Development and Application of Magnesium Citrate-Functionalized Starch-Based Nanomaterials in Enhancing the Fortification of Vitamin D3: Batch and Release Performance Studies

Amal M. Badran, Afif Hethnawi*, Uthumporn Utra*, Nor Shariffa Yussof and Raghad Rajabi, 
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Abstract

Recently, diverse strategies have been developed to formulate food micronutritional supplements like magnesium (Mg2+) and vitamin D3 (VD3). Nevertheless, the progress in food supplement formulations is limited, due to their undesirable interactions with various food ingredients. In the last few decades, starch has been widely used to prepare micro or nano-carriers for different micronutrients following diverse physical and chemical methods, due to its excellent surface features, the possibility of derivation from various reagents, biodegradability, and biocompatibility. However, most of these methods have not yet been tested in the laboratory scales, failed partially or completely in producing uniform particles in nanoscale domains, and require multiple formulation steps. Herein, starch nanomaterials (SNMs) are fabricated as an effective carrier for VD3 and Mg2+ by ultrasonication under moderate conditions. Initially, the SNMs were prepared by ultrasonication using equal masses of native corn starch (NCS) and high amylose corn starch (HACS). The generated materials were then grafted with magnesium, in citrate form at room conditions, as a primary functionalization step, forming magnesium citrate-grafted SNM (MNM-Mg), which were used as sorbents for VD3. Experimentally, a set of analytical methods including atomic force microscopy (AFM), Brunauer–Emmett–Teller (BET) surface area analysis, Fourier-transform infrared spectroscopy (FT-IR), Zeta sizer, and X-ray diffraction analysis (XRD) were used to determine the size, surface properties, functionality, stability, and morphology of the prepared nanomaterials. The adsorptive behavior of VD3 on MNM-Mg surfaces was investigated by analyzing the equilibrium adsorptive data using various isotherm models including Langmuir, BET, Toth, and Redlich–Peterson. Furthermore, the release kinetics for the MNM-Mg after adsorbing VD3 (MNM-Mg-VD3) were tested in a phosphate buffer solution at pH 7.4, mimicking human bloodstream conditions. Our results showed the successful synthesis of stable MNM-Mg (Z potential of −36 mV) with an estimated average size of 10 nm and a BET surface area of 28 m2/g. To the best of our knowledge, the VD3 that was loaded on our primarily modified nanomaterials with magnesium citrate, compared with the physically mixed VD3 MNM-Mg with VD3(MNM-Mg+VD3 (PM)) and directly administrated, tended to be completely released after 5 h with lower diffusivity and greater controlled release performance.

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功能化柠檬酸镁淀粉基纳米材料在强化维生素 D3 中的开发与应用:批次和释放性能研究
最近,人们开发了多种策略来配制食品微量营养补充剂,如镁(Mg2+)和维生素 D3(VD3)。然而,由于它们与各种食品成分的不良相互作用,食品补充剂配方的研究进展有限。在过去的几十年里,淀粉因其优异的表面特性、可从各种试剂中衍生、生物可降解性和生物相容性,已被广泛应用于通过各种物理和化学方法制备不同微量营养素的微型或纳米载体。然而,这些方法大多尚未在实验室规模上进行测试,部分或完全无法生产出纳米级域的均匀颗粒,而且需要多个配制步骤。在此,研究人员在温和的条件下,通过超声波制造了淀粉纳米材料(SNMs),作为 VD3 和 Mg2+ 的有效载体。首先,使用等质量的原生玉米淀粉(NCS)和高淀粉玉米淀粉(HACS)通过超声波制备 SNM。然后在室温条件下以柠檬酸盐形式接枝镁,形成柠檬酸盐接枝镁 SNM(MNM-Mg),作为 VD3 的吸附剂。实验中采用了一系列分析方法,包括原子力显微镜(AFM)、布鲁诺-艾美特-泰勒(BET)表面积分析、傅立叶变换红外光谱(FT-IR)、Zeta 定标器和 X 射线衍射分析(XRD),以确定制备的纳米材料的尺寸、表面性质、功能性、稳定性和形态。通过使用各种等温线模型(包括 Langmuir、BET、Toth 和 Redlich-Peterson)分析平衡吸附数据,研究了 VD3 在 MNM-Mg 表面的吸附行为。此外,还在模仿人体血液条件的 pH 值为 7.4 的磷酸盐缓冲溶液中测试了吸附 VD3 后的 MNM-Mg(MNM-Mg-VD3)的释放动力学。结果表明,我们成功合成了稳定的 MNM-Mg(Z 电位为 -36 mV),其平均尺寸估计为 10 nm,BET 表面积为 28 m2/g。据我们所知,与直接给药的物理混合 VD3 MNM-Mg(MNM-Mg+VD3 (PM))相比,负载在我们主要用柠檬酸镁修饰的纳米材料上的 VD3 在 5 小时后趋于完全释放,扩散率更低,控释性能更好。
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