ISSN 0965545X, Polymer Science, Ser. A, 2014, Vol. 56, No. 2, pp. 205–210. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Dubrovskii, A.N. Zelenetskii, S.A. Uspenskii, V.N. Khabarov, 2014, published in Vysokomolekulyarnye Soedineniya. Ser. A, 2014, Vol. 56, No. 2,
pp. 206–212.
205
INTRODUCTION
Sodium hyaluronate is the sodium salt of hyalu
ronic acid, a highmolecularmass biopolysaccharide
of the glycosaminoglycan family. A molecule of hyalu
ronic acid is built of regularly alternating disaccharide
units composed of residues of Dglucuronic acid and
NacetylDglucosamine. In disaccharide units, ami
nosaccharide is linked to Dglucuronic acid via β1,4
glycosidic bonds, while the disaccharide units are con
nected via β1,3glycosidic bonds [1]. The carboxyl
groups of hyaluronic acid impart it with polyelectro
lyte properties, so that, in aqueous solutions, the acid
is charged negatively. Note that, if a macromolecule
occurs in the form of the sodium salt, almost all disac
charide units are charged.
The rheological properties of sodium hyaluronate
solutions are of interest for the development of ideas
about many biological processes. For example, it has
been proposed that they determine the mechanical
properties of synovial fluid and the study of these
properties is important for gaining insight into the
mechanisms of joint lubrication and diseases of joints.
The rheological properties of sodium hyaluronate
solutions have been the subject of many studies [2–
10]. As is shown in [3, 5–10], the viscosity values of
aqueous solutions of this polymer strongly depend on
shear rate . In a wide range of values, viscosity
decreases with an increase in shear rate. However, at
very low shear rates, which depend on the molecular
mass and concentration of the polymer, Newtonian
behavior is observed. The rheology of hyaluronic acid
solutions is extremely sensitive to the presence of pro
tein admixtures in solution, which lead to the aggrega
tion of polymer chains (formation of transient physi
cal crosslinks, that is, gels) [3, 6]. Aggregation is prac
tically absent in the case of hyaluronic acid of the
bacterial origin and may be distinct in the case of ani
mal hyaluronic acid. Proteinfree solutions of sodium
hyaluronate in a buffer salt solution simulating physi
ological conditions are viscoelastic liquids featuring
behavior typical for solutions of linear polyelectrolytes
at a high concentration of the salt [6].
The addition of borax to the solution of sodium
hyaluronate makes it possible to obtain
10
Bcontaining
pharmaceutical preparations that show promise for
the neutroncapture therapy of tumor diseases [11].
These preparations are complex compounds formed
via the wellknown reaction of sugar binding with
borate, a reaction that is in wide use in the analytical
chemistry of boron and sugars [12]. The existence of
hyaluronic acid complexes with borax has been con
firmed in IR studies [11]. These complexes are stable
γ
·
γ
·
Effect of Borax Additives on the Rheological Properties
of Sodium Hyaluronate Aqueous Solutions
S. A. Dubrovskii
a,
*, A. N. Zelenetskii
b
, S. A. Uspenskii
c
, and V. N. Khabarov
c
a
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow, 119991 Russia
b
Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences,
Profsoyuznaya ul. 70, Moscow, 117393 Russia
c
Martinex Research Centre, Vtoraya Vladimirskaya ul. 12, korp. 3, Moscow, 111123 Russia
*email: sd@chph.ras.ru
Received July 5, 2013;
Revised Manuscript Received October 11, 2013
Abstract—The rheological properties of sodium hyaluronate aqueous solutions are studied, and the effect of
borax additives on them is investigated. It is shown that, at low concentrations, sodium hyaluronate behaves
as a typical linear polyelectrolyte in the limit of a high concentration of the salt in both a 0.1 M NaCl aqueous
solution and a saltfree solvent. The addition of 1 mole of borax per basemole of the polymer to the solution
of sodium hyaluronate significantly decreases the specific viscosity of the solution if no salt is added and has
practically no effect on the viscosity of the solution in 0.1 M NaCl. The viscosity of a semidilute solution of
sodium hyaluronate without the added salt decreases as the shear rate is increased in the range 1.5–656 s
–1
.
With an increase in temperature, viscosity decreases and its dependence on shear rate becomes less pro
nounced. The same effect is exerted by small amounts of borax. The properties of saltfree solutions are
explained by the presence of admixtures of lowmolecularmass ions in them that screen the Coulomb repul
sion of charges linked to sodium hyaluronate chains, and the effect of borax may be rationalized by the
screening effect of ions resulting from the hydrolysis of borax.
DOI: 10.1134/S0965545X14020047
RHEOLOGY