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81.
《Electroanalysis》2006,18(23):2305-2313
The multiple square‐wave voltammetry (MSWV) allied to gold microelectrode (Au‐ME) was used to establish an electroanalytical procedure for the determination of the paraquat and diquat pesticides in river sediment samples. For both pesticides, two reduction peaks, at around ?0.70 V (peak 1) and around ?1.00 V vs. Ag/AgCl 3.00 mol L?1 (peak 2), with profile of the totally reversible redox process, were observed. The experimental and voltammetric conditions showed that the best conditions to reduce paraquat and diquat were a pH of 6.0, a frequency of 250 s?1, a scan increment 2 mV, a square‐wave amplitude of 50 mV and pulse number of 8 pulses of potential in each step of staircase of potential. Under such conditions, the detection limit of 0.044 μg L?1 (0.044 ppb) and 0.360 μg L?1 (0.360 ppb ) for peak 1 and peak 2 of paraquat and 0.159 μg L?1 (0.159 ppb) and 0.533 μg L?1 (0.533 ppb) for peak 1 and peak 2 of diquat, respectively, were obtained. These results are an order of magnitude of about two less than those obtained and published in the literature. Also, the electroanalytical procedure proposed was applied for the determination of adsorption isotherms of pesticides on river sediments samples collected from Mogi‐Guaçu River in Sao Paulo State, Brazil. The experimental data were fitted using the Langmuir and Freundlich isotherms models; and the results indicated low intensities of adsorption process of the pesticides in the samples employed with distribution coefficients (Kd) lower 5.0, and paraquat showed slightly higher affinity than diquat in the sediments. The increase in organic matter and organic carbon leads to an increase in the Kd values, and consequently an increase in the organic matter constant (KOM) organic carbon constant (KOC) values. All results demonstrated that isotherms “L” type in the Giles classification were obtained, indicating that sediments have a medium affinity for the pesticides, and no strong competition from the solvent used (in this case Na2SO4) for adsorption sites occurs. 相似文献
82.
Based on the group theory analysis and quantum chemical calculations within the framework of SW X α method (in relativistic approximation for core electrons and non-relativistic for valence ones), the existence possibility of square planar complexes [M4C] and [M4C]2? (M = Al, Ga, In, Tl, Sc, and Y) in gas phase has been shown. The extraction of Kt2[M4C] square planar complexes of carbon in the crystal state is possible too. A high stability of these complexes, in comparison with usual tetrahedral, is achieved due to the formation of five-and four-center bonds (bonds M-M and M-C). 相似文献
83.
Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter)
in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other
solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried
film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were
ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic
solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic
and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface
tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling
points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics
of colloidal particles in the drying dissipative pattern formation. 相似文献
84.
据Mahlanobis距离判别法,利用计算机多元统计判别程序,对14例甲亢思者和21例健康人的血清中锌、铁、铜、锰、镁和锶等元素浓度差异进行分类判别研究。选择锌、铁、钙、锶作判别特征参量时,患者和健康人的分类准确率为100%,服碘前与服碘后的甲亢患者分类准确率为92.7%,分类研究指出,甲亢患者血清中的铁和锶浓度高于健康人,经服碘治疗后,患者血清中上述元素浓度降低与健康人相近。 相似文献
85.
导数阴极溶出方波伏安法测定卡那霉素注射液含量 总被引:2,自引:0,他引:2
研究了汞 卡那霉素络合物的电化学行为 ,并建立了导数阴极溶出方波伏安法测定卡那霉素注射液含量的方法。在 pH 4 .7的HOAc NaOAc缓冲溶液中 ,在约 0 .12 6V (vs.SCE)处出现一个汞 卡那霉素络合物的还原峰 ,卡那霉素的浓度在 0 .0 2~ 1.5mg·ml- 1之间与导数方波伏安图的峰高存在良好的线性关系 ,回归方程ip(10 - 4A) =3.6C(mg·ml- 1) + 0 .4 6 ,相关系数为 0 .992 0。方法简便、灵敏、准确 ,可用于卡那霉素注射液含量测定 相似文献
86.
傅里叶变换近红外光谱法测定大麦中蛋白质、淀粉和赖氨酸含量 总被引:13,自引:0,他引:13
采用傅里叶变换近红外光谱法测定大麦中蛋白质、淀粉、赖氨酸的含量,并用光谱影响值法(leverage)对异常值进行判断和处理。蛋白质、淀粉和赖氨酸含量近红外光谱分析模型的测定系数R。分别为0.985、0.973和0.978;检验集的化学值与模型预测值的相关系数r分别为0.9853、0.9644和0.9172,分析模型的预测相对标准偏差RSD分别为4.0%、2.4%和5.4%,该结果可替代经典分析方法,满足农产品快速分析的需要。 相似文献
87.
近红外光谱-径向基神经网络在异烟肼片无损定量分析中的应用 总被引:1,自引:1,他引:1
应用异烟肼片粉末的近红外漫反射光谱数据分别结合偏最小二乘法(PLS)和径向基神经网络(RBFNN)建立定量分析模型,并用所建模型对预测集样品进行了预测,结果表明:应用RBFNN所建立的定量分析模型优于PLS模型,相关系数(r)值由0.99593提高到0.99734,交互验证均方根误差(RMSECV)值由0.00523下降到0.00423,预测均方根误差(RMSEP)值由0.00614下降到0.00501。 相似文献
88.
用P(SR)Cl_2和P(SR′)_3作n-酸配体,分别与Fe_3(CO)_9(μ_3-S)_2进行取代反应,得到6种新的一取代产物Fe_3(CO)_8(μ_3-S)_2L和3种新的二取代产物Fe_3(CO)_7(μ_3-S)_2L_2,并对它们进行了IR、~1H NMR和MS表征,测定了其中一种取代物Fe_3(CO)_8(μ_3-S)_2[P(SC_6H_5)Cl_2]的分子和晶体结构。 相似文献
89.
Cobas JC Constantino-Castillo V Martín-Pastor M del Río-Portilla F 《Magnetic resonance in chemistry : MRC》2005,43(10):843-848
(1)H NMR scalar coupling constants are a rich source of information on molecular structure, but their extraction from spectra can be less than straightforward. Previous approaches to J extraction include methods proposed by Hoye, Golotvin, and the 'modified J-doubling' method. Here we describe the ACCA method, currently implemented in the NMR package MestReC, which allows a high degree of automation in the extraction of coupling patterns even in the case of complex multiplets with sublinewidth splitting. The new approach is illustrated by application to strychnine, for which it has detected previously unreported couplings. 相似文献
90.
Wilfried A. Knig Detlef Icheln Torsten Runge Ingo Pforr Adolf Krebs 《Journal of separation science》1990,13(10):702-707
Transferring the site of specific substitution of dipentylated cyclodextrins with methyl or acyl residues from the secondary 3-hydroxyl group to the primary 6-hydroxyl group was expected to provide new information on the mechanism of chiral recognition. The 3-position points towards and the 6-position points away from the cyclodextrin cavity which via inclusion complex formation is supposed to play a major role in chiral separation. The “inverse” 6-O-acyl-2,3-di-O-pentyl-cyclodextrins displayed almost no enantioselectivity but the corresponding 6-O-methyl derivatives are a versatile supplement to the chiral capillary GC phases nowadays available. Among the compounds that could be enantiomerically resolved are alcohols, amino acids, alkyl halides, bicyclic ethers, acetals, olefins, other hydrocarbons and chiral pharmaceuticals. 相似文献