigrodigitatus), prawns (Macrobrachium macrobrachium), and periwinkles (Tympanotonus fuscatus) from the crude oil-impacted Niger Delta region, were investigated. The concentrations of PAHs were measured by coupled gas chromatography-mass spectrometry after repeated extraction by ultrasonication in hexane and cleaning up in silica gel. The origin of PAHs was deduced using established mathematical protocols. Health risk from the consumption of contaminated seafood was evaluated for 60 kg bodyweight individuals at a fish consumption rate of 36.94 g per person per day. Different tissue concentrations of PAHs residues at low, moderate, and chronic levels were revealed. Mean total PAHs varied from 4.55 to 6.36 mg kg-1 in catfish, 4.61 to 7.75 mg kg-1 in prawns, and 4.91 to 6.14 mg kg-1 in periwinkles. The tissue concentrations were high above PM2.
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