Total Syntheses of Crinipellins Enabled by Cobalt‐Mediated and Palladium‐Catalyzed Intramolecular Pauson–Khand Reactions

Efficient total syntheses of the naturally occurring, potent antibiotic compounds (?)‐crinipellin A and (?)‐crinipellin B are described. The key advanced intermediate, a fully functionalized tetraquinane core, was constructed by a novel thiourea/palladium‐catalyzed Pauson–Khand reaction. This intermediate can serve as a common intermediate for the collective total synthesis of other members of the crinipellin family.     

Carbon Nanozymes: Enzymatic Properties,Catalytic Mechanism,and Applications

Nanozymes have advantages over natural enzymes, such as facile production on large scale, long storage time, low costs, and high stability in harsh environments. Carbon nanomaterials (CNMs), including fullerenes, carbon nanotubes, graphene, carbon quantum dots, and graphene quantum dots, have become a star family in materials science. As a new class of nanozymes, the catalytic activity of CNMs and their hybrids has been extensively reported. In this Minireview, recent progress of CNMs based artificial enzymes, focusing on those with peroxidase‐like activity, has been summarized. The enzymatic properties, catalytic mechanisms, and novel applications of CNM nanozymes in sensing, therapy, and environmental engineering are discussed in detail. Additionally, we also highlight the remaining challenges and unsolved problems. With the fast development of bionanotechnology, the unique enzymatic properties and advantages of CNM nanozymes have received much attention and will continue to be an active and challenging field for the years to come.     

Thermo‐Driven Controllable Emulsion Separation by a Polymer‐Decorated Membrane with Switchable Wettability

A thermoresponsive Poly(N‐isopropylacrylamide) (PNIPAAm)‐modified nylon membrane was fabricated via hydrothermal route. Combining rough structure, proper pore size, and thermoresponsive wettability, the membrane can separate at least 16 types of stabilized oil‐in‐water and water‐in‐oil emulsions at different temperatures. Below the LCST (ca. 25 °C), the material exhibits hydrophilicity and underwater superoleophobicity, which can be used for the separation of various kinds of oil‐in‐water emulsions. Above the LCST (ca. 45 °C), the membrane shows the opposite property with high hydrophobicity and superoleophilicity, and it can then separate stabilized water‐in‐oil emulsions. The material exhibits excellent recyclability and high separation efficiency for various kinds of emulsions and the hydrothermal method is facile and low‐cost. The membrane shows good potential in real situations such as on‐demand oil‐spill cleanup, industrial wastewater treatment, remote operation of oil/water emulsion separation units, and fuel purification.     

One‐step Synthesis and Enhanced Thermoelectric Properties of Polymer–Quantum Dot Composite Films

Conventional syntheses of polymer–inorganic composite thermoelectric materials suffer major problems such as inhomogeneity, large particle size, and oxidation that result in ineffective loading. Now a one‐step synthesis can be used to fabricate high‐quality small‐sized anions codoped poly(3,4‐ethylenedioxythiophene):dodecylbenzenesulfonate/Cl‐tellurium (PEDOT:DBSA/Cl‐Te) composite films using a series of novel Te^IV‐based oxidants. The synchronized production of PEDOT and Te results in thick and homogeneous films containing evenly distributed and well‐protected Te quantum dots. Owing to the heavily doped crystalline polymer matrix as well as the <5 nm unoxidized Te quantum dot loading, at low Te concentrations as 2.1–5.8 wt %, the films exhibits high power factors of about 100 μW m^?1 K^?2, which is 50 % higher compared to a pure PEDOT:DBSA film.     

Enhanced redox stability and optical contrast of electrochromic copolymers from selenophene and 3-methylthiophene

Journal of Solid State Electrochemistry - A series of poly(selenophene-co-3-methylthiophene) films were synthesized by electrochemical copolymerization of selenophene and 3-methylthiophene under...     

Highly Sensitive Silver Nanorod Arrays for Rapid Surface Enhanced Raman Scattering Detection of Acetamiprid Pesticides

The determination of pesticide residue on agricultural products is increasingly important.Exposure to pesticides can cause severe acute reactions in humans, including aplastic anemia and leukemia.In this work, we developed a rapid and sensitive method to detect acetamiprid pesticide residue based on surface-enhanced Raman scattering.Silver nanorod (AgNR) arrays were fabricated by oblique angle deposition technology and were used as SERS substrates.Prior to detection, the AgNR arrays were cleaned with nitric acid solution or a mixture of methanol and acetone.Compared to the unwashed AgNR arrays, the AgNR arrays washed with methanol and acetone shows a signal enhancement 1000 times greater than the unwashed AgNR array due to the effective removal of the impurities on its surface.The limit of detection of acetamiprid was determined to be 0.05 mg/L.In addition, the molecular structure of acetamiprid was simulated and the corresponding vibration modes of the characteristic bands of acetamiprid were calculated by density function theory.To demonstrate its practical application, the AgNRs array substrates were applied successfully to the rapid identification of acetamiprid residue on a cucumber's surface.These results confirmed possibility of utilizing the AgNRs SERS substrates as a new method for highly sensitive pesticide residue detection.     

Insights into the N‐Heterocyclic Carbene (NHC)‐Catalyzed Intramolecular Cyclization of Aldimines: General Mechanism and Role of Catalyst

One of the most challenging questions in the Lewis base organocatalyst field is how to predict the most electrophilic carbon for the complexation of N‐heterocyclic carbene (NHC) and reactant. This study provides a valuable case for this issue. Multiple mechanisms (A, B, C, D, and E) for the intramolecular cyclization of aldimine catalyzed by NHC were investigated by using density functional theory (DFT). The computed results reveal that the NHC energetically prefers attacking the iminyl carbon (AIC mode, which is associated with mechanisms A and C) rather than attacking the olefin carbon (AOC mode, which is associated with mechanisms B and D) or attacking the carbonyl carbon (ACC mode, which is associated with mechanism E) of aldimine. The calculated results based on the different reaction models indicate that mechanism A (AIC mode), which is associated with the formation of the aza‐Breslow intermediate, is the most favorable pathway. For mechanism A, there are five steps: (1) nucleophilic addition of NHC to the iminyl carbon of aldimine; (2) [1,2]‐proton transfer to form an aza‐Breslow intermediate; (3) intramolecular cyclization; (4) the other [1,2]‐proton transfer; and (5) regeneration of NHC. The analyses of reactivity indexes have been applied to explain the chemoselectivity, and the general principles regarding the possible mechanisms would be useful for the rational design of NHC‐catalyzed chemoselective reactions.     

A highly stable black phosphorene nanocomposite for voltammetric detection of clenbuterol

A nanocomposite was prepared from graphene-like two-dimensional black phosphorene (BP, an allotrope of phosphorus) and nafion (Nf) treated with isopropanol (IP). A glassy carbon electrode (GCE) modified with this nanocomposite was found to be a viable sensor for voltammetric determination of clenbuterol (CLB). Unlike previously reported pure BP, the BP nanocomposite was stable towards water and oxygen. Its morphology, structure, electrochemically active surface area and electrochemical stability were investigated. The BP-Nf (IP) modified GCE displayed good electrochemical stability and electrocatalytic capacity with a low working potential of 0.94 V (vs. SCE), excellent peak current response for CLB in a linear concentration range of 0.06–24 μM with a detection limit of 3.7 nM (3σ/m) and a sensitivity of 0.14 μA·μM^?1·cm^?2 under optimal conditions. A sensing mechanism for the electro-oxidation of CLB was suggested and verified by density functional theory calculations under imitation of aqueous solution conditions. The sensor was successfully applied to the determination of CLB in bovine meat and bovine serum samples.

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Graphical abstract Highly-stable black phosphorene (BP) nanocomposite based on Nafion (Nf) was used to modify a glassy carbon electrode (GCE). It is shonw to be a viable electrochemical platform for sensitive voltammetric determination of trace clenbuterol (CLB) in bovine beef and bovine serum.

     

Grayanane diterpenoids with diverse bioactivities from the roots of Pieris formosa

During our continuing study on the roots of Pieris formosa, twelve new grayanane diterpenoids (1–12), together with eight known compounds (13–20), were obtained. Their structures with absolute configurations were characterized by a series of spectroscopic methods and X-ray diffraction. Compounds 1, 2, 4–5, 7–8, 14, and 19 exhibited significant analgesic activity in an acetic acid-induced writhing test. In particular, 7 and 14 were found to be 5 times more potent than morphine in the acetic acid-induced writhing test model. Compounds 1, 4, 9, 13, and 18 showed antifeedant activity against Plutella xylostella at 0.5 mg/mL. Compound 4 exhibited a 38.3% inhibitory effect against the KCNQ2 potassium channel at a concentration of 10 μM.     

Diterpenoids from the fruits of Rhododendron molle, potent analgesics for acute pain

Rhododendron molle G. Don is one of the most potent traditional Chinese medicines for pain relief. Prior investigations have shown that Rhododendrons are rich sources of terpenoids. In our continuing efforts to identify structurally unique and biologically interesting diterpenoids, the fruits of R. molle were collected from Guangxi Province. A chemical study was carried out on the EtOH extract, which led to the isolation of 18 diterpenoids including 12 new compounds. The isolation and structural elucidation of new compounds 1–12, as well as the evaluation of the antinociceptive activities of these compounds were reported.