1 s2.0 S0003267013015687 Main

Analytica Chimica Acta 814 (2014) 1–22
Contents lists available at ScienceDirect
Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca
Review
Electrical field-induced extraction and separation techniques:

Promising trends in analytical chemistry – A review
Yadollah Yamini a,∗ , Shahram Seidi b , Maryam Rezazadeh a
a
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
b
Department of Analytical Chemistry, Faculty of Chemistry, K.N. Toosi University of Technology, Tehran, Iran
h i g h l i g h t s g r a p h i c a l a b s t r a c t
• Sample preparation is an important

issue in analytical chemistry.
• Application of electrical potential
reduces time and enhances selectiv-
ity in sample preparation.
• Review provides an overview of prin-
ciples and applications of electrical
fields in sample preparation.
• Advantages, disadvantages and point
to the corresponding limitations of
these techniques are discussed.
• Review is interested for readers that
are appreciated to field of electro-
chemically modulated extractions.
a r t i c l e i n f o a b s t r a c t
Article history: Sample preparation is an important issue in analytical chemistry, and is often a bottleneck in chemical
Received 20 July 2013 analysis. So, the major incentive for the recent research has been to attain faster, simpler, less expensive,
Received in revised form 7 December 2013 and more environmentally friendly sample preparation methods. The use of auxiliary energies, such as
Accepted 16 December 2013
heat, ultrasound, and microwave, is one of the strategies that have been employed in sample prepara-
Available online 24 December 2013
tion to reach the above purposes. Application of electrical driving force is the current state-of-the-art,
which presents new possibilities for simplifying and shortening the sample preparation process as well as
Keywords:
enhancing its selectivity. The electrical driving force has scarcely been utilized in comparison with other
Sample preparation
Electroextraction
auxiliary energies. In this review, the different roles of electrical driving force (as a powerful auxiliary
Voltage energy) in various extraction techniques, including liquid-, solid-, and membrane-based methods, have
Electrical driving force been taken into consideration. Also, the references have been made available, relevant to the develop-
Microextraction ments in separation techniques and Lab-on-a-Chip (LOC) systems. All aspects of electrical driving force in
Membrane-based extraction extraction and separation methods are too specific to be treated in this contribution. However, the main
Abbreviations: CEC, capillary electrochromatography; CE, capillary electrophoresis; CPs, chlorophenols; DEHP, di-(2-ethylhexyl) phosphate; DPV, differential pulse
voltammetry; ELMME, electrochemical liquid membrane microextraction; EMLC, electrochemically modulated liquid chromatography; ED, electrodialysis; EF, electro-
filtration; EME, electrokinetic membrane extraction; EMIS, electromembrane ion source; EM-SPME, electromembrane surrounded solid phase microextraction; EMF,
electro-microfiltration; EO, electro-osmosis; FID, flame ionization detector; HIS, histidine; HF-LPME, hollow fiber-based liquid-phase microextraction; ITIES, interface between
two immiscible electrolyte solutions; IC, ion chromatography; LOC, Lab-on-a-Chip; LLE, liquid–liquid extraction; LDS-USAEME, low-density solvent based ultrasound-
assisted emulsification microextraction; LPME, liquid-phase microextraction; ␮TAS, Micro Total Analysis Systems; MEMS, microelectromechanical systems; ME, microchip
electrophoresis; MEC, microchip electrochromatography; MWCO, molecular weight cut-off; NPPE, 2-nitrophenyl pentyl ether; NPOE, 2-nitrophenyl octyl ether; N.E., non-
electrically; PHE, phenylalanine; PEME, pulsed electromembrane extraction; SPE, solid-phase extraction; SLM, supported liquid membrane; TDP, tridecyl phosphate; TEHP,
tris(2-ethylhexyl) phosphate; TRY, tryptophan; VALC, voltage-assisted liquid chromatography.
∗ Corresponding author. Tel.: +98 21 82883417; fax: +98 21 88006544.
E-mail addresses: [email protected], [email protected] (Y. Yamini).
0003-2670/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.aca.2013.12.019
2 Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22
aim of this review is to provide a brief knowledge about the different fields of analytical chemistry, with
an emphasis on the latest efforts put into the electrically assisted membrane-based sample preparation
systems. The advantages and disadvantages of these approaches as well as the new achievements in these
areas have been discussed, which might be helpful for further progress in the future.
© 2013 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Electrochemical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Electrically assisted extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Liquid-based extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Solid-based extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Membrane-based extraction techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.1. Electromembrane extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. The other roles of electrical driving force in analytical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5. Concluding remarks and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Yadollah Yamini was born in 1968 in Dizajkhalil Shahram Seidi is currently an assistant professor at
(Shabestar, Iran), and obtained his B.Sc. from Mazan- the Department of Analytical Chemistry, K.N. Toosi
daran University (Babolsar, Iran, 1990), his M.Sc. University of Technology (Tehran, Iran). He got his
from Tarbiat Modares University (Tehran, Iran, 1992) bachelor‘s degree (B.Sc.) in applied chemistry from
under the supervision of Dr. M. Ashraf Khorassani, Arak University (Arak, Iran) in 2006. He received his
and his Ph.D. from Tarbiat Modares University (1996) master’s degree (M.Sc.) at the National University of
under the supervision of Prof. M. Shamsipur. He has Iran (Shahid Beheshti University, SBU, Tehran, Iran),
been a faculty member of Tarbiat Modares Univer- under the direction of Prof. Nahid Mashkouri Najafi
sity since 1997, and was promoted to Professor in and Prof. Alireza Ghasempour in 2008. In 2012, he
2006. Professor Yamini’s research involves the devel- obtained his Ph.D. in analytical chemistry from Tar-
opment of sample preparation methods based on the biat Modares University (TMU), under the direction of
elimination or reduction of organic solvents, such Prof. Yadollah Yamini. He attended a Postdoctoral Fel-
as solid-phase extraction, supercritical fluid extrac- lowship at TMU in 2012. His research focuses mainly
tion, solvent microextration, solid-phase microextraction, electromembrane on the development of miniaturized sample preparation methods, especially
microextraction, and supramolecular solvent microextraction. He is the referee electrically driven ones, as well as separation techniques.
of manuscripts for more than 45 different ISI journals. He has published more
than 245 scientific articles in the ISI journals. Also, he wrote a chapter, entitled
“Environmental applications of cloud-point extraction”, from Comprehensive
Sampling and Sample Preparation, which was published by Elsevier in 2012.
These innovative techniques are derived from traditional sam-
ple treatment methods, namely liquid–liquid extraction (LLE) and
solid-phase extraction (SPE). The benefits, which motivated the
research and development of sample preparation techniques, are
analytical improvement, scaling down the sample sizes, overcom-
Maryam Rezazadeh is currently a Ph.D. student in ing the sample matrix effects, automation, speed of response, and
analytical chemistry at the Department of Chem-
istry, Tarbiat Modares University (TMU), under the lower costs.
direction of Prof. Yadollah Yamini. She received her In recent years, a number of general reviews on sample prepara-
bachelor’s degree (B.Sc.) in pure chemistry at the tion have been documented, covering different aspects of various
National University of Iran (Shahid Beheshti Univer-
sity, SBU, Tehran, Iran) in 2009. She got her master’s methods [1–8]. Electric field-induced extraction is a topic that is
degree (M.Sc.) under the direction of Prof. Yadol- less investigated.
lah Yamini at TMU in 2011. Her field of interest is Fig. 1A–D illustrates the number of publications related to
the development of new microextraction technolo-
gies, with an emphasis on electrically induced sample
some of the main electrically assisted extraction techniques with
preparation methods and separation techniques. the keywords of “electromembrane extraction”, “electrochemically
solid-phase extraction”, “electroextraction”, and “electrochemi-
cally modulated liquid–liquid extraction” that are limited to the
titles and keywords of articles incorporated in the Scopus database
[9]. Fig. 1E shows the total number of publications in each year,
obtained by summation of publications associated with the men-
1. Introduction tioned techniques in different years. Although this graph is not
an exact criterion for all publications concerning the electrically
Analytes of environmental or biological origin, which usually assisted extraction methods, it can provide useful insight into these
occur in complex matrices, are able to disturb the separation and techniques. Regarding Fig. 1E and the number of citations of elec-
data analysis stages. With regard to these concerns, a series of steps trically assisted sample preparation techniques accessible at online
are required to remove the interfering substances, preconcentrate databases, it can be concluded that these methods are gradually
the analytes, and increase the sensitivity. As a consequence, the becoming quite commonplace in analytical chemistry.
development of new analyte extraction methods and technologies The starting point for electrically induced extraction techniques
has received major attention from the analytical research commu- dates back to the beginning of the 19th century, when the initial
nities around the world. studies on the migration capability of particles in solutions under
Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22 3
Fig. 1. Evolution of the number of publications related to some of the main electrically assisted extraction techniques; (A) electromembrane extraction, (B) electrochemically
solid phase extraction, (C) electroextraction, (D) electrochemically modulated liquid extraction and (F) total number of publications in each year related to the mentioned
techniques in different years (Scopus database, Tuesday 18th December 2012).
an electric field and the extension of this phenomenon to the sep- made through the use of electric field in sample preparation
aration methods were carried out [10–12]. and separation techniques, different new electrically enhanced
The advantages of using the electric field in separation tech- microextraction methods have been introduced in recent years
niques led to more comprehensive works by various research [24–29].
groups to investigate the potential of this new driving force in According to the following equation, the relative distribution of
sample pretreatment methods. an ion (KD ) between two phases can be altered via the application
Electrically driven sample pretreatment was first exploited for of different voltages [30]:
preparative purposes, with the innovation of a U-tube apparatus by
Tiselius [13]. Then, electrodialysis (ED) was extensively employed ZF
ln kD = (E − E 0 ) (1)
due to the selective transportation capacity of its membranes; so RT
that the ED today is considered as a routine sample pretreatment
technique with various areas of application like industries, food, where E is the equilibrium ion transfer potential (the Galvani poten-
and bioanalysis [14–18]. In subsequent years, the electric field was tial difference between the phases), and E0 is the standard potential
utilized for sample pretreatment purposes in liquid-phase extrac- difference of transfer that is related to the standard Gibbs energy of
tion methods [19–23]. transfer. R, T, F, and Z are the universal gas constant, temperature,
With the emergence of modern trends in analytical chemistry, Faraday’s constant, and the charge of the ion distributed across the
in terms of simplification and miniaturization of analytical proce- interface, respectively.
dures, and minimization of organic solvent consumption in sample In this way, it becomes possible to control different proper-
preparation, during the last decade, and noticeable improvements ties of an extraction system, such as selectivity, clean-up rate, and
Application of Electrical Field in Analytical Chemistry
Electrochemical Extraction Separation

techniques techniques techniques
Liquid based methods

Electrosynthesis of membranes,
Solid based methods
Hyphenation with sample

Electrochemical reactions
separation techniques
Combination with sample
Membrane based
preparation methods
preparation methods
Electrically driven
SPE and SPME sorbents
Electrodeposition
methods
Electrokinetic trapping
Charge (electrical assisted)
Size exclusion (iltration)

Solubility/diffusivity
On/In-line
EMLC
VALC
CEC
Off-line
CE
ELMME
SPME
ITIES
SPE
LLE
Non-Electrically
Electrically
assisted
assisted
Electrokinetic membrane
Electro-microiltration
Liquid membranes
Molecular sieving
Reverse osmosis
Micro iltration
Electroiltration
Electro-osmosis
Nano iltration
Ultra iltration
Gas separation
Pervaporation
Electrodialysis
extraction
Fig. 2. Different applications of electrical driving force in analytical chemistry (the gray boxes are related to non-electrically based techniques to give a more comprehensive
insight).
efficiency, with the aid of a variable potential difference imposed and current novelties and applications of electrically assisted sam-
across the liquid–liquid or solid–liquid phase boundaries. ple pretreatment techniques, and the review papers represented
Various applications of electrical driving force to analytical by some specialist researchers is conducted [30,41–45].
chemistry can be generalized to extraction, separation, and electro- The advantages, disadvantages, and limitations of these tech-
chemical techniques. More details on each method are represented niques are discussed, which can help the future scientists to
in Fig. 2, and will be discussed in the next sections. One of the clear overcome the existing problems and improve the electrically
benefits of electrically assisted extraction techniques is their easy induced sample preparation methods. Finally, the outlook for the
integration and implementation with the chip-based devices; this developments of these techniques is given.
subject is an interesting area of investigation nowadays [31–40]. This review offers an overview of the most recent advances
In this paper, the focus is on electrically asisted membrane- in the area of electrochemically modulated extraction techniques,
based extraction techniques, to give a general ideaof the impact of which might be of interest to more experienced users, especially
electric field on sample treatment processes and also to evaluate the the practitioners who are experts in environmental and bioanalysis
actual potential of these methods. A conceptual clustering method methods.
is exploited, as a powerful and inventive way, to well scrutinize
the different features of various electrically assisted techniques as 2. Electrochemical techniques
well as to cause the information to be kept in mind for a longer
period of time. In addition, a concise description of the theoretical Electrical driving forces have been widely employed in those
principles of these methods is presented, for a better understand- sample pretreatment techniques that are followed by electro-
ing of them. To this end, a comprehensive survey of the previous chemical processes. Among these techniques, electrodeposition is
known as a proper method for separation and preconcentration of procedure rather than an electrochemical detection technique. The
extremely low amounts of analytes in bulk samples, which is instru- system works on the principle that an aqueous phase (donor phase)
mentally very simple. Speciation [46], and increasing of selectivity flows over a stationary jellified organic phase (acceptor phase). The
[47] and sensitivity of spectrometry techniques [48] are the other electrochemical basis of the ITIES is that the ions are dissolved
remarkable achievements of electrodeposition. in each electrolyte solution and then transferred across the inter-
Furthermore, electrochemical techniques have been utilized face according to their Gibbs energies, which induces an electric
extensively in combination with sample preparation methods with potential difference. In all published works for the ITIES extractions,
the electric field applied throughout extraction, as well as those the analytes are determined electrochemically, and no reports can
without electrical driving force [25,49–51]. For example, Saraji et al. be found on determination by means of chromatography systems.
used in situ differential pulse voltammetry coupled with hollow However, Arrigan et al. predicted the combination of ITIES extrac-
fiber-based liquid-phase microextraction for electrochemical anal- tion method with chromatographic techniques in the future.
ysis of desipramine in plasma and urine samples [50]. The results Electrochemical liquid membrane microextraction (ELMME) is
indicated that both the selectivity and sensitivity of the method a new sample preparation strategy based on a three-phase sys-
increased owing to the elimination of interferences. tem consisting of a solid support, an organic liquid, and an aqueous
One of the very attractive uses of electric fields, which is rarely liquid, which combines liquid membrane extraction with electro-
pointed out in the literature, is in synthesizing and preparing the chemical detection. This technique was established by Zhu et al. in
membranes [52,53] and solid-phase sorbents for SPE or solid-phase 2009 [25]. In the ELMME, the target substance initially undergoes
microextraction (SPME) [54–57]. an electrochemical reaction that changes its redox states, causing
Electrochemical reactions, which take place as a result of elec- it to have more affinity with the organic liquid phase in the absence
tron transfer between chemical compounds and electrode surfaces, of extra redox reagents. After the extraction, the extracted species
are another outcome of applying the electric fields. Electrochem- near the electrode surface could be directly determined through an
ical reactions have been widely explored, as drastic tools to find electrochemical method with no other additional steps. The ELMME
different chemical information, individually or together with other is a green sample preparation process and a typical technique of
analytical techniques (e.g., mass spectrometry or spectroscopic integrating the separation and analysis procedures. The excellent
methods) [58]. Nevertheless, it should be noted that these reactions enrichment performance, simplicity, stability, trouble-free opera-
are not desirable phenomena in the cases of extraction, purification, tion, low cost, and less consumption of organic solvents make this
and separation processes; since (as will be shown later) they cause method worthy to be further scrutinized.
serious problems during some extraction procedures, and are one
of the main restricting agents.
3.2. Solid-based extraction techniques
3. Electrically assisted extraction techniques Electrochemical methods have found amazing applications in
SPE and SPME techniques, comprising synthesis of sorbents and
The use of electrochemistry in manipulating the extractions of enhancement of extraction efficiency [28,64–69]. In the case of syn-
ionic and neutral analytes for sample preparation has been studied thesis of sorbents, the electrochemical methods afford tailoring of
via solid–liquid, liquid–liquid, and membrane extraction methods. key characteristics including thickness, conductivity, degree of oxi-
Utilization of electrical driving force, as the auxiliary energy, leads dation, color, and morphology [70]. This fact has propelled various
to substantial improvements. research groups toward the synthesis of new coatings [55,71–73].
Among these coatings, conducting polymers have attracted a lot of
interest due to their multifunctional properties [55].
3.1. Liquid-based extraction techniques
The concept of utilizing electric fields in SPE is derived from a
technique termed electrochemically modulated liquid chromatog-
The LLE is one of the oldest sample preparation methods, which
raphy (EMLC) [30]. The EMLC was originally proposed by Fujinaga
has been exploited so far because of its simplicity and acceptable
et al. in 1963 [74], then by Blaedel and Strohl [75], and indepen-
extraction efficiency. Nonetheless, this technique has some draw-
dently by Roe in 1964 [76]. Usually, electric fields have two different
backs; so that several attempts have been made to compensate
effects on the solid-based extraction methods; first is a direct influ-
them. Application of auxiliary energies, such as the electric field, is
ence on the surface of solid sorbent that allows the manipulation
one of these efforts, which has received much attention.
of extraction [64–69], and second is an indirect influence, which
The idea of liquid–liquid electroextraction was first proposed in
either permits electrokinetic migration of charged analytes toward
1992 by Stichlmair et al. for extraction of fuchsine acid [23]. Gener-
the solid sorbent [77] or facilitates elution stage [28]. Electrically
ally, the functions of electric field in LLE can be classified into two
assisted solid-phase extraction/microextraction and electrokinetic
groups. The first is the dispersion of one liquid phase in another
trapping are the instances of direct and indirect effects of electric
to enhance mass transfer and extraction efficiency [59], and the
fields on solid-based extraction techniques, respectively.
second is the transport of charged species across a sharp phase
According to the literature, the increasing interest in using elec-
boundary that is formed between the two immiscible liquid phases,
tric fields in solid-based extraction methods can be attributed to
namely liquid–liquid electroextraction [60,61]. Liquid–liquid elec-
several reasons:
troextraction can be carried out off-line or on-line in tandem with
some analytical instruments like capillary electrophoresis (CE) or
high-performance liquid chromatography (HPLC) [60,62]. Both the 1. The features of conducting polymers can be modified by varying
direct current (d.c.) and alternating current (a.c.) electric fields can the conditions throughout electropolymerization step to enable
be employed in liquid–liquid electroextraction, even though most the extraction of analytes with different sizes and charges.
reports are associated with the d.c. one [63]. 2. Compared to conventional solid-based extraction, in which a
Electrochemically modulated liquid–liquid extraction tech- material with a fixed number of exchange sites is employed,
nique, which is also called the interface between two immiscible electrically assisted extraction offers higher flexibility; since, in
electrolyte solutions (ITIES), is another electrically driven extrac- this method, the characteristics of the material and thus the
tion method that was introduced by Arrigan et al. in 2005 [24]. number of its exchange sites can be externally controlled via
The authors suggested the ITIES system as a sample preparation electrochemically controlling the charge of the material [78,79].
Membrane
Structures
Symmetrical aspects Material aspects
Microsieves
Asymmetrical Symmetrical
Nanocomposite Membranes
Ceramic Membranes
Porous
Porous
Dense
Dense
layer
layer
skin
skin
Track-etched Membranes
Anodized Alumina Membranes
Polymer Membranes
Fabrication Processes
Template Leaching
Streching of a Polymer Film
Phase Inversion
Coating of Membranes
Interfacial Polymerisation
Fig. 3. A general classification of membrane structures based on symmetrical and material aspects. The dashed rectangle indicates different fabrication process of polymeric
membrane.
3. The use of polymer-based fiber films in solid-based extrac- solids) [84]. A general classification of membrane structures in
tion techniques can be extended to the analysis of neutral, terms of symmetry and composition is depicted in Fig. 3. Because
electro-inactive analytes by taking advantage of electrochemi- of a wide variety of polymeric materials, more research attempts
cally controlled hydrophobic/hydrophilic ‘switching’ [80]. have been made to develop polymeric membranes in compari-
4. Electrically assisted solid-based extraction methods can be son with other membranes; the different fabrication processes for
exploited for the extraction of ions and analytes that normally synthesis of this type of membranes are represented in Fig. 3.
need to be derivatized prior to traditional solid-based extraction For a detailed description, interested readers are referred to Ref.
[81,82]. [84].
5. In electrically assisted solid-based extraction techniques, the Fig. 2 illustrates some membrane-based separation procedures
extraction and desorption stages are merely performed through arranged according to the mechanism of separation. Discussion
altering the potential of conducting polymer-coated electrode. about sample preparation methods with no electrical driving forces
Therefore, in these methods, it is not necessary to change the is beyond the scope of this review; perfect information on these
solvent to allow desorption of compounds [31]. techniques is available in the literature [84,85]. Procedures, in
6. Desorption of electrostatically held analytes, by varying the which electric fields are used, include: ED, electro-osmosis (EO),
electrochemical potential of polymer, may also be more rapid electrofiltration (EF), electro-microfiltration (EMF), and electroki-
relative to the desorption techniques commonly utilized in con- netic membrane extraction (EME).
ventional solid-based extractions [32]. This makes the above The ED and EO have similar principles; so that in both methods
method particularly interesting for use in conjunction with an electric field is applied between two electrodes that are located
miniaturized analytical systems. on both sides of a membrane or fiber [42,81]. Nevertheless, in the
ED, charged solutes are transported across the membrane, which is
3.3. Membrane-based extraction techniques normally an ion exchange or a molecular weight cut-off (MWCO)
membrane, whereas in the EO it is the solvent that passes through
Since initial membrane experiments on osmosis were carried the membrane. The generated molecular flux in the ED is owing to
out in the 18th century using biological membranes, and a func- diffusion and impact of potential difference, and, in this technique,
tional synthetic reverse osmosis membrane was produced from separation is achieved based on the charges of solutes and their
cellulose acetate polymer by Sidney Loeb [83], membranes have molecular masses.
found applications in various parts of modern sample prepara- Filtration is a term that has been established to indicate a spe-
tion and separation methods implemented in industrial societies cific domain of membrane technology in between ultrafiltration
worldwide. and reverse osmosis [42,84]. The EF is a kind of filtration process
From the 18th century until now, a big revolution has happened carried out in the presence of an electric field. Various filtration
in development of various membranes for different applications procedures are categorized in terms of membrane pore size; so
ranging from nanofiltration (partial desalination) to ultrafiltra- that membranes with pore sizes in the range of 50 nm to 5 ␮m are
tion (virus removal) and microfiltration (elimination of suspended exploited for microfiltration [42,84].
Fig. 4. (A) The primary equipment for electromembrane extraction, (B) effects of container volume and stirring rate on the extraction recovery.
Application of voltage improves the efficiencies of all electrically analytes migrate across a 200 ␮m-thick SLM, located in the pores of
assisted membrane-based processes, like ED, EO, and EF, compared a porous hollow fiber, into an aqueous acceptor solution inside the
to non-electrically (N.E.) ones; nonetheless, bubble formation and lumen of hollow fiber. Theoretical studies were carried out to exam-
thermal degradation of membrane are important impediments to ine the obvious mechanism and the extraction kinetics of EME, and
increasing of voltage in the former processes [86]. Extensive stud- the influences of various parameters on the EME efficiency. The
ies on the ED, EO, and EF techniques have been comprehensively primary EME setup was exploited for extraction of several classes
reviewed in the literature by different specialists [42,84,86]. Mean- of analytes, comprising acidic, basic, and zwitterionic compounds,
while, it is worth mentioning that utilization of membranes and and inorganic cationic/anionic species, and coupled to various ana-
electrical driving forces is not restricted to sample treatment meth- lytical instruments, like HPLC, CE, ion chromatograph (IC), and gas
ods in analytical chemistry. For instance, electromembrane ion chromatograph (GC) with different detectors, for analysis of accep-
source (EMIS) technique is considered as a potential approach for tor phase composition. Although the EME markedly reduces the
direct mass spectrometric (MS) sampling under ambient condi- extraction time and provides more efficient extraction and sam-
tions [87]. The EMIS affords both the on-line sampling and MS ple clean-up, especially in comparison with HF-LPME, it suffers
characterization of inorganic ions. It even seems to be a fairly suit- from some weaknesses. Hence, scientists have tried to develop new
able method for examining by far the largest organic entities such extraction setups and novel techniques to overcome these difficul-
as biomolecules. In various EMIS applications, a dense network ties.
of moderately long (10–20 ␮m), yet very narrow (submicrome-
ter), channels in track membrane governs the transport of charged
species as well as the field structure [87]. 3.3.1.1. Theoretical studies on EME. In order to figure out the influ-
After a brief discussion about these techniques, now we will ential variables in EME, this extraction method has been explored
focus on the uses of a more recent electrically assisted membrane- theoretically. Commonly, two different sets of parameters affect the
based procedure, EME, for a variety of sample types, which extraction efficiency of EME. The first group incorporates setup-
have drawn special attention in the area of analytical sample related parameters and the other consists of parameters that are
pretreatment. The concept of EME was initially suggested by connected with extraction procedure and mechanism. Here is a
Pedersen-Bjergaard and Rasmussen in 2006 [29]. Several reviews brief explanation of each class of variables.
are available, in which the EME has been partially or completely 3.3.1.1.1. Setup-related parameters. Electrode materials: Since
described by the originators and also some experts [30,41–45,88]. electrolysis may occur at the surface of electrodes, they should be
This review intends to view the EME from a different perspective made of inert materials such as platinum, which is a good choice
and present recent developments, novelties, and innovations rele- for this aim.
vant to this method. Electrode distance: The distance between electrodes is a signifi-
cant parameter for successful EME. As it is known, the strength of
an electric field (E) is gained from the equation below:
3.3.1. Electromembrane extraction
The basis of EME is the migration of charged species in an electric V
field. The applied voltage in the EME system causes ionizable com- E= (2)
d
pounds to be transported from an aqueous sample solution across
a supported liquid membrane (SLM) into an acceptor phase. The wherein d is the inter-electrode distance and V is the applied volt-
primary EME setup is displayed in Fig. 4A; the features of this setup age. It is apparent that if electrical charges cannot cross an organic
are similar to hollow fiber-based liquid-phase microextraction (HF- membrane, the behavior of electrodes and phase interfaces will
LPME), except that the former employs two platinum electrodes be analogous to that of a capacitor. Under these circumstances,
that are placed in the sample solution and acceptor phase and thus the polarized SLM can act as a dielectric capacitor [89]. Eq. (2) is
supply the electric field. In the EME, a d.c. potential, typically in a well-known equation, which defines the breakdown voltage of a
the range of 1–300 V, is applied to make the ionized forms of target capacitor and the electric current that passes through the dielectric
of a capacitor or the organic liquid membrane in an electromem- improvement of extraction efficiency. In the meantime, to impreg-
brane system [90]. nate a non-polar organic solvent, the hollow fiber must possess an
The electric current level should be controlled in an elec- appropriate hydrophobicity, and the pore size of hollow fiber can
tromembrane process to enable phase transfer and electrokinetic affect the capillary forces, which helps retention of organic solvent
migration of analytes, and avoid any electrochemical reactions. and control of sample cleanup.
The breakdown voltage of a capacitor fully determines the criti- Container characteristics: Mass transfer in an EME system is
cal voltage of an electromembrane system, which depends on the accomplished by convection and electrokinetic migration. In small
inter-electrode distance. As seen from Eq. (2), increasing of the compartments, the effect of electric field on the migration of ana-
distance between electrodes diminishes the strength of electric lytes is greater in comparison with large compartments [95]. The
field and the current level, and therefore limits the phase trans- influences of volume of container and stirring rate on the extraction
fer of analytes. On the other hand, decreasing of inter-electrode recoveries of a group of model analytes were scrutinized simul-
distance raises the electric current and lowers the breakdown volt- taneously; the obtained results are depicted in Fig. 4B. Variation
age, thereby making the dielectric conductive; in these conditions, of the average response demonstrated that the impact of electric
sparking may happen, which can even cause breaking of electrodes. field declined and the importance of stirring increased by increasing
Moreover, placing the electrodes very close to each other leads to the container volume. Also, stirring was effective even with small
the enhanced migration of ions through the SLM and Joule heating. compartments.
This phenomenon may result in system instability and punctuation 3.3.1.1.2. Parameters related to extraction procedure and mecha-
of the SLM due to a rise in temperature [91–93]. nism. The flux of analytes, driven by an electrical potential over a
The differences in the optimum inter-electrode distances in var- SLM, in EME has been described by means of a mathematical model
ious publications may be attributed to the fact that this parameter based on the Nernst–Planck equation [96]. It was assumed that the
is affected by the configuration of the EME setup. Accordingly, the EME process is analogous to the ionthophoretic transportation of
optimized value of inter-electrode distance in an EME setup cannot drugs through the skin, and the modified theoretical expression of
be employed for another setup with a different configuration. Even the latter [97–102] was employed to describe the flux of analytes in
though inter-electrode distance has been considered as an effec- EME. The results from the mathematical model were verified exper-
tive parameter in the majority of EME publications, its impact has imentally, and it was proved that the following equation could be
only been explained descriptively and no experimental investiga- exploited to determine the flux of analytes across the SLM:
tions have been documented for it in the literature. The influence of
Di

x−1

inter-electrode distance can be straightforwardly anticipated and Ji = 1+ (Cih − Cio exp(−)) (4)
h ln x x − exp(−)
described by means of theoretical rules (Eq. (2)).
It should be taken into account that there are some limitations wherein Di is the diffusion coefficient of analyte, h is the thickness
on increasing the inter-electrode distance, owing to the restricted of membrane, Cih is the analyte concentration at the SLM/sample
internal diameter of sample container. This subject must be consid- interface, and Cio is the analyte concentration at the acceptor/SLM
ered for preparation of a setup for the EME; so that the EME setup interface. Also, is a function of electrical potential [96], and is the
must possess the ability to maintain the inter-electrode distance ratio of the total ionic concentration in the sample solution to that
constant. in the acceptor solution, which is defined as the ion balance. There-
Thickness of electrodes: The breakdown voltage of a capacitor is fore, the flux of analytes (or the extraction efficiency) is affected by
directly dependent on the surfaces of electrodes [94]. For this rea- the nature of the SLM that determines the diffusion coefficients of
son, the electric current passing through the phase interfaces is target substances (Di ), the thickness of SLM, and the ionic strengths
raised by increasing the surfaces of electrodes or enhancing their of the donor and acceptor phases (), which are principally deter-
thicknesses. Hence, the thickness of electrodes should be consid- mined via the pHs of both phases and the applied voltage. Moreover,
ered; so that the electric current of a system must be adequate to time is another influential parameter in the extraction efficiency of
facilitate phase transfer of analytes, but it must be controlled to pre- EME.
vent from electrochemical reactions, instability problems, and (in Composition of organic liquid membrane: Choosing the composi-
some cases) sparking. The thickness of electrodes is affected by the tion of organic liquid membrane is one of the most essential steps
inner diameter of hollow fiber, and a significant amount of accep- in the EME technique. The extractability of analytes is highly influ-
tor phase is lost using thick electrodes. So, the electrodes must have enced by the nature of the SLM, and it has been revealed that the
suitable diameters and be firm enough to possess physical stabil- extraction recovery improves as the viscosity of the organic sol-
ity and have constant inter-electrode distance. Consequently, this vent decreases [103]. The SLM should be water-immiscible and
parameter should be tested to reach the most favorable extraction have a polarity similar to that of polypropylene fiber so that it
conditions. can be easily immobilized within the pores of the fiber. The SLM
Hollow fiber characteristics: Hollow fibers, which act as a liq- should also have an appropriate electrical resistance to keep the
uid membrane supporter, are commercially accessible with given electric current of the system in its lowest possible level, even
characteristics. They have internal diameters of 150, 300, 600, and after applying high voltages, and possess specific chemical proper-
1200 ␮m. When the hollow fiber inner diameter is known, the ties to permit phase transfer and electrokinetic migration of model
collected volume of acceptor phase (Vcylinder ) can be calculated analytes [104]. Meanwhile, charged analytes should have proper
theoretically: solubility in the SLM, in order to be transported across it. The
organic solvents, which are utilized as the SLM for extraction of
Vcylinder = r 2 h (3)
different kinds of analytes, are tabulated in Table 1 [104–131]. In
where r and h are hollow fiber internal diameter and height, respec- summary, the lipophilicities of the organic liquid membrane and
tively. Using thicker electrodes becomes practically feasible by the analyte should be consistent with each other, and the SLMs
enhancing the inner diameter of hollow fiber. In this way, repeata- with high values of log P are suitable for hydrophobic compounds,
bility and reproducibility may increase; as the inter-electrode while hydrophilic analytes prefer the more hydrophilic organic
distance is more likely to remain unchanged during an extrac- solvents [133]. Although 2-nitrophenyl octyl ether (NPOE) is an
tion procedure. Besides, increasing of the hollow fiber length (and excellent organic solvent for extraction of non-polar basic sub-
thus reduction of its internal diameter) also results in the enhance- stances, it is not efficient for extraction of polar compounds with
ment of available surface of organic phase, which may lead to the small values of log P (the log P value for the non-charged form of
Table 1
The organic solvents used as SLM in EME, and their properties.
SLM Analyte ERa % Ref
Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

volumeb surface heteroatoms
(cm3 ) areab (Å)
NPOE 5.35 4 0 240.825 55.05 Basic >2.5 1, 2 35–90 [107,125,130]

3, 4 16–95 [29,104,107,125]
5, 6 0–76 [29,104,107,119]
7, 8 0–24 [104,107]
2.5–2.0 1, 2 0–79 [29,104,107]
3, 4 0–48 [107]
5, 6 69 [104]
7, 8 83 [110]
2.0–1.5 1, 2 0–70 [29,104]
3, 4 55 [123]
1.5–1.0 1, 2 0–33 [104,107]
Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

3, 4 0 [104,107]
7, 8 0 [107]
1.0–0.5 3, 4 0 [107]
0.5> 3, 4 0 [107]
5, 6 0–55 [104,107,128]
7, 8 0 [104,107]
9, 10 0 [107]
Dihexyl ether 5.12 1 0 232.979 9.23 Basic >2.5 3, 4 0 [29]

5, 6 0 [29]
2.5–2.0 1, 2 0 [29]
2.0–1.5 1, 2 0 [29]
1-Octanol 2.88 1 1 158.095 20.23 Basic >2.5 3, 4 3 [29]

5, 6 3–95 [29,124]
2.5–2.0 1, 2 7 [29]
2.0–1.5 1, 2 4 [29]
0.5> 5, 6 46–77 [128]
Metal 0.5> – 90–107c [113]
Acidic >2.5 1, 2 14 [115]
3, 4 16, 25 [115]
5, 6 95 [124]
2.5–2.0 3, 4 18–20 [115]
0.5> 3, 4 22 [115]
5, 6 39–61 [128]
1-Octanone 2.95 1 0 157.908 17.07 Basic >2.5 3, 4 – [29]

5, 6 – [29]
2.5–2.0 1, 2 – [29]
2.0–1.5 1, 2 – [29]
Acidic 1.5–1.0 5, 6 20.9 [131]
1.0–0.5 5, 6 24.2 [131]
0.5> 5, 6 21.8 [131]
7, 8 11.4 [131]
Dodecyl acetate 5.88 2 0 263.112 26.3 Basic >2.5 3, 4 0 [29]

5, 6 0 [29]
2.5–2.0 1, 2 0 [29]
2.0–1.5 1, 2 0 [29]
9
10
Table 1 (Continued)

(cm3 ) areab (Å)
NPOE + DEHPd 5.35 4 0 240.825 55.05 Basic >2.5 3, 4 0–75 [29,104,118]

5, 6 0–4 [29,104]
7, 8 10 [104]
2.5–2.0 1, 2 5–31 [29,104]
5, 6 0 [104]
2.0–1.5 1, 2 13–30 [29,104]
5, 6 54–62 [118]
1.5–1.0 1, 2 2–37 [104,127]
3, 4 59 [104]
0.5> 3, 4 0–10.8 [104,114]

5, 6 0.6–37 [104,114,121]
7, 8 13 [104]
Kerosene 3.76–10.76 0 0 164.634–419.399 0 Basic >2.5 3, 4 0 [29]

5, 6 0 [29]
2.5–2.0 1, 2 0 [29]
2.0–1.5 1, 2 0 [29]
Silicone oil AS 4 – 1 0 – 17.07 Basic >2.5 3, 4 0 [29]

5, 6 0 [29]
2.5–2.0 1, 2 0 [29]
2.0–1.5 1, 2 0 [29]
Soybean oil – – – – – Basic >2.5 3, 4 0 [29]

5, 6 0 [29]
2.5–2.0 1, 2 0 [29]
2.0–1.5 1, 2 0 [29]
Peppermint oil 2.76 1 0 175.053 17.07 Basic >2.5 3, 4 13 [29]

(menthone)
5, 6 78–79 [29]
2.5–2.0 1, 2 73 [29]
2.0–1.5 1, 2 73 [29]
NPOE + TEHPd 5.35 4 0 240.825 55.05 Basic >2.5 3, 4 0–78 [104,122]

5, 6 53–83 [104]
7, 8 31 [104]
2.5–2.0 1, 2 53–91 [104,120]
3, 4 63–66 [120]
5, 6 70 [104]
2.0–1.5 1, 2 17–57 [104,120]
3, 4 70 [120]
1.5–1.0 1, 2 78 [104]
3, 4 0 [104]
0.5> 3, 4 0 [104]
5, 6 0 [104]
7, 8 0 [104]
Table 1 (Continued)

(cm3 ) areab (Å)
NPOE + TEHP + DEHPd 5.35 4 0 240.825 55.05 >2.5 3, 4 0–61 [104]

5, 6 0–5 [104]
7, 8 – [104]
2.5–2.0 1, 2 39–64 [104]
5, 6 – [104]
2.0–1.5 1, 2 69 [104]
1.5–1.0 1, 2 7 [104]
3, 4 44 [104]
0.5> 3, 4 6 [104]
5, 6 10–53 [104,126]
7, 8 23 [104]

1-Heptanol 2.37 1 1 141.589 20.23 Acidic >2.5 1, 2 61 [105]
3, 4 11–86 [105]
5, 6 74–91 [105]
2.5–2.0 5, 6 8 [105]
1.0–0.5 3, 4 100 [105]
0.5> 5, 6 34 [105]
Inorganic anion 0.5> 5, 6 95.9–106.7c [111]
1-Ethyl-2- 2.94 3 0 134.092 45.82 Basic >2.5 1, 2 38–70 [108,130]

nitrobenzene
3, 4 63–95 [106,108]
5, 6 54–80 [106,108]
2.5–2.0 1, 2 80 [106]
7, 8 70 [110]
2.0–1.5 1, 2 78 [106]
1-Isopropyl-4- 3.43 3 0 151.348 45.82 Basic >2.5 3, 4 59 [106]

nitrobenzene
5, 6 88–91 [106]
2.5–2.0 1, 2 93 [106]
2.0–1.5 1, 2 86 [106]
1-Nitropropane 0.94 3 0 90.835 45.82 Basic >2.5 3, 4 0 [106]

5, 6 0 [106]
2.5–2.0 1, 2 0 [106]
2.0–1.5 1, 2 0 [106]
1-Nitropentane 1.96 3 0 151.348 45.82 Basic >2.5 3, 4 7 [106]

5, 6 3–5 [106]
2.5–2.0 1, 2 11 [106]
2.0–1.5 1, 2 7 [106]
Nitrobenzene 1.92 3 0 101.275 45.82 Basic >2.5 1, 2 8–10 [130]

3, 4 14 [106]
5, 6 7–11 [106]
2.5–2.0 1, 2 14 [106]
7, 8 14 [110]
2.0–1.5 1, 2 8 [106]
11
12
Table 1 (Continued)

(cm3 ) areab (Å)
Dodecyl-2- 7.58 4 0 306.852 55.05 Basic >2.5 3, 4 7 [106]

nitrophenylether
5, 6 5, 3 [106]
2.5–2.0 1, 2 11 [106]
2.0–1.5 1, 2 7 [106]
2-Nitrophenyl pentyl 3.82 4 0 191.304 55.05 Basic >2.5 5, 6 60–75 [107]

ether (NPPE)
7, 8 83–85 [107]
2.5–2.0 1, 2 47 [107]
3, 4 55 [107]
2.0–1.5 1, 2 2 [107]
3, 4 37 [107]

NPPE + TEHPd Basic 2.5–2.0 1, 2 43 [107]
3, 4 70 [107]
2.0–1.5 1, 2 60 [107]
3, 4 36 [107]
NPPE + DEHPd Basic 1.0–0.5 3, 4 6–19 [107]

0.5> 3, 4 2 [107]
5, 6 6 [107]
4-Nitro-m-xylene + di- 2.97 3 0 133.825 45.82 Basic 0.5> >10 0 [109]

isobutyl
ketoned
1-Octanol + DEHP + 4- Basic 0.5> >10 61–78 [109]

nitro-m-xylene + di-
isobutyl
ketone
1-Octanol + DEHP + 4- 2.88 1 1 158.095 20.23 Basic 0.5> >10 32–49 [109]
nitro-m-xylened
1-Octanol + DEHP + di- 2.88 1 1 158.095 20.23 Basic 0.5> >10 46–61 [109]
isobutyl
ketoned
4-Nitro-m- 2.97 3 0 133.825 45.82 Basic 0.5> >10 52–73 [109]

xylene + DEHP + di-
isobutyl
ketoned
1- Basic 0.5> >10 43–59 [109]

Octanol + DEHP + NPOE
1-Octanol + DEHPd 2.88 1 1 158.095 20.23 Basic 1.0–0.5 >10 0–42 [103]
>10 2–53 [103]
0.5> >10 34–57 [109]
Metal 0.5> – 6.6–11.1 [112]
Toluene 2.72 0 0 105.709 0 Acidic 0.5> 1, 2 87–106c [92]

3, 4 87–106c [92]
5, 6 87–106c [92]
Table 1 (Continued)

(cm3 ) areab (Å)
Tetrahydrofurfuryl −0.37 2 1 98.33 29.46 Basic 0.5> >10 Current [116]

alcohol
Tetrahydrofurfuryl −0.37 2 1 98.33 29.46 Basic 0.5> >10 0 [116]

alcohol + DEHPd
2-Phenylethanol 1.5 1 1 119.757 20.23 Basic 0.5> >10 Current [116]
2- 1.5 1 1 119.757 20.23 Basic 0.5> >10 0 [116]

Phenylethanol + DEHPd
Isophorone + DEHPd 1.5 1 0 152.644 17.07 Basic 0.5> >10 Current [116]

Isophorone Basic 0.5> >10 0 [116]
Furfuryl alcohol 0.21 2 1 86.044 33.37 Basic 0.5> >10 Current [116]
Furfuryl 0.21 2 1 86.044 33.37 Basic 0.5> >10 0 [116]

alcohol + DEHPd
Santolina alcohol 3.08 1 1 180.043 49.46 Basic 0.5> >10 Current [116]
Santolina 3.08 1 1 180.043 49.46 Basic 0.5> >10 Acceptable [116]

alcohol + DEHPd
1-Chloropinacolone 0.99 1 0 136.129 17.07 Basic 0.5> >10 0 [116]
1- 0.99 1 0 136.129 17.07 Basic 0.5> >10 Current [116]

Chloropinacolone + DEHPd
Acetophenone (and 1.67 1 0 120.964 17.07 Basic 0.5> >10 Current [116]
+DEHP)
Cyclohexanone (and 0.82 1 0 102.952 17.07 Basic 0.5> >10 Current [116]
+DEHP)
Benzaldehyde (and 1.45 1 0 101.099 17.07 Basic 0.5> >10 Current [116]
+DEHP)
1,2,4-Trifluoro-5- 1.8 3 0 113.904 45.82 Basic 0.5> >10 0 [116]

nitrobenzene (and
+DEHP)
2-Octyl-1-dodecano 8.83 1 1 356.553 2023 Basic 0.5> >10 0 [116]

(and +DEHP)
2-Nitrophenethyl 1.59 4 1 131.598 66.05 Basic 0.5> >10 0 [116]

alcohol (and +DEHP)
2-Hexyl-1-decanol 6.80 1 1 290.526 20.23 Basic 0.5> >10 0 [116]

(and +DEHP)
2-Nonanone 3.02 1 0 174.216 17.07 Basic 0.5> >10 0 [116]
2-Nonanone + DEHPd 3.02 1 0 174.216 17.07 Basic >10 Acceptable [116]
13
14
Table 1 (Continued)

(cm3 ) areab (Å)
Methylacetophenone 2.18 1 0 137.471 17.07 Basic 0.5> >10 0 [116]
Methylacetophenone + DEHPd 2.18 1 0 137.471 17.07 Basic 0.5> >10 Acceptable [116]

3-Nitrostyrene (and 2.41 3 0 127.223 45.82 Basic 0.5> >10 0 [116]
+DEHP)
Perillyl alcohol 3.08 1 1 161.843 20.23 Basic 0.5> >10 0 [116]

d
Perillyl alcohol + DEHP 3.08 1 1 161.843 20.23 Basic >10 Acceptable [116]
1-Nonanol 3.39 1 1 174.602 20.23 Basic 0.5> >10 0 [116]
1-Nonanol + DEHPd 3.39 1 1 174.602 20.23 Basic 0.5> >10 0–32 [116]
1-Nonanol + tridecyl 3.39 1 1 174.602 20.23 Basic 0.5> >10 0–24 [116]
phosphate (TDP)d
2-Octanone + DEHPd 2.95 1 0 157.908 17.07 Basic 0.5> >10 0–40 [116]
d
2-Octanone + TDP 2.95 1 0 157.908 17.07 Basic 0.5> >10 3–58 [116]
Eugenol 2.4 2 1 156.283 29.46 Basic 0.5> >10 Acceptable [117]
Methanol −0.69 1 1 42.548 20.23 Anion 0.5> 1, 2 7.2 [129]

3, 4 8.4–32 [129]
5, 6 72.7 [129]
DEHP 2.83 4 1 327.775 65.57
TEHP 9.48 4 0 469.062 54.57
TDP 4.78 4 2 – 82.23

a
DEHP: di-(2-ethylhexyl) phosphate, ER%: extraction recovery percent, NPPE: 2-nitrophenyl pentyl ether, NPOE: 2-nitrophenyl octyl ether, TDP: tridecyl phosphate, TEHP: tris-(2-ethylhexyl) phosphate.
b
The log P values are related to non-charged compounds (reference: www.chemspider.org).
c
Relative recoveries were reported.
d
Properties were reported for constituent solvent.
compound). Pedersen–Bjergaard and his research team figured out presence of propranolol and betaxolol (hydrophobic ␤-blockers).
how to modify the NPOE for extraction of polar drugs with the aid of They considered the fact that a liquid membrane of pure NPOE is
some additives like di-(2-ethylhexyl) phosphate (DEHP) and tris(2- efficient for extraction of non-polar drugs (the addition of DEHP
ethylhexyl) phosphate (TEHP) [105]. Studies also confirm that high to NPOE has a negative impact on their extractability), while the
content of heteroatoms diminishes the solubility of target analytes addition of DEHP to the liquid membrane is required for extraction
in the SLM [103], and that the recoveries decline as the number of polar substances [121]. All represented works confirm that the
of heteroatoms in the chemical structures of analytes increases composition of SLM is of vital importance to the EME efficiency, and
(Table 1). Nevertheless, the reduction of solubility as a result of affects the extraction recovery, extraction speed, system stability,
high content of heteroatoms may be compensated via the addition range of applied voltage, and selectivity.
of some carriers [119]. Ion balance (): It is deduced from Eq. (4) that the decreasing
It was demonstrated that singly charged basic drugs with of ion balance results in the enhancement of flux. So, high recov-
log P > 2 could be effectively extracted by means of nitro-aromatic eries may be acquired, when the ion concentration in the acceptor
compounds as the SLM [103]. However, for medium polar ana- solution is high compared to the donor solution [96]. Ionic con-
lytes (1 < log P < 2), the addition of TEHP to the SLM is needed to centrations of the phases are chiefly determined by phase pHs. For
acquire a good liquid membrane composition, and for extremely this reason, a pH gradient is essential for an excellent extraction. To
polar drugs (log P < 1), the addition of DEHP to the SLM is neces- extract the typical basic analytes, the sample solution should have
sary to attain admissible extraction recoveries [103]. Furthermore, an adequate pH value, in order to convert the target analytes into
a mixture of NPOE, DEHP, and TEHP could be beneficial to extrac- their ionized forms and make them able to migrate through the
tion of most hydrophilic compounds [105,126]. As it is observed electric field. If the pH value of the acceptor phase is low (below
from the data in Table 1, another parameter, which should be the pKa values of the basic analytes), the analytes are straightfor-
considered for selection of SLM, is the number of H-acceptor or wardly released into the acceptor solution. The pH gradient is more
H-donor functionalities in an organic solvent. According to Table 1, important, when the SLM contains an ion-pairing reagent such as
organic solvents, containing several H-acceptor groups, are appro- DEHP; because a fairly high concentration of H+ is needed in the
priate SLMs for extraction of basic analytes. Hence, nitro-aromatic acceptor phase to establish an interaction with the anionic carrier
compounds with a higher number of H-acceptor (4) and a lower (DEHP) and release the cationic analytes. It was revealed that the
number of H-donor groups (0) are excellent solvents for basic pH variation in the acceptor phase noticeably influences the extrac-
drugs. In contrast, a proper liquid membrane for extraction of tion efficiency, but the change in the pH of donor solution has no
acidic analytes is the one that possesses a relatively high num- significant effect on the extraction recovery [104,123].
ber of H-donor functionalities. Accordingly, long-chain alcohols are Yamini et al. designed some experiments to thoroughly scru-
desirable alternatives for this aim [106]. Because water-immiscible tinize the impact of ion balance [123]. They showed that the flux
solvents with a high number of H-donor and a low number of H- of analytes is proportional to (based on the theoretical model
acceptor groups have not still been discovered, the EME faces some (Eq.4)); not only the ratio of the total ionic concentration of the
difficulties in the extraction of acidic drugs. Alcohols have the same donor phase to that of the acceptor phase affects the flux, but also
number of H-donor and H-acceptor functionalities (1), and thus the exact ionic concentrations (or pHs) of the donor and acceptor
could be employed for extraction of both the acidic [92,106,129] phases influence the extraction recovery independently. Neverthe-
and basic [108,110,113,114,117,118,124,128,129] analytes. less, the role of acceptor phase pH is more important. For example,
Gjelstad and coworkers examined the role of SLM composition = 10 could be obtained, when there are 1 mM HCl in the acceptor
in selective extraction of basic drugs under a moderately low elec- phase (Ca ) and 10 mM HCl in the donor phase (Cd ), or when Ca = 10
trical potential difference [133]. They proved that the mass transfer and Cd = 100, or when Ca = 100 and Cd = 1000. All of these cases have
of protonated basic drugs across the SLM was largely dependent on identical values of ion balance, and the first has the lowest recovery
structure. Since basic drug substances with log P values below 2.3 and the latter the greatest. Since it has been demonstrated that the
were too polar to penetrate into the SLM under low-voltage condi- variation in the pH of donor solution has no substantial effect on the
tions, almost no mass transfer was observed for them using NPOE extraction recovery [123], the results could be explained by the role
as the SLM [132]. The number of basic functionalities was another of acceptor phase pH; so that the extraction recovery improves as
effective parameter, and almost no mass transfer was detected the concentrations of ionic species in the acceptor phase increase.
for more hydrophobic dibasic drugs (log P ≥ 2.3), whereas substan- However, the donor phase pH should not be overlooked. In fact, the
tial mass transfer was observed for monobasic drugs. In addition, optimal pH of donor solution depends on the nature of analytes. In
differences in mass transfer were detected for hydrophobic and these procedures, proper conditions must be applied so that all of
monobasic drugs, which appeared to be partly correlated with the the analytes exist in their ionized forms, while has its minimum
polar surface areas of the drugs. Investigations by Nojavan et al. value.
verified that the type of electrical charge has no effect on the extrac- The impact of ion balance was tested for extraction of doubly
tion efficiencies of analytes, and that the charge position might charged drugs with medium polarity (1 < log P < 2) [103]. It was
be an influential parameter [128]. Balchen et al. explored various figured out that the ion balance could enhance the extraction effi-
analyte–SLM interactions affecting the extraction efficiency [118]. ciencies of these analytes. The extractability of doubly charged basic
They stated that pure eugenol, which is capable of establishing drugs improved as the pH of donor solution was raised owing to
solvent interactions, could be exploited for extraction of hydropho- charge reduction (only one ionizable group in the chemical struc-
bic peptides. Nonetheless, the addition of DEHP into 1-octanol led ture of each drug could be ionized, making the drug singly charged)
to the formation of a suitable solvent for both the hydrophobic [103].
and hydrophilic peptides, which caused the extraction to proceed Gjelstad et al. proved that the EME of basic drugs from the sam-
based on ionic interactions between the peptides and DEHP (as an ple solution could also be done at higher pH values (pH 10–11)
ion-pairing reagent). Besides, complexation of the peptides with [133]. This phenomenon was probably due to the extraction of
the crown ether present in the SLM composition was crucial for the analytes via a mixed-mode mechanism at high pH values
improving the selectivity for the most hydrophobic peptides [118]. [133]. Since the analytes were partially ionized, the charged ana-
In a recent work by Yamini et al., SLM engineering was employed for lytes were extracted by electrokinetic migration and the neutral
highly selective extraction of drugs [121]. They proposed a method analytes could be extracted through a passive diffusion mech-
for selective extraction of atenolol (hydrophilic ␤-blocker) in the anism. Nonetheless, the results indicated that the mixed-mode
Fig. 5. Condenser effect and current behavior of an EME system by applying voltage.
Current vs. time reproduced with permission from Elsevier-modified Ref. [105].
mechanism did not affect the extraction kinetics, and that the EME (Fig. 5). The amounts of peak current and final stabilized current
system reached equilibrium after 5 min [133]. Hence, the EME of the depend on the polarities of the SLM and analytes, the applied poten-
charged analyte molecules was the principal mechanism, even at tial, and the total concentrations of ions in both the donor and
high pH values. Other possible reasons for this phenomenon (i.e., acceptor phases. For instance, typical stabilized currents of 5 ␮A
the extraction of basic drugs at high pH values) were the estab- and 200 ␮A were reported, when a voltage of 300 V was applied
lishment of equilibrium at each pH value for the analytes, and the across two different SLMs consisting of pure NPOE and NPOE with
efficient extraction of the drugs, which partially existed in their 25% (w w−1 ) DEHP, respectively [105]. This phenomenon could be
cationic forms, toward the cathode, even at pHs greater than their ascribed to the increasing of liquid membrane polarity by addi-
pKa values. tion of DEHP, which led to the decreasing of the liquid membrane
Applied voltage and extraction time: The major driving force for electrical resistance [105].
the migration of analytes across the liquid membrane is produced The observed current in EME may be attributed to two differ-
by the electric field. The strength of an electric field is dependent ent sources: ion exchange current (iex ) and electrolysis reaction (ie ).
on the applied voltage, and thus the applied voltage influences the The ion exchange current is produced by the migration of cations
flux of analytes through the membrane [96]. Although it is antic- and anions in opposite directions through the SLM under an elec-
ipated that the extraction recovery will improve as the applied tric field, and the exchange of ions between the donor and acceptor
voltage is enhanced, there are some limitations on increasing of phases (iex ). Ion transportation across the SLM has been experi-
voltage. In some cases, the enhancement of voltage may lead to mentally confirmed in a recent paper by Dryfe et al. [136]. Ie is
a decline in recovery because of mass transfer resistance, which probably generated via the electrolysis reactions on the surfaces of
is due to the build-up of boundary layers of ions at the inter- electrodes. Therefore, the total current in EME (it ) can be calculated
faces on both sides of SLM or the saturation of analytes in the by the following equation:
acceptor phase. Also, when the pH is slightly raised in the accep-
tor solution (in the case of extraction of basic analytes) owing to it = iex + ie (5)
electrolysis, the analytes are back-extracted into the donor phase,
causing the extraction efficiency to diminish. Consequently, the Suppose that no electrolysis reactions take place on the sur-
extractability may decrease by increasing the strength of electric faces of electrodes (particularly at the beginning of the extraction
field [108,119,120,124,127,134,135]. Kjelsen et al. revealed that by procedure), then:
improving the sample-to-SLM distribution ratio, the EME could be
it = iex (6)
performed at potential differences (5–10 V) obtainable by common
batteries [107]. They also figured out that the range of applied As it is known, iex is not measurable; so, what is the origin of
voltage is determined by the nature of SLM, and the range may the observed current at the beginning of extraction operation? The
become broader as the electrical resistance of the liquid membrane origin of this current comes back to different electromobility of
is enhanced. Thus, for some organic liquid membranes, such as various anions and cations that cross the membrane in opposite
long-chain alcohols, the applied voltage is limited to 100 V, whereas directions (Fig. 5). If the migration rate of both anions and cations to
NPOE can tolerate up to 300 V. It is worthy to note that a rise in the be equal through the SLM, the ion exchange current cannot be mea-
applied voltage makes the system instable due to an increase in sured. Therefore, with ignoring of electrolysis reactions (an ideal
the current level. If the resistance of the system is assumed con- supposition) no electrical current should be observed in EME.
stant (for a typical SLM), one can prove, by using Ohm’s law, that Actually, current behavior in EME is like a capacitance; at the
the current will be raised by enhancing the applied voltage. beginning of extraction by applying voltage a double layer is sud-
3.3.1.1.3. The nature of observed current in EME. By applying denly created in both sides around the SLM and a condenser effect is
a potential difference over the liquid membrane in EME, a short created (Fig. 5). The initial peak current is due to this effect, which
peak current is initially observed, followed by a slow and gradual charged the sample and acceptor solutions [105]. This process is
decline in current until reaching a stabilized level in the system expected to be crucial for electrokinetic migration in the system
[105]. After this initial peak current, the current was principally other hand, by accumulation of the ions, the charge density of the
determined by the flow of ions across the liquid membrane. double layer increases over time (Fig. 6B) and results in an increase
in Joule heating and a decrease in the electrical resistance of the
3.3.1.2. Applications. Several works have been published using pri- SLM. Therefore, even by applying a relatively low voltage in a long
mary EME setup for extraction of different analytes. EME is still time, the resistance of the system is gradually reduced. Thus, the
a new microextraction technique. Therefore, application of the current level increases with time if the applied voltage is constant.
method for extraction of different compound from different matri- Also, such a structure may act as a parallel-plate capacitor, which
ces should be investigated. has a known charge capacity. So, a limited amount of charge can
Since the first application of EME method was reported be accumulated on the double layer and with the increase in the
for extraction of basic drugs [29], this technique has extraction time some sparking may be observed. Therefore, pulsed
been wildly used for extraction of this class of analytes electromembrane extraction (PEME) was introduced as an efficient
[93–96,103,105,107,109,111,119–123,125–127,132,133,137,138]. alternative using a simple and inexpensive electronic device which
The efficiency of EME has been compared with conventional creates pulsed voltage in combination with common d.c. constant
HF-LPME [95,120,127] and it was shown that using elec- power supplies [134]. In this method, the duration of the pulse is
trical field impressively improves extraction recovery and long enough for the analytes to migrate from the sample solution,
reduces extraction time. However, by reversing the direction through the SLM, and into the acceptor phase; but it is so short that
of electrical field, EME could effectively perform for extrac- the thickness of the boundary layer is minimized (Fig. 6C). Hence,
tion of acidic compounds [92,106,116,124,139,140] and organic PEME could increase stability by decreasing the thickness of the
anions [129]. EME has been used for extraction of metal ions double layer at the interfaces and improve extractability by elim-
[113,114,141] and inorganic anions [112,142] as well as peptides inating this mass transfer barrier and PEME could be introduced
[104,108,110,117,118,143,144] and amino acids [115,145]. This as an efficient microextraction technique with higher preconcen-
method is capable of coupling with different analysis techniques tration factors, relatively short extraction time, higher precision,
such as HPLC [92,93,104,108,110,116–124,126–128,133,140,144], and a more stable system (even by applying high voltages) in
CE [29,95,96,103–107,109–115,130,132,137–139,141,143], and comparison with conventional EME [134]. In another work, PEME
IC [129,142]. Coupling of EME to CE has been fully reviewed by followed by HPLC–ultraviolet detection (HPLC–UV) was employed
Gjelstad et al. [88]. More recently, Fakhari et al. coupled EME with for simultaneous extraction of histidine (HIS), phenylalanine (PHE)
differential pulse voltammetry using modified screen-printed and tryptophan (TRY) [145]. It was observed that PEME offers more
electrode for the determination of sufentanil in urine and plasma efficient extraction and stability in comparison with conventional
samples [91]. This new analytical approach presents advan- EME for extraction and quantification of amino acids in foods and
tages of both EME and electrochemical determination such as biological samples which can attribute to minimization of thickness
good selectivity and cleanup, low cost, high sensitivity and easy of double layer at the interfaces.
operation. Also, taking into account that zwitterions have no mobility in
an electrical field at their isoelectric point, two-way PEME was
3.3.1.3. EME setup development. Despite the high potential of EME performed as a novel approach for highly selective extraction of
method for efficient extraction of ionizable compounds in relatively TRY as a model analyte using the isoelectric pH of TRY for accep-
short time, it associated with some drawbacks. tor phase [145]. To this end the outage period was substituted
The main trouble of EME is that electrical potential differences by backward step at which the direction of electrical field was
above 300 V were found to be inappropriate (especially in analy- reversed. Therefore, at the backward step PHE and HIS are trans-
sis of real samples containing large amounts of ionic components) ferred again into donor phase while TRY remains in the acceptor
due to the system suffering from bubble formation at the elec- phase.
trodes, instability problems, punctuation of the SLM and sparking Although, selectivity is one of the advantages of EME method,
[104,108,110,111,113,119,120]. It was claimed that the punctu- there is some limitation in extraction of different classes of ana-
ation of SLM (particularly when analyzing the drugs in human lytes. According to the direction of electrical field, EME could be
plasma samples), which leads to decreased resistance between the performed for extraction of acidic or basic compounds. For simul-
electrodes as well as system instability as a result of an increase taneous analysis of acidic and basic drugs, Basheer et al. designed
in the current level, may be due to the emulsifying capacity of an interesting EME setup using four sheets of porous polypropylene
plasma [110]. Therefore, Gjelstad et al. demonstrated that adding membrane which were combined and heat-sealed at three edges
microliter amounts of the SLM organic solvent to the bottom of the [147]. Their EME setup is shown in Fig. 7A. In this work, analytes
hollow fiber can improve the system stability [109]. However, it were extracted across the SLM and into an aqueous phase and then
seems that the emulsifying capacity of plasma is not the only rea- transferred to an organic acceptor phase. The first step (from sam-
son for this event, and the presence of high concentration levels ple solution to aqueous phase) is based on electrokinetic migration
of ionic species may be the main cause. Thus, controlling of the and the transport mechanism for the analytes into organic acceptor
level of electrical current seems to be more beneficial to solving phase is passive diffusion and the flux is basically controlled by dis-
this problem. tribution ratios. Finally, the organic acceptor phase was analyzed
Two different methods were suggested to overcome the insta- by gas chromatography followed by mass spectrometry detection
bility problems of EME including the application of stabilized (GC–MS) [147].
constant direct electrical current [146] and pulsed voltage instead Yamini et al. introduced a simple and different setup utilizing
of constant d.c. voltage [134]. two pieces of hollow fiber for simultaneous extraction of acidic and
One solution for the difficulties of analysis of real samples and basic analytes (Fig. 7B) [135]. The details have been explained in
the instability of the extraction system was presented by Yamini a recent review [88]. In comparison with sheet membranes, the
et al. [134]. By applying suitable voltage, all ionic species in the volume of acceptor phase is more repeatable in their setup, when
solution select appropriate orientations under the electrical field hollow fibers were employed as acceptor phase containers, and
and the ambulations of ions form two sheets of charges on both the precision of the proposed method may be increased. Since the
sides of SLM, which have opposite polarities and are separated most effective transport mechanism for the analytes is electroki-
by the organic phase (Fig. 6A). This boundary layer leads to mass netic migration during the extraction, the extraction time may be
transfer resistance and decreases the extraction efficiency. On the decreased in comparison with Basheer’s setup [135]. Fakhari et al.
Fig. 6. Schematic diagram of PEME setup at (A) beginning of pulse duration, (B) end of pulse duration, and (C) end of outage period.
Reproduced with permission from Elsevier-modified Ref. [134].
utilized this setup followed by CE to simultaneous determination of More recently, electromembrane surrounded solid phase
ibuprofen (an acidic drug) and thebaine (a basic drug) from plasma microextraction (EM-SPME) coupled with GC followed by FID (GC-
and urine samples [148]. FID) was for the first time introduced by Yamini and coworkers
Another disadvantage of EME is its incompatibility with GC [151]. Their setup was consisted of a pencil lead which was used
instrument. The GC is a simple and fast analysis technique which as a cathode and located into the lumen of the hollow fiber. Sub-
can be easily coupled with different types of sensitive detectors stantial selectivity and cleanup, simplicity, compatibility with GC,
such as flame ionization detector (FID) and mass spectrometer. inexpensive and rapid extraction are the main advantages of the
The acceptor phase of EME is an aqueous solution and direct injec- presented method. Moreover, possibility to apply high voltages as
tion of water may cause some problems for GC. However, there well as analysis of complicated matrices could be provided by this
is an EME report for direct injection of aqueous acceptor phase method. The results showed that EM-SPME may have a great poten-
into GC injection port [125]; the main challenge in the coupling tial as a microextraction technique, and opens a new era to this field
of EME with GC is to substitute the acceptor phase with an organic of analytical chemistry.
solvent. The other EME drawback is that it is a non-exhaustive extrac-
Recently, Guo et al. reported the EME followed by low-density tion method and recoveries were limited due to the system reach
solvent based ultrasound-assisted emulsification microextraction equilibrium. To overcome this limitation, Eibak et al. introduced
(EME-LDS-USAEME) combined with derivatization for determin- a new EME setup for exhaustive extraction of basic drugs from
ing chlorophenols (CPs) in water samples and analysis by GC–MS human plasma sample (Fig. 7D) [152]. The basis of their work was
[149]. However, this method has been applied to the analysis to increase the ratio between organic- and aqueous donor phase by
of CPs in simple matrices, for which good results could only be optimization of the surface available for electrokinetic migration.
obtained by ultrasound-assisted emulsification microextraction Therefore, three pieces of hollow fibers were used to increase the
(USAEME). Therefore, Yamani and his research group presented the volume of acceptor phase and the contact area between SLM and
first coupling of EME with dispersive liquid–liquid microextraction the donor phase [152]. In another work this EME setup was used
(DLLME) to develop a new pretreatment method for extraction of to study the properties of biopolymers (alginate and chitosan) as
tricyclic antidepressants from biological samples [150]. To this end sampling media for dried blood spots [153]. Also, basic drugs were
(as it is shown in Fig. 7C), after the EME step, the acceptor solu- extracted under stagnant conditions demonstrating that admissi-
tion was collected and injected into an alkaline solution (pH = 12) ble detection limits are obtainable by extraction from a few dozen
for converting extracted analytes to their neutral forms. Follow- microliters of biological fluids [152,154,155].
ing that, the DLLME procedure was performed on this solution. Also, the application of carbon nanotubes was considered for
Two-phase EME was another proposed method for making EME enhancing the absorption capacity of the SLM and increasing the
compatible with GC. Nevertheless, the first successful attempt to extraction recoveries [156,157].
EME coupling with GC was published by Basheer et al. [147]. As Since 2006, the EME has been associated with rapidly progress-
it was discussed above, the aim of their work was simultaneous ing. This is due to its advantages such as selectivity and sample
extraction of acidic and basic drugs. To achieve this goal, a combi- cleanup which eliminated interferences to the high extent in com-
nation of EME and conventional HF-LPME was performed and the plicated matrices, preconcentration, fast kinetics with exact control
analytes were finally transferred into organic acceptor phase [147]. of the beginning, and termination of the extraction. It seems that
Hence, the GC–MS was employed for analysis of final acceptor solu- the EME is opening new doors for microextraction techniques and
tion [147]. it may followed by some extra developments in the future.
Fig. 7. Equipment for (A and B) simultaneous extraction of acidic and basic analytes, (C) EME coupled with DLLME, and (D) exhaustive electromembrane extraction.
Reproduced with permission from Elsevier-modified Refs. [135,147,150,152].
4. The other roles of electrical driving force in analytical understanding, instrumental, advantages, disadvantages, and
techniques recent developments, is available in the literature [158–176].
Another way that electrical driving forces affect the separa-
Electrical driving force has been created substantial improve- tion techniques is the combination of electrically assisted sample
ments in separation techniques by different ways (Fig. 2). The roles preparation methods with these techniques. As shown in Fig. 2, the
of this auxiliary energy in separation techniques can be classified electrically assisted sample preparation techniques can be coupled
as the following: off-line or on/in-line with different separation techniques. Up to
now, the most reported works have been used an off-line coupling
1- The separation techniques that are based on the electrical driv- and a few publications can be found for on-line combination with
ing forces, such as CE, capillary electrochromatography (CEC), separation techniques in the literature.
voltage-assisted liquid chromatography (VALC) and EMLC, It is worth mentioning that electrically assisted extraction tech-
microchip electrophoresis (ME), and microchip electrochro- niques not only can be used as sample preparation methods but
matography (MEC). also they can be utilized as detector in separation techniques.
2- The separation techniques that are coupled, off-line or on/in- Application of a new type of amperometric detector for nonre-
line, with an electrically assisted extraction method as a sample dox ions based on ion-transfer reactions at the microinterface
preparation process. between water and NPOE-poly(vinyl chloride) gel [177,178], as
3- The separation techniques, in which an electrically assisted well as polypyrrole (PPy) and overoxidized sulfonated polypyrrole
extraction method is used for detection. (OSPPy) electrodes as a potentiometric detector in IC to determine
some anions and cations in water samples [64] are the instances
The efficiency of separation processes can usually be assured that can be enumerated.
either by an energy input or by external forces (Fig. 2). Huge In recent years, miniaturized designs termed Lab-on-a-Chip
changes were obtained in separation techniques by invention of (LOC) has attracted the attentions to perform downscaled labora-
electrically assisted ones. A comprehensive discussion about the tory analyses and for high throughput and highly specific analysis
CE, CEC, ME, MEC, EMLC, and VALC, including the theoretical in chemistry, biology and medicine [179]. LOCs are a subset of
microelectromechanical systems (MEMS) which also indicated by Undoubtedly, the use of electrical driving force, in the course of
“Micro Total Analysis Systems” (␮TAS) [38,179–182]. With ␮TAS recent years, has received renewed attentions in different fields of
technology, chemical analysis can be performed on very small science. On the other hand, what can be stated about the impacts
sample sizes and with a very low consumption of chemicals and that these concepts have had on the “real world”? In fact, the
reagents due to the small dimensions of the devices. The small answers to these questions will be so different depending on the
dimensions and short diffusion distances also give the potential considered application field. In the case of analytical chemistry,
for very rapid analysis [38]. although more studies are required to really establish the funda-
One of the first applications of LOCs in analytical chemistry mental roles and the effects of the electric fields but according
was their benefits in separation techniques. Due to smaller sep- to what was discussed here, glorious future is expected for elec-
aration lengths of electrophoretic techniques which is following trically assisted sample preparation techniques so that they will
by increase in electrical fields, these techniques are perfectly create enormous developments in this concept.
suited for downscaling. Several review articles have been pub- Fabrication of new membranes and coating films, development
lished that provide printed guides to the best improvements and and improvement of new electrically assisted sample prepara-
advances related to different chip based chromatography tech- tion methodologies, more efforts toward ␮TAS technology, trying
niques [168,183–187]. to overcome limitations and drawbacks of existing electrically
Typical processes such as filtration [188–190] and dialy- induced extraction methods, endeavor in order to on-line coupling
sis [191,192] had been initially implemented upon microchips. with different analysis instruments such as chromatographic and
Recently, several reports have been emerged on implementation of spectrometric ones and investigation of applicability of electrically
some electrically assisted liquid and solid based extraction meth- assisted extraction methods as detector in separation technique are
ods as well as membrane-based approaches [31–40]. Regarding the definitely interesting directions in the future.
chip based sample preparation methods which explained in the
literature, it can be concluded that miniaturization of extraction Acknowledgements
techniques is one of the more attractive challenging todays and a
bright future as well as enormous revolution is predicted in this The support, provided by the Grant Agency of the National Elite
field of analytical chemistry. Foundation (Shahid Chamran’s Scientific Prize, Grant No: 15/37651,
Tehran, Iran), is highly appreciated.
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Analytica Chimica Acta 814 (2014) 1–22

Contents lists available at ScienceDirect

Analytica Chimica Acta

Electrical ﬁeld-induced extraction and separation techniques:

• Sample preparation is an important

Application of Electrical Field in Analytical Chemistry

Electrochemical Extraction Separation

Liquid based methods

Solid based methods

Hyphenation with sample

Charge (electrical assisted)

Size exclusion (iltration)

Symmetrical aspects Material aspects

Anodized Alumina Membranes

Streching of a Polymer Film

SLM Analyte ERa % Ref

Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

NPOE 5.35 4 0 240.825 55.05 Basic >2.5 1, 2 35–90 [107,125,130]

Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

Dihexyl ether 5.12 1 0 232.979 9.23 Basic >2.5 3, 4 0 [29]

1-Octanol 2.88 1 1 158.095 20.23 Basic >2.5 3, 4 3 [29]

1-Octanone 2.95 1 0 157.908 17.07 Basic >2.5 3, 4 – [29]

Dodecyl acetate 5.88 2 0 263.112 26.3 Basic >2.5 3, 4 0 [29]

SLM Analyte ERa % Ref

Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

NPOE + DEHPd 5.35 4 0 240.825 55.05 Basic >2.5 3, 4 0–75 [29,104,118]

Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

Kerosene 3.76–10.76 0 0 164.634–419.399 0 Basic >2.5 3, 4 0 [29]

Silicone oil AS 4 – 1 0 – 17.07 Basic >2.5 3, 4 0 [29]

Soybean oil – – – – – Basic >2.5 3, 4 0 [29]

Peppermint oil 2.76 1 0 175.053 17.07 Basic >2.5 3, 4 13 [29]

NPOE + TEHPd 5.35 4 0 240.825 55.05 Basic >2.5 3, 4 0–78 [104,122]

SLM Analyte ERa % Ref

Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

NPOE + TEHP + DEHPd 5.35 4 0 240.825 55.05 >2.5 3, 4 0–61 [104]

Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

1-Ethyl-2- 2.94 3 0 134.092 45.82 Basic >2.5 1, 2 38–70 [108,130]

1-Isopropyl-4- 3.43 3 0 151.348 45.82 Basic >2.5 3, 4 59 [106]

1-Nitropropane 0.94 3 0 90.835 45.82 Basic >2.5 3, 4 0 [106]

1-Nitropentane 1.96 3 0 151.348 45.82 Basic >2.5 3, 4 7 [106]

Nitrobenzene 1.92 3 0 101.275 45.82 Basic >2.5 1, 2 8–10 [130]

SLM Analyte ERa % Ref

Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

Dodecyl-2- 7.58 4 0 306.852 55.05 Basic >2.5 3, 4 7 [106]

2-Nitrophenyl pentyl 3.82 4 0 191.304 55.05 Basic >2.5 5, 6 60–75 [107]

Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

NPPE + DEHPd Basic 1.0–0.5 3, 4 6–19 [107]

4-Nitro-m-xylene + di- 2.97 3 0 133.825 45.82 Basic 0.5> >10 0 [109]

1-Octanol + DEHP + 4- Basic 0.5> >10 61–78 [109]

4-Nitro-m- 2.97 3 0 133.825 45.82 Basic 0.5> >10 52–73 [109]

1- Basic 0.5> >10 43–59 [109]

Toluene 2.72 0 0 105.709 0 Acidic 0.5> 1, 2 87–106c [92]

SLM Analyte ERa % Ref

Typea Log Pb H-acceptorb H-donorb Molar Polar Type Log Pb Number of

Tetrahydrofurfuryl −0.37 2 1 98.33 29.46 Basic 0.5> >10 Current [116]

Tetrahydrofurfuryl −0.37 2 1 98.33 29.46 Basic 0.5> >10 0 [116]

2-Phenylethanol 1.5 1 1 119.757 20.23 Basic 0.5> >10 Current [116]

2- 1.5 1 1 119.757 20.23 Basic 0.5> >10 0 [116]

Y. Yamini et al. / Analytica Chimica Acta 814 (2014) 1–22

Furfuryl 0.21 2 1 86.044 33.37 Basic 0.5> >10 0 [116]

Santolina 3.08 1 1 180.043 49.46 Basic 0.5> >10 Acceptable [116]

1-Chloropinacolone 0.99 1 0 136.129 17.07 Basic 0.5> >10 0 [116]

1- 0.99 1 0 136.129 17.07 Basic 0.5> >10 Current [116]