Highly Sensitive Silver Nanorod Arrays for Rapid Surface Enhanced Raman Scattering Detection of Acetamiprid Pesticides

The determination of pesticide residue on agricultural products is increasingly important.Exposure to pesticides can cause severe acute reactions in humans, including aplastic anemia and leukemia.In this work, we developed a rapid and sensitive method to detect acetamiprid pesticide residue based on surface-enhanced Raman scattering.Silver nanorod (AgNR) arrays were fabricated by oblique angle deposition technology and were used as SERS substrates.Prior to detection, the AgNR arrays were cleaned with nitric acid solution or a mixture of methanol and acetone.Compared to the unwashed AgNR arrays, the AgNR arrays washed with methanol and acetone shows a signal enhancement 1000 times greater than the unwashed AgNR array due to the effective removal of the impurities on its surface.The limit of detection of acetamiprid was determined to be 0.05 mg/L.In addition, the molecular structure of acetamiprid was simulated and the corresponding vibration modes of the characteristic bands of acetamiprid were calculated by density function theory.To demonstrate its practical application, the AgNRs array substrates were applied successfully to the rapid identification of acetamiprid residue on a cucumber's surface.These results confirmed possibility of utilizing the AgNRs SERS substrates as a new method for highly sensitive pesticide residue detection.     

界面张力在基板诱导共混物分散相粒子粗化生长加速现象中的作用

通过相差显微镜和计算机图像处理来研究两相聚合物体系的粗化过程 .将具有不同聚比的乙烯 聚醋酸乙烯酯 (EVAc)共聚物与聚丙烯 (PP)共混 ,制备不同相界面张力的系列共混物薄膜 .观察了在玻璃基板的作用下 ,不同界面张力体系的分散相粒子粗化行为 ,发现界面张力在约 0 4 8·1 0 - 5N cm以上的体系中分散相粒子的粗化有明显的加速现象 ,粒子体积生长与时间关系的指数大于 1 0 ;而两相界面张力较低的情况下 ,选择具有不同表面极性的基板对同一体系试验 ,我们均未发现有粗化加速现象产生 ,且采用不同基板之间的试验结果差异很小 ,亦即当高分子共混物的相界面张力大于一定值时 ,仅与基板存在有关 ,粒子的粗化行为被加速     

Synthesis of the C23-C32 fragment of spirangien

The synthesis of the C23-C32 fragment of spirangien A is reported using Evans’ alkylation, Evans-Metternich aldol reaction and a substrate controlled stereoselective reduction.     

底物与条件控制苯胺与丙烯醛/烯酮的化学选择性偶联反应（英文）

金属催化碳氢键活化已经成为制备高附加值有机化合物的一类高效方法,由于碳氢键广泛存在,所以对它们进行化学、区域、立体选择性的活化作为一大挑战已经被人们日益所关注,然而氧化还原选择性控制的研究十分少见.通常而言,有机氧化还原反应定义为得失氢氧原子,例如消除氢负离子为氧化反应,而失去一个质子则为中性反应.在已有的研究中单独的氧化、还原反应已经被广泛研究,而且被大量用于医药合成、精细化工品的制备以及各类先进材料的生成.但是在同一反应体系下同时调控三种氧化态的研究目前未见报道,因此发展这类选择性控制的反应十分重要.我们此前已经实现了Rh(Ⅲ)/Ir(Ⅲ)催化苯胺和烯酮还原偶联合成四氢喹啉和高烯丙基苯胺两种产物,同时也能得到中性的1,2-二氢喹啉产物.在此工作的基础上,我们希望能够进一步实现相同反应组分的氧化偶联.为此,我们仔细分析取代的苯胺与烯酮的可能反应路径,发现可能的关键物种G—含有Rh(Ⅲ)的六元杂环中间体有望实现这类氧化过程,当用丙烯醛做底物时,物种G有可能实现円-氢消除得到氧化的二氢喹啉酮和Cp*RhXH,通常Cp*RhXH很容易发生自身的还原消除得到Cp*Rh(Ⅰ)使反应终止,但是,丙烯醛的存在有可能重新活化Cp*RhXH使得催化循环一直进行下去.另一种情况是中间体G发生质子解然后脱水得到亚胺物种,亚胺很容易被亲核试剂进攻得到中性的氮杂缩醛类产物.当然,外加银盐氧化剂还有可能得到另一种氧化型的喹啉盐.基于这种思路,我们发展了Rh(Ⅲ)-催化碳氢活化N-取代的苯胺与丙烯醛/烯酮的选择性偶联反应,反应可以化学选择性专一地制备三类不同的杂环化合物.当氮-吡啶基苯胺与丙烯醛反应时,反应类型为氧化过程,经历了转移氢化的过程,其中烯醛为主要的氢受体,得到二氢喹啉酮产物;如果定位基换成嘧啶时,在相似的反应条件下,反应类型为氧化还原中性过程,生成氮杂缩醛醚类产物;氮-吡啶基苯胺和烯酮反应在AgBF_4的氧化作用下同样可以发生氧化反应得到喹啉盐类化合物.至此,我们实现了导向基团对氧化反应和中性反应的控制,氧化剂的种类对反应路径的改变.反应的底物范围广泛,官能团容忍性好,我们期待这类氧化还原多样性的杂环合成方法能促进更多新颖反应的发现.     

玻璃基板作用下高分子共混物薄膜相形态发展过程

研究了玻璃基板作用下极性高聚物为低组分的共混物薄膜在退火条件下相形态的发展过程 .选用聚苯乙烯 (PS) 聚甲基丙烯酸甲酯 (PMMA)与聚苯乙烯 (PS) 聚ε 己内酯 (PCL)两个体系 ,在玻璃基板上Spin Coating成膜后退火 .由于共混物薄膜中极性相对较大的高聚物组分 (PMMA和PCL)相对于极性较小的PS组分对玻璃基板具有更好的润湿性 ,所以在上述的两个共混薄膜体系中其相形态分别显示PMMA和PCL在低组分比例下最终发展成为连续相 .利用扫描电镜以及元素分析很好地验证了以上的结论 ,并且对其机理进行了解释 .此外 ,改变PS的分子量与PCL共混 ,研究了组分粘度对薄膜相形态发展的影响 .结果表明 ,PS组分粘度越大 ,共混物薄膜相结构发展速度越慢     

Dependence of magnetic characteristics on sputtering-power and substrate-temperature in amorphous Tb40(FeCoV)60 films

The amorphous Tb₄₀(Fe₄₉Co₄₉V₂)₆₀ films were deposited at different sputtering powers and substrate temperatures. The microstructural and magnetic characteristics were investigated by means of field emission scan electron microscope, magnetic force microscope and vibrating sample magnetometer. Our results show that with increasing sputtering power, out-of-plane coercivity decreases monotonically while saturation magnetization has a maximum value of 231 kA/m for the sample prepared at 50 W. The as-deposited alloy films are amorphous, whereas the coercivity and saturation magnetization are strongly dependent on the substrate temperature. An out-of-plane hysteresis loop with coercivity below 22 mT and saturation magnetization over 290 kA/m is obtained combining dc power and substrate temperature. The dominant mechanism of room temperature coercivity appears to be domain wall pinning, rather than nucleation under all conditions measured. The variation of saturation magnetization is similar to that of perpendicular magnetic anisotropy with either sputtering power or substrate temperature according to the difference of magnetic domain structure.     

Determination of Attogram Quantities of Silver via Quenching of the Solid Substrate Room-Temperature Phosphorescence of Rhodamine B Based on the Catalysis of its Oxidation by Potassium Persulfate

A new method of SS-RTP for the determination of trace silver has been established. This method is based on the fact that Ag⁺, when activated by ,-bipyridyl (bipy) in a media of HAc–NaAc (pH=4.9), can catalyze the reaction of Rhodamine B (RhoB) oxidized by K₂S₂O₈, thus causing the Solid Substrate Room-Temperature Phosphorescence (SS-RTP) of RhoB to be quenched. The activating efficiency of bipy is 6.7 times higher than that of o-phenanthroline (phen). The reduction of the phosphorescence intensity (I_p) of RhoB is directly proportional to the concentration of Ag⁺ ions in the range of 1.6016.0agspot^–1 (0.40µLspot^–1). The regression equation of the working curve can be expressed as I_p=18.78+5.100m_Ag+ (agspot^–1) (r=0.9994, n=6), the detection limit is 0.28agspot^–1. This rapid, accurate and sensitive method has been successfully applied to the determination of trace silver in tea and human hair samples, and the results agree well with the Atomic Absorption Spectroscopy (AAS) method. The mechanism of the catalyzing reaction is also discussed.     

DMF竞争性抑制大豆脂氧酶好氧催化及其松弛底物抑制的综合作用

在大豆脂氧酶催化亚油酸的氧化反应中加入溶剂二甲基甲酰胺DMF(lgP为-1.01)可将底物亚油酸浓度提升到232 mmol/L而不产生底物抑制作用, 并使平衡产率从38.93%提高到66.09%. 在有底物存在时, 质量分数为5%的DMF基本不影响酶活; 此时体系具有最大的Kss与Ki值, 表明5%DMF对底物抑制作用的松弛效应最强, 而对酶的抑制作用最小.     

Acyclic phenylalkanediols as substrates for the study of enzyme recognition. Regioselective acylation by porcine pancreatic lipase: a structural hypothesis for the enzymatic selectivity

The regioselective acylation of phenylalkanediols catalysed by porcine pancreatic lipase (PPL) was the reaction used for modelling different areas in the active site of the enzyme. With this aim, different racemic or prochiral (1,n)-diols, with n ranging from 2 to 6 were resolved via transesterification with vinyl acetate, and the results were explained according to microcrystalline enzyme structure. Thus, we describe a logical model for explaining the enzyme regio and stereoselectivity, based on three residues of the active site (Ser153, Phe216 and His264) which turned out to be crucial for the substrate binding and transformation.     

Development of a long-term stable organic membrane-based thin-film microsensor using new-type substrate surface treatment

A novel long lifetime organic membrane-based thin-film Cu(II) microsensor has been elaborated. The advantages of the suggested microsensor include: excellent stability, long lifetime, and reasonable good selectivity. The significant improvements of the lifetime (>4 months) of the organic membrane-based thin-film microsensors have been realized for the first time using new-type electrodeposition treatment of the solid-state substrate surface in combination with a new nebulization method for applying the organic membrane coating mixture on the thin-film gold substrate. The electrochemical behavior of the thin-film microsensor in terms of ionic sensitivity, limit of detection, the effect of the pH, dynamic response time, Nernstian response interval, selectivity coefficients and lifetime has been evaluated. The results are compared to those obtained with the conventional ion-selective and coated graphite rod macroelectrodes prepared with the same ionophore. The reliability of the suggested thin-film microsensor with the low cost of its microfabrication makes it promising for the miniaturized application.