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Md. Ibrahim H. Mondal , Mst. Sarmina Yeasmin, Md. Saifur Rahman
Polymer and Textile Research Lab., Department of Applied Chemistry and Chemical Engineering, Rajshahi University, Rajshahi 6205, Bangladesh
Article history: Alpha-cellulose extracted from corn husks was used as the raw material for the production of food-grade carboxymethyl
Received 9 February 2015 cellulose (CMC). Preparation of CMC from husk cellulose was carried out by an etherifica-tion process, using sodium
Received in revised form 17 April 2015 hydroxide and monochloroacetic acid (MCA), with ethanol as the supporting medium. Characterizations of CMC were
Accepted 23 April 2015 Available online 1
carried out by analyzing the spectra of FTIR, XRD patterns and SEM photomicrographs. Degree of substitution (DS) was
May 2015
determined with respect to particle size using chemical methods. Solubility, molecular weight and DS of CMC increased with
decreased cellulose particle sizes. Microbiological testing of the prepared CMC was done by the pour plate method.
Keywords:
Concentrations of heavy metals such as arsenic, lead, cadmium and mercury in the purified CMC were measured by Atomic
Cellulose
Absorption Spectroscopy technique and found to be within the WHO/FAO recommended value. A comparative study with
Carboxymethyl cellulose
Corn husk CMC available in the international market was conducted. The purity of the prepared CMC was higher, at 99.99% well above
Food grade the purity of 99.5% for standard CMC. High purity CMC showed a yield 2.4 g/g with DS 2.41, water holding capacity 5.11
Etherification g/g, oil holding capacity 1.59 g/g. The obtained product is well suited for pharmaceutical and food additives.
1. Introduction prepared by the reaction of monochloroacetic acid with alkali cel-lulose [4].
Cellulose is a common natural polymer. It can be found widely in plants There are several grades of CMC depending on their applica-tions such as
which are used as raw material for producing modified cellulose. Due to the technical, semi-purified and purified. Purified CMC is a white to cream
abundant supply of the polymer in nature, modified cellulose is now colored, tasteless, odorless, free-flowing powder
advancing in terms of production and innovation. The sources can range from [5] and used in a variety of industries including the food, deter-gents,
wood even to the agricul-tural waste. Corn or maize husk is an agricultural personal care, pharmaceutical etc. [6,7]. High purity grades are employed as
waste obtained from corn fields which is a rich source of cellulose. food additives [4] also known as cellulose gum
[8]. In the food industry, it can be used as suspending agent, water loss
Cellulose is a linear, high molecular weight, biodegradable polymeric reducer, thickener, emulsifying agent and stabilizer or dispers-ing agent. It is
material. However, due to its strong inter- and intra-molecular hydrogen used as a preservative for coating of fresh fruit and thickener for
bonds, cellulose neither melts nor dissolves readily in hot or cold water [1] pharmaceutical products [911].
and in most common organic solvents [2,3]. In order to utilize cellulose in the Some authors have reported the synthesis of CMC from various cellulosic
food indus-try, cellulose must be converted into its derivatives. One of the sources such as raw cellulose [7], paper sludge [12], wood residue [13], cotton
most common derivatives is carboxymethyl cellulose (CMC), also referred to linters [14,15], fibers [16] etc. There is consid-erable interest in finding
as Na-CMC which is currently finding an increasing number of applications. cheaper alternative methods to produce CMC. Recently cultivation of corn has
CMC is manmade modified cellulose, a linear, long-chain, water-soluble, tremendously increased in Bangladesh [17] and huge amounts of corn husks
anionic polysaccharide which is are either thrown away as waste or burnt. However, these are applications
with low added value, causing disposal as well as environment pollution
problems.
Corresponding author. Tel.: +880 1914254992; fax: +880 721750064.
The purpose of the present research is to investigate the
E-mail addresses: mihmondal@yahoo.com, mihmondal@gmail.com suitabil-ity of the corn husk as a source to produce high purity
(Md.I.H. Mondal).
food-grade CMC. Every year in Bangladesh, large amounts of
http://dx.doi.org/10.1016/j.ijbiomac.2015.04.061 0141-
CMC are being
8130/ 2015 Elsevier B.V. All rights reserved.
Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150 145
imported to meet domestic demand and the importance of CMC is increasing 2.3. Characterization
day-by-day [18]. Therefore, there is a need to produce CMC from locally
available cheap raw material, such as corn husk agricultural waste, 2.3.1. Measurement of CMC yield
economically on a large scale. The novelty of this study is the synthesis of CMC yield was measured based on a dry weight basis. The net weight of
CMC with higher DS as well as higher purity so that it can be used for food- dried CMC was divided by the weight of cellulose to get the yield value [21],
based products and pharmaceuticals. as follow:
2.1. Materials
2.3.2. Determination of degree of substitution
Corn husks were collected from the Wheat Research Insti-tute, Rajshahi, To determine the degree of substitution, 0.5 g of dried sodium CMC was
Bangladesh. Chemicals used during the study were sodium hydroxide (Merck,
ashed gently between 450 and 550 C for 24 h, and then dissolved in 100 mL
India), monochloroacetic acid (BDH, England), standard CMC (BDH, of distilled water. 20 mL of this solution was titrated with 0.1 N sulphuric acid
England), ethanol (Merck, Germany), methanol (Merck, Germany), glacial using methyl red as an indicator. After the first end point, the solution was
acetic acid (BDH, England), silver nitrate (BDH, England), n-hexane (Merck, boiled and titrated to a sharp end point. The carboxymethyl content was
Germany), sodium chlorite (Merck, Germany), etc. All chemicals used were calculated from the degree of substitution [22], as follow:
of reagent grade and used without further purification.
0.162 B
it attained a constant weight. Gel content was calculated according to the Table 1
Preparation of CMC from corn husk cellulose in aqueous ethanolic medium with dif-ferent
following equation [26]:
particle sizes (30% NaOH in the celluloseliquor ratio, 1:2.7; 120% ClCH 2 COOH in the
W1
Gel Content (%) = 100
celluloseliquor ratio, 1:1.2; temperature, 55 C; time, 3.5 h).
W0 Particle size Degree of Yield of CMC Solubility
( m) substitution (DS) (%)
where W0 is the weight before extraction and W1 is the weight after
1071 0.21 100.89 Insoluble in water
extraction. 340 0.38 115.75 Insoluble in water
149 1.52 195.51 Highly soluble in water
2.5. CMC content 100 2.21 210.87 Highly soluble in water
74 2.41 240.58 Highly soluble in water
Scheme 1. Flow chart for the preparation of CMC from corn husk cellulose.
CMC, with DS less than 0.40, is insoluble in water. Above this value of DS, the fact that a greater number of carboxymethyl groups were sub-stituted for
CMC is fully soluble, with its hydro affinity increasing with increasing DS the hydroxyl groups of the cellulose molecules. These carboxymethyl groups
[30]. are hydrophilic. Therefore, an increase of DS increases the ability of CMC to
From Table 2, it can be seen that the DS, intrinsic viscosity and molecular immobilize water in a system [20].
weight of the prepared CMC increased gradually with the decrease of The results of moisture content, ash content, gel content, WRC and ORC
cellulose particle sizes. The highest DS obtained was 2.41 with respect to of standard CMC and that of prepared CMC are listed in Table 3. From Table
particle size 74 m. Smaller cellulose particle sizes have larger surface area, so 3, it can be seen that moisture content and ORC of standard CMC and
excess reactants can penetrate into the cellulose at the same time. prepared CMC are almost the same. However, ash content, gel content and
Etherification mainly depends upon the accessibility of reactants and the WRC of prepared CMC are higher than that of standard CMC. The high WRC
availability of the acti-vated hydroxyl groups [18]. When particle size implies that prepared CMC is highly hydrophilic. During etherification, more
decreases, surface area as well as the number of available free OH groups for hydroxyl groups were replaced by carboxymethyl groups, which are
substi-tution reaction increases, thus DS increases. Reduction in particle size hydrophilic [20]. The high gel content implies high reactivity [26]. The high
of cellulose could enhance the affinity between cellulose par-ticles and ash content implies high DS, perhaps because more hydroxyl groups are
reactants. Thus such smaller particle size increases the etherification rate as substituted by sodium salts of carboxymethyl groups during the etherification
well as the carboxymethyl substitution rate [31]. The molecular weight of the reaction.
prepared CMC increased with the increase of DS. Such molecular weight also
increased with the decrease of particle size. As the DS increased the number
of OH groups were replaced by heavier carboxymethyl groups. As a result the 3.5
molecular weight of the final product CMC increased [18].
Intrinsicviscosity
3
2
2.5
0.5
Viscosity of a polymer solution depends mainly on the concen-tration and
size (i.e., molecular weight) of the dissolved polymer. Thus more the intrinsic 1.5
viscosity, larger the polymer size as well as the higher the molecular weight. 1
0
There is a direct relationship between intrinsic viscosity and DS of the
prepared CMC. Intrinsic viscosity increases with the increase of DS as
0.21 0.38 1.52 2.21 2.41
presented in Fig. 1. The effect of DS on viscosity was due to
Degree of Substitution
Fig. 1. Relationship between degree of substitution and intrinsic viscosity of pre-pared CMC.
Table 2
Determination of DS and molecular weight of prepared CMC
as a function of particle Table 3
a where, value of
sizes (molecular weight was calculated from equation [ ] = KM Determination of water holding capacity (WHC), oil holding capacity (OHC), mois-ture, ash
5
k = 37 10 dL/g and a = 0.61 at 35 C). and gel contents of synthesized CMC (DS = 2.41) and standard CMC (DS = 0.8).
Particle size Degree of Intrinsic Molecular
( m) substitution (DS) viscosity ( ) weight (Da) Samples name Moisture Ash WHC OHC Gel content
1071 0.21 0.36 79,163 content (%) content (%) (g/g) (g/g) (%)
340 0.38 0.54 153,886 Standard CMC 2.22 14.23 4.12 1.58 99.06
149 1.52 2.21 1,550,516 Prepared CMC 2.21 18.05 5.11 1.59 99.96
100 2.21 2.64 2,075,165
74 2.41 3.00 2,558,967
148 Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150
Table 4 Table 6
Physicochemical characteristics of corn husk CMC. CMC grades and typical applications (6).
Fig. 2. FTIR spectra of (a) raw corn husk powder and (b) purified extracted cellulose.
The infrared spectra of prepared CMC and standard CMC sam-ples have
been shown in Fig. 3. It is evident from Fig. 3b that the broad absorption band
1
at 3434.92 cm is due to the stretching fre-quency of the OH group and a
1
band at 2924.07 cm is attributable to C H stretching vibration. The presence
1
of a new and strong absorption band at 1620.16 cm confirms the stretching
1
vibra-tion of carboxyl groups (COO ) and 1423.81 cm is assigned to
1
carboxyl groups as salts [40,41]. The bands around 1329.32 cm and
1
1112.65 cm are assigned to -OH bending vibration and
1
C O C stretching, respectively. Wavelength 894 cm detected 1,4-
glycoside of cellulose [42]. The IR spectra of the standard CMC procured
from the market are also recorded in Fig. 3a and the pat-terns of two spectra,
prepared CMC and standard CMC are almost similar. Fig. 4. X-ray diffractogram of (a) pure husk cellulose and (b) carboxymethylated cellulose (DS
= 2.41).
Fig. 3. FTIR spectra of (a) standard CMC (DS = 0.8 and (b) synthesized CMC (DS = 2.41).
150 Md.I.H. Mondal et al. / International Journal of Biological Macromolecules 79 (2015) 144150
Fig. 5. SEM image of (a) cellulose and (b) CMC at 500 magnification (200 m size bar).
solubility [43] as lower crystallinity represents higher solubil-ity [12]. During [13] O. Egbuchunam, E.E. Okicimen, Indian J. Chem. Technol. 10 (6) (2003) 619622.
the carboxymethylation process, the cellulose molecules are placed in an [14] Z. Nagieb, M.E. Sakhawy, K. Samir, Int. J. Polym. Mater. 50 (2001) 163173.
[15] I.A. Jahan, F. Sultana, M.N. Islam, M.A. Hossain, J. Abedin, Bangladesh J. Sci. Ind. Res.
alkaline solution. The swelling of the cellulose granules exert a tension on 42 (2007) 2936.
neighboring crystallines of cel-lulose molecules and tend to distort them. [16] H. Gu, J. He, Y. Huang, G. Guo, Fibers Polym. 13 (6) (2012) 748753.
Further swelling leads to uncoiling or dissociation of their double-helical [17] M.M. Uddin, M. Saifur, S. Yeasmin, M.M. Rahman, Md.I.H. Mondal, J. Innov. Dev.
Strategy 7 (2) (2013) 59.
region and the breakup of their crystalline structure [44]. [18] A.B.M.F. Alam, Md.I.H. Mondal, J. Appl. Polym. Sci. 128 (2) (2013) 12061212.
[19] Md.I.H. Mondal, M.M.U. Haque, J. Appl. Polym. Sci. 103 (2007) 23692375.
[20] A. Latif, T. Anwar, S. Noor, J. Chem. Soc. Pak. 29 (2) (2007) 143150.
[21] P. Rachtanapun, J. Kasetsart, Nat. Sci. 43 (2009) 259266.
3.3. SEM analysis
[22] T. Abel, K.N. Maurice, N.J. Noah, H.N. Ntede, M. Richard, N. Emmanuel, RASAYAN J.
Chem. 4 (2011) 17.
SEM analysis is a technique for examining granules morphol-ogy since it [23] B. Brandrup, E.H. Immergut, E.A. Grulke, Polymer Hand Book, fourth ed., John Wiley &
has a large depth of field, which allows a large amount of sample to focus at Sons, Inc, New York, NY, 1998, pp. VII/46.
[24] J.A. Larrauri, P. Ruperez, B. Borroto, S. Saura-Calixto, Food Sci. Technol. 29 (8) (1996)
one time. The SEM also produces images of high resolution, which means 729733.
that closely spaced features can be examined at high magnification. Fig. 5 [25] R. Rane, S. Patil, D. Gangolli, K. Ingawale, Res. J. Recent Sci. 1 (10) (2012) 5962.
represents the morphologi-cal structures of pure husk cellulose and prepared [26] O.H. Lin, R.N. Kumar, H.D. Rozman, M.A.M. Noor, Carbohydr. Polym. 59 (2005) 5769.
CMC with DS 2.4. The CMC molecules are rod-like (or ribbon shaped) which [27] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper
is sim-ilar to other reported images for a typical CMC molecule [45,46]. Add 10, JECFA, Geneva, 2002, pp. 15 (Issue 52, 59th session).
Figures clearly show that the conversion of cellulose to CMC leads to [28] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper,
Add 5, JECFA, Rome, 1997, pp. 5152 (Issue 52, 59th session).
changes in its ribbon shape. [29] K.K. Sharma, L.K. Sharma, A Textbook of Physical Chemistry, third ed., Vikas Publishing
House Pvt. Ltd., New Delhi, 1994, pp. 586.
[30] V.K. Varshney, P.K. Gupta, S. Naithani, R. Khullar, A. Bhatt, P.L. Soni, Carbohydr. Polym.
63 (2006) 4045.
4. Conclusion
[31] A.I. Yeh, Y.C. Huang, S.H. Chen, Carbohydr. Polym. 79 (2010) 192199.
[32] International oenological codex (2012 Issue), www.oiv.int/oiv/files/ CODEX 2012 EN.pdf
While corn husks have been used on a small scale as a fuel for direct
[33] JECFA, Compendium of food additive specifications, in: FAO Food and Nutrition Paper,
combustion in cooking and heating, their use as chemical feedstock for large-
Add 5, JECFA, Rome, 1997, pp. 160 (Issue 52, 59th session).
scale production is a more modern concept. Yet this concept has potential to [34] A. Das, A Text Book on Medical Aspects of Bioinorganic Chemistry, CBS, Delhi, 1990,
help in reducing the pollution problem. -cellulose was extracted from corn pp. 1758.
[35] US International Trade Commission, Purified carboxymethyl cellulose from Finland,
husks and etheri-fication reaction was carried out by the infusion of cellulose
Mexico, Netherlands, and Sweden, Invs. Nos. 731-TA-1084-1087 (Final), in: USITC
with NaOH and monochloroacetic acid. High purity food-grade CMC was Publication 3787, US International Trade Commission, 2005, pp. 14.
successfully produced as an additive for pharmaceutical and food industries.
[36] JECFA, Specifications for the identity and purity of food additives and their toxicological
evaluation: some emulsifiers and stabilizers and certain other substances, in: Wld. Hlth.
Org. Techn. Rep. Ser. 10, No. 373, JECFA, 1967, pp. 11.
References [37] JECFA, Evaluation of certain food additives and contaminants, in: WHO Tech-nical
Report Series 53, No. 896, JECFA, 2000, pp. p. 11f.
[38] M.I. Khalil, A. Hasem, A. Habeish, Starch 42 (1990) 6063.
[1] Y. Choi, S. Maken, S. Lee, E. Chung, J. Park, B. Min, Korean J. Chem. Eng. 24 (2) (2007) [39] D. Bhattacharyya, R.S. Singhal, P.R. Kulkarni, Carbohydr. Polym. 27 (1995) 247253.
288293.
[2] K. Hattori, E. Abe, T. Yoshida, J. Cuculo, Polym. J. 36 (2) (2004) 123130. [40] A. Bono, P.H. Ying, F.Y. Yan, C.L. Muei, R. Sarbatly, D. Krishnaiah, Adv. Natl. Appl. Sci.
[3] M.P. Adinugraha, D.W. Marseno, M. Haryadi, Carbohydr. Polym. 62 (2005) 164169. 3 (1) (2009) 511.
[41] D.R. Biswal, R.P. Sing, Carbohydr. Polym. 57 (2004) 379387.
[4] M. Mohkami, M. Talaeipour, BioResources 6 (2) (2011) 19882003. [42] R.G.P. Viera, G.R. Filho, R.M.N. Assuncao, C.S. Meireles, J.G. Vieira, G.S. Oliveira,
[5] P. Mario, D.W. Adinugrada, M. Haryadi, Carbohydr. Polym. 62 (2005) 164169. Carbohydr. Polym. 67 (2007) 182189.
[6] V. Stigsson, G. Kloow, U. Germgard, Paper Asia 17 (10) (2001) 1621. [43] J. Zhang, D. Wu, J. Appl. Polym. Sci. 46 (1992) 369374.
[7] H.D. Heydarzadeh, G.D. Najafpour, A.A. Nazari-Moghaddam, World Appl. Sci. J. 6 (4) [44] M. Fang, A. Fowler, J. Tomkinson, S. Hill, Carbohydr. Polym. 47 (2002) 245252.
(2009) 564569. [45] P. Rachtanapun, R. Suriyatem, Value added of durian husk: synthesis of
[8] C. Barba, D. Montane, M. Rinaudo, X. Farriol, Cellulose 9 (2002) 319326. carboxymethyl cellulose from durian husk, in: Project Report, Chiang Mai Uni-versity,
[9] N. Olaru, L. Olaru, A. Stoleriu, D. Timpu, J. Appl. Polym. Sci. 67 (1998) 481486. Thailand, 2009, pp. 155.
[10] H. Togrul, N. Arslan, Carbohydr. Polym. 54 (2003) 7382. [46] M. Moosavi-Nasab, A.R. Yousefi, H. Askari, M. Bakhtiyari, World Acad. Sci. 14 (2010)
[11] J. Xue, M. Ngadi, Food Hydrocoll. 23 (2009) 286295.
14771481.
[12] X. He, S. Wu, D. Fua, J. Nia, J. Chem. Technol. Biotechnol. 84 (2009) 427434.