ESR study of carboxymethyl cellulose radical

formed by OH radical attack

Seiichi Saiki*, Naotsugu Nagasawa, Akihiro Hiroki, Norio Morishita, Masao Tamada,
Hisaaki Kudo, Yosuke Katsumura
453-2 Watanuki Takasaki Gunma
370-1292
Japan Atomic Energy Agency
Takasaki, Gunma, Japan
saiki.seiichi@jaea.go.jp
Carboxymethyl cellulose (CMC) [Fig.1] at highly
OR
concentrated
aqueous
solution
undergoes
CH2OR
RO
crosslinking reaction and gelation by ionizing
O
O
O
O
irradiation, though cellulose and its derivatives are
O
CH2OR
usually
classified
to
radiation-degradation
OR
RO
polymer.1,2,3 The radiation-induced reaction
R: CH2COO- or H
mechanism of CMC aqueous solution has not been
Figure 1: Carboxymethyl cellulose (CMC)
known well. Radiation-induced crosslinking and
degradation of polymer aqueous solution are generally caused by reaction with water
radiolysis products, especially OH radical. In this topic, ESR spectra of CMC radical, formed
by reaction with OH radical, were measured directly in aqueous solution to discuss about
CMC radical related to crosslinking reaction.
In our ESR measurement, two methods as the origin of OH radical were used, UV-photolysis
of hydrogen peroxide (H2O2) and electron beam irradiation. In case of UV-photolysis, mixed
CMC/H2O2 aqueous solution was flown through a flat quartz cell fitted to the cavity of Xband ESR spectrometer (JEOL JES-TE200), and OH radicals were produced by UVirradiation into the cavity. Sample solution was continuously flown during measurement with
N2 gas bubbling to remove O2. As for electron beam irradiation, CMC aqueous solution with
N2O gas bubbling was irradiated by electron accelerator (energy: 2MeV). ESR measurements
were started 6 min after irradiation.
As a result of UV-photolysis experiment, ESR spectra of CMC radical formed by reaction
with OH radical were successfully observed in aqueous solution [Fig.2]. To assign the spectra,
two kinds of radical candidates, radicals located on carbon atom of glucopyranose ring or
carboxymethyl groups, should be considered because OH radical generally abstracts
C6

Intensity /a.u.

RO

OR

OCHCOO-

RO

CH2OCHCOOO

0.5 mT

CH2OR
O

C2
CH2OR
O

O
-OOCHCO

Magnetic field /mT

Figure 2: ESR spectrum of CMC radicals

(10mM CMC/ 10mM H2O2, UV-irradiation)

R : CH2COO- or H

OR

C3

Figure 3: Radicals located on carboxymethyl groups

hydrogen atom on carbon atom from organic solute. Compared about split pattern and
hyperfine coupling constant with similar radical4,5 to radical candidates, experimental ESR
spectra were separated as overlapping of [Triplet x Doublet] and [Doublet], and each
spectrum was identified as radicals located on the secondary carbon atom of carboxymethyl
groups linking to C6 and C2/C3 [Fig.3].
As for electron beam irradiation, almost same spectra as the case of UV-photolysis
experiment were observed even 6min after irradiation. This means that long-lived CMC
radicals are formed by OH radical attack and located on carboxymethyl groups.
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