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Active edible coatings for smart food preservation and sustainability: A review 用于智能食品保鲜和可持续性的活性食用涂料研究进展
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-06 DOI: 10.1016/j.carpta.2025.101061
Mahmuda Tasnim , Md. Nahidul Islam
Active edible coatings have progressed from basic biopolymer layers to advanced multifunctional systems aimed at mitigating food quality deterioration and addressing sustainability challenges. This research investigates the shift from traditional polymers to novel, sustainable materials derived from agro-industrial by-products, emphasizing their significance in advancing circular bioeconomy initiatives and reducing reliance on synthetic plastics. This study contributes by synthesizing recent advancements in innovative and active preservation techniques. The methods encompass antibacterial and antioxidant properties, controlled-release systems, and nano-enhancements that govern gas exchange, moisture transfer, and biochemical degradation. Additionally, novel manufacturing techniques such as electrospraying, electrospinning, and layer-by-layer assembly are assessed for their effectiveness in designing coating microstructures and controlling release kinetics, thus exceeding traditional methods. This review analyzes next-generation active edible coatings that serve as bioactive barriers, prolonging shelf life, preserving sensory qualities, and promoting environmentally sustainable food preservation by integrating sustainability, material innovation, and practical effectiveness.
活性食用涂层已经从基本的生物聚合物层发展到先进的多功能系统,旨在减轻食品质量恶化和解决可持续性挑战。本研究调查了从传统聚合物到新型可持续材料的转变,这些材料来源于农业工业副产品,强调了它们在推进循环生物经济倡议和减少对合成塑料的依赖方面的重要性。本研究通过综合创新和有效保存技术的最新进展作出贡献。这些方法包括抗菌和抗氧化性能,控制释放系统,以及控制气体交换,水分转移和生化降解的纳米增强。此外,新的制造技术,如电喷涂、静电纺丝和层接层组装,在设计涂层微观结构和控制释放动力学方面的有效性也得到了评估,从而超越了传统的方法。本文综述了结合可持续性、材料创新和实用效果的新一代可食用活性涂料,它们具有生物活性屏障、延长保质期、保持感官品质和促进环境可持续食品保鲜的作用。
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引用次数: 0
Sulfated modification and biomedical applications of β-glucans: A review β-葡聚糖的磺化改性及其生物医学应用综述
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-06 DOI: 10.1016/j.carpta.2025.101063
Zeming Zhang , Haoyu Wang , Mengqing Li , Yuxuan Liu , Kaiping Wang , Jinglin Wang
β-glucans, a type of naturally occurring polysaccharide with β-glycosidic linkages, are widely recognized for their immunomodulatory and therapeutic properties, whereas their inherent properties often restrict their further applications. Sulfated β-glucans have emerged as versatile derivatives of β-glucans with enhanced physicochemical properties, driven by the introduction of sulfate groups onto their backbone. They also exhibit novel or improved bioactivities compared to their unmodified counterparts, owing to their modified molecular structures and strengthened interactions with biological targets. This review summarizes recent advancements in sulfation methods, including the chlorosulfonic acid-pyridine method, sulfur trioxide method, and sulfuric acid method, highlighting their mechanisms, advantages, and limitations. Structural characterization techniques and various biomedical applications are discussed to elucidate the sulfation patterns and provide a theoretical basis for further use and development of sulfated β-glucans. Conclusively, sulfation serves as a promising strategy for fine-tuning β-glucan functionalities and expanding their potential in food and pharmaceutical areas.
β-葡聚糖是一种天然存在的具有β-糖苷键的多糖,因其免疫调节和治疗特性而被广泛认可,然而其固有的特性往往限制了其进一步的应用。硫酸盐酸化β-葡聚糖作为β-葡聚糖的多用途衍生物,由于在其骨架上引入硫酸盐基团,具有增强的物理化学性质。由于它们的分子结构被修饰,与生物靶标的相互作用增强,与未修饰的分子相比,它们还表现出新的或更好的生物活性。本文综述了近年来磺化方法的研究进展,包括氯磺酸-吡啶法、三氧化硫法和硫酸法,重点介绍了它们的机理、优点和局限性。讨论了结构表征技术和各种生物医学应用,阐明了磺化模式,为磺化β-葡聚糖的进一步利用和开发提供了理论基础。总之,磺化是一种很有前途的策略,可以微调β-葡聚糖的功能,扩大其在食品和制药领域的潜力。
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引用次数: 0
Chitin and cellulose nanomaterials sulfation by mechanochemistry 几丁质和纤维素纳米材料的机械化学硫化
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-05 DOI: 10.1016/j.carpta.2025.101062
Daniela Duarte-Serrano , Aurélie Vallin , Caroline Hadad , José Miguel González Domínguez , Maria Emilia Cano , Arash Jamali , Stéphanie Guénin , Anne Wadouachi , Albert Nguyen Van Nhien
Natural sulfated polysaccharides (NSP) are widely used in food, medical, and cosmetic applications. Chemical sulfation is typically required to mimic NSP properties, but it often involves toxic solvents, excess reagents, and long heating times. We report for the first time the sulfation of well-defined cellulose and (oxidized)-chitin nanomaterials by mechanochemistry using a sulfur trioxide–pyridine complex offering a greener alternative. In contrast to their unmodified counterparts, the sulfated compounds S-NanoCel, S-NanoChit, and SONanoChit exhibited significantly lower turbidity values of 25, 45, and 158 NTU, respectively, confirming their excellent water dispersibility. The presence of covalently bound sulfate groups was confirmed by FTIR spectroscopy with characteristic bands near 1250 and 820 cm⁻¹ and 13C NMR. Elemental analysis revealed degrees of substitution (DS) between 0.22 and 0.78, with S-NanoCel showing the highest DS. X-ray diffraction showed that the unmodified nanomaterials had crystallinity values ranging from 80 to 93 %. After sulfation, the crystallinity was reduced and is no longer quantifiable, although the overall crystalline structure remained visible, with lattice arrangements corresponding to the alignment of the polysaccharide chains. Finally, biological evaluation demonstrated that sulfated oxidized chitin exhibited the strongest heparanase inhibitory activity (IC₅₀ = 0.7 µg·mL⁻¹), suggesting its potential as a heparan sulfate analog.
天然硫酸多糖(NSP)广泛应用于食品、医疗和化妆品等领域。化学磺化通常需要模拟NSP性质,但它通常涉及有毒溶剂,过量试剂和长时间加热。我们首次报道了利用三氧化硫-吡啶配合物,通过机械化学对定义明确的纤维素和(氧化的)几丁质纳米材料进行磺化,提供了一种更环保的选择。与未经改性的化合物相比,硫酸盐化合物S-NanoCel、S-NanoChit和SONanoChit的浊度值显著降低,分别为25、45和158 NTU,证实了它们出色的水分散性。在1250和820 cm附近的FTIR光谱和13C NMR的特征波段证实了共价结合的硫酸盐基团的存在。元素分析表明,S-NanoCel的取代度在0.22 ~ 0.78之间,取代度最高。x射线衍射表明,未经改性的纳米材料的结晶度在80% ~ 93%之间。硫酸化后,结晶度降低,无法量化,但整体晶体结构仍然可见,其晶格排列与多糖链的排列相对应。最后,生物学评价表明,硫酸氧化甲壳素具有最强的肝素酶抑制活性(IC₅₀= 0.7 μ g·mL⁻¹),表明其作为硫酸肝素类似物的潜力。
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引用次数: 0
Autoclave-assisted green extraction of a hierarchical self-assembling polysaccharide from Flammulina velutipes Mycelium for ultra-efficient cryoprotection of frozen egg yolk 高压灭菌辅助绿色提取金针菇菌丝体中分层自组装多糖的超高效冷冻保护蛋黄
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101047
Lujie Qin , Lihua Tang , Ziyue Ling , Yin Fu , Yan Cao , Zhongyi Chang , Deming Jiang , Hongliang Gao , Caifeng Jia
This study developed a novel autoclave-assisted extraction technology to isolate a cryo-active polysaccharide (FVP-N1) from Flammulina velutipes mycelium and evaluated its potential as a natural cryoprotectant. FVP-N1 demonstrated significant ice recrystallization inhibition (IRI) activity, reducing ice crystal size by 92.38 % compared to the control. Structural analysis identified FVP-N1 as a heteropolysaccharide (MW: 6.76×105 Da) composed of glucose, xylose, and mannose (molar ratio 44.11:36.82:14.93), featuring a backbone of 1,3,4-linked α-d-glucopyranosyl residues interspersed with 1,3-linked α-d-mannopyranosyl units. Critical structural motifs included O4-branched side chains terminated by β-d-xylopyranosyl residues. Morphological studies (SEM/AFM) revealed hierarchical self-assembly into porous lamellar sheets aggregated into spherical clusters interconnected by fibrillar chains, suggesting a dual IRI mechanism involving ice surface adsorption and hydrogen-bond-mediated water ordering. Notably, FVP-N1 at an ultra-low concentration (0.005 % w/v) effectively maintained fluidity, protein solubility, and moisture homogeneity in frozen egg yolk. These findings elucidate the ​​structure-function relationship of FVP-N1 and validate its practical utility as a highly effective, natural cryoprotectant for industrial frozen food applications.
本研究开发了一种新的高压灭菌辅助提取技术,从金针菇菌丝体中分离出一种低温活性多糖(FVP-N1),并对其作为天然冷冻保护剂的潜力进行了评价。FVP-N1表现出明显的冰再结晶抑制(IRI)活性,与对照相比,冰晶大小减少了92.38%。结构分析表明,FVP-N1是一种由葡萄糖、木糖和甘露糖(摩尔比为44.11:36.82:14.93)组成的杂多糖(MW: 6.76×105 Da),其主链由1,3,4连接的α-d-葡萄糖吡喃基残基与1,3连接的α-d-甘露吡喃基单元点缀而成。关键结构基序包括由β-d-木吡喃基残基端部的o4支链。形态学研究(SEM/AFM)揭示了层次化自组装成多孔片层,并通过纤维链相互连接成球形团簇,这表明存在双重IRI机制,包括冰表面吸附和氢键介导的水排序。值得注意的是,超低浓度(0.005% w/v)的FVP-N1能有效保持冷冻蛋黄的流动性、蛋白质溶解度和水分均匀性。这些发现阐明了FVP-N1的结构-功能关系,并验证了其作为工业冷冻食品应用的高效天然冷冻保护剂的实用性。
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引用次数: 0
Ultrasound-assisted removal of chlorpyrifos using magnetic activated carbon– carboxymethyl cellulose hydrogel beads derived from orange peel waste 超声波辅助去除毒死蜱用磁性活性炭-羧甲基纤维素水凝胶珠从橘子皮废料
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101048
Mehdi Barzegarzadeh, Mohammad Sadegh Amini-Fazl
Chlorpyrifos, an organophosphate insecticide, has been frequently detected in water resources, raising concerns about environmental and health risks. In this study, hydrogel beads based on carboxymethyl cellulose (CMC) were synthesized by incorporating magnetic activated carbon derived from orange peel waste (0–30 wt%). The prepared composites were characterized using FT-IR, XRD, FESEM, BET, VSM, and other techniques. Adsorption parameters were optimized through the Taguchi method, identifying the optimal conditions at an initial chlorpyrifos concentration of 90 mg/L, adsorbent dosage of 2 g/L, contact time of 60 min, and solution pH of 9. The hydrogel containing 30 wt% magnetic activated carbon (CMC/MAC30) exhibited nearly 100 % removal efficiency. Nonlinear fitting revealed that the adsorption process followed the Toth model under ultrasonic irradiation and the Sips model in its absence. According to the Langmuir model, the maximum adsorption capacity increased from 162.96 to 211.86 mg/g upon ultrasonic treatment, attributed to enhanced mass transfer via cavitation. Comparative analysis with previously reported adsorbents confirmed the superior adsorption capacity of CMC/MAC30. Moreover, the adsorbent maintained 92 % removal efficiency after eight regeneration cycles. Importantly, CMC/MAC30 was also evaluated in simulated agricultural wastewater containing competing ions, where the removal efficiency decreased from ∼100 % to ∼70 %, yet still demonstrated the strong potential of the adsorbent in realistic complex matrices. These findings highlight CMC/MAC30, especially when assisted by ultrasound, as a promising green adsorbent for the efficient removal of chlorpyrifos from aqueous environment.
毒死蜱是一种有机磷杀虫剂,经常在水资源中被发现,引起人们对环境和健康风险的担忧。本研究以柑桔皮废料为原料,以0-30 wt%的磁性活性炭为原料,合成了羧甲基纤维素(CMC)为基材的水凝胶珠。采用FT-IR、XRD、FESEM、BET、VSM等技术对制备的复合材料进行了表征。采用田口法对吸附参数进行优化,确定了毒死蜱初始浓度为90 mg/L、吸附剂用量为2 g/L、接触时间为60 min、溶液pH为9的最佳条件。含有30 wt%磁性活性炭(CMC/MAC30)的水凝胶的去除率接近100%。非线性拟合表明,超声辐照下吸附过程遵循Toth模型,无超声辐照时遵循Sips模型。根据Langmuir模型,超声处理后的最大吸附容量从162.96 mg/g增加到211.86 mg/g,这是由于空化传质增强所致。通过与已有报道的吸附剂的对比分析,证实了CMC/MAC30具有较好的吸附能力。在8次再生循环后,吸附剂的去除率仍保持在92%。重要的是,CMC/MAC30还在含有竞争离子的模拟农业废水中进行了评估,其中去除效率从~ 100%下降到~ 70%,但仍然显示出吸附剂在现实复杂基质中的强大潜力。这些发现突出了CMC/MAC30,特别是在超声辅助下,作为一种有前途的绿色吸附剂,可以有效地去除水中环境中的毒死蜱。
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引用次数: 0
Starch–Chitosan microcapsules as biopolymeric carriers of halotolerant PGPB: Enhancing safflower‐mediated phytoremediation and salinity tolerance 淀粉-壳聚糖微胶囊作为耐盐PGPB的生物聚合物载体:增强红花介导的植物修复和耐盐性
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101055
Fateme Aghamir , Ghasem Eghlima , Zinab Moradi Alvand , Leila Ordibehesti , Mohsen Farzaneh , Hasan Rafati
Soil salinity limits agriculture in arid and semi-arid regions where large-scale leaching is impractical. Biopolymer-based microencapsulation for bioinoculant delivery offers a sustainable approach to rehabilitating saline soils and improving crop performance. We evaluated twelve halotolerant plant growth-promoting rhizobacteria (PGPB ) applied as free cells and chitosan–starch microcapsules, with or without organic liquid fertilizer (OLF), to enhance safflower (Carthamus tinctorius L.) growth and soil desalination. Greenhouse factorial trials (three replications) assessed morphological, physiological, and biochemical plant traits, and soil Na⁺, K⁺, Ca²⁺, and electrical conductivity (EC). Data were analyzed using factorial ANOVA (LSD, p < 0.05) in SAS v9.4, with multivariate relationships explored by PCA in Python (scikit-learn v1.4.0). Microencapsulation enhanced PGPB viability, colonization, and function. Integrator strains (Rhizobium sp., Agrobacterium tumefaciens, Rhizobium radiobacter) reduced EC by up to ∼51%. Specialist strains (Pseudomonas fluorescens, Micrococcus luteus) increased targeted metabolites, while persistent strains (Bacillus licheniformis, Kushneria sp.) maintained remediation. The chitosan–starch carrier provided mechanical protection, enzyme stabilization, and promoted exopolysaccharide-mediated soil aggregation. Combining diverse PGPB types with biopolymer encapsulation and organic amendments offers a scalable, low-impact solution for salinity mitigation. These greenhouse findings demonstrate the potential of microencapsulated halophilic PGPB for sustainable saline soil management, pending further field validation and biosafety assessment.
土壤盐度限制了干旱和半干旱地区的农业,在这些地区大规模淋洗是不切实际的。以生物聚合物为基础的微胶囊用于生物接种剂的输送,为恢复盐碱地和提高作物性能提供了一种可持续的方法。研究了12种耐盐植物促生长根瘤菌(PGPB)作为游离细胞和壳聚糖淀粉微胶囊,在添加或不添加有机液肥(OLF)的情况下,促进红花(Carthamus tinctorius L.)生长和土壤淡化的效果。温室析因试验(3个重复)评估了植物的形态、生理和生化特性,以及土壤Na +、K +、Ca +和电导率(EC)。在SAS v9.4中使用因子方差分析(LSD, p < 0.05)对数据进行分析,并在Python (scikit-learn v1.4.0)中使用PCA探讨多变量关系。微胶囊化增强了PGPB的活力、定植和功能。整合菌(根瘤菌、农杆菌、放射根瘤菌)可减少EC高达51%。特殊菌株(荧光假单胞菌、黄体微球菌)增加了目标代谢物,而持久菌株(地衣芽孢杆菌、库什纳菌)维持了修复。壳聚糖-淀粉载体提供了机械保护、酶稳定和促进外多糖介导的土壤聚集。将不同的PGPB类型与生物聚合物封装和有机改性相结合,提供了一种可扩展的、低影响的盐度降低解决方案。这些温室研究结果表明,微囊化的嗜盐PGPB在盐碱地可持续管理方面具有潜力,有待进一步的实地验证和生物安全性评估。
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引用次数: 0
Ascorbic acid-assisted extraction of bioactive pectin from cocoa and coffee husks with antioxidant and anti-inflammatory potential 抗坏血酸辅助提取具有抗氧化和抗炎作用的可可和咖啡果胶
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101058
Sofía Mares-Bou , Damaris A. Pazmiño-Eugenio , William Cheung , Carolina I. Contreras-Monzón , Andy Hernández-Montoto , Gloria Gallego-Ferrer , Joel Girón-Hernández , Piergiorgio Gentile
Pectin, a multifunctional polysaccharide with food, pharmaceutical and biomedical applications, can be sustainably extracted from Theobroma cacao and Coffea arabica pod husk waste. This study optimized an eco-friendly, ascorbic-acid-assisted acid extraction to maximize galacturonic acid (GalA) content, achieving optimal conditions for cocoa (R= 0.02 g/mL, P= 45:55 v/v AA:HCl, T= 65 min) and coffee (R= 0.01 g/mL, P= 100:0 v/v AA, T= 65 min). The extraction yielded pectin with ≥74% GalA, meeting USP/FCC pharmaceutical-grade criteria, with cocoa and coffee husk yields of ∼7% and ∼21%, respectively. Dialysis increased purity, raising molecular weight up to ∼297,000 Da and narrowing dispersity. Extracted pectin exhibited higher total phenolic and flavonoid contents than commercial citrus pectin and showed superior antioxidant capacity (ORAC up to 53.1 mg TE/g; DPPH up to 2420 mg TE/g), supported by metabolomic profiling that identified abundant antioxidant metabolites such as protocatechuic acid, trigonelline and catechol. In vitro assays with human dermal fibroblasts demonstrated cytocompatibility at 0.1 mg/mL, mild ROS-scavenging effects and selective modulation of inflammatory cytokines, with cocoa pectin reducing IL-6 and dialyzed coffee pectin showing strong IL-6 suppression.
果胶是一种具有食品、制药和生物医学用途的多功能多糖,可以从可可树和阿拉比卡咖啡豆荚废料中可持续提取。本研究优化了一种环保的抗坏血酸辅助酸提取工艺,以最大限度地提高半乳糖醛酸(GalA)的含量,获得了可可(R= 0.02 g/mL, P= 45:55 v/v AA:HCl, T= 65 min)和咖啡(R= 0.01 g/mL, P= 100:0 v/v AA, T= 65 min)的最佳提取条件。提取得到的果胶GalA含量≥74%,符合USP/FCC药品级标准,可可和咖啡壳的得率分别为~ 7%和~ 21%。透析提高了纯度,将分子量提高到约297,000 Da,并缩小了分散性。提取的果胶比商品柑橘果胶具有更高的总酚和类黄酮含量,并具有更好的抗氧化能力(ORAC高达53.1 mg TE/g, DPPH高达2420 mg TE/g),代谢组学分析鉴定出丰富的抗氧化代谢物,如原儿茶酸、葫芦丝碱和儿茶酚。体外实验表明,在0.1 mg/mL浓度下,可可果胶可降低IL-6,咖啡果胶可明显抑制IL-6,具有轻微的ros清除作用和选择性调节炎症细胞因子。
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引用次数: 0
Nanoparticle formation of an antimicrobial peptide induced by sulfated β-cyclodextrin: Application to alkaloid encapsulation 磺化β-环糊精诱导抗菌肽纳米颗粒的形成:在生物碱包封中的应用
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101053
Zsombor Miskolczy , Mónika Megyesi , Beáta Mándityné Huszka , István Mándity , László Biczók
The association of polyanionic β-cyclodextrin (βCD) derivatives with the nonaggregating polycationic antimicrobial peptide Dhvar4 was studied in water at 296 K without a buffer to explore their potential for forming nanoparticles capable of encapsulating bioactive isoquinoline alkaloids. The βCD bearing sulfobutyl ether moieties formed a 1:1 inclusion complex with Dhvar4, exhibiting a binding constant of (1.1 ± 0.3) × 105 M–1. In contrast, βCD substituted with SO₃⁻ groups (S13βCD) promoted the self-assembly into nanoparticles with a narrow and uniform size distribution. When Dhvar4 was present in large excess relative to S13βCD, positively charged nanoparticles were produced. Conversely, negatively charged nanoparticles were obtained at S13βCD/Dhvar4 charge ratios above 2.5, which maintained their size for at least 30 days. The incorporation of pharmaceutically active isoquinoline alkaloids had minimal impact on the properties of nanoparticles formed in the presence of a >35 molar% excess of S13βCD over Dhvar4. Encapsulation efficiencies of 99 % and 72 % were achieved for coralyne and sanguinarine, respectively. Job plot and isothermal titration calorimetry measurements demonstrated that each S13βCD macrocycle could bind ∼13 molecules of these alkaloids. The present findings lay the groundwork for future biological validation and applications of nanoparticles composed of three types of biomedically important compounds.
研究了聚阴离子β-环糊精(βCD)衍生物与非聚集性聚阳离子抗菌肽Dhvar4在296 K无缓冲条件下的结合,以探索它们形成能够包封生物活性异喹啉生物碱的纳米颗粒的潜力。含βCD的磺基丁基醚部分与Dhvar4形成1:1的包合物,结合常数为(1.1±0.3)× 105 M-1。相比之下,用SO₃⁻(S13βCD)取代的βCD促进了纳米粒子的自组装,使其具有窄而均匀的尺寸分布。当Dhvar4相对于S13βCD大量过量存在时,产生带正电的纳米颗粒。相反,当S13βCD/Dhvar4电荷比大于2.5时,可获得带负电的纳米颗粒,其尺寸保持至少30天。具有药理活性的异喹啉生物碱的掺入对在Dhvar4上超过35摩尔%的S13βCD存在下形成的纳米颗粒的性质影响最小。包封率分别为99%和72%。工作图和等温滴定量热测量表明,每个S13βCD大环可以结合约13个这些生物碱分子。本研究结果为未来由三种重要生物医学化合物组成的纳米颗粒的生物学验证和应用奠定了基础。
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引用次数: 0
Corrigendum to “Mechanical, physical, water vapor barrier, and functional properties of carboxymethyl cellulose/anthocyanin/TiO2 films for real-time food quality monitoring” [Carbohydrate Polymer Technologies and Applications 11 (2025) 100877] “用于实时食品质量监测的羧甲基纤维素/花青素/TiO2薄膜的机械、物理、水汽屏障和功能特性”的勘误表[碳水化合物聚合物技术与应用11 (2025)100877]
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101043
Pimonpan Kaewprachu , Chalalai Jaisan , Saroat Rawdkuen , Wirongrong Tongdeesoontorn , Thomas Karbowiak , Pascal Degraeve , Passakorn Kingwascharapong , Samart Sai-Ut , Papungkorn Sangsawad
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引用次数: 0
Charge density-driven IPN formation and recovery in hyaluronic acid/κ-carrageenan hydrogels: Novel insights from echo-DWS microrheology, bulk rheology and FTIR 透明质酸/κ-卡拉胶水凝胶中电荷密度驱动的IPN形成和恢复:来自echo-DWS微流变学、体流变学和FTIR的新见解
IF 6.5 Q1 CHEMISTRY, APPLIED Pub Date : 2025-12-01 DOI: 10.1016/j.carpta.2025.101042
Foluso Akin-Ige , Cindy Rivera , Valentina de Gennaro , Yael Faroud Rivera , Samiul Amin
This study investigates how ion valency and coordination behavior modulate the formation, viscoelasticity, and recovery of hyaluronic acid (HA)/κ-carrageenan (κCG) hydrogels. Hydrogels were prepared by combining HA and κCG in the presence of monovalent (K+), divalent (Ca2+), and trivalent (Al3+) ions at concentrations of 15–60 mM. Microrheology, Fourier-transform infrared (FTIR) spectroscopy, and bulk oscillatory rheology were employed to correlate molecular interactions with mechanical behavior.
Frequency sweep measurements revealed that the moduli of the hyaluronic acid/κ-carrageenan (HA–κCG) blend increased by nearly two orders of magnitude relative to HA alone, confirming synergistic network reinforcement. Among ion-enriched systems, Ca2+ produced the highest Gplateau (20 kPa) and lowest modulus loss between 25 °C and 37 °C (<10%), while Al3+ induced intermediate moduli. Recovery tests demonstrated that Ca2+-enriched hydrogels recovered 55% of their initial elasticity within 15 min, compared to 30% for K+ and 40% for Al3+ systems. Microrheology confirmed corresponding trends in probe confinement, with subdiffusive exponents (α) ranging from 0.18 (K+) to 0.32 (Ca2+).
FTIR analysis revealed that while K+ primarily stabilized κCG helices, Ca2+ reinforced sulfate junction zones, and Al3+ introduced additional HA–carboxylate coordination. Collectively, these results demonstrate that both ion charge and concentration govern the balance between elasticity and deformability in HA–κCG systems, defining whether true interpenetrating or semi-interpenetrating networks emerge. These insights establish design guidelines for improvement of mechanical performance in chemically unmodified HA-based hydrogels.
本研究探讨了离子价和配位行为如何调节透明质酸(HA)/κ-卡拉胶(κCG)水凝胶的形成、粘弹性和恢复。在15-60 mM的浓度下,将HA和κCG结合在一价(K+)、二价(Ca2+)和三价(Al3+)离子下制备水凝胶。利用微流变学、傅里叶变换红外(FTIR)光谱和体振荡流变学分析分子相互作用与力学行为的关系。频率扫描测量显示,透明质酸/κ-卡拉胶(HA -κCG)共混物的模量比单独的HA增加了近两个数量级,证实了协同网络的增强。在离子富集体系中,Ca2+在25°C和37°C之间产生最高的Gplateau ' (~ 20 kPa)和最低的模量损失(<10%),而Al3+诱导中间模量。恢复测试表明,富含Ca2+的水凝胶在15分钟内恢复了初始弹性的~ 55%,而K+为~ 30%,Al3+为~ 40%。微流变学证实了探针约束的相应趋势,亚扩散指数(α)范围为0.18 (K+)至0.32 (Ca2+)。FTIR分析显示,K+主要稳定了κCG螺旋,Ca2+增强了硫酸盐连接区,Al3+引入了额外的ha -羧酸配位。总的来说,这些结果表明,离子电荷和浓度共同控制着HA -κCG系统中弹性和变形性之间的平衡,决定了是否出现真正的互穿或半互穿网络。这些见解为改进未经化学修饰的ha基水凝胶的机械性能建立了设计指南。
{"title":"Charge density-driven IPN formation and recovery in hyaluronic acid/κ-carrageenan hydrogels: Novel insights from echo-DWS microrheology, bulk rheology and FTIR","authors":"Foluso Akin-Ige ,&nbsp;Cindy Rivera ,&nbsp;Valentina de Gennaro ,&nbsp;Yael Faroud Rivera ,&nbsp;Samiul Amin","doi":"10.1016/j.carpta.2025.101042","DOIUrl":"10.1016/j.carpta.2025.101042","url":null,"abstract":"<div><div>This study investigates how ion valency and coordination behavior modulate the formation, viscoelasticity, and recovery of hyaluronic acid (HA)/<span><math><mi>κ</mi></math></span>-carrageenan (<span><math><mi>κ</mi></math></span>CG) hydrogels. Hydrogels were prepared by combining HA and <span><math><mi>κ</mi></math></span>CG in the presence of monovalent (K<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span>), divalent (Ca<sup>2+</sup>), and trivalent (Al<sup>3+</sup>) ions at concentrations of 15–60 mM. Microrheology, Fourier-transform infrared (FTIR) spectroscopy, and bulk oscillatory rheology were employed to correlate molecular interactions with mechanical behavior.</div><div>Frequency sweep measurements revealed that the moduli of the hyaluronic acid/<span><math><mi>κ</mi></math></span>-carrageenan (HA–<span><math><mi>κ</mi></math></span>CG) blend increased by nearly two orders of magnitude relative to HA alone, confirming synergistic network reinforcement. Among ion-enriched systems, Ca<sup>2+</sup> produced the highest <span><math><msubsup><mrow><mi>G</mi></mrow><mrow><mtext>plateau</mtext></mrow><mrow><mo>′</mo></mrow></msubsup></math></span> (<span><math><mo>∼</mo></math></span>20 kPa) and lowest modulus loss between 25 <span><math><mrow><mo>°</mo><mi>C</mi></mrow></math></span> and 37 <span><math><mrow><mo>°</mo><mi>C</mi></mrow></math></span> (<span><math><mrow><mo>&lt;</mo><mn>10</mn><mtext>%</mtext></mrow></math></span>), while Al<sup>3+</sup> induced intermediate moduli. Recovery tests demonstrated that Ca<sup>2+</sup>-enriched hydrogels recovered <span><math><mo>∼</mo></math></span>55% of their initial elasticity within 15 min, compared to <span><math><mo>∼</mo></math></span>30% for K<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> and <span><math><mo>∼</mo></math></span>40% for Al<sup>3+</sup> systems. Microrheology confirmed corresponding trends in probe confinement, with subdiffusive exponents (<span><math><mi>α</mi></math></span>) ranging from 0.18 (K<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span>) to 0.32 (Ca<sup>2+</sup>).</div><div>FTIR analysis revealed that while K<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> primarily stabilized <span><math><mi>κ</mi></math></span>CG helices, Ca<sup>2+</sup> reinforced sulfate junction zones, and Al<sup>3+</sup> introduced additional HA–carboxylate coordination. Collectively, these results demonstrate that both ion charge and concentration govern the balance between elasticity and deformability in HA–<span><math><mi>κ</mi></math></span>CG systems, defining whether true interpenetrating or semi-interpenetrating networks emerge. These insights establish design guidelines for improvement of mechanical performance in chemically unmodified HA-based hydrogels.</div></div>","PeriodicalId":100213,"journal":{"name":"Carbohydrate Polymer Technologies and Applications","volume":"12 ","pages":"Article 101042"},"PeriodicalIF":6.5,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145684137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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Carbohydrate Polymer Technologies and Applications
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