CN105816518B - 一种核桃青皮酚类天然抗氧化剂及其制备方法和应用 - Google Patents
一种核桃青皮酚类天然抗氧化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于添加剂加工制造技术领域,公开了一种核桃青皮酚类天然抗氧化剂及其制备方法和应用。本发明以新鲜核桃青皮为原料,经挑选和清洗后进行干燥,再经破碎、超声‑微波协同辅助提取、微孔滤膜过滤、大孔树脂纯化、真空冷冻干燥后制得核桃青皮酚类天然抗氧化剂。所得产品中酚类含量在85.25%以上,抗氧化活性保留率在95%以上。本发明方法制得的酚类抗氧化剂产品天然、无毒,具有比Vc和BHT更强的自由基清除能力及抗氧化活性,可广泛应用于食品、保健品、药品、化妆品及日用品领域。
Description
技术领域
本发明属于保健食品加工技术领域,特别涉及一种核桃青皮酚类天然抗氧化剂及其制备方法和应用。
背景技术
核桃青皮,又称青胡桃皮、青龙衣,其味辛、苦,性涩、平。核桃青皮曾在《本草纲目》上被记载有治疗“心腹诸痛”、“急气心痛”、“腰脚重痛”等功效,核桃青皮在我国民间,被用于治疗妇女痛经、风火牙痛、中晚期癌症痛、胃痛等症状。从核桃青皮中提取出的胡桃醌及其衍生物,在医学上有治疗食道癌、胃癌、肝癌和自发性乳腺癌。核桃青皮中含有多种对植物病原菌有抑菌作用的成分,在体外胡桃醌能中和白喉毒素及破伤风。
核桃中对人体有益的多酚类物质主要集中在青皮、种皮部分,且青皮中多酚类物质的绝对含量相对较高,因此核桃青皮可以作为提取多酚类物质的一种新资源,但目前其利用较少。核桃青皮内含有核桃酚类、胡桃甙、α-氢化胡桃-4-葡萄糖甙、金丝桃苷、扁蓄苷、鞣质、没食子酸、丹宁、四氢萘酮等酚类物质。核桃青皮多酚类物质是一类高效的天然抗氧化剂,能够通过清除自由基,对自由基诱发的生物大分子造成损伤,从而起到保护的作用;同时它还能防止辐射诱发的DNA断裂,维持蛋白质的构型构象和细胞膜的流动性,具有抗氧化、抗衰老、抗癌的作用,可广泛应用于医药及功能食品领域,具有广阔的市场前景。
目前常用于提取核桃青皮多酚物质的方法主要有溶剂提取法、微波辅助提取法、超声波辅助提取法以及螯合剂辅助提取法等方法。溶剂提取法一般提取时间为1~4h,所需时间长且提取效率不高;超声波辅助提取法利用超声波产生的空穴效应和热效应,加速溶质的扩散和溶解,提取的时间在0.5~1h左右;螯合剂辅助提取法则是将与金属螯合的多酚物质置换,从而提高多酚提取效果;微波辅助提取法是利用微波辐射能引起细胞内部温度迅速上升,使细胞内部压力超过细胞壁膨胀承受能力,细胞破裂后有效成分自由流出,同时微波所产生的电磁场加速溶质扩散速率,提取时间一般为1~10min,提取时间大大缩短且提取效率高,相对于传统的溶剂提取法有明显的优势。然而经溶剂提取得到的仅仅为多酚物质的粗产品,酚类含量低,杂质多,需进一步进行纯化,达到抗氧化剂的实际要求。现在分离纯化多酚类化合物的方法主要有金属离子沉淀分离法、柱层析分离法、色谱分离法及膜分离技术等。颜贻谦等人通过往橄榄酚类乙醇粗提液中加入适量氯化铝并调节pH值,使酚类络合沉淀,然后加入盐酸溶液溶解沉淀,再用乙酸乙酯多次萃取,萃取液浓缩去除乙酸乙酯,并经真空干燥制得橄榄酚类产品,产品酚类含量达76%;刘畅等通过Sephadex LH20葡聚糖凝胶色谱对多种原料:菜籽、油菜籽、核桃等提取得到的多酚物质进行分离纯化,结果显示其产品的纯度都得到了提高;李琼等利用AB-8大孔树脂纯化后,核桃青皮总多酚的纯度从原来的7.65%提高到36.36%,提高了4.8倍。但是,现有技术中这些制备方法在制备过程中存在的提取率低、纯度低、成本高、酚类物质抗氧化活性下降等缺陷,不能适应现代活性成分提取技术的发展趋势。
超声-微波协同辅助提取技术是从核桃青皮粉末中提取酚类物质的操作单元。该技术利用超声波振动的空穴作用以及微波的高能作用,克服常规超声波和微波提取各自的不足,避免长时间高温高压条件下萃取或合成反应引起的分解,不破坏提取的有效成分的结构以及活性,提高目标产物的得率与质量。
大孔树脂纯化是纯化高抗氧化活性酚类物质的操作单元。大孔树脂是一种具有多孔海绵状结构人工合成的聚合物吸附剂,依靠树脂骨架和被吸附的分子(吸附质)之间的范德华力,通过树脂巨大的比表面积进行物理吸附而达到从水溶液中分离提取水溶性较差的有机大分子的目的。采用大孔树脂提取纯化天然植物中的有效活性成分,具有操作简单、成本较低、树脂可反复使用等优点,适于工业化规模生产。
真空冷冻干燥则是将湿物料或溶液在较低温度(-10℃~-50℃)下冻结成固体,然后在真空(1.3~13帕)下使其中的水分不经液态直接升华成气态,最终使物料得以脱水。真空冷冻干燥技术可大大地提高干燥速率,缩短干燥时间;由于在低温条件下进行,不容易改变物质的性能,保持物质的营养成分、形状、功能性质;物料的含水率也可达到很低的程度,方便长期储存、长途运输。
利用超声-微波协同辅助提取,结合大孔树脂纯化和真空冷冻干燥所制备的核桃青皮酚类天然抗氧化物质,整个预处理、提取、纯化及干燥过程均在较低温度下进行,可以稳定酚类物质的活性和功效,同时具有得率高、纯度高、活性高、绿色环保、易于大规模产业化生产等优点,适应现代活性成分提取技术的发展趋势。
发明内容
为了克服现有技术的缺点与不足,本发明的首要目的在于提供一种核桃青皮酚类天然抗氧化剂的制备方法。该方法得率高、纯度高、活性高、绿色环保、易于大规模产业化生产。
本发明的再一目的在于提供上述制备方法制备得到的核桃青皮酚类天然抗氧化剂。
本发明的又一目的在于提供上述核桃青皮酚类天然抗氧化剂的应用。
本发明的目的通过下述技术方案实现:
一种核桃青皮酚类天然抗氧化剂的制备方法,包括以下操作步骤:以新鲜核桃青皮为原料,经挑选和清洗后进行干燥,再经破碎、超声-微波协同辅助提取、微孔滤膜过滤、大孔树脂纯化、真空冷冻干燥后制得核桃青皮酚类天然抗氧化剂。
上述核桃青皮酚类天然抗氧化剂的制备方法,具体包括以下操作步骤:
(1)选取新鲜核桃青皮,清水洗净后干燥至含水率降至12%以下,粉碎后过筛,得到核桃青皮粉末,密封后置于室温条件下干燥避光保存;
(2)称取核桃青皮粉末,以纯水为溶剂,料液比为1:20~60,在50℃下超声-微波协同辅助提取1小时,微波功率为400W,微波处理时间为5min,超声功率为700W,超声处理时间为5min;得到核桃青皮酚类物质提取液;
(3)将步骤(2)所得核桃青皮多酚粗提液进行微孔滤膜过滤处理,操作条件为温度30±5 ℃,滤膜孔径大小为0.45µm ,压力0.1MPa;
(4)将步骤(3)所得滤液进行大孔树脂纯化,操作条件为上样浓度1.5 mg/mL、上样pH值4.0、洗脱剂乙醇浓度40%、上样流速2 mL/min、洗脱流速1 mL/min、洗脱体积55 mL,收集纯化液;
(5)将步骤(4)所得纯化液进行冷冻干燥,操作条件为冷阱温度-57 ℃,真空度200 Pa,得到核桃青皮酚类天然抗氧化剂。
步骤(1)所述干燥是在50℃、风速为2.5 m/s的电热恒温鼓风干燥箱内进行干燥;所述过筛是过50目筛。
步骤(2)所述料液比为1:40。
一种根据上述制备方法制备得到的核桃青皮酚类天然抗氧化剂,所述核桃青皮酚类天然抗氧化剂纯度≥85.25%,抗氧化活性保留率≥95%。
上述的核桃青皮酚类天然抗氧化剂在制备清除自由基和抗氧化的食品、保健品、药品、化妆品及日用品领域中的应用。
与现有技术相比,本发明具有以下优点及有益效果:
本发明利用超声-微波协同辅助提取,结合大孔树脂纯化和真空冷冻干燥所制备的核桃青皮酚类天然抗氧化物质,整个预处理、提取、纯化及干燥过程均在较低温度下进行,可以稳定酚类物质的活性和功效,产品安全性高,具有比Vc和BHT更强的自由基清除能力及抗氧化活性,同时具有得率高、纯度高、活性高、绿色环保、易于大规模产业化生产等优点,适应现代活性成分提取技术的发展趋势。
附图说明
图1是不同料液比对多酚浓度的影响示意图;
图2是辅助提取方法对多酚含量的影响示意图;
图3是不同质量浓度的核桃青皮多酚对吸附效果的影响示意图;
图4是上样液pH值对吸附效果的影响示意图;
图5是乙醇体积分数对解吸效果的影响示意图;
图6是上样流速与多酚质量浓度关系示意图;
图7是洗脱流速对解吸效果的影响示意图;
图8是洗脱体积对多酚质量浓度的影响示意图;
图9是纯化前后核桃青皮多酚对ABTS自由基的清除能力示意图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
(1)选取新鲜核桃青皮,清水洗净后在50℃、风速为2.5 m/s的电热恒温鼓风干燥箱内进行干燥至含水率降至12%以下,粉碎后过50目筛,得到核桃青皮粉末,密封后置于室温条件下干燥避光保存;
(2)称取核桃青皮粉末,以纯水为溶剂,料液比为1:40,在50℃下超声-微波协同辅助提取1小时,微波功率为400W,微波处理时间为5min,超声功率为700W,超声处理时间为5min;得到核桃青皮酚类物质提取液;所得提取液中多酚含量为68.35 mg/g DW,其对ABTS自由基的清除率为77.31%。
将上述步骤(2)中的料液比设置为1:20、1:30、1:40、1:50、1:60,其他步骤和参数条件同上,进行对比试验,结果如图1所示,在料液比1:20~1:60范围内,随着料液比的增加,多酚提取量逐渐上升并趋于平缓。考虑到较大的料液比会消耗更多的能量和时间,而且会增加后续工艺的难度,因此,从实际生产操作条件和成本考虑,料液比选取1:40。
上述步骤(2)采用的是超声微波联合提取法,将其与单独超声辅助提取法、单独微波辅助提取法和水提取法对比,具体参数条件相同,结果如图2所示,采用四种提取方式所得多酚的含量及其对ABTS自由基清除率从大到小依次为:超声微波联合提取法>超声辅助提取法>微波辅助提取法>水提取法。
实施例2
(1)选取新鲜核桃青皮,清水洗净后在50℃、风速为2.5 m/s的电热恒温鼓风干燥箱内进行干燥至含水率降至12%以下,粉碎后过50目筛,得到核桃青皮粉末,密封后置于室温条件下干燥避光保存;
(2)称取核桃青皮粉末,以纯水为溶剂,料液比为1:40,在50℃下超声-微波协同辅助提取1小时,微波功率为400W,微波处理时间为5min,超声功率为700W,超声处理时间为5min;得到核桃青皮酚类物质提取液;
(3)将步骤(2)所得核桃青皮多酚粗提液进行微孔滤膜过滤处理,操作条件为温度30±5 ℃,滤膜孔径大小为0.45µm ,压力0.1MPa;
(4)将步骤(3)所得滤液使用D101树脂进行大孔树脂纯化,对纯化条件进行筛选,得出最佳操作条件为上样浓度1.5 mg/mL、上样pH值4.0、洗脱剂乙醇浓度40%、上样流速2mL/min、洗脱流速1 mL/min、洗脱体积55 mL,收集纯化液;
(5)将步骤(4)所得纯化液进行冷冻干燥,操作条件为冷阱温度-57 ℃,真空度200 Pa,得到核桃青皮酚类天然抗氧化剂。该产品中的多酚含量为815.25 mg/g DW,纯化其对ABTS自由基的清除率为95.22%,如图9所示,核桃青皮多酚对ABTS自由基的清除能力与呈显著的量效关系,核桃青皮多酚具有较好的ABTS自由基清除能力,在浓度为300 μg /mL时,纯化前核桃青皮多酚可以清除92%左右的ABTS自由基。经过大孔树脂的纯化,核桃青皮多酚的ABTS自由基清除能力得到了显著的提高,在200 μg /mL浓度下对ABTS自由基的清除率为95.22%。
上述步骤(4)中所述的对纯化条件进行筛选,分别是不同质量浓度的核桃青皮多酚对吸附效果的影响(如图3所示)、上样液pH值对吸附效果的影响(如图4所示)、乙醇体积分数对解吸效果的影响(如图5所示)、上样流速与多酚质量浓度关系(如图6所示)、洗脱流速对解吸效果的影响(如图7所示)、洗脱体积对多酚质量浓度的影响(如图8所示),从图3-8可以得出以下结论:
图3显示核桃青皮多酚的浓度对D101树脂吸附量的影响,总体呈现先升高后下降的趋势。当多酚浓度为1.5 mg/ml时,D101树脂的吸附量为36.0 mg/ml达到最大。因此,上样提取液多酚的最佳浓度为1.5 mg/ml;
图4显示样液pH值为4时,D101树脂对核桃青皮多酚的吸附量达到最大,pH值大于4,吸附量显著降低;
图5显示D101树脂的解吸率随着乙醇体积分数的增大,呈现先升高后下降的趋势,但当乙醇体积分数为40%时,解吸率为81.36%达到最大。因此,选用40%乙醇溶液对核桃多酚进行洗脱;
图6显示上样流速分别为1 mL/min、2 mL/min、4 mL/min时,泄漏点分别出现在4.5mL、3.6 mL、3.0 mL附近,流速为1 mL/min时,虽然泄漏点出现的最迟,但流速最慢,导致生产周期长。综合考虑,选择上样流速为2 mL/min;
图7显示随着洗脱流速的增大,解吸率呈现先上升后下降的趋势。当洗脱流速为1mL/min时,D101树脂的解吸率为最大85.0%。当洗脱流速超过1 mL/min时,解吸率逐渐下降;
图8显示动态条件下D101树脂上吸附的多酚物质极易洗脱,多酚物质的洗脱高峰也相对集中,在洗脱体积为10-15 mL内,洗脱液中的核桃青皮多酚含量较高。当洗脱体积达到45 mL后,洗脱液质量浓度接近0且基本不再变化,说明洗脱体积为45 mL,多酚基本上全部洗脱下来。但为了保证树脂吸附的多酚彻底洗脱下来,在后续的实验中将用55 mL作为最佳的洗脱体积。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种核桃青皮酚类天然抗氧化剂的制备方法,其特征在于包括以下操作步骤:以新鲜核桃青皮为原料,经挑选和清洗后进行干燥,再经破碎、超声-微波协同辅助提取、微孔滤膜过滤、大孔树脂纯化、真空冷冻干燥后制得核桃青皮酚类天然抗氧化剂;
所述制备方法具体包括以下操作步骤:
(1)选取新鲜核桃青皮,清水洗净后干燥至含水率降至12%以下,粉碎后过筛,得到核桃青皮粉末,密封后置于室温条件下干燥避光保存;
(2)称取核桃青皮粉末,以纯水为溶剂,料液比为1:20~60,在50℃下超声-微波协同辅助提取1小时,微波功率为400W,微波处理时间为5min,超声功率为700W,超声处理时间为5min;得到核桃青皮酚类物质提取液;
(3)将步骤(2)所得核桃青皮多酚粗提液进行微孔滤膜过滤处理,操作条件为温度30±5 ℃,滤膜孔径大小为0.45µm,压力0.1MPa;
(4)将步骤(3)所得滤液进行大孔树脂纯化,操作条件为上样浓度1.5 mg/mL、上样pH值4.0、洗脱剂乙醇浓度40%、上样流速2 mL/min、洗脱流速1 mL/min、洗脱体积55 mL,收集纯化液;
(5)将步骤(4)所得纯化液进行冷冻干燥,操作条件为冷阱温度﹣57 ℃,真空度200 Pa,得到核桃青皮酚类天然抗氧化剂;
所述核桃青皮酚类天然抗氧化剂纯度≥85.25%,抗氧化活性保留率≥95%。
2. 根据权利要求1所述的一种核桃青皮酚类天然抗氧化剂的制备方法,其特征在于:步骤(1)所述干燥是在50℃、风速为2.5 m/s的电热恒温鼓风干燥箱内进行干燥;所述过筛是过50目筛。
3.根据权利要求1所述的一种核桃青皮酚类天然抗氧化剂的制备方法,其特征在于:步骤(2)所述料液比为1:40。
4.一种根据权利要求1~3任一项所述制备方法制备得到的核桃青皮酚类天然抗氧化剂,其特征在于:所述核桃青皮酚类天然抗氧化剂纯度≥85.25%,抗氧化活性保留率≥95%。
5.根据权利要求4所述的核桃青皮酚类天然抗氧化剂在制备清除自由基和抗氧化的食品、保健品、药品、化妆品及日用品领域中的应用。
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CN107455740B (zh) * | 2017-07-24 | 2020-12-11 | 韩瑞峰 | 一种青皮核桃微胶囊粉及其制备方法 |
CN109430432A (zh) * | 2018-10-24 | 2019-03-08 | 云南农业大学 | 一种添加到核桃油中的天然抗氧化剂及其应用 |
CN110302240A (zh) * | 2018-10-24 | 2019-10-08 | 河北科技大学 | 提取核桃分心木中多酚的方法 |
CN109431933B (zh) * | 2018-11-28 | 2021-11-09 | 山东师范大学 | 一种防晒护色发乳及其制备方法和应用 |
CN113789221A (zh) * | 2021-09-15 | 2021-12-14 | 西华大学 | 一种抑制精炼猪油酸败的生物防腐剂制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102219810A (zh) * | 2011-05-06 | 2011-10-19 | 叶城三诺农业科技开发有限公司 | 从核桃青皮中制备高纯度单宁酸的工艺方法 |
CN103319321A (zh) * | 2013-06-09 | 2013-09-25 | 吕梁学院 | 一种胡桃青皮中胡桃醌及衍生物的提取方法 |
CN103340923A (zh) * | 2013-06-20 | 2013-10-09 | 吕梁学院 | 一种核桃鞣质的制备方法 |
CN104055838A (zh) * | 2014-07-15 | 2014-09-24 | 新疆农业大学 | 一种核桃青皮多酚的提取方法 |
CN105412221A (zh) * | 2015-12-22 | 2016-03-23 | 桂林双象生物科技有限公司 | 一种青钱柳山绿茶提取物复合茶的制备方法 |
-
2016
- 2016-04-29 CN CN201610285834.0A patent/CN105816518B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102219810A (zh) * | 2011-05-06 | 2011-10-19 | 叶城三诺农业科技开发有限公司 | 从核桃青皮中制备高纯度单宁酸的工艺方法 |
CN103319321A (zh) * | 2013-06-09 | 2013-09-25 | 吕梁学院 | 一种胡桃青皮中胡桃醌及衍生物的提取方法 |
CN103340923A (zh) * | 2013-06-20 | 2013-10-09 | 吕梁学院 | 一种核桃鞣质的制备方法 |
CN104055838A (zh) * | 2014-07-15 | 2014-09-24 | 新疆农业大学 | 一种核桃青皮多酚的提取方法 |
CN105412221A (zh) * | 2015-12-22 | 2016-03-23 | 桂林双象生物科技有限公司 | 一种青钱柳山绿茶提取物复合茶的制备方法 |
Non-Patent Citations (2)
Title |
---|
核桃青皮的强抗氧化活性成分及其抗氧化稳定性;田平平 等;《中国农业科学》;20160131;第49卷(第3期);第543-553页 * |
超声波-微波联合提取山核桃壳多酚及其稳定性;孙海涛 等;《北方园艺》;20151230(第24期);第135-139页 * |
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