Novel biocomposite of carboxymethyl chitosan and pineapple peel carboxymethylcellulose as sunscreen carrier

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Novel biocomposite of carboxymethyl chitosan and pineapple peel carboxymethylcellulose as sunscreen carrier Lucksanee Wongkom, Ampa Jimtaisong ∗ School of Cosmetic Science, Mae Fah Luang University, 333 Moo 1, Thasud, Muang, Chiang Rai 57100, Thailand

a r t i c l e

i n f o

Article history: Received 13 June 2016 Received in revised form 16 October 2016 Accepted 20 October 2016 Available online xxx Keywords: Biocomposite Ferulic acid crosslinker Hydrophilic sunscreen carrier

a b s t r a c t This study aims to prepare of biocomposite of carboxymethyl chitosan (CM-chitosan) and carboxymethylcellulose (CMC) from Ananas comosus (pineapple) peel for use as broad spectrum sunscreen carrier. Biocomposite was produced by using ferulic acid (FA), a plant extract, as crosslinker with the optimal ratio of CMC: CM-chitosan: FA at 1:2:4%w. FT-IR technique demonstrated that crosslinking may occur at amine group of CM-chitosan and carboxyl group of FA and hydrogen bonding between hydroxyl group of CMC and carboxyl group of FA. Biocomposite is pale yellow powder and present fibre bundle-like surface in the SEM image. DSC, TGA and XRD results indicated that new compound was formed. The particle size of biocomposite is 626 nm determined by using Zetasizer. Hydrophilic TiO2 and phenylbenzimidazole sulphonic acid (PBSA) were used as sunscreen agent at ratio of TiO2 : PBSA at 2:1%w. The biocomposite sunscreen possesses the SPF value of 2.47 with boost star rating of 3 at 2% compound. The results obtained indicate that the biocomposite was successfully prepared from CM-chitosan and pineapple peel CMC and the system can be used as matrix delivery system for hydrophilic sunscreens. © 2016 Elsevier B.V. All rights reserved.

1. Introduction Pineapple (Ananas comosus) is a tropical fruit which mainly processed for food industry [1]. During pineapple processing it is necessary to get rid of unuse or wastes such as peel, core, stem, crown and leaves [2]. The pineapple wastes, such as peel and leaves were reported be used as hydrogels [3] and nanofibers [4] due to its entanglement, branching, and relatively inexpensive characteristics [4]. Recently, there is a great interest in blending of natural polymer or cellulose to create a new material, namely biocomposite, with versatile properties. Chitosan is an interesting candidate as it is expected to be miscible with cellulose because the similarity in backbone structure [5,6]. This miscible will contribute to improvement in the physical, chemical, mechanical and biological properties [7]. The combination of chitosan with cellulose has been reported to form transparent film with antimicrobial properties [8,9]. In order to blend chitosan with polymer or cellulose to reach the desired properties, a cross-linker will be included in the preparation to form crosslinking reaction. The chemical crosslinking of chitosan and hydroxypropyl cellulose blends with glyoxal and glutaraldehyde was reported [5]. Chemical crosslinking agents,

∗ Corresponding author. E-mail addresses: [email protected], [email protected] (A. Jimtaisong).

e.g., glutaraldehyde, glyoxal and formaldehyde, are highly effective reagents and generally resulting in composite with good mechanical properties. However, these chemicals are not preferred owning to their physiological toxicity [10,11]. Thus, a search for natural cross-linker, e.g., polyphenols, is currently investigated [12]. Ferulic acid, commonly found in commelinid plants, is of great interest candidate because it showed high potential to be good cross-linker [13]. Moreover, it is generally used in cosmetics as it is reported to have antioxidant, whitening and UV-protection properties [14]. Ultraviolet (UV) radiation is known to cause skin cancer, sunburn and photo-ageing skin. Thus, the use of sunscreen product is an effective way to protect the harmful effect of UV radiation [15,16]. Technically, the ideal sunscreen would compose of both chemical and physical UV filter to protect against broad spectrum of UV rays and meet the consumer requirements [17]. A chemical filter, phenylbenzimidazole sulphonic acid (PBSA), is a water-soluble UVB sunscreen agent with photostable property. Moreover, it is reported to boost photoprotective effect of both physical and chemical UV filters. However, PBSA is reported to cause free radicals and oxygen-sensitive reaction, which induce damage to DNA in vitro [18]. Thus, the application of PBSA in sunscreen product with appropriate delivery system may enhance efficacy of sunscreen product without causing damage to the DNA or cells [19]. Therefore, this work aims to prepare biocomposite using Ananas comosus peel and CM-chitosan for use as novel matrix for hydrophilic sunscreens.

http://dx.doi.org/10.1016/j.ijbiomac.2016.10.069 0141-8130/© 2016 Elsevier B.V. All rights reserved.

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Fig. 1. SEM micrograph of commercial CMC and CMC from pineapple peel at 10×.

Fig. 2. SEM micrograph of biocomposite of commercial CMC(a) and CMC from pineapple peel(b) at 10×.

Ferulic acid, an extract from rice, was chosen as a cross-linker. PBSA and TiO2 were selected as sunscreen candidates. The preparation conditions were explored. The biocomposite was characterized using various spectroscopic techniques and the UV screening properties of biocomposite were also reported.

2. Experimental 2.1. Materials Chitosan (MW 1.5 × 106 daltons) was of Marine Bio Resources Co, Ltd. (Thailand). Ananas comosus was collected from Nang Lae district, Chiang Rai province (Thailand). Ferulic acid (FA) was from Tsuno Rice Fine Chemicals Co, Ltd., Japan. Titanium dioxide (TiO2 ) was supplied by Shanghai Creation Technology&Trade Co, Ltd., China. Phenylbenzimidazole sulphonic acid (PBSA) was from DSM (The Netherlands). Deionized water was purified by purifiers (MilliQ/Millipore, United States). Carboxymethylcellulose (CMC) was of Ashland (United States). Carboxymethyl chitosan (CM-chitosan) was synthesized according to the previous study [20].

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2.2. Methods 2.2.1. Preparation of biocomposite Cellulose fibre and carboxymethylcellulose (CMC) from Ananas comosus (pineapple) peel were prepared following the previous studies [3,21] with modifications. The biocomposite was prepared by mixing CM-chitosan solution with CMC solution and then FA solution was added as a cross linker, the reaction was kept under magnetic stirring for 60 min. The biocomposite was separated by centrifugation and then dried at ambient temperature. To prepare biocomposite as delivery system for sunscreen, PBSA and TiO2 were added into CM-chitosan and CMC solution, the reaction mixture was mixed homogeneously prior to addition of natural cross-linker FA. The optimal concentration of PBSA and TiO2 (1–3%w) was studied.

2.2.2. Fourier transform infrared spectroscopy (FT-IR) FT-IR spectra of samples were obtained by using Fourier transform infrared spectroscopy (FT-IR) (PerkinElmer, FT-IR Spectro GX, United States). Samples were recorded from 4000 to 400 cm−1 at resolution 4 and 16 scans per sample using KBr diffusion method.

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Fig. 3. FT-IR spectra of FA, CMC, CM-chitosan, CMC- FA complex and CM-chitosan-FA complex.

2.2.3. Scanning electron microscopy (SEM) Surface morphology of samples was examined by using scanning electron microscopy, SEM (Leo, 1450VP LEO, Germany). Samples were coated with gold on a double sided aluminium tape. 2.2.4. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) Thermal analysis was investigated by using Differential scanning calorimetry, DSC (Mettler Toledo 822e, Switzerland) and Thermogravimetric analysis, TGA (Mettler Toledo 851e, Switzerland). DSC was recorded at heating rate of 10 ◦ C/min between temperature 25–500 ◦ C under N2 atmosphere. Samples about 2–5 mg were prepared into aluminum pan and blank aluminum pan was used as control. TGA was analyzed at heating rate of 10 ◦ C/min between 25 and 500 ◦ C under N2 atmosphere. Samples about 2–5 mg were prepared into alumina crucibles and blank alumina crucibles was used as control. 2.2.5. X-ray diffraction (XRD) The diffraction pattern was verified by using X-ray Diffractometer, XRD (PANalytical, X’Pert Pro MPD, The Netherlands) with CuK-Alpha1 radiation. Sample (1–2 g) was measured at 2Â = 5 − 60◦ with scan speed 0.001–0.002◦ min−1 . 2.2.6. Sun protection factor (SPF) Sun protection factor, SPF, was studied by using an SPF analyzer (Optometrics LLC/SPF 290F, United States). Samples (2% compound) was applied on transpore tape at concentration of 0.1 ␮L/cm2 and investigated at wavelength between 290 and 400 nm. 3. Results and discussion 3.1. Preparation of biocomposite Pineapple peel CMC is cellulose ether prepared in aqueous alkaline medium using monochloroacetic acid and about 22% yield Please cite this article in press as: http://dx.doi.org/10.1016/j.ijbiomac.2016.10.069

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was obtained. The successful preparation of pineapple peel CMC has been confirmed by comparing with commercial CMC using FT-IR, DSC, and TGA techniques [22]. The SEM analysis showed that the synthesized CMC has rough surface, which may cause by using strong chemicals [23] while commercial CMC possesses a relative smooth surface, Fig. 1. The biocomposite was then prepared by adding the ferulic acid (FA) into a suspension mixture of CMC and CM-chitosan. An opaque solution was formed which indicated that the crosslinking occurred [24]. Various ratios of polymers and crosslinking agent in biocomposite preparation were investigated. The concentration of FA was studied by fixing the CMC: CM-chitosan ratio at 1: 2%w and FA was varied from 1.0 to 4.7%w. It was found that at 1–2.7% FA, the mixture was still clear and there was no precipitate obtained. At 3.3%w FA, small amount of solid occurred and when using FA at 4 and 4.7%w, the yield of precipitate was relatively close, Table 1. However, at 4.7%w FA, it resulted in a hard and rough texture solid, thus a ratio of 1:2:4%w (FA5, Table 1) was chosen due to it exhibited soft texture which is more suitable for application. Next, concentration of CMC was investigated by fixing CM-chitosan: FA at 2:4%w. It showed that at 0–1%w CMC, the yield of precipitate was quite similar but increasing the CMC further to 4%w the obtained precipitate decreased about 50%. Preparation at CMC1%w resulted in the smoothest texture with good yield (CMC3, Table 1), thus, this concentration was chosen to study the effect of CM-chitosan which it was varied from 0 to 3.3%w. The results guided that at 2%w CM-chitosan (CMCS3), the resulting composite possessed a reasonable yield with light yellow color, smooth and soft texture which is suitable for utilization as delivery system in cosmetics. Thus, the optimal ratio of CMC: CM-chitosan: FA is at 1:2:4%w, respectively. Biocomposites of commercial CMC and pineapple peel CMC exhibited fibre bundle-like surface observed by SEM technique (Fig. 2). The FT-IR spectra of the biocomposites are very similar to that of ferulic acid (data was not shown) and this was not possible to interpret the formation of new compounds. Thus, CMC and CM-chitosan was separately mixed with FA and the

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Fig. 4. DSC(a) and TGA(b) of biocomposites produced using commercial CMC and CMC from pineapple peel.

Table 1 Effects of CMC, CM-Chitosan and FA on the preparation of biocomposites. Code No

FA 1 FA 2 FA 3 FA 4 FA 5 FA 6 CMC 0 CMC 1 CMC 2 CMC 3 CMC 4 CMC 5 CMCS 0 CMCS 1 CMCS 2 CMCS 3 CMCS 4 CMCS 5

Weight ratio (%w) CMC

CM-chitosan

FA

1 1 1 1 1 1 0 0.34 0.66 1 2 4 1 1 1 1 1 1

2 2 2 2 2 2 2 2 2 2 2 2 0 0.66 1 2 2.7 3.3

1 2 2.7 3.3 4 4.7 4 4 4 4 4 4 4 4 4 4 4 4

Precipitate (g)

Physical appearance

None None None 0.14 0.24 0.26 0.29 0.27 0.29 0.28 0.17 0.18 0.40 0.44 0.33 0.32 0.34 0.27

– – – soft, light yellow powder soft, light yellow powder light yellow with hard and rough texture soft, yellow powder soft, light yellow powder soft, light yellow powder soft and smooth, light yellow powder soft and smooth, light yellow powder soft and smooth, light yellow powder soft, very light yellow powder soft, very light yellow powder soft, light yellow powder soft and smooth, light yellow powder soft and smooth, strong yellow powder soft and smooth, strong yellow powder

Bold values are varied parameters and the selected conditions.

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Fig. 5. XRD pattern of biocomposite of commercial CMC and biocomposite of CMC from pineapple peel.

Table 2 SPF values of biocomposite sunscreens. Sample

PBSA (P): TiO2 (T)ratio

SPF

Boost star rating

P1 P2 P3 T1 T2 T3 PTP2TP3TPT3PT2PT2(a)a

1: 02: 03: 00: 10: 20: 3 1: 12: 13: 11: 31: 21: 2

1.331.792.041.793.324.44 1.701.982.152.092.002.47

1 1 1 3 3 3 2 2 1 3 3 3

a

Biocomposite sunscreen from pineapple peel CMC

FT-IR characteristic was investigated. CMC exhibited absorption peak at 1600–1640 cm−1 and 1400–1450 cm−1 (C O and its salt), 1030 cm−1 (CHOCH2 ) and 1605 cm−1 (C O) [25]. Ferulic acid possessed peak at 3438 cm−1 (O H), 2900 cm−1 (C H), 1737 cm−1 (C O) and 1515 cm−1 (C C) [26]. After CMC solution was mixed with FA solution at 1:1%w, a pale yellow precipitate was formed. The FA-CMC complex exhibited broad peak at 3430 cm−1 which may shift from 3555 cm−1 of CMC and 3440 cm−1 (O H) of FA. The changes may due to the hydrogen bonding between hydroxyl group of CMC and carboxyl group of ferulic acid [27]. It should be noted here that FA-CMC complexes produced from commercial CMC and pineapple peel CMC exhibited relatively similar physical appearance and characteristic FT-IR peaks. The mixing of CM-chitosan and FA solution (FA-CM-chitosan complex) resulted in light brown sticky film. The complex exhibited absorption peak at 3400 cm−1 which may shift from 3440 cm−1 (O H) of FA and 3426 cm−1 (O H, N H) in CM-chitosan. Moreover, sharp peak at 1628 cm−1 (N H, COO) and 1439 cm−1 (COO) in CM-chitosan were also shifted to 1650 cm−1 and 1522 cm−1 with less intensity in the compound (Fig. 3). The changes indicated that the crosslinking may occur at amine group of chitosan and carboxylic group of FA [13]. DSC thermogram of both biocomposites showed relatively similar endothermic peaks at 100, 166 ◦ C and in the range of 190–200, 220–230 and 300–330 ◦ C and the correspondingly weight loss was also revealed in TGA analysis as shown in Fig. 4. Moreover, XRD analysis was also used to investigate the formation of both biocomposites and the results are illustrated in Fig. 5. It can be seen that both exhibited quite similar patterns which indicated same crystallinity. However, biocomposite of CMC from pineapple peel exhibited two peaks of 2Â at 26◦ and 29◦ which is

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different from commercial CMC, and these peaks may assign to cellulose I crystalline which still left in the compound. Though, its presence was not crucial for biocomposite preparation as seen from results of other analysis techniques mentioned earlier. Additionally, both biocomposites exhibited absorption properties at 280–350 nm determined by UV–vis spectrophotometry which indicated that they have UVA and UVB protection [22]. The sun protection may contribute from a cross-linker FA [14]. The as-prepared biocomposites solution (2 mL) was filled in cuvette without air bubbles and the particle size of samples was measured by using Zetasizer nano (Malvern ZS90, United Kingdom) and the particle size are 748 ± 29.854 nm (Pdi = 0.325 ± 0.068) and 626 ± 2 nm (Pdi = 0.14 ± 0.12) for biocomposites using commercial CMC and CMC from pineapple peel, respectively. All results indicated that pineapple peel CMC can be used to prepare biocomposite which have the properties quite similar to that when use commercial CMC. 3.2. Preparation of biocomposite containing sunscreens Sunscreen products are technically prepared by including both chemical and physical UV filters in order to meet the consumer requirements as broad spectrum (protection against UVA/UVB) and high UV protection product. To prepare biocomposite as delivery system for broad spectrum sunscreen, PBSA which absorb mostly UVB radiation and hydrophilic TiO2 which block UVB/UVA were added into biocomposite system. In order to determine the optimal concentration of both sunscreen agents, an aqueous form of each sunscreen (1–3%w) was blended with CMC and CM-chitosan solution, after that FA solution was added at ambient temperature and reaction was maintained for 60 min. It must be stated here that

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Fig. 6. SEM images of PBSA, TiO2 and biocomposite containing sunscreens.

the commercial CMC was primarily used to prepare biocomposite sunscreen for this part justified by its availability and the pineapple peel CMC was then used to compare with the selected optimal system. It was found that SPF value increased when increasing concentration of both sunscreen (Table 2). When using PBSA at high concentration, hard, yellow plates were formed. TiO2 at high concentration showed white opaque characteristic when applied on the skin. The mixture of both sunscreen at the PBSA: TiO2 ratio of 1:2%w (PT2) was selected as optimal condition as it provided

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the SPF value of 2.00 which is relatively close to those with 2 and 3%w PBSA (P2T and P3T) and presented higher UVA protection with boost star rating of 3. The biocomposite sunscreen using pineapple peel CMC was then prepared at this concentration, and the system exhibited the same boost star rating with relative higher SPF value of 2.47, Table 2. The higher SPF may result from a better or even distribution of sunscreen agents in the system. SEM images of sunscreen agents and biocomposite sunscreen, both from commercial and pineapple peel CMC, are presented in Fig. 6. The addition of

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Fig. 7. FT-IR spectra of biocomposite, biocomposite containing sunscreen, PBSA and TiO2 .

Fig. 8. DSC(a) and TGA(b) of biocomposite, biocomposite containing sunscreen, PBSA and TiO2 .

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sunscreens into the system resulted in different surface morphology of the biocomposite. The distribution of the PBSA and TiO2 in the biocomposites’ matrix is remarkably uniform with no aggregation of particles. This is useful in term of controlling the distribution of sunscreen for application in cosmetic vehicles. The FT-IR spectra of sunscreens and biocomposite containing sunscreen are shown in Fig. 7. The basic absorption peaks of PBSA showed characteristic peaks at 1631 cm−1 (N H), 1233 cm−1 and 1174 cm−1 (C N) [19]. The characteristic peaks of TiO2 are 3369 cm−1 (O H), 1456 cm−1 (Ti-O-Ti) and 788 cm−1 (Ti-O) [28]. When both sunscreens were added into biocomposite the characteristic peaks exhibited at 3290 cm−1 (O H), 1648 cm−1 (N H, COO), 1497 cm−1 (Ti-O-Ti) and 744 cm−1 (Ti-O) which confirmed the presence of sunscreen agent in the matrix. DSC thermogram and TGA curve of biocomposite and biocomposite containing sunscreens are shown in Fig. 8. The endothermic peak of biocomposite containing sunscreens was in the range of 75 and 360 ◦ C which related to the loss of water molecules and degradation of a cellulose structure, respectively [29]. TGA curve of biocomposite containing sunscreens showed water loss and decomposition of compound at range of 80–420 ◦ C which is relatively higher than that of blank biocomposite and this is due to the contained TiO2 . 4. Conclusions Biocomposite was successfully prepared from pineapple peel CMC and CM-chitosan using ferulic acid as a cross-linker at optimal ratio of CMC:CM-chitosan:FA at 1:2:4%w. The FI-IR results demonstrated that crosslinking may occur at amine group of CMchitosan and carboxyl group of ferulic acid and hydrogen bonding between hydroxyl group of the CMC and carboxyl group of ferulic acid. The biocomposite was demonstrated to be a good matrix for hydrophilic TiO2 and PBSA sunscreen at ratio of 2:1%w, respectively, and it showed SPF value of 2.47 with boost star rating of 3 at 2% compound. Acknowledgements This work is financially supported by the Higher Education Research Promotion Project of Thailand 2014 (project no. 2557A30762001) and Mae Fah Luang University is acknowledged for space and facilities support.. References [1] L.M.J. de Carvalho, I.M. de Castro, C.A.B. da Silva, A study of retention of sugars in the process of clarification of pine apple juice (Ananas comosus, L. Merril) by micro- and ultra-filtration, J. Food Eng. 87 (2008) 447–454. [2] S. Ketnawa, P. Chaiwut, S. Rawdkuen, Pineapple wastes: a potential source for bromelain extraction, Food Bioprod. Process. 90 (2012) 385–391. [3] X. Hu, K. Hu, L. Zeng, M. Zhao, H. Huang, Hydrogels prepared from pineapple peel cellulose using ionic liquid and their characterization and primary sodium salicylate release study, Carbohydr. Polym. 82 (2010) 62–68. [4] L.M.M. Costa, G.M. de Olyveira, B.M. Cherian, A.L. Leao, S.F. de Souza, M. Ferreira, Bionanocomposites from electrospun PVA/pineapple nanofibers/Stryphnodendron adstringens bark extract for medical applications, Ind. Crop. Prod. 41 (2013) 198–202.

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