新型罗丹明类荧光探针中间体的合成及表征

目的研究一类新型罗丹明类细胞钙离子荧光探针并合成一系列荧光中间体。方法以间氨基苯酚为起始原料,制备对甲苯磺酸(3-氨基)苯酚酯2,对甲苯磺酸(3-N,N-二烯丙基)苯酚酯3,对甲苯磺酸(3-N,N-二苄基)苯酚酯3’,在脱去对甲苯磺酸保护基后与邻苯二甲酸酐反应。结果合成荧光中间体N,N,N,N-四烯丙基取代罗丹明5和N,N,N,N-四苄基取代罗丹明6。得到对甲苯磺酸(3-N,N-二苄基)苯酚酯3’单晶结构。荧光中间体5和6的结构经核磁共振光谱,红外光谱,质谱证实。结论合成的新型荧光中间体,为性能优良的罗丹明类荧光探针的合成提供了新思路。     

几种酰亚胺和酰胺的N-烷基化反应——邻苯二甲酰亚胺、琥珀酰亚胺和乙酰苯胺在相转移条件下N-烷基化反应的研究

本文研究了邻笨二甲酰亚胺、琥珀酰亚胺和乙酰苯胺在相转移条件下的N-烃基化反应,结果表明,对于前两种化合物的N-烃基化反应,聚乙二醇(PEG)600是很好的催化剂,乙酸乙酯是理想的溶剂,反应在固、液两相下可顺利地完成。用此方法,合成了一系列相应的N-取代酰亚胺;并通过保护、水解的方法,以季铵盐为相转移催化剂,合成了带有羟基的N-取代乙酰苯胺。     

异脲盐法合成胍及其N-取代嘧啶胺衍生物的研究

采用异脲盐法合成一系列N-取代胍和N-取代-4-(3-吡啶基)嘧啶-2-胺类化合物。以O-甲基异脲硫酸盐为起始原料,与脂肪胺类或芳香胺类化合物反应合成脂肪胍或芳香胍类化合物(1),再以3-乙酰吡啶和N,N-二甲基甲酰胺二甲基缩醛(DMF-DMA)为原料反应合成3-(二甲基氨基)-1-(3-吡啶基)-2-丙烯-1-酮(2),将化合物(1)和(2)在碱性条件下反应,最终得到目标产物N-取代-4-(3-吡啶基)嘧啶-2-胺(3)。合成出了6个N-取代胍及其相应的衍生物N-取代-4-(3-吡啶基)嘧啶-2-胺类化合物,并用1H NMR,IR和元素分析表征了目标产物的结构。该方法路线简捷环保、原料廉价易得、反应条件较温和。     

N-取代苯并咪唑酯类衍生物的合成及表征

目的合成苯并咪唑酯及其衍生物,并对其合成方法进行改进研究。方法以邻苯二胺为起始原料合成了苯并咪唑-2-甲酸乙酯(1)和苯并咪唑-2-乙酸乙酯(2),再以丙酮为溶剂,分别与乙酰氯,苯甲酰氯和二茂铁甲酰氯常温反应3 h。结果合成了N-取代苯并咪唑-2-甲酸乙酯酰胺衍生物(1a-1c),N-取代苯并咪唑-2-乙酸乙酯酰胺衍生物(2a-2c),并通过IR,1H NMR,MS和元素分析确定了分子结构。结论合成方法简便、易行、产率高,为进一步形成配合物奠定了良好基础。     

顺丁烯二酸二异辛酯合成新方法

在以顺丁烯二酸和异辛醇为原料,用DMAP/DCC催化合成顺丁烯二酸二异辛酯的实验中,考察了对甲苯磺酸、浓硫酸和N,N-二环己基碳酰亚胺(DCC)、4-二甲氨基吡啶(DMAP)等几种催化剂的催化性能.结果表明,在室温条件下DCC/DMAP的催化活性高,是一种比较好的酯化反应催化剂.同时考察了反应时间、醇酸比、催化剂用量、反应温度对合成顺丁烯二酸二异辛酯收率的影响.实验结果表明,当反应时间为4h,异辛醇与顺丁烯二酸的物质的量之比为2.2:1(mol/mol),反应温度为20℃时,顺丁烯二酸二异辛酯的收率可达到91.3%.     

钛酸酯催化合成3-乙酰氨基-N，N-二-（β-烷酰氧乙基）苯胺

用钛酸酯为催化剂，通过3-乙酰氨基-N，N-二-(β-羟乙基)苯胺与乙酸及丙酸的酯化反应，合成了3-乙酰氨基-N，N-二-(β-烷酰氧乙基)苯胺对影响反应的因素进行了讨论。用IR、NMR对结构进行了表征，酯的收率为98%以上。     

6-甲基-尿嘧啶及其N-取代衍生物合成

目的 对6-甲基尿嘧啶及其N-取代衍生物的合成方法进行研究和改进.方法 用醋酸锌作催化剂,二甲苯作溶剂,使乙酰乙酸乙酯和氨基甲酸乙酯在140℃反应6 h,得到6-甲基-2,3-二氢-1.3-噁嗪-2,4-二酮,噁嗪二酮再和氨或N-取代胺,在150～160℃二反应2 h,合成出了目标产物.结果 合成出6-甲基尿嘧啶和6种N-取代-6-甲基尿嘧啶衍生物,用1H NMR和元素分析表征了目标化合物的结构;产率为76.1%～90%.结论 该方法原料易得,不用酸性催化剂,条件温和,是合成N-取代尿嘧啶理想方法.     

利用硅烷基化反应合成脱氢氨基酸

N-三氟乙酰甘氨酸在三乙胺存在下与三氟甲磺酸三甲基硅烷酯发生甲基硅烷基化反应生成2-(N-三氟乙酰-N-三甲基硅烷基)氨基-1，1-二(三甲基硅烷氧基)乙烯．醛与所生成的取代乙烯发生加成反应生成2-(N-三氟乙酰-N-三甲基硅烷基)氨基-3-三甲基硅烷氧基-羧酸三甲基硅烷酯，再经α、β消除反应就得到脱氢氨基酸．用这一新方法合成的a、8-脱氢氨基酸可用于合成新型的多肽和肽生物碱．     

α-取代氯代膦酸酯的新合成方法

报道了以N,N-二甲基甲酰胺为催化剂,α-取代膦酸酯与氯化亚砜进行反应合成α-取代氯代膦酸酯的新方法.反应条件温和,收率较高.     

无溶剂条件下三氯化铁高效催化合成N1-取代的3,4-二氢嘧啶-2(1H)-酮

无溶剂、80℃条件下,三氯化铁为催化剂,芳香醛、β-酮酯、单取代(硫)脲三组分"一锅法"高效合成了一系列N1-取代的3,4-二氢嘧啶酮.考察了原料配比、催化剂用量和反应温度对产率的影响,确定较佳反应条件为:n_醛:n_酯:n_脲=1:1:1,三氯化铁3 mol%,反应温度80℃.在较佳反应条件下,考察了各种芳香醛、乙酰乙酸乙酯(乙酰乙酸甲酯)、单取代脲(硫脲)的反应效果,并合成了八种新物质.所有产品结构通过IR、1H NMR、13C NMR和元素分析进行表征.最后提出了可能的催化作用机理.该方法具有操作简单、不使用任何有机溶剂、反应条件温和、催化剂廉价易得、底物范围广等优点.     

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