高效液相色谱双波长法测定维药艾米斯丸中芹菜素、胡椒碱、木香烃内酯、去氢木香烃内酯的含量

目的：HPLC法测定人血浆中头孢替坦二钠含量不确定度的评定。方法：对测定过程中不确定度的来源进行分析评定，包括测定重复性、称量、标准溶液的配制、含药血浆的配制、血浆样本的处理、仪器、标准曲线拟合等，计算合成不确定度和扩展不确定度。结果：人血浆中低（1.2 μg·mL^-1）、中（27.0 μg·mL^-1）、高（270.0 μg·mL^-1） 3个浓度的扩展不确定度分别为0.12，2.50，28.65 μg·mL^-1（k=2，P=95%）。结论：HPLC法测定人血浆中头孢替坦二钠含量的不确定度主要由血浆样本配制和处理，标准曲线拟合（低浓度）及仪器允差引入。

低温热解焦油中油馏分加氢脱氮和芳烃加氢宏观动力学的研究

在滴流床反应器装置上，采用3822催化剂对天祝煤MRF工艺热解焦油210℃～360℃馏分进行了加氢处理，考察了加氢处理工艺条件对加氢脱氮和芳烃加氢饱和反应过程的影响，根据加氢产品性能数据发现，加氢脱氮反应宏观动力学可用假一级反应模型表示，总芳烃和多环芳烃加氢反应均符合一级动力学反应。

重整C_9芳烃的综合利用

重整Ｃ９芳烃主要来源于炼厂重整装置二甲苯塔底油，其组成相对简单，含有大量的偏三甲苯、甲乙苯、均三甲苯和连三甲苯等，是发展精细化工的宝贵资源，具有很高的附加值。我国重整Ｃ９芳烃的利用起步较晚，金陵石化公司南京炼油厂于８０年代初首先分离出纯度大于９８％的...

HPLC同时测定木香顺气丸中5种成分的含量

目的建立同时测定木香顺气丸中5种活性成分含量的方法。方法采用高效液相色谱法(HPLC),色谱柱为Kromasil C18柱(250 mm×4.6 mm,5μm),以乙腈为流动相A,0.2%磷酸溶液为流动相B,梯度洗脱:0~5 min,10%A;5~20 min,10%→20%A;20~40 min,20%→60%A;40~60 min,60%A;分段设定检测波长:0~20.0 min为210 nm(木香烃内酯、去氢木香内酯);20.0~30.0 min为292 nm(和厚朴酚);30.0~45.0 min为211 nm(厚朴酚);45.0~60.0 min为250 nm(甘草酸),流速1.0 m L/min,柱温30℃,进样量20μL。结果香烃内酯、去氢木香内酯、和厚朴酚、厚朴酚和甘草酸分离度良好,进样量分别在0.025~1.008,0.031~1.232,0.022~0.864,0.058~2.304,0.045~1.800μg范围内线性关系良好,r均大于0.9990,平均加样回收率为99.2%~99.7%(RSD=0.74%~1.05%)。5批样品中香烃内酯、去氢木香内酯、和厚朴酚、厚朴酚和甘草酸含量分别在6.17~6.51,2.74~2.89,13.2~13.66,2.54~2.87,4.40~4.65 mg/g。结论本方法专属性好、灵敏度高、准确度高,为木香顺气丸的质量控制提供依据。

由C^＋9重芳烃制取轻芳烃

国外由重芳烃制取苯等轻芳烃有多种方法，其中由重芳烃热脱烷基和催化加氢脱烷基制苯的方法比较成熟。正在开发的工艺还有重芳烃加氢裂解或非临氢裂解制取Ｃ＿６～Ｃ＿８的轻芳烃以及水蒸气转化法制苯等过程。我国Ｃ＿９重芳烃产量逐年增加，而轻芳烃供需矛盾日益加剧，故应重视由Ｃ＿９重芳烃制取轻芳烃的研究开发工作。

渣油热接触改质反应机理——Ⅲ.反应组分色谱指纹特征变化

以胜利减压二线油为基础油,并分别混入胜利减渣的饱和烃和芳烃组分,采用长岭炼油厂提供的工业2#热载体,在固定流化床反应装置上进行渣油热接触改质反应试验。反应的原料和液体产物的色谱指纹特征分析结果表明,基础油反应主要是汽化,大分子烃反应以热裂化反应机理为特征,C25以下饱和烃及3环以下芳烃热反应的转化率很低,面C25以上饱和烃及3环以上芳烃则发生较明显的热裂化反应。

Preparation of Aryldiazonium Salt Monolayers on Si（100） Surface by Chemomechanical Method

Functionalizing and patterning of the silicon surface can be realized simultaneously by the chemomechanical method. The oxide-coated crystalline silicon （100） surface is scratched with a diamond tool in the presence of aryldiazonium salt （C6H5N2BF4）. Scratching activates the silicon surface by removing the passivation oxide layer to expose fresh Si atoms. The sur- face morphologies before and after chemomechanical reaction are characterized with atomic force microscopy. Time-of-flight secondary ion mass spectroscopy confirms the presence of C6H5 and provides evidence for the formation of self-assembled monolayer （SAM） on silicon surface via Si-C covalent bonds by scratching the silicon in the presence of C6H5N2BF4. C6H5 groups further bond with surface Si atoms via Si-C covalent bonds as confirmed from infrared spectroscopy results. We propose that chemomechanical reaction, which occurred during scratching the silicon surface, produce C6H5 groups from aryldiazonium salt. The relevant adhesion of SAM is measured. It is found that SAM can reduce the adhesion of silicon. The monolayer can be used as anti-adhesion monolayer for micro/nanoelectromechanical systems components under different environments and operating conditions.

Distribution and Sources of Polycyclic Aromatic Hydrocarbon (PAH) in Marine Environment of China

Polycyclic aromatic hydrocarbons (PAHs) are potentially carcinogenic and mutagenic compounds that have raised considerable environmental concern. The highest concentrations of PAHs in the coastal sediment samples in China was 5.8-11.0μg/g (dry weight) in the core from the Huangpu River, Shanghai. The second highest concentration of PAHs was 4.42μg/g (dry weight) in surface sediment of Victoria Harbour in Hong Kong, and 5.73μg/g (dry weight) in sediment of Jiaozhou Bay, Qingdao City. The low concentrations of PAHs were always in the sediments far away from industrial zones and cities, and ranged from 0.10 to 0.30μg/g (dry weight). Several environmental parameters are considered for the identification of sources of PAHs in marine environment. High proportion of naphthalene, low molecular weight PAHs and alkylated PAHs, plus high ratio of phenanthrene to anthracene (>15) and low ratio of fluoranthene to pyrene (<1) suggested a petrogenic source. According to these parameters, the Changjiang (Yangtze) River estuary of Shanghai, Jiaozhou Bay of Qingdao City, Zhujiang (Pearl) River mouth, Jiulong River mouth and most of Hong Kong coastal waters were heavily contaminated by PAHs from petrogenic sources. However, PAHs in rural coastal areas were dominated by pyrolytic origin PAHs. This review clearly showed that oil pollution and incomplete combustion of oil, coal and biomass are the main reason for PAHs anormalies in the study areas.

Potential therapeutic significance of increased expression of aryl hydrocarbon receptor in human gastric cancer

AIM： To determine the functional significance of aryl hydrocarbon receptor （AhR） in gastric carcinogenesis, and to explore the possible role of AhR in gastric cancer （GC） treatment. METHODS： RT-PCR, real-time PCR, and Western blotting were performed to detect AhR expression in 39 GC tissues and five GC cell lines. AhR protein was detected by immunohistochemistry （IHC） in 290 samples： 30 chronic superficial gastritis （CSG）, 30 chronic atrophic gastritis （CAG）, 30 intestinal metapiasia （IN）, 30 atypical hyperplasia （AH）, and 70 GC. The AhR agonist tetrachlorodibenzo-para-dioxin （TCDD） was used to treat AGS cells. MTr assay and flow cytometric analysis were performed to measure the viability, cell cycle and apoptosis of AGS cells.RESULTS： AhR expression was significantly increased in GC tissues and GC cell lines. IHC results indicated that the levels of AhR expression gradually increased, with the lowest levels in CSG, followed by CAG, IM, AH and GC. AhR expression and nuclear translocation were significantly higher in GC than in precancerous tissues. TCDD inhibited proliferation of AGS cells via induction of growth arrest at the G1-S phase. CONCLUSION： AhR plays an important role in gastric carcinogenesis. AhR may be a potential therapeutic target for GC treatment.

Speeds of Sound and Excess Isentropic Compressibilities of Butyl Acetate＋Aromatic Hydrocarbons

Speed of sound data for butyl acetate＋benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressibilities （ Ks^E ） were computed from speed of sound and density data, derived from molar excess volume data. The Ks^E values were analyzed by using graph theoretical approach. The Ks^E values evaluated by graph theory compared reasonably well with their corresponding experimental values. The Ks^E data were also expressed in terms of Redlich-Kister polynomial equation to derive the coefficients and the standard deviation.

Distribution and characterizing sources of polycyclic aromatic hydrocarbons of surface water from Jialing River

Sixteen priority polycyclic aromatic hydrocarbons(PAHs) in surface water samples were analyzed by gas chromatograph-mass spectrometer(GC-MS) to study their distribution and characterizing sources.The water samples were collected from five sites(J1-J5) in the Jialing River of Chongqing downtown area from September 2009 to August 2010.The results demonstrate that the concentration of total PAHs in three samples upstream are relatively higher than those in other two sites downstream,with average concentration of total PAHs for each site ranging from 811.5 ng/L to 1585.8 ng/L.The 2,3 and 4-ring PAHs for sampling stations account for 13.0%,56.6% and 28.6%,respectively,in total PAHs.There are obvious tendencies of seasonal change for PAHs concentration in surface water.The PAHs concentration in April of wet season is 1 301.6 ng/L,which is 1.3 times the lowest amount of total PAHs in August of flood season.Ratios of specific PAH compounds were used to characterize the possible pollution sources.Experimental results indicate that the PAHs in surface water samples are primarily from pyrolytic PAHs because of factories along these sites,while the direct leakage of petroleum products may be significant for two sites,Jiahua Bridge(J4) and Huanghuayuan Bridge(J5),because of the wharf boat nearby.

Characterization of Average Molecular Structure of Heavy Oil Fractions by ~1H Nuclear Magnetic Resonance and X-ray Diffraction

The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.

The expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients

Objective:The coal-fired pollution in Xuanwei area has been considered to be local main reason for high incidence of female lung cancers.The aim of the study was to investigate the expression of PAH-DNA adducts in lung tissues of Xuanwei female lung cancer patients, and to explore the relationship between the large number of coal-fired pollution PAHs materials and the high incidence of Xuanwei female lung cancers.Methods:We totally collected each 20 cases of Xuanwei female lung cancer patients, Xuanwei male lung cancer patients, non-Xuanwei female lung cancer patients and collected each 10 cases of Xuanwei, non-Xuanwei female patients with benign lung lesions.The cancer tissues, adjacent cancer tissues and normal lung tissues were collected in lung cancer patients and only the normal tissues were collected in benign lung lesion patients.There were total 80 cases and 200 tissues.Using immunofluorescence, we detected the expression of PAH-DNA adducts in each group.Image pro-plus 6.0 software was used to analyze the images and did part quantified analysis.SPSS 13.0 statistical software was used to analyze the data.Results:The positive expressions of PAH-DNA adducts in lung cancer tissues, adjacent cancer tissues and normal lung tissues of Xuanwei female lung cancer patients were 90%, 80% and 65%, respectively.They were higher than the positive expressions of PAH-DNA adducts in Xuanwei male lung cancer patients (35%, 30% and 30%) and non-Xuanwei female lung cancer patients (20%, 15% and 10%; P<0.01).The expression of PAH-DNA adducts in lung tissues of Xuanwei female benign lung lesion patients (70%) was higher than that in non-Xuanwei female benign lung lesion patients (10%).With the direction changing from cancer tissues, adjacent cancer tissues to normal lung tissues, the expression of PAH-DNA adducts was decreased but had no statistical difference (P>0.05).Conclusion:The expression of PAH-DNA adducts in lung tissues of Xuanwei females was higher than that in Xuanwei males and non-Xuanwei females.

Vapor-Liquid Equilibrium of Toluene-Polycyclic Aromatic Hydrocarbon System in Sub- and Supercritical State

The phase behaviors of toluene/polycyclic aromatic hydrocarbon mixture systems were investigated with a continuous-flow type apparatus at 573.2, 598.2, 623.2 and 648.2 K, while the pressure changed from 1 to 5MPa. The pseudo-binary phase behaviors were predicted with the Peng-Robinson equation of state with interaction parameters between toluene and pseudo-components considered. The phase diagrams of the system have been classified following the category of phase boundary diagram models. The extraction selectivity and efficiency of tolu-ene as a solvent was discussed by comparing with that of hexane. The prediction model for selectivity was also suggested.

Use of antioxidant enzymes of clam Ruditapesphilippinarum as biomarker to polycyclic aromatic hydrocarbon pollution

The typical organic pollutant polycyclic aromatic hydrocarbon(PAH) anthracene was selected as a contaminant to investigate its eff ects on the activities of superoxide dismutase(SOD), catalase(CAT) and glutathione peroxidase(GSH-Px) in the clam Ruditapes philippinarum. The results show that SOD, CAT and GSH-Px had diff erent induction and inhibition reactions to anthracene stress, and that three diff erent organs in R. philippinarum(visceral mass, muscle tissue and mantle) had diff erent sensitivities to anthracene stress. This study suggest that SOD activities of the visceral mass, CAT activitities of the mantle and the visceral mass, and GSH-Px activity of the muscle tissue could be used as sensitive indicators of anthracene stress in R. philippinarum.

Polycyclic aromatic hydrocarbon formation under simulated coal seam pyrolysis conditions

Coal seam pyrolysis occurs during coal seam fires and during underground coal gasification. This is an important source of polycyclic aromatic hydrocarbon （PAH） emission in China. Pyrolysis in a coal seam was simulated in a tubular furnace. The 16 US Environmental Protection Agency priority controlled PAHs were analyzed by HPLC. The effects of temperature, heating rate, pyrolysis atmosphere, and coal size were investigated. The results indicate that the 3-ring PAHs AcP and AcPy are the main species in the pyrolysis gas. The 2-ring NaP and the 4-ring Pyr are also of concern. Increasing temperature caused the total PAH yield to go through a minimum. The lowest value was obtained at the temperature of 600℃. Higher heating rates promote PAH formation, especially formation of the lower molecular weight PAHs. The typical heating rate in a coal seam, 5 ℃/min, results in intermediate yields of PAHs. The total PAHs yield in an atmosphere of N2 is about 1.81 times that seen without added N2, which indicates that an air flow through the coal seam accelerates the formation of PAHs. An increase in coal particle size reduces the total PAHs emission but promotes the formation of 5- and f-ring PAHs.

SYNTHESIS OF FUNCTIONAL MACROMOLECULE INTERMEDIATE THROUGH ACYLATION CATALYZED BY [Emim]Cl-AlCl_3 IONIC LIQUID

Acylation reaction of anthracene with oxalyl chloride in the presence of [Emim]Cl-AlCl3 ionic liquid has been investigated. Pure 1,2-aceanthryenedione, which is used as intermediate of functional aromatic polymer material, was obtained by recrystalling the reaction mixture with aether and was determined by GC/MS, 1↑HNMR and FTIR analysis. The influences of various parameters, such as the contents of AlCl3 in [Emim]Cl-AlCl3, the amount of acylation agent, amount of [Emim]Cl-AlCl3, reaction temperature and reaction time were investigated. The optimum conditions were as follows： the molar fraction of AlCl3 in ionic liquid [x（AlCl3）] being 0.67, molar ratio of ionic liquid to anthracene being 2：1, molar ratio of oxalyl chloride to anthracene being 2：1, reaction temperature being 40℃ and reaction time being 6h. Under above conditions, the yield and selectivity of 1,2-aceanthrylenedione can reach 91.5% and 98.3% respectively. Further more, [Emim]Cl-AlCl3 ionic liquid, compared with metal halides such as AlCl3, was found to catalyze the reaction as a novel environmental friendly catalyst and solvent and can be reused.

A 200-Year Record of Polycyclic Aromatic Hydrocarbons Contamination in an Ombrotrophic Peatland in Great Hinggan Mountain, Northeast China

Peat bogs are regarded as one of the faithful archives of atmospheric polycyclic aromatic hydrocarbons(PAHs) deposition, and a large number of studies on PAHs accumulation in peatlands have been reported in Europe and North America. Comparatively little information is available on peat chronological records of atmospheric PAHs flux in China. We investigated the concentrations and historical accumulation rates of PAHs(AR PAHs) through geochemical analysis of three 210Pb-dated ombrotrophic peat cores from Great Hinggan Mountain, northeast China. Eight USEPA priority PAHs were detected and they are naphthalene(Nap), acenaphthylene(Acl), acenaphthene(Ace), fluorence(Flu), phenanthrene(Phe), anthracene(Ant), fluoranthene(Fla) and pyrene(Pyr), respectively. The average total eight PAHs(tPAHs) concentrations are 135.98- 262.43 μg kg-1 and the average AR tPAHs over the last two centuries are 96.45- 135.98 μg m-2 yr-1. The Ace, Acl and Phe account for 30.93- 54.04%, 25.29- 35.81%, and 9.14- 19.84% of the tPAHs, respectively, and have significant positive correlations with the tPAH. As a result, they are regarded as the iconic compounds of PAHs pollution in this area. A ca.200-yr atmospheric PAHs contamination history was reconstructed from the temporal sequences of bothconcentration and AR tPAHs, suggesting the variation of local environmental pollution. The main sources of the PAHs are identified by two isomer ratios as petrogenic origin including oil extraction and refining process as well as their combustions for industrial development. In addition, the contribution of coal combustion for industrial activities and resident heating could not be ignored. But prior to 1860, the undeveloped industry and most of agricultural activities might mainly account for the low level of PAHs, although it could infer a long-range input of atmospheric PAHs from other industrial areas. Therefore, there is a global implication to study longterm PAHs pollution records and all the results will provide practical significance in formulating policies to achieve sustainable and healthy development.

Linkage of Aromatic Ring Structures in Saturates, Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

The linkage of aromatic ring structures in vacuum residues was important for the refining process. The Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with collision-induced dissociation(CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions(SARA), and each fraction was characterized by CID technology. According to the experimental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.

Correlation of Viscosities for Alkane, Aromatic and Alcohol Family at High Pressure by Modified Tait Equation

A new model was proposed to calculate the viscosity of fluids under the pressure ranging from 0.1 to 110MPa by improving the Tait equation, in which the viscosity μ of liquids was linked with activation volume V. The model with two adjustable parameters a and fl was applied in calculating viscosities for alkane, aromatic and alcohol family at high pressure. Results show that calculated values of viscosity are in good agreement with the experimental ones, and the average relative deviations for alkanes, aromatics and alcohols are 0.56%, 0.31% and 0.66%, respectively. Besides, the errors correlated by the model proposed in this paper were equivalent to the ones from the pure empirical Tait equation, and obviously superior to those from Eyring equation.