食品科学 ›› 2026, Vol. 47 ›› Issue (15): 287-296.doi: 10.7506/spkx1002-6630-20260202-011

• 包装贮运 • 上一篇    下一篇

基于离子液体增敏的pH值响应智能指示膜制备与虾鲜度可视化监测

陈琪璟,缪文华,陈思嘉,鲁慧琪,宋茜,赵亚东,郑斌   

  1. (1.浙江海洋大学食品与药学学院,浙江?舟山 316022;2.浙江工业大学食品科学与工程学院,浙江?杭州 310014)
  • 出版日期:2026-08-15 发布日期:2026-08-24
  • 基金资助:
    “十四五”国家重点研发计划项目(2023YFD2401504);舟山市重大产业科技攻关项目(2024C03004)

Preparation and Application of pH-responsive Intelligent Indicator Film based on Ionic Liquid Sensitization for Visual Monitoring of Shrimp Freshness

CHEN Qijing, MIAO Wenhua, CHEN Sijia, LU Huiqi, SONG Qian, ZHAO Yadong, ZHENG Bin   

  1. (1. College of Food and Pharmacy, Zhejiang Ocean University, Zhoushan 316022, China; 2. College of Food Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China)
  • Online:2026-08-15 Published:2026-08-24

摘要: 为解决传统水产品新鲜度监测中灵敏度不足的问题,本研究以氨基酸离子液体甘氨酸盐酸盐(glycine hydrochloride,[Gly]Cl)为绿色溶剂,通过碳二亚胺偶联法制备了壳聚糖-阿魏酸接枝物(chitosan grafted ferulic acid,CS-g-FA),并将其与聚乙烯醇(polyvinyl alcohol,PVA)和玫瑰茄花青素(roselle anthocyanin,RA)复合,同时添加[Gly]Cl作为增敏剂,制备一种高灵敏pH值响应智能指示膜(PVA/CS-g-FA/G/RA膜)。系统探究不同组分对指示膜的颜色响应特性、物理性能和微观形貌等的影响,并评价其在南美白对虾新鲜度监测中的应用效果。结果表明,[Gly]Cl通过氢键相互作用促进RA的去质子化,显著增强了指示膜的pH值敏感性,在水产品腐败特征pH值区间(pH 6~8)内,PVA/CS-g-FA/G/RA膜的∆E值从14.66±0.92增加至29.65±0.74。该指示膜对氨气展现出极佳的响应性,在80 mmol/L氨水条件下暴露90 min后,∆E值高达30.01±0.24。添加[Gly]Cl后,该指示膜的断裂伸长率回升至(10.35±0.90)%,水蒸气透过率提升至(2.64±0.50)×10-7 g/(m·Pa·s),有利于挥发性碱性物质的渗透。此外,该指示膜表现出优异的紫外阻隔能力和抗氧化活性,1,1-二苯基-2-三硝基苯肼自由基清除率达(86.73±0.71)%,且微观结构均匀致密。在南美白对虾新鲜度监测应用中,PVA/CS-g-FA/G/RA膜的颜色由深紫红色逐渐转变深红褐色,最后转变为深灰褐色,能够直观清晰地区分虾肉新鲜、次新鲜和腐败状态,其∆E值与总挥发性盐基氮含量呈显著正相关(R2=0.956 55)。综上,PVA/CS-g-FA/G/RA膜具有优异的环境敏感性与生物活性,在水产品智能指示包装领域具有广阔的应用前景。

关键词: 离子液体;壳聚糖;阿魏酸;智能指示膜;可视化;新鲜度监测

Abstract: In order to address the problem of insufficient sensitivity of traditional methods for the freshness monitoring of aquatic products, this study employed the amino acid-based ionic liquid glycine hydrochloride ([Gly]Cl) as a green solvent. Chitosan grafted ferulic acid (CS-g-FA) was prepared by the carbodiimide coupling method and complexed with polyvinyl alcohol (PVA) and roselle anthocyanin (RA). Subsequently, [Gly]Cl was added as a sensitizer to prepare a highly sensitive pH-responsive intelligent indicator film (PVA/CS-g-FA/G/RA). This study investigated the effects of different components on the color response characteristics, physical properties and microstructure of the indicator film, and evaluated its application performance in monitoring the freshness of Penaeus vannamei. The results demonstrated that [Gly]Cl promoted the deprotonation of RA through hydrogen bond interaction, which significantly enhanced the pH sensitivity of the indicator film. Within the characteristic pH range (pH 6–8) for the spoilage of aquatic products, the ∆E value of the PVA/CS-g-FA/G/RA film increased from 14.66 ± 0.92 to 29.65 ± 0.74. After exposure to 80 mmol/L ammonia for 90 min, the ∆E value reached as high as 30.01 ± 0.24, indicating excellent response to ammonia. After addition of [Gly]Cl, the elongation at break of the indicator film increased to (10.35 ± 0.90)%, and its water vapor permeability rose to (2.64 ± 0.50) × 107 g/(m·Pa·s), thereby facilitating the penetration of volatile alkaline substances. In addition, the indicator film displayed excellent UV barrier ability and antioxidant activity, with a 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging rate of (86.73 ± 0.71)%, and possessed a uniform and compact microstructure. This film clearly differentiated fresh, semi-fresh and spoiled P. vannamei, its color changing gradually from deep purplish-red to deep reddish-brown and finally to deep grayish-brown. Its ∆E value showed a significantly positive correlation with total volatile basic nitrogen (TVB-N) content (R2 = 0.956 55). In summary, the PVA/CS-g-FA/G/RA film, with its outstanding environmental responsiveness and biological activity, holds broad application prospects in the field of intelligent indicator packaging for aquatic products.

Key words: ionic liquid; chitosan; ferulic acid; intelligent indicator film; visualization; freshness monitoring

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