Hyperacmosin R,a New Decarbonyl Prenylphloroglucinol with Unusual Spiroketal Subunit from Hypericum acmosepalum

Two previously undescribed polycyclic polyprenylated acylphloroglucinols, hyperacmosins R-S (1–2), were obtained from the aerial parts of Hypericum acmosepalum. Their structures were elucidated by extensive spectroscopic analysis and electronic circular dichroism calculation (ECD). Compound 1 featured an unprecedented 5,8-spiroketal subunit as well as the loss of C-2′ carbonyl in the phloroglucinol ring. In addition, compounds 1 and 4 showed weak hepatoprotective activity against paracetamol-induced HepG2 cell damage at 10 μm. The plausible biosynthetic pathway of 1 was proposed via a retro-Clasisen reaction and decarboxylation.     

Facile synthesis of metal-polyphenol-formaldehyde coordination polymer colloidal nanoparticles with sub-50 nm for T_1-weighted magnetic resonance imaging

Plant polyphenol-based coordination polymers(CPs) with ultra-small particle size and tailorable compositions are highly desired in biomedical applicatio ns,but their synthesis is still challenging due to the sophisticated coordination assembly process and unavoidable self-oxidation polymerization of polyphenol. He rein,a general ligand covalent-modification mediated coordination assembly strategy is proposed for the synthesis of water-dispersible CPs with tunable metal species(e.g., Gd,Cu,Ni,Zn,Fe)and ultra-small diameter(8.6-37.8 nm) using nontoxic plant polyphenol(e.g..tannic acid,gallic acid) as a polymerizable ligand.Polyphenol molecules react with formaldehyde firstly,which can effectively retard the oxidation induced self-polymerization of polyphenol and lead to the formation of metal ions containing CPs colloidal nanoparticles.These ultrafine nanoparticles with stably chelated metal io ns are highly water dispersible and thus advantageous for bioimaging.As an example,ultra-small Gd contained CPs exhibit higher longitudinal relaxivity(r_1=25.5 L mmol ~1 s ~1) value with low r_2/r_1(1.19) than clinically used Magnevist(Gd-DTPA,r_1=3.7 L mmol ~1 s ~1).Due to the enhanced permeability and retention effect,they can be further used as a positive contrast agent for T_1-weighted MR imaging of tumour.     

波纹结构迎爆面泡沫金属对甲烷-空气混合气体爆炸能量的吸收特性

为进一步探究气体爆炸荷载下异构迎爆面泡沫金属的吸能特性,在前期开展锯齿结构迎爆面材料吸能特性实验的基础上,以3种波纹结构迎爆面（凸面型、凹面型和凹凸连续型）泡沫金属材料为研究对象,利用自主搭建的气体爆炸管网实验平台,开展了该泡沫金属材料在甲烷-空气混合气体爆炸荷载下的吸能特性测定实验。采用不同波纹结构迎爆面阻隔爆材料,测定了管道内爆炸冲击波超压、火焰传播速度和火焰温度等随时间和空间的变化,分析了不同波纹结构迎爆面阻隔爆材料的吸能效果。结果表明：(1)迎爆面为波纹结构的泡沫金属材料对爆炸超压的衰减效果优于迎爆面为锯齿结构的泡沫金属材料和迎爆面为平面结构的泡沫金属材料,且迎爆面为凸面型波纹结构和凹凸连续型波纹结构的泡沫金属材料对超压衰减的速率高于迎爆面为锯齿结构和凹面型波纹结构的泡沫金属材料;迎爆面为锯齿结构的泡沫金属材料对火焰传播速度的衰减略强于迎爆面为波纹结构和平面结构的泡沫金属材料;迎爆面为波纹结构的泡沫金属材料对火焰温度的衰减效果优于迎爆面为锯齿结构及平面结构的泡沫金属材料。(2)在本文实验条件下,3种波纹结构（凸面型、凹面型和凹凸连续型）迎爆面泡沫金属材料的熄爆参数分别为5.338、4.340和6.090 MPa·℃,低于锯齿结构迎爆面材料的熄爆参数17.680 MPa·℃,且远低于熄爆参数安全值390 MPa·℃,波纹结构迎爆面材料具有良好的防护效果。(3)这3种迎爆面为波纹结构的泡沫金属材料均具有良好的吸能特性,均优于迎爆面为锯齿形结构的泡沫金属材料,且明显优于迎爆面为平面结构的泡沫金属材料。

     

Synthesis of P123-Templated and DVB-Cross-linked Meso-macroporous Poly (ionic liquids) with High-Performance Alkylation

Meso-macroporous poly (ionic liquids) (MPILs) were successfully synthesized through a novel strategy with P123 (PEO₂₀PPO₇₀PEO₂₀) as the pore-forming agent and divinylbenzene as crosslinker. Then effects of reaction temperature and the molar ratio of ionic liquid to divinylbenzene (IL to DVB) were systematically investigated together with the morphology and structure of MPILs. It was found the MPILs owned a meso-macroporous channel-like structure, large surface area (up to 732 m²/g), large pore volume (1.42 cm³/g) and high thermal stability. Meanwhile, the Brunauer–Emmett–Teller surface of MPILs could be fabricated by adjusting the reaction temperature and especially the IL to DVB molar ratio. In the probe reaction of alkylation of styrene and o-xylene, a 100% conversion of styrene and 96.4% PXE yield was acquired, and this is more expert than common commercial liquid acid catalyst. This work might develop a novel way for synthesizing porous heterogeneous polymer catalysts in the future and owning a promising future applied in other acidic catalytic reactions.     

High Catalytic Performance of Mesoporous Dual Brønsted Acidic Ternary Poly (Ionic Liquids) for Friedel‐Crafts Alkylation

A newfangled cross‐linked dual Brønsted acidic ternary mesoporous poly (ionic liquids)(MPILs) with mesoporous structure was successfully synthesized with divinylbenzene as cross linker, 1‐vinyl‐3‐butyl imidazole bromide and sodium p‐styrene sulfonate as functional group through an ordinary post‐modification method and anion exchange process. A sponge‐like mesoporous tunnel structure was observed and the obtained P (BVS‐SO₃H)‐SO₃CF₃ sample appeared a relatively high thermal stability, a large surface area (up to 286.8 m²/g) and great pore volume (0.73 cm³/g). The abundant dual acidic group of sulfonic acid and trifluoromethanesulfonic acid of the composite in the polymer framework impart Brønsted acidity. For the sake of demonstrating our claims, the sample has been used as a novel solid acid catalyst for the reaction of alkylation of o‐xylene with styrene to 1‐diphenylethane (PXE). Under optimal reaction conditions (reaction under 120 °C for 3 hr, catalyst amount was 0.5 wt% of the reaction system, and the mass ratio of o‐xylene/styrene was 7.5:1, a 100% conversion of styrene and 93.7% PXE yield was acquired. After four times recycle, the yield remains 53.3%. Comparing with the commercial liquid acid catalyst, it processing a higher catalytic property and recyclability. Moreover, this fresh dual acidic heterogeneous catalyst owning a promising future applied in other acidic catalytic reactions and provide a new method to modify catalyst.     

Preparation and characterization of core–shell polymer particles with protonizable shells prepared by oxyanionic polymerization

A series of polystyrene (PS)/poly(vinyl acetate) (PVAc) crosslinked particles (240, 210, or 90 nm) with different concentrations of PS (75, 50, or 25 wt %) were prepared by soap‐free emulsion polymerization. Based on the crosslinked polymer particles, three series of monodisperse core–shell particles with pH‐sensitive poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) shells were synthesized by oxyanionic polymerization. During the oxyanionic polymerization, the acetate groups of PVAc were hydrolyzed, and the hydroxyl groups that formed on the surfaces of the particles, acting as initiators, were transferred to ? O^?K⁺ by DMSO^?K⁺ (where DMSO is dimethyl sulfoxide) at the same time; then, ? O^?K⁺ initiated the polymerization of 2‐(dimethylamino)ethyl methacrylate. ¹H NMR and Fourier transform infrared studies confirmed the existence of PDMAEMA shells, and the contents of PDMAEMA were measured by elemental analysis. Because the PDMAEMA chain could be protonated at a low pH, these core–shell particles could adsorb negatively charged modified magnetite particles, and at higher pHs, the magnetite particles could be released again; this process was reversible. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6081–6088, 2004     

Remarks on the Global Attractor of the Weakly Dissipative Benjamin－Ono Equation

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Monoacylation of unprotected symmetrical diamines with resin-bound benzoic acids

A protocol for monoacylation of unprotected symmetrical diamines with a resin-bound benzoic acid is described. The nature of the resin (gel-based polystyrene vs highly crosslinked macroporous polystyrene) was found to play a minor role in acylation selectivity. Rather, the concentration of the diamine dictates the ratio of mono- and diacylated products. Thus, by employing a high concentration of symmetrical diamine (e.g., 1 M, 20 equiv), monoacylation can be selectively achieved for a variety of unprotected symmetrical alkyl and aryl diamines.     

Fusopoltide A and fusosterede A,A polyketide with a pentaleno[1,2-c]pyran ring system and A degraded steride,from the fungus Fusarium solani

Fusopoltide A (1), a novel polyketide featured a pentaleno[1,2-c]pyran ring, and fusosteride A (2), a new steride with A/B-ring degraded, together with a known ergosterol peroxide (3), were isolated from a solid culture extract of Fusarium solani. The structures of 1 and 2 were elucidated by detailed interpretation of their HRESIMS and NMR spectroscopic data and their absolute configurations were determined by X-ray crystallographic analysis and the electronic circular dichroic (ECD) method, respectively. The postulated biogenetic pathways of 1 and 2 were also discussed. Compound 1 exhibits inhibitory activity against cyclooxygenase-2 (COX-2) with an IC₅₀ value of 3.45?μM.