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ISSN 1061933X, Colloid Journal, 2012, Vol. 74, No. 6, pp. 645648. Pleiades Publishing, Ltd., 2012.

Original Russian Text V.Yu. Baranovskii, V.G. Ganev, V.B. Petkova, Kh.Ch. Voicheva, M.V. Dimitrov, 2012, published in Kolloidnyi Zhurnal, 2012, Vol. 74, No. 6, pp. 675679.

Hydrogels Based on Polycarboxylic AcidAgarAgar Complexes

V. Yu. Baranovskiia, V. G. Ganeva, V. B. Petkovab, Kh. Ch. Voichevaa, and M. V. Dimitrovb
Institute of Polymers, Bulgarian Academy of Sciences, ul. Akad. G. Bonchev 103, Sofia, 1113 Bulgaria
Sofia Medical University, Pharmaceutical Department, ul. Dunav 2, Sofia, 1000 Bulgaria
Received December 19, 2011

AbstractIR spectroscopy and viscometry data have shown that poly(acrylic acid) and poly(methacrylic
acid) form complexes with agaragar in aqueous solutions as they do with other polysaccharides. The poly
acidagaragar complexes are typical hydrogels. The swelling index of hydrogels based on the poly(meth
acrylic acid)agaragar complex has been found to be markedly lower than that of poly(acrylic acid)agar
agar complex. The hydrogels based on the complex of crosslinked poly(acrylic acid) with agaragar can be
of practical interest as polymeric carriers for drugs.
DOI: 10.1134/S1061933X12060026

INTRODUCTION The AA macromolecule contains up to 80% of aga

Agaragar (AA) hydrogels are widely applied in rosea linear polysaccharide consisting of alternat
various fields of human activity, e.g., in the light and ing residues of 30substituted Dgalactopyranose
food industries, agriculture, biotechnology, microbi and 40substituted 3,6anhydroLgalactopyra
ology, pharmacology, medicine, etc. nose:

CH2 H CH2 H H O 1
O H O 1 O 3 H OH 1
4 H
O 4 O
3 H OH 1 H

AA dissolves in water at 8385C with the forma Being a polysaccharide, AA must also form com
tion of a true solution. Subsequent cooling of a solu plexes with PAA and PMAA. However, there are no
tion with a concentration above 0.5% to 3540C data in the literature on the interaction of AA with the
gives rise to a hydrogel. above polyacids in aqueous solutions. Therefore, the
The sources of AA are red and brown see algae; i.e., goal of this work is to study the complexation of AA
AA is a renewable natural substance. with PAA and PMAA in aqueous media.
By its chemical structure, AA belongs to the class of
polysaccharides. There are numerous reports devoted EXPERIMENTAL
to the investigation of the complexation of polysac
charides with polycarboxylic acids, namely, PAA and PMAA were obtained by heterogeneous
poly(acrylic acid) (PAA) and poly(methacrylic acid) polymerization of the corresponding monomers in
(PMAA), in aqueous solutions (see, e.g., [115]). Var toluene under nitrogen at 60C using AIBN as an ini
ious cellulose derivatives, such as methyl [15], tiator. Residual monomers were washed off with tolu
hydroxyethyl [68], hydroxypropyl [913], and ene. The resulting polyacids were dried in vacuum at
hydroxypropylmethylcellulose [14, 15], are mainly 70C to a constant weight. The molecular masses of
used as polysaccharides. The physicochemical proper the polymers thus obtained were determined by vis
ties of the resulting complexes have been studied as cometry. For PAA, [] = (1.05 103) 0.54 in 2N
functions of medium pH and temperature, reagent NaOH at 25C [16] and, for PMAA, [] = (6.6
concentrations, and ionic strength of solutions. In 10 4)M 0.5 in 0.002 N HCl at 30C [17]. According to
most cases, the complexes have a nonstoichiometric the viscometry data, = 2.3 105 and = 9 104
composition. for PAA and PMAA, respectively.

646 BARANOVSKII et al.

sp washed with distilled water and dried at 60C to a con

0.09 stant weight. Swelling indices Q were determined in
1 the same way as in the case of the hydrogel of the
0.08 PAA/AA complex.
0.07 IR spectra were measured with a Bruker spectrom
0.06 3 eter using samples pelleted with KBr. Differential
spectra were obtained by subtracting the IR spectrum
of AA from the IR spectra of PMAA/AA or PAA/AA
0.04 complexes.
0.01 Figure 1 shows the dependences of specific viscos
ity sp of aqueous mixed solutions of AA with PAA and
0 0.5 1.0 1.5 2.0 PMAA at a constant concentration of a polyacid (PA)
= [AA]/[PA] on the = [AA]/[PA], mass/mass, ratio, where [AA]
is the mass concentration of AA and [PA] = const =
Fig. 1. Dependences of specific viscosity sp on for 0.01 g/dL. At low AA concentrations, the system
mixed aqueous solutions of (1) PAA with AA and forms true solutions without gelation.
(2) PMAA with AA and (3) aqueous solution of free AA at The incorporation of AA macromolecules into a
CPA = 0.01 g/L and 25.
solution of a free PA leads to a decrease in solution sp.
This effect results from the formation of PAAA com
AA (for microbiological purposes, Fluka) was used plex particles, which have a more compact conforma
as received. tion than initial PAA or PMAA macromolecules have.
The compaction of the complex particles is caused by
The interaction between the polyacids and AA was the formation of hydrogen bonds between COOH
studied in dilute aqueous solutions. AA concentration groups of a PA and OH groups of AA and, as a conse
was no higher than 0.02% to exclude gelation. The vis quence, the hydrophobization of the interaction prod
cometric measurements were performed using an uct.
Ubbelohde capillary viscometer with a thermostating The value of that corresponds to the minimum of
accuracy of 0.1. the sp() dependence is in consistence with the com
AApolyacid complexes were obtained by mixing position of a PA/AA complex. However, at this value
equal volumes of aqueous 2% solutions of the compo of , the number of hydrogen bonds between COOH
nents at 8590. At this temperature, an aqueous groups of a polyacid and OH groups of AA in the com
AA + polyacid mixed solution represented a homoge plex is far from maximum. This is reasonable, because
neous transparent system. Subsequent cooling to there are substantial steric hindrances for the forma
room temperature yielded a hydrogel, which was dried tion of maximum possible number of hydrogen bonds.
at 60C to a constant weight. An individual AA hydro It is essential only that the observed sp dependence
gel was obtained through AA dissolution in water at indicates the fact of the complexation between the
8590C followed by cooling to room temperature. To polyacids and AA.
estimate swelling indices Q, dried samples of the com An increase in sp is associated with the accumula
plexes were placed into aqueous solutions with tion of free, uncomplexed AA macromolecules in the
required pH values. The Q value was calculated by the solutions. This is supported by the concentration
formula Q = (m m0)/m0, where m and m0 are the dependence of sp for solutions of free AA.
masses of a sample swollen to the equilibrium state and Thus, the viscometry data show that AA forms
an initial dry complex, respectively. complexes with PAA and PMAA in aqueous solutions.
Hydrogels based on crosslinked PAA and AA were Figure 2 demonstrates the IR spectra of (1) PAA
obtained by redox polymerization of acrylic acid and (2) PMAA, as well as the differential IR spectra of
(AAc) in aqueous solutions of AA at 85C using N,N (3) PAA/AA and (4) PMAA/AA complexes relative to
methylenebisacrylamide (MBAA) as a crosslinking the spectrum of free AA. As can be seen from the com
agent and (NH4)2S2O8 + Na2S2O5 as a redox initiator. parison of spectra 1 and 3, the absorption band at
Reaction mixtures of the following compositions were 1711 cm1, which corresponds to the stretching vibra
applied: (1) 20 mL 2 + 1 g AA + 1 mL AAc + 0.1 g tions C=O in free PAA, shifts to 1736 cm1 upon its
MBAA + 0.005 g (NH4)2S2O8 + 0.005 g Na2S2O5 and complexation with AA. The highfrequency shift of
(2) 20 mL 2 + 1 g AA + 1 mL AAc +0.05 g the stretching vibration bands C=O in the IR spectra of
MBAA + 0.005 g (NH4)2S2O8 + 0.005 g Na2S2O5. PAA and PMAA upon complexation with polysaccha
The compositions of both of the reaction mixtures dif rides is explained as follows. The formation of a chem
fered only in the content of the crosslinking agent: in ical (covalent or hydrogen) bond between the func
mixture 2, MBAA concentration was half that in tional groups of interacting polymers increases the
mixture 1. Resulting hydrogels were repeatedly energy required for the excitation of stretching vibra

COLLOID JOURNAL Vol. 74 No. 6 2012