Holzforschung 2016; aop
Hao Li, Yonghong Deng*, Haisong Wu, Yuan Ren, Xueqing Qiu*, Dafeng Zheng and ChunLi Li
Self-assembly of kraft lignin into nanospheres
in dioxane-water mixtures
DOI 10.1515/hf-2015-0238
Received November 11, 2015; accepted January 25, 2016; previously
published online xx
Abstract: Kraft lignin (KL), a by-product in the pulping
and papermaking industry, is an abundant, renewable
resource. In this work, nanosphere formation of KL has
been investigated via self-assembly induced by adding
water to a KL/dioxane solution. The KL nanospheres were
characterized by scanning electron microscopy (SEM),
transmission electron microscopy (TEM), dynamic light
scattering (dynLS) and static light scattering (statLS).
It was found that the nanoparticles have uniform nano-
spherical morphologies, including a small hollow cavity
space in the interior. The π-π interactions between the aro-
matic rings of KL are demonstrated to be an important driv-
ing force in the self-assembly process. The KL nanosphere
sizes can vary by hundreds of nanometers depending
upon the preparation conditions. These newly obtained
KL nanospheres have the advantages of biocompatibility,
biodegradability, low toxicity, easy preparation, and low
cost. Thus KL nanospheres are attractive for applications
in life science, medicine, biology, food science, and agri-
culture. This approach presented here is an economically
feasible and facile strategy for the sustainable utilization
of kraft lignin.
Keywords: kraft lignin, nanospheres, renewable resources,
self-assembly, sustainable chemistry
*Corresponding authors: Yonghong Deng and Xueqing Qiu, School
of Chemistry and Chemical Engineering, South China University
of Technology, Wushan Road, Guangzhou, P.R. China,
Tel.: +86 020 87114722, Fax: +86 020 87114721,
e-mail: yhdeng08@163.com (Y. Deng);
xueqingqiu66@163.com (X. Qiu)
Hao Li: School of Chemical Engineering, Hebei University of
Technology, Guangrong Street, Tianjin, P.R. China; and School of
Chemistry and Chemical Engineering, South China University of
Technology, Wushan Road, Guangzhou, P.R. China
Haisong Wu, Yuan Ren and Dafeng Zheng: School of Chemistry
and Chemical Engineering, South China University of Technology,
Wushan Road, Guangzhou, P.R. China
ChunLi Li: School of Chemical Engineering, Hebei University of
Technology, Guangrong Street, Tianjin, P.R. China
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Introduction
Nanomaterial research is a flourishing science which also
has many commercial applications. Nanospheres have
size-dependent physical and chemical properties. They
can be prepared based on inorganic matters (Nie et  al.
2009), organic matters (Horn and Rieger 2001), amphiphi-
lic polymers (Ikkala and Ten Brinke 2002), and biopoly-
mers (Mohanpuria et  al. 2008). Nanospheres can be
applied for preparing advanced materials, for drug deliv-
ery (Kataoka et al. 2012), material separation (Wang et al.
1998), microreactors and catalysis (Vriezema et al. 2005;
Lu et al. 2015). Recently, their commercial exploration is
in focus. The formation of nanospheres via self-assembly
of polymers has attracted increasing attention in the past
decade, driven by a wide range of possible applications in
science and technology.
Lignin, like cellulose and hemicelluloses, is a major
component of plant materials. It belongs to the most abun-
dant renewable resource in nature, constituting approxi-
mately 15–30% of wood (Doherty et  al. 2011). Industrial
lignins are by-product of the various pulping processes,
but they are also left behind after acid hydrolysis of
biomass in the course of ethanol production. Nowadays,
the kraft process is dominating among the pulping pro-
cesses resulting in the byproduct kraft lignin (KL), which
is recovered from the black liquor after pulping (Chakar
and Ragauskas 2004). KLs are rich in phenolic hydroxyl
and carboxyl groups as a result of splitting reactions of
the lignin network during the pulping process (Gellerstedt
and Lindfors 1984). The KLs have an amphiphilic quality
(Shen and Rosenholm 1998). KL can be used as biochemi-
cal and biofuel after chemical degradation or pyrolysis
(Werhan et al. 2011; Azadi et al. 2013), polymer materials
by blending (Stewart, 2008), adhesion agent (Engelmann
and Ganster, 2014), carbon fiber (Brodin et al. 2012), acti-
vated carbons, and many types of industrial dispersants
after chemically modification (Zhou et al. 2010; Gan et al.
2013; Lou et  al. 2013). Essential properties of lignins are
biocompatibility, biodegradability, low toxicity, ultra-
violet resistance (Fernández-Pérez et al. 2014; Qian et al.
2015) and oxidation resistance (Košíková et  al. 2006).
Nevertheless, KL is mainly burnt in a recovery boiler to
2      H. Li et al.: Self-assembly of kraft lignin
recover the pulping chemicals and to obtain energy. Thus,
the amount of isolated and commercially available KL is
quite low (Strassberger et al. 2014).
KL as a natural amphiphilic polymer was not yet
considered for nanoparticle preparation by self-assem-
bly because of its complicated chemical structure.
Recently, it was observed that KL can form nanospheres
in a THF-water mixture after being chemically modified
by an acetylating agent (Qian et al. 2014a,b). However,
the acetylatation of KL is expensive and complicated
as it requires the use of glacial acetic acid and acetyl
bromide. In our group, the preparation of lignin-based
nanospheres has also been investigated in a more
simple, low-cost, and safe manner. It was discovered
that KL can easily form nanospheres via self-assembly
in a dioxane-water mixture. The particle size of these KL
nanospheres can be easily controlled within a certain
range, thereby its adaptability for various applications
is enhanced.
During the preparation of the present paper, Lievonen
et al. (2016) published a method to obtain spherical lignin
nanoparticles by dissolving KL in THF and subsequently
introducing water into the system through dialysis. The
process needs 24  h reaction time. In view of a possible
industrial application, the health hazards emerging from
THF have also to be considered.
In our research, the utilization of dioxane (though
also toxic) is preferred as the lignin nanoparticles formed
in the presence of this solvent are more uniform in size
and have a thicker shell. The uniformity improves the
performance in many applications (Song et al. 2007; Fang
et al. 2014). The thicker shell contributes to stabilization of
the particles and their performance in some applications
(Harris et  al. 2006). The preparation of KL nanospheres
in presence of dioxane occurs only in a few minutes. The
particles formed by self-assembly will be characterized by
transmission electron microscopy (TEM), scanning elec-
tron microscopy (SEM), dynamic light scattering (dynLS)
and static light scattering (statLS). The controlling of the
particle size will also be in focus.
Materials and methods
KL was provided by Jinan Shengquan Group Co., Ltd. in Shandong
province, China, which was separated from black liquor by acid pre-
cipitation. The product from the factory was used directly without
any further treatment. The dioxane is of analytical grade reagent and
the water was ultrapure.
KL nanospheres were prepared by first dissolving KL in dioxane
during 72 h. The supernatant part served for nanosphere prepara-
tion. The UV control showed that about 82% of kraft lignin (KL) was
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dissolved (1 g KL in 1 L dioxane). Ultrapure water was dropped to this
solution by a peristaltic pump under magnetic stirring.
In the study of dynLS, statLS, SEM, TEM and UV-Vis spectrum,
the samples were first prepared at a water content of 90.0% (by wt).
Then, the solution was placed in a dialysis bag with a molecular cut-
off of 1000 g mol-1 and dialyzed against continuous renewal ultrapure
water for 3 days to remove the dioxane. The concentration of the stock
solution, after dialysis was measured again by UV spectroscopy. Sev-
eral other samples with varying concentrations were prepared for
statLS measurement by diluting the stock solution with water. For
the UV and FTIR measurements, the KL samples, which did not form
the nanospheres, were obtained from the supernatant part of the KL/
dioxane solution by rotary evaporation.
A commercial laser light scattering (LLS) instrument was
applied (ALV/CGS-3, ALV GmbH, Germany) that was equipped with a
multi–digital time correlator (ALV-7004) and a solid-state He-Ne laser
(JDS-Uniphase, output power = 22 mW, 632.8 nm). For details of LLS
instrumentation and theory see Li et al. (2014). For KL nanospheres
in water, the specific refractive index increment (dn/dc) was 0.5237,
which was measured on a BI-DNDC instrument (DNDC-2010, WEG,
Kerpen, Germany) at 20°C.
TEM was performed on a JEM-2100F microscope. A drop of the
KL nanospheres solution was deposited onto the copper grids that
were coated with a thin carbon film and then dried at room temper-
ature (r.t.) for several hours. The SEM observations were conducted
on a Zeiss Merlin instrument. The specimens for this purpose were
prepared by the vertical deposition technique, which involves
immersing the silicon substrates into the KL nanospheres solution
at a certain angle, pumping out the solution at a slow speed. After
this, the KL nanospheres were fixed on the silicon substrates. Then,
the silicon substrates, which contain the KL nanospheres, were
tested.
The UV-Vis spectrophotometer (UV-2450, Shimadzu Corp.,
Japan) and a Vector 333 FT-IR spectrometer (Bruker, Germany) was
used for characterization.
Results and discussion
Preparation and characterization
The KL/dioxane solution was first prepared as described
in the experimental section. Then, the KL molecules were
driven to self-assembling by the slow addition of ultrapure
water to the system. Dioxane is a good solvent for KL, and
water is a precipitant for KL. The slow water addition is
progressively worsening the KL solution. Eventually, the
KL molecules begin to aggregate, which is reflected by a
sudden change in the scattered light intensity. Figure  1
presents the experimental curves of the scattered light
intensity from the KL solutions as a function of added
water content. At low water content, the scattered light
intensity changes very little. However, when the water
content reached a critical value, the scattered light inten-
sity increased rapidly. This is indicative of aggregation
 H. Li et al.: Self-assembly of kraft lignin      3

3000 a
1.0
Scattered light intensity (a.u.)

2500
0.8
2000

Intensity (a.u.)
0.6
1500
0.4
1000
0.2
500
0
0
10 100 1000
0 10 20 30 40 50 60
Rh (nm)
Water content (w%)
b -16
Figure 1: Scattered light intensity versus the water content in the
solution. -17

ln(KC/R), KC/R (mol g-1)

The initial KL concentration in dioxane was 1 mg ml-1.
-18

processes. The subsequent characterization by TEM, SEM, -19

dynLS and statLS reveal important structural features of

KL nanospheres obtained.
The data of dynLS and statLS are very conclusive
concerning the shape and internal structure of the KL
nanospheres. Because the size of the KL nanospheres
changes with the preparation conditions (as described in
the following section), only representative nanospheres
obtained at an initial concentration of 3.69  mg ml-1 with
a water dropping speed 0.055 ml s-1 were selected for this
purpose.
The average hydrodynamic radius (Rh) and poly-
dispersity of the nanospheres in aqueous solution was
determined by dynLS (Figure 2a). The z-averaged hydrody-
namic radius (Rh) is 145.5 nm with a polydispersity (μ2/Γ2)
of 0.038. The statLS reveals the weight-average mass of the
KL nanospheres (Mw, p) and the radius of gyration (Rg). The
data that were obtained by extrapolations regarding C and
θ through the Zimm plot analysis (Figure 2b) are summa-
rized in Table 1.
The values of  < Rg > / < Rh >  provide more information
concerning the morphology of the resultant aggregates.
Theoretically, for a uniform nondraining solid sphere,
a non-draining thin shelled vesicle, and a random coil,
the ratios of  < Rg > / < Rh >  are 0.774, 1.0, and 1.5~1.8,
respectively (Peng et  al. 2003; Yao et  al. 2004). For a
polymeric vesicle or a hollow sphere, the experimen-
tal value of  < Rg > / < Rh >  may be less or  > 1.0, depend-
ing on the thickness and the density of the wall (Duan
et  al. 2001; Peng et  al. 2003; Yao et  al. 2004). In this
work,  < Rg > / < Rh >  was 0.832 (Table  1), which is within
the range of a uniform non-draining solid sphere and a
non-draining thin shelled vesicle. This value is a slightly
larger than 0.774 but much  < 1.0, thus the samples are
-20
-21
0 5 10 15 20 25
(q2+kC)×10-3 (µm2)
Figure 2: (a) Distribution of the hydrodynamic radius (Rh) of the KL
nanospheres in aqueous solution. (b) Typical Zimm plot of light scat-
tering photometry of typical KL nanospheres in aqueous solution.
Table 1: Results of dynLS and statLS measurements of KL
nanospheres.
 < Rg > (nm)   121.1
 < Rh >  (nm)   145.45
 < Rg > / < Rh >    0.832
Mw, m (g mol-1)  3.28 × 103
Mw, p (g mol-1)   9.082 × 108
 < Nagg > a   2.77 × 105
 < ρ > b (g cm-3)   0.117
a
 < Nagg >  = Mw, p/Mw, m.
b
ρ = Mw, p/(NA4π < Rh > 3/3).
approximately spherical solid spheres, but still maintain
a hollow characteristic. Accordingly, the preliminary
assumption is that the formed aggregates are thick-
shelled hollow spheres with only a small hollow cavity
in the interior. The average aggregate number for each
nanosphere was estimated to be 5.15 × 104 based upon
the equation  < Nagg >  = Mw, p/Mw, m. The average apparent
structural density (ρ) of the nanospheres, which was
determined by the equation  < ρ >  = Mw, p/(NA4π < Rh > 3/3),
was calculated to be 0.117 g cm-3. When compared with

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4      H. Li et al.: Self-assembly of kraft lignin

the solid colloids spheres prepared via acetylated KL
(Qian  et  al. 2014b), the KL nanospheres of the present
study have a lower ρ value.
The hollow cavity space in the interior of the parti-
cles was also indicated by TEM and SEM. The TEM image
without staining is presented in Figure 3a. The remarkable
feature of the aggregates is the readily evident contrast
between the central and outer portion, which is a typical
TEM feature of hollow spheres that has been reported
for different types of particles with central cavity (Duan
et al. 2001). The diameter of the particles in Figure 3a is
between 200 and 400 nm, which is comparable to that
measured by LLS. SEM provides mainly surface informa-
tion, which is based on the secondary electrons donated
by the electron beam that is emitted onto the surface of
the sample for imaging. SEM image (Figure 3b) of this
sample also shows the sphere’s structural characteristics,
on which a remarkable contrast is visible between the
central and the edge parts of an aggregate. Some “sunken
crevices” and “collapsed holes” which exhibit a concave
central area, can be occasionally observed on the surface
of the aggregates; these structures are caused by the
drying process of the hollow spherical structures. These
features demonstrate the morphology of typical conven-
tional hollow spheres. The imaging results are consistent
with the assumptions based on the  < Rg > / < Rh >  values.
The shell thickness of these KL nanospheres is thicker
than the spherical lignin nanoparticles obtained by
Lievonen et  al. (2016). Thicker shells may be beneficial
to the performance of nanospheres in some applications
(Harris et al. 2006).
Mechanism for the formation of KL
nanospheres
Lignin is a complex phenolic polymer, which shows a
tendency for aggregation in solution by π-π interactions
among their benzene groups (Sarkanen et  al. 1982; Sar-
kanen et al. 1984; Deng et al. 2011). The assembly process
for KL nanospheres should have unique characteristics
due to the obvious differences in the molecular structure
and the way of aggregation, although the method for their
preparation is similar to that of other nanospheres based
on block polymers (Cameron et  al. 1999). The formation
mechanism of KL nanospheres was studied by UV and
FTIR spectroscopy.
By UV spectroscopy (Figure  4), two forms of KL
samples were compared. One sample was the dioxane
soluble KL that did not form nanospheres (KL) in water,
which was obtained by dissolving dioxane soluble KL in
NaOH and then dialyzing it against ultrapure water to
remove the alkali. The concentration of KL solution for
UV test was only about 50 mg l-1, which was so low that
the already dissolved KL would not reprecipitate even
though the alkali was removed. The other sample was the
KL nanospheres in water, which were obtained by dialyz-
ing the water-dioxane mixed solvent against the ultrapure
water to remove the dioxane. The chemical compositions
of these two samples are the same, and the only difference
is the aggregate form of KL; one sample has formed nano-
spheres but the other has not.
Figure 4 shows that the UV absorption character-
istics of KL and KL nanospheres in aqueous solution,

Figure 3: TEM (a) and SEM (b) of the KL nanospheres.

The initial KL concentration in dioxane was 3.69 mg ml-1 and the dropping speed of water was 0.055 ml s-1.

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 H. Li et al.: Self-assembly of kraft lignin      5

3.5
KL
KL nanospheres Peak 1423.4 cm-1
3.0
Peak 1510.2 cm-1
2.5
Absorbance (a.u.)

Transmittance
2.0 KL in water
KL nanospheres in water
1.5

1.0

0.5

0 Peak 1511.2 cm-1 Peak 1424.4 cm-1

200 300 400 500 600 700
Wavelength (nm) 1600 1550 1500 1450 1400
Wavenumber (cm-1)
Figure 4: UV-Vis absorption spectra of KL and KL nanospheres
in aqueous solution.The absorbance at λ280 nm was adjusted to Figure 5: FTIR spectra of KL and KL nanospheres from 1600 to
facilitate the comparison. 1400 cm-1.
Note the shift related to the aromatic skeletal vibration at 1511 and
1424 cm-1.

which are quite different despite their identical chemi-

cal composition. Thus the aggregating environments of
Control of particle size
the aromatic rings are significantly different between the
KL and KL nanospheres samples. Normally, the common
Different particle sizes are often needed for the various
irregular aggregation manner cannot lead to large UV
applications of nanospheres (Letchford and Burt 2007). In
spectral differences of kraft lignins. Previous studies
general, many factors have impact on the size of polymer
showed that the irregular aggregation of lignin would
nanospheres. In the present case, the dropping speed of
only lead a slight shape change of their UV spectra
the water is the most accessible factor to this purpose.
(Deng et  al. 2010; Deng et  al. 2012). Here, the shape of
Figure  6 describes the relationship between Rh and
the UV spectra for KL nanospheres has changed a lot
the dropping speed at a fixed initial KL concentration of
compared to the KL sample, though both KL and KL
3.69 mg ml-1. As the dropping speed of water increased, the
nanospheres have a Amax, 283 nm (exactly, at 282.5  nm for
Rh decreased sharply. This is the result of a competition
KL and at 283.5  nm for KL nanospheres). However, the
between the thermodynamic and kinetic control during
latter exhibit a broader absorption band in the longer
the self-assembly process. The self-assembly process of
wavelength region and also show a shoulder towards the
the macromolecules and the aggregation morphology are
longer wavelength region and the shoulder is increased
compared to the λmax. Shortly, the UV spectrum of KL
nanospheres shows a bathochromic shift. This shift is
indicative to an increased J-aggregation (a kind of π-π
aggregation). Deng et al. (2011) reported already a typical 300

J-aggregation for KL. Thus, it can be concluded that the

bathochromic shift in Figure 4 is mainly caused by much
stronger π-π interactions, which cannot be seen in case
Rh (nm)

200
of an irregular aggregation.
The FTIR spectra of KL and the KL nanospheres
are presented in Figure  5. The two bands related to the
100
aromatic units at 1511.2 cm-1 and 1424.4 cm-1 shifted to
1510.2  cm-1 and 1423.4 cm-1, respectively, in case of KL
nanospheres. The changes in the peak positions are attrib- 0 0.05 0.10 0.15 0.20 0.25
uted to the aromatic groups of lignin being in a different Dropping speed of water (ml s-1)

environment, which can also be interpreted that the KL Figure 6: Average hydrodynamic radius (Rh) of KL nanospheres as a
nanospheres have a stronger π–π interaction among the function of water dropping speed.
aromatic groups than does the KL sample. The initial KL concentration in dioxane was fixed at 3.69 mg ml-1.

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6      H. Li et al.: Self-assembly of kraft lignin
Figure 7: SEM images of KL nanospheres obtained at water dropping speeds of 0.0116 ml s-1 (a) and 0.1174 ml s-1 (b).
The initial KL concentration in dioxane was fixed at 3.69 mg ml-1.
mostly driven by thermodynamics, and sometimes these
forces can reach the thermodynamic equilibrium state;
however, the increased dropping speed of the water limits
the time for growing aggregates. The lack of time causes
the aggregates to remain in a “frozen” state, which hinders
the formation of a stable thermodynamic structure. Once
the “frozen” state is reached, all KL single molecules can
contribute to nanosphere formation and thus their con-
centration in the solution is low. As a result, the size of the
nanospheres cannot be increased over time.
The representative SEM images of the KL nanospheres
obtained at two different water dropping speeds are illus-
trated in Figure  7. The particle sizes that were obtained
by the two preparation conditions are evidently different
from each other. The size distributions are both narrowly
distributed around a certain range. The diameters of the
particles in Figure 7 are comparable to the size measured
by dynLS.
By controlling the water dropping speed, the size of
KL nanospheres can be easily regulated in a certain range.
This method is simple and cost-effective and permits the
adaptation to different application fields.
Conclusions
The formation of nanospheres via self-assembly can be
achieved by adding water to a KL/dioxane solution. The
obtained materials have uniform nanospherical mor-
phologies, including a small hollow cavity space in the
interior. The sizes of the KL nanospheres can vary by hun-
dreds of nanometers depending on the preparation con-
ditions. The π-π interaction between the aromatic rings
of KL is probably the most important driving force in the
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self-assembly process. This approach is an inexpensive
and recyclable route for creation of nanomaterials with
tailored properties. The application of KL nanospheres
is not yet explored, and this is a research goal in our
laboratories.
Acknowledgments: The work was supported by the
National Basic Research Program of China (973 Program)
(2012CB215302), the State Key Program of National Natu-
ral Science of China (21436004), and the National Natural
Science Foundation of China (21374032).
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