Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Hybrid manufacturing of highly stretchable functionalized membrane for

joint wound treatment
Liu Yang a, Yi Lou b, Guoping Zhang a, Yue Sun a, Yang Yang d, Jindan Wu d, Yanyuan Ye a,
Xiaofan Chu a, Lei Du a, *, 1, Zhihua Jiang b, *, Huaizhong Xu c
a
School of Fashion Design & Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
b
Department of General Surgery, Hangzhou Children’s Hospital, Hangzhou 310014, China
c
Department of Biobased Materials Science, Kyoto Institute of Technology, Kyoto 606-8585, Japan
d
College of Textile Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China

G R A P H I C A L A B S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: Biofluid management of wounds is crucial to promote wound healing. Currently, traditional wound dressings
Directional Water Transportation designed for directional-water-transport face challenges in treating joint wounds. In this study, a functionalized
Janus Membrane bilayer membrane featuring high resilience, exceptional directional-water-transport capabilities, and antibac­
Wound Dressing
terial properties is proposed by a hybrid manufacturing combining solution electrospinning (SE) and melt
3D Printing
electrowriting (MEW). Firstly, an electrospun nonwoven fabric treated with oxygen plasma serves as a hydro­
Electrospinning
philic layer followed by printing a MEW scaffold. The MEW fabricates a polycaprolactone (PCL) scaffold con­
taining silver nanoparticles (AgNPs), forming the hydrophobic layer with antibacterial properties. The cyclic
tensile test reveals that the MEW scaffold with a knit-like structure can effectively retain its original shape,
surpassing the MEW scaffolds with the structures of lattice, serpentine, and sinusoidal. The bilayer membrane
exhibits impressive mechanical properties, including an elongation at break of 439% and minimal plastic
deformation of 2.9% after ten cyclic drawings at 20% strain. Furthermore, it demonstrates efficient directional-
water-transport performance (the value of accumulative one-way transport capability is 1280%) and excellent

* Corresponding authors.
E-mail addresses: dulei@zstu.edu.cn (L. Du), 2450134718@qq.com (Z. Jiang).
1
ORCID: 0000–0002-1115–3972

https://doi.org/10.1016/j.colsurfa.2023.132655
Received 7 August 2023; Received in revised form 15 October 2023; Accepted 23 October 2023
0927-7757/© 2023 Elsevier B.V. All rights reserved.
L. Yang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655

antibacterial activity (antibacterial rates against E. coli and S. aureus exceed 99.99%). Overall, this bilayer
membrane shows competitive potential as a wound dressing to promote wound healing, particularly for joint
wounds.

1. Introduction of a composite wound dressing. To identify an appropriate mechanical

The accumulation of excessive exudates in the wound can result in
overhydration, increasing the infection risks and hindering the healing
process [1]. Recently, the Janus bilayer membrane has gained consid­
erable attention due to its excellent directional transportation capacity,
which enables the effective absorption of exudates while preventing skin
infection [2–4]. Electrospinning is a facile technology to tailor Janus
nanofibrous bilayer membranes with asymmetric wetting properties [5,
6]. Qi et al. fabricated a multilayer electrospun membrane that featured
a hydrophobic-to-hydrophilic gradient structure with the effect of
self-pumping [7]. However, the elongation at break of this dressing is
very limited, which may not treat the wounds at joints properly. Efforts
were made to fabricate joint wound dressings. For instance, poly­
caprolactone / quaternized chitosan-graft-polyaniline nanofibrous
membranes with different quaternized chitosan-graft-polyaniline pro­
portions [8] and a bilayered nanofibrous membrane [9] were fabricated.
The maximum elongation at break of these membranes reaches 82%.
The maximum strain value of the electrospun membranes is similar to
that of human skin, while limitations still exist when applied to joints.
The frequent movements of joints lead to poor fitting of the dressing,
which may damage the dressing itself and compromise the overall
protection provided to the wound [10]. Therefore, it is urgent to develop
a new wound dressing that not only inhibits bacterial growth but also
exhibits remarkable stretchability and directional-water-transport ca­
pabilities to adapt to frequent movement and create an optimal micro­
environment for wound healing.
As a leading additive manufacturing technology, melt electrowriting
(MEW) enables scientists to print high-resolution and porous structures
[11]. MEW combines the strengths of electrospinning and additive
manufacturing, allowing precise control of the pore size and structure of
membranes [12–14]. We successfully created a hydrophobic layer with
customizable pore sizes by MEW for the Janus membrane, which has a
significant improvement in the overall directional-water-transport per­
formance [15,16]. MEW allows the design and precise preparation of
fiber membrane with various porosities and shapes because of its pro­
grammable characteristics [17]. It has the potential to tailor the
microarchitectures to meet the mechanical demands of biomedical ap­
plications [18]. Several groups applied MEW to adjust the mechanical
properties of soft tissues including heart valve tissue [19] and myocar­
dial tissue [20,21], providing valuable inspiration for developing wound
dressings with mechanical properties suitable for joint applications.
Polycaprolactone (PCL) is a gold-standard polymer commonly-used
in MEW for its low melting temperature and ease of fabrication [22].
In most cases, neat PCL is not ideal for medical applications due to its
bio-inert nature, while fillers can provide active properties and improve
the bio-functionality of the printed scaffolds [23,24]. To enhance the
antibacterial activity, silver nanoparticles (AgNPs) were incorporated
into the MEW scaffold, due to their broad-spectrum antibacterial ac­
tivity [25]. AgNPs disrupt the function of ribosome and DNA by pene­
trating bacteria cell walls and damage proteins and phosphorus inside
the bacterial cell [26]. Nevertheless, loading nanoparticles significantly
alters the mechanical properties of PCL composites. As the concentration
of nanoparticles increases, the elongation at break of the fiber mem­
branes fabricated by the PCL composites decreases, as previously
demonstrated [16,27,28]. This adverse effect is particularly problematic
for joint dressings, which require excellent mechanical properties.
Therefore, it is essential to improve the mechanical properties of the
MEW scaffolds to extend MEW’s application.
In this context, MEW was utilized to prepare the hydrophobic layer
property for the joint wounds, a linear (lattice) and three nonlinear
(serpentine, sinusoidal, and knit-like) structures were printed, and the
stretchability of the dressings was evaluated through tensile and cyclic
tensile tests. Additionally, a dense nanofiber membrane with excellent
elasticity was fabricated as the hydrophilic layer using the electro­
spinning technique and enhancing its hydrophilicity through oxygen
(O2) plasma treatment. By integrating liquid transport capability, anti­
bacterial activity, and mechanical strength, our innovative design offers
new insight into developing multifunctional wound dressings for the
next generation.
2. Materials and methods
2.1. Materials
Polycaprolactone (PCL, Mn = 45,000 g/mol, CAS number 704105)
pellets were sourced from Sigma Aldrich, America. Silver nitrate
(AgNO3, purity 99.8%, CAS number 7761–88–8) and Glutaraldehyde
(50% in H2O, CAS number 111–30–8) were purchased from Aladdin,
China. Tea polyphenols (TP, purity 98%, CAS number 84650–60–2)
were supplied by Shanghai Jinsui BioTechnology, China. Poly(styrene-
block-butadiene-block-styrene) (SBS) copolymer (D1102 JSZ) was ob­
tained from Kraton, America. Tetrahydrofuran (THF, purity 99%, CAS
number 109–99–9) and N, N-Dimethylformamide (DMF, purity 99%,
CAS number 68–12–2) were purchased from Tianjin Yongda Chemical
Reagent, China. Ethanol (purity ≥ 99.5%, CAS number 64–17–5) was
supplied by Hangzhou Gaojing Fine Chemical Co., Ltd., China.
2.2. Preparation of the bilayer membrane
Fig. 1 is the flow diagram of preparing a bilayer membrane using
solution electrospinning (SE) and melt electrowriting (MEW). In brief,
solution electrospun SBS nonwoven fabric is produced first as a matrix to
hold the following printed MEW scaffold, forming a functionalized
bilayer membrane.
SBS is a thermoplastic elastomer known for its exceptional tensile
strength. The SBS was dissolved in a co-solvent mixture (THF / DMF = 7
/ 3, vol. / vol.), forming a 15 wt% spinning dope. The spinning pa­
rameters were fixed at an applied voltage of 15 kV, a flow rate of 20 μL/
min, a nozzle-to-collector distance of 17 cm, and a needle size of 25
gauge. To enhance its hydrophilicity, the hydrophobic SBS fabric was
treated with O2 plasma on both sides using a cold plasma instrument
(HD-1B, Changzhou Zhongke Changtai Plasma Technology, China) at a
power of 80 W with a duration of 90 s
PCL-AgNPs composite material prepared with 2 wt% AgNO3 was
selected as the raw material for MEW. The detailed preparation methods
of PCL-AgNPs pellets were reported in our previous study [16]. Briefly,
AgNO3 at a concentration of 2 wt% (i.e., proportional to the total weight
of PCL) and TP of 30 wt% (i.e., proportional to the total weight of
AgNO3) were selected for the synthesis of AgNPs and mixed them with
PCL. The pellets were then filled in a plastic syringe embedded into a
self-built MEW device and kept heating at 75 ℃ for two days. The MEW
printer consists of a 3D translation system (HS0010–902, NSK, Japan,
repeatability precision = 1 µm), a high voltage applied system
(DW-P103–1ACH2, Dongwen High Voltage Power Supply, China), a
feeding system (RP. NR-4–2, Fujikura, Japan) and an electrically heating
system (AI-208, Shanghai Gaohan Automation Equipment, China). The
positive voltage is connected to the spinneret to generate an electric
potential between the nozzle and the collector. The motion of the print

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L. Yang et al.
head is controlled by G-code (Artsoft Mach 3, version 2.0, America). The
processing parameters including voltage, pressure (supplied by nitrogen
gas), nozzle-to-collector distance, and nozzle size were maintained at
fixed values of 3 kV, 200 kPa, 3 mm, and 27 gauge, respectively. The
critical translation speed (CTS) represents the point at which the col­
lector speed matches the molten jet speed as it touches the moving
surface. Since we provided that matching the printing speed with the
CTS can keep the fidelity during the print of nonlinear patterns, a CTS
measurement was conducted prior to printing [13]. Before printing, the
SBS fabric was resting on the collector and fixed with masking tape.
Subsequently, lattice, serpentine, sinusoidal, and knit-like patterns were
printed at CTS. All protocols were performed at room temperatures in a
range of 25–27 ℃ and relative humidities in a range of 30–35%.
2.3. Characterization
2.3.1. Physical and chemical characterization
The morphologies of MEW scaffolds with different structures and
bilayer membrane were observed using a field-emission scanning elec­
tron microscope (FE-SEM, Ultra-55, Zeiss, Germany) operating at an
accelerating voltage of 3 kV. Before SEM analysis, specimens were
coated with a thin layer of platinum at 40 mA for 40 s. Meanwhile, the
frequency distribution of the main elements in the composition of the
MEW patterned scaffolds was carried out through the elemental map­
ping test using SEM-energy dispersive X-ray spectrometry (SEM-EDS)
with an increased operating voltage of 10 kV. The chemical composition
of the fibers was further reinforced using X-ray photoelectron spec­
troscopy (XPS, Escalab 250Xi, Thermo Scientific, America) equipped
with an Al Kα excitation source.
2.3.2. Mechanical test of the MEW and the bilayer membranes
To evaluate the tensile properties of the MEW scaffolds, the tensile
strength and cyclic tensile tests were performed under a tensile tester
(STA-1150, Orientec, Japan). Both effective length and width of the
samples were controlled at 10 mm. The stretching speed was set at
20 mm/min. Cyclic tensile tests comprised ten cycles with a maximum
Fig. 1. Schematic diagram of fabricating a bilayer membrane using solution electrospinning and melt electrowriting. Lattice, serpentine, sinusoidal, and knit-like
patterns are electrowritten on an electrospun SBS nonwoven fabric, forming a hydrophilic-hydrophobic bilayer membrane.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655
strain of 20%. Each measurement was repeated at least 4 times to ensure
reliability and accuracy. The entire cyclic tensile test process was
recorded by a digital camera (XW200, Shenzhen Hayear Electronics,
China). The recorded video footage was subsequently edited by CapCut
(version 2.4.0).
2.3.3. Water contact angle test of the SBS fabrics before and after plasma
treatment
The water contact angles (WCAs) of the fabrics before and after O2
plasma treatment were measured by an optical contact angle instrument
(DSA20, Krüss, Germany), and the change of contact angles after a
3.5 μL deionized water droplet placed on the surface of fabrics were also
recorded. Each group was tested at least 5 times.
2.3.4. Breakthrough pressure test of the bilayer membrane
In order to determine the breakthrough pressure of the bilayer
wound dressing in both positive and reverse directions, a glass tube with
an inner diameter of 1.6 cm was employed. The breakthrough pressure
was measured by recording the height of the water column that the
composite dressing could withstand before the first water droplet
penetrated through it. The height of the water column at this point was
considered as the breakthrough pressure. Each group was tested at least
5 times.
2.3.5. Directional-water-transport properties of the bilayer membrane
The moisture management property of the bilayer membrane was
quantitatively characterized using a moisture management tester (MMT,
M290, SDL Atlas, China). In particular, the sample was placed between
two horizontal electric resistance sensors, keeping the testing area as
5 cm × 5 cm. The side of knit-like scaffold was continuously dripped
with a total of 0.2 g saline water (0.9% NaCl) for 20 s. The measuring
process lasted for 120 s. The test was repeated at least 5 times. The one-
way water transportation performance can be appraised using the
accumulative one-way transport capability (AOTC) and overall moisture
management capability (OMMC) equation as following [29];
L. Yang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655

∫
[Ub − Ut ]
AOTC = (1) A− B
T Bacterial activity (%) = × 100% (3)
A
OMMC = 0.25BAR + 0.5AOTC + 0.25BSS (2)
where A and B signify the number of bacterial colonies in the control and
experimental groups, respectively.
where moisture content in the surfaces of bottom (Ub) and top (Ut)
Furthermore, to clarify the impact of different samples on the bac­
layers, total testing time (T), bottom layer absorption rate (BAR), and
teria, the morphology of bacteria on the surface of different samples was
bottom layer spreading speed (BSS) are given.
observed using SEM. In detail, the samples after coculture in each group
were washed with PBS. The samples were then transferred into sealed
2.3.6. Antibacterial assay of bilayer membrane
tubes containing 5 mL of 2.5% glutaraldehyde and held at 4 ℃ for 4 h to
The antibacterial activities of the plasma-treated SBS fabric, MEW
solidify the bacterial cells on samples. Excess glutaraldehyde was sub­
knit-like scaffold, and bilayer membrane against Escherichia coli (E. coli)
sequently removed by washing specimens with deionized water several
as Gram-negative bacteria and Staphylococcus aureus (S. aureus) as Gram-
times. Then, bacterial cells on samples were dehydrated by sequential
positive bacteria were evaluated using the spread plate method. Prior to
exposure to a graded ethanol series using a graded ethanol series (10%,
the experiment, each side of the 1.5 cm × 1.5 cm samples was sterilized
30%, 50%, 60%, 70%, 80%, 90%, 100%, and 100% for 10 min each),
with UV light for 1 h. The samples were then immersed into a 10 mL
and the samples were placed in a fume hood to dry naturally. Finally, the
centrifuge tube containing 5 mL bacterial suspension of the same con­
bacteria on the surface of samples in each group were examined by SEM.
centration (107 CFU/mL) for overnight coculture in a shaking incubator
at 37 ℃ and 150 rpm. A bacterial solution without samples was pre­
2.3.7. Statistical analysis
pared as the control group. After incubation, the bacterial suspension
The quantitative results were expressed as mean ± standard devia­
was serially diluted, and 100 μL of the diluted bacterial suspensions
tion. Statistical analysis was performed using one-way analysis of vari­
from each group was inoculated onto a nutrient agar plate respectively.
ance (ANOVA) and least significant difference-t-test (LSD-t) between
Eventually, the agar plates were cultured in a constant temperature
groups. Statistically significant levels were denoted as * ** p < 0.001,
incubator at 37 ℃ for 24 h. Three parallel samples were set for each
* * p < 0.01, and * p < 0.05.
concentration in each group. The number of bacterial colonies in each
plate was counted three times, and the number of colony-forming units
3. Results and discussion
(CFU) was calculated by multiplying the number of colonies with the
dilution factors. The bacterial activity of each sample was calculated
3.1. Physicochemical properties of the bilayer membrane
according to the following equation [10];

Fig. 2 displays the SBS fabrics before (Fig. 2a, b) and after (Fig. 2c, d)

Fig. 2. SEM images of SBS fabrics before (a, b) and after (c, d) plasma treatment. MEW scaffolds printed in the patterns of (e) lattice, (f) serpentine, (g) sinusoidal,
and (h) knit-like. (i) The enlarged image of (h), and the corresponding element maps of Carbon (j), Oxygen (k), and Silver(l).

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L. Yang et al.
plasma treatment; the MEW scaffolds in shapes of lattice (Fig. 2e),
serpentine (Fig. 2f), sinusoidal (Fig. 2g), and knit-like (Fig. 2h); the
element maps of the MEW scaffold (Fig. 2i-l); and the bilayer membrane
under different magnifications (Fig. 2m-p). The fiber diameter of the
SBS fabric ranges from sub-micrometers to micrometers, forming a
micro-porous and compact membrane. The MEW can print the intended
patterns precisely for 20 layers, suggesting that the addition of Ag fillers
would not reduce the printability of PCL. Fig. 2l and the XPS spectrum in
Fig. S1 (supplementary material) demonstrate that the AgNPs are uni­
formly dispersed in the PCL. Although the SBS fabric is an insulator
placed on the collector, the MEW scaffold can be well directly written on
the plasma-treated SBS matrix using our custom-built MEW device.
3.2. Mechanical properties
3.2.1. Tensile test
Fig. 3 shows the tensile test results of the MEW scaffolds, the SBS
fabrics, and the bilayer membrane. The representative curves were
displayed in dark colors, and other curves were presented in light colors.
For the MEW scaffolds (Fig. 3a), the elongation at break of lattice,
serpentine, sinusoidal, and knit-like scaffolds was approximately 185%,
300%, 300%, and 620%; the breaking force was approximately 0.48 N,
0.60 N, 0.53 N, and 0.56 N, respectively. The specific data was pre­
sented in the form of mean ± standard deviation in Table S1. All the
nonlinear scaffolds have better mechanical properties than the lattice
scaffold. The serpentine and sinusoidal scaffolds have similar mechan­
ical properties mainly due to the similar curvature of the curves.
Remarkably, the knit-like scaffold owned the highest elongation at
break, and it also exhibited typically nonlinear J-shaped mechanical
properties at the initial stages of elongation, resembling the mechanical
behavior of human skin [29,30]. Fig. S2 shows the states of the MEW
scaffolds after the tensile test. All the lateral fibers were not sufficiently
stretched, influencing the cohesion of the fibers in the vertical direction.
Such property resulted in the structure possible to achieve the desired
mechanical properties of MEW scaffolds.
In Fig. 3b, the elongation at break of the SBS fabric reduced
approximately from 630% to 400%, and the breaking force decreased
approximately from 0.54 N to 0.47 N after the plasma treatment. Simi­
larly, the specific data was presented in Table S2. Thus, the etching of
the sample surface through the O2 plasma treatment has a negative ef­
fect on the mechanical properties of the SBS fabric. For the bilayer
membrane, the breaking force is approximately 0.93 N, almost equaling
to the sum of the breaking forces of the SBS fabric and knit-like scaffold.
The elongation at break of the bilayer membrane (440%) is close to the
elongation at break of the plasma-treated SBS fabric, which is caused by
the large stretching force loading on the bilayer membrane. The
experimental results show that the bilayer membrane has better
Fig. 3. Force-strain curves of the (a) MEW scaffolds and the (b) SBS fabric, plasma-treated SBS fabric, and bilayer membrane.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655
mechanical properties compared with the membrane prepared by single
electrospinning [8,9].
3.2.2. Cyclic tensile test
Fig. 4 displays the results of the cyclic tensile test for the MEW
scaffolds, the SBS fabrics, and the bilayer membrane. The first step is to
find out the optimum MEW structure used for the hydrophobic layer.
Apart from the knit-like structure, the rest three structures exhibit
obvious hysteresis loops in Fig. 4a, b, c. That is, the unloading curves did
not follow the loading curves, and considerable residual strain was
presented after the cyclic drawing. Specifically speaking, the lattice,
serpentine, and sinusoidal scaffolds exhibited 12.5%, 8.0%, and 10.0%
residual strains, respectively, after ten cyclic drawings, indicating that
these scaffolds presented prominent inelastic strain. Meanwhile, the
force at 20% strain gradually decreased with the cyclic drawing due to
the stress relaxation of the scaffold. Since the PCL is not an elastomer,
the effective curvature of the structure directly determines the elasticity
of the scaffold. With the feature of large curvature, the knit-like struc­
ture in the latitude direction showed high elasticity and had almost
identical loading and unloading curves (Fig. 4d). Thus, the knit-like
structure maintained its original morphology after repeated drawings.
Although the additive manufacturing cannot execute the knitting pro­
cess, the similar weft-knitted structure provides remarkable resilience
during the cyclic drawing process. Video S1 presents the cyclic drawing
process of the MEW scaffolds. The lattice, serpentine, and sinusoidal
scaffolds were deformed after the first circulation since the image is out
of focus, while the knit-like structure did not show clear deformation
after strain recovered.
To demonstrate the hysteresis accurately, the hysteresis area was
used to calculate the energy dissipation after cyclic drawing. The area
enclosed by the loading curve represents the energy required when a
material is stretched to a specified strain; the area enclosed by the
unloading curve represents the energy recovered and stored when the
material returns to its initial length. The difference between these two
areas represents the dissipated energy. For the lattice, serpentine, and
sinusoidal structures, a prominent hysteresis area existed after the first
loading-unloading process, indicating the significant energy loss or
plastic deformation of the scaffolds (Fig. 4h). These structures may lose
their usability after suffering a small deformation. For the knit-like
scaffold, its hysteresis area did not show significant change thor­
oughly, meaning limited energy dissipation occurred. Therefore, we
believe that the knit-like scaffold is suitable to be used as a hydrophobic
layer for the bilayer membrane.
Theoretically, the SBS elastomer would not show the hysteresis loop
for the cyclic tensile test, while both the untreated and plasma-treated
SBS nonwoven fabrics have clear hysteresis loops in Fig. 4e, f. Unlike
the MEW scaffolds, this stress relaxation here occurred by the structural
L. Yang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655

Fig. 4. Cyclic tensile test results of the MEW scaffolds in the (a) lattice, (b) serpentine, (c) sinusoidal, and (d) knit-like based structures, the (e) SBS fabric, the (f)
plasma-treated SBS fabric, and the (g) bilayer membrane. (h) Hysteresis area of the above-mentioned membranes at different cycles.

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L. Yang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655

damage. A portion of the random SBS fibers separated from each other
after drawing, causing irrecoverable deformation. From the first circu­
lation, we can find that the plasma-treated SBS fabric has higher applied
force (0.23 N) and residual strain (7.1%) than the applied force (0.12 N)
and residual strain (4.4%) loaded on the untreated SBS fabric. For the
rest circulations, the hysteresis area of the plasma-treated SBS fabric is
relatively larger than that of the untreated SBS fabric, indicating that the
plasma-treated SBS fabric experienced significant energy dissipation
during the 2nd to 10th tensile cycles compared to the untreated SBS
fabric. We believe that the plasma treatment destroyed the amorphous
portion within the fibers, which increased the possibility of stress
relaxation after drawing.
For the bilayer membrane, the residual strain was reduced to 2.9%,
indicating a recovery rate of over 97% after the ten cyclic drawings.
Compared with the single plasma-treated SBS fabric, the bilayer mem­
brane has reduced energy dissipation, suggesting that the knit-like
scaffold modifies the dissipation to a certain extent.
3.3. Directional-water-transport properties of the bilayer membrane
The plasma-treated SBS fabric was intended to be utilized as the
hydrophilic layer in the bilayer membrane. The hydrophilia were eval­
uated through the variation of the dynamic water contact angle (WCA),
as depicted in Fig. 5a, b. For the plasma-treated SBS fabric, the droplet
disappeared within 2.0 ± 0.7 s, indicating a WCA of 0◦ . In contrast, the
untreated SBS fabric exhibited an average WCA of 129.3 ± 0.7◦ and
remained constant over time. These results demonstrate that the surface
wettability of the SBS fabric can be significantly improved by the plasma
treatment. It is known that the plasma treatment results in the formation
of new functional groups (such as carboxyl and hydroxyl groups) on the
surface of the SBS fabric [31,32], which profoundly impact the surface
wettability of the SBS fabric.
The moisture management performance of the bilayer wound dres­
sing was tested to demonstrate its directional-water-transport ability.
The moisture contents on the top (hydrophobic layer) and the bottom
(hydrophilic layer) were measured and plotted against time. Fig. 5c
provides a quantitative analysis of the water transport behavior within

Fig. 5. Optical images of the droplet during water contact angle test on SBS fabrics (a) before O2 plasma treatment (0 s, 10 s), and (b) after O2 plasma treatment (0 s,
2 s); (c) moisture management tester (MMT) analysis of the bilayer membrane. The insert images represent the wettability of the top and the bottom surfaces. The dry
and the wet states are colored in black and blue, respectively; (d) breakthrough pressure of the bilayer membrane; schematic illustrations for the directional-water-
transport mechanism of bilayer membrane when water is dropped on the (e) hydrophobic side and the (f) hydrophilic side.

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L. Yang et al.
120 s. During the initial water intake (5–15 s), water was not detected in
the top layer, while it was detected in the bottom layer. This suggested
that water penetrated the top layer and diffused along the horizontal
direction on the bottom layer. Until the end of the test, it was observed
that the moisture content of the top layer remained significantly higher
than that of the bottom layer. Furthermore, the final wetting state shown
in the inset images of Fig. 5c confirmed that most water had been
absorbed by the hydrophilic layer, with only a small proportion
remaining on the surface of the hydrophobic layer. According to the wet
healing theory, maintaining a moderate level of moisture can effectively
promote the wound healing process [33]. The AOTC and OMMC values
measured by MMT were 1280% and 0.823, respectively, reaching the
highest-level Grade 5 standard according to the grading of MMT [34].
Additionally, the directional-water-transport properties of the mem­
branes and fabrics previously reported were summarized in Fig. S3,
which showed that this work not only provided excellent AOTC but also
showed relatively higher OMMC results than many reported works
[34–38]. The results indicated that the bilayer wound dressings possess
directional-water-transport performance.
The breakthrough pressure of the bilayer wound dressing was
measured in both the positive (i.e., from the knit-like scaffold to the
plasma-treated SBS fabric) and the reverse directions (i.e., from the
plasma-treated SBS fabric to the knit-like membrane). As indicated in
Fig. 5d, the positive breakthrough pressure was 2.0 ± 0.2 cm, while the
reverse breakthrough pressure was 4.7 ± 0.4 cm. The difference in
breakthrough pressure between the two directions indicated the effec­
tive directional water movement capability of bilayer membrane.
As shown in Fig. 5e, when the hydrophobic layer is positioned up­
ward, a water droplet is subjected to two opposing forces, namely the
Fig. 6. Optical images of bacterial agar plate count of different groups against (a) E. coli and (b) S. aureus; (c) antibacterial rate of different samples, ** p < 0.01,
*** p < 0.001 compared to control group; ◆◆◆p < 0.001 compared to SBS fabric group; SEM observation of bacterial morphology after coculture with different
samples (d) E. coli and (e) S. aureus.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655
downward hydrostatic pressure (FHP) related to the weight of the droplet
and the upward hydrophobic force (FHF) provided by the hydrophobic
layer. Once the FHP exceeds the FHF, the water droplet will penetrate the
hydrophobic layer and contacts the underlying hydrophilic substrate.
Upon encountering the hydrophilic layer, the droplet tends to be
absorbed into it due to the downward capillary forces (FCF). This ab­
sorption is facilitated by the FCF in the horizontal direction, leading to
water being drawn into the substrate through numerous contact points
[39]. Conversely, in Fig. 5f, the FCF quickly captures and disperses the
water within the hydrophilic layer when water is dropped onto the
hydrophilic side. In addition, the FHP will promote the dispersion of
water in the hydrophilic layer. Significantly, as water spreads over a
large area of the hydrophilic layer, the mass per unit area of the water is
reduced. Thus, the FHP per unit area is decreased [40]. Furthermore, the
hydrophobic layer below exerts an upward FHF on the liquid, preventing
it from dripping. Consequently, the combined effects of FCF within the
hydrophilic layer and the upward FHF from the hydrophobic layer create
a barrier that hinders its easy passage through the hydrophobic layer.
3.4. Antibacterial activity of bilayer membrane
Fig. 6a-b shows the colony growth of E. coli and S. aureus after 24 h
for the control group, plasma-treated SBS fabric, MEW knit-like scaffold,
and the bilayer membrane. Compared with other experimental groups,
the SBS fabric group still had more colony formation, and the calculated
antibacterial rate of the SBS fabric against E. coli and S. aureus was only
17.79% and 13.32%, respectively. In contrast, the knit-like scaffold and
bilayer membrane demonstrated high antibacterial activity without
colony formation. Fig. 6c further illustrates that the antibacterial rates of
L. Yang et al.
the knit-like scaffold and bilayer membrane against E. coli and S. aureus
exceeded 99.99%, significantly higher than those of the SBS scaffold.
These results indicate that the presence of AgNPs in the hydrophobic
layer contributes to the notable antibacterial activity of the composite
wound dressings. Furthermore, according to the XPS spectra in Fig. S1,
the primary antibacterial agent is Ag0 rather than Ag+ [26].
To further explore the antibacterial effects, the bacteria morphology
after coculturing with different fiber membranes was further investi­
gated using SEM. Fig. 6d shows that the E. coli cells after coculturing
with the SBS fabric maintained a rod shape without damage, whereas
the surface of bacteria exhibited wrinkles and cracks after coculturing
with the knit-like scaffold and bilayer membrane. Similarly, the S. aureus
cells on the SBS fabric had intact sphere-shaped morphology with
smooth cell membranes, while the surface of the bacteria exhibited
wrinkles and cracks after coculturing with the knit-like scaffold and
bilayer membrane (Fig. 6e). The leakage of cellular contents on the fi­
bers, indicated by the red arrow, further confirmed damage to the
bacterial cell membranes [41]. The reason for this phenomenon is that
AgNPs can generate free radicals (reactive oxygen species, ROS), induce
oxidative stress on bacterial cell membrane, and disrupt bacterial
cellular contents, leading to bacterial death [42].
4. Conclusions
Two distinct electrospinning techniques were employed in this work
to rationally fabricate a bilayer Janus membrane. It introduces a novel
approach for joint wound dressing featuring excellent stretchability,
directional-water-transport, and antibacterial properties. It has been
proven that the structure has a significant impact on the mechanical
properties of the PCL MEW scaffolds. Compared with other structures,
the knit-like scaffold exhibited a J-shaped performance in the force-
strain curve during the initial stretching stage, resembling the deform­
able behavior of skin. Additionally, it also displayed remarkable elastic
recovery, making it an ideal choice for the hydrophobic layer in the
composite dressings. The SBS nonwoven fabric, produced through
electrospinning and subsequently treated with O2 plasma, exhibited
good hydrophilicity and elasticity, serving as the hydrophilic layer.
Moreover, the antibacterial assay and moisture management test
demonstrated that the bilayer membrane displayed desirable antibac­
terial activity and directional-water-transport performance. In sum­
mary, this study provides new ideas for using MEW to scaffold structure
design to enhance its mechanical properties and opens new possibilities
for combining MEW and electrospinning techniques in developing next-
generation joint wound dressings with exceptional characteristics.
CRediT authorship contribution statement
Liu Yang: Investigation, Writing - original draft. Yi Lou: Method­
ology. Guoping Zhang: Validation. Yue Sun: Writing - review & edit­
ing. Yang Yang: Methodology, Investigation. Jindan Wu: Validation,
Data curation. Yanyuan Ye: Validation. Xiaofan Chu: Investigation. Lei
Du: Conceptualization, Methodology, Writing - original draft, Funding
acquisition. Zhihua Jiang: Methodology, Funding acquisition. Huaiz­
hong Xu: Supervision, Writing - review & editing, Project
administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
Data will be made available on request.
9
Colloids and Surfaces A: Physicochemical and Engineering Aspects 680 (2024) 132655
Acknowledgments
This study is financially supported by the Zhejiang Provincial Key
Research and Development Program (2023C01196), the Fund of China
Scholarship Council (202007295002), the Key Project of Hangzhou
Health Science and Technology Plan (Z20230087), the 2021
Outstanding Graduate Dissertation Cultivation Fund Project of Zhejiang
Sci-Tech University (LW-YP2021052), the National Training Program of
Innovation and Entrepreneurship for Undergraduates (202210338020),
and the Zhejiang University Student Science and Technology Innovation
Activity Plan (2023R406082).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.colsurfa.2023.132655.
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