紫燕草化学成分的研究

自云南省产的半边莲科植物紫燕草(Lobelia hybrida)的全草中分离出了9种化合物,结构已经波谱法和化学法确定。除棕榈酸β-香树素酯外,其余均为生物碱,有去氢半边莲定、8,10-乙基山梗二酮、8,10-二乙基半边莲醇酮、山梗新碱、山梗烷醇、半边莲定、去甲半边莲定及去氢山梗新碱。其中去氢山梗新碱为新化合物。     

一种含吡啶环和三氟甲基取代基的芳香二胺的合成与表征

以4-三氟甲基苯甲醛、4'-硝基苯乙酮和醋酸铵为原料,在冰醋酸介质中,通过改进的Chichibabin反应得到了二硝基化合物4-(4-三氟甲基苯基)-2,6-二(4-胺基苯基)吡啶(TMPBNPP),继而用Pd/C和水合肼将TMPBNPP进行还原,成功合成了一种新型含吡啶环和三氟甲基侧基的芳香二胺4-(4-三氟甲基苯基)-2,6-二(4-胺基苯基)吡啶(TMPBAPP),2步反应总收率为48;,并用核磁共振谱、红外光谱和X-射线衍射等手段对其结构进行了分析表征.     

2,6-双吡唑基吡啶Cu(Ⅱ)配合物对环己烯的催化氧化反应

将2,6-双(吡唑基)吡啶(bpp)进行N-烷基化反应后与Cu~(2+)盐发生配位反应,制得4种Cu(Ⅱ)-bpp固体配合物,分别采用核磁共振谱、紫外/可见吸收光谱和元素分析对固体催化剂的结构进行结构表征.将配合物作为催化剂应用于环己烯的氧化反应中,结果表明,在以叔丁基过氧化氢为氧化剂时,环己烯主要氧化生成2-环己烯-1-酮.在2,6-双(1-甲基-5-叔丁基-1H-吡唑-3-基)吡啶的Cu(Ⅱ)配合物做催化剂时,环己烯在323 K反应8 h的转化率达到62.58%,2-环己烯-1-酮的选择性达到97.68%.     

4-亞苄基-2,2,5,5-四甲基氢化呋喃酮-3的若干反应

1) 4-苯甲酰基-2,2,5,5-四甲基氢化呋喃酮-3(Ⅲ)不能由相应的氢化呋喃酮与苯甲酸酯缩合而得,但可通过呋喃酮与苯甲醛缩合产物与溴加成,然后再经醇钠作用而得。 2) 二溴化物(Ⅱ)对热不稳定,与环己胺或吡啶作用时能脱去一分子溴而生成α,β-不饱和酮(Ⅰ),与氢化吡啶作用时除(Ⅰ)外还生成产物(Ⅳ)。 3) α,β-不饱和酮(Ⅰ)与氢化吡啶或吗福林进行加成,得到相应的产物(V_a)与(V_b)。     

稀土固体超强酸SO4^2-／TiO2-Ce（Ⅳ）催化合成环己酮乙二醇缩酮

制备了固体超强酸催化剂SO4^2-／TiO2-Ce(Ⅳ)，并利用该催化剂催化合成了环己酮乙二醇缩酮，探讨SO4^2-／TiO2-Ce(Ⅳ)对缩酮反应的催化活性，较系统地研究了酮醇物质的量比、催化剂用量、反应时间诸因素对产品收率的影响．实验表明：SO4^2-／TiO2-Ce(Ⅳ)是合成环己酮乙二醇缩酮的良好催化剂，在n(酮)：n(酮)=1：1.5，催化剂用量为反应物料总质量的0.5％，环己烷为带水剂，反应时间1．0h的优化条件下，环己酮乙二醇缩酮的收率可达85．7％．     

N,N’-二(2,6—二乙酰吡啶-4-基-)N,N’-二甲基-1,6-己二胺的合成

从4-氯-2,6-二乙酸吡啶,经4步合成了N,N’-二(2,6-二乙酰吡啶-4-基-)-N,N’-二甲基-1,6-己二胺,通过元素分析,红外光谱,核磁共振谱和热分析确定了它的分子的结构式。     

TEBA存在时醛和丁酮的缩合反应

在相转移催化剂TEBA(三乙基苄基氯化铵)和少量10%氢氧化钠溶液存在时,龙脑烯醛和丁酮能顺利地发生羟醛缩合反应,脱水后生成四个产物:3-甲基-5-(2,2,3-三甲基环戊-3-烯-1-基)戊3-烯-2-酮(Ⅰ),6-(2,2,3-三甲基环戊-3-烯-1-基)己-4-烯-3-酮(Ⅱ),3-甲基-5-(2,2,3-三甲基环戊-3-烯-1-基)戊-4-烯-2-酮(Ⅲ)和6-(2,2,3-三甲基环戊-3-烯-1-基)己-5-烯-3-酮(Ⅳ).其中Ⅰ的含量大于70%,可用作合成人造檀香醇(Sandalore)的原料。当TEBA存在时,也能催化加速正丁醛和苯甲醛与丁酮的缩合反应,反该产物与不加TEBA的情况相同。     

5H-茚并[1,2-b]吡啶的某些5-取代衍生物的合成

报告了文题化合物的合成方法。实验结果表明,5-溴-5H-茚并[1,2-b]吡啶(Ⅱ)的溴原子比较活泼,可被多种亲核试剂所取代。溴代物与含活泼亚甲基的丙二酸二乙酯反应,溴被(二乙氧羰基-)甲基取代,经水解,生成5-(二羧基-甲基)-5H-茚并[1,2-b]吡啶(Ⅳ),再经脱羧,即转化成5-羧甲基-5H-茚并(1,2-b)吡啶(Ⅴ)。溴代物与饱和环状仲胺哌啶反应,溴被哌啶子基取代,生成5-哌啶子基-5H茚并(1,2-b)吡啶(Ⅶ)。溴代物与芳胺类化合物邻-氨基苯甲酸酯反应,溴被N-芳胺基取代,生成5-(邻-烷氧羰基苯胺基)-5H-茚并[1,2-b]吡啶(Ⅷ)和5-(邻-烷氧羰基苯亚胺基)-5H-茚并[1,2-b]吡啶(IX)。所得各种反应产物,均经波谱分析得以证实。     

氨基醇取代吡啶酰胺锌(Ⅱ)配合物的合成与光谱表征

合成了4种氨基醇取代吡啶酰胺分子吡啶-2,6-二[N-(1'-羟乙基)甲酰胺]、吡啶-2,6-二[N-(2'-羟丙基)甲酰胺]、吡啶-2,6-二[N-(1'-甲基-2'-羟乙基)甲酰胺]、吡啶-2,6-二[N-(1',1'-二甲基-2'-羟基)甲酰胺]的锌(Ⅱ)配合物,通过元素分析方法确定了配合物的化学组成,比较分析了配位前后游离配体与配合物的红外和紫外吸收光谱,并采用紫外光谱滴定法对配体与Zn(Ⅱ)离子在溶液中的配位行为进行了模拟研究。结果显示4种锌(Ⅱ)配合物的配位模式相同,均为1∶1型(ML),其中酰胺键的N原子和吡啶环的N原子作为配位原子参与金属离子Zn(Ⅱ)配位成键。     

铜基N-杂环Pincer配合物的合成、表征以及对芳香化合物的催化研究

将Pincer形配体2,6-双(5-叔丁基-1H-吡唑-3-基)吡啶(H_2L)与CuBr_2反应,合成一种新的配合物[H_2LCuBr_2](H_2L=2,6-双(5-叔丁基-1H-吡唑-3-基)吡啶),并进行元素分析、紫外-可见(UV-Vis)光谱、傅里叶变换红外光谱(FT IR)和热重分析等表征。在70℃条件下的乙腈溶液中,以过氧化氢为氧化剂,以H_2LCuBr_2为催化剂,分别对芳族底物如异丙苯、苯乙烯、α-甲基苯乙烯和苯甲醇进行了氧化催化活性测试。实验证明该催化剂对苯甲醇、苯乙烯和α-甲基苯乙烯的氧化表现出良好的催化活性,主要产品分别为苯甲醛、苯甲醛和苯乙酮。苯甲醇在8 h内转化率为51. 77%,选择性95. 46%;苯乙烯在4 h内转化率为94. 84%,选择性81. 07%;α-甲基苯乙烯在4 h内转化率为99. 80%,选择性97. 91%。通过对苯甲醇氧化反应的质谱跟踪监测,提出了合理的催化反应机理。     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

A computer generator for randomly layered structures

AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…     

An Index mechanism for multi-scale view in spatial databases

There are numerous geometric objects stored in the spatial databases. An importance function in a spatial database is that users can browse the geometric objects as a map efficiently. Thus the spatial database should display the geometric objects users concern about swiftly onto the display window. This process includes two operations:retrieve data from database and then draw them onto screen. Accordingly, to improve the efficiency, we should try to reduce time of both retrieving object and displaying them. The former can be achieved with the aid of spatial index such as R-tree, the latter require to simplify the objects. Simplification means that objects are shown with sufficient but not with unnecessary detail which depend on the scale of browse. So the major problem is how to retrieve data at different detail level efficiently. This paper introduces the implementation of a multi-scale index in the spatial database SISP (Spatial Information Shared Platform) which is generalized from R-tree. The difference between the generalization and the R-tree lies on two facets: One is that every node and geometric object in the generalization is assigned with a importance value which denote the importance of them, and every vertex in the objects are assigned with a importance value,too. The importance value can be use to decide which data should be retrieve from disk in a query. The other difference is that geometric objects in the generalization are divided into one or more sub-blocks, and vertexes are total ordered by their importance value. With the help of the generalized R-tree, one can easily retrieve data at different detail levels.Some experiments are performed on real-life data to evaluate the performance of solutions that separately use normal spatial index and multi-scale spatial index. The results show that the solution using multi-scale index in SISP is satisfying.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the