The preparation of high activity DMFC Pt/C electrocatalysts using a pre-precipitation method

It is suggested that a Pt/C cathodic catalyst for the direct methanol fuel cell (DMFC) can be prepared with a pre-precipitation method, in which, H2PtCl6 is precipitated onto the carbon black as (NH4)(2)PtCl6 before H2PtCl6 is reduced to Pt. The electrocatalytic activity of this Pt/C-A catalyst for oxygen reduction is excellent because the Pt/C catalyst prepared with this pre-precipitation method possesses a small average particle size, low relative crystalinity and a large electrochemically active surface area. In addition, the pre-precipitation method is simple and economical and it can be used to prepare a Pt/C catalyst on a large scale.

Electrochemical H2S sensor with H2SO4 pre-treated Nafion membrane as solid polymer electrolyte

It is reported for the first time that the performance of the electrochemical H2S sensor with the Nation membrane pre-treated with the concentrated H2SO4 as the solid electrolyte is much more stable than that for the sensor with the Nation membrane without H2SO4 pretreatment. The sensitivity of the sensor is about 2.92 muA/ppm. The response time of the sensor is about 9 s. The detection limit is about 0.1 ppm. Therefore, this kind of the electrochemical H2S gas sensor may be desirable for the practical application.

Self-assembly of the pre-formed inclusion complexes between cyclodextrins and alkanethiols on gold electrodes

A new kind of self-assembled monolayer (SAM) formed in aqueous solution through the pre-formed inclusion complexes (abbreviated CD . C-n) between alpha-, beta-cyclodextrins (CDs) and alkanethiols (CH3(CH2)(n-1)SH, n = 10, 14 and 18) was prepared successfully on gold electrodes. High-resolution H-1 NMR was used to confirm the formation of CD . C-n. X-ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry were used to characterize the resulting SAMs (denoted as M-CD . Cn). It was found that M-CD . Cn were more stable against repeated potential cycling in 0.5 M H2SO4 than SAMs of CH3(CH2)(n-1)SH (denoted as M-Cn), with a relative sequence of Mbeta-CD . Cn > Malpha-CD . Cn > M-Cn. In addition, an order of blocking the electron transfer between gold electrodes and redox couples (both Fe(CN)(6)(3-) and Ru(NH3)(6)(3+)) in solution, M-CD . C10 > M-CD . C14 > M-CD . C18, was observed. A plausible explanation is provided to elucidate some of the observations. (C) 1997 Elsevier Science S.A.

Simultaneous determination of monoamine and amino acid neurotransmitters in rat endbrain tissues by pre-column derivatization with high-performance liquid chromatographic fluorescence detection and mass spectrometric identification

A sensitive and efficient method for simultaneous determination of glutamic acid (Glu), gamma-amino-butyric acid (GABA), dopamine (DA), 5-hydroxytryptamine (5-HT) and 5-hydroxyindole acetic acid (5-HIAA) in rat endbrains was developed by high-performance liquid chromatography (HPLC) with fluorescence detection and on-line mass spectrometric identification following derivatization with 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC). Different parameters which influenced derivatization and separation were optimized. The complete separation of five neurotransmitter (NT) derivatives was performed on a reversed-phase Hypersil BDS-C-18 column with a gradient elution. The rapid structure identification of five neurotransmitter derivatives was carried out by on-line mass spectrometry with electrospray ionization (ESI) source in positive ion mode, and the BCEOC-labeled derivatives were characterized by easy-to-interpret mass spectra. Stability of derivatives, repeatability, precision and accuracy were evaluated and the results were excellent for efficient HPLC analysis. The quantitative linear range of five neurotransmitters were 2.441-2 x 10(4) nM, and limits of detection were in the range of 0.398-1.258 nM (S/N = 3:1). The changes of their concentrations in endbrains of three rat groups were also studied using this HPLC fluorescence detection method. The results indicated that exhausting exercise could obviously influence the concentrations of neurotransmitters in rat endbrains. The established method exhibited excellent validity, high sensitivity and convenience, and provided a new technique for simultaneous analysis of monoamine and amino acid neurotransmitters in rat brain. (C) 2008 Elsevier B.V. All rights reserved.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

储层评价目标驱动的地震叠前叠后综合反演方法研究

The exploration and development of natural gas in the north of Ordos basin have been one important part in China’s energy stratagem. Reservoir in upper Palaeozoic group is of lithological trap and its prediction is a crux in a series of works. Based on foregoing seismic reservoir prediction, seismic data are re-processed with some optical methods and pre-stack information is used in corresponding inversions. Through the application of diverse methods, a series of techniques for reservoir prediction come into being. Several results are achieved as flowing: 1. A set of log processing and interpretation methods is developed. Porosity, permeability and gas saturation models are rebuilt. 2. Based on the petro-physics analysis of reservoirs in upper Palaeozoic group, the equations about lithology, property, hydrocarbon and elastic parameters are established. 3. Forward modeling based on elastic wave theory is first applied in the study area and increases the resolution of modeling results. 4. A series of techniques such as pre-stack time migration and others are combined to improve the data quality. 5. Pre-stack seismic inversion is first employed in the north of Ordos Basin and brings the results of EI, P-impedance, S-impedance and other elastic parameters. 6. In post-stack inversion, logs indicating reservoir parameters are rebuilt and boost the resolution of lithology inversion. 7. Amplitude, coherence, frequency-discomposed amplitude, waveform and other sensitive attributes are extracted to describe sands distribution. Seismic modes standing for sands of P1x3, P1x2 are established. 8. Among 9 proposed wells, 8 wells encountered sands and became production wells. The output of DK13 amounts to 510,000 m3 per day. Keywords：the north of Ordos Basin, reservoir prediction, pre-stack inversion, post-stack inversion, seismic attributes．

地震波谱元法数值模拟和偏移研究

With the development of both seismic theory and computer technology, numerical modeling technology of seismic wave has achieved great advancement during the past half century. The current methods under development include finite differentiation method (FDM), finite element method (FEM), pseudospectral method (PSM), integral equation method (IEM) and spectral element method (SEM). They exert their very important roles in every corner of seismology and seismic prospecting. Large quantity of researches towards spectral element method in the end of last century bring this method to a new era, which results in perfect solution of many difficult problems. However, parts of posterior works such as seismic migration and inversion which base on spectral element method have never been studied widely at least up to the present whereas are of importance to seismic imaging and seismic wave propagation. Based on previous work, this paper uses spectral element method to investigate the characteristics and laws of the seismic wave propagation in isotropic and anisotropic media. By thoroughly studying this high-accuracy method, we implement a kind of reverse-time pre- and post-stack migration based on SEM. In order to verify the validity of the SEM method, we have simulated the propagation of seismic wave in several different models. The simulation results show that: (1) spectral element method can be used to model any complex models and the computational results are comparable with the expected results and the analytic results; (2) the optimum accuracy can be achieved when the rank is between 4 and 9. When it is below 4, the dispersion may occur; and when it is above 9, the time step-length will be changed accordingly with the reducing space step-length in order to keep the computation stability. This will exponentially increase the computation time and at the same time the memory even if simulating the same media. This paper also applies explosive reflection surface imaging technology, time constancy principle of wave-filed extrapolation and least travetime raytracing technology of surface source to SEM pre- and post-stack migration of isotropic and anisotropic media. All imaging results derived by the above methods agree well with the real geological models and the position of interface and inflexions can also return to their right location well. This indicates that the method proposed in this paper is a kind of technology with high accuracy and robust stability. It can serve as an alternative method in real seismic data processing. All these work can boost the development of high-accuracy seismic imaging, and therefore have significant inference value.

太阳活动变化对中低纬电离层的影响

With the variations of solar activity, solar EUV and X-ray radiations change over different timescales (e.g., from solar cycle variation to solar flare burst). Since solar EUV and X-ray radiations are the primary energy sources for the ionosphere, theirs variations undoubtedly produce significant and complicated effects on the ionosphere. So the variations of solar activity significantly affect the ionosphere. It is essential for both ionospheric theory and applications to study solar activity effects on the ionosphere. The study about solar activity variations of the ionosphere is an important part of the ionospheric climatology. It can enhance the understanding for the basic processes in the ionosphere, ionospheric structure and its change, ionosphere/thermosphere coupling, and so on. As for applications, people need sufficient knowledges about solar activity variations of the ionosphere in order to improve ionospheric models so that more accurate forecast for the ionospheric environments can be made. Presently, the whole image about the modalities of ionospheric solar activity variations is still unknown, and related mechanisms still cannot be well understood. This paper is about the effects of the 11-year change in solar activity to the low- and mid-latitude ionosphere. We use multi-type ionospheric observations and model to investigate solar activity effects on the electron density and ionospheric spatial structure, and we focus on discussing some related mechanisms. The main works are as follows: Firstly, solar activity variations of ionospheric peak electron density (NmF2) around 1400 LT were investigated using ionosonde observations in the 120°E sector. The result shows that the variation trend of NmF2 with F107 depends on latitudes and seasons. There is obvious saturation trend in low latitudes in all seasons; while in middle latitudes, NmF2 increases linearly with F107 in winter but saturates with F107 at higher solar activity levels in the other seasons. We calculated the photochemical equilibrium electron density to discuss the effects induced by the changes of neutral atmosphere and dynamics processes on the solar activity variations of NmF2. We found that: (1) Seasonal variation of neutral atmosphere plays an important role in the seasonal difference of the solar activity variations of NmF2 in middle latitudes. (2) Less [O]/[N2] and higher neutral temperature are important for the saturation effect in summer, and the increase of vibrational excited N2 is also important for the saturation effect. (3) Dynamics processes can significantly weaken the increase of NmF2 when solar activity enhances, which is also a necessary factor for the saturation effect. Secondly, solar activity variations of nighttime NmF2 were investigated using ionosonde observations in the 120°E sector. The result shows that the variation trends of NmF2 with F107 in nighttime are different from that in daytime in some cases, and the nighttime variation trends depend on seasons. There is linear increase trend in equinox nighttime, and saturation trend in summer nighttime, while the increase rate of NmF2 with F107 increases when solar activity enhances in winter nighttime (we term it with “amplification trend”). We discussed the possible mechanisms which affect the solar activity variations of nighttime NmF2. The primary conclusions are as follows: (1) In the equatorial ionization anomaly (EIA) crest region, the plasma influx induced by the pre-reversal enhancement (PRE) results in the change of the variation trend between NmF2 and F107 from “saturation” to “linear” after sunset in equinoxes and winter; while the recombination process at the F2-peak is the primary factor that affects the variation trend of NmF2 with F107 in middle latitudes. (2) The recombination coefficient at the F2-peak height reaches its maximum at moderate solar activity level in winter nighttime, which induces NmF2 attenuates more quickly at moderate solar activity level. This is the main reason for the amplification trend. (3) The change of the recombination process at the F2-peak with solar activity depends on the increases of neutral parameters (temperature, density et al.) and the F2-peak height (hmF2). The seasonal differences in the changes of neutral atmosphere and hmF2 with solar activity are the primary reasons for the seasonal difference in the variation trend of nighttime NmF2 with F107. Finally, we investigated the solar activity dependence of the topside ionosphere in low latitudes using ROCSAT-1 satellite (at 600 km altitude) observations. The primary results and conclusions are as follows: (1) Latitudinal distribution of the plasma density is local time, seasonal, and solar activity dependent. In daytime, there is a plasma density peak at the dip equator. The peak is obviously enhanced at high solar activity level, and the strength of the peak strongly depends on seasons. While at sunset, two profound plasma density peaks (double-peak structure) are found in solar maximum equinox months. (2) Local time dependence of the latitudinal distribution is due to the local time variation of the equatorial dynamics processes. Double-peak structure is attributed to the fountain effect induced by strong PRE. Daytime peak enhances with solar activity since the plasma density increases with solar activity more strongly at the dip equator due to the equatorial vertical drift, and its seasonal dependence is mainly due to the seasonal variations of neutral density and the equatorial vertical drift. In the sunset sector, seasonal and solar activity dependences of the latitudinal distribution are related to the seasonal and solar activity variations of PRE. (3) The variation trend of the plasma density with solar activity shows local time, seasonal, and latitudinal differences. That is different from the changeless amplification trend at the DMSP altitude (840 km). Profound saturation effect is found in the dip equator region at equinox sunset. This saturation effect in the topside ionosphere is realated to the increase of PRE with solar activity. Solar activity variation trend of the topside plasma density was discussed quantitatively by Chapman-α function. The result shows that the effect induced by the change of the scale height is dominant at high altitudes; while the variation trend of ROCSAT-1 plasma density with solar activity is suggested to be related to the changes of the peak height, the scale height, and the peak electron density with solar activity.

地震反射系数成像方法研究

Reflectivity sequences extraction is a key part of impedance inversion in seismic exploration. Although many valid inversion methods exist, with crosswell seismic data, the frequency brand of seismic data can not be broadened to satisfy the practical need. It is an urgent problem to be solved. Pre-stack depth migration which developed in these years becomes more and more robust in the exploration. It is a powerful technology of imaging to the geological object with complex structure and its final result is reflectivity imaging. Based on the reflectivity imaging of crosswell seismic data and wave equation, this paper completed such works as follows: Completes the workflow of blind deconvolution, Cauchy criteria is used to regulate the inversion(sparse inversion). Also the precondition conjugate gradient(PCG) based on Krylov subspace is combined with to decrease the computation, improves the speed, and the transition matrix is not necessary anymore be positive and symmetric. This method is used to the high frequency recovery of crosswell seismic section and the result is satisfactory. Application of rotation transform and viterbi algorithm in the preprocess of equation prestack depth migration. In equation prestack depth migration, the grid of seismic dataset is required to be regular. Due to the influence of complex terrain and fold, the acquisition geometry sometimes becomes irregular. At the same time, to avoid the aliasing produced by the sparse sample along the on-line, interpolation should be done between tracks. In this paper, I use the rotation transform to make on-line run parallel with the coordinate, and also use the viterbi algorithm to complete the automatic picking of events, the result is satisfactory. 1. Imaging is a key part of pre-stack depth migration besides extrapolation. Imaging condition can influence the final result of reflectivity sequences imaging greatly however accurate the extrapolation operator is. The author does migration of Marmousi under different imaging conditions. And analyzes these methods according to the results. The results of computation show that imaging condition which stabilize source wave field and the least-squares estimation imaging condition in this paper are better than the conventional correlation imaging condition. The traditional pattern of "distributed computing and mass decision" is wisely adopted in the field of seismic data processing and becoming an obstacle of the promoting of the enterprise management level. Thus at the end of this paper, a systemic solution scheme, which employs the mode of "distributed computing - centralized storage - instant release", is brought forward, based on the combination of C/S and B/S release models. The architecture of the solution, the corresponding web technology and the client software are introduced. The application shows that the validity of this scheme.

Determination of alcohols by high-performance liquid chromatography with fluorimetric detection after pre-column derivatisation with carbazole-9-N-acetic acid and chromatographic behaviour of alcoholic derivatives

Alcohols were derivatised to their carbazole-9-N-acetic acid (CRA) esters with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC . HCl) as the dehydrating agent. Studies on derivatisation conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives. The retention behaviour of alcohol derivatives was investigated by varying mobile phase compositions (ACN-water and MeOH-water). The parameters from the equation log k'=A-BX were evaluated by retention data of derivatives using an isocratic elution with different mobile phases. The results indicated that the parameters derived allowed computation of retention factors in good agreement with experiments. At the same time, a general equation was derived that makes possible predictions of partition coefficient in binary mobile phases with different proportions of organic solvent to water based on some simple regression analysis. The LC separation for the derivatised alcohols containing higher carbon alcohols showed good reproducibility on a reversed-phase C-18 column with gradient elution. The detection limits (excitation at 335 nm, emission at 360 nm) for derivatised alcohols (signal-to-noise ratio=3:1) were in the range of 0.1-0.4 pg per injection. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis of nanometric-size magnesium nitride by the nitriding of pre-activated magnesium powder

Magnesium nitride (Mg3N2) was synthesized by the reaction of magnesium in the highly reactive form (Mg*) with nitrogen at 450 degrees C under normal pressure. The effect of doping with nickel dichloride on the nitridation of Mg* was investigated. Differential thermal analysis (DTA) of Mg* systems and transmission electron microscopy (TEM) measurement of the product formed were carried out. TEM measurement showed that the particle size of the Mg3N2 synthesized was in the nanometric range. The dependence of nitridation of the NiCl2-doped Mg* on temperature was investigated at temperatures ranging from 300 to 500 degrees C. The nitridation of NiCl2-doped Mg* could occur even at temperature as low as 300 degrees C. (C) 1999 Kluwer Academic Publishers.

Application of liquid pre-column capillary electrophoresis technique to the study of interaction between drug enantiomers and human serum albumin

Based on the chiral separation of several basic drugs, dimetindene, tetryzoline, theodrenaline and verapamil, the liquid pre-column capillary electrophoresis (LPC-CE) technique was established. It was used to determine free concentrations of drug enantiomers in mixed solutions with human serum albumin (HSA). To prevent HSA entering the CE chiral separation zone, the mobility differences between HSA and drugs under a specific pH condition were employed in the LPC. Thus, the detection confusion caused by protein was totally avoided. Further study of binding constants determination and protein binding competitions was carried out. The study proves that the LPC technique could be used for complex media, particularly the matrix of protein coexisting with a variety of drugs.

Analysis of phenols by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence labeling reagent, has been synthesized and applied for the derivatization of phenols. Taken phenol, p-chlorophenol, 2,5-dimethylphenol, 2,4-dichlorophenol and 1,4-dihydroxybenzene as testing standards, the effects of derivatization conditions, such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration, have been systematically studied. Under the optimized conditions, CEOC reacts readily with the phenols to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. The single step derivatization reaction could be finished within 20 min even at room temperature. Such a method has been successfully applied to the analysis of phenols in printing ink by high-performance liquid chromatography. (c) 2005 Elsevier B.V. All rights reserved.