花青素的生物合成研究进展

doi:10.3969/j.issn.0253-2417.2020.03.001

摘要/Abstract

摘要：

花青素是主要存在于植物中的一种黄酮类物质，具有较强的生物活性如抗癌、抗氧化等，广泛用于营养保健领域。大部分的花青素是通过物理或化学的手段从植物中直接提取，但是该方法产量低，受到时间、地域以及季节的限制，同时提取到的花青素多为混合物。近年来，花青素的生物合成受到研究人员的广泛关注，由于生物合成花青素过程可以人为控制，而且得到的产品纯度较高，因此受到广泛的研究。独立的花青素不能稳定存在于环境中，需要经过糖基化、酰基化、甲基化等修饰才能增加其稳定性，修饰后的花青素已能通过微生物合成并且在培养基中看到明显的颜色变化。综述了花青素的生物合成途径，以及修饰方法；简单介绍了从植物中提取、微生物合成花青素的制备技术，分析了影响花青素合成的因素，最后展望了花青素未来研究的方向。

关键词: 花青素, 生物合成, 生物修饰

Abstract:

Anthocyanin is a kind of flavonoid which mainly exists in plants. It has strong biological activities such as anti-cancer and anti-oxidation, and is widely used in the field of nutrition and health care. Most anthocyanins are extracted directly from plants by physical or chemical means, but the yield is low, and the extracted anthocyanins are mostly mixtures due to the restrictions of time, region and season. Biosynthesis of anthocyanins have attracted much attention by researchers worldwide in recent years. As the biosynthesis of anthocyanins can be controlled artificially and the purity of the obtained products is high, it has been widely studied. Anthocyanins cannot exist stably in the environment, and need to be modified by glycosylation, acylation and methylation to increase their stability. The modified anthocyanins can be synthesized by microorganisms and significant color changes can be seen in the medium. The biosynthesis and modification of anthocyanins were reviewed in this paper, and the preparation technology of anthocyanin synthesis from plants and microorganisms was briefly introduced, the factors affecting anthocyanin synthesis were analyzed, and finally the future research direction of anthocyanin was predicted.

Key words: anthocyanin, biosynthesis, biomodification

中图分类号:

TQ35

许倩,张晨,吴嘉维,欧阳嘉. 花青素的生物合成研究进展[J]. 林产化学与工业, 2020, 40(3): 1-11.

Qian XU,Chen ZHANG,Jiawei WU,Jia OUYANG. Research Progress in Biosynthesis of Anthocyanins[J]. Chemistry and Industry of Forest Products, 2020, 40(3): 1-11.

图/表 5

参考文献 59

1	MARTINS N , RORIZ C L , MORALES P , et al. Food colorants:Challenges, opportunities and current desires of agro-industries to ensure consumer expectations and regulatory practices[J]. Trends in Food Science & Technology, 2016, 52, 1- 15. doi: 10.1016/j.tifs.2016.03.009
2	HARBORNE J B , WILLIAMS C A . Anthocyanins and other flavonoids[J]. Natural Product Reports, 2004, 21 (4): 539- 573. doi: 10.1039/b311404j
3	谢烨, 孙毅, 黄继荣. 拟南芥中花青素的修饰[J]. 植物生理学报, 2013, 49 (2): 101- 110.
	XIE Y , SUN Y , HUANG J R . Anthocyanin modification in aradidopsis[J]. Plant Physiology Journal, 2013, 49 (2): 101- 110.
4	PASCUAL-TERESA D , MORENO D A , GARCIA-VIGUERA C . Flavanols and anthocyanins in cardiovascular health:A review of current evidence[J]. International Journal of Molecular Sciences, 2010, 11 (4): 1679- 1703. doi: 10.3390/ijms11041679
5	PATRAS A , BRUNTON N P , O'DONNELL C , et al. Effect of thermal processing on anthocyanin stability in foods; mechanisms and kinetics of degradation[J]. Trends in Food Science & Technology, 2010, 21 (1): 3- 11.
6	WOODWARD G , KROON P , CASSIDY A , et al. Anthocyanin stability and recovery:Implications for the analysis of clinical and experimental samples[J]. Journal of Agricultural and Food Chemistry, 2009, 57 (12): 5271- 5278. doi: 10.1021/jf900602b
7	HE J , GIUSTI M M . Anthocyanins:Natural colorants with health-promoting properties[J]. Annual Review of Food Science and Technology, 2010, 1 (1): 163- 187. doi: 10.1146/annurev.food.080708.100754
8	VALENTI L , RISO P , MAZZOCCHI A , et al. Dietary anthocyanins as nutritional therapy for nonalcoholic fatty liver disease[J]. Oxidative Medicine and Cellular Longevity, 2013, 2013, 1- 8.
9	WALLACE T C , SLAVIN M , FRANKENFELO C L . Systematic review of anthocyanins and markers of cardiovascular disease[J]. Nutrients, 2016, 8 (1): 1- 13.
10	李泓烨.紫甘薯花青素对酒精性肝损伤和对肝癌的影响及其机制的研究[D].成都:西南交通大学, 2015.
	LI H Y. The study on effect on alcoholic liver injury and liver cancer with mechanism of anthocyanins from purple sweet potato[D]. Chengdu: Southwest Jiaotong University, 2015.
11	SPRINGOB K , NAKAJIMA J , YAMAZAKI M , et al. Recent advances in the biosynthesis and accumulation of anthocyanins[J]. Natural Product Reports, 2003, 20 (3): 288- 303. doi: 10.1039/b109542k
12	贾赵东, 马佩勇, 边小峰, 等. 植物花青素合成代谢途径及其分子调控[J]. 西北植物学报, 2014, 34 (7): 1496- 1506.
	JIA Z D , MA P Y , BIAN X F , et al. Biosynthesis metabolic pathway and molecular regulation of plants anthocyanin[J]. Acta Botanica Boreali-Occidentalia Sinica, 2014, 34 (7): 1496- 1506.
13	WINKEL-SHIRLEY B . Flavonoid biosynthesis. A colorful model for genetics, biochemistry, cell biology, and biotechnology[J]. Plant Physiology, 2001, 126 (2): 485- 493. doi: 10.1104/pp.126.2.485
14	赵启明, 李范, 李萍. 花青素生物合成关键酶的研究进展[J]. 生物技术通报, 2012, (12): 25- 32.
	ZHAO Q M , LI F , LI P . Research advances on core enzymes of anthocyanidin biosynthesis[J]. Biotechnology Bulletin, 2012, (12): 25- 32.
15	ZHU S J , WU J J , DU G C , et al. Efficient synthesis of eriodictyol from L-tyrosine in Escherichia coli[J]. Applied and Enviro nmental Microbiology, 2014, 80 (10): 3072- 3080. doi: 10.1128/AEM.03986-13
16	PANDEY R P , PARAJULI P , KOFFAS M A G , et al. Microbial production of natural and non-natural flavonoids:Pathway engineering, directed evolution and systems/synthetic biology[J]. Biotechnology Advances, 2016, 34 (5): 634- 662. doi: 10.1016/j.biotechadv.2016.02.012
17	SHI M Z , XIE D Y . Biosynthesis and metabolic engineering of anthocyanins in Arabidopsis thaliana[J]. Recent Patents on Biotechnology, 2014, 8 (1): 47- 60.
18	ZHANG H R , STEPHANOPOULOS G . Engineering E. coli for caffeic acid biosynthesis from renewable sugars[J]. Applied Microbiology and Biotechnology, 2013, 97 (8): 3333- 3341. doi: 10.1007/s00253-012-4544-8
19	NAKAJIMA J I , TANAKA Y , YAMAZAKI M , et al. Reaction mechanism from leucoanthocyanidin to anthocyanidin 3-glucoside, a key reaction for coloring in anthocyanin biosynthesis[J]. Journal of Biological Chemistry, 2001, 276 (28): 25797- 25803. doi: 10.1074/jbc.M100744200
20	NAKAMURA N , FUKUCHI-MIZUTANI M , FUKUI Y , et al. Generation of pink flower varieties from blue torenia hybrida by redirecting the flavonoid biosynthetic pathway from delphinidin to pelargonidin[J]. Plant Biotechnology, 2010, 27 (5): 375- 383. doi: 10.5511/plantbiotechnology.10.0610a
21	ZHA J , ZANG Y , MATTOZZI M , et al. Metabolic engineering of Corynebacterium glutamicum for anthocyanin production[J]. Microbial Cell Factories, 2018, 17 (1): 143. doi: 10.1186/s12934-018-0990-z
22	FORKMANN G. Genetics of Flavonoids[M]//HARBORNE J B. The Flavonoids: Advances in Research Since 1986.London: Chapman and Hall, 1993: 538-564.
23	HOLTON T A , CORNISH E C . Genetics and biochemistry of anthocyanin biosynthesis[J]. Plant Cell, 1995, 7 (7): 1071- 1083. doi: 10.2307/3870058
24	YONEKURA-SAKAKIBARA K , NAKAYAMA T , YAMAZAKI M , et al. Modification and Stabilization of Anthocyanins[M]. New York: Springer, 2008: 169- 190.
25	SAITO N , TATSUZAWA F , MIYOSHI K , et al. The first isolation of C-glycosylanthocyanin from the flowers of Tricyrtis formosana[J]. Tetrahedron Letters, 2003, 44 (36): 6821- 6823. doi: 10.1016/S0040-4039(03)01747-7
26	JOSHI C P , CHIANG V L . Conserved sequence motifs in plant S-adenosyl-L-methionine-dependent methyltransferases[J]. Plant Molecular Biology, 1998, 37 (4): 663- 674. doi: 10.1023/A:1006035210889
27	JONSSON L M V , DONKER-KOOPMAN W E , UITSLAGER P , et al. Subcellular localization of anthocyanin methyltransferase in flowers of Petunia hybrida[J]. Plant Physiology, 1983, 72 (2): 287- 290. doi: 10.1104/pp.72.2.287
28	GERATS A G M , FARCY E , WALLROTH M , et al. Control of anthocyanin synthesis in Petunia hybrida by multiple allelic series of the genes An1 and An2[J]. Genetics, 1984, 106 (3): 501- 508.
29	QUATTROCCHIO F . Regulatory genes controlling anthocyanin pigmentation are functionally conserved among plant species and have distinct sets of target genes[J]. The Plant Cell, 1993, 5 (11): 1497- 1512. doi: 10.2307/3869734
30	BRUGLIERA F, DEMELIS L, KOES R, et al. Genetic sequences having methyltransferase activity and uses therefor: US 7807877[P]. 2010-10-05.
31	MATERN U , REICHENBACH C , HELLER W . Efficient uptake of flavonoids into parsley (Petroselinum hortense) vacuoles requires acylated glycosides[J]. Planta, 1986, 167 (2): 183- 189. doi: 10.1007/BF00391413
32	SEITZ H H U . The uptake of acylated anthocyanin into isolated vacuoles from a cell suspension culture of Daucus carota[J]. Planta, 1987, 170 (1): 74- 85. doi: 10.1007/BF00392383
33	JORDHEIM M , GISKE N H , ØYVIND M. Andersen . Anthocyanins in Caprifoliaceae[J]. Biochemical Systematics & Ecology, 2007, 35 (3): 153- 159. doi: 10.1016/j.bse.2006.09.010
34	SUZUKI H , NAKAYAMA T , YONEKURA-SAKAKIBARA K , et al. cDNA cloning, heterologous expressions, and functional characterization of malonyl-coenzyme a:Anthocyanidin 3-o-glucoside-6″-o-malonyltransferase from dahlia flowers[J]. Plant Physiology, 2002, 130 (4): 2142- 2151. doi: 10.1104/pp.010447
35	朱良玉, 周丽萍, 王化, 等. 笃斯越橘酰化花青素稳定性分析[J]. 中国酿造, 2017, 36 (5): 136- 140.
	ZHU L Y , ZHOU L P , WANG H , et al. Stability analysis of Vaccinium uliginosum anthocyanins after acylation modification[J]. China Brewing, 2017, 36 (5): 136- 140.
36	CACACE J E , MAZZA G . Optimization of extraction of anthocyanins from black currants with aqueous ethanol[J]. Journal of Food Science, 2003, 68 (1): 240- 248. doi: 10.1111/j.1365-2621.2003.tb14146.x
37	LEE J , WROLStTAD R E . Extraction of anthocyanins and polyphenolics from blueberry processing waste[J]. Journal of Food Science, 2004, 69 (7): C564- 573.
38	王宏, 付燕秋, 韩静, 等. AB-8大孔树脂吸附黑枸杞中花青素行为研究[J]. 林产化学与工业, 2016, 36 (4): 79- 86.
	WANG H , FU Y Q , HAN J , et al. Adsorption behavior of AB-8 resin for anthocyanins from Lycium ruthenicum Murray[J]. Chemistry and Industry of Forest Products, 2016, 36 (4): 79- 86.
39	CHANDRASEKHAR J , MADHUSUDHAN M C , RAGHAVARAO K S M S . Extraction of anthocyanins from red cabbage and purification using adsorption[J]. Food and Bioproducts Processing, 2012, 90 (4): 615- 623. doi: 10.1016/j.fbp.2012.07.004
40	王辉. 木棉花红色素的提取及性质研究[J]. 林产化学与工业, 2001, 21 (2): 57- 61.
	WANG H . Study on exeraction and characterization of red pigment from bombax malabaricum[J]. Chemistry and Industry of Forest Products, 2001, 21 (2): 57- 61.
41	田喜强, 董艳萍, 赵东江. 黑米花青素的浸提工艺优化及稳定性研究[J]. 中国酿造, 2016, 35 (6): 161- 164.
	TIAN X Q , DONG Y P , ZHAO D J , et al. Optimization of extraction process for anthocyanins from black rice and research on its stability[J]. China Brewing, 2016, 35 (6): 161- 164.
42	BLACKHALL M L , BERRY R , DAVIES N W , et al. Optimized extraction of anthocyanins from Reid Fruits', Prunus avium, 'Lapins' cherries[J]. Food Chemistry, 2018, 256, 280- 285. doi: 10.1016/j.foodchem.2018.02.137
43	YAN Y J , CHEMLER J , HUANG L X , et al. Metabolic engineering of anthocyanin biosynthesis in Escherichia coli[J]. Applied & Environ-mental Microbiology, 2005, 71 (7): 3617- 3623.
44	TURNBULL J J , NAKAJIMA J , WELFORD R W D , et al. Mechanistic studies on three 2-oxoglutarate-dependent oxygenases of flavonoid biosynthesis anthocyanidin synthase, flavonol synthase, and flavanone 3β-hydroxylase[J]. Journal of Biological Chemistry, 2004, 279 (2): 1206- 1216. doi: 10.1074/jbc.M309228200
45	YAN Y J , LI Z , KOFFAS M A G . High-yield anthocyanin biosynthesis in engineered Escherichia coli[J]. Biotechnology and Bioengineering, 2008, 100 (1): 126- 140. doi: 10.1002/bit.21721
46	LEONARD E , YAN Y J , CHEMLER J , et al. Characterization of dihydroflavonol 4-reductases for recombinant plant pigment biosynthesis applications[J]. Biocatalysis and Biotransformation, 2009, 26 (3): 243- 251.
47	LIM C G , WONG L , BHAN N , et al. Development of a recombinant Escherichia coli strain for overproduction of the plant pigment anthocyanin[J]. Applied & Enviro nmental Microbiology, 2015, 81 (18): 6276- 6284.
48	SOLOPOVA A , VAN TILBURG A Y , FOITO A , et al. Engineering Lactococcus lactis for the production of unusual anthocyanins using tea as substrate[J]. Metabolic Engineering, 2019, 54, 160- 169. doi: 10.1016/j.ymben.2019.04.002
49	CRESS B F , LEITZ Q D , KIM D C , et al. CRISPRi-mediated metabolic engineering of E. coli for O-methylated anthocyanin production[J]. Microbial Cell Factories, 2017, 16 (1): 1- 14. doi: 10.1186/s12934-016-0616-2
50	汤睿, 雷雨婷, 任春梅. 外源尿黑酸对拟南芥幼苗花青素生物合成的影响[J]. 湖南农业大学学报(自然科学版), 2019, 45 (1): 39- 43.
	TANG R , LEI Y T , REN C M . Effect of exogenous homogentisate on anthocyanin biosynthesis in Arabidopsis thaliana seedlings[J]. Journal of Hunan Agricultural University(Natural Sciences), 2019, 45 (1): 39- 43.
51	HIRATSUKA S , ONODERA H , KAWAI Y , et al. ABA and sugar effects on anthocyanin formation in grape berry cultured in vitro[J]. Scientia Horticulturae, 2001, 90 (1/2): 121- 130.
52	QUIROGA A M , BERLI F J , MORENO D , et al. Abscisic acid sprays significantly increase yield per plant in vineyard-grown wine grape (Vitis vinifera L.) cv. cabernet sauvignon through increased berry set with no negative effects on anthocyanin content and total polyphenol index of both juice and win[J]. Journal of Plant Growth Regulation, 2009, 28 (1): 28- 35. doi: 10.1007/s00344-008-9070-7
53	BAN T , ISHIMARU M , KOBAYASHI S , et al. Abscisic acid and 2, 4-dichlorophenoxyacetic acid affect the expression of anthocyanin biosynthetic pathway genes in 'Kyoho' grape berries[J]. Journal of Horticultural Science and Biotechnology, 2003, 78 (4): 586- 589. doi: 10.1080/14620316.2003.11511668
54	JEONG S T , GOTO-YAMAMOTO N , KOBAYASHI S , et al. Effects of plant hormones and shading on the accumulation of anthocyanins and the expression of anthocyanin biosynthetic genes in grape berry skins[J]. Plant Science, 2004, 167 (2): 247- 252. doi: 10.1016/j.plantsci.2004.03.021
55	EL-KEREAMY A , CHERVIN C , ROUSTAN J P , et al. Exogenous ethylene stimulates the long-term expression of genes related to anthocyanin biosynthesis in grape berries[J]. Physiologia Plantarum, 2003, 119 (2): 175- 182. doi: 10.1034/j.1399-3054.2003.00165.x
56	ZHANG W , CERTIN C , KIKUCHI M , et al. Integration of jasmonic acid and light irradiation for enhancement of anthocyanins in Vitis vinifera suspension cultures[J]. Plant Science, 2002, 162 (3): 459- 468. doi: 10.1016/S0168-9452(01)00586-6
57	BELHADJ A , TELEF N , SAIGNE C , et al. Effect of methyl jasmonate in combination with carbohydrates on gene expression of PR proteins, stilbene and anthocyanin accumulation in grapevine cell cultures[J]. Plant Physiology & Biochemistry, 2008, 46 (4): 493- 499.
58	WEN P F , CHEN J Y , KONG W F , et al. Salicylic acid induced the expression of phenylalanine ammonia-lyase gene in grape berry[J]. Plant Science, 2005, 169 (5): 928- 934. doi: 10.1016/j.plantsci.2005.06.011
59	AZUMA A , YAKUSHIJI H , KOSHITA Y , et al. Flavonoid biosynthesis-related genes in grape skin are differentially regulated by temperature and light conditions[J]. Planta, 2012, 236 (4): 1067- 1080. doi: 10.1007/s00425-012-1650-x

[1]	王宏, 付燕秋, 韩静, 赵宇明, 刘栋. AB-8大孔树脂吸附黑枸杞中花青素行为研究[J]. 林产化学与工业, 2016, 36(4): 79-86.
[2]	许敬亮, 陈小燕, 肖仕圆, 袁振宏. 长链燃料醇生物合成研究进展[J]. 林产化学与工业, 2016, 36(4): 140-146.
[3]	姜贵全, 方桂珍, 师振鑫, 张卓睿, 庞久寅. 超临界CO₂萃取除脂后再经纤维素酶辅助提取落叶松树皮原花青素[J]. 林产化学与工业, 2014, 34(2): 97-102.
[4]	张梦;谢益民;杨海涛;姚兰. 肌醇在植物体内的代谢概述——肌醇作为细胞壁木聚糖和果胶前驱物的代谢途径[J]. 林产化学与工业, 2013, 33(5): 106-114.
[5]	胡国元;李伟伟;袁军;魏凌云. 茯苓多糖的修饰技术及其构效关系研究进展[J]. 林产化学与工业, 2013, 33(5): 121-126.
[6]	姜永新;朱宏涛;王军民;张颖君;张加研;华燕;赵平. 松树皮原花青素片段化产物的LC-ESI-MS分析[J]. 林产化学与工业, 2013, 33(4): 117-120.
[7]	徐曼;陈笳鸿;汪咏梅;吴冬梅;吴在嵩;张亮亮;. 落叶松原花青素的没食子酰化及其抗氧化活性增强效应[J]. 林产化学与工业, 2010, 30(6): 55-60.
[8]	杨兰;王成章;陈虹霞;叶建中;陈西娟. S-多萜醇及其化学合成研究进展[J]. 林产化学与工业, 2010, 30(3): 121-126.
[9]	田建华. 沙棘全果渣中原花青素提取纯化工艺研究[J]. 林产化学与工业, 2009, 29(S1): 207-209,.
[10]	王婧;李淑君. 落叶松树皮乙醇提取物的抗氧化性能研究[J]. 林产化学与工业, 2009, 29(S1): 143-148.
[11]	贾佳;杨磊;祖元刚. 落叶松树皮原花青素的匀浆提取及响应面法优化[J]. 林产化学与工业, 2009, 29(3): 78-84.
[12]	姜贵全;方桂珍;庞久寅. 地榆根提取低聚原花青素的研究[J]. 林产化学与工业, 2007, 27(S1): 129-132.
[13]	罗欣;姚开;贾冬英;何强. 原花色素在生物体内的吸收和代谢与生物可利用性[J]. 林产化学与工业, 2006, 26(1): 109-115.
[14]	杨磊;苏文强;汪振洋;杨冬梅. 落叶松树皮提取物中低聚原花青素含量测定方法的研究[J]. 林产化学与工业, 2004, 24(S1): 111-114.
[15]	杨磊;苏文强;李艳杰;宋豪;刘文彬. 正交试验法优选低聚原花青素的提取工艺[J]. 林产化学与工业, 2004, 24(2): 57-60.