硫辛酸酯的实验室制备方法及其在化妆品中的应用进展

doi:10.3969/j.issn.1001-1803.2021.04.014

摘要/Abstract

摘要：

硫辛酸既是药品,也是一种多功能抗氧化剂。以硫辛酸为原料的化妆品虽性能优秀,但也存在不少问题,如不易保存、刺激性强等。且硫辛酸的不稳定性和弱水溶性也给实验人员带来研究上的不便。将硫辛酸和其他功效性原料结合为硫辛酸酯,可以改善硫辛酸的不足,同时增进功效。酯化反应是化学界最经典的反应之一,催化方式多而繁杂,且各自具有独特的优缺点。但据统计,只有其中几种方法使用频次最高,许多优秀的酯化方法常常被忽视。该文从化学催化和生物酶催化两个方面综述了硫辛酸酯的实验室制备方法,对每种方法的优劣加以分析,并对硫辛酸酯在化妆品方面的应用前景进行了展望。

关键词: 硫辛酸酯, 酯化反应, 化妆品, 生物酶催化, 化学催化

Abstract:

Lipoic acid is both a drug and a multi-functional antioxidant. The cosmetics using lipoic acid as raw material have excellent performance, but they also have many problems, such as being not easy to preserve and strong irritation. The instability and poor water solubility of lipoic acid also bring inconvenience to professionals in research. The combination of lipoic acid with other functional materials as lipoic acid esters can improve the deficiency of lipoic acid and enhance the efficacy. The esterification reaction is one of the most classic reactions in the chemical world. There are many catalytic methods, and each method has unique advantages and disadvantages. However, according to statistics, only a few of them were most frequently used, and many excellent esterification methods had often been ignored. The laboratory preparation methods of lipoic acid esters were summarized from the aspects of chemical catalysis and biological enzyme catalysis. The advantages and disadvantages of each method were analyzed, and the application prospect of lipoic acid esters in cosmetics was discussed.

Key words: lipoic acid ester, esterification reaction, cosmetics, enzymatic catalysis, chemocatalysis

中图分类号:

TQ658

宋京九,郭晓丹,王东,祝钧. 硫辛酸酯的实验室制备方法及其在化妆品中的应用进展[J]. 日用化学工业, 2021, 51(4): 356-362.

SONG Jing-jiu,GUO Xiao-dan,WANG Dong,ZHU Jun. Laboratory preparation of lipoic acid esters and their application prospect in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2021, 51(4): 356-362.

图/表 2

参考文献 51

[1]	Luo J, Shuang S. Lipoic acid alleviates schistosomiasis-induced liver fibrosis by upregulating Drp1 phosphorylation[J]. Acta Tropica, 2020: 105449.
[2]	Amorousy D E, Eiafify D. Effects of alpha lipoic acid as a supplement in obese children and adolescents[J]. Cytokine, 2020,130:155084. doi: 10.1016/j.cyto.2020.155084 pmid: 32259774
[3]	Peng P, Zhang X, Qi T, et al. Alpha‐lipoic acid inhibits lung cancer growth via mTOR‐mediated autophagy inhibition[J]. FEBS Open Bio, 2020,10(4) .
[4]	Zhu Shuiran, He Caihong, Zhong Xiaoxia, et al. Feasibility and prognostic analysis of epalrestat combined with α-lipoic acidin the treatment of diabetic peripheral neuropathy[J]. China Medicine and Pharmacy, 2019 ( 14) : 37-40.
[5]	Wang Wenjing. Clinical analysis of -lipoic acid combined with mecobalamin in the treatment of diabetic peripheral neuropathy[J]. Electronic Journal of General Stomatology, 2018,5(20) : 123-125.
[6]	Baziar N, Nasli-Esfahani E, Djafarian K, et al. The beneficial effects of alpha lipoic acid supplementation on Lp-PLA2 mass and its distribution between HDL and apob-containing lipoproteins in type 2 diabetic patients: a randomized, double-Blind, placebo-controlled trial[J]. Oxidative Medicine and Cellular Longevity, 2020: 1-13. pmid: 19750024
[7]	Suzuki Y J, Tsuchiya M, Packer L. Thioctic acid and dihydrolipoic acid are novel antioxidants which interact with reactive oxygen species[J]. Free Radical Research, 1991,15(5) : 255-263.
[8]	Stevens B, Perez S R, Small R D. The photoperoxidation of unsaturated organic molecules-IX. lipoic acid inhibition of rubrene autoperoxidation[J]. Photochemistry and Photobiology, 1974,19(4) : 315-316.
[9]	Ou P, Tritschler H J, Wolff S P. Thioctic (lipoic) acid: a therapeutic metal-chelating antioxidant?[J]. Biochemical Pharmacology, 1995,50(1) : 123-126.
[10]	Brot N, Weissbach L, Werth J, et al. Enzymatic reduction of protein-bound methionine sulfoxide[J]. Proceedings of the National Academy of Sciences, 1981,78(4) : 2155-2158.
[11]	Yang Zhuangqun, Wang Zhenghui, Hu Xioayi, et al. Effects of α-lipoic acid on cultured human melanocytes in vitro[J]. The Chinese Journal of Dermatovenereology, 2004,18(2) : 71-73.
[12]	Arivazhagan P, Panneerselvam C. Effect of DL-α-lipoic acid on neural antioxidants in aged rats[J]. Pharmacological Research, 2000,42(3) : 219-222.
[13]	Streicher H. Use of an （R）-enantiomer of lipoic acid in cosmetics and dermatologicals: US20030180337[P]. 2003-09-25.
[14]	Onishchenko. Dermatological and/or cosmetological medium stimulating hair growth, medium affecting hair follicle cell multiplication: RU2357722[P]. 2009-06-10.
[15]	Schuhbauer H, Winkler S, Rudholzner M, et al. Stable, acid, aqueous solution containing alpha-lipoic acid （derivatives）, method for the production thereof and use of the same: US20040266858[P]. 2004-12-30.
[16]	Kentaro T N, Tomoko H, Takeshi O, et al. Modulating effects of a novel skin-lightening agent, α-lipoic acid derivative, on melanin production by the formation of DOPA conjugate products[J]. Bioorganic and Medicinal Chemistry, 2007,15(5) : 1967-1975.
[17]	Picott F, Bosco M, Stucchil , et al. Polysaccharide derivatives of lipoic acid, their preparation, use as skin cosmetics and medical devices: EP2222712[P]. 2017-03-01.
[18]	Lara H H, Blank D M, Christine, et al. Activating a silver lipoate nanocluster with a penicillin backbone induces a synergistic effect against S. aureus biofilm[J]. ACS Omega, 2019: 4(26) : 21914-21920. pmid: 31891070
[19]	Xu Changlong, Zhang Aidong, Cao Xiaohua. Synjournal of thioctic N-hydroxysuccinimide esters[J]. Guangdong Chemical Industry, 2006,33(7) : 22.
[20]	Zhang Luyun, Xu Qian, Xia Guangqing, et al. Synjournal and biological activity of lipoic acid ester derivatives[J]. Chemical Journal of Chinese Universities, 2018,39(10) : 96-103.
[21]	Hu Minhua, Ye Wenfeng, Li Jiaming, et al. Synjournal, molecular docking and antitumor activity of N-aryl Salicylamide derivatives[J]. Chemical Reagent, 2014,36(1) : 27-31.
[22]	Bernin R, Crisante F, Nicolo M, et al. Synjournal of a novel ester of hydroxytyrosol and α-lipoic acid exhibiting an antiproliferative effect on human colon cancer HT-29 cells[J]. European Journal of Medicinal Chemistry, 2011,46(1) : 439-446.
[23]	Wang Huiqi. Study on the preparation and properties of phytosteryl lipoate[D]. Wuxi: Jiangnan University, 2018.
[24]	Peng Lei. Study glycyrrhetinic acid derivatives and screening of biological activity[D]. Jilin: Jilin Agricultural University, 2016.
[25]	Zhang Yue. Study of cholesterol ester derivatives and biological activity[D]. Jilin: Jilin Agricultural University, 2016.
[26]	Cravero R M, Luna L E, Barboza A V. A novel method for the synjournal of (1, 8-Dioxo-2, 3, 4, 5, 6, 7, 8, 9-octahydro-1H-xanthen-9-yl) acetic acids on solid phase[J]. Synjournal, 2011 ( 24) : 4027-4032.
[27]	Olejarz W, Wrzosekm, Jóźwiak M, et al. Synjournal and anticancer effects of α-lipoic ester of alloxanthoxyletin[J]. Medicinal Chemistry Research, 2019,28(5) : 788-796.
[28]	Picotti F, Fabbian M, Gianni R, et al. Hyaluronic acid lipoate: synjournal and physicochemical properties[J]. Carbohydrate Polymers, 2013,93(1) : 273-278.
[29]	Cabrita J F, Viana A S, Eberle C, et al. Electrooxidation of pyrrole-terminated self-assembled lipoic acid derivatives[J]. Surface Science, 2009,603(16) : 2458-2462.
[30]	Zhang Luyun, Xu Qian, Cong Li, et al. Study on synthetic methodology of thioctanoic acid ester derivatives[J]. Journal of Tonghua Teachers College, 2018,39(12) : 48-52.
[31]	Biresaw G, Compton D, Evan K, et al. Lipoate ester multifunctional lubricant additives[J]. Industrial & Engineering Chemistry Research, 2016,55(1) : 373-383.
[32]	Najafabadi B K, Hesari M, Workentin M S, et al. New ferrocene based dithiolate ligands[J]. Journal of Organometallic Chemistry, 2012,703:16-24.
[33]	Koufak M, Kizirid C, Nikoloudaki F, et al. Design and synjournal of 1, 2-dithiolane derivatives and evaluation of their neuroprotective activity[J]. Bioorganic & Medicinal Chemistry Letters, 2007,17(15) : 4223-4227. pmid: 17531485
[34]	Xu Miaojun, Yang Zhenzhen, Wu Lingling, et al. Syntheses and antitutmor activities of α-lipoic acid and its acylhydrazine derivatives[J]. Chemistry Bulletin, 2012,75(9) : 837-841.
[35]	Bi Yajing, Yan Hong, Zeng Yi. Heterogeneous synthesis of lipoic acid ester derivatives under microwave irradiation[C]// Chinese Electronics Society. Proceedings of the 12th National Conference on Microwave Energy Applications. Chengdu: Chinese Electronics Society, 2005: 4.
[36]	Tao Naimin. Study on synthesis technology of lipoic acid[D]. Tianjin: Tianjin University, 2016.
[37]	Manova D, Gallier F, Taktak L, et al. Lipase-catalyzed amidation of carboxylic acid and amines[J]. Tetrahedron Letters, 2018,59(21) : 2086-2090.
[38]	Biresaw G, Laszlo J A, Evans K O, et al. Synjournal and tribological investigation of lipoyl glycerides[J]. Journal of Agricultural and Food Chemistry, 2014,62(10) : 2233-2243.
[39]	Kontham V, Padmaja K V. Tribological studies of α-lipoic acid esters as effective environmentally friendly multifunctional lubricant additives[J]. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2019,41(6) : 700-712.
[40]	Hsieh S W, Lee M R, Tsai C W, et al. Enzymatic synjournal, purification and identification of bioactive trehalose ester derivatives for health applications[J]. Food and Bioproducts Processing, 2015,95:163-172.
[41]	Ishihara K, Katsube Y, Kumazawa N, et al. Enzymatic preparation of arbutin derivatives: lipase-catalyzed direct acylation without the need of vinyl ester as an acyl donor[J]. Journal of Bioscience and Bioengineering, 2010,109(6) : 554-556.
[42]	Klak S S, Balkrishnaa M, Prasad B N. Enzymatic synjournal and characterization of 1‐lipoyl‐2‐palmitoyl phosphatidylcholine: a novel phospholipid containing lipoic acid[J]. European Journal of Lipid Science and Technology, 2014,116(10) : 1347-1353.
[43]	Fadnavisa N W, Koteshwar K. Remote control of stereoselectivity: lipase catalyzed enantioselective esterification of racemic α-lipoic acid[J]. Tetrahedron: Asymmetry, 1997,8(2) : 337-339.
[44]	Dr W, Ulrich H D. Schindler H D. Medicated shampoo for hair care and treatment: DE4419783[P]. 1995-12-07.
[45]	Bosco M, Stucchi L, Fabbian M, et al. Use of glycosaminoglycan lipoate esters in the trichology field: US20140308228[P]. 2014-10-16
[46]	Piotti F, Fabbian M, Gianni R, et al. Hyaluronic acid lipoate: synjournal and physicochemical properties[J]. Carbohydrate Polymers, 2013,93(1) : 273-278. pmid: 23465930
[47]	Kim J H, Na Y, Lee B C, et al. Novel lipoic acid conjugated compounds and skin external applicationa containing thereof: WO2007105854[P]. 2007-09-20.
[48]	Kim J H, Sim G S, Bae J T, et al. Synjournal and anti‐melanogenic effects of lipoic acid‐polyethylene glycol ester[J]. Journal of Pharmacy and Pharmacology, 2008,60(7) : 863-870. doi: 10.1211/jpp.60.7.0007 pmid: 18549672
[49]	Lu C, Kim B M, Chai K Y. Design, synjournal and evaluation of Pegylated lipoic acid derivatives with functionality as potent anti-melanogenic agents[J]. European Journal of Medicinal Chemistry, 2011,46(10) : 5184-5188. doi: 10.1016/j.ejmech.2011.07.056 pmid: 21890247
[50]	Wang Chenglin, Lu Chichong. Study on the combined antioxidant activity of vitamin E and a-lipoic acid[J]. Beijing Chemical, 2019 (3) : 10-17.
[51]	Gelo P M, Desmurs J R, Ksaaem T, et al. Synjournal of new antioxidant conjugates and their in vitro hydrolysis with Stratum corneum enzymes[J]. International Journal of Cosmetic Science, 2008,30(3) : 195-204. doi: 10.1111/j.1468-2494.2008.00438.x pmid: 18452436