Appelerichsen1456

The solid-state cultivation of Acaulium sp. H-JQSF isolated from Armadillidium vulgare produces acautalides A-C (1-3) as skeletally unprecedented Diels-Alder adducts of a 14-membered macrodiolide to an octadeca-9,11,13-trienoic acid. The acautalide structures, along with the intramolecular transesterifications of 1-acylglycerols, were elucidated by mass spectrometry, nuclear magnetic resonance, chemical transformation, and single-crystal X-ray diffraction. https://www.selleckchem.com/products/nor-noha-dihydrochloride.html Compounds 1-3 were found to be neuroprotective with antiparkinsonic potential in the 1-methyl-4-phenylpyridinium-challenged nematode model, with the magnitude impacted by the glycerol esterification.Ruthenium(II) complexes, like [(tbbpy)2Ru(dppz)]2+ (Ru-dppz; tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dppz = dipyrido-[3,2-a2',3'-c]phenazine), have emerged as suitable photosensitizers in photoredox catalysis. Since then, there has been ongoing interest in the design of π-extended Ru-dppz systems with red-shifted visible absorption maxima and sufficiently long-lived excited states independent of the solvent or pH value. Herein, we explore the photophysical properties of protonation isomers of the linearly π-extended [(tbbpy)2Ru(L)]2+-type complexes bearing a dppz ligand with directly fused imidazole (im) and methyl-imidazole units (mim) as L. Steady-state UV-vis absorption, resonance Raman, as well as time-resolved emission and transient absorption spectroscopy reveal that Ru-im and Ru-mim show desirable properties for the application in photocatalytic processes, i.e., strong visible absorbance and two long-lived excited states in the 3ILCT and 3MLCT manifold, at pH values between 3 and 12. However, protonation of the (methyl-)imidazole unit at pH ≤ 2 unit causes decreased excited-state lifetimes and an emission switch-off.Ni(COD)2-catalyzed cycloaddition reactions to access pyridines have been extensively studied. However, this catalyst typically requires drying procedures and inert-atmosphere techniques for the reactions. Herein, we report operationally simple nickel(0) catalysis to access substituted pyridines from various nitriles and 1,6-diynes without the aid of air-free techniques. The Ni-Xantphos-based catalytic manifold is tolerant to air, moisture, and heat while promoting the [2 + 2 + 2] cycloaddition reactions with high reaction yields and broad substrate scope. In addition, we disclose that not only the steric effect but also the frontier molecular orbital interactions can play a critical role in determining the regiochemical outcome of nickel-catalyzed [2 + 2 + 2] cycloaddition for the synthesis of substituted pyridines.Pickering emulsions (PEs) achieve interfacial stabilization by colloidal particle surfactants and are commonly used in food, cosmetics, and pharmaceuticals. Carbon nanotubes (CNTs) have recently been used as stabilizing materials to create dynamic single emulsions. In this study, we used the formation of Meisenheimer complexes on functionalized CNTs to fabricate complex biphasic emulsions containing hydrocarbons (HCs) and fluorocarbons (FCs). The reversible nature of Meisenheimer complex formation allows for further functionalization at the droplet-water interface. The strong affinity of fluorofluorescent perylene bisimide (F-PBI) to the CNTs was used to enhance the assembly of CNTs on the FC-water interface. The combination of different concentrations of the functionalized CNTs and the pelene additive enables predictable complex emulsion morphologies. Reversible morphology reconfiguration was explored with the addition of molecular surfactants. Our results show that the interfacial properties of functionalized CNTs have considerable utility in the fabrication of complex dynamic emulsions.Silicone elastomer-based fouling release coatings have been gaining increased attention in marine antibiofouling. However, the lack of fouling resistance limits their application. Introducing a zwitterionic polymer into silicone enhances its fouling resistance, but their incompatibility makes this challenging. In this work, a silicone elastomer with zwitterionic pendant chains has been prepared by grafting a telomer of tertiary carboxybetaine dodecafluoroheptyl ester ethyl acrylate (TCBF) and 3-mercaptopropyltriethoxysilane to the bis-silanol-terminated poly(dimethylsiloxane) (PDMS). The fluorocarbon groups drive the telomer onto the surface in the film formation process, while the TCBF groups hydrolyze and generate zwitterions on the surface, which is confirmed by attenuated total reflection infrared spectra analysis and water contact angle measurements. Bioassays using marine bacteria (Pseudomonas sp.) and diatoms (Navicula incerta) demonstrate that the antifouling efficacy is improved as the telomer content increases. The bacteria and diatom adhesion decreases by 95 and 81%, respectively, for the PDMS with 30 wt % telomer compared with the unmodified PDMS control. Meanwhile, the fouling release performance of PDMS is maintained with a pseudobarnacle removal strength of ∼0.1 MPa. This work provides a facile way to fabricate efficient silicone-based antifouling coatings.Cascade radical cyclization of N-arylacrylamides is an attractive method to prepare 3,3-disubstituted oxindoles. As the reported methods often require additives and/or photocatalysts, we herein report an additive- and photocatalyst-free deaminative strategy for their synthesis under mild conditions, enabled by photoactivation of an electron donor-acceptor (EDA) complex. DFT studies indicated that the involvement of an explicit xylene solvent molecule can greatly enhance the photoactivity of the EDA complex between N-arylacrylamides and Katritzky salts.A bifunctional metal-organic framework (MOF) was successfully designed to realize the purification of 4-chlorophenol (4-CP) under simulated sunlight irradiation. Owing to the large-size mesopores of the MOF matrix NU-1000, β-CMCD (carboxylic β-cyclodextrin) could be incorporated into the frameworks with a density of 2.4% to pre-enrich the pollutant of 4-CP. Meanwhile, the photodegradation promoter [Pd(II) meso-tetra(4-carboxyphenyl)porphine] was in situ co-assembled with the organic ligand to realize its synchronous degradation. As for the current integrator, a Langmuir model was used to explain the adsorption isotherm, and the Langmuir-Hinshelwood model exhibited a better fit to its catalytic degradation behavior. Thanks to the simultaneous presence of a capturer and a photodegradation promoter, the adsorption capacity of 4-CP reached as high as 296 mg g-1, which was further completely detoxified within 60 min under simulated sunlight irradiation with a half-life time of only 5.98 min. Such excellent integrated decontamination properties prefigure the great promising potential of multifunctional MOFs in the field of pollution purification.We have developed a protocol for the synthesis of diaryl thio-/selenoethers by the reaction of aryl chalcogenocyanates with electron rich arenes/hetero arenes via HFIP promoted C-H activation. The reaction produces chalcogenides in good to excellent yields under mild conditions without the need of a transition metal as a catalyst. The HFIP-mediated reactions tolerated a wide range of functional groups and set the stage for the synthesis of diversely decorated chalcogenides. A mechanism involving activation of the C-H bond through hydrogen bonding is proposed.A photocatalysis strategy for the regioselective synthesis of 3-functionalized coumarins is reported. With visible light irradiation, a direct and regioselective C(sp2)-C(sp3) coupling reaction of 3-(2-hydroxyphenyl)acrylates with ethers or thioethers occurs by using Ru(bpy)3Cl2·6H2O as a photocatalyst and TBHP as an oxidant. The cascade process involves alkenylation of the C(sp3)-H bond of ethers and lactonization, furnishing 3-alkylated coumarins as the final products. This approach is characterized by a broad substrate scope, mild reaction conditions, and simplified operation. The synthesis of 3-alkylated coumarins could be realized by a one-pot procedure, starting from commercially available salicylaldehyde.We present a [Au7(SR)7] ring as a new type of protection ligand in a new atomic structure of Au15(SR)13 nanocluster for the first time based on the ring model developed to understand how interfacial interaction dictates the structures of protection motifs and gold cores in thiolate-protected gold nanoclusters. This new Au15(SR)13 model shows a tetrahedral Au4 core protected by one [Au7(SR)7] ring and two [Au2(SR)3] "staple" motifs. Density functional theory (DFT) calculations show that the newly predicted Au15(SR)13 (R = CH3/Ph) has a lower energy of 0.24/0.68 eV than previously proposed isomers. By comparing calculated optical absorption spectra (UV), circular dichroism (CD) spectra, and powder X-ray diffraction (XRD) patterns with related experimental spectra, the calculated CD spectra of the newly predicted Au15(SR)13 (R = CH3/Ph) cannot reproduce the experimental results, indicating that the newly predicted Au15(SR)13 is a new structure that needs to be confirmed by experiment. In addition, DFT calculations also show that the newly predicted Au15(SR)13 (R = CH3/Ph) exhibits a large HOMO-LUMO gap, suggesting its high chemical stability. The proposition of the [Au7(SR)7] ring as a protection ligand in the newly predicted Au15(SR)13 not only enriches the types of protection ligands in thiolate-protected gold nanoclusters but also further confirms the effectiveness and rationality of the ring model for understanding the interfacial interaction between the protection motifs and gold cores in thiolate-protected gold nanoclusters.The present study describes the development of a novel liposome nanocarrier system. The liposome was coated with Lactobacillus acidophilus CICC 6074 S-layer protein (SLP) to improve the intestinal absorption of the cholesterol-lowering peptide Leu-Gln-Pro-Glu (LQPE). The SLP-coated liposomes were prepared and characterized with morphology, particle size, zeta potential, membrane stability, Fourier transform infrared spectroscopy, and dual-channel surface plasma resonance. The results showed that SLP could successfully self-assemble on liposomes. Then, LQPE liposomes and SLP-coated LQPE liposomes (SLP-L-LQPE) were prepared. SLP-L-LQPE not only showed better sustained release properties and gastrointestinal tolerance in vitro but also increased the retention time in mice intestine. Transepithelial transport experiment indicates that the transshipment of LQPE increased significantly after being embedded by liposomes and coated with SLP. The research provides a theoretical basis for the study of SLP-coated liposomes and a potential drug delivery system for improving the intestinal absorption of peptides.There is an ever-increasing demand for higher-performing polymeric materials counterbalanced by the need for sustainability throughout the life cycle. Copolymers comprising ester, carbonate, or ether linkages could fulfill some of this demand as their monomer-polymer chemistry is closer to equilibrium, facilitating (bio)degradation and recycling; many monomers are or could be sourced from renewables or waste. Here, an efficient and broadly applicable route to make such copolymers is discussed, a form of switchable polymerization catalysis which exploits a single catalyst, switched between different catalytic cycles, to prepare block sequence selective copolymers from monomer mixtures. This perspective presents the principles of this catalysis, catalyst design criteria, the selectivity and structural copolymer characterization tools, and the properties of the resulting copolymers. Uses as thermoplastic elastomers, toughened plastics, adhesives, and self-assembled nanostructures, and for programmed degradation, among others, are discussed.