二环非经典噻吩电子结构和性质的DFT理论研究

采用杂化的DFT理论,研究7种二环非经典噻吩电子密度拓朴结构、芳香性以及HOMO-LUMO能级差(△EL-H)、电子亲和势(EA)和电离能(IP)等电子性质.7种化合物都为平面构型,分子体系中所有化学键都具有π键特征,环平面上有较强的共轭作用,具有比单环化合物小得多的HOMO-LUMO能级差.7种化合物中,TT、BT和TPZ的EA相对较大,有较强的束缚电子的能力.TTh、TF、TP和BTh的EA为负值,束缚电子能力较弱,还原态不稳定,但其IP相对较小.因此,在低能隙导电聚合物的分子设计中,TT、BT和TPZ可作为电子受体,而TTh、TF、TP和BTh可作为电子供体.     

基于三环非经典噻吩的低能带隙低聚物的分子设计及DFT研究

以[1,2,5]噻重氮并[3,4-b]噻吩并[3,4-e]吡嗪(TTP)为受体,以噻吩并[3,2-b]噻吩(TT)、噻吩(Th)、吡咯(Py)和呋喃(Fu)为供体,设计了四类供体-受体型共轭低聚物。采用杂化的密度泛函方法(B3L,YP),研究了六类低聚物的电子结构和性质。AIM分析显示,随着聚合度增加,体系共轭程度增强。随着聚合度增加,低聚物的HOMO-LUMO能级差逐渐减小,电离能降低,电子亲和势增大。Py不但是一个强的电子供体,也是一个潜在的氢键供体。在含Py结构单元的低聚物中,由于分子内氢键的存在使这类低聚物具有较大的分子内电荷迁移值。所设计的4种基于TTP的四聚体均具有较小的HOMO-LUMO能级差(<0.5 eV),因此其相应的聚合物的能隙会更小,可能是潜在的导电聚合物材料。     

乙炔基双二茂铁丙烷衍生物的密度泛函理论研究

为揭示取代基对金属有机化合物乙炔基双二茂铁丙烷电子结构的影响,采用密度泛函理论方法模拟计算了乙炔基双二茂铁丙烷及其2个衍生物苯炔基双二茂铁丙烷及二茂铁炔基双二茂铁丙烷的电子结构、前线轨道、电离能(IP)以及电子亲和势(EA),并讨论了取代基对化合物能级和能隙的影响。计算结果表明,电子在基态与激发态间的跃迁,主要是发生在双二茂铁丙烷和乙炔基苯或乙炔基二茂铁之间。取代基为苯基时化合物最高占据轨道(HOMO)能级降低量小于最低空轨道(LUMO)能级降低量,因此二者之间的能隙总体降低。取代基为二茂铁基时化合物HOMO能级增加,LUMO能级降低,从而使HOMO-LUMO能隙降低。结合化合物6-苯炔基双二茂铁丙烷电子亲和势最大以及化合物6-二茂铁炔基双二茂铁丙烷电离能最小,可见苯基取代使炔基双二茂铁丙烷类化合物电子传输能力增强,而二茂铁基取代则可以使该类化合物的空穴传输能力增强,这使炔基双二茂铁丙烷类化合物在功能导电材料方面具有较好的应用前景。     

丹参酮分子结构及光谱性质的理论研究

采用量子化学密度泛函理论(DFT)在B3LYP/6-31G水平上对丹参酮Ⅰ、丹参酮ⅡA、隐丹参酮3个典型的丹参酮类化合物分子几何构型进行优化,分析分子前线轨道能级及分布特征.用含时密度泛函理论(TD-DFT)在相同水平对上述化合物分子进行电子吸收光谱研究.并且以乙醇为溶剂,计算其对分子结构和光谱性质的影响.计算结果表明:丹参酮Ⅰ分子骨架发生共轭形成大π键,为刚性的平面分子结构;丹参酮Ⅰ、丹参酮ⅡA、隐丹参酮分子共轭体系依次缩小.分子HOMO-LUMO能隙随着分子共轭体系的减少而增大.3个分子的九λmax均主要来源于电子的π→π跃迁.乙醇对上述化合物分子结构和光谱性质有一定影响,吸收光谱均发生红移.同时还发现,乙醇改变了丹参酮Ⅰ的λmax主要电子跃迁来源轨道.丹参酮Ⅰ在气相条件下λmax主要来源于分子中的HOMO→LUMO+2的π→π跃迁;而在乙醇中λmax主要来源于HOMO-5→LUMO的π→π跃迁,该跃迁存在明显的分子内电子转移现象.     

烷基化芳胺抗氧抗腐添加剂分子结构特性的理论研究

采用量子化学方法,在B3LYP/6-31G~*水平上对8种烷基化芳胺抗氧抗腐添加剂的平衡几何构型、净电荷及前线轨道组成和能级等进行了理论计算研究,探讨了这些化合物的结构特征。研究表明,这些添加剂胺基和苯环形成的共轭平面构成了活性部位,其HOMO和LUMO均为π-分子轨道。由共轭大π-键的离域性和HOMO与LUMO的反应性预测表明,不饱和的共轭体系不仅能与氧自由基结合,还因共轭体系的孤对电子更易转移而与金属形成配位键和化学吸附膜,添加剂的电子结构性质表明具有抗氧抗腐蚀性能。     

共轭性取代对咔唑类衍生物结构和光谱性质影响的理论研究

用密度泛函理论(DFT)和含时密度泛函理论(TD。DFT)对咔唑的6种共轭基团取代衍生物的电子结构和吸收光谱性质进行了比较研究。对衍生物的基态分子结构运用B3LYP/6-31G(d)水平进行全优化,分析了电荷的分布和前线分子轨道等性质。结果表明,与母体咔唑相比,各衍生物均形成了分子内氢键,共轭体系的π键成分增大,能级差减小,激发能降低,分子的最大吸收波长向长波方向移动,即发生红移。前线分子轨道分析表明该类化合物吸收光谱主要对应分子中的HOMO→LUMO电子跃迁,且为π-π~*跃迁。共轭性基团的引入扩大了分子结构的共轭范围,增强了分子内电子的转移,改善了咔唑类化合物的光电性能。本文为新型含咔唑基团的光电功能材料的设计合成提供了理论参考。     

白芷香豆素分子电子结构及光谱性质的理论研究

采用量子化学密度泛函理论在B3LYP/6-31+G**水平上对白芷中的5种香豆素类化合物分子几何构型进行全优化:用含时密度泛函理论在相同水平对上述化合物分子进行电子吸收光谱研究.为模拟真实条件,采用PCM模型,以甲醇为溶剂,计算其对分子电子结构和光谱性质的影响.计算结果表明:标题化合物分子母环发生共轭形成大π键,为刚性...     

香豆素磺酰脲类化合物降血糖活性的定量构效关系研究

目的：研究新型香豆素磺酰脲化合物降血糖作用与化学结构之间的关系，为进一步设计合成该类化合物提供理论依据。方法：选择10个降血糖活性较强的化合物，利用MM!分子力学和CNDO／2量子化学方法计算有关结构参数并进行定量构效关系研究。结果：香豆素-6-磺酰脲类化合物的降血糖活性与磺酰脲基与母核的二面角呈负相关；与母核1位碳原子LUMO轨道本征矢量负相关；与化合物分子的偶极矩正相关。结论：推测分子中7-位甲基的引入不利于磺酰脲基与香豆素母环共平面，降低化合物的降血糖活性；香豆素母环上引入供电子基团不利于增加降血糖活性，可尝试引入吸电子基团；化合物分子偶极矩的增加对降血糖活性有利。     

二氯-4,5-二氮芴-9-酮合钯(Ⅱ)及其席夫碱衍生物能带结构的理论研究

二氯-4,5-二氮芴-9-酮合钯(Ⅱ)配合物(PddafoCl2)是一类大环间呈现π-π堆积层状的晶体.其结构中的羰基官能团,可与含氮的亲核试剂伯胺(RNH2)生成含碳氮席夫碱的衍生物.在共轭环间的π-π堆积下其有序的堆积结构可能产生具半导体性质,但对标题体系的席夫碱衍生物的导电性理论研究还未有见相关报道.基于局域密度(LDA)泛函理论,第一原理赝势平面波法,采用Materials Studio 4.0软件中的CASTEP程序包中的LDA/CA-PZ法研究二氯-4,5-二氮芴-9-酮合钯配合物及其席夫碱衍生物(其中R'=-CN、-COOH、-NO2、-CHO、-CH3、-CH2CH3)共7个体系的能带结构,结果表明该系列体系的能隙在(1.082 6～1.622 2)eV之间,Fermi能级上截距在(7.5147～8.4538)electrch s.eV-1之间.与二氯-4,5-二氮芴-9-酮合钯配合物相比,连接吸电子取代基后的席夫碱衍生物,能隙明显缩少,导电性增强,其中以连接氰基的化合物2的能隙最小.构建不同的席夫碱衍生物,配合物呈现不同的导电性.随R'取代基团电负性增强,体系的导电性能增强,这一规律在实际应用中有理论指导和预测作用.二氯-4,5-二氮芴-9-酮合钯(Ⅱ)及它的席夫碱衍生物有望在不同的领域获得广泛的应用.     

插烯系硫靛发色体电子光谱的含时密度泛函理论研究

在密度泛函理论的B3LYP/6-31 G~*水平上对硫靛染料发色体及其插烯系化合物的几何构型进行优化计算;在获得基态稳定结构的基础上,应用含时密度泛函理论在相同水平下计算其电子吸收光谱,探讨了发色体的延伸对电子吸收光谱的影响,得到了与实验值基本一致的变化规律。结果表明,发色体的纵向延伸使光谱产生轻微的红移。通过对前线轨道组成进行自然布居分析,揭示了硫靛染料的发光均源自分子中HOMO-LUMO(π→π~(?))电子跃迁。     

基于DFT和从头算方法的几个三元杂环化合物的理论研究

使用Gaussian94程序包和密度泛函方法(DFT)B3LYP以及从头算方法MP2在B3LYP／6-311 G**基组水平上,对4种三元杂环化合物环丙烷、环氧乙烷、环乙亚胺和硫杂环丙烷进行了全优化,其理论数据和文献数据符合得很好,这表明该方法是可靠的。接着,应用振动模式分析和电子布居分析对它们进行了研究,而且提供了一些热动力学数据。     

Molecular modeling of tricyclic compounds with anilino substituents and their intercalation complexes with DNA sequences

Although 9-anilinoacridines are among the best studied antitumoral intercalators, there are few studies about the effect of isosteric substitution of a benzene moiety for a heterocycle ring in the acridine framework. According to these studies, this approach may lead to effective cytotoxic agents, but good cytotoxic activity depends on structural requirements in the aniline ring which differ from those in 9-anilinoacridines. The present paper deals with molecular modeling studies of some 9-anilino substituted tricyclic compounds and their intercalation complexes (in various DNA sequences) resulting from docking the compounds into various DNA sequences. As expected, the isosteric substitution in 9-anilinoacridines influences the LUMO energy values and orbital distribution, the dipole moment, electrostatic charges and the conformation of the anilino ring. Other important differences are observed during the docking studies, for example, changes in the spatial arrangement of the tricyclic nucleus and the anilino ring at the intercalation site. Semiempirical calculations of the intercalation complexes show that the isosteric replacement of a benzene ring in the acridine nucleus affects not only DNA affinity but also base pair selectivity. These findings explain, at least partially, the different structural requirements observed in several 9-anilino substituted tricyclic compounds for cytotoxic activity. Thus, the data presented here may guide the rational design of new agents with different DNA binding properties and/or a cytotoxic profile by isosteric substitution of known intercalators.     

Molecular modeling of tricyclic compounds with anilino substituents and their intercalation complexes with DNA sequences

Although 9-anilinoacridines are among the best studied antitumoral intercalators, there are few studies about the effect of isosteric substitution of a benzene moiety for a heterocycle ring in the acridine framework. According to these studies, this approach may lead to effective cytotoxic agents, but good cytotoxic activity depends on structural requirements in the aniline ring which differ from those in 9-anilinoacridines. The present paper deals with molecular modeling studies of some 9-anilino substituted tricyclic compounds and their intercalation complexes (in various DNA sequences) resulting from docking the compounds into various DNA sequences. As expected, the isosteric substitution in 9-anilinoacridines influences the LUMO energy values and orbital distribution, the dipole moment, electrostatic charges and the conformation of the anilino ring. Other important differences are observed during the docking studies, for example, changes in the spatial arrangement of the tricyclic nucleus and the anilino ring at the intercalation site. Semiempirical calculations of the intercalation complexes show that the isosteric replacement of a benzene ring in the acridine nucleus affects not only DNA affinity but also base pair selectivity. These findings explain, at least partially, the different structural requirements observed in several 9-anilino substituted tricyclic compounds for cytotoxic activity. Thus, the data presented here may guide the rational design of new agents with different DNA binding properties and/or a cytotoxic profile by isosteric substitution of known intercalators.     

Insight into the structural requirements of proton pump inhibitors based on CoMFA and CoMSIA studies

In the present study, a series of 179 quinoline and quinazoline heterocyclic analogues exhibiting inhibitory activity against Gastric (H+/K+)-ATPase were investigated using the comparative molecular field analysis (CoMFA) and comparative molecular similarity indices (CoMSIA) methods. Both the models exhibited good correlation between the calculated 3D-QSAR fields and the observed biological activity for the respective training set compounds. The most optimal CoMFA and CoMSIA models yielded significant leave-one-out cross-validation coefficient, q(2) of 0.777, 0.744 and conventional cross-validation coefficient, r(2) of 0.927, 0.914 respectively. The predictive ability of generated models was tested on a set of 52 compounds having broad range of activity. CoMFA and CoMSIA yielded predicted activities for test set compounds with r(pred)(2) of 0.893 and 0.917 respectively. These validation tests not only revealed the robustness of the models but also demonstrated that for our models r(pred)(2) based on the mean activity of test set compounds can accurately estimate external predictivity. The factors affecting activity were analyzed carefully according to standard coefficient contour maps of steric, electrostatic, hydrophobic, acceptor and donor fields derived from the CoMFA and CoMSIA. These contour plots identified several key features which explain the wide range of activities. The results obtained from models offer important structural insight into designing novel peptic-ulcer inhibitors prior to their synthesis.     

非下采样Contourlet变换的彩色图像融合

为了提高图像融合的效果,以多聚焦的彩色图像为研究对象,提出了一种基于非下采样Contourlet变换的多聚焦彩色图像融合算法。对IHS模型的亮度分量I进行NSCT分解,根据多聚焦图像的成像特点和分解后的高低频系数相关性,对分解后的低频系数采用"区域能量取大"和高频系数采用"绝对值和取大"的融合准则进行融合,再进行非下采样Contourlet逆变换,得到融合后的亮度分量,并由此计算融合后的色调分量和饱和度分量,实现彩色图像的融合。实验结果表明,该方法的融合效果优于小波变换的融合结果,针对IHS模型的融合结果也明显优于RGB模型的融合结果。     

基于 NDIS中间层驱动的高速网络设备监测技术 *

传统的基于应用层的网卡监测方式已难以对高速网卡活动信息进行实时、准确监测。为此 ,分析基于 NDIS( network driver interface specification)中间层驱动和 Windows网络数据包过滤技术的特点 ,采用核心态 NDIS中间层驱动程序实现了与底层网络接口设备具体细节无关的高速网络设备监测技术 ,设计并实现了 Windows平台下基于 NDIS的网卡监测器。它分为应用层和驱动层两个模块 ,能够在保证高性能的情况下在数据链路层同时对多个网卡进行精确监测 ,其主要特点是对所     

结合多分辨率与块分割的不同聚焦图像融合

提出了一种结合多分辨率与图像块分割的图像融合新方法。该方法除将多分辨率融合图像块作为可能位于源图像的模糊区域与清晰区域交界处位置的最终融合图像块之外,还将多分辨率图像融合方法获取的融合图像与源图像进行分块比较,选用与多分辨率融合图像块相似的源图像块作为最终融合图像块。实验结果表明,该方法能有效提高常用的多分辨率图像融合方法的融合效果。     

阵列化锰铜高压传感器的研制

通过传感器的结构设计、敏感材料和封装材料的研制以及采用新的传感器制备工艺,制作了一种新型的薄膜式锰铜传感器。采用熔融石英材料作为绝缘基板。在绝缘基板上沉积锰铜敏感薄膜。并在敏感薄膜的上面沉积SiO2封装层薄膜。根据"后置"式传感器由阻抗匹配原则,计算出铝靶板中的最高压力为51.68GPa,SiO2封装材料中的压力为35.396GPa。     

Using MERIS fused images for land-cover mapping and vegetation status assessment in heterogeneous landscapes

In this paper we evaluate the potential of ENVISAT–Medium Resolution Imaging Spectrometer (MERIS) fused images for land-cover mapping and vegetation status assessment in heterogeneous landscapes. A series of MERIS fused images (15 spectral bands; 25 m pixel size) is created using the linear mixing model and a Landsat Thematic Mapper (TM) image acquired over the Netherlands. First, the fused images are classified to produce a map of the eight main land-cover types of the Netherlands. Subsequently, the maps are validated using the Dutch land-cover/land-use database as a reference. Then, the fused image with the highest overall classification accuracy is selected as the best fused image. Finally, the best fused image is used to compute three vegetation indices: the normalized difference vegetation index (NDVI) and two indices specifically designed to monitor vegetation status using MERIS data: the MERIS terrestrial chlorophyll index (MTCI) and the MERIS global vegetation index (MGVI).

Results indicate that the selected data fusion approach is able to downscale MERIS data to a Landsat-like spatial resolution. The spectral information in the fused images originates fully from MERIS and is not influenced by the TM data. Classification results for the TM and for the best fused image are similar and, when comparing spectrally similar images (i.e. TM with no short-wave infrared bands), the results of the fused image outperform those of TM. With respect to the vegetation indices, a good correlation was found between the NDVI computed from TM and from the best fused image (in spite of the spectral differences between these two sensors). In addition, results show the potential of using MERIS vegetation indices computed from fused images to monitor individual fields. This is not possible using the original MERIS full resolution image. Therefore, we conclude that MERIS–TM fused images are very useful to map heterogeneous landscapes.