CN106420843A - 一种紫菜类菌孢素氨基酸及其制备方法和应用 - Google Patents
一种紫菜类菌孢素氨基酸及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种紫菜类菌孢素氨基酸及其制备方法和应用。所述紫菜类菌孢素氨基酸,包括shionorine和Porphyra‑334,其制备方法为,紫菜烘干粉碎后过筛处理,加入乙醇液,辅助超声破碎提取;提取完成后过滤除去滤渣,将得到的提取液减压蒸馏浓缩处理得浓缩粗提液;再在浓缩粗提液中加入无水乙醇,醇沉除杂,离心去除沉淀后,减压蒸馏浓缩,即得紫菜类孢菌素氨基酸。紫菜类菌孢素氨基酸属于天然多酚类小分子物质,自身具有抗氧化防御功能,有效清除自由基,也能够有效清除因紫外线辐射而引起的皮肤机体内活性氧簇,抑制自由基的生成。紫菜类菌孢素氨基酸在制备防晒化妆品中有广泛应用。
Description
技术领域
本发明涉及一种紫菜类菌孢素氨基酸及其制备方法,以及涉及其在防晒化妆品中的具体应用,属于天然物质提取和营养学分析技术领域。
技术背景
近年来,由于臭氧层破环现象严重,到达地球表面的紫外线日渐增加,过量的紫外线照射会加速皮肤的光老化,给人类皮肤健康造成严重威胁。而能够到达地球表面的紫外线主要为中波段(280~320nm)和长波段(320~400nm)区域,因此,国内外抵抗紫外线而研发的防晒类化妆品多针对于对抗中波段(UVB区)和长波段(UVA区)紫外线。研究发现,中波段紫外线透射能力强,作用效果快,可在短时间内破坏皮肤细胞内的核酸及蛋白,导致皮肤出现红肿、晒斑、炎症等现象。因此,对中波段紫外线的防护已成为防晒产品开发的重点。然而,长波段(UVA区)虽然相对中波段作用效果缓慢,但该波段紫外线能够直接到达皮肤的真皮层,致使血管损伤及其周围炎症细胞的侵袭,导致皮肤色素沉积,经长期积累,导致皮肤不可逆性衰老。
目前,市面上开发生产的防晒化妆品多存在作用效果单一、预防波段阈值较窄的特点,而针对于全波段的紫外防护产品又存在化学防护剂添加量超标。所以,针对于不同波段紫外线对皮肤损伤的特点,研发针对于紫外全波段、天然植物中提取UV防护剂已成为研究的重点。
紫菜中提取得到类菌孢素氨基酸在紫外线吸收方面具有显著功效,但是在化妆品中如何具体应用未见报道。由于从海藻中提取的类菌孢素氨基酸各组分间分子结构上存在的差异,其特征性波长吸光范围也有所不同,目前未见对其主要成分的单独研究。
发明内容
本发明的目的是提供一种从紫菜中提取制备得到类菌孢素氨基酸作为天然紫外防护剂,并将其应用于制备防晒化妆品中,进行对长波段紫外线的防护研究,以弥补现有技术的不足。
本发明选取紫菜这一类菌孢素氨基酸(MAAs)含量较高的海藻为原料,提取并分离纯化其中的MAAs化合物及各组分,并结合不同组分就其自身的吸光特性,比较其防晒作用效果,研究开发应用于防晒化妆品的生产工艺中。
为达到上述目的,本发明采取的具体技术方案为:
一种紫菜类孢菌素氨基酸,包括shionorine和Porphyra-334,两者的总体含量为93wt%以上,其中shionorine 55-60wt%,Porphyra-334 33-38wt%。
一种紫菜类菌孢素氨基酸是shionorine。
上述紫菜类菌孢素氨基酸的制备方法包括:紫菜烘干粉碎后过筛处理,加入乙醇液,辅助超声破碎提取;提取完成后过滤除去滤渣,将得到的提取液减压蒸馏浓缩处理得浓缩粗提液;再在浓缩粗提液中加入无水乙醇,醇沉除杂,离心去除沉淀后,减压蒸馏浓缩,即得紫菜类孢菌素氨基酸。
进一步的,上述加入乙醇液的浓度优选为20%,上述醇沉除杂过程中乙醇液的终浓度为80%。
进一步的,在上述乙醇提取过程中保持提取温度为40-45℃。
进一步的,上述制备方法还包括紫菜类菌孢素氨基酸的进一步分离纯化:将制得的紫菜类菌孢素氨基酸进行高效液相色谱分离,根据色谱峰收集主要峰值附近的洗脱液,分离制得紫菜类菌孢素氨基酸化合物中的主要组分,经鉴定为shionorine和Porphyra-334。
进一步的,所述高效液相色谱中,液相色谱条件为:色谱仪:Agilent 1200 series高效液相色谱仪;色谱柱:Zorbax SB-C18柱(5 μm packing;250*4 mm I.D);检测器:紫外检测器 330 nm;流动相:A相:甲醇;B相:0.2%乙酸溶液,流速为1 mL/min;柱温:25℃。
进一步的,上述鉴定方法采用质谱方法。
进一步的,上述质谱方法具体为:质谱(ESI-TOF/MS)检测条件:正离子电离模式;喷雾气压: 45p si;干燥气:N2;流速:10.0 L/min;破 碎 电 压:100 V;全扫描(Scan)质荷比(m/z)范围为:200-800;在该条件下通过对比质谱碎片峰及特征性断裂方式,解析得到从紫菜中提取的类菌孢素氨基酸主要组分为shionorine和Porphyra-334。
上述紫菜类菌孢素氨基酸在抗紫外线方面的应用。
上述紫菜类菌孢素氨基酸在制备防晒化妆品中的应用。
上述shionorine在制备防晒化妆品中的应用。
针对MAAs化合物、shinorine和Porphyra-334组分,在200-400nm波段处进行紫外全波长扫描,经扫描测试发现,紫菜类菌孢素氨基酸及shinorine和Porphyra-334组分在该波段内具有较强的紫外吸收,并且shinorine的紫外吸收范围和强度更好。另外,根据类菌孢素氨基酸的结构特征,发现该物质本身存在多位酚羟基,这些多羟基结构可作为H供体,有利于化合物本身发生氧化反应,从而清除自由基;体外抗氧化实验证明,类菌孢素氨基酸能有效清除超氧阴离子自由基(·O2 -),羟基自由基(·OH)和DPPH。而利用对自由基的清除作用,可有效抑制紫外线引起的活性氧簇(ROS)的聚集,从而针对基于p38MAPK和核转录因子kappaB(NF-κB)信号传导通路在光老化发生机制中的发生作用。
本发明的优点和有益效果:
1.目前,市售防晒产品一般多采用化学合成型防晒剂作为主要功效成分,这类产品往往存在着严重的安全性隐患,为达到相应的防晒指数,往往添加的UV防晒剂量过高,易产生堵塞毛孔、皮肤过敏等炎症性问题。而从紫菜中提取的类菌孢素氨基酸作为天然的紫外防护剂,不但防护剂本身无任何过敏性反应,同时因其本身具有较强的紫外吸收能力,能有效抵御中波段、长波段紫外线带来的伤害。
2.化学合成型防晒产品由于防晒剂紫外吸收有效波长范围较窄,为达到同时防御UVA、UVB波段的紫外线,常常需添加多种复配化学防护剂,这很容易导致产品因化学添加剂量过高导致产品超出安全标准值。而类菌孢素氨基酸本身的紫外吸收范围广,能同时有效抵御UVA、UVB波段紫外线带来的损伤,非常适合作为天然全波段紫外防护剂使用。
3.紫菜类菌孢素氨基酸属于天然多酚类小分子物质,自身具有抗氧化防御功能,有效清除超氧阴离子自由基(·O2 -),羟基自由基(·OH)和DPPH;其也能够有效清除因紫外线辐射而引起的皮肤机体内活性氧簇,抑制自由基的生成。即从源头上起到天然抗皮肤老化的功效。尤其是shionorine,通过动物实验证明,其抗紫外线效果明显优于Porphyra-334,吸收波段更为广泛,其在防晒化妆品中有良好的应用价值。
附图说明
图1为shinorine化学式结构图。
图2为Porphyra-334化学式结构图。
图3为紫菜类菌孢素氨基酸及其组分的紫外吸收波长扫描图。
图4为实施例3中小鼠皮肤紫外损伤防护效果图。
图5为实施例3中小鼠皮肤紫外损伤的病理切片图。
图6为实施例3中小鼠皮肤紫外损伤的电镜扫描图。
具体实施方式
实施例1:
紫菜类菌孢素氨基酸的提取:取条斑紫菜烘箱烘干后粉碎,粉碎后的紫菜粉经20目过筛,在浓度为20%的乙醇液中45℃浸提2.5小时,其中料液比为 1∶40(g/ml),离心取上清液,过滤后收集浸提液,减压蒸馏,将粗提液加入乙醇溶液,至乙醇浓度为80%,至-20℃冷冻醇沉稳定24小时,除去蛋白及核酸杂质,得到MAAs化合物。
实施例2:
紫菜中类菌孢素氨基酸各组分的分离制备:将得到的紫菜MAAs化合物经超纯水复溶,并将溶液过22μm的有机滤膜处理,得到的滤液应用制备柱经高效液相色谱分离并制备MAAs化合物中的主要组分。液相色谱条件为:色谱仪:Agilent 1200 series高效液相色谱仪;色谱柱:Zorbax SB-C18柱(5 μm packing;250*4 mm I.D);检测器:紫外检测器 330 nm;流动相:A相:甲醇;B相:0.2%乙酸溶液,流速为1 mL/min;柱温:25℃。在该条件下分离并收集MAAs化合物主要组分的吸收峰,分别收集了保留时间为6.159 min和6.773 min处两个主要吸收峰,收集液蒸馏浓缩后冷冻干燥备用。
将分离得到的紫菜类菌孢素氨基酸组分进行鉴定:其中质谱(ESI-TOF/MS)检测条件:正离子电离模式;喷雾气压: 45p si;干燥气:N2;流速:10.0 L/min;破 碎 电 压:100V;全扫描(Scan)质荷比(m/z)范围为:200-800。在该条件下通过对比质谱碎片峰及特征性断裂方式,解析得到从紫菜中提取的类菌孢素氨基酸主要组分为shionorine和Porphyra-334,其化学结构式分别见图1、图2;并对紫菜类菌孢素氨基酸、shionorine和Porphyra-334进行紫外吸收波长扫描,结果见图3,可以看出shionorine吸收波段更广和吸收效果更强。
实施例3:
以下通过具体的动物实验说明本发明中紫菜类菌孢素氨基酸作为天然紫外防护剂功效成分对防护紫外线辐射的效果。
1.实验条件:三级动物实验室,温度:18-22摄氏度,湿度:空调调节。
2.实验对象:洁净雄性ICR小鼠60只,体重18~22克,由北京动物研究所提供。
3.药材及仪器:紫菜类菌孢素氨基酸由本实验室制备,Na2S,无水乙醇,紫外灯管UVA-340 40W,UVB-313 40W。
4.实验方法:将ICR小鼠随机分为正常组(NC)、模型组(MC)、阳性对照组(MP)、MAAs化合物涂抹组(T-MAAs)、Porphyra-334涂抹组(T- Porphyra-334)、shinorine涂抹组(T-shinorine),每组10只实验小鼠。各组小鼠每隔一天用6%的Na2S乙醇溶液(75%)进行脱毛处理背部(2 cm *3cm)。其中,NC组小鼠只脱毛不做其他处理,T-MAAs、T- Porphyra-334、T-shinorine 组小鼠分别外涂10 mg/mL的MAAs、Porphyra-334、shinorine水溶液120μL,MP组外1 mg/mL维生素C水溶液120μL,MC组涂抹等量的去离子水。各组小鼠给药20min后,置于紫外灯箱中照射,使用累加辐照法,从0.5 MED/天至4 MED/天,持续照射4周。每天拍照记录小鼠背部皮肤辐照损伤情况。实验结束后,颈椎脱臼处死小鼠,取背部皮肤用4%的甲醛溶液固定,切片并进行HE染色,显微镜下观察并拍照记录各组小鼠损伤情况。另取各组小鼠皮肤于2.5%的戊二醛固定液中固定,扫面电镜下观察小鼠皮肤胶原纤维的损伤情况。
实验结果:如图4所示,与空白对照组相比,模型组(MC)小鼠裸露背部由早期轻度红斑形成,逐渐发展为颜色加深、脱屑、增厚,严重者出现粗糙变硬,失去弹性和光泽;表明辐照造模成功。与模型组(MC)相比,外涂MAAs组大部分小鼠背侧表皮仅有稍许皮肤增厚,略有脱屑,颜色加深。外涂Porphyra-334样品组小鼠背部粗糙、褶皱显现得到明显缓解,外涂shinorine组小鼠皮肤表面红斑、水泡现象得到明显改善。
如图5所示,从病理切片中可以看出,正常组(NC)小鼠表皮细胞排列整齐,结构完整,细胞分层清晰,细胞成分和数量适中,厚度正常,表皮与真皮分界清楚;真皮层可见波浪状纤维组织,分布均匀,排列有序,疏密有致。与正常组(NC)相比,辐照模型组(MC)小鼠表皮层增厚并伴有角质层变厚,分层不清;真皮层纤维组织发生变性、破坏,纤维排列紊乱,分布不均,真皮层纤维组织出现断裂、破碎,甚至消失。说明造模成功。与模型组相比,外涂MAAs组、Porphyra-334组、shinorine组小鼠皮肤组织的受损程度得到明显缓解。其中外涂Porphyra-334组小鼠表皮层稍有增厚,真皮层纤维组织少见断裂、破碎,色素沉积现象明显减轻;外涂shinorine组小鼠皮肤组织胶原纤维排布致密、有序,对皮肤组织中胶原及细胞的损伤程度明显减轻。说明MAAs化合物及其组分外用能够有效地改善紫外线造成的皮肤损伤。
如图6所示,空白对照组小鼠其胶原纤维分布均匀,排列紧密,胶原直径大小相等,可见胶原周期性横纹;而经紫外辐射模型组胶原纤维排列紊乱,分布不均匀,胶原纤维束边缘分散 ;与辐射模型组相比,外涂MAAs组、Porphyra-334组、shinorine组小鼠胶原损伤现象得到明显改善。其中,外涂shinorine组小鼠胶原纤维边缘离散现象明显减轻,胶原纤维分布状况有所改善,胶原束排列较紧密, 作用效果较Porphyra-334组更为明显。
实施例4
类孢菌素氨基酸防晒霜的制备
鉴于紫菜类菌孢素氨基酸良好的抗紫外线和防护效果,将其紫菜类菌孢素氨基酸化合物及单一组分作为天然的全波段紫外防护剂的功效成分,添加至防晒霜中,制备天然防晒化妆品。采用霜剂化妆品的常规基质和工艺制备成防晒霜。其具体配方和制备工艺如下:
配方表:以质量百分比计算(W/%)
制备工艺:首先将以上A相物料按质量比例混合后,水浴加热至80摄氏度,使油相物料充分溶解,再按配方表将B相物料按质量比例混合后,蒸汽加热至80摄氏度。在A相持续搅拌状态下缓慢投入B相,直至霜剂成型。继续80摄氏度保温10min后,至室温冷却,冷却至40~50摄氏度以下,根据实验要求,按不同编号对比加入的紫外防护剂,投入C相物料并充分搅拌,投入D相物料调节防晒霜pH值至3.5~5,制成防晒霜。
防晒霜的性能测试
防晒系数的测定:按照配方表,配置5种防晒产品。其中1号产品为不添加UV-防护剂的空白霜剂,2号产品为添加紫菜类菌孢素氨基酸化合物作为UV-防护剂的防晒霜,3号产品为添加Porphyra-334标准品作为UV-防护剂的防晒霜。4号产品为添加shinorine标准品作为UV-防护剂的防晒霜,5号产品为添加甲氧基肉桂异辛酯作为UV-防护剂的防晒霜。精确称取每种防晒霜50 mg,溶于50 ml无水乙醇中,用紫外分光光度计测定每种防晒霜在280~360nm处的紫外吸光值。
防晒霜紫外防护性能的检测:
各项指标的检测结果表:
Claims (10)
1.一种紫菜类孢菌素氨基酸,其特征在于,包括shionorine和Porphyra-334,两者的总体含量为93wt%以上,其中shionorine 55-60wt%,Porphyra-334 33-38wt%。
2.权利要求1所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,该方法包括:紫菜烘干粉碎后过筛处理,加入乙醇液,辅助超声破碎提取;提取完成后过滤除去滤渣,将得到的提取液减压蒸馏浓缩处理得浓缩粗提液;再在浓缩粗提液中加入无水乙醇,醇沉除杂,离心去除沉淀后,减压蒸馏浓缩,即得紫菜类菌孢素氨基酸。
3.如权利要求2所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,上述加入乙醇液的浓度为20%,上述醇沉除杂过程中乙醇液的终浓度为80%。
4.如权利要求2所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,在上述乙醇提取过程中保持提取温度为40-45℃。
5.如权利要求2所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,该制备方法还包括紫菜类菌孢素氨基酸的进一步分离纯化:将制得的紫菜类菌孢素氨基酸进行高效液相色谱分离,根据色谱峰收集主要峰值处的洗脱液,分离制得紫菜类菌孢素氨基酸化合物中的主要组分,经鉴定为shionorine和Porphyra-334。
6.如权利要求5所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,所述高效液相色谱中,液相色谱条件为:色谱仪:Agilent 1200 series高效液相色谱仪;色谱柱:ZorbaxSB-C18柱;检测器:紫外检测器 330 nm;流动相:A相:甲醇;B相:0.2%乙酸溶液,流速为1mL/min;柱温:25℃。
7.如权利要求5所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,上述鉴定方法采用质谱方法。
8.如权利要求7所述的紫菜类菌孢素氨基酸的制备方法,其特征在于,上述质谱方法具体为:质谱检测条件:正离子电离模式;喷雾气压: 45p si;干燥气:N2;流速:10.0 L/min;破 碎 电 压:100 V;全扫描质荷比范围为:200-800;在该条件下通过对比质谱碎片峰及特征性断裂方式,解析得到从紫菜中提取的类菌孢素氨基酸主要组分为shionorine和Porphyra-334。
9.权利要求1所述的紫菜类菌孢素氨基酸在制备防晒化妆品中的应用。
10.权利要求1所述的shionorine在制备防晒化妆品中的应用。
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