Advances in Colloid and Interface Science 284 (2020) 102272

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Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Historical Perspective

Electrophoretic deposition of polymers and proteins for biomedical

applications
Rebecca Sikkema 1, Kayla Baker 1, Igor Zhitomirsky ⁎
Department of Materials Science and Engineering, McMaster University, Hamilton, ON, Canada

a r t i c l e i n f o a b s t r a c t

Article history: This review is focused on new electrophoretic deposition (EPD) mechanisms for deposition biomacromolecules,
12 September 2020 such as biopolymers, proteins and enzymes. Among the rich literature sources of EPD of biopolymers, proteins
Available online 19 September 2020 and enzymes for biomedical applications we selected papers describing new fundamental deposition mecha-
nisms. Such deposition mechanisms are of critical importance for further development of EPD method and its
Keywords:
emerging biomedical applications. Our goal is to emphasize innovative ideas which have enriched colloid and in-
Polymer
Protein
terface science of EPD during recent years. We describe various mechanisms of cathodic and anodic EPD of
Enzyme charged biopolymers. Special attention is focused on in-situ chemical modification of biopolymers and
Electrophoretic deposition crosslinking techniques. Recent innovations in the development of natural and biocompatible charged surfac-
Film tants and film forming agents are outlined. Among the important advances in this area are the applications of
Mechanism bile acids and salts for EPD of neutral polymers. Such innovations allowed for the successful EPD of various elec-
trically neutral functional polymers for biomedical applications. Particularly important are biosurfactant-polymer
interactions, which facilitate dissolution, dispersion, charging, electrophoretic transport and deposit formation.
Recent advances in EPD mechanisms addressed the problem of EPD of proteins and enzymes related to their
charge reversal at the electrode surface. Conceptually new methods are described, which are based on the use
of biopolymer complexes with metal ions, proteins, enzymes and other biomolecules. This review describes
new developments in co-deposition of biomacromolecules and future trends in the development of new EPD
mechanisms and strategies for biomedical applications.
© 2020 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Fundamental aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Electrophoretic mobility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Deposition yield. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Electrode reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. EPD mechanisms of cationic polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. EPD of chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. EPD of chiral polyelectrolytes: poly-l-lysine and poly-l-ornithine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. EPD of polyethylenimine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. EPD mechanisms of anionic polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1. EPD of alginic acid and alginates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2. EPD of hyaluronic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.3. EPD of polyacrylic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. EPD of electrically neutral polymers and chemically modified polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.1. EPD of polyetheretherketone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.2. EPD of cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

⁎ Corresponding author.
E-mail address: zhitom@mcmaster.ca (I. Zhitomirsky).
1
The authors contributed equally

https://doi.org/10.1016/j.cis.2020.102272
0001-8686/© 2020 Elsevier B.V. All rights reserved.
R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

5.3. EPD of polymethylmethacrylate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

5.4. EPD of polyaniline and polypyrrole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.5. EPD of poly(tetrafluoroethylene) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. EPD of proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6.1. Colloidal behavior of proteins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6.2. EPD of collagen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6.3. EPD of gelatin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.4. EPD of bovine serum albumin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.5. EPD of other proteins and enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
7. Co-EPD of polymers and proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.1. Co-EPD of chitosan with other polymers and proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.2. Co-EPD of alginate with other polymers and proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.3. Co-EPD of hyaluronic acid with other polymers and proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8. EPD of other polymers and polymer-protein composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
9. Conclusions and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Introduction concentration in the bulk of the suspensions or solutions [14,15]. There-

Electrophoretic deposition (EPD) is an important technique for depo-
sition of various materials and composites from colloidal suspensions or
solutions of macromolecules [1–3]. It offers advantages of high deposition
rate and the possibility of uniform film formation on substrates of large
surface area. EPD allows for excellent control of film thickness and depo-
sition rate. It can be used for the deposition of thin films, patterned films
and thick coatings. EPD is a low cost and versatile technique for the depo-
sition of polymers, ceramics, metals, hydroxides and other organic and in-
organic materials [1,4–6]. EPD is especially attractive for biomedical
applications, due to the high purity of the deposits and the possibility of
uniform deposition on substrates of complex shapes [7,8]. Of particular
importance for biomedical applications [8] is the EPD of multilayer
films, containing individual layers of controlled thickness and composi-
tion. Moreover, EPD allows for the fabrication of films of graded composi-
tion and controlled morphology. The possibility to co-deposit different
organic and inorganic composites at room temperature is another benefit
of EPD for various biomedical applications. EPD literature contains excel-
lent reviews describing various applications of this technique [1–3,6,9,10].
The process of EPD involves electrophoretic transport of charged
particles or polymer macromolecules towards the electrode and then
film formation at the electrode surface [11,12]. This method requires
the use of stable suspensions of charged particles or stable solutions of
charged macromolecules [2]. Many fundamental studies focused on
the development of new techniques for particle charging and disper-
sion. The studies highlighted the importance of particle-dispersant
and particle-solvent interactions for the development of electrostati-
cally or electrosterically stabilized suspensions [11]. Significant atten-
tion has been focused on the analysis of electrophoretic mobility of
rigid particles, polyelectrolytes and particles, containing adsorbed poly-
electrolytes [11]. Another important factor is the structure of dispersing
agents [13]. There has been significant progress in the development of
advanced dispersants, containing chelating functional groups and
charged groups. The metal chelating groups promote dispersant adsorp-
tion on the particle surface, whereas charged groups are critical for par-
ticle dispersion and their electrophoretic transport [13].
Mutual repulsion of particles or macromolecules is a key factor for the
fabrication of stable suspensions or solutions, however it is detrimental
for the film formation. The particles or macromolecules must coagulate
at the electrode surface to form a film [10]. Therefore, special electrode
conditions must be achieved, which allow coagulation of the particles or
macromolecules electromigrating from the stable bulk suspensions or so-
lutions to the electrode surface. Investigations showed that zeta potential
value as well as the sign of the zeta potential are influenced by particle
fore, accumulation of the particles or macromolecules at the electrode
surface can result in changes in their zeta potential. Significant pH
changes [11] close to the anode or cathode surface due to electrochemical
decomposition of water or other solvents result in changes of zeta poten-
tial as well. Various materials, such as oxide and hydroxide particles, pro-
teins, enzymes and some polymers exhibit charge reversal at their
isoelectric points. The pH changes at the electrode surface can lead to
the charge reversal of the electromigrating species close to the electrode
surface, which result in mutual electrostatic repulsion of the material
and electrode [11]. Such pH changes prevent deposit formation. There-
fore, it is important to avoid mutual repulsion of colloidal particles or mac-
romolecules and their repulsive interactions with electrodes. The
fabrication of adherent films requires the deposition of binding or film-
forming agents. Therefore, the success in EPD of materials depends on
the advances in the development of efficient deposition mechanisms.
The objective of this review is to describe recent advances in the de-
velopment of deposition mechanisms for EPD of biopolymers, proteins
and enzymes. The EPD of biopolymers is important for tissue engineering,
fabrication of advanced implants, coatings and bone-substitute materials.
The co-deposition of biopolymers, proteins and enzymes is critical for the
development of films and coatings with enhanced functionality and bio-
sensors. The EPD of biopolymers provides a platform for the incorporation
of other functional materials, such as antimicrobial agents, bioceramics,
bioglass and drugs in the composite coatings. This review is different
from other reviews, which are focused on various biomedical applications
of EPD techniques [8,16]. Among the rich literature sources of EPD of bio-
polymers, proteins and enzymes for biomedical applications we selected
papers describing new fundamental deposition mechanisms. Such depo-
sition mechanisms are of critical importance for further development of
EPD method and its emerging biomedical applications. Our goal is to em-
phasize innovative ideas which have enriched colloid and interface sci-
ence of EPD during recent years. We describe recent innovations in the
deposition mechanisms for EPD of cationic and anionic biopolymers. Par-
ticular attention is focused on recent progress in the development of nat-
ural and biocompatible charging and film-forming agents, which allowed
for the EPD of electrically neutral polymers for biomedical applications.
We discuss advances in the fundamental mechanisms for EPD of pro-
teins and enzymes. New strategies are described, that are based on the
use of polymer-metal ion complexes and complexes of the biopolymers
with organic molecules. New electrochemical cross-linking and charge
compensation techniques are presented. Another important area cov-
ered by this review is the application of chemically modified polymers
and in-situ polymer modifications for the fabrication of adherent coat-
ings with advanced functionality. We discuss various mechanisms and

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R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

chemical reactions, which exert influence on particle charge, suspension
stability, electrophoretic transport and deposit composition. Recent in-
novations in co-deposition mechanisms and future trends are discussed.
2. Fundamental aspects
2.1. Electrophoretic mobility
The electrophoretic mobility μ of a rigid spherical particle is given by
an equation [17]:
where M0 is the initial mass of the material in the suspension or solu-
tion, k is kinetic constant.
Equations (2.3)–(2.5) were derived using an assumption that all the
particles or macromolecules arriving to the electrode surface are depos-
ited. However, the deposition yield is influenced by the rate of deposit
formation which depends on the rate of electrode reactions and other
factors. In the case of EPD of an individual material the deposit compo-
sition is defined by the composition of the material used for deposition.
In the case of co-deposition, the deposit composition can be controlled
by the use of co-dispersants for deposition of different components.

2εϵ0 ζ 2.3. Electrode reactions

μ¼ f ðκaÞ ð2:1Þ
3η
Electrode reactions play an important role in the film formation by
where ε is the dielectric constant of the solvent, ε0 is the vacuum dielec-
cathodic and anodic EPD. It will be shown below that such reactions
tric permittivity, 1/κ is the Debye length, ζ is the zeta potential, η is the
can facilitate or prevent deposit formation. Different electrochemical re-
viscosity of the solvent, and a is the particle radius. The function f (κa)
actions [11] result in a local pH increase at the cathode surface. The ca-
changes from 1 for κa<<1 to 1.5 for κa>>1.
thodic reaction which consumes H+
The electrophoretic mobility of a spherical polyelectrolyte [18] is de-
scribed by an equation: 2Hþ þ 2e− ! H2 ð2:6Þ
" #
λ
ρ 2 λ2 1 þ 2κ brings about a small increase in pH at the electrode surface. In aqueous
μ¼ 1 þ ð2:2Þ
ηλ2 3 κ2 1 þ λκ solutions, the reduction of water generates OH− and brings a more ap-
preciable increase in pH
where ρ is charge density, λ=(γ/η)1/2, γ is the frictional coefficient of
2H2 O þ 2e− ! H2 þ 2OH− ð2:7Þ
the polyelectrolyte.

2.2. Deposition yield However, this reaction brings about H2 evolution, which can result
in porous polymer films. Electrochemical reactions in other solvents
EPD is usually performed on conductive substrates. Chemical stabil- can also contribute to the local pH increase. In methanol solutions in-
ity of the substrates in the EPD bath is an important factor for the fabri- creased pH at cathode can result from the reactions:
cation of adherent coatings. In the case of anodic EPD, the
2Hþ þ 2CH3 OH þ 2e− ! 2H2 O þ C2 H6 ð2:8Þ
electrochemical oxidation and dissolution of the substrate must be
avoided. Consistent results can be obtained on different conductive 2CH3 OH þ 2e− ! 2OH− þ C2 H6 ð2:9Þ
chemically stable substrates.
The deposit mass M in the EPD process [19] can be described by the Tertiary alcohols produce OH- in the reaction
Hamaker equation:
ROH þ 2e− ! R− þ OH− ð2:10Þ
M ¼ μEtSC ð2:3Þ
If dissolved oxygen or hydrogen peroxide are present in solutions
where C is concentration of particles or macromolecules, E is electric
the following reactions can occur
field, S is electrode area and t is the deposition time. The layer thickness
is controlled by the variation of the electric field, concentration of the O2 þ 2H2 O þ 4e− ! 4OH− ð2:11Þ
deposited material, electrophoretic mobility and deposition time. De-
posit uniformity of insulating materials is controlled by the electric field. H2 O2 þ 2e− ! 2OH− ð2:12Þ
It is in this regard that the deposition rate is usually higher in the area of
lower deposit thickness due to the higher local electric field and it be- Additionally, nitrate and perchlorate ions in the electrolyte can con-
comes lower in the area of higher thickness due to the lower local elec- tribute to the pH increase
tric field. High voltage allows the deposition of thick films at a high
deposition rate. However, high voltage can result in porous films due NO3 − þ H2 O þ 2e− ! NO2 − þ 2OH− ð2:13Þ
to gas evolution at the electrode surface.
Equation (2.3) describes the deposition yield in relatively concen- NO3 − þ 7H2 O þ 8e− ! NH4 þ þ 10OH− ð2:14Þ
trated suspensions or solutions. In the suspensions of lower concentra- − −
ClO4 þ H2 O þ 2e− ! ClO3 þ 2OH− ð2:15Þ
tion the increase in film thickness and continuous shift of the film-
suspension interface boundary must be considered [17,20] and the de- − −
ClO4 þ 4H2 O þ 8e− ! Cl þ 8OH− ð2:16Þ
posit mass is given by the equation:

M ¼ μEtSCCf =ðCf −CÞ ð2:4Þ Various electrochemical reactions result in pH decrease at the anode
surface. The electrochemical decomposition of water results in H+ gen-
where Cf is particle concentration in the film. eration and significant local pH decrease:
In very dilute suspensions, the reduction of particle concentration in
the suspension during the deposition process must be taken into con- 2H2 O ! O2 þ 4Hþ þ 4e− ð2:17Þ
sideration and the deposit mass is given by the equation [21]:
The generation of H+ can be achieved by electrochemical oxidation
 
M ¼ M0 1−e−kt ð2:5Þ of phenolic molecules, such as hydroquinone [22]. In this reaction, the
hydroquinone is transformed to 1,4-benzoquinone at electrode

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R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

potentials of 0.3–0.4 V, which are lower than the potential for water
electrolysis [22]:

C6 H6 O2 ! C6 H4 O2 þ 2Hþ þ 2e− ð2:18Þ

3. EPD mechanisms of cationic polyelectrolytes

3.1. EPD of chitosan

Chitosan (Chit) is found in the shells of crustaceans and is the second

most abundant polysaccharide in nature. Chit has advanced film-
forming abilities, good mechanical properties, chemical stability, and
biocompatibility. It has become widely popular for use in various bio-
medical applications including drug delivery, antimicrobial coatings,
scaffolding, and implant materials [23,24]. Due to processing advan-
tages of EPD and unique physicochemical properties of Chit, EPD is an
effective way to fabricate various Chit products for biomedical applica-
tions [25].
Cathodic deposition of Chit was first achieved and described in detail
by Wu et al. [25]. The chemical structure of Chit includes primary amino
groups. Chit is insoluble in water at pH=7, however it becomes a solu-
ble cationic polyelectrolyte at low pH due to protonation of the amino
groups [25]:

Chit−NH2 þ Hþ ! Chit−NH3 þ ð3:1Þ

The pKa of Chit is about 6.3 and at pH below its pKa most of the
amino groups are protonated. The pKa value depends on Chit molecular
weight and degree of acetylation [26].
The mechanism of cathodic EPD is based on the electrophoretic
transport of the protonated Chit-NH+ 3 towards the electrode surface,
where local pH increase resulted in the charge neutralization and depo-
Fig. 2. (a) Reflection photomicrograph of the gold-patterned silicon wafer before
sition of water insoluble films [25]: deposition. (b) Fluorescence photomicrograph of the Chit film, containing fluorescently
labeled nanoparticles electrodeposited onto the patterned gold cathodes. (c) Fluorescence
Chit−NH3 þ þ OH− ! Chit−NH2 ð3:2Þ intensity profile for the image in part b [27]. Reproduced with permission. Copyright
2005 American Chemical Society.

It was shown [27] that functional nanoparticles suspended in Chit

solutions become co-deposited with chitosan (Fig. 1).
This method provided an avenue for the development of advanced
strategies for controlling the surface chemistry of various biomedical
devices, fabrication of patterned films (Fig. 2), biosensors and implants.
The unique feature of Chit, compared to other cationic polyelectro-
lytes, is its relatively low pKa value, which was critically important for
the incorporation of various biologically active molecules into the Chit
Fig. 1. Co-deposition of Chit with functional nanoparticles. Chit chains near the cathode
experience a higher pH and become insoluble (indicated by thick lines), forming a film.
Nanoparticles suspended in the Chit solution become entrapped when Chit is
electrodeposited [27]. Reproduced with permission. Copyright 2005 American Chemical
Society.
matrix [25]. EPD allowed for the fabrication of relatively thick films
from aqueous solutions [25] and co-deposition of Chit with proteins, en-
zymes, other biomolecules and polymers [26–29]. This pH responsive
cathodic neutralization mechanism has been extensively studied and
conditions of the EPD process have been varied. EPD in a mixed
ethanol-water solvent [30–32] allowed for reduced cathodic H2 gas evo-
lution at relatively high voltages, which are required for the electropho-
retic co-deposition of Chit with hydroxyapatite and other materials
[31,32]. The weight of the deposited layer is proportional to applied
voltage, as well as deposition time. However, the hydrogen gas evolu-
tion at the cathode surface leads to air bubble entrapment in the depos-
ited Chit layer, creating a porous film. When the growth rate remains
low, a dense film is formed.
Attention has been paid to the benefits of using alternating current
(AC) rather than direct current for the electrophoretic deposition of
Chit. One advantage of AC EPD is that Chit can be deposited along
with sensitive enzymes or proteins, whose functionality may be
destroyed or inactivated during DC deposition [33]. AC deposition is
also useful when depositing on non-planar substrates, specifically to
get more homogenous coatings on scaffolds for orthopedics or bone
and tissue engineering [33]. A final benefit of AC deposition is that it re-
duces hydrogen bubble formation at the cathode to produce a more ho-
mogeneous layer [33].
Chit forms polymer-metal ion complexes with metal ions in solu-
tions [34]. In such complexes metal ions are attached to the NH2 groups
of Chit. The complexes behave as polyelectrolytes in solutions. The use
of Chit-metal ion complexes allowed the fabrication of composites,

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R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

containing metal oxide or hydroxide particles in the polymer matrix. In

this strategy, the local pH increase facilitated EPD of Chit and
electrosynthesis of metal oxides or hydroxides [34].
Interest in catechol modified Chit (Chit-Cat) was generated follow-
ing the investigation of the outstanding adsorption properties of mussel
adhesive proteins (MAPs), containing catechol groups [35]. The adhe-
sion of MAPs to inorganic materials is attributed to the complexation
of metal atoms on material surfaces by the OH groups of catechol. The
modification of Chit with catechol resulted in advanced properties for
applications in biomedical implants and biosensors [35]. A two-step de-
position method [36] involved cathodic EPD of Chit and an anodic
electro-grafting process. In the electro-grafting step, Chit coated sub-
strates were immersed in catechol solutions and an anodic process
has been utilized for oxidizing the catechol to o-quinone, which cova-
lently reacted with amine groups of Chit [36]. Another deposition
method was based on the one-step EPD mechanism [37]. Chit was mod-
ified with 3,4-dihydroxybenzaldehyde (DHBA) molecules using a Schiff
base reaction before the deposition process. EPD has been utilized
for the deposition of the Chit-Cat, which showed cationic properties in
solutions [37]. The one-step deposition procedure allowed for the
co-EPD of Chit-Cat with other functional materials for biomedical
applications [37].
Deposition of Chit has also been performed by anodic EPD [38]. An-
odic deposition involves a chemical modification of chitosan and forma-
tion of a covalently modified crosslinked gel. The anodic mechanism
begins with the oxidation of Cl- to Cl2. The anodically generated Cl2
then undergoes water hydrolysis to produce hypochlorous acid (HOCl):

−
Cl2 þ H2 O ! HOCl þ Cl þ Hþ ð3:3Þ

HOCl is a very reactive reagent and will partially oxidize Chit to pro-
duce aldehyde species. The aldehyde species readily reacts with amines
to form Schiff base linkages, which produce the covalently crosslinked
Fig. 3. SEM images of cross sections of (a) PLL and (b) PLO films prepared by EPD. F – film,
film [38]. Unlike cathodic deposits, the chemically crosslinked film will S – platinized silicon wafer substrate, arrows show film thickness [42]. Reproduced with
not re-dissolve if introduced to acidic conditions, but will exhibit swell- permission. Copyright 2011 Elsevier.
ing. Another important feature to note is that the aldehyde group gener-
ated from the oxidative reactions are reactive towards amines of
proteins, allowing protein to be deposited with chitosan.

3.2. EPD of chiral polyelectrolytes: poly-l-lysine and poly-l-ornithine

Poly-l-lysine (PLL) and poly-l-ornithine (PLO) are commonly used as

coating agents to promote cell adhesion [39,40]. PLL and PLO are used
for the fabrication of enantiospecific surfaces, which play an important
role in the analytical recognition, separation of racemic compounds
and the fabrication of chiral drugs [41]. The polymers contain amino
groups, which are protonated in acidic solutions. The protonated cat-
ionic macromolecules PLL-H+ and PLO-H+ can be used for cathodic
EPD [42]. The deposition mechanism [42] involved electrophoretic
transport of PLL-H+ and PLO-H+ towards the cathode, where local pH
increase resulted in deprotonation and formation of insoluble films:

PLL−Hþ þ OH− ! PLL þ H2 O ð3:4Þ

Fig. 4. Film mass measured using quartz crystal microbalance versus deposition time for
PLO−Hþ þ OH− ! PLO þ H2 O ð3:5Þ the PLL films prepared from 0.2 g L−1 PLL-H+ solution at deposition voltages of (a) 3 V
and (b) 5 V [42]. Reproduced with permission. Copyright 2011 Elsevier.

This EPD method allowed the formation of uniform films (Fig. 3). The
deposition yield was controlled by polymer concentration, applied volt-
age and deposition time (Fig. 4). A similar mechanism has been used for
the deposition of PLL, modified with catechol [43]. The films of the mod-
ified polymer showed improved adhesion. The deposition method was
used for the surface modification of biomedical implants [43].
3.3. EPD of polyethylenimine
Polyethylenimine (PEI) with either linear or branched chemical
structure has been widely used in different biomedical fields, such as
controlled drug delivery, gene therapy, antimicrobial coatings and

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R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

biomedical imaging [44]. Branched PEI (BPEI) contains primary, second-

ary and tertiary amino groups [45]. BPEI is widely used as a dispersing
and charging agent for the deposition of various materials [46,47]. How-
ever, EPD of pure BPEI films for biomedical applications presents diffi-
culties, because BPEIs are liquids at all molecular weights and BPEIs
are well soluble in water. In contrast, the chemical structure of linear
PEI (LPEI) contains only secondary amines and LPEIs are water insoluble
solids [45]. LPEI was protonated in acidic solutions and dissolved in
water:

LPEI þ Hþ ! LPEI−Hþ ð3:6Þ

The deposition mechanism [45] involved cataphoresis of protonated

LPEI-H+ towards the cathode surface, where local pH increase resulted
in deprotonation and formation of LPEI films:

LPEI−Hþ þ OH− ! LPEI þ H2 O ð3:7Þ

The deposition yield was controlled by variation of LPEI-H+ concen-

tration, deposition time and voltage (Fig. 5).
The method allowed co-EPD of LPEI and bioceramics, drugs and pro-
teins [45,48]. LPEI can be solubilized in solutions of metal salts [48] to
form soluble complexes of LPEI and metal ions (Mz+). The deposition
mechanism is based on the cataphoresis of the cationic complexes
LPEI-Mz+. In this case cathodic deposition of LPEI is combined with
electrosynthesis of nanostructured metal oxides or hydroxides:
LPEI−Mzþ þ zOH− ! LPEI þ MOz=2 þ ðz=2ÞH2 O
LPEI−Mzþ þ zOH− ! LPEI þ MðOHÞz
Fig. 6. SEM image of AlgH film obtained from 1 g L−1 AlgNa solution at a current density of
1mA cm−2 and deposition duration of 5min (A- film; Si-silicon substrate; film cross-
section is shown using arrows) [49]. Reproduced with permission. Copyright 2008 Elsevier
(AlgNa) solutions by a galvanostatic method. The local pH reduction
by anodic reaction (2.17) facilitated film formation. The deposition
mechanism involved electrophoresis of anionic Alg- macromolecules to-
ð3:8Þ ward the anode surface, where local pH decrease allowed for the forma-
tion of water insoluble alginic acid films [49]:
ð3:9Þ −
Alg þ Hþ ! AlgH ð4:1Þ

The use of LPEI complexes [48] is promising for thin film deposition
for biosensor applications.
4. EPD mechanisms of anionic polyelectrolytes
4.1. EPD of alginic acid and alginates
Alginate is a naturally occurring polysaccharide derived from brown
algae. It is a highly attractive polymer for biomedical applications due to
its low toxicity, biocompatibility, biodegradability and low cost [49,50].
Alginate is a promising material for the encapsulation of proteins,
enzymes and drugs, the fabrication of biosensors and coatings for
biomedical implants [51].
It is known [49,52] that alginate is soluble in water and negatively
charged at pH>3. However, it precipitates at lower pH to form a neutral
gel. EPD of alginic acid films was performed [49] from sodium alginate
Film thickness was varied in the range of 0.1–3 μm (Fig. 6) by varia-
tion of deposition time at a constant current density. This method
allowed for the formation of uniform films on various conductive sub-
strates. It was shown [32,49,53] that EPD of AlgH and composites is a
promising method for the surface modification of biomedical implants.
Another strategy (Fig. 7) has been developed for the deposition of
calcium alginate (AlgCa) [54,55]. EPD was performed from AlgNa solu-
tions, containing dispersed CaCO3 particles. The pH decrease at the
anode surface resulted in the dissolution of CaCO3 in the reaction:
CaCO3 þ 2Hþ ! Ca2þ þ H2 O þ CO2 ð4:2Þ
The locally released Ca2+ interacted with Alg- macromolecules accu-
mulated at the electrode surface to form Ca-crosslinked hydrogel net-
work [54]. It was shown that calcium alginate can be deposited

Fig. 5. Images (SEM) of cross-sections of PEI films obtained from 1 g L−1 LPEI-H+ solutions at deposition voltage of 10 V and deposition times of (a) 3 min and (b) 10 min, arrows show film
(F) and conductive Pt layer deposited on silicon substrate (S) [45]. Reproduced with permission. Copyright 2013 Maney

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R. Sikkema, K. Baker and I. Zhitomirsky Advances in Colloid and Interface Science 284 (2020) 102272

Fig. 7. Schematic illustration of the mechanism for calcium alginate electrodeposition. (a) Water electrolysis generates excess protons (H+ ions) at the anode surface. (b) The protons
migrate away from anode and release Ca2+ from CaCO3 particles suspended in solution. (c) The released Ca2+ ions crosslink alginate chains, forming a gel. (d) Overall picture of
electrodeposition of calcium alginate. The proton concentration decreases with the distance away from the electrode surface. The highest concentration of free calcium ions is
associated with the dissolution front of the CaCO3 particles (the interface between dissolved and undissolved CaCO3) during the deposition [55]. Reproduced with permission.
Copyright 2008 The Royal Society of Chemistry

without requiring extreme pH gradient [55]. The ability to form calcium
alginate films at mild pH conditions is beneficial for many biomedical
applications [56]. A three-step electrodeposition mechanism was pro-
posed, which involved proton generation by electrochemical decompo-
sition of water, consumption of protons in reaction with CaCO3,
formation of Ca2+ ions and interaction of alginate with Ca2+ ions [55].
The deposition mechanism was confirmed [55] using pH-
responsible dyes for the analysis of pH gradient, Ca2+ indicator dyes
to investigate the Ca2+ gradient and in-situ Raman spectroscopy for
the detection of Ca2+-alginate interactions. The hydrogel density in-
creased with increasing deposition time. The hydrogel was softer at
the beginning of the deposition process and became harder with in-
creasing deposition time, because H+ generation resulted in a continu-
ous release of Ca2+ ions and enhanced alginate crosslinking. It was
shown [57] that the hydrogel density can be described as an exponential
function of current density and time. Another method allowed for the
fabrication of patterned films by light-addressable EPD [58]. The ap-
proach was based on the application of voltage to a photoconductive
substrate and a counter electrode [58]. Light illumination of a local
point of the substrate generated a conductive point that acted as a
photo-anode to electrochemically produce protons and create a pH gra-
dient. The local pH reduction facilitated dissolution of CaCO3 and
crosslinking of alginate macromolecules accumulated at the local points
under the influence of an electric field [58].
An EPD method [59] has been developed for the deposition of iron
alginate. The deposition mechanism was based on the different coordi-
nation chemistry of Fe2+ and Fe3+ ions [59]. Binding of alginate carbox-
ylate groups by Fe2+ is low, whereas Fe3+ has a strong binding ability.
The deposition mechanism was based on the use of a solution, con-
taining AlgNa and FeSO4. The electrochemical oxidation of Fe2+ re-
sulted in the formation of Fe3+ ions close to the anodic substrate.
The Fe3+ ions acted as crosslinking agents for the alginate gel at
the anode surface. As a result, iron alginate films were obtained by
anodic EPD [59].
The EPD mechanisms of alginate have been utilized for various thin
film applications, such as surface modification of biomedical implants,
biosensors, drug-delivery systems and antimicrobial films [8].
4.2. EPD of hyaluronic acid
Hyaluronic acid (HyH) is a naturally occurring polysaccharide found
abundantly throughout the human body but primarily in the skin, joints
and cornea [60,61]. It is a biodegradable, non-immunogenic, non-
adhesive and bioactive material. The chemical structure of HyH contains
alternating units of glucuronic acid and N-acetylglucosamine [52]. HyH
coatings on biomedical implants provided improved biocompatibility
and bioactivity [62]. The negative charge of hyaluronate at high pH re-
sults from the dissociated COO- group. The pH reduction results in

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R. Sikkema, K. Baker and I. Zhitomirsky
protonation of the COO− groups and charge neutralization. Hyaluronate
exhibits an isoelectric point at pH=2.5[63]. A gel-like behavior was ob-
served at this pH. However, the pH reduction results in the dissolution
of the gel at pH=1.6. Hyaluronate macromolecules exhibited a positive
charge below the isoelectric point due to the protonation of -NH groups
[63]. EPD mechanism [52,62] of the deposition of HyH films from so-
dium hyaluronate (HyNa) solutions involved dissociation of HyNa
HyNa ! Hy− þ Naþ
and electrophoresis of anionic Hy− macromolecules, containing COO−
groups. The accumulation of Hy− at the anode surface and charge neu-
tralization of the COO− groups
Hy− þ Hþ ! HyH
allowed for the formation of HyH films [52,62].
The charge reversal of hyaluronate at very low pH is detrimental for
the anodic EPD of HyH due to the electrostatic electrode-polymer repul-
sion. Therefore, pH variations at the electrode surface must be limited. It
was found that a mixed water-ethanol solvent was beneficial for HyH
deposition [52], because the lower dielectric constant of the mixed sol-
vent facilitated gel formation. In aqueous solutions the deposition rate
was very low for HyNa concentration below 1 g L-1 and increased signif-
icantly in the range of 3-5 g L-1 [62,64]. Film thickness was varied in the
range of 0-20 μm by variation of deposition time at a constant cell volt-
age. A similar approach has been utilized [65] for the deposition of
dopamine-conjugated HyH, which showed improved adhesion to the
substrate, redox-active properties and biocompatibility.
4.3. EPD of polyacrylic acid
Polyacrylic acid (PAA) is a biocompatible polyelectrolyte that is com-
monly used as a dispersant [66]. PAA coatings enhance biocompatibility
and provide corrosion protection of metallic implants. PAA is a promis-
ing material for drug delivery and tissue engineering [66].
PAA is soluble in water and exhibits anionic properties in solutions at
pH > 4. The negative charge of PAA macromolecules is attributed to
deprotonated COO− groups [66]. However, PAA becomes protonated
and insoluble at pH < 4. EPD of PAA was performed [66] from aqueous
PAA solutions at pH=8. The deposition mechanism involved electro-
phoresis of charged dissociated PAA towards the anode surface, where
local pH decrease facilitated protonation and formation of insoluble
PAA films. Excellent coating uniformity (Fig. 8) resulted from the insu-
lating properties of PAA and electric field dependent deposition rate.
Fig. 8. SEM image of a cross-section of a PAA film, deposited on a platinized silicon
substrate from the 1 g L−1 PAA solution at a constant voltage of 5 V and a deposition
time of 2 min [66]. Reproduced with permission. Copyright 2011 Elsevier
Advances in Colloid and Interface Science 284 (2020) 102272
5. EPD of electrically neutral polymers and chemically modified
polymers
5.1. EPD of polyetheretherketone
Polyetheretherketone (PEEK) is a polyaromatic thermoplastic poly-
mer, which exhibits high thermal and chemical stability [67]. It has a
modulus of elasticity similar to that of bone, and good strength, stiffness
and toughness, making it a prime candidate for medical implant devices.
ð4:3Þ
PEEK has been used as a bone replacement material for spinal surgeries,
cranial implants and other orthopedic devices such as screws or plates
[67]. EPD of PEEK has been developed for the fabrication of coatings
on various substrates. Coated metallic or alloy implants showed ad-
vanced mechanical properties, biocompatibility, chemical stability, and
corrosion protection properties [68,69].
Wang et al. [70] showed that PEEK exhibits a pH dependent charge,
ð4:4Þ
which was associated with chemical reactions involving surface car-
bonyl groups. The PEEK particles were positively charged below the iso-
electric point at pH = 5 and negatively charged in the higher pH range
(Fig. 9). The charge of PEEK particles is attributed to the reactions [21],
which involve surface OH groups:
At low pH PEEK−OH þ Hþ ! PEEK−OH2 þ ð5:1Þ
At high pH PEEK−OH þ OH− ! PEEK−O− þ H2 O ð5:2Þ
PEEK films were deposited by anodic EPD from suspensions at pH
above the isoelectric point. However, no cathodic deposition was
achieved at lower pH. The anodic deposition method allowed for good
control of the deposition yield by variation of deposition time or current
density.
Investigations [70] showed advantages of constant current deposi-
tion, compared to constant voltage deposition for the fabrication of
films with improved adhesion and uniformity. Other studies [71,72]
showed that PEEK was negatively charged in the pH range between 2
and 12. As a result, PEEK was deposited anodically at different pH. The
optimum pH for PEEK deposition was found to be pH = 5.5 in ethanol
[70] and pH = 8 in ethanol-isopropanol mixed solvent [73]. It was dem-
onstrated [74] that the difference in isoelectric point data can result
from difference in concentrations of colloidal particles in suspensions.
Deposition yield measurements showed that relatively high deposit
Fig. 9. ζ-potential as a function of pH for PEEK suspension [70]. Reproduced with
permission. Copyright 2003 Elsevier
8
R. Sikkema, K. Baker and I. Zhitomirsky
mass can be achieved [70]. It was found that improved film uniformity
can be achieved from suspensions of low conductivity [73].
Improved dispersion and charging of PEEK particles in suspensions
was achieved using citrate anions [75,76]. The adsorption of citrate on
the PEEK particles resulted in increasing zeta potential of the particles.
The local pH decrease at the anode facilitated particle discharge and co-
agulation [75].
PEEK is a hydrophobic material and fabrication of aqueous suspen-
sions of PEEK presents difficulties. However, the use of surfactants
allowed for the fabrication of aqueous PEEK suspensions for EPD [77].
The addition of a cationic surfactant allowed for the fabrication of posi-
tively charged PEEK particles. The best suspension stability and highest
absolute values of zeta potential were achieved using anionic surfac-
tants. Anodic EPD (Fig. 10) was achieved from aqueous suspensions at
a high deposition rate [77].
Cathodic and anodic EPD of PEEK was also performed using cationic
and anionic polyelectrolytes, which acted as charging and dispersing
agents for PEEK [78,79]. Moreover, polyelectrolytes facilitated the fabri-
cation of adherent films.
5.2. EPD of cellulose
Cellulose is a promising material for biomedical scaffolds, and
wound healing applications [80]. Deposition of cellulose nanocrystals
(CNs) was performed by anodic EPD [81]. It was found [81] that CNs
prepared by hydrolysis with sulfuric acid possess a negative charge at-
tributed to the surface sulfate groups. The presence of these sulfate
groups allowed the fabrication of stable suspensions for EPD and film
formation.
A cathodic EPD method has been developed [82] for the deposition
of quaternized hydroxyethyl cellulose ethoxylate (QHECE) films. The
cationic properties of QHECE resulted from N+(CH3)3 groups. The depo-
sition mechanism involved QHECE electrophoresis and formation of a
gel layer at the electrode surface. The multiple hydroxyl groups of
QHECE facilitated gel formation. The deposition yield was well de-
scribed by the Hamaker equation. Film thickness was varied in the
range of 0.1–7 μm by variation of QHECE concentration and deposition
time at a constant voltage. The use of mixed water-ethanol solvent
allowed for low film porosity, due to reduced H2 evolution at the cath-
ode surface.
An anodic EPD method has been developed [83] for the deposition of
carboxymethyl cellulose (CMCH) from solutions of CMC sodium salt
(CMCNa). The deposition mechanism involved the electrophoresis of
anionic CMC− macromolecules, pH decrease at the electrode surface,
Fig.10. (a) Schematic representation of deposit formation in a glass tube and (b) cross section of the deposit from 30 wt.% PEEK suspension with addition of methyl violet indicator formed
in 10 min [77]. Reproduced with permission. Copyright 2015 Elsevier
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Advances in Colloid and Interface Science 284 (2020) 102272
charge neutralization, and formation of protonated water-insoluble
CMCH film at the electrode surface.
5.3. EPD of polymethylmethacrylate
Polymethylmethacrylate (PMMA) is an important material for vari-
ous applications in ophthalmology, orthopaedic devices, scaffolds, fillers
for bone cavities, drug delivery systems, biosensors, bone and dental ce-
ments [84]. PMMA colloids, prepared by chemical polymerization
methods, showed a negative surface charge in water and were success-
fully deposited by anodic EPD [85,86]. The deposition method allowed
good control of deposition rate and deposit microstructure [85]. Another
method [84] was based on the use of a bile salt, sodium cholate (NaCh),
which served as a multifunctional solubilizing, charging, dispersing and
film-forming agent. Investigations [84] revealed PMMA-Ch− interac-
tions, which facilitated PMMA charging in solutions and deposition of
PMMA films. Two different interaction mechanisms have been sug-
gested [84]. One mechanism involved hydrogen bonding of the PMMA
carbonyl group and hydroxyl group of Ch−. Another mechanism is re-
lated to the unique amphiphilic structure of cholic acid. It involved the
attraction of the hydrophobic side of Ch− to PMMA. The charged hydro-
philic side of Ch− governed the PMMA solubility in water and its electro-
kinetic properties. The adsorbed Ch− imparted a negative charge to the
PMMA molecules, which electromigrated to the anode under the influ-
ence of an electric field. The discharge of the Ch− species in the low pH
region at the electrode surface
−
Ch þ Hþ ! ChH ð5:3Þ
allowed for the film formation [84].These mechanisms successfully
produced thin PMMA films with improved deposition control.
5.4. EPD of polyaniline and polypyrrole
Polyaniline (PANI) and polypyrrole (PPy) are advanced materials for
biosensing applications due to their high conductivity and redox prop-
erties. PANI films were obtained by cathodic EPD [87,88]. In this
method, PANI in the emeraldine base form was dissolved in formic
acid (Fig. 11). Formic acid protonated PANI at the amine sites,
converting it into the conducting form [88]. The solution of PANI in
formic acid was dispersed in acetonitrile. However, PANI is insoluble
in acetonitrile. As a result, PANI formed spherical particles with a typical
size of ~100 nm in the acetonitrile solvent. The particles were positively
charged due to PANI dissociation in acetonitrile. The colloidal
R. Sikkema, K. Baker and I. Zhitomirsky
Fig. 11. Formation of polyaniline colloids by dispersing polyaniline/formic acid solution into acetonitrile [88]. Reproduced with permission. Copyright 2005 The American Chemical Society
suspensions of positively charged particles were used for film formation
by cathodic EPD. It was shown [88] that the key aspect of this EPD
method lies in the unique combination of formic acid and acetonitrile.
The method allowed for good control of the deposition yield and film
morphology.
AC deposition allowed for improved film quality, compared to DC
deposition [89]. PANI fibers in the dedoped form exhibited a negative
charge in water and were deposited by anodic EPD [90]. PPy particles
were functionalized and dispersed in water using chlorophyll molecules
[91]. The functionalized PPy was cathodically co-deposited with
bioceramics.
5.5. EPD of poly(tetrafluoroethylene)
Poly(tetrafluoroethylene) (PTFE) is an important material for bio-
medical implant applications [92]. Many PTFE applications are based
on the use of thin films and coatings [93,94]. It was found that PTFE ac-
quired a negative charge in ethanol [75]. However, PTFE suspensions
were unstable and produced electrophoretic deposits of low quality
[75]. Improved suspension stability was achieved using polyvinylpyr-
rolidone (PVP) as a steric dispersant. PVP adsorption on PTFE involved
interactions between fluorine atoms of PTFE and hydrogen atoms of
PVP. However, PVP adsorption resulted in a reduced zeta potential of
PTFE [75]. PTFE charging and dispersion were also achieved using an-
ionic surfactants, such as sodium dodecyl benzene sulfonate [95]. The
anionic surfactant adsorbed on PTFE particles in the suspensions and
enhanced their electromigration towards the electrode surface.
EPD of PTFE was performed using natural surfactants, such as
bile acids (BAH) and bile acid sodium salts (BANa). Sodium cholate
(ChNa) [96], sodium deoxycholate (DChNa) [97] and sodium chenode-
oxycholate (CDChNa) [98] were used as charging and dispersing agents
for PTFE. The strong dispersion power of BAH and BANa is related to
their anionic properties and amphiphilic chemical structure, containing
a steroid nucleus with concave hydrophilic and convex hydrophobic
sides. The deposition mechanism involved anaphoresis of PTFE parti-
cles, containing adsorbed Ch−, DCh− and CDCh−. The local pH decrease
at the anode surface resulted in charge neutralization:
BA− þ Hþ ! BAH
where BA− = Ch−, DCh− and CDCh− . Charge neutralization allowed
the coagulation of PTFE particles and formation of PTFE films. The
Advances in Colloid and Interface Science 284 (2020) 102272
insolubility of BAH in water and film forming properties of BAH were
beneficial for the formation of adherent continuous PTFE films (Fig.
12), which provided corrosion protection of stainless steel substrates.
Lithocholic acid (LChH) [99] was used for the dispersion and charging
of PTFE in ethanol. In this method, LChH acted as a dispersing and charg-
ing agent for EPD of PTFE. These mechanisms provide methods for de-
veloping more stable and improved films by EPD.
6. EPD of proteins
6.1. Colloidal behavior of proteins
Proteins consist of amino acids and exhibit a pH-dependent charge.
The protonation of amino groups of proteins at low pH results in a
total positive charge, whereas the proteins acquire a negative charge
at high pH due to deprotonation of carboxylic groups. Proteins have dif-
ferent isoelectric points depending on their structure. EPD of proteins
presents difficulties due to charge reversal at the isoelectric points. Pro-
tein macromolecules are positively charged in solutions at a pH below
the isoelectric point and electromigrate towards the cathode. However,
charge reversal occurs in the high pH region at the cathode surface.
Therefore, electrostatic repulsion of the protein molecules and cathodic
substrate prevents deposit formation. In contrast, protein macromole-
cules are negatively charged in solutions at a pH above the isoelectric
point and electromigrate towards the anode. However, charge reversal
of the proteins in the low pH region at the anode surface prevents depo-
sition due to electrostatic repulsion of the positively charged protein
macromolecules and positively charged anodic substrate. EPD of pro-
teins and enzymes is usually performed from aqueous solutions at
mild pH conditions in order to keep their biological functionality.
6.2. EPD of collagen
Collagen is a major protein found in bones and connective tissues.
Collagen has been widely used in a number [100,101] of forms as a bio-
material due to its high biocompatibility. In orthopedic surgery collagen
has been applied in bone grafts and implant coatings for replacing bone
ð5:4Þ defects.
Many investigations were focused on the co-deposition of collagen
with other materials and the development of deposition mechanism.
The isoelectric point of collagen reported in literature [102] varied in
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R. Sikkema, K. Baker and I. Zhitomirsky
Fig. 12. SEM images of films, prepared from 1 g L−1 DChNa solutions, containing 5 g L−1 PTFE at a cell voltage of 50 V and annealed at 350 °C [97]. Reproduced with permission. Copyright
2020 Elsevier.
the range of 4.8-9 depending on the source of collagen. The application
of an electric field to the collagen solutions at pH below the isoelectric
point resulted in collagen fibril accumulation at a finite distance away
from the cathode [103]. This was attributed to the charge reversal of
the collagen in the high pH region close to the cathode surface. How-
ever, film deposition was achieved in the presence of Ca2+ ions in the
solutions. It was found that the presence of Ca2+ ions enhanced the as-
sembly of collagen at the cathode. Composite calcium phosphate-
collagen films were obtained [103]. Ling et al. [104] combined
electrosynthesis of calcium phosphate and EPD of collagen and
highlighted the influence of collagen-calcium phosphate interactions
for the incorporation of collagen into the composite films. At the high
pH region at the cathode surface the charged COO− groups of collagen
served as nucleation sites for the calcium phosphate crystals. In this
mechanism [104], mineralization of collagen at the cathode surface
was achieved and mineralized collagen fibers or sheets were deposited
cathodically. Another study [105] suggested the formation of composite
calcium phosphate-collagen coatings occurred in several stages, includ-
ing formation of a thin calcium phosphate layer, cathodic self-assembly
of collagen fibrils, and formation of composites. Yang et al. [106] sug-
gested the formation of collagen-phosphate complex ions, which
interacted with Ca2+ ions at the cathode surface to form a collagen-
calcium phosphate composite. It was found that collagen-substrate
chemical interactions play an important role in the collagen deposition
[107]. Further development of this mechanism [108] allowed the fabri-
cation of mineralized collagen coatings with controlled loading of bo-
vine serum albumin (BSA), which co-mineralized with collagen. The
BSA content in the coating was varied by the variation of electrode po-
tential and pH gradient. Magnetically assisted EPD [109] allowed the de-
position of aligned collagen nanofibers. The use of magnetic iron oxide
nanoparticles and their interactions with collagen facilitated the forma-
tion of the aligned structures. The coatings showed promising perfor-
mance for various applications in tissue engineering. The investigation
[110] of electroadsorption of collagen showed that collagen structure
near an electrified interface is influenced by the electric field.
Cationic collagen was obtained through the modification of the car-
boxyl groups by esterification with methanol. The esterification resulted
in the shift of the isoelectric point to higher pH values and facilitated
cathodic deposition [111].
Collagen films were obtained in a conventional electrochemical cell
without the need for a supporting substrate [112]. The mechanism of
film formation was based on the pH-dependent charge of collagen and
creation of an alkaline-acidic interface in the electrochemical cell. Film
location was controlled by adjusting the bulk electrolyte pH and
electrosynthesized films remained intact upon drying [112]. This
method has been utilized for the fabrication of collagen membranes.
The speed of membrane formation, mechanical and other properties
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Advances in Colloid and Interface Science 284 (2020) 102272
can be adjusted by the variation of cell geometry, applied voltage and
electrolyte composition [113,114].
6.3. EPD of gelatin
Gelatin is a mixture of water-soluble proteins of high average molec-
ular masses, present in collagen. Gelatin is widely used for food, phar-
maceutical, sensor and food applications [115]. EPD of gelatin was
achieved using Fmoc-phenylalanine (Fmoc-Phe) as a pH-responsive
gel-forming agent. EPD was performed at 37°C from a bath, containing
gelatin and Fmoc-Phe. The use of hydroquinone allowed low pH gener-
ation at the anode surface at a reduced potential. The pH reduction re-
sulted in sol-gel transition of Fmoc-Phe. It was found that the obtained
gel contained gelatin. Upon cooling, the gelatin chains undergo a sepa-
rate sol-gel transition. After gelatin forms a gel network, the Fmoc-
Phe can be removed by leaching with pH 8 buffer [115].
6.4. EPD of bovine serum albumin
In many investigations bovine serum albumin (BSA) was used as a
model protein for the development of EPD. Alternating current (AC)
EPD is a promising method for BSA deposition [116]. The interest in
AC EPD is attributed to the possibility to reduce gas evolution and pH
changes at the electrode surface. It is in this regard, accumulation of
BSA at the electrode surface presents difficulties due to pH changes at
cathode and anode, which result in charge reversal of BSA at the elec-
trode surface. In order to concentrate BSA at the electrode surface AC
signals of an asymmetrical wave shape were applied [117]. The com-
bined effect of AC and DC signals resulted in significant increase of the
deposition yield. In this approach gas bubble formation was suppressed
and electrode pH shift was reduced [117].
6.5. EPD of other proteins and enzymes
Zein is a promising biocompatible protein for biomedical and phar-
maceutical applications [118]. Zein films were deposited by anodic
EPD from solutions in 90% ethanol [118]. It was found that the increase
in deposition voltage resulted in improved mechanical properties and
water resistance of the film. This effect partially resulted from the orien-
tation of the molecules in an electric field. It was suggested that zein
precipitates at the electrode surface at a local pH~5–6 [119].
Mussel adhesive protein (Mefp-1) [120] is a promising material for
biomedical implant applications due to excellent adhesion to different
substrates, biocompatibility and corrosion protection properties. Mefp-
1 showed a positive charge in solutions and was deposited by cathodic
EPD [120].
R. Sikkema, K. Baker and I. Zhitomirsky
Pronectin F+ (PN) is an artificial protein, which exhibits excellent
cell-adhesive properties. The cationic properties of PN allowed for the
deposition of PN films by cathodic EPD [121].
Silk fibroin (SF) is an important protein for the surface modification
of biomedical implants, because SF exhibits antithrombogenic proper-
ties and promotes cell adhesion and tissue repair [122].
SF nanospheres were deposited by anodic EPD [122–124]. SF
showed a negative charge at pH > 5 and a positive charge at pH < 3.
The SF nanospheres formed stable suspensions at pH > 5. The optimiza-
tion of SF concentration, deposition voltage and current allowed the op-
timization of pH at the anode surface and fabrication of films by EPD
[122]. The deposition mechanism involved SF charge neutralization by
H+ generated in anodic electrode reactions. The application of an elec-
tric field resulted in alignment of SF molecules, which allowed the fab-
rication of adherent films [125].
SF has also been co-deposited with octacalcium phosphate (OCP) by
cathodic EPD [126]. In this mechanism, SF was positively charged in the
solution and acquired a negative charge at the electrode surface. The
negatively charged SF interacted with positively charged Ca2+ ions
and basic amino groups of SF interacted with phosphate anions,
resulting in the co-precipitation of SF and OCP [126]. Zhang et al.
showed that SF can be positively charged by covalent coupling with tet-
racycline and deposited by cathodic EPD [127].
Many investigations focused on the deposition of enzymes for appli-
cation in biosensors. Different strategies have been developed to avoid
problems related to the charge reversal at the electrode surface. EPD
of glucose oxidase (GO) was performed by a constant voltage anodic
EPD method, which involved the use of anodic pH gradient [128]. EPD
of GO, catalase and other enzymes was achieved using asymmetrical al-
ternating voltages [129–131]. It was found that migration of GO in an
electric field is related to signal asymmetry. The deposition was
achieved only on one of the two electrodes. When the electric signal
was inversed the deposition was observed on the other electrode
[129]. Cathodic EPD of enzymes was combined with electrosynthesis
of ZnO [132]. This strategy was based on chemical interaction of ZnO
and enzymes, which allowed for enzymes immobilization and deposi-
tion. It is important to note that the high isoelectric point of ZnO is an-
other beneficial factor for enzyme immobilization, because
electrostatic attraction can facilitate immobilization. EPD of GO was
also enhanced in the presence of a non-ionic detergent [133], which
allowed for reduction of GO agglomeration and modification of the sur-
face pH gradient at the anode surface.
7. Co-EPD of polymers and proteins
7.1. Co-EPD of chitosan with other polymers and proteins
Chit was used for the surface modification of monodispersed poly-
styrene colloidal particles [134]. The adsorbed Chit imparted a charge
to the particles and allowed for their cathodic EPD [134]. Chit has
been utilized as a charged carrier for EPD of polyethylene oxide (PEO)
[135]. The deposition mechanism [135] involved the formation of
charged Chit-PEO complexes, which facilitated co-EPD of both
polymers.
Investigations of hemoglobin deposition showed that the reversal of
the hemoglobin charge at the electrode surface prevented film forma-
tion [136]. However, hemoglobin was co-deposited with chitosan for
application in thin film biosensors. It was found that chemical and elec-
trostatic interactions of Chit and hemoglobin facilitated their co-
deposition [136]. The proposed mechanisms of co-deposition of Chit
and gelatin involved complexation and electrostatic interactions
[137–139] which promoted the formation of composite films. It was
shown that Chit-gelatin interactions and co-deposition rates are influ-
enced by the molecular weights of both materials [139]. The addition
of H2O2 to the EPD bath allowed for pH gradient generation without
generation of H2 bubbles, which improved coating morphology [140].
12
Advances in Colloid and Interface Science 284 (2020) 102272
Chit-gelatin films prepared by EPD were cross-linked with different or-
ganic molecules [140,141]. The ability to control the coating composi-
tion and morphology by variation of the deposition conditions
allowed the development of advanced coatings, which showed
enhanced cell adhesive response [142].
Chit has also been co-deposited with SF, heparin and albumin by ca-
thodic EPD [143–145]. The proposed deposition mechanism involved
the formation of complexes [145]. The addition of negatively charged
SF to the solution of positively charged Chit resulted in formation of pos-
itively charged complexes. The zeta potential of the complexes was
lower than that of Chit due to partial compensation of the positive
charge of Chit by the negative charge of SF. The formation of the com-
plexes was also confirmed by the larger size of the complexes, com-
pared to the size of Chit or SF alone [143]. The composite coating
showed increased shear and tensile bond strength and enhanced
biocompatibility.
Chit provided a suitable matrix for the incorporation of various en-
zymes by cathodic EPD from mixed solutions of Chit and enzymes
[146–149]. Chit and GO were also crosslinked [150] with low-
concentration glutaraldehyde to facilitate their co-deposition. The com-
posite films showed promising performance for applications in
biosensors.
7.2. Co-EPD of alginate with other polymers and proteins
Alginate was used as a charging, dispersing and film-forming agent
for EPD of other polymers or proteins from mixed solutions or suspen-
sions of polymer particles in alginate solutions. Polyvinyl alcohol
(PVA) is an electrically neutral polymer. PVA was co-deposited with
alginic acid from mixed solutions [151]. It was suggested that interac-
tions of PVA and alginate resulted in interpenetrating charged polymer
networks of anionic alginate and electrically neutral PVA. In this model
[151], alginate dragged PVA toward the anode and facilitated the fabri-
cation of composite PVA-AlgH films. In another investigation [152], co-
EPD from mixed solutions of anionic alginate and anionic hyaluronate
allowed for the deposition of composite AlgH-HyH and AlgH-heparin
films.
Anodic EPD has been developed for the fabrication of composite
AlgH-CNs films [81]. CNs exhibited a negative charge in suspensions,
which resulted from the method of their preparation. Alginate facili-
tated CNs dispersion and allowed the formation of adherent composite
films.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) micro-
spheres (MS), loaded with antibiotic were successfully co-deposited
with AlgH [153]. It was suggested that interactions of COO− groups of
alginate and carbonyl groups of PHBV facilitated Alg− adsorption on
the MS and allowed their transport to the substrate surface. The deposi-
tion mechanism of composite AlgH-PHBV films involved two separate
processes: EPD of alginate adsorbed on PHBV MS and EPD of non-
adsorbed alginate. Investigations [153] showed that the MS content in
the films was proportional to the MS concentration in the suspensions
in agreement with the Hamaker equation.
AlgH was co-deposited with myoglobin (Mb) [154] by electrochem-
ical cycling in the potential range between –1.1 and +1.0 V versus sat-
urated calomel electrode. It was shown that the formation of AlgH gel at
positive potentials facilitated the formation of Mb loaded AlgH for
the application in biosensors. Constant voltage EPD was used for
co-deposition of AlgH with glucose oxidase [148], horseradish peroxi-
dase [155], albumin [144] and hemoglobin [156] for application in
biosensors.
EPD method allowed for the co-deposition of calcium alginate with
agarose [157] and hemoglobin [158] from mixed solutions. Iron alginate
was co-deposited with various biomolecules such as bovine serum albu-
min [59], lysozyme [159] and DNA [160]. Obtained films were used for
electrochemically triggered biomolecule release.
R. Sikkema, K. Baker and I. Zhitomirsky
7.3. Co-EPD of hyaluronic acid with other polymers and proteins
Anodic EPD of HyH was combined with electropolymerization of
polydopamine(PDA) for the fabrication of PDA-HyH films, which
showed improved properties for various applications, including im-
plantable bioelectrodes, biosensors, and prosthetics [161]. Anodic EPD
of HyH was combined [162] with electropolymerization of poly(3,4-
ethylenedioxythiophene) (PEDOT) for the fabrication of composite
HyH-PEDOT films for application in biosensors. In the proposed deposi-
tion mechanism anionic HyH was used as a dopant for PEDOT
electropolymerization.
HyH was co-deposited with BSA from aqueous solutions for applica-
tion in biomedical implants [64]. Constant voltage anodic EPD allowed
for the fabrication of composite films of controlled thickness in the
range of 0–80 μm. The proposed deposition mechanism [64] was
based on chemical interactions of HyNa and BSA, which resulted in
the formation of complexes [163]:
nBSA þ mHyNa ! ðnBSAÞðmHy− Þ þ mNaþ
The total charge of BSA is negative at pH above its isoelectric point
(pH~5) [64]. Therefore, electrostatic repulsion can be expected between
negatively charged BSA and Hy− at pH > 5 in aqueous solutions. How-
ever, localized bonding of Hy− to cationic sites of BSA can be expected at
pH > 5. The total charge of BSA is positive at pH < 5 and electrostatic at-
traction of cationic BSA and anionic Hy− promoted complex formation.
The BSA–hyaluronate complexes [163,164] are soluble in neutral or
weakly acidic solutions and precipitate in more acidic solutions at pH <
5. It was suggested [64] that the co-deposition mechanism of HyH and
BSA was associated with (nBSA)(mHy−) complex formation. In bulk so-
lutions an electric field provided electrophoresis of anionic BSA and Hy−
or (nBSA)(mHy−) complexes towards the anode, where low pH at the
surface promoted the formation of (nBSA)(mHy−) complexes and co-
deposition [64] of BSA and HyH. A similar approach has been developed
for co-deposition of hemoglobin and HyH [156]. The addition of
Fig. 13. Schematic of the co-EPD mechanism of Hb or BSA with anionic PSM. The deposition mechanism involves electrophoretic transport of negatively charged proteins and PSM toward
the anode in the basic bulk solutions, their accumulation at the electrode surface, charge reversal of the proteins, electrostatic coagulation and film formation [166]. Reproduced with
permission. Copyright 2017 Elsevier.
Advances in Colloid and Interface Science 284 (2020) 102272
hemoglobin to the HyNa solutions resulted in a significant increase of
the deposition rate due to co-deposition of both materials. Film thick-
ness was varied in the range of 10–50 μm [156]. Sun et al. [165] reported
the formation of mixed micelles of hyaluronic acid-g-dopamine (Hya-g-
DA) and bovine hemoglobin (BHb) in aqueous solutions. The formation
of charged mixed micelles in the bulk solutions facilitated the EPD of the
HyH-g-DA – BHb coatings for biomedical applications.
8. EPD of other polymers and polymer-protein composites
Poly(styrene-alt-maleic acid) (PSM) and polygalacturonic acid
(PGA) exhibit a number of unique properties, which are important for
diverse biomedical applications, including biosensors, implants and
drug delivery [166,167]. PSM and PGA were deposited by anodic EPD
method, which was based on the local pH decrease at the anode surface
[166,167]. An EPD method has been developed for the co-deposition of
PSM with BSA and Hb [166]. PSM created non-covalent bonds with BSA
and Hb and anodic deposits were obtained by electrophoresis and elec-
ð7:1Þ trostatic heterocoagulation (Fig. 13) of positively charged BSA or Hb
with anionic PSM at the anode surface [166]. PGA was co-deposited
with other functional materials, such as drugs, antimicrobial agents,
bioceramics and bioglass [167]. PAA was used as a charging agent for
the deposition of poly (D,L-lactide-co-glycolic acid) for biomedical
stents [168]. Poly(caprolactone) was deposited by cathodic EPD [169]
using triethanolamine as a charging agent and obtained coatings were
used for corrosion protection of biomedical implants.
Polyethylene glycol (PEG) is an important polymer for the develop-
ment of antifouling surfaces. PEG coatings are used to reduce adsorption
of proteins and platelets and to prevent bacterial adhesion. PEG was
modified with cationic amino groups [170–173] and anionic carboxylic
groups [172] for film formation by cathodic and anodic EPD, respec-
tively. PEG molecules for cathodic EPD [174–176] were also terminated
with NH2 groups on both terminals (NH2-PEG-NH2). Improved coating
morphology and enhanced antifouling properties were obtained using
pulse deposition [177]. The deposition mechanism was similar to that
13
R. Sikkema, K. Baker and I. Zhitomirsky
of other polyelectrolytes, containing amino and carboxylic groups. PEG
zwitterions [178,179] were synthesized and used for cathodic EPD.
Such zwitterions contained amino and carboxylic groups on different
terminals (NH2-PEG-COOH). The interactions of such groups facilitated
coating formation [178]. PEG forms coordination bonds with metal ions
in solutions and acquires a positive charge, which allows cathodic EPD
of PEG to be combined with electrosynthesis of metal hydroxides [180].
9. Conclusions and future trends
EPD of biopolymers, proteins and enzymes is an area of significant
research interest, which is motivated by various biomedical applica-
tions. Cathodic EPD mechanisms have been developed for deposition
of Chit, PLL, PLO and PEI. Different strategies have been developed for
the deposition of chemically modified cationic polymers, which are ben-
eficial for the fabrication of films with enhanced adhesion for biomedi-
cal implants and advanced redox properties for application in
biosensors. The use of charged polymer-metal ion complexes for ca-
thodic EPD is a promising avenue for the development of advanced
composites. Novel EPD mechanisms have also been developed for the
deposition of composites, which are based on the use of complexes of
the cationic polymers with functional organic molecules.
Various mechanisms have been discovered for anodic EPD of algi-
nates, hyaluronates, polyacrylic acid and other anionic polymers. The
success in the anodic EPD of the anionic biopolymers and their applica-
tions has driven the development of chemically modified polymers with
anionic groups and application of anodic EPD for their deposition. Sig-
nificant progress has been achieved in co-deposition of anionic poly-
mers with other functional materials.
Remarkable advances have been achieved in the EPD of proteins and
enzymes, which are promising for the surface modification of biomedi-
cal implants and development of advanced biosensors. An important
EPD avenue resulted from the use of cationic and anionic polymers for
the fabrication of composite coatings, containing proteins and enzymes.
In this approach, the problems related to charge reversal at the elec-
trode surface can be avoided.
Significant advances have been achieved in EPD of electrically neu-
tral polymers, such as PEEK, PPy, PANI, PMMA and PTFE. The use of poly-
electrolytes, such as cationic Chit or anionic AlgNa is a promising avenue
for the charging and deposition of neutral polymers. The growing colloi-
dal science of advanced natural dispersants provided mechanisms for
the use of bile salts as efficient charging, dispersing and film forming
agents for EPD of PMMA and PTFE. It is expected that further progress
in understanding of the fundamental properties of bile salts and their in-
teractions with polymers in colloidal solutions will result in the devel-
opment of new mechanisms and EPD of other functional biopolymers.
Despite the impressive progress achieved in the EPD of polymers for
biomedical applications, further scientific and technological advances
are necessary. The primary research drive in this area is the need for
EPD of electrically neutral functional polymers. Further advances can
be achieved by the development of biocompatible and natural dispers-
ing and charging agents.
Several advanced polymers are of particular interest for biomedical
EPD applications, such as poly(ε-caprolactone), polypropylene and
other electrically neutral polymers. Many investigations in EPD of such
polymers are focused on non-biomedical applications, due to the use
of toxic solvents or non-biocompatible charged additives. For example,
polyvinylidene fluoride (PVDF) and poly(vinylidene fluoride-co-
trifluoroethylene) P(VDF-TrFE) are important materials for application
in biosensors and medical implantable devices [181–183]. The interest
in various applications of PVDF and P(VDF-TrFE) is attributed to their
good chemical stability and advanced ferroelectric, piezoelectric, and
mechanical properties. EPD of PVDF and P(VDF-TrFE) films was per-
formed for antibiotic biosensors [181], piezoelectric, energy harvesting
[184], energy storage [185,186] and other [187] applications. PVDF par-
ticles were charged using the chemical reaction [185] of acetone and I2,
14
Advances in Colloid and Interface Science 284 (2020) 102272
which resulted in H+ generation and its adsorption on the particles.
However, this approach can result in deposit contamination and corro-
sion of electrodes. Poor dispersion of PVDF and P(VDF-TrFE) is a bottle-
neck hindering the deposition of such polymers for applications in
implantable devices and sensors. This problem must be addressed by
the development of efficient biocompatible charged dispersants and
new EPD mechanisms.
The use of co-polymers for EPD is a promising strategy for the devel-
opment of films and coatings for various biomedical applications. How-
ever, insufficient attention has been paid in the literature to the
synthesis and application of functional co-polymers, containing cationic
and anionic charged groups. Especially promising are fundamental in-
vestigations, focused on interactions of polymers with polyelectrolytes
and natural surfactants in colloidal solutions. It is expected that further
progress in this field will results in advanced mechanisms and novel
applications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This work was supported by the Natural Sciences and Engineering
Research Council of Canada.
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