Cruz-Amaya Karen S, Hernández-Martínez Diego, Del-Toro-Sánchez Carmen L, Carvajal-Millan Elizabeth, Martínez-Robinson Karla, DeAnda-Flores Yubia B, Cornejo-Ramírez Yaeel I
Departamento de Investigación y Posgrado en Alimentos, Universidad de Sonora, 83000 Hermosillo, Sonora, Mexico.
Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, 83000 Hermosillo, Sonora, Mexico.
ACS Omega. 2024 Jun 21;9(26):28564-28576. doi: 10.1021/acsomega.4c02536. eCollection 2024 Jul 2.
Considering the FAO perspectives for agriculture toward 2030, many natural sources will be no longer profitable for the synthesis of many biomaterials. Triticale ( Wittmack) is a cereal crop synthesized to withstand those marginal conditions; however, it is primarily used as fodder worldwide. We reported for the first time the synthesis of a natural anionic hydrogel with gastrointestinal pH stimulus-response as a new alternative of smart material, based on Eronga triticale starch as sustainable biomass, using citrate (p ∼3.1, 4.7, and 6.4) as cross-linking agent. The scanning electron microscopy and X-ray diffraction exhibited A and B-type starch granules, and semicrystallinity A-type. The presence of the anionic sensing group (COOH) was verified by infrared spectroscopy, the interactions by hydrogen bonds between starch and glycerol and esterification between starch and citric acid were identified by H NMR spectra, and through thermal analysis hydrogels exhibited four endothermic curves (179-319 °C, ∼0.711-39 kJ/mol ). The results showed that the slight addition of glycerol increases the thermal stability, but a higher amount of glycerol decreases the intermolecular forces affecting the thermal stability contrary, the mechanical properties could be benefited. The rheological analyses showed viscoelastic tendency (' > ″) with high stability (Tanδ < 1) in frequency, time, and strain sweeps. Gastrointestinal pH sensitivity (∼2-7.8) was verified (α ≤ 0.01) following Fick's diffusive parameters, which resulted in a tendency to gradually release BSA with increasing pH ∼3-7 by anomalous and case-II diffusion, showing greater release at pH ∼7.8/3.5 h (80-96%). We aim to expand the biomaterials area focusing on triticale starch due to its limited reported investigations, low-cost, green modification, and its rheological performance as plastic.
考虑到粮农组织对2030年农业的展望,许多天然来源将不再适合用于合成多种生物材料。小黑麦(Wittmack)是一种为适应边缘条件而合成的谷类作物;然而,它在全球主要用作饲料。我们首次报道了基于埃龙加小黑麦淀粉作为可持续生物质,以柠檬酸盐(p ∼3.1、4.7和6.4)作为交联剂,合成了一种具有胃肠道pH刺激响应的天然阴离子水凝胶,作为智能材料的新替代品。扫描电子显微镜和X射线衍射显示出A和B型淀粉颗粒以及A型半结晶性。通过红外光谱验证了阴离子传感基团(COOH)的存在,通过1H NMR光谱确定了淀粉与甘油之间的氢键相互作用以及淀粉与柠檬酸之间的酯化作用,并且通过热分析水凝胶呈现出四条吸热曲线(179 - 319 °C,∼0.711 - 39 kJ/mol)。结果表明,少量添加甘油可提高热稳定性,但大量甘油会降低影响热稳定性的分子间作用力,相反,机械性能可能会受益。流变学分析表明,在频率、时间和应变扫描中具有粘弹性趋势(' > ″)且稳定性高(Tanδ < 1)。按照菲克扩散参数验证了胃肠道pH敏感性(∼2 - 7.8)(α ≤ 0.01),这导致在pH ∼3 - 7时,牛血清白蛋白通过异常扩散和II型扩散有逐渐释放的趋势,在pH ∼7.8/3.5 h时释放量更大(80 - 96%)。由于对小黑麦淀粉的研究报道有限、成本低、绿色改性以及其作为塑料的流变性能,我们旨在扩大以小黑麦淀粉为重点的生物材料领域。