Radiation Physics and Chemistry 124 (2016) 130–134

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Radiation Physics and Chemistry

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

Crosslinking of polysaccharides in room temperature ionic liquids

by ionizing radiation
Atsushi Kimura n, Naotsugu Nagasawa, Akihiko Shimada, Mitsumasa Taguchi
Japan Atomic Energy Agency, 1233 Watanuki, Takasaki, Gunma 370-1292, Japan

H I G H L I G H T S

Water is a key material for radiation-crosslinked chemical gels.

RTILs are involved in the crosslinked cellulose gels.

Chitin gel was first produced in RTILs by ionizing radiation.

art ic l e i nf o a b s t r a c t

Article history: Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were
Received 7 September 2015 investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis.
Received in revised form Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with
22 October 2015
phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-
Accepted 23 October 2015
acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium
Available online 24 October 2015
acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red
Keywords: shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and
Cellulose oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-
Chitin
crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the
Gel
cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations,
Room temperature ionic liquid
Ionizing radiation and its gel fraction increased with the dose and reached 86% at 60 kGy.
& 2015 Elsevier Ltd. All rights reserved.

1. Introduction Carboxylate-based RTILs, in particular, have high proton-accepting

Natural polysaccharides have been recognized to be the most
promising materials in recent years because of outstanding prop-
erties such as high biocompatibility and biodegradability, and
procurability from animals and plants on the Earth. So functional
materials have only been produced by using radiation crosslinking
technique either from polysaccharide derivatives or using cross-
linking reagents (Fei et al., 2000; Wach et al., 2001; Zhao et al.,
2008; Nagasawa et al., 2004). Some polysaccharides are, however,
radiation degradation type polymers and have poor solubility in
water and organic solvents as well as low chemical reactivity
(Kumar, 2000). These limitations could be circumvented by use of
specific solvents such as room temperature ionic liquids (RTILs).
n
Corresponding author. Fax: þ81 27 346 9422.
E-mail addresses: kimura.atsushi81@jaea.go.jp (A. Kimura),
nagasawa.naotsugu@jaea.go.jp (N. Nagasawa),
shimada.akihiko@jaea.go.jp (A. Shimada),
taguchi.mitsumasa@jaea.go.jp (M. Taguchi).
ability and can cleave the hydrogen bonds of polysaccharide main
chains to form solution in the concentration range of 0.1–20 wt%
(Swatloski et al., 2002; Heinze et al., 2005; Fukaya et al., 2008).
In the previous study, we have produced the chemical gels
without any crosslinking reagent by γ-ray irradiation from neat
cellulose in the carboxylate-based RTILs under humid conditions
for the first time (Kimura et al., 2014). The paste-like solution
obtained by mixing 20 wt% cellulose in EMI-acetate under dehy-
drated conditions was irradiated with γ-rays at a dose of 10 kGy
but no insoluble product was obtained under this condition. In this
case, radiation-induced reactive species are considered to be
mainly hydrogen atom and solvated electron. Their formation
yields may not sufficient to cause the crosslinking of cellulose.
Therefore, water was added to sample solution to enhance the
radiation-induced crosslinking of cellulose. A chemical gel was
obtained by the γ-ray irradiation of cellulose in EMI-acetate under
humid condition at a dose of 10 kGy. The yield of the cellulose
chemical gel increased with a water content in EMI-acetate.
Thereby water would play a crucial role to be the source of the

http://dx.doi.org/10.1016/j.radphyschem.2015.10.025
0969-806X/& 2015 Elsevier Ltd. All rights reserved.
 A. Kimura et al. / Radiation Physics and Chemistry 124 (2016) 130–134
reactive species for the crosslinking of cellulose and control the
crystallinity of cellulose in EMI-acetate. Water is decomposed by
the ionizing radiation, resulting in the formation of a hydroxyl
(OH) radical, hydrated electron, hydrogen atom, proton and hy-
droxide ion (Getoff, 1996). The OH radical especially is produced at
high yield upon water radiolysis and has the high reactivity toward
saturated hydrocarbons (Buxton et al., 1988). The radiation-in-
duced crosslinking of cellulose is considered to be initiated by the
OH radical. On the other hand, the OH radical is also scavenged by
the alkylimmidazolium-based RTILs to form their radicals (Behar
et al., 2001; Wishart et al., 2005).
Reaction of cellulose with the OH radical in RTILs is not made
clear, and it is important to clarify its reaction mechanisms under
humid condition. The yields of the radiation-induced OH radicals
changing with water contents in carboxylate-based RTILs, EMI-
acetate, were investigated by use of the scavenging method in the
present study. Cellulose gel was also produced using fluorescent
carboxylate-based RTILs to confirm the involvement of RTILs to the
crosslinking of cellulose. XPS analysis of the cellulose gel was
carried out to investigate chemical structures and components in
detail. Moreover, chitin gels were also produced in RTILs by io-
nizing radiation. Chitin is the second large quantity polysaccharide
next to cellulose and widely distributed over nature as cell wall
components of fungi, seaweeds and crustaceans. On the other
hand, no radiation-crosslinking material has been produced
without chemical modification as well as cellulose. The outcomes
of these studies are expected to provide insights on new ways of
functionalizing materials including cellulose, chitin and other
natural polysaccharides.
2. Experimental
2.1. Sample preparation and γ-ray irradiation
Cellulose (Microcrystalline grade, Merck) and chitin (Funakoshi
Co., Ltd.) were used as received and dissolved in the solution of
9 wt% LiCl (Wako, 98%) in N, N-dimethylacetamide (DMAc, Wako,
97%). Their viscosity-average molecular weights were measured
using an Ostwald viscometer to be 1.2  105 and 9.3  104 g mol  1,
respectively. These polysaccharides at initial concentrations in the
range 10–30 wt% were mixed with each RTILs to obtain paste-like
solutions. 1-Ethyl-3-methylimidazolium acetate (EMI-acetate, Al-
drich, 90%) and 1-butyl-3-methylimidazolium chloride (BMI-
chloride, TCI, 98%) were purchased and used without further
purification. 1, 3-Dibutylimidazolium acetate (DBI-acetate) was
synthesized by anion exchange with DBI-chloride (Fukaya et al.,
2008), which has been reported as a highly fluorescent hydrophilic
ionic liquid (Chen et al., 2011). All the sample solutions were
prepared in a glove box (Sanplatec) under dry or wet air saturated
conditions, and the water contents were controlled by changing
the humidity of the surrounding air. Phenol (Wako, 499.0%) was
used as a scavenger to estimate the yield of the OH radical in RTILs.
The cellulose and chitin solutions were irradiated using a 60Co
γ-ray source at the Japan Atomic Energy Agency, Takasaki, in the
dose range of 5–100 kGy (Gy¼J kg  1) with the dose rates ranging
from 5 to 10 kGy h  1. Dosimetric experiments were carried out
with an ethanol–chlorobenzene dosimeter and an alanine-based
dosimeter (Kojima et al., 1993; Kimura et al., 2014).
2.2. Analysis of polysaccharide gels
The irradiated sample solutions were washed with a solution of
5 wt% LiCl/DMAc on a stainless steel mesh (SUS316, 200 mesh) for
2 days. Residual matters were washed with water and ethanol
repeatedly for 2 days, and then vacuum-dried in oven at 353 K for
131
2 days. The yield of the gel was estimated by the following
equation:
Gel fraction (%) = ( W /W0 ) × 100 (1)
where W0 and W are the initial mass of the dried sample before
irradiation and the final mass of the insoluble product obtained
after irradiation, washing, and drying, respectively. Infrared spec-
tra of the sample solutions before and after γ-ray irradiation were
recorded by use of FTIR spectrophotometer (Shimadzu, FTIR-
8900). The XPS measurements were performed with ULVAC-PHI,
PHI 5000 Versa Probe II spectrometer using Al Kα (hν ¼1486.6 eV)
X-ray radiation. Spot size of X-rays for measuring was 100 μm.
Survey scans over 0–1100 eV binding energy range with 1.0 eV
step were taken at an analyzer pass energy of 117.4 eV. Absorption,
emission, and excitation spectra of the polysaccharide gels before
and after irradiation were measured with an absorbance (HITACHI,
U-3300) and fluorescent spectrophotometer (HITACHI, F-4500). An
HPLC (Agilent, 1100 series) with a reversed phase column (Shodex,
RSpak DE-613 and GL Sciences, Inertsil C8-3) at 313 K was used for
analyses of phenol in RTILs before and after γ-ray irradiation. Flow
rate of 30 vol% acetonitrile in 1.0  10  2 mol dm  3 phosphoric
acid aqueous solution as an eluent was 1.0  10  3 dm3 min  1, and
the sample solutions were injected at 2.5  10  4 dm3 in the HPLC.
Absorbance of phenol and its irradiation products were monitored
at 280 nm using a UV/VIS detector (Waters, 2487 Dual λ Absor-
bance Detector).
3. Results and discussion
3.1. Estimation of the yields of hydroxyl radicals in RTILs under hu-
mid condition
Phenol was selected as a scavenger because the OH radical rapidly
attack phenol with the rate constant of kOH ¼6.6  109 mol  1 dm3 s  1
(Field et al., 1982), while the hydrated electrons (e  ) and hydrogen
atoms (H) react slowly with phenol (ke ¼ 2  107 mol  1 dm3 s  1,
kH ¼1.7  109 mol  1 dm3 s  1) (Buxton et al., 1988). G-values of the
primary yields of OH radicals, e  and H are 2.7, 2.6 and 0.6 in water by
γ-ray irradiation (Buxton et al., 1988), and more than 94% of phenol
molecules were degraded by OH radicals in the presence of oxygen
(Field et al., 1982; Elliot et al., 1990; Kimura et al., 2012). Scavenging
capacity of phenol with OH radicals in EMI-acetate is estimated by
following equation (Eq. (2)).
Scavengingcapacity = k OH × [Scavenger] (2)
3
20 wt% cellulose is calculated to be 1.2 mol dm in a mono-
mer unit and the rate constant of cellulose monomer unit with the
OH radical is assumed to be about 5  107 mol  1 dm3 s  1 by that
of saturated hydrocarbons (Buxton et al. 1988). The scavenging
capacity can be calculated to be 6  107 s  1. Thereby the initial
concentration of phenol was set at 10  10  3 mol dm  3 because
the rate constant is 6.6  109 mol  1 dm3 s  1. The yield of the OH
radicals estimated using phenol/EMI-acetate solution can be ap-
plied to cellulose/EMI-acetate solution. Phenol in water reacts with
the radiation-induced OH radical to produce catechol and hydro-
quinone mainly (Hashimoto et al., 1979), and the yield of the OH
radical could be evaluated as the sum of G-values of catechol and
hydroquinone formations. Schuler and many researchers have
been already reported that dimerization of phenol is occurred by
ionizing radiation of phenol aqueous solution under deoxygenated
condition such as N2O and N2 saturated (Ye and Schuler, 1989;
Taguchi et al., 2006). However, production yields of phenol dimers
in this experiment are considered to be low from the following
two points: (1) production of OH-adducts from phenol by OH
132
10000
Concentration of phenol (µ mol dm-3)
9800
Phenol
Catechol
9600
Hydroquinone
9400
9200
9000
0 5
Dose (kGy)
Fig. 1. Concentration of phenol, catechol and hydroquinone in EMI-acetate with
water content of 34% as function of dose under air saturated condition.
Table 1
Water content dependence of G-values of phenol and its irradiation products in
EMI-acetate.
Water contents (w/w%) 0 2
1
G(-Phenol)/(100 eV) 0 0.03
G(Catechol)/(100 eV)  1 nd 0.002
G(Hydroquinone)/(100 eV)  1 nd nd
G(OH)/(100 eV)  1 0 0.002
radicals which is a competitive reaction of dimerization is en-
hanced by dissolved oxygen under aerated condition (Hashimoto
et al., 1979; Mvula et al., 2001). (2) Reaction efficiency of dimer-
ization of phenol increases with dose rate of ionizing radiation (Ye
and Schuler, 1989; Taguchi et al., 2006). Dose rate of γ-rays in this
work (10 kGy h  1 ¼ 2.8 Gy s  1) is about one thousandth of that of
electron beam. Concentration of phenol at 10  10  3 mol dm  3 in
EMI-acetate with water content of 34% decreased with the in-
creasing absorbed dose, and those of catechol and hydroquinone
increased as shown in Fig. 1. G-values of phenol and their irra-
diation products were estimated from the slope of the fitted lines
in Fig. 1. The G-value of the OH radical formation (sum of G-value
of catechol and hydroquinone) increased from 0.002 to 0.043 in
the range of water content from 2 to 34 wt% as shown in Table 1.
Crosslinking mechanisms of cellulose in EMI-acetate under
humid condition are represented as follows. As can be seen in
Table 1, the OH radical reacts with cellulose in EMI-acetate under
humid condition more than 18% of water content without being all
scavenged by EMI-acetate (Eq. (3)) because of the decrease in the
concentration of EMI-acetate.
 OHþ EMI þ -HO  EMI þ 
Moreover, water content in EMI-acetate increased the yield of
the OH radical, which abstract hydrogen from cellulose to produce
cellulose radicals (Isogai and Kato, 1998).
[Cellulose]  Hþ  OH-[Cellulose]  þH2O
Generally speaking, the stability and reactivity of the radicals
are important factors for crosslinking of polymer main chain. In
solid state, the radicals are stable but its reactivity is less so as not
to be crosslinked. While in liquid state, the radicals have high re-
activity but less stability so most of polymers are mainly decom-
posed. Fei et al. found a suitable paste-like condition using water
for crosslinking of polysaccharide derivatives under γ-ray
A. Kimura et al. / Radiation Physics and Chemistry 124 (2016) 130–134
Concentration of OH-adducts (µ mol dm-3)
irradiation (Fei et al., 2000). The radiation-induced grafting of
100 monomer to cellulose also has improved in RTILs (Hao et al.,
2009), and it can be considered to be due to the stabilization of the
cellulose radicals in RTILs. Thereby the production of the cellulose
80
gel is considered to be achieved by preparing a paste-like solution
composed of water and RTILs as a reaction field for the radiation
60 crosslinking. The radicals are considered to react with each other
to form the cellulose gel under humid conditions as represented in
Eq. (5).
40
[Cellulose]  þ[Cellulose]  -[Cellulose] [Cellulose] (5)
On the other hand, EMI radicals (Eq. (3)) acting the crosslinking
20 agent may react with the cellulose.
[Cellulose]  HþHO-EMI þ  -[Cellulose] EMI þ  þH2O (6)
0
10 15
3.2. Analyses of molecular structure of radiation-crosslinked cellu-
lose gel
3.2.1. Fluorescent analysis of cellulose gel produced in DBI-acetate
Emission spectrum of DBI-acetate with a maximum wavelength
at 395 nm was detected when excited at 323 nm and was similar
to that of DBI-chloride. The 20 wt% cellulose DBI-acetate solution
with a water content of 18 wt% was irradiated with γ-rays at a
dose of 10 kGy under humidity-controlled air conditions, followed
7 18 34
by washing with the LiCl/DMAc solution to produce the cellulose
0.03 0.08 0.1 gel with the yield of 20%. Emission and excitation spectra of the
0.002 0.006 0.024 crosslinked cellulose gel after the washing and drying were ob-
nd 0.002 0.019
tained as shown in Fig. 2. Emission spectrum of the crosslinked
0.002 0.008 0.043
cellulose gel with a maximum wavelength at 415 nm was detected
when excited at 323 nm, while that of neat cellulose was not.
These results indicate that DBI-acetate is also incorporated in the
cellulose gel. Most imidazolium-based RTILs have asymmetrical
immidazolium rings due to different alkyl substitutes, but DBI-
acetate has the symmetrical one. Butyl substitutes linking to N
atoms in DBI enhanced not only the symmetry but also the degree
of the planarity and rigidity, which contributed to the improve-
ment of the conjugations of the π–π* bonds (Chen et al., 2011). The
fluorescence spectrum of the cellulose gel was red-shifted about
20 nm from that of original DBI-acetate, indicating that chemical
structure of butyl substitutes in DBI-acetate changed, for example
connecting to the cellulose main chain, by γ-ray irradiation
Intensity (a.u.)
(3)
(4)
300 400 500
Wavelength (nm)
Fig. 2. Fluorescence spectra of the crosslinked cellulose gel. Dotted line: excitation
spectrum monitored at 415 nm. Line: emission spectrum excited at 323 nm.
 A. Kimura et al. / Radiation Physics and Chemistry 124 (2016) 130–134 133

consequently to decrease the symmetry.

Cellulose should be oxidized with the OH radical to produce
100
cellulose radicals as mentioned in Eq. (4). Reaction of cellulose
radicals with DBI þ is considered to be occurred simultaneously
with the direct crosslinking of cellulose radicals (Eq. (5)) because 80

Gel fraction (%)

polymer chains of cellulose are solvated by carboxylate-based
RTILs (Heinze et al., 2005; Fukaya et al., 2008). Note that DBI-
acetate is assumed to act as the crosslinking agent of cellulose by 60
the result of the fluorescent measurement of the cellulose gel.

2[Cellulose]  þ DBI þ -[Cellulose] DBI þ  [Cellulose] (7)

40
3.2.2. XPS analysis of cellulose gels
Chemical structure change of cellulose in EMI-acetate by γ-ray
irradiation was also investigated by FT-IR measurement but the
20
spectra before and after irradiation were almost the same. This
result indicates that most of cellulose keeps original molecular
structure even after the irradiation. XPS analysis of the cellulose 0
gel, therefore, was carried out to investigate chemical structures
0 20 40 60 80 100
and components in detail. XPS spectra of neat cellulose and the
cellulose gels were recorded and shown in Fig. 3.
Dose (kGy)
The expected elements, C and O, of neat cellulose were de- Fig. 4. Gel fraction of 10 wt% chitin in BMI-chloride with water content of 17 wt% at
tected in the spectrum (Fig. 3a), while additional weak N(1S) peak 298 K as function of absorbed dose. Solid line is a guide to the eye.
was obtained in that of the cellulose gel (Fig. 3b). A calculation of
the chemical composition based on the observed peak areas of Halide-based RTILs could dissolve the chitin at 10 wt% but car-
neat cellulose (a) and the cellulose gel (b) lead to C:O:N ratios of boxylate-based RTILs does not. Because ionic radii of carboxylate
6.0:5.2:0 and 6.0:4.2:0.1. The error of the ratio of the chemical are larger than that of halide, which do not really affect steric
composition is 73%. Solid cellulose under deoxygenated condi- hindrance to chitin having branched side chains. The paste-like
tion is degraded by ionizing radiation to produce hydrogen, carbon solution of chitin in BMI-chloride with water contents of 17 wt%
monoxide and carbon dioxide, and the corresponding yields have was irradiated with γ-rays at a dose of 80 kGy, and then washed
been reported to be 3.2, 6.0 and 0.9, respectively (Tissot et al., with 5 wt% LiCl/DMAc solution to obtain the chitin gel at a yield of
2013). Decrease in the oxygen ratio of the cellulose gel is due to be 80%. The fraction of the chitin gel increased with dose and reached
the carbon monoxide and carbon dioxide developed from cellulose 86% at 60 kGy, and when irradiation dose exceeded it, the gel
after the irradiation. The N(1S) peak in the XPS spectrum was
fraction decreased slightly due to the degradation as shown in
considered to be derived from the EMI-acetate. It is calculated
Fig. 4.
from the C:O:N ratio of the cellulose gel that EMI-acetate molecule
The crosslinking density (p0/q0) for 10 wt% chitin in BMI-
is attached to a rate of one to 20 cellulose monomers.
chloride was estimated using the Charlesby–Rosiak equation (Eq.
(8)) to be 0.62 (Olejniczak et al., 1991).
3.3. Production of chitin gel in RTILs by ionizing radiation
p0 ⎛ p ⎞ D v − Dg
s + s1/2= +⎜ 2 − 0 ⎟
Based on the result of the production of the radiation-cross- q0 ⎝ q0 ⎠ D v −D (8)
linked cellulose gel, modification of chitin in RTILs was carried out
by ionizing radiation. Chitin is a branched polysaccharide and has The crosslinking in BMI-chloride occurs more effectively than
a similar molecular structure of cellulose. But no radiation-cross- the scission reaction to obtain chitin gel as well as cellulose though
linked material has been also produced from chitin directly. the chitin has radiation degradability. No chitin gel was produced

O 15000
O
20000
Intensity (a.u.)
Intensity (a.u.)

10000 C
C
10000
5000
N(1S)

0 0
1000 800 600 400 200 0 1000 800 600 400 200 0
Energy (eV) Energy (eV)
Fig. 3. X-ray photoelectron spectroscopy spectra of (a) neat cellulose and (b) radiation-induced cellulose gel.
134 A. Kimura et al. / Radiation Physics and Chemistry 124 (2016) 130–134
in BMI-chloride under dehydrated condition by ionizing radiation.
Thereby water is also important for the crosslinking of chitin as
well as cellulose. The chitin gel is considered to be produced by the
crosslinking with side chain of acetylamino group, which react
with radiation-induced OH radicals to produce acetoamide radi-
cals (Smith and Wood, 1966). By establishing the radiation cross-
linking technology of chitin, the radiation crosslinking of other
natural polysaccharide having radiation degradability such as
chitosan, alginate and starch are expected in RTILs with water.
4. Conclusion
Water plays a crucial role to be the source of the radiation-
induced OH radical for the crosslinking of cellulose in RTILs. The
cellulose gel was produced by γ-ray irradiation in fluorescent
carboxylate-based RTILs. Emission spectrum of the crosslinked
cellulose gel has the slightly red-shifted emission of DBI-acetate,
indicating that carboxylate-based RTIL would act as the cross-
linking agent of cellulose. Radiation-crosslinked cellulose gel in-
clude N atom, which is considered to be derived from the EMI-
acetate. The chitin gel was first produced in EMI-chloride by γ-ray
irradiation at high yield. The radiation induced crosslinking tech-
nique using RTILs has great potential for creation of functional
biocompatible and biodegradable materials.
Acknowledgments
This work was supported in part by the JSPS KAKENHI Grant
number 25871093.
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