Sintering of nanopowders of amorphous silicon nitride under ultrahigh pressure

Nanopowders of amorphous silicon nitride were densified and sintered without additives under ultrahigh pressure (1.0-5.0 GPa) between room temperature and 1600 degrees C. The powders had a mean diameter of 18 nm and contained similar to 5.0 wt% oxygen that came from air-exposure oxidation, Sintering results at different temperatures were characterized in terms of sintering density, hardness, phase structure, and grain size. It was observed that the nanopowders can be pressed to a high density (87%) even at room temperature under the high pressure. Bulk Si3N4 amorphous and crystalline ceramics (relative density: 95-98%) were obtained at temperatures slightly below the onset of crystallization (1000-1100 degrees C and above 1420 degrees C, respectively. Rapid grain growth occurred during the crystallization leading to a grain size (>160 nm) almost 1 order of magnitude greater than the starting particulate diameters, With the rise of sintering temperature, a final density was reached between 1350 and 1420 degrees C, which seemed to be independent of the pressure applied (1.0-5.0 GPa), The densification temperature observed under the high pressure is lower by 580 degrees C than that by hot isostatic pressing sintering, suggesting a significantly enhanced low-temperature sintering of the nanopowders under a high external pressure.

High-yield extraction of endohedral rare-earth fullerenes

The technique of high-temperature high-pressure extraction with pyridine has been successfully utilized to extract a wide variety of endohedral rare-earth fullerenes of the type Ln@C-2n (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb). Ln@C-80, Ln@C-82, and Ln(2)@C-80 for most of the rare-earth metals can be produced with high-yield and selectively extracted from the carbon-are evaporation soot. Metallofullerenes containing Sm, Eu, and Yb (which could have +2 oxidation states) are especially difficult to extract. Some possible reasons for the high-yield extraction are discussed. The laser desorption mass spectrometric characterization results indicate a relationship between the extraction yields of metallofullerenes and the oxidation states and ionic radii of the rare-earths.

High-yield Synthesis and Extraction of Gd@C-2n

Endohedral metallofullerene Gd@C-2n were synthesized with high-yield using the carbon-arc discharge method of activating the Gd2O3-containing graphite anode in situ and back-burning technique. A series of Gd@C-2n for 2n from 70 to 96 were effectively extracted by toluene at high-temperature and under high-pressure condition. Gd@C-82, Gd@C-74 were considered to be fairly stable and soluble metallofullerene species.

DETERMINATION OF AMINOPYRINE AND ITS METABOLITE IN BIOLOGICAL FLUID BY LIQUID-CHROMATOGRAPHY ELECTROCHEMISTRY WITH A GLASSY-CARBON ELECTRODE DISPERSED WITH ALPHA-ALUMINA PARTICLES

A sensitive high-performance liquid chromatographic method has been developed for the quantitative determination of aminopyrine (AM) and its metabolite 4-aminoantipyrine (AAN). The method utilizes reverse-phase chromatography/amperometric detection with a glassy carbon electrode dispersed with alpha-arumina particles as the working electrode, on which the oxidation of AM and AAN was greatly improved compared with that on a bare glassy carbon electrode. As a result, the detection limit was as low as 1.4 ng for AM and 0.8 ng for AAN, and the calibration plots for the above compounds have wide linear ranges from 100 ng/mL to 100 mu g/mL and 60 ng/mL to 80 mu g/mL (for AM and AAN, respectively). The above method was applied for the detection of these materials in human urine with satisfactory results.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Extraction of Nitraria tangutorum seed oil by supercritical carbon dioxide and determination of free fatty acids by HPLC/APC/IMS with fluorescence detection

The seed oil from Nitraria tangutorum samples was obtained by supercritical carbon dioxide extraction methods. The extraction parameters for this methodology, including pressure, temperature, particle size and extraction time, were optimized. The free fatty acids in the seed oil were separated with a pre-column derivation method and 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-p-toluenesulfonate (BDETS) as a labeling regent, followed by high-performance liquid chromatography (HPLC) with fluorescence detection. The target compounds were identified by mass spectrometry with atmospheric pressure chemical ionization (APCI in positive-ion mode). HPLC analysis shows that the main compositions of the seed oil samples were free fatty acids (FFAs) in high to low concentrations as follows: linoleic acid, oleic acid, hexadecanoic acid and octadecanoic acid. The assay detection limits (at signal-to-noise of 3:1) were 3.378-6.572 nmol/L. Excellent linear responses were observed, with correlation coefficients greater than 0.999. The facile BDETS derivatization coupled with mass spectrometry detection allowed the development of a highly sensitive method for analyzing free fatty acids in seed oil by supercritical CO2 extraction. The established method is highly efficient for seed oil extraction and extremely sensitive for fatty acid profile determination. (C) 2007 Elsevier B.V. All rights reserved.

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.

Determination of 30 free fatty acids in two famous Tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

Comparative analysis of allantoin quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid in Nitraria tangutorum Bobr. Seed by HPLC-APCI-MS and CE

This paper describes the simultaneous determination of allantoin, quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid (MTCCA) in Nitraria tangutorum Bobr seed by HPLC-APCI-MS and CE (capillary electrophoresis) methods. The final optimized chromatographic conditions were investigated in a reversed-phase Eclipse XDB-C8 column (150 x 4.6 mm, 5 mu m). A seventeen-minute gradient elution, (A: aqueous acetonitrile 20% (v/v); B: aqueous acetonitrile 60% (v/v); C: pure acetonitrile 100%) at a flow rate of 1.0 mL/min was selected for the separation of three natural products with diode array detection (DAD) at 220 nm. A CE experiment was carried out in a fused silica capillary with 32 mmol/L boric acid (pH 10), 32 mmol/L SDS and acetonitrile (10.0%, v/v). The applied potential and temperature was, respectively, set at 19 kV and 25 degrees C. After development, the validation was performed in parallel for HPLC and CE, with the same standards and sample to avoid differences due to the manipulation. The validation parameters of both techniques were adequate for the intended purpose.

HPLC-APCI-MS determination of free fatty acids in Tibet folk medicine Lomatogonium rotatum with fluorescence detection and mass spectrometric identification

A simple and sensitive method for the determination of free fatty acids (FFAs) using acridone-9-ethyl-p-toluenesulfonate (AETS) as a fluorescence derivatization reagent by high performance liquid chromatography (HPLC) has been developed. Free fatty acid derivatives were separated on an Eclipse XDB-C-8 column with a good baseline resolution and detected with the fluorescence of which excitation and emission wavelengths of derivatives were set at lambda(ex) 404 and lambda(em) 440 nm, respectively. Identification of 19 fatty acid derivatives was carried out by online post-column mass spectrometry with an atmospheric pressure chemical ionization (APCI) source under positive-ion detection mode. Nineteen FFAs from the extract of Lomatogonium rotatum are sensitively determined. The results indicate that the plant Lomatogonium rotatum is enriched with an abundance of FFAs and FFAs of higher contents, which mainly focus on even carbon atoms, C-14, C-16, and C-18. The validation of the method including linearity, repeatability, and detection limits was examined. Most linear correlation coefficients for fatty acid derivatives are > 0.9989, and detection limits (at signal-to-noise of 3: 1) are 12.3-43.7 fmol. The relative standard deviations (RSDs) of the peak areas and retention times for 19 FFAs standards are < 2.24% and 0.45%, respectively. The established method is rapid and reproducible for the separation determination of FFAs from the extract of Lomatogonium rotatum with satisfactory results.

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.

Determination of five pharmacologically active compounds extracted from Rhodiola for natural product drug discovery with HPLC-APCI-MS

A rapid and sensitive liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS) assay for the determination of five pharmacologically active compounds (PAC) extracted from the traditional Chinese medicine, Rhodiola , namely salidroside, tyrosol, rhodionin, gallic acid, and ethyl gallate has been developed. In this method, PAC could be baseline separated and detected with DAD at 275 nm. The validation of the method, including sensitivity, linearity, repeatability, and recovery, was examined. The linear calibration curves were acquired with correlation coefficient >0.999 and the limits of detection LOD (at a signal-to-noise ratio=3:1) were between 0.058 and 1.500 mu mol/L. It was found, that the amounts of PAC varied with different species of Rhodiola . The established method is rapid and reproducible for the separation of five natural pharmacologically active compounds from extracts of Rhodiola with satisfactory results.

天津滨海新区软土不同含砂量的强度特征研究

Based on the features of soft soil in Tianjing Coastal New Developing Area, this kind of soil with different content of sand was researched systematically, according to the indoor experiment, about its characteristics of strength and deformation. The main results are summarized in the following: Firstly, on the basis of geological engineering investigation, the systemic experiments about the physical characteristics were conducted. The test soil samples were taken from the gray and gray-yellow silty soft soil which was formatted by near-shore marine sediment and marine-continental interactive sediment. The original condition of the sample soil was in saturation and the basic indexes are: liquid limit36.1%, plastic limit 18.8%, plasticity index. Then, the condensation characteristics of the soft soil were analyzed through high-pressure consolidation tests. The results show that，in various loading serials, the coefficient of compressibility under P=100kPa and 200kPa are all larger than 0.5MPa-1. So the sample soil is a kind of high-compressibility soil. Secondly, triaxial strength of undisturbed soil and remoulded soil was researched by using triaxial test. The types of stress-strain curve of both undisturbed and remoulded soil are the stress stabilization and softening type, which show the specific plastic character. Furthermore, the cohesion and friction angle of undisturbed soil changes, when the ambient pressure is different, instead of a stable value for all time; the cohesion and friction angle of remoulded soil changes with the compactness and sand-carrying capacity which is wholly higher than undisturbed soil. At last, the stress-strain results of both undisturbed and remoulded soil were normalized by using the ambient pressure as the normalization factor. The results show that, there are all some normalization characters in both undisturbed and remoulded soil, however, the feature of normalization of undisturbed soil is worse than the remoulded ones. The main reason is that the undisturbed samples are worse in equality and the unavoidable disturb through the process of sampling and experiments will also make them can not put up good normalization. Therefore, it is feasible to normalize the soil in Tianjing Coastal New Developing Area with the ambient pressure as normalization factor.

通过第一性原理计算研究内地核的结构与成分

The determination of the composition and structure of the Earth’s inner core has long been the major subject in the study of the Earth’s deep interior. It’s widely believed that the Earth’s core is formed by iron with a fraction of nickel. However, light elements must exist in the inner core because the earth core is less dense than pure iron-nickel alloy (~2-3% in the solid inner core and ~6-7% in the liquid outer core). The questions are what and how much light element is there in the iron-nickel alloy. Besides the composition, the crystal structure of the iron with or without light element is also not well known. According to the seismological observations, the sound waves propagate 3-4% faster along the spin axis than in the equatorial plane. That means the inner core is anisotropic. The densest structure of iron-nickel alloy should be h.c.p structure under the very high pressures. However, the h,c,p structure does not propagate waves anisotropic ally. Then what is the structure of the iron-nickel alloy or the iron-nickle-light element alloy. In this study, we tried to predict the composition and the structure of the inner core through ab initio calculation of the Gibbs free energy, which is a function of internal energy, density and entropy. We conclude that the h.c.p structure is more stable than the b.c.c structure under high pressure and 0 K, but with the increase of temperature, the free energy of the b.c.c structure is decreasing much faster than the h.c.p structure caused by the vibration of the atomics, so the b.c.c structure is more stable at high temperatures. With the addition of light elements (S or Si or both), the free energy of b.c.c. decreases even faster, about 3at% of Si not only explains why the inner core is about 2-3 % lighter than the iron-nickle alloy, but also reasons why the inner core is anisotropic, since the b.c.c. structure becomes more stable than the h.c.p structure at 5500-6000K and b.c.c. is anisotropic in propagating seismic waves. Therefore, we infer that the inner core of the earth is formed by b.c.c iron and a fraction of nickel plus ~3at.% Si, with a temperature higher than 5500K, which is consistent with the studies from other approaches.

沾化凹陷泥质岩油气藏成藏特征研究

Mudstone reservoir is a subtle reservoir with extremely inhomogeneous, whose formation is greatly related to the existence of fracture. For this kind of reservoir, mudstone is oil source rock, cover rock and reservoir strata, reservoir type is various, attitude of oil layer changes greatly, and the distribution of oil and gas is different from igneous or clastic rock reservoir as well as from carbonate reservoir of self-producing and self-containing of oil and gas. No mature experience has been obtained in the description, exploration and development of the reservoir by far. Taking Zhanhua depression as an example, we studied in this thesis the tectonic evolution, deposit characteristics, diagenesis, hydrocarbon formation, abnormal formation pressure, forming of fissure in mudstone reservoir, etc. on the basis of core analysis, physical simulation, numerical simulation, integrated study of well logging and geophysical data, and systematically analyzed the developing and distributing of mudstone fissure reservoir and set up a geological model for the formation of mudstone fissure reservoir, and predicted possible fractural zone in studied area. Mudstone reservoir mainly distributed on the thrown side of sedimentary fault along the sloping area of the petroleum generatiion depression in Zhanhua depression. Growing fault controlled subsidence and sedimentation. Both the rate of subsidence and thickness of mudstone are great on the thrown side of growing fault, which result in the formation of surpressure in the area. The unlocking of fault which leads to the pressure discharges and the upward conduct of below stratum, also makes for the surpressure in mudstone. In Zhanhua depression, mudstone reservior mainly developed in sub-compacted stratum in the third segment of Shahejie formation, which is the best oil source rock because of its wide spread in distribution, great in thickness, and rich in organic matter, and rock types of which are oil source mudstone and shale of deep water or semi-deep water sediment in lacustrine facies. It revealed from core analysis that the stratum is rich in limestone, and consists of lamina of dark mudstone and that of light grey limestone alternately, such rock assemblage is in favor of high pressure and fracture in the process of hydrocarbon generation. Fracture of mudstone in the third segment of Shahejie formation was divided into structure fracture, hydrocarbon generation fracture and compound fracture and six secondary types of fracture for the fist time according to the cause of their formation in the thesis. Structural fracture is formed by tectonic movement such as fold or fault, which develops mainly near the faults, especially in the protrude area and the edge of faults, such fracture has obvious directivity, and tend to have more width and extension in length and obvious direction, and was developed periodically, discontinuously in time and successively as the result of multi-tectonic movement in studied area. Hydrocarbon generation fracture was formed in the process of hydrocarbon generation, the fracture is numerous in number and extensively in distribution, but the scale of it is always small and belongs to microfracture. The compound fracture is the result of both tectonic movement and hydrocarbon forming process. The combination of above fractures in time and space forms the three dimension reservoir space network of mudstone, which satellites with abnormal pressure zone in plane distribution and relates to sedimentary faces, rock combination, organic content, structural evolution, and high pressure, etc.. In Zhanhua depression, the mudstone of third segment in shahejie formation corresponds with a set of seismic reflection with better continuous. When mudstone containing oil and gas of abnormal high pressure, the seismic waveform would change as a result of absorb of oil and gas to the high-frequency composition of seismic reflection, and decrease of seismic reflection frequency resulted from the breakage of mudstone structure. The author solved the problem of mudstone reservoir predicting to some degree through the use of coherent data analysis in Zhanhua depression. Numerical modeling of basin has been used to simulate the ancient liquid pressure field in Zhanhua depression, to quantitative analysis the main controlling factor (such as uncompaction, tectonic movement, hydrocarbon generation) to surpressure in mudstone. Combined with factual geologic information and references, we analyzed the characteristic of basin evolution and factors influence the pressure field, and employed numerical modeling of liquid pressure evolution in 1-D and 2-D section, modeled and analyzed the forming and evolution of pressure in plane for main position in different periods, and made a conclusion that the main factors for surpressure in studied area are tectonic movement, uncompaction and hydrocarbon generation process. In Zhanhua depression, the valid fracture zone in mudstone was mainly formed in the last stage of Dongying movement, the mudstone in the third segment of Shahejie formation turn into fastigium for oil generation and migration in Guantao stage, and oil and gas were preserved since the end of the stage. Tectonic movement was weak after oil and gas to be preserved, and such made for the preserve of oil and gas. The forming of fractured mudstone reservoir can be divided into four different stages, i.e. deposition of muddy oil source rock, draining off water by compacting to producing hydrocarbon, forming of valid fracture and collecting of oil, forming of fracture reservoir. Combined with other regional geologic information, we predicted four prior mudstone fracture reservoirs, which measured 18km2 in area and 1200 X 104t in geological reserves.