无定形磷酸钙（ACP）由于其pH的灵敏度高、生物体内排斥反应小、可在生物体内自动降解的特点和无定形的结构，引发了大量的机理和应用研究。但ACP性质不稳定，团聚严重并且容易转变为结晶态，限制了其应用范围。Pickering乳液是一种由固体颗粒稳定的乳液体系。与表面活性剂稳定的传统乳化剂相比，Pickering乳液的稳定性更强，因为它的稳定性主要依赖于固体颗粒在油水界面上的吸附和覆盖。目前以ACP为颗粒稳定Pickering乳液的文献报道较为有限。因此本文将ACP与Pickering乳液相互结合，研究了新型Pickering乳液的应用领域，同时提高乳液的稳定性和可控性、有助于开发环境友好型的乳液产品，减少对环境的污染和损害。

本研究通过化学沉淀法制备了无定形磷酸钙，利用硬脂酸（Sa）对ACP进行了表面改性。使用ACP颗粒稳定Pickering乳液，制备了稳定的Pickering乳液，并考察了其乳化特性和应用研究。具体研究如下：

（1）利用化学沉淀法与硬脂酸乙醇回流法成功制备了疏水改性的ACP（Sa-ACP），研究了Sa-ACP颗粒的表面特性、稳定Pickering乳液的能力和在药物释放方面的应用，发现Sa-ACP稳定Pickering乳液并制备缓释水凝胶是一种可行、有效且环保的方法。通过接触角测试、FT-IR、SEM和XRD等表征研究发现Sa的存在不仅使ACP表面具有疏水特性，还能改善ACP团聚严重的问题，同时成功减缓了ACP向晶态结构转变。用4 wt% Sa-ACP稳定了Pickering乳液，对乳化性能进行了研究。发现在碱性条件、油水比为1:1及颗粒浓度为1.0 w/v%时，制备的乳液更加稳定。利用ACP在溶液中自释放Ca²⁺的特性，与海藻酸钠（SA）交联构建了负载姜黄素的Pickering乳液水凝胶。在Sa-ACP含量、海藻酸钠浓度在0.25-1.0 wt%区间以及pH=1.2、7.4的条件下，可以有效调控姜黄素的释放量。

（2）本章利用ACP为乳化剂制备了稳定性较好的O/W型Pickering乳液，研究了Pickering乳液体系（PE体系）对水溶液中的腐殖酸吸附，发现PE体系吸附腐殖酸要比ACP单独吸附腐殖酸有更大的吸附量。在优化条件下，PE体系最大吸附量为56.65 mg/g。腐殖酸在Pickering乳液体系中的吸附符合准一阶动力学模型，其中准一阶动力学方程的R²＞0.9，并且实验数据很好的拟合了Langmuir吸附等温线模型。通过对热力学参数的计算发现ΔH＜0、ΔS＜0且ΔG＜0，说明该吸附过程是能够自发进行的放热反应，且随着吸附的进行，体系混乱程度减小。

（3）利用Sa-ACP制备了O/W型Pickering乳液，其中分散相为二氯甲烷，连续相为壳聚糖水溶液，通过壳聚糖与三聚磷酸钠（TPP）离子交联制备了壳聚糖多孔微球，发现制备的多孔微球对腐殖酸具有很强的吸附能力。通过SEM分析发现，Pickering乳液模板法制备的壳聚糖微球具有三维网状结构，与直接交联得到的微球相比，有更丰富的孔隙结构和更大的孔隙率。ACP与三维网状结构的存在增强了壳聚糖多孔微球的吸附能力。对水溶液中的腐殖酸进行吸附实验发现，pH值在4-6范围内有更好的吸附量，pH值在8-10范围下，吸附量明显降低。在283 K下，壳聚糖多孔微球最大吸附量为316.27 mg/g。壳聚糖多孔微球吸附腐殖酸的过程符合准二阶动力学模型，说明吸附过程主要受化学作用控制，吸附等温线数据很好的拟合了Langmuir吸附等温线模型，为单分子层吸附，并且该吸附过程是自发进行的，放热的，并且伴随着系统的有序性增加。经过五个周期的循环吸附，吸附量降低25.41%，具有良好的再生吸附性能和潜在的实用价值。

Amorphous calcium phosphate (ACP) has triggered a large number of mechanistic and applied researches due to its high pH sensitivity, low rejection in organisms, automatic degradation in organisms, and amorphous structure. However, ACP is unstable, agglomerates heavily and tends to transform into crystalline state, limiting its application. Pickering emulsion is an emulsion system stabilized by solid particles. Compared with surfactant-stabilized conventional emulsifiers, Pickering emulsions are more stable because their stability mainly depends on the adsorption and coverage of solid particles at the oil-water interface. There are limited literature reports on stabilization of Pickering emulsions with ACP as nanoparticles. Therefore, the combination of ACP and Pickering emulsions has been investigated as an application area for new Pickering emulsions, while improving the stability and controllability of the emulsions, contributing to the development of environmentally friendly emulsion products, and reducing the pollution and damage to the environment.

In this study, amorphous calcium phosphate (ACP) was prepared by chemical precipitation method and surface modification of ACP using stearic acid (Sa) was carried out. Stabilized Pickering emulsions were prepared using ACP particles and their emulsification properties and application studies were investigated. The specific studies are as follows:

(1) Hydrophobically modified ACP (Sa-ACP) was successfully prepared using the chemical precipitation method with ethanol stearate reflux method. The surface properties of Sa-ACP particles, the ability to stabilize Pickering emulsions, and the application in drug release were investigated, and it was found that it is a feasible, effective, and environmentally friendly method to stabilize Pickering emulsions and to prepare slow-release hydrogels with Sa-ACP. Characterization studies such as contact angle tests, FT-IR, SEM and XRD revealed that the presence of Sa not only gives hydrophobic properties to the ACP surface, but also improves the problem of severe agglomeration of ACP, and at the same time successfully slows down the transformation of ACP to a crystalline structure. Pickering emulsion was stabilized with 4 wt% stearic acid modified amorphous calcium phosphate (Sa-ACP) and the emulsification properties were investigated. The emulsions obtained were found to be more stable under alkaline conditions, an oil-water ratio of 1:1 and a particle concentration of 1.0 w/v%. Pickering emulsion hydrogels loaded with curcumin were constructed by cross-linking ACP with sodium alginate (SA) utilizing the property of self-releasing Ca²⁺ in solution. Under the conditions of Sa-ACP content, sodium alginate concentration in the range of 0.25-1.0 wt% and pH=1.2, 7.4, curcumin release can be effectively regulated.

(2) In this chapter, O/W type Pickering emulsions with good stability were prepared using ACP as an emulsifier, and the adsorption of humic acid in aqueous solution by Pickering emulsion system (PE system) was investigated, and it was found that the adsorption of humic acid by PE system had a larger adsorption capacity than that of ACP alone. Under the optimized conditions, the maximum adsorption amount of PE system was 56.65 mg/g. The adsorption of humic acid in Pickering emulsion system conformed to the quasi-first-order kinetic model, in which the quasi-first-order kinetic equation had R²＞0.9, and the experimental data fitted the Langmuir adsorption isotherm model very well. Calculations of the thermodynamic parameters revealed that ΔH＜0, ΔS＜0 and ΔG＜0, indicating that the adsorption process is an exothermic reaction that can be carried out spontaneously, and the disorder of the system decreases as the adsorption proceeds.

(3) O/W type Pickering emulsion was prepared using Sa-ACP, in which the dispersed phase was dichloromethane and the continuous phase was chitosan aqueous solution. Chitosan porous microspheres were prepared by ionic cross-linking of chitosan with sodium tripolyphosphate (TPP), and it was found that the prepared porous microspheres had a strong adsorption capacity for humic acid. SEM analysis revealed that the chitosan microspheres prepared by the Pickering emulsion template method had a three-dimensional reticular structure with a richer pore structure and larger porosity compared with those obtained by direct crosslinking, and the presence of ACP and the reticular structure enhanced the adsorption capacity of the chitosan porous microspheres. The adsorption experiments on humic acid in aqueous solution revealed better adsorption at low pH and much lower adsorption at high pH, with a maximum adsorption of 316.27 mg/g by chitosan porous microspheres at 283 K. The adsorption of humic acid by chitosan porous microspheres conformed to the quasi second-order kinetic model, which was mainly based on the chemical adsorption, and the adsorption isotherms data were well fitted to the Langmuir adsorption isotherm model for monomolecular layer adsorption, and the adsorption process was spontaneous, exothermic, and accompanied by an increase in the order of the system. After five cycles of cyclic adsorption, the adsorption amount only decreased by 25.41%, which has good regenerative adsorption performance and potential practical value.

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