高效液相色谱柱后衍生法测定谷物中9种氨基甲酸酯类农药及3种代谢物残留量

研究了用ＷａｔｅｒｓＣａｒｂａｍａｔｅ分析系统柱后衍生化荧光检测器测定谷物中氨基甲酸酯类农药残留量的方法。用ＷａｔｅｒｓＣａｒｂａｍａｔｅＡｎａｌｙｓｉｓＣｏｌｕｍｎ对９种农药和３种代谢产物进行分离,碱液水解,ＯＰＡ柱后衍生,有很好的选择性、重现性和灵敏度,最低检出限为５μｇ／ｋｇ。     

过硫酸钾引发苯乙烯微乳液聚合

以具有Ｙ型结构的乳化剂ＨＯＡ制备苯乙烯微乳液，能有效提高体系中单体浓度和单体对乳化剂的比例，用过硫酸眼具有苯乙烯含量较高的微乳液聚合，记录聚合速率随转化率的变化，观测到了聚合恒速期的存在，恒速期随单体浓度减小，过硫酸钾浓度增加及乳化剂浓度增加而缩短，还研究了聚合动力学，探讨了微乳液聚合的机理。     

乳腺癌术前灰阶超声与彩色多普勒超声联合应用对预后的预测价值

目的探究乳腺癌术前灰阶超声与彩色多普勒超声联合应用对预后的预测价值。方法选取温州医科大学附属第一医院2013年5月—2015年5月期间收治的乳腺癌患者83例,治疗前均行灰阶超声与彩色多普勒超声检查,分析患者超声检查结果、临床征象与术后随访2年期间患者预后的关系,从而分析术前灰阶超声与彩色多普勒超声联合应用对乳腺癌患者预后的预测价值。结果乳腺癌肿块边界清晰、边界不清晰、边界恶性晕的患者2年无瘤生存率依次降低,边界恶性晕与边界不清晰患者死亡率均显著高于边界清晰患者(P0.05);肿瘤≥2 cm患者2年无瘤生存率显著低于2 cm患者;淋巴结转移患者2年无瘤生存率显著低于无转移患者(P0.05);血流分级Ⅱ级患者2年无瘤生存率明显低于0级(P0.05),Ⅲ级患者2年无瘤生存率显著低于0级和Ⅰ级(P0.05)。结论乳腺癌患者术前联合应用灰阶超声与彩色多普勒超声检查可确定肿瘤边界、大小及淋巴转移等征象,其与患者无瘤生存率、死亡率等预后指标密切相关,可作为预测乳腺癌患者预后的重要方法。     

毛细管气相色谱法测定保健食品、中药材中的五氯硝基苯残留

建立保健食品中五氯硝基苯残留量的毛细管气相色谱检测方法.样品经正己烷超声提取,硫酸净化,采用分流不分流进样方式,用弱极性毛细柱程序升温分离,电子俘获检测器检测,外标法定量.五氯硝基苯浓度在0.005～0.10 μg/mL范围内与峰面积线性相关,线性相关系数r=0.9996,方法检出限为0.0006 mg/kg,0.02...     

N2分子在强激光场中的场致电离

研究了在强激光脉冲中各种不同取向的N2分子发生场致电离的电离几率和表观电离效率.用量子化学方法计算了N2+分子离子在各种不同取向上的势能曲线,然后用传递矩阵方法得到了N2分子在不同方向上的电离几率,经过角度平均之后得到了各种取向的所有N2分子的总电离几率,并对计算结果进行了激光时间和空间修正.用800nm和70fs的激光脉冲对N2分子进行了在强激光场中的电离实验,得到了N2分子电离后产生的电子的角度分布图和电离几率随激光功率密度变化的关系曲线.实验结果和理论计算结果符合得很好.     

毛细管柱气相色谱法测定人血清中有机氯农药残留量

提出了毛细管气相色谱测定人血清中有机氯农药残留量的方法。利用正己烷超声提取人血清样品中有机氯农药六六六和滴滴涕,所得萃取液作气相色谱测定,用甲酸及浓硫酸净化、磺化处理后,电子捕获检测器检测。在优化的试验条件下,8种有机氯农药同分异构化合物组分在20 min内能够很好的分离,其质量浓度与色谱峰面积在0.4～10μg·L~(-1)浓度范围内呈线性关系,检出限(3S/N)在0.07～0.30μg·L~(-1)之间。方法的日内的相对标准偏差为2.9%～5.4%,日间的相对标准偏差为4.5%～8.9%。方法的加标回收率在81.5%～117.6%范围。     

Construction of 3D hierarchical SnO2 microspheres from porous nanosheets towards NO decomposition

Three-dimensional (3D) hierarchical architectures are currently attracting worldwide interest owing to their fascinating morphology-dependent properties and potential applications. Herein we constructed SnO₂ microspheres with 3D hierarchical flower-like architectures self-assembled with porous SnS₂ nanosheets by a facile hydrothermal method with subsequent calcination. The chemical and physical properties as well as photocatalytic application of SnO₂ microspheres were investigated. The size and morphology were examined with scanning electron microscopy and transmission electron microscopy. The phase and crystalline structure were determined with powder X-ray diffraction. The UV–Vis absorption property was determined with UV–Vis diffuse reflectance. The photocatalytic activities were evaluated with nitrogen monoxide (NO) decomposition under UV–Vis light irradiation. The effects of calcination temperature on morphology and NO decomposition were also studied.     

Kinetics of Reaction of Bromo-epoxy Resin with Oleic Acid catalyzed by Dimethyl benzyl amine

The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism     

Kinetics of Reaction Bisphenol-S Epoxy Resin with Methylacrylic Acid

The reaction kinetics of bisphenol-S epoxy resin with methyl-acrylic acid in the presence of quaternary ammonium salt catalyst was studied. The reaction rate constants at different temperatures were determined. The reaction is first order with respect to epoxy group, zero order with respect to methylacrylic acid and 0.71 order with respect to quaternary ammonium salt catalyst, respectively. The mechanism of this reaction was discussed.     

Catalytic effect of copper on the hexacyanoferrate(III)-cyanide redox reaction-I The uncatalysed and catalysed reactions

A kinetic study of the hexacyanoferrate(III)-cyanide redox reaction has been made in connection with development of a new catalytic method for copper. The reaction kinetics change with time from first- to second-order dependence with respect to hexacyanoferrate(III). The reaction is nearly inverse first-order with respect to hexacyanoferrate(II) and first-order with respect to cyanide. The reaction shows a strong positive primary salt effect, but a very small increase in the reaction rate with temperature is found. A parallel reaction proceeds with a first-order dependence with respect to hydroxide. A tentative mechanism is proposed for the first reaction, involving the formation of cyanogen radicals. The second reaction corresponds to the well-known decomposition of hexacyanoferrate(III) in alkaline medium. The catalysed reaction exhibits similar kinetics with respect to hexacyanoferrate(II) and (III) but is zero-order with respect to cyanide and hydroxide and first-order with respect to catalyst. The proposed mechanism involves two consecutive interactions of the hexacyanoferrate(III) with copper(I) and with copper(II) cyanide complexes respectively, followed by a 2-electron oxidation of a co-ordinatively bridging cyanide group.     

痤疮患者血清锌水平及加锌治疗效果

测定了60例寻常痤疮患者和60例健康正常人血清锌浓度,结果表明,寻常痤疮患者血清中锌的浓度明显低于正常人水平。对40例寻常痤疮患者在按常规治疗的同时给予口服硫酸锌治疗一个月,加锌治疗组的治疗有效率为90％,明显高于仅按常规治疗组的有效率（75％）。     

Bioconvective Homann flow of tangent hyperbolic nanofluid due to spiraling disk with convective and zero mas flux constraints

The phenomenon of bioconvection in nanomaterials presents novel applications in the biotechnology, biofuels, enzymes, biomedical engineering and energy systems. Current exploration explores the applications of bioconvection in Homann flow of nanofluid due to spiraling of disk theoretically. The generalized model namely tangent hyperbolic fluid is used to predicts the rheological and thermal impact. The stability of nanofluid is ensured with interaction of motile microorganisms. The Boungrino nanofluid model with thermophoresis and Brownian motion features is used to perform the analysis The thermal distribution of nanofluids is proceeded by utilizing the zero mass thermal constraints. The similarity variables are introduced in order to estimating the dimensionless formulation. The Keller Box method with higher efficiency is imposed with implicit finite difference numerical algorithm. The main observations reveal that with enhancing the radial velocity and azimuthal velocity decreases with increasing sparling angle. For highly viscous case, a decrement in the azimuthal velocity has been observed.     

The dispersion polymerization of unsaturated monomers initiated by the macromonomeric initiator

The dispersion polymerizations of styrene (St) and methyl methacrylate (MMA) initiated by poly(oxyethylene) macroinimer (PEO-MIM) in ethanol/water were investigated at 50, 60 and 80°C. The polymerisation rate vs. conversion dependence was described by with a maxim at the beginning of polymerisation. Polymerization was faster with MMA than with St. The limiting conversion was inversely proportional to temperature and was much more pronounced with St. The rate of polymerization increased with temperature. The overall initial activation energy increased with conversion and reached value ca. 25 kJ.mol⁻¹ for MMA and 50 kJ.mol⁻¹ for styrene at ca. 60% conversion. The particle size was observed to decrease with increasing the macroinimer concentration. The polymer dispersions were unstable and a large amount of coagulum appeared during the polymerisation especially in the styrene-containing reaction system.     

液液分散微萃取/GC-MS法测定婴幼儿一次性用品中5种致敏原物质

建立了同时测定婴幼儿一次性用品中5种致敏原物质(柠檬烯、沉香醇、柠檬醛、乙酸苄酯和肉桂醛)的分散液液微萃取/气相色谱-质谱(DLLME/GC-MS)检测方法。样品经乙腈浸泡提取、水分散和盐析后用四氯化碳萃取浓缩,采用GC-MS测定,外标法定量。目标物在0.01~10 mg/kg范围内线性关系良好,相关系数在0.99以上。方法检出限为0.01~0.1 mg/kg。加标回收率为78.7%~106%,相对标准偏差为2.4%~11.3%。该方法前处理简单,灵敏度高,可满足纸尿裤、婴儿专用湿巾等一次性婴幼儿用品中5种致敏原物质的检测要求。     

Oxidative fluorination of P-H bonds in the coordination sphere of tungsten

The reaction of triphenylcarbenium tetrafluoroborate with primary or secondary phosphine pentacarbonyltungsten complexes gives the corresponding mono or diflurorophosphine complexes. The mechanism probably involves transient phosphenium complexes. The reaction is compatible with P-O but not with P-N bonds.     

配合物3AgNO3·2[C3H7S(CH2)2SC3H7]的晶体结构

本文测定了配合物3AgNO3·2BPrTE的晶体结构, 该晶体属三斜晶系, 空间各为PI,晶胞参数: a=0.8945(1), b=1.2355(2), c=1.3572(5)nm; α=98.69(2)°, β=92.74(2)°, γ=90.45(1)°; V=1.480nm^3; Z=2, 分子中三个Ag原子的配位数均为5, 但它们的配位多面体各不相同, Ag(3)为四方锥体, Ag(2)为三角双锥, Ag(1)则介于两者之间, NO3^-以单齿、不等长双齿和等长双齿两种形式配位于Ag原子。配体BPrTE也具有两种构象, 反式构象具有C1对称性, 并以两种形式和Ag原子配位, 偏转式构象不具有C4对称性, 与Ag原子形成五元螯合环, 分子为三维无限长链结构。     

铁铝复合柱撑粘土的制备、酸性与表征(II)

用UV-DRS、Mossbauer谱、XPS、程序升温还原(TPR)等技术对新型铁铝复合柱撑粘土(FeAl-PILC)进行了表征, 用IR、吡啶吸附IR、正丁胺吸附-TPD手段, 考察了其表面羟基和酸性. 结果表明, 层间柱铁铝聚合物中铁-铝间存在着相互作用. Fe/Al比<0.5时, 相互作用强, 铁的分散度大, 难还原. Fe/Al≥0.5时, 相互作用较弱, 易还原, 焙烧后易生成α-Fe_2O_3s. 随Fe/Al的增加, 其表面酸性逐渐减弱.     

Ca2+、La3+及Eu3+对NaDC胶团的作用

在水溶液中将脱氧胆酸钠（ＮａＤＣ）分别与ＣａＣＬ２、ＥｕＣｌ３及ＬａＣｌ３反应,改变反应物浓度和配比,合成了系列脱氧胆酸络全物。利用红外光谱（ＦＴＩＲ）、元素分析、ＩＣＰ分析及Ｘ身材线粉末衍射谱,对它们的组成和结构进行了研究。结果表明：水溶液中ＣａＣｌ２与ＮａＤＣ的反应不是简单离子间的反应,改变其反应物浓度和配比,生成组成和结构不同的络合物;而ＬｎＣｌ３与ＮａＤＣ反应时,反应物浓度和配比的改变不影     

可聚合二苯甲酮类光引发剂的合成及其光聚合性能研究

以4-(2,3-环氧丙氧基)二苯甲酮(EBP)和丙烯酸为原料,通过开环反应合成了含有不饱和双键的可聚合光引发剂4-(丙烯酸-2-羟基丙酯-3-氧基)二苯甲酮(AEBP).采用红外光谱(FT-IR)、核磁共振氢谱(¹HNMR)对其结构进行表征,利用紫外吸收光谱对AEBP的紫外吸收波长进行表征,通过实时红外(RT-IR)研究了AEBP引发丙烯酸酯单体的光聚合动力学.采用萃取法对比了BP与AEBP引发固化体系后的迁移性.结果表明,随AEBP浓度增加,单体最终转化率增加;当助引发剂N,N-二甲氨基苯甲酸-乙酯(EDAB)浓度为1.2%时,单体最终双键转化率最高;AEBP对双官能度单体的引发效率较之三官能度单体的好;聚合速率随光照强度的增强而变快;固化后AEBP的迁移性比传统的BP大大降低.     

The influence of the preliminary adsorption of water on the adsorption of organic solvent vapors on fullerene materials

The preliminary adsorption of water considerably decreased the sorption capacity of fullerene-containing materials with respect to benzene. The effect grew stronger as the content of fullerenes in the adsorbent increased. The possibility of increasing adsorption capacity by treatment with water was studied. The dependence of the sorption capacity of fullerene materials with respect to benzene on the relative water vapor pressure and the sorption capacity with respect to water at the preadsorption stage was determined.