Preparation and Properties of pH-responsive PVA/CMC Hydrogels

LIU Lirui; DONG Shiyuan; QIAO Jingcheng; ZHANG Gaimei; SHI Jiazi; FU Yabo; QIAO Junwei; LIU Hui

doi:10.19554/j.cnki.1001-3563.2026.03.005

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Packaging Engineering ›› 2026, Vol. 47 ›› Issue (3) : 44-51. DOI: 10.19554/j.cnki.1001-3563.2026.03.005

Advanced Materials

Preparation and Properties of pH-responsive PVA/CMC Hydrogels

LIU Lirui¹, DONG Shiyuan¹, QIAO Jingcheng¹, ZHANG Gaimei¹, SHI Jiazi¹, FU Yabo¹, QIAO Junwei², LIU Hui^1,*

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Abstract

The work aims to develop a biodegradable pH indicator material suitable for fresh food preservation, enabling non-destructive and visual monitoring of food freshness. Poly(vinyl alcohol)/carboxymethyl cellulose (PVA/CMC) was employed as the polymer matrix, while black goji berry anthocyanin (BA) acted as the color-sensitive component. The PVA/CMC-BA composite hydrogel was prepared with sodium tripolyphosphate (STPP) via ionic and hydrogen-bond synergistic crosslinking. Fourier transform infrared spectroscopy and X-ray diffraction analyses revealed intermolecular interactions (such as hydrogen bonding) among the components, and the incorporation of BA significantly enhanced the crystallinity of the composite hydrogel. When the BA content was 4 wt%, the hydrogel exhibited optimal mechanical properties, with a tensile strength of 0.319 MPa and an elongation at break of 163%. The antioxidant activity increased with the BA concentration, reaching a maximum DPPH radical scavenging rate of 81%. The composite hydrogel demonstrated a distinct and visually perceptible color transition under varying pH conditions. In pork preservation experiments, when the total volatile basic nitrogen (TVB-N) value reached 10-15 mg/100 g, the color difference (ΔE) of the hydrogel exceeded the human perceptibility threshold, enabling early spoilage warning. These results suggest that the PVA/CMC-BA hydrogel integrates excellent mechanical strength, antioxidant capability, and pH sensitivity, showing great potential as a biodegradable, visual freshness indicator for chilled meat and other perishable foods.

Key words

smart packaging / carboxymethyl cellulose / polyvinyl alcohol / black goji berry anthocyanins / pH indicator

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LIU Lirui, DONG Shiyuan, QIAO Jingcheng, ZHANG Gaimei, SHI Jiazi, FU Yabo, QIAO Junwei, LIU Hui. Preparation and Properties of pH-responsive PVA/CMC Hydrogels[J]. Packaging Engineering. 2026, 47(3): 44-51 https://doi.org/10.19554/j.cnki.1001-3563.2026.03.005

References

[1] ASLAM M, ALI RAZA Z, SIDDIQUE A.Fabrication and Chemo-Physical Characterization of CuO/Chitosan Nanocomposite-Mediated Tricomponent PVA Films[J]. Polymer Bulletin, 2021, 78(4): 1955-1965.
[2] SIRVIÖ J A, HONKANIEMI S, VISANKO M, et al.Composite Films of Poly(vinyl alcohol) and Bifunctional Cross-Linking Cellulose Nanocrystals[J]. ACS Applied Materials & Interfaces, 2015, 7(35): 19691-19699.
[3] 李章康, 白绘宇. 聚乙烯醇/纤维素包装材料的研究进展[J]. 塑料包装, 2018, 28(4): 16-19.
LI Z K, BAI H Y.The Research Development of Polyvinyl Alcohol/Cellulose Packaging Materials[J]. Plastics Packaging, 2018, 28(4): 16-19.
[4] GAO C, WANG S, LIU B J, et al.Sustainable Chitosan-Dialdehyde Cellulose Nanocrystal Film[J]. Materials, 2021, 14(19): 5851.
[5] 宋亭, 张丽媛, 于润众. 基于玉米秸秆纳米纤维素复合膜的研制及性能研究[J]. 食品与发酵工业, 2023, 49(21): 137-144.
SONG T, ZHANG L Y, YU R Z.Preparation and Properties of Corn Straw Nano-Cellulose Composite Membrane[J]. Food and Fermentation Industries, 2023, 49(21): 137-144.
[6] 张丽平, 余晓琴. 羧甲基纤维素钠(CMC)在食品工业应用的情况和研究动态[J]. 中国食品添加剂, 2006, 17(1): 118-125.
ZHANG L P, YU X Q.Application of CMC in Food Industry and Its Development[J]. China Food Additives, 2006, 17(1): 118-125.
[7] 陈妮娜, 曾稍俏, 黄木花, 等. 羧甲基纤维素基可食性复合膜的制备及在葡萄保鲜中的应用[J]. 河南工业大学学报(自然科学版), 2016, 37(6): 96-102.
CHEN N N, ZENG S Q, HUANG M H, et al.Preparation of Carboxymethyl cellulose-Based Edible Composite Film and Its Application in Preservation of Grapes[J]. Journal of Henan University of Technology (Natural Science Edition), 2016, 37(6): 96-102.
[8] JIANG G Y, HOU X Y, ZENG X D, et al.Preparation and Characterization of Indicator Films from Carboxymethyl-Cellulose/Starch and Purple Sweet Potato (Ipomoea Batatas (L.) Lam) Anthocyanins for Monitoring Fish Freshness[J]. International Journal of Biological Macromolecules, 2020, 143: 359-372.
[9] 陈宝定, 谢锐邦, 黄丽婕, 等. CMC-PVA-β-CD三元复合水凝胶的制备[J]. 合成树脂及塑料, 2024, 41(1): 12-17.
CHEN B D, XIE R B, HUANG L J, et al.Preparation of CMC-PVA-β-CD Ternary Composite Hydrogel[J]. China Synthetic Resin and Plastics, 2024, 41(1): 12-17.
[10] 宋金香, 李美真, 赵士毅, 等. 天然黑枸杞色素在桑蚕丝染色工艺中的应用[J]. 毛纺科技, 2021, 49(5): 32-37.
SONG J X, LI M Z, ZHAO S Y, et al.Application of Natural Black Lycium Barbarum Pigment in Mulberry Silk Dyeing Process[J]. Wool Textile Journal, 2021, 49(5): 32-37.
[11] 樊振江, 孟楠, 栗亚琼, 等. 黑枸杞花青素提取工艺研究及其包装薄膜的制备与应用[J]. 中国食品添加剂, 2024, 35(8): 64-73.
FAN Z J, MENG N, LI Y Q, et al.Optimization of Extraction Process of Anthocyanins from Lycium Ruthenicum and the Preparation and Application of Packaging Films with Them[J]. China Food Additives, 2024, 35(8): 64-73.
[12] QIN Y, LIU Y P, YONG H M, et al.Preparation and Characterization of Active and Intelligent Packaging Films Based on Cassava Starch and Anthocyanins from Lycium Ruthenicum Murr[J]. International Journal of Biological Macromolecules, 2019, 134: 80-90.
[13] 王芳. 基于花青素的猪肉新鲜度智能指示包装膜的制备与研究[D]. 西安: 陕西科技大学, 2020.
WANG F.Preparation and Exploration of Intelligent Indication Packaging Film for Anthocyanin-Based Pork Freshness[D]. Xi’an: Shaanxi University of Science & Technology, 2020.
[14] 张潇, 周海旭, 高晗, 等. 紫甘蓝中花青素提取工艺及其抗氧化研究[J]. 河南科技学院学报(自然科学版), 2024, 52(3): 62-68.
ZHANG X, ZHOU H X, GAO H, et al.Extraction Technology and Antioxidant Research of Anthocyanins from Purple Cabbage[J]. Journal of Henan Institute of Science and Technology (Natural Science Edition), 2024, 52(3): 62-68.
[15] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准食品pH值的测定: GB 5009.237— 2016[S]. 北京: 中国标准出版社, 2017.
Determination of pH Value of Food in National Food Safety Standard: GB 5009 GB 5009.237-2016[S]. Beijing: Standards Press of China, 2017.
[16] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准食品中挥发性盐基氮的测定: GB 5009.228— 2016[S]. 北京: 中国标准出版社, 2017.
Determination of Volatile Base Nitrogen in Food Safety National Standards: GB 5009 GB 5009.228-2016[S]. Beijing: Standards Press of China, 2017.
[17] LAN W J, ZHANG R, AHMED S, et al.Effects of Various Antimicrobial Polyvinyl Alcohol/Tea Polyphenol Composite Films on the Shelf Life of Packaged Strawberries[J]. LWT, 2019, 113: 108297.
[18] 王红雨, 陈世广, 鄢云华, 等. 淀粉/聚乙烯醇/花青素复合膜的制备及其对牛奶新鲜度的指示[J]. 食品与发酵工业, 2025, 51(7): 228-235.
WANG H Y, CHEN S G, YAN Y H, et al.Preparation of Starch/Poly Vinyl Alcohol/Anthocyanin Composite Film and Its Indication for Milk Freshness[J]. Food and Fermentation Industries, 2025, 51(7): 228-235.
[19] JEYARAM S, GEETHAKRISHNAN T. Vibrational Spectroscopic, Linear and Nonlinear Optical Characteristics of Anthocyanin Extracted from Blueberry[J]. Results in Optics, 2020, 1: 100010.
[20] QI Y Y, LI Y N.Colorimetric Films Based on Polyvinyl Alcohol and Anthocyanins Extracted from Purple Tomato to Monitor the Freshness of Shrimp[J]. Polymers, 2024, 16(4): 495.
[21] GEOFFROY T R, MEDA N R, STEVANOVIC T.Suitability of DPPH Spiking for Antioxidant Screening in Natural Products: The Example of Galloyl Derivatives from Red Maple Bark Extract[J]. Analytical and Bioanalytical Chemistry, 2017, 409(22): 5225-5237.
[22] 吴奕婷, 马淑凤, 王利强. 纤维素/海藻酸钠/槲皮素@ZIF-8复合气凝胶的制备及猪肉保鲜应用[J]. 食品与发酵工业, 2025, 51(22): 180-188.
WU Y T, MA S F, WANG L Q.Fabrication of Cellulose/Sodium Alginate/quercetin@ZIF-8 Composite Aerogel and Its Application in Pork Preservation[J]. Food and Fermentation Industries, 2025, 51(22): 180-188.
[23] DENG N, HU Z Q, LI H, et al.Physicochemical Properties and Pork Preservation Effects of Lotus Seed Drill Core Powder Starch-Based Active Packaging Films[J]. International Journal of Biological Macromolecules, 2024, 260: 129340.
[24] 杜月红, 王琳, 高晓光, 等. 猪肉新鲜度指示标签的制备及应用[J]. 肉类研究, 2020, 34(5): 41-47.
DU Y H, WANG L, GAO X G, et al.Preparation and Application of Indicator Labels for Identification of Pork Freshness[J]. Meat Research, 2020, 34(5): 41-47.