Acta Biomaterialia 9 (2013) 56985707

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Acta Biomaterialia
journal homepage: www.elsevier.com/locate/actabiomat

Controlled biomineralization of electrospun poly(e-caprolactone) bers to

enhance their mechanical properties
Jingwei Xie a,, Shaoping Zhong b, Bing Ma a, Franklin D. Shuler c, Chwee Teck Lim b
a

Marshall Institute for Interdisciplinary Research and Center for Diagnostic Nanosystems, Marshall University, Huntington, WV 25755, USA
Department of Bioengineering, National University of Singapore, Singapore 117576, Singapore
c
Department of Orthopaedic Surgery, Joan C. Edwards School of Medicine, Marshall University, Huntington, WV 25701, USA
b

a r t i c l e

i n f o

Article history:
Received 1 June 2012
Received in revised form 24 September
2012
Accepted 30 October 2012
Available online 3 November 2012
Keywords:
Electrospinning
Polydopamine
Fibers
Surface modication
Coating

a b s t r a c t
Electrospun polymeric bers have been investigated as scaffolding materials for bone tissue engineering.
However, their mechanical properties, and in particular stiffness and ultimate tensile strength, cannot
match those of natural bones. The objective of the study was to develop novel composite nanober scaffolds by attaching minerals to polymeric bers using an adhesive material the mussel-inspired protein
polydopamine as a superglue. Herein, we report for the rst time the use of dopamine to regulate
mineralization of electrospun poly(e-caprolactone) (PCL) bers to enhance their mechanical properties.
We examined the mineralization of the PCL bers by adjusting the concentration of HCO3 and dopamine
in the mineralized solution, the reaction time and the surface composition of the bers. We also examined mineralization on the surface of polydopamine-coated PCL bers. We demonstrated the control of
morphology, grain size and thickness of minerals deposited on the surface of electrospun bers. The
obtained mineral coatings render electrospun bers with much higher stiffness, ultimate tensile strength
and toughness, which could be closer to the mechanical properties of natural bone. Such great enhancement of mechanical properties for electrospun bers through mussel protein-mediated mineralization
has not been seen previously. This study could also be extended to the fabrication of other composite
materials to better bridge the interfaces between organic and inorganic phases.
2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction
Great advances in the development of bone scaffolds with various compositions and structures have been achieved using
numerous techniques. One such technique, electrospinning, has
been attracted much attention for fabrication of nanober scaffolds
for use in bone tissue regeneration in that a non-woven mat of
electrospun nanobers can serve as an idea scaffold to mimic the
extracellular matrix for cell attachment and nutrient transportation owing to its high porosity and large surface-area-to-volume
ratio [1,2]. Some studies have demonstrated that electrospun bers
of a polymer alone can serve as bone tissue engineering scaffolds
and enhance bone regeneration to some extent. Other studies have
suggested the use of some inorganic materials, like bioactive
glasses, which have been processed into bers or tubes by the electrospinning technique for bone tissue regeneration [35]. However, the mechanical properties of pure polymeric scaffolds are
far from those of natural bone, and nanobers/tubes made of inorganic materials are very brittle and hard to manipulate. Recent efforts have focused on the development of composite nanober
Corresponding author. Tel.: +1 304 696 3833; fax: +1 304 696 3839.
E-mail address: xiej@marshall.edu (J. Xie).

scaffolds which can better mimic the composition and further

match the mechanical properties of natural bone. Incorporating
an inorganic phase material (e.g. hydroxyapatite, octacalcium
phosphate), which is one of the compositions of natural bone or
bone precursors, into an organic phase material (e.g. biodegradable
polymeric nanobers) is generally used to enhance the mechanical
properties of nanober scaffolds. Two approaches of incorporation
of inorganic phase materials include encapsulating inorganic phase
materials (e.g. hydroxyapatite nanoparticle, nanorods) inside polymeric nanobers and depositing inorganic phase materials on the
surface of polymeric nanobers to form uniform coatings [611].
The encapsulation of inorganic materials could improve the
mechanical properties of brous materials. However, the ber
surface is not optimized as a support to maintain desirable cell
substrates interaction. Direct deposition of inorganic materials on
the nanober surface can not only enhance its mechanical properties, but also provide a favorable substrate for cell proliferation and
osteogenic conduction [11,12].
To this end, many studies have investigated the deposition of
minerals on the electrospun polymeric bers. In principle, the
morphology and grain size of minerals deposited on the bers
can be tailored by controlling the composition of the mineralized
solution, the surface charge of substrate and the surface chemistry

1742-7061/$ - see front matter 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.actbio.2012.10.042

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Fig. 1. Schematic illustrating the formation of composite bers. Method I: plasma-treated, electrospun PCL bers were coated with polydopamine in a 0.2 mg ml 1 dopamine
solution at pH 8.5 for 4 h and subsequently mineralized in 10 SBF solution containing different amounts of NaHCO3. Method II: plasma-treated, electrospun PCL bers were
directly mineralized in the 10SBF solution in the presence of different amounts of NaHCO3 and dopamine.

properties. It was demonstrated that Mg2+ and HCO3 can act as

inhibitors of crystal growth and, by varying their concentrations,
the morphology and grain size of minerals can be controlled
[11,13,14]. The dose-dependent effects of amelogenin were also
found to signicantly inhibit apatite crystal growth and cause octacalcium phosphate (OCP) crystals to change from a plate-like
shape to a curved shape [15]. In the same study, it was shown that
the presence of bovine serum albumin in the mineralized solution
can greatly alter the plate-like OCP crystals into a round-edged,
curved shape, indicating a general inhibitory effect [15]. The presence of cetyl trimethylammonium bromide, poly L-aspartic acid
and polyacrylic acid in the mineralized solution was examined
with regard to the formation of mineral crystals as well [1618].
A charged surface was also thought to be an important factor that
greatly affects the nucleation of minerals onto substrates. It was reported that a negative surface is favorable for the heterogeneous
nucleation of calcium phosphate [1921]. Separate studies additionally examined the inuence of different surface functional
groups (e.g. carboxyl, carbonyl, amino, hydroxyl groups), and their
combinations of substrates, on the nucleation and growth of crystals during mineral deposition [9,10].
However, the attachment of minerals to polymeric materials on
the micro/nanoscale remains a big challenge as they represent
inorganic phase materials and organic phase materials, respectively, and thus exhibit signicant differences in their mechanical
properties. Prior studies have demonstrated that the control of
morphology and grain size of minerals deposited on the electrospun polymeric bers can enhance the mechanical properties
(e.g. stiffness) to a certain extent [11,22]. However, none of them
attempted to enhance the mechanical properties by attaching minerals to electrospun polymeric bers with a ller or glue. In the
present work, we aim to develop novel composite nanober scaffolds by attaching minerals (inorganic phase) to polymeric bers
(organic phase) through an adhesive material the mussel-

Table 1
Composition of mineralization solution.
Composition of 10SBF solution

Concentration (g l

NaCl
CaCl2
NaH2PO4
H2O

58.43
2.77
1.39

inspired protein polydopamine as a glue. We hypothesized that

these hybrid ber scaffolds could have superior mechanical properties compared to unmodied bers.
2. Materials and methods
2.1. Fabrication of PCL bers
The electrospinning set-up used in the present work was similar
to those described in our previous publications [23,24]. Poly(ecaprolactone) (PCL) (Mw = 80,000 g mol 1; SigmaAldrich, St. Louis,
MO) was dissolved in a solvent mixture consisting of dichloromethane and N,N-dimethylformamide (Fisher Chemical, Waltham,
MA) with a ratio of 4:1 (v/v) at a concentration of 10% (w/v). Polymer solution was loaded into a 10 ml plastic syringe with a 22
gauge needle attached and pumped at a ow rate of 0.5 ml h1
using a syringe pump. The working distance between the tip of
the needle and the collector was about 15 cm and a voltage of
12 kV was applied. Alignment of electrospun bers was achieved
by making use of a high-speed rotating mandrel as a collector.
2.2. Fabrication of composite bers
Composite bers were fabricated in two different ways, as
indicated in Fig. 1. One was to coat mussel-inspired protein on
the surface of plasma-treated, electrospun bers and subsequently

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Fig. 2. SEM images of mineralized PCL nanobers which were produced using method I shown in Fig. 1. Plasma-treated, electrospun PCL nanobers were coated with
polydopamine for 4 h in 0.2 mg ml 1 dopamine solution at pH 8.5 and mineralized in 10SBF solution containing 0.01 M (A, C) or 0.04 M (B, D) NaHCO3 at 37 C for 24 h.

Fig. 3. SEM images mineralized PCL bers which were produced using method I shown in Fig. 1. Plasma-treated, electrospun PCL bers were coated with polydopamine for
4 h in 0.2 mg ml 1 dopamine solution at pH 8.5 and mineralized in 10SBF solution containing 0.01 M (A, B) or 0.04 M (C, D) NaHCO3 at 37 C for 72 h.

J. Xie et al. / Acta Biomaterialia 9 (2013) 56985707

perform biomineralization of polydopamine-coated bers. Specically, nanober materials were treated with plasma for 8 min and
then immersed in 0.2 mg ml 1 dopamine
HCl in Tris buffer (pH 8.5)
for 4 h [23]. Polydopamine-coated nanober materials were then
washed with deionized water to remove excess monomer. Subsequently, the ber mat was immersed in a supersaturated solution
of 10-fold concentrated simulated body uid (10SBF), which was
prepared from NaCl, CaCl2 and NaHPO4
H2O in the presence of different amounts of NaHCO3. The composition of the 10SBF is
shown in Table 1. The ion concentrations in the 10SBF solution
were 1 M Na+, 2.5  10 2 M Ca2+ and 1.0  10 2 M HPO4 . The
other way to fabricate composite bers is to directly biomineralize
bers in the 10SBF solution in the presence of different amounts
of dopamine and NaHCO3. The minerals coated on the electrospun
bers can come close to the composition of inorganic phase in

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native bone as mineralization in SBF mimics the mineral formation

in the human body.
2.3. Characterization of bers
The morphology of nanober scaffolds was characterized by
scanning electron microscopy (SEM; FEI, Nova 2300, Oregon). To
avoid charging, polymer ber samples were xed on a metallic
stud with double-sided conductive tape and coated with platinum
for 40 s in a vacuum at a current intensity of 40 mA using a sputter
coater. SEM images were acquired at an accelerating voltage of
15 kV.
The ber surface chemistry was examined by AXIS His X-ray
photoelectron spectroscopy (XPS; Kratos Analytical Inc., NY) and
associated curve-tting software. For all samples, a survey

Fig. 4. SEM images of mineralized PCL bers which were produced using method II shown in Fig. 1. Plasma-treated, electrospun PCL bers were mineralized in 10SBF
solution containing 0.04 M NaHCO3 and 0 mg ml 1 (A), 0.02 mg ml 1 (B), 0.1 mg ml 1 (C), 0.2 mg ml 1 (D), 0.4 mg ml 1 (E) or 1 mg ml 1 (F) dopamine at 37 C for 24 h.

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J. Xie et al. / Acta Biomaterialia 9 (2013) 56985707

Fig. 5. SEM images of mineralized PCL bers which were produced using method II shown in Fig. 1. Plasma-treated, electrospun PCL bers were mineralized in 10SBF
solution containing 0.01 M NaHCO3 and 0 mg ml 1 (A, B), 0.04 mg ml 1 (C, D), or 1 mg ml 1 (E, F) dopamine at 37 C for 2 h.

spectrum was recorded over a binding energy range of 01100 eV

using a pass energy of 80 eV. In all cases, the survey spectra recorded the presence of oxygen (O1s, 533 eV), carbon (C1s,
285 eV), calcium (Ca2p, 347.8 eV, Ca2s, 466.1 eV), phosphorus
(P2p, 133.7, P2s, 190.9 eV) and nitrogen (N1s, 399 eV) at the
surface.

rate of 1% s1 at room temperature while related displacement and

force values were recorded.

2.4. Mechanical testing of bers

In this work, we chose PCL as the model material because it is a

biocompatible and biodegradable polymer that has been approved
by the US Food and Drug Administration for certain human clinical
applications [25]. We rst coated electrospun PCL bers with polydopamine following our recent study [23]. Specically, PCL bers
were plasma treated and immersed in 0.2 mg ml 1 dopamine
solution at pH 8.5 for 4 h. The morphologies of the polydopamine-coated and uncoated bers were similar, with both ber
populations demonstrating consistent ber diameters and limited

Fiber mats composed of uniaxially aligned bers were cut into

sections and xed onto a paper frame. The gauge length and width
were set to 10 and 5 mm, respectively, according to the frame size
and the thickness of each sample, as predetermined by light
microscopy. Samples were mounted on a nano tensile tester (Nano
Bionix, MTS, USA) and the edge of frame was cut before testing the
ber samples. Ten samples were stretched to failure at a low strain

3. Results
3.1. Fabrication of composite bers

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Fig. 6. SEM images of mineralized PCL bers which were produced using method II shown in Fig. 1. Plasma-treated, electrospun PCL bers were mineralized in 10SBF
solution containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine at 37 C for different times: (A) 1 h; (B) 24 h; (C) 48 h; and (D) 72 h. The reaction solution was changed every
24 h.

surface roughness. Subsequently, we immersed polydopaminecoated PCL bers in 10SBF solution at 37 C for 24 h in the presence of 0.01 and 0. 04 M NaHCO3. Fig. 2 shows the inuence of
NaHCO3 concentration on the mineralization of the polydopamine-coated PCL bers. At the low concentration (0.01 M), large,
thin, plate-like minerals tended to be formed, and a loose structure
of minerals was observed on the bers (Fig. 2A and C). At the high
concentration (0.04 M), the minerals on the bers were of a smaller
grain size and a denser coating of minerals was seen compared to
the samples fabricated in the low-concentration NaHCO3 (Fig. 2B
and D). The diameter of the bers in Fig. 2D is around 1.2 lm.
We also investigated the mineralization of polydopaminecoated PCL bers at these two concentrations for a longer time period (72 h). At low concentration, more plate-like minerals were
seen on the surface of bers and the brous morphology was still
visible (Fig. 3A and B). In contrast, minerals coated on the ber surface in the presence of the higher concentration of NaHCO3 were
dense and smooth (Fig. 3C and D). The ber diameter was around
2.8 lm after 72 h coating.
In order to examine the inuence of dopamine, we explored the
mineralization of PCL bers for 24 h in the presence of 0.04 M
NaHCO3 and a series of concentrations of dopamine (Fig. 4). With
increasing dopamine concentration from 0.02 to 0.2 mg ml 1, there
was no evident variation in mineral morphology and grain size
(Fig. 4AD). When the dopamine concentration reached 0.4 and
1 mg ml 1, the mineral morphology changed from plate-shape to
nanorod-shape, then further to particle-shape (Fig. 4E and F).
We also examined the inuence of dopamine on the mineralization in the presence of a low concentration of NaHCO3. Plasma-

treated PCL bers were mineralized in 10SBF solution containing

0.01 M NaHCO3 and different amounts of dopamine for 2 h. In the
absence of dopamine, few plate-like minerals were deposited on
the PCL bers (Fig. 5A and B). With increasing dopamine concentration, the morphology of the minerals changed signicantly
(Fig. 5). Also, more minerals were deposited on the bers, and
the grain size of the minerals decreased dramatically (Fig. 5E and
F).
We next examined the mineralization of PCL bers in 10SBF
solution containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine at
37 C for different times (Fig. 6). Dense and smooth mineral coatings were observed. The ber diameters increased with increasing
mineralization time.

3.2. XPS characterization of composite bers

Fig. 7 shows a typical XPS survey spectrum of PCL bers before
and after mineralization. The wide XPS scan in Fig. 7A identied
carbon and oxygen as the major constituents of PCL bers, as expected. Fig. 7BD conrm that the surface of mineral-coated PCL bers was primarily composed of carbon, calcium, phosphorous,
oxygen and nitrogen. The spectra peaks for Ca2s, Ca2p, P2s and
P2p originated from the mineral coatings. The N1s peak originated
from the polydopamine. The surface composition is quantied in
Table 2. The Ca/P ratio for the mineralized samples is close to
1.67, which is the Ca/P ratio of hydroxyapatite.
Figs. 8 and 9 show the typical C1s and Ca2p spectra of the bers
before and after coating with mineral. It can be seen that the

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Fig. 7. Survey scan XPS spectra for (A) plasma-treated PCL bers, (B) HAP-PDA-PCL bers (24 h), (C) HAP/PDA-PCL bers (24 h) and (D) HAP/PDA-PCL bers (48 h). HAP-PDAPCL bers (24 h): plasma-treated PCL bers were coated with polydopamine in 0.2 mg ml 1 dopamine solution at pH 8.5 for 4 h prior to mineralization in 10SBF solution
containing 0.04 M NaHCO3 for 24 h. HAP/PDA-PCL bers (24 h) and HAP/PDA-PCL bers (48 h): plasma-treated PCL bers were mineralized in 10SBF solution containing
0.4 M NaHCO3 and 0.2 mg ml 1 dopamine for 24 or 48 h. The reaction solution was changed every 24 h.

Table 2
Surface elemental analysis of various ber samples.
At.%

PCL

HAP-PDAPCL(24 h)

HAP/PDAPCL(24 h)

HAP/PDAPCL(48 h)

C
O
Ca
P
N

73.1
26.9

29.73
45.35
15.51
8.82
0.59

15.7
52.1
19.0
12.9
0.3

16.1
51.5
18.4
11.3
2.7

PCL bers: plasma-treated PCL bers. HAP-PDA-PCL(24 h): plasma-treated PCL ber
were coated with polydopamine in 0.2 mg ml 1 dopamine solution at pH 8.5 for 4 h
prior to mineralization in 10SBF solution containing 0.04 M NaHCO3. HAP/PDAPCL(24 h) and HAP/PDA-PCL(48 h): plasma-treated PCL bers were mineralized for
24 or 48 h in 10SBF solution containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine. The reaction solution was changed every 24 h.

intensity of the C1s band decreased while the Ca2p and N1s bands
increased.
3.3. Mechanical testing of composite bers
Fig. 10 demonstrates that the mineral coatings had functional
consequences with regard to the mechanical properties of the
scaffolds composed of uniaxially aligned composite bers. HAP/

PDA-PCL (24 h) and HAP/PDA-PCL(48 h) indicate the samples

which were mineralized in the 10SBF solution containing
0.04 M NaHCO3 and 0.2 mg ml 1 dopamine for 24 and 48 h, respectively. HAP-PDA-PCL(24 h) indicates the samples coated with
polydopamine in 0.2 mg ml 1 dopamine solution at pH 8.5 for
4 h prior to mineralization in the 10SBF solution containing
0.04 M NaHCO3 for 24 h. Evidently, the elastic modulus (Youngs
modulus), dened as the slope of stressstrain curve in the elastic
deformation region, increased dramatically, from 86 MPa for the
PCL ber samples to 459 MPa for the HAP/PDA-PCL(24 h) samples,
and further to 730 and 768 MPa for the HAP-PDA-PCL(24 h) and
HAP/PDA-PCL(48 h) samples, respectively, suggesting that the bers become much stiffer after coating. It is seen that minerals
could also signicantly enhance the ultimate tensile strength of
the ber samples, increasing from around 36 MPa for the PCL bers
to 157 MPa for the HAP/PDA-PCL(24 h) samples and further to
285 MPa for both the HAP-PDA-PCL(24 h) and HAP/PDA-PCL(48 h)
samples. The area covered under the stressstrain curve represents
the toughness, which is dened as the ability to absorb mechanical
(or kinetic) energy up to failure. Accordingly, we quantied the
area under the stressstrain curve and found that toughness
showed a similar trend to the elastic modulus and ultimate tensile
strength. The toughness increased from 21.6 J m3 for the PCL bers to 80.5 J m3 for the HAP/PDA-PCL(24 h) samples and further

J. Xie et al. / Acta Biomaterialia 9 (2013) 56985707

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Fig. 8. Typical XPS C1s spectra for (A) plasma-treated PCL bers, (B) HAP-PDA-PCL bers (24 h), (C) HAP/PDA-PCL bers (24 h) and (D) HAP/PDA-PCL bers (48 h). HAP-PDAPCL bers (24 h): plasma-treated, electrospun PCL bers were coated with polydopamine in 0.2 mg ml 1 dopamine solution at pH 8.5 for 4 h prior to mineralization in
10SBF solution containing 0.04 M NaHCO3 for 24 h. HAP/PDA-PCL bers (24 h) and HAP/PDA-PCL bers (48 h): plasma-treated, electrospun PCL bers were mineralized in
10SBF solution containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine for 24 or 48 h. The reaction solution was changed every 24 h.

to 137.4 J m3 for the HAP/PDA-PCL(48 h) samples. The HAP-PDAPCL(24 h) samples showed comparable toughness to the HAP/
PDA-PCL(48 h) samples.

4. Discussion
Biomineralization of electrospun bers provides a useful platform from which to fabricate biomimetic materials for bone tissue
engineering, as they can recapitulate both the topography of the
extracellular matrix and the composition of bone. Although previous studies examined the effect of different ions (e.g. HCO3 and
Mg2+) and proteins in the mineralized solution, the surface charges
and the surface functional groups of substrates on the mineralization of electrospun bers (e.g. morphology and grain size), the
mechanical properties of the obtained mineralized bers were
not optimal, which could be due to their failure to use a glue
to bridge the two dissimilar materials of the mineral coatings
(inorganic phase) and the polymeric bers (organic phase). Our recent study demonstrated a uniform coating of polydopamine a
mussel-inspired protein which has been demonstrated to adhere
to many different substrates, ranging from metals to oxides and
polymers, on electrospun PCL bers [23]. In the present study,
we examined the mineral deposition on PCL bers via two different

approaches: mineralization of polydopamine-coated bers and

mineralization of PCL bers in 10SBF solutions in the presence
of dopamine. We demonstrated the control of the morphology,
grain size and thickness of the mineral coating on the PCL bers
with and without prior polydopamine coating. The mineral
coatings result in signicant improvement in the mechanical properties (e.g. Youngs modulus, ultimate tensile strength and toughness) of bers.
Based on the results of our research, we have proposed two
mechanisms for the mineralization of polydopamine-coated PCL bers and plasma-treated PCL bers in the presence of dopamine. In
the rst case, Ca2+ ions in the mineralized solutions bind to polydopamine and subsequently the nucleation of CaP minerals takes
place, followed by crystal growth. In the second case, Ca2+ ions
bind to RCOO on the surface of plasma-treated PCL bers and
nucleate, and dopamine polymerization occur simultaneously in
the mineralized solution. Other than deposition onto bers, polydopamine could also be deposited onto certain facets of mineral
crystals or onto the whole surface of the minerals. This may inhibit
the growth of CaP mineral crystals along certain directions or inhibit the overall growth of CaP minerals.
Previous studies have demonstrated that a higher HCO3 concentration in the mineralized solution could lead to a smaller grain
size [11,13,14]. Our results are in line with those studies. However,

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Fig. 9. Typical XPS Ca2p spectra for (A) plasma-treated PCL bers, (B) HAP-PDA-PCL bers (24 h), (C) HAP/PDA-PCL bers (24 h) and (D) HAP/PDA-PCL bers (48 h). HAP-PDAPCL bers (24 h): plasma-treated, electrospun PCL bers were coated with polydopamine in 0.2 mg ml 1 dopamine solution at pH 8.5 for 4 h prior to mineralization in
10SBF solution containing 0.04 M NaHCO3. HAP/PDA-PCL bers (24 h) and HAP/PDA-PCL bers (48 h): plasma-treated, electrospun PCL bers were mineralized for 24 or
48 h in 10SBF solution containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine. The reaction solution was changed every 24 h.

the grain size of the minerals deposited on the bers was too large
in some of the previous studies, resulting in elimination of the brous morphology after mineral deposition and thus the loss of
the ability of the ber scaffolds to biomimic extracellular matrix
[12]. In the present study, the bers after the mineral coating retained their brous morphology. More importantly, for the rst
time we have demonstrated that dopamine in 10SBF solution
can affect the mineralization of PCL bers. Increasing the dopamine
concentration in the mineralized solution can greatly decrease the
grain size and change the morphology of the minerals from plates
to rods and further to particles. In addition, HCO3 ions were demonstrated to affect not only the morphology and grain size during
biomineralization, but also the dissolution kinetics of the minerals.
A recent study showed that mineral coatings with increased HCO3
substitution presented more rapid dissolution kinetics in an environment decient in calcium and phosphate, which can be used
as carriers for the regulation of growth factor release [26]. The
same principle could also be applied to our mineralized nanober
scaffolds.
Recently, macro-tensile measurements of nonwoven PCL ber
scaffolds showed a Youngs modulus of around 3.8 MPa and a
strain at break of 170% [27]. In separate studies, it was demonstrated that the additive of nanohydroxyaptite could make the tensile strength increase from 0.81 MPa (0% nHAP) to 1.32 MPa (25%

nHAP) and further to 1.44 MPa (50% nHAP) [28,29]. Accordingly,

the elastic modulus increased from 3.32 to 3.5 MPa and further
to 3.69 MPa. However, these studies demonstrated an increase in
the Youngs modulus (stiffness) and ultimate tensile strength of
electrospun PCL bers to certain degree by the creation of composite bers or polymer blend bers. Our recent study showed higher
modulus, ultimate tensile stress and toughness in aligned nanober scaffolds relative to random scaffolds [30]. In this work, we
chose to test the mechanical properties of uniaxially aligned PCL ber scaffolds with and without mineral coatings, indicating that
the biomineralization of bers mediated by a mussel-inspired protein can greatly enhance the mechanical properties, including
Youngs modulus (9-fold), ultimate tensile strength (8-fold)
and toughness (6-fold). Although our recent study demonstrated
that polydopamine coating could result in PCL bers with a higher
Youngs modulus [23], PCL bers without a prior coating of polydopamine were directly mineralized in 10SBF containing NaHCO3
and dopamine and showed great improvement compared to polydopamine-coated PCL bers with regard to Youngs modulus and
toughness.
In a future study, we will fabricate nanober scaffolds with gradations in both mineral content and ber organization to repair
tendon-to-bone insertion sites [22,31]. In addition, adiposederived stem cells (ADSCs) may be an optimal cell source for

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(NCRR), funded by the ofce of the Director, National Institutes

of Health (NIH) and supported by the NIH roadmap for Medical Research and start-up funds from Marshall Institute for Interdisciplinary Research and Center for Diagnostic Nanosystems at
Marshall University.
Appendix A. Figures with essential colour discrimination
Certain gures in this article, particularly Fig. 1, is difcult to
interpret in black and white. The full colour images can be found
in the on-line version, at http://dx.doi.org/10.1016/j.actbio.2012.
10.042.
References

Fig. 10. Stressstrain curves for various brous samples. HAP-PDA-PCL (24 h):
plasma-treated, electrospun PCL bers were coated with polydopamine in
0.2 mg ml 1 dopamine solution at pH 8.5 for 4 h prior to mineralization in 10SBF
solution containing 0.04 M NaHCO3. HAP/PDA-PCL (24 h) and HAP/PDA-PCL (48 h):
plasma-treated, electrospun PCL bers were mineralized in 10SBF solution
containing 0.04 M NaHCO3 and 0.2 mg ml 1 dopamine for 24 or 48 h. The reaction
solution was changed every 24 h.

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]

tendon-to-bone tissue engineering due to their pluripotency (i.e.

they can differentiate into both tendon-forming broblasts and
bone-forming osteoblasts), high proliferation rates and capacity
for matrix deposition [3235]. We will also examine the response
of ADSCs, including attachment, proliferation and differentiation,
to the nanober scaffolds with dual gradients.
5. Conclusions
We have demonstrated the biomineralization of electrospun
PCL bers by making use of polydopamine as a ller or bioglue
to bridge the minerals and polymeric bers. We found that the
morphology, grain size and thickness of the CaP mineral coating
on PCL bers can be readily controlled by adjusting the composition of the mineralized solution, the surface properties of the bers
and the duration of the mineralization. The mineral coating can
greatly enhance the mechanical properties of the bers, which
may be useful as scaffolding materials for hard tissue engineering,
such as for bone. This work also has signicant implications for
fabrication of other composite or hybrid materials.
Acknowledgements
This work was supported in part by grant number
UL1RR033173 from the National Center for Research Resources

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