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Membranes www.afm-journal.de

Dopamine: Just the Right Medicine for Membranes


Hao-Cheng Yang, Ruben Z. Waldman, Ming-Bang Wu, Jingwei Hou, Lin Chen,
Seth B. Darling,* and Zhi-Kang Xu*

in molecular structure to the dihydroxy-


Mussel-inspired chemistry has attracted widespread interest in membrane phenylalanine in mussel foot proteins,
science and technology. Demonstrating the rapid growth of this field over which has been revealed to be responsible
the past several years, substantial progress has been achieved in both for the strong adhesive capacity of mus-
mussel-inspired chemistry and membrane surface engineering based on sels onto marine substrates. PDA has
been found to adhere onto nearly all kinds
mussel-inspired coatings. At this stage, it is valuable to summarize the most
of substrates, including some challenging
recent and distinctive developments, as well as to frame the challenges and low-surface-energy ones, via similar prin-
opportunities remaining in this field. In this review, recent advances in rapid ciples. The adhesive mechanism is caused
and controllable deposition of mussel-inspired coatings, dopamine-assisted by a few different interactions including
codeposition technology, and photoinitiated grafting directly on mussel- hydrogen bonds, chelation, electro-
static and hydrophobic interactions.[2,3]
inspired coatings are presented. Some of these technologies have not yet
Significantly, PDA coatings offer a chemi-
been employed directly in membrane science. Beyond discussing advances in cally and physically versatile platform for
conventional membrane processes, emerging applications of mussel-inspired further modification (Scheme 1).[4] For
coatings in membranes are discussed, including as a skin layer in nanofiltra- instance, the catechol groups can form
tion, interlayer in metal-organic framework based membranes, hydrophilic covalent bonds with thiol- or amino-
layer in Janus membranes, and protective layer in catalytic membranes. terminated reagents through Michael
addition or Schiff base reactions, which
Finally, some critical unsolved challenges are raised in this field and some
is useful to graft polymers, small mole­
potential pathways are proposed to address them. cules, and biomolecules onto PDA-
coated surfaces.[5,6] PDA coatings can
chelate metal ions and can coordinate
with metal/metal oxide nanoparticles from the solution,
1. Introduction
which can initiate further mineralization or metallization.[7,8]
It has been ten years since the first report concerning mussel- These systems can act as a hydrogen bond donor and also
inspired chemistry for surface modification was published.[1] interact with charged molecules through electrostatic inter-
In the past decade, mussel-inspired chemistry has attracted actions.[9] Moreover, the phenol structure endows PDA with
immense research effort and become a hot research focus in strong reducibility, which can directly reduce silver nitrate
materials science. Dopamine, a well-known neurotransmitter (a strong oxidant) to silver nanoparticles after chelating silver
in the human body, can self-polymerize to form polydopamine ions from solution.[10] These diverse features render PDA a
(PDA) in weak alkaline solutions with the participation of powerful tool to adjust the surface properties of materials.
oxygen, and form a surface coating on a variety of material sur- Membranes are 2D porous materials with permselectivity,
faces under ambient temperature. Dopamine is quite similar and have a large surface area directly contacting and interacting

Dr. H.-C. Yang, Dr. S. B. Darling Dr. J. Hou


Nanoscience and Technology Division UNESCO Centre for Membrane Science and Technology
Argonne National Laboratory School of Chemical Engineering
Lemont, IL 60439, USA University of New South Wales
E-mail: darling@anl.gov Sydney 2052, Australia
R. Z. Waldman, Dr. S. B. Darling Dr. J. Hou
Institute for Molecular Engineering Department of Materials Science and Metallurgy
University of Chicago University of Cambridge
Chicago, IL 60637, USA Cambridge CB3 0FS, UK
M.-B. Wu, Prof. Z.-K. Xu L. Chen
MOE Key Laboratory of Macromolecular Synthesis Energy Systems Division
and Functionalization Argonne National Laboratory
Department of Polymer Science and Engineering Lemont, IL 60439, USA
Zhejiang University Dr. S. B. Darling
Hangzhou 310027, China Institute for Molecular Engineering
E-mail: xuzk@zju.edu.cn Argonne National Laboratory
Lemont, IL 60439, USA
DOI: 10.1002/adfm.201705327

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Scheme 1. Possible paths for further functionalization of polydopamine coatings.

with a fluid medium.[11,12] Therefore, the properties of mem- membranes based on mussel-inspired chemistry.[25] In that
brane surfaces profoundly impact membrane performance review, we summarized the polymerization and adhesion
across different applications and processes. Although many mechanisms of mussel-inspired chemistry, and demonstrated
surface modification strategies for membranes have been the role of these materials in contexts that include: membrane
developed over the past decades including surface coating,[13] surface coatings, interlayers for membrane modifications, and
grafting[14–18] and assembling,[19] it remains a challenge to selective layers or fillers in membrane fabrication (Scheme 2).
modify membrane surfaces uniformly and controllably.[20,21] Despite the promise offered by such materials, several fac-
This is especially true for commercial membranes com- tors limit their widespread application in membrane technolo-
posed of low-surface-energy polymers such as polyethylene gies. These drawbacks include tedious deposition times, the
(PE), polypropylene (PP), polyvinylidene fluoride (PVDF) and unavoidable formation of PDA aggregates, and poor coating
polytetrafluoroethylene (PTFE).[22] Therefore, mussel-inspired stability in strongly acidic or alkaline environments. Many
deposition is of particular interest to the membrane research groups have spent effort attempting to address one or more
community for its facile technical processing, broad applica- of these issues by moving beyond the conventional dopamine
bility to various substrates including the low-surface-energy deposition.
ones,[23,24] and broad potential for postfunctionalization for Over the past three years, great progress has been achieved
diverse uses. In 2015, we first reviewed the fundamentals in this field, and we believe it is time to highlight the most
and major developments in surface engineering of polymer significant progress made in addressing the limitations of

Scheme 2. Roles dopamine/polydopamine play in membrane science.

Adv. Funct. Mater. 2018, 1705327 1705327 (2 of 14) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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PDA-modifications in membrane science. This review will Wei et al. used ammonium persulfate as an oxidant to facili-
focus on the latest representative developments, particularly tate dopamine deposition. This approach not only accelerates
those from the past three years. We hope this review will help the dopamine oxidation and polymerization, but also enables
clarify the remaining challenges in mussel-inspired surface and the deposition to be conducted under neutral or even acidic
interface engineering of polymer membranes. conditions (the conventional dopamine polymerization can be
This review will be divided into three parts. In the first only performed in alkaline solution).[27] Lee’s group presented
section, we will present some exciting advances in mussel- an ultrafast deposition process by adding sodium periodate to
inspired surface chemistry, some of which may not yet have the dopamine solution. The mixed solution was sprayed onto
been applied in membrane science. In the second section, we polyethylene battery separators and formed a PDA coating
present the emerging developments of mussel-inspired chem- within one minute. However, this method cannot adequately
istry in membrane manufacture and applications. Finally, we decorate the inner pores of the membranes because the coating
discuss the major challenges remaining in this field and some forms too fast—the aqueous solution cannot easily diffuse into
potential opportunities in future research. the inner pores via spray-coating.[28] To address this issue, our
group developed a dip-coating technology using CuSO4/H2O2
as the oxidant.[29] The generated free radicals promoted the
2. Recent Advances in Mussel-Inspired dopamine polymerization and shortened the deposition time to
around 10 minutes. Even hydrophobic membranes can be inte-
Surface Chemistry
grally modified by this approach if prewetted by ethanol before
Recent advances in mussel-inspired chemistry provide deposition. Moreover, extraneous free radicals can improve the
researchers with new approaches to functionalize polymer proportion of covalent bonds in PDA coatings, enhancing their
membranes more easily, efficiently, and diversely. In this stability in both polar solvents and acidic or alkaline solutions.
section, we will first introduce the latest developments in rapid Lastly, the Cu2+ ions embedded in the PDA coating endowed
and controllable deposition of PDA. We then turn to dopa- the membrane with excellent antibacterial properties.
mine-assisted codeposition, which can overcome the intrinsic Beyond the use of oxidants, the deposition rate can be also
deficiencies of dopamine deposition and broaden the surface promoted by codepositing dopamine with reactive components.
properties of resulting coatings. Lastly, we highlight photoini- For example, polyethyleneimine (PEI), an amino-rich polymer,
tiated grafting directly from the PDA surface as a promising can accelerate the deposition process by reacting with PDA
technology in future membrane surface modification. through Michael addition or Schiff base reactions—though a
complete deposition still takes four hours.[30] More details about
the codeposition will be discussed in Section 2.2. Addition-
2.1. Rapid and Controllable Deposition of PDA ally, oxidoreductases such as laccase was also reported to oxi-
dize the polyphenols to form material-independent coatings.[31]
Time-consuming and nonselective deposition is the main limi- Inspired by this research, our group developed a green strategy
tation to the practical application of mussel-inspired modifi- to fabricate thin film composite nanofiltration membranes by
cation of surfaces. One of the most appealing developments laccase-triggered codeposition of tea catechins and chitosan.[32]
in this field is the rapid and controllable deposition of PDA All of the afore-mentioned methods involve a second com-
on material surfaces (Table 1). The oxidation of catechol to ponent, which may influence the intrinsic properties of PDA.
o-quinone is the key step during dopamine polymerization.[26] Therefore, various routes to accelerate the reaction rate without a
Therefore, the primary strategy to accelerate dopamine polym- second component have been pursued. Freeman’s group applied
erization is to enhance the oxidation environment. In 2009, an oxygen atmosphere instead of air atmosphere to promote the

Table 1. Comparison of different strategies to accelerate dopamine deposition.

Method Solution pH Substrate Time Deposition speeda) References


Air, r.t. 8.5 Silicon wafer 24 h −1 [1]
2.1 nm h
Oxidant (NH4)2S2O8 7.0 Polyether sulfone 2h 35 nm h−1 [27]
Oxidant NaIO4 7.5–8.5 Silicon wafer 1 min ≈20 nm min−1 [28]
Oxidant CuSO4/H2O2 8.5 Silicon wafer 40 min 43 nm h−1 [29]
Laccase 8.5 PET film 15 h 2.7 nm h−1 [31]
Oxygen 8.5 Silicon wafer 30 min 8.8 nm h−1 [33]
Microwave radiation 8.6 Gold wafer 15 min 72 nm h−1 [34]
UV irradiation 7.0–8.5 Silica surface <2 h ≈3 nm h−1 [37]
Electric field 6.0 Gold wafer 1h ≈30 nm h−1 [41]
Microplasma 5.0 Silicon wafer 40 min 52.5 nm h−1 [43]

a)These
data show the maximum deposition speed mentioned in the literature. It should be noted that the thickness may not increase linearly with time and may also be
affected by the substrates.

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dopamine oxidation in solution.[33] The oxygen-enriched depo- their codeposition on polymer materials. The oxygen generated
sition resulted in a smoother surface compared to the conven- from the anode was beneficial for dopamine oxidation at voltages
tional deposition in air, which could also improve the permeating higher than the −1.23 V required for water splitting. Moreover,
and antifouling performance of PDA-coated membranes. Lee’s if the substrates were located in different positions between the
group also reported a rapid, oxidant-free PDA deposition tech- anode and cathode, the depositing components with charges
nology with the assistance of microwave radiation.[34] Generally, were driven by the electronic field to directionally deposit onto
increasing the temperature can improve the reaction kinetics the substrates.[42] This feature makes the technique suitable for
but also decrease the oxygen solubility in the solution, which anisotropic/asymmetric Janus membrane fabrication, which
ultimately slows down the overall deposition process by sup- will be discussed in Section 3.3. Recently, Wang et al. found that
pressing dopamine oxidation. Microwave irradiation overcomes microplasma could also assist and regulate the rapid deposition
this limitation by simultaneously increasing the temperature of PDA by generating reactive oxygen species.[43] Generating reac-
of the system and generating free radicals, which counteracts tive oxygen species is the key mechanism for the rapid deposition
the reduced oxygen solubility to realize a faster reaction. Simi- of PDA, particularly in neutral or even acidic environments.
larly, both UV radiation and electronic fields can be applied to
accelerate and control the PDA deposition on demand. Reactive
oxygen species are known to be generated under UV light, which 2.2. Dopamine-Assisted Codeposition
can trigger the dopamine polymerization under neutral or even
acidic environments. Therefore, by using lithography masks, Pure PDA coatings cannot meet all the diverse demands on
PDA can be selectively deposited under UV light to pattern the membrane surface properties. Therefore, in most cases, PDA
surface.[35–37] Such kind of patterned surface is promising to be itself only serves as a linker to introduce other components
applied in electrics, biochips and sensors.[38] The UV irradiation onto the membranes for surface functionalization. There are
can also trigger the polymerization and deposition of phenolic two major protocols to achieve this goal: premodification and
compounds in plants on various substrates.[39] Compared with postfunctionalization. In the case of premodification, dopamine
dopamine, plant phenolic compounds are low-cost, easy-to-get is primarily grafted onto polymers that are then deposited onto
and environment friendly. Researchers also found electric fields the surfaces. This process requires complicated synthesis[44]
could enhance and regulate PDA deposition.[40] Kang et al. inves- and sometimes the protection and deprotection of phenolic
tigated the oxidation/reduction characteristics of dopamine by hydroxyl groups in dopamine.[45] In contrast, postfunction-
cyclic voltammetry with Ag/AgCl as a reference, and found its alization procedures are simple. The desired components are
main oxidation peak at +0.4 V. Therefore, PDA can be depos- covalently or noncovalently connected to the PDA-modified sur-
ited onto the electrode under an acidic environment by electro- face through chemical or physical interactions between them.
chemical oxidation at a higher voltage.[41] We also applied an A third strategy for modifying PDA termed dopamine-assisted
electric field on dopamine/polyelectrolyte solutions to regulate codeposition has recently emerged (Figure 1). Compared to the

Figure 1. Schematic illustration of the representative codeposition components and their potential interactions with dopamine. The potential code-
positing components include polycations (e.g., polyethyleneimine (PEI) and poly(allylamine hydrochloride) (PAH)), polyanions (e.g., poly(styrene
sulfonate) (PSS) and poly(acrylic acid) (PAA)), zwitterionic polymers (e.g., poly(sulfobetaine methacrylate) (PSBMA) and poly(methacryloyloxyethyl
phosphorylcholine) (PMCP)), nonionic polymers (e.g., poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), and poly(N-vinyl pyrrolidone) (PVP)),
polysaccharide (e.g., hyaluronic acid (HA) and dextran), and small molecules (e.g., folic acid, teramethyloxysilane (TEOS), and KH-560).

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aforementioned strategies, dopamine-assisted codeposition can the deposition process. Evidence points to high molecular
greatly simplify procedures and enrich possible coating func- weight polymers being detrimental to the deposition process,
tionality by integrating the deposition and functionalization in though an underlying mechanism is still elusive.[55]
a single simultaneous step. In 2012, Lee and co-workers first Beyond polymers, small molecules such as inorganic precur-
proposed the concept of dopamine-assisted codeposition.[4] In sors were also reported as second components in dopamine-
that work, a second component of interest, such as polymeri- assisted codeposition to fabricate organic–inorganic hybrid
zation initiators, antibacterial agents, tertiary amines, growth coatings. For example, Shao’s group codeposited dopamine with
factors, or polysaccharides, were codeposited onto the material silanes (i.e., tetramethyloxysilane and KH-560) for hydrophilic
surfaces with dopamine for different uses. modification of PVDF membranes.[56,57] This process is compli-
Interactions between dopamine and the second component cated because it involves simultaneous dopamine self-polymer-
dictate the parameters of codeposition. Zhang et al. investi- ization, silane hydrolysis and polycondensation, as well as any
gated the codeposition behavior of dopamine and nonionic potential reactions between dopamine and silanes. The silane-
polymers including poly(ethylene glycol) (PEG), poly(N-vinyl coupling agents were hydrolyzed to nanoparticles and inter-
pyrrolidone) (PVP) and poly(vinyl alcohol) (PVA), where acted with PDA to form hybrid coatings. Generally, the selected
hydrogen bonding is the only interaction between them.[46] inorganic precursors should not be hydrolyzed too quickly, or
While relatively weak hydrogen bonds facilitate the codepo- be too reactive with dopamine as that may affect dopamine
sition of PDA and polymers, strong hydrogen bonds may polymerization. This approach in dopamine-assisted codeposi-
overwhelm the noncovalent interactions within PDA itself tion can also advantageously affect the surface morphology. The
and impede the deposition. As a result, PVA or PEG could same group found that by codepositing dopamine with folic
be codeposited onto the surface with dopamine, while PVP, acid, they could construct a rough surface with hierarchical
with its strong hydrogen-bond acceptor species, would sup- structures for further superhydrophobic modification.[40,58]
press PDA deposition. Based on this principle, polyhydroxy
compounds such as dextran[47] and hyaluronic acid[48] could
also be deposited with dopamine for their antifouling prop- 2.3. Photoinitiated Direct Grafting
erties. Polyelectrolytes may also interact with PDA through
electrostatic interactions because the catechol group of the Surface-initiated grafting polymerization is one of the most
PDA is negatively charged while the amino group is posi- popular techniques in membrane surface engineering and
tively charged. Ball’s group revealed that both polycations can be extended to PDA-coated surfaces. Generally, initia-
and polyanions could effectively inhibit PDA aggregate for- tors are immobilized onto the membrane surface and then
mation, but that the polyanions could further suppress the initiate the growth of functional polymer brushes.[59] PDA
PDA deposition.[49] A possible explanation is polycations can coatings always act as a substrate-independent interlayer to
still form a cross-linked network with PDA through cova- anchor the initiators on the membrane surfaces. For example,
lent bonds although both polycations and polyanions can many researchers covalently immobilized 2-bromoisobutyryl
interrupt the noncovalent aggregation of PDA. The detailed bromide onto PDA-modified surfaces and initiated the atom
mechanisms involved are still unexplored. It should be noted transfer radical polymerization (ATRP) for constructing func-
chemical reactions are involved in the codeposition of dopa- tional polymer coatings.[60] Although this provides a universal
mine and amine compounds, which we will discuss individu- strategy to graft polymers onto the membrane surfaces,[61–63]
ally later in this review. Interestingly, zwitterionic polymers, the disadvantages of conventional ATRP cannot be avoided.
such as poly(methacryloyloxyethyl phosphorylcholine)[50] and These disadvantages include heavy metal contamination, as
poly(sulfobetaine methacrylate)[51] could be also applied in well a complex fabrication process involving the balance of
dopamine-assisted codeposition. The local electrostatic inter- dopamine deposition, initiator immobilization and monomer
actions contribute to this process,[52] and some researchers polymerization.
ascribed their interactions to hydrogen bond and cation–π As mentioned in Section 2.1, the radical nature of PDA
interactions.[53] Combined with the H2O2/CuSO4-assisted makes it a promising candidate to initiate radical polymeriza-
rapid deposition we developed, the codeposition process with tion under proper conditions. Zhou’s group first reported a
zwitterionic polymers could be accelerated without significant photoinduced grafting polymerization of various vinyl mono-
decrease in fouling resistance.[54] mers directly onto PDA-coated substrates under simulated
Polyamines are quite different from other polyelectrolytes sunlight irradiation (Figure 2).[64] It should be mentioned that
when codeposited with dopamine because they can react the PDA was deposited onto the surface under UV irradia-
with PDA during the deposition process. As mentioned in tion, which is necessary to bring it to the photoexcited state.
Section 2.1, we developed the codeposition of dopamine with After that, they found other polyphenols, such as green tea
low-molecular-weight PEI, an amino-rich polymer, on PP polyphenol, could also generate radicals and initiate the poly­
membrane surfaces.[30] The incorporation of PEI improved the merization under UV irradiation on material surfaces.[35] This
deposition rate and suppressed the formation of PDA aggre- strategy has been employed in fabricating stimuli-responsive
gates by suppressing the noncovalent interactions within them, hollow spheres for controlled pesticide release by Sheng et
leading to a thin and uniform surface. Moreover, the covalent al.[65] As a competitive strategy to graft functional polymers
network between PDA and PEI can promote stability under onto surfaces, the PDA-initiated photografting is a promising
strong acidic and alkaline environments. It should be noted that approach to be applied in membrane surface modification in
the molecular weight of polymers would significantly influence future research.

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noncovalent bonds within PDA aggregates


to make the coating uniformly thin and
dense (Figure 3a). The positively charged
PDA/PEI nanofiltration membranes showed
a rejection above 90% to divalent cations
after cross-linking by glutaraldehyde.[66]
Similarly, other phenol/amine combina-
tions such as catechol/PEI[67] can be applied
in nanofiltration membrane fabrication by
direct deposition. Moreover, inorganic com-
ponents such as SiO2 nanoparticles could
be incorporated in this layer to enhance the
surface mechanical strength of the mem-
brane, promoting the structural stability
and compaction resistance during long-term
filtration processing.[68] Similarly, Zhu et
al. codeposited PDA with PEI-modified Cu
nanoparticles to prepare a loose nanofiltra-
tion membrane with excellent antibacterial
performance.[69]
The codeposition process for uni-
form dense layers can also be triggered
by enzymes. Qiu et al. reported a laccase-
triggered catechins/chitosan nanofiltration
membrane with a negatively charged surface
(Figure 3b).[32] The laccase could facilitate
oxidation of catechins and following reac-
tions with chitosan, leading to a dense layer
Figure 2. a) Schematic illustration of photoinitiated surface grafting on PDA-coated substrates
under simulated sunlight. b) Two strategies to fabricate patterned polymer-grafted surfaces. with a Na2SO4 rejection around 99%. The
c) Fluorescence images of different polymer-grafted patterned surfaces dyed by fluorescent rapid deposition processes triggered by the
molecules. Reproduced with permission.[64] Copyright 2015, The Royal Society of Chemistry. oxidants can also facilitate the formation of
thin and dense selective layers. For example,
our group reported a uniform, compact and
3. Emerging Developments in Membranes stable PDA membrane by using H2O2/CuSO4 as the oxidant.
and Membrane Technologies The as-prepared membrane showed improved solvent resist-
ance because more covalent bonds formed in the coating,
In most of the recent literature, mussel-inspired surface enabling the membrane to filter out nanoparticles in organic
coatings are used as a modifying layer or an interlayer for solvents.[70] Through a similar process, Wang et al. fabricated
postmodification. It has been gradually recognized these coat- a loose PDA/PEI nanofiltration membrane in the presence of
ings can play diverse roles in membranes and membrane pro- H2O2/CuSO4, demonstrating high flux and rejection to various
cesses. In this section, we discuss the emerging applications dye molecules.[71]
of mussel-inspired coatings, and demonstrate their advantages The wide distribution of surface pores is one of the major
compared to conventional methods or materials. challenges facing nanofiltration membranes. Therefore, Du
et al. selectively modified a PDA/PEI nanofiltration membrane
by filtrating sodium 3-mercapto-1-propanesulfonate (SMPS)
3.1. As a Selective Layer in Nanofiltration aqueous solution to narrow down the pore size distribution
(Figure 3c).[72] The SMPS can pass through the large pores and
Significant progress has been made in the field of mussel- react with PDA through Michael addition, whereas it is rejected
inspired nanofiltration membranes over the past several years. by the small pores. That team also developed a contra-diffusion
Although mussel-inspired coatings have been used as an inter- strategy to fabricate PDA/PEI nanofiltration membranes with
layer or surface-modifying layer in nanofiltration membranes narrow pore size distributions (Figure 3d).[73] DA/PEI solution
for some time, they have only recently been directly imple- and ammonium persulfate solution were separately settled at
mented as the selective layer in nanofiltration. In general, a each side of an ultrafiltration substrate. The ammonium per-
pure PDA coating cannot satisfy the requirement of thin and sulfate diffused through the membrane and oxidized the DA/
dense skin layer because large PDA aggregates formed in the PEI to form the dense selective layer at the substrate surface,
solution always adhere to the substrate surface, leading to both resulting in narrow pore size distribution because more PDA/
low rejection and low flux during nanofiltration. The PDA/PEI PEI was formed at the pores. The membrane showed high
codeposition strategy developed by our group overcomes the monovalent ion/divalent ion selectivity and great potential in
drawbacks of conventional PDA deposition by destroying the chemical products separation.

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Figure 3. a) Fabrication process of PDA/PEI nanofiltration skin layer on an ultrafiltration substrate. Reproduced with permission.[66] 2015, Elsevier.
b) Laccase-triggered polymerization and deposition for catechins/chitosan nanofiltration membranes. Reproduced with permission.[32] 2016, the Royal
Society of Chemistry. c) Self-regulating process of PDA/PEI nanofiltration membranes. The rejection increases with the reaction time while the flux
remains unchanged. The molecular weight cutoff reflects the narrowing of pore size distribution. MPSIs is the abbreviation of 3-mercapto-1-propane-
sulfonate ions. Reproduced with permission.[72] 2016, the Royal Society of Chemistry. d) PDA/PEI nanofiltration membranes fabricated by contra-
diffusion process. The membrane shows a narrow cumulative distribution of pore size and high monovalent ion/divalent ion selectivity. Reproduced
with permission.[73] 2016, American Chemical Society.

3.2. As an Intermediate Layer for Promoting Compatibility glycol from water.[75] The hydrogen bonds between amino
in MOF-Based Membranes groups in PDA and hydroxyl groups in PVA also contributed
to the high permeability and selectivity. In these cases, the PDA
Metal-organic framework (MOF) materials have drawn growing acts as an interlayer to improve the interfacial compatibility and
attention in gas separation membranes due to their regular avoid defect formation in MOF-involved MMMs. Cao et al. fab-
nanopores with high selectivity. There are two strategies to ricated a MMM composed of PDA-coated CAU-1-NH2 (a kind of
include MOFs in membrane materials. One way is to blend MOF material) and polymethylmethacrylate as the separator for
MOF particles with polymer matrix to form mixed matrix mem- Li–air batteries.[76] CAU-1-NH2 facilitates O2 permeation while
branes (MMMs), and the other is to grow a dense MOF film resisting moisture and CO2. The PDA coating could suppress
on a porous substrate. The interfacial compatibility between void formation between the MOF particles and polymer matrix
MOFs and polymer matrix/substrate is crucial in both cases. as well as trap CO2 through the abundant hydroxyl groups.
In the case of MMMs, interfacial defects between MOF fillers Alternatively, some researchers utilized PDA to fabricate MOF-
and polymer matrix are detrimental to the selectivity of mem- based nanocomposites as the fillers. For example, Rao et al.
branes during gas separation. Wang et al. modified ZIF-8, a grew UiO-66-NH2 onto graphene oxide sheets through the PDA
type of zeolitic imidazolate MOF, with an ultrathin PDA layer interlayer, which was blended with Nafion to fabricate proton
and blended it with an intrinsically microporous polyimide exchange membranes for fuel cells.[77]
(Figure 4a).[74] The authors suggested the secondary or primary Recently, supported MOF membranes have attracted wide-
amine groups from PDA would form hydrogen bonds with the spread interest owing to their highly diversified structures and
tertiary amine from polyimide, and the promoted interfacial regular pore size. A modified surface is required for in situ
compatibility is beneficial for both permeability and ideal selec- growth of uniform and continuous MOF layers. In general,
tivity of the MMMs. Similarly, Zhang et al. fabricated PVA-based functional groups such as amino and carboxyl groups could
MMMs with PDA-coated MOF particles to separate ethylene chelate the metal ions from the solution to form the nucleation

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Figure 4. a) Schematic illustration of the mixed matrix membrane fabricated by incorporating PDA-coated ZIF-8 particles into a polyimide matrix and
the hydrogen bonds at the polyimide/PDA interface. b) Schematic illustration of depositing MOFs on the polypropylene fibrous membranes by using
PDA layer as nucleation center.

sites on the surface. In 2013, Huang’s group first reported a Though several fabrication strategies have already been
ZIF-8 membrane on a PDA-coated Al2O3 porous substrate for reported, it is still difficult to quickly and easily create Janus
gas separation.[78,79] Catechol groups from the PDA coating membranes. Fabrication processes such as single-surface
serve as nucleation sites to chelate zinc ions from solution. After photochemical reactions and vapor treatments are complicated
this first report, they demonstrated the potential of a PDA inter- and amenable only to a limited choice of substrates. Recently,
layer to induce MOF or zeolite growth on various other sub- we developed a mussel-inspired single-surface deposition
strates, mostly inorganic materials.[80–82] Recently, Zhou et al. strategy to prepare Janus flat and hollow fiber membranes.[91–93]
showed that PDA could enable various MOFs to grow even on For flat membranes, the hydrophobic membranes were simply
inert PP surfaces via layer-by-layer deposition, which makes it floated on the interface of a DA/PEI solution (Figure 5a). The
possible to build various thin MOF films on polymer substrates membrane surface in contact with the solution was hydrophi-
(Figure 4b).[83] In addition, the PDA-modified scaffold can act as lized by PDA/PEI while the air-facing side remained hydro-
a template rather than a support for thin MOF film growth. For phobic.[91] For hollow fiber membranes, the DA/PEI solution
example, Wang and co-workers fabricated a sub-200 nm ZIF-8 was pumped into the lumen side of hydrophobic hollow fiber
membrane within a PDA-coated carbon nanotube (CNT) layer membranes for single-surface hydrophilization (Figure 5b).[93]
by a contra-diffusion method.[84] The PDA-coated CNT layer The as-prepared Janus flat membrane shows superior per-
acted as pseudoseeds to induce ZIF-8 growth, and the formed formance in bubble aeration compared to the hydrophobic or
crystals hinder a further increase of film thickness. Similar pro- hydrophilic membranes with similar pore size (Figure 5c,d).[91]
cesses have been used by Zhang et al. to prepare free-standing The hydrophilic side, which is superaerophobic underwater,
ZIF-8 membranes for high-performance hydrogen separation.[85] allows the bubble to depart from the surface when still small
in size, while the hydrophobic side reduces the operation pres-
sure by trapping the air into the pores. Such Janus membranes
3.3. As a Hydrophilic Coating in Janus Membranes can be also implemented in both oil-to-water and water-to-oil
emulsification by simply switching the emulsifying direction
The Janus membrane is an emerging concept that refers to a (Figure 5e).[92] Similar to its role in aeration processes, the
membrane with opposing properties on either surface.[86] Most asymmetric Janus structure efficiently reduces the operating
of the reported examples are membranes with asymmetric pressure without significant change in emulsion size. Janus
wettability. Such membranes have drawn increasing research hollow fiber membranes can improve the comprehensive
interest because they can simultaneously satisfy competing performance in direct contact membrane distillation.[93] The
requirements in challenging applications. For example, in the underlying idea in applying Janus membranes to membrane
case of membrane reactors based on oxidases, the hydrophilic distillation is to reduce the mass transfer resistance but main-
layer is preferred to maintain the enzyme activity as a support, tain the heat transfer resistance by introducing a hydrophilic
while the hydrophobic layer is necessary to keep a stable air/ layer on the permeate side (Figure 5f). Very recently, Wang
water interface for better mass transfer.[87,88] Another example et al. reported a facile “peel-off” method to obtain the Janus
is demulsification. The hydrophobic layer pulls the oil from the membranes.[94] The PET-supported PTFE membranes were
feed while the hydrophilic layer facilitates oil coalescence and uniformly modified by hydrophilic PDA-based coatings, and
also keeps the droplet spherical for continuous driving force then the surface coating on PTFE side was peeled off by an
from the curved interface.[89,90] adhesive tape to make the hydrophobic surface. In contrast to

Adv. Funct. Mater. 2018, 1705327 1705327 (8 of 14) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 5. Schematic illustration of the Janus membrane preparation and applications. a) Preparation of Janus flat sheet membrane by floating a
hydrophobic membrane on DA/PEI solution. Reproduced with permission.[91] Copyright 2017, Wiley. b) Preparation of Janus hollow fiber membrane by
pumping DA/PEI solution through the lumen side of a hydrophobic hollow fiber membrane. Reproduced with permission.[93] Copyright 2017, Elsevier.
c) Dynamic water contact angles on each side of the Janus flat membrane. d) Bubbling through a hydrophobic membrane (top) and a Janus membrane
with the hydrophilic side toward water (bottom). Reproduced with permission.[91] Copyright 2017, Wiley. e) Schematic illustration of oil-to-water and
water-to-oil emulsification through Janus membrane. Reproduced with permission.[92] Copyright 2017, American Chemical Society. f) Direct contact
membrane distillation through a Janus membrane. The hydrophilic layer can facilitate mass transfer with a relatively minor effect on the heat transfer.
Reproduced with permission.[93] Copyright 2017, Elsevier. g) Carbon nanotube Janus membrane for switchable oil-in-water and water-in-oil emulsion
separation. Reproduced with permission.[95] Copyright 2016, The Royal Society of Chemistry.

the direct asymmetric modification, this method could be con- 3.4. As a Protective Layer in Catalytic Membranes
cluded as the asymmetric post-treatment followed by the uni-
form modification. As was discussed in our previous review, PDA and its deriva-
Beyond asymmetric surface modification, Hu et al. reported tives are versatile and have many unexplored properties, one
a composite Janus membrane by filtrating hydrophobic of which is superior free radical scavenging.[96,97] Polymer
carbon nanotubes and hydrophilic PDA-coated carbon nano- membranes uniformly suffer from degradation by free radicals
tubes sequentially on a mixed cellulose ester filter membrane during membrane cleaning or photocatalytic processes. Some
(Figure 5g).[95] After removing the substrate, the as-prepared researchers have immobilized photocatalysts on polymer mem-
membrane was applied in pressure-responsive oil/water emul- brane surfaces to degrade surface foulants.[98] Unfortunately, the
sion separation. The membrane can separate water-in-oil emul- most common commercial membranes, including PP, PVDF,
sions by allowing oil permeation with an operating pressure polysulfone, poly(ether sulfone), and polyacrylonitrile, show
lower than the intrusion pressure of water. At operating pres- poor chemical stability under UV light or in strong oxidizing
sures exceeding the water intrusion pressure, the same device environments.[99] As a consequence, combining photocatalysts
can be used for oil-in-water emulsion separations. with polymer membranes risks degrading the membrane.

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FeOOH nanorods with the abovementioned PDA/PEI nanofil-


tration membrane and enabled self-cleaning under visible light
after filtrating dye solutions.[103] Some researchers have also
demonstrated that dopamine could promote catalytic perfor-
mance by facilitating electron transfer during photocatalysis.[104]

3.5. Other Applications

Beyond the afore-mentioned applications, mussel-inspired sur-


face coatings have been used in other membrane processes
such as oil/water separation, affinity membrane chromatog-
raphy, molecularly imprinted membranes, forward osmosis,
and gas separation. We will briefly introduce the recent devel-
opments in these fields. The PDA or PDA-based coatings play
three familiar roles in these applications: surface coatings,
interlayers for better compatibility and interlayers for further
functionalization.

3.5.1. Oil/water Separation

Oil/water separation is a long-studied but still hot topic in cur-


rent research owing to continuing increase in crude oil spills
and related accidents. In 2004 and 2011, the pioneering work
from Jiang’s group introduced the concept of superwetta-
bility to this field, which revealed the principal role of surface
properties in separation performance of membranes.[105,106]
Mussel-inspired chemistry provides a facile and promising
surface-modification approach to introduce special wettability
Figure 6. a) Schematic illustration of PDA as a free-radical-scavenger layer behavior and hierarchical structures onto surfaces, potentially
in photocatalytic membrane. b) Membrane performance of the nascent, offering exciting opportunities in this type of separation. In
TiO2-blended and TiO2/PDA-coated PSf membranes after several cycles of general, hydrophilic membranes are oleophobic underwater,
UV irradiation. Reproduced with permission.[100] Copyright 2016, Elsevier. enabling selective water permeation and oil rejection. Con-
versely, hydrophobic/oleophilic membranes allow oil to pass
PDA, however, can serve as a protective layer to scavenge active through. Such membranes can be prepared by the following
radicals generated during the catalysis process. For example, protocols: direct PDA deposition, dopamine-assisted codepo-
Feng et al. deposited PDA onto polysulfone ultrafiltration mem- sition, and postmodification of a PDA-coated surface. In early
branes and immobilized amino-tailed TiO2 nanoparticles onto studies, researchers directly applied PDA-coated membranes
its surface (Figure 6).[100] The PDA layer can protect the under- in oil/water separation because the pure PDA coating is hydro-
lying membrane from the attack of free radicals generated philic.[107] However, the aromatic structure in PDA limits its
under UV light, leading to better chemical stability compare to hydrophilicity and antifouling property. Later, some modi-
the TiO2-blended membrane without PDA. Moreover, contami- fied processes were developed to promote surface wettability.
nants on the surface were easily degraded by the TiO2 photocat- Codeposition with a second hydrophilic component including
alysts under UV light, yielding a self-cleaning membrane with polymers, inorganic precursors, or particles is one such strategy
a mitigated risk of self-degradation. In another study, Wu et al. as mentioned in Section 2.2.[30,56,57,108–110] As a testament to the
prepared TiO2-PDA hybrid nanospheres and blended them into versatility of PDA, both hydrophilic and hydrophobic mem-
polysulfone membranes.[101] The PDA-absent catalytic mem- branes have been achieved via PDA postmodification. For
brane showed a significant flux increase and rejection decrease example, Gao et al. grafted PEI onto PDA-coated carbon nano-
caused by degradation after several cycles of UV light irradia- tubes to fabricate a superhydrophilic membrane for ultrafast
tion, while the PDA-containing one retained good separation separation of oil-in-water nanoemulsions,[111] and Xu et al.
performance during long-term operation. anchored perfluorodecanethiol onto Ag metalized PDA coatings
PDA can play even further advantageous roles in coupling for superhydrophobic membranes.[112] Our group developed a
catalytic functionality to membranes. For example, during cat- biomineralization strategy based on the PDA/PEI interlayer to
alyst immobilization, the catechol groups in PDA can chelate fabricate superhydrophilic/superoleophobic membranes for oil-
ions from the solution to initiate the in situ catalyst growth in-water emulsion separation.[113,114] Rigid mineral coatings can
or directly catch the catalyst crystals. Our group grew FeOOH also improve the structure stability of the membranes. It should
nanorods on PDA-coated surfaces to trigger photo-Fenton be mentioned the PDA-based coating can adsorb heavy metals
reactions in the presence of H2O2.[102] Similarly, we integrated or charged dye molecules through chelation and electrostatic

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interactions, which has been integrated with oil/water separa- skin layer and substrates, or improve the antifouling prop-
tion functionality by some research groups.[108,115] erty of the membrane though PDA-mediated hydrophiliza-
tion.[128–133] Similarly, PDA coatings were employed in pressure
retarded osmosis (PRO) membranes to improve the antifouling
3.5.2. Affinity Membrane Chromatography properties.[134,135] A work of particular merit is presented by
Yang et al. who coated PDA on both sides of a cellulous triac-
Affinity separation refers to a separation process through etate FO membrane followed by Ag metallization. The as-pre-
specific adsorption of molecules in a feed stream to tailored pared membranes were then applied in osmotic microbial fuel
adsorptive sites on the membrane surface. The interactions cells.[136] The Ag/PDA composite coating showed excellent anti-
between target molecules and adsorptive sites should be revers- fouling and antibacteria properties, and has since been widely
ible, stable and specific. Luo and co-workers developed a series reported for other different kinds of membranes.[136–139]
of affinity membranes based on mussel-inspired interlayers to
separate biochemical mixtures.[116–120] For example, they grafted
different “ligand” molecules, including dodecyl mercaptan, 3.5.5. Gas Separation
histidine and PEI onto PDA-coated membranes through cat-
echol-amino or catechol-thiol reactions. The membranes can Though most examples of PDA-involved gas separation mem-
selectively adsorb human serum albumin (HSA) through elec- branes are MOF-based membranes already presented in Section 3.2,
trostatic interaction between HAS and PEI, or immunoglobulin PDA-based coatings can be also applied in polymer-based gas
G (IgG) through hydrophobic interaction between IgG and alkyl separation membranes. Li et al. fabricated a triple-layer thin
chain or by specific affinity between IgG and histidine.[116] The film composed of polydimethylsiloxane (PDMS), PDA, and
PDA-coated membranes grafted by amino-rich polymers such polyvinylamine on porous substrates for CO2/N2 separation.[140]
as PEI and polyallylamine can purify α1-antitrypsin, a thera- The highly permeable PDMS layer can decrease transmem-
peutic protein can prevent proteolysis and tissue breakdown, brane resistance while the polyvinylamine layer can facilitate
from pretreated human plasma fraction IV through electrostatic the transport of CO2. The PDA layer was applied to improve the
interactions.[117] Recently, they applied PDA/PEI-coated mem- interfacial compatibility between them. Fang et al. deposited a
branes to selectively adsorb laccase, a copper-containing oxidase PDA layer onto the PDMS interlayer as the selective layer to
enzyme, from a fermentation broth and obtain a laccase-immo- collect hydrocarbons from nitrogen, which could enhance both
bilized biocatalytic membrane. This process integrated enzyme separation selectivity and permeability due to its high affinity
purification with immobilization, leading to both high enzyme for hydrocarbons and defect-free dense structure.[141]
purity and high enzyme loading.[118] Although only electrostatic
and hydrophobic interactions were applied in the abovemen-
tioned examples due to their relatively high specificity, other 4. Challenges and Opportunities
interactions such as hydrogen bonds, coordination, or compli-
cated multi-interactions could also have relevance. Mussel-inspired surface chemistry has become one of the most
popular technologies in membrane surface engineering over
the past decade. Although it has been widely investigated and
3.5.3. Molecularly Imprinted Membranes (MIMs) applied in different membranes and membrane processes,
there are still key challenges remaining in this field, which rep-
MIMs are another class of membranes designed to separate resent opportunities for exciting future research.
target molecules through specific recognition and adsorption by First, dopamine-assisted codeposition is expected to be
molecularly imprinted polymers. Li and co-workers contributed widely applied in membrane surface engineering because
significantly to MIMs based on mussel-inspired chemistry. In it can bring more functionality to the surface compared to
some cases, the PDA coating served as a platform to enable in conventional dopamine deposition. However, the under-
situ fabrication[121–123] of rigid and hierarchical inorganic layers lying mechanisms of codeposition are still unclear because
onto the membrane surface, followed by imprinted polymeriza- of the complicated interactions and reactions in the solution.
tion on the inorganic surfaces. In another approach, PDA coat- Though some researchers have proposed plausible descrip-
ings with grafted initiators could directly initiate the imprinted tions for the codeposition process, there are limited experi-
polymerization on membrane surfaces.[124,125] PDA can be also mental data in the literatures. The effect of molecular weight
deposited onto nanoparticle surfaces, directly acting as the on codeposition processes is another critical but poorly under-
imprinted polymer layer,[126] or initiating imprinted polymeri- stood problem. Deeper insight into these topics will allow for
zation after anchoring ATRP initiators.[127] These nanoparticles easily adjustable processing parameters to fine-tune novel
were then blended with membrane polymers to fabricate MIMs coating properties.
through phase inversion processes. Second, more and more researchers employ mussel-inspired
coatings as interlayers to further functionalize membrane sur-
faces, or to improve interfacial compatibility during membrane
3.5.4. Forward Osmosis (FO) fabrication. While this type of work successfully uses PDA as a
means to an important end, there has been little thought given
In forward osmosis, most researchers applying PDA coatings to how the intrinsic properties of PDA can be integrated into
seek to enhance the interfacial compatibility between the FO coating functionality. Such intrinsic properties include its ability

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as a radical-scavenger, which has been demonstrated in the cat- Acknowledgements


alytic protection layers discussed in Section 3.4. We expect that
Financial support is acknowledged to the National Natural Science
these merits will attract widespread interest as a focus in future
Foundation of China (21534009). Use of the Center for Nanoscale
research. Furthermore, we should pay more attention to the Materials, an Office of Science user facility, was supported by the U. S.
common properties of such coatings. For example, the hydro- Department of Energy, Office of Science, Office of Basic Energy Sciences,
philicity of mussel-inspired coatings can play more diverse under Contract No. DE-AC02-06CH11357. This material is based upon
roles in membrane fabrication. It has been well established work supported by Laboratory Directed Research and Development
that mussel-inspired interlayers can improve the interfacial (LDRD) funding from Argonne National Laboratory, provided by the
Director, Office of Science, of the U.S. Department of Energy under
compatibility between skin layer and support layer in thin film
Contract No. DE-AC02-06CH11357.
composite membranes. It is only now being realized that such
interlayers can also adjust the polymerization process by tuning
the surface wettability and capillary effect of porous support
layer, resulting in a thin and uniform skin layer with both high Conflict of Interest
flux and salt rejection.[142,143] Moreover, the mussel-inspired The authors declare no conflict of interest.
deposition shows its superiority in Janus membrane fabrication
over other modifying methods because the PDA-based coatings
can be easily deposited onto low-surface-energy hydrophobic
surfaces for hydrophilization. Keywords
Third, the low utilization efficiency is still a main obstacle Janus membranes, membranes, metal-organic framework membranes,
to up-scaling to widespread application of these materials. nanofiltration, photocatalysis, polydopamine
During conventional mussel-inspired deposition, dopamine
Received: September 15, 2017
is oxidized and polymerized both in bulk solution and on the
Revised: October 11, 2017
membrane surface. Even with the development of alternative
Published online:
cheap phenols and amines,[144–148] precursor that is polym-
erized in the solution is essentially wasted. Minimization of
resources employed in membrane coating is an important
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