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【典藏版】绿色化妆品的新挑战:化妆品配方中的天然食品成分

【典藏版】绿色化妆品的新挑战:化妆品配方中的天然食品成分 Jerry出海记
2023-01-24
229
导读:这篇评论描述了营养化妆品配方中使用的主要食物和生物活性分子,它们的护肤效果以及允许在食物中添加活性成分的分析技术。

摘要:如今,人们对生态学和可持续性等问题给予了极大的关注。许多消费者选择 "绿色化妆品”,即环保的面霜、化妆品和美容产品,希望它们对健康无害并减少环境污染。此外,在COVID-19大流行期间,连续发生的小型封锁事件增长了人们的意识,即身体美容与外部和内部的幸福感有关。因此,消费者对化妆品的偏好已经下降,而对护肤品的偏好却在增加。营养化妆品将食物补充的好处与美容治疗的优势结合起来,以提升我们的身体之美,满足市场新需求。食品化学和化妆品化学结合在一起,从而促进内部和外部的健康。营养化妆品优化了营养微量元素的摄入,以满足皮肤和皮肤附属物的需要,改善它们的状况,延缓衰老,从而帮助保护皮肤免受环境因素引起的老化作用。文献中的许多研究表明,这些补充剂的充分摄入、皮肤质量的改善(包括美学和组织学)以及伤口愈合的加速之间有显著的相关性。这篇评论描述了营养化妆品配方中使用的主要食物和生物活性分子,它们的护肤效果以及允许在食物中添加活性成分的分析技术。

关键词:植物化学分析;食品分析;香料;调味品;营养化妆品

1.简介

2020年,美容和护肤品行业必须重新塑造自己,以快速响应一个不可预测和需要关注的市场新要求。一直以来最重要的挑战是(现在也是)在 "自然 "和 "化妆品的化学成分 "之间找到一个平衡点。在这种多变的背景下,一些关于行业趋势和相关确定因素出现了积极的复苏迹象。化妆品行业未来的关键词是 "可持续性"(2020年为18.9%,而2018年为13.2%,基于受访样本的回答),"天然/有机"(10.9%),"护理"(7.8%),"道德"(7.5%),"电子商务"(7.1%),"社会美容"(7.0%),"个性化"(6.7%),以及 "安全"(6.3%)[1]。如果一种化妆品的配方含有从植物中提取的活性成分,如矿物质和植物,而不是在实验室中通过化学方法合成的类似活性成分,就可以被认为是 "绿色"。如果是根据有机作物规律通过尊重自然和植物的加工方法,以生态可持续的方式生产的,那就更好了。建议在距离原料产地零公里处或在其附近的实验室上生产这些化妆品,或者还可以使用可持续的运输手段,以减少对环境的影响。不是所有的绿色产品都是一样的。因此有必要区分天然成分、天然来源和有机成分的概念。天然成分是指未经加工或通过机械、人工、天然溶剂或重力手段加工、溶于水,加热去除水分以及通过任何手段从空气中提取的化学物质。天然来源是指来自植物、矿物或动物界的物质,经过化学加工、与其他成分结合(不包括石油和化石燃料衍生的成分)、植物原料中提取,以及使用皂化、发酵、缩合或酯化反应,以提高成分性能或使其可持续。在美国和欧洲,天然化妆品处于混乱状态,因为目前还没有官方法规对如何将 "有机 "和 "天然 "这两个词应用到化妆品中做出准确的定义。美国农业部对 "有机 "进行管理。国家有机计划(NOP),是美国农业部农业营销服务的一部分,认证有机产品。因此,只有含有或由农业成分组成的化妆品,并满足USDA/NOP有机生产的要求,才能根据NOP的规定获得认证[2]。有四个可适用于认证有机产品的类别,包括认证的有机化妆品:100%的有机产品(它们是用100%的有机认证成分生产的);有机产品(它们最多可以含有5%的非有机产品,不包括水和盐);"生产"(它们是用至少70%的有机认证成分生产的,不包括水和盐);以及特定有机成分(它们含有有机和非有机物质的组合)[3]。在欧洲,这个市场由ISO(国际标准化组织)发布的ISO 16128(2016年11月)[4]监管,这是一套新的指导方针,适用于欧洲市场上任何声称是天然/有机的产品,欧盟法规EC 1223/2009[5]和EU 655/2013[6]要求标签上的每项声明必须有充分和可核实的证据支持。近年来,绿色化妆品领域出现了新的趋势:营养化妆品,一种用于头发、皮肤和指甲的食品补充剂,可以获得由内至外的美丽。营养化妆品,或所谓的 "美容补充剂",是三个研究领域共同的科学研究的结果:食品、药品和个人护理。营养化妆品可以是软或硬的凝胶、胶囊、药片、糖浆、软糖或小袋,含有浓缩的透明质酸、矿物质、维生素或植物提取物,具有改善个人护理的功能[7]。在欧盟和美国层面,没有针对营养化妆品的具体监管框架。然而,食品补充剂的规则适用于美容补充剂[7]。在这项工作中,修订了与化妆品有关的食物基质、可用于化妆品配方的生物活性分子、生产生物活性化妆品成分的生态友好技术,以及有助于提纯和计量植物和动物基质中活性成分的分析技术。我们的目标是阐明营养化妆品市场的情况,以帮助消费者做出明智的选择,并等待绿色化妆品的具体规定。

2.植物细胞培养技术

消费者对天然产品兴趣的增长决定了从芳香植物、草药和药用植物中提取的物质被用作药妆和新化妆品配方的活性成分。它们含有生物活性分子(例如,酚酸、多酚、三萜、茋、黄酮、甾体、甾体皂苷、类胡萝卜素、甾醇、脂肪酸、糖类、多糖、肽等)[8],其质量和水平取决于气候条件和农业实践[9,10]。生物活性提取物也可以通过藻类、蘑菇、植物来源的副产品[11-14]和植物细胞培养技术[15,16]获得。后者是一种天然和合适的技术,用于生产护发、化妆、护肤和补充成分。移植体是用来启动细胞培养的植物组织。移植体表面的细胞体积增长、分裂、脱分化,并形成一个被称为茧的团块。在体外,使用正确的生长培养基可以无止尽的培养。在液体培养基中,细胞构成一个快速生长的单个细胞或小群细胞的悬浮培养物[17]。植物细胞培养在受控条件下生产高价值成分(初级和次级代谢物)。它们的优点是通过胚胎发育生长为整株植物,并且使用生物反应器可以独立于管理方法和土壤及气候条件进行繁殖,还可以在短期内产生高水平且无污染的植物化学物质[18-19]。 从植物细胞培养物中提取的化妆品符合市场的安全要求,因为它们不含病原体、污染物和农用化学品的残留物,这些物质经常污染植物提取物,而且很少含有用于抵御病原体和害虫攻击的植物合成的有毒化合物和潜在过敏原[20]。

3.天然抗衰老

天然抗衰老成分包括用于屏障修复、保湿、抗炎、皮肤美白和防晒剂成分。

3.1 保湿剂

皮肤保湿剂可以是润肤剂、闭塞剂和保湿剂。润肤剂在皮肤上覆盖一层保护膜,使其水润和舒缓,有助于减少皮肤剥落和粗糙感。用作润肤剂的食物包括黄油和油脂,如乳木果油、可可油、库布库油、芒果油、康波油和穆鲁穆鲁油;以及杏仁油、鳄梨油、摩洛哥坚果油、琉璃苣油、橄榄油、巴巴苏油、西兰花油、菜籽油、奇亚籽油、蓖麻油、椰子油、报春花油、棕榈油、百香果油、石榴油、树莓油、红花油和太阳花油。闭塞剂具有形成表皮屏障,阻止经表皮失水,调节角质细胞增殖的作用[21]。用作闭塞性的食物有油和蜡,如橄榄油、荷荷巴油和椰子油;以及小烛树蜡和蜜蜡[22]。椰子油和蓖麻油同时具有润肤剂和闭塞剂的功能。保湿剂是亲水保湿剂,可将水分从真皮吸收到角质层,并从环境中结合水蒸气[23]。蜂蜜、透明质酸、山梨醇、甘油是保湿剂的例子[24]。

3.2. 屏障修复剂

皮肤屏障可以阻止经表皮的水分流失,并抵御病原体[25]。屏障修复剂包括必需脂肪酸、酚类化合物、生育酚、磷脂、胆固醇和神经酰胺。必需脂肪酸的比例是修复屏障的一个关键点。较高的亚油酸与油酸的比例具有更好的皮肤屏障潜力[26]。它增强了皮肤屏障的渗透性[26,27],是角质层脂质基质的一个重要组成部分[28]。油酸破坏了皮肤屏障,成为植物油中其他生物活性分子的渗透性增强剂[29]。抗氧化合物(生育酚和酚类)可调节皮肤屏障的平衡、伤口愈合和炎症[30,31]。磷脂作为化学渗透性增强剂[32],通过控制共价结合的羟基神经酰胺和抑制胸腺基质淋巴生成素和趋化因子来显示抗炎作用[33]。胆固醇和神经酰胺是角质层中其他重要的脂质类别[34]。质膜中的胆固醇可能是观察到的跨细胞膜的氧梯度大小的一个基本因素[35]。在角质层中发现了12种甘油酰胺亚类[36]。神经酰胺会影响皮肤的紧致和丰满。局部使用神经酰胺霜可减少IL31,并破坏皮肤屏障的物理性质和功能[37]。一些天然油含有脂肪酸,在维持皮肤屏障方面发挥关键作用。亚麻籽油、核桃油和奇亚油含有omega-3s,葡萄籽油、红花油、葵花籽油、黑加仑籽油、月见草油和琉璃苣油含有omega-6s [34]。

3.3. 皮肤增白剂

皮肤增白剂降低了黑色素(皮肤色素)的浓度。当黑色素减少时,肤色就会变浅。皮肤增白剂的作用是抑制黑色素的生成。皮肤美白剂作为酪氨酸酶(黑素生成的关键酶)和/或黑素体转移(在皮肤表皮的基底层中黑素细胞中的色素颗粒)的抑制剂[38,39]或增加表皮更新以及抗炎和抗氧化活性的作用[40]。种族差异、慢性炎症、激素变化和紫外线照射是可以确定色素沉着过少或过多的条件的因素[41]。通常使用的活性成分包括柑橘提取物、曲酸、甘草提取物、白桑椹提取物、熊莓提取物、印度醋栗、维生素C、维生素B3、对苯二酚、维甲酸、白藜芦醇和α-和β-羟基酸[42]。

3.4消炎成分

外源性刺激有时可以影响伤口、皮肤老化、炎症性皮肤病或皮肤致癌。皮肤屏障的损伤决定了提供组织修复和控制感染的炎症反应。最初,角质形成细胞和先天免疫细胞(例如白细胞、树突状细胞和肥大细胞)被激活[43],并相继产生细胞因子(如IL-1α、IL-6和TNF-α),吸引免疫细胞到受伤部位。最后产生ROS、弹性蛋白酶和蛋白酶[43]。因此,炎症参与了痤疮的发病机制,并决定了痤疮患者的疼痛、肿胀和发红皮肤。甘草根、姜黄、燕麦、洋甘菊和坚果是一些具有抗炎活性的食用植物[44,45]。

3.5 防晒霜成分

基于波长紫外线辐射分为三大类:UV-A(320–400 nm)、UV-B(280–320 nm)和UV-C(100–280 nm)。长期暴露在紫外线辐射下会引起水肿、红斑、色素沉着、光老化、免疫抑制和皮肤癌[46,47]。持续暴露于紫外线辐射可导致色素沉着、损伤、晒伤、黑斑、胶原纤维降解、皱纹光老化和癌症[48,49]。UV-A光子对成纤维细胞和角质形成细胞造成损伤[50]。在皮肤中,UV-A作用于细胞发色团,并产生活性氧物种(例如,超氧化物、过氧化氢和羟基自由基)[51]。氧化应激会导致DNA损伤[52]。UV-B被称为燃烧的光线,被认为是太阳辐射中最活跃的成分。它可以对DNA和蛋白质产生直接和间接不良影响[53],诱导免疫抑制和皮肤癌[54]。最危险的紫外线波长是UV-C。幸运的是,这些辐射在到达我们的皮肤之前就被大气吸收了[55]。它们是强大的诱变剂,可引发癌症和免疫介导的疾病[56]。芦荟,绿茶,椰子油、葡萄籽和生姜含有防止光老化和皮肤癌的成分[24]。


4.皮肤抗氧化系统

活性氧(ROS)是最外层电子层含有未配对的电子和激发氧分子的原子或分子。活性氧具有高度的反应性,并且寿命很短,因为是在产生它们的介质中发生反应。氧分子、过氧化氢和单线态氧不是自由基,而是在开始氧化反应过程中产生自由基。这些物种统称为ROS。在人类代谢过程中产生ROS和活性氮物种(RNS)[57]。自由基与其他自由基反应、间接铁硫蛋白、过渡金属(如铁和铜)诱导羟基形成。过氧化氢反应性不强,但可以通过膜与过渡金属反应生成羟基自由基(芬顿反应)[58]。羟基自由基对身体产生一些有害影响,而极短的半衰期使得其在体内捕获具有挑战性。羟基自由基可以攻击其他分子以捕获氢离子,并通过添加或转移其电子与化合物发生反应[59]。脂质、蛋白质和DNA是最容易受到氧化损害的分子。氨基酸的氧化影响了蛋白质的分解、聚集和消化(人体对这些变化没有修复机制)。当ROS攻击酶时,酶就会失去功能性。当ROS攻击多不饱和脂肪酸(脂质过氧化)时,影响了膜流动性、结构、选择性和经表皮水分流失,导致皮肤干燥。此外,脂质过氧化过程增强了环氧合酶、磷脂酶的表达,并增强了前列腺素引起上皮炎症[60,61]。当ROS氧化低密度脂蛋白(LDL)时,ox-LDL释放肿瘤坏死因子-α、白介素-6和一氧化氮,导致动脉粥样硬化[62]。当活性氧攻击DNA时引起突变、致癌和衰老。人体很少有修复DNA的复杂机制[63-65]。一些羟基自由基,超氧化物、过氧化氢和氧单线态在皮肤中产生[58],因此可以将它们用作评估炎症严重程度的指标。当皮肤暴露于自由基时,通过抑制酶的活性来减少ROS的产生,这会间接产生氧代谢物,增加DNA修复酶,提高皮肤的物理保护(通过增强膜的稳定性),并干扰ROS的生物靶标[66]。皮肤细胞受到抗氧化剂的保护,如维生素E、C和A、类胡萝卜素、泛醌、尿酸、激素(如雌二醇和雌激素)、硫辛酸和酶(例如过氧化氢酶、超氧化物歧化酶和谷胱甘肽)[67]。抗氧化剂分子可以阻止自由基(ROS)的氧化,减少形成或淬灭已形成的ROS[67]。维生素C、α-生育酚(维生素E和衍生物)、谷胱甘肽、泛醌是一级抗氧化剂分子(或清除自由基的抗氧化剂)的例子。一级抗氧化剂分子通过链式终止反应将质子转移到自由基物种来减少ROS的氧化反应[68]。硫辛酸和N-乙酰半胱氨酸是次级抗氧化剂的典型例子。它们通过充当几种酶系统的辅助因子来辅助初级抗氧化剂。此外,金属螯合剂被认为是次级抗氧化剂,因为它们中和过渡金属防止在皮肤中产生自由基。通常,次级抗氧化剂与一级抗氧化剂结合使用,以保护一级抗氧化剂不被降解[69]。谷胱甘肽激素(GSH)还原酶、GSH过氧化物酶、谷胱甘S-转移酶(GSTs)组成抗氧化酶系统,在金属辅助因子(如Cu、Zn、Mn和Se)的帮助下直接中和ROS[70]。皮肤中发现的抗氧化剂浓度表明抗氧化剂在人类表皮中呈现梯度浓度(在基底层中的浓度较高,往上浓度递减)。抗氧化剂分子的浓度和酶降低了内在因素(年龄)和外在因素(大气成分)对皮肤的影响。阳光(特别是紫外线UVA和UVB)导致皮肤产生ROS。UVB辐射通过激活NADPH氧化酶和呼吸链反应,提高一氧化氮合酶的表达,增强高活性阴离子过氧化氢、黑色素细胞以及金属蛋白酶(能够降解胶原蛋白的酶)的活性,来提高单线态氧的含量 [71,72]。UVA辐射通过内部发色基团的光敏化(如卟啉和核黄素)和糖化产物[73],以及激活NADPH氧化酶[74]产生单线态氧。UVB辐射会诱发红斑(提高前列腺素E2的合成)[75],造成皮肤粗糙(氧化脂质)[76],产生角质层中羰基化蛋白质(SCCP),并刺激皮脂分泌[77]。因此有必要通过外用药或饮食补充抗氧化剂来保护皮肤[78,79]。

5.测定天然提取物抗氧化活性的方法

基于化学和细胞的检测方法可以评估天然提取物的抗氧化潜力。基于化学的方法有测量单电子转移(SET测定)或氢转移(HAT测定)(例如,ORAC,TRAP)。SET方法包括清除自由基(如DPPH)或减少金属离子(如FRAP、CUPRAC)[80-82]。有必要使用两种方法(SET和HAT)来正确评估总抗氧化活性[83-85],因为在天然提取物中,可能有不止一类分子具有抗氧化活性。

5.1.用于测定抗氧化能力的方法

5.1.1. 光谱方法

5.1.1.1 Trolox等效抗氧化能力(TEAC)测试

TEAC是一种清除自由基的方法。它评估了清除ABTS自由基的能力[86]。可以使用两种不同的氧化剂来获得目标:高锰酸钾-H2O2或过硫酸钾。这两种药剂都能氧化ABTS,产生ABTS·+(有颜色),然后加入抗氧化剂会导致绿色的颜色消失,可用分光光度评估(λ为734nm)[78,85]。这种方法可以检测亲脂性和亲水性提取物的抗氧化潜力,并且不受离子强度的影响[85]。简而言之,K2S2O8(3mM)与溶解在蒸馏水(8mM)中的ABTS在室温下、黑暗中反应16小时。然后将ABTS·+溶液稀释在磷酸盐缓冲溶液(pH7.4)和NaCl溶液(在PBS中为150mM)。在730nm处读取1.5的吸光度。反应动力学是通过在2小时内每15分钟读数来获得。反应时间是确定的(一般为30分钟)。标准品(100 µm)和样品(100 µm)与ABTS·+(2900 µm)在固定的时间反应[85]。抗氧化能力可表示为Trolox当量[85]。

5.1.1.2 2,2-二苯基-1-苦酰肼(DPPH)试验

DPPH可检测化合物转移一个电子的能力[79]。抗氧化剂将DPPH自由基还原为DPPH-H[79]。在515 nm处吸光度值(DPPH吸光度)下降表示抗氧化潜力。这个测试高估了含有许多酚基的抗氧化剂如黄酮醇[86]。简言之,样品(20µL)加入到3 mL DPPH溶液中(6×10-5mol/L),使用分光光度计进行分析。每5分钟读取一次517 nm处的吸光度,直到达到稳定状态。这个使用6-羟基-2,5,7,8-四甲基铬-2-羧酸绘制校准曲线(Trolox)。结果表示为mmol Trolox当量(TE)kg−1FW[87]。

5.1.1.3 铁还原抗氧化能力(FRAP)测试

FRAP测定抗氧化剂还原三联吡啶三嗪铁(Fe3+-TPTZ)为亚铁(Fe2+-TPTZ)的能力。抗氧化剂的能力与λ为593nm处的吸光度呈正相关。[87]. FRAP不能检测具有自由基淬灭能力的蛋白质和硫醇。该试验在pH值为3.6时进行[79]。简而言之,将盐酸(40 mmol/L)、氯化铁(12 mmol/L)和醋酸钠缓冲液(300 mmol/L,pH 3.6)以1:1:10的比例加入TPTZ(10 mmol/L)溶液中。将样品和标准抗氧化剂溶液(均为1 mmol/L)加入到FRAP溶液中(3 mL)。它们必须在37◦C下反应90分钟,然后在λ为593 nm处进行分光光度测量。

5.1.1.4 铜还原抗氧化能力(CUPRAC)测试

CUPRAC法测量抗氧化剂在30分钟后450 nm处还原Cu(II)-neocuproine(Nc)的能力[88]。该试验在pH7下进行,检测亲脂性和亲水性抗氧化剂的抗氧化潜力[88],并确定硫醇型抗氧化剂的还原能力[89]。简而言之,样品(0.1 mL)与蒸馏水(1 mL)、氯化铜(0.4262 g溶于H2O并加水稀释至250 mL)、新古霉素(7.5 × 10-3M)和乙酸铵缓冲溶液(19.27 g溶于水并稀释至250 mL;pH 7)按1:1:1混合,得到总反应混合物为4.1 mL。它们必须在室温下反应30分钟,然后在λ为450nm处进行分光光度测量。结果以µM  Trolox当量表示 [89]。

5.1.2.体外细胞方法

5.1.2.1 二氯氟环辛(DCFH)试验

DCFH试验测定抗氧化剂在人类肝癌细胞(HepG2细胞)中阻止2,2'-偶氮(2-脒基丙烷)(ABAP)产生的过氧自由基将二氯荧光素(dichlorofluorecin)氧化为二氯荧光黄(dichlorofluorescein)(DCF)的能力。抗氧化能力与细胞荧光增长呈负相关(λexc = 485 nm, λem = 538 nm)[90]。简而言之,在37◦C,5%二氧化碳:95%的空气中,将骨髓单核细胞(HL-60,1×106个细胞/毫升)悬浮在含有10%胎牛血清(FBS)和抗生素的RPMI 1640培养基中。将细胞悬液(125 µL)加入平板,用测试材料处理30分钟,并用12-肉豆蔻酸盐(PMA,100 ng/ml)刺激30分钟。然后将细胞加入分子探针(5 µg/mL DCFH-DA)并孵育15分钟。DCFH-DA是一种非荧光探针,可扩散到细胞中。使用荧光测量系统测量DCF的水平。

5.1.2.2 脂质过氧化物水平的测定

脂质过氧化的检测可以评价皮肤角质形成细胞(HaCaT)氧化情况。肾上腺素用于诱导脂质过氧化。抗氧化能力与细胞荧光生长呈负相关(λexc = 510 nm,λem = 580 nm)。简单地说,将HaCaT(1.8×104)接种在96孔板中,然后与样品或受体阻滞剂(ICI-118,551)孵育24小时。随后在磷酸盐缓冲盐水(PBS)中洗涤细胞,在37◦C下与脂质过氧化传感器(dyeC11-Bodipy)培养30 min。最后,用肾上腺素(50µM)进行脂质过氧化。过氧化物脂质的水平由荧光测量系统测得。

5.1.2.3 细胞中羰基化蛋白水平的测定

通过使用针对2,4-二硝基酚(DNP)的特异性抗体进行酶联免疫吸附试验(ELISA),可以评估来自成年人类皮肤的自发转化的非整倍体永生角质细胞系(HaCaT细胞)的蛋白羰基化水平。肾上腺素被用来诱导蛋白质羰基化。抗氧化剂的能力与细胞荧光的增长呈负相关[16]。简而言之,将HaCaT(1.5 × 104)细胞放在96孔板中,与样品或ICI-118,551和肾上腺素(50μM)培养24小时。随后,用PBS清洗细胞并在4%多聚甲醛(PFA)中固定。然后,用PBS和0.05%的聚乙二醇山梨醇单月桂酸酯(Tween 20)清洗细胞,并在室温下用2 N HCl中的2,4-二硝基苯肼(DNPH;5 mM)培养1小时。通过ELISA方法测量针对DNP的特异性抗体(sc69697)来评估羰基化产物。将皮肤切口与样品和肾上腺素(56 nM)孵化24小时。随后,用PFA固定6小时,在PBS中清洗,在蔗糖(15%和30%)中孵化,在最佳切割温度(OCT)介质中固定,冷冻,并在-80℃储存。冰冻切片(10 µm)在室温下用2N盐酸中的DNPH(5 mM)孵育1小时,用PBS/EtOH(1:1)和PBS/Tween 20清洗。将载玻片在BSA中孵育30分钟,用PBS/Tween 20洗涤,用抗DNP抗体(1:50稀释)孵育,然后与共轭抗体Alexa Fluor 488混合。使用荧光显微镜测量信号。

6.抗氧化剂生物可及性体外测试方法

生物可及性显示了在每一步消化后可能被吸收的抗氧化剂的浓度。这是了解生物利用度[91]的必要条件。一些体外试验显示,抗氧化剂水平可用于调节生理功能。

6.1胃消化过程的模拟

在pH值为2(胃的pH值)的样品中模拟胃消化模式,其包含了人工唾液和胃蛋白酶。简而言之,样品在37◦C下与人工唾液(6 mL)、胃蛋白酶(14,800 U;0.5 g)、盐酸(0.1 N)培养2小时,并在55 rpm的振动器中反应[91]。样品的酸化可以防止胃蛋白酶在pH≥5时发生变性。

6.2肠道消化模拟

通过在pH值为5.5-6时添加的胆汁盐和胰蛋白酶,并重新调整pH至6.5获得肠道消化液[91]。简而言之,用NaHCO3(1 N)将样品的pH值调整到6.5,并先后与胰蛋白酶(8 mg/mL;1:1;v/v)、胆汁盐(50 mg/mL)和20 mL水混合。该溶液在37◦C培养2小时,并在55rpm的摇床中混合。最后,将溶液(30 mL)离心(4000×g rpm,4◦C)1小时。收集上清液(生物可及部分)并使用分光光度法进行分析[91]。

7.体内法对皮肤氧化损伤的评价

Vertuani及其同事提出了一个在体内评估皮肤氧化损伤的方案[92]。在这个模型中,烟酸甲酯(M.N.)被用来增强前列腺素和环氧化酶的合成(一个炎症过程),并通过测量以下内容来评估抗氧化潜力:

·通过Tewameter TM 210(Courage-khazaka,德国科隆)测定经表皮失水以确定角质层的屏障功能。

·用反射仪Chromameter(CR-300 Minolta)测定刺激前后各部位的皮肤颜色。

·使用激光多普勒灌注成像仪(PIM1.0 Lisca Development AB,瑞典)进行皮肤微循环。

通过DermAnalyzer®进行皮肤颜色分析,这是一个新的软件程序,由Manfredini及其同事开发,使用CIE L*a*b*色彩空间参数(由法国国际照明委员会指定的色彩空间,因此其缩写为CIE)[92]。

简而言之,研究是在两组相同的健康志愿者身上进行的,一组用待测产品治疗,另一组用安慰剂。测量是在压力前、急性压力和恢复时间后进行。在一个封闭的房间里(温度=20±2◦C;相对湿度=40±5%),一天的同一时间,样品经过大约30分钟的驻留后进行测量。在测量前对探头进行校准。然后,将它们放在皮肤上30秒以获得测量结果。Tewameter探头测量水的蒸发率(g/h/m2)。色度计用CIE L*a*b*和CIE L*C*h色彩空间测量色彩,以数字形式精确传达色彩。激光多普勒灌注图像测量微循环,使用激光束扫描组织,用光电二极管检测反射光,处理后的信号产生一个图像,显示组织中的灌注情况。

8.具有抗氧化潜力、植物

学物质和维生素

植物次生代谢产生的分子(植物化学物质)可以保护植物免受大气因子、微生物和害虫的攻击。其中一些物质(如酚酸、多酚、半胱氨酸亚砜、类胡萝卜素)可以与自由基反应,在人类和动物中形成稳定的化学物种。植物化学物质具有广泛的生物效应(例如光保护、抗衰老、抗炎、抗菌、抗病毒和抗癌作用),有利于我们的健康。一些维生素(如E、C和A)具有抗氧化潜能和护肤能力。例如维生素C可以调节胶原蛋白的合成。维生素E能中和自由基和使皮肤软化。维生素A控制皮肤细胞更新,增加胶原蛋白的产生,尽量减少烧伤、疤痕和妊娠纹。

8.1.食品提取物中抗氧化剂定量的分析程序

在文献中已经提出了几种分析方法来确定天然提取物中的单一抗氧化化合物。然而,虽然有许多常规使用的测试方法,但缺乏一个标准化的验证程序。因此有必要验证分析方法,以实现正确的剂量和数据可追溯性,等待关于在化妆品中使用天然来源的活性成分的严格立法。定量抗氧化剂的分析程序包括两个基本步骤:从有机基质中提取和定量。

8.1.1.酚类

植物酚类有一个带有羟基的苯环和一些取代基(如酯苷和糖苷)。一些植物酚类物质含有一个以上的羟基组。酚的分类是基于酚环的数量和酚环上存在的取代基的数量和类型。简单酚类物质的例子是酚酸(例如没食子酸和阿魏酸)。多酚的例子包括二苯乙烯(如白藜芦醇)、查尔酮和氟黄酮。黄酮类化合物进一步分为黄酮醇、黄烷醇、黄酮、异黄酮和花青素。酚类药物具有促进皮肤愈合和保护皮肤的作用。茶黄素可预防单纯型疱疹(HSV-1),并防止紫外线诱导的光老化和光免疫抑制。花青素可减少太阳辐射引起的皮肤损伤,减了UVA刺激的ROS形成和脂质过氧化,并调节负责炎症反应的NF-kB-和MAPK依赖的通路。从天葵中分离的酚类化合物在人皮肤成纤维母细胞上具有抗弹性蛋白酶和抗mmp-1 的活性。(β)-儿茶素的醛类多缩合物具有抗弹性蛋白酶和抗胶原蛋白酶的活性[105]。开心果的多酚能减少紫外线引起的皮肤红斑。口服多酚可减少皮肤粗糙度,改善皮肤的水合作用和弹性。外用药和口服药的组合疗法可以增强效果。

8.1.1.1 总酚类物质的提取方法

目前提出了一些提取酚类物质的方法,其中包括固体提取 (SE)、超声波、微波辅助萃取(MAE)、分子印迹聚合物、固相萃取(SPE)、加压液体萃取(PLE)、酶辅助萃取(EAE)和超临界氟液萃取(SFE)。SPE方法是首选的方法,因为它们操作简单,而且提取时间较短。采用了几种类型的固定相(例如C8色谱柱、氨基相色谱柱、二元醇键合相色谱柱、十八烷基C18和十八烷基C18端盖)。

8.1.1.2 总酚剂量法:福林酚试验

福林-酚是一种基于酚类物质的羟基与福林-酚试剂反应的比色法。多酚水平与吸光度呈正相关(λ 765 nm)。

8.1.2.类胡萝卜素

主要的类胡萝卜素类化合物有叶黄素和胡萝卜素。胡萝卜素是严格的疏水性分子,而叶黄素在其结构中具有极性基团。有一些类胡萝卜素是严格的碳氢化合物(如番茄红素和β-胡萝卜素),在其结构中没有任何取代物,一些具有环氧基团(如。diadinoxanthin,violaxanthin),一些带有乙酰基(例如,fucoxanthin,dinoxanthin),最后一些带有乙炔(例如,diato-,allo-,diadino-,pyro-,croco-,hetero-和monadoxanthin)。皮肤中的类胡萝卜素在对紫外线辐射的光保护中具有重要作用,因为它们具有抗氧化和抗炎作用。虾青素可以增强超氧化物歧化酶、过氧化氢酶的活性[110],并抑制酪氨酸酶的活性[111]。口服可以改善皮肤状况,减少皮肤色素沉着和黑色素的合成[112]。β-胡萝卜素可防止自由基的形成。它能抑制皱纹形成和皮肤松弛,减少金属蛋白酶-9的激活,改善5α-氢过氧化物的合成,并保护人们免受晒伤疾病的影响[113]。β-胡萝卜素在口服补充时的皮肤光保护效果比外用时更好,即使其保护系数在两种应用形式中有所不同[104]。口服β-胡萝卜素的防晒系数(SPF)为4,而外用β-胡萝卜素的SPF值为10至40[114]。补充番茄红素可以减少皮肤粗糙度[115];补充叶黄素类可以增加皮肤的水合作用[116];补充叶黄素可以保护皮肤免受损伤和光老化[116]。玉米黄质和叶黄素的口服和外用治疗能改善皮肤层的水合作用和皮肤弹性[117],并能抵御皮肤的氧化损伤和蓝光损伤[118]。叶黄素减少细胞膜的脂质过氧化,清除自由基[114]。番茄红素能提亮皮肤,减少皮肤的粗糙度[119],具有防晒效果,可作为一种防晒剂。

8.1.2.1类胡萝卜素提取方法

类胡萝卜素的溶解度取决于它们的分子结构(叶黄素,胡萝卜素)。一般来说,四氢呋喃被认为是溶解类胡萝卜素的最佳溶剂,但它需要与抗氧化剂(如丁基氢基甲苯-BHT)一起使用,因为它会形成过氧化物。叶黄素(如黄体素)可溶于醇[121],胡萝卜素(如β-胡萝卜素)溶于疏水溶剂。一些胡萝卜素提取方法使用酶(用于分解含有胡萝卜素的植物组织)、有机溶剂(如己烷和乙酸乙酯,因为它们是亲脂化合物)和水溶性溶剂(如丙酮和四氢呋喃)在食物基质中完成渗透[122]。有时还需添加碳酸镁或碳酸钙来中和有机酸。提取使必须重复多次直到残渣和滤液变为无色。二氧化碳超临界流体萃取(SFE)是一种液-液萃取的替代方法。提取物无化学残留,仅需要少量的有机溶剂,萃取效率随温度和压力的增加而提高,因此具有低成本,无毒,生态兼容的特点[121]。另一种提取类胡萝卜素的方法是MSPD(基质固相分散)。在这种情况下,需使用包渗相固体支撑材料(如C18)提取样品[121]。

8.1.2.2 类胡萝卜素定量方法

最常用的测定类胡萝卜素的方法是紫外/可见分光光度法。紫外/可见光谱提供了类胡萝卜素‘发色团’的信息,该发色团在(λ400-500 nm)[121]范围内被吸收。例如,番茄红素在λ 502 nm和λ 455 nm处用分光光度法进行定量。

8.1.3.维生素

维生素A、C和E被用于皮肤老化和紫外线防护治疗[123]。它们的酯化形式在外用制剂中比游离形式更具有稳定性[124]。视黄醇棕榈酸酯对干燥和粗糙的皮肤上皮和异常的角质化有好处[125]。维生素C能增强皮肤的水合作用[126]。醋酸生育酚具有清除自由基,减少DNA损伤、角质细胞死亡[127]、皮肤粗糙,并改善角质层的水化的活性[128]。维生素C和E的外用组合可最大限度地发挥光保护作用 [129]

8.1.3.1 测量维生素A剂量的AOAC法(AOAC官方方法970.64)

AOAC测定维生素A的方法建议用丙酮-正己烷提取,然后过滤,用水进行第二次提取以去除丙酮,并对esane提取物进行色谱分析(使用活性二氧化镁硅藻土柱作为固定相,丙酮作为流动相),并结合色度计[130]的使用。

8.1.3.2 维生素C的剂量测定方法

先用3%偏磷酸-乙酸对食品基质中的维生素C进行提取,然后用Norit将其氧化为脱氢抗坏血酸,再与邻苯二胺反应得到荧光衍生物,用反相色谱法分离得到荧光衍生物(固定相:10umμBondapak C18;流动甲醇;水/55:45)并用荧光进行检测[131]。

8.1.3.3 维生素E的剂量测定方法

维生素E的剂量测定方法是:先提取a-生育酚,然后对脂质提取物进行皂化和TLC色谱法,并通过比色法进行鉴定。为测定a-生育酚醋酸酯的剂量,先提取样品,通过氧化色谱法提取天然a-生育酚,然后用皂化和比色法[132]鉴定a-生育酚乙酸酯。

8.1.4.S-烃基半胱氨酸硫酸盐亚砜(ACSOs)

ACSOs具有抗氧化的特性。它们能提高天冬氨酸转氨酶、丙氨酸转氨酶和乳酸脱氢酶活性,降低硫代巴比妥酸活性物质、谷胱甘肽水平以及谷胱甘肽s-转移酶和谷胱甘肽过氧化物酶活性[133]。ACSOs及其转化产物由于具有抗氧化活性和对硫氧还蛋白还原酶、醇脱氢酶、胰蛋白酶、RNA和DNA聚合酶的抑制能力[134],因此具有抗菌潜力。角蛋白分子中的N-乙酰-l-半胱氨酸可与二硫化物桥相互作用,引起指甲肿胀软化,从而促进药物渗透[135]。

8.1.4.1 S-烃基半胱氨酸硫酸盐亚砜(ACSOs)剂量法

ACSOs的剂量测定方法建议用甲醇:氯仿:水为12:5:3提取分离,并在-20℃下保存一夜,依次加入非对映体s-丁基-l-半胱氨酸亚砜作为内标,并在室温下离心(12,000*g 5min)分离相。接下来在30℃的旋转蒸发器上浓缩上相。最后提取液重新悬浮在0.03M HCL溶液,通过0.45um过滤器过滤,并用HPLC(高效液相色谱法)(固定相:C18 Hypersil ODS(液相色谱微预柱);流动相0.03M HCL;二极管阵列探测器)[136]进行分析。

8.1.5. 甲基黄嘌呤

甲基黄嘌呤(咖啡因、茶碱和可可碱)是很好的抗氧化剂[137],因为甲基黄嘌呤对羟基自由基的产生和羟基自由基氧化破坏DNA有淬灭作用[138]。咖啡因可以改善人类皮肤中紫外线介导的皮肤反应[139]。它对于因头发生长阶段过早终止而导致脱发的受试者有效[140],并能促进油类化妆品中的脂肪分解和脂肪氧化[141]。咖啡因控制脂肪分解过程,调节儿茶酚胺的分泌,从而激活β-2肾上腺素受体,激活脂肪酶的细胞内环状腺苷单磷酸(cAMP)的浓度[142],阻断α-肾上腺素受体[143,144],并抑制磷酸二酯酶。[145]。

8.1.5.1 总甲基黄嘌呤剂量方法

甲基黄嘌呤的分离方法有:固相萃取(SPE)、液-液萃取(LLE)、微波辅助萃取(MAE)、超声辅助萃取(UAE)、固相微萃取(SPME)和超临界流体萃取(SFE)[146-148].水是甲基黄嘌呤的适宜溶剂,但选择性较低。因此,第二次提取涉及二氯甲烷或氯仿来完成分离。在SPE中,超临界二氧化碳与水、甲醇、乙醇或异丙醇被用作溶剂[147]。甲基黄嘌呤最常用的分析方法是使用C18柱(固定相)与质谱检测器的反相高效液相色谱法(RP-HPLC)[149]。Paradka和lrudayaraj(2006)描述了一种基于傅里叶变换红外(FTIR)光谱的快速(5-10min)、无损且可靠,用于测定食品中甲基黄嘌呤的常规剂量的方法。本实验采用偏最小二乘(PLS)和主成分回归(PCR)2法测定两个光谱区域甲基黄嘌呤的剂量(1500-1800cm-1和2800-3000cm-1)[150]。

9.化妆品制剂中的食品

9.1.绿茶

绿茶(G.T,Camellia sinensis)(表1)提取物含有儿茶素衍生物(如表儿茶素,表儿茶素,表没食子儿茶素,和表没食子儿茶素-3-没食子酸酯),可以清除自由基。含6%G.T.的配方具有持久的保湿效果,改善微循环,减少皮肤粗糙[151]。局部应用G.T.可防止紫外线氧化损伤,减少基质金属蛋白酶、胶原酶和透明质酸酶的产生[152,153]并减少紫外线诱导的红斑[154]。经常口服和局部使用茶可以减少皮脂分泌,预防和治疗寻常痤疮[155]。抗痤疮活性可归因于对痤疮丙酸杆菌的抗菌特性,增加皮脂细胞SEB-1细胞系的凋亡,调节MLPK-SREBP-1(M位点蛋白激酶-固醇调节元件结合蛋白1)来减少脂肪生成,并通过减少NF-kB产生来减少炎症[155]。此外,表没食子儿茶素-3-没食子酸酯通过促进头皮毛囊真皮乳头细胞的增殖和抗凋亡作用促进头发生长,并延长头发的生长期阶段[156]。

9.2.咖啡树

咖啡(表1)含有抗氧化化合物,如原花青素、奎宁酸、咖啡酸和绿原酸[157]。咖啡酸可以减少ROS形成和酪氨酸酶合成[158,159],因此可作为美白剂。此外,使用6周的0.1%咖啡酸洗面奶和1%咖啡酸乳霜可减少光损伤患者的皱纹、细纹和色素沉着[160]。

9.3葡萄树

葡萄(表1)含有白藜芦醇,这是一种具有抗氧化特性的二苯乙烯,能够抑制皮肤癌、紫外线介导的皮肤老化和其他炎症性疾病[161]。葡萄籽多酚化合物(原花青素和原花青素)具有美白特性[162],因为它们可以抑制ROS和清除自由基[162]。原花青素的美白机制与其降低黑色素生物合成的抗氧化特性有关。口服富含原花青素的葡萄籽提取物可改善黄褐斑妇女的色素沉着状况。

9.4石榴

石榴(表1)含有鞣花酸、安石榴苷和石榴酸。鞣花酸和安石榴苷通过抑制酪氨酸酶和促进抗真菌、抗炎作用来增强皮肤健康[163-165]。此外,石榴酸抑制紫外线诱导的辐射[166]作用。鞣花酸是一种酚类成分,由于具有螯合酪氨酸酶中的铜离子[167],并减少UVB诱导的色素沉着[168],因此可以作为化妆品配方中的美白成分。石榴还能改善真皮[169]的厚度、水化作用、弹性值,皮肤皱纹[170],减少糖基化,清除自由基,以及抑制美拉德反应中果糖胺的形成[171]。此外,皮肤糖基化会影响胶原蛋白,使皮肤失去弹性。因此,石榴提取物可以消除由紫外线损伤和皮肤老化而造成的皱纹。

9.5. 大豆

大豆(表1)含有异黄酮,可减少紫外线诱导的氧化DNA损伤[172]和皮肤光老化[173-175]。异黄酮可刺激成纤维细胞增殖,减少胶原蛋白分解,并阻碍蛋白酪氨酸激酶活性[176-179]。含有一种以上异黄酮和异黄酮形式的苷元(非偶联形式)的提取物具有更好的效果[180-182]。一些抗衰老防晒霜和面部保湿霜通常含有这些异黄酮。

9.6. 芦荟

芦荟(表1)含有芦荟素[183],通过抑制黑色素生成,并降低酪氨酸酶和DOPA聚合酶的作用产生美白效果[156,183-185]。芦荟的粘多糖和氨基酸成分(例如精氨酸、组氨酸、苏氨酸、甘氨酸、丝氨酸和丙氨酸)可改善角质层的保水性[186]。芦荟凝胶具有抗氧化特性。它增强了皮肤细胞中的金属硫蛋白、超氧化物歧化酶和谷胱甘肽过氧化物酶活性。芦荟使皮肤有弹性,减少皱纹,改善成纤维细胞产生的弹性蛋白和胶原蛋白[187]。芦荟凝胶具有伤口愈合作用。它保持伤口湿润,减少炎症过程,增强上皮细胞迁移和胶原蛋白的快速成熟[188]。最后,在大鼠模型表明芦荟凝胶通过毛囊皮脂腺靶向促进头发生长[189]。

9.7. 柑橘柠檬

柠檬中的橙皮苷(黄烷酮)和抗坏血酸(表1)可降低酪氨酸酶活性并阻止黑色素生物合成[157,183]。此外,柠檬醛、D-柠檬烯和β-蒎烯具有脱色作用。它们会降低酪氨酸酶活性和L-二羟基苯丙氨酸(L-DOPA)氧化[190]。橙皮苷和抗坏血酸可用于抗衰老化妆品,因为它们是抗氧化的化合物[40,191,192]。透明质体和甘油体载体用于改善柠檬提取物在皮肤结构中的抗氧化能力[193]。维生素C用于抗衰老产品中,以减少细纹,改善胶原蛋白的产生[191]。柠檬衍生产品对受真菌和晒伤影响的易长粉刺的皮肤产生积极影响[194]。柠檬汁与橄榄油混合可用于治疗头皮和头发疾病[195]。

9.8. 仙人掌果

仙人掌果(表1)对皮肤、头发和指甲具有修复和抗衰老特性。高水平的亚油酸刺激细胞更新,有利于快速深入渗透真皮层,油酸和硬脂酸有利于皮肤保湿和胶原蛋白的产生,而棕榈酸可防止皱纹,增强皮肤的屏障功能[196]。

9.9. 无花果

无花果(表1)含有无花果素和酚类化合物,可用于制备针对干燥和急性受损皮肤的护肤品[197]。无花果提取物中所含的植物化学物质可减轻由于压力荷尔蒙活动引起的皮肤损伤,例如氧化、炎症、皮肤变成苍白的颜色和皮肤屏障的改变。在临床试验中,用无花果提取物治疗可恢复常规表皮,改善皮肤亮度,并减少皮脂产生和去角质[16]。含有无花果果实提取物的外用乳膏可以减少色素沉着过度、皱纹、痤疮和雀斑[198]。

9.10. 洋蓟

洋蓟提取物(表1)具有抗炎和抗氧化特性。此外,它还可以增强内皮细胞的血管舒张和微循环,减少NO产生,保护淋巴管免受ROS形成的影响,并通过加强紧密连接复合物来改善细胞凝聚力[199]。另外它增加了粗糙度和皮肤弹性。因此,化妆品配方中的洋蓟提取物被用作光保护剂,并增强粗糙度和皮肤弹性[200]。

9.11. 番木瓜

番木瓜(表1)用于抗皮肤老化的化妆品,因为它含有类黄酮(例如山奈酚,槲皮素,杨梅素及其糖苷)和酚酸(例如阿魏酸,咖啡酸)[201,202][203,204]。番木瓜果实代谢产物可以清除ROS,降低NF-κB,提高SOD和CAT活性[204],下调MMPs表达,并对胶原蛋白降解具有光保护作用。咖啡酸通过抑制NF-κB和AP-1信号传导来减少皮肤红斑[205]。半胱氨酸内肽酶和乳糜蛋白酶具有蛋白水解和抗菌作用[206-209]。

9.12. 光甘草

甘草(表1)具有抗氧化、抗炎和紫外线保护潜力[210]。它含有具有脱色能力和抑制酪氨酸酶作用的黄酮类化合物(例如光甘草定、光环素、异甘草苷元素、甘草醛酮A和甘草素)[211],用于预防色素沉着障碍(例如老年斑、黄褐斑和光化损伤部位)[212]。此外,甘草提取物可用作除臭剂,因为它可减少足部、腋窝和头部区域散发的难闻气味,防止常驻皮肤细菌产生的双乙酰形成[213]。最后,甘草的水醇提取物可改善头发生长[214]。

9.13. 可可豆

可可豆(表1)含有多酚(例如黄烷-3-醇,原花青素,花青素)和甲基黄嘌呤(例如,可可碱和咖啡因)[215],具有抗氧化和抗自由基特性[216,217]。局部应用可可多酚调节胶原蛋白I、III、IV和糖胺聚糖的产生[216]。口服具有抗炎、抗氧化和光保护作用[217]。掺入微乳液中的可可提取物用于护肤配方[218]。

9.14. 杏仁

杏仁富含三萜类化合物(例如尿果酸、白桦酸和齐墩果酸)、猫肝苷、黄酮醇糖苷、酚酸(例如原儿茶酸和香草酸)、植物甾醇、脂肪酸和脂溶性维生素[219,220]。李子提取物具有抗氧化特性[221]。它可用于治疗湿疹和丘疹[222]。杏仁油滋养、软化和强化头发[223]。

9.15. 椰子

椰子油的氧化稳定性归因于高含量的饱和脂肪酸(如肉豆蔻酸、月桂酸和棕榈酸)[224]。椰子油保护我们的皮肤免受紫外线的伤害。它可以阻挡20%的紫外线[225]。椰奶可以软化皮肤并去除脸上的黑斑,因为它富含天然脂肪酸并含有防腐剂[226]。食用椰子油具有强大的抗炎作用[227]。椰子油涂抹四肢可以滋润皮肤[228]。相反,如果在洗发前后用于头发上,它可以减少蛋白质损失[229]。椰子油可用作天然除臭剂[228]、身体磨砂膏、唇部磨砂膏、剃须膏和个人清洁剂(如肥皂、洗发水和洗涤剂)[229-232]。

表1 化妆品配方中使用的一些食品成分

10.化妆品配方中天然产物的运输

许多具有美白功效的天然产品无法渗透到皮肤中,在环境中不稳定,在胃中易降解,生物可及性和可溶性差,并且具有快速新陈代谢和不受约束地释放的特点,无法发挥其生物活性,因此他们并不能用于化妆品配方中。但一些输送系统解决了此问题。其中,食品级材料比如蛋白质(例如:乳清蛋白、明胶、酪蛋白、谷物蛋白、大豆蛋白和豆类蛋白质)、脂质和多糖(例如淀粉、果胶、纤维素、藻酸盐、壳聚糖和胶质)由于其安全性和生物降解性而被采用。例如石榴生物活性复合体被添加到几种纳米结构中(例如,纳米乳液,植物体,纳米脂质体,纳米颗粒,类脂质体和纳米囊泡)被运输到指定部位。

10.1脂质纳米封装体系

基于脂质的纳米封装体系被广泛应用。因为其稳定性和便于控制释放,并维持释放曲线。

10.1.1脂质体

脂质体是具有单层膜或多层的球形双层囊泡,可以保护和封装亲脂性和亲水性化合物。脂质体通常由磷脂酰胆碱组成的,具有疏水性尾巴和亲水头。它们有不同的尺寸大小(从20纳米到几微米) 。维生素(如A·E和K)和抗氧化剂(如辅酶Q10·类胡萝卜素和番茄红素)包裹在脂质体中,以提高其化学和物理稳定性。它们分散在水中,在4-25摄氏度下,脂质体在水溶液或水醇溶液中可保存2-3年不等。由多糖和胶原蛋白、γ-球蛋白或白蛋白的混合物覆盖的磷脂聚合而成的脂质体也很稳定。通过采用具有饱和酰基链的磷脂(如氢化大豆)来防止氧化并避免在pH值接近4.5-6.5时酯基的水解,或将脂质体分散在带有表面活性剂的脂质溶液中,可以保持脂质体的稳定性。一些专门的脂质体是用酶制成的,如核酸内切酶(从微球菌中提取的酶,可以识别阳光损伤并去除受损DNA)和光裂解酶(含有一种从海洋植物中提取的光活化酶,可以免受阳光的伤害)。

10.1.2类脂囊泡

类脂囊泡是单层或双层的类细胞球面双分子层的纳米囊泡 。它们由水合非离子表面活性剂(例如司盘,吐温类,脱水山梨醇酯,烷基酰胺,冠醚,类固醇表面活性剂,以及聚氧乙烯烷基醚),伴有或不伴有胆固醇和脂质自组装而成。他们的尺寸范围从100nm到200nm不等。多种保湿,抗皱,美白肌肤面霜,护发素和修护洗发水的配方中含有类脂囊泡。

10.2纳米乳液

       纳米乳液是一种液体分散剂,其中表面活性剂结合了稳定的油相和水相。有三种类型的纳米乳液(油包水,水包油和双连续相纳米乳液),尺寸从50nm到200nm不等。它们通常具有低粘度,高界面面积,高增溶能力,高动力学稳定性。在化妆品中,纳米乳剂被用来使活性成分快速渗透和积极运输,改善狭窄缝隙的渗透,并在乳液、防晒霜、除臭剂、洗发水、护发素、头发精华和指甲油中为皮肤提供水分。

10.3纳米粒子

     纳米颗粒在化学成分和形态上有所不同。不过,它们可以用作防晒剂制剂(例如,二氧化钛-纳米颗粒,氧化锌-纳米颗粒,氧化铈-纳米颗粒和二氧化锆-纳米颗粒)和物理紫外线过滤器。此外,二氧化硅和粘土纳米颗粒还可作为增稠剂。

“金纳米颗粒”(直径范围从5到400纳米)显示出各种形式(例如纳米球,纳米壳,纳米立方体,纳米柱,纳米簇,纳米棒和纳米三角形分支)。它们具有无细胞毒性,惰性,环境中高稳定性,生物相容性,抗菌和抗真菌性,可用于面膜,抗衰老面霜,除臭剂,化妆水等。“脂质纳米颗粒”(纳米结构脂质载体(NLC)和固体脂质纳米粒用于控制活性物质的释放和改善皮肤水合作用,增强闭塞效果。此外,它们还提高了见光易水解的氧化化合物的稳定性。在化妆品配方中,脂质纳米粒子用于运输视黄醇,辅酶Q10,生育酚和抗坏血酸棕榈酯。

10.4硅膜和囊泡

有机硅与各种活性成分(例如,铝),可作为化妆品活性物质的递送囊泡。硅囊泡可降低粘性并保护活性物质免水解。在化妆品中,有机硅可用于防晒(硬脂基聚二甲基硅氧烷可改善阳光保护系数)和头发护理配方中,因为它们可以增加光泽,可控性和减少飞散。

10.5多壁输送系统

     多壁输送系统(MDS)结合结构化囊泡和高精度剪切工艺,为化妆品配方提供长效的稳定性。双亲磷酸分子(例如,聚甘油,油酸和氨基酸残基的衍生物)制作MDS。因此MDS赋予脂质体稳定性,并维持和保护皮肤稳定,优化化妆品的性能。

10.6乳液

     一些乳液输送系统(例如,微乳液,纳米乳液,液晶,多种乳液和皮克林乳液)被用于化妆品中。

微乳剂的直径小于100纳米。它们是由表面活性剂分子和辅助表面活性剂稳定的油和水的透明(或半透明)的分散体。表面活性剂具有非离子基团,这决定了它们具有良好的皮肤耐受性和的亲油亲水平衡性。辅助表面活性剂增强了界面流动性,并调节表面活性剂的亲水-亲油平衡(HLB)。保湿配方中采用了微乳剂,因为它们具有良好的美学外观,易于使用,并且在使用区域没有粘性[255]。多功能硅氧烷季铵盐聚合物微乳剂被用于头发护理配方中,因为它们可以提供热保护和调理性,延长颜色持久性和提高产品的透明度[256]。纳米乳剂的液滴直径小于100纳米。它们具有良好的使用感(如快速渗透)和保湿能力。它们被用于环状凝胶、水样液体、透明牛奶、乳液和晶莹剔透的凝胶。在头发护理配方中使用阳离子纳米乳剂可以提高头发的干燥程度(经过几次洗发后)。[253]

 液态晶体是一种不完全熔化的状态。它增强了乳剂的稳定性,防止液体凝聚。由于液态晶体具有的彩色外观,满足了化妆品多样化的需求。进入液晶基质的亲脂性材料受到保护,不会发生光降解和热降解[258]。多重乳剂是分散相包裹着微小液滴的乳剂。多重乳剂可以是水/油/水(W/O/W),其中外部水相与油层分离,以及油/水/油(O/W/O),其中水将两个油相分开。在化妆品中,最常用的类型是W/O/W。它们需要两种稳定的表面活性剂,一种是低HLB(癸二酸甘油酯、混合甘油三油酸酯或山梨醇三油酸酯,形成初级乳化),另一种是高HLB表面活性剂(聚氧乙烯醚和聚山梨醇酯,实现二级乳化)[259]。在化妆品中,它们被用于含有皮肤脂质、香水、自由基清除剂和维生素的个人护理配方中[260]。皮克林乳液是固体颗粒(如氧化锌或二氧化钛)稳定的油包水(w/o)、油包水(o/w)的乳液,甚至是多重乳液。配方师可以通过添加环糊精来克服它们给皮肤带来的干燥或暗沉感。

11.结论

文献中报道了摄入食品补充剂和皮肤健康之间的显著相关性。不幸的是,目前没有具体的立法来规范它们作为化妆品的使用。已经做了许多努力来通过提高生物利用度的载体改善在我们身体部位中使用活性成分的效果,但是没有正式或有效的方法使我们能够识别和评估从食物中获得的所有活性成分。对这一信息的精确了解可以使化妆品效果最大化,减少不良反应,最重要的是,它可以帮助立法者制定在化妆品中使用食源性生物活性的法规。

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文章出处Molecules. 2021 Jun 26;26(13):3921. doi: 10.3390/molecules26133921.

作者:Irene Dini, Sonia Laneri

译者:林苏宁,陈晨,王润泽,

          包筱钰,王玺润,盛晓钰             

          徐州工程学院21、22级化妆品专业

主编:陈立莹,基础研究工程师

编辑:林沛东,项目工程师

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