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221.
Arakawa R Shimomae Y Morikawa H Ohara K Okuno S 《Journal of mass spectrometry : JMS》2004,39(8):961-965
A low molecular mass polyester was analyzed by desorption/ionization on porous silicon (DIOS) mass spectrometry. The results were compared with those of matrix-assisted laser desorption ionization (MALDI) mass spectrometry using matrixes of alpha-cyano-4-hydroxycinnamic acid (CHCA) and 10,15,20-tetrakis(pentafluorophenyl)porphyrin (F20TPP). The CHCA matrix was not suitable for characterization of low molecular mass components of the polyester because the matrix-related ions interfered with the component ions. On the other hand, the F20TPP matrix showed no interference because no matrix-related ions appeared below m/z 822. However, the solvent selection for determining optimal conditions of sample preparation was limited, because F20TPP does not dissolve readily in any of the available organic solvents. In the DIOS spectra, the polymer ions were observed at high sensitivity without a contaminating ion. No matrix is needed for DIOS spectra of low molecular mass polyesters, facilitating sample preparation and selectivity of a precursor ion in post-source decay measurements. 相似文献
222.
223.
本文通过研究一系列盐类化合物在底物三乙醇胺和甘油醚中的快原子轰击质谱,总结出它们的加合阳离子系列,并从快原子轰击质谱的离化机理和亚稳跃迁结果探讨了这些离子的来源。 相似文献
224.
Characteristic features of the kinetics of solid-state cage reactions with distributed parameters of the relaxing matrix were
considered. Depending on the ratio of the constants of the reaction rate and relaxation of environment, the kinetics of chemical
conversions can be either exponential or nonexponential. Plausible reasons for the unsteady-state character of the kinetics
of the processes of two types,viz., the reactions of alkyl radicals in amorphous alcohol matrices and conversions in biological systems, were discussed. The
main reason for the unsteady-state character of the reactions of the first type is a dispersion of the equilibrium distances
between the reagents. Kinetics of the reactions of the second type, such as rebinding of the ligands in the heme-containing
proteins (e.g., in myoglobin), is determined by the distances in the pairs of reagents and the relaxation transitions.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 469–476, March, 1997. 相似文献
225.
Based on the classifications of the four nucleic acid bases, we introduce a new 2-D method of DNA representation: TB-curve, which avoids loss of information accompanying alternative 2-D representation in which the curve standing for DNA overlaps and intersects itself. The method is illustrated on the coding sequence of the first exon of human beta-globin gene. 相似文献
226.
Determination of Organophosphorus Pesticides in Soil by MMSPD-GC-NPD and Confirmation by GC-MS 总被引:1,自引:0,他引:1
A novel method, modified matrix solid-phase dispersion (MMSPD), has been developed for quantitative analysis of organophosphorus
pesticide residues in soil. It was based on matrix solid-phase dispersion (MSPD) and continuous liquid-solid extraction (continuous
LSE), using Florisil as sorbent and dichloromethane as the recycling solvent. Two soils with different texture and physicochemical
properties were studied to validate the method. The effect of residence time of pesticides in soil was also studied. MMSPD
was compared with MSPD and continuous LSE respectively. Determination was carried out by gas chromatography with nitrogen-phosphorus
detection (GC-NPD). The method gave recoveries ranging from 72–105% with relative standard deviations (RSDs) lower than 15%
for the pesticides studied. The limits of detection (LODs) ranged from 0.1 to 0.6 ng g−1. Two pesticide residues have been detected in real soil samples from Fujian, China, using MMSPD. The pesticides were confirmed
by gas chromatography-mass spectrometry (GC-MS) in a selected-ion monitoring (SIM) mode.
Revised: 4 and 9 April 2006 相似文献
227.
S. Jayaraman R. Srinivasan J. E. McGrath 《Journal of polymer science. Part A, Polymer chemistry》1995,33(10):1551-1563
The synthesis of 3-phenylethynylphenol, and its applicability as a high temperature cross-linking endcap for high Tg polyarylene ethers is described. It was synthesized in high yields and purity using the palladium catalyzed coupling reaction between the protected 3-bromo or iodo phenol and phenylacetylene. The yield of the reaction was found to be highly dependent on the structure of the halide used, the reaction temperature, and the concentration of phenylacetylene. The use of the protected phenol in the palladium catalyzed reaction was also extended to the high yield synthesis of 3-ethynylphenol and protected 4-ethynylphenols. The complete synthesis of 3-phenylethynylphenol, 3-ethynylphenol, and protected 4-ethynylphenol in high yields has been demonstrated and is discussed herein. Three new phenylethynyl functionalized arylene ether matrix resins have been synthesized in high yields and purity by reacting 3-phenylethynylphenol with 4,4′-dichlorodiphenyl sulfone, 4,4′-difluorobenzophenone, and bis(4-fluorophenyl)phenyl phosphine oxide, via nucleophilic poly(arylene ether) synthesis conditions. These low molecular weight materials undergo thermally induced chain extension/branching to yield an insoluble three-dimensional network at reaction temperatures of around 380°C. The low molecular weight arylene ethers endcapped with the phenylethynyl group demonstrate excellent flow characteristics and a wide processing window of about 250°C. Crosslinking of the 4,4′-bis(3-phenylethynyl phenoxy)diphenyl sulfone system for 30 min at 350°C in air afforded a Tg value of 265°C by differential scanning calorimetry measurements. Trace metal analysis for palladium and copper showed absence of these metals that would otherwise detract from the excellent thermal stability. The synthesis and characterization of these phenylethynyl endcapped arylene ether matrix resins is discussed. © 1995 John Wiley & Sons, Inc. 相似文献
228.
N. Angelescu M. Bundaru G. Costache C. J. Thompson 《Journal of statistical physics》1986,43(1-2):33-49
A generalizedO(n) matrix version of the classical Heisenberg model, introduced by Fuller and Lenard as a classical limit of a quantum model, is solved exactly in one dimension. The free energy is analytic and the pair correlation functions decay exponentially for all finite temperatures. It is shown, however, that even for a finite number of spins the model has a phase transition in then limit. The transition features a specific heat jump, zero long-range order at all temperatures, and zero correlation length at the critical point. The Curie-Weiss version of the model is also solved exactly and shown to have standard mean-field type behavior for all finiten and to differ from the one-dimensional results in then limit. 相似文献
229.
Hong Tao Gao Dong Mei Dai Tong Hua Li 《中国化学快报》2007,18(4):495-498
Non-negative matrix factorization(NMF)is a technique for dimensionality reduction by placing non-negativity constraints onthe matrix.Based on the PARAFAC model,NMF was extended for three-dimension data decomposition.The three-dimension non-negative matrix factorization(NMF3)algorithm,which was concise and easy to implement,was given in this paper.The NMF3algorithm implementation was based on elements but not on vectors.It could decompose a data array directly without unfolding,which was not similar to that the traditional algorithms do.It has been applied to the simulated data array decomposition andobtained reasonable results.It showed that NMF3 could be introduced for curve resolution in chemometrics. 相似文献
230.
On the basis of the structures and properties of the ClO/ClO? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C1), 20.54 (EC2: C2, 2B), 20.69 (EC3: C1), 20.70 (EC4: Cs, 2A′), and 20.69 (EC.5: C2h, 2Bu) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献