1 3 J IRAN CHEM SOC DOI 10.1007/s13738-016-1023-7 ORIGINAL PAPER The application of electrochemical detection in capillary electrophoresis Sima Najafi Gamat 1 · Lida Fotouhi 1 · Zahra Talebpour 1 Received: 20 May 2016 / Accepted: 5 December 2016 © Iranian Chemical Society 2016 separation technique [1, 2]. CE is a family of electrokinetic separation technique, in which ions are separated based on their electrophoretic mobility under the application of an electric field between the extremes of the capillary [3]. There are many electrophoretic mechanisms used in CE, including capillary zone electrophoresis (CZE) [4, 5], micellar electrokinetic capillary chromatography (MEKC) [6, 7], non-aqueous capillary electrophoresis (NACE) [8, 9], capillary gel electrophoresis (CGE) [10, 11], microe- mulsion electrokinetic capillary chromatography (MEEKC) [12, 13], capillary isoelectric focusing (CIEF) [14, 15], and capillary electrochromatography (CEC) [16, 17]. Because of the variety in electrophoretic mobility (based on the dif- ference in charge, polarity, hydrophobicity, and molecular weight), it can serve as a versatile method in separation and analysis of ions, medicinal plants, enantiomers, clinical tests, food, carbohydrates, and environmental samples [18, 19]. CE has also become the technique of choice in many analytical laboratories where analysis of small quantities of materials must be accurately, efficiently, and expeditiously carried out. This technique is highly preferred among more advanced separation techniques (e.g., HPLC) and has been established as a valuable complimentary approach in numerous important areas. Among its many advantages, high efficiency, simplicity and flexibility, the possibility of automated analytical equipment, short analysis time, and on-line detection of the separated peaks can be named [20]. Portable instrumentation has gained much interest in recent years, and accordingly, the CE is an especially good choice for portable analysis due to its unique properties such as ease of installation, operation and maintenance, and fast separation. Microchip capillary electrophoresis, a miniature form of CE, emerged in the early 1990s as an interesting and novel approach to the high-speed separation of biological compounds including DNA and proteins [21]. Abstract The coupling of electrochemistry and capillary electrophoresis may present an interesting approach in the environmental oxidative samples and biological systems. The attractive advantages with respect to new material in chemically modified electrodes and electrode configura- tion provide a wide scope for the developments of capil- lary electrophoresis with electrochemical detection. In this review, recent advances in the design and application of electrochemical (EC) detection systems in capillary elec- trophoresis (CE) are reviewed, with the objective of pro- viding an overview of the capillary electrophoresis elec- trochemical (CE-EC) construction and detection of a broad scale of compounds, from small inorganic ions to organic species and biomolecules. In addition, CE-EC applications are summarized for various specific electrochemical detec- tions including amperometry, conductivity, capacitively coupled contactless conductivity detection (C4D), and vol- tammetry. Here, the achievements in CE-EC for the time period between 2012 and 2016 are reviewed. Keywords Amperometry · Capillary electrophoresis · Conductivity · Electrochemical detection · Voltammetry · Microchip electrophoresis Introduction In the last three decades, capillary electrophoresis has become an all-purpose, widespread, and a well-established * Lida Fotouhi lfotouhi@alzahra.ac.ir 1 Department of Chemistry, Faculty of Physics and Chemistry, Alzahra University, Vanak, Tehran, Iran