20 - Bioinspired Underwater Adhesives

Review
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Bioinspired Underwater Adhesives

Hailong Fan* and Jian Ping Gong*
adhesive, causing plasticization, swelling,

Underwater adhesives are in high demand in both commercial and industrial erosion, degradation, or hydrolysis of
sectors. Compared with adhesives used in dry (air) environments, adhesives adhesives, which eventually leads to cohe-
used for wet or submerged surfaces in aqueous environments have specific sive failure.[8,9] Therefore, the develop-
challenges in development and performance. In this review, focus is on adhe- ment of underwater adhesives remains a
significant challenge.
sives demonstrating macroscopic adhesion to wet/underwater substrates.
An efficient way of developing under-
The current strategies are first introduced for different types of underwater water adhesives is by taking inspiration
adhesives, and then an overview is provided of the development and perfor- from nature. For instance, sessile marine
mance of underwater adhesives based on different mechanisms and strate- organisms such as mussels and sandcastle
gies. Finally, the possible research directions and prospects of underwater worms use L-3,4-dihydroxyphenylalanine
(DOPA) to achieve permanent under-
adhesives are discussed.
water adhesion, whereas aquatic creatures
such as remora and clingfish use unique
microstructures for temporary under-
1. Introduction water attachment.[10–13] Inspired by these unique underwater
adhesion strategies, significant progress has been made in the
Adhesives are widely used in our daily lives as well as in indus- design and fabrication of novel underwater adhesives in the
tries. Nowadays, numerous types of polymeric adhesives for past decade.
diverse applications are commercially available. In most cases, Previous reviews on underwater adhesion have mainly
these adhesives work only on dry solid surfaces in air by forming focused on the micromechanics and bonding mechanisms.
permanent or reversible bonds with the surface. However, in Adhesives for soft and wet tissues and hydrogels have been dis-
many applications, adhesives that bond with wet surfaces or cussed in other recent reviews.[1,14–16] However, only a few have
surfaces submerged in aqueous media are required, such as been devoted to bulk underwater adhesives.[10,12,13,16–20] In this
in the case of implantable devices and wound dressing in the review, we summarize the currently reported adhesives that
medical field, water-based energy devices, underwater sen- show macroscopic adhesion to mainly, but not limited to, solid
sors, underwater repair, and marine industry.[1–5] Therefore, the surfaces under wet and underwater conditions. We provide an
development of novel underwater adhesives with outstanding overview of the development and performance of underwater
performance for diverse applications in aqueous environments adhesives based on different bonding methods and mecha-
has become an essential goal of adhesive research. nisms. In addition, we discuss the possible research directions
However, achieving strong interfacial bridging in aqueous and perspectives for underwater adhesives.
media is more challenging than achieving the same in air. Gen-
erally, a hydration layer is formed by water on the surfaces of
most materials upon their exposure to aqueous environments, 2. Current Design Strategies for
which prevents molecular-level bridging between the adhesive
Underwater Adhesion
and the substrate. In addition, water drops tend to become
trapped at the interface, which reduces the contact area macro- The keys to achieving wet adhesion are the breaking down of
scopically.[6,7] Moreover, the prolonged exposure of glued joints the hydration layer and interaction with the substrate surface,
to water results in the permeation of water molecules into the which can be designed at different length scales (Figure 1).[21–23]
To achieve dehydration at the molecular level (∼nm), hydro-
phobic organic solvents, monomers, and polymers have been
H. L. Fan, J. P. Gong used to remove the hydration layer and facilitate surface wet-
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD)
Hokkaido University ting, especially for hydrophobic substrates.[24,25] The use of
N21W10, Kita-ku, Sapporo 001-0021, Japan water-absorbing fillers, including inorganic substances and
E-mail: fanhl@icredd.hokudai.ac.jp; gong@sci.hokudai.ac.jp hydrophilic polymers, is an alternative strategy that is widely
J. P. Gong used for wet surfaces.[26–28] At a larger length scale (μm to mm),
Faculty of Advanced Life Science surface microstructures can promote water drainage to prevent
Hokkaido University
N21W11, Kita-ku, Sapporo 001–0021, Japan
permanent water trapping.[29]
Accompanied by the dehydration process, the interfacial
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202102983. bonding of adhesives is achieved by the formation of covalent/
non-covalent bonds (∼nm), which highly depends on the inter-
DOI: 10.1002/adma.202102983 facial chemistry between the adherend and the adhesive.[10] For
Adv. Mater. 2021, 33, 2102983 2102983 (1 of 21) © 2021 Wiley-VCH GmbH
15214095, 2021, 44, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202102983 by Indian Institute Of Science Education And Research Bhopal, Wiley Online Library on [11/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Figure 1. Currently implemented dehydration and bonding strategies for underwater adhesives at different length scales.
common substrates without any chemically reactive functional thereby improving the mechanical strength.[34] Toughening
group such as glass, metals, and plastics, non-covalent interac- materials have been widely reviewed in literature.[21,22,33,35,36]
tion (such as hydrogen bonding, ionic bonding, and cation-π The various underwater adhesives developed in the past
interaction) is the common adhesion mechanism of interfacial decade can be generally classified into two major categories
bonding. For substrates with reactive functional groups such based on the bonding method: glue-type and tape-type adhe-
as pretreated solid surfaces and tissues, interfacial bonding sives (Figure 2). Glue-type adhesives are made from liquid
can be achieved by the formation of covalent bonds.[16,30] At precursor solutions that are cured underwater during which
the polymeric length scale (nm to μm), flexible polymer chains molecular-level interfacial interactions occur. Subsequently,
are favored as they can adopt different conformations more the liquids are polymerized and/or crosslinked to form solids.
efficiently to accommodate the deformation required to form Glue-type adhesives generally have a high bonding strength
molecular bonds with the substrate. In the case of soft sub- and usually fail cohesively, which indicates that the adhe-
strates (e.g., hydrogels and tissues), the formation of trapped sion strength is much stronger than the cohesion strength.
entanglements can enhance interfacial bonding.[30] At a larger However, they require long curing times and the bonding
length scale (μm to mm), uneven surfaces or special micro- is generally irreversible. By contrast, tape-like adhesives are
structures can induce mechanical interlocking between the soft solids that can directly adhere to wet surfaces through
adhesive and the substrate, which can enhance underwater molecular interactions and/or physical suction. This type of
adhesion.[14,31] Moreover, inspired by nature, surface micro- adhesive usually exhibits instant and reversible adhesion.
structures that induce sucking mechanisms and surface chan- However, their bonding strength is generally weak because
nels for fast water drainage have been recently reported. of the poor interfacial contact resulting from inefficient dehy-
In addition to strong interfacial adhesion, the tough dration and the surface roughness of the substrates. Accord-
mechanical strength of bulk adhesives is an important factor ingly, glue-type adhesives are usually developed with a focus
for preventing cohesive failure. In general, the design principle on the design of chemical structures for solidification/curing
for tough materials involves the incorporation of reversible to ensure strong cohesion, whereas tape-type adhesives are
dynamic bonds or multiple networks that can dissipate energy designed with a focus on dehydration and the formation of
during deformation.[32,33] Moreover, a uniform polymer network strong interfacial bridging, which is a problem involving dif-
can prevent local stress concentration during deformation, ferent length scales.
Figure 2. Current underwater adhesives. a) Glue-type underwater adhesives, which are in liquid form and require a curing process to solidify. The
liquid can be monomer solutions, polymer solutions, polymer melts, coacervates, or their mixtures. b) Tape-type underwater adhesives, which are
soft viscoelastic elastomers or gels. Glue-type adhesives form full molecular bonding with the substrate, thus demonstrating strong and irreversible
adhesion, whereas tape-type adhesives usually have very weak but reversible adhesion due to the difficulty of forming molecular bonding in water.
Figure 3. Illustration of common test methods for underwater adhesion. a) Lap shear test. b) Tensile test. c) Tack test. d) Peeling test.
Underwater adhesion strength is generally measured by lap solution (such as phosphate buffered saline (PBS) buffer, saline
shear, tensile, tack, and peeling tests, as shown in Figure 3. The water, and seawater) followed by the application of external
underwater adhesion strength of glue-type adhesives is usu- pressure to the substrates for a certain period (seconds to min-
ally measured by the lap shear test (Figure 3a) and tensile test utes). Subsequently, the joint is maintained in the solution for a
(Figure 3b). The adhesion strength is defined as the maximum certain time (hours to days) to allow curing. During the curing
tensile force required for joint failure per unit area of joint. The process, the glue undergoes polymerization or crosslinking to
underwater adhesion strength of tape-type adhesives is usu- form polymer networks. The final cured bulk materials can be
ally measured by the tack test (Figure 3c). Generally, a piece of plastic films, elastomers, or hydrogels, depending on the nature
adhesive is fixed on the head of a probe, which is then pressed of the polymers.[25,37,38] Tables 1–4 list the glue-type underwater
against the substrate surface submerged in a liquid for a cer- adhesives and their adhesion strengths reported in literature.
tain time under a prescribed pressure. Subsequently, the probe It should be mentioned that only the systems glued and cured
is retracted until full detachment. Here, the adhesion strength underwater are shown in these tables.
is defined as the maximum tensile force during retraction per
nominal contact area. The peeling test is another common
method for the measurement of underwater adhesion strength 3.1. Monomer Solutions
(Figure 3d). In the peeling test, the adhesive and the substrate
are glued underwater, and then the adhesive is peeled from the Epoxy resin adhesives are typical glue adhesives based on
substrate surface at a certain angle (90° or 180°). The adhesion hydrophobic monomers, which are low-viscosity liquids before
strength for the peeling test is defined as the average load per curing. The adhesion performance strongly depends on the
width of the bonding line. The lap shear test and tensile test properties of the epoxy resin and curing agent.[39] Dolez et al.
have also been used for tape-type adhesives. studied the underwater adhesion of two vinyl-based ester resin
systems having different hydrophobicities.[40] They found that
the underwater adhesion strength of the less hydrophobic resin
3. Glue-Type Underwater Adhesives was almost independent of the substrate material (1.2–1.8 MPa),
whereas that of the more hydrophobic resin was lower for
Glue-type underwater adhesives are a type of liquid adhesive hydrophilic metal substrates (0.8–1.2 MPa) but considerably
that requires a curing process to enhance their cohesion and higher for hydrophobic plastic substrates (2.5–3.2 MPa). More-
ensure strong underwater adhesion. These types of adhesives over, upon aging, the more hydrophobic resin did not suffer
could be monomer solutions, polymer solutions, polymer adhesion loss for one month, whereas the adhesion of the less
melts, coacervates, or their mixtures. Generally, the joint is hydrophobic resin dramatically decreased after 20 days in water.
formed by applying glue between two substrates in an aqueous The results indicate that the high affinity of the resin to water
Table 1. Main components, measurement conditions, and adhesion performances of glue-type underwater adhesives based on monomer solutions.
Monomer solutions
Main components Substrates Test method Curing condition Adhesion strength Remarks Ref.
DGEBA SS Lap shear 7 d in water 1.2–5.9 MPa Stable in 80°C water 7 d [39]
DGEBA or SS Lap shear 40–50 min in water 0.5–2.1 MPa – [88]
DGEBF
Bis-GMA Metal, plastics Lap shear Blue light 2–6 MPa Aging depends on [40]
1 s to 10 min in water hydrophilicity
Cyanoacrylate Metal, plastics Lap shear Blue light 3–5.5 MPa Adhesion decrease 50% [89]
10–125 s in water in water after 30 min
Glycerol Iron Lap shear 12 h 5–20 MPa – [90]
monomethacrylate–PU
prepolymer
AAm, Ye’elimite Ceramic, Al, Lap shear 3–48 h in water 0.28–3.7 MPa Nanocrystals anchor [26]
plastic, wood on rough surface
DA, Alg-Na Glass, Al Lap shear 2 h in water 250–400 kPa – [38]
DA, Alg-Na, glycerol Glass, Al Lap shear Overnight in water 3–6 kPa (lap shear) – [43]
Tensile test 100–200 kPa (Tensile)
PEI, IPDI, Al Lap shear 0–24 in water 2.8 MPa (1 min) Catalyst-filled [91]
DABCO, 10 MPa (24 h) microcapsules
Glycerol
4-arm-pentaerythritol-DB24C8 Glass, metal, plastics, wood Lap shear 24 in water 0.2–3.2 MPa Hot-melt process [44]
DGEBA: diglycidyl ether of bisphenol A; DGEBF: diglycidyl ether of bisphenol F; bis-GMA: bis-phenol A diglycidyl ether dimethacrylate; PU: polyurethane; IPDI: isophorone
diisocyanate; DABCO: 1,4-diazabicyclo[2.2.2]octane; DB24C8: dibenzo-24-crown-8; SS: stainless steel; Al: aluminum.
makes the interfacial bonding more susceptible to weakening to control.[43] The unskilled operation of injecting water-based
by water attack. glue underwater may cause the diffusion of components. To
Zhou et al. synthesized a series of Mannich base curing resolve this problem, the authors further improved the adhe-
agents having different hydrophobicities and rigidities and sives using glycerol as a dispersant for alginate, dopamine,
studied the relationship between underwater adhesion and the Tris, and ferric salts.[43] When the high-viscosity glycerol glue
structure of the curing agents.[39] The epoxy cured with phenol- was applied to the adherend underwater, water and glycerol
modified m-xylylenediamine exhibited the highest underwater interdiffused, and the components (alginate, dopamine, Tris,
adhesion (5.9 MPa) and excellent durability. They explained that and ferric salts) dissolved and interacted with each other to
the introduction of a phenol group increased the hydropho- form a gel (Figure 4a).
bicity of the adhesive, thereby enhancing the interfacial adhe- To remove interfacial water, Pan et al. proposed an alter-
sion and cohesion strength.[39] native strategy of adding a water-absorbing filler to develop
Compared with hydrophobic glue adhesives, hydrophilic underwater adhesives.[26] They mixed an acrylamide (AAm)
systems present a greater challenge in the removal of the monomer, a crosslinker, an initiator, and the inorganic filler,
hydration layer. In recent years, mussel-inspired catechol ye’elimite, to form a paste-like hydrogel precursor. When the
chemistry has provided a new design strategy for underwater precursor is applied to a submerged surface, ye’elimite absorbs
adhesives because the catechol group can form strong bonds the surface water by the hydration process and generates
with various substrates in water.[23,41] Inspired by mussel nanocrystals, which enhance the network strength and accel-
foot proteins (mfps), Cholewinski et al. developed a hydrogel erate the gelation of the system. As a result, a high adhesion
composite glue using separate adhesive and polymer precur- strength was achieved on a ceramic surface (239.95 kPa) after
sors.[38] They coated the substrates with a dopamine–Fe–Tris 3 h of curing; the strength further increased to 3.7 MPa after
(tris(hydroxymethyl)aminomethane) solution and injected an two days of curing.
alginate (Alg) solution in between, following which the sub- In addition to monomers, supramolecular underwater
strates were pressed together. In this sandwich-like structure, adhesives assembled from low-molecular-weight molecules
dopamine (DA) auto-oxidizes into polydopamine (Tris-HCl have been recently developed by Li et al.[44] They incorporated
buffer, pH 8.5), which can coat any type of surface to induce dibenzo-24-crown-8 into four-armed pentaerythritol (P1) and
interfacial adhesion,[42] whereas the Fe3+ ions bridge polydopa- obtained a low-melting-point (52 °C) molecule that can be used
mine and the interdiffused alginate by forming coordination as a hot melt glue (Figure 4b). The supramolecular adhesive
bonds with the catechol group of dopamine and the carboxylate exhibited robust adhesion under high moisture and under-
group of alginate, thereby providing strong cohesion. Although water conditions to hydrophilic substrates such as steel and
the adhesives demonstrated a high underwater adhesion glass (>1.5 MPa) but relatively weak adhesion to hydrophobic
strength of up to 400 kPa, the bonding process was difficult plastic substrates (poly(methyl methacrylate (PMMA) and
Table 2. Main components, measurement conditions, and adhesion performances of glue-type underwater adhesives based on polymer solutions.
Polymer solutions
Components Substrates Test method Bonding condition Curing time Adhesion strength Remarks Ref.
P(DHS-co-VTEA-co-St) Al Lap shear Oxidizing agent 150–400 kPa Solvent: CH3Cl/CH3OH [37]
24 h in seawater
P(DHS-co-St) Al Lap shear 24 h in seawater 2–3 MPa Solvent: CH3Cl [48]
P(THS-co-St) Al Lap shear 72 h in water 3–5 MPa Solvent: CH3Cl/CH3OH [52]
Tensile test
P(DMA-co-BA) Metal, plastics Lap shear Oxidizing agent 0.2–1.2 MPa Solvent: CH3Cl [92]
24 h in water
P(THS-co-BA) Glass, plastics, tissue Lap shear 6 d in water/seawater ≈1 MPa Solvent: CH3Cl/CH3OH [51]
PVP-catechol Glass Lap shear Oxidizing agent 0.8–1.4 MPa Solvent: CH2Cl2/CH3OH [49]
24 h in water/seawater Wet adhesion > dry adhesion
PVP-catechol Glass, Al Lap shear Oxidizing agent 1.0–1.3 MPa Solvent: CH2Cl2/CH3OH [50]
24 h in seawater
P(DA-alt-BGOP) Glass, metal Lap shear Oxidizing agent 0.8–1.1 MPa Solvent: CHCl3/CH3OH [53]
7 d in seawater
P(DMA-co-MMA-co- MAEP) SS Lap shear Oxidizing agent 80–500 kPa Solvent: CH3OH [47]
24 h in water
P(NIPAM)-g-P(DMAAm) Glass Tack test Temperature trigger gelation ≈65 kPa Sol–gel transition [93]
Bridging polymer + EDC + NHS Tissue 180° peel test Wet surface >1000 J m–2 Aqueous solution [30]
<1h Physical and covalent bonding
Chitosan + EDC + NHS Hydrogels 180° peel test Wet surface ≈2000 J m–2 Aqueous solution [94]
1.5 h Physical and covalent bonding
Citrate-catechol Tissue Lap shear Wet surface 140–240 kPa Aqueous solution [95]
2 h in humid
TA + silk fibroin +HA Bone Lap shear Wet surface 600–950 kPa Aqueous solution [96]
P(DA-co-triacrylate) Tissue Lap shear Oxidizing agent 20–40 kPa (15 min) Solvent: acetone [97]
15 min, 1 h, 1 d in water 60–90 kPa (1 d) Degradable, low cytotoxicity
PVA Glass, metal, plastics Lap shear 7 d in water 100–300 kPa Solvent: DMSO [98]
VTEA:p-vinyltolyltriethylammonium chloride; St: styrene; THS: 3,4,5-trihydroxystyrene; DMA: dopamine methacrylate; BA: N-butyl acrylate; BGOP: 2,2-bis(4-glycidyloxy-
phenyl) propane; MMA: methacrylamide; MAEP: monoacryloxyethyl phosphate; DMAAm: N,N-dimethylacrylamide; EDC: 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide;
HA: hydroxyapatite.
polytetrafluoroethylene (PTFE), <0.65 MPa) because the interfacial that the extended structures facilitated the facile interaction
adhesion is mainly driven by hydrogen bonding. In addition, P1 of P1 with surfaces through supramolecular interactions,
exhibited robust adhesion compared with the control molecules including hydrogen bonds, hydrophobic interactions, and coor-
without closed ring-type crown ether structures. They considered dinate bonds.
Table 3. Main components, measurement conditions, and adhesion performances of glue-type underwater adhesives based on polymer melts.
Polymer melts
Polyester-catechol Glass, metal, plastics Lap shear 12 h in water, 10 min UV, 24 h 100–700 kPa – [25]
in water
Polyester-catechol Tissue Tack test UV 300 s in water 10–20 kPa Degradable, nontoxic, antioxidant [54]
Poly(glycerol sebacate acrylate) Wet tissue Tensile test UV 30 s ≈20 kPa Hemostatic property [99]
Anthracenyl-PEI Glass Tensile test 2–150 s UV in water 100 kPa (2 s) Reversible [27]
600 kPa (120 s) (photo-/thermal-responsive)
Liquid PDMS + PTFE particles Glass, metal Lap shear No curing ≈2 kPa (lap) – [100]
Tensile test 8–35 kPa (tensile)
Hyperbranched polythioether + Tissues Lap shear UV in saline water 20–40 kPa Non-hemolytic [101]
PEG-dMA + initiator
Table 4. Main components, measurement conditions, and adhesion performances of glue-type underwater adhesives based on coacervates.
Coacervates
P(AAm-co-MAEP-co-DMA) + Bone Lap shear Oxidizing agent 50–120 kPa Adhered in PBS buffer 4 [69]
P(AAm-co-APMA) 24 h in 100% humidity months
P(MAEP-co-DMA) + amine- Al Lap shear Oxidizing agent 350–800 kPa – [70,72]
modified gelatin + Ca2+/Mg2+ 24 h in water
P(MOEP-co-DMA) + P(AAm- Al Lap shear Oxidizing agent 400–1200 kPa Create a second network [71]
co-APMA) + PEG-dA 20–24 h in water
Protein-DOPA + HA Metal, tissue Lap shear Oxidizing agent 100–880 kPa sealed ex vivo urinary [102]
12 h in water fistulas
PAE + lignosulfonate Glass, metal, plastics, ceramics Lap shear Instant or 2 d in water 14–120 kPa (instant) Adhesion stable in pH [103]
300–450 kPa (2 d) 6–10, 1.0 m NaCl, 100 °C
PAE + TA Glass, metal, plastics, wood Lap shear 24 h in water 80–450 kPa Reusable [104]
12 cycles without
decrease
PAE + Li-TFSI Glass, metal, plastics, wood Tensile test Instant 40–80 kPa Reusable [105]
10 cycles without
decrease
P(AAc-g-NIPAM) + Glass Tack test Temperature or ionic strength 1–10 kPa Thermoresponsive [74–76]
P(DMAPAA-g-NIPAM) trigger gelation Ionic strength
responsive
P(NIPAM-b-AAc-b-NIPAM) Glass Tack test Temperature trigger gelation 14 kPa Thermoresponsive [77]
+ P(DMAEMA)
PAH + PPi or TPP Glass, plastics Lap shear 3 h in water 250–450 kPa Cycle 2 decrease 50% [58,83]
Short peptide + POMs Glass, metal, plastics Lap shear 2 h in water 30–40 kPa Reusable [81]
3 cycles without
decrease
Histidine + H4SiW12O40 Glass, metal, plastics, wood Lap shear 4 h in air 15–440 kPa Electrochromic features [79]
NA + H6P2W18O62 Glass, SS, plastics Lap shear 15 min in water 3–15 kPa Aqueous Batteries [80]
Glutathione + POMs Glass, metal, plastics Lap shear 40 min in air 20–55 kPa Redox-responsive [82]
Test underwater
P(AAc) + amorphous CaCO3 Glass, Al, plastics, tissue Lap shear 24 h in water 10–250 kPa Reusable [106]
Cycle 6 decrease 30%
PVA + TA Glass, metal, plastics Tack test 3 s in water 50–70 kPa Reusable [85]
10 cycles without
decrease
PEG + TA Tissue Tensile test 1 min wet surface ≈100 kPa Reusable [84]
PEG + H4SiW12O40 Tissue Tensile test 60 s wet surface ≈110 kPa Reusable [61]
Hybrid polyester Glass Lap shear 15 min in water 60–100 kPa – [63]
Tack test 10 min UV
Hyperbranched polymer Glass, metal, plastic, wood, Lap shear Underwater 10–14 kPa (0 h) Reusable [64]
with catechol ceramic 0, 2, 12 h 100–140 kPa (2 h) Cycle 2 decrease 40%
200–400 kPa (12 h)
P(NIPAM-co-AAc-co-MEA) Glass, Si, plastics Tack test Instant in water 4–8 kPa (40 °C) Thermosensitive [60]
+ Mn+ 2–4 kPa (20 °C)
Pluronic P123 + H4SiW12O40 Glass, plastic, wood Tack test 10 s in water 300–600 kPa Electrochromic features [107]
APMA:N-(3-aminopropyl)methacrylamide hydrochloride; MOEP: 2-(methacryloyloxy) ethyl phosphate; PEG-dA: polyethylene glycol-diacrylate; PAE: polyamidoamine-epi-
chlorohydrin; Li-TFSI: bis(trifluoromethane) sulfonimide lithium salt; AAc: acrylic acid; DMAPAA: dimethylaminopropyl acrylamide; DMAEMA: 2-(dimethylamino)ethyl
methacrylate; PAH: poly(allylamine); NA: 3-(2-naphthyl)-l-alanine; MEA: 2-methoxyetheyl acrylate.
3.2. Polymer Solutions strategy is to introduce catechol or gallol groups onto the
polymer chains by copolymerization or post-modification
In addition to catechol-based monomers, polyphenolic polymers (Figure 5a). The copolymers reported in this category are gener-
can also be used to develop underwater adhesives. A common ally water immiscible. Therefore, the glues consist of polymers
Figure 4. Underwater adhesives synthesized from monomer solutions. a) Illustration of water activation of glycerol-dispersed algae–mussel glue.
Reproduced with permission.[43] Copyright 2020 American Chemical Society. b) Chemical structure, macroscopic view, and underwater adhesion of
low-molecular-weight supramolecular adhesives. Reproduced with permission.[44] Copyright 2020 American Chemical Society.
and organic solvents (Table 2), with chloroform or dichlo- definite chemical structures and molecular weights. Therefore,
romethane being the most commonly used solvents owing to they can be used to not only develop underwater adhesives,
their higher density than that of water. but also study the adhesion mechanism based on the rela-
Compared with dopamine-based monomer glue systems, tionship between polymer properties and adhesion strength.
whose polymerization process and final structures are less For example, Wilker et al. synthesized a series of biomimetic
understood,[45,46] polymers with catechol or gallol groups have polymers by copolymerizing 3,4-dihydroxystyrene and ionic
Figure 5. Underwater adhesives synthesized from catechol-based copolymer solutions. a) Incorporation of catechol (R = H) or gallol (R = OH) group
onto polymer chains by copolymerization or post-modification. b) Poly(catechol-ionic) copolymers synthesized by Wilker’s group.[37,47] c) Catechol-based
copolymers with different polarities synthesized by Wan’s group.[50] d) Synthetic route of a catechol-based copolymer with alternating sequence.[53]
monomers and studied their underwater adhesion to metal is attributed to the tridentate-related interfacial bonds, which are
substrates (Figure 5b).[37,47] They found that the underwater stronger and more stable than the bidentate and monodentate-
adhesive strength of the catechol-based polymers containing related bonds under wet conditions. In addition, considering
either cationic or anionic groups was higher than that of the cohesive failure of adhesives, they chose styrene as a comon-
the control polymers without ionic groups. It is considered omer because it would increase the cohesive interactions, further
that the charged groups can interact with metallic surfaces improving the underwater adhesion.[52] By optimizing the mole-
through ionic, coordinate, or hydrogen bonding, which gener- cular weight, gallol content, and curing conditions, a high under-
ally improves the adhesion. However, the amount of charged water bonding strength of ≈5 MPa was achieved for the copol-
groups needs to be carefully tuned because an excessively high ymer adhesive, which is currently the highest bonding strength
charge density decreases the adhesion. achieved for mussel-inspired underwater adhesives.
Furthermore, they studied the relationship between mole- Recently, Zhou and co-workers synthesized catechol-func-
cular weight and underwater adhesion using a simple neu- tionalized polymers with alternating sequences by epoxy-amino
tral copolymer, poly(catechol-styrene).[48] They found that the click chemistry (Figure 5d), which increases the catechol con-
adhesive performance first increased and then decreased with tent of the polymer and allows the control of the polymer
increasing molecular weight of the polymer. When the mole- sequence.[53] As a result, the polymer exhibited a high adhesive
cular weight of the polymer was ≈85 000 g mol–1, the glue exhib- strength under both dry and underwater conditions. This work
ited the highest underwater adhesion strength of ≈2.5 MPa. In a provides an efficient and facile strategy for synthesizing under-
polymer glue system, low-molecular-weight polymers efficiently water adhesives with controlled sequences, which play a key
wet the adherend surface, whereas high-molecular-weight poly- role in material properties but is often overlooked.
mers endow the glue with enhanced cohesion through chain
entanglement. Therefore, the glue exhibits the best underwater
adhesion at an optimum molecular weight. 3.3. Polymer Melts
Further, Wan and co-workers studied the structures of mfps
to determine whether the chemical structure of the polymer Because the majority of currently available polymer glues require
backbone affects underwater adhesion.[49] They synthesized organic solvents, which may be harmful to humans and the envi-
four copolymers with different polarities but similar catechol ronment, underwater adhesives based on solvent-free polymer
contents and molecular weights (Figure 5c)[50] and compared melts have attracted considerable attention in recent years (Table
their underwater bonding properties. They found that the 3). To prepare adhesives with good spreadability, low-viscosity
polarity of the polymers contributes to strong underwater polymer melts are required. However, a low viscosity decreases
bonding, with the underwater bonding strength increasing the cohesive strength, which results in poor adhesion. Therefore,
with an increase in the polarity of the polymer backbone. For as a general strategy, crosslinkable moieties are introduced into
example, the underwater bonding strength of the polymer with low-glass transition temperature (Tg ) polymers. Moreover, sur-
the poly(N-vinylpyrrolidone) (PVP) backbone (1.0 MPa), having face dehydration is realized by two distinct strategies: increasing
the highest dielectric constant, was much higher than that polymer hydrophobicity to break the hydration layer and utilizing
of the polymer with the polystyrene backbone (0.2 MPa). We polymer hydrophilicity to absorb interfacial water.
believe that the effect of polymer polarity on adhesion might be For instance, Joy and co-workers designed a polyester adhesive
related to the modulus of the adhesives in water. After curing, sealant with three characteristic components (Figure 6a):[25,54]
the low-polarity polymer becomes a rigid plastic film, whereas 1) soybean-oil-derived aliphatic chains that can reduce the Tg
the high-polarity polymer becomes a relatively soft material. and increase the hydrophobicity of the polymer to remove inter-
Generally, a soft adhesive has a high resistance against crack facial water, 2) catechol groups, which provide strong interfacial
growth and exhibits a high adhesion strength. interactions, and 3) coumarin units that undergo a crosslinking
Ejima and co-workers studied the effect of phenolic compounds reaction under UV irradiation, thus increasing the cohesive
(phenol, catechol, and gallol) on underwater adhesion proper- strength of the material. As a result, the developed polyester
ties.[51] They found that the adhesive performance of the gallol- glue exhibited not only high underwater adhesion in water
based copolymers was much better (seven times higher) than that (700 kPa), but also other properties such as cell compatibility,
of the catechol-based copolymers in water. Such robust adhesion hydrolytic degradability, and radical scavenging ability.
Figure 6. Underwater adhesives synthesized from polymer melts. a) Chemical structure of polyester containing three characteristic components
reported by Joy and co-workers.[25] b) Anth-PEI (polyethylenimine) as a reversible underwater glue reported by Wang et al.[27]
Wang et al. synthesized a reversible underwater glue based originates from the liquid–liquid phase separation of a solution
on the dynamic covalent bonding of anthracene groups via (Figure 7a).[55,56] This phenomenon is driven by molecular asso-
the [4+4] dimerization reaction (Figure 6b).[27] In their strategy, ciations, including electrostatic interactions between oppositely
anthracenyl groups were introduced on polyethylenimine charged polyelectrolytes,[57] or cationic polyelectrolytes and mul-
(PEI). The fluidic viscous hydrophilic polymer served as a glue tivalent anions,[58] as well as coordinate bonding,[59,60] hydrogen
when spread on the adherend surface and absorbed the inter- bonding,[61,62] hydrophobic interactions,[63,64] and cation–π inter-
facial water molecules. Upon irradiation, the polymer melt actions.[65] Coacervates have unique characteristics such as a
formed a network by the covalent crosslinking of the anthra- high polymer density, low viscosity, high diffusivity, and low
cene moieties, which resulted in strong underwater adhesion. interfacial tension.[65–67] Nature has taken advantage of coacer-
The crosslinks dissociated upon heating at 70 °C, leading to the vating proteins to achieve underwater adhesion. For instance,
partial conversion of the adhesive back into the fluidic viscous sessile organisms such as sandcastle worms and mussels gen-
state, which resulted in poor adhesion. Such stimuli-responsive erate adhesive proteins in aqueous media through coacervation,
adhesion endows the adhesives with underwater transport- thus realizing robust adhesion in seawater.[17,68] Inspired by
ability in response to temperature. It should be mentioned that this, various coacervate-based underwater adhesives have been
the glue dissolves in water in several minutes in the absence of developed in recent years because of the beneficial properties of
UV curing. coacervates for underwater adhesion (Table 4).
Stewart and co-workers developed a series of underwater
adhesive coacervates inspired by sandcastle worms.[69–73] They
3.4. Coacervates synthesized an anionic polymer containing phosphate and
catechol groups and a cationic polymer with amine groups
A coacervate is a liquid consisting of a polymer-rich liquid phase (Figure 7b). Upon mixing, the oppositely charged polymers
in thermodynamic equilibrium with a dilute phase. A coacervate coalesced into a dense coacervate fluid, which can be injected
Figure 7. Underwater adhesives synthesized from coacervates. a) Schematic of complex coacervate based on oppositely charged polyelectrolytes,
polycations, and anionic polyoxometalates, and hydrogen bonds induced by polymer/tannic acid systems. b) Adhesive comprises dopamine-containing
poly-phosphate, poly-aminated gelatin, and divalent cations designed by Stewart and co-workers.[70] c) Electrochromic feature of POM-based adhesive
coacervates. Reproduced with permission.[80] Copyright 2018 Wiley-VCH. d) Chemical structure of tannic acid.
and adhered to a surface under water. Covalent crosslinking polymer immediately self-aggregated to form coacervates while
through catechol moieties solidifies the adhesive, resulting in displacing the hydration layer of the surface, thereby ensuring
strong underwater adhesion after curing.[70] To further increase close contact of catechol to the surface. This resulted in rapid
the adhesion strength, they created a second polymer network and strong underwater adhesion in various aqueous environ-
within the crosslinked coacervate network, achieving a max- ments without the use of any oxidant.
imum shear bond strength of ≈1.2 MPa.[71] In addition, they In summary, owing to full contact at the molecular level and
evaluated the potential application of such adhesive coacervates strong macroscopic mechanical interlocking, glue-type under-
in the biomedical field. In their in vivo test model, the adhe- water adhesives generally delaminate within the adhesive film
sives served as a sealant for the defects in a fetal membrane (cohesive failure), which indicates that the adhesion strength is
patch.[73] much stronger than the cohesion strength. Despite their high
Kamperman and co-workers introduced a poly(N-isopropyl adhesion strength, glue-type adhesives have certain disadvan-
acrylamide) (PNIPAM) segment into a polyelectrolyte coac- tages such as a long curing time (varying from hours to days),
ervate and developed a multi-responsive complex coacervate generally irreversible adhesion, and the need for organic sol-
underwater adhesive.[74–77] The adhesive is a fluid coacervate vents in some cases. Therefore, performance improvement can
at room temperature and has a high ionic strength. With an be achieved by a variety of approaches such as enhancing the
increase in temperature or a decrease in the ionic strength of bulk mechanical strength under aqueous conditions by intro-
the environment, the thermoresponsive chains self-associate ducing an energy dissipation mechanism, reducing the curing
into hydrophobic domains. Consequently, the fluid transitions time by introducing external stimuli (light, temperature, pH,
into a viscoelastic gel with underwater adhesiveness. ionic strength, etc.), introducing dynamic crosslink mechanism
Small multivalent molecules can also strongly bind to to realizing reversible adhesion, improving strategy to reduce
oppositely charged polyelectrolytes and form coacervates. For or not use organic solvent, rapidly and efficiently expelling
example, polyoxometalates (POMs) are a large family of inor- water from a large joint area. Moreover, a deeper understanding
ganic nanoclusters with a polyanionic surface, uniform size, of the underwater mechanism is also needed not only from
and well-defined topological redox properties.[78] They have the view of chemistry but also the mechanics and physics of
been used as crosslinkers to connect polycations and form materials.
networks via electrostatic interactions. For example, Li and co-
workers developed a series of multifunctional wet adhesives by
the one-step self-assembly of cationic biomolecules and poly- 4. Tape-Type Underwater Adhesives
oxometalates.[79–82] The POM-based coacervates exhibited not
only adhesion to various substrates, but also electrochromic Tape-type underwater adhesives are soft solids that can directly
properties (Figure 7c). Other types of multivalent anions such adhere to substrates in water. Achieving strong underwater
as pyrophosphate (PPi) and tripolyphosphate (TPP) can also adhesion is much more challenging for tape-type adhesives
interact with cationic polymers to form underwater adhesive than it is for glue-type adhesives. This is because of two rea-
coacervates.[58,83] sons. First, breaking the hydration layer at the interface of a
In addition to electrostatic interactions, hydrogen bonding joint is more difficult in the case of bulk materials than it is
and hydrophobic interactions have also been used to fabri- in the case of molecule-based liquid glues. Second, water drop-
cate underwater adhesive coacervates. For example, Lee et al. lets can easily become trapped at the soft interface, which not
chose the natural compound tannic acid (TA, Figure 7d) to only decreases the real contact area, but also introduces crack
crosslink nonionic polymers (polyvinyl acetate, PVA and poly- defects. To resolve these problems, different strategies have
ethylene glycol, PEG) into coacervates.[84,85] Because TA is rich been proposed to improve the underwater performance of tape-
in pyrogallol and catechol groups, it can form strong multiple type adhesives.
hydrogen bonds with polymers.[62,86,87] The TA-based coacer- Based on the bonding mechanism, tape-type adhesives can
vates exhibited instant underwater adhesion to diverse sub- be divided into two main categories: molecular interaction-
strates, and the adhesive capability could be retained in water based adhesives and physical suction-based adhesives. The
even after 24 h. Moreover, the coacervates exhibited reversible former are materials based on molecular interactions at the
adhesion and it maintained nearly 100% adhesion after 10 interface, whereas the latter are materials with microstruc-
adhesion–detachment cycles cycles. tures that can drain water and provide adhesion by the suction
Zeng and co-workers recently reported a novel type of adhe- effect accompanied by capillarity. The fabrication of tape-type
sive coacervate formed by mixing silicotungstic acid and non- adhesives that are completely based on molecular interactions
ionic PEG in water.[61] They found that the adhesion strength is facile; however, they have low adhesion strengths especially
of the coacervate on wet tissue surfaces is much higher than for hydrophilic polymer systems. By contrast, physical suction-
that on dried surfaces because the presence of water increased based adhesives typically exhibit excellent adhesion perfor-
the mobility of the PEG chains. This adhesive was successfully mance such as good underwater adhesion, high repeatability,
applied as a hemostatic agent to treat organ injuries without and no chemical contamination on the adhered surfaces. How-
any hemolytic activity, which suggests its potential application ever, they usually require a delicate structural design, compli-
in hemostasis. cated fabrication processes, and are difficult to mass produce.
Cui et al. synthesized a hyperbranched polymer with a hydro- The tape-type underwater adhesives based on molecular inter-
phobic backbone and hydrophilic catechol side branches.[64] actions and bioinspired microstructures reported in literature
Upon contact with water, the hydrophobic chains of the are summarized in Tables 5–7.
Table 5. Tape-type underwater adhesives based on nanometer-thick polymer coatings, plastic films, and elastomers.
Nanometer-thick polymer coatings

Components (Material type) Substrates Test method Bonding condition Curing time Adhesion strength/energy Remarks Ref.
CB[7] Fc coating Lap shear 1 h in water ≈340 kPa host-guest binding [108]
then maintain
P(DOPA-co-AD-co-MEA) + Si Tack test 0 s in water Thermosensitive [109]
P(NIPAM-co-CD) 4 kPa (flat)
10 kPa (pillar)
Plastic films
Components Substrates Test method Bonding condition Adhesion strength Remarks Ref.
Curing time
P(CA-co-EHA-co- DMAEMA-co- SS Tack test Wet surface 100–150 kPa – [120]
AAc) 5s
P(AAc-co-NHS ester) + gelatin Tissue 180° peel test Wet surface 400–710 J m–2 (peel) Surface water [28]
or chitosan Lap shear 5s 80–140 kPa (lap shear and absorption
Tensile test tensile)
Boc-L-DOPA-OMe Glass Tack test 5 min in water 91–265 kPa – [121]
P(BA-co-AAc-co-DMA) SS, plastic 180° peel test 24 h in water 400–2000 J m–2 – [122]
P(BA-co-AAc-co-Lysine-DOPA) SS 180° peel test 24 h in water 600–1280 J m–2 – [123]
P(EHA-co-AAc) Glass Tack test 100 s 400–500 kPa – [124]
Aldehyde dextran sponge Wet tissue Lap shear Wet surface ≈100 kPa Surface water [125]
10 min absorption
Buckypaper Tissue 90° peel test Wet surface 90–190 J m–2 (peel) Surface water [126]
Lap shear 30 s ≈20 kPa (lap shear) absorption
Elastomers
Components Substrates Test method Bonding condition Adhesion strength Remarks Ref.
Curing time
P(PPO-co-GBC) SS Tack test 5s 240 kPa Thermal sensitive [112]
180° peel test 500 J m–2
Thermoresponsive shape Glass Tack test Minutes in water/oil 1.6–1.8 MPa Glassy/rubbery states [110]
memory polymer transition by heat
PDMS Glass, plastics 90° peel test Underwater 80–100 J m–2 Janus structure [111]
P(IPDI-co-PTMG-co-DA) Tissue Tensile test 2 h in water 19 kPa – [2]
P(DMA-co-BA-co-TMSPMA)/ SS Lap shear 1–3 d in water ≈0.8 MPa Solvent treated surface [24]
P(DMA-co-BA)
PVP + PU Surface treated glass 45°–180° peel test Wet surface ≈140 J m–2 dissolving–wetting– [127]
adhering process
AD: adamantine; CA: catechol acrylate; EHA: 2-ethylhexyl acrylate; Boc-L-DOPA-OMe: methyl(S)-2-[(tert-butoxycarbonyl)amino]-3-(3,4-dihydroxyphenyl)propanoate;
P(PPO-co-GBC): poly(propylene oxide-co-glycidyl butyrate carbonate); PTMG: polytetramethylene glycol; TMSPMA: 3-(trimethoxysilyl)propyl methacrylate.
4.1. Adhesives Based on Molecular Interactions with host molecules cucurbit[7]uril (CB[7]) and a “hook” sur-
face with guest molecules aminomethylferrocene (Fc)—using
As bulk adhesives, molecular interaction-based tape-type mate- a “velcro”-type mechanism (Figure 8a). Because the host–guest
rials can be nanometer-thick polymer coatings, plastic films, complex is formed via water disposal, their “velcro” exhibited
elastomers, and hydrogels, whose underwater adhesion abilities excellent adhesion strength in water. Moreover, reversible adhe-
vary based on the material properties and bonding mechanisms sion could be achieved by changing the valence state of the Fc
(Tables 5 and 6). guests. The oxidation of Fc into Fc+, whose binding affinity to
A major challenge in the underwater adhesion of molecular CB[7] is much lower than that of Fc, decreased the adhesion
interaction-based tape-type adhesives is the displacement of ability of “velcro.”
interfacial water and formation of an effective contact surface. Zhao et al. designed a smart surface with switchable under-
To resolve these issues, Ahn et al. proposed an ideal method water adhesive properties.[109] In this strategy, they combined
using supramolecular host–guest chemistry.[108] They function- host–guest interaction, catechol chemistry, and a thermorespon-
alized two silicon surfaces—a “loop” surface functionalized sive polymer in one system (Figure 8b). At low temperatures
Table 6. Tape-type underwaçter adhesives based on hydrogels.
Hydrogels
Components Substrates Test method Bonding condition- Adhesion strength Remarks Ref.
Curing time
P(DMAAm) or P(AAm) P(AAc) brush Tack test 0 s in water <2 kPa – [128]
P(HEMA-co-DMA) Glass, metal, plastic Tack test 5 min in water 2–6 J m–2 – [129]
Alginate-catechol Glass, gelatin, gold Tack test 15 min in water 0.6–1.2 J m–2 – [130]
CD Azobenzene hydrogel Lap shear 5 min in water 6 kPa – [131]
P(MATAC-co-AAm) P(AAc) gel Tack test 1–1200 s in water 10–20 kPa – [132]
P(AAm) + TA + Alg-Na Glass, Al, plastic, tissue Lap shear Underwater 5–20 kPa – [133]
P(AAc-co-MBA) Glass Tack test 240 s in water ≈3 mN – [134]
Hydrophobically-modified Tissue Tensile test 2 d in water 5–15 kPa Wound dressing [135]
gelatin
P(AAc) + TA + chitosan + Al3+ Glass, tissue Lap shear 10 s in water 4–18 kPa Reusable (5 cycles) [136]
Specific adhesion to
tissues
P(cation-adj-π) Glass, metal, plastics, Tack test 10 s in seawater 60 kPa Reusable (16 cycles) [117,118]
hydrogels Lap shear Stable 14 d
Ionic bonding in
seawater
P(cation-co-πrich) Glass, metal, plastics Tack test 10 s in water 100–180 kPa Reusable (50 cycles) [3]
Lap shear Stable 100 d
P(AAc-co-BA-co-Aa) Glass, metal, plastics Lap shear 30 min in 5–15 kPa (lap shear) Adhesive in organic [137]
organogel 90° peel test Water, saltwater, 200–400 J m–2 (peel) solvents
organic solvent
P(AAc-co-BA-co-Aa) Glass, metal, plastics Lap shear 5 min to 24 h in water 40–71 kPa Solvent exchange [113]
organogel
P(AAc-co-MEA-co-Aa-co-AU) Glass, metal, plastics Lap shear 30 min 5–25 kPa – [138]
P(AAm-co-urushiol) + Glycerol Glass 180° peel test 2 min in water 200–400 J m–2 (peel) Antifreezing [139]
Lap shear Then 30 min in air ≈16 kPa (lap shear) anti-heating
P(ACG) + polycations Tissues, hydrogel 180° peel test 0–8 h in water 120–250 J m–2 Stable 8 h [140]
Janus structure cytocompatibility
P(AAm-co-SMA) + SDS + Fe3+ Glass, metal, plastics Tack test Wet surface 15–60 kPa Reusable (50 cycles) [114]
120 s Stable 15 d
Polydiolcitrates/P(GMA) Glass, silica, metal, plastics Tack test 0 s in water 50–100 kPa Thermosensitive [141]
HPMC/SiW-P(DMAEMA)/Fe3+ Glass, metal, plastics Lap shear 1 h in water 45–55 kPa – [142]
Silk fibroin + TA Tissue Lap shear Wet surface 120–150 kPa – [143]
20 min in humid
Hydrazide-derivatized Cellulose membrane 90° peel test Wet surface 20–50 J m–2 – [144]
P(NIPAM-co-AAc)
PEG-dA + TA Glass, tissue Tensile test In water 130 kPa (tensile) – [145]
Lap shear 22 kPa (lap shear)
PAH-catechol Glass, tissue, PET Lap shear 1 h in water 1.5–10 kPa – [146]
P(AAc-co-UCAT) + chitosan Tissue 180° peel test 2 min in water 900–1200 J m–2 Tissue-selective [147]
30 min in air adhesion
P(AAm-co-MAEDS) + P(LMA) Glass, metal, plastics Lap shear 5 min in seawater 5–35 kPa Organohydrogel [148]
+ laponite Strength decrease
during soaking
P([MATAC][TFSI]) Glass, metal, plastics, wood Lap shear 12 h in water 200–700 kPa Ionic liquid gel [149,150]
Reusable (5 cycles)
Stable 10 d
P(HEMA-co-PEG-dA) PDMS, PS Lap shear 5 min in water 1.8–2.4 kPa Drainage [151]
Polyampholyte Glass, PS, PA, tissue Tack test 10 s in water 12–27 kPa Drainage [29]
DMAAm: N,N-dimethylacrylamide; HEMA: 2-Hydroxyethyl methacrylate; MATAC: 2-(methacryloyloxy)-ethyltrimethylammonium chloride; MBA: N,N′-methylenebisacrylamide;
Aa: acrylated adenine; AU: acrylate uracil; ACG: N-acryloyl 2-glycine; GMA: glycidyl methacrylate; HPMC: hydroxypropyl methylcellulose; SiW: tungstosilicic acid; UCAT:
3-((8,11,13)-pentadeca-trienyl)benzene-1,2-diol; MAEDS: [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl); LMA: lauryl methacrylate; PA: Polyampholyte.
Table 7. Tape-type underwater adhesives çbased on bioinspired microstructures.
Inspiration Polymer Substrates Test method Adhesive strength Remarks Ref.

Beetle PVS Glass Tack test 140–170 mN – [159]
Bio-inspired PDMS Hydrophobic and hydro- Peel test <1.2 J m–2 – [160]
philic treated
Remora fish PDMS glass Tack test 270 kPa (tack test) 65 cycles [156]
Lap shear 195 kPa (lap shear)
Gecko PU coating P(DMA-co-MEA) Glass Tack test ≈0.4 N 100 cycles [161]
Gecko PDMS coating Glass, silicon wafer, Tack test ≈10 kPa (40°C) [157]
poly(DA-MEA-NIPAM) plastics ≈2 kPa (20°C) 10 cycles
Thermosensitive
Bio-inspired PEGDMA Glass, Au, tissue Tack test ≈120 kPa (tack test) [162]
Lap shear ≈15 kPa (lap shear) 100 cycles
capillary adhesion
Octopus PUA silicon wafer Tack test 35–45 kPa 10 000 cycles [154,163]
Octopus PUA silicon wafer Tack test 120 kPa 100 cycles [155]
Bioinspired Parylene/Germanium nanowire Itself Lap shear ≈220 kPa Interpenetration [164]
forests
Bioinspired HEMA-co-PEGDA hydrogel PDMS, PS Lap shear 1.8–2.4 kPa – [151]
Suction cup polyurethane Glass Tack test ≈1 MPa Switchable adhesion by retraction [158,165]
velocity
Amphibians and PDMS Silicon wafer, tissue Peel test 15–25 J m–2 (peel) – [166]
Octopus Tack test 40–50 kPa (tack)
Octopus PDMS Glass Tack test ≈40 kPa Mfps coated [167]
Clingfish Silicone elastomer Silicone elastomer Tack test ≈14 kPa – [168]
Gecko PDMS Glass, plastics Tack test 10–40 mN Self-peeling switchable [169]
Hook PEG-dMA Adhesive itself Tensile test 80–140 kPa (tensile) Swelling induced interlocking [31]
Lap shear 600–800 kPa (lap shear)
PVS: polyvinylsiloxane; PUA: poly(urethane acrylate); PEG-dMA: poly(ethylene glycol)-dimethacrylate; PS: polystyrene.
(25 °C, below the lower critical solution temperature, LCST), target surface. Above the LCST, P(NIPAM-co-CD) becomes
the thermosensitive polymer P(NIPAM-co-CD) (CD: b-cyclo- hydrophobic and collapses into agglomerates. As a result, the
dextrin) is water soluble and exposed on the surface, forming DOPA group is exposed on the surface, which results in inter-
a swelling layer. Thus, the adhesive moiety, DOPA, is spatially facial adhesion. Owing to this mechanism, the adhesive coating
stabilized and confined underneath the hydrated P(NIPAM) exhibited good underwater adhesion at a high temperature
chains, screening the interfacial interaction of DOPA with the (40 °C) but weak adhesion at a low temperature (25 °C).
Figure 8. Adhesives based on molecular interactions. a) Supramolecular “Velcro” strategy for underwater adhesion based on CB[7]- and Fc-modified
surfaces. Reproduced with permission.[108] Copyright 2013 Wiley-VCH. b) Schematic of the screening and recovery of interfacial interaction of DOPA
under different temperatures. Reproduced with permission.[109] Copyright 2017 Springer Nature.
The dehydration strategy involving the use of water- Similarly, Park et al. achieved reversible super-strong under-
absorbing materials has also been implemented for tape-type water adhesion by experimenting with the glassy state and
adhesives. For example, Zhao and co-workers developed a dry rubbery state of epoxy-based elastomer.[110] They heated the
film made from a combination of a biopolymer and a copol- elastomer to a compliant rubbery state to make contact with
ymer containing N-hydroxysuccinimide (NHS) groups.[28] The a submerged substrate under an applied preload. Full contact
adhesion mechanism is based on the absorption of interfacial was achieved by squeezing out the water layer at the soft inter-
water by the dried biopolymer film, which results in fast tem- face under pressure. Thereafter, the temperature was reduced
porary adhesion to the tissue surface. Subsequently, covalent to below Tg, at which the interface of the elastomer was tempo-
bonds were formed between the NHS and amine groups on rarily fixed in its glassy state. As a result, robust bonding was
the tissue surface. Thus, the tape exhibited strong adhesion to achieved with an underwater adhesion strength of 1.8 MPa.
diverse wet tissue surfaces, demonstrating excellent application Moreover, the permanent shape recovered after reheating,
potential as a tissue adhesive and sealant. leading to the reinvasion of the interface by water; this resulted
In addition to nanometer-thick polymer coatings and in reversible adhesion.
plastic films, hydrophobic elastomers are also used for Another strategy is the introduction of a solvent to lower the
underwater adhesives.[2,110,111] Because there is no curing Tg of the polymers. For example, Liu et al. found that the appli-
process, the adhesion performance of the elastomer is pres- cation of a small amount of hydrophobic solvent (e.g., chloro-
sure sensitive and highly dependent on its modulus, which form and methyl benzoate) on the surface of a catechol-based
is determined by the relation between its Tg and the working elastomer (≈0.3 mg cm–2) increased the underwater adhesion
temperature. For example, Beharaj et al. synthesized a sus- strength of the material (≈0.9 MPa).[24] It was demonstrated that
tainable and responsive adhesive composed of carbonate the hydrophobic solvent absorbed on the surface of the tape
terpolymers.[112] They found that the applied tack force can soften the polymers and repel the hydration layer on the
and temperature strongly affected its underwater adhesive adherend, thereby enabling their close contact to form strong
strength. Under an applied pressure of 20 kPa and a dwell interactions (Figure 9a).
time of 5 s, the adhesive exhibited a low adhesive strength Because of polymer hydrophilicity and the presence of highly
with adhesion failure at 20 °C. This is because such a low swollen networks in hydrogels, achieving strong underwater
external force cannot induce a good contact between the highly adhesion is more difficult for hydrogels than it is for hydro-
viscous polymer (Tg: −9 °C) and the substrate. Increasing the phobic elastomers. Most of the reported hydrogel adhesives
temperature to 37 °C significantly increased the adhesion usually have poor underwater adhesion (<20 kPa). To displace
strength because the polymer viscosity decreased at higher interfacial water and form strong interfacial interactions,
temperatures, which allowed it to flow and wet the surface introducing hydrophobic groups, inspired by marine adhe-
with a larger contact area under a slight pressure, and the sive proteins, into hydrogels has recently become a common
adhesive failed cohesively. A further increase in temperature design strategy. For example, Gao and co-workers developed an
to 50 °C reduced the adhesion strength and caused cohesive organogel by copolymerizing anionic and hydrophobic mono-
failure, indicating a further weakening of interchain cohe- mers in dimethyl sulfoxide (DMSO) and studied its underwater
sion, namely, a lower viscosity of the polymer. Temperature- adhesion ability.[113] They found that the organogel can adhere
dependent adhesion enables the thermoresponsive adhesion to substrates under water, and the solvent exchange process
of highly viscous polymer glue. dramatically affects the underwater adhesion, that is, longer
Figure 9. a) Underwater adhesive elastomer composed of semi-interpenetrating polymer networks with a water-repelling liquid surface. Reproduced
with permission.[24] Copyright 2020 American Chemical Society. b) Underwater adhesive hydrogels with a hydrophobic surface. (1) Schematic of the
fabrication of P(AAm-co-SMA)-SDS-Fe3+ underwater adhesive hydrogel. (2) Schematic of the self-hydrophobization process to achieve firm underwater
adhesion between the hydrogel and substrate. Reproduced with permission.[114] Copyright 2019 Wiley-VCH.
the immersion time, better is the adhesion strength. During Electrostatic interaction is a common design strategy for
the solvent exchange process, water diffused into the organogel underwater adhesion. However, electrostatic interactions
and replaced DMSO, leading to strong interfacial bonding normally diminish in high-salt solutions, such as seawater,
and aggregation of hydrophobic segments in the gel, which due to the Debye screening effect.[7] Nature utilizes adjacent
enhanced the cohesion. Thus, 24 h of immersion of the joint cationic–aromatic amino acid sequences to maintain this
in water resulted in a high underwater adhesion strength of interaction in saline media; this provides a design model
≈70 kPa owing to the formation of hydrogels with hydrophobic for the development of marine adhesives.[115] However, the
aggregations at the bonding interface and in the bulk of the synthesis of polymers with designed sequences remains
hydrogels. a major challenge in polymer chemistry.[116] Recently, we
Cui and co-workers developed hydrogels that demonstrated found that copolymer hydrogels with adjacent cation–
repeatable, long-lasting underwater adhesion to various sub- aromatic sequences, poly(cation-adj-π) (adj denotes adjacent
strates.[114] The hydrogels were fabricated using the hydrophilic and π denotes aromatic monomers), can be synthesized
monomer acrylamide, hydrophobic monomer stearyl meth- through cation–π complex-aided free-radical polymerization
acrylate (SMA), sodium dodecyl sulfate (SDS), and Fe3+ ions (Figure 10).[117] Poly(cation-adj-π) hydrogels exhibit fast,
(Figure 9b). They found that the introduction of Fe3+ ions can strong, and reversible adhesion to negatively charged surfaces
reconfigure the SDS micelle structure, resulting in the forma- in seawater (≈60 kPa). In this system, the aromatic groups
tion of a hydrogel with a hydrophobic surface. As a result, the repel interfacial water, whereas the cationic groups form
hydrophobic tails of the surfactants on the gel surface can dis- strong electrostatic interactions with the negatively charged
place the water molecules at the interface; thus, the hydrogel surface. During retraction, the adjacent aromatic groups pre-
exhibited strong underwater adhesion to hydrophobic sub- vent water molecules and salt ions from readily reinvading
strates (≈50 kPa) but weak adhesion to hydrophilic substrates the interface, thereby delaying the rehydration process.
(20 kPa). Moreover, the bulk energy dissipation of the viscoelastic gel
Figure 10. Underwater adhesive hydrogels with an adjacent cationic–aromatic sequence. Reproduced with permission.[117] Copyright 2019 Springer
Nature.
due to dynamic cation–π interaction also effectively retards 4.2. Adhesives Based on Suction
interfacial exfoliation, leading to robust adhesion. By contrast,
hydrogels with random cationic/aromatic sequences exhibit In addition to molecular attraction that usually leads to perma-
poor adhesion in seawater.[118] nent bonding, natural organisms achieve temporary underwater
However, as a polyelectrolyte, poly(cation-adj-π) hydro- adhesion via physical suction. For example, octopuses use the
gels significantly swell in water because of the high ionic suckers on their arms to capture preys in the sea,[152] whereas
osmotic pressure of the dissociated counterions.[119] Thus, remoras use the suction disk on the dorsal side to adhere to
the highly swollen hydrogels are fragile in water and have other large species to obtain a free ride in the sea.[153] Such
poor underwater adhesion. To achieve strong adhesion of underwater adhesion originates from special micro/nanostruc-
the poly(cation-π) hydrogel in water, we further improved the tures by the formation of a pressure differential between the
structure of the poly(cation-adj-π) hydrogels by increasing interior and exterior of the suction disk to achieve temporary
the fraction of aromatic monomers in the copolymers, which adhesion.[13] Inspired by these marine organisms, underwater
enhanced the hydrophobic/cation-π attraction to balance the adhesives working via physical suction and capillary forces have
electrostatic repulsion between the polymer chains.[3] We been developed in the recent years (Table 7).
found that hydrogels with a high aromatic monomer frac- Pang and co-workers designed an adhesive system with
tion exhibited not only strong mechanical properties, but also dome-like protuberances similar to the suction cups of octo-
robust, repeatable underwater adhesion to various substrates puses.[154] The octopus-inspired adhesive exhibited strong adhe-
(≈180 kPa). Moreover, the adhesion was durable in water for sion to various surfaces under different conditions, including
over a year. dry, moist, underwater, and oil environments. Moreover, the
Permanent interfacial water drop entrapment is another adhesive exhibited high reusability and could be repeatedly
problem for the underwater adhesion of tape-type adhesives. used more than 10 000 times. The authors studied the adhesion
To resolve this issue, our group introduced patterned micro- mechanism and found that the micrometer-scale domes in the
structures on the surface of polyampholyte hydrogels inspired artificial adhesive enhanced the suction stress. During deforma-
by clingfish (Figure 11).[29] These surface grooves can rapidly tion under an applied preload, the interfacial water was trapped
drain water and delay crack propagation during detachment. in the upper chambers, which made the lower parts serve as
Moreover, polyampholyte hydrogels can form reversible ionic vacuum chambers; this resulted in a strong suction stress. The
bonds with charged surfaces (positively or negatively charged adhesive with dome-like protuberances exhibited high adhe-
surfaces) to form interfacial bridging along with ionic bonds in sion in the normal direction and a poor peeling strength. To
the bulk that efficiently dissipate energy during deformation. improve the underwater adhesion performance, they further
Thus, patterned polyampholyte hydrogels exhibit fast, revers- developed an adhesive tape with meniscus-controlled 3D micro-
ible underwater adhesion on both negatively and positively tips (Figure 12a).[155] The adhesive exhibited robust adhesion in
charged substrates in water. both the normal and peeling directions on various surfaces.
Figure 11. Underwater adhesive hydrogels inspired by clingfish. a) Multiscale design strategy of polyampholyte hydrogel. b) Chemical structures of
monomers for fabrication of polyampholyte hydrogel. c) Optical photos of the deformation of flat and patterned gels during debonding from the glass
substrates. Reproduced with permission.[29] Copyright 2018 Wiley-VCH.
Figure 12. a) Octopus-inspired adhesive patches with meniscus-controlled, unfoldable 3D microtips. Reproduced with permission.[155] Copyright 2018
Wiley-VCH. b) Remora-inspired adhesive. Reproduced with permission.[156] Copyright 2019 American Chemical Society. c) Design and preparation of
thermoresponsive gecko-like adhesive. Reproduced with permission.[157] Copyright 2018 Wiley-VCH. d) Velocity-dependent adhesion of cupped micro-
structures. Reproduced with permission.[158] Copyright 2018 Wiley-VCH.
Inspired by the suction disk of remoras, Kwak and co-workers In summary, the adhesive strength of tape-type adhesives
fabricated an adhesive with a lamellar structure with ordered is generally weaker than that of glue-type underwater adhe-
micrometer-sized spinules on it (Figure 12b).[156] Owing to the sives due to the poor interfacial contact of tape-type adhesives,
microstructures and the soft nature of polydimethylsiloxane which generally leads to adhesive failure. For molecular inter-
(PDMS), the remora-inspired adhesive exhibited strong under- action-based tape-type adhesives, the removal of the water layer
water adhesion in both the normal and horizontal directions. remains a major challenge. Although dehydration has been
Zhou and co-workers developed an underwater thermoresponsive achieved at the molecular level to a certain extent by increasing
gecko-like adhesive by decorating a thermoresponsive copolymer the surface hydrophobicity of tape-type adhesives, the efficient
onto mushroom-shaped PDMS pillar arrays (Figure 12c).[157] The drainage of interfacial water at the macroscopic level remains a
adhesive exhibited strong underwater adhesion at 40 °C (above the challenge especially for large-area adhesion. However, this issue
LCST) but weak adhesion at 20 °C (below the LCST). By further is often overlooked. In addition, increasing the surface hydro-
integrating Fe3O4 nanoparticles into the PDMS, the local tempera- phobicity of adhesives brings a new problem: it usually favors
ture of the adhesives could be engineered by near-infrared laser hydrophobic substrates rather than hydrophilic ones. There-
radiation. This adhesive can be used for the controllable capture fore, enhancing the interfacial interactions and introducing a
and release of objects in water. Hensel and co-workers designed water drainage mechanism are the main research challenges in
an adhesive with deformable cupped microstructures, which this field.
exhibited switchable underwater adhesion upon adjustment of its Further, the underwater adhesive performance of suction-
retraction velocity (Figure 12d).[158] The adhesion strength of the based tape-type adhesives significantly depends on the micro-
adhesive changed with retraction velocity: the adhesive exhibited structures. Although a high adhesion strength has been
a high adhesion strength of ≈1 MPa at a high retraction velocity achieved for some adhesive systems (up to the megapascal
of 20 µm s–1 and a low adhesion strength of <0.2 MPa at a low level), limited progress has been made in the field of tape-type
retraction velocity of 0.5 µm s–1. The transition velocity depended adhesives compared with the progress made in other types of
on the cup size, cup angle, and rim width. The authors attributed adhesives. Combining the strategies of introducing microstruc-
the switchable adhesion to the self-sealing property of the micro- tures and molecular level adhesion mechanism would be an
structures, that is, faster and stronger pulls improved the sealing efficient way to improve the adhesion performance in future
ability, which in turn enhanced the adhesion. research.
5. Conclusion and Outlook Acknowledgements

This research was supported by JSPS KAKENHI (Grant Numbers
In the past decade, significant progress has been made in
JP17H06144, JP17H06376, and JP21K14676), and the Institute for Chemical
the research on adhesives applied to wet or underwater sur- Reaction Design and Discovery (WPI-ICReDD) established by the World
faces. Diverse strategies, especially those inspired by marine Premier International Research Initiative (WPI), MEXT, Japan.
organisms, have been proposed for the development of under-
water adhesives. The adhesion strength of these adhesives
has increased from several kilopascals to hundreds and even
thousands of kilopascals. Meanwhile, the range of materials
Conflict of Interest
used to prepare underwater adhesives has expanded from The authors declare no conflict of interest.
epoxy resins to supramolecular assemblies, elastomers, hydro-
gels, and other materials.[2,44,117,134] Moreover, the function
of adhesives has also expanded from its traditional function Keywords
of bonding objects in water to multiple functions, including
stimulus responsiveness (temperature, light, ionic strength, adhesives, bioinspired, glue, tape, underwater adhesion
electric fields, magnetic field, etc.),[27,74,157,170,171] biocompat-
Received: April 20, 2021
ibility,[28,30] and electrochromic ability.[79,80] The realization Revised: June 7, 2021
of multiple functions in underwater adhesive systems has Published online: September 17, 2021
broadened the application prospects of adhesives. However,
compared with the adhesives used under dry conditions,
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Hailong Fan received his B.S. (2011), M.S. (2014), and Ph.D. (2017) degrees from Renmin
University of China. He then joined Prof. Jian Ping Gong’s group at Hokkaido University as a
postdoctoral research fellow in 2017. In April 2020, he was promoted to an assistant professor-
ship in WPI-ICReDD at Hokkaido University. His current research focuses on the design and
synthesis of functional hydrogels with controlled monomer sequences.
Jian Ping Gong is a distinguished professor at Hokkaido University, Japan. She graduated from
Zhejiang University, China, and received a Doctor of Engineering degree from Tokyo Institute of
Technology. She joined the faculty at Hokkaido University in 1993. Her research focus is novel
hydrogels with high mechanical performance and functionalities. She received several awards,
including Wiley Polymer Science Award (2001), The Award of the Society of Polymer Science,
Japan (2006), The Chemical Society of Japan Award (2011), The DSM Materials Sciences Award
(2014), and the MEXT Commendation for Science and Technology, Japan (2019).

20 - Bioinspired Underwater Adhesives

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Bioinspired Underwater Adhesives

adhesive, causing plasticization, swelling,

Nanometer-thick polymer coatings

Table 6. Tape-type underwaçter adhesives based on hydrogels.

Table 7. Tape-type underwater adhesives çbased on bioinspired microstructures.

Inspiration Polymer Substrates Test method Adhesive strength Remarks Ref.

5. Conclusion and Outlook Acknowledgements

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