Enhancement of the Stability of W/O/W Double Emulsion by Chitosan Modified Rice Husk Silica
Corresponding email: lanny.sapei@staff.ubaya.ac.id
Published at : 01 Jul 2022
Volume : IJtech
Vol 13, No 3 (2022)
DOI : https://doi.org/10.14716/ijtech.v13i3.4752
Sapei, L., Agustriyanto, R., Fitriani, E.W., Levy, Z., Sumampouw, C., 2022. Enhancement of the Stability of W/O/W Double Emulsion by Chitosan Modified Rice Husk Silica. International Journal of Technology. Volume 13(3), pp. 584-595
| Lanny Sapei | Department of Chemical Engineering, Faculty of Engineering, University of Surabaya, Raya Kalirungkut, Surabaya 60293, East Java, Indonesia |
| Rudy Agustriyanto | Department of Chemical Engineering, Faculty of Engineering, University of Surabaya, Raya Kalirungkut, Surabaya 60293, East Java, Indonesia |
| Endang Wahyu Fitriani | Department of Pharmaceuticals, Faculty of Pharmacy, University of Surabaya, Raya Kalirungkut, Surabaya 60293, East Java, Indonesia |
| Zerravym Levy | Department of Chemical Engineering, Faculty of Engineering, University of Surabaya, Raya Kalirungkut, Surabaya 60293, East Java, Indonesia |
| Cindy Sumampouw | Department of Chemical Engineering, Faculty of Engineering, University of Surabaya, Raya Kalirungkut, Surabaya 60293, East Java, Indonesia |
The awareness of the need for healthy food continues
to increase, hence, the demand for healthy food is also increasing. Water-in-oil-in-water
Chitosan; Emulsion; pH; Rice husk silica; W/O/W
The emulsion has been widely found in many diverse
processed foods both in the forms of oil-in-water (O/W) and water-in-oil (W/O)
emulsions. One of those examples is mayonnaise which is an oil in water emulsion
and contains a high concentration of oil of about 60 to 70% (Morley, 2016). However,
nowadays the demand for healthier food products with much lower oil content has
been increasing. The oil content was reduced in W/O/W emulsion, leading to the
development of lower-calorie foods with acceptable taste (Yildirim, 2016).
Pickering emulsion has recently gained an
attraction to reduce the use of polymeric emulsifiers since it had demonstrated
higher stability against shear stress and changes in
Chitosan is a biopolymer derived from
chitin which is biodegradable, biocompatible, not toxic, and has mucoadhesive
properties (Muharam et al., 2015;
Krisanti et al., 2020). Chitosan as a polycationic biopolymer may
be acted as an emulsifier and emulsion stabilizer through adsorption of the
protective layer at oil-water interfaces, viscosity enhancement, and
interaction with surface-active agents (Klinkesorn, 2013). Chitosan behaved as a weak cationic
polyelectrolyte at pH < 6.5 when most of its amino groups were protonated (Tiraferri et al., 2014; Bhutto et
al., 2021). At
higher pH of about 7-8, dissolved chitosan was able to strengthen the
interfacial layer O/W emulsion due to the polymer chains aggregation (Mwangi et al., 2016). Silica
accumulated in living tissues generally referred to as biosilica was amorphous
and tended to be hydrophilic due to the presence of hydroxyl groups on their
surface (Sapei et al., 2008;
Dhaneswara et al., 2019; Sapei, 2020). It is well known that natural silica
particles are negatively charged in pure water. As the pH was increased above
pH 2, the silica surface developed a net negative charge primarily due to the
deprotonation of the silanol group (Dyab, 2012). The high positive charge on -NH3
groups of chitosan when dissolved in aqueous acidic media at pH < 6.5 would
likely adhere to negatively charged surfaces such as anionic polysaccharides
and synthetic polyanions to give polyelectrolyte complexes and multilayer
surfaces (Klinkesorn, 2013; Tiraferri
et al., 2014). Furthermore, O/W emulsion was stabilized by
silica particles of which hydrophobicity was modified by chitosan particles
addition (Alison et al., 2016; Alison
et al., 2018). The
hydroxyl groups of silica were suggested to play an important role in the
interaction with the polyelectrolyte of chitosan in the formation of a stable
adsorption layer (Tiraferri
et al., 2014).
Furthermore, the stability of W/O/W stabilized by silica-chitosan was dependent
on pH since pH may have affected particle charge and rheological properties of
the emulsion (Klinkesorn, 2013;
Alison et al., 2016). At acidic pH, rice husk silica tended to be chargeless (Sapei et al., 2018) which may have
limited its interaction with chitosan. On the other hand, the positive charges of
chitosan tended to be decreased as pH was progressing towards neutral pH (Tiraferri et al., 2014; Mwangi et
al., 2016; Alison et al., 2018). The chitosan concentration may have affected
its adsorption behavior on the silica surface (Li & Xia, 2011; Tiraferri et al., 2014). A recent study
demonstrated the use of chitosan solution to coat the oil globules which
entrapped insulin-containing internal aqueous phase due to polyelectrolyte
complex formation with alginate present in the outer aqueous phase (Faghmous et al., 2020). This
chitosan-coated W/O/W multiple emulsion seemed to be promising to be developed
as a drug delivery system.
Chitosan can be applied for bodyweight
reduction, maintenance of LDL-cholesterol, amelioration of inflammation, and
reduction of intestinal transit time according to the European Food Safety
Authority (Manigandan et al., 2018). Biosilica
could also be used as a food additive and used for biomedical applications
because of its health benefits (Alshatwi et al., 2015). The
electrostatic interaction between oppositely charged chitosan and biosilica
particles has not been extensively explored yet. Let alone its role in
strengthening the interfacial layer between oil and water, which became the
main concern in this article. This principle
has been exploited in wastewater treatment using the coagulation-flocculation
process described in the recent studies (Bahrodin et al., 2021; Fard et
al., 2021; Iloamaeke et al., 2021). The pollutant removal efficiency
was highly dictated by the wastewater pH depending on the coagulant agent and
its mechanism (Bahrodin et al., 2021; Sibiyaet al., 2021).
Alum as the coagulant became soluble and positively charged in the acidic
environment was easily adsorbed onto the negatively charged surface of the
colloids leading to charge neutralization and pollutant removal (Bahrodin et al., 2021).
Furthermore, the color removal efficiency increased as pH decreased from 10 to
2 when
The stability of
W/O/W double emulsion stabilized by rice husk silica was much improved from
approximately 60% to about 80-100% when chitosan in the form of particles and
solution was added into the outer aqueous phase, respectively. The
stabilization mechanisms seemed different between those added with chitosan
particles and those added with soluble chitosan. Chitosan particles
electrostatically adsorbed on the silica particles at the oil-water interfaces
forming a rigid barrier thus preventing flocculation and coalescences of
globules. On the other hand, soluble chitosan drastically enhanced the
viscosity of the outer aqueous phase thus retarding the flocculation and
coalescence rates of oil globules. The pH of the outer aqueous phase played an
important role in dictating the positive charge of chitosan particles and the
negative charge of silica particles thus influencing the extent of their
electrostatic attraction. The pH 4 seemed optimal for achieving W/O/W double
emulsion with high stability. The presence of the inner aqueous phase within
the microstructure of W/O/W double emulsion was more pronounced at pH 4
compared to those prepared at another pH. The chitosan concentration also
affected the overall stability of the W/O/W double emulsion. Fewer chitosan
particles seemed preferable to have effectively adhered to the silica particles
while increased soluble chitosan was advantageous for improving the viscosity
of the outer aqueous phase. The combination of rice husk silica and chitosan as
emulsifiers of the secondary emulsions seemed potential to be used for the
development of low-calorie and healthy food emulsion-based products.
We thank Ms. Dyah Ayu Ambarsari for the technical
assistance. The research was funded by Ministry of Research and Technology/
National Research and Innovation Agency of the Republic of Indonesia under the
research grant scheme of “Fundamental Research” 2020 (contract number:
027/SP-Lit/LPPM-01/RistekBRIN/Multi/FT/III/2020).
| Filename | Description |
|---|---|
| R3-CE-4752-20210812111021.JPG | Effect of pH on the stability of W/O/W emulsion stabilized with 0.5% rice husk silica and 1.25% chitosan particle |
| R3-CE-4752-20210812111050.jpg | Illustrated mechanisms of W/O/W emulsion stabilization by mixing rice husk silica and chitosan in two forms in the outer aqueous phase. A) chitosan particle; B) chitosan solution |
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