CN113480579B - 一种酚酸类活性物质及其制备方法和应用 - Google Patents
一种酚酸类活性物质及其制备方法和应用 Download PDFInfo
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- CN113480579B CN113480579B CN202110748350.6A CN202110748350A CN113480579B CN 113480579 B CN113480579 B CN 113480579B CN 202110748350 A CN202110748350 A CN 202110748350A CN 113480579 B CN113480579 B CN 113480579B
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- phenolic acid
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Abstract
本发明提供了一种酚酸类活性物质及其制备方法和应用，涉及天然活性成分的提取制备及应用技术领域。本发明提供的酚酸类活性物质包括对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸中的至少一种化合物，所述化合物的总含量为100‑500mg/g。本发明制备得到酚酸类活性物质中酚羟基的总含量为7.0‑14.0mmol/g，具有优异的抗氧化、抑菌、抗炎、美白等生物活性，可应用于抗炎舒敏、祛痘除痕、美白淡斑、祛皱抗衰等化妆品的开发。
Description
技术领域
本发明涉及天然活性成分的提取制备及应用技术领域，特别涉及一种酚酸类活性物质及其制备方法和应用。
背景技术
酚酸类活性物质包括对香豆酸、咖啡酸、原儿茶酸、没食子酸、鞣花酸、丹参素、丹酚酸、迷迭香酸等，具有优异的抗氧化、抗炎、抗菌、美白淡斑、降血脂、抗肿瘤、防治心脑血管疾病等生物活性，在医药、食品保健、化妆品、动植物营养等领域有着广泛的应用。
酚酸类活性物质通常从天然产物中分离提取，或采用有机合成、生物合成的方法制造。木质素是自然界储量最丰富的芳香族化合物，地球每年可产生6×1014t左右木质素，是极具潜力的可再生碳资源。在我国工业生产中，木质素年产量超过1100万吨，部分用于燃烧供能、低值化工产品等，大量被遗弃，有效利用率不到20％，这造成生物质资源巨大浪费和生态环境污染。由于木质素本征结构中具有与酚酸类化合物相类似的结构单元，因此，以木质素为原料来制备酚酸类化合物是实现木质素废弃物高值利用的有效途径，且具有技术可行性。
目前，利用木质素制备酚酸类化合物多采用化学法和生物法。化学法通过热解、气化、水解、还原和氧化等方法将木质素解聚成小分子酚类化合物，其中，催化氧化方法可得到对羟基苯甲酸、香草酸等酚酸类化合物，产物收率<15％，得不到对香豆酸、咖啡酸、原儿茶酸、没食子酸等高活性的酚酸类化合物，且由于制备过程采用均相金属盐催化剂和有机溶剂，致使后续分离提取操作将产生大量废液、废渣等，环境污染较大。生物法多采用木质素氧化酶、锰过氧化氢酶、漆酶等酶工程或嗜热芽孢杆菌等微生物发酵方式，将木质素转化为粘康酸等小分子酸类、酚类、酚酸类等化合物，得到的对香豆酸、咖啡酸、原儿茶酸、没食子酸等酚酸类化合物含量非常低，通常≤200μg/g，目标产物含量较低，致使产物从发酵液中分离提取难度增加，耗能增加，且发酵和提取过程废液量大大增加。因此，亟待开发一种利用木质素制备对香豆酸、咖啡酸、原儿茶酸、没食子酸等高活性酚酸类化合物的绿色高效合成方法。除此之外，目前还未见有将此种酚酸类化合物混合原料应用于化妆品的生产。
发明内容
本发明的主要目的是提供一种酚酸类活性物质及其制备方法，旨在解决目前采用的化学法或生物法制备酚酸类化合物有效成分含量低，分离困难、废弃物多，对环境污染大等问题。
为实现上述目的，第一方面，本发明提出了一种酚酸类活性物质，包括对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸中的至少一种化合物，所述化合物的总含量为100-500mg/g。
本发明提供的酚酸类活性物质中所含的对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸属于高活性酚酸类化合物，具有优异的抗氧化、抑菌、抗炎、美白等生物活性。
作为本发明所述酚酸类活性物质的优选实施方式，所述酚酸类活性物质中酚羟基的总含量为7.0-14.0mmol/g。
第二方面，本发明还提出一种酚酸类活性物质的制备方法，包括以下步骤：
(1)将木质素、催化剂、反应溶剂加入反应容器中，氧气置换排尽釜内空气后，充入0.5-1.5MPa氧气，在120-180℃下搅拌反应2-12h，冷却至室温，过滤分离所述催化剂，收集反应液，再用所述反应溶剂洗涤滤饼，合并洗出液和反应液，减压蒸馏、真空干燥后得到中间产物A；
(2)将所述中间产物A、碘代环己烷、N,N-二甲基甲酰胺加入反应容器中，搅拌回流反应12-36h，停止反应，冷却至室温，用正己烷洗涤，洗涤后反应液经减压蒸馏、真空干燥后得到所述酚酸类活性物质。
本发明技术方案中，作为本发明所述酚酸类活性物质的制备方法的优选实施方式，木质素与催化剂的质量比为木质素：催化剂＝1:0.1-1，木质素的质量与反应溶剂的体积之比为木质素：反应溶剂＝1g:20-50ml；木质素的质量与碘代环己烷的体积之比为木质素：碘代环己烷＝1g:5-10ml，木质素的质量与N,N-二甲基甲酰胺的体积之比为木质素：N,N-二甲基甲酰胺＝1g:10-40ml。
第三方面，本发明还提出一种酚酸类活性物质的制备方法，包括以下步骤：
(1)将木质素、碘代环己烷、N,N-二甲基甲酰胺加入反应容器中，搅拌回流反应12-36h，停止反应，冷却至室温，用正己烷洗涤，洗涤后反应液经减压蒸馏、真空干燥后得到中间产物B；
(2)将所述中间产物B、催化剂、反应溶剂加入反应容器中，氧气置换排尽釜内空气后，充入0.5-1.5MPa氧气，在120-180℃下搅拌反应2-12h，冷却至室温，过滤分离所述催化剂，收集反应液，再用所述反应溶剂洗涤滤饼，合并洗出液和反应液，减压蒸馏、真空干燥后得到所述酚酸类活性物质。
作为本发明所述酚酸类活性物质的制备方法的优选实施方式，木质素的质量与碘代环己烷的体积之比为木质素：碘代环己烷＝1g:5-10ml，木质素的质量与N,N-二甲基甲酰胺的体积之比为木质素：N,N-二甲基甲酰胺＝1g:10-40ml；木质素与催化剂的质量比为木质素：催化剂＝1:0.1-1，木质素的质量与反应溶剂的体积之比为木质素：反应溶剂＝1g:20-50ml。
本发明酚酸类活性物质的制备方法中，作为反应原料的木质素可以先与催化剂、反应溶剂混合反应后得到中间产物A，再将中间产物A与碘代环己烷、N,N-二甲基甲酰胺反应制备得到酚酸类活性物质；也可以先将木质素与碘代环己烷、N,N-二甲基甲酰胺混合反应得到中间产物B，再将中间产物B与催化剂、反应溶剂混合反应制备得到酚酸类活性物质。即催化剂、反应溶剂、碘代环己烷、N,N-二甲基甲酰胺的加入时机可以进行上述调整，不会影响产物的组成和性质。
作为本发明所述酚酸类活性物质的制备方法的优选实施方式，所述木质素包括木质素磺酸、碱木质素、有机溶剂解木质素、酶解木质素中的至少一种。
作为本发明所述酚酸类活性物质的制备方法的优选实施方式，所述催化剂为MnOx/C、MoOx/C、VOx/C、CuOx/C中的至少一种。
MnOx/C、MoOx/C、VOx/C、CuOx/C催化剂的金属氧化物活性组分中Mn4+、Mo6+、V5+、Cu2+等能与木质素结构单元中Cα-O、Cβ-O、Cγ-O等氧原子配位并活化相应和相邻C-O、C-C、C-H等化学键，促进Cα-Cβ、Cβ-O键氧化断裂、促进Cγ-OH氧化形成CαOOH、CγOOH等酚基羧酸；催化剂中碳基载体表面含芳环、羟基、羰基、羧基等官能团，可通过氢键、Π-Π堆积等分子间作用力，促进木质素向催化剂表面扩散、与催化剂金属氧化物活性中心吸附反应。整体而言，选用MnOx/C、MoOx/C、VOx/C、CuOx/C催化剂有利于木质素催化氧化解聚生成香草酸、阿魏酸等酚酸类物质。
作为本发明所述酚酸类活性物质的制备方法的优选实施方式，所述反应溶剂为甲醇、乙二醇、二甲基亚砜、γ-戊内酯中的至少一种。
本发明所选择的上述反应溶剂对木质素具有很好的溶解、分散性，有利于反应底物木质素分子在液相溶液中与催化剂接触反应。
第四方面，本发明还提出一种酚酸类活性物质在化妆品、保健品中的应用。
本发明制备得到的酚酸类活性物质表现出优异的抗氧化、抑菌、抗炎、美白等生物活性，可应用于抗炎舒敏、祛痘除痕、美白淡斑、祛皱抗衰等化妆品以及保健品的开发。
相对于现有技术，本发明的有益效果为：
(1)本发明技术方案通过以木质素为原料，制备含有对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸等高活性酚酸类化合物等高活性酚酸类化合物的酚酸类活性物质，制备的酚酸类活性物质中酚羟基含量高，具有优异的抗氧化、抑菌、抗炎、美白等生物活性，可应用于保健品、化妆品等康美产业领域；
(2)本发明提供的酚酸类活性物质的木质素源制备方法，具有路线方法新颖、制备过程低碳绿色、制备过程效率高、原料及生产成本低，产物后处理简单且低能环保等特点，制备的酚酸类活性物质的收率>75％，高活性酚酸类化合物含量为100-400mg/g。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将通过具体实施例对本发明作进一步说明。
实施例1
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g有机溶剂解木质素、0.5g MoOx/C、40mLγ-戊内酯(GVL)加入高压反应釜中，冲入1MPa氧气，180℃搅拌反应3h，停止搅拌，冷却至室温，反应液过滤分离，用10mLγ-戊内酯(GVL)洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到中间物；
(2)将中间物置入圆底烧瓶中，加入20mL N,N-二甲基甲酰胺(DMF)和6mL碘代环己烷，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到0.802g黄色的酚酸类活性物质。
实施例2
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g酶解木质素、1.0g CuOx/C、40mL乙二醇加入高压反应釜中，冲入1MPa氧气，180℃搅拌反应5h，停止搅拌，冷却至室温，反应液过滤分离，用10mL乙二醇洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到中间物；
(2)将中间物置入圆底烧瓶中，加入20mL N,N-二甲基甲酰胺(DMF)和6mL碘代环己烷，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到0.753g黄色酚酸类活性物质。
实施例3
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g碱木质素、0.5g VOx/C、40mL甲醇加入高压反应釜中，冲入1MPa氧气，150℃搅拌反应8h，停止搅拌，冷却至室温，反应液过滤分离，用10mL甲醇洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到中间物；
(2)将中间物置入圆底烧瓶中，加入20mL N,N-二甲基甲酰胺(DMF)和6mL碘代环己烷，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到0.798g黄色酚酸类活性物质。
实施例4
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1g木质素磺酸、1.0g MnOx/C、40mL DMSO加入高压反应釜中，冲入1MPa氧气，150℃搅拌反应8h，停止搅拌，冷却至室温，反应液过滤分离，用10mL DMSO洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到中间物；
(2)将中间物置入圆底烧瓶中，加入20mL N,N-二甲基甲酰胺(DMF)和6mL碘代环己烷，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到0.818g黄色酚酸类活性物质。
实施例5
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g有机溶剂解木质素、8mL碘代环己烷、20mL N,N-二甲基甲酰胺(DMF)加入圆底烧瓶中，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到中间物；
(2)将中间物、0.5g MoOx/C、40mLγ-戊内酯(GVL)加入高压反应釜中，冲入1MPa氧气，180℃搅拌反应3h，停止搅拌，冷却至室温，反应液过滤分离，用10mLγ-戊内酯(GVL)洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到0.812g黄色酚酸类活性物质。
实施例6
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g酶解木质素、8mL碘代环己烷、20mL N,N-二甲基甲酰胺(DMF)加入圆底烧瓶中，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到中间物；
(2)将中间物、1.0g CuOx/C、40mL乙二醇加入高压反应釜中，冲入1MPa氧气，180℃搅拌反应5h，停止搅拌，冷却至室温，反应液过滤分离，用10mL乙二醇洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到0.764g黄色酚酸类活性物质。
实施例7
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1.0g碱木质素、8mL碘代环己烷、20mL N,N-二甲基甲酰胺(DMF)加入圆底烧瓶中，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到中间物；
(2)将中间物、0.5g VOx/C、40mL甲醇加入高压反应釜中，冲入1MPa氧气，150℃搅拌反应8h，停止搅拌，冷却至室温，反应液过滤分离，用10mL甲醇洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到0.808g黄色酚酸类活性物质。
实施例8
本实施例提供了一种酚酸类活性物质。
本实施例酚酸类活性物质的制备方法包括以下步骤：
(1)将1g木质素磺酸、8mL碘代环己烷、20mL N,N-二甲基甲酰胺(DMF)加入圆底烧瓶中，搅拌回流反应24h，停止搅拌，溶液冷却至室温后转移至分液漏斗中，20mL正己烷洗涤3次，洗涤后反应溶液进行减压蒸馏、真空干燥，得到中间物；
(2)将中间物、1.0g MnOx/C、40mL DMSO加入高压反应釜中，冲入1MPa氧气，150℃搅拌反应8h，停止搅拌，冷却至室温，反应液过滤分离，用10mL DMSO洗涤滤饼2次，合并滤液，减压蒸馏、真空干燥后得到0.826g黄色酚酸类活性物质。
效果例1
按照如下公式计算实施例1-8制备得到的酚酸类活性物质的收率，收率＝(酚酸类活性物质的质量/木质素原料的质量)*100％，实施例1-8制备得到的黄色酚酸类活性物质的收率如下表1所示。
表1.实施例1-8制备得到的黄色酚酸类活性物质的收率(％)
| 序号 | 收率 | 序号 | 收率 |
| 实施例1 | 80.2 | 实施例5 | 81.2 |
| 实施例2 | 75.3 | 实施例6 | 76.4 |
| 实施例3 | 79.8 | 实施例7 | 80.8 |
| 实施例4 | 81.8 | 实施例8 | 82.6 |
效果例2
采用HPLC-UV分析方法对实施例1-8制备得到的酚酸类活性物质的组成进行分析，具体分析测试方法如下：准确称取酚酸类化合物样品50mg，用色谱级甲醇定容至25mL，超声10min使酚酸类化合物完全溶解，用HPLC-UV定量分析酚酸类化合物活性成分含量：色谱柱采用C18柱，以乙腈/0.1％磷酸水溶液为流动相，272nm为检测波长，用标准曲线法计算各活性成分的量。
实验测得实施例1-8制备得到的酚酸类活性物质均含有对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸。并且，实施例1-8制备得到的酚酸类活性物质中上述各酚酸类活性成分的总含量如下表2所示。
表2.实施例1-8制备得到的酚酸类活性物质中活性成分的总含量(mg/g)
| 序号 | 活性成分总含量 | 序号 | 活性成分总含量 |
| 实施例1 | 454 | 实施例5 | 423 |
| 实施例2 | 338 | 实施例6 | 308 |
| 实施例3 | 274 | 实施例7 | 242 |
| 实施例4 | 198 | 实施例8 | 161 |
对比例1
本对比例提供了一种化妆品常用的抗氧化功能化合物白藜芦醇。
对比例2
本对比例提供了一种化妆品常用的抑菌抗炎功能化合物水杨酸，浓度为1％。
对比例3
本对比例提供了一种化妆品常用的美白功效功能化合物烟酰胺。
效果例3
采用福林酚(Folin-Ciocalteu)测试方法对实施例1-8制备得到的酚酸类活性物质、以及对比例1-3的酚羟基含量进行分析，具体分析测试方法如下：将15mL F-C酚试剂与135ml甲醇混合，配制F-C溶液；取4mL F-C溶液与0.1mg/ml酚酸类化合物样品甲醇溶液混合，室温搅拌5min，加入3.2mL 7.5％碳酸钠水溶液，室温搅拌30min，在765nm处测量样品的吸光度值。采用邻苯二酚标准曲线计算酚酸类化合物的酚羟基含量。
实施例1-8制备得到的酚酸类活性物质中酚羟基含量如下表3所示。
表3.实施例1-8制备得到的酚酸类活性物质中酚羟基含量(mmol/g)
| 序号 | 酚羟基总含量 | 序号 | 酚羟基总含量 |
| 实施例1 | 13.4 | 实施例7 | 9.7 |
| 实施例2 | 12.0 | 实施例8 | 7.6 |
| 实施例3 | 10.8 | 对比例1 | 8.9 |
| 实施例4 | 8.7 | 对比例2 | 7.2 |
| 实施例5 | 12.5 | 对比例3 | - |
| 实施例6 | 11.0 |
效果例4
以实施例1-8制备得到的酚酸类活性物质、以及对比例1-3的物质为测试对象，对其抗氧化功效、抑菌功效、抗炎功效、美白功效进行评价。相关测试数据下表4所示。
(1)抗氧化功效评价方法
DPPH·自由基清除：配置0.01mg/mL，0.025mg/mL，0.05mg/mL，0.1mg/mL待测样品甲醇溶液，依次移取3.0ml待测样品溶液于10ml比色管中，分别加入3.0ml 0.15mM的DPPH·甲醇溶液，摇匀，室温避光反应30min，在517nm处测量样品的吸光度值A1；同样条件，甲醇代替DPPH·溶液测定本底吸光度值A2；样品溶剂代替样品测定空白值A0。DPPH·的清除率(％)＝(A0-(A1-A2))/A0*100％。DPPH·清除率与待测样品浓度拟合曲线，DPPH·清除率为50％时待测样品的浓度，即得到IC50值。
(2)抑菌功效评价方法
体外抑制痤疮丙酸杆菌实验：将痤疮丙酸杆菌接种于加有琼脂粉的梭菌增菌培养基斜面上，在(37±1)℃环境下厌氧培养48-72h。待菌落长满后用5mL梭菌增菌培养基将菌落进行洗脱。收集洗脱液将其浓度调整为106CFU/mL，并用平板法进行活菌计数。称取1g试验样品加入到上述0.1mL菌悬液中，并加入9mL PBS混合后，取1mL至于3个平行平皿内，再加入梭菌增菌培养基在(37±1)℃环境下厌氧培养48-72h后菌落计数，以上实验重复3次，取其平均数，同时设置生理盐水为空白对照。
抑菌率X＝(A-B)/A×100％
式中，A为对照样品平均回收菌落数；B为试验样品平均回收菌落数。
(3)抗炎功效评价方法
采用脂多糖LPS诱导RAW264.7小鼠巨噬细胞模型进行抗炎功效测试。方法：体外培养巨噬细胞Raw264.7，以不同浓度(0.1mg/L、0.5mg/L、1mg/L、2mg/L、5mg/L、10mg/L)LPS处理Raw264.7，结合细胞活力以及炎症相关因子(NO、TNF-α)等的变化程度确定LPS最佳刺激响应条件，并基于该刺激条件(5mg/L LPS)通过受试物处理前后炎症因子水平变化，开展抗炎标准物质以及待测活性物的功效评价。
评价方法：细胞接种24h后进行受试物处理1h，然后加入5mg/L LPS，置于37℃、5％CO2培养箱中培养24h，收集细胞培养上清液，分别用一氧化氮试剂盒和ELISA试剂盒进行炎症相关因子NO和TNF-α含量的分析，同时评价相应空白组，每组实验独立重复3次。
(4)美白功效评价方法
A、体外酪氨酸酶抑制率实验：加入PBS缓冲液、0.5g/L L-酪氨酸溶液和不同浓度的样品溶液，置于37℃水浴中恒温10min后，加入500U/mL的酪氨酸酶溶液，混匀，再置于37℃水浴中反应10min，迅速移入比色皿中，测得475nm处的吸光度值。
B、α-MSH诱导B16-F10细胞模型黑色素合成抑制实验：选择对数生长期的B16-F10细胞，用质量分数0.25％胰蛋白酶消化后，以DMEM完全培养基配成密度为5×104个/mL的细胞悬液，接种于96孔培养板，每孔2mL，于37℃、5％CO2培养箱内培养24h。镜下观察细胞贴壁后，分别加入含有受试物和α-MSH的培养基，并设置空白对照组和阳性对照组，每孔2mL，每一浓度做3个平行。于37℃、5％CO2培养箱内孵育72h后，弃掉上清液并收集细胞，加入400μL的1mol/L NaOH溶液(含有质量分数10％DMSO)，80℃下恒温2h，取100μL在酶标仪490nm处测其吸光度值。
表4.实施例1-8、对比例1-3的功效评价结果
注：①美白功效评价：实施例1-8酚酸类化合物和对比例3烟酰胺的受试浓度为0.5％；
②抑菌抗炎功效评价：实施例1-8酚酸类化合物和对比例2的受试浓度为0.05％。
由表4结果可以看出，利用木质素制备的酚酸类化合物，相比于对比例提供的活性物，其DPPH·清除的IC50值低，表现高抗氧化活性；其痤疮丙酸杆菌抑制率均为99.99％，表现高抑菌活性；LPS诱导RAW264.7小鼠巨噬细胞模型评价，其NO和TNF-α炎症因子含量更低，表现高抗炎活性；体外酪氨酸酶抑制实验和α-MSH诱导B16-F10细胞模型黑色素合成抑制实验评价，在相同受试浓度下，酚酸类化合物的酪氨酸酶抑制率IC50和B16-F10细胞黑色素分泌抑制率更低，表现良好的美白功效。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。
Claims (5)
1.一种酚酸类活性物质的制备方法，其特征在于，所述酚酸类活性物质包括对羟基苯甲酸、原儿茶酸、没食子酸、鞣花酸、对香豆酸、咖啡酸、阿魏酸、丹参素、迷迭香酸中的至少一种化合物，所述化合物的总含量为100-500mg/g；
所述酚酸类活性物质中酚羟基的总含量为7.0-14.0mmol/g；
所述制备方法的步骤如下：
（1）将木质素、催化剂、反应溶剂加入反应容器中，氧气置换排尽釜内空气后，充入0.5-1.5 MPa氧气，在120-180 oC下搅拌反应2-12 h，冷却至室温，过滤分离所述催化剂，收集反应液，再用所述反应溶剂洗涤滤饼，合并洗出液和反应液，减压蒸馏、真空干燥后得到中间产物A；
（2）将所述中间产物A、碘代环己烷、N,N-二甲基甲酰胺加入反应容器中，搅拌回流反应12-36 h，停止反应，冷却至室温，用正己烷洗涤，洗涤后反应液经减压蒸馏、真空干燥后得到所述酚酸类活性物质；
或步骤如下：
（1）将木质素、碘代环己烷、N,N-二甲基甲酰胺加入反应容器中，搅拌回流反应12-36h，停止反应，冷却至室温，用正己烷洗涤，洗涤后反应液经减压蒸馏、真空干燥后得到中间产物B；
（2）将所述中间产物B、催化剂、反应溶剂加入反应容器中，氧气置换排尽釜内空气后，充入0.5-1.5 MPa氧气，在120-180 oC下搅拌反应2-12 h，冷却至室温，过滤分离所述催化剂，收集反应液，再用所述反应溶剂洗涤滤饼，合并洗出液和反应液，减压蒸馏、真空干燥后得到所述酚酸类活性物质；
所述催化剂为MnOx/C、MoOx/C、VOx/C、CuOx/C中的至少一种。
2.如权利要求1所述的酚酸类活性物质的制备方法，其特征在于，所述木质素为木质素磺酸、碱木质素、有机溶剂解木质素、酶解木质素中的至少一种。
3.如权利要求1所述的酚酸类活性物质的制备方法，其特征在于，所述反应溶剂为甲醇、乙二醇、二甲基亚砜、γ-戊内酯中的至少一种。
4.如权利要求1所述的酚酸类活性物质的制备方法，其特征在于，木质素与催化剂的质量比为木质素：催化剂=1:0.1-1，木质素的质量与反应溶剂的体积之比为木质素：反应溶剂=1g:20-50ml。
5.如权利要求1所述的酚酸类活性物质的制备方法，其特征在于，木质素的质量与碘代环己烷的体积之比为木质素：碘代环己烷=1g:5-10ml，木质素的质量与N,N-二甲基甲酰胺的体积之比为木质素：N,N-二甲基甲酰胺=1g:10-40ml。
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