EXPERT-SYSTEM FOR ELUCIDATION OF STRUCTURES OF ORGANIC-COMPOUNDS

An expert system for the elucidation of the structures of organic compounds-ESESOC-II has been designed. It is composed of three parts: spectroscopic data analysis, structure generator, and evaluation of the candidate structures. The heart of ESESOC is the structure generator, as an integral part, which accepts the specific types of information, e.g. molecular formulae, substructure constraints, and produces an exhaustive and irredundant list of candidate structures. The scheme for the structural generation is given, in which the depth-first search strategy is used to fill the bonding adjacency matrix (BAM) and a new method is introduced to remove the duplicates.

INTRAANNULAR AND INTERANNULAR SUBSTITUENT MIGRATION AND INTRAMOLECULAR IPSO SUBSTITUTION OF BIPHENYL DERIVATIVES IN MASS-SPECTROMETRY

Biphenyl derivatives undergo extensive intraannular substituent migrations and subsequent intramolecular ipso substitutions giving rise to a fluorenyl cation and a biphenylene radical cation as common products in mass spectrometry. For biphenyls bearing an alkyl group, interannular substituent migration resulting in a substituted tropylium ion is also observed. Electron-withdrawing groups are found to be much more favourable to these reactions than the electron-donating ones.

聚苯乙烯增韧用橡胶的发展

详细叙述了聚苯乙烯（ＰＳ）的增韧方法及所用胶种。采用特殊结构的低顺式聚丁二烯橡胶（ＢＲ）和低粘度、无凝胶的高顺式ＢＲ增韧ＰＳ可制得性能优异，且各种物性均衡的高抗冲ＰＳ。指出，高顺式ＢＲ有可能成为最理想的增韧胶种。

[(O)MoCu_3(μ_3-S)_3(μ_3-Cl)(PPh_3)_3]·2THF的合成及其晶体结构

固体化合物(NH_4)_6Mo_7O_(24)·4H_2O和(PPh_3)_2CuCl与饱和液体NH_4HS反应获得桔红针状标题晶体。晶体空间群为P2_1/c,晶胞参数a=11.742(2),b=28.186(7),c=19.304(3),β=100.57(2)°,V=6280.4(?)~3,D_c=1.46g/cm~3,Z=4,F(000)=2816。在3≤2θ≤45°范围内收集到8414个独立衍射强度数据,其中3856个I≥1.5σ(I)强度数据参加结构计算。标题化合物分子是以{MoCu_3S_3Cl}类立方烷型簇为核心的分子,Mo—Cu的平均距离为2.716。

SYNTHESES AND CRYSTAL-STRUCTURES OF TRIINDENYLLANTHANIDE COMPLEXES (ETA-5-C9H7)3LN.OC4H8 (LN=ND,GD,ER)

The complexes named in the title (eta-5-C9H7)3Ln.OC4H8 (Ln = Nd, Gd, Er) were synthesized by the reaction of anhydrous lanthanide trichlorides with indenyl potassium and cyclooctadienyl potassium (1:2:1 molar ratio) in THF. The complexes were characterized by elemental analysis, infrared and H-1-NMR spectroscopy, and mass spectrometry. In addition, the crystal structures of (eta-5-C9H7)3Nd.OC4H8 (1) and (eta-5-C9H7)3Gd.OC4H8 (2) were determined by an X-ray diffraction study. Complexes 1 and 2 belong to hexagonal space group P6(3) with unit cell parameters a = b = 11.843(3), c = 10.304(4) angstrom, V = 1251.7(9) angstrom-3, D(c) = 1.49 g.cm-3, Z = 2 for 1, and a = b = 11.805(2), c = 10.236(2) angstrom, V = 1235.4(6) angstrom-3 D(c) = 1.54 g.cm-3, Z = 2 for 2. The structures were solved by Patterson and Fourier techniques and refined by least-squares to final discrepancy indices of R = 0.049, R(w) = 0.053 using 925 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 1, and R = 0.023, R(w) = 0.025 using 1327 independent reflections with I greater-than-or-equal-to 3-sigma(I) for 2. Coordination numbers for Nd3+ and Gd3+ are 10; the average bond lengths Nd-O and Gd-O are 2.557(21) and 2.459(13) angstrom, respectively. The structural studies showed the complexes to have 3-fold symmetry, but the THF molecule has no such symmetry; consequently the arrangement of carbon atoms in the THF molecule are disordered.

涂渍FFAP、PEG-20M、XE-60硅膜改性弹性玻璃毛细管柱的研制

硅膜改性弹性玻璃毛细管柱做为一种新柱型,它具有类似弹性石英柱的柔性和惰性,也具有玻璃柱制作容易、材质易得的优点。硅膜做为固定相载体的色谱特性研究目前报道还很少,非极性硅酮相在其上的交联我们曾做过报

K助化Co-Mo/Al_2O_3催化剂的表征

以XRD,XPS和TPR研究了一系列K助化的Co-Mo/Al_2O_3催化剂,考察了K对Co和Mo在载体上分散的影响。实验表明,K的加入分解了原来存在於催化剂中的CoMoO_4,促进了Mo的硫化还原,是提高水煤气变换反应的一个因素。

预处理石墨对合成金刚石性能的影响

本文介绍了对合成金刚石用石墨片进行预处理的方法。研究表明,用已处理过的石墨片可合成出粒度粗、强度高、完整单晶多的金刚石,金刚石中Ni,Mn,Co,Si 的含量明显减少,而氮的含量明显增加。并观察到触媒片两面都能均匀地生长理想的金刚石晶体。该预处理方法不仅提高金刚石的质量,而且有可能为认识石墨转化为金刚石的机理提供一些依据。

(Ce,Gd,Mn)MgB_5O_(10)磷光体的合成及其发光

本文采用固相反应的方法合成了一系列(Ce,Gd,Mn)MgB_5O_(10)磷光体。观察到合成温度、灼烧时间、原料配比对磷光体的形成和发光亮度有重要影响。X射线衍射分析表明,磷光体结构与LaMgB_5O_(10)相同,属单斜晶系、空间群P2_(1/c)。用EPR确定了磷光体中锰离子为二价。测定了(Ce_(0.2)La_(0.2))MgB_5O_(10),(Gd_(0.7)La_(0.3))MgB_5O_(10),(Mn_(0.05)La_(0.95))MgB_5O_(10),(Ce_(0.2)Mn_(0.05)La_(0.75))MgB_5O_(10),(Gd_(0.95)Mn_(0.05))MgB_5O_(10)、(Ce_(0.2)Gd_(0.8))MgB_5O_(10)和(Ce_(0.2)Gd_(0.75)Mn_(0.05))MgB_5O_(15)等磷光体的光谱。根据光谱数据讨论了(Ce_(0.2)Gd_(0.75)Mn_(0.05))MgB_5O_(10)磷光体中能量传递过程为:Ce~(3+)→Mn~(2+),Gd~(3+)→Mn~(2+)以及Ce~(3+)→Gd~(3+)→Mn~(2+),其中Ce~(...

Amorphane sesquiterpenes from a marine Streptomyces sp.

The chemical investigation of the crude extract of the marine-derived Streptomyces sp. M491 yielded three new sesquiterpenes, namely, 10 alpha,11-dihydroxyamorph-4-ene (4), 10 alpha,15-dihydroxyamorph-4-en-3-one (6), and 5 alpha,10 alpha,11-trihydroxyamorphan-3-one (7). In addition, the known compounds 10 alpha-hydroxyamorph-4-en-3-one (2), o-hydroxyacetanilide, genistein, prunetin, and indole-3-carbaldehyde and the macrolide antibiotic chalcomycin A were identified. The structures were determined on the basis of spectroscopic analysis, especially 1D and 2D NMR data. This is the first report of these sesquiterpenes from bacteria.

Coherence between solar activity and the East Asian winter monsoon variability in the past 8000 years from Yangtze River-derived mud in the East China Sea

AMS(14)C dating and grain-size analysis for Core PC-6, located in the middle of a mud area on the inner shelf of the East China Sea (ECS), were used to rebuild the Holocene history of the East Asian winter monsoon (EAWM). The 7.5-m core recorded the history of environmental changes during the postglacial transgression. The core's mud section (the upper 450 cm) has been formed mainly by suspended sediment delivered from the Yangtze River mouth by the ECS Winter Coastal Current (ECSWCC) since 7.6 kyr BP. Using a mathematical method called "grain size vs. standard deviatioW', we can divide the Core PC-6's grain-size distribution into two populations at about 28 mu m. The fine population (< 28 mu m) is considered to be transported by the ECSWCC as suspended loads. Content of the fine population changes little and represents a stable sedimentary environment in accord with the present situation. Thus, variation of mean grain-size from the fine population would reflect the strength of ECSWCC, which is mainly controlled by the East Asian winter monsoon. Abrupt increasing mean grain size in the mud section is inferred to be transported by sudden strengthened ECSWCC, which was caused by the strengthened EAWM. Thus, the high resolution mean grain-size variation might serve as a proxy for reconstruction of the EAWM. A good correlation between sunspot change and the mean grain-size of suspended fine population suggests that one of the primary controls on centennial- to decadal-scale changes of the EAWM in the past 8 ka is the variations of sun irradiance, i.e., the EAWM will increase in intensity when the number of sunspots decreases. Spectral analyses of the mean grain-size time series of Core PC-6 show statistically significant periodicities centering on 2463, 1368, 128, 106, 100, 88-91, 7678, and 70-72 years. The EAWM and the East Asian summer monsoon (EASM) agree with each other well on these cycles, and the East Asian Monsoon (EAM) and the Indian Monsoon also share in concurrent cycles in Holocene, which are in accord with the changes of the sun irradiance. (c) 2005 Elsevier B.V. All rights reserved.

雨生红球藻Rubisco在虾青素积累过程中的表达分析

虾青素因其具有极强的抗氧化性及优越的着色作用，被广泛应用于营养保健和水产养殖中，备受国内外研究者的关注。红球藻是目前虾青素的生物来源中较有优势的一条途径。 我们选取雨生红球藻作为研究材料，收集其生长过程中四个不同的阶段，分别为绿色游动细胞阶段，绿色不动细胞阶段，绿褐色不动细胞阶段（开始积累虾青素），以及红色不动孢子阶段。本研究中提取了核酮糖-1,5-二磷酸羧化/加氧酶（Rubisco）的粗提液，并测定了酶活。其编码基因rbcL的mRNA表达量也被测定。另外，光合速率与呼吸速率的比值（P/R）通过测定与计算得出，各个阶段藻细胞中虾青素的含量由分析得出。本研究还应用了叶绿素荧光测定方法，确定了光系统II潜在最大活性（Fv / Fm），光系统II实际活性（ΦPSII），电子传递速率（ETR）和非光化学淬灭参数（NPQ）。 结果表明，绿色游动细胞的生长状态最佳，其P/R、Fv / Fm、ΦPSII均为最大，NPQ为最小。这说明在此状态的细胞中，光系统II的活性最强；但是其Rubisco活性与rbcL表达量均为最小。相比之下，在绿褐色不动细胞中，P/R和NPQ的值较低，Fv / Fm、ΦPSII和ETR值都最小，但Rubisco活性与rbcL表达量均为最高。 结合工业生产虾青素的方法，我们认为，Rubisco或许参与了虾青素的合成，而非Calvin循环为色素合成提供前体和能量。因此，在生产过程中适当加入碳源，比如CO2，可以有效增大虾青素的产量。

铜管不锈钢管腐蚀性能及铁牺牲阳极保护研究

铜管一直是电厂凝汽器的主要应用管材，但由于其抗冲刷和抵御污染物腐蚀的能力差，特别不耐氨蚀，美国和欧洲大量使用不锈钢管替代铜管作为冷凝管，然而不锈钢管在我国的运用仅处于初步阶段。 常使用锌、铝阳极对铜管进行牺牲阳极保护，然而存在着电位差过大、阳极溶解过快的问题。铁基牺牲阳极与铜电位差适当、来源广泛、价格便宜，在一些工程上有所应用，但是目前针对铁基牺牲阳极的理论研究报道很少。 本文选用紫铜管、304不锈钢管作为实验用管材，首先运用实验室全浸实验、极化曲线和电化学阻抗研究了二者在海水和淡水中的腐蚀性能以及CO2、溶解氧对其腐蚀的影响。结果表明：CO2会加速二者的腐蚀，溶解氧却对它们的腐蚀影响不同，促进铜管的腐蚀却抑制不锈钢管的腐蚀；随浸泡时间的延长，紫铜管由于表面产物膜的生成耐蚀性提高，304不锈钢管的耐蚀性却降低；淡水中，304不锈钢管和紫铜管都具有很好的耐蚀性能。随后，运用失重法和极化曲线对比研究了紫铜管、304不锈钢管的氨蚀性能，运用SEM分析和电化学阻抗研究了紫铜在不同浓度氨溶液中的腐蚀机理。发现，304不锈钢管的耐氨蚀能力远远好于铜管；溶解氧是影响氨蚀的关键因素，其对二者氨蚀的影响也不同；紫铜管在低氨浓度和高氨浓度溶液中腐蚀机理和产物不同，低氨浓度时形成保护性的产物膜（CuO 和Cu(OH)2），高氨浓度时由活化溶解控制，生成可溶的[Cu (NH3)4]2+。 选用工业纯铁、35钢为牺牲阳极材料。恒电流实验结果表明它们具有良好的牺牲阳极性能；通过极化曲线和自腐蚀电位测试分析，认为将二者用于铜管牺牲阳极保护是可行的；实验室阴极保护效果测试表明，工业纯铁和35钢对紫铜管具有良好的保护效果，保护度达90%以上。

中国近海栉孔扇贝群体遗传结构及遗传变异与生长的关系

本文以凝胶电泳方法，以等位基因酶和可溶性蛋白为探针研究了中国近海栉孔扇贝(Chlamys farreri)5个不同自然分布群体的遗传结构及遗传变异与生长的关系。在所研究的23个位点中，只有Mdh-1在5个群体中为纯合状态，其余位点都不同程度地处于多态或杂合态。大多数位点的等位基因及基因型分布频率都处在不平衡状态。对各位点的D值检验表明，大多数位点都杂合子缺失。杂合子过剩或处于Hardy-Weinberg平衡的位点为19.64-22.32%。杂合度以海洋岛和长岛群体最高，都是0.304，荣成和大连群体次之，分别为0.290和0.287，青岛群体为0.219。位点有效等位基因数及密码子差数在群体间的变化与杂合度基本一致。用这三个参数构建的遗传变异综合评价指数在这5个群体从北至南依次为0.726，0.542，0.658，0.547和0.133。多态位点比例在P ≤ 0.99水平下，海洋、大连、长岛及荣成4个群体都在0.800以上，仅青岛群体为0.565。在Est7个位点从高纬度向低纬度在等位基因数目上存在梯度递减渐变性。在某些等位基因的分布频率或从高纬度或从低纬度向相对方向递变。除了单向渐变外，也存在双向渐变现象。栉孔扇贝这5个群体在遗传相似性方面基本上是群体间的差异（I > 0.900）。相比之下，大连、长岛两群体间的相似性最大。由于辽东沿岸流和黄海冷水团的作用，海洋岛群体与邻近群体的基因交流较差，使之在遗传上相对较为独立。从遗传变异不平、杂合子缺失特征及等位基因的渐变性也证明，该群体已具相当程度的分化，这主要是由于环境隔离所造成的“孤岛效应”的结果。通过对5个群体形态数量性状生与群体遗传变异的比较表明，遗传变异不平较高的群体，其生长速度也较快，二者基本呈平行关系，唯海洋岛与长岛的结果相悖，其原因可能与两海区间初级生产力水平有关。从个体杂合度与第一年生长壳高关系的研究可以发现，海洋、大连和青岛群体在杂合度与生长间基本呈正相关关系，而在长岛与荣成群体内存在杂合度与生长具不同相关性的子群体，并证明个体杂合度超过0.300以上，其与生长的关系基本上处于不定向状态。在环境和遗传双重压力下，青岛群体的变异水平较低。