Total Synthesis of Lajollamycin B

The first total synthesis of lajollamycin B, a structurally novel nitro-tetraene spiro-β-lactone/γ-lactone antibiotic, is described. The convergent synthesis involves the construction of the C8′–C11′ nitrodienylstannane and its coupling with the segment prepared from the C1′–C7′ ω-iodoheptadienoic acid and the right-hand heterocyclic fragment, which has been utilized for our previous syntheses of oxazolomycin A. The revision of the geometry of the terminal Δ^{10′, 11′}-double bond from E to Z is also described for the structure of natural lajollamycin B.     

In Situ Anchoring of Pyrrhotite on Graphitic Carbon Nitride Nanosheet for Efficient Immobilization of Uranium

Enrichment of U^VI is an urgent project for nuclear energy development. Herein, magnetic graphitic carbon nitride nanosheets were successfully prepared by in situ anchoring of pyrrhotite (Fe₇S₈) on the graphitic carbon nitride nanosheet (CNNS), which were used for capturing U^VI. The structural characterizations of Fe₇S₈/CNNS-1 indicated that the CNNS could prevent the aggregation of Fe₇S₈ and the saturation magnetization was 4.69 emu g⁻¹, which meant that it was easy to separate the adsorbent from the solution. Adsorption experiments were performed to investigate the sorption properties. The results disclosed that the sorption data conformed to the Langmuir isotherm model with the maximum adsorption capacity of 572.78 mg g⁻¹ at 298 K. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that the main adsorption mechanism are as follows: U^VI is adsorbed on the surface of Fe₇S₈/CNNS-1 through surface complexation initially, then it was reduced to insoluble U^IV. Thereby, this work provided an efficient and easy to handle sorbent material for extraction of U^VI.     

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

The precise synthesis of poly(thioester)s with diverse structures is still a significant challenge in the polymeric materials field. Herein, we report a novel approach to the synthesis of well‐defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts. Both the cation and anion have strong effects on the copolymerization. [PPN]OAc ([PPN]=bis(triphenylphosphine)iminium) with a bulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with a completely alternating structure, controlled molecular weight, and narrow polydispersity. The poly(thioester) obtained from succinic thioanhydride and propylene sulfide is a typical semicrystalline material, possessing a high refractive index of up to 1.78. Because it uses readily available monomers, this method is expected to open up a new route to poly(thioester)s with diverse structures and properties.     

Interior gradient and Hessian estimates for the Dirichlet problem of semi-linear degenerate elliptic systems: A probabilistic approach

In this paper, we give interior gradient and Hessian estimates for systems of semi-linear degenerate elliptic partial differential equations on bounded domains, using both tools of backward stochastic differential equations and quasi-derivatives.     

基于供应方生产能力的应急物资生产模型

利用期权契约所建立的政企合作储备应急物资模式能够有效解决政府单独储备模式所造成的物资储备量过少或过多而引起的困境。然而由于应急物资的需求特性,若应急物资供应企业采用按单生产方式安排生产储备计划,势必会造成库存水平升高,引发资金周转困难等问题,对政企之间的长期合作造成不利影响。基于此,本文设计了基于供应方生产能力的应急物资生产模型。该模型在政府利用批发价格契约与期权契约采购应急物资的基础上,研究了供应方根据自身生产能力进行柔性生产时的生产与储备问题。通过推导政企双方最优决策后,重点分析了期权权利金,执行价格,加急生产成本等参数对供应方生产决策的影响,并证明与按单生产模式相比,柔性生产模式可有效降低供应方的库存量与生产成本,提高其利润,继而提高整体供应链的利润水平,有助于促进政企之间长期稳定的合作。     

时间敏感选项依赖下的基础设施恢复决策研究

突发事件发生后,基础设施之间的恢复依赖为恢复过程带来了严重挑战。为了能够在突发事件后高效而有序的实现基础设施恢复运行,根据相互之间的恢复依赖关系制定合理的恢复决策非常关键。本文基于网络流理论,以累积恢复效能最大化为目标,建立了时间敏感选项依赖下的恢复设计与调度决策混合整数规划模型。然后,讨论了模型在完全中心化、完全分散和信息共享决策环境下的应用方法。最后,通过真实基础设施数据集测试了模型,结果表明:(1)该模型在突发事件后的基础设施恢复决策中具有应用可行性;(2)决策环境显著影响存在恢复依赖的基础设施网络整体累积恢复效能;(3)与完全分散决策环境相比,在信息共享决策环境下独立决策的整体累积恢复效能可以得到大幅提升。     

One-Pot Synthesis of Enantioenriched β-Amino Secondary Amides via an Enantioselective [4+2] Cycloaddition Reaction of Vinyl Azides with N-Acyl Imines Catalyzed by a Chiral Brønsted Acid

A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides.     

A simple,rapid and reliable liquid chromatography–mass spectrometry method for determination of methotrexate in human plasma and its application to therapeutic drug monitoring

A simple, rapid and reliable liquid chromatography–electrospray ionization tandem mass spectrometry method was established and validated for the determination of methotrexate in human plasma. After a straightforward protein precipitation by acetonitrile–water (70:30, v/v), methotrexate (MTX) and p‐aminoacetophenone (used as internal standard, IS) were separated on a Column C₁₈ column (50 × 2.1 mm, 3 µm; Column Technology, Fremont, CA, USA) using a gradient elution with mobile phase of acetonitrile and 0.03% acetic acid aqueous solution at a flow rate of 0.5 mL/min. The total chromatographic runtime was 5 min for each injection. Quantification detection was performed in a triple‐quadruple tandem mass spectrometer under positive mode monitoring the following mass transitions: m/z 455.3 → 308.3 for MTX and m/z 136.1 → 94.4 for IS. The calibration curve was linear over the range of 0.05–25.0 µmol/L with a lower limit of quantification of 0.05 µmol/L. The intra‐ and interday precisions were <5.2%, the accuracy varied from ?4.1 to 4.5%. The recovery was >94%. The LC‐MS/MS method showed an excellent agreement with the existing HPLC‐UV method using Passing–Bablok regression and Bland–Altman difference plot analysis. The validated LC‐MS/MS can be successfully applied to the routine therapeutic drug monitoring of MTX in clinical laboratories. Copyright © 2015 John Wiley & Sons, Ltd.     

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Different ratios of methane/air in the low power arc discharges assisted methane combustion were studied at atmospheric pressure. Plasma emission spectroscopy was recorded by an optical emission spectrometer. The possible physical and chemical reaction process and mechanisms were discussed. With a plasma in the on or off state, the physical appearances of the methane combustion flame were observed and compared, the temperature of the flame in the main combustion zone was investigated. The gas compositions of CH₄, CO and O₂ were analyzed by the gas chromatography and flue gas analyzer. The results showed that when plasma was in the on state, the temperature of flame increased and the combustion efficiency enhanced in stable combustion due to decrease of CH₄, CO and O₂; the combustion enhancement was more obvious at low ratio of methane/air; the rich combustion limits in terms of the ratio of methane/air was extended from 16% to 21%.