Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.

计算层状介质中电磁场的层矩阵法

As an important branch of electrical prospecting method, the artificial source frequency domain electromagnetism method has received more and more attention. But when conducts the fundamental research, people often isolated study some concrete method, so the research results of one method are very difficult to apply to another method directly. This article will possess the artificial source frequency domain EM method to an 1D model simply. It is stratified medium model, with an electric or magnetic source in or outside of it. Then take the horizontal electric dipole source as an example to introduce how to computing the EM field in stratified medium. Because layer matrix is the key of establishing equations, so we call it the layer-matrix method. The key of layer-matrix method is establishing equations by using layer matrixes in wavenumber(kx, ky, z) domain, then obtains the electromagnetic field value of wavenumber domain. After Fourier transform, we can get electromagnetic field of any position in spatial domain. The layer matrix technique theoretically can calculate electromagnetic field of any position for any source, is suitable for many kinds of electromagnetic method. After introduction of the layer matrix method, this article has done some CSAMT, MCSEM and Wireless Electro-Magnetic Method (WEM) modeling with layer matrix method separately. In CSAMT modeling, we get electromagnetic field dissemination characteristics considering wave number of the air, and obtain three-dimensional distribution characteristics of the electromagnetic field. In MCSEM modeling, we get electromagnetic field dissemination characteristics with and without considering the airwave, and obtain three-dimensional distribution characteristics of electromagnetic field. In WEM modeling, we get electromagnetic field’s difference between considering the ionosphere and not considering it, and recognize the ionosphere’s influence of electromagnetic field. With the layer matrix technique, we have got some new understandings of EM dissemination rules of different situations. All analysis results indicate that the layer-matrix technique is credible and effective, and are worthy of further thorough research and development.

高温高压下Z轴水晶的电导率实验研究

电导率测量的过程历经了从直流-交流-阻抗谱的过程，已经为地球物理学家借助于高温高压手段研究固体深部物质电学性质所广泛认同的。本文首先介绍了阻抗谱法测定水晶电导率的实验原理，进而采用该方法在10^-1～10^6Hz的频率范围以及1．0—4．0GPa和823—1073K条件下，借助于YJ-3000t紧装式六面顶高压设备对沿Z轴方向生长的水晶进行了的电导率实验就位测量。实验结果表明：在选择的频率范围，样品的复阻抗的模和相角都对频率具有很强的依赖性；随着温度的升高，电阻迅速降低，电阻率降低，电导率增大；在压力1．0—4．0GPa，其活化焓分别为：0．8548eV、0．8320eV、0．8172eV、0．7834eV，独立于温度的指前因子分别为：1．003S／m、1．778S／m、3．082S／m、6．987S／m，活化焓随着压力的升高而降低，指前因子随着压力的升高而增大。