Preparation and Properties of Chitosan Salicylaldehyde Hydrogel Loaded with Anthocyanins
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摘要: 在蓝莓花色苷(ACNs)存在下,以水杨醛为交联剂原位构筑了负载ACNs的壳聚糖水凝胶(ACNs/CS-SA),表征了其结构和形貌,研究了其稳定性、溶胀性能和缓释性能。FT-IR和XRD表征结果表明ACNs通过物理包埋均匀分散在水凝胶三维网络结构中;TG-DTG表征结果表明凝胶包埋显著提高了ACNs的热稳定性;ACNs/CS-SA的溶胀性能和缓释性能均展现出pH响应性;在pH2.7、4.6、6.7介质中,ACNs/CS-SA 24 h累计释药率分别为74.28%±4.58%、40.72%±4.04%和15.70%±1.71%;释放过程符合Weibull方程,R2分别为0.99405、0.95165和0.99712。鉴于ACNs/CS-SA的pH响应性能和对ACNs热稳定性的提高,本研究有望为新型药物包封材料的开发和ACNs的应用提供理论和实验基础。Abstract: In the presence of blueberry anthocyanins (ACNs), chitosan hydrogel crosslinking with salicylaldehyde (ACNs/CS-SA) was constructed. The structure and morphology of ACNs/CS-SA were characterized. The stability, swelling properties and ACNs controlled-release behaviors for the ACNs/CS-SA were investigated in the media of different pH. ACNs were uniformly dispersed in three-dimensional network structure of CS-SA hydrogel by physical embedding, which was confirmed by FT-IR and XRD characterization. The thermal stability of ACNs was significantly improved due to gelation, which was confirmed by TG-DTG characterization. Both the swelling properties and ACNs controlled-release behaviors for the ACNs/CS-SA exhibited pH response. In buffer media of pH2.7, 4.6 and 6.7, the cumulative release rates of ACNs for 24 h were 74.28%±4.58%, 40.72%±4.04% and 15.70%±1.71%, and the release process followed Weibull equation with the correlation coefficients R2 0.99405, 0.95165 and 0.99712, respectively. This study lays a theoretical and experimental foundation for the development of novel drug encapsulation materials and the application of ACNs owing to the ACNs/CS-SA pH responsiveness and ACNs thermal stability improvement.
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Key words:
- anthocyanins /
- chitosan hydrogel /
- stability /
- pH response /
- sustained release properties /
- dynamics
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表 1 100% ACNs/CS-SA释放动力学模型分析
Table 1. Release dynamics model analysis of 100% ACNs/CS-SA
模型 方程 R2 pH2.7 准一级 $\rm Q = 64.22519 \times [1 - \exp ( - 0.00683t)] $ 0.89566 准二级 $\rm Q = 1/(0.01328+1.63956/x) $ 0.95617 Higuchi $\rm Q = 1.94371{t^{1/2}}+12.00928 $ 0.91015 Weibull $\rm Q = 77.49016 \times \{ 1 - {e^{ - {{[0.00362(t+15.10121)]}^{0.7096}}}}\} $ 0.99405 Pepaas $\rm Q = 6.90565{t^{0.33862}} $ 0.95904 pH4.6 准一级 $\rm Q = 34.54011 \times [1 - \exp ( - 0.01705t)] $ 0.81687 准二级 $\rm Q = 1/(0.02534+1.21956/x) $ 0.91344 Higuchi $\rm Q = 0.94346{t^{1/2}}+13.24074 $ 0.76389 Weibull $\rm Q = 46.15881 \times \{ 1 - {e^{ - {{[0.00613(t - 7.72996)]}^{0.40212}}}}\} $ 0.95165 Pepaas $\rm Q = 7.594{t^{0.24816}} $ 0.88208 pH6.7 准一级 $\rm Q = 16.46357 \times [1 - \exp ( - 0.00273t)] $ 0.96812 准二级 $\rm Q = 1/(0.0473+19.09845/x) $ 0.94464 Higuchi $\rm Q = 0.46828{t^{1/2}}+0.02852 $ 0.83522 Weibull $\rm Q = 15.6828 \times \{ 1 - {e^{ - {{[0.00289(t+29.80457)]}^{1.63029}}}}\} $ 0.99712 Pepaas $\rm Q = 0.61095{t^{0.45867}} $ 0.84236 -
[1] ZHANG Y Z, YIN L Q, HUANG L, et al. Composition, antioxidant activity, and neuroprotective effects of anthocyanin-rich extract from purple highland barley bran and its promotion on autophagy[J]. Food Chemistry,2021,339(3):127849. [2] MILENKOVIC D, KRGA I, DINEL A L, et al. Nutrigenomic modification induced by anthocyanin-rich bilberry extract in the hippocampus of ApoE-/-mice[J]. Journal of Functional Foods,2021,85(10):104609. [3] GARCIA C, BLESSO C N. Antioxidant properties of anthocyanins and their mechanism of action in atherosclerosis[J]. Free Radical Biology and Medicine,2021,172(8):152−166. [4] GHAREAGHAJLOU N, HALLAJ-NEZHADI S, GHASEMPOUR Z. Red cabbage anthocyanins: Stability, extraction, biological activities and applications in food systems[J]. Food Chemistry,2021,365(12):130482. [5] PIMENTA INADA K O, REVOREDO SILVA T B, ARAUJO LOBO L, et al. Bioaccessibility of phenolic compounds of jaboticaba (Plinia jaboticaba) peel and seed after simulated gastrointestinal digestion and gut microbiota fermentation[J]. Journal of Functional Foods,2020,67(4):103851. [6] LEE J Y, JO Y U, SHIN H, et al. Anthocyanin-fucoidan nanocomplex for preventing carcinogen induced cancer: Enhanced absorption and stability[J]. International Journal of Pharmaceutics,2020,586(8):119597. [7] GUYOT C, CERRUTI M, LEROUGE S. Injectable, strong and bioadhesive catechol-chitosan hydrogels physically crosslinked using sodium bicarbonate[J]. Materials Science and Engineering:C,2021,118(1):111529. [8] XIE C J, WANG Q, YING R F, et al. Binding a chondroitin sulfate-based nanocomplex with kappa-carrageenan to enhance the stability of anthocyanins[J]. Food Hydrocolloid,2020,100(3):105448. [9] JIN W P, XIANG L, PENG D F, et al. Study on the coupling progress of thermo-induced anthocyanins degradation and polysaccharides gelation[J]. Food Hydrocolloids,2020,105(8):105822. [10] LIU L Y, ZHANG D D, SONG X X, et al. Compound hydrogels derived from gelatin and gellan gum regulates the release of anthocyanins in simulated digestion[J]. Food Hydrocolloids,2022,127(6):107487. [11] LI L, ZHANG P, LI C C, et al. In vitro/vivo antitumor study of modified-chitosan/carboxymethyl chitosan “boosted” charge-reversal nanoformulation[J]. Carbohyd Polymers,2021,269(10):118268. [12] IFTIME M M, MORARIU S, MARIN L. Salicyl-imine-chitosan hydrogels: Supramolecular architecturing as a crosslinking method toward multifunctional hydrogels[J]. Carbohyd Polymers,2017,165(2):39−50. [13] IFTIME M M, AILIESEI G L, UNGUREANU E, et al. Designing chitosan based eco-friendly multifunctional soil conditioner systems with urea controlled release and water retention[J]. Carbohydrate Polymers,2019,223(11):115040. [14] LIU C X, DONG C F, LIU S H, et al. Multiple chiroptical switches and logic circuit based on salicyl-imine-chitosan hydrogel[J]. Carbohyd Polymers,2021,257(4):117534. [15] BARDA C, GRAFAKOU M E, KALPOUTZAKISA E, et al. Chemical composition of Crepis foetida L. and C. rubra L. volatile constituents and evaluation of the in vitro anti-inflammatory activity of salicylaldehyde rich volatile fraction[J]. Biochemical Systematics and Ecology,2021,9(6):104256. [16] JANES D, KREFT S. Salicylaldehyde is a characteristic aroma component of buckwheat groats[J]. Food Chemistry,2008,109(2):293−298. doi: 10.1016/j.foodchem.2007.12.032 [17] SCHMIDT L, WIELSCH N, WANG D, et al. Tissue-specific profiling of membrane proteins in the salicin sequestering juveniles of the herbivorous leaf beetle, Chrysomela populi[J]. Insect Biochemistry and Molecular Biology,2019,109(6):81−91. [18] 王洪玲, 崔维真, 刘强, 等. 水杨醛交联壳聚糖构筑新型壁材包囊花椒油研究[J]. 食品与发酵工业,2022,48(8):199−204. [WANG Hongling, CUI Weizhen, LIU Qiang, et al. New wall material prepared by salicylaldehyde crosslinking chitosan encapsulated Zanthoxylum bungeanum oil[J]. Food and Fermentation Industries,2022,48(8):199−204. doi: 10.13995/j.cnki.11-1802/ts.029885 [19] 谢凤英, 李凤凤, 张爽, 等. 黑米花色苷酰化修饰红外光谱分析[J]. 光谱学与光谱分析,2018,38(8):2386−2389. [XIE Fengying, LI Fengfeng, ZHANG Shuang, et al. Analysis of acylation modification of black rice anthocyanins using Fourier transform infrared spectroscopy (FTIR)[J]. Spectroscopy and Spectral Analysis,2018,38(8):2386−2389. [20] 薛宏坤, 李鹏程, 钟雪, 等. 高速逆流色谱分离纯化桑葚花色苷及其抗氧化活性[J]. 食品科学,2020,41(15):96−104. [XUE Hongkun, LI Pengcheng, ZHONG Xue, et al. Separation and purification of anthocyanins from mulberry fruit by high-speed counter-current chromatography and their antioxidant activity[J]. Food Science,2020,41(15):96−104. doi: 10.7506/spkx1002-6630-20190715-193 [21] 王锋, 邓洁红, 谭兴和, 等. 花色苷及其共色作用研究进展[J]. 食品科学,2008,29(2):472−476. [WANG Feng, DENG Jiehong, TAN Xinghe, et al. Research progress on anthocyanins and copigmentation[J]. Food Science,2008,29(2):472−476. doi: 10.3321/j.issn:1002-6630.2008.02.104 [22] WANG D, MA Y, ZHANG C, et al. Thermal characterization of the anthocyanins from black soybean (Glycine max L.) exposed to thermogravimetry[J]. LWT-Food Science and Technology,2014,55(2):645−649. doi: 10.1016/j.lwt.2013.10.007 [23] WEN Y Y, LIU J, JIANG L, et al. Development of intelligent/active food packaging film based on TEMPO-oxidized bacterial cellulose containing thymol and anthocyanin-rich purple potato extract for shelf life extension of shrimp[J]. Food Packaging and Shelf Life,2021,29(9):100709. [24] HERAS-MOZOS R, HERNANDEZ R, GAVARA R, et al. Dynamic covalent chemistry of imines for the development of stimuli-responsive chitosan films as carriers of sustainable antifungal volatiles[J]. Food Hydrocolloids,2022,125(4):107326. [25] 董翠芳, 王洪玲, 刘长霞, 等. pH响应的壳聚糖-糠醛水凝胶的构筑及自愈合性能[J]. 高分子材料科学与工程,2020,36(11):127−133,138. [DONG Cuifang, WANG Hongling, LIU Changxia, et al. Fabrication of pH responsive chitosan-furfural hydrogel and its self-healing abilit[J]. Polymer Materials Science & Engineering,2020,36(11):127−133,138. doi: 10.16865/j.cnki.1000-7555.2020.0253 [26] IFTIME M M, TARTAU L M, MARIN L. New formulations based on salicyl-imine-chitosan hydrogels for prolonged drug release[J]. International Journal of Biological Macromolecules,2020,160(10):398−408. [27] CRACIUN A M, TARTAU L M, PINTEALA M, et al. Nitrosalicyl-imine-chitosan hydrogels based drug delivery systems for long term sustained release in local therapy[J]. Journal of Colloid and Interface Science,2019,536(2):196−207. [28] 刘中垒, 李国玉, 谭勇, 等. 红花黄色素缓释骨架片的研制及其体外释放度的研究[J]. 石河子大学学报(自然科学版),2009,27(3):328−333. [LIU Zhonglei, LI Gongyu, TAN Yong, et al. The preparation of safflower yellow sustained-release matrix tablets and their drug release in vitro[J]. Journal of Shihezi University (Natural Science),2009,27(3):328−333. doi: 10.3969/j.issn.1007-7383.2009.03.014