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1.
在25 ℃,pH7.00的条件下,研究了希夫碱型大环多胺铜配合物对α-吡啶甲酸对硝基苯酚酯(PNPP)的催化水解反应,其表观速率常数为1.61×10-3 s-1,是PNPP自发水解速率常数的88倍;同时研究了非离子表面活性剂Brij35、阳离子表面活性剂CTAB、阴离子表面活性剂SDS及pH值、温度、铜配合物浓度对催化水解反应的影响,用所建立的三元复合物(MmLlS)催化反应通用数学模型,计算出催化反应相应的热力学和动力学参数.结果表明,配体中活化的羟基作为亲核物种对羧酸酯有较强的亲核反应能力,能有效地促进PNPP的水解.  相似文献   

2.
在30℃和pH8.0的条件下,研究了三乙醇胺与Ce(Ⅲ)形成的金属配合物对双(对硝基苯酚)磷酸酯(BNPP)的催化水解作用,实验发现,该金属配合物对BNPP有高效快速的催化水解作用,在pH8.0时,其水解的表观一级速率常数为1.42×10-2s-1,为BNPP自发水解的1.27×109倍,接近于天然酶的活性水平.提出了催化反应的机理,建立了催化反应的动力学数学模型,获得了相关的热力学和动力学参数.  相似文献   

3.
在有和无阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)和中性表面活性剂Brij35三种胶束和预胶存在下研究了对4-硝基苯酚苯甲酸酯(PNPB)碱性水解反应的动力学.实验结果表明,CTAB和Brij35胶束和预胶束对4-硝基苯酚苯甲酸酯碱性水解反应均有显著的催化作用,而SDS胶束和预胶束对4-硝基苯酚苯甲酸酯碱性水解反应有禁阻作用.这种催化和禁阻作用主要来自于胶束所产生的局部浓度效应,静电效应和微极性效应.应用假相动力学模型,获得了胶束和预胶束催化反应相关的热力学和动力学参数.  相似文献   

4.
实验合成了单核配合物4-氯-2,6-二(N-羟已基氨基甲基)苯酚合铜,研究了不同pH条件下在不同的3种表面活性剂(CTAB,LSS,Brij35)所生成的胶束溶液中催化PNPP水解的动力学.结果表明,阳离子表面活性剂(CTAB)加快了PNPP的水解,两性离子表面活性剂(LSS)对反应先催化后抑制,而非离子表面活性剂(Brij35)则抑制了反应的进行.用三元复合物模型进行动力学处理,得到了相关的热力学和动力学参数.  相似文献   

5.
合成并表征了单核和双核肟基铜(Ⅱ)配合物,研究了这两种配合物在不同胶束体系中催化羧酸酯水解的动力学,用相应的动力学模型处理得到了相关的动力学和热力学参数.研究结果表明,两种配合物在阳离子表面活性剂CTAB(十六烷基三甲基溴化铵)所生成的胶束溶液中催化PNPP(对硝基苯基α-吡啶甲酸酯)和PNPA(对硝基苯基乙酸酯)水解的活性高于在非离子表面活性剂胶束Brij35(聚氧乙烯(23)十二烷基醚)中的催化作用;单核Cu(II)配合物在金属胶束相中催化PNPP水解和双核Cu(II)配合物在金属胶束相中催化PNPA水解的一级速率常数与它们在缓冲溶液中自发水解的速率常数相比,kN分别提高了大约20747倍和32014倍.  相似文献   

6.
添加剂对La-H2O2模拟酶体系催化BNPP水解的影响   总被引:1,自引:1,他引:0  
研究了在pH7.00时,La^3 和H2O2摩尔比和表面活性剂CTAB、TritonX-100,pH缓冲剂N-2-羟乙基哌嗪-N-2-乙磺酸(HEPES)、三羟甲基胺基甲烷(Tris),离子强度调节剂KCl,KNO3及KClO4对La—H2O2体系催化BNPP水解反应的影响。实验结果表明,当[La^2 ]:[H2O2]=1:1时,La^3 和H2O2对BNPP的催化活性最大,所加表面活性剂、缓冲物质和盐均使La^3 -H2O2体系催化BNPP水解反应的表观速率常数减小。  相似文献   

7.
合成并表征了单核和双核肟基铜(Ⅱ)配合物,研究了这两种配合物在不同胶束体系中催化羧酸酯水解的动力学,用相应的动力学模型处理得到了相关的动力学和热力学参数、研究结果表明,两种配合物在阳离子表面活性剂CTAB(十六烷基三甲基溴化铵)所生成的胶束溶液中催化PNPP(对硝基苯基α-吡啶甲酸酯)和PNPA(对硝基苯基乙酸酯)水解的活性高于在非离子表面活性剂胶束Brij35(聚氧乙烯(23)十二烷基醚)中的催化作用;单核Cu(II)配合物在金属胶束相中催化PNPP水解和双核Cu(II)配合物在金属胶束相中催化PNPA水解的一级速率常数与它们在缓冲溶液中自发水解的速率常数相比,kN分别提高了大约20747倍和32014倍。  相似文献   

8.
利用紫外-可见分光光度法研究金属离子Ce(Ⅲ)-Tris(三羟甲基氨基甲烷)体系催化双(对硝基苯酚)磷酸酯(BNPP)的动力学,探索不同催化反应条件对催化效率和体系稳定性的影响和催化作用机理.结果表明,在金属离子Ce(Ⅲ)与Tris具有适当的配比,反应体系在适当的酸度和温度条件下,催化体系对双(对硝基苯酚)磷酸酯(BNPP)的水解有显著的催化作用,并且催化体系稳定,具有重现性,其催化活性基是由金属离子Ce(Ⅲ)和Tris形成的配合物.  相似文献   

9.
作者研究了30℃时,Brij35胶束溶液中大环Schiff碱的Cu(Ⅱ)和Zn(Ⅱ)配合物催化PNPP和PNPA水解反应的动力学,结果表明,两种配合物催化PNPP和PNPA水解反应的机理是不同的,Cu(Ⅱ)配合物仅催化PNPP的水解,其机理是外部氢氧根离子对羰基的亲核进攻,而Zn(Ⅱ)配合物能同时加速PNPP和PNPA的水解,其机理为锌键合的氢氧根离子对PNPP羰基的分子内亲核进攻和锌键合的氢氧根离子对PNPA羰基的分子间亲核进攻.Zn(Ⅱ)配合物的催化活性高于Cu(Ⅱ)配合物。  相似文献   

10.
合成了3个配体N,N,N′,N′,-四(2-羟乙基)-1,3-丙二胺(1),N,N,N′,N′,-四(2-羟乙基)-1,10-癸二胺(2),N,N,N′,N′,-四(2-羟乙基)-1,4-对甲苯二胺(3)及其与二价金属离子Zn (II)和Co(II)形成的金属配合物.在25℃,不同pH值下,研究了这些金属配合物在Brij35胶束溶液中催化PNPP水解的反应.其结果表明在催化PNPP水解反应中,其活性物种为2∶1(配体金属离子)的单核金属配合物.不同金属配合物的催化活性与配合物的桥联配体及反应的微环境相关.  相似文献   

11.
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.  相似文献   

12.
何延凌 《科技信息》2008,(4):258-258
Language is a means of verbal communication. People use language to communicate with each other. In the society, no two speakers are exactly alike in the way of speaking. Some differences are due to age, gender, statue and personality. Above all, gender is one of the obvious reasons. The writer of this paper tries to describe the features of women's language from these perspectives: pronunciation, intonation, diction, subjects, grammar and discourse. From the discussion of the features of women's language, more attention should be paid to language use in social context. What's more, the linguistic phenomena in a speaking community can be understood more thoroughly.  相似文献   

13.
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.  相似文献   

14.
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。  相似文献   

15.
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.  相似文献   

16.
AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…  相似文献   

17.
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.  相似文献   

18.
In the 19th century the society was controlled by men, and women were just appendants of them, they had not any rights and freedom. But Jane was an exception, she showed some characteristics of early feminist. Jane showed her characteristics of feminism in three aspects: rebellion, equality, and independence. These characteristics were helpful to her success, and feminism is the only way out for women of that time.  相似文献   

19.
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-  相似文献   

20.
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-  相似文献   

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