International Journal of Biological Macromolecules 144 (2020) 624–631

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Antibacterial phase change microcapsules obtained with lignin as the

Pickering stabilizer and the reducing agent for silver
Xiang Li, Yanbin Wang, Bijia Wang, Xueling Feng, Zhiping Mao, Xiaofeng Sui ⁎
Key Lab of Science and Technology of Eco-Textile, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, People's
Republic of China
Innovation Center for Textile Science and Technology of DHU, Donghua University, Shanghai 201620, People's Republic of China

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

Article history: This paper provides a novel and facile method to synthesize antibacterial phase change microcapsules
Received 30 October 2019 (microPCMs) decorated with silver particles, where lignin was acting as both the Pickering stabilizer and the re-
Received in revised form 2 December 2019 ducing agent for silver. First lignin Pickering emulsions at various oil-to-water ratios and lignin loading were pre-
Accepted 2 December 2019
pared. Then, n-eicosane encapsulated in polyurea (PU) shells was prepared via interfacial polymerization of
Available online 5 December 2019
isophorone diisocyanate (IPDI) and ethylene diamine/diethylene triamine (EDA/DETA) in a Pickering emulsion
Keywords:
stabilized by lignin particles. The results showed that the lignin particles were embedded in the microPCMs
Lignin particles shell. These lignin particles were utilized to reduce silver ions, resulting in silver particles decorated microPCMs
Pickering emulsion (Ag/lignin microPCMs). The resulting Ag/lignin microPCMs exhibited a well-defined core-shell spherical mor-
Phase change microcapsules phology with high phase-transition enthalpy (177.6 J/g), high encapsulation efficiency (69.0%) and good thermal
Antibacterial activity durability. As well, the Ag/lignin microPCMs presented good antibacterial activity, showing great potential in in-
dustrial applications such as biomedical, textile and construction areas.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction three phenylpropanoids (p-coumaryl, coniferyl and sinapyl alcohols)

[20–22]. The heterogeneous and complex chemical structure of lignin
Phase change materials (PCMs), a type of energy storage materials may limit its applications; however, it can be used to produce value-
with latent heat, will leak out to the surrounding environment when added functional materials [23–27]. Recently, lignin nanoparticles
phase change occurs [1–3]. Phase change microcapsules (microPCMs), have been reported to stabilize the oil-in-water emulsion as Pickering
in which PCMs are encapsulated by the shell materials, are often used stabilizer [28,29], and the lignin-based Pickering emulsion template
to prevent the leakage of PCMs, expanding their application in textiles has been applied in macroporous foams [30], multilayer microcapsules
and construction [4–6]. Since the first microPCMs were developed, [31] and molecularly imprinted polymers [32]. Lignin nanoparticles
there have been performance enhancement in their conductivity [7–9] were also shown to efficiently stabilize oil-in-water emulsions, followed
and flammability [10], and value-added functionalities such as solar- by preparing poly(lactic acid)/lignin blends in our previous work [33].
driven [11] and photo-thermal conversion [12] also have been intro- Furthermore, abundant functional groups such as carbonyl, car-
duced to expand their applications. Molecular surfactants are used as boxyl, phenolic or aliphatic hydroxyls, etc. are found in lignin [34]. It re-
the emulsifiers in the process of making microPCMs, while an emerging veals that the phenolic hydroxyls in lignin molecule are easily oxidized
trend is to replace surfactants with solid particles in so-called Pickering to quinone/hydroquinone [35], which would readily generate metallic
emulsions [13,14]. Pickering stabilizers such as Fe3O4 [15], graphene silver when combining with silver ions [36]. The lignin-Ag system has
[16], Si3N4 [17], rice-husk-char [18], and SiO2 nanoparticles [19] have already been applied in making composite UV-shielding and antibacte-
been utilized in preparation of functional microPCMs. rial films [37], optical sensors [38], and plant-inspired adhesive
Lignin, one of the most renewable and biodegradable natural re- hydrogels with good cell affinity [39].
source, is a complex amorphous polyphenol biopolymer consisting of Herein, we designed and synthesized antibacterial microPCMs with
n-eicosane core and polyurea (PU) shells via Pickering emulsion
templating, where lignin was acting as both the emulsion stabilizer
⁎ Corresponding author at: Key Lab of Science and Technology of Eco-Textile, Ministry
of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua
and the reducing agent to incorporate silver. In this paper, n-eicosane,
University, Shanghai 201620, People's Republic of China. with large phase-transition enthalpy (N250 J/g) and transition temper-
E-mail address: [email protected] (X. Sui). ature closing to human body, was used as phase change core [40–42].

https://doi.org/10.1016/j.ijbiomac.2019.12.016
0141-8130/© 2018 Elsevier B.V. All rights reserved.
 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631 625

PU was selected as the shell for its favorable physical and chemical sta- water were dropped under continuous stirring (500 rpm) over 30 min.
bilities [43,44]. The preparation of Ag/lignin microPCMs is shown in The emulsion was allowed to react at 60 °C for 3 h, after which a second
Scheme 1. Initially, Pickering emulsion of melted n-eicosane and IPDI batch of EDA/DETA aqueous solution was introduced in the same way.
was formed using lignin particles as the stabilizer. Then, the PU shell After 30 min, lignin microPCMs (LP2) formed was isolated by filtration
was formed by interfacial polymerization with addition of ethylene and washed with 50 mL D.I. water for three times. To a suspension
diamine/diethylene triamine (EDA/DETA) solution. Finally, with the (10 mL) containing 1 g of the lignin microPCMs was added 2 mL aque-
addition of silver nitrate, silver ions were reduced by lignin, and the ous AgNO3 solution (0.08 g in 2 mL water). The mixture was under con-
microPCMs decorated with silver particles were obtained. By adopting tinuous stirring (500 rpm) for 8 h at ambient temperature. The resulting
the Ag/lignin system in preparation of Pickering emulsion templated Ag/lignin microPCMs were isolated again by filtration and 50 mL D.I.
microPCMs, we aim at expanding their applications in biomedicine, tex- water washing for three times and air-dried at ambient temperature.
tiles, construction, and related fields. Otherwise, 0.2 and 0.8 wt% lignin suspension and 2:8 and 3:7 (w/v)
oil-to water ratios were also used to prepare lignin Pickering emulsion,
2. Experimental as shown in Table 1.

2.1. Materials
2.4. Characterization
n-Eicosane was purchased from Acros. Lignin was purchased from
Sigma-Aldrich. Isophorone diisocyanate (IPDI) was obtained from Yan- 2.4.1. Morphological test
tai Wanhua Polyurethane Co., Ltd. Ethylene diamine (EDA), diethylene The emulsion droplets were dropped on heated glass slides (60 °C)
triamine (DETA) and acetone were obtained from Sinopharm Chemical and were observed on an ECLIPSE E100 optical microscope (O.M)
Reagent Co., Ltd. Silver nitrate (AgNO3) was obtained from Shanghai (Nikon, Japan). Dynamic light scattering (DLS) (Nano-ZS, Malvern, UK)
Zhanyun Chemical Co., Ltd. and laser particle size analyzer (S3500, Microtrac, America) were uti-
lized to analyze the particle size distribution of the lignin particles and
2.2. Preparation of lignin suspension the corresponding emulsions at ambient temperature, respectively.
Field emission scanning electron microscope (FE-SEM) (S-4800, Hitachi,
Lignin powder (1 g) was dissolved in 100 g of 4:1 (w/w) acetone/ Japan) was utilized to observe the morphology of lignin particles. Scan-
water co-solvent. Stirring was continued for 3 h at ambient temperature ning electron microscope (SEM) (TM3030, Hitachi, Japan) was utilized
to ensure complete dissolution of lignin. The insoluble impurities were to observe the morphology of the microPCMs. The morphology of re-
removed by filtration before the solution was diluted with additional duced silver particles was observed via transmission electron micros-
60 mL water. The diluted solution was stirred at ambient temperature copy (TEM) utilizing a JEM-2100 microscope (JEOL, Japan) operating
for 24 h, during which acetone evaporated gradually leading to the for- at 200 kV.
mation of lignin particles. The mass fraction of the resulting lignin sus-
pension was determined by a moisture analyzer (MX-50, AND, Japan)
to be 1.2 wt%. 2.4.2. Surface elemental analysis
Surface elemental distribution of the microPCMs was performed by
2.3. Synthesis of Pickering emulsions and Ag/lignin microPCMs FE-SEM as described in Section 2.4.1 coupled with an energy dispersive
X-ray spectroscope (EDS). Chemical compositions on the microPCMs
The preparation of Ag/lignin microPCMs is illustrated in Scheme 1. In surface were analyzed using X-ray photoelectron spectroscope (XPS)
detail, lignin suspension was diluted to 0.4 wt%. IPDI (0.4 g) and n- (AXIS UItra DLD, Kratos, UK) with a monochromatic using Al-Kα radia-
eicosane (1.4 g) at 60 °C was added to 18 mL of the diluted lignin sus- tion. Pass energies of 160 eV at 15 kV and 5 mA and of 40 eV at 15 kV
pension. The lignin stabilized O/W Pickering emulsion at the oil-to- and 10 mA were used for wide spectra and individual photoelectron
water ratio of 1:9 (w/v), named as LP2, was obtained by homogenizing lines, respectively. Silver content in the microPCMs was measured by in-
at 9000 rpm for 3 min, to which EDA (0.05 g) and DETA (0.1 g) in 10 mL ductively coupled plasma (ICP) (Prodigy, Leeman, America).

Scheme 1. Preparation of Ag/lignin microPCMs. (a) Pickering emulsion, (b) Lignin microPCMs with PU shell, (c) Ag/lignin microPCMs decorated with silver particles.
626 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631

Table 1 Lignin Pickering emulsions were observed using an optical micro-

Pickering emulsions at various oil-to-water ratios and lignin suspensions and particle di- scope at ambient temperature and the images are shown in Fig. 2. At
ameters of their microPCMs.
ambient temperature, the n-eicosane in the emulsion droplets solidified
Samples Oil-to-water Concentration of lignin Particle and contracted slightly, leading to a rough spherical shape (Fig. 2b). The
ratio suspensions diameter emulsion of LP2 at 60 °C is shown in Fig. S1a. The droplets were spher-
(w/v) (wt%) (μm)
ical and the droplets surface was covered with lignin particles. The Pick-
LP1 1:9 0.2 31.6 ± 2.4 ering emulsion templating approach allows for the self-assembling of
LP2 1:9 0.4 22.7 ± 1.4
lignin particles at the oil-water interface. Comparing the three LP sam-
LP3 1:9 0.8 17.0 ± 1.1
LP4 2:8 0.4 40.1 ± 1.9 ples, LP3 showed the least particle sizes due to 0.8 wt% concentration
LP5 3:7 0.4 53.9 ± 2.9 of lignin suspension (Fig. 2a–c). As shown in Fig. S1b, these lignin/n-
eicosane/IPDI microPCMs displayed monodispersity with a mean parti-
cle size of 31.6 ± 2.4 μm, 22.7 ± 1.4 μm, and 17.0 ± 1.1 μm, respectively
2.4.3. Thermal analysis (Table 1). With increasing the oil content, particle sizes increased
The permeability of the encapsulated n-eicosane in the microPCMs (Fig. 2b, d&e) and particle diameter of LP2, LP5 and LP6 were 22.7 ±
was analyzed by thermogravimetric analysis (TGA) (209F3, Netzsch, 1.4 μm, 40.1 ± 1.9 μm and 53.9 ± 2.9 μm, respectively (Table 1). But,
Germany). Each sample was weighted out about 5 mg in the alumina particle distribution of LP5 displayed polydispersity with three peaks
crucible. The weight loss of the sample at 120 °C for 1 h with N2 protec- of 65.31 μm (66%), 26.91 μm (25.2%) and 9.27 μm (8.8%) (Fig. S1c).
tion was calculated by TGA analysis. Pure n-eicosane was used as a Fig. 2f also showed LP5 of nonuniform or jerky particles shapes. Thus,
reference. lignin Pickering emulsion with 0.4 wt% lignin concentration and 1:9
Phase-change performance of the microPCMs was determined by w/v oil-to-water ratio was chosen to prepare the lignin microPCMs.
dynamic differential scanning calorimetry (DSC) (214 Polyma, Netzsch, Morphologies of lignin microPCMs (LP2) and Ag/lignin microPCMs
Germany). The microPCM samples were weighted out about 5 mg in the were investigated by SEM. FTIR showed that the isocyanate (-NCO)
aluminum pans. DSC curves were obtained by the heating or cooling group peak about 2300 cm−1 did not appear in lignin microPCMs
temperature at the rate of 10 °C/min conditions in the range of (Fig. S2), indicating no residual isocyanate group. According to the
−10 °C to 70 °C with N2 protection. In order to assess the durability SEM images in Fig. 3, the mostly spherical microPCMs exhibited a
against repeated heating and cooling, the process was cycled for 100 rough surface with protuberances. The protuberances were confirmed
times. to be lignin particles concerning they could be dissolved and washed
off by NaOH (pH = 11, see Fig. 3d). The indentations in the shell after
NaOH treatment to dissolve lignin (Fig. 3d) indicated that lignin parti-
2.4.4. Antibacterial activity
cles were embedded in the PU shell of microPCMs. This was likely due
The antibacterial activity was evaluated though inhibiting the sur-
to the participation of lignin hydroxyls in condensation with IPDI to
vival and growth of the bacterial against Gram-positive strain Staphylo-
form the PU shell [29,45]. After the incorporation of silver, silver ions
coccus aureus and Gram-negative strain Escherichia coli. Initially, these
were reduced on the shell of microcapsules [37,46], the microPCMs be-
two strains were cultivated in the Luria-Bertani medium at 37 °C for
came darker in shades (Fig. 3a & e). However, the silver was so tiny to be
24 h in reserve. 0.25 g of microPCMs and 2 mL of the bacteria suspension
captured on the SEM images (Fig. 3f & g). The well-defined core-shell
were added into 23 mL of a phosphate buffered saline solution. These
structure of the microPCM was demonstrated in the cross section
mixtures were cultivated in a shaker incubator at 37 °C for 24 h. The cul-
view shown in Fig. 3h.
tivated mixtures were diluted 100 times, and homogenously casted on
the Luria-Bertani agar medium and incubated at 37 °C for another
3.2. Surface elemental analysis
12 h. The antibacterial activities were evaluated by visual examination
of the Petri dishes.
EDS mapping images demonstrating the distribution of C, N, O and
Ag are presented in Fig. 4a. According to the images in Fig. 4a, the distri-
3. Results and discussion bution of silver in the selected region was not even on the microPCMs
surface due to the aggregation of silver particles. Lignin suspension
3.1. Morphologies was also utilized to reduce silver ions, and the TEM proveed the agglom-
erated silver particles (Fig. S3). The EDS spectra and elemental constitu-
As shown by the FE-SEM image in Fig. 1a, the lignin particles were tions of the microPCM samples are present in Fig. 4b & c. Characteristic
uniformly spherical and demonstrated monodispersity with an average peaks of elemental Ag were observed on the surface of Ag/lignin
diameter of 473 nm and PDI of 0.060 (Fig. 1b). microPCM but not on the lignin microPCM. It also showed that the

Fig. 1. (a) FE-SEM and (b) DLS of lignin particles prepared by acetone/water co-solvents.
 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631 627

Fig. 2. O.M of lignin/n-eicosane suspensions with various concentrations of lignin suspension of (a) 0.2 wt%, (b) 0.4 wt%, (c) 0.8 wt% and various oil-to-water rates of (b) 1:9 w/v, (d) 2:8 w/
v and (e & f) 3:7 w/v at ambient temperature.

content of silver element was about 1.62 wt% in the selected region. For 3.3. Thermal properties
the intact Ag/lignin microPCMs, silver content determined by ICP was
1.42 mg/g. The isothermal TGA curves for pure n-eicosane, lignin microPCMs
XPS spectra of the two microPCMs are compared in Fig. 5a, in which and Ag/lignin microPCMs are plotted in Fig. 6a. After being heated at
the characteristic peaks for Ag only presented in the XPS curve of Ag/lig- 120 °C for 60 min, weight loss due to evaporation reached 57 wt% for
nin microPCMs. The decoupled Ag 3d peaks were observed at 374.5 eV pure n-eicosane, while the encapsulated microPCMs showed only 7 wt
and 368.5 eV in Fig. 5, which corresponded to the Ag 3d3/2 and Ag 3d5/2 % weight loss. It was clear that the encapsulation by the PU shell effec-
spin-orbit couplings, respectively. Moreover, the Ag 3d5/2 signal peak at tively prevented the loss of the PCM (n-eicosane) upon heating.
367.4 eV of silver oxide was not observed. The result indicated the silver DSC curves and the calculated data are presented in Fig. 6b and
element was in the metallic state rather than the oxidized state [47,48]. Table 2. Most of paraffin PCMs have a rotator phase transition tempera-
The results proved the exclusive presence of metallic silver in the shell ture (Tr) above the crystallization temperature (Tc) due to the metasta-
confirming the successful reduction of silver ions by lignin. ble rotator phase [49]. n-Eicosane has the Tc of 29.0 °C, Tr of 30.2 °C and

Fig. 3. Optical images of (a) lignin microPCMs and (e) Ag/lignin microPCMs; SEM images of lignin microPCMs and (b–c) before and (d) after washing with NaOH; and (f–h) SEM images of
Ag/lignin microPCM.
628 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631

Fig. 4. (a) Elemental mappings of Ag/lignin microPCMs; EDS spectrum of (b) lignin microPCMs and (c) Ag/lignin microPCMs.

the melting temperature (Tm) of 41.2 °C. The melting and crystallization internal space of microcapsules, resulting in the crystallization defects
temperatures of two microPCMs were slightly lower than that of n- and ultimately decreases in the melting and crystallization tempera-
eicosane. Motion of the n-eicosane molecules is limited by the confined tures [50].

Fig. 5. (a) XPS curves of lignin microPCMs and Ag/lignin microPCMs; (b) Ag 3d peaks of Ag/lignin microPCMs.
 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631 629

Fig. 6. (a) Isothermal TGA curves of n-eicosane, lignin microPCMs and Ag/lignin microPCMs heated at 120 °C. (b) DSC curve of n-eicosane, lignin microPCMs and Ag/lignin microPCMs.

Thermal capacity is a crucial parameter for PCMs. The melting en- Fig. 7 shows the cycle curves of the Ag/lignin microPCMs over 100
thalpy of pure n-eicosane was high of 257.4 J/g (Table 2). The lignin heating-cooling circulations. The cooling curve started to deviate
microPCMs and Ag/lignin microPCMs had markedly lower melting en- slightly from the original one at the 50th cycle. The DSC curve of the
thalpies of 179.4 J/g and 177.6 J/g, respectively, because PU shell 100th cycle remained unchanged compared to that of the 50th cycle.
underwent no phase change and didn't absorb nor release latent heat These results demonstrated that the Ag/lignin microPCMs had good
upon heating or cooling. Therefore, the weight percentage of the thermal stability and durability during the heating-cooling cycles.
amount of PCM encapsulated determines the thermal capacity of
microPCMs. Microencapsulation efficiency (Effen) was calculated as the 3.4. Antibacterial activity
percentage of the core PCMs in microcapsules using Eq. (1) [42]:
The results of the antibacterial activity are shown in Fig. 8. The lignin
ΔH m;micro microPCMs and Ag/lignin microPCMs as the antibacterial agents were
E f f en ¼  100% ð1Þ
ΔH m;eico added to the bacteria solution to inhibit the bacterial survival and
growth. Petri dish with lignin microPCMs was full of the bacterial colo-
where ΔHm,micro and ΔHm,eico are the recorded melting enthalpies of the nies, whereas that with Ag/lignin microPCMs had no bacterial colonies.
microPCMs and the pure n-eicosane, respectively. The Effen of lignin This result indicated that the Ag/lignin microPCMs decorated with a
microPCMs prepared herein was calculated to be 69.7%, which was small number of silver exhibited good antibacterial activity.
slightly higher than that of the Ag/lignin microPCMs (69.0%), because
the incorporated silver increased the shell weight. 4. Conclusions
Energy-storage efficiency (Effes) as an indicator of the storing and re-
leasing of latent heat by the microcapsules, was evaluated by Eq. (2) The antibacterial Ag/lignin microPCMs were successfully synthe-
[42]: sized using Pickering emulsion templating where lignin particles served
as both the emulsion stabilizer and the reducing agent for silver. Lignin
ΔH m;micro þ ΔH c;micro Pickering emulsion with a 0.4 wt% lignin concentration and 1:9 (w/v)
E f f es ¼  100% ð2Þ
ΔH m;eico þ ΔHc;eico oil-to-water ratio was chosen to prepare the lignin microPCMs. n-
Eicosane encapsulated in PU shells was prepared via the interfacial po-
where ΔHc,micro is the crystallization enthalpy of the microPCMs, and lymerization in a Pickering emulsion stabilized by lignin particles. Re-
ΔHc,eico is the crystallization enthalpy of pure n-eicosane. Effes values sults showed that the lignin particles were embedded in the PU shell
were found to closely resemble the corresponding Effen's (Table 2), indi- of microPCMs and reduced the silver ions on the microPCMs surface.
cating that encapsulation didn't interfere with the releasing of latent
heat. The thermal storage capability (Ces) of microPCMs was calculated
according to Eq. (3) [42]:

E f f es
C es ¼  100% ð3Þ
E f f en

where Effes and Effen are obtained by Eqs. (1) and (2), respectively. As
shown in Table 2, Ces's of lignin microPCMs and Ag/lignin microPCMs
were over 99%, indicating the thermal ability of n-eicosane core was
not compromised by the PU/lignin shell of the microPCMs.

Table 2
Data of n-eicosane and microPCMs extracted from DSC analysis.

Samples Crystallizing Melting Effen Effes Cffes

(%) (%) (%)
Tc Tr ΔHc Tm ΔHm
(°C) (°C) (J/g) (°C) (J/g)

n-Eicosane 29.0 30.2 256.7 41.2 257.4 – – –

Lignin microPCMs 22.4 27.7 177.8 41.0 179.4 69.7 69.5 99.7
Ag/lignin microPCMs 22.2 27.5 175.5 40.9 177.6 69.0 68.7 99.5
Fig. 7. DSC curves of Ag/lignin microPCMs over 100 heating-cooling cycles.
630 X. Li et al. / International Journal of Biological Macromolecules 144 (2020) 624–631

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