文献类型：期刊文献

中文题名：油茶皂素化学修饰与溶血性的构效关系研究

英文题名：Structure-activity Relationship Between Chemical Modification and Hemolytic Activity of Camellia Saponin

作者：李胜男[1,2,3] 程贤[1,2] 李盼盼[1,2] 陈玉湘[1,2] 蒋建新[1] 毕良武[1,2]

第一作者：李胜男

机构：[1]中国林业科学研究院林产化学工业研究所,江苏省生物质能源与材料重点实验室,国家林业和草原局林产化学工程重点实验室,林木生物质低碳高效利用国家工程研究中心,江苏南京210042;[2]南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京210037;[3]北京林业大学材料科学与技术学院,北京100083

年份：2025

卷号：45

期号：1

起止页码：81-88

中文期刊名：林产化学与工业

外文期刊名：Chemistry and Industry of Forest Products

收录：;北大核心:【北大核心2023】；

基金：国家自然科学基金青年项目(32201512)。

语种：中文

中文关键词：油茶皂素;化学修饰;结构表征;溶血活性;构效关系

外文关键词：camellia saponin;chemical modification;structural characterization;hemolytic activity;structure-activity relationship

分类号：TQ35

摘要：为阐明油茶皂素及其衍生物与溶血活性的构效关系,为油茶皂素结构修饰提供理论指导,从而为油茶皂素药物开发提供理论基础。以油茶皂素为原料,通过酸水解、碱水解和还原反应合成油茶皂素化学修饰产物,基于红外光谱(FT-IR)、电喷雾-质谱(ESI-MS)和核磁共振氢谱(1H NMR)对目标产物进行结构表征,并测试了油茶皂素及其修饰产物的溶血活性。采用密度泛函理论方法(DFT)在B3LYP/6-311++G**水平上对油茶皂素代表性化合物山茶皂素B2(camellia saponin B2)进行量子化学计算,基于化合物的几何结构、自然布居分析(NPA)电荷、前线分子轨道等参数深入研究油茶皂素结构与溶血活性之间的关系。产物的结构表征结果发现:红外光谱中碱水解产物的羟基峰强度增加,而酯基官能团的羰基峰强度减弱,表明在碱水解过程中酯基被还原为羟基。溶血活性测试结果表明:油茶皂素及其修饰产物的溶血率具有浓度依赖性,随着化合物质量浓度的增加,溶血率逐渐增加;相同质量浓度时,油茶皂素碱水解产物的溶血率明显低于原料、酸水解产物和还原产物,推测油茶皂素的酯基官能团对其溶血活性起着重要作用;0.25 g/L时,碱水解产物的溶血率为41.81%。此外DFT计算结果表明:camellia saponin B2的溶血活性位点位于苷元上的酯基部位,因此碱水解能够通过消除酯基基团而降低油茶皂素的溶血活性。
In order to clarify the structure-activity relationship between camellia saponin and its derivatives and hemolytic activity,provide theoretical guidance for structure modification of camellia saponin,and a foundation for drug development of oleifera saponin.The chemical modification products of camellia saponin were generated through acid hydrolysis,alkali hydrolysis and reduction reactions.The target products were structurally characterized based on Fourier transform infrared spectroscopy(FT-IR),electrospray ionization-mass spectrometry(ESI-MS)and nuclear magnetic resonance spectroscopy(1 H NMR),and the hemolytic activity of the camellia saponin and its modified products were tested.Quantum chemical calculations of the camellia saponin compounds were carried out at the level of B3LYP/6-311++G**using the density-functional theory method(DFT),and the relationship between the structure of camellia saponin B2 and hemolytic activity were investigated in depth on the basis of parameters such as the geometry structure,natural population analysis(NPA)charges and frontier molecular orbitals of the compounds.The structural characterization results showed that in FT-IR,the intensity of the hydroxyl peak of the alkali hydrolysis product increased,while the intensity of the carbonyl peak in ester group decreased,indicating that the ester group was reduced to a hydroxyl group during the alkali hydrolysis process.The results of the hemolytic activity test showed that the hemolytic rate of camellia saponin and its modified products was concentration-dependent,and the hemolytic rate gradually increased with the increase of compound mass concentration.At the same mass concentration,the hemolysis rate of the base hydrolysate of camellia saponin was significantly lower than that of the raw material,acid hydrolysis and reduction products.It was speculated that the ester functional group of camellia saponin played an important role in the hemolytic activity of the compound.The hemolysis rate of base hydrolysate was 41.81%at a mass concentration of 0.25 g/L.In addition,DFT calculations showed that the hemolytic activity site of camellia saponin was located at the ester on the aglycone.Therefore,alkaline hydrolysis could reduce the hemolytic activity of camellia saponin.