免费文献传递   相关文献

红辣椒中类胡萝卜素的研究进展



全 文 :收稿日期:2012-05-07 接受日期:2012-09-10
* 通讯作者 Tel:86-013327107406;E-mail:huangyanchun0791@163. com
天然产物研究与开发 Nat Prod Res Dev 2013,25:562-565,571
文章编号:1001-6880(2013)4-0562-05
红辣椒中类胡萝卜素的研究进展
黄延春* ,李云霞
内蒙古师范大学化学与环境科学学院,呼和浩特 010022
摘 要:红辣椒中含有丰富的类胡萝卜素,不但具有一定的营养价值,而且是应用广泛的食品着色剂。本文主
要阐述了红辣椒中类胡萝卜素的分离鉴定方法、种类、结构,及在对红辣椒的加工、贮存过程中影响类胡萝卜素
稳定性因素的研究情况,为红辣椒的开发应用研究提供参考。
关键词:红辣椒;辣椒红素;辣椒玉红素;玉米黄质;类胡萝卜素
中图分类号:Q949. 91 文献标识码:A
Research Progress on Carotenoids in Red Pepper
HUANG Yan-chun* ,LI Yun-xia
Chemistry & Environment Science College of Inner Mongolia Normal University,Hohhot 010022,China
Abstract:Red pepper is a kind of important vegetable in diet. Carotenoids in red pepper,normally used as food color-
ants,are nutritious and have attracted more attention recently. In this paper,the isolation and identification methods,
chemical structures and stabilization of carotenoids are reviewed.
Key words:red pepper;capsanthin;capsorubin;zeaxanthin;carotenoid
红辣椒属一年生草本植物,品种繁多,世界各地
广泛种植。红辣椒中的主要成分有提供香辣味的辣
椒素、二氢辣椒素、降二氢辣椒素[1-3]、脂肪酸[4,5]、
多酚[6,7]、糖[8]、维生素[9]、类胡萝卜素等[10]。其中
类胡萝卜素在植物的生命中起着重要的作用,其合
成由光控制。随着辣椒的成熟,叶绿体转化成有色
体,叶绿素逐渐减少,类胡萝卜素增加。日光对加强
类胡萝卜素的合成是有效的,绿光和蓝光抑制类胡
萝卜素的生成[11,12]。红辣椒中的类胡萝卜素在收
获后的干燥过程中,在光的照射下仍会进行生物合
成,一直到水分全部脱去才结束。在这一过程中,类
胡萝卜素的含量会增加 20% ~ 40%[13]。类胡萝卜
素可以作为食品、化妆品的着色剂被广泛应用,而且
具有丰富的营养价值。但是类胡萝卜素的稳定性较
差,使它的应用受到较大的限制。因此,对红辣椒中
类胡萝卜素稳定性的研究成为一个重要课题。本文
综述了红辣椒中类胡萝卜素在不同条件下稳定性的
研究进展,为类胡萝卜素的开发应用提供参考。
1 红辣椒中类胡萝卜素的种类及结构
红辣椒呈现鲜艳的颜色,主要是由于其含有丰
富的类胡萝卜素。红辣椒中类胡萝卜素的成分及含
量随着产地的不同而不同[14],但基本都包括两个系
列,红色系列和黄色系列[15,16]。其中,含量较多的
是辣椒红素、南瓜黄质、玉米黄质、β-胡萝卜素、β-
玉米黄质[17]。红辣椒中各种类胡萝卜素的结构如
表 1 所示。
2 红辣椒中类胡萝卜素的分离及检测
红辣椒中类胡萝卜素的生物合成非常复杂,种
类较多。红辣椒中的各种类胡萝卜素是科研工作者
花费大量时间,采用各种先进的分离检测手段鉴定
出来的。
A. Aczél利用高压薄层色谱分离了辣椒红素和
辣椒玉红素。这是一种具有选择性的分离,能准确
地确 定 红 色 素 的 色 价[18]。M. Isabel Mínguez-
Mosquera 等利用反相高压液相色谱(HPLC) ,通过
丙酮和水的梯度洗脱,在 450 nm 的紫外光下检测,
分离和鉴定了红辣椒果实、辣椒粉、辣椒油中的十四
种类胡萝卜素[19]。D. Hornero-Méndez 等采用 UV-
Visible、IR、MS、TLC 和 HPLC 分离鉴定出了红辣椒
中南瓜黄素[20]。Dámaso Hornero-Méndez 等采用快
速分光光度法确定了辣椒粉和辣椒油中类胡萝卜素
中的部分红色成分和黄色成分。这一方法可直接用
于丙酮提取液,避免了皂化,最小化了色素降解造成
的误差,减少了样品的处理,缩短了分析时间[21]。
Péter A. Biacs等提取得到了红辣椒中脂肪酸类胡萝
卜酯和未酯化的低相性和表相性的类胡萝卜素。采
用高压液相色谱将其分离,发现辣椒红素单酯中主
要含有不饱和脂肪酸,辣椒红素二酯和辣椒玉红素
中主要含有饱和脂肪酸[22]。M. H. Gnayfeed 等的研
究发现,利用次临界丙烷萃取辣椒粉,比较容易得到
类胡萝卜素和维生素,不易得到辣椒素[23]。
365Vol. 25 黄延春等:红辣椒中类胡萝卜素的研究进展
3 红辣椒中类胡萝卜素稳定性的研究
红辣椒中类胡萝卜素的稳定性是制约类胡萝卜
素在食品及化妆品等领域应用的一个重要因素。因
此,对红辣椒中类胡萝卜素的稳定性的研究成为一
个重要课题。
3. 1 干燥的影响
Maria Isabel Mínguez-Mosquera等研究了不同品
种红辣椒在缓慢干燥和研磨过程中类胡萝卜素含量
的变化。结果表明,湿度为 85% ~ 88%的红辣椒在
温和的条件下干燥,类胡萝卜素的含量等于或高于
最初的产品。这个事实说明,果实在干燥期间仍在
进行新陈代谢,存在着各种类胡萝卜素的合成,从而
增加了黄色成分和红色成分;另外,干果实在研磨阶
段,研磨机产生的热导致了黄色成分的降解,红色成
分未发生变化[24]。这一实验结果与 Antonio Pérez-
Gález等的研究结果相似,其研究发现,在果实干燥
(温度在 60 ℃左右)研磨的过程中,类胡萝卜素的
含量在不同的时间段有时高有时低[25]。
3. 2 贮藏的影响
Antonio Raffo等研究了使用聚乙烯包装和热水
处理后包装低温贮藏的红辣椒中辣椒红素、南瓜黄
素 A、玉米黄素、β-胡萝卜素、β-玉米黄素含量的变
化。结果表明,未包装、包装及使用 53 ℃热水处理
后包装低温贮藏 21 d的红辣椒中,五种类胡萝卜素
的含量变化不一样。未包装的红辣椒中辣椒红素的
含量减少,南瓜黄素 A 的含量减少,玉米黄素、β-胡
萝卜素、β-玉米黄素的含量增多;包装的红辣椒中
辣椒红素的含量稍有减少,南瓜黄素 A 的含量未
变,玉米黄素、β-胡萝卜素、β-玉米黄素的含量稍有
增多;使用 53 ℃热水处理后包装低温贮藏 21 d 后
五种类胡萝卜素的含量基本未变。从以上结果我们
可以看出,短时间的贮藏对类胡萝卜素的影响较
小[16]。
Ayhan Topuz等研究了 γ 射线及贮藏对辣椒粉
中的辣椒红素、辣椒玉红素、南瓜黄素、隐黄素、紫黄
素的影响。在较大强度的辐射下或较长时间的贮
藏,除了辣椒玉红素外,其它色素均有明显减少。但
是辐射的影响弱于贮藏时间的影响,例如,在强度为
10 kGy的 γ 射线照射下,辣椒红素减少 11. 1%,而
10 个月的贮藏辣椒红素会减少 42. 1%[26]。
3. 3 温度的影响
Manuel Jarén-Galán 等研究了温度对红辣椒油
树脂中类胡萝卜素含量的影响。在 60 ℃以下,升高
温度红辣椒中的黄色色素被破坏的速率快一些;60
℃以上,升高温度红辣椒中的红色色素被破坏的速
率快一些。总之,升高温度,红辣椒油树脂中类胡萝
卜素总含量减少[27]。
Ute Schweiggert 等研究了干辣椒和辣椒粉中游
离的类胡萝卜素和酯化类胡萝卜素在不同温度下的
稳定性。将干辣椒和辣椒粉分别加热到 80、90、100
℃,保持 5 min 和 10 min,然后冻干。检测发现,干
辣椒中的类胡萝卜素减少 25% ~ 34%,辣椒粉中的
类胡萝卜素减少 20% ~ 53%。研究还发现,在室温
下贮存 4 个月后,干辣椒中游离的类胡萝卜素和酯
化类胡萝卜素含量分别下降 16. 7% ~ 9. 6%,辣椒
粉中二者分别下降 39. 7% ~ 38. 8%。可见,类胡萝
卜素在干辣椒中更稳定,干辣椒中酯化类胡萝卜素
比游离的类胡萝卜素更稳定[28]。这一研究结果与
Péter A. Biacs等[22]的结果一致。
3. 4 填加物的影响
Antonio Raffom 等研究了在 70 ℃的烤箱中干
燥、研磨辣椒时,未加入和加入不同比例辣椒种子的
情况下,类胡萝卜素的降解情况。结果表明,在最初
阶段,热降解速率与混合种子的比例成反比。随着
干燥时间的增长,混合种子的比例越少,热降解速率
越慢,类胡萝卜素损失越少。从整个反应过程来看,
加入的种子越多,降解速率越快,主要是由于种子中
富含不饱和脂肪酸(主要是亚油酸) ,它具有氧化作
用。因此,在辣椒粉产品中,为了减少类胡萝卜素的
损失,不要填加辣椒种子[29]。
Peter A. Biacs 等的研究发现,在室温下贮存不
同辣椒粉 150 d,未加入任何抗氧化剂的辣椒粉中,
类胡萝卜素有 27%的降解,加入 δ-生育酚的有 20%
的降解,加入抗坏血酸的有 15%的降解;在冷冻的
条件下贮存以上三种辣椒粉,其中类胡萝卜素的降
解率分别为 15%,13%和 5%。可见,在辣椒粉加入
一定量的抗氧化剂可以增加类胡萝卜素的稳定
性[30]。
4 结语
到目前为止,各国科研工作者利用各种测试手
段已确定的红辣椒中类胡萝卜素的种类及结构达
26 种之多,其应用前景非常广阔。但是由于类胡萝
卜素的稳定性较差,红辣椒主要以辣椒粉、辣椒酱、
辣椒油等出现在市场上。为了提高红辣椒的应用价
465 天然产物研究与开发 Vol. 25
值,扩大红辣椒中类胡萝卜素的应用范围,必须对提
高类胡萝卜素的稳定性做更深入地研究。
参考文献
1 Reusch M,et al. Determination of capsaicinoids in low pun-
gency paprika. Z Lebensm Unters Forsch,1996,202:334-
336.
2 Seong SH,et al. Suppression of phorbol ester-induced NF-kB
activation by capsaicin in cultured human promyelocytic leu-
kemia cells. Arch Pham Res,2002,25:475-479.
3 Han SL,et al. Oviposition-stimulating activity of (E)-capsai-
cin identified in capsicum annuum fruit and related com-
pounds towards Helicoverpa assulta. Chemoecology,2006,
16:153-157.
4 Gálvez AP,et al. Fatty acid composition of two new pepper
varieties(Capsicum annuum L. Cv. Jaranda and Jariza).
Effect of drying process and nutritional aspects. JAOCES,
1999,76:205-208.
5 Malchev E,et al. Indentification and changes in the higher
fatty acids of dried red pepper and redpepper powder. Z Leb-
ensm Unters Forsch,1989,189:229-231.
6 Oboh G,Joao Batista T,Rocha. Polyphenols in red pepper
[Capsicum annuum Var. aviculare (Tepim) ]and their pro-
tective effect on some pro-oxidants induced lipid peroxidation
in brain and liver. Eur Food Res Techno,2007,225:239-
247.
7 Gorinstein S,et al. A comparative study of phenolic com-
pounds and antioxidant and antiproliferative activities in fre-
quently consumed raw vegetables. Eur Food Res Technol,
2009,228:903-911.
8 Rácz MP,et al. Enzymatic determination of the sugars in red
pepper. Z Lebensm Unters Forsch,1981,172:115-117.
9 Guerrero JLG,Guirado CM. Fuentes MMR Nutrient composi-
tion and antioxidant activity of 10 pepper (Capsicum annuum
)varieties. Eur Food Res Technol,2006,224:1-9.
10 Fekete M,et al. Spectrophototric method for determining the
pigment content of ground paprika. Z Lebensm Unters Forsch,
1976,161:31-33.
11 Lopez M,et al. Carotenoids from capsicum annuum Fruits:In-
fluence of spectral quality of radiation. Biologia Plantarum
(praha) ,1986,28:100-104.
12 Pilarski J,Kocurek M. The content of photosynthetic pigments
and the light conditions in the fruits and leaves of sweet pep-
per. Acta Physiol Plant,2005,27:173-182.
13 Mosquera MIM,et al. Competition between the processes of
biosynthesis and degradation of carotenoids during the drying
of peppers. J Agric Food Chem,1994,42:645-648.
14 Ayuso MC,et al. Quality characteristics of different red pep-
per cultivars (Capsicum annuum L.)for hot paprika produc-
tion. Eur Food Res Technol,2008,227:557-563.
15 Deli J,et al. Separation and identification of carotenoids from
different coloured paprika (Capsicum annuum )by reversed-
phase high-performance liquid chromatography. Eur Food Res
Technol,2001,213:301-305.
16 Scalia S,Francis GW. Preparative scale reversed-phase
HPLC method for simultaneous separation of carotenoids and
carotenoid esters. Chromatographia,1989,28:129-132.
17 Raffo A,et al. Internal quality and antioxidants content of
cold-stored red sweet peppers as affected by polyethylene bag
packaging and hot water treatment. Eur Food Res Technol,
2007,225:395-405.
18 Aczél A. The over-pressured thin-layer chromatographic sepa-
ration of capsanthin-capsorubin. Fresenius Z Anal Chem,
1988,330:462.
19 Mosquera MIM,Méndez DH. Separation and quantification of
the carotenoid pigments in red peppers (Capsicum annuum
L.) ,paprika and oleoresin by reversed-phase HPLC. J Agric
Food Chem,1993,41:1616-1620.
20 Méndez DH,Mosquera MIM. Isolation and identification of
the carotenoid capsolutein from Capsicum annuum as cucurb-
itaxanthin A. J Agric Food Chem,1998,46:4087-4090.
21 Méndez DH,Mosquera MIM. Rapid spectrophotometric deter-
mination of red and yellow isochromic carotenoid fractions in
paprika and red pepper oleoresins. J Agric Food Chem,2001,
49:3584-3588.
22 Biacs PA,et al. Studies on the carotenoid pigments of paprika
(Capsicum annuum L. var Sz-20). J Agric Food Chem,
1989,37:350-353.
23 Gnayfeed MH,et al. Supercritical CO2and subcritical propane
extraction of pungent paprika and quantification of carote-
noids,tocopherols,and capsaicinoids. J Agric Food Chem,
2001,49:2761-2766.
24 Mosquera MIM,et al. Carotenoid content of the varieties
jaranda and jariza(Capsicum annuum L.)and response dur-
ing the industrial slow drying and grinding steps in paprika
processing. J Agric Food Chem,2000,48:2972-2976.
25 Gález AP,et al. Dependence of carotenoid content and tem-
perature-time regimes during the traditional slow drying of
red pepper for paprika production at La Vera county. Eur
Food Res Technol,2005,221:645-652.
26 Topuz A,Ozdemir F. Influence of r-irradiation and storage on
the carotenoids of sun-dried and dehydrated paprika. J Agric
Food Chem,2003,5:4972-4977.
( 下转第 571 页)
565Vol. 25 黄延春等:红辣椒中类胡萝卜素的研究进展
28 Silva JMC,et al. Biological activities of the sulfated polysac-
charide from the vascular plant Halodule wrightii. Rev Bras
Farmacogn,2011,22,no. 1.
29 Tang LH(汤鲁宏) ,et al. Study on the anti-coagulation effect
of extract from Cyanea nozakii. Nat Prod Res Dev (天然产物
研究与开发) ,2010,22:490-492.
30 Chen SG(陈士国). Structure and bioactivity analysis of sev-
eral acid polysaccharides from sea animal:Searching for al-
ternatives to Heparin(几种海洋动物酸性多糖的结构和活
性研究). Qingdao:Ocean University of China,PhD. 2010.
31 Qi WJ(齐文静). Preparation of high activity low molecular
weight heparin and activity study(高活性低分子量肝素的
制备及活性研究). Wuhan:Wuhan University of Technolo-
gy,MsD. 2010.
32 Li YL(李艳玲) ,Huang LQ(黄荣清). Study on the activity
of bloodsucker as anticoagulant and analysis on its chemical
components. J Tra Chin Vet Med (中兽医医药杂志) ,2010,
29:7-11.
33 Wang YQ(汪艳秋) ,et al. Anticoagulant and antithrombotic
effects of polysaccharide of Codium fragile. Anhui Med
Pharm(安徽医药)2011,15:804-805.
34 Chen SG,et al. Sulfation of a squid ink polysaccharide and its
inhibitory effect on tumor cell metastasis. Carbohyd Polym,
2010,81:560-566.
35 Fan LH,et al. Synthesis and anticoagulant activity of pectin
sulfates. J Appl Polym Sci,2012,124:2171-2178.
36 Yang XM(杨曦明) ,et al. Study on anti-coagulation activity
of polyporus albicans teng sulfate. Chin J Lab Diagn (中国
实验诊断学) ,2010,14:1031-1034.
37 Song YM(宋玉民) ,et al. Preparation and preliminary study
of anticoagulant properties of heparin hybrid materials. Chin
J Inorg Chem (无机化学学报) ,2011,27:631-636.
38 Paliwal R,et al. Recent advances in search of oral heparin
therapeutics. Med Res Rev,2012,32:388-409.
39 Herczeg M,et al. Synthesis of disaccharide fragments of the
AT-III binding domain of heparin and their sulfonatomethyl
analogues. Carbohyd Res,2011,346:1827-1836.
40 Chaidedgumjom A,et al. Effect of(1-3)-and(1-4)-linkages
of fully sulfated polysaccharides their anticoagulant activity.
Carbohyd Res,2002,337:925-933.
41 Mao WJ,et al. Chemical characteristic and anticoagulant activity
of the sulfated polysaccharide isolated from Monostroma latissi-
mum (Chlorophyta). Int J Biol Macromol,2009,44:70-74.
42 Maeda M,et al. Heparinoid-active sulphated polysaccharides
from Monostroma niiidum and their distribution in the Chlo-
rophyta. Phytochemistry,1991,30:3611-3614.
43 Cipriani TR,et al. Influence of molecular weight of chemical-
ly sulfated citrus pectin fractions on their antithrombotic and
bleeding effects. Thromb Haemost,2009,101:860-866.
44 Shen Y(沈元). Studies on the Preparation and Anticoagulant
activity of Starch-Based Sulfates Derivatives (淀粉基硫酸酯
衍生物的制备及其抗凝血活性研究). Wuhan:Wuhan U-
niversity of Technology,MsD. 2010.
45 Wijesinghe W,Jeon YJ. Biological activities and potential in-
dustrial applications of fucose rich sulfated polysaccharides
and fucoidans isolated from brown seaweeds:A review. Car-
bohyd Polym,2012,88:13-20.
46 Durig J,et al. Anticoagulant fucoidan fractions from Fucus
vesiculosus induce platelet activation in vitro. Thromb Res,
1997,5,479-491.
47 Majdoub H,et al. Anticoagulant activity of a sulfated polysac-
charide from the green alga Arthrospira platensis. Biochimica
et Biophysica Acta,2009,1790:1377-1381.
48 Li Q(李青). Studies on the modification and application of
amylose,Guar Gum and Konjac Glucomannan (直链淀粉、
瓜胶、魔芋多糖的改性及性能和应用的研究). Wuhan:
Wuhan University,PhD. 2004.
49 Mulloy B,Mourao PAS,Gray E. Structure / function studies of
anticoagulant sulphated polysaccharides using NMR. J Bio-
technol,2000,77:123-135.
50 Mouro PA. Use of sulfated fucans as anticoagulant and
atithrombotic agents:Future perspectives. Curr Pharm De-
sign,2004,10:967-981.
51 Fonseca RJ,et al. Effects of oversulfated and fucosylated
chondroitin sulfates on coagulation. Thromb Haemost,2010,
103:
櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵櫵
994-1004.
( 上接第 565 页)
27 Galán MJ,Mosquera IM. Quantitative and qualitative changes
associated with heat treatments in the carotenoid content of
paprika oleoresins. J Agric Food Chem,1999,47:4379-4383.
28 Schweiggert U,et al. Effects of processing and storage on the
stability of free and esterified carobenoids of red peppers
(Capsicum annuum L.)and hot chilli peppers (Capsicum
frutescents L.). Eur Food Res Technol,2007,225:261-270.
29 Gálvez AP,et al. Participation of pepper seed in the stability
of paprika carotenoids. JAOCS,1999,76:1449-1454.
30 Biacs PA,et al. Factors affecting stability of colored sub-
stances in paprika powders. J Agric Food Chem,1992,40:
363-367.
175Vol. 25 尹馨梓等:多糖硫酸酯化修饰及其抗凝血作用研究进展