固定化神经酰胺-薄膜凝胶协同抗污的广谱性与耐久性研究

Universality and sustainability are two main challenges in marine antifouling coatings due to the complexity of the marine environment and the diversity of the fouling organisms. Focuses are on the development of both physical antifouling coatings and green antifouling agents. In this research, ceramides, which act as a second messenger in cell apoptosis, will be immobilized to hydration multilayer films mediated by nanodiamonds, and construct multilayer films for resisting the attachment of marine fouling organisms. The synergistic effects of ceramide induced apoptosis and adhesion impedance from hydration films are anticipated. The project will fully explore the antifouling mechanism of ceramide against series fouling organisms, with the help of tracing ability of nanodiamond particles. The antifouling activity and universality of immobilized ceramide will be validated. The influence of assembly conditions, loading and distribution of the nanodiamond particles on modulus and stability of the multilayer films will be studied, and hydrated films with both fouling organism resistance and high stability will be constructed. The contribution of film self-repair ability to its sustainability against marine fouling will be explored, and the possible application of ceramide-hyration multilayer synergy film in marine antifouling industry will be foreseen. The corporation of multiple effects is designed to improve the economy and effectiveness of marine antifouling coatings. The results gained from this original work will provide a new insight into appropriate usage of expensive, scarce sourced bioactive molecules in marine antifouling fields and facilitate the design and construction of environment-friendly marine antifouling coatings with long-term versatile performances.

海洋环境的复杂性和污损生物的多样性给抗污涂层的广谱性和耐久性带来极大挑战，物理抗污涂层的设计和绿色抗污剂的开发是两大研究热点。本项目将在细胞凋亡中充当第二信使的神经酰胺经纳米金刚石介导固定到薄膜凝胶中，构建阻抗海洋污损生物附着的多层膜，预期实现神经酰胺诱导调亡和薄膜凝胶阻抗粘附的协同作用。本项目借助纳米金刚石示踪作用充分探究神经酰胺对不同污损生物的抗污机制，验证固定化神经酰胺的抗污活性和普适性；研究组装条件和纳米金刚石的装载量及分布对多层膜模量和环境稳定性的影响规律，获得阻抗污损生物附着的高稳定性薄膜凝胶；考察多层膜自修复能力对其抗污持久性的贡献，探究神经酰胺-薄膜凝胶协同作用多层膜作为海洋抗污涂层的应用潜力。本项目通过多途径协同作用提高海洋抗污涂层的经济性和有效性，为价格昂贵、来源稀少的生物活性分子用于海洋抗污的经济化使用设计提供新思路，并为广谱、持久、绿色海洋抗污涂层的构建提供新方法。

因项目负责人单位调动，研究方向从原先的海洋新材料转变为骨组织生物材料，本项目继续沿用原定的以多糖为组装体的层层组装技术来固定小分子药物这一思路，研究骨化三醇原位缓释体系对骨质疏松症患者骨再生的促进作用。骨质疏松症是一种系统性骨骼疾病，它对骨髓间充质干细胞（BMSCs）的生存能力产生了负面影响，延缓了骨愈合过程。然而，骨质疏松症导致的成骨减少的某些机制尚不明确，骨质疏松症患者的骨再生尚无针对性治疗。在本研究中，我们首先研究了骨质疏松症相关骨生成缺陷的潜在机制，发现双侧卵巢切除大鼠骨髓间充质干细胞（OVX-rBMSCs）通过抑制钙敏感受体（CaSR）而抑制其细胞活性和干细胞功能。同时，我们证实了骨质疏松常用药骨化三醇（Calcitriol）能够逆转OVX导致的对CaSR的抑制作用，并上调OVX-rBMSCs的成骨分化活性。据此，我们设计了不同的Calcitriol-Ca2+体系用以促进骨质疏松伴随的骨缺损修复。我们将透明质酸（HA）和壳聚糖（CHI）多层膜覆盖多孔双相陶瓷磷酸钙（BCP），然后将骨化三醇加入到BCP支架中，构建了复合支架。我们构建了具有微孔结构的HA/CHI多层膜，大大增强了支架上OVX-RBMSCs的细胞粘附和增殖，同时Calcitriol持续激活CaSR，从而提高了OVX-RBMSCs的成骨分化能力。体外和在体实验均表明，多层包膜结合骨化三醇可显著促进骨质疏松性骨髓间充质干细胞的粘附、增殖和成骨分化，从而增加去卵巢大鼠骨缺损模型中骨组织的长入和矿化。进一步我们还设计了装载Calcitriol-Ca2+的可注射水凝胶体系，在骨质疏松大鼠股骨髁缺损模型中促进了骨缺损的修复。综上所述，这种Calcitriol-Ca2+复合体系有望用在临床上，作为针对骨质疏松症患者骨再生的安全可靠、经济有效的新方法。

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