Bromophenols coupled with nucleoside bases and brominated tetrahydroisoquinolines from the red alga Rhodomela confervoides

Three new bromophenols C-N coupled with nucleoside base derivatives (1-3) and three new brominated 1,2,3,4-tetrahydroisoquinolines (5-7, together with a new brominated tyrosine derivative (4, have been isolated from polar fractions of an ethanolic extract of the red alga Rhodomela confervoides. By spectroscopic and chemical methods including HRMS and 2D NMR data, their structures were determined as 7-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]-3,7-dihydro-1H-purine-2,6-dione (1), 7-(2,3-dibromo-4,5-dihydroxybenzyl)-3,7-dihydro-1H-purine-2,6-dione (2, 9-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]adenine (3), (-)-8S-(3-bromo-5-hydroxy-4-methoxy)phenylalanine (4), (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (5), methyl (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (6), and methyl (-)-3S-6-bromo-8-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (7). Compounds 5-7 were semisynthesized by using 4 as the starting material.

甘肃黄芪对多柔比星心肌病大鼠心肌组织部分基因表达的影响

目的 比较正常大鼠和多柔比星心肌病大鼠心肌组织部分基因表达谱的差异,探讨甘肃黄芪对上述基因表达谱的影响.方法 30只Wistar大鼠随机分3组:对照组即生理盐水组(n=10),多柔比星组(n=10)和黄芪+多柔比星组(n=10).分别从3组心肌组织中抽提总RNA,用Cy3,Cy5荧光标记,经逆转录合成动物来源的eDNA探针;eDNA探针与4000点基因表达谱芯片杂交,结果由软件分析表达信号.结果 共有923条基因出现差异表达,其中586条基因表达下调,337条基因表达上调.凋亡相关基因表达在多柔比星心肌病时上调;氧化和能量代谢相关基因的表达在多柔比星心肌病时下调.6个在多柔比星组上调的基因在黄芪+多柔比星组下调,8个在多柔比星组下调的基因在黄芪+多柔比星组上调,3个在多柔比星组上调的基因在黄芪+多柔比星组表达进一步增强.结论 凋亡和能量代谢障碍及免疫因素在多柔比星心肌病的发病机制中参与作用,甘肃黄芪对多柔比星诱导的心肌病大鼠的心脏保护作用是通过多基因多途径调节相关基因表达而实现的.

高原鼠兔对高寒草甸土壤有机质及湿度的作用

为探讨高原鼠兔对土壤理化性质的作用,本研究于2005年8月,采用灼烧和烘干法,分别测定了高原鼠兔栖息及被灭杀地区土壤有机质含量及湿度.结果表明:高原鼠兔栖息地区,0～5 cm及6～10 cm土壤层有机质含量和湿度均极显著或显著高于被灭杀地区;11～30 cm土壤层,二者无显著的差异;31～50 cm土壤层,有机质含量差异极显著,而土壤湿度则无显著差异.说明,高原鼠兔活动可增加高寒草甸土壤表层有机质含量和湿度,进而改变土壤理化性质,促进生态系统物质循环.

传统藏药材高原香薷的矿质元素分析

对传统藏药材香薷中高原香薷种的17种微量元素进行了分析。结果表明，在高原香薷中人体必需微量元素Cu、Zn、Fe、Mn、Co、Ni、Se等含量较高，尤其以Cu、Fe、Mn元素的含量为高。Na、Ca等宏量元素含量亦较高。

不同海拔地区紫外线B辐射状况及植物叶片紫外线吸收物质含量的分析

对不同海拔地区的太阳 UV- B辐射和植物叶片的光学特性进行了比较研究。结果表明 :位于高海拔地区的海北高寒草甸生态系统定位站 ,太阳 UV- B辐射明显高于相近纬度的西宁、兰州和南京地区。UV- B辐射与总辐射和 PAR的日变化规律相似 ,都受太阳高度角的直接影响 ,在当地太阳正午时最高。UV- B/Q的日变化也为单峰曲线 ,海北站地区的 UV- B/Q高于西宁的同期测定结果。对珠芽蓼等植物的研究表明 ,生长于海北站地区的珠芽蓼 ,其叶片中紫外线吸收物质的含量明显高于西宁的同种植物 ,也略高于海拔较高的达坂山和小达坂山山顶的同种植物。叶绿素含量以海北站珠芽蓼最低 ,达坂山和小达坂山的同种植物最高。珠芽蓼叶片中类胡萝卜素的含量以西宁最低, 海北站、达坂山和小达坂山依次升高。海北站矮嵩草与从海北站移植到西宁生长4年的同种植物相比, 叶片中紫外线吸收物质、叶绿素、类胡萝卜素的变化与生长于两地区的珠芽蓼相同。

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.

Lack of altitudinal trends in phytochemical constituents of Swertia franchetiana (Gentianaceae)

Diverse biological characters commonly vary with altitude in species that have a wide altitudinal distribution, partly at least as a result of adaptation to differences in aridity, but whether such variation exists for phytochemical constituents remains unknown. Therefore, levels of seven important phytochemical constituents of Swertia franchetiana (swertiamarin, oleanolic acid, swertisin, mangiferin, 1,5,8-trihydroxy-3-methoxyxanthone, 1,8-dihydroxy-3,7-dimethoxyxanthone and 1,8-dihydroxy-3,5-dimethoxyxanthone) were studied and statistically compared, using materials collected from sites ranging from 2200 to 3960 m in altitude. Swertiamarin was the most abundant in all samples, then mangiferin, oleanolic acid and the other three xanthones. Throughout the distributional range of this species, no altitudinal trend was detected for other constituents except 1,8-dihydroxy-3,7-dimethoxyxanthone, which showed a negative correlation with altitude. However, the concentration of 1, 8-dihydroxy-3,7-dimethoxyxanthone and mangiferin showed a significantly latitudinal and longitudinal correlation. (C) 2004 Elsevier Ltd. All rights reserved.

青岛晚白垩世岩石圈结构特征：劈石口晚白垩世基性脉岩及其捕虏体提供的证据

The occurrence of Late Cretaceous mafic dykes and their entrained peridotite and granulite xenoliths as well as clinopyroxene xenocrysts in the Qingdao region provide us a precious opportunity to unveil the nature and characteristics of the Late Mesozoic lithospheric mantle and lower crust beneath the Jiaodong region, and the change of the magma sources. These studies are of important and significant for understanding the lithospheric evolution in the eastern North China Craton. There were two periods of magma activities in Late Mesozoic in Qingdao Laoshan region, one was around 107Ma in the Early Cretaceous and the other around 86Ma in the Late Cretaceous according to the whole rock K-Ar age determination. The Early Cretaceous mafic dykes and the Late Cretaceous mafic dyke (i.e. Pishikou mafic dike) have completely different geochemical characteristics. The Early Cretaceous mafic dykes are enriched in LILE, strongly depleted in HFSE (Nb, Ta, Zr, Hf) and characterized by the highly radiogenic Sr and Nd isotopic compositions. These geochemical features indicate that the Early Cretaceous mafic dykes were derived from an enriched lithospheric mantle. In contrast, the Late Cretaceous mafic dyke is enriched in LILE, without HFSE depletion (Nb, Ta, Zr, Hf) and has less radiogenic Nd and Sr isotopic compositions. These geochemical features indicate that the Late Cretaceous mafic dyke was derived from the asthenosphere modified by subducted pelagic sediment contamination. The intrusive age of the Late Cretaceous mafic dyke provides further information for the termination of the lithosphere thinning for the eastern North China Crtaon. Pishikou Late Cretaceous mafic dyke contains abundant peridotitic xenoliths, granulite xenoliths and clinopyroxene xenocrysts. The peridotitic xenoliths can be divided into two types: high Mg# peridotites and low Mg# peridotites, according to their textural and mineral features. The high-Mg# peridotites have high Fo (up to 92.2) olivines and high Cr# (up to 55) spinels. The clinopyroxenes in the high# peridotites are rich in Cr2O3 and poor in Al2O3. The low-Mg# peridotites are typified by low Mg# (Fo <90) in olivines and low Cr# (Cr# <0.14) in spinels. The clinopyroxenes in the low-Mg# peridotites are rich in Al2O3 and Na2O and poor in Cr2O3. These two type peridotites have similar equilibrated temperatures of 950C-1100C. The Clinopyroxenes in the high-Mg# peridotites generally have high and variable REE contents (REE = 5.6-84 ppm) and LREE-enriched chondrite-normalized patterns ((La/Yb)N>1). In contrast, the clinopyroxenes in the low-Mg# peridotites have low REE contents (REE = 12 ppm) and LREE-depleted patterns ((La/Yb)N<1). The textural, mineral and elemental features of the low-Mg# peridotites are similar to those of the low-Mg peridotites from the Junan, representing the newly-accreted lithospheric mantle. However, the mineralogical and petrological features of the high-Mg# peridotites are similar to those of the high-Mg# peridotites from the Junan region, representing samples from the old refractory lithospheric mantle that was strongly and multiply affected by melts of different origins Late Cretaceous mafic dike in the Qingdao region also contains two types of granulite xenoliths according to the mineral constituents: the pyroxene-rich granulites and the plagioclase-rich granulites. Equilibrated temperatures calculated from the cpx-opx geothermometers are in a range of 861C - 910C for the pyroxene-rich granulites and of 847C - 890C for the plagioclase-rich granulites. The equilibrated pressure for the plagioclase-rich granulites is in a range of 9.9-11.7 kbar. Combined with the results of the peridotitic xenoliths, a 40C temperature gap exists between the peridotite and the granulite. The petrological Moho was 33~36 km at depths, broadly consistent with the seismic Moho estimated from the geophysical data. This indicates that there was no obvious crust-mantle transition zone in the Qingdao region in the Late Mesozoic. Pishikou Late Cretaceous mafic dyke entrained lots of clinopyroxene xenocrysts which are characterized by the chemical zoning. According to the zoning features, two types of clinopyroxene xenoliths can be classified, the normal zoning and the revise zoning. The normally-zoned clinopyroxene xenocrysts have LREE-depleted REE patterns in the cores. In contrast, the revisely-zoned clinopyroxenes have LREE-enriched REE patterns in the cores. According to the rim and core compositions of xenocrysts, all the rims are balanced with the host magma. Meanwhile, the origins of the cores were complicated, in which the normally-zoned clinopyroxenes were derived form the lithospheric mantle and some of the reversely-zoned clinopyroxnes were originated from the lower crust. Other revisely-zoned clinopyroxenes had experienced complex geological evolution and need to be further investigated. According to the above results, a simplified lithospheric profile has been established beneath the Qingdao region and a constraint on the nature and characteristics of the lithospheric mantle and lower crust has been made.

赣中周潭群石榴石、斜长石和黑云母微区化学成分特征及其地球动力学意义

周潭群变质岩中石榴石、斜长石和黑云母微区化学成分变化明显,石榴石变斑晶具典型的生长环带,由晶体中心向两侧边缘XMg 、XFe值以光滑曲线递增,XCu 、XMn值以光滑曲线递减,反映其增温过程;晶体最边缘的化学成分反映变质峰期的温度条件。通过石榴石变斑晶生长环带剖面分析,应用Grt-Bi 温度计和GASP 压力计,确定本区变质作用p T 轨迹为顺时针形式,发生于大陆碰撞造山带环境。

多形态自然硒的首次发现及其成因初探

在湖北省恩施市渔塘坝的富硒碳质硅质岩、碳质页岩及其废弃岩中堆中，作者首次发现了多种形态的自然硒。本文根据自然硒的产出环境和成因将其分为三种，一种产于近地表废弃“石煤”堆中；一种与构造作用有关；另一种与表生风化作用有关。近地表废弃“石煤”堆中的自然硒是与岩层（或自燃）有关，见有晶形完好、颗粒粗大的晶体；与构造作用有关的自然硒多为毛发状、针状；与表生风化作用有关的自然硒颗粒细小，针状晶体少见.

初论地幔热柱与铀成矿的关系

中国东南部分着大面积的中生代中酸性火山岩，是我国重要的火山岩型铀矿产区。铀矿的分布主要受区域性的断裂构造所控制。对于本区的铀成矿机理前人已进行了系统的研究，本文将从地幔柱的角度进行探讨。在初步介绍了地幔柱的研究现状之后，认为中国东南地幔热柱不仅是中酸性火山岩形成的热动力，而且也是成矿矿化剂（CO2）的重要来源，它与太平洋－亚欧板块碰撞是统一的，同时参与了地幔交代和岩石圈减薄。地幔柱的脉冲式运动可能是中国东南多次成矿的动力来源和矿化剂的提供者。

黔东—湘西早古生代岩石圈热状态与高产热率HHPRM型地幔源区

岩石圈热结构和热状态的研究对于大陆裂解、变质作用及活化构造形成机制等大陆动力学问题的研究十分重要。通过地球化学、构造地质学和综合分析，以贵州省镇远地区金伯利岩-钾镁煌斑岩和黔东-湘西一带的晚元古代地层为例，研究了扬子地块东南缘早古生代岩石圈热结构与热状态。提出高放射性元素产热率的HHPRM型地幔源区，进一步讨论HHPRM型地幔源区形成与演化的大陆动力学机制。认为古富集无幔（HHPRM型地幔源区）是镇远一带的早古生代钾镁煌斑岩-金伯利岩的岩浆源区，镇远地区金伯利岩-钾镁煌斑岩岩浆源区深度（H）在208-244km，形成温度在1547-1403℃间，该温度和深度范围属软流层，具有形成金刚石太床的地质条件。建议在贵州244km，形成温度在1547-1403℃间，该温度和深度范围属软流层，具有形成金刚石矿床的地质条件。建议在贵州-湖南-广西三省交界区的金伯利岩和钾镁煌斑岩岩群中应进一步开展金刚石矿床研究与勘查工作。