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Article
In situ 3D printing of liquid metal-hydrogel
hybrid for multifunctional soft bioelectronics
and devices
Caicai Jiao, Qian Wang,
Liangtao Li, ..., Lingnan Song,
Sijia Fu, Liang Hu

cnhuliang@buaa.edu.cn

Highlights
Facile in situ 3D printing method
for liquid metal (LM)-hydrogel
hybrids

Low Young’s modulus and

excellent electrical
interconnection

May directly serve as the bio-

interface of hydrogel
bioelectronics or devices

Jiao et al. report a facile in situ 3D printing method to fabricate liquid metal-
hydrogel hybrids, which enable not only mechanical compliance to soft tissues but
also demonstrate potential in bioelectronics applications. This work may set up a
universal but multifunctional platform for the development of hydrogel
bioelectronics and devices.

Jiao et al., Cell Reports Physical Science 4,

101640
November 15, 2023 ª 2023 The Authors.
https://doi.org/10.1016/j.xcrp.2023.101640
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Article
In situ 3D printing of liquid metal-hydrogel
hybrid for multifunctional soft
bioelectronics and devices
Caicai Jiao,1 Qian Wang,1 Liangtao Li,1 Wuliang Chen,1 Jingjing Liu,2 Yifei Xu,2 Lingnan Song,3
Sijia Fu,3 and Liang Hu1,4,*

SUMMARY
Hydrogels have high water content, excellent biocompatibility, and
tissue-matched compliance, which are favorable for interfacing with
biological tissues, and they have attracted wide attention in soft
electronics. However, current difficulties, such as interconnection is-
sues with the metallic interface, and deficient fabrication strategies
still pose great challenges. Here, a facile in situ 3D printing method
is developed to fabricate liquid metal (LM)-hydrogel hybrids, which
enable mechanical compliance to soft tissues (
10 kPa), thus serving
as the bio-interface of hydrogel bioelectronics or devices. More-
over, LM-hydrogel hybrids have good electrical interconnection
with conventional electrical interfaces due to the excellent wetting
and alloyed behavior of LM and commonly used metallic conductors.
The LM-hydrogel hybrid can also be directly used for electronic com-
ponents or devices without any further encapsulation or assembly
process. Such LM-hydrogel hybrid via this convenient and almost
automatic in situ 3D printing method may set up a multifunctional
platform for hydrogel bioelectronics and devices.

INTRODUCTION
Hydrogels are promising candidates for soft electronics because they have a large
amount of water and possess tissue-matched Young’s modulus, which enables
wide applications in soft robotics,1 flexible electronics,2 and soft bioelectronics.3–5
In developing hydrogel-based bioelectronics and devices, multi-materials and struc-
tures assembly and integration are often necessary to fulfill certain functions,6–8 and
it is still confronted with great challenges in some aspects. For example, the inter-
connection between a traditional metallic interface and hydrogel may face delami-
nation or disconnection issues especially when subjected to strain, bending, or tor-
sion due to the intrinsic mechanical mismatch and weak interaction between those
materials. Besides, the assembly of multi-materials with large modulus differences
1Beijing Advanced Innovation Center for
can significantly influence the compliance of the whole device. Soft or fluidic conduc-
Biomedical Engineering, School of Biological
tive structures or patterns are also introduced into hydrogel-based electronic de- Science and Medical Engineering, Beihang
vices including nanomaterials-based composites,9,10 conductive polymers,7,11,12 University, Beijing 100191, China
and ionic liquids13 and even hydrogels.14 However, the low and unstable conductiv- 2School of Automation Engineering, Northeast
Electric Power University, Jilin 132012, China
ity of these soft conductors can significantly impair the performance of the devices.
3Schoolof Electronic and Information
Engineering, Beihang University, Beijing 100191,
Gallium-based liquid metals (LMs) with high electrical conductivity are emerging as China
advanced materials for flexible and soft electronics. Besides, LM has excellent wet- 4Lead contact
ting and alloyed behavior with commonly used metallic conductors such as cop- *Correspondence: cnhuliang@buaa.edu.cn
per,15 silver,16 and gold,17 so the contact resistance with these metallic conductors https://doi.org/10.1016/j.xcrp.2023.101640

Cell Reports Physical Science 4, 101640, November 15, 2023 ª 2023 The Authors. 1
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
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should be much smaller compared to most soft conductive composite or polymer

materials. Thus, the LM-based soft devices can have good electrical interconnection
due to the excellent contact. Most current reported methods for fabricating LM and
hydrogel hybrids including surface printing,18–20 layer-by-layer,21,22 or template-
sacrifice process,23 which either cannot fabricate 3D LM patterns or require a sophis-
ticated template eluting process. The LM allows for 3D printing due to the presence
of an oxide layer on the surface, which allows it to be molded into many shapes.24,25
At present, researchers have developed a variety of LM 3D printing methods
including material extrusion-based 3D printing,26 externally assisted 3D printing,27
and physical field-assisted 3D printing,28 etc. The 3D printing methods for LM-hy-
drogel hybrids have also been reported. However, the printing hydrogels used
are either hard to shape for further application27,29 or not biocompatible as bio-
interface materials for bioelectronics.30 Besides, most of the LM-hydrogel hybrid
bioelectronics have been applied mostly in physical or chemical sensing applica-
tions,14,21,23,31 while other biomedical applications especially implantable elec-
tronics and devices are rarely reported.

To address these points and to provide a widely applicable hydrogel bioelectronics

platform, here we propose a facile in situ 3D printing method for the fabrication of
LM-hydrogel hybrids via one-step crosslink for the potential application of soft
and implantable bioelectronics. Most soft electronic devices, such as the printed
metallic (Au) patterns or structures used in electronic devices, are often removed
from the printing matrix or substrate and transferred to soft materials as encapsula-
tion. "In situ" printing here means that we print LM directly in the hydrogel matrix,
and the LM together with the printing hydrogel matrix as a part of LM-hydrogel
hybrid soft bioelectronics and devices. After printing, there is no need for secondary
encapsulation, so the LM-hydrogel hybrid can be directly used for electronic de-
vices. Uniquely, the hydrogel used here contains gelatin, sodium alginate (SA),
and potassium chloride (referred to as GSP below), which not only play the role of
supporting matrix and electrolyte for LM printing but also can directly serve as the
bio-interface of hydrogel bioelectronics or devices after one-step cross-linking by
Ca2+. As GSP hydrogel owns excellent mechanical compliance to soft tissues,
biocompatibility, and ionic conductivity, we achieve the quick fabrication of hydro-
gel-based bioelectronics or devices possibly for implantable bioelectronics
including soft near-field communication (NFC) tags, multi-mode pressure sensors,
and soft bioelectrodes for in vitro signal recording and in vivo electrical stimulation.
These demonstrations reveal the great potential for future soft and implantable bio-
electronics and devices. More importantly, due to the giant supercooling effect,32,33
the gallium we used in this work stays liquid (even kept at 4 C) when it is encapsu-
lated in the GSP hydrogel. Thus, the whole LM-hydrogel hybrid is soft and compliant
rather than solid and hard inside. Besides, room temperature LMs (EGaIn and Galin-
stan) are also suitable for this in situ 3D printing method.

RESULTS AND DISCUSSION

In situ 3D printing of liquid metal-hydrogel hybrids
Figure 1A illustrates the integrated fabrication process of LM-hydrogel hybrids with
microstructures via an in situ 3D printing method. The 3D LM wire-like structures can
be printed via electrochemically induced oxidation in the GSP hydrogel in the first
step.32,34 In the second step, the gelatin network can be solidified at 4 C, while
the SA network can be cross-linked by Ca2+, so the LM-hydrogel hybrids can be
taken out for further application scenarios. The GSP hydrogel is a double-network
hydrogel where the gelatin network and SA network interpenetrate with each other.

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Figure 1. In situ 3D printing of liquid metal-hydrogel hybrids

(A) Schematic illustration of in situ 3D printing process of LM-hydrogel hybrids.
(B) Images of single-layer and bilayer LM-hydrogel hybrids. Scale bars: 1 cm.
(C) Photographs of LM-hydrogel hybrids at (i) initial, (ii) torsion, and (iii) bending. Scale bars: 1 cm.
(D) Photographs of traditional hard metal-hydrogel hybrids at (i) initial, (ii) torsion, and (iii) bending. Red circles indicate the separation of the traditional
hard metal from hard metal-hydrogel hybrids. Scale bars: 1 cm.
(E) LM pattern on the polydimethylsiloxane (PDMS) surface and images of corresponding electrical resistances for LM pattern before (upper right) and
after (lower right) twisting, respectively.
(F) Ag pattern obtained after drying by Ag nanoparticle ink on the PDMS surface and images of corresponding electrical resistances for Ag pattern
before (upper right) and after (lower right) twisting, respectively.

The components of the GSP hydrogel are simple and commonly used in tissue engi-
neering, which also illustrates its biocompatibility for implantable applications. The
printing instrument used here is composed of a 3D printing system (Dobot Magi-
cian), a DC power source, and a syringe pump. Specifically, the anode of the DC
power source is connected to the printing nozzle, while the cathode is put into the
supporting matrix composed of gelatin, SA, and potassium chloride (KCl). The
pre-precursor mixture was used as the printing support medium, and the LM was
used as the printing ink. During the printing process, because the anode is

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connected to the nozzle, when the LM is extruded from the nozzle, the electrochem-
ical anodization leads to the decrease of the surface tension of the LM, so we can
obtain the LM wires. Photographic images of 3D printed LM-hydrogel hybrids with
different single-layer patterns (spiral, heart, circular, U-shaped pattern, and zigzag
serpentine) and bilayer patterns are shown in Figures 1B and S1, and a video demon-
stration of the printing process is provided as Video S1. We demonstrate a bilayer
LM structure can be printed in the hydrogel by changing the depth of the nozzle (Fig-
ure S2). In the process of printing bilayer LM-hydrogel hybrids, when the nozzle is
always in a vertical state, we can obtain a double-layer structure with parallelism.
More importantly, this technique can directly print 3D structures in the direction of
height continuously, as demonstrated in Figure S3. Using this method by controlling
the depth of the nozzle, single or multilayer LM patterns can be printed and encap-
sulated in the soft double-network hydrogel in an efficient way, which can fulfill
diverse functions as introduced in the following sections.

Mechanical compliance and structural stability are key requisites for hydrogel elec-
tronics and devices. Compared with the traditional hard metal-hydrogel hybrids,
there is no delamination or disconnection between LM and the LM-hydrogel hybrids,
and it can deform with LM-hydrogel hybrids when twisted and bent (Figure 1C). And,
the hard metals can be easily separated from hard metal-hydrogel hybrids due to the
mismatching of the elastic modulus, accompanied by the destruction of the hard
metal-hydrogel hybrid (Figure 1D). The conductivity test also proved the LM pat-
terns are still connected after twisting 90 over 50 times (Figure 1E), while the Ag
pattern printed by Ag nanoparticle ink can easily break under the same condition
(Figure 1F).

Printing parameters exploration and material characterization

The printing conditions for continuous LM wires forming in the GSP hydrogel are
investigated, including the rheological property of the printing hydrogel, the elec-
trochemical oxidative conditions, the flow rate of the LM, and the motion parameters
of the nozzle. The viscosity of the printing system here is crucial for printing, which is
determined by the proportion and concentration of the components of gelatin and
SA. The preliminary studies reveal that the 3D printing of LM can be realized on con-
dition that the gelatin concentration is between 20 and 100 mg mL1 (Figure S4) and
SA concentration is between 0 and 1.0 wt % (Figure S5). The viscosity of this hydrogel
system is characterized, and the results suggest all the supporting matrices exhibit a
strong shear thinning behavior as the shear rate increases from 0 to 1,000 s1, allow-
ing the LM to be smoothly extruded through the nozzle (Figures 2A and 2B). And,
both their viscosities increased as the gelatin or SA concentrations increased. Low
concentration cannot support the heavy LM wires, while high concentration is too
viscous, which can easily block the nozzle, thus hindering LM printing. So, the opti-
mized composition of the hydrogels is determined as 50 mg mL1 gelatin and
0.5 wt % SA for follow-up experiments. At the optimal printing concentration, on
the one hand, when the nozzle moves, due to shear thinning behavior, the viscosity
of the printing system is decreased to facilitate the nozzle movement and to allow
smooth LM wires printing; and on the other hand, the viscosity of the printing system
can support the LM wires suspended in the printing matrix. Afterward, the rheology
properties of the GSP hydrogels are evaluated. It can be observed that the storage
modulus G’ was higher than the loss modulus G’’, indicating the hydrogel had solid-
like structure and certain mechanical strength (Figure S6). With the increase of
gelatin concentrations, the storage modulus G0 of GSP hydrogels changes little,
while the storage modulus G0 increases with the increase of SA concentrations,

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Figure 2. Printing parameters exploration and material characterization

(A and B) viscosity of the supporting matrices with varying (A) gelatin concentrations (at a fixed SA concentration: 0.5 wt %) and (B) SA concentrations (at
a fixed gelatin concentration: 50 mg/mL).
(C) Smooth LM wire printing conditions. Blue: smooth LM wire. Red: defective LM wire.
(D) (i) Photograph (scale bar: 3 mm) and (ii) microscope image (scale bar: 200 mm) of printed parallel LM wires according to nozzle inner diameters.
(E) The plot of wire diameters versus nozzle inner diameters under different flow rates. Data are presented as mean G SD, n = 6.
(F) The plot of wire diameters versus printing velocities under different flow rates. Data are presented as mean G SD, n = 6.
(G) FTIR spectra of gelatin, SA, and GSP hydrogel.
(H) SEM image of GSP hydrogel. Scale bar: 200 mm. The inset image is a magnified part. Scale bar: 50 mm.
(I) The corresponding elastic modulus from tensile stress-strain curves of GSP hydrogel and LM-hydrogel hybrid. Insets: images of GSP hydrogel and
LM-hydrogel hybrid, respectively. Scale bars: 1 cm. Data are presented as mean G SD, n = 3.

indicating that the ionic-crosslinked SA network has a great influence on the rheo-
logical properties of GSP hydrogels.

The velocity of the nozzle, the voltage applied, the electrolyte KCl concentration,
and the flow rate of LM for continuous wire forming are evaluated as shown in Fig-
ure 2C. In this experiment, the flow rate of LM is 450 mL min1, and the nozzle inner
diameter is 0.84 mm. When the applied voltage is too low (<1 V), the LM is likely to

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form droplets instead of continuous smooth LM wires. When the LM wire is printed in
the "red" area as shown in Figure 2C (the electrolyte KCl concentration or the
applied voltage is too high), the surface of the LM wire becomes black, and when
the LM wire is printed in the "blue" area, the surface of the LM wire is smooth
with no black layer (Figure S7), which is consistent with the phenomenon in the pre-
vious work.32,35 As a result, continuous LM wire can be printed at a speed of
5–100 mm s1 at appropriate voltage and electrolyte KCl concentration.

Under the printing conditions, we explore the resolution of the wires, which is re-
vealed to be more dependent on nozzle inner diameter rather than the flow rate
and motion velocity. Figure 2D shows the images of printed parallel LM wires with
different nozzle inner diameters in the range of 0.21–0.84 mm using an identical
printing velocity (20 mm s1) and flow rate (400 mL min1) and a wider nozzle inner
diameter resulting in a wider LM wire diameter. It is seen that the wire diameter in-
creases with the nozzle inner diameter linearly, and the minimum diameter of about
290 mm can be achieved using a nozzle with an inner diameter of 0.21 mm (Figure 2E).
Meanwhile, the wire diameter increases slightly with the increasing flow rate for a
constant nozzle inner diameter. In Figure 2F, the results suggest the diameter of
the LM wire is positively dependent on the flow rate. When the flow rate is fixed,
the diameter of the LM wire reaches the maximum when the printing velocity is
40 mm s1 within the range of 5–100 mm s1 printing velocity. When the printing ve-
locity is too low, the LM accumulates at the starting position, while when the printing
velocity is too high, the LM wire is slightly stretched by the tensile force during print-
ing, resulting in a smaller diameter of the LM wire. Based on the above studies, we
selected optimized printing conditions for subsequent experiments: the velocity of
the nozzle, 20 mm s1; the voltage applied, 3 V; and the electrolyte KCl concentra-
tion, 40 mM.

We evaluate the chemical structure, morphology, and mechanical properties of the

GSP hydrogels. In the Fourier transform infrared (FTIR) spectra (Figure 2G), the
peaks at 1,650 and 1,435 cm1 in gelatin spectra belong to amide I and amide
II, and the peak at around 3,200–3,700 cm1 belongs to the -OH and the -NH2
groups. The hydroxyl peak of the SA spectra was observed at around 3,200–
3,700 cm1 and the -C-H groups at around 2,955 cm1. Moreover, the peaks at
1,645 and 1,430 cm1 in SA spectra can be attributed to asymmetric stretching vi-
bration and the symmetrical stretching vibration of carboxyl group, and the peak
at 1,040 cm1 can be attributed to the stretching of C-O-C. In GSP hydrogel
spectra, all the characteristic peaks of individual components were observed,
demonstrating the formation of GSP hydrogels. It can be found from the SEM im-
age (Figure 2H) that the hydrogels have large pore sizes, and the presence of KCl
can be clearly observed. We also evaluate the mechanical properties of the GSP
hydrogel and LM-hydrogel hybrid (Figure 2I). Obviously, there was no significant
influence on elastic modulus. The obtained elastic modulus of the GSP hydrogel
and LM-hydrogel hybrid was about 11 kPa, which is well-matched to skeletal mus-
cles (E
10 kPa36). In addition, GSP hydrogel is ionically conductive and has a con-
ductivity of 1.31 S m1 (Figure S8).

Fabrication of functional LM-hydrogel hybrid electronics

One example of LM-hydrogel hybrid electronics is an LM-hydrogel NFC tag with an
in situ 3D printing spiral coil in GSP hydrogel, which is also suitable for wireless com-
munications of wearable or implantable devices. This LM-hydrogel NFC tag is flex-
ible and compliant to a curved surface such as the back of a hand (Figure 3A). The
successful link to the default official website of Beihang University with a smartphone

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Figure 3. LM-hydrogel NFC tag

(A) Schematic illustration showing the communication between the smartphone and the NFC tag. The image shows that the LM-hydrogel NFC tag fits
well on the hand under bending conditions.
(B) LM-hydrogel NFC tag was scanned by a smartphone to open a website.
(C and D) Impedance spectra and phase angles of (C) copper spiral coil and (D) LM-hydrogel spiral coil as a function of frequency.

demonstrated the NFC function of this LM-hydrogel NFC tag (Figure 3B and Video
S2). We have fabricated a copper spiral coil with the same size and the same turns as
the LM spiral coil. And impedance characteristics of the two representative coils are
measured by the impedance analyzer (WAVE KERR WK6500B). Figures 3C and 3D
demonstrated and measured the impedance characteristics of the copper and
LM-hydrogel spiral coils, respectively. We can observe that the LM-hydrogel spiral
coil demonstrates capacitive behavior at frequencies below 13.56 MHz, while the
copper spiral coil demonstrates inductive behavior throughout the frequency range
of measurement. Further observation of Figure 3D also reveals the resonance
behavior at the frequency of 13.56 MHz, which corresponds to the operation fre-
quency of NFC. The resonance at 13.56 MHz facilitates the efficient power transmis-
sion between the TX coil and the RF generator (typically with a standard 50-U imped-
ance), by minimizing the imaginary part of the coil impedance (to about 30 U and
zero phase as shown in Figure 3D).

Apart from simple single-layer patterns, double layers of LM-hydrogel hybrid circuits
can be also achieved via this in situ printing method, which is beneficial to the
development of 3D electronics with higher density and complexity. Figure S9 shows
a multilayer LM-hydrogel hybrid electronic, which consists of two LM circuits and two
LEDs. Interestingly, two LM circuits can be switched on at the same time to light up
two LEDs, or one of them can be switched on to light up one LED, proving that the
two circuits are independent of each other. Collectively, these demonstrations show

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Figure 4. LM-hydrogel hybrid multi-mode pressure sensors

(A) Schematic illustration of the single-resistive-type pressure sensor.
(B) Response of the linear single-resistive-type pressure sensor to gentle and brutal finger presses,
respectively.
(C) A comparison of sensing mechanisms between (i) linear and (ii) U-shaped single resistance pressure
sensors. Red zone: the area where pressure is applied. ll0 and lU0 represent the initial equivalent length of
LM in linear and U-shaped single resistance sensors; and llS and lUS represent the total length of LM in the
red zone in linear and U-shaped single resistance sensors. Scale bars: 1 cm.
(D) Relative resistance variation versus pressure for the single-resistive type-pressure sensor.
Sensitivities were determined by the slopes from the fitted lines (dashed lines). Insets: photos of the
linear and U-shaped single-resistive-type pressure sensors, respectively. Scale bars: 1 cm.

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Figure 4. Continued
(E) Schematic illustration of the hybrid resistive pressure sensor.
(F) Relative resistive change on writing the number ‘‘2,’’ the letter ‘‘W,’’ and the word ‘‘OK,’’ where
each was written three times to exhibit repeatability.
(G) A comparison of sensing mechanisms of (i) 1 3 1, (ii) 2 3 2, and (iii) 3 3 3 type hybrid resistive
pressure sensors. Red zone: the area where pressure is applied. Scale bars: 1 cm.
(H) Relative resistance variation versus pressure for the hybrid resistive pressure sensor.
Sensitivities were determined by the slopes from the fitted lines (dashed lines). Insets: photos of
1 3 1, 2 3 2, and 3 3 3 type hybrid resistive pressure sensors, respectively. Scale bars: 1 cm.

the practicability of this method for fabricating complex structures and multilayer
circuits.

The properties of this LM-hydrogel hybrid circuit such as self-healing performance,

dehydration, and biodegradability are examined. The mechanically cut circuit can
be simply brought together along the cut line to relight up the LED, which should
be due to the self-healing performance of LM, while the GSP hydrogel itself cannot
self-heal (Figure S10). Hydrogels are commonly soft but vulnerable materials with
high water content, which easily dehydrate, break, or buckle, resulting in structural
and/or functional damage to hydrogels. The dehydration test suggests the hybrid
can shrink with its whole size decreased to 70.4% while maintaining the LM conduc-
tivity after directly placing it at room temperature (26 C) for 3 h (Figure S11). When
the LM-hydrogel hybrid circuit is re-immersed in water, the hydrogel expands and
restores to 92.16% of its original volume within 3 h. Furthermore, the LM pattern
also retained its integrity and connection within the hydrogel by observation and
electrical test, suggesting that this LM-hydrogel hybrid circuit maintains its function
during dehydration, which is beneficial for long-term use under moisture-varying en-
vironments. Notably, after one or three dehydration/hydration processes, the FTIR
spectra (Figure S12) of the GSP hydrogels were consistent with that of the original
GSP hydrogel, proving that the molecular structure of the hydrogel did not change.
It can be found from the SEM images (Figure S13) that after dehydration/hydration
processes, the pore size of the hydrogel becomes smaller, the network structure be-
comes more compact, and no clear KCl was observed. It can be seen from energy-
dispersive X-ray (EDS) spectra that after one and three dehydration/hydration pro-
cesses, the weight percentage of K element decreased from 6.63% to 0.35% and
0.01%, respectively, which was due to the dissolution of KCl into deionized water
during the hydration process. It can be seen from the degradation curve that the
hybrid (F832 mm) can be completely degraded after 16 h in 5 mL of PBS (Fig-
ure S14). Using this LM-hydrogel hybrid circuit can effectively solve the environ-
mental pollution caused by electronic waste and reduce the harmful impact of elec-
tronic waste on environmental pollution.

LM-hydrogel hybrid multi-mode pressure sensors

The LM-hydrogel hybrids not only can be applied as soft electronics but also show
potential in the application of pressure sensors. Two types of pressure sensors are
conceptually demonstrated including the single resistive type and the hybrid resis-
tive. When the ohmmeter is connected to the two points of the LM wire in the hydro-
gel, it forms the single-resistive-type sensor, where the response of the sensor is only
dependent on the resistance change of the LM wire (Figure 4A). This pressure
response can be used for finger force as an application demonstration. When the
sensor is pressed by a finger, the resistance value increases rapidly, and the
response is stable at each time (Figure S15). The pressure sensor can respond to
gentle and brutal finger pressure with significant differences, which proves its sensi-
tivity for finger pressing (Figure 4B). The corresponding resistance (R) can be

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calculated as equation R = rl=S = rV =S 2 , where r is the electrical resistivity of LM, l

is the length, S is the cross-sectional area, and V is the volume. Compression defor-
mation causes a decrease in the cross-sectional area of LM, which leads to an in-
crease in resistance. The pressure sensor can also respond to torsion (Figure S16)
and bending (Figure S17) signals. The cross-sectional area of LM decreases
under torsion and bending, thus resulting in the increase of resistance. Therefore,
the resistance change rate increases under torsion and bending. As the hydrogel
is hyperelastic while the LM is linear elastic, the combined sensor response to the
force is not linear as predicted (Figure 4C). The sensitivity (S) can be defined as
S = dðDR =R0 Þ =ds, where DR is the value of resistance change, R0 is the value of
initial resistance, and s is the value of pressure. LM can be equivalent to a cylindrical
channel. Since lu0 > 2ll0 , RU0 > 2Rl0 . At the same pressure, OR is positively correlated
with the lengths of the LM under force. Since, lUs < 2lls , DRU < 2DRl . In conclusion, the
resistance change rate DRl =Rl0 = 2DRl =2Rl0 > DRU =2Rl0 > DRU =RU0 . Therefore,
the relative variation of LM is essential for dramatically improving the sensitivity of
single resistance pressure sensors. In Figure 4D, the sensitivity increased sharply
with an increase in applied pressure. According to the response curve, we divide
the response into three linear ranges where the sensitivity of the linear single resis-
tive pressure sensor is 0.45 kPa1 in the range of 0–5 kPa, 0.99 kPa1 in the range of
5–9 kPa, and 5.59 kPa1 in the range of 9–12 kPa. As a control, the sensitivity of the
U-shaped single resistance pressure sensor is 0.05 kPa1 below 5 kPa and 0.47 kPa1
in the range of 5–12 kPa, respectively, which is much lower than that of the linear sin-
gle resistance type.

When the ohmmeter is connected to the top and bottom surface of the LM-hydrogel
hybrid, it forms the hybrid resistive sensor, in which the pressure response of the
sensor is related to the resistance of both LM and hydrogel. The schematic circuit di-
agram for this pressure measurement is shown in Figure 4E, and the response curve
of this hybrid schematic sensor is depicted (Figure 4F), which presents excellent
sensing performance. The sensor can recognize different writing signals by quite
different patterns, such as the number ‘‘2,’’ the letter ‘‘W,’’ and the word ‘‘OK,’’
demonstrating its good repeatability and excellent ability to record handwriting.
Moreover, we designed the hybrid resistive pressure sensors with three different
LM structures (Figure 4G). For hybrid resistive pressure sensors, the resistance
change mainly depends on the following three factors: (1) caused by intrinsic piezor-
esistive effect—the resistance changes of hybrid resistive pressure sensor, (2) the ge-
ometry shape and number of LM wires are different in the hybrid resistive pressure
sensor, and (3) the change of contact resistance. When pressure is applied, the resis-
tance changes caused by the intrinsic piezoresistive effect and the LM wires are rela-
tively small, while the resistance change caused by the contact resistance is domi-
nant. Compared with 1 3 1 and 2 3 2 types, 3 3 3 type hybrid resistive pressure
sensors have more LM wires, which means that the LM has a larger contact area
with the hydrogel. Therefore, under the same conditions, the resistance change
DR caused by the contact resistance of a 3 3 3 type hybrid resistive pressure sensor
is larger (DR333 > DR232 > DR131 ). The initial resistance R0 of the three different types
of hybrid resistive pressure sensors is basically the same (R10 zR20 zR30 ). In conclu-
sion, the resistance change rate DR333 =R30 > DR232 =R20 > DR131 =R10 . Therefore, the
sensitivity of the hybrid resistance pressure sensor can be changed by designing the
LM structure. The denser the LM structure is, the higher is the sensitivity of the
sensor. It was found that the 1 3 1 type hybrid resistive pressure sensor showed
the lowest sensitivity at only 0.56 kPa1, and the resistance was almost linearly
responsive to the compressive pressure within 12 kPa. The 2 3 2 and 3 3 3 type
hybrid resistive pressure sensors have a sensitivity of 0.66 kPa1 below 5 kPa, while

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the sensitivity increases to 3.09 and 5.70 kPa1 in the range of 5–12 kPa, respectively
(Figure 4H).

The performances of recently reported pressure sensors are summarized in Table S1.
Compared to previously reported soft pressure sensors, the sensitivity of hybrid
pressure sensors is relatively larger than most of the elastomer-based and hydro-
gel/nanomaterial-based pressure sensors, especially when at a higher pressure
working range (5–12 kPa). Moreover, by altering the LM patterns via this in situ 3D
printing method, the sensing response including sensitivity and working range can
be changed for both types, which can be used for a wide range of applications.

Biomedical applications of LM-hydrogel hybrid electrodes

The high water content and soft tissue-matched modulus of LM-hydrogel hybrid elec-
tronics render them highly promising for biomedical applications. LM wire was in situ
3D printed into GSP hydrogel to form the LM-hydrogel hybrid electrode (Figure S18A).
As a proof of concept, LM-hydrogel hybrid electrodes made applications as epidermal
electrodes to record the electromyogram (EMG) (Figure 5A) and electrocardiogram
(ECG) (Figure 5B) signals. This is because the LM-hydrogel hybrid electrodes have
low modulus and can form a good interface with human skin. For EMG recording,
the signal-to-noise ratio (SNR) of the EMG signals recorded by the LM-hydrogel hybrid
electrodes was 32.71 dB, which was higher than that recorded by the commercial Ag/
AgCl electrodes (26.81 dB). As shown in Figures 5C and 5D, the LM-hydrogel hybrid
electrodes successfully collected the EMG signals and showed higher peaks, exhibiting
higher response signal intensity than commercial Ag/AgCl electrodes. Therefore, the
LM-hydrogel hybrid electrodes are more promising to detect human EMG signals
with high precision. For ECG recording, the SNR of the ECG signals recorded by the
LM-hydrogel hybrid electrodes was 31.86 dB, which was higher than that recorded
by the commercial Ag/AgCl electrodes (22.65 dB). And both commercial Ag/AgCl
electrodes (Figure 5E) and LM-hydrogel hybrid electrodes (Figure 5F) showed distinct
features of P waves, QRS waves, and T waves, which confirms that the performance of
the LM-hydrogel hybrid electrodes was comparable to that of the commercial Ag/AgCl
electrodes. The above results are due to the fact that the LM-hydrogel hybrid elec-
trodes have good compliance to human skin without producing a considerable imped-
ance, so good human signals can be recorded.

For in vivo electrical stimulation of the tibialis anterior (TA) muscle, a pair of LM-hy-
drogel hybrid electrodes were used to trigger the movements of the rat hindlimbs
(Figure 5G). As a reference, the pure GSP hydrogel without containing LM wire
was used as a conventional ionically conductive electrode (Figure S18B). In compar-
ison, under the same stimulation intensities (3 V), clearly stable ankle joint move-
ments (35 ) are observed by using LM-hydrogel hybrid electrodes, while no ankle
joint movements are observed by using pure GSP hydrogel electrodes (Figures 5H
and 5I). Next, we investigated the contraction force of TA muscles under different
intensities. The threshold of the response by TA muscle electrical stimulation was
1.25 V for the LM-hydrogel hybrid electrodes, while no muscle forces were observed
for pure GSP hydrogel electrodes even at 3 V (Figure 5J). Figure 5K shows force data
obtained from the TA muscle stimulation with different frequencies. The results show
that with the increase of frequency, we can clearly observe three different muscle
contraction patterns: continuous single contractions, incomplete tetanic contrac-
tion, and complete tetanic contraction. The result indicated that at high stimulation
frequencies, the tetanic muscle forces were observed, while at low stimulation fre-
quencies, the twitch muscle forces were observed. Moreover, electrical stimulation
can stimulate a large muscle force at high stimulation frequencies. Finally, we

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Figure 5. Biomedical applications of LM-hydrogel hybrid electrodes

(A and B) Schematic illustration of (A) EMG and (B) ECG.
(C and D) Representative human EMG signals were recorded using (C) commercial Ag/AgCl electrodes and (D) LM-hydrogel hybrid electrodes.
(E and F) Representative human ECG signals were recorded using (E) commercial Ag/AgCl electrodes and (F) LM-hydrogel hybrid electrodes.
(G) Schematic illustration of the rat TA muscle stimulation experimental setup (left) and image of the LM-hydrogel hybrid electrodes on the TA muscle
(right).
(H and I) Images of the ankle joint movement in response to TA muscle electrical stimulation using (H) LM-hydrogel hybrid electrodes and (I) pure GSP
hydrogel electrodes.
(J and K) Force measured while stimulating the TA muscle at various stimulation intensities (1–3.25 V) and frequencies (10, 20, 40, 60, 80, 100 Hz, at 3 V).
(L) Schematic illustration of the rat sciatic nerve stimulation experimental setup (left) and image of the LM-hydrogel hybrid electrodes on the sciatic
nerve (right).
(M and N) Images of the ankle joint movement in response to sciatic nerve electrical stimulation using (M) LM-hydrogel hybrid electrodes and (N) pure
GSP hydrogel electrodes.
(O and P) Force is measured while stimulating the sciatic nerve at various stimulation intensities (1–3.25 V) and frequencies (10, 20, 40, 60, 80, 100 Hz, at
3 V).

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demonstrate the sciatic neural stimulation based on a rat model (Figure 5L). As a
result, the ankle joint movements varied from 0 to 10 without and with electrical
stimulation, while no ankle joint movements were observed by using pure GSP hy-
drogel electrodes, respectively (Figures 5M and 5N). In addition, force is measured
from stimulation of the sciatic nerve with different voltages and different fre-
quencies. The threshold of the response by sciatic nerve electrical stimulation was
1.25 V (Figure 5O), and neural stimulation was performed by monitoring the force
values induced by applying different frequencies of electrical stimulation to the rat
sciatic nerve (Figure 5P). However, the muscle forces were not observed for pure
GSP hydrogel electrodes under different stimulation intensities and different stimu-
lation frequencies. These results demonstrate that LM-hydrogel hybrid electrodes
have better electrical stimulation performance than pure GSP hydrogel electrodes.
This is due to the fact that in the LM-hydrogel hybrid electrodes when the external
wire is connected to the LM, the current flows through the LM, so that there is a
higher current density around the LM. The contact sites between the LM-hydrogel
hybrid electrodes and the tissues have a high current density, so as to achieve the
electrical stimulation function. In the pure GSP hydrogel electrodes without LM,
the external wire is connected to the end of the hydrogel, and the current density
of the whole hydrogel is uniform and low. The contact sites of pure GSP hydrogel
electrodes and the tissues have low current density, so they cannot achieve electrical
stimulation function.

Conclusions
We have reported an in situ 3D printing method for fabricating an LM-hydrogel
hybrid that is based on two materials: hydrogel supporting matrix and conductive
and flexible LM ink. The supporting matrix consists of a gelatin-SA double-network
hydrogel. Firstly, it has low viscosity and shear thinning behavior that enables LM
printing. Secondly, after printing, the gelatin network was solidified at 4 C, and
the SA network was cross-linked by CaCl2 to form a double-network hydrogel. LM
has good flexibility so that it is seamlessly integrated with the hydrogel matrix. As
a result, there is no delamination or disconnection occurring in the LM-hydrogel
hybrid, resulting in a longer use time. To illustrate the multifunctional applications,
we demonstrate this LM-hydrogel hybrid for soft and biocompatible bioelectronics
and devices including soft NFC tags, multi-mode pressure sensors, and soft
bioelectrodes for in vitro signal recording and in vivo electrical stimulation. This
LM-hydrogel hybrid has excellent electronic connection with conventional electrical
interface, tissue-matched compliance, and good biocompatibility. In the present
study, the demonstrated LM-hydrogel hybrids are still simple in structure and
have relatively low resolution (290–570 mm) mainly due to the limited performance
of the home-made 3D LM printer. However, this printing method can be compatible
with advanced 3D printing instruments with higher resolution and more functions.
Thus customization, complexity, and automation for the fabrication of LM-based
soft devices should be realized for more applications. Therefore, the development
of this in situ 3D printing technology is of great significance.

EXPERIMENTAL PROCEDURES
Resource availability
Lead contact
Further information and requests for resources and reagents should be directed to
and will be fulfilled by the lead contact, Liang Hu (cnhuliang@buaa.edu.cn).

Materials availability
This study did not generate new unique materials.

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Data and code availability

The data underlying this study are available in the article and supplemental informa-
tion or from the lead contact upon request.

Materials
Gallium-based LM with a purity of 99.99% was purchased from Mai Xi company. SA
and KCl were obtained from Sinopharm Chemical Reagent Co. Gelatin and calcium
chloride (CaCl2) were purchased from BOSF. Deionized water (resistivity: 18.25 MU
cm1) was used in all experiments.

In situ 3D printing of LM-hydrogel hybrids

An in situ 3D printing method is employed to fabricate the LM-hydrogel hybrids,
with a 3D printing system (Dobot Magician), a DC power source, and a syringe
pump. Specifically, the anode of the DC power source is connected to the printing
nozzle, while the cathode is put into the supporting medium composed of gelatin,
SA, and KCl, which was referred to as GSP. In the printing process, the pre-precur-
sor mixture was used as the printing support medium, and the LM was used as the
printing ink. Pre-precursor solution was prepared by adding 0.5 wt % SA and
40 mM KCl in deionized water for 12 h to ensure that all monomers were dissolved.
The pre-precursor solution was then mixed with 50 mg mL1 gelatin at 60 C for
30 min. Subsequently, the mixture was poured into a square plastic Petri dish
and cooled until proper printing viscosity was achieved. For each experiment,
the syringe pump was injecting LM into the supporting medium at a constant in-
jection rate, and the nozzle was moved in the supporting medium along pro-
grammed paths for LM printing. The square plastic Petri dish filled with 40 mL
of the pre-precursor mixture was cooled at 4 C for 2 h and immersed into
120 mL of CaCl2 solution (0.1 M) for another 3 h. Multilayer LM-hydrogel hybrids
were printed by changing the depth of the nozzle. Photographs of different print-
ing patterns were taken using a digital camera (FDR-AX60, SONY) under a bright
field. The diameters of LM wires were measured in inverted optical microscope im-
ages (OLYMPUS IX71, Japan).

Rheology measurements
Viscosity measurements were carried out using a rheometer (Brookfield, R/S plus)
over shear rates from 0 to 1,000 s1. Rheology measurement was characterized using
a DHR-2 rheometer (TA Instruments, Waters Ltd., USA), equipped with a parallel
plate of 40 mm diameter. Silicone oil was used to avoid the evaporation of water dur-
ing the test. The frequency sweep experiment was conducted under a fixed strain of
1.0%, and the angular frequency was swept from 0.01 to 100 rad s1 to obtain the
storage modulus (G’) and loss modulus (G’’). All experiments were performed at
25 C and repeated three times.

Electromechanical characterization
Tensile tests of GSP hydrogels and LM-hydrogel hybrids were carried out on a uni-
versal testing machine (AGS-X, Shimadzu, Japan) at a stretching speed of 100 mm
min1. The samples were prepared in a dumbbell shape (50 mm in length, 4 mm
in width, and 3 mm in thickness) for the tensile test. The elastic modulus was calcu-
lated based on the initial linear regime (2%–10% of strain) of the obtained stress-
strain curve. Each sample was tested three times.

The electrochemical impendence spectroscopy of GSP hydrogel was measured us-

ing an electrochemical workstation (CHI660E, CH Instruments). The GSP hydrogel
(10 mm 3 10 mm 3 3 mm) was sandwiched between two platinum sheets for the

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measurement. The conductivity of GSP hydrogel was calculated according to the

following equation:

s = l = ðRb 3 SÞ;
where l represents the thickness of GSP hydrogel, Rb represents the resistance of
GSP hydrogel obtained from impendence data, and S represents the effective con-
tact area between GSP hydrogels and platinum sheets.

The electrical properties of the LM-hydrogel hybrid pressure sensors were tested by
a custom designed smart data-acquisition-system, which contains a computer-
controlled universal testing machine (AGS-X, Shimadzu, Japan) and an electrical
signal analyzer (Keysight, 34461A). The pressure was applied at a compression
speed of 1 mm min1, and the corresponding resistance was measured using the
electrical signal analyzer.

Dehydration/hydration process and characterization

The GSP hydrogel was placed at room temperature (26 C) for 3 h and then re-
immersed in deionized water. The FTIR spectra were used to measure changes in
the chemical structure of the gelatin, SA, original GSP hydrogel, and GSP hydrogel
after dehydration/hydration process in the wavenumber range of 400–4,000 cm1.
SEM images and EDS spectra of the samples (original GSP hydrogel, GSP hydrogel
after one dehydration/hydration process, and GSP hydrogel after three dehydra-
tion/hydration processes) were carried out on a ZEISS GeminiSEM 300 scanning
electron microscope.

In vitro degradation evaluation

LM-hydrogel hybrid disks (F832 mm) were weighed (m0) and submerged in 5 mL of
PBS at 37 C to assess the degradation. At the appointed time, the samples were
collected, dried, and weighed (mt). The degradation fraction was calculated accord-
ing to the following equation (n = 5):

Degradation fraction ð%Þ = ðm0  mt Þ = m0 3 100%

Fabrication of LM-hydrogel NFC tag

LM spiral coils were printed in GSP hydrogel by an in situ 3D printing method
mentioned above. A commercial NFC chip (NTAG213) was connected to both
ends of the LM coil to form an LM-hydrogel NFC tag. Briefly, the smartphone was
placed near the NFC tag, which was attached to the person’s hand. Through wireless
communication, we can scan the website previously encoded in the NFC tag.

Fabrication of pressure sensor

Two types of pressure sensors, the single resistive type and the hybrid resistive, were
fabricated by the in situ 3D printing method. The single-resistive-type pressure
sensor contains only one LM wire with a length of 30 mm in GSP hydrogel
(70 mm 3 50 mm 3 3 mm), and the hybrid resistive pressure sensor contains a dou-
ble-layer LM structure in GSP hydrogel (100 mm 3 100 mm 3 5 mm).

Fabrication of LM-hydrogel hybrid electrodes

We made two types of electrical stimulation electrodes: (1) LM wire was in situ
3D printed into GSP hydrogel to form the LM-hydrogel hybrid electrode for biomed-
ical experiments and (2) pure ionically conductive GSP hydrogel electrode without
containing LM wire as a control group. The shape of the electrode is cuboid
(40 mm 3 5 mm 3 2 mm).

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In vitro human EMG/ECG recording

Human EMG/ECG signals were recorded via a three-lead system. The commercial
Ag/AgCl electrodes and LM-hydrogel hybrid electrodes were attached to the hu-
man skin. For in vitro human EMG recording, the commercial Ag/AgCl electrodes
and LM-hydrogel hybrid electrodes were attached to the volunteer’s arm. The sub-
ject periodically made a fist to excite the target muscle. For in vitro human ECG
recording, the two electrodes placed on the left upper limb and the right upper
limb were positive and negative electrodes. Another electrode was attached to
the right lower limb and served as a reference electrode. The EMG/ECG signals
were collected using an RM6240E multi-channel physiological signal acquisition
and processing system.

In vivo electrical stimulation

All the animal experiments were approved by the animal ethics committee of Bei-
hang University (BM20220115). The male Sprague Dawley rats (280–300 g) were
used for the in vivo studies, and six animals were used in each experiment.

For TA muscle stimulation, the rats were anesthetized, and their hind limbs were de-
pilated and disinfected with medicinal alcohol for surgery. The TA muscle was surgi-
cally exposed and the two LM-hydrogel hybrid electrodes/pure ionically conductive
GSP hydrogel electrodes were placed on it. The rat was placed on a warming pad,
and the ankle of the right leg was connected to a muscle tension transducer
(JZ101), which was connected to a laptop through data acquisition. Then, a multi-
channel physiological signal acquisition and processing system (RM6240E) was
used for the test. Firstly, the effect of stimulation intensity on muscle contraction
was investigated. The stimulation parameters were set to positive voltage stimula-
tion and intensity-increasing stimulation. The initial intensity was set to 1 V, the
intensity increment was set to 0.25 V, and the pulse width was set to 0.2 ms. Next,
the effect of different stimulation frequencies (10, 20, 40, 60, 80, 100 Hz) on muscle
contraction was explored. Positive voltage stimulation (at 3 V) was applied, the stim-
ulation mode was set to timed stimulation, and the pulse width was set to 0.2 ms. The
stimulation period was set to 1 s and was repeated every 6 s, respectively. A protrac-
tor marker was placed under the rat hindlimb to measure the ankle joint motion
angles.

For sciatic nerve stimulation, all surgical procedures followed the previously
reported work.3 After anesthetizing and shaving, the sciatic nerve was exposed by
dissecting the vastus lateralis muscle and biceps femoris muscle. Two electrodes
(LM-hydrogel hybrid electrodes/pure ionically conductive GSP hydrogel electrodes)
were attached to the exposed sciatic nerve. The rat was placed on a warming pad,
and the ankle of the right leg was connected to a muscle tension transducer
(JZ101), which was connected to a laptop through data acquisition. Then, the sciatic
nerve was electrically stimulated, inducing muscle contraction. A multi-channel
physiological signal acquisition and processing system (RM6240E) was used to
observe the effects of different stimulation intensities (1–3.25 V, at 1 Hz) and
different stimulation frequencies (10, 20, 40, 60, 80, 100 Hz, at 3 V) on muscle
contraction. A protractor marker was placed under the rat hindlimb to measure
the ankle joint motion angles.

Statistical analysis
All experimental data were obtained by at least three replicates. Statistical analysis
was performed using GraphPad Prism 8. All data are represented as means G stan-
dard deviation (SD).

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Article

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.xcrp.
2023.101640.

ACKNOWLEDGMENTS
This work is supported by the Beijing Natural Science Foundation (grant no.
L223017), the National Natural Science Foundation of China (grant nos.
U20A20390, 11827803), and the 111 Project (project no. B13003).

AUTHOR CONTRIBUTIONS
C.J. and L.H. conceived the idea and designed the experiments. C.J. executed the
experiments, analyzed the data, and wrote the manuscript. Q.W. and L.L. assisted
the in vivo electrical stimulation experiment. W.C. assisted the in vitro human
EMG/ECG recording. J.L., Y.X., L.S., and S.F. provided useful suggestions about
the LM-hydrogel NFC tag. All authors discussed the experiments and gave consent
for this publication under the supervision of L.H.

DECLARATION OF INTERESTS
The authors declare no competing interests.

Received: June 2, 2023

Revised: September 13, 2023
Accepted: September 21, 2023
Published: October 18, 2023

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