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Effect of pH on Swelling Profile of Glutaraldehyde Crosslinked Adenanthera

pavonina L. Galactomannan

Article in IOP Conference Series Materials Science and Engineering · June 2020
DOI: 10.1088/1757-899X/809/1/012023

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Effect of pH on Swelling Profile of Glutaraldehyde Crosslinked

Adenanthera pavonina L. Galactomannan
To cite this article: L A Cavalcante et al 2020 IOP Conf. Ser.: Mater. Sci. Eng. 809 012023

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ICAMC 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 809 (2020) 012023 doi:10.1088/1757-899X/809/1/012023

Effect of pH on Swelling Profile of Glutaraldehyde

Crosslinked Adenanthera pavonina L. Galactomannan

L A Cavalcante1, a, B S Batista2, b, A P G Fonseca3, c, A J D Balteiro3, d, F M B

Amaral4,8, e, F Mendes5,6,7, f, A A M Macêdo1, g.
1
Federal Institute of Education, Science and Technology of Maranhão, IFMA,
Research Laboratory, Imperatriz, Brazil; 2Federal University of Maranhão, UFMA
Advanced Campus, Imperatriz, Brazil;3Polytechnic Institute of Coimbra, ESTESC
Coimbra Health School, Department Biomedical Laboratory Sciences, Coimbra,
Portugal; 4Polytechnic Institute of Coimbra, ESTESC Coimbra Health School,
Department Complementary Sciences, Coimbra, Portugal;5Polytechnic of Coimbra,
ESTeSC, DCBL, Coimbra, Portugal; 6CNC. IBILI Consortium/ Center for Innovative
Biomedicine and Biotechnology (CIBB), University of Coimbra, Coimbra, Portugal;
7
Biophysics Institute, Coimbra Institute for Clinical and Biomedical Research (iCBR)
area of Environment Genetics and Oncobiology (CIMAGO), Faculty of Medicine,
University of Coimbra, Coimbra, Portugal.8I3N - University of Aveiro, Aveiro,
Portugal.

a
[email protected], [email protected],
c
[email protected], [email protected],
e
[email protected], [email protected] and
g
[email protected].

Abstract. Galactomannans are neutral natural polymers isolated from legume endosperm and
with wide use in the biomedical field. As a consequence, there is a need to investigate
materials for their properties in order to better understand and apply them. In this study, we
analyzed the influence of pH medium on the crosslinking process of galactomannan and
glutaraldehyde, changing the pH medium from 3 to 7, using a strong base. The Fourier
Transform Infrared Spectrum (FTIR) and the swelling profiles of the glutaraldehyde
crosslinked galactomannan were evaluated. We have found that the glutaraldehyde-
galactomannan crosslinking process is highly sensitive to the variation of pH medium.
According to our results, best swelling capacity was achieved for samples prepared at pH=5,
suggesting that this pH medium conditions is suitable for possible production of hydrogels
prepared from glutaraldehyde-galactomannan.

1 Introduction
Polymers are macromolecules with physical properties that depend on factors such as chemical
composition, mechanical configuration and length of the polymer chain [1]. Polysaccharides are
polymers joined by glycosidic bonds in the α or β forms. They are rich in OH groups, able to form
intra or intermolecular hydrogen bridges, which favors the control of solubility [2,3].
Galactomannans are polysaccharides composed of (Figure 1) D-mannose and D-galactose [4]. They
present a linear skeleton consisting of D-mannopyranose β - (1 → 4). According to Dea and Morrison
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ICAMC 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 809 (2020) 012023 doi:10.1088/1757-899X/809/1/012023

[5] there is substitution of D – mannopyranose (C - 6) hydroxyl for D – galactopyranose α - (1 → 6) in

varying degrees of substitution. What differs in galactomannans is the mannose / galactose ratio as
well as the species-dependent distribution throughout the skeleton of mannopyranose.

Figure 1. Galactomannan crosslinking with Glutaraldehyde.

In polymers, the crosslinking process increases mechanical and chemical resistance as well as
decreases deformation. In the production of hydrogels, the crosslinking agents must have molecules
with low molar mass and reactive functional groups to allow intercrossing between polymer chains [6].
In this study, Adenanthera pavonina L. galactomannan was crosslinked with glutaraldehyde (0.3
mol/L) using different pH medium, ranging from 3 to 7, in order to study its influence on the
crosslinking process. Fourier transform infrared spectroscopy was used to identify existing functional
groups and changes between different samples according to the pH variation of the preparation
medium. Also the determination of the swelling degree was performed for all the samples, considering
the importance of this characteristic for future applications of this biomaterials as hydrogels.

2 Methodology

2.1 Materials
Adenanthera pavonina L. seeds were collected in Imperatriz, Maranhão, in January 2019. They were
harvested, selected, washed and kept in a cool place until use. In addition, for the crosslinking of
galactomannan (Gal), glutaraldehyde (GA) chemical reagent was used.

2.2 Methods
2.2.1 Galactomannan extraction from Adenanthera pavonina L. seeds. In order to obtain the
Galactomannan, the process started with the collection of the seeds of Adenanthera pavonina L.,
followed by the selection and cleaning of the seeds. Then they will pass through a heating and
swelling stage. Finally, the seeds were manually separated from the endosperm and lyophilized.
2.2.2 Galactomannan crosslinking. A solution of 0.3 mol/L of Glutaraldehyde was prepared and its pH
was adjusted with acetic acid. The solution was added to the fine powder of galactomannan and stirred
for 24 hours. After stirring, the solution was placed on a petri dish for formatting. Three different
galactomannan films were obtained and identified as G2G03P3, G2G03P5 and G2G03P7, according
to the respective pH medium (3, 5 and7).
2.2.3 Determination of the swelling degree of galactomannan. The samples’ swelling was obtained
dipping the samples G2G03P3; G2G03P5 and G2G03P7 in 50 mL of distilled water. The immersion
time periods were 20, 40, 60 and 80 minutes. After this process excess water was removed and the
sample masses were weighted. Equation 1 was used to determine the swelling degree.

𝐺𝐼 = [(𝑀 − 𝑚)/𝑚] × 100 (1)

Where: GI = swelling degree; M = swollen mass and m = initial mass.

2
ICAMC 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 809 (2020) 012023 doi:10.1088/1757-899X/809/1/012023

2.2.4 Infrared characterization with fourier transform. FTIR spectrum was obtained from the Bruker
Fourier transform spectrometer, model Vertex 70V. Potassium Bromide (KBr) pellet technique was
used and each measure was performed taking 64 scans.

3 Results and discussion

3.1 Infrared Fourier Transform as a function of pH

The FTIR spectrum allows the identification of chemical groups. The transmittance data of
galactomannan in the infrared region is shown in Figure 2. The band between 810-820 cm-1 refers to
the α-D-galactose linking unit, the band between 870-880 cm-1 the β-D-manose linkage unit [7,8],
while the band between 950 cm-1 - 970 cm-1 was attributed to the axial deformation (C − OH) of C-4
[9]. At 1027cm-1, the band may be related to the vibrational torsion of the CH2. Already the band at
1160 cm-1 can be attributed to the module connection vibrational angular voltage δ(C―O) due to
pyranose ring [9,10]. In addition, the region between 1350 cm-1 and 1450 cm-1, attributed to
symmetrical deformations of groups CH2 e COH [7,8]. While the wavelength at 1640 cm-1 presents
bands on account of the vibration of (O-H) of adsorb and stretch water molecules (C-O) of the
carboxylate group (-COO-)[11]. The band centered at 1740 cm-1 is associated with carbonyl C=O
group. Also between 2930 cm-1 and 2940 cm-1 band can be referred to stretch C-H of the CH2
grouping and the 3420 cm-1 to the vibrational stretching of the group O-H [7].

G2G03P3
G2G03P5
G2G03P7
Transmittance (%)

813
1639 D-Galactose
C=O
2735 1717
C-O 1384 1025 872
CH D-Mannose
2940 CH
C-H 2 2
3413 1149
OH C-H
963
C-OH

4000 3500 3000 2500 2000-1 1500 1000 500

Wavelength (cm )

Figure 2. FTIR spectra of reticulated Galactomannan in glutaraldehyde 0.3 mol/L, in pH 3, pH 5 e

pH 7.

3.2 Swelling degree as a function of pH

Figure 3 shows the swelling profile of glutaraldehyde crosslinked Adenanthera pavonina L.
galactomannan at pH 3, 5 and 7; It is observed that the sample G2G03P5 presented a higher swelling
degree compared to G2G03P3, for a dipping period of 20 min. It is also noted that lower pH (higher
H+ concentration) medium correspond to a decrease of the swelling degree, which should be caused by
protonation of carboxylic groups in the polysaccharide structure, leading to more interactions between
carboxylic and hydroxyl groups, forming more hydrogen bonds. This effect explains the decrease of
free volume accessible to water molecules, lowering water penetration [12–15]. Meanwhile, the
sample G2G03P7 has no swelling capacity at all since it solubilized.
In addition, crosslinking hinders the mobility of the polymer chain, decreasing solubility of the
polysaccharide[16]. The reticulating agent (glutaraldehyde) favors an increase of the crosslinking
degree, affecting hydrogels structure. This phenomena, directly related with an higher degree of
ramifications of the polymer and folding of polymer chains allied to eventual reticulation points [17],
greatly affects water absorption capacity.

3
ICAMC 2019 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 809 (2020) 012023 doi:10.1088/1757-899X/809/1/012023

Figure 3. Swelling degree (%) for increasing periods, from 20 min to 80 min using 0.3 mol / L
glutaraldehyde crosslinked galactomannan at pH=3 and pH= 5.

4 Conclusion
This research analyzed the influence of pH medium on the crosslinking process of
galactomannan and glutaraldehyde. Three different pH preparation medium were used (pH=3,
5 and 7). The FTIR response of the hydrogels that resulted from crosslinking process revealed
that the bands of the OH and C=O functional groups presented an increasing intensity
associated to the higher pH medium. Meanwhile, our results point out that to a higher pH
medium, during crosslinking, corresponds a higher swelling degree, suggesting a high
sensitivity of this parameter to pH variation. Finally, considering its simplicity, this
preparation method, can be easily scalable and be applied in the production of hydrogels for
commercial purposes.

5. Reference
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Acknowledgements
The authors are grateful to the Foundation for Research and Scientific and Technological
Development of Maranhão - FAPEMA for financial support through EDICT FAPEMA No. 36/2017
International Cooperation Process COOPI-07965/17 and the Scientific and Technological
Development Council (CNPq), a Foundation for Science and Technology (FCT), Portugal (Strategic
Projects UID/NEU/04539/2013 and UID/NEU/04539/2019) and COMPETE-FEDER (POCI-01-0145-
FEDER-007440) Funded by National Funds via FCT (Foundation for Science and Technology)
through the Strategic Project UIDB/04539/2020 and UIDP/04539/2020 (CIBB).

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