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51.
ICP-AES中内标法的应用研究 Ⅲ.用内标法校正基体干扰 总被引:1,自引:0,他引:1
通过观测基体对分析元素发射强度的干扰情况,分析干扰机制,从而确定用来校正基体干扰的内标元素与分析元素的匹配条件。实验结果表明,只要选择合适的内标元素,可以校正基体干扰。 相似文献
52.
J. L. Martínez Vidal A. Garrido Frenich T. López López I. Martínez Salvador L. Hajjaj el Hassani M. Hassan Benajiba 《Chromatographia》2005,61(3-4):127-131
An analytical method for determining residues of twenty pesticides by liquid chromatography (LC) coupled to electrospray ionisation (ESI) tandem mass spectrometry (MS-MS) in eight commodities, cucumber, tomato, pepper, green bean, eggplant, zucchini, melon and watermelon, has been developed and validated. On one hand, calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract of each target matrix. On the other hand, calibration curves and recoveries for each commodity were compared. Cucumber was selected as potential reference matrix for the target vegetables. 相似文献
53.
肿瘤的生长依赖于血管的生成,新生血管不仅为肿瘤生长提供必需的营养物质,而且为肿瘤细胞扩散提供了重要的途径。1997年哈佛大学的O'Reilly等发现了一种内源性新血管生成抑制因子内皮抑素(Endoscatin),显示出特异抑制激活的血管内皮细胞增殖和肿瘤新血管生成的生物学活性,其抗肿瘤作用具有高效、低毒、无耐药性的优点。目前,内皮抑素的研究引起了国内外广泛的兴趣,在美国已进行以安全性为目的的I期临床实验,国内也有多家公司对内皮抑素进行了抗肿瘤研究并申报一类新药。内皮抑素有望成为医治肿瘤而又没有化疗和放疗的毒副作用的一种新的治疗方法,但是否能作为药物应用于临床,尚需对内皮抑素的结构特点及抑制肿瘤和内皮细胞的作用机制等方面进行许多深入的研究。 相似文献
54.
Matrix isolation infrared studies of complexes formed between substituted phenols and trimethylamine
Infrared spectroscopy and matrix isolation technique have been used to study the 1 : 1 complexes formed between 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) or 2-chloro-4,6-dinitrophenol (CNP) and trimethylamine (TMA) isolated in solid argon. The results were analyzed in relation to the type of complex formed. Depending on the proton-donor ability of the phenol three different types of hydrogen bonded complexes have been identified in argon matrices. The weakest phenol in the series, TCP (pKa = 6.72), forms a strong molecular hydrogen bonded complex with TMA as indicated by the broad ν(OHN) absorption with a maximum at 2490 cm−1 and a band at 811 cm−1 due to the νs(C3N) mode of the perturbed amine. The strongest phenol, CNP (pKa = 2.01), interacts with TMA in an argon matrix to form ionic complex with the proton transferred to the base molecule. This is evidenced by the presence of the ν(NH+---O−) absorption between 3000−1800 cm−1, by the νas(C3N+) and νs(C3N+) absorptions due to the protonated amine and by numerous product bands due to the relatively strongly perturbed modes of the phenol ring. The interaction between TMA and a phenol of intermediate strength, PCP (pKa = 4.74), in solid argon probably leads to the formation of two types of hydrogen bonded complexes: an ionic complex with the proton transferred to the amine molecule and a pseudosymmetric one with the proton more or less equally shared between the phenol and amine molecules. In this case the protonic absorption consists of two broad features situated in the 3000–1600 cm−1 and 950–400 cm−1 regions due to the ν(NH+O−) and ν(OHN) modes, respectively. 相似文献
55.
The use of a so-called trihedral and a T-shaped cross-flow pneumatic nebulizer with dual solution loading for inductively coupled plasma optical emission spectrometry has been studied. By these devices analyte clouds from two solutions can be mixed during the aerosol generation step. For both nebulizers the correction of matrix effects using internal standardization and standard addition calibration in an on-line way was investigated and compared to elemental determinations using a conventional cross-flow nebulizer and calibration with synthetic standard solutions without matrix matching. A significant improvement of accuracy, both for calibration with internal standardization and standard addition, was obtained in the case of four synthetic solutions containing each 40 mmol L− 1 Na, K, Rb and Ba as matrix elements and 300 μg L− 1 Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb as analytes. Calibration by standard addition in the case of dual solution loading has been shown to be very useful in the determination of elements at minor and trace levels in steel and alumina reference materials. The results of analysis for minor concentrations of Cr, Cu and Ni in steel as well as for Ca, Fe, Ga, Li, Mg, Mn, Na, Si and Zn in alumina powder certified reference materials subsequent to sample dissolution were found to be in good agreement with the certificates. Limits of detection were found to be only slightly above those for a conventional cross-flow nebulizer and a precision better than 3% was realized with both novel nebulizers. 相似文献
56.
Non-negative matrix factorization (NMF), with the constraints of non-negativity, has been recently proposed for multi-variate data analysis. Because it allows only additive, not subtractive, combinations of the original data, NMF is capable of producing region or parts-based representation of objects. It has been used for image analysis and text processing. Unlike PCA, the resolutions of NMF are non-negative and can be easily interpreted and understood directly. Due to multiple solutions, the original algorithm of NMF [D.D. Lee, H.S. Seung, Nature 401 (1999) 788] is not suitable for resolving chemical mixed signals. In reality, NMF has never been applied to resolving chemical mixed signals. It must be modified according to the characteristics of the chemical signals, such as smoothness of spectra, unimodality of chromatograms, sparseness of mass spectra, etc. We have used the modified NMF algorithm to narrow the feasible solution region for resolving chemical signals, and found that it could produce reasonable and acceptable results for certain experimental errors, especially for overlapping chromatograms and sparse mass spectra. Simulated two-dimensional (2-D) data and real GUJINGGONG alcohol liquor GC-MS data have been resolved soundly by NMF technique. Butyl caproate and its isomeric compound (butyric acid, hexyl ester) have been identified from the overlapping spectra. The result of NMF is preferable to that of Heuristic evolving latent projections (HELP). It shows that NMF is a promising chemometric resolution method for complex samples. 相似文献
57.
. Molecular matrix elements of a physical operator are expanded in terms of polycentric matrix elements in the atomic basis
by multiplying each by a geometrical factor. The number of terms in the expansion can be minimized by using molecular symmetry.
We have shown that irreducible tensor operators can be used to imitate the actual physical operators. The matrix elements
of irreducible tensor operators are easily computed by choosing rational irreducible tensor operators and irreducible bases.
A set of geometrical factors generated from the expansion of the matrix elements of irreducible tensor operator can be transferred
to the expansion of the matrix elements of the physical operator to compute the molecular matrix elements of the physical
operator. Two scalar product operators are employed to simulate molecular two-particle operators. Thus two equivalent approaches
to generating the geometrical factors are provided, where real irreducible tensor sets with real bases are used.
Received: 3 September 1996 / Accepted: 19 December 1996 相似文献
58.
Bunai K Ariga M Inoue T Nozaki M Ogane S Kakeshita H Nemoto T Nakanishi H Yamane K 《Electrophoresis》2004,25(1):141-155
We analyzed ABC transporter solute-binding proteins (SBPs) of the Bacillus subtilis membrane using a proteomic approach. We prepared a washed cell membrane fraction that was insoluble in 134 mM nondetergent sulfobetaine and then extracted proteins using mixtures of detergents in a stepwise manner. The membrane proteins were resolved by three two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) or two one-dimensional (1-D) PAGE procedures, electroblotted, and digested in the presence of 5% or 80% acetonitrile. Thereafter, matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF MS) identified 637 proteins corresponding to 15.9% of the total cellular proteins. We predicted that among these, 256 were membrane proteins, 101 were lipoproteins or secretory proteins and 280 were soluble proteins containing peripheral proteins that function in both the cytoplasm and the cell membrane such as SecA and FtsY. Among the 637 proteins, we identified 30 SBPs among 38 importers predicted by a bioinformatic search of the genome. We confirmed expression of the genes for the 30 SBPs using DNA microarray analysis. We compared the 2-D gel separation profiles of submembrane fractions solubilized by 1% n-dodecyl-beta-D-maltoside from cells cultured on Luria Bertani (LB), S7, and S7 medium without glutamate as well as DNA microarray data on LB and S7. The results suggested that YcdH, YtmK and YurO are binding proteins for Mn(++), glutamate and glucose, respectively, and that YqiX and YxeM are binding proteins for amino acids (tryptophan in S7 medium). 相似文献
59.
Rainer P. H. Garten 《中国化学会会志》1994,41(3):259-274
Selected prominent problems in the analysis of advanced ceramic materials are surveyed. The importance of reliability of results is discussed in the field of elemental trace- and microanalysis in view of its interaction with economy, power of detection, local resolution and speciation selectivity. Particular problems in the analysis of major constituents, trace components and microlocal distributions are based on the striking propertics of ceramics; they are exemplified. Analytical assistance must start from the beginning of the production processing, in the preparation of the powdered base materials. Determination of the stoichiometry requires high accuracy and differentiation of chemical species in bulk and surface analysis of ceramic base powders. Element trace determination by direct instrumental methods requires standard reference materials for calibration; these are currently inavailable in a sufficient variety. For optimum reliability and power of detection, element traces must be prepared in isolated form in a small excitation volume for analysis. A review on the state-of-the-art of wet-chemical combined procedures is presented. Decomposition position procedures are emphasized, due to their risk of contributing severe systematic error. Combustion in elementary fluorine is presented for decomposition of refractory materials. The performance of some direct procedures is discussed. Very efficient methods are available for element trace determinations in ceramic materials, offering high detection power. Several approaches for high-resolution local microanalysis in non-conductive ceramic materials are identified as the most promising development in the analysis of sintered compact ceramic products and devices. 相似文献
60.