含有C���H，O有机化合物结构解析专家系统的研究

本文系统地介绍了一个有机化合物结构解析专家系统的研究过程，该系统包括约束知识库，整体结构产生器，和结构验证器三个部分。本工作侧重两个部分，即约束规则的生成和整体结构对接。所涉及的章节为第六——十章。第一——五章为本论文的文献综述部分。第六章介绍了结构解析专家系统的总体设计及理论依据，我们的专家系统的总体设计是：由分子式或光谱数据出发，推导出与未知化合物的分子式和光谱数据相一致的结构片断。应用离散数学，布尔代数，图论，数理逻辑，拓扑学，组合数学等各种理论手段，将结构片断穷举生成整体结构，即候选化合物。最后应用模式识别，波谱模拟，涨力能计算等方法进行结构验证，自动排除与各种约束条件不一致的候选化合物，以求得该未知化合物的最终结构。在理想的情况下，最终结构应是唯一的。对于复杂的化合物，系统可能给出一组最终结构。结构输出采用Carhart方案，即以化合物结构的二维联接表为基础，首先生成三维空间的一个构象，之后再投影到二维平面上。第七章是利用~（13）C-NMR波谱信息以产生结构生成的约束规则。具体方法是利用我们已建立的CIAC-~（13）C-NMR数据库系统进行~（13）-NMR化学位移与带有键属性的子结构相关研究。首先根据文献选出化合物中常见的子结构，进行数据库检索并统计出有关的化学位移。建立子结构与~（13）C-NMR化学位移相关表，当进行未知化合物的结构解析时，应用上述相关表寻找出未知化合物中的子结构约束条件。为了确保知识库的全面性以及结构生成的穷举性，第八章介绍一个子结构自动生成算法。其算法的思路是：首先选出常见元素的所有的基本结构基元，依次以每个结构基元为中心，然后考虑它与所有选定的结构基元联接情况。上述两种方案所得的相关表中的子结构是含有多种杂原子的，录O，N，S，P���卤素等。第九章介绍一个整体结构生成的算法及原理和程序设计思想。整体结构生成的过程是：首先生成一级亚结构向量，然后生成二级亚结构向量，再生成三级亚结构向量，由三级结构碎片进行对接，得到整体结构。目前该系统仅可对接含有C���H，O的化合物。第十章给出两个结构解析示例。

纳米硅(nc-Si:H )/晶体硅(c-Si)异质结太阳电池的数值模拟分析

运用美国宾州大学发展的AMPS程序模拟分析了n-型纳米硅(n+-nc-Si:H)/p-型晶体硅(p-c-Si)异质结太阳电池的光伏特性.分析表明,界面缺陷态是决定电池性能的关键因素,显著影响电池的开路电压(VOC)和填充因子(FF),而电池的光谱响应或短路电流密度(JSC)对缓冲层的厚度较为敏感.对不同能带补偿(bandgap offset)的情况所进行的模拟分析表明,随着ΔEc���增大,由于界面态所带来的开路电压和填充因子的减小逐渐被消除,当ΔEc���到0.5eV左右时界面态的影响几乎完全被掩盖.界面层的其他能带结构特征对器件性能的影响还有待进一步研究.最后计算得到了这种电池理想情况下(无界面态、有背面场、正背面反射率分别为0和1)的理论极限效率ηmax=31.17% (AM1.5,100mW/cm2,0.40-1.10μm波段).

全球变化背景下科尔沁沙地生态系统C���N循环过程

工业革命以来，由于人口的快速增加和人类活动的强烈干扰（主要包括煤炭、石油等石化燃料的燃烧、化肥生产和使用）导致土地利用/覆被变化、大气CO2浓度升高、N沉降等一系列全球环境变化问题。有关陆地生态系统生物地球化学循环，尤其是陆地生态系统C���N循环及其耦合过程方面的研究成为全球变化科学研究领域的重要内容。 干旱/半干旱地区占地球陆地总面积的1/3。与湿润地区相比较，干旱/半干旱地区生态系统稳定性比较差，往往属于生态脆弱区。因此，全球变化对干旱/半干旱地区生态系统影响更加敏感。科尔沁沙地位于我国北方干旱/半干旱地区，是我国典型的农牧交错区和生态脆弱区。科尔沁沙地是世界上人口密度最高的干旱/半干旱地区之一，人类活动对其影响剧烈。然而，有关科尔沁沙地生态系统C���N元素生物地球化学循环过程对土地利用/覆被变化、N沉降等全球变化响应及其反馈机制的研究非常缺乏。因此，本文以科尔沁沙地退化沙质草地、农田、不同年龄樟子松和杨树人工林等生态系统为对象，开展了造林、模拟N沉降和凋落物管理对生态系统C���N元素循环过程影响的研究。 在科尔沁沙地东南缘，以退化沙质草地、樟子松（Pinus sylvestris var. mongolica）人工林（15、24和30年生）、杨树（Poplus xiaozhuanica）人工林（7、11和15年生）为对象，研究草地转变为林地对生态系统C���N储量影响；以退化草地、榆树疏林草地和32年生樟子松人工林为对象，比较草地造林对土壤C���N循环过程及其土壤微生物性状的影响；以农田和5、10、15年生杨树人工林为对象，研究退耕还林对生态系统C���N储量和循环过程影响；以35年生樟子松人工林为对象，模拟研究N沉降和凋落物管理对生态系统C���N循环过程影响。通过上述研究，得到以下主要结果： （1）草地生态系统总C���量为34.38 Mg ha-1，15、24和30年生樟子松人工林生态系统总C���量分别为43.56、60.45和66.59 Mg ha-1，7、11和15年生杨树人工林生态系统总C���量分别为34.54、48.26和78.77 Mg ha-1；与农田相比，退耕5年的杨树人工林生态系统总C���储量下降13%，而10年和15年杨树人工林分别增加了176%和5倍；随着人工林年龄的增加，地上植被生物量C���储量占生态系统总C���储量的比例逐渐增加，并主要分配在树干。草地生态系统总N库储量为2.54 Mg ha-1，15、24和30年生樟子松人工林生态系统总N库储量分别为1.96、2.10和2.19 Mg ha-1，7、11和15年生杨树人工林生态系统总N库储量分别为2.27、1.84和2.60 Mg ha-1；与农田相比，退耕5年的杨树人工林生态系统总N库储量下降32%，而10年和15年杨树人工林分别增加了47%和76%；农田和草地造林后生态系统N储量依然主要分配在土壤中。 （2）草地和农田造林后土壤C���N库储量的变化受多因子的影响，例如林龄、树种种类以及立地条件等。农田和草地造林初期，土壤C���N库储量表现出下降趋势，随着林龄的增加，土壤C���N储量逐渐恢复。草地营造樟子松人工林30年后，0–60 cm深度土壤C���N储量依然显著低于草地；与草地相比，15年生杨树人工林土壤C���N储量差异不显著。在立地条件较好的情况下，10年杨树人工林土壤C���N储量已显著高于农田；然而，在立地条件相对较差的情况下，15年杨树人工林土壤C���N储量仍然与农田相比差异不显著。 （3）土地利用变化能够强烈地改变土壤C���N循环过程。与草地或疏林草地相比，32年生樟子松人工林土壤C���N、P���量显著降低；土壤C���N矿化过程发生显著变化，并且受季节变化的影响；在不同季节，土壤微生物量碳含量、代谢熵（qCO2）、微生物熵（MBC/TOC���以及土壤酶活性等在不同土地利用条件下表现出规律不一致。同样，农田退耕杨树人工林能够显著影响土壤C���N矿化过程，土壤无机氮（铵态氮+硝态氮）含量，土壤微生物量碳含量以及土壤微生物活性。草地造林在一定程度上导致土壤质量下降。而农田造林有利于土壤质量改善，尤其在在立地条件较好情况下。 （4）N添加增加对沙地樟子松人工林地上和地下C���N元素含量影响不大；N添加1年后，仅林下植被C���N含量显著增加，高氮处理（N15）凋落物N含量显著增加。N添加抑制了沙地樟子松人工林凋落物的早期分解和N、P���素释放。5、6、8和9月份土壤无机N含量均随着N输入增加表现出一定程度的增加，然而，7月份N添加导致土壤无机N含量降低。N添加对土壤潜在N矿化速率影响不显著。7和8月份N添加影响土壤C���化速率，而其它月份影响不显著。低氮处理（N5）有利于增加土壤微生物量碳含量，而高氮处理（N15）在一定程度上降低土壤微生物量碳含量。 （5）凋落物输入变化（凋落物添加和凋落物移出）在一定程度上改变了35年生沙地樟子松人工林生态系统C���N循环过程。凋落物移出（C0）增加了林下植被C���量，降低了树木叶片N含量。凋落物移出抑制了凋落物分解和P���素的释放，而增加了C���素的早期释放速率，对N元素释放过程影响不显著。凋落物输入变化对不同月份土壤无机N含量和土壤N矿化过程影响均不显著。仅在6月份凋落物移出显著抑制了土壤C���化速率，其它月份差异均不显著。凋落物管理对土壤微生物量碳含量影响不显著。 以上研究结果表明，土地利用变化、N沉降和凋落物输入改变等能够影响半干旱地区沙地生态系统C���N储量和循环过程。尤其是土地利用变化强烈改变沙地生态系统C���N储量、分配格局和循环过程，并且受到多因子的影响。科尔沁沙地樟子松人工林生态系统C���N元素生物地球化学循环存在密切的耦合关系。今后有必要进一步结合3S技术、同位素技术、模型模拟以及分子生物学技术等，从微观-宏观不同尺度上，研究半干旱地区沙地生态系统C���N循环过程对全球变化的响应及其反馈机制。

Novel chemical synthesis of Pt-Ru-P electrocatalysts by hypophosphite deposition for enhanced methanol oxidation and CO tolerance in direct methanol fuel cell

A novel method was developed to prepare the highly active Pt-Ru-P/C catalyst. The deposition of phosphorus significantly increased electrochemical active surface (EAS) area of catalyst by reduces Pt-Ru particle size. TEM images show that Pt-Ru-P nanoparticles have an uniform size distribution with an average diameter of 2 nm. Cyclic voltammetry (CV), Chronoamperometry (CA), and CO stripping indicate that the presence of non-metal phosphorus as an interstitial species Pt-Ru-P/C catalyst shows high activity for the electro-oxidation of methanol, and exhibit enhanced performance in the oxidation of carbon monoxide compared with Pt-Ru/C catalyst. At 30 degrees C and pure oxygen was fed to the cathode, the maximum power density of direct methanol fuel cell (DMFC) with Pt-Ru-P/C and Pt-Ru/C catalysts as anode catalysts was 61.5 mW cm(-2) and 36.6 mW cm(-2), respectively. All experimental results indicate that Pt-Ru-P/C catalyst was the optimum anode catalyst for direct methanol fuel cell.

A carbon-supported Pd-P catalyst as the anodic catalyst in a direct formic acid fuel cell

In this paper, it is reported for the first time that a carbon-supported Pd-P (Pd-P/C) catalyst for the anodic catalyst in the direct formic acid fuel cell (DFAFC) can be prepared. The Pd-P/C catalyst shows that its electrocatalytic activity and especially its stability for the oxidation of formic acid are much higher than that of a Pd/C catalyst. Therefore, the Pd-P/C catalyst may have practical applications in DFAFCs.

PEK-C/PPS共混体系的相容性和结晶行为

结晶-非晶高聚物共混体系的相容性和结晶行为的研究已有许多报道。本工作研究了含酞侧基聚芳醚酮(PEK-C)与聚苯硫醚(PPS)共混物的相容性和结晶行为。 PEK-C���徐州工程塑料厂产品,未作封端处理,η?p/c=0.70;PPS为日本东丽产品。两者用双螺杆挤出机在320～350℃制成共混物。仪器为Perkin-Elmer DSC-7型差示扫描量热仪,升温速率10℃/min;DDV-Ⅱ-EA型全自动动态粘弹谱仪和理学D/max-ⅡBX-射线衍射仪。

Baseline health-related quality-of-life data as prognostic factors in a phase III multicentre study of women with metastatic breast cancer.

The potential value of baseline health-related quality-of-life (HRQOL) and clinical factors in predicting prognosis was examined using data from an international randomised phase III trial which compared doxorubicin and paclitaxel with doxorubicin and cylophosphamide as first line chemotherapy in 275 women with metastatic breast cancer. The European Organisation for Research and Treatment of Cancer (EORTC) QLQ-C30 and the related breast module (QLQ-BR23) were used to assess baseline HRQOL data. The Cox proportional-hazards regression model was used for both univariate and multivariate analyses of survival. In the univariate analyses, performance status (P<0.001) and number of sites involved (P=0.001) were the most important clinical prognostic factors. The HRQOL variables at baseline most strongly associated with longer survival were better appetite, physical and role functioning, as well as less fatigue (P<0.001). The final multivariate model retained performance status (P<0.001) and appetite loss (P=0.005) as the variables best predicting survival. Substantial loss of appetite was the only independent HRQOL factor predicting poor survival and was strongly correlated (/r/>0.5) with fatigue, role and physical functioning. In addition to known clinical factors, appetite loss appears to be a significant prognostic factor for survival in women with metastatic breast cancer. However, the mechanism underlying this association remains to be precisely defined in future studies.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

TP53 R249S Mutations, Exposure to Aflatoxin, and Occurrence of Hepatocellular Carcinoma in a Cohort of Chronic Hepatitis B Virus Carriers from Qidong, China

<p>Hepatocellular carcinoma (HCC) has a high mortality in East Asia and Sub-Saharan Africa, two regions where the main etiologic factors are chronic infections with hepatitis B vir-us and dietary exposure to aflatoxin. A single base substitution at the third nucleotide of codon 249 of TP53 (R249S) is common in HCC in these regions and has been associated with aflatoxin-DNA adducts. To determine whether R249S may be detected in plasma DNA before HCC diagnosis, we conducted a case-control study nested in a cohort of adult chronic hepatitis B virus carriers from Qidong County, People's Republic of China. Of the 234 plasma specimens that yielded adequate DNA, only 2 (0.9%) were positive for R249S by restriction fragment length polymorphisms, and both of them were controls. Of the 249 subjects tested for aflatoxin-albumin adducts, 168 (67%) were positive, with equal distribution between cases and controls. Aflatoxin-albumin adduct levels were low in the study, suggesting an overall low ongoing exposure to aflatoxin in this cohort. The R249S mutation was detected in 11 of 18 (61%) available tumor tissues. To assess whether low levels of mutant DNA were detectable in pre-diagnosis plasma, 14 plasma specimens from these patients were analyzed by short oligonucleotide mass analysis. Nine of them (64%) were found to be positive. Overall, these results suggest that HCC containing R249S can occur in the absence of significant recent exposure to aflatoxins. The use of short oligonucleotide mass analysis in the context of low ongoing aflatoxin exposure may allow the detection of R249S in plasma several months ahead of clinical diagnosis. (Cancer Epidemiol Biomarkers Prev 2009;18(5):1638-43)p>

Placental antioxidant enzyme status and lipid peroxidation in pregnant women with type 1 diabetes: The effect of vitamin C and E supplementation

<p>AIM: In view of the increased rates of pre-eclampsia observed in diabetic pregnancy and the lack of ex vivo data on placental biomarkers of oxidative stress in T1 diabetic pregnancy, the aim of the current investigation was to examine placental antioxidant enzyme status and lipid peroxidation in pregnant women with type 1 diabetes. A further objective of the study was to investigate the putative impact of vitamin C and E supplementation on antioxidant enzyme activity and lipid peroxidation in type 1 diabetic placentae.p><p>METHODS: The current study measured levels of antioxidant enzyme [glutathione peroxidase (Gpx), glutathione reductase (Gred), superoxide dismutase (SOD) and catalase] activity and degree of lipid peroxidation (aqueous phase hydroperoxides and 8-iso-prostaglandin F2α) in matched central and peripheral samples from placentae of DAPIT (n=57) participants. Levels of vitamin C and E were assessed in placentae and cord blood.p><p>RESULTS: Peripheral placentae demonstrated significant increases in Gpx and Gred activities in pre-eclamptic in comparison to non-pre-eclamptic women. Vitamin C and E supplementation had no significant effect on cord blood or placental levels of these vitamins, nor on placental antioxidant enzyme activity or degree of lipid peroxidation in comparison to placebo-supplementation.p><p>CONCLUSION: The finding that maternal supplementation with vitamin C/E does not augment cord or placental levels of these vitamins is likely to explain the lack of effect of such supplementation on placental indices including antioxidant enzymes or markers of lipid peroxidation.p>