Chapter 4

Membrane coated cotton wound dressings

4.1 Introduction

Biopolymers have gained popularity during recent times, being prompted by increasing
environmental awareness, growing public health and environmental regulations, and are
therefore being considered as alternatives to synthetic polymers [1]. They are well applicable in
the areas of wound dressings, sutures, tissue engineering and drug delivery [2-6]. Chitosan,
chitin, polysaccharides, cellulose and starch are popular biopolymers. Chitosan is positively
charged and is water soluble and is readily reacts with many negatively charged materials [7]. In
order to overcome the low water sorption characteristic of chitin, polyacrylic acid has been
grafted on it to obtain a hydrogel characteristics for wound dressing application [8]. Chitosan
holds a great promise in therapeutic applications due to its antimicrobial nature, scar prevention,
and biocompatibility [9-14]. Wound dressing is one such application wherein all these properties
are found [15]. Asymmetric chitosan membrane has been prepared, which are tissue compatible
and impermeable to exogenous microorganism due to its top layer and inherent antimicrobial
property, and also exhibit excellent oxygen permeability, controlled evaporative water loss and
enhanced fluid drainage ability [16]. Similarly, silver sulfadiazine incorporated asymmetric
membrane has been prepared, and it acts as a rate controlling release of the sulfadiazine and
silver ion in a sustained way [17]. It also exhibited prolonged antibacterial activity and decreased
potential silver toxicity. Nano particles have penetrated into the biomedical field [18]. Silver
nanocrystalline chitosan wound dressing composed of nano silver and chitosan have been used
for treating deep partial thickness wounds. They improve wound healing and resist infection,
accompanied by reduction in risk of silver absorption [19]. Membranes have been prepared
using chitosan blended with polyethylene glycol [20-23]. Polyethylene glycol exhibits
outstanding characteristics such as protein resistance, low toxicity, immunogenicity, and
biocompatibility. Thus chitosan-polyethylene glycol blends improve the biological
characteristics of blend membranes. Wound dressings from electrospun materials potentially
offer many advantages over conventional process with its huge surface area and microporous
structure. These membranes have been found to promote wound healing and induce cell
migration and proliferation [24]. Chitosan has been blended with polyethylene glycol (molecular
weight 20,000) in different ratios and the mixture was coated on cotton fabric followed by the
freeze drying to develop porous membranes [25]. The proportion of polyethylene glycol in the
blend significantly influences the morphology and the physical structure. The physical structure
and surface morphology as a function of the polyethylene glycol molecular weight have been
investigated.
4.2 Membrane morphology

Investigation have shown that chitosan-polyethylene coated cotton membranes are porous in
nature and the porosity ranges between 50-70% [25]. The molecular weight of polyethylene
glycol strongly influences the porosity development in these membranes. The effects of these are
shown in Figures 1 to 3. A systematic evaluation of the porous structure proceeds with the
polyethylene glycol molecular weight and their amount. Similar observations have been made
wherein a regular porous structure with a top dense layer has been observed [17]. Polyethylene
of different molecular weights has been investigated for the structure property correlation. The
molecular weight of the polyethylene glycol strongly influences the porosity and density of the
membranes. There is a distinct trend in the partial loss of elongated porous structure and in the
formation of the collapsed structure due to the increase of the polyethylene glycol content. With
the increase in the molecular weight of polyethylene glycol, the porous structure becomes more
opened, and the pore size ranges between 75-120 microns. As can be visualized from figures 4.2
and 4.3, the pores become more elongated and larger in size with the addition of polyethylene
glycol having molecular weights of 10000 and 20000 respectively, into the chitosan matrix [26].
The porous structure of polyethylene glycol with 20000, molecular weight, at 50% content
becomes wide open with the appearance of large pits. When the compatibility between chitosan
and polyethylene glycol are better, the phase separation diminishes. The molecular interaction
between chitosan and polyethylene glycol with molecular weight of 4000, is much better as
compared to that with of polyethylene glycol having higher molecular weight of 10000 and
20000. This could be attributed to the fact that polyethylene glycol with molecular weight of
4000 has higher number of terminal hydroxyl groups per unit mass and is expected to act more
intensely due to higher extent of hydrogen bonding with chitosan molecules. Hence polyethylene
glycol with molecular weight of 4000 gives better compatibility with chitosan and low level of
phase separation, and thus does not affect pore such significantly.

Figure 1 – SEM photographs of coating on padded fabrics [26]

 (a) Chitosan coated cotton membrane, and chitosan polyethylene coated membranes
with
(b) 10% polyethylene glycol with molecular weight of 4000
(c) 30% polyethylene glycol with molecular weight of 4000
(d) 50% polyethylele glycol with molecular weight of 4000
(e)

Figure 2 – SEM photographs of coating on padded cotton fabric [26]

(a) Chitosan coated cotton membrane, and chitosan polyethylene coated membranes
with molecular weight of 1000
(b) 10% polyethylene glycol with molecular weight of 10000
(c) 30% polyethylene glycol with molecular weight of 10000
(d) 50% polyethylele glycol with molecular weight of 10000
Figure 3 - SEM photographs of coating on padded cotton fabric [26]

(a) Chitosan coated cotton membrane, and chitosan polyethylene coated membranes
with molecular weight of 20000
(b) 10% polyethylene glycol with molecular weight of 20000
(c) 30% polyethylene glycol with molecular weight of 20000
(d) 50% polyethylele glycol with molecular weight of 20000

In the case of polyethylene glycol with molecular weight of 20000, the hydrogen bonding
interaction is weak, and therefore leads to more isolation of polyethylene glycol molecules from
the chitosan matrix. This is reflected by collapsing of pores in a regular fashion. With the
increase in the polyethylene glycol content in the chitosan, larger pore size and higher porous
structure can be seen in the membranes [22]. This results from the weak interaction of
polyethylene glycol with the chitosan chains. The observed diminishing porous morphology in
polyethylene glycol added membranes is the reflection of the limited interactions of these two
components in the blended matrix [26]. Based on the interaction of the polyethylene glycol with
chitosan matrix and the generated morphology as well as the porosity, it could be proposed that
polyethylene glycol with molecular weight of 20000 is the most appropriate additive for the
dressing development.
4.3 Membrane characterization

Figure 4 shows the differential scanning calorimetry thermograms of membranes in

temperature range between 400C – 800C. The melting of the polyethylene glycols of different
molecular weights is suppressed as the blended component increases in the chitosan matrix as
compared with virgin polyethylene glycol [26]. The decrease in melting point is higher in the
case of polyethylene glycol with molecular weight of 4000 as compared to that of polyethylene
glycol with molecular weight of 20000. The results indicate that strong hydrogen bonding
between polyethylene glycol with molecular weight of 4000 and chitosan molecules interferes
with the crystallization process of polyethylene glycol during the membrane fabrication step and
is reflected in the diminishing melting temperature.

Figure 4 – Thermograms from differential scanning calorimetry at different molecular weights of

polyethylene glycol (---- virgin; __ blended) [26]

With the increase in the molecular weight of polyethylene glycol, the interaction is less effective
due to relatively lower content of hydroxyl groups and polyether chain is not much affected
during the crystallization process. Hence the melting temperature is not significantly affected.
Studies have shown that the corrected heat of fusion value for polyethylene glycol with
molecular weight of 4000 in membrane is much lower than that for pure polyethylene glycol.
But, in the case of polyethylene glycol with molecular weight of 10000, the difference between
corrected and inherent values is less pronounced. This difference is even much less for
polyethylene with molecular weight of 20000. This could be attributed to the fact that chitosan -
polyethylene glycol association is stronger in polyethylene glycol with molecular weight of 4000
as compared to polyethylene glycol with molecular weight of 20000, and does not permit the
polyethylene component with molecular weight of 4000. This supports the strong interaction of
polyethylene glycol (4000 mw) with chitosan molecules, which interferes with its crystalline
structure. Similar findings have been reported in earlier research [22].

Figure 5 shows the thermogravimetric analysis thermograms of pure chitosan and composite
membranes. Chitosan shows a typical multi-step degradation pattern. However, the polyethylene
glycol containing composite membranes show better thermal stability as compared to the
chitosan coated membranes [26]. Moreover, polyethylele glycol (20000m.w) shows the most
stable matrix as compared to the other blended membranes. This could be attributed to the better
thermal stability of polyethylene glycol (2000 m.w) which is also reflected by the enhanced
thermal stability of membranes.

Figure 5 – Thermogravimetric analysis of chitosan coated membrane and chitosan polyethylene

glycol coated membranes with polyethylene glycol having molecular weights of 4000,

1000, and 20000. [26]

4.4 Membrane properties

Figure 4.6 shows the variation of air and water permeability of membranes with the
changes in molecular weight of polyethylene glycol. This is indicted as the pressure required to
force water to pass through the membrane. The air permeability decreases in chitosan-
polyethylene glycol composite membrane (molecular weight of 4000) as compared to the virgin
chitosan coated membrane. But the permeability of the membranes increases with the increase in
molecular weight of polyethylene glycol. The decrease in the permeability of the polyethylene
(4000 m.w) membrane is caused due to the changes in porosity with the addition of polyethylene
glycol. The SEM micrographs shown in the previous figures indicate that the porosity changes
significantly in the blended membranes and may lead to lowering in the permeability [26]. The
compatibility of the polyethylene component with chitosan decreases with the increase in
molecular weight, and in turn results in more open and larger porous structure. This results in
increase in air permeability. The water permeability also increases significantly as seen from the
lower pressure needed for water to pass through. The importance of large pore size in enhancing
the permeability has been shown in earlier research [21].

Figure 6 – Variation in air permeability and water permeability of membranes with polyethylene

glycol molecular weight in chitosan polyethylene glycol coated membranes[26]

Studies have indicated that polyethylene glycol with molecular weight of 20000 has been
evaluated as the appropriate component for the blended wound dressing. Its bending length has
been measured as the flexibility in the membranes. An interesting finding is that the bending
length of chitosan coated fabric is 11 times greater than that of uncoated cotton fabric (Figure 7).
Figure 7 – Bending length of fabrics having different polyethylene glycol (20,000 moleuclar

weight ) contents in chitosan polyethylene glycol coated membrane. [26]

The addition of polyethylene glycol to chitosan reduces the bending length based on its content.
The bending length is found to decrease with increase in the polyethylene glycol content in the
blend. These findings could be comprehended from the plasticizing effect of polyethylene glycol
component in the membrane. Chitosan has a glass transition temperature of 170 0C, has a rigid
molecular structure, and hence its coating onto cotton fabric imparts a very good rigidity. The
addition of polyethylene glycol to the chitosan results in a flexible structure. With the increase in
polyethylene glycol, the flexibility improves and results in lower bending length. The glycols are
known for imparting the plasticization effect in the hydrogels. This is where, glycerine has been
observed to plasticization in chitosan based hydrogels [26]. Other researches have supported the
investigations on chitosan-gelatin complex in combination with glycerol and sorbitol [27]. The
films casted from this combination exhibits plasticizing effect of the glycol.

References

1. Krajewska B, Seperation purification technology, 41(2005)305.

2. Czaja W, Krystynowicz A, Bielicki S, & Brown RM, Biomaterials, 27 (2006) 145.

3. Liu XD, Nishi N, Tokura S, & Sakairi N, Carbohydrate Polymers, 44 (2001)233.

4. Martino AD, Sittinger M, & Risbud MV, Biomaterials, 26 (2005)5983.

5. Dang JM, & Leong KW, Advanced drug delivery review, 58(2006)487.
6. Ishihara M, Nakanishi K, Ono K, Sato M, Kikuchi M, Saito Y, Yura H, Matsui T, Hattori H,
Uenoyama M,

& Kurita A, Biomaterials, 23(2002)833.

7. Dutta PK, Dutta J, & Tripati VS, Journal of scientific Indian research, 63(2004)20.

8. Tanodekaew S, Prasitsilp M, Swasdison S, Thavorniyutikarn B, Pothsree T, & Pateepason R,

Biomaterials, 25(2004)453.

9. Paul W & Sharma C P, Trends Biomater Artif Organs, 18 (2004) 18.

10.Saxena S, Ray A R , Kapil A, Pavon – Djavid G,Letourneur D,Gupta B, Meddahi – pelle A,

Macromol Biosci, 11(2011) 373.

11. Shelma R, Paul W & Sharma C P, Trends Biomater Artif Organs, 22 (2008) 111.

12.Ueno H, Yamada H,Tanaka I, Kaba N, Matsuura M, Okumura M, Kadosawa T & Fujinaga T,

Biomaterials, 20 (1999) 1407.

13.Muzzarelli R, Tarsi R, Tarsi R, Fillipini O, Giovanetti E, Biagini G, & Varaldo PE,

Antimicrobial agents

chemotherm, 34(1990) 2019.

14. Williams GM, Herbert JQ, US Patent 4532134,1985.

15. Kojima K, Okamoto Y, Miyatake K, Kitamura Y, & Minami S, Carbohydrate Polymres,

37(1998)109.

16. Mi FL, Shyu SS, Wu Y, Lee ST, Shyong JY, & Huang RN, Biomaterials, 22(2001)165.

17. Mi FL, Wu YB, Shyu SS, Chao AC, Lai JY& Su CC, Journal of membrane science,
212(2003)237.

18. Brun F, Travan A, Accardo A, & Paoletti S, Biomedical scientific instrument, 46(2010)

19. Lu S, Gao W, & Gu HY, Burns, 34(2008)623.

20. Zhang M, Li XH, Gong YD, Zhao NM & Zhang XF, Biomaterials, 23(2002)2641.

21. Zeng M & Fang Z, Journal of membrane science, 245(2004)95.

22. Zeng M, Fang Z, & Xu C, Journal of membrane science, 230(2004)175.

23. Jaehwan Kim, Zhijiang Cai & Yi Chen, Journal of nano technology, engineering, and
medicine,
 1(2010)1.

24. Chen JP, Chang GY, & Chen JK, Colloids and surfaces A: Physiochem engg aspects, 313-
314(2008)183.

25. Gupta B, Arora A, Saxena S, & Alam MS, Polymer advanced technology, 20(2009)58.

26. Bhuvanesh G, Shalini S, Abha A, & Mohammed SA, Indian journal of fibre and textile

research, 36(2011)272.