Abstract
This study introduced a fructooligosaccharides/trehalose-based natural deep eutectic solvent (NADES) to enhance the freeze-thaw (F-T) stability of surimi in 3D-printed products. After five F-T cycles, the deformation rate of the control, the commercial antifreeze, and the NADES-treated group is 25.30%, 7.05%, and 3.70%, respectively. LF-NMR analysis revealed that NADES hindered the migration of immobile water to free water during the F-T process. Moreover, NADES mitigated the decline in the energy storage modulus and loss modulus of surimi and myofibrillar protein (MP), enhancing the self-supporting capability of surimi 3D-printed products and preserving MP structure. Throughout F-T cycling, NADES effectively maintained intermolecular force stability, preventing solubility reduction, turbidity increase, and surface hydrophobicity increase, thereby decreasing MP aggregation. NADES effectively enhances the structural stability and thermal stability of MP while inhibiting degradation reactions in MP. This study provides a theoretical foundation for the enhancement of surimi 3D printed products and frozen food quality.
Highlights
- The FOS-trehalose-based natural deep eutectic solvent (NADES) was cryoprotective.
- NADES improved shape retention in 3D-printed products against commercial antifreeze.
- NADES samples outperformed the commercial antifreeze in rheological properties.
- NADES preserved myofibrillar protein (MP) structure during freeze-thaw (F-T) cycles.
- NADES was effective in inhibiting the oxidative denaturation and degradation of MP.
Introduction
3D printing technology offers a novel approach for the food industry to develop high-quality products. This technology, known for its personalized customization and waste reduction, has enabled the creation of space food, plant-based alternatives, and lab-grown meat (Enfield, Pandya, Lu, McClements, & Kinchla, 2023; Handral, Hua Tay, Wan Chan, & Choudhury, 2022; Shi, Zhang, & Mujumdar, 2024; Wen, Chao, Che, Kim, & Park, 2023). Surimi, with its unique rheological properties, serves as an ideal material for food 3D printing. Its favorable extrusion behavior and reliable shape retention facilitate the precise fabrication of customized products with controlled structures, positioning it as a key focus in food 3D printing research (Liang et al., 2024). Mirror carp, a cost-effective freshwater fish in North China, is renowned for its high protein content, low fat levels, and abundant availability. Utilizing mirror carp surimi as a 3D printing material offers substantial benefits in creating innovative surimi products (Lou et al., 2024). However, there is limited research on the storage, transportation, and further processing of 3D-printed surimi products. Therefore, the challenges associated with post-printing processing of these items should not be underestimated.
Surimi products typically have high moisture and protein content, particularly myofibrillar protein (MP), making them prone to bacterial growth and spoilage (Han & Li, 2024; Shi et al., 2023). Cryopreservation is the primary method for preserving surimi products and can also help maintain the intricate 3D structure of 3D-printed items by fixing their shape. However, temperature fluctuations during frozen storage and transportation can result in repeated freeze-thaw (F-T) cycles, leading to dehydration (Gao et al., 2024). These temperature variations induce the formation of large, irregular ice crystals and recrystallization phenomena, causing irreversible damage to muscle fibers and protein structures, which compromises water retention (Du et al., 2023). Water loss can significantly affect the shape and structure of 3D-printed surimi products, which is unacceptable given the precision and integrity required for such items (Tian et al., 2023). Effectively controlling the shape and quality degradation of surimi 3D-printed products during frozen storage is a critical challenge for advancing 3D printing technology.
Novel physical field-assisted freezing technologies, including ultra-high pressure and ultrasonic-assisted freezing, can combat quality deterioration in surimi products by employing them to regulate ice crystal size and minimize water loss (Zhang, Fan, Xu, & Xu, 2024). However, the high cost of implementing such technologies hinders practical application. Therefore, the addition of antifreeze agents becomes even more practical. However, the high sweetness of commercial antifreeze (4% sorbitol +4% sucrose, w/w, SS) the chronic disease risk of polyphosphates, and the high production cost of antifreeze proteins, antifreeze peptides, and polyphenols make them difficult to apply on a large scale (Chen et al., 2022; Chen et al., 2023; Tian, Walayat, Ding, & Liu, 2022). Hence, proposing a novel antifreeze strategy would advance the development of surimi 3D printing technology.
Natural deep eutectic solvents (NADES) were initially discovered in cold-resistant animals and plants. They are synthesized from natural substances such as amino acids and sugars for various applications (Abbott, Capper, Davies, Rasheed, & Tambyrajah, 2003). NADES are characterized by a unique supramolecular network structure formed by hydrogen bonds, which controls water migration and lowers the freezing point, thus enhancing frost resistance (Tian, Sun, & Zhu, 2022; Du, Kong, et al., 2023; Wu et al., 2024). Tian, Sun, and Zhu (2022) pioneered the application of amino acid-based NADES for frozen preservation of chicken breast, verifying that Pro: Sor (1:1) delivers optimal freeze protection. Simultaneously, NADES constructed from trehalose and citric acid significantly suppresses moisture loss in surimi during F-T cycles and effectively mitigates protein freeze-induced denaturation (Du, Kong, et al., 2023; Li, Wang, Li, & Xia, 2023). Recently, Li, Liang, Jiang, Zhang, and Shi (2025) demonstrated the efficacy of betaine-based NADES in enhancing the quality of frozen shrimp surimi, further confirming its potential as an eco-friendly antifreeze agent in the frozen muscle food industry. Beyond the application of small-molecule NADES in traditional frozen muscle foods, macromolecules such as polysaccharides become ideal raw materials for preparing NADES in novel frozen muscle foods, particularly 3D-printed products.
Fructooligosaccharides (FOs) are an oligosaccharide rich in hydroxyl structure, which can play a key role in structural support, anchoring water molecules, and improving the frost resistance of muscle food. As a polyhydroxy oligosaccharide, oligofructose provides abundant hydrogen-bonding sites, enabling the formation of a dense, three-dimensional dynamic hydrogen-bond network in synergy with trehalose. Its excellent solubility and viscosity characteristics further enhance the rheological properties and molding stability of 3D printing inks. This network not only effectively anchors water molecules and inhibits ice crystal growth and recrystallization, but more crucially, trehalose’s unique “water displacement” effect forms a protective layer on the surfaces of biomacromolecules such as proteins (Du, Kong, et al., 2023). Combined with oligofructose’s water-binding capacity, this achieves dual enhancement of structural protection and freeze resistance at the molecular level. Lou et al. (2024) prepared polysaccharide-based NADES using FOs and trehalose. This NADES enhances the rheological properties and 3D-printing characteristics of printing inks made from mirror carp surimi. However, there remains a lack of in-depth research on the improvement of F-T stability in 3D-printed surimi products and its underlying mechanisms.
This study developed NADES based on FOs and trehalose to mitigate structural softening and moisture loss in 3D-printed products caused by ice crystal growth and recrystallization induced by F-T cycles. Through microstructural analysis, moisture characteristics, and basic quality assessments, it was confirmed that this approach effectively enhances the F-T stability of 3D-printed surimi products. Second, repeated freeze-thaw cycles induce ice crystal growth and recrystallization, which not only disrupts the precisely formed printed structures but also triggers water migration, protein denaturation, and oxidative deterioration, all of which are further compounded by the lack of systematic and in-depth studies on the structural evolution of myofibrillar proteins, water dynamics, and the synergistic rheological-network interactions within 3D-printed fish paste systems during such cycles. Therefore, it further investigated the mechanism by which NADES improves F-T stability in surimi 3D-printed products by examining the rheological, structural, thermal stability, oxidative denaturation, and degradation of MP under F-T cycles.
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Xin Du, Xindi Zeng, Xinjiang Lou, Xiufang Xia, Qian Liu, Xianzhe Zheng, The improvement of freeze-thaw stability of surimi 3D printing products by fructooligosaccharides/trehalose-based natural deep eutectic solvent, Food Chemistry, Volume 507, 2026, 148275, ISSN 0308-8146, https://doi.org/10.1016/j.foodchem.2026.148275.
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