Paecilomycines A and B,Novel Diterpenoids,Isolated from Insect‐Pathogenic Fungi Paecilomyces sp. ACCC 37762

Two new diterpenoids, named paecilomycine A ( 1 ) and paecilomycine B ( 2 ), including a novel skeleton with a five‐membered lactone ring, together with three known labdane diterpenoids, rel‐(1R,3S,4aS,5R,8aS)‐5‐[(3E)‐4‐carboxy‐3‐methylbut‐3‐en‐1‐yl]decahydro‐3‐hydroxy‐1,4a‐dimethyl‐6‐methylidenenaphthalene‐1‐carboxylic acid ( 3 ), botryosphaerin E ( 4 ), and agathic acid ( 5 ), were isolated from solid culture of the insect pathogenic fungi strain Paecilomyces sp. The structures of all compounds were established on the basis of comprehensive spectroscopic studies. The relative configurations of 1 and 2 were determined by single‐crystal X‐ray diffraction analyses.     

The Convenient Synthesis of 11‐Methyl‐3,8‐disubstituted‐12‐aryl‐3,4,7,8,9,12‐hexahydro‐1H‐chromeno[2,3‐b]quinoline‐1,10(2H)‐dione Derivatives

The 2‐arylidene‐3‐oxobutanenitrile derivatives 2 were prepared by the Knoevenagel condensation between aldehydes and 3‐oxobutanenitrile 1 , which was obtained by acid hydrolysis of β‐aminocrotononitrile. 3‐Acetyl‐2‐amino‐4H‐chromen‐5(6H)‐one derivatives 3 were synthesized by reaction of 2‐arylidene‐3‐oxobutanenitrile 2 and 5‐substituted‐1,3‐cyclohexanedione in ethylene glycol. The 11‐methyl‐3,8‐disubstituted‐12‐aryl‐3,4,7,8,9,12‐hexahydro‐1H‐chromeno[2,3‐b]quinoline‐1,10(2H)‐dione derivatives 4 were obtained by Friedländer reaction of compounds 3 with 5‐substituted‐1,3‐cyclohexanedione, using p‐toluenesulfonic acid monohydrate as catalyst. The structures of all novel compounds were characterized by elemental analysis, IR, MS, and ¹H NMR spectra. The crystal and molecular structure of compound 4f has been determined by single crystal XRD analysis.     

Susceptibility of Ureaplasma urealyticum to Methylene Blue‐Mediated Photodynamic Antimicrobial Chemotherapy: An in vitro Study

The aim of this study was to detect the susceptibility of Ureaplasma urealyticum to methylene blue‐mediated photodynamic antimicrobial chemotherapy (PACT). Three U. urealyticum strains including the standard serotype 1 and 5, and a clinically collected strain were used in this study. Strains were first incubated in 96‐well culture plates in the presence of methylene blue with decreasing concentrations (from 1 to 0.015625 mg mL^?1) for 20 or 60 min, and then submitted to irradiation with a light‐emitting diode laser with a power density of 100 mW cm^?2 for 8, 17, 34 or 68 min. Regrowth of the strains was performed soon after irradiation. A significant inactivation effect was observed after PACT. Longer incubation time induced more extensive inactivation of U. urealyticum. No difference in response to PACT was observed between the two biovars of U. urealyticum. It was concluded that PACT had a significant inactivation effect on U. urealyticum, and it might be a promising alternative treatment for resistant U. urealyticum infections.     

Synthesis of Bi2WO6/Bi2O3 Composite with Enhanced Photocatalytic Activity by a Facile One‐step Hydrothermal Synthesis Route

In this study, the characterization and photocatalytic activity of Bi₂WO₆/Bi₂O₃ under visible‐light irradiation was investigated in detail. The results suggested that Bi₂WO₆/Bi₂O₃ can be synthesized by a facile one‐pot hydrothermal route using a super big 200 mL Teflon‐lined autoclave with optimal sodium oleate/Bi molar ratio of 1.25. Through the characterization of Bi₂WO₆/Bi₂O₃ by X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared, UV‐vis diffuse reflectance spectra and Photoluminescence spectra, it was found that the as‐prepared composite possessed smaller crystallite size and higher visible‐light responsive than the pure Bi₂WO₆. Moreover, it was expected that the as‐prepared composites exhibited enhanced photocatalytic activity for the degradation of Rhodamine B under visible‐light irradiation, which could be ascribed to their improved light absorption property and the reduced recombination of the photogenerated electrons and holes during the photocatalytic reaction. In general, this study could provide a principle method to synthesize Bi₂WO₆/Bi₂O₃ with enhanced photocatalytic activity by one‐step hydrothermal synthesis route for environmental purification.     

How Does Photoreceptor UVR8 Perceive a UV‐B Signal?

UVR8 is the only known plant photoreceptor that mediates light responses to UV‐B (280–315 nm) of the solar spectrum. UVR8 perceives a UV‐B signal via light‐induced dimer dissociation, which triggers a wide range of cellular responses involved in photomorphogenesis and photoprotection. Two recent crystal structures of Arabidopsis thaliana UVR8 (AtUVR8) have revealed unusual clustering of UV‐B‐absorbing Trp pigments at the dimer interface and provided a structural framework for further mechanistic investigation. This review summarizes recent advances in spectroscopic, computational and crystallographic studies on UVR8 that are directed toward full understanding of UV‐B perception at the molecular level.     

A Molecular Platform for Multistate Near‐Infrared Electrochromism and Flip‐Flop,Flip‐Flap‐Flop,and Ternary Memory

A diruthenium complex with a redox‐active amine bridge has been designed, synthesized, and studied by single‐crystal X‐ray analysis and DFT and TDDFT calculations. It shows three well‐separated redox processes with exclusive near‐infrared (NIR) absorbance at each redox state. The electropolymerized film of a related vinyl‐functionalized complex displays multistate NIR electrochromism with low operational potential, good contrast ratio, and long retention time. Flip‐flop, flip‐flap‐flop, and ternary memories have been realized by using the obtained film (ca. 15–20 nm thick) with three electrochemical inputs and three NIR optical outputs that each displays three levels of signal intensity.     

Two new xanthones from the pericarp of Garcinia mangostana

Two new xanthones, designated garcimangosxanthone F (1) and garcimangosxanthone G (2), were isolated from the EtOAc-soluble fraction of ethanolic extract from the pericarp of Garcinia mangostana. Their structures were established as 1,6,7-trihydroxy-5-(3-methylbut-2-enyl)-8-(3-hydroxy-3-methylbutyl)-6′,6′-dimethylpyrano[2′,3′:3,2]xanthone and 1,6,7-trihydroxy-5-(3-methylbut-2-enyl)-8-(3-hydroxy-3-methylbutyl)-6′,6′-dimethyl-4′,5′-dihydropyrano[2′,3′:3,2]xanthone, respectively, on the basis of their 1D, 2D NMR and MS data interpretation.     

Synthesis of Functional Poly(disubstituted acetylene)s through the Post‐Polymerization Modification Route

We report the recent progress in the preparation of functional poly(disubstituted acetylene)s (PDSAs) through post‐polymerization modification routes. The metathesis polymerization of disubstituted acetylene monomers activated by Mo/W–Sn complex catalysts, which do not tolerate highly polar functionalities, was assumed to be a key step in the polymer synthetic procedures. We and other groups have explored several approaches to prepare PDSAs with latent reactive functionalities, which are inactive to Mo/W–Sn complex catalysts but can be used as highly reactive sites for post‐polymerization modification. Click chemistry, Michael‐type addition reactions, the use of activated esters and other strategies are demonstrated by recently published examples. These works indicate that post‐polymerization modification is an efficient route to the synthesis of various functional PDSAs.     

High‐throughput salting‐out‐assisted liquid–liquid extraction for the simultaneous determination of atorvastatin,ortho‐hydroxyatorvastatin,and para‐hydroxyatorvastatin in human plasma using ultrafast liquid chromatography with tandem mass spectrometry

A high‐throughput, specific, and rapid liquid chromatography with tandem mass spectrometry method was established and validated for the simultaneous determination of atorvastatin and its two major metabolites, ortho‐hydroxyatorvastatin and para‐hydroxyatorvastatin, in human plasma. A simple salting‐out‐assisted liquid–liquid extraction using acetonitrile and a mass‐spectrometry‐friendly salt, ammonium acetate, was employed to extract the analytes from human plasma. A recovery of more than 81% for all analytes was achieved in 1 min extraction time. Chromatographic separation was performed on a Kinetex XB C₁₈ column utilizing a gradient elution starting with a 60% of water solution (1% formic acid), followed by increasing percentages of acetonitrile. Analytes were detected on a tandem mass spectrometer equipped with an electrospray ionization source that was operated in the positive mode, using the transitions of m/z 559.3 → m/z 440.2 for atorvastatin, and m/z 575.3 → m/z 440.2 for both ortho‐ and para‐hydroxyatorvastatin. Deuterium‐labeled compounds were used as the internal standards. The method was validated over the concentration ranges of 0.0200–15.0 ng/mL for atorvastatin and ortho‐hydroxyatorvastatin, and 0.0100–2.00 ng/mL for para‐hydroxyatorvastatin with acceptable accuracy and precision. It was then successfully applied in a bioequivalence study of atorvastatin.     

Ionic liquid and aqueous two‐phase extraction based on salting‐out coupled with high‐performance liquid chromatography for the determination of seven rare ginsenosides in Xue‐Sai‐Tong injection

A method of ionic liquid salt aqueous two‐phase extraction coupled with high‐performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg₆, F₄, 20(S)‐Rg₃, 20(R)‐Rg₃, Rk₃, Rk₁, and Rg₅ in Xue‐Sai‐Tong injection. The injection was mixed with ionic liquid 1‐butyl‐3‐methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two‐phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue‐Sai‐Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections.