Materials Science and Engineering C 41 (2014) 119–126

Contents lists available at ScienceDirect

Materials Science and Engineering C

journal homepage: www.elsevier.com/locate/msec

Poly(L-lactide) and poly(butylene succinate) immiscible blends: From

electrospinning to biologically active materials
Nikoleta Stoyanova a, Dilyana Paneva a, Rosica Mincheva b, Antoniya Toncheva a, Nevena Manolova a,
Philippe Dubois b, Iliya Rashkov a,⁎
a
Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev St, bl. 103A, BG-1113 Sofia, Bulgaria
b
Laboratory of Polymeric and Composite Materials, Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons — UMONS, Place du Parc 20, B-7000 Mons, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: For the first time the preparation of defect-free fibers from immiscible blends of high molar mass poly(lactic acid)
Received 24 October 2013 (PLA) and poly(butylene succinate) (PBS) in the whole range of the polyester weight ratios is shown.
Received in revised form 4 April 2014 Electrospinning using the solvent–nonsolvent approach proved most appropriate. Moreover, electrospinning re-
Accepted 18 April 2014
vealed crucial for the obtaining of PLA/PBS materials maintaining integrity. DSC and XRD analyses attested for a
Available online 28 April 2014
plasticizing effect and for increased PLA crystallinity at PBS addition to PLA. The mechanical properties of the PLA/
Keywords:
PBS mats were controlled by the alignment of the fibers and changed from plastic to brittle materials upon in-
Electrospinning creasing the PBS content. Drug loading and tests against pathogenic microorganisms suggested that the obtained
Poly(butylene succinate) mats can find application as antibacterial fibrous materials.
Poly(L-lactide) © 2014 Elsevier B.V. All rights reserved.
Crystallinity
Mechanical properties
Biological activity

1. Introduction improve PLA thermal and mechanical properties when blended and ma-
terials from PLA/PBS blends have been prepared by extrusion [6–12].
Materials from biodegradable and non-toxic biocompatible poly- The miscibility, the phase and crystallization behavior, and the mor-
mers which are synthesized entirely or partially from annually renew- phology of PLA/PBS blends were reported in the literature [6,15]. Inter-
able resources have drawn great interest [1]. Their use is imposed by estingly, despite the improved crystallization of PLA in the presence of
the need for replacement of the conventional materials derived from PBS, thermal analyses showed two distinct melting peaks over the en-
petroleum sources as well as in the viewpoint of environmental pollu- tire composition range, thus classifying the materials as semicrystal-
tion prevention. Among all, the biocompatible and thermoplastic line/semicrystalline blends. Moreover, small-angle X-ray scattering
poly(lactide) PLA is one of the most promising biobased polymers [2], revealed that, in a blend system, the PBS component was expelled out
finding applications going from drug-carriers and implants to packaging of the interlamellar regions of PLA. Finally, for more than 40 wt.% PBS,
and textiles. More recently, PLA-based materials have found more dura- significant crystallization-induced phase separation was observed. The
ble applications in automotive, communication and electronic indus- thus suggested immiscibility of both polymers [15] is limiting the appli-
tries [3,4]. However, drawbacks such as mechanical brittleness and cations of PLA/PBS blend materials without compatibilization. A possi-
low crystallization rate are often obstacles to PLA practical uses. With bility to overcome the problem might be found in the electrospinning
this respect, PBS — a partially biobased polyester, with thermal and me- technique.
chanical properties comparable with those of low density polyethylene Electrospinning is a cutting-edge technique that allows micro- and
and polypropylene [5] was studied as a PLA modifier [6–14]. Because of nanofibrous polymer materials to be easily prepared [16–22]. Because
its high flexibility (low glass-transition temperature), PBS has found ap- of their high surface-to-volume ratio and porous structure, the fibrous
plications as films, laminates, molded foams and injection-molded mats are well suited for applications such as filters, scaffolds for cell
products in various fields, such as agriculture and packaging. The PBS and tissue engineering, and carriers of bioactive substances.
relatively rapid crystallization rate and flexibility were believed to Electrospinning of immiscible polymer blends containing PLA is already
reported in the literature [23]. The concept resulted in freezing the
⁎ Corresponding author. Tel./fax: +359 2 9793468/+359 2 8700309. phase structure generated during electrospinning, thus preserving the
E-mail address: [email protected] (I. Rashkov). co-continuous or interpenetrating phase morphologies within the

http://dx.doi.org/10.1016/j.msec.2014.04.043
0928-4931/© 2014 Elsevier B.V. All rights reserved.
120 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126

fibers. Noteworthy, unlike PLA that can be easily electrospun from The dynamic viscosity of the spinning solutions was measured by
solutions of diverse in nature solvent systems based on chloroform or Brookfield LVT viscometer equipped with an adaptor for small samples,
dichloromethane [24], the electrospinning of PBS solutions encounters a spindle, and a camera SC 4-18/13 R at 20 ± 0.1 °C; the measurements
certain difficulties and reports on the electrospinning of PBS are still were performed in triplicate and the mean values with their standard
scarce. deviations were used.
The preparation of fibrous materials from PBS with a number aver- For the incorporation of K5N8Q and 5Cl8HQ spinning solutions of
age molar mass of ca. 75,000 g/mol by electrospinning has been report- PLA/PBS = 80/20 (w/w) in DCM/EtOH = 90/10 (w/w) at total polymer
ed [25]. Mixed solvent systems such as chloroform/2-chloroethanol at a concentration of 10 wt.% were used; the concentration of K5N8Q and
ratio of 7/3 or 6/4 (w/w), dichloromethane/2-chloroethanol at a ratio of 5Cl8HQ was 10 or 20 wt.% in respect to the polymer weight, respective-
7/3 or 6/4 (w/w) and chloroform/3-chloro-1-propanol at a ratio of 9/1 ly. In the case of K5N8Q due to its poor solubility, the electrospinning
(w/w) have been used. It proved preferable to avoid the use of high boil- was performed from a stable dispersion.
ing solvents such as 2-chloroethanol and 3-chloro-1-propanol when the The electrospinning was carried out using an electrospinning set-up
polymer materials are intended to find application in the biomedical consisting of a high voltage power supply (up to 30 kV); a pump [NE-
domain or simply to come into contact with human body. A short com- 300 Just Infusion™ Syringe Pump (New Era Pump Systems Inc., USA)]
munication presenting few SEM micrographs of porous fibers prepared for delivering the spinning solution at a constant rate; a syringe provid-
by electrospinning of PBS with a molar mass of 20,000 g/mol using chlo- ed with a positively charged metal needle with inner diameter of 0.6
roform as solvent was published in 2008 [26]. It has been found that mm and a custom-made grounded rotating aluminum collector. The
the electrospinning of PBS with a molar mass as high as 200,000– electrospinning was performed under the following conditions: feeding
300,000 g/mol using chloroform as solvent is very difficult to achieve rate: 3 mL/h, applied voltage: 25 kV, tip-to-collector distance: 17 cm,
when the polymer concentration is lower than 10 wt.% or higher collector rotating speed: 600 or 1900 rpm, humidity: 70% and tempera-
than 15 wt.% [27]. By using PBS with a weight average molar mass MW ture: 20 °C. The obtained mats were dried additionally under reduced
3 × 105 g/mol and a chloroform/ethanol solvent system at a ratio of 75/ pressure (320 Pa) at r.t. for 8 h.
25 (v/v) and polymer concentration of 11% (w/v) PBS/wollastonite mats
have been electrospun [28]. DCM/trifluoroacetic acid (90/10 v/v) solvent 2.3. Characterization of the electrospun materials
system has been used for electrospinning of 1,6-diisocyanatohexane-
extended PBS [29]. Despite the up-to-here described interest, and most The morphology of the fibers was examined by a scanning electron
probably because of the significant difficulties in performing the microscope (SEM). The samples were vacuum-coated with gold and ob-
electrospinning, there are no literature data on the elaboration of fibrous served by a Jeol JSM-5510 SEM. The fiber morphology was evaluated by
materials from these two immiscible commercially available high molar applying the criteria for complex evaluation of electrospun materials as
mass PLA and PBS polymers through this method. described elsewhere [30] using the ImageJ software by measuring the
Therefore, the present study aims at preparing defect-free fibers diameters of at least 20 fibers from each SEM micrograph.
from immiscible blends of PLA and PBS from 100/0 to 10/90 (w/w). The thermal behavior of the prepared new fibrous materials was
The role of the solvent system and the total polymer concentration on followed by differential scanning calorimetry (DSC). The analyses
fiber morphology was studied. DSC and XRD were used to evaluate crys- were performed using a PerkinElmer DSC 8500 differential scanning
tallinity and crystallization rate of the polyesters in the fibrous mats, and calorimeter in nitrogen atmosphere at a heating rate of 10 °С/min. PLA
tensile tests were used to determine their mechanical properties. Drug (χPLA PBS
c , %) and PBS (χc , %) crystallinity degree was calculated using
loading and tests with pathogenic microorganisms were also performed the following equations:
as possible material application. h

i
PLA PLA PLA PLA;0 PLA
χc ;% ¼ ΔH m −ΔH cc = ΔHm W  100 ð1Þ
2. Experimental
h
i
2.1. Reagents PBS PBS PBS;0 PBS
χc ; % ¼ ΔH m = ΔHm W  100 ð2Þ

Poly(butylene succinate) (PBS, Bionolle 1003; Shōwa Denkō

where WPLA is the PLA weight fraction, and WPBS — the PBS weight frac-
Kabushiki-gaisha — Japan; MW = 97,600 g/mol, MW /Mn = 2.56 as
tion in the spinning solution; ΔH0m is the heat of fusion of 100% polymer
determined by size-exclusion chromatography using polystyrene stan-
crystal: ΔHPLA,0
m = 93.0 J/g [31]; ΔHPBS,0
m = 210.0 J/g [32]. The measure-
dards); poly(L-lactide) (PLA, Ingeo™ Biopolymer 4032D, NatureWorks
ments were performed in triplicate and the mean values with their
LLC — USA; MW = 259,000 g/mol; MW /Mn = 1.94; as determined by
standard deviations were used for interpreting the obtained results.
size-exclusion chromatography using polystyrene standards), dichloro-
The absence/presence of a crystalline phase in the fibrous materials
methane (DCM, Merck); ethanol (abs. EtOH, Merck); the potassium salt
was assessed by X-ray diffraction analysis (XRD). XRD spectra were re-
of 5-nitro-8-hydroxyquinoline (K5N8Q) and 5-chloro-8-quinolinol (5-
corded at r.t. using a computer controlled D8 Bruker Advance powder
chloro-8-quinolinol; 95% 5Cl8HQ; Sigma-Aldrich) were of analytical
diffractometer with a filtered CuKα radiation source and a luminescent
grade of purity.
detector. The analyses were performed in the 2θ range from 5° to 50°
with a step of 0.02° and counting time of 1 s/step.
2.2. Preparation of PLA/PBS fibrous materials by electrospinning Mechanical properties were evaluated by tensile measurements per-
formed on the fibrous scaffolds using a Zwick/Roell Z 2.5 apparatus, load
Spinning solutions in DCM or DCM/EtOH [DCM/EtOH = 90/10 cell 2 mV/V, type Xforce P, Nominal Force 2.5 kN and test Xpert II. The
or 80/20 (w/w)] were prepared for PLA/PBS blends of PLA/PBS = specimens' thickness was around 50 μm. The stretching rate was
100/0; 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/ 10 mm/min, and the initial length between the clamps was 60 mm.
90 and 0/100 (w/w). For preparation of the solutions, PLA and PBS The fibrous materials were tested along the circumferential direction
were first dissolved separately in DCM; for the dissolution of PBS of the collector on which the mat was deposited, and the mean values
heating at 40 °C for 2 h was necessary. Then, the solutions were were calculated.
mixed at stirring. The total polyester concentration was 10 or The water contact angle of the mats was determined using Easy
15 wt.%. In the case of the DCM/EtOH solvent systems, ethanol was Drop DSA20E KRÜSS GmbH device at r.t. A drop of deionized water
added after the mixing of PLA and PBS solutions in DCM. (10 μL) was deposited on the mats surface. From the images of the
 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126 121

PLA PLA/PBS = 90/10 (w/w) PLA/PBS = 80/20 (w/w)

PLA/PBS = 20/80 (w/w) PLA/PBS = 10/90 (w/w) PBS

Fig. 1. Representative SEM images of PLA/PBS fibers prepared at PLA/PBS from 100/0 to 0/100 (w/w) at total polymer concentration of 10 wt.% and by using a mixed solvent system DCM/
EtOH; collector rotating speed: 600 rpm; magnification: ×1000.

droplets on the surface of the mats acquired by a digital camera and 3. Results and discussion
processed by a software program the average values of the water con-
tact angles were determined based on at least 10 measurements. The 3.1. Electrospinning and fiber morphology
samples for the water contact angle measurements were cut in the col-
lector rotation direction and collector axis direction. Attempts to obtain uniform PLA/PBS fibers from both immiscible
polymers were performed by electrospinning their blend solutions at
2.3.1. Microbiological tests 30 kV and at collector rotating speed of 600 rpm. DCM — a common sol-
The antibacterial activity of PLA/PBS = 80/20 (w/w) mats contain- vent for both polyesters was first studied at total polymer concentration
ing 10 wt.% K5N8Q or 20 wt.% 5Cl8HQ was monitored against the path- of 10 wt.% (Fig. S1). Thus, cylindrical defect-free fibers were obtained up
ogenic microorganism Staphylococcus aureus (ATCC 6538 P). In order to to PLA/PBS = 70/30 (w/w). Further increase in PBS content resulted in
measure the zones of inhibition, in vitro studies were performed using spindle-like defects along the fibers (to 50 wt.% PBS) or beaded fibers
Tryptone glucose extract agar (DIFCO Laboratories, Detroit, USA) solid (PBS content from 80 wt.% to 100 wt.%). Further experiments were per-
medium. The surface of the solid agar was inoculated with a suspension formed at a total polymer concentration of 15 wt.% (DCM, 30 kV, 600
of S. aureus bacterial culture with a cell concentration of 1 × 105 cells/mL rpm) allowing the obtaining of defect-free fibers at 50 wt.% PBS (mean
and on the surface of the agar in each Petri dish two mats (disks with diameter of 7.3 ± 2.1 μm) (Fig. S2). However, the electrospinning pro-
diameters of 10 mm and weight 1.0 mg) from drug-(non)containing cess was ineffective (and even impossible at higher PBS content) due
PLA/PBS = 80/20 (w/w) were placed. The Petri dishes were incubated to rapid phase separation and gelation of the spinning solution. For
for 24 h at 37 °C and subsequently the zones of inhibition around the overcoming these problems, the solvent–nonsolvent approach was
disks were measured. The average diameters of the zones of inhibition attempted. It is known that adding a certain amount of a poor solvent
were determined using the ImageJ software based on 15 measurements to the spinning solution assists in the formation of fibers during
in 15 different directions for each zone. electrospinning [33,34]. Thus, in the present study DCM was partially

A B
3500 500
Mean fiber diameter value, nm

3000
400
Dynamic viscosity, cP

2500

300
2000

1500
200

1000
100
500

0 0
100/0 80/20 60/40 40/60 20/80 0/100 100/0 80/20 60/40 40/60 20/80 0/100
PLA/PBS, w/w PLA/PBS, w/w

Fig. 2. Mean fiber diameter (A), and dynamic viscosity (B) for different PLA/PBS weight ratios; total polymer concentration: 10 wt.%; collector rotating speed: 600 rpm.
122 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126

Fig. 3. DSC thermograms (first heating run, A) and XRD patterns (B) at selected PLA/PBS weight ratios. DCM/EtOH; collector rotating speed: 600 rpm.

Table 1
Thermal characteristics of PLA/PBS mats as obtained from DCM/EtOH at 600 rpm.

PLA/PBS Tg PLA Tcc PLA ΔH cc PLA J/g⁎ Tm PLA ΔH m PLA χPLA Tcc PBS Tm PBS ΔHm PBS χPBS
°C °C °C J/g⁎ %⁎⁎ °C °C J/g⁎ %⁎⁎

100/0 67 90 21.2 167 31.3 10.9 – – – –

90/10 58 78 15.3 168 33.6 21.9 – – – –
80/20 51 70 18.1 166 34.4 21.9 – 114 6.0 14.3
70/30 53 – – 168 26.3 22.7 91 114 16.8 26.7
60/40 54 – – 168 24.2 25.1 89 114 27.2 32.4
50/50 52 – – 166 19.2 29.5 88 110 35.6 29.8
40/60 52 – – 168 20.4 35.0 89 114 38.6 30.6
30/70 52 – – 168 9.2 30.4 88 114 52.5 35.7
20/80 48 – – 167 16.2 50.0 88 112 52.0 31.0
10/90 48 – – 168 6.5 70.0 – 114 67.9 36.0
0/100 – – – – – – – 116 77.0 36.0
⁎ The enthalpies are not recalculated taking into account the respective polyester content.
⁎⁎ Crystallinity degrees are calculated as described in the Exp. Part. ΔHccPBS is not presented since the cold crystallization overlapped PBS melting.
 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126 123

fabricated using DCM/EtOH were in the range 1800–600 nm depending

on the PBS content (Fig. 2A).
As seen, d continuously decreased upon increasing PBS content and
the thinnest defect-free fibers were obtained at 90 wt.% PBS (590 ±
140 nm). This effect might be related to the changes in the dynamic vis-
cosity of the spinning solutions (Fig. 2B). Indeed, the dynamic viscosity
decreased upon increasing PBS content — the polyester of lower molar
mass (MW = 97,600).

3.2. Crystallinity and mechanical properties of the fibrous mats

The as prepared fibrous mats were further characterized in terms of

crystallinity and mechanical properties.
Representative DSC thermograms of PLA/PBS mats depending on the
PBS content are shown in Fig. 3A. Concerning the PLA component, Tg, Tcc
and Tm were detected at low PBS content. This occurrence of cold crys-
tallization is in agreement with literature data on electrospun PLA mate-
rials and might be explained by the rapid solvent evaporation
hampering the polyester crystallization [35–40].
Moreover, Tg and Tcc decreased with ca. 20 °C upon increasing PBS
content to 20 wt.% (Table 1). In parallel, the enthalpy of cold crystalliza-
tion decreased with ca. 15%, thus suggesting some miscibility between
the polyesters in the amorphous state at low PBS content. These data
are in agreement with the literature on PLA/PBS materials prepared by
extrusion [6,8,17], evidencing the role of PBS as plasticizer for PLA. Fur-
ther increase in PBS content did not influence the PLA Tg, but led to the
disappearance of Tcc, suggesting that blending with PBS most probably
influenced the PLA crystallization and crystallization rate. In agreement,
the melting endotherm of PLA turned bimodal and the corresponding
crystallinity increased. The second Tm newly occurring at higher tem-
peratures (max at 176 °C for PLA/PBS = 20/80, w/w) might be ascribed
to the formation of crystals which are organized to a greater extent, as
observed for PLA/PBS extruded blends [8]. It is to be noted that the
PBS Tg was difficult to observe due to the high crystallinity and crystal-
lization rate of the polyester. Therefore, avoiding any speculation on
electrospinning induced miscibility of the PLA/PBS blends based on Tg
determination is preferable.
Fig. 4. Stress–strain curves recorded during mechanical tests of PLA/PBS mats prepared at
a collector rotating speed of 600 (A) or 1900 (B) rpm; solvent system: DCM/EtOH; the
Regarding PBS, no significant difference in thermal behavior was de-
samples were cut in such a manner so that their length axis coincided with the direction tected between the neat and the blended fibrous mats. PBS is rapidly crys-
of the collector rotation. tallizing polyester of high crystallinity [32], making its Tg difficult to
assess. Therefore, no values were collected from the DSC analyses. The
polyester melting appeared at ca. 116 °C and was directly preceded by a
cold crystallization exotherm in agreement with the literature data [32].
replaced by EtOH — a poor solvent for both PBS and PLA, while the total Interestingly, Tm was not influenced by the mat composition and the cor-
polymer concentration, the voltage and the collector rotating speed responding enthalpy of melting increased upon increasing PBS content.
were kept constant (10 wt.%, 30 kV and 600 rpm, respectively). It was The obtained results were confirmed by the performed XRD analyses.
found that the addition of only 10 wt.% EtOH to DCM significantly im- XRD data on films of PLA and PBS homopolyesters are available in
proves the electrospinning of PLA/PBS = 50/50 (w/w) solutions. In con- the literature [41,42]. According to the literature, the PLA pattern
trast to DCM, the fibers obtained from DCM/EtOH = 90/10 (w/w) were presents diffraction peaks at 2θ = 14.8°, 16.6°, 19.0°, 22.4° and 29.2°
cylindrical and defect-free. Their mean diameter was 1.1 ± 0.4 μm. Fur- distinctive for the α-form of optically pure PLLA (or PDLA) crystallizing
ther increase of EtOH content in the spinning solution [DCM/EtOH = in a pseudo-orthorhombic unit cell containing l03 helices [42], while
80/20 (w/w)] was counterproductive as spindle-like defects appeared PBS presents diffraction peaks at 2θ = 19.6°, 21.9°, 22.8° and 29.1° as-
along the fiber axis (Fig. S2). Therefore the preparation of defect-free fi- cribed to its α-form (monoclinic system of 21 helices) [41]. As seen
brous materials from PLA/PBS at the whole range of weight ratios was from Fig. 3B, the XRD patterns of PLA/PBS = 100/0 and 80/20 (w/w)
studied in the system DCM/EtOH = 90/10 (w/w) at total polymer con- mats revealed only the presence of an amorphous halo. Diffractions
centration of 10 wt.% (further denoted as DCM/EtOH). for crystal phase were not observed, thus confirming the hindered crys-
SEM micrographs of the obtained fibers are presented in Fig. 1. As tallization of the polyesters during the electrospinning process as evi-
seen, the use of DCM/EtOH (30 kV, 600 rpm) allowed the obtaining of denced by DSC. In the XRD pattern of PLA/PBS = 50/50 (w/w) mat a
randomly deposited defect-free fibers from the immiscible PLA and diffraction at 2θ = 22.6° was registered, and in the XRD pattern of
PBS up to 80 wt.% PBS. Even at PLA/PBS = 10/90 (w/w) only few PLA/PBS = 20/80 (w/w) mat: two diffractions were observed at 2θ =
spindle-like defects appeared and the mats were predominantly com- 19.6° and 22.6°, respectively. These values of 2θ are characteristic for
posed of defect-free fibers. For neat PBS the obtained fibrous material both PLA and PBS crystal structure, and their attribution cannot be
consisted of fibers (mean diameter: 170 ± 48 nm) and bead-like defects done only on the basis of the XRD data. However and taking into consid-
(mean diameter: 7.8 ± 2 μm). This pattern is quite different as com- eration their crystallinity degree calculated by DSC (Table 1), it can be
pared to DCM solutions, thus confirming the pertinence of the sol- assumed that the registered diffractions were due to the crystal struc-
vent–nonsolvent approach. The mean diameters of PLA/PBS fibers (d) ture of both PLA and PBS.
124 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126

A B
500 600 rpm 12.5 600 rpm 1900 rpm
1900 rpm *

Young's Modulus, MPa

Tensile strength, MPa

400 10.0 *

300 7.5

200 5.0

* *
100 2.5

0 0.0
100/0 80/20 50/50 20/80 100/0 80/20 50/50 20/80
PLA/PBS, w/w PLA/PBS, w/w

C D
150 60 PLA/600 rpm
600 rpm 1900 rpm
PLA/1900 rpm
50 PBS/600 rpm
125

Crystallinity degree, %
PBS/1900 rpm
Elongation, %

100 40
*
75 * 30

50 20

25 * * 10

0 0
100/0 80/20 50/50 20/80 100/0 80/20 50/50 20/80
PBS content, wt.% PLA/PBS, w/w

Fig. 5. Dependence of Young's modulus (A), tensile strength (B) and elongation at break (C) of PLA/PBS mats, and the crystallinity degree of PLA and PBS (D) in the fibrous materials on PBS
content in the mats, prepared at collector rotation speed of 600 or 1900 rpm; solvent system: DCM/EtOH. The samples for which a break during the tests was detected are marked with an
asterisk; thus, the obtained values may be considered as elongation at break.

It is worth to be mentioned that solvent-cast films from PBS and was observed. This necking after the yield point gave evidence for the oc-
PLA/PBS lost their integrity and became very brittle on drying. In currence of inelastic deformation. The subsequent increase of the stress
sharp contrast, PLA/PBS fibrous mats maintained integrity and could led to hardening of the samples most probably due to the additional ori-
be easily handled without fragmentation. In order to determine their entation of the fibers during specimens' elongation. Partial tearing of the
mechanical properties tensile tests on mats of defect-free fibers were samples was observed after reaching the maximum tensile stress. Further
performed. increase in PBS content (PLA/PBS = 50/50 (w/w) and PLA/PBS = 20/80
The stress–strain curves of PLA/PBS fibrous materials at different PBS (w/w)) resulted in distinct break point, and the absence of necking, indi-
contents are presented in Fig. F4A. Digital images of the samples after cating quasi-ductile fracture behavior of these materials. One possible ex-
testing are shown as well. planation of this finding might be the alignment of the fibers during
As seen, before reaching the ultimate tensile strength, the PLA/PBS = stretching. However, based on the DSC and XRD data alteration in the
100/0 (w/w) and PLA/PBS = 80/20 (w/w) mats displayed typical strain blend morphology: a transition from dispersed structure to bicontinuous
behavior of thermoplastic materials. At low stress values (in the elasto- one and again to dispersed structure; alteration in the crystallinity of the
plasticity range) they rapidly reached the yield point after which necking blends and by interfacial adhesion [43] should not be neglected. Effects of

A B C
1985±400 nm 953±475 nm 760±310 nm
Fig. 6. SEM micrographs of PLA/PBS fibers prepared at total polymer concentration of 10 wt.% using DCM/EtOH in absence (A) and presence of the drug: 10 wt.% K5N8Q (B) or 20 wt.%
5Cl8HQ (C) (in respect to the total polymer weight); collector rotating speed: 1900 rpm; the collector rotation direction is indicated by a white arrow.
 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126 125

S. aureus PLA/PBS PLA/PBS/K5N8Q PLA/PBS/5Cl8HQ

Fig. 7. Digital images of the zones of inhibition against S. aureus, detected after a 24-h contact of the drug-(non)containing PLA/PBS fibrous materials with the bacterial cells. Left image —
blank control.

additional orientation of the macromolecules during specimen elongation ionogenic nature of the drugs used. This decrease is in accordance with
[44] are not to be excluded. To verify the hypothesis, fibrous materials previous findings about fibrous materials prepared by electrospinning
were obtained at higher collector rotation speed (1900 rpm), known to of polymer solutions containing an ionogenic low molecular weight ad-
increase the degree of fibers' alignment. According to theoretical simula- ditive [40,46,47]. The performed measurements of the water contact
tions confirmed by experimental measurements [44], mats with higher angle showed that the incorporation of the bioactive compounds did
degree of fiber alignment are characterized by improved mechanical not alter the water contact angle value, i.e. the mats remained hydropho-
strength, but reduced failure strain (shorter linear part of the stress–strain bic. K5N8Q and 5Cl8HQ are broad-spectrum antibacterial agents with
curves) in comparison to less aligned and randomly deposited fibers. Sim- minimum inhibitory concentration against S. aureus of 0.25 μg/mL for
ilar trends were observed for the PLA/PBS fibrous materials. As seen from 5Cl8HQ [48] and 16 μg/mL for K5N8Q [49]. The antibacterial activity of
Fig. 4B, the higher collector rotating speed affected significantly the yield the electrospun mats was assessed by performance of microbiological
point value. Furthermore, the linear part of the stress–strain curves for the tests against this microorganism. The results obtained by determination
samples prepared at 1900 rpm narrowed significantly upon increasing of the zones of inhibition after a 24-h contact of the fibrous materials
the collector rotation speed (Fig. 4B), attesting for reduced flexibility of with the bacterial cells are shown in Fig. 7.
the fibrous materials. Thus, higher degree of alignment of the fibers in A blank sample (without any fibrous material) is presented as well.
the materials obtained at the higher collector rotating speed might be As expected PLA/PBS mats did not exhibit any antibacterial activity.
stated (Fig. S3A and B). Well-distinguished zones of inhibition of the bacterial cells growth
At low collector rotation speed (600 rpm), the Young's modulus, the were detected for the drug-containing PLA/PBS = 80/20 (w/w)
tensile strength and the elongation did not significantly depend on the mats. The diameter of the zones of inhibition of PLA/PBS/K5N8Q and
PBS content and were determined to be ca. 100 MPa, 2.5 MPa and PLA/PBS/5Cl8HQ mats did not differ sufficiently, being 37.5 mm and
90%, respectively (Fig. F5A, B and C). At higher collector rotation speed 40.0 mm, respectively. The observation of zones of inhibition is evidence
(1900 rpm), the detected Young's modulus and tensile strength that the incorporated drugs in the mats retain their antibacterial
increased by a factor of ca. 4 (350 MPa and 9.0 MPa, respectively), re- activity.
maining almost independent on the PBS content. The obtained results
are in correlation with the calculated higher crystallinity of PLA in 4. Conclusions
PLA/PBS = 100/0 (w/w) mats prepared by applying higher collector ro-
tating speed (Fig. 5D). Concerning the elongation (Fig. 5C), the highest For the first time, immiscible blends of PLA and PBS were
value (130 ± 5%) was obtained for PLA/PBS = 80/20 (w/w). In electrospun to obtain defect-free fibrous mats in the entire range of
order to explain this result, several hypotheses including polyester mis- PLA/PBS weight ratios. Different conditions as solvent system and total
cibility, blend morphology and crystallinity need more exhaustive polymer concentration were tested in order to determine the optimal
investigations. electrospinning conditions. The fiber morphology patterns showed the
pertinence of the solvent–nonsolvent approach. DSC and XRD analyses
3.3. Drug loading and biological activity attested for the role of PBS on the crystallinity of the electrospun mats.
Blending PLA with PBS decreased its Tg and suppressed its cold crystal-
One of the potential applications of the new fibrous PLA/PBS mate- lization, suggesting for a plasticizing effect of PBS. Moreover, a second
rials is as carriers of low molecular weight bioactive substances with Tm for PLA appeared at higher temperatures, confirming the influence
targeted behavior, e.g. having antibacterial and antimycotic activity [45]. of PBS on PLA crystallization and crystallization rate. These observations
In addition, the PLA/PBS mats prepared in this study were rather hydro- were clearly confirmed by XRD.
phobic (the determined water contact angles were in the range 127– The electrospinning process revealed crucial for the obtaining of
132°). Regarding biomedical applications, the incorporation of an anti- PLA/PBS blend materials maintaining integrity and allowed the prepara-
bacterial agent in PLA/PBS mats would often be advisable since such tion of fibrous materials which mechanical properties changed from
materials may be a good substrate for biofilm formation. In the present plastic to brittle depending on the PBS content. The alignment of the
study two 8-hydroxyquinoline (8HQ) derivatives were used as model blend fibers was controlled by the collector rotation speed and was
drugs: the potassium salt of 5-nitro-8-hydroxyquinoline (K5N8Q) found to increase the modulus and the tensile strength of the fibrous
and 5-chloro-8-quinolinol (5Cl8HQ). As a polymer carrier PLA/PBS = materials. Drug loading and tests involving pathogenic microorganisms
80/20 (w/w) mats prepared by using of DCM/EtOH as solvent and at a suggested that the obtained mats can find application as antibacterial fi-
collector rotating speed of 1900 rpm were selected due to the lower di- brous materials.
ameter values and adequate mechanical behavior (especially regarding
their elasticity behavior). SEM micrographs of the prepared fibers as Acknowledgments
well as their mean diameters values are shown in Fig. 6.
The incorporation of these 8HQ derivatives led to a decrease of the Financial support from the Bulgarian Science Fund (Grant DCVP 02/2/
mean diameter value of the fibers, which might be attributed to the 2009) is gratefully acknowledged. The authors thank the bilateral
126 N. Stoyanova et al. / Materials Science and Engineering C 41 (2014) 119–126

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