Transport phenomena in chitosan synthetic membranes with emphasis on the effect of variations in the ratio of matrix-solvent.

Transport phenomena in chitosan synthetic membranes with emphasis on the effect of
variations in the ratio of matrix/solvent

This content has been downloaded from IOPscience. Please scroll down to see the full text.

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 114.79.59.53
This content was downloaded on 02/07/2015 at 04:24

Please note that terms and conditions apply.

2015 J. Phys.: Conf. Ser. 622 012004

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

Transport phenomena in chitosan synthetic membranes with
emphasis on the effect of variations in the ratio of
matrix/solvent
N Nyoman Rupiasih1,2,3,4, Yayuk Eka Puspita 1 and Made Sumadiyasa 1
1
Department of Physics, Faculty of Mathematics and Natural Sciences, Udayana
University, Kampus Bukit Jimbaran, Badung, Bali 80362, Indonesia
2
Group Research Material Sciences and Technology-Polymer and Biomaterial
E-mail: rupiasih69@yahoo.com
Abstract. The object of this research was investigating the transport phenomena of chitosan
synthetic membranes with emphasis on the effect of variations in the ratio of matrix/solvent.
The study was focused on the effect of amount of chitosan as matrix and electrolytes solutions
on the characteristics of current density of chitosan membranes. A series of chitosan
membranes with various ratios of components was used such as 1%, 2%, 3% and 4%. The
electrolytes solutions, NaCl and CaCl2, with various concentrations, 0.1 mM, 1 mM, 10 mM,
100 mM and 1000 mM, were used. Ion transport processes were carried out in a cell membrane
model which composed of two compartments named compartment 1 and 2, and the potential
difference was measured using a pair of Activon AEP jnct Single 12 x 120 mm calomel
electrodes. All the measurements were conducted at room temperature, 28.8 oC. The result

showed that the current density increased with some parameters e.g. increased in the ratio of
concentration of solution, C1:C2; increased in the amount of chitosan, 1%, 2%, 3% and 4%;
and increased in the size of Stokes radii of the selected cations, Na+ and Ca+2.

Keywords: Chitosan synthetic membrane, electrolyte solution, current density, ion
diffusion

1. Introduction
Chitosan is a biopolymer composed of glucosamine and N-acetyl glucosamine units linked by 1-4
glucosidic bonds. It is a cationic polysaccharide obtained by de-N-acetylation of chitin under alkaline
conditions [1-3]. Recently, chitosan has attracted great interest due to its specific properties such as
biodegradability, biocompatibility, non-toxic, antibacterial, physiological inert and bioactivity [4-5].
These biological characteristics provide chitosan a wide field of applications as a material part in bioenvironments systems, such as pharmaceutical and biomedical engineering, food industry, agriculture
and wastewater treatment. Such applications involve as drug carriers, wound-healing agents, chelating
3

Author to whom any correspondence should be addressed: rupiasih69@yahoo.com; 4 Grant: RM Udayana
University No: 104.41/UN14.2/PNL.01.03.00/2014 date 3 Maret 2014

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution

of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd
1

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

agents, hemodialysis membranes and surgical dressing materials, biodegradable coating or film for
food packaging, coating of seeds and leaves to improve plants’ resistance to diseases, and coating of
fertilizers and pesticides for their controlled release to soil [1, 5-10]. Chitosan is readily converted to
fibers, membranes, coatings, powders and solutions, further enhancing its usefulness [1].
Chitosan membranes have been used for active transport of chloride ions in aqueous solution
[1]. The other applications are as a carrier and/or a selective barrier controlling the transport rate of the
substances involved, chitosan having a powerful chelating ability provides protection of the systems
against destructive effects of heavy metal ions [11].
The development of synthetic membranes had always been inspired by the fact that the selective
transport through biological membranes is enabled by highly specialized macromolecular and

supramolecular assemblies based on and involved in molecular recognition [12], the use of membranes
as ion exchanger. The ion exchange membrane has been used for the traditional applications, such as
electrodialysis concentration or desalting of solutions, diffusion dialysis to recover acids, and
electrolysis of sodium chloride solution. Recently it also used in various fields as a polymeric film
having ionic groups [13] such as ion-exchange membranes for protein separation [14].
Most ion-exchange membranes are made of synthetic polymers; only a few are from natural
polymers e.g. chitosan, cellulose and alginate [14]. Chitosan can be used as an anion-exchange
membrane directly [15], cellulose derivatives such as cellulose phosphate [16], cellulose acetate [17]
and alginate [18] are used as cation-exchange membranes.
In the present study, we prepared a series of chitosan membranes by varying the ratio of
components e.g. matrix/solvent. The purpose of this work was to study of transport phenomena in
those various synthetic membranes. The effects of concentration and electrolytes on their
characteristics were also reported.
2. Materials and methods
2.1 Materials
NaCl, CaCl2 and other reagents used in this study were obtained from commercial sources.
2.2 Transport in chitosan membranes
A series of chitosan membranes e.g. M1, M2, M3 and M4, have prepared by varying the ratios of
components (matrix/solvent) such as 1%, 2%, 3% and 4% respectively. The electrolytes solutions used
were NaCl and CaCl2 with various concentrations, 0.1 mM, 1 mM, 10 mM, 100 mM and 1000 mM.

Ion transport processes carried out in a cell membrane model which composed of two compartments
named compartment 1 and 2, and the potential difference was measured using a pair of Activon AEP
jnct Single 12 x 120 mm calomel electrodes. C1 and C2 is concentration of solution in compartment 1
and compartment 2, respectively. In the transport processes, C1 are varies as 0.1 mM, 1 mM, 10 mM,
100 mM and 1000 mM whereas C2 is kept constant 0.1 mM. All the measurements were conducted at
room temperature, 28.8 oC.
3. Results and discussion
3.1 Characteristic of potential difference (V) vs Log (C1/C2)
Figure 1a and 1b show the potential difference of membranes as function of Log (C1/C2) when the
membranes in contact with NaCl and CaCl2 solution, respectively. In general, Figure 1a and 1b show
that the potential difference (V) increased as increasing the ratio of concentration, C1:C2. This result
is in accordance to the Nernst equation (Hobbie, Russell K, 1978) [19], which illustrates that the
potential difference is due to differences in concentration in compartment 1 and 2 e.g. proportional to
Log (C1/C2). Both figures also show that the increased of potential difference in CaCl2 solution was
bigger compared with NaCl solution, the graph look sharper.

2

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

M1
M2
M3
M4

80

M1
M2
M3
M4

100
Potential Difference (mV)

Potential Difference (mV)

100

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

60
40
20

80
60
40
20

0

0
0

1

2

Log (C1/C2)

3

4

0

1

2
Log (C1/C2)

(a)

3

4

(b)

Figure 1. The potential difference (V) vs. Log (C1/C2) graphs of chitosan membranes in contact with
a) NaCl solution and b) CaCl2 solution.
Figure 2a and 2b show the potential difference in each membrane in contact with various
concentrations (0.1, 1, 10, 100 and 1000 mM) of NaCl and CaCl2 solution, respectively. It shows an
increased in the potential difference with increased in the amount of matrix constituents of membranes
from 1%, 2%, 3% and 4% which named as membrane M1, M2, M3 and M4, respectively. This
explains that increased in the amount of matrix constituent result a more positive membranes formed,
which affects the diffusion characteristics of the membranes itself.
120
0,1 (mM)
1 (mM)
10 (mM)
100 (mM)
1000 (mM)

100
80

0,1 (mM)

1 (mM)
10 (mM)
100 (mM)
1000 (mM)

100
Potential Difference (mV)

Petential Difference (mV)

120

60
40

80
60
40
20

20

0

0
M1

M2

M3

M1

M4

Chitosan Membrane

M2

M3

M4

Chitosan Membrane

(a)

(b)

Figure 2. The potential difference (V) vs. chitosan membranes (M1, M2, M3 and M4) graphs in
various concentrations e.g. 0.1, 1, 10, 100 and 1000 mM of a) NaCl solution and b) CaCl2
solution.
3.2 Characteristic of current density vs. Log (C1)
Figure 3 and Figure 4 show that at small ratios (C1: C2 is small) e.g. 0.1 mM : 0.1 mM, 1 mM : 0.1
mM and 10 mM : 0.1 mM, the current density (J) increased gently. The increased is rising sharply at
bigger ratios e.g. 100 mM : 0.1 mM and at the highest ratio e.g. 1000 mM : 0.1 mM, the increased is

3

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

very sharp. The both figures also show that the increased of the current density is greater when the
membranes in contact with CaCl2 solution compared with NaCl solution. This result can be described
that the numbers of Cl-1 ions in CaCl2 solution are double compared in NaCl solution, that is one Cl-1
ion for one Na+ ion and two Cl-1 ions for one Ca2+ ion. These mean that the driving force is double
when the membranes in contact with CaCl2 solution, the graphs in Figure 4 look sharper.

Current Density (μAm-2)

100
2.5

80
1.5

60
0.5

40
0.1

-0.5 1

10

20

0
0.1

1

10

100

1000

C1 (mM)
M1

M2

M3

M4

Figure 3. Current density vs. C1 (concentration of NaCl solution in compartment 1) semi log
graphs.
100
Current Density (μAm-2)

2.5

80
1.5

60
0.5

40

0.1

-0.5 1

10

20
0

0.1

1

10

100

1000

C1 (mM)
M1

M2

M3

M4

Figure 4. Current density vs. C1 (concentration of CaCl2 solution in compartment 1) semi log
graphs.

4

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

Increasing the amount of matrix (chitosan) also affects ion transport characteristics of the membranes
as shown in Figure 5. It shows that the current density is increased with increasing the amount of
matrix e.g. 1%, 2%, 3% and 4% which named as membrane M1, M2, M3 and M4 respectively. This
result is consistent with the increased in the value of the potential difference measured.
100

0,1 (mM)
1 (mM)
10 (mM)
100 (mM)
1000 (mM)

60

-2

80

Current Density ( Am )

-2

Current Density ( Am )

100

40

20

0

0,1 (mM)
1 (mM)
10 (mM)
100 (mM)
1000 (mM)

80

60

40

20

0
M1

M2

M3

M4

M1

M2

Chitosan Membrane

M3

M4

Chitosan Membrane

(a)

(b)

Figure 5. Current density vs. chitosan membranes (M1, M2, M3 and M4) graphs in various
concentrations (0.1, 1, 10, 100 and 1000 mM) of a) NaCl solution and b) CaCl2 solution.
3.3 Effect of electrolyte solutions on current density
Figure 6 describe the effect of electrolyte solutions to the ion transport characteristics of chitosan
membranes. The graphs show similar pattern for all membranes, M1, M2, M3 and M4, e.g. the graph
is sharper as membranes in contact with CaCl2 solution compared with NaCl solution. This is in
accordance with the increased in the size of Stokes radii of the selected cations, Na+ and Ca+2. The
numbers of Cl-1 ions in CaCl2 solution are double compared in NaCl solution, that is one Cl-1 ion for
one Na+ ion and two Cl-1 ions for one Ca2+ ion.
1.0

1.0

NaCl
CaCl2

0.8

0.6

0.6

2

J (x10 A/m )

0.8

-4

-4

2

J (x10 A/m )

NaCl
ICaCl2

0.4

0.4

0.2

0.2

0.0

0.0
0

1

2

3

4

5
2

6

0

7

-3

1

2

3

4

5
2

V(C1-C2)/(Log(C1/C2)) (x10 VM)

-3

V(C1-C2)/(Log(C1/C2)) (x10 VM)

(a)

(b)

5

6

7

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

1.0

1.0
NaCl
CaCl2

0.8

0.6

0.6

-4

2

J (x10 A/m )

0.8

-4

2

J (x10 A/m )

NaCl
CaCl2

0.4

0.2

0.4

0.2

0.0

0.0
0

1

2

3

4

5
2

6

7

0

-3

1

2

3

4

5
2

V(C1-C2)/(Log(C1/C2)) (x10 VM)

6

7

-3

V(C1-C2)/(Log(C1/C2)) (x10 VM)

(c)

(d)

Figure 6. Current density vs. {V(C1-C2) / (Log(C1/C2))2}, subsequently: a) M1, b) M2, c) M3
and d) M4.

4. Conclusion
The study about transport phenomena in chitosan synthetic membranes with emphasis on the effect of
variations in the ratio of matrix/solvent has been described. The results showed that the current density
is increased with some parameters such as increased in the ratio of concentration of solution, C1:C2;
increased in the amount of matrix (chitosan), 1%, 2%, 3% and 4% which named as M1, M2, M3 and
M4 respectively; and increased in the size of Stokes radii of the selected cations, Na+ and Ca+2.
Acknowledgments
This work was financially supported by the Ministry of National Education, Republic of Indonesia,
under Fundamental Research Grant of Udayana University No: 023.04.2.415253/2014, 5 December
2013, MAK 2013.109.011.521119, Year Budget 2014 are highly acknowledged.
References:
[1]

[2]

[3]

[4]
[5]

[6]
[7]

Ying Wan, Katherine A. M. Creber, Brant Peppley and V. Tam Bui, 2003, Synthesis,
Characterization and Ionic Conductive Properties of Phosphorylated Chitosan Membranes.
Macromol. Chem. Phys. 204, pp 850-858.
Jolanta Kumirska, Mirko X. Weinhold, Jorg Thöming and Piotr Stepnowski, 2011, Biomedical
Activity of Chitin/Chitosan Based Materials-Influence of Physicochemical Properties Apart
from Molecular Weight and Degree of N-Acetylation. Polymers 3, pp 1875-1901.
Srinivasa R. Popuri, Y. Vijaya, Veera M. Boddu and Krishnaiah Abburi, 2009, Adsorptive
removal of copper and nickel ions from water using chitosan coated PVC beads. Bioresource
Technology 100, pp 194-199.
Krajewska B, 2004, Application of chitin-and chitosan-based materials for enzyme
immobilizations: a review. Enzyme and Microbial Technology 35, pp 126-139.
Sandford PA, 1989, Chitosan: Commercial Uses and Potential Applications. In: Skjak-Braek G,
Anthonsen T, Sandford P. Chitin and Chitosan – Sources, Chemistry, Biochemistry, Physical
Properties and Applications. London: Elsevier Applied Science, pp 51-69.
Dutta PK, Rayikumar MNV and Dutta J, 2002, Chitin and chitosan for versatile applications.
Journal of Macromolecular Science, C42 (3), pp 307-354.
Brine CJ, 1989, Controlled Release Pharmaceutical Applications of Chitosan. In: Skjak-Braek
G, Anthonsen T, Sandford P (Eds.). Chitin and Chitosan – Sources, Chemistry, Biochemistry,

6

ScieTech 2015
Journal of Physics: Conference Series 622 (2015) 012004

[8]

[9]
[10]

[11]
[12]
[13]

[14]

[15]
[16]
[17]
[18]
[19]

IOP Publishing
doi:10.1088/1742-6596/622/1/012004

Physical Properties and Applications. London: Elsevier Applied Science, pp 679-691.
Ueno H, Yamada H, Tanaka I, Kaba N, Matsuura M, Okumura M, Kadosawa T and Fujinaga T.
1999, Accelerating effects of chitosan for healing at early phase of experimental open wound
in dogs. Biomaterials 20, pp 1407-1414.
Cho YW, Cho YN, Chung SH, Yoo G and Ko SW, 1999, Water-soluble chitin as a wound
healing accelerator. Biomaterials 20, pp 2139-2145.
Hadwiger, LA, Fristensky B and Riggleman RC. Chitosan, 1984, A Natural Regulator in PlantFungal Pathogen Interactions, Increases Crop Yields. In: Zikakis JP (Ed.). Chitin, Chitosan,
and Related Enzymes. Orlando: Academic Press, pp 291-302.
Barbara Krajewska, 2001, Diffusion of metal ions through gel chitosan membranes, Reactive &
Functional Polymers 47, pp 37-47.
Mathias Ulbricht, 2006, Advanced functional polymer membranes. Polymer 47, pp 2217-2262.
T. Sata, 1991, Ion Exchange Membranes and Separation Processes with Chemical Reactions.
Reviews Of Applied Electrochemistry 26, Journal Of Applied Electrochemistry 21, pp 283294.
Xin Chen, Jiahao Liu, Zhicheng Feng and Zhengzhong Shao, 2005, Macroporous
Chitosan/Carboxymethylcellulose Blend Membranes and Their Application for Lysozyme
Adsorption. Journal of Applied Polymer Science 96, pp 1267-1274.
Zeng, X. F. and Ruckenstein, E. 1998, J Membr Sci 148, p. 195.
Li, W., Zhao, H., Teasdale, R. R., John, R. and Zhang, S. 2002, Anal Chim Acta 464, p. 331.
Barragan, V. M., Rueda, C. and Ruizbauza, C. J 1995, Colloid Interface Sci, 172, p. 361.
Zhang, L. N., Zhou, J. R., Zhou, D. C. and Tang, Y. R. 1999, J Membr Sci 162, p. 103.
Hobbie, Russel K. 1978, Intermediate Physic for Medicine and Biology. Second Edition. John
Willey and Son. Singapore, pp 45-105.

7

Transport phenomena in
chitosan synthetic membranes
with emphasis on the effect of
variations in the ratio of matrix
solvent
by Ni Nyoman Rupiasih

FILE

RUPIASIH-UNUD_SCIET ECH_PAPER_2015-PUBLISHED.DOCX
(249.66K)

T IME SUBMIT T ED

26-JAN-2016 05:40AM

WORD COUNT

SUBMISSION ID

623938237

CHARACT ER COUNT 12489

2100

Transport phenomena in chitosan synthetic membranes with
emphasis on the effect of variations in the ratio of matrix
solvent
ORIGINALITY REPORT

17

13%

16%

10%

SIMILARIT Y INDEX

INT ERNET SOURCES

PUBLICAT IONS

ST UDENT PAPERS

%

PRIMARY SOURCES

1

Ulbricht, M.. "Advanced functional polymer
membranes", Polymer, 20060322

1%

Publicat ion

2

3

www.vetmed.hokudai.ac.jp
Int ernet Source

Ying Wan. "Synthesis, Characterization and
Ionic Conductive Properties of
Phosphorylated Chitosan Membranes",
Macromolecular Chemistry and Physics,
04/2003

1%
1%

Publicat ion

4

5

6

7

www.rsu.ac.th
Int ernet Source

shodhganga.inflibnet.ac.in
Int ernet Source

Submitted to 8936
St udent Paper

Keisuke Kurita. "Chitin and Chitosan:
Functional Biopolymers from Marine

1%
1%
1%
1%

Crustaceans", Marine Biotechnology, 06/2006
Publicat ion

8

9

10

11

12

Submitted to University of Warwick
St udent Paper

www.slideshare.net
Int ernet Source

Submitted to University of Northampton
St udent Paper

etd.lib.fsu.edu
Int ernet Source

Pawlicka, A., R.I. Mattos, C.E. Tambelli, I.D.A.
Silva, C.J. Magon, and J.P. Donoso.
"Magnetic resonance study of chitosan biomembranes with proton conductivity
properties", Journal of Membrane Science,
2013.

1%
1%
1%
1%
1%

Publicat ion

13

Jayakumar, R., M. Prabaharan, P. T.
Sudheesh Kumar, S. V., T. Furuike, and H.
Tamur. "Novel Chitin and Chitosan Materials
in Wound Dressing", Biomedical Engineering
Trends in Materials Science, 2011.

1%

Publicat ion

14

15

Submitted to 7034
St udent Paper

Li, Z.. "Biomimic synthesis of CdS
nanoparticles with enhanced luminescence",

1%
1%

Materials Letters, 200305
Publicat ion

16

Xiashi Zhu. "Determination of Trace
Cadmium in Water Samples by Graphite
Furnace Atomic Absorption Spectrometry
after Cloud Point Extraction", Microchimica
Acta, 04/2006

1%

Publicat ion

17

Submitted to The University of the South
Pacific

1%

St udent Paper

18

www.otempo.pt

1%

Int ernet Source

EXCLUDE QUOT ES

ON

EXCLUDE
BIBLIOGRAPHY

OFF

EXCLUDE MAT CHES

< 1%