一种色氨酸修饰的香豆素类Cu2+荧光探针的合成及性能研究

摘要:本文设计、合成了一种色氨酸修饰的香豆素类荧光探针香豆素色氨酸甲酯,它以色氨酸基团作为金属离子的识别位点、以香豆素基团作为荧光信号基团.实验结果表明:在水溶液中该探针能够对Cu2+表现出荧光猝灭效应,而相同测试条件下其他重金属离子的加入对探针的荧光发射几乎没有影响,因此该探针对Cu2+表现出选择性识别作用.     

双丹酰基组氨酸作为Fe3+荧光探针的研究

以丹磺酰基为荧光基团、以组氨酸为识别基团,设计并合成了一种识别Fe3+的双丹酰基组氨酸(DHD)荧光探针.通过核磁共振波谱、质谱、紫外-可见吸收光谱、荧光光谱等对产物进行了表征和识别性能的研究.结果表明:探针分子能够在水溶液中以物质的量1 : 1的结合比荧光识别Fe3+,表现出高灵敏度和高选择性,且具有很强的抗离子干扰能力和荧光恢复能力.     

罗丹明类铜离子荧光探针的合成及其应用研究

设计、合成了一种基于罗丹明B的铜离子荧光分子探针RF。研究发现在V乙腈∶V水=1∶1介质中,化合物RF最大发射波长为566 nm,Cu2+可使探针RF的荧光强度明显增大,同时溶液颜色从无色变为桃红色。该荧光探针对Cu2+具有较高的灵敏度和较好的选择性。RF的选择性荧光增强是由于其对Cu2+的识别开环引起的。该探针对Cu2+的识别是不可逆的,而且pH对探针RF在中性水溶液中检测Cu2+几乎没有影响。     

一种基于萘异硫氰酸酯的Hg2+反应型荧光探针

以萘异硫氰酸酯为反应基团和荧光基团,设计、合成了一种能够识别Hg2+的荧光探针（HBN）,利用质谱、核磁共振方法表征了其结构,并利用紫外-可见吸收光谱、荧光发射光谱,对HBN识别Hg2+的性能进行了测试及分析.研究发现,HBN在50%乙腈水溶液中对Hg2+表现出非常高的选择性和灵敏度,其荧光强度随Hg2+浓度的增强而不断增强,当Hg2+浓度为探针浓度2倍时荧光强度不再上升,同时质谱检测到新物质的生成,显示了该探针属于Hg2+反应型荧光探针。     

丹酰基团修饰的喹啉衍生物作为Cu2+和Hg2+荧光探针的研究

合成并表征了一种具有良好水溶性的荧光探针—8?(丹磺酰氨基)喹啉,它能够在水溶液中荧光识别和检测Cu2+和Hg2+.随着这2种离子浓度的增加,该探针的荧光发射强度均发生较大程度的猝灭,而相同测试条件下,其他9种所测试的常见重金属离子对该荧光探针的荧光发射性质几乎没有影响.因此,这是一种对Cu2+和Hg2+具有选择性识别的荧光探针.     

一种高水溶性的比率比色型氰根离子荧光探针

为了快速、便捷地检测氰根离子,以相互共轭的香豆素和半花菁为荧光团,以半花菁基团中极化的C=N双键为识别基团,设计、合成了一种新型比率比色型水溶性的可检测氰根离子的探针。探针的结构通过1H NMR、IR和HRMS等方法进行了表征,并研究了该探针的检测机理、选择性、方法的分析特性及其作为比色型探针的应用。该探针通过与氰根离子发生亲核加成反应来调节荧光团之间的共轭和分子内电荷转移(ICT)效应,从而发生荧光信号和颜色的变化。这提供了一种能够在水溶液中不借助任何仪器直接检测氰根离子的实用体系。     

表面富S2-的硫化镉量子点的合成及其在汞离子定量分析中的应用

在水溶液中采用柠檬酸三钠和六偏磷酸钠作为稳定剂,通过控制较低浓度的无机镉源溶液和硫源溶液缓慢接触反应,在冰水浴条件下一步成功合成了荧光稳定性好、表面富硫的水溶性CdS量子点.并利用Hg2+与CdS富硫表面的过量S2-的特异结合反应所引起的量子点的荧光淬灭效应,实现了对水溶液中痕量汞离子的选择性定量分析检测.考察了不同种类缓冲溶液、pH值条件、量子点浓度等因素对荧光淬灭程度的影响,在优化的最佳实验条件下,汞离子分析测定的线性范围为0.05～33μmol.L-1.     

构建碳点—罗丹明B比率探针检测汞离子污染

双发射比率探针以其优良的抗干扰性能成为近年来荧光探针研究的热点。本文采用微波法合成碳点,并构建了碳点-染料的新型比率探针,可以用于定量检测汞离子(Hg~(2+))污染。该比率探针检测汞离子的线性范围为0.56～5.0μmol·L~(-1),检出限为0.56μmol·L~(-1)。随着汞离子浓度的增加,比率探针体系在紫外灯下的颜色会从紫色逐渐变化为橙色,从而实现汞离子的可视化筛查。实验发现在汞离子检测中,当其他金属离子的浓度为汞离子浓度10倍时,比率探针对汞离子仍有较强的选择性。使用此方法对实际自来水样品进行了检测,自来水中没有检出汞离子;而在自来水的3种浓度汞离子加标回收实验中,加标回收率均为91.17%～104.83%.     

槲皮素作为荧光探针对醋酸根离子的识别作用

为了探讨天然产物槲皮素作为荧光探针检测醋酸根离子的选择性和灵敏性,实验将不同种类阴离子加入到槲皮素的二甲亚砜溶液中,考查槲皮素溶液的荧光强度变化.实验发现:槲皮素的二甲亚砜溶液在500 nm处有一荧光发射峰,加入醋酸根离子时,该峰强度明显增强,而其他阴离子(C1-、Br-、I-、ClO4-、H2PO4-)对该峰强度无明显影响,同时在Q-Ac-中加入其他阴离子未引起荧光强度的变化.表明槲皮素对醋酸根离子具有较好的选择性;荧光滴定光谱表明槲皮素对醋酸根离子具有较高的灵敏度,且荧光滴定曲线线性关系较好(R2 =0.995),线性范围为1.0× 10-6～8.0× 10-6 mol/L,最低检测限为1.0× 10-7 mol/L;通过Job曲线得到槲皮素与醋酸根离子作用的化学计量比为3:2,稳定常数为3.11×104.核磁等实验表明,醋酸根离子的加入破坏或减弱了体系原有的氢键,促进了槲皮素分子内电荷转移,使槲皮素的荧光强度增强.用该方法检测了样品中微量的醋酸根离子,回收率为98.82％～100.96％,测定结果稳定.     

罗丹明类荧光探针的合成及在铜离子测定中的应用

合成了对铜离子有很强选择性的罗丹明类荧光探针。在乙腈/水(体积比1∶1)溶液中,当加入Cu2+后,探针显桃红色,随Cu2+浓度增大,荧光强度增强,发射荧光波长红移。并在2.8×10-7~2.8×10-5mol/L范围内,Cu2+离子浓度与荧光强度呈现良好的线性关系。其它常见离子引起很小的荧光光谱变化,合成的试剂可用于高选择性的检测铜。     

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.     

A computer generator for randomly layered structures

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

海南岛地体及其毗邻陆缘晚中生代—新生代古地磁研究和构造演化

本文叙述了对海南岛及其毗邻大陆边缘白垩纪到第四纪地层岩石进行古地磁研究的全部工作过程。通过分析岩石中剩余磁矢量的磁偏角及磁倾角的变化,提出海南岛白垩纪以来经历的构造演化模式如下:早期伴随顺时针旋转而向南迁移,后期伴随逆时针转动并向北运移。联系该地区及邻区的地质、地球物理资料,对海南岛上述的构造地体运动提出以下认识:北部湾内早期有一拉张作用,主要是该作用使湾内地壳显著伸长减薄,形成北部湾盆地。从而导致了海南岛的早期构造运动,而海南岛后期的构造运动则主要是受南海海底扩张的影响。海南地体运动规律的阐明对于了解北部湾油气盆地的形成演化有重要的理论和实际意义。     

Exciton Seebeck in Molecular Systems

Various applications relevant to the exciton dynamics,such as the organic solar cell,the large-area organic light-emitting diodes and the thermoelectricity,are operating under temperature gradient.The potential abnormal behavior of the exicton dynamics driven by the temperature difference may affect the efficiency and performance of the corresponding devices.In the above situations,the exciton dynamics under temperature difference is mixed with     

Achieving Unusual States of Matter Under High Pressure

The elongation method,originally proposed by Imamura was further developed for many years in our group.As a method towards O(N)with high efficiency and high accuracy for any dimensional systems.This treatment designed for one-dimensional(ID)polymers is now available for three-dimensional(3D)systems,but geometry optimization is now possible only for 1D-systems.As an approach toward post-Hartree-Fock,it was also extended to     

《Chinese Science Bulletin》SUBJECT INDEX TO VOLUME 59(2014)

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An on-line scaling method for improving scalability of a database cluster

The explosive growth of the Internet and database applications has driven database to be more scalable and available, and able to support on-line scaling without interrupting service. To support more client's queries without downtime and degrading the response time, more nodes have to be scaled up while the database is running. This paper presents the overview of scalable and available database that satisfies the above characteristics. And we propose a novel on-line scaling method. Our method improves the existing on-line scaling method for fast response time and higher throughputs. Our proposed method reduces unnecessary network use, i.e. , we decrease the number of data copy by reusing the backup data. Also, our on-line scaling operation can be processed parallel by selecting adequate nodes as new node. Our performance study shows that our method results in significant reduction in data copy time.     

An improved R-tree based on childnode''s probability

R-Tree is a good structure for spatial searching. But in this indexing structure,either the sequence of nodes in the same level or sequence of traveling these nodes when queries are made is random. Since the possibility that the object appears in different MBR which have the same parents node is different, if we make the subnode who has the most possibility be traveled first, the time cost will be decreased in most of the cases. In some case, the possibility of a point belong to a rectangle will shows direct proportion with the size of the rectangle. But this conclusion is based on an assumption that the objects are symmetrically distributing in the area and this assumption is not always coming into existence. Now we found a more direct parameter to scale the possibility and made a little change on the structure of R-tree, to increase the possibility of founding the satisfying answer in the front sub trees. We names this structure probability based arranged R-tree (PBAR-tree).     

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.     

Integrating GIS Web services based on mediating architecture

The geographic information service is enabled by the advancements in general Web service technology and the focused efforts of the OGC in defining XML-based Web GIS service. Based on these models, this paper addresses the issue of services chaining,the process of combining or pipelining results from several interoperable GIS Web Services to create a customized solution. This paper presents a mediated chaining architecture in which a specific service takes responsibility for performing the process that describes a service chain. We designed the Spatial Information Process Language (SIPL) for dynamic modeling and describing the service chain, also a prototype of the Spatial Information Process Execution Engine (SIPEE) is implemented for executing processes written in SIPL. Discussion of measures to improve the functionality and performance of such system will be included.