Multiple Reaction Pathways Operating in the Mechanism of Vinylogous Mannich‐Type Reaction Activated by a Water Molecule

A systematic search for reaction pathways for the vinylogous Mannich‐type reaction was performed by the artificial force induced reaction method. This reaction affords δ‐amino‐γ‐butenolide in one pot by mixing 2‐trimethylsiloxyfuran, imine, and water under solvent‐free conditions. Surprisingly, the search identified as many as five working pathways. Among them, two concertedly produce anti and syn isomers of the product. Another two give an intermediate, which is a regioisomer of the main product. This intermediate can undergo a retro‐Mannich reaction to give a pair of intermediates: an imine and 2‐furanol. The remaining pathway directly generates this intermediate pair. The imine and 2‐furanol easily react with each other to afford the product. Thus, all of these stepwise pathways finally converge to give the main product. The rate‐determining step of all five (two concerted and three stepwise) pathways have a common mechanism: concerted Si? O bond formation through the nucleophilic attack of a water molecule on the silicon atom followed by proton transfer from the water molecule to the imine. Therefore, these five pathways have comparable barriers and compete with each other.     

基于生物-生态耦合工艺的农村生活污水处理研究

开发低投资、低能耗、低维护的生活污水处理工艺是解决农村污水处理问题的关键。采用无动力升流式厌氧生物滤池(UAF)与潜流式人工湿地(SFW)耦合工艺处理农村生活污水,考察了耦合工艺在不同水力停留时间(HRT)下对生活污水的处理效果,并通过增加SFW内的植株密度改善脱氮除磷效果。结果表明:UAF与SFW耦合工艺无动力消耗,免维护,适合农村地区的生活污水处理,对氮、磷的去除主要依靠SFW阶段完成,通过增加芦苇的植株密度可以明显增强SFW内生物的脱氮除磷能力,并保证UAF与SFW耦合工艺的处理性能稳定在较高水平。在t(HRT)UAF=18h,t(HRT)SFW=3d的条件下,UAF与SFW耦合工艺出水COD、氨氮、总氮、总磷的平均质量浓度分别为44.07,4.25,13.36和0.44mg/L,达到《城镇污水处理厂污染物排放标准》(GB 18918-2002)一级A标准。     

人工蜂群算法及其应用

为促进人工蜂群算法理论和应用的发展, 在分析人工蜂群算法的基本原理基础上, 针对算法的不足, 全面地归纳了国内外学者对算法的改进研究, 对算法的蜜源初始化、更新策略的改进、调整策略的改进、适应度函数的选择以及与其他算法的融合进行综述, 提出了更有效的改进策略。同时从多方面综述了人工蜂群算法的应用, 并对人工蜂群算法的发展方向进行了总结和展望。     

数据中心启发式反向人工蜂群虚拟机整合节能策略

针对数据密集型作业的特点,提出一个基于CPU和图形处理器(GPU)两个影响因素构建计算节点的能耗评估模型.该模型基于原虚拟机选择节能算法(ABCS)在虚拟机选择节能策略中的能效优势,进一步利用启发式思想改进蜂群优化算法,寻求虚拟机整合的最优解.在CloudSim 3.0云计算模拟器中的实验结果表明,启发式反向蜂群算法能在保证服务质量的前提下,有效降低虚拟机迁移次数,进而降低数据中心的能耗(节能25%~30%).     

Development and validation of an LC–MS/MS method for the quantification of artificial sweeteners in human matrices

Artificial sweeteners are widely used as substitutes for sugar. The sweeteners are generally considered safe, however their whereabouts during pregnancy and lactation and the effect on child development are poorly explored. There is a need for new tools to measure these substances during pregnancy and lactation. Here, we describe the development and validation of a sensitive liquid chromatography–tandem mass spectrometry method for the simultaneous quantification of acesulfame, cyclamate, saccharin and sucralose in human plasma, umbilical cord blood, amniotic fluid and breast milk. The samples were prepared by protein precipitation and separated on a Luna Omega Polar C₁₈ column (2.1 × 50 mm, 1.6 μm). Electrospray ionization in negative mode and multiple reaction monitoring were used to monitor the ion transitions. The validated concentration ranges were from 1 to 500 ng/ml (10–500 ng/ml for sucralose). Interassay precisions were all ≤15% and the accuracies were within ±15%. Stability, linearity, dilution integrity, carryover and recovery were also examined and satisfied the validation criteria. Finally, this analytical method was successfully applied on spiked samples of plasma, umbilical cord blood, amniotic fluid and breast milk, proving its suitability for use in clinical studies on artificial sweeteners, including during pregnancy and lactation.     

Pyrimidoquinazolinophenanthroline Opens Next Chapter in Design of Bridging Ligands for Artificial Photosynthesis**

The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)₃]²⁺ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD⁺ to NADH was achieved, highlighting the potential of this system for photocatalytic applications.     

金属铁络合物光催化二氧化碳还原

二氧化碳(CO₂)光催化还原技术因兼具解决能源和全球变暖问题的潜力而受到关注。金属铁络合物作为分子型催化剂,具有价格低廉、量子效率高、结构可调控和选择性好等优势,表现出优异的CO₂光催化还原性能,成为CO₂光催化还原领域的研究热点。本文综述了近年来基于金属铁络合物光催化二氧化碳还原研究进展。介绍了铁金属络合物(如:铁卟啉、铁多吡啶、五齿铁配合物)CO₂均相光催化还原体系,总结了体系的构成以及作用机理等,着重关注了体系的催化效率和产物的选择性。此外,综述了以半导体纳米材料/量子点作为光敏剂,金属铁络合物作为催化剂的非均相催化体系的研究进展。最后,对该领域未来的研究方向和所面临的挑战做出展望。     

人工智能在锂离子电池研发中的应用

锂离子电池已成为解决现代社会储能问题的最佳解决方案之一。然而,电池材料和器件开发都是复杂的多变量问题,传统的依赖研究人员进行实验的试错法在电池性能提升方面遇到了瓶颈。人工智能（AI）具有强大的高速、海量数据处理能力,是上述突破研究瓶颈的最具潜力的技术。其中,机器学习 (ML) 算法在评估多维数据变量和集合之间的组合关联方面的独特优势有望帮助研究人员发现不同因素之间的相互作用规律并阐明材料合成和设备制造的机制。本综述总结了锂离子电池传统研究方法遇到的各种挑战,并详细介绍了人工智能在电池材料研究、电池器件设计与制造、材料与器件表征、电池循环寿命与安全性评估等方面的应用。最重要的是,我们介绍了AI和ML在电池研究中面临的挑战,并讨论了它们应用的缺点和前景。我们相信,未来实验科学家、数学建模专家和AI专家之间更紧密的合作将极大地促进AI和ML方法用以解决传统方法难以克服的电池和材料问题。     

Determination of Cytotoxic Activity of Sanguinaria canadensis Extracts against Human Melanoma Cells and Comparison of Their Cytotoxicity with Cytotoxicity of Some Anticancer Drugs

Melanoma is an enormous global health burden, and should be effectively addressed with better therapeutic strategies. Therefore, new therapeutic agents are needed for the management of this disease. The aim of this study was the investigation of cytotoxic activity of some isoquinoline alkaloid standards and extracts obtained from Sanguinaria canadensis—collected before, during, and after flowering—against three different human melanoma cells (A375, G361, SK-MEL-3). The cytotoxicity of these extracts was not previously tested on these melanoma cell lines. Determination of alkaloid contents was performed by HPLC-DAD using Polar RP column and mobile phase containing acetonitrile, water, and 1-butyl-3-methylimidazolium tetrafluoroborate. The cytotoxicity of alkaloid standards was investigated by determination of cell viability and calculation of IC₅₀ values. Significant differences were observed in the alkaloids content and cytotoxic activity of the extracts, depending on the season of collection of the plant material. In the Sanguinaria canadensis extracts high contents of sanguinarine (from 4.8543 to 9.5899 mg/g of dry plant material) and chelerythrine (from 42.7224 to 6.8722 mg/g of dry plant material) were found. For both of these alkaloids, very high cytotoxic activity against the tested cell lines were observed. The IC₅₀ values were in the range of 0.11–0.54 µg/mL for sanguinarine and 0.14 to 0.46 µg/mL for chelerythrine. IC₅₀ values obtained for Sanguinaria canadensis extracts against all tested cell lines were also very low (from 0.88 to 10.96 µg/mL). Cytotoxic activity of alkaloid standards and Sanguinaria canadensis extracts were compared with the cytotoxicity of anticancer drugs—etoposide, cisplatin, and hydroxyurea. In all cases except the one obtained for cisplatin against A375, which was similar to that obtained for Sanguinaria canadensis after flowering against the same cell line, IC₅₀ values obtained for anticancer drugs were higher than the IC₅₀ values obtained for sanguinarine, chelerythrine, and Sanguinaria canadensis extracts. Our results showed that Sanguinaria canadensis extracts and isoquinoline alkaloids, especially sanguinarine and chelerythrine, could be recommended for further in vivo experiments in order to confirm the possibility of their application in the treatment of human melanomas.     

遥感估算植被覆盖度的角度效应分析

植被覆盖度是植被在地面的垂直投影面积占统计区总面积的百分比.由于植被反射的二向性特性,不同角度估算的植被覆盖度原则上不可比,另外,不同观测角度对应像元不同的采样面积,对于非均一地表这种面积差异引起的角度效应也非常显著.本文除了考虑植被的二向性反射,还重点模拟分析了由于像元的采样面积差异引起的角度效应及其带来的植被覆盖度估算误差.模拟结果表明:相比天顶观测,在倾斜40°观测时,对于作物和裸土混合,由于面积误差带来的红光波段反射率差异已高达56%,同时引起的植被覆盖度估算误差达到23%,因此研究植被覆盖度的角度效应问题很有必要.