CN117486956A - 一种甜菜红酰基化产物及其制备方法 - Google Patents
一种甜菜红酰基化产物及其制备方法 Download PDFInfo
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- CN117486956A CN117486956A CN202311248589.2A CN202311248589A CN117486956A CN 117486956 A CN117486956 A CN 117486956A CN 202311248589 A CN202311248589 A CN 202311248589A CN 117486956 A CN117486956 A CN 117486956A
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- betalain
- lipase
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- beet red
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/44—Preparation of O-glycosides, e.g. glucosides
- C12P19/60—Preparation of O-glycosides, e.g. glucosides having an oxygen of the saccharide radical directly bound to a non-saccharide heterocyclic ring or a condensed ring system containing a non-saccharide heterocyclic ring, e.g. coumermycin, novobiocin
-
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Abstract
本发明属于生物化学结构修饰技术领域,公开了一种甜菜红酰基化产物及其制备方法,其结构式如下式Ⅰ所示。所述甜菜红酰基化产物的制备方法包括以下步骤:(1)将甜菜红和酚酸分别溶解后的溶液混合均匀;并加入脂肪酶,在搅拌条件下进行催化反应;(2)反应结束后,除去溶剂,制得粗产物。本发明将具有生物活性的酚酸接枝到甜菜红素分子,从而提高了甜菜红素的稳定性和抗氧化活性,其抗氧化性活性甚至高于维生素C和水溶性维生素E。
Description
技术领域
本发明涉及生物化学结构修饰技术领域,具体涉及一种具有增效稳定抗氧化活性的甜菜红酰基化产物及其制备方法。
背景技术
天然色素具有巨大的健康效益,能够帮助人体避免各种各样的危害,特别在慢性疾病的形成和发展方面,被认为是理想的保健食品。甜菜红素是杂环酪氨酸衍生的色素,酚羟基和环状胺基部分使这类化合物具有还原性。体外实验中,甜菜红素在无机体系和有机体系中都表现出抗氧化的能力,抑制低密度脂蛋白氧化的效果良好,具有促进免疫系统、化学治疗癌症和预防心血管疾病、神经变性疾病的作用。因此,甜菜红素可以应用于食品、制药和化妆品行业。甜菜红素不溶于有机溶剂,且对于还原剂和氧化剂的耐受性较差。在有光和氧气存在的条件下,甜菜红素很容易降解。另外,甜菜红色素随着pH的增加、温度的升高、时间的延长,其降解程度均逐渐增大,对甜菜红色素的稳定性、抗氧化活性的研究,可以有效地缓解甜菜红色素在食品加工、包装以及商品流通过程中引起的变色和褪色,提高稳定性以及抗氧化活性,对于食品的开发应用具有积极影响。
申请号为CN202110616032.4的中国发明专利公开了一种复合壁材的甜菜红素微胶囊的制备方法,该发明专利以麦芽糊精-大米蛋白-菊芋多糖为壁材原料,包覆甜菜红素,该复合型壁材麦芽糊精-大米蛋白-菊芋多糖可以提高甜菜红素的稳定性,提升甜菜色素胶囊产品外观,且能为甜菜红素微胶囊提供附加营养价值。申请号为CN202110513626.2的中国发明专利公开了一种甜菜红素纳米脂质体及其制备方法与应用,该发明专利将大豆卵磷脂和胆固醇溶于有机溶剂中与甜菜红素溶液混合,通过除去有机溶剂,当达到胶态后加入吐温80 的PBS溶液减压水合得甜菜红素纳米脂质体溶液。所制备的脂质体稳定性较高,脂质分子不易被水解或氧化,形态规则,粒径小,安全无毒,具有良好的抗肿瘤效果。申请号为CN201711396874.3的中国发明专利公开了一种提高甜菜红色素稳定性的方法,该发明采用大豆蛋白纤维作为保护剂来提高甜菜红色素稳定性,对甜菜红色素因热引起的降解能起到很好的抑制效果。
上述专利虽然在一定程度上通过微胶囊化、脂质体、包埋等来提高甜菜红素的稳定性,其仅局限通过外部条件的改变来提高甜菜红素的稳定性,却很少提高甜菜红素的抗氧化活性,同时鲜有涉及到通过生物催化的方法通过对甜菜红素的化学结构修饰,从根本上解决天然色素的稳定性差和抗氧化性活性低的问题。
发明内容
针对现有技术的不足,本发明提供了一种具有增效稳定抗氧化活性的甜菜红酰基化产物及其制备方法,通过生物酶催化的方法对甜菜红素进行酰基化改性,将酚酸类化合物与甜菜红配基分子缔合形成酰基糖苷,减少醛亚胺键断裂的可能,从而提高甜菜红素的稳定性,同时利用酚酸的抗氧化能力来提高甜菜红素的抗氧化活性,拓宽其应用领域和范围。
为实现以上目的,本发明通过以下技术方案予以实现:
一种甜菜红酰基化产物,结构式如下所示:
式中,s=0或1
R1为-CH=CH-或
R2、R3、R4、R5、R6相同或不同地为-H、-OH、-O-CH3中的一种或几种,其中至少一个为-OH。
所述甜菜红酰基化产物的制备方法,包括以下步骤:
(1)将甜菜红和酚酸分别溶解后的溶液混合均匀;并加入脂肪酶,在搅拌条件下进行催化反应;
(2)反应结束后,除去溶剂,制得粗产物。
优选地,所述反应温度为40~60℃,反应时间为12~48h。
优选地,所述甜菜红与酚酸的摩尔比为1:1~1:20。
优选地,所述脂肪酶的浓度为5~100mg/mL。
优选地,所述脂肪酶为固定化南极假丝酵母脂肪酶、固定化米黑根毛霉脂肪酶、固定化嗜热丝孢菌脂肪酶、来源于黑曲霉的丙烯酸树脂重组脂肪酶、Amano酰基转移酶、来源于蜂蜜曲霉的酰基转移酶I、APS Amano lipase脂肪酶、Lipozyme CACB、TLZM、Lipozyme435中的至少一种。
优选地,所述甜菜红的溶剂为水,酚酸的溶剂为甲醇、乙醇、乙酸乙酯、丙酮、异丙醇、氯仿、四氢呋喃、2-甲基四氢呋喃、正辛醇、乙二醇、丙三醇中的至少一种;
所述酚酸为绿原酸、阿魏酸、龙胆酸、香草酸、肉桂酸、丁香酸、芥子酸、对香豆酸、咖啡酸、原儿茶酸、没食子酸中的至少一种。
优选地,所述粗产物还经如下纯化处理:将粗产物溶解后,静置分层,取上层液体离心以除去脂肪酶和未反应酚酸,再通过过滤,除去悬浮物质,最后,经过冷冻干燥即制得甜菜红酰基化产物。
优选地,所述上层液体离心的速率为1000~5000rpm。
优选地,所述滤膜孔径为0.22~0.8μm;所述冷冻干燥的时间为24~72h。
上述制备方法的反应过程如下式所示:
与现有技术相比,本发明具备以下有益效果:
(1)本发明通过对甜菜红素糖苷键上亚甲基基团进行结构修饰,将具有生物活性的酚酸接枝到甜菜红素分子,从而提高甜菜红素的稳定性和抗氧化活性。
(2)本发明所涉及到的酶催化反应条件温和、处理简单、无需高温高压等严苛条件,避免甜菜红素在结构修饰过程中由于高温、强酸或强碱等外界环境引起降解,使其稳定性降低。
(3)本发明所制备的甜菜红酰基化产物具有显著的抗氧化性活性,甚至高于维生素C和水溶性维生素E,可以拓宽甜菜红的应用领域和范围。
附图说明
图1为实施例1制备的甜菜红咖啡酸酰基化产物的红外光谱图,其中,甜菜红(a-BT)、咖啡酸(b-)、甜菜红咖啡酸酰基化产物(c-BT-g-CA);
图2为实施例1制备的甜菜红咖啡酸酰基化产物的紫外可见光谱图,其中,甜菜红(a-BT)、咖啡酸(b-)、甜菜红咖啡酸酰基化产物(c-BT-g-CA);
图3为实施例1制备的甜菜红咖啡酸酰基化产物的核磁氢谱图,其中,甜菜红(a-BT)、咖啡酸(b-CA)、甜菜红咖啡酸酰基化产物(c-BT-g-CA);
图4为实施例1制备的甜菜红咖啡酸酰基化产物的DPPH自由基吸收能力,其中,维生素C(a-VC)、甜菜红咖啡酸酰基化产物(b-BT-g-CA)、甜菜红(c-BT);
图5为实施例1制备的甜菜红咖啡酸酰基化产物的ORAC氧自由基吸收能力,其中,水溶性维生素E(a-VE)、甜菜红咖啡酸酰基化产物(b-BT-g-CA)、甜菜红(c-BT)。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
实施例1甜菜红咖啡酸酰基化产物
(1)将甜菜红(0.5mmol)溶解5.0mL的去离子水中,在室温下搅拌溶解。
(2)将咖啡酸(0.5mmol)溶解5.0mL的乙醇中,并在室温下搅拌溶解。
(3)将上述材料混合,并加入50.0mg固定化南极假丝酵母脂肪酶,在40℃下搅拌12h。
(4)通过旋转蒸发除去乙醇。然后再添加适量的去离子水以溶解酰基化产物,于4℃冰箱静置,分层。然后在1000r/min作用下离心5min,以除去脂肪酶和未反应的咖啡酸。再通过微孔滤膜(0.22μm)过滤,除去悬浮物质。最后,经过24h的冷冻干燥去除水分,收集样品即为甜菜红咖啡酸酰基化产物。
实施例2甜菜红没食子酸酰基化产物
(1)将甜菜红(0.5mmol)溶解5.0mL的去离子水中,在室温下搅拌溶解。
(2)将没食子酸(10.0mmol)溶解5.0mL的氯仿中,在室温下搅拌溶解。
(3)将上述材料混合,并加入1000.0mg固定化米黑根毛霉脂肪酶,在60℃下搅拌48h。
(4)通过旋转蒸发除去氯仿。然后再添加适量的去离子水以溶解酰基化产物,于4℃冰箱静置,分层。然后在5000r/min作用下离心10min,以除去脂肪酶和未反应的没食子酸。再通过微孔滤膜(0.8μm)过滤,除去悬浮物质。最后,经过72h的冷冻干燥去除水分,收集样品即为甜菜红没食子酸酰基化产物。
实施例3甜菜红对香豆酸酰基化产物
(1)将甜菜红(0.5mmol)溶解5.0mL的去离子水中,在室温下搅拌溶解。
(2)将对香豆酸(5.0mmol)溶解5.0mL的丙酮中,在室温下搅拌溶解。
(3)将上述材料混合,并加入500.0mg固定化米黑根毛霉脂肪酶,在50℃下搅拌36h。
(4)通过旋转蒸发除去丙酮。然后再添加适量的去离子水以溶解酰基化产物,于4℃冰箱静置,分层。然后在3000r/min作用下离心8min,以除去脂肪酶和未反应的对香豆酸。再通过微孔滤膜(0.45μm)过滤,除去悬浮物质。最后,经过48h的冷冻干燥去除水分,收集样品即为甜菜红对香豆酸酰基化产物。
实施例4甜菜红龙胆酸酰基化产物
(1)将甜菜红(0.5mmol)溶解5.0mL的去离子水中,在室温下搅拌溶解。
(2)将龙胆酸(3.0mmol)溶解5.0mL的乙酸乙酯中,在室温下搅拌溶解。
(3)将上述材料混合,并加入200.0mg固定化米黑根毛霉脂肪酶,在40℃下搅拌24h。
(4)通过旋转蒸发除去乙酸乙酯。然后再添加适量的去离子水以溶解酰基化产物,于4℃冰箱静置,分层。然后在2000r/min作用下离心10min,以除去脂肪酶和未反应的龙胆酸。再通过微孔滤膜(0.45μm)过滤,除去悬浮物质。最后,经过36h的冷冻干燥去除水分,收集样品即为甜菜红龙胆酸酰基化产物。
实施例5甜菜红肉桂酸酰基化产物
(1)将甜菜红(0.5mmol)溶解5.0mL的去离子水中,在室温下搅拌溶解。
(2)将肉桂酸(2.0mmol)溶解5.0mL的正辛醇中,在室温下搅拌溶解。
(3)将上述材料混合,并加入100.0mg固定化米黑根毛霉脂肪酶,在45℃下搅拌24h。
(4)通过旋转蒸发除去正辛醇。然后再添加适量的去离子水以溶解酰基化产物,于4℃冰箱静置,分层。然后在1500r/min作用下离心8min,以除去脂肪酶和未反应的肉桂酸。再通过微孔滤膜(0.22μm)过滤,除去悬浮物质。最后,经过24h的冷冻干燥去除水分,收集样品即为甜菜红肉桂酸酰基化产物。
利用德国Tensor 27红外光谱(FT-IR)对实施例1-实施例5所制备的甜菜红酰基化产物的官能团的变化进行分析。
利用日本岛津的紫外分光光度计(U765S)对实施例1-实施例5所制备的甜菜红酰基化产物的官能团变化进行分析。
利用德国布鲁克核磁共振波谱NMR(Bruker Avance NEO 600)对实施例1-实施例5所制备的甜菜红酰基化产物进行分析。
本试验通过测定甜菜红及其酰基化产物的最大吸收波长下的吸光度值衰减率ΔA,研究甜菜红及其酰基化产物稳定性。ΔA越大说明甜菜红及其酰基化产物降解越快。
吸光度值衰减率:ΔA/%=Δ(A0-At)/A0
式中:A0为起始时最大吸收波长对应的吸光度;At为t时在最大吸收波长对应的吸光度。
通过DPPH自由基清楚能力和ORAC氧自由基吸收能力来测定甜菜红酰基化产物的体外抗氧化活性。
在ORAC测定中,将DPPH溶解于无水乙醇中配置成0.2mM的溶液。将维生素C(VC)(作为标准)、甜菜红(BT)和甜菜红酰基化产物稀释不同的浓度。之后将5.0mL样品与5.0mL的DPPH溶液于棕色玻璃瓶中混合用铝箔纸包裹,并于黑暗处避光反应30min,在517nm处测定吸光值As。其中,以5.0mL超纯水加上5.0mL无水乙醇作为空白调零,以5.0mL超纯水加上5.0mLDPPH溶液作为对照组Ac。DPPH自由基清除能力计算公式如下:
对比Vc的DPPH自由基清除率进行计算,得到样品的DPPH值表示为μmol Vcequiv./g。
在ORAC测定中,用磷酸缓冲盐溶液PBS(pH 7.4,75mM)将Trolox(水溶性维生素E)(作为标准)、甜菜红(BT)和甜菜红酰基化产物稀释至20.0μg/mL。将20μL稀释的Trolox溶液和样品加入96孔板中,使用PBS溶液作为空白对照。将板置于微孔板读取器中,在37℃下放置10min、随后加入200μL荧光钠盐(0.96mM),并将平板在37℃下再放置20min。之后,将20μL的2-乙酰基-4-丁酰胺基苯酚(ABAP)(119mM)加入孔中(空白PBS对照除外)。将板置于微孔板读取器中,然后在485nm的激发波长和538nm的发射波长下每5min测量一次光密度值,持续270min。绘制荧光淬灭曲线。
图1为实施例1制备的甜菜红咖啡酸酰基化产物的红外光谱图,其中,甜菜红素(a-BT)、咖啡酸(b-CA)、甜菜红咖啡酸酰基化产物(c-BT-g-CA)。在甜菜红素(a-BT)的红外谱图中,在3500~3000cm-1的宽吸收带是甜菜红素中-COOH、-OH、=CH、-NH-以及吡啶杂芳环的叠加振动吸收峰,在2898cm-1是甜菜红素葡糖基的-CH2的伸缩振动峰,在1642cm-1、1471cm-1、1372cm-1处吸收峰是甜菜红素苯环骨架结构的特征吸收峰,在1080cm-1是甜菜红素葡糖基的-C-O-C-的振动吸收峰。在咖啡酸(b-VA)的红外谱图中,3450cm-1、3223cm-1是咖啡酸苯环的酚羟基-OH振动吸收峰,1600、1445、1276、1214cm-1咖啡酸苯环骨架结构的特征吸收峰。与甜菜红素(a-BT)的红外光谱相比,在甜菜红咖啡酸酰基化产物(c-BT-g-CA)的红外谱图中,3300cm-1处-OH的伸缩振动吸收峰变强变宽,表明在甜菜红素结构中引入了-OH,另外在1642、1449、1290cm-1处出现了苯环骨架结构的特征吸收峰,同时在1018cm-1处-CH=CH-的伸缩振动吸收峰变强,表明在甜菜红素结构中引入了咖啡酸。以上结果表明,咖啡酸接枝到甜菜红素的结构上,甜菜红咖啡酸酰基化产物成功制备。
图2为实施例1制备的甜菜红咖啡酸酰基化产物的紫外-可见光谱图,其中,甜菜红素(a-BT)、咖啡酸(b-CA)、甜菜红咖啡酸酰基化产物(c-BT-g-CA)。在甜菜红素(a-BT)的紫外-可见谱图中,在526nm的可见光区域出现了最大吸收波长,在268nm紫外光区域出现了较低的吸收峰。在咖啡酸(b-CA)的紫外-可见谱图中,在326nm处出现了最大吸收波长,其为苯环的特征峰。在甜菜红咖啡酸酰基化产物(c-BT-g-CA)的紫外-可见谱图中,在315nm处出现了一个强吸收峰,这主要由于在甜菜红素分子结构中接枝咖啡酸,导致甜菜红素的基本生色团甜菜醛氨酸结构发生变化,由于接枝的是带有苯环结构的酚酸,导致甜菜红咖啡酸酰基化产物分子结构发生了蓝移现象,使得最大吸收峰发生了偏移。以上结果也可证明咖啡酸成功接枝到甜菜红素上。
图3为实施例1制备的甜菜红素-阿魏酸共聚物的核磁氢谱图,其中,甜菜红素(a-BT)、咖啡酸(b-CA)、甜菜红咖啡酸酰基化产物(c-BT-g-CA)。在甜菜红素(a-BT)的核磁氢谱中化学位移主要分布在3.0~5.5ppm之间。在咖啡酸(b-CA)的核磁氢谱中化学位移主要分布在6.0~12.0ppm之间,其中6.0~8.0ppm之间的化学位移对应的咖啡酸苯环骨架的氢原子。相比甜菜红素(a-BT),在甜菜红咖啡酸酰基化产物(c-BT-g-CA)的核磁氢谱中,在6.0~8.0ppm之间的出现新的峰,其为苯环的特征峰,表明咖啡酸成功接枝到甜菜红素的结构上。
图4为实施例1制备的甜菜红咖啡酸酰基化产物的DPPH自由基清除能力,其中,维生素C(a-VC)、甜菜红咖啡酸酰基化产物(b-BT-g-CA)、甜菜红(c-BT)。从图中可以看出随着样品浓度的增加,DPPH自由基清除能力逐渐增大,在样品浓度在1~16μg/mL时,甜菜红咖啡酸酰基化产物(b-BT-g-CA)的DPPH自由基清除能力显著高于甜菜红(c-BT),同时比维生素C(a-VC)的DPPH自由基清除能力还要高。当DPPH自由基清除为50%时,甜菜红咖啡酸酰基化产物(b-BT-g-CA)和维生素C的浓度分别为10.08μg/mL和14.12μg/mL,甜菜红咖啡酸酰基化产物(BT-g-CA)相当于7.96×103μmol Vc equiv./g,即为7.96mmol Vc equiv./g。可以看出经过酰基化改性,甜菜红的DPPH自由基清除能力大大增加,表明其抗氧化活性显著提升。
图5为实施例1制备的甜菜红咖啡酸酰基化产物的ORAC氧自由基吸收能力,其中,水溶性维生素E(a-VE)、甜菜红咖啡酸酰基化产物(b-BT-g-CA)、甜菜红(c-BT)。从图中可以看出当样品浓度同为20.0μg/mL,三种样品延缓荧光色钠淬灭的能力依次为BT-g-CA>VE>BT,可以看出经过酰基化改性,甜菜红的ORAC氧自由基吸收能力大大增加,从而延长荧光色钠的淬灭时间,表明甜菜红咖啡酸酰基化产物的抗氧化活性显著提升。
表1为实施例1产物在不同pH值条件下的吸光度值衰减率ΔA
从表1可以看出,在中性或者弱酸性的条件下甜菜红(BT)和甜菜红咖啡酸酰基化产物(BT-g-CA)随着贮藏时间的延长都发生一定程度的降解,在弱酸或者中性的条件下,二者的降解速率比较缓慢,但甜菜红咖啡酸酰基化产物(BT-g-CA)的整体降解率比甜菜红(BT)小,表明,经过酰基化改性可以提高甜菜红的稳定性。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种甜菜红酰基化产物,其特征在于,结构式如下所示:
R2、R3、R4、R5、R6相同或不同地为-H、-OH、-O-CH3中的一种或几种,其中至少一个为-OH。
2.权利要求1所述甜菜红酰基化产物的制备方法,其特征在于,包括以下步骤:
(1)将甜菜红和酚酸分别溶解后的溶液混合均匀;并加入脂肪酶,在搅拌条件下进行催化反应;
(2)反应结束后,除去溶剂,制得粗产物。
3.根据权利要求2所述的制备方法,其特征在于,所述反应温度为40~60℃,反应时间为12~48 h。
4.根据权利要求3所述的制备方法,其特征在于,所述甜菜红与酚酸的摩尔比为1:1~1:20。
5.根据权利要求4所述的制备方法,其特征在于,所述脂肪酶的浓度为5~100 mg/mL。
6.根据权利要求5所述的制备方法,其特征在于,所述脂肪酶为固定化南极假丝酵母脂肪酶、固定化米黑根毛霉脂肪酶、固定化嗜热丝孢菌脂肪酶、来源于黑曲霉的丙烯酸树脂重组脂肪酶、Amano酰基转移酶、来源于蜂蜜曲霉的酰基转移酶I、APS Amano lipase脂肪酶、Lipozyme CACB、TLZM、Lipozyme 435中的至少一种。
7.根据权利要求2-6任意一项所述的制备方法,其特征在于,
所述甜菜红的溶剂为水,酚酸的溶剂为甲醇、乙醇、乙酸乙酯、丙酮、异丙醇、氯仿、四氢呋喃、2-甲基四氢呋喃、正辛醇、乙二醇、丙三醇中的至少一种;
所述酚酸为绿原酸、阿魏酸、龙胆酸、香草酸、肉桂酸、丁香酸、芥子酸、对香豆酸、咖啡酸、原儿茶酸、没食子酸中的至少一种。
8.根据权利要求7所述的制备方法,其特征在于,所述粗产物还经如下纯化处理:将粗产物溶解后,静置分层,取上层液体离心以除去脂肪酶和未反应酚酸,再通过过滤,除去悬浮物质,最后,经过冷冻干燥即制得甜菜红酰基化产物。
9.根据权利要求8所述的制备方法,其特征在于,所述上层液体离心的速率为1000~5000rpm。
10.根据权利要求9所述的制备方法,其特征在于,所述滤膜孔径为0.22~0.8μm;所述冷冻干燥的时间为24~72h。
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