اصلاح کامپوزیت نشاسته-اسید اولئیک با استفاده از روش اصلاح نوری تشدیدیافته به کمک نانو دی‌اکسید تیتانیوم: بررسی خصوصیات کاربردی در بسته‌بندی مواد غذایی

نوع مقاله : مقاله پژوهشی فارسی

نویسندگان

• رحمت اله پورعطا ¹
• حمید جهانگیر اصفهانی ²
• ایمان شهابی قهفرخی ²

¹ گروه شیمی، دانشگاه زنجان، زنجان، ایران.

² گروه علوم و صنایع غذایی، فناوری مواد غذایی، دانشگاه زنجان، زنجان، ایران.

https://doi.org/10.22067/ifstrj.2021.40178.0

چکیده

در میان پلیمرهای زیست‌تخریب‌پذیر، استفاده از نشاسته به علت قیمت ارزان و دسترسی آسان از اهمیت به‌سزایی برخوردار است، اما به علت مقاومت کم و آبدوستی زیاد در این بیوپلیمر، هنوز استفاده از آن در صنعت بسته‌بندی عملیاتی نشده است. هدف از این پژوهش، اصلاح ویژگی‌های آبدوستی و مکانیکی فیلم نشاسته با استفاده هم‌زمان از اسید اولئیک، نانو دی‌اکسید تیتانیوم (TiO₂) و پرتو فرابنفش (UV-C) بود. در این پژوهش، محلولِ نشاسته- اسیداولئیک- TiO₂ تهیه؛ و به‌منظور بهبود خصوصیات کاربردی آن، این محلول در بازه‌های زمانی (صفر، 30، 60 و 90 دقیقه) توسط پرتوUV-C  اصلاح گردید، سپس فیلم آن به روش قالب‌گیری محلول تهیه شد. جهت بررسی خصوصیات کاربردی فیلم در بسته‌بندی مواد غذایی ضخامت، مقاومت مکانیکی، زاویه تماس، نفوذپذیری نسبت به بخارآب، جذب رطوبت، محتوای رطوبت و حلالیت فیلم‌ها مورد بررسی قرار گرفتند. آزمون‌ها در قالب طرح کاملا تصادفی اجرا، و نتایج آن به روش دانکن مورد مقایسه قرار گرفتند. نتایج نشان دادند، که با افزودن اسید اولئیک و TiO₂ به محلول نشاسته، زاویه تماس به‌طور قابل‌ملاحظه‌ای از 26/72 به 34/90 درجه افزایش و نفوذپذیری نسبت به بخارآب و جذب رطوبت فیلم‌های نشاسته‌ای کاهش می‌یابد. در مطالعه خواص مکانیکی نیز مشاهده شد که با افزودن اسید اولئیک و TiO₂، مقاومت کششی و الاستیسیته کاهش و کشش‌پذیری و انرژی کششی تا لحظه پاره شدن افزایش یافته است. با اعمال پرتودهی در بازه زمانی کوتاه‌مدت (30 دقیقه)، تمامی پارامترهای مربوط به خواص مکانیکی افزایش، و حلالیت به آب و جذب رطوبت فیلم‌های نشاسته‌ای کاهش یافتند. به‌نظر می‌رسید، استفاده همزمان از UV-C و TiO₂ باعث بهبود اثر پرتو UV-C جهت ایجاد اتصالات عرضی در ماتریس بیوپلیمر به صورت نشاسته- نشاسته و نشاسته- اسید اولئیک شود؛ با این حال، استفاده از TiO₂ باعث تشدید اثر پرتوی UV-C و تسریع تغییرات آن در بازه زمانی کوتاه‌تری (30 دقیقه) شد. به‌طور کلی به‌منظور بهبود خاصیت آبگریزی وخواص مکانیکی فیلم نشاسته، استفاده از اسید اولئیک و TiO₂ به‌صورت توأم بهترین نتایج این پژوهش را در برداشته است. از این رو یک گام رو به جلو برای استفاده صنعتی از نشاسته در بسته‌بندی مواد غذایی به حساب می‌آید.

کلیدواژه‌ها

• آب‌گریزی
• اسید اولئیک
• نشاسته
• نانو TiO2
• UV

موضوعات

• فناوری مواد غذایی

عنوان مقاله [English]

Photo-Modification of starch-oleic acid by TiO2: investigation of food packaging properties

نویسندگان [English]

• Rahmatollah Pourata ¹
• Hamid Jahangir-Esfahani ²
• Iman Shahabi-Ghahfarrokhi ²

¹ Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, Iran.

² Department of Food Science and Engineering, Faculty of Agriculture, University of Zanjan, Zanjan, Iran.

چکیده [English]

Introduction: Among the bio-based materials which used in the food packaging, starch is interested as an ecofriendly material. This interest is mainly due to its acceptable film forming properties, easy access, renewability and low cost. Nevertheless, high hydrophilic and weak mechanical properties have been limited its utilization as a commercial packaging material. Many researches have been done to reduce hydrophilic properties of starch using chemical modification, irradiation, and composition with nanoparticles and other biopolymers. Most of the methods are based on blocking the hydroxyl groups of starch chains with hydrophobic agents, formation of emulsions and blocking of the pores. Fatty acids, such as oleic acid (OA) are lipid derivatives that can potentially improve the moisture barrier properties of hydrophilic films. OA is a yellow liquid at room temperature and miscible with biopolymer without further heating treatment. Due to the polar nature of biopolymers, OA needs to surfactant to get homogenous distribution in the matrix of biopolymers. On the other hand, OA is not very sensitive to oxidation which increases its safety in food packaging applications. Titanium dioxide (TiO₂) is an inert, cheap and nontoxic material with broad application as a food pigment and potential activity against a wide variety of microorganism due to its photocatalytic activity.TiO₂ is the most commonly used semiconductor, photocatalyst which activated by UV ray. The main purpose of the current study was modification of starch hydrophilicity using OA, nano-titanium dioxide and UV ray. In this study OA and TiO₂ added at the optimized condition and the solution was irradiated by UV ray.
 
Materials and Methods: A starch solution 5 (wt. %) in distilled water was prepared. This solution was mixed and heated (85 ˚C for 15 min) until the starch gelatinized. Thus, plasticizer (glycerol, 40 wt. % of dry base) was incorporated into the solution to achieve more-flexible films. OA 1(wt. % of dry base) mixed with Tween 80 as emulsifier (10 wt. % of the OA). This solution was mixed and heated (50 ˚C for 10 min). Then, 10 ml of distilled water was added to the solution, and homogenized by ultrasonic homogenizer (Dr. Hielscher, Teltow, Germany) for 7 min. The suspension of TiO₂ nanoparticles in water was prepared so that the final TiO₂ content in film specimens was 2 (wt % of dry base). The suspensions were stirred for 10 min, and homogenized by ultrasonic homogenizer for 60 min. The TiO₂ suspension was added to starch solution gradually and mixed for 10 min. Afterward, OA- Tween 80 solution was added to starch solution gradually and mixed for 10 min.
The starch solution containing TiO₂ and OA was homogenized by ultrasonic homogenizer for 7 min. Film forming solution placed under three UV-C lamps (8w, Phillips, Holland) at a distance of 5 cm. The solutions were stirred simultaneously with UV irradiation. After 0, 30, 60 and 90 min of UV exposure, the air bubbles were removed and the solutions were casted into flat, leveled, non-stick disposable 15 cm-Petri dishes. Each of the dishes were contain 43 g which dried for 48 hours at room temperature. All the film specimens were conditioned at 50-55% relative humidity and room temperature for 48 hours before subjected to further analysis.
Moisture content (MC), moisture absorption (MA), solubility in water (SW), water vapor permeability (WVP), surface properties, visual properties and mechanical properties of the film specimens were measured. The chemical structure of the films was investigated by FTIR spectroscopy.
Results and Discussion: The results shown that water contact angle of the starch film was increased by adding OA and TiO₂. But it was decreased after UV exposure of the starch-OA-TiO₂ solution. WVP of the starch based films was decreased by its composition with OA and TiO₂. But no change was observed after UV exposure of the starch-OA-TiO₂ compositions. MC of the starch-OA-TiO₂ film had no change, simultaneously.
 However, the tensile strength and Young’s modulus were decreased by adding OA-TiO₂. Elongation at break and tensile energy to break were increased, simultaneously. However, the mechanical properties of the starch-OA-TiO₂ nanocomposites were changed by UV exposure but these changes did not follow a specific trend.
Although, whiteness index (WI) and total color difference (ΔE) were not changed by OA-TiO₂ composition. But yellowness index (YI) was changed, simultaneously. After UV irradiation ΔE and YI were increased and WI was decreased. The results, demonstrated that the virgin starch-OA-TiO₂ composition was the best modification method to decrease the sensibility of starch based films to moisture as a packaging material. UV irradiation at short time (30 min) was the optimum condition to modify sensibility of the films to moisture and mechanical properties among the UV cured films.

کلیدواژه‌ها [English]

• Hydrophobicity
• Oleic acid
• Starch
• nano TiO2
• Ultraviolet ray

مراجع

1. Almasi, H., Ghanbarzadeh, B., & Pezeshki, N. A. (2009). Improving the physical properties of starch and starch–carboxymethyl cellulose composite biodegradable films. Iranian Journal of Food Science And Technology, 6(3), 1-11.
2. Hassannia-Kolaee, M. Khodaiyan F. Pourahmad, R & Shahabi-Ghahfarokhi, I. (2015). Functional Properties of Composite Edible Film Based Made with Whey Protein-Pullulan. Journal of Agricultural Engineering Research,16(3),45-56
3. Jahangir-Esfahani,H, Shahabi-Ghahfarrokhi, I & Pourata, R. (2020) Modification of hydrophilic properties of starch film by simultaneous use of oleic acid and UV ray.Food Research, 29 (4),125-138

4.       Jahangir Esfahani, H., Shahabi-Ghahfarrokhi, I. (2018). A Review of the Methods for Modification of Hydrophilic Properties of Starch Based Biopolymers as a Biodegradable Food Packaging Material.9(34),32-45

5. Jahangir-Esfahani, H., Shahabi-Ghahfarrokhi, I & Pourata, R. (2020). Photochemical Modification of Starch-Oleic Acid Composite as a Biodegradable Film in Food Packaging.Iranian Journal of Biosystem Engineering.51(3),643-654
6. Ashton, H., & Fletcher, D. (1962). Development and use of color standards for egg yolks. Poultry science, 41(6), 1903-1909. https://doi.org/10.3382/ps.0411903
7. Campos, A. d., Marconcini, J., Martins-Franchetti, S., & Mattoso, L. (2012). The influence of UV-C irradiation on the properties of thermoplastic starch and polycaprolactone biocomposite with sisal bleached fibers. Polymer degradation and stability, 97(10), 1948-1955. https://doi.org/10.1016/j.polymdegradstab.2011.11.010
8. Díaz, O., Candia, D., & Cobos, Á. (2016). Effects of ultraviolet radiation on properties of films from whey protein concentrate treated before or after film formation. Food Hydrocolloids, 55, 189-199. https://doi.org/10.1016/j.foodhyd.2015.11.019
9. Fei, P., Shi, Y., Zhou, M., Cai, J., Tang, S., & Xiong, H. (2013). Effects of nano‐TiO2 on the properties and structures of starch/poly (ε‐caprolactone) composites. Journal of Applied Polymer Science, 130(6), 4129-4136. https://doi.org/10.1002/app.39695
10. Gennadios, A., Rhim, J., Handa, A., Weller, C., & Hanna, M. (1998). Ultraviolet radiation affects physical and molecular properties of soy protein films. Journal of food science, 63(2), 225-228. https://doi.org/10.1111/j.1365-2621.1998.tb15714.x
11. Ghanbarzadeh, B., & Almasi, H. (2011). Physical properties of edible emulsified films based on carboxymethyl cellulose and oleic acid. International journal of biological macromolecules, 48(1), 44-49. https://doi.org/10.1016/j.ijbiomac.2010.09.014
12. Ghasemlou, M., Khodaiyan, F., Oromiehie, A., & Yarmand, M. S. (2011). Characterization of edible emulsified films with low affinity to water based on kefiran and oleic acid. International journal of biological macromolecules, 49(3), 378-384. https://doi.org/10.1016/j.ijbiomac.2011.05.013
13. Goudarzi, V., & Shahabi-Ghahfarrokhi, I. (2017). Photo-producible and photo-degradable starch/TiO₂ bionanocomposite as a food packaging material: Development and characterization. International journal of biological macromolecules. https://doi.org/10.1016/j.ijbiomac.2017.08.058
14. Goudarzi, V., Shahabi-Ghahfarrokhi, I., & Babaei-Ghazvini, A. (2017). Preparation of ecofriendly UV-protective food packaging material by starch/TiO 2 bio-nanocomposite: Characterization. International journal of biological macromolecules, 95, 306-313. https://doi.org/10.1016/j.ijbiomac.2016.11.065
15. Goudarzi, V., & Shahabi-Ghahfarrokhi, I. (2017). Production of starch film by photochemical reactions: Physicochemical characterization. Food Research,26(3),519-530.
16. Jamal Abadi, M., & Sarem Nejad, S. (2015). Investigation on the Physicochemical Properties of Ultrasound Treated Wheat Starch. Food Science and Technology, 13(53), 127-136.
17. Kim, J. K., Jo, C., Park, H. J., & Byun, M. W. (2008). Effect of gamma irradiation on the physicochemical properties of a starch-based film. Food Hydrocolloids, 22(2), 248-254. https://doi.org/10.1016/j.foodhyd.2006.11.010
18. Kovács, V., Gondor, O. K., Szalai, G., Majláth, I., Janda, T., & Pál, M. (2014). UV-B radiation modifies the acclimation processes to drought or cadmium in wheat. Environmental and experimental botany, 100, 122-131. https://doi.org/10.1016/j.envexpbot.2013.12.019
19. Li, X.-M., Reinhoudt, D., & Crego-Calama, M. (2007). What do we need for a superhydrophobic surface? A review on the recent progress in the preparation of superhydrophobic surfaces. Chemical Society Reviews, 36(8), 1350-1368. DOI:https://doi.org/10.1039/B602486F
20. Oleyaei, S, A., Ghanbarzadeh, B., Moayed, A, A., Poursani, P, & Khatamian, M. (2015). Preparation and Characterization of Nanostructural and Physicochemical Properties of Starch-TiO2 Biocomposite Films. Innovative Food Technologies. 2 (4),87-101
21. Li, Y., Jiang, Y., Liu, F., Ren, F., Zhao, G., & Leng, X. (2011). Fabrication and characterization of TiO₂/whey protein isolate nanocomposite film. Food Hydrocolloids, 25(5), 1098-1104. https://doi.org/10.1016/j.foodhyd.2010.10.006
22. Li, Z., Mi, L., Wang, P.-N., & Chen, J.-Y. (2011). Study on the visible-light-induced photokilling effect of nitrogen-doped TiO 2 nanoparticles on cancer cells. Nanoscale research letters, 6(1), 356. https://doi.org/10.1186/1556-276X-6-356
23. Li, Z., Pan, X., Wang, T., Wang, P.-N., Chen, J.-Y., & Mi, L. (2013). Comparison of the killing effects between nitrogen-doped and pure TiO₂ on HeLa cells with visible light irradiation. Nanoscale research letters, 8(1), 96. https://doi.org/10.1186/1556-276X-8-96
24. Linsebigler, A. L., Lu, G., & Yates Jr, J. T. (1995). Photocatalysis on TiO₂ surfaces: principles, mechanisms, and selected results. Chemical reviews, 95(3), 735-758. https://doi.org/10.1021/cr00035a013
25. Linthorst, J. (2010). An overview: origins and development of green chemistry. Foundations of chemistry, 12(1), 55-68. https://doi.org/10.1007/s10698-009-9079-4
26. Lv, J., Shen, Y., Peng, L., Guo, X., & Ding, W. (2010). Exclusively selective oxidation of toluene to benzaldehyde on ceria nanocubes by molecular oxygen. Chemical communications, 46(32), 5909-5911. https://doi.org/10.1039/C0CC00777C
27. Mohanty, A., Misra, M., & Hinrichsen, G. (2000). Biofibers, biodegradable polymers and biocomposites: an overview. Macromolecular materials and Engineering, 276(1), 1-24. https://doi.org/10.1002/(SICI)1439-2054(20000301)276:1<1::AID-MAME1>3.0.CO;2-W
28. Ojagh, S. M., Rezaei, M., Razavi, S. H., & Hosseini, S. M. H. (2010). Development and evaluation of a novel biodegradable film made from chitosan and cinnamon essential oil with low affinity toward water. Food Chemistry, 122(1), 161-166. https://doi.org/10.1016/j.foodchem.2010.02.033
29. Ozdemir, M., & Floros, J. D. (2004). Active food packaging technologies. Critical reviews in food science and nutrition, 44(3), 185-193. https://doi.org/10.1080/10408690490441578
30. Shahabi-Ghahfarrokhi, I., & Babaei-Ghazvini, A. (2018). Using photo-modification to compatibilize nano-ZnO in development of starch-kefiran-ZnO green nanocomposite as food packaging material. International journal of biological macromolecules. 124, 922-930. https://doi.org/10.1016/j.ijbiomac.2018.11.241
31. Shahabi-Ghahfarrokhi, I., Khodaiyan, F., Mousavi, M., & Yousefi, H. (2015). Effect of γ-irradiation on the physical and mechanical properties of kefiran biopolymer film. International journal of biological macromolecules, 74, 343-350. https://doi.org/10.1016/j.ijbiomac.2014.11.038
32. Singh, J., Kaur, L., & McCarthy, O. (2007). Factors influencing the physico-chemical, morphological, thermal and rheological properties of some chemically modified starches for food applications—A review. Food Hydrocolloids, 21(1), 1-22. https://doi.org/10.1016/j.foodhyd.2006.02.006
33. Sionkowska, A., Skopinska-Wisniewska, J., Planecka, A., & Kozlowska, J. (2010). The influence of UV irradiation on the properties of chitosan films containing keratin. Polymer degradation and stability, 95(12), 2486-2491. https://doi.org/10.1016/j.polymdegradstab.2010.08.002
34. Slavutsky, A. M., & Bertuzzi, M. A. (2015). Formulation and characterization of nanolaminated starch based film. LWT Food Science and Technology, 61(2), 407-413. https://doi.org/10.1016/j.lwt.2014.12.034
35. Tang, S., Zou, P., Xiong, H., & Tang, H. (2008). Effect of nano-SiO2 on the performance of starch/polyvinyl alcohol blend films. Carbohydrate Polymers, 72(3), 521-526. https://doi.org/10.1016/j.carbpol.2007.09.019
36. Vargas, M., Albors, A., Chiralt, A., & González-Martínez, C. (2009). Characterization of chitosan–oleic acid composite films. Food Hydrocolloids, 23(2), 536-547. https://doi.org/10.1016/j.foodhyd.2008.02.009
37. Wang, X.-Y., Mertz, D., Blanco-Andujar, C., Bora, A., Ménard, M., Meyer, F., Bégin-Colin, S. (2016). Optimizing the silanization of thermally-decomposed iron oxide nanoparticles for efficient aqueous phase transfer and MRI applications. RSC Advances, 6(96), 93784-93793. DOI: 1039/C6RA18360C
38. Zhou, J., Wang, S., & Gunasekaran, S. (2009). Preparation and characterization of whey protein film incorporated with TiO2 nanoparticles. Journal of food science, 74(7), N50-N56. https://doi.org/10.1111/j.1750-3841.2009.01270.x