微波辅助萃取-气相色谱-负化学电离/电子轰击电离-飞行时间质谱法测定烟草中农药残留

建立了微波辅助萃取结合气相色谱-飞行时间质谱(GC-TOF MS)技术在负化学电离(NCI)源和电子轰击电离(EI)源两种模式下测定烟草中24种农药残留的分析方法。烟叶样品于100℃下用二氯甲烷-正己烷(3:1, v/v)混合溶剂微波萃取10 min,萃取液经弗罗里硅土固相萃取柱净化后进行检测分析。在NCI源和EI源质谱模式下,24种农药的线性关系均良好(r²>0.99),相对标准偏差分别小于8.6%和9.1%,定量限分别为0.3~6.9 μg/kg和10.2~44.9 μg/kg,加标回收率分别为75.2%~94.8%和75.0%~95.1%。比较两种离子源模式下的色谱图和质谱图,NCI源模式较EI源模式的选择性好、灵敏度高、基质干扰小、图谱简单易于解析,检出限低一个数量级以上,在分析低含量、复杂基质的样品时更具优势。     

金属锑基硫族团簇的合成、结构及电催化氧还原反应性能

为探索金属硫族团簇材料的多样性结构及其光电应用, 利用溶剂热法, 以含孤对电子的金属 Sb(Ⅲ)与硫元素采用不对称的配位几何方式结合, 合成了 Sb 基硫族团簇化合物[Sb₄S₅(S₃)]·C₅H₁₁N(1)和(C₅H₁₂N)₂[In₂Sb₂S₇] (2)。2 种化合物分别由{SbS₃}或{InS₄}配位单元之间以顶点共享的方式组合而成。电催化氧还原反应(ORR)研究表明, 化合物2 的极限电流密度和半波电位均高于化合物1, 表明其 ORR性能更好。Koutecky-Levich图分析表明, 由混合金属构筑而成的层状化合物2 的 ORR催化过程以四电子路径为主。     

双钻头打孔机作业的优化模型

对于双钻头打孔机的孔群加工问题分为两部分解决.首先建立刀具转换次数最少的优化模型.将钻头A和钻头B每阶段使用某一刀具的状态设为0-1变量建立模型,用LINGO程序求解.另外根据10种孔型所需刀具及加工次序,将整个双钻头打孔作业任务分成3个阶段,在每一阶段,以打孔个数较多的钻头刀具作为基准刀具,使用贪心算法遍历打孔;另一个刀具以两钻头距离大于3cm为约束,确定可行点集合,在可行点集合中制定最优打孔路线,进而可求打孔作业总时间,作业总成本.     

Decarboxylative Trifluoromethylating Reagent [Cu(O2CCF3)(phen)] and Difluorocarbene Precursor [Cu(phen)2][O2CCF2Cl]

This article describes the new economic decarboxylative trifluoromethylating reagent [Cu(phen)(O₂CCF₃)] ( 1 ; phen=1,10‐phenanthroline) and the efficient difluorocarbene precursor [Cu(phen)₂][O₂CCF₂Cl] ( 2 ). Treatment of copper tert‐butoxide with phen and subsequent addition of trifluoroacetic acid or chlorodifluoroacetic acid afforded air‐stable complexes 1 and 2 , respectively, which were characterized by X‐ray crystallography. The copper(I) ion in 1 is coordinated by a bidentate phen ligand, a monodentate trifluoroacetate group, and a molecule of CH₃CN in a distorted tetrahedral coordination geometry. The molecular structure of 2 adopts an ionic form that consists of a [Cu(phen)₂]⁺ cation and a chlorodifluoroacetate anion. Complex 1 reacted with a variety of aryl and heteroaryl halides to form trifluoromethyl (hetero)arenes in good yields. The corresponding Hammett plot exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest‐to‐excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper‐mediated formation of difluorocarbene and subsequent concerted addition of difluorocarbene to the phenol to form a three‐center transition state.     

Defining and using microbial spectral databases

This work shows how fingerprints of mass spectral patterns from microbial isolates are affected by variations in instrumental condition, by sample environment, and by sample handling factors. It describes a novel method by which pattern distortions can be mathematically corrected for variations in factors not amenable to experimental control. One uncontrollable variable is "between-batch" differences in culture media. Another, relevant for determination of noncultured extracts, is differences between the cells' environmental experience (e.g., starved environmental extracts versus cultured standards). The method suggests that, after a single growth cycle on a solid medium (perhaps, a selective one), pyrolysis MS spectra of microbial isolates can be algorithmically compensated and an unknown isolate identified using a spectral database defined by culture on a different (perhaps, nonselective) medium. This reduces identification time to as few as 24 h from sample collection. The concept also proposes a possible way to compensate certain noncultured, nonisolated samples (e.g., cells concentrated from urine or impacted from aerosol or semi-selectively extracted by immunoaffinity methods from heavily contaminated matrices) for identification within half an hour. Using the method, microbial mass spectra from different labs can be assembled into coherent databases similar to those routinely used to identify pure compounds. This type of data treatment is applicable for rapid detection in biowarfare and bioterror events as well as in forensic, research, and clinical laboratory contexts.     

Sm–Co and Nd–Fe–B thin films with perpendicular anisotropy for high-density magnetic recording media

Sm–Co and Nd–Fe-B thin films have been prepared by sputtering. Particular efforts are concentrated on the perpendicular texture growth of the films. The Sm–Co and Nd–Fe–B thin films with perpendicular magnetic anisotropy can be prepared on Cu and W underlayer, respectively. Those underlayers play an important role to prevent oxidation and improve crystal lattice orientation. Perpendicular coercivity and remanent squareness ratio are higher than 10 kOe and almost 1.0, respectively, in both films prepared under optimum conditions.     

Self-assembled L10 FePt thin films for high-density magnetic recording

A new technique, which utilizes the interlayer diffusion, for preparation of self-assembled nanodot magnetic structures has been proposed. L1₀-phase Pt/FeCu and Pt/FeAg films have been successfully synthesized by this technique. Both the coercivity of Pt/FeCu and Pt/FeAg films exhibited, respectively 4.1 and 8.0 kOe in perpendicular direction. Pt/Fe and Pt/FeAg films show positive values, while Pt/FeCu shows negative value in δm plot. The results indicate that the exchange coupling between the grains has been decoupled in the self-assembled nanodot structure in Pt/FeCu film.