Studies in Surface Science and Catalysis, volume 158

J. Cejka, N. Zilkov~iand P. Nachtigall (Editors)

9 2005 Elsevier B.V. All rights reserved. 2073

Modified bentonite with NazCO3 as possible antacid medicament

C.F. Linares* and A. Torres

Laboratorio de Catfilisis y Metales de Transicifn. Facultad de Ciencias y Tecnologia.

Departamento de Quimica. Universidad de Carabobo. Valencia. Edo. Carabobo. Venezuela.
Apartado Postal 3336. e-mail: clinares@thor.uc.edu.ve

A bentonite from Yaracuy State (Venezuela) was hydrothermically modified by using

NazCO3 at different concentrations (from 1.0 to 3.0 M). Their textural properties and
composition were physical and chemically characterized by different techniques such as:
XRD, FT-IR, chemical analysis and BET surface area. A pH increase of a synthetic gastric
juice, by addition of these modified bentonites, was observed. This increment was larger
when the modified bentonites were treated with concentrated sodium carbonate. On the other
hand, a small interaction between the modified bentonites and pepsin was observed. Even
though, the sodium carbonate salts were determined outside of the bentonite sheets, these
modified bentonites could be used as support of sodium carbonate for its dispersions and
effectiveness as antacid.

1. INTRODUCTION

Bentonites are a class of clay mainly conformed by montmorillonite, quartz, microscopic

crystals of carbonate, mica and other impurities. They are composed by expansible lamellar
sheets containing high concentrations of water together with some cations such as sodium,
potassium, calcium, magnesium and others. Frequently, they are used for cosmetic and
medical purposes due to their high specific area, sorptive capacity, rheological properties,
chemical inertness and low or null toxicity for the patient. Such properties seem to be
acceptable for using these bentonites as possible antacid drug [ 1].
On the other hand, the gastric acidity is referred as an increment in the hydrochloric acid
concentration and consequently a decrease in pH. Normally, antacid medicaments are used
against hyperacidity but they can be toxics or too expensive.
Our group has worked in the modification of kaolin with sodium carbonate to be used as
antacid and we have demonstrated that the modified kaolin is able to control the gastric pH
and it did not interact with pepsin, a vital enzyme in the gastric digestive process. Besides,
bentonites are more expansible than kaolin and they could contain inside of the sheets a
higher sodium carbonate concentration [2]:
The aim of this research was to evaluate the capacity of modified bentonites in
controlling the gastric pH and studying the bentonite-pepsin interaction.

Corresponding author: C. F. Linares, e-mail: clinares@uc.edu.ve, Tel: +58-241-28678805

2074

2. EXPERIMENTAL

2.1. Hydrothermal transformation of bentonite

Bentonite was obtained from an ore at Yaracuy State (Venezuela). These clays had
previously been quantitatively and qualitatively analyzed. Then, this betonite was
hydrothermally transformed according to a previously reported procedure [2, 3]. During a first
stage, portions of bentonite were mixed with different sodium carbonate solutions (1.0, 1.5,
2.0 and 3.0 M) using a 1" 4 solid/liquid ratio under continuous mechanical agitation at 25~
for 24 hours; in a second stage, the slurry was exposed at 100 ~ for 1 hour at atmospheric
pressure in reflux condition. Finally, the mixtures were centrifuged and the sediments were
dried.

2.2. Characterization
The modified bentonites were characterized by XRD, BET surface area and FTIR. XRD
studies were conducted using a Phillips PW 3442 diffractometer with a CuKct radiation
(1.54060/~) for crystalline phase detection between 4 and 80~ (20) and the obtained patterns
were compared with JCPDS data files. Physisorption measurements were performed with a
Beckman Coulter SA 3100 instrument; BET surface areas were determined by nitrogen
adsorption at-196~ with an Ar/N2 ratio of 70/30. The presence of functional groups and
evaluation of the solids purity were achieved by FTIR; spectra were recorded in a Perkin-
Elmer 283 spectrometer in a range of 4000-400 cm -~. Samples were mixed with KBr and
pressed into a disc.

2.3. Antacid capacity

The antacid capacity of the modified clays was evaluated using the methodology
previously reported [4]. Solids were tested in the presence of synthetic gastric juice (HCI +
pepsin, pH= 1.5), containing 50 to 1000 mg of the solids with an aliquot of 20 mL of
synthetic gastric juice. This dispersed solution was shaken during one hour at 37~ to
simulate the rhythmical movements of the stomach. The solution was then filtered and an
aliquot of 10 mL was potentiometrically titrated with previously standardized NaOH using an
Acumment AB 15 pH meter with glass electrode and a sensitivity of + 0.05 pH units. The pH
of the solutions was evaluated in two ways: (a) directly, with a calibrated pH meter, named as
"experimental pH", (b) by potentiometric titration (theoretical pH = -log[H+]), where [H§
corresponds to the free proton concentration determined in the acid-base titration.
The solid-pepsin interaction was measured by UV-visible spectroscopy by means of an
HP 8452A equipment with diode arrangement, using a filtered aliquot from modified
bentonite/gastric juice mixture. The spectrum was recorded between 200 and 400 nm. Spectra
were taken before and after contacting the solids with the synthetic gastric juice. Finally, FT-
IR spectroscopy was applied to solids after the interaction with the synthetic gastric juice.
Previous to the analysis by FT-IR, the solids were washed with abundant distillated water

3. RESULTS AND DISCUSSION

XRD spectrum of bentonite without sodium carbonate showed the phases corresponding to
bentonite, but other phases as kaolin/montmorillonite, quartz and muscovite were also
identified. Table 1 shows the composition of original bentonite. This clay presents a high
content in silicon, which can be associated to quartz. The higher CaO content in comparison
to alkalis content (Na20, K20) refers to this clay as a calcium bentonite. These types of
 2075

bentonites are not very expansible in relation to sodium betonites. On the other hand, the
lower Fe203 content is associated to the white color found in our bentonite

Table 1
Chemical analysis of original bentonite

Elemental Weight composition

composition (%)
SiO2 63 i 2
A1203 13.6+0.6
Fe203 0.96+0.01
CaO 0.15+0.03
Alkalis (Na20, K20) 0.087+0.001

Fig. 1 shows XRD spectra of original and modified bentonite using 3.0 M sodium
carbonate concentration. Some phases, such as Na2CO3.10H20 y NazCa(CO3)2.5H20 were
very hard to determine them. If amorphous salts of sodium carbonate or very small crystals of
these salts are generated on the surface of the modified bentonites during the hydrothermal
process, they cannot diffract and are not able to be detected by XRD.

----- Original bentonite

bentonite (3M)
....................... M o d i f i e d

I Na2c03.10H20, NaZCa(CO3)2.SI-I20

|
| . . . . , . . . . i . . . . , . . . . , . . . . , . . . . i . . . . , . . . . , . . . . i . . . . . . . . . , . . . . , . . . . , . . . . | - 9

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2theta
Fig. 1. XRD of modified bentonite using 3.0 M Na2CO3 solution.

Fig. 2 shows FTIR spectra of original and modified bentonite. The band at 1460 cm -I
represents carbonate anions placed on the surface of bentonite. This band disappears when the
clay is washed with abundant distillated water which indicates that the sodium carbonate is
present on the surface of the modified clay. As we mentioned above, calcium bentonite does
not expand its sheets and they cannot occlude carbonate species.
2076

washed _A ........

lk t
. . . .

3500 3000 2500 2000 1500 1000 500

Wavelenght (cm-1)

Fig. 2. FTIR of modified bentonite with 3.0 M sodium carbonate and washed with distillate water in
1"10 relation solid: water.

Table 2 shows the surface areas of original and modified bentonite. As can seen, the
surface area of the original bentonite is lower in comparison with other values reported for
bentonites. These results can be associated to the presence of quartz (or other more dense
phases) in the composition of the treated materials which decrease the porosity of bentonite.
Furthermore, another possible cause is related to original composition of bentonite (calcium
bentonite) which, as w e mentioned above, they are less expansible than sodium bentonites.
When the bentonite is modified with sodium carbonate, the surface area decreases due to the
accumulation of this salt on the surface of solid. This decrease is higher when the sodium
carbonate is more concentrated

Table 2
Surface area of the original and modified bentonite using different concentrations of sodium
carbonate.

Bentonite Surface area

(m2/g)
Original 10.20
0.5 M Na2CO3 7.95
1.0 M Na2CO3 7.71
1.5 M Na2CO3 7.56
2.0 M Na2CO3 7.24
3.0 M Na2CO3 6.69

Fig. 3 shows the pH of the solutions as a function of bentonite mass for 3.0M bentonite.
In general, the behavior of:all assayed modified bentonites was very similar, including the
original clay used as reference: the theoretical and experimental pH increased as the weight of
 2077

the studied solids. However, the experimental pH values were higher than those of the
theoretical ones. The observed difference could be due to the way in which both pH values
were determined. The experimental pH values were obtained using a glass electrode which is
only sensitive to the amount of free protons in the synthetic gastric juice; while, the
theoretical pH values were determined using the expression pH=-log[H +] which is applied to
results of the acid-base titrations. During the neutralization procedure with NaOH, other ions
or species such as magnesium, calcium and pepsin enzyme along with free proton ions can
interact with the O H groups making the calculated pH lower than the experimental one.
Rivera et al. [3, 5] reported similar results. These authors suggest using experimental pH as a
more effective way to determine the neutralization capacity of zeolites.

7
6
5
4
I--o--TI
~ E

3
. Q..cl--
.---- [] -0 ''~''O''a "

I
O , , , , , , , , , , |

0 50 150 250 350 450 550

Bentonite mass (mg)
Fig. 3. Experimental (E) and theoretical (T) pH determined for 3.0 M sodium carbonate bentonite in
the presence of synthetic gastric juice

According to the previous explanation, we determined the experimental pH versus

different amount of modified bentonites (Fig. 4). The results show increases of the pH values
as the sodium carbonate concentration increased during the modification reaction. Using 225
mg of 3.0 M bentonite, it is possible to achieve a pH between 3 and 4 (optimum pH) while it
is necessary more than 1000 mg of 1.0 M bentonite to achieve the same pH values. Lesser
doses than those used for 1.0 M bentonite are necessary for the 2.0 and 1.5 M bentonites. Of
course, the neutralization capacity is associated to a larger content of carbonate in the
bentonite. At low pH values, we also observed that all the modified bentonites showed a
plateau due to a buffer system formed by carbonate salt. This buffer is eliminated when the
sodium carbonate is increased in the reaction medium.
Similarly, it is well known that the enzymatic function of the pepsin is highly influenced
by the pH of the gastric juice of the stomach. Piper and Fenton (cited by Fordtran et al.) [6]
indicate that extreme acidity or basicity of the gastric juice denaturalize the enzymatic activity
of pepsin, which shows its higher activity at pH = 2. At pH = 5 the enzyme starts to
deactivate; at pH = 7, the enzyme is irreversibly denatured and lose its activity. From Fig. 4, it
is observed that doses as small as 225 mg. of 3.0, 2.0 or 1.5 M bentonites are enough to reach
the optimum pH necessary to control the hyperacidity of the stomach and to maintain a high
enzymatic activity of the pepsin. Quantities higher than 225 mg of 3.0.M, 425 mg of 2.0 M or
800 mg of 1.5 M bentonite are not recommended because, although they show extraordinary
2078

therapeutic properties on the control of the acidity, these doses reduce the enzymatic activity
of the pepsin.
Although, the sodium carbonate was determined outside of the bentonite sheets, these
modified bentonites can be used for dispersing the carbonate salt which achieved due to a
high contact between the antacid (sodium carbonate) and the free protons of the reaction
medium.

7 -- 2 . 0 M
- - ~ 1.5 M
r

3
2J 9 i - . ~ - - . . . . - .

0 200 400 600 800 1000

Bentonite mass (rag)
Fig. 4. Experimental pH vs bentonite mass to different sodium carbonate concentrations (capacity of
neutralization)

To determine the interaction of the synthesized solids with pepsin, variable quantities of
modified clays, depending on its antacid activity (pH between 3 and 4), were mixed with the
synthetic gastric juice. Fig. 5 shows the UV-visible spectrum of solutions from 3M bentonite
before and after interaction with the synthetic gastric juice.

2.5

2.0

8 1.5

1.0 Pepsin solution

_i Modified bentonite (3M)

0.5

0
195 200 2'50 3"00 350 400 450 5"00 5"50 6"00 650 760 750 800
Wavelenght (rim)

Fig. 5. Pepsine UV-Visible spectra recorded after and before the contact with modified bentonite (3M)
 2079

The UV-visible spectrum of original acid solution with pepsin, without interaction with
any solid, shows a maximum at 272 nm and a minimum at 250 nm. After interaction with 3M
bentonite, a small decrease in the maximum absorbance of the pepsin was observed. This
small decrease is probably due to adsorption of the enzyme onto the surface of the bentonite.
These results show that there was not a chemical reaction between the enzyme and the solid.
The interactions pepsin-solid were also determined by FT-IR spectroscopy. Fig. 5
shows the spectra of the solids after the contact with the synthetic gastric juice. Just before the
FT-IR spectrum was recorded, the solids were washed three times with abundant distillated
water. Under such experimental conditions, we cannot observe any band corresponding to
pepsin. These results show that the interaction bentonite-pepsin is weak, and it can be
eliminated by water.

3.0

2.0~

o~~4~_.~
bentonite
3500 3000 2500 2000 1500 1000 500
Wavelen~t (cm- 1)
Fig. 6. FTIR spectra of modified bentonites contacted with gastric synthetic juice and after washed
with abundant distillate water

4. C O N C L U S I O N S

The hydrothermal treating of calcium bentonites using sodium carbonate was not effective to
incorporate this salt inside of the framework. Sodium bentonite must be assayed for a possible
occlusion of the sodium carbonate into the structure of clay. Finally, it was possible to use
these bentonites as support of effective antacids as sodium carbonate. They could be used in
combination with other properties of clays as anti flatulent. Those medical properties of the
clays, in combination with an antacid effect, make this material a good multipurpose medical
drug.

ACKNOWLEDGEMENT

Authors are grateful to FONACIT F-2001000774 and CDCH-UC for financial support.. We
also acknowledge the insightful comments of Prof. Oscar Valbuena and Prof. G. Pinto
2080

REFERENCES

[1] J. Konta, Appl. Clay Sci.,10 (1995) 275

[2] C.F Linares, L. Afonso and M. Rosa-Brussin, J. Applied. Sci., 4(3) (2004) 472.
[3] A. Rivera, G. Rodriguez-Fuentes and E. Altshuler, Microporous Mesoporous Mater., 24 (1998)
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[4] C.F. Linares, S. Sfinchez, C. Urbina de Navarro, K. Rodriguez and M.R. Goldwasser.
Microporous Mesoporous Mater., 77(2005)215
[5] A. Rivera, G. Rodriguez-Fuentes, I. Garcia and M. Mir, Actas de XV Simposium
Iberoamericano de Catfilisis., C6rdoba. Argentina, 3 (1996) 1521
[6] J.S. Fordtran, S. Morawski and Ch.T. Richardson. New. Engl. J. Med., 288 (1973) 923