氨基酸插层结构缓释钙的组装及在皮肤表皮屏障功能修复中的应用

Sensitive skin disease, which caused by the imbalance of the epidermal barrier function due to the loss of Ca2+, has become a health hazard to people's skin disease. But there is no calcium resource available to the supplement of skin calcium. The composition and structure of LDHs can be tailored, the lamellar metal cations has releasability, and interlayer anions are exchangeability. In this project, Mg, Zn, Ca and other metal ions with different coordination structures and lattice energies were introduced into the laminates, in the meantime the amino acid anions were introduced into the interlayers to product a new type of amino acid intercalated Ca-based LDHs. The sustained-release performance of Ca2+ in the different crystal-field was studied using quantum-chemical theory; the influence of sustained-release behavior of amino acid caused by the composition of the sheet and the interaction between the host-guest was studied using supermolecule theory; the effect of transdermal absorption and the repair of skin epidermal barrier of the material were investigated by extracorporeal transdermal absorption experiment; to examine its practical application effect, we use it in as functional cosmetics. It is of great theoretical significance to strengthen the understanding of the crystal structure theory and study the slow release of LDHs slab and its interlayer ions. In addition, the study has important practical significance on the slow-release of calcium source through transdermal absorption and reduce the sensitive skin disease.

敏感性皮肤症已成为危害人们皮肤健康的大众症，皮肤中钙流失导致的表皮屏障功能失调是该症的主要成因，但目前尚无可用于皮肤补钙的钙源。LDHs组成和结构具有极大的可调控性，其层板金属阳离子具有可释放性、层间阴离子具有可交换性。本项目将Mg、Zn、Ca等与层板氧具有不同配位结构和晶格能的金属离子引入层板，将氨基酸阴离子引入层间，构筑氨基酸插层结构钙基LDHs新型材料，利用量子化学理论研究Ca在不同晶体场作用下的缓释性能，利用超分子理论研究层板组成和主客体相互作用对氨基酸离子缓释行为的影响；用体外透皮吸收实验考察材料的经皮吸收效果和对皮肤表皮屏障功能的修复作用；将其用于功能性化妆品中，考察其实际应用效果。本课题对于研究LDHs层板和层间离子同时缓慢释放、加强对其晶体结构理论的认识具有重要的理论意义；此外，本课题对于研究可通过透皮吸收的缓释钙源、降低敏感皮肤症发病率具有重要的实际意义。

皮肤中Ca流失会导致表皮屏障功能失调，进而产生敏感性皮肤症，在我国发病率高达30%以上，已成为严重危害人们皮肤健康的大众症。传统的氨基酸钙通过经皮给药方式给皮肤补钙，起到了良好的效果，但使用时Ca2+浓度会在较短时间内达到较大值，需增加给药次数和给药剂量，降低了于皮肤对Ca2+的有效吸收，严重影响了使用效果。.本课题利用层状复合金属氢氧化物（LDHs）层板金属阳离子和层间阴离子种类和数量的可调控性以及缓释性，在主体层板上引入Ca2+、Mg2+等具有不同晶格能的金属离子，在层间引入氨基酸阴离子，构筑了多种氨基酸插层结构钙基LDHs，研究了层板配位结构、电荷密度和主客体相互作用等对缓释性能的影响，以及透皮吸收和对皮肤屏障的修复性能。结果表明，层间客体对Ca2+、Mg2+的缓释性能影响较大，而层板组成和层板电荷密度对Ca2+的缓释行为影响较小；氨基酸插层LDHs中的Mg2+、Ca2+、Al3+和氨基酸离子均能同时控制释放，且具有缓释作用，层板中Ca2+的引入显著提高了氨基酸的释放量及最终浓度；此外，不同种类及浓度的促进剂等辅助助剂对氨基酸钙的吸收有明显的促进作用，单位面积累积渗透量大幅提高，增渗倍数可达5.73以上。.本课题构筑了多种氨基酸插层结构钙基LDHs皮肤表皮屏障功能修复材料，研究揭示了其主客体结构与缓释性能之间的科学本质，获得了氨基酸插层结构LDHs透皮吸收的科学规律。皮肤科临床实验结果表明，项目产品可以有效抑制人体皮肤炎症反应，对皮肤屏障损伤修复及过敏的治疗具有非常好的疗效，具有良好的应用前景。

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