Accepted Manuscript

Title: Structure and properties of hydroxyapatite/Hydroxyethyl

cellulose acetate composite films

Author: K. Azzaoui E. Mejdoubi A. Lamhamdi S. Zaoui M.

Berrabah A. Elidrissi B. Hammouti Moustafa M.G. Fouda
Salem S. Al-Deyab

PII: S0144-8617(14)00865-0
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2014.08.089
Reference: CARP 9226

To appear in:

Received date: 23-7-2014

Revised date: 12-8-2014
Accepted date: 13-8-2014

Please cite this article as: Azzaoui, K., Mejdoubi, E., Lamhamdi, A., Zaoui, S., Berrabah,
M., Elidrissi, A., Hammouti, B., Fouda, M. M. G., and Al-Deyab, S. S.,Structure
and properties of hydroxyapatite/Hydroxyethyl cellulose acetate composite films,
Carbohydrate Polymers (2014), http://dx.doi.org/10.1016/j.carbpol.2014.08.089

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 1 Structure and properties of hydroxyapatite / Hydroxyethyl
2 cellulose acetate composite films
3
4 K. Azzaoui1*, E. Mejdoubi1, A. Lamhamdi1, S. Zaoui1, M. Berrabah1, A. Elidrissi2,
5 B. Hammouti2, Moustafa M. G. Fouda3**, Salem S. Al-Deyab3

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6

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7 1
L.C.S.M.A. Faculté des Sciences, Université Mohammed Premier, 60 000 Oujda, Morocco
8 2
L. C A.E-URAC18. Faculté des Sciences, Université Mohammed Premier, 60 000 Oujda, Morocco

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9 3
Petrochemical Research Chair, Department of Chemistry, College of Science, King Saud University,
10 P.O. Box: 2455, Riyadh 11451, Saudi Arabia

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11
12
13 Highlights

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14  Synthesis of HAp / HECA composite films was successfully achieved.
15  The composite was characterized by FEG-SEM , FTIR and TGA.
16  HAp nanoparticles was dispersed and well immobilized in the film.
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17  A strong interaction occurred between HAp and HECA matrix.

18  Results show good thermal stability and miscibility of the composite.

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19
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20
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22 Abstract
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23 The main aim of this research work was to develop a new inorganic–organic film. Hydroxyapaptite
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24 (HAp) particles that represent the inorganic phase was mixed well with Hydroxyethyl cellulose
25 Acetate (HECA), which representing the organic phase and then the inorganic–organic films were
26 fabricated by evaporating of the solvent. The structure as well as the properties of the formed films
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27 were characterized using different analytical tools such as field emission scanning electron microscopy
28 (FEG-SEM), thermo-gravimetric analysis (TGA), Fourier transform infra-red (FT-IR) spectroscopy.
29 The obtained results revealed that, the HAp nanoparticles was well dispersed and well immobilized
30 throughout the formed films. This can be attributed to the role of the nano-and micropores in the
31 HECA substrate. In addition, a strong interaction occurred between HAp and HECA matrix. The
32 results showed also good thermal stability and miscibility as well.
33
34 Keywords: Composite; hydroxyapatite; hydroxyethyle cellulose Acetate; Biomaterials

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36
37
38
39
40 *
Corresponding author at: Laboratoire du Solide Mineral, Fac Sci. Univ Mohammed Premier Oujda
41 Morocco, Tel./Fax ; +536500603,

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42 ∗∗ Corresponding author at : Petrochemical Research Chair, Chemistry Department, College of

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43 Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi Arabia., Tel. ; +966 560773127.
44 E-mail addresses ; k.azzaoui@yahoo.com (Khalil Azzaoui), m_gaballa@yahoo.com,
45 mmfoudah@ksu.edu.sa (M.M.G. Fouda).

46

47
1. Introduction

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Recently, most of composite substances made from organic and inorganic phases have been appealed
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48 much attention. It is noticed that, polymer–composite substances have been broadly used in
49 biomedical applications (Abdel-Mohsen, Aly, Hrdina & Montaser, 2012; Hassan, Abdel-Mohsen &
50
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Elhadidy, 2014; Ramakrishna, Mayer, Wintermantel & Leong, 2001). Natural polymers (Abdel-
51 Mohsen et al., 2013; Abdel-Mohsen et al., 2012), such as cellulose, chitin (Abdel-Mohsen et al., 2014;
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52 Abdel-Mohsen, Aly & Hrdina, 2012; Fouda, El-Aassar & Al-Deyab, 2013; Přichystalová et al., 2014),
53 corn protein, starch (El-Hamshary, Fouda, Moydeen & Al-Deyab, 2014; El-Rafie, El-Naggar,
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54 Ramadan, Fouda, Al-Deyab & Hebeish, 2011; Hebeish, El-Naggar, Fouda, Ramadan, Al-Deyab & El-
55 Rafie, 2011) and soy protein isolate (SPI) (Bhardwaj, Mohanty, Drzal, Pourboghrat & Misra, 2006; Lu
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56 & Larock, 2007; Yan, Chen & Bangal, 2007) have become significant due to their renewability,
57 biocompatibility, biodegradability, and non-toxicity (Cheung, Lau, Lu & Hui, 2007; Juntaro, Pommet,
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58 Kalinka, Mantalaris, Shaffer & Bismarck, 2008; Ragauskas et al., 2006; Sgriccia, Hawley & Misra,
59 2008; Svagan, Samir & Berglund, 2008; Yang, Lue, Qi, Sun, Zhang & Zhang, 2009). Cellulose is
60 considered one of the most abundant natural polymers (Abdel-Rahman, Abdel-Mohsen, Fouda, Al
61 Deyab & Mohamed, 2013; Fouda & Fahmy, 2011; Hashem, Elshakankery, El-Aziz, Fouda & Fahmy,
62 2011; Hebeish et al., 2011), which is renewable and biodegradable and biocompatible too (Granja,
63 Barbosa, Pouységu, De Jéso, Rouais & Baquey, 2001). It has been established a list of language
64 applications in several fields such as textile manufacturing (Abdel-Mohsen, Aly, Hrdina, Montaser &
65 Hebeish, 2012) and has been widely used in the biomedical field as tissue engineering because of
66 their well biocompatibility, similar to the hard and soft tissues mechanical properties of materials
67 (Miyamoto, Takahashi, Ito, Inagaki & Noishiki, 1989; Risbud & Bhonde, 2001).

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 68 In order to improve the solubility of cellulose as well as its derivatives, Chemical modification has
69 been carried out; using proper chemical entities such as: introducing water-soluble units(El-Shafei,
70 Fouda, Knittel & Schollmeyer, 2008), hydrophilic parts, in addition to bulky and hydrocarbon groups
71 (Samaranayake & Glasser, 1993). Cellulose ether as well as Hydroxyethyl cellulose (HEC) are
72 frequently been applied into the industry due to their biocompatibility since they improve workability
73 of the fresh material and their adherence to the substance too.

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74

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75 Hydroxyapaptite (HAp) in principal, is considered an inorganic component of natural bone (Azzaoui
76 et al., 2014), and is mainly used in the field of tissue engineering due to its excellent biocompatibility,

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77 bioactivity, non-inflammatory, non-toxicity and osteoconductivity (Murugan & Ramakrishna, 2004).
78 HAP has been utilized as resin for the refining of proteins and plasmid DNA, since its surface has both

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79 positive and negative ions (such as Ca2+, PO43−), which can electrostatically bind with basic and acidic
80 biomacromolecules, respectively (Schröder, Jönsson & Poole, 2003).
81

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82 Lately, the high affinity of HAp towards protein has been utilized for binding and releasing
83 biologically active molecules (Jongpaiboonkit, Franklin-Ford & Murphy, 2009). It is noticed that the
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84 incorporation of HAp into poly (L-lactide) leads to an improvement in the protein adsorption capacity.
85 This can be attributed to that; HAp has not only a high affinity to protein but also alter the scaffold
86 surface morphology making them more appropriate for protein absorption (Wei & Ma, 2004). No dout
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87 that, natural polymers are most likely, biocompatible and biodegradable, hence they are important for
88 tissue engineering, as a result, the incorporation of n- HAp into the biopolymer matrix leads to an
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89 improvement in mechanical properties, in addition, incorporation of nanotopographic features can

90 mimic the nanostructure of bone (Swetha, Sahithi, Moorthi, Srinivasan, Ramasamy & Selvamurugan,
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91 2010).
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93 In the present work, the synthesis of new cellulose derivative (HECA) that is soluble in most organic
94 solvents as DMF, starting from Hydroxyethyl cellulose (HEC) prepared from "Stipa Tenacissima"
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95 cellulose of Eastern Morocco and acetic anhydride (Elidrissi, El barkany, Amhamdi & Maaroufi,
96 2013) has been described. The resulted product (HECA) will have the same characteristic properties
97 that each biopolymer; Cellulose acetate (CA) and hydroxyethyl cellulose (HEC) has. The resulted
98 product (HECA) is mixed well at the same time with hydroxyapatite modified by PEG 1000 to give
99 the corresponding membrane.
100

101 2. Materials and methods

102 2.1. Materials

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103 Hydroxyethyl cellulose Acetate (HECA) and Hydroxyapatite (HAp) was synthesized in our
104 laboratory. Ca (NO3)2. 4H2O (99 %), (NH4)2HPO4 (99%) and PEG 1000 were purchased from Aldrich;
105 Germany. High purity distilled water was used throughout the whole experiments.
106

107 2.2. Hydroxyethyl cellulose acetylating

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108 2 g of HEC (8.83 mmol) were subjected to drying at 40°C for 24hrs. The dried sample was kept in a

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109 three-necked flask. Different amounts of acetic anhydride were added respectively to the mixture 1 (8,
110 83 mmol); 1.5; 2; 3; 6; 9; 12 and 15. The reaction time as well as the reaction temperature have been

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111 changed respectively between (15; 30; 45; 60 and 90 min) and (0; 25; 50; 60; 90 °C). The mixture was
112 left under stirring for 15 min. Perchloric acid is added slowly at room temperature and the mixture is

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113 left again under stirring for complete homogenization. According to the solubility diagram, determined
114 using HSP, water or diethyl ether was used as medium for the precipitation of the obtained product.
115 The product was filtered using vacuum pump, followed by washing three times with cold water /cold

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116 ether and left for drying at 60°C for 24 h and finally is kept in desiccator having P2O5 for one week.
117 The resulted HECA was further purified using the dissolution-precipitation method in different
118 solvents taking into account their DS according to the solubility stadium diagram, which already
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119 presented. The recovered product was characterized and evaluated using different analytical
120 techniques (Fig. 1).
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122
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2.3. Synthesis of thin film PLA/ PCL/ HAp

123 Calcium nitrate tetra hydrate and di-ammonium hydrogen phosphate were used, as starting
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124 constituents reagents used in the preparation of hydroxyapatite. HAp was synthesized according to the
125 modified wet chemical method described by Azzaoui et al 2013; “At 25°C, 11.76 g of Ca (NO3)2,
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126 4H2O was first dissolved in a 100 ml volume of water”. “A solution of 4.06 g (NH4)2HPO4 was
127 dissolved in 100 ml volume of water and then added to the Ca (NO3)2, 4H2O solution over a period of
128
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30 min”. “The amount of reagents in the solution was calculated to obtain a Ca/P molar ratio value
129 equals 1.67, corresponding to a stoichiometric Hap”. “About of the polyethylene glycol was added
130 along with the mixture”. “The pH of the slurry was measured digitally during the precipitation
131 reaction, reaching a final value of pH 10,5” (Azzaoui et al., 2013).

132 HECA polymer were dissolved in DMF at 40 °C under stirring in order to form solution named A.
133 Hydroxyapatite (HAp) that dispersed in DMF at room temperature is considered as (Solution B), is
134 further added to solution A. The colour of the resulted mixture is turned to opaque milky white after
135 about 30min. In addition, with temperature control to 40°C and with a rate of 2 °C/min for almost 2
136 hours, thin films were obtained, and then cleaned in absolute ethanol to remove any possible
137 impurities in the formed film (Fig. 2).

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138

139 3. Results and discussion

140 Using FTIR analysis, the interaction between inorganic and organic constituents has been extensively
141 studied. Fig. 3 displays the FTIR spectra of unmodified HEC (1) and Hydroxyethyl cellulose acetate
142 samples (HECA) with different degree of substitution; [DS=2,4]. As soon as the acetylation reaction

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143 between acetic anhydride and HEC takes place, the modification may be verified by the carbonyl ester

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144 band at 1739 cm-1 and the OH broad band intensity, assigned to alcohol, decrease to 3480 cm-1. The
145 peaks located at ~ 2948 cm-1and ~ 2885 cm-1are attributed to ν(C-H) and ν(C-H2) groups respectively

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146 (Garside & Wyeth, 2003). The band located also at 1647 cm-1 corresponds to the bending mode of the
147 naturally absorbed water (Pastorova, Botto, Arisz & Boon, 1994). The absorbance at 1375 cm-1 arises

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148 from the C-CH3 vibration, moreover the peak at 1242 cm-1 is originated from ν(C-O) ester vibration.
149 However, the bands allocated to the hydroxyl ion of hydroxyapatite are found at 3572 cm-1 and 630
150 cm-1. The bands allocated to groups of PO43- are observed at 1090 cm-1, 1047 cm-1, 962 cm-1, 602 cm-1

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151 and 572 cm-1. We also observe the decrease in band intensity of the hydroxyl (OH-) located and 3435
152 cm-1 630 cm-1 of the IR spectra of the grafted materials when the level of grafting increases. We also
153 note the change in the intensity of the bands at 2879 - 2849 cm-1 for composite A, due to vibrations ν
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154 (CH) and ν (C-H2) groups, respectively (Liu, Sun, Zhang, Ren & Geng, 2006), and a displacement of
155 the 2879 - 2950, 2925 - 2955 and 2943 – 2960 cm-1 for the composites B, C and D, respectively. Other
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156 vibration bands were observed around 1638 cm-1 corresponds to the bending mode of water absorbed
157 naturally (Zhou, Zhang, Li, Wu & Cheng, 2005). The absorbance at 1373 cm-1 is derived from the
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158 vibration-CH3 (spectrum A), and a movement thereof to 1376 1379 and 1384 cm-1. The peak at 1239
159 cm-1 is originated ν (CO) Vibration (spectrum A) ester, and a movement thereof to 1236, 1240 and
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160 1253 cm-1.

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161 3.1. Thermal study

162 TGA diagrams show/display that composites have two stages of weight loss: the first is recorded
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163 between 25 and 160° C corresponds to desorption of water adsorbed on the surface of the apatite and
164 light little organic matter related to apatitic matrix. The second stage of HEC decompose between 266-
165 356 ° C and 280-375 ° C for HECA. While HECA / HAp / PEG 1000 have three mass loss: the first
166 between 25 - 100 ° C, the second between 269-353 ° C, and the third between 581-624 ° C,
167 respectively. This increase in the decomposition temperature suggested that the thermal stability of
168 HECA is more important than that of HEC, and the thermal stability of HECA / HAp / PEG 1000
169 composite is higher than that of HECA. Similar results were also observed in the case of acetates
170 cellulose (Liu, Sun, Zhang, Ren & Geng, 2006). The TGA and DTG curves of the films were shown in
171 Fig. 4. Noticeably, the thermal stability of all films increased with loading of HAp nanoparticles.
172 Results designated further the strong interaction occurred between the cellulose and HAp.

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173

174 3.2. Characterization by DSC

175 Fig. 5 shows different thermal phenomena (observed by differential scanning calorimetry) that occur
176 on / composite HECA/ HAp/ PEG 1000. The glass transition around 99°C and a melting temperature
177 of the composite around the order of 256°C. It is well documented in the literature that in the case of

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178 HECA, the principle endothermic peak is mostly due to the depolymerization of HEC, while the heat

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179 is due to the formation of CO2. Each thermal transition will be discussed in the following paragraphs.
180

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181 3.3. Morphology of HECA / HAp / PEG 1000 composite

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182 The observation of particle composites based HECA / HAp / PEG 1000 by microscopic SEM-FEG
183 can appreciate the size, shape, distribution and microstructure of granules. Fig.6 shows FEG-SEM
184 observation images of treated hydroxyapatite particles. It may be noted that the size distribution of

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185 about 92 nm. The composite nanoparticles is visible to show that these nanoparticles are highly
186 granular and composed of crystals of small size gives it its properties bioactivity.
187
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3.4. NMR Study

188 Initially, all samples must be purified. The represented spectra; Fig. 7 (a) displays the peak ascribed to
189 the water at ~3 ppm. The methylene proton of HEC was between ~3.5 ppm and ~3.6 ppm and were
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190 overlapped with the broad ring proton signals (2.8~5.6 ppm) of cellulose. The synthesis of HECA was
191
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successfully evidenced by the presence of a novel signals at 2.0 ppm and at 4.11 ppm which are
192 ascribed respectively to the acetyl protons and to the methylene in α of the ester. The DS values of
193 HECA samples were also predictable using 1H NMR technique from the acetyl protons to the total
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194 HEC proton integrations as declared in section 3.3.2 (eq. 18), and the results are summarized in table 1
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195 too.
196 Fig. 7 (b), depicts the carbon ring of HECA with DS = 2.4, in DMSO-d6 at 360°K. The signals at 21
197 ppm and ~170 ppm in the 13C NMR spectra designate the presence of the carbon of acetyl group and
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198 the carbonyl ester respectively. The assignments of the other peaks are, according to Qi Zhou et al.
199 (Zhou, Zhang, Li, Wu & Cheng, 2005) and Juli et al. (Li, Xie, Cheng, Nickol & Wang, 1999), ascribed
200 to the HEC carbon region (60 – 105 ppm).
201 Based on the above results, a schematic model of hydrogen bonding between CO groups in HECA and
202 the surface of OH groups in HAp nanoparticles was considered as revealed in Fig. 8. The molecular
203 chains of HECA polymer are randomly twisting and inhibit reversible phase from irreversible strain
204 that hang on the physical twisting during inter-transition from glassy state to rubbery state.
205 Nevertheless, in the nanocomposites the interpenetrating networks were designed due to a physical
206 crosslinking by the weak interaction, which worked as a stationary phase during the recovery of

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207 memory shape, as shown in Fig. 8. The model may also be used to describe the above results (e.g., the
208 outcome from FTIR, TGA/TDA and DSC).
209

210 4. Conclusion

211 Grafting the HAp was successfully incorporated into the matrix HECA. The porous structure of the

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212 composite, HECA / HAp / PEG 1000 has been playing an important role in the stabilization and

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213 dispersion of TETA particles due to the interaction of strong intermolecular hydrogen bonding
214 between HECA and HAp. Particles HAp were uniformly dispersed and immobilized in inorganic-

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215 organic composites. The analysis by FT-IR spectroscopy showed the presence of specific interaction
216 between HECA and HAp in mixtures HECA / HAp / PEG 1000. In addition, the film morphology

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217 observed by FEG-SEM microscopy shows that mixtures HECA / HAp / PEG 1000 are more
218 homogeneous and particles HECA incorporated into the matrix of HAp are thinner.
219

220

221 an
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222 Acknowledgment
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223 The Authors extend their appreciation to the Deanship of Scientific Research at king Saud
224 University for funding the work through the research group project no. RGP-No. 089.
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225
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319 antibacterial activity of new fluorescent chitosan derivatives. International Journal of Biological

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320 Macromolecules, 65, 234-240.
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322 W. J., Hallett, J. P., Leak, D. J., Liotta, C. L., Mielenz, J. R., Murphy, R., Templer, R., &
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349 Zhou, Q., Zhang, L., Li, M., Wu, X., & Cheng, G. (2005). Homogeneous hydroxyethylation of
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352

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352
353 List of Figure and Table Captions :
354 Fig.1: Acylation reaction HEC.

355 Fig.2: Synthesis of membranes based on HECA / HAp / PEG 1000.

356 Fig.3: Infrared absorption spectra of composite HECA / TETA / PEG 1000, with molar ratios

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357 respectively. a= 100/00, b= 10/80/10, c= 20/70/10 and d=30/60/10.

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358 Fig.4: TGA and DTA curves of HEC, and HECA HAp / HAp / PEG 1000 composite with molar ratios

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359 respectively. A= 10/80/10; B = 100/00.00.

360 Fig.5: DSC curves of HECA/ HAp/ PEG 1000 composite.

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361 Fig .6: SEM- FEG composite HECA/ HApt/ PEG 1000 composite with molar ratio.A= 10/80/10.

362 Fig. 7: 1H NMR Spectra of HECA DS = 2.4 (a) and 13C NMR Spectra of HECA DS = 2.4(b).

363

364
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Fig .8. Schematic model of the weak interaction between the CO groups in HECA and the HApt.
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365 Table 1. Results and conditions of the HEC acetylation. a: acetylation without catalyst; X: non soluble

366 ;O: soluble; b: 1 eq; a mount to acetyl one hydroxyl group; c: determined by volumetric method (ref).
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377
378 Table 1.
T DS. DS 1H Solvent
Spl T (°C) Eq.nb.b
(min) IR-TF HMR EtOH THF DMSO H2O

1 60 60 1 0.41 - O x O x

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2 60 60 1,5 0.57 - O x O x

3 60 60 2 0.7 0.72 O x O x

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4 60 60 3 1.07 1.27 O x O x

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5 60 60 6 1.4 - O O O x

6 60 60 9 1.61 - O O O x

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7 60 60 12 2.24 2.4 x O O x

8 60 60 15 2.6 c - x O O
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9 15 25 6 0.26 - x x O O

10 30 25 6 0.34 - O x O O
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14 60 0 6 0.35 - O x O O

15 60 25 6 0.6 - O x O x
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16 60 50 6 1.14 - O x O x

17 60 60 6 1.4 - O O O x

18 60 85 6 3.2 - O O O x

S.ca 60 25 6 0.26 - O x O O

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382 Figure 1.

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400 Figure 2.

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420 Figure 3.
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435 Figure 4.
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454

455 Figure 5.

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468 Figure 6.

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