10种芳香化合物的分离及紫外和荧光光谱研究

采用反相高效液相色谱梯度洗脱，在SinoChrom ODS-BP型色谱柱（4．6mm×200mm，5μm）上，实现了包括5种荧光衍生试剂母体分子（咔唑、1，2-苯并-3，4-二氢咔唑、吖啶酮、2-苯基-1-氢-菲[9，10-d]咪唑、吡唑并[3，4-b]-7-甲基喹啉）在内的10种含氮芳香化合物的基线分离。通过测定每种物质的紫外吸收曲线，得到了它们的最大紫外吸收波长和摩尔吸光系数（ε），并探讨了分子结构、摩尔吸光系数（ε）和灵敏度之间的关系。扫描了它们的荧光激发和发射光谱，得出了它们的最大激发波长和发射波长。

柱前衍生-高效液相色谱分离测定及质谱鉴定脂肪胺

采用新型荧光衍生试剂2-(2-苯基-1-氢-菲[9,10-d]咪唑)-乙酸(PPIA)进行柱前衍生,经荧光检测实现了脂肪胺的高效液相色谱(HPLC)分离测定及柱后质谱鉴定.60℃下在乙腈溶剂中用N-乙基-N′-[ (3-二甲氨基) 丙基 ]碳二亚胺盐酸盐(EDC)做缩合剂,衍生反应15 min可获得稳定的荧光产物.脂肪胺衍生物荧光检测波长为380 nm(激发波长为260 nm).在Eclipse XDB-C8 色谱柱上,采用梯度洗脱对12种脂肪胺衍生物进行了优化分离,测定了造纸厂废水、大鼠端脑和酸奶中脂肪胺的含量.经柱后在线质谱大气压化学电离源(APCI Source)正离子模式实现了各种脂肪胺衍生物的质谱鉴定,借助对活性中间体的质谱解析确定了衍生反应的反应机理.该方法具有良好的重现性和回收率,多数脂肪胺的线性回归系数大于0.9996;检出限为3.1～18 fmol (S/N＝3∶ 1)

高寒湿地太阳辐射和地表反射率变化的统计学特征

依据祁连山海北高寒湿地植物生长期观测的太阳总辐射(E_g)和反射辐射(E_r)资料, 分析了高寒湿地Eg和地表反射率(A)的日及季节变化特征. 结果表明:祁连山海北高寒湿地, 有较强的Eg, 但A较低. 年内1～12月E_g的平均日总量达17.3 MJ•m~(-2), 其中植物生长期的5～9月平均日总量为20.0MJ•m~(-2), 表现出4～7月高, 冷季低的变化特征. A的日、季节变化均表现 "U"型变化过程. 2004年1～12月A的年平均值为0.32, 植物生长季的5～9月平均值为0.18, 植物非生长季的10月～翌年4月平均值为0.43. 其中1月最高(0.70), 7月最低(0.16).

唐古特大黄染色体的核型分析

目的对蓼科（Polygonaceae）植物唐古特大黄（Rheum tanguticum Maxim、ex Balf．）染色体核型进行研究。方法采用常规压片方法，并结合显微摄影对染色体进行检测分析。结果唐古特大黄体细胞染色体数目为2n=22；核型公式为K（2n）=22=20m＋2sm，核型为“1A”型。结论唐古特大黄染色体的核型属于较原始的类型。

柱前衍生-反相高效液相色谱荧光测定及质谱鉴定土壤和苔藓中的脂肪酸

合成新型荧光衍生试剂1-[2-(对甲苯磺酸酯)乙基]-2-苯基咪唑[4，5．f]9，10-菲(TSEPIP)，将其作为柱前衍生化试剂，在Eclipse XDB-Cs色谱柱上，采用梯度洗脱实现了30种游离脂肪酸(FFA)衍生物的基线分离。利用柱后在线的串联质潜以APCI大气压化学电离源正离子模式实现了各组分的质谱定性。对土壤与两种苔藓(狭叶绢藓、曲尾藓)中FFA组分的定量结果表明，苔藓植物从土壤中富集了大量的游离脂肪酸。荧光检测的激发和发射波长分别为λ_(ex)=260 mn，λ_(em)=380 nm。绝大多数脂肪酸的线性回归系数大于0．9993，检出限为3．2～37 fmol。建立的方法具有良好的重复性，对实际样品测定结果满意。

荧光衍生试剂1-[2-（对甲苯磺酸醋）乙基]2-苯基咪唑[4,5-f]9,10-菲的合成及其在长链脂肪酸分析中的应用

合成了新的荧光衍生试剂1-[2-（对甲苯磺酸酯）乙基]-2-苯基咪唑[4,5-f]9,10-菲（TsEPIP），并将其作为柱前衍生化试剂，在Eclipse XDB-C：色谱柱上采用梯度洗脱实现了11种长链（C_(20)～C_(30)）游离脂肪酸（FFA）衍生物的基线分离。利用柱后在线的串联质谱并以大气压化学电离源（APCI）的正离子模式实现了各组分的质谱定性。对土壤及3种苔醉（东亚毛灰鲜、锦丝鲜、羽平鲜）中FFA组分的定量结果表明，苔鲜植物从土壤中富集了大量的长链游离脂肪酸。荧光检测的激发波长和发射波长分别为260 nm和380 nm。线性回归系数大于0.9996，检测限为26.19～76.67 fmol。所建立的方法具有良好的重现性，对实际样品的测定结果令人满意。

栽培川西獐牙菜中6种药用成分的测定方法和动态积累研究

采用反相高效液相色谱法对川西獐牙菜中6种药用成分不同生长期的含量进行了测定.色谱柱为Kromasil C18(250 mm×4.60 mm,5 μm),流动相为甲醇-0.02%的磷酸水溶液,检测波长260 nm.该方法具有很好的线性关系和回收率.结果显示,川西獐牙菜全草的最佳采收期为9月中旬(花果期).

川西獐牙菜与抱茎獐牙菜中酮的高效液相色谱分析

采用反相高效液相色谱法同时分离和测定了龙胆科獐牙菜属的川西獐牙菜和抱茎獐牙菜中几种酮的含量.色谱柱为Kromasil C_(18)(250 mm * 4.60 mm i.d., 5 μm),流动相为甲醇-0.1%的磷酸水溶液(体积比为73∶27),流速1 mL/min,检测波长260 nm,柱温20 ℃.实验结果表明,该方法具有很好的线性关系与精密度,方法简单、准确、实用性强.

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.

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.

博兴洼陷新生代构造-沉积演化及其对鲁西隆起的响应

The West Shandong Uplift and its adjacent basins, with same evolutional history before Mesozoic, are an important basin-orogenic systems in North China. After late Mesozoic, tectonic differentiation between basin and orogenic belt gradually displayed in the study area. The Boxing sag is a part of Jiyang Depression near to West Shandong Uplift, in which the whole Mesozoic and Cenozoic strata are preserved. Based on the analysis of sedimentary records in the Boxing sag, the Cenozoic structural and sedimentary evolutions in Boxing Sag and its response to Western Shandong uplift are discussed in this dissertation. The main conclusions in this research are presented as follows. Based on Seismic and well logging profile interpretation, fault growth index, thickness difference between bottom wall and top wall and fault activity rate from Eocene to Pliocene are studied. Boxing sag had three main faults, NE, NW and NEE trending faults. Research shows that the activity of the NW trending fault in the Boxing sag became weaken from E1-2S4 to N2m gradually. The evolution of NE and the NEE trending fault can be divided into three episodes, from E1-2k to E2s4, from E2s3 to E3s1, from N2m to E3d. The analysis of Paleogene samples of heavy mineral assemblages shows that metamorphic rocks represented by garnet, intermediate-acid igneous rocks represented by the assemblage of apatite, zircon and tourmaline became less from E1-2k to N2g, and sedimentary rocks represented by the assemblage of pyrite, barite and limonite also became less. Intermediate-basic igneous rocks represented by the assemblage of leucoxene, rutile and ilmenite and metamorphic rocks represented by epidote became more and more. Electronic microprobe analysis shows that glaucophane and barroisite are existed in Kongdian Formation and the 4th member of Shahejie Formation, and they demonstrate that Western Shandong and Eastern Shandong are all the source regions of the Boxing Sag, and they also indicate that oceanic crust existed before the collision between the Yangtze and North China continent. The fact that Eastern Shandong is the source region of Boxing Sag also indicates that Western Shandong was not high enough to prevent sediment from Eastern Shandong at E1-2k and E2s4. The results of the dating of five detrital zircons of Boxing Sag show Kongdian Formation and the 4th member of Shahejie Formation have the age peaks of 2800Ma and 700-800. It means that Eastern Shandong is the source region of Boxing Sag at early Paleogene and Western Shandong is not high enough to prevent the sediment from Eastern Shandong. The ages of 160-180 and 220-260 Ma, which exist in the Guantao Formation and Paleogene, are common in Eastern Shandong and rare in Western Shandong,and it implied that Western Shandong is a low uplift at 24Ma. The Paleogene strata have almost same age groups, while the Guantao Formation has significant variations of age groups, and this indicates that Boxing Sag and Western Shandong uplift had taken place tremendous changes. The results of apatite fission track in Boxing sag show that three times uplifts happened at the source region at 60 Ma, 45Ma and 15Ma respectively, and the Boxing sag experienced two subsidences at 60Ma, 45Ma and one uplift at 20Ma.

甘肃西峰晚第三纪红粘土地层中的蜗牛化石记录及其古环境意义

In this study, 260 mollusk fossil samples from a Red Clay sequence at Xifeng, Gansu province, in the northern China were analyzed quantitatively. 12 fossil species and four fossil zones have been identified. Three main ecological groups were determined based on ecological requirement of each mollusk taxon. According to fossil composition and succession of three ecological groups, the author discussed the origin and sedimentary environment of the red clay deposits, and the process of ecological environmental changes as well as the variations of the East Asia monsoons during 6.2-2.4 Ma in the Loess Plateau. A preliminary study on periodicity of paleoclimatic changes was also conducted by using spectral analysis method. The main results and conclusions are presented as follows:A continuous land mollusk fossil sequence of 6.2-2.4 Ma from Xifeng Red Clay Formation has been established, which provided a basic data for studying the environmental changes during late Miocene to Pliocene.The study of composition and preservation condition of mollusk fossils reveals a terrestrial in situ ecological population in the Red Clay Formation. All of identifiable mollusk species are composed of terrestrial taxa, which support the view that the Red Clay is an eolian origin, similar to the overlying Quaternary loess deposits.The mollusk record reveals the processes of ecological and environmental changes during 6.2-2.4 Ma in the Loess Plateau. Climatic changes experienced cold and dry from 6.2-5.4 Ma, warm and wet during 5.4-4.5 Ma, mild and moderate from 4.5-3-4 Ma, to rapid cooling and drying after 3.4 Ma. From '5.4- 2.4 Ma, climate was stepwise cooling. The cooling trend is in good agreement with a general1 0global cooling trend during this period, as documented by marine 5 0 records.4. Three remarked ecological shifts took place in mollusk assemblages from 6.2-2.4 Ma, focused on about 5.4, 4.5 and 3.4 Ma. The warming shift around 5.4 Ma was probably related to the rising of the global temperature. The cooling shifts around 4,5 and 3.4 Ma however might be closely linked to the uplift of Tibet Plateau and the development of Northern Hemisphere ice sheet.The succession in mollusk ecological groups also recorded the variability of the East Asian winter and summer monsoon. The winter monsoon dominated two periods from 6.2-5.4 Ma and from 3.4-2.4 Ma, while the summer monsoon was strong during 5.4-4.5 Ma. The variations in winter and summer monsoons were in phase during 4.5-3.4 Ma. Monsoon regimes changed with the duration about 1 Ma, which roughly corresponds to the cycle driven by tectonic activity on the time scales of ICP-IO7 years. In addition, mollusk fossils recorded the large amplitude and high frequency fluctuations overlapped on 105-107 years climate cycle.The maximum entropy spectral analysis and filter-band analysis of total mollusk individuals and three typical ecological groups suggest that the climate changes controlled mainly by solar insolation had periods about 70 ka and 40 ka on the time scales of 105 during late Miocene-Pliocene. Climatic periodicity intensified from 4.0 Ma, which reflected strengthened forcing by high latitude ice volume.

上地幔橄榄石电导率影响因素及高压相变初探

人们对上地幔标志性矿物橄榄石的认识，基本上是经历一个从直流到交流，又从交流到阻抗谱的认识过程．本文主要通过对橄榄石电导率的影响因素出发，包括温度、压力、铁镁比值、氧逸度等因素的影响和制约．用目前国际高温高压学术界公认的阻抗谱技术探讨了橄榄石在高压下的相变，并在此基础上，进一步研究地球物理学家非常关心的热点问题-冷地幔的实验室的模拟，并作了充分的论证．

贵州水银洞卡林型金矿床首次发现大量次显微-显微可见自然金颗粒

在贵州水银洞卡林型金矿床原生富矿石的一条含砷黄铁矿细脉中发现有100余粒次显微-显微自然金颗粒（0．1～6μm），并具有清晰的显微岩相学结构。提出了该类型金矿次显微-显微可见自然金颗粒的形成过程可能与含Au热液-岩石相互作用过程中含Fe碳酸盐矿物溶解释放Fe的大量硫化物化而导致热液中Au的过饱和有关，含Fe碳酸盐赋矿围岩是形成高品位大型卡林型金矿床最重要的控制因素之一。