223 resultados para Surfactant flooding
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本文简要评述了扫描探针显微学研究的发展过程、目前状况及发展方向,着重介绍了扫描探针显微学(SPM)在分子组装体研究中的一些应用。采用扫描探针显微学结合电化学的方法对自组装膜(SAMs)、表面活性剂(surfactant)、纳米颗粒(nanoparticles)等分子组装体系进行了研究,并结合IR、QCM、XPS、XRD等多种手段对分子组装体在电极表面的形态和结构进行了探讨。主要结果如下:1.SPM研究以杂多酸为基础的分子组装体我们通过将AsMo_(11)V0_(40)~(4-)杂多酸阴离子从其酸性溶液中自吸附至金表面的方法,制备了一类新的无机自组装膜。我们利用QCM、STM和电化学方法分别研究了AsMo_(11)VO_(40)~(4-)自组装膜的吸附过程、在Au表面的结构和电化学性质。QCM数据表明这个自组装过程可以用Langmuir吸附等温式来描述,其吸附自由能为-20 KJ/mol。 通过QCM测得的AsMo_(11)VO_(40)~(4-)自组装膜的表面覆盖度的最大值为1.7 * 10~(-10)mol/cm~2,这相当于一个AsMo_(11)VO_(40)~(4-)阴离子的密堆积单层。AsMo_(11)VO_(40)~(4-)自组装膜的循环伏安图上出现三对可逆的氧化还原峰,每对峰所对应的自组装膜的表面覆盖度都亦为1.78 * 10~(-10) mol/cm2,和QCM结果一致。现场STM图像显示AsMo_(11)VO_(40)~(4-)自组装膜十分的均一没有如何多层或聚集体的结构。高分辨STM图进一步显示在Au(111)表面的sMo_(11)VO_(40)~(4-)自组装膜于+0.7 V(vs.Ag | AgCl)表现出二维有序的四方晶体结构,晶格间距为10-11 A。这个值与sMo_(11)VO_(40)~(4-)阴离子的直径十分接近。从STM图我们也估算出AsMo_(11)VO_(40)~(4-)自组装膜的表面覆盖度为1.8 * 10~(-10) mol/cm~2,这和QCM以及电化学的实验结果都很接近。我们进一步研究了一种新的以杂多酸为基础的有机无机复合膜--砷钼钒杂多酸的十一烷基吡啶盐(CPMVA)--的制备、结构和电催化性质。通过在这种盐的丙酮溶液中循环电位扫描,我们可以在HOPG电极表面制备稳定的CPMVA膜。我们利用XPS、STM和电化学多种手段来表征CPMVA膜的结构和性质。这些研究表明:在新剥离HOPG表面CPMVA膜的结构为自聚集的分子团,而在预阴极化HOPG表面CPMVA膜的结构为自有序单层。CPMVA膜在酸性和丙酮溶剂中部表现出可逆的氧化还原动力学行为,这说明这种新类型的膜甚至能在有机溶剂中用作催化剂。当溶液的pH值大于7.O时,CPMVA膜也能维持其稳定性,它对pH值的依赖程度明显小于其无机物形式的膜(H_4AsMo_(11)VO_(40))对pH值的依赖程度。CPMVA膜对Br0_3-的还原表现出很好的电催化活性,催化电流与BrO_3~-的浓度的平方成正比。这种有很高稳定性的新类型杂多酸膜在催化剂领域中将有很广阔的应用前景。2.电化学STM研究吸附在金属表面的表面活性剂聚集体由于电位诱导引起的结构变化表面活性剂在表面的吸附已广泛地被用于限制电极表面的活性和稳定溶液中的胶体和纳米粒子,但是人们对表面活性剂在电极表面的结构和由于电位变化所引起的结构改变并不清楚。在这个工作中我们利用现场STM观察了电位控制下表面活性剂十二烷基磺酸钠(SDS)在Au(111)表面的吸附。STM图像显示通过控制电位SDS在Au(111)表面有一从半圆柱胶束单层向致密双层膜过渡的构象变化。我们也建立了SDS聚集体在Au(111)表面电位诱导结构变化的模型。就我们所知,这是第一次系统地研究表面活性剂聚集体在金属表面的电位诱导结构变化。3.在固体表面构筑有序的聚苯胺分子导线我们提出了一种新的通过分子设计构筑有序聚苯胺分子导线的新方法。首先,根据Saveant的方法我们在HOPG表面修饰上有序的4-氨基苯单层,然后溶液中的苯胺分子通过阶跃的方法被层层电聚合在4-氨基苯单层修饰的HOPG表面,形成有序的聚苯胺分子导线。FTIR-ERS和XPS结果证实HOPG表面上形成了聚苯胺。SPM图显示在HOPG表面的聚苯胺平面结构为有序的3~(1/2) * 3~(1/2) R 30°。小角X-射线反射结果表明聚苯胺分子导线是垂直站立在HOPG表面。电化学测量进一步表明聚苯胺分子导线的形成有利于加速电子传递速率。这种先分子设计后电聚合的方法可能会成为一类在固体表面制备有序导电聚合物分子导线的新方法。依据上一个实验,我们在金表面通过自组装的方法构筑了绝缘分子导线。我们选择β-环糊精(β-CD)作为包络4-氨基硫酚的理想主体分子。β-CD和4-氨基硫酚形成的包络物首先被自组装到Au表面,然后也通过阶跃的方法被层层电聚合在自组装膜修饰的Au表面,形成有序的聚苯胺分子导线。FTIR-ERS和XPS结果证实Au表面上形成了聚苯胺。低电流STM(LC-STM)图像表明在Au(111)表面的聚苯胺分子线为六角的二维有序,分子与分子之间的最相邻距离为15.5±0.5 A。这种先进行CD超分子自组装后电聚合的方法可能会成为一类制备导电聚合物绝缘分子导线的新方法。4.SPM研究在HOPG表面电化学合成的纳米材料我们通过脉冲恒电位方法从稀的苯胺酸性溶液(1mM苯胺 + 1 M HClO_4)在HOPG表面制备聚苯胺纳米颗粒。我们利用FTIR-ERS、XPS、TM-AFM手段来表征聚苯胺纳米颗粒的组成和结构。FTIR-ERS和XPS结果表明制得的聚苯胺纳米颗粒主要以亚胺形式存在。TM-AFM图像显示分散于HOPG表面的聚苯胺纳米颗粒的表面覆盖度约为10~(10)cm~(-2)。这些纳米颗粒都为圆盘型,直径为200到600埃,高度为10到30埃。这些纳米颗粒的大小随聚合电量由5.7 μC/cm~2增加到19.3 μC/cm~2而增大。我们提出了一种通过分子设计在HOPG表面制备金属纳米粒子的新方法。第一步,根据Saveant的方法我们在HOPG表面修饰上一个4-氨基苯单层。第二步,通过配位相互作用Ag~+能在4-氨基功能化的HOPG表面形成单层。第三步,通过脉冲恒电位方法我们就能在4-氨基苯功能化的HOPG制备Ag纳米颗粒。电化学测量证明了在HOPG表面上Ag纳米颗粒的形成。STM图像显示通过这种方法制得的Ag纳米颗粒的大小十分均一且在HOPG表面上的分散度很高。这种新方法可被广泛地用来在碳表面制备各种金属纳米粒子。
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植物生长和生产力受到自然界各种形式的生物和非生物胁迫因子的影响。这些胁迫包括低温、高温、盐碱、干旱、洪水、重金属、虫害、病害和紫外线辐射等等。而人类活动大大加剧了这些胁迫所带来的影响。由于人类污染而导致臭氧层衰减以及由此产生的地球表面紫外辐射增强已经成为全球气候变化的一个主要方面。UV-B胁迫,甚至当前的辐射水平,所带来的影响已经引起科学工作者的广泛关注。 为了生存和繁殖,植物不得不面临环境中各种潜在胁迫所带来的负面影响。然而,植物生活型的不可移动性决定了其逃避胁迫的局限性。因此,绝大多数植物都是通过对胁迫作出反应,通过修复或者更新组织来降低伤害。而植物应对环境变化的能力则是由其生长模式的种属特异性和本身的遗传组成所决定。在自然界,植物常常同时面临多种胁迫,这些胁迫所引发的植物反应可能具有叠加、协同或者拮抗作用。沙棘是一种具刺、具有固氮功能的多年生雌雄异株灌木,广泛分布于亚欧大陆的温带地区和亚洲亚热带的高海拔地区。在中国,沙棘常常被用作植被恢复中的先锋树种而大量栽培。本文采用沙棘作为模式植物,试图探索木本植物对低温,UV-B辐射增强以及其与干旱的复合胁迫的响应以及沙棘对这些胁迫响应是否具有种群差异性。 对来自南北两个种群的沙棘进行短日照和低温处理,检测了其在抗寒锻炼和抗寒性发育过程中存在的性别差异。结果表明,短日照和低温都分别能够诱导抗寒锻炼的发生,而两者同时存在对所有实验植株抗寒性的大小具有叠加效应。然而,短日照和低温所诱导的抗寒性在两个种群中都具有性别差异性,雄性植株比雌雄植株对短日照和低温更为敏感。同时,南北种群间也存在差异性,北方种群的植物比南方种群的植物对短日照和低温敏感,从而在短日照下抗寒锻炼的发生时间更早,低温诱导的抗寒性更大。短日照和低温诱导植物增加抗寒性的同时伴随着脱落酸的变化。脱落酸的变化因处理,种群和性别的不同而不同。这些生理反应表明不同的沙棘种群,不同的植株性别对同一环境胁迫可能存在不同的生存策略。 比较了来自高低两个海拔的沙棘种群对于干旱和UV-B辐射增强以及两者复合胁迫条件下的生理生态反应。干旱使两个种群中植株总的生物量,总叶面积,比叶面积,叶片含碳量,含磷量,木质素含量和碳氮比显著降低,使根冠比,粗根细根比和叶片脱落酸含量显著增加。干旱而非UV-B使得δ13C 值显著增加。但是,比较而言,来自高海拔的种群对干旱反应更为强烈,而来自低海拔的种群对UV-B更敏感。在UV-B辐射增强的处理下,干旱所诱导的脱落酸的积累被显著抑制。而且我们检测到在一些指标上存在显著的干旱×UV-B交互作用,如两个种群中在总生物量上,低海拔种群中在总叶面积,粗根细根比上,高海拔种群中在比叶面积,δ13C值,木质素含量上都存在明显的交互作用。这些结果表明这两个种群对胁迫具有不同的适应性反应,来自高海拔的种群比来自低海拔的种群更能够抵御干旱和UV-B胁迫。 室外实验表明,UV-B 去除/增补对沙棘高低两个海拔种群的影响都不大。对生物量的积累,植株高度以及一些常见的胁迫反应生理指标比如丙二醛、ABA 和游离脯氨酸都没有显著影响。UV-B 的效应比UV-A 大,植物反应在无UV 和仅有UV-A 的处理间没有什么区别。然而,UV-B 去除的两个处理和UV-B 存在的两个处理间存在显著区别。UV-B 使得两个种群都显著降低了比叶面积(SLA),但却使长期用水效率增加。但UV-B对光合色素和光合系统II 的影响不大。总体看来,来自低海拔的种群对UV-B 更为敏感。 Plant is adversely affected by various abiotic and biotic stress factors. These stressors includelow temperature, heat, salt, drought, flooding, heavy metal toxicity, wounding by herbivores,infecting by pathogenic microorganisms, ultraviolet (UV) radiation and so on. Variousanthropogenic activities have accentuated the existing stress factors. One of the mostimportant aspects of global change is that of stratospheric ozone depletion caused by seriousanthropogenic pollution and the resulting increase in UV radiation reaching the surface of theEarth. Scientists have become concerned about the effects that considerable UV-B stress, evenat current levels. In order to survive and reproduce, plants have to be able to cope with lots of potentiallyharmful stress factors that are almost constantly present in their environment. Most plants’responses under stress are to neutralize the stress, repairing the damage or regrowing newtissue rather than to avoid it due to their sessile life style. The plant defense capacity dependson plant-specific modular growth patterns and genetic make-up that allows for flexibleresponses to changing environments. Plants usually encounter several stresses simultaneouslyunder field conditions, and the stresses may cause a variety of plant responses, which can beadditive, synergistic or antagonistic. Sea buckthorn (Hippophae rhamnoides L.), a thorny nitrogen fixing deciduously perennialshrub, which is widely distributed throughout the temperate zones of Asia and Europe and thesubtropical zones of Asia at high altitudes. It has been widely used in forest restoration as thepioneer species in China. In this paper, we used sea buckthorn as a model, tried to get some understand of how plants fight low temperature, enhanced UV-B radiation level and thatcombination of drought. And also, want to know whether does there exist some populationspecific responses to such stressors. Sexual differences in cold acclimation and freezing tolerance development of two contrastingsea buckthorn (Hippophae rhamnoides L.) ecotypes from northern and southern regions inChina were recorded after exposure to short day photoperiod (SD) and low temperature (LT).The results demonstrated that cold acclimation could be triggered by exposing the plants toSD or LT alone, and that a combination of both treatments had an additive effect on freezingtolerance in all plants tested. However, development of freezing tolerance was dependent onthe sex of plants under SD and LT, the males were clearly more responsive to SD and LT thanthe females in both ecotypes studied. On the other hand, development of freezing tolerancewas also ecotype-dependent, the northern ecotype was more responsive to SD and LT than thesouthern ecotype, resulting in earlier cold acclimation under SD and higher freezing toleranceunder LT. Moreover, development of freezing tolerance induced by SD and LT wasaccompanied by changes in ABA levels. These alterations in ABA levels were different indifferent treatments, ecotypes and sexes. Therefore, the differences in SD and LT-inducedphysiological responses showed that the different ecotypes and the different sexes mightemploy different survival strategies under environmental stress. Two contrasting populations from the low and high altitudinal regions were employed toinvestigate the effects of drought, UV-B and their combination on sea buckthorn. Droughtsignificantly decreased total biomass, total leaf area, specific leaf area,leaf carbon (C),phophous (P), lignin content and the ratio of C: N in both populations, and increasedroot/shoot ratio, fine root/coarse root ratio and abscisic acid content (ABA), in bothpopulations. Drought but not UV-B resulted in significantly greater carbon isotopecomposition (δ13C) values in both populations. However, the high altitudinal population wasmore responsive to drought than the low altitudinal population. The drought-inducedenhancement of ABA in the high altitudinal population was significantly suppressed in thecombination of drought and elevated UV-B. Moreover, significant drought × UV-B interactionwas detected on total biomass in both populations, total leaf area and fine root/coarse root inthe low altitudinal population, specific leaf area, δ13C value and leaf lignin content in the high altitudinal population. These results demonstrated that there were different adaptive responsesbetween two contrasting populations, the high altitudinal population exhibited highertolerance to drought and UV-B than the low altitudinal population. A field experiment was conducted to investigate effects of UV-B exclusion/supplementationon two altitudinal populations of sea buckthorn. UV-B exclusion or supplementation had littleeffects on both populations investigated. For instance, the total biomass, plant height andsome physiological index such as Malondialdehyde (MDA), ABA and free proline were notchanged significantly. The UV-B effects are more significant than that of UV-A, nodifferences were found between treatments of excluded UV and excluded UV-B. However,compared with treatments of UV-B exclusion (including absent of UV-B and all UV band),the present of UV-B (including near ambient environment and enhanced UV-B) significantdecreased specific leaf area, and increased long time water use efficiency as evaluated by δ13Cvalue. UV-B had little effects on photosynthetic pigments and Photosystem II (PSII). The lowaltitude population is more sensitive to UV-B than that of the high altitude population.
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Magnetic nanoparticles of nickel ferrite (NiFe2O4) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at similar to 11 nm and then decreases for larger particles. Typical blocking effects were observed below similar to 225 K for all the prepared samples. The superparamagnetic blocking temperature (T-B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles. (c) 2008 Elsevier B. V. All rights reserved.
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Polyurea microcapsules about 2.5 mum in diameter containing phase change material for thermal energy storage application were synthesized and characterized by interfacial polycondensation method with toluene-2,4-diisocyanate and ethylenediamine as monomers in an emulsion system. Hexadecane was used as a phase change material and OP, which is nonionic surfactant, and used as an emulsifier. The chemical structure and thermal behavior of the microcapsules were investigated by FTIR and thermal analysis respectively. The results show encapsulated hexadecane has a good potential as a solar energy storage material.
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For heat energy storage application, polyurea. microcapsules containing phase change material, n-eicosane, were synthesized by using interfacial polymerization method with toluene- 2,4-diisocyanate (TDI) and diethylenetriamine (DETA) as monomers in an emulsion system. Poly(ethylene glycol)octyl-phenyl ether (OP), a nonionic surfactant, was the emulsifier for the system. The experimental result indicates that TDI was reacted with DETA in a mass ratio of 3 to 1. FT-IR spectra confirm the formation of wall material, polyurea, from the two monomers, TDI and DETA. Encapsulation efficiency of n-eicosane is about 75%. Microcapsule of n-eicosane melts at a temperature close to that of n-eicosane, while its stored heat energy varies with core material n-eicosane when wall material fixed. Thermo-gravimetric analysis shows that core material n-eicosane, micro-n-eicosane and wall material polyurea can withstand temperatures up to 130, 170 and 250 degreesC, respectively.
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Aluminum was incorporated into the mesoporous framework of ethane-silica by one-pot condensation of Al(OiPr)(3) with 1,2-bis(trimethoxysilyl)ethane using octadecyltrimethylammonium chloride as surfactant. Powder X-ray diffraction patterns, nitrogen sorption analysis, and TEM results reveal the formation of an ordered mesoporous material with uniform porosity. Al-27 MAS NMR confirms the incorporation of aluminum in the framework. The synthesized materials exhibit extremely high hydrothermal stability in boiling water (no obvious change of mesostructure and textural properties was observed even after refluxing in water for 100 h), which could be mainly contributed to the ethane-bridged mesoporous framework. The aluminum-containing mesoporous ethane-silicas are efficient catalysts for the alkylation of 2,4-di-tert-butylphenol by cinnamyl alcohol to yield a flavan.
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A modified subcell approach was adopted to evaluate the current density distributions of proton exchange membrane fuel cells (PEMFCs) with different electrodes. Conventional hydrophobic electrodes showed better performance under flooding conditions compared to hydrophilic electrodes. The thin-film hydrophilic electrode performed better in the absence of liquid water, but it was more readily flooded. A composite catalyst layer was designed with 2/3 of the area from the inlet prepared hydrophilic and the remaining 1/3 area hydrophobic. The composite catalyst layer with commercial scale dimension showed notable enhanced performance in the concentration polarization region. (C) 2004 The Electrochemical Society.
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Experimental data are presented to show the influence of the enhanced oil recovery system's components, alkali, surfactant, and polymer, on the demulsification and light transmittance of the water separated from the emulsions. Among which, the effects of surfactants, polyoxyethylene (10) alkylphenol ether (OP-10) and sodium petroleum sulfonate (CY-1) on emulsion stability, are the strongest of any component, the effects of polymer, hydrolytic polyacrylamide (HPAM) 3530S, on emulsion stability are the weakest. This research also suggests a possible emulsion minimization approach, which could be implemented in refineries utilizing microwave radiation. Compared with conventional heating, microwave radiation can effectively enhance the demulsification rate by an order of magnitude and increase the light transmittance of the water separated from the emulsions. The demulsification efficiency may reach 100% in a very short. time under microwave radiation.
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With the objective of making calcium alginate gel beads with small and uniform size, membrane emulsification coupled with internal gelation was proposed. Spherical gel beads with mean size of about 50 mum, and even smaller ones in water, and with narrow size distribution were successfully obtained. Experimental studies focusing mainly on the effect of process parameters on bead properties were performed. The size of the beads was mainly dependent on the diameter of the membrane pores. High transmembrane pressure made for large gel beads with wide size distribution. Low sodium alginate concentration produced nonspherical beads, whereas a high concentration was unsuitable for the production of small beads with narrow distribution. Thus 1.5% w/v was enough. A high surfactant concentration favored the formation of small beads, but the adverse effect on mass transfer should be considered in this novel process. (C) 2002 Wiley Periodicals, Inc.
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Adoption of a sintered stainless steel fiber felt was evaluated as gas diffusion backing in air-breathing direct methanol fuel cell (DMFC). By using a sintered stainless steel fiber felt as an anodic gas diffusion backing, the peak power density of an air-breathing DMFC is 24 mW cm(-2), which is better than that of common carbon paper. A 30-h-life test indicates that the degraded performance of the air-breathing DMFC is primarily due to the water flooding of the cathode. Twelve unit cells with each has 6 cm(2) of active area are connected in series to supply the power to a mobile phone assisted by a constant voltage diode. The maximum power density of 26 mW cm(-2) was achieved in the stack, which is higher than that in single cell. The results show that the sintered stainless steel felt is a promising solution to gas diffusion backing in the air-breathing DMFC, especially in the anodic side because of its high electronical conductivity and hydrophilicity. (C) 2004 Elsevier B.V. All rights reserved.
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Capillary isoelectric focusing (cIEF) and capillary zone electrophoresis (CZE) was on-line hyphenated by a dialysis interface to achieve a 2D capillary electrophoresis (CE) system. The system was used with just one high-voltage power supply and three electrodes (one cathode shared by the two dimensions). The focused zone in the first dimension (i.e. the cIEF) was driven to the dialysis interface by electroosmotic flow (EOF), besides chemical mobilization from the first anode to the shared cathode. And then in the second dimension (i.e. the CZE), the separated zone was further separated and driven by an inverted EOF, which originated from the charged layer of a cationic surfactant adsorbed onto the inner wall of the capillary. Finally, a solution of ribonuclease was rapidly separated to assess the feasibility of the two-dimensional CE implement. (C) 2003 Elsevier B.V. All rights reserved.
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The microenvironment of the aqueous core phase in the black soap film of cationic surfactant cetyltrimethylammonium bromide with the anionic dye Brilliant Yellow as spectral probe has been studied by UV-vis spectroscopy. Under neutral and basic conditions, the dye aggregates in the films exist as both the acid and base forms in contrast to a preference of the base form in the bulk solutions. The specific property of black soap film, that the intrinsic pH value of the aqueous core phase insensitively responds to pH changes of the bulk solution, is directly observed through UV-vis spectra.
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We report a novel method termed matrix suppressed laser desorption/ionization to improve the analysis of low-mass molecules by MALDI-TOF mass spectrometry. In this method, the surfactant of cetrimonium bromide (CTAB) is added to the conventional matrix of alpha-cyano-4-hydroxycinnamic acid solution to prepare the MALDI samples. During the MALDI process, the presence of CTAB could substantially or even completely suppress the matrix-related ion background. As a result, very clean mass spectra can be routinely obtained in the low-mass range. In addition, the presence of CTAB can significantly improve the mass resolution of low-mass molecules. It is seen that high-quality spectra were routinely obtained at a matrix/CTAB ratio of 1000:1. This method has been successfully used to analyze a variety of low-mass molecules.
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This review surveys the recent progress in the adsorbed stationary phases for capillary electrochromatography (CEC). Adsorption-based methods for preparation of stationary phase are novel approaches in CEC, which allow rapid and facile preparing stationary phases with desirable selectivity onto an open-tubular fused-silica capillary, a baresilica or ion-exchange packed column or a monolithic silica or polymer column. A variety of adsorbing agents have been developed as adsorbed stationary phases, including ionic long-chain surfactant, protein, peptide, amino acid, charged cyclodextrin (CD), basic compound, aliphatic ionene, and ion-exchange latex particle. The adsorbed stationary phases have been applied to separation of neutral, basic and acidic organic compounds, inorganic anions and enantiomers. They have also been applied to on-line sample concentration, fast separation and study of the competitive binding of enantiomers with protein.