Characterization of propylene/ethylene copolymers sequentially polymerized with delta-TiCl3/Et2AlCl catalyst system

Morphological studies of a series of propylene/ethylene sequential polymers have been carried out by permanganic etching and transmission electron microscopy, as an aid to characterization, in conjunction with differential scanning calorimetry. The materials were synthesized using a titanium-based catalyst, with propylene and either ethylene or ethylene/propylene mixture introduced successively, with the aim of examining whether a proportion of block copolymer is obtained. These materials show a complicated phase structure which does not simply reflect polymerization time but varies greatly, especially in regard to the order of introduction of the monomers, and their morphology differs in a number of ways from that of typical commercial materials. Comparison of the materials, as synthesized and after extraction with heptane, suggests that there is a certain amount of material which can compatibilize polypropylene- and ethylene-rich phases, but it was not possible to decide whether it does in fact have block structure.

Assembly of the subcellular parts of Bryopsis hypnoides Lamouroux into new protoplasts

The chloroplasts, mitochondria, and protoplasm devoid of mature chloroplasts (PMC) of Bryopsis hypnoides Lamouroux were isolated by low-speed and sucrose density centrifugation. The PMC aggregated in artificial seawater, and then protoplasts without mature chloroplasts (PtMCs) were formed. Transmission electron microscopy and cytochemical studies indicated that there were mitochondria, nuclei, vesicles, and other small cell organelles in the PtMCs. Scanning electron microscopy showed that there were holes on the surface of 1-h PtMCs and then fewer holes on the surface of 24-h PtMCs, suggesting that a healing process occurred. The plasma membrane was formed over the surface of the PtMCs. However, the cell wall was not regenerated, and the newly formed PtMCs were ruptured and died in 3 days. Light intensity during alga maintenance before use influenced significantly (one-way ANOVA, P < 0.0001) on the number of PtMCs formed; the highest number of PtMCs was formed at 20A mu mol/(m(2) s). When isolated chloroplasts were transferred into seawater, there were only two or three chloroplasts aggregated together. However, isolated mitochondria and the mixed six layers of cell organelles (separated by sucrose density centrifugation) could not aggregate in the artificial seawater. This indicates that the conjunction of cell organelles is important for their aggregation.

Relative paleointensity of the geomagnetic field during the past 200 ka from the West Philippine Sea and its chronological significance

Our rock magnetic analysis of core Ph05 from the West Philippine Sea demonstrates that the core preserves a strong, stable remanent magnetization and meets the magnetic mineral criteria for relative paleointensity (RPI) analyses. The magnetic minerals in the sequence are dominated by pseudosingle-domain magnetite, and the concentration of magnetic minerals is at the same scale. Both the conventional normalizing method and the pseudo-Thellier method were used in conjunction with the examination of the rock magnetic properties and natural remanent magnetization. Susceptibility (chi), anhysteretic remnant magnetization (ARM) and saturation isothermal remnant magnetization (SIRM) were used as the natural remanent magnetization normalizer. However, coherence analysis indicated that only ARM is more suitable for paleointensity reconstruction. The age model of core is established based on oxygen isotope data and AMS(14)C data, which is consistent with the age model estimated from RPI records. The relative paleointensity data provide a continuous record of the intensity variation during the last 200 ka, which correlates well with the global references RPI stacks. Several prominent low paleointensity values are identified and are correlated to the main RPI minima in the SINT-200 record, suggesting that the sediments have recorded the real changes of geomagnetic field.

Simultaneous determination of four phases of copper in geological samples

According to the specific property of respective phases in copper ore, optimal extracting condition for, tour phases of copper with five infusion was examined. After a series of experiments, for example, different weight Of sample, artificial mixed single phases sample and repeated experiment, the extracting ratio constants foil all phases in different infusions were obtained. The mathematical model which is on the basis of the stable extracting constant is established. Based on the purpose-control genetic algorithms, we only need to determine the total copper in the sample in different infusions under the selected condition, then the value of respective phase could be calculated. The-relative standard deviation are (%) free oxidized copper phase:1.5, conjunction oxidized copper phase: 17.6,, secondary copper sulfide phase: 1.9, primary copper sulfide phase : 2.7,total copper: 0.8.

Observational evidence of the Yellow Sea warm current

The Yellow Sea Warm Current (YSWC) is one of the principal currents in the Yellow Sea in winter. Former examinations on current activity in the Yellow Sea have not observed a stable YSWC because of the positioning of current meters. To further understand the YSWC, a research cruise in the southern Yellow Sea was carried out in the winter of 2006/2007. Five moorings with bottom-mounted acoustic Doppler current profilers (ADCP) were deployed on the western side of the central trough of the Yellow Sea. The existence and distributional features of the YSWC were studied by analyzing three ADCP moorings in the path of the YSWC in conjunction with conductivity-temperature-depth (CTD) data over the observed area in the southern Yellow Sea. The results show the following. (1) The upper layer of the YSWC is strongly influenced by winter cold surge; its direction and speed often vary along a south-north axis when strong cold surges arrive from the north. (2) The YSWC near the bottom layer is a stable northwest flowing current with a speed of 4 to 10 cm/s. By combining the analyses of the CTD data, we speculate that the core of the YSWC may lie near the bottom. (3) On a monthly average timescale, the YSWC is stably oriented with northward flow from the sea surface to the sea floor.

羟基自由基降解琼胶及其产物的活性研究

琼胶是一种从石花菜等红藻中提取的，目前生产工艺和结构等方面研究比较成熟的海藻多糖，广泛应用于医药、仪器等行业。但是，海藻多糖因为具有分子量大，粘度大，溶解度较小的等特点，而使其应用范围受到限制。利用降解的手段对其进行修饰，降低分子量和粘度，改善溶解性，可以拓展其应用范围。并且根据文献报道，琼 胶寡糖具有一些特殊的生物活性，如抗氧化性，抗炎症等。因此，对琼胶降解的研究具有生要意义。本研究中，为了选择一种合适的降解方法，进行了几种水解方法的尝试，其中包括在不同湿度和酸度下盐酸水解，过氧化氢和醋酸催化水解，Fenton体系羟基自由基降解。对于酸水解和Fenton体系氧化还原降解方法，通过粘度法对反应的速度进行了比较，表明氧化还原降解反应中琼胶的粘度降低比较快，并且具有代表性和新意，确定为本实验的降解琼胶的方法并对氧化还原降解所得的产物进行了活性实验。通过模仿自然界普遍存在的氧化还原降解反应，利用Vc诱导的Fenton体系产生的羟基自由基氧化还原降解琼胶得到低分子量的琼胶。降解产物经过高速离心、60％乙醇沉淀，除去分子量比较大的降解产物和磷酸盐，得到可溶于60％乙醇的分子量估计小于3000的降争产物，其产率为85％。利用经Sephadex-G25凝胶色谱分离所香的不同分子量的级分进行分子量和α－葡萄糖苷酶抑制活性关系的实验。降解产物对α－葡萄糖苷酶的抑制率和各级分的浓度呈线性正相关，并且各级分的IC_(50)则随着分子量的降低而降低。另外，对所得的降解产物混合物进行了红外吸收光谱、质子去偶核磁共震碳谱和负离子基质辅助激光诱导－飞行时间质谱结构分析。结果表明，氧化还原降解反应的专一性差，在得到寡糖的同时，在光谱图中出现一些比较复杂的副产物的结构信息。最后，根据MTT法的原理，以有体皮肤成纤维细胞为材料，通过紫外线辐射产生自由基造成氧化损伤，研究降解产物对成纤维细胞的保护作用。当无紫外线辐射时，降解产物对成纤维细胞具有显著的促进生长增殖作用：当经UVa、UBb辐射时则可以显著地表现出对损伤的保护作用，并且这种促进生长和保护作用呈显著的量效关系，表明降解产物具有清除基自由基的作用。但是，因为氧化还原降解以应的机理尚不十分明的以及琼羟胶的特殊结构，使得反应的副产物很难预测，也就使得分离工作难以进行，所以，根据目前所得的信息，尚不能确定是降解产物的什么级分产生的以上两种生物活性。

渤海湾盆地济阳坳陷东部走滑构造特征及其对油气成藏的影响研究

研究区位于郯庐断裂中段与济阳坳陷的构造结合部，区内走滑构造广泛发育，主要的走滑断裂有7条，分别是郯庐断裂带的东西两支、垦东断层、孤东断层、长堤断层、埕东断层和发育于垦东凸起中部的浅层走滑构造带。走滑构造带与油气富集带有着明显的对应关系。 通过对研究区内二维、三维地震测线和平面构造图的精细解释和分析，分别揭示了各走滑断裂在平面、剖面和三维空间上的构造形态。根据走滑断裂及其伴生构造的平面和剖面上的几何学特征，将研究区内的走滑断裂划分为三种类型：成熟型走滑断裂、隐伏型走滑断裂、不连续型的走滑断裂。 从理论模式研究入手，推导了拉分盆地中盆地的走滑速率与沉降速率之间的关系，证实了走滑速率同盆地的几何形状参数、最大沉降深度和盆地的沉降速率存在着稳定的数值关系。通过对莱州湾地区潍北凹陷基底沉降历史的分析，建立了潍北凹陷沉降速率与郯庐断裂中段走滑速率之间的经验关系式，进而求出郯庐断裂中段新生代右行走滑位移量的大小为40km。 运用2DMove软件，对研究区内四条典型剖面进行构造复原，计算出了各条剖面每个时期的伸展参数，对研究区构造活动强度进行了定量分析，揭示了研究区的构造演化规律。通过运用Ansys软件进行有限元模拟，恢复了晚白垩世晚期-古近纪早期研究区内的构造应力场和应变场，揭示了扭张作用是研究区内走滑断层开始走滑的主要原因。 通过上述分析，结合对究区内近几年勘探开发成功和失败的实例分析，全面探讨了走滑活动对于油气成藏“生”、“储”、“盖”、“圈”、“运”、“保”各因素的影响。

The nitrogen isotopic composition of dissolved nitrate in the Yangtze River (Changjiang) estuary, China

The nitrogen isotopic composition of dissolved nitrate (delta N-15-NO3-) in surface water of the Yangtze River estuary was determined in four seasons of 2006. delta N-15-NO3- ranged from 0.4 parts per thousand to 6.5 parts per thousand and varied with seasons and geographic regions, reflecting the dynamics of nitrogen cycling in the estuarine ecosystem. delta N-15-NO3- was markedly lower in February than in other seasons and exhibited conservative mixing, which was probably attributed to the NO3- being sourced from the atmospheric deposition and agricultural fertilizer. In the upper estuary, the influence of riverine inputs was important during all surveys. in the turbidity maximum zone, nitrification was found with nitrate depleted in N-15 in May, whereas denitrification resulting in heavy delta N-15-NO3- played an important role in August. More enriched delta N-15-NO3- values coinciding with losses of nitrate concentrations based on the conservative mixing model were found in the adjacent marine area in May, and may reflect obvious phytoplankton assimilation of dissolved nitrate. In this manner, delta N-15-NO3- may be a sensitive indicator of nitrogen sources and biogeochemical processing existing in this estuary in conjunction with the variations of dissolved nitrate and other environmental factors. (C) 2009 Elsevier Ltd. All rights reserved.

Seasonal changes in the distribution of dissolved organic nitrogen in coastal and open-ocean waters in the North East Pacific: sources and sinks

The distribution of dissolved organic nitrogen (DON) and nitrate were determined seasonally (winter, spring and summer) during three years along line P, i.e. an E-W transect from the coast of British Columbia, Canada, to Station P (50degreesN, 145degreesW) in the subarctic North East Pacific Ocean. In conjunction, DON measurements were made in the Straits of Juan de Fuca and Georgia within an estuarine system connected to the NE Pacific Ocean. The distribution of DON at the surface showed higher values of 4-17 muM in the Straits relative to values of 4-10 muM encountered along line P, respectively. Along line P, the concentration of DON showed an inshore-offshore gradient at the surface with higher values near the coast. The equation for the conservation of DON showed that horizontal transport of DON (inshore-offshore) was much larger than vertical physical mixing. Horizontal advection of DON-rich waters from the coastal estuarine system to the NE Pacific Ocean was likely the cause of the inshore-offshore gradient in the concentration of DON. Although the concentration of DON was very variable in space and time, it increased from winter to summer, with an average build up of 4.3 muM in the Straits and 0.7 muM in the NE subarctic Pacific. This implied seasonal DON sources of 0.3 mmol N m(-2) d(-1) at Station P and 1.5 mmol N m(-2) d(-1) in the Straits, respectively. These seasonal DON accumulation rates corresponded to about 15-20% of the seasonal nitrate uptake and suggested that there was a small seasonal build up of labile DON at the surface. However, the long residence times of 180-1560 d indicated that the most of the DON pool in surface waters was refractory in two very different productivity regimes of the NE Pacific. (C) 2002 Elsevier Science Ltd. All rights reserved.

LC-DAD-ESI-MS Characterization of Carbohydrates Using a New Labeling Reagent

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupling to liquid chromatography with electrospray ionization mass spectrometry for the detection of carbohydrates from the derivatized rape bee pollen samples is reported. Carbohydrates are derivatized to their bis-NMP-labeled derivatives. Derivatives showed an intense protonated molecular ion at m/z [M+H](+) in positive-ion detection mode. The mass-to-charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative analysis of carbohydrates. This characteristic fragment ion is from the cleavage of C2-C3 bond in carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose and glyceraldehydes and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids such as galacturonic acid and glucuronic acid (m = n - 2, n is carbon number of carbohydrate). No interferences for all aliphatic and aromatic aldehydes presented in natural environmental samples were observed due to the highly specific parent mass-to-charge ratio and the characteristic fragment ions. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed-phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected.

Application of 2-(11H-benzo[a] carbazol-11-yl) Ethyl Carbonochloridate as a Pro-column Derivatization Reagent of Amino Acid by High Performance Liquid Chromatography with Fluorescence Detection

On a reversed phase Hypersil BDS C-18 (200 mm x 4. 6 mm, 5 mu m) column, 20 amino acids, which were derivatized using 2-(11H-benzo [a] carbazol-11-yl) ethyl carbonochloridate (BCEC-Cl) as pre-column derivatization reagent, were separated in conjunction with a gradient elution. Optimum derivatization was obtained by reacting of amino acids with BCEC-Cl at room temperature for 5 min in the presence of sodium borate catalyst in acetonitrile solvent. The fluorescence excitation and emission wavelengths were 279 nm and 380 nm respectively. The identification of amino acid derivatives from hydrolyzed bovine serum albumin and bee pollen was carried out by post-column mass spectrometry with electrospray ion source in positive ion mode. Linear correlation coefficients of the amino acid derivatives were > 0.9990, and detection limits (at signal to noise of 3:1) were 1.49 - 19.74 fmol for the labeled amino acids.

Analysis of carbohydrates in a tibetan medicine using new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone, by HPLC with DAD detection and ESI-MS identification

A new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP), coupling with liquid chromatography (LC) with electrospray ionization mass spectrometry (ESI-MS) for the detection of carbohydrates from a famous Tibetan medicine is reported. Carbohydrates were derivatized to their bis-NMP-labeled derivatives. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose, and fucose could be successfully detected by UV and ESI-MS. Derivatives showed intense protonated molecular ion at m/z [M+H]+ in positive ion mode. The mass to charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative identification of carbohydrates; this characteristic fragment ion was from the cleavage of C2-C3 bond in the carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose, and glyceraldehydes, and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids, such as galacturonic acid and glucuronic acid (m=n-2, n is carbon atom number of carbohydrate). Compared with the traditional 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent, currently synthesized NMP show the advantage of higher sensitivity to carbohydrate compounds with UV and ESI-MS detection.

Analysis of saturated free fatty acids from pollen by HPLC with fluorescence detection

A sensitive method for the determination of free fatty acids using 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-dimidazol-1-yl) ethyl-p-toluenesuIfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K2CO3 catalyst at 90 degrees C for 40 min in N,N-dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C8 column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post-column APCI/MS in positive-ion detection mode. ANITS-fatty acid derivatives gave an intense molecular ion peak at mlz [M+H](+); with MS/MS analysis, the collision-induced dissociation spectra of m/z [M+H](+) produced the specific fragment ions at mlz [M-345](+) and mlz 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were lambda(ex) = 250 nm and lambda(em) = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are > 0.9999. Detection limits, at a signal-to-noise ratio of 3 : 1, are 24.76-98.79 fmol for the labeled fatty acids.

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization 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 with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

西秦岭新生代火山岩中的地幔捕虏体和捕虏晶研究

Western Qinling, a conjunction region of the North China Craton, the Yangtze Craton and the Tibetan Plateau, has very complicated history of geologic and tectonic evolution. Previous studies mainly focus on tectonics and petrology of volcanic rocks in the western Qinling. Therefore, little is known about the Cenozoic lithospheric mantle beneath the western Qinling. Mafic, ultramafic and/or alkaline volcanic rocks and their entrained mantle peridotitic xenoliths and xenocrysts are known as samples directly from the lithospheric mantle. Their petrological and geochemical characteristics can reflect the nature and deep processes of the lithospheric mantle. Cenozoic volcanic rocks in the western Qinling contain abundant mantle xenoliths and xenocrysts, which provide us an opportunity to probe the lithospheric mantle beneath this region and a new dimension to insight into geologic evolution. Cenozoic volcanic rocks (7-23 Ma) from the western Qinling are sparsely distributed in the Lixian-Dangchang-Xihe Counties, Gansu Province, China. Volcanic rocks contain plenty of mantle-derived xenoliths, including spinel lherzolites with subordinate wehrlite, dunite, olivine websterite, clinopyroxenite and garnet lherzolite, and few olivine, clinopyroxene and spinel xenocrysts. These peridotitic xenoliths show clear deformed textures and their major minerals show excellent orientation. Thus, these peridotites are typical deformed peridotites. Olivine xenocrysts have clearly-zoned textures. The peridotitic xenoliths can be divided into two groups based on their compositions, namely, the H-type and L-type. The H-type peridotites are characterized by high Fo (>90) in olivines in which fine-grained ones have higher Fo than the coarse grains, low CaO (<20 %) in clinopyroxenes, high Cr# (>40) in spinels and high equilibration temperatures. They may represent the refractory lithospheric mantle. In contrast, the L-type peridotites contain low Fo (<90) olivines (with lower Fo in fine-grained olivines), high CaO (>20 %) clinopyroxenes, low Cr# (<20) spinels and low equilibration temperatures. They experienced low degree of partial melting. The Cenozoic lithospheric mantle beneath the western Qinling was refractory in major element compositions based on the mineral compositions of xenoliths and xenocrysts and experienced complicated deep processes. The lithospheric mantle was modified by shear deformation due to the diapirism of asthenosphere and strong tectonic movements including the collision between North China Craton and Yangze Craton and the uplift of Tibetan Plateau, and then underwent metasomatism with a hydrous, Na, Ti and Cr enriched melt.