粉状巯基棉富集——水中痕量CH_3Hg~+及Hg~(2+)的冷原子荧光测定

本文提出了一种新的高巯基粉状巯基棉的合成方法,按此法合成的流基棉含量在2.2%～2.5%之间.在盐酸介质中,用溴水在室温下快速分解甲基汞,冷原子荧光测定的新方法.将粉状巯基棉与稀释剂按一定比例混合装柱,用于富集水体中溶解态痕量Hg~(2+)和CH_3Hg~+,富集流速100ml/min.检出限CH_3Hg~+为4.2×10~(-5)μg/l,Hg~(2+)为6.6×10~(-5)μg/l.

(η~5-C_9H_7)_2Yb(THF)_2的晶体结构

双(茚基)镱(Ⅱ)四氢呋喃配合物(η~5-C_9H_7)_2Yb(THF)_2的晶体属单斜晶系,C_c空间群,晶体学参数a=13.506(4),b=11.081(2),c=15.577(5),β=92.68(3)°,V=2329(1),D_c=1.56g/cm~3,Z=4,μ=42.4cm~(-1),F(000)=1088,最终编离因子R=0.029,R_w=0.031。中心离子Yb~(2+)与两个茚基以η~5形式成键且与两个四氢呋喃中的氧成键,茚基的两个质心和四氢呋喃中的两个氧形成扭曲的四面体,Yb~(2+)在四面体的中心。Yb~(2+)的配位数为8。Yb~(2+)到质心In1的距离为2.52,到质心In2的距离为2.40。Yb~(2+)到O(1)的键长为2.356(7),到O(2)的键长为2.417(5)。

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

SYNTHESES OF METHYLCYCLOPENTADIENYL DERIVATIVES OF LANTHANIDES (LN = LA-ND) AND CRYSTAL-STRUCTURES OF [(THF)2LI(MU-CL)2]2[MECPND(THF)] AND [LI(DME)3][MECPLA(NPH2)3]

The reaction of LnCl3.2LiCl with 1 equiv of MeCpNa in THF gives the complexes [(THF)2Li(mu-Cl)2]2[MeCpLn(THF)] (Ln = Nd (1), La (2)) in good yield. These precursors react further with 2 equiv of LiNPh2 to produce the new complexes [Li(DME)3][MeCpLn(NPh2)3] (Ln = La (3), Pr (4), Nd (5)). They have been characterized by elemental analyses and IR and NMR spectra, as well as by structural analyses of 1 and 3. The chloride 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.130 (5) angstrom, b = 17.343 (5) angstrom, c = 17.016 (5) angstrom, beta = 108.54 (3)-degrees, V = 3393.87 angstrom3, Z = 4, and D(c) = 1.45 g/cm3. Least-squares refinement led to a final R value of 0.051 (I greater-than-or-equal-to 3-sigma(I(o))) for 2004 independent reflections. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 18.335 (6) angstrom, b = 16.576 (5) angstrom, c = 17.461 (6) angstrom, beta = 96.04 (3)-degrees, V = 5277.17 angstrom3, D(c) = 1.26 g/cm3, Z = 4, and R = 0.057 (I greater-than-or-equal-to 2.5-sigma(I(o))) for 3378 reflections. The structure of 3 consists of discrete ion pairs [Li(DME)3]+ and [MeCpLa(NPh2)3]- with average La-N and La-C(ring) distances of 2.459 (8) and 2.84 (1) angstrom, respectively.

THE ALGEBRAIC-METHOD ESTIMATING +/-PI/2 TYPE OF PHASES OF STRUCTURE FACTORS

The algebraic formulas of 1.5 and 2.5 rank which can be applied to estimating +/- pi/2 type of phases for P2(1)2(1)2(1) space group were derived using the method of structure factor algebra. Both types of the formulas are satisfactory for two known crystal structures in estimating their +/- pi/2 type of phases.

±(π/2)型相角的代数估算方法

从P2_12_12_1空间群的归一化结构因子表达式出发,应用结构因子代数方法,推出了可用于±(π/2)型相角估算的1.5阶和2.5阶代数

±π/2型相角的代数估算方法

本文以 P2_12_12_1空间群为例,采用结构因子代数方法推导出适用于±π/2型相角估算的1.5阶和2.5阶代数公式,并应用于两个已知晶体结构的±π/2相角计算,获得了令人满意的结果.

Development of the East Asian summer monsoon: Evidence from the sediment record in the South China Sea since 8.5 Ma

128 samples from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea were analyzed for grain size, clay minerals, biogenic opal content and quartz in order to reconstruct changes in East Asian monsoon climate since 8.5 Ma. An abrupt change of terrigenous mass accumulation rate (MAR), clay mineral assemblage, median grain size and biogenic opal MAR about 5.2 Ma suggests that between 8.5-5.2 Ma the source of terrigenous sediment was mainly in the region of surface uplift and basaltic volcanism in southern Vietnam. A simple model of East Asian summer monsoon evolution was based on the clay/feldspar ratio, kaolinite/chlorite ratio and biogenic opal MAR. The summer monsoon has two periods of maximum strength at 8.5-7.6 Ma and 7.1-6.2 Ma. Subsequently, there was a relatively stable period at 6.2-3.5 Ma, continued intensification about 3.5-2.5 Ma, and gradually weakening after 2.5 Ma. Since I Ma the monsoon has intensified, with remarkable high-frequency and amplitude variability. Simultaneous increase in sedimentation rates at ODP Sites 1143, 1146 and 1148, as well as in MAR of terrigenous materials, quartz, feldspar and clay minerals at ODP Site 1143 at 3.5-2.5 Ma, may be the erosional response to both global climatic deterioration and the strengthening of the East Asian summer monsoon after about 3-4 Ma. (c) 2006 Elsevier B.V. All rights reserved.

胶州湾海洋链霉菌抑菌活性筛选、2株抑菌活性菌株的鉴定及次级代谢产物的研究

本文对256株胶州湾海洋链霉菌进行了抑菌活性的筛选，并选取10株典型菌株进行化学筛选，获得2株有研究价值的菌株。通过大规模发酵，获得纯化的次级代谢产物，进行了结构解析。通过与其他5株活性菌株的16S rRNA基因序列比较，并结合生理生化、形态特征和培养特征分析，探讨了这两株菌的分类地位。 　　采用液体扩散法，选用金黄色葡萄球菌、大肠杆菌、绿脓杆菌、八叠球菌、隐球菌、白色念珠菌、Mucor miehei (TÜ 284)和Streptomyces viridochromogenes (TÜ57) 8株受试菌进行抑菌活性的筛选，结果22%的菌株显示出对至少一种受试菌具有抑制作用(抑菌圈Æ ³ 8 mm)。根据菌株的形态特征和抑菌活性特点，选择M024、M028、M042、M083、M086、M095、M097、M124、M134和M226 10株链霉菌进行化学筛选。考察了8种培养基和4种培养条件，结果发现菌株M095在Meat extract培养基、pH 6.5、28℃和95 r/min条件下，菌株M097在Meat extract培养基、pH 7.8、 28℃、95 r/min(条件Ⅰ)和M2+培养基、pH 7.8、 35℃、110 r/min(条件Ⅱ)条件下，可供进一步研究。 对菌株M095(24 L规模)和M097(Ⅰ为30 L规模，Ⅱ为14 L规模)进行发酵，采用乙酸乙酯提取和柱层析分离纯化次级代谢产物，通过ESI-MS、EI-MS、1H-NMR和13C-NMR等波谱解析，鉴定出次级代谢产物的结构。发现菌株M095产生一抑菌活性很强的化合物全霉素，首次证实该全霉素具有抑制丝状真菌的作用；菌株M097主要产生10个化合物，其中8个具有不同程度的生物活性，另外两个化合物中，Aloesaponaria Ⅱ为首次从微生物野生菌株(wild strain)中获得，化合物Cui D为一新结构的蒽醌类化合物。 经分子鉴定，初步认为本实验分离的7株活性海洋链霉菌分属于4个链霉菌类群，结合生理生化、形态特征和培养特征分析，认为菌株M095可能为灰色链霉菌的变种，M097可能为球孢类群中的一个新种。

近2千万年以来东亚季风演化的南海沉积矿物学记录

本论文通过对南海南部ODP1143站和北部ODP1146站两个长柱状沉积物的陆源矿物组成和堆积速率、生物硅含量和堆积速率、粘土矿物组成、结晶学特征、微形貌和化学成分、陆源物质粒度和元素地球化学的综合研究，分析了1143站和1146站的陆源物质来源的演变，分别建立了南海南部和北部的季风演化代用指标，并与黄土、深海风尘沉积、海洋微体古生物记录对比，重建了东亚季风在近20 Ma以来的长期演化，并探讨了青藏高原隆升在季风长期演化中的驱动作用。 地质背景和元素地球化学分析表明ODP1143站的陆源物质主要来自于湄公河的输入。但陆源物质堆积速率、中值粒径、粘土矿物组合、蒙脱石结晶度指数和生物硅含量和堆积速率在5.2 Ma前后的变化表明ODP1143站的湄公河物源在10–5.2 Ma可能受到了越南区域性地壳隆升和玄武岩喷发的影响。而自~5.2 Ma以来，到达ODP1143站的沉积物受湄公河流域内部物源通量所控制。 ODP1146站的陆源物质为多物源、多传输方式供应，并且近20 Ma以来各个物源/传输方式的强度发生了改变。粒度端员组分模拟揭示出，近20 Ma以来风尘平均贡献了20%物质到1146站，河流输入贡献80%。河流输入中，75%来自珠江和台湾，25%来自吕宋岛。1146站的沉积环境、粘土矿物、地球化学分析表明河流输入的石英、长石来自珠江、台湾；蒙脱石主要来自于吕宋岛，高岭石主要来自于珠江，伊利石和绿泥石来自于珠江、台湾、长江。 ODP1146站17–15 Ma间异常高的陆源物质(石英、长石、蒙脱石、高岭石)、生物硅和碳酸盐的堆积速率暗示了在17–15 Ma南海周围地区发生了强烈的构造活动，这可能与南海扩张停止有关。而ODP1146站稀土元素地球化学、粘土矿物结晶学特征在3 Ma以来的明显变化显示近3 Ma以来台湾物质的输入强度显著加强，这可能与3 Ma以来台湾造山活动加强有关。 ODP1143站粘土矿物/长石、高岭石/绿泥石比值和生物硅含量和堆积速率、陆源物质堆积速率的指标组合被用来建立了一个简单的东亚夏季风演化模型。结果显示8.5–7.6 Ma和 7.1–6.2 Ma分别为两个较强的夏季风阶段，在6.2–3.5 Ma为一相对稳定的阶段，然后在3.5–2.5 Ma不断加强，随后从2.5 Ma以来又不断减弱，直到1.0 Ma夏季风强度又再次加强，并且变化幅度和频率加大。 ODP1146站风尘含量、风尘堆积速率、(伊利石+绿泥石)/蒙脱石、(石英+长石)%、陆源物质的平均粒径被用来作为南海北部季风演化的代用指标。研究表明，近20 Ma以来东亚冬季风强度、亚洲内陆干旱程度和冬季风相对夏季风强度在12−9 Ma、8−4 Ma有所加强，在3 Ma以来显著加强。相比而言，夏季风强度在15−3 Ma间比较稳定，在3 Ma可能与冬季风同步加强。 ODP1143站、1146站、1148站的线性沉积速率，以及1143、1146站的总陆源物质、石英、长石和粘土矿物的物质堆积速率在3.5–2.5 Ma的几乎同时增加，代表着对3.5 Ma以来全球气候恶化和东亚夏季风加强的侵蚀响应。青藏高原的阶段性隆升可能促进了东亚季风在8 Ma和3 Ma左右的加强，但两极冰川扩展和全球变冷也是一个可能因素，也可能季风演化是二者共同作用的结果。我们的研究结果倾向于支持青藏高原阶段性隆升在东亚季风长期演化中的驱动作用。

鼠兔属5个种的分子分类及进化

构建了甘肃鼠兔、黄河鼠兔、藏鼠兔、高原鼠兔和红耳鼠兔的mtDNA限制性内切酶图谱,并以PAUP程序建立其分子系统树。结果表明,鼠兔亚属的4个物种与耗兔亚属的红耳鼠兔存在明显的长度变异(1kb),从而为两亚属的划分提供了新的遗传标记。同时,甘肃鼠兔和黄河鼠兔的遗传分化已达明显的物种级别,因而进一步证实它们均为独立种。在系统树中,黄河鼠兔与高原鼠兔亲缘关系最近,然后是藏鼠兔,最后是甘肃鼠兔与前3种构成一对姊妹群。依据遗传距离计算了分歧年代。两亚属的分歧时间约距今8.8×104ha,相当于中国哺乳动物时代的保德期中期;鼠兔亚属内4种的分歧发生于约距今（2.5～4.2）×104ha的上新世晚期，相当于榆社期晚期。

Analysis of phenols by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence labeling reagent, has been synthesized and applied for the derivatization of phenols. Taken phenol, p-chlorophenol, 2,5-dimethylphenol, 2,4-dichlorophenol and 1,4-dihydroxybenzene as testing standards, the effects of derivatization conditions, such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration, have been systematically studied. Under the optimized conditions, CEOC reacts readily with the phenols to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. The single step derivatization reaction could be finished within 20 min even at room temperature. Such a method has been successfully applied to the analysis of phenols in printing ink by high-performance liquid chromatography. (c) 2005 Elsevier B.V. All rights reserved.