【作者】 陈彦平；

【导师】 刘振春；

【作者基本信息】 吉林农业大学 ， 食品科学， 2007， 硕士

【摘要】 番茄红素是一种非常重要的类胡萝卜素，具有多种生理功能，是一种很有应用前景的功能性天然色素。1875年，Millardet最早从番茄中获得番茄红素的粗提物，当时命名为solanorubin。1903年Schunck研究发现番茄中的红色素的吸收光谱与胡萝卜素不同，将这种红色素命名为Lycopene。作为脂肪烃，番茄红素不溶于水，难溶于甲醇等有机溶剂，可溶于乙醚、石油醚、己烷、丙酮，易溶于氯仿、二硫化碳、苯、油脂等，色泽为红色，熔点174℃。它主要存在于番茄、西瓜、南瓜、李、柿、胡椒果、桃、木瓜、芒果、番石榴、葡萄、葡萄柚、红莓、云莓、柑桔等的果实和茶的叶片及萝卜、胡萝卜、芜菁、甘蓝等的根部。其中在番茄中含量最高，且成熟度越高，番茄红素的含量越高。凡能导致类胡萝卜素氧化的因素如光、温度、氧气、pH值及表面活性剂均能影响番茄红素。存在于番茄和番茄制品中的番茄红素比较稳定，而离体番茄红素的稳定性较差。科学研究已证实，番茄红素具有抗氧化和清除自由基能力，能减缓动脉粥样硬化，阻止低密度胆固醇的氧化，可有效防止心血管疾病的发生，它还具有抑制基因突变，预防恶性肿瘤，延缓人体衰老，提高肌体免疫力等多种功能。目前，保健食品越来越受到人们重视，保健食品市场的崛起使得传统的医药行业面临挑战，生病服药的概念正遭受到以预防疾病为主概念的冲击。特别是当今人们更加注重天然植物的活性成分对疾病的预防作用，更注重饮食对健康的重要性。番茄红素作为一种非常有前途的抗氧化剂正在不断受到人们的普遍关注。我国每年番茄产量达1000多万吨，现在全国许多地方正在进行农作物结构调整，压缩粮食用地，大力发展经济作物，因此，增加以番茄为原料生产富含番茄红素的功能食品、保健食品和食品添加剂是番茄的综合开发和利用的一条切实可行的重要途径。虽然我国番茄红素研究与生产尚在起步，但如果在现有番茄品种的基础上选择高番茄红素含量的番茄作为原料进行加工，采用先进的超临界萃取工艺，将会很快解决红色产业问题。本文以番茄为原料提取番茄红素，主要对番茄红素的酶辅助超临界CO₂流体萃取、纯化、以及番茄红素的稳定性进行了研究。主要内容和结论如下：1外加果胶酶和纤维素酶对提取液中番茄红素浓度的提高具有显著性作用，研究了反应温度、pH值、加酶量、反应时间对果胶酶和纤维素酶破壁效果即提取液中番茄红素浓度的影响。对于果胶酶和纤维素酶，反应温度在30-35℃内番茄红素浓度呈增加趋势，在30℃的时候达到最大；而在35-60℃内番茄红素浓度变化都呈下降趋势；pH值在3.2-4.0内，番茄红素浓度随pH值的升高而升高，pH值超过4.0后，番茄红素浓度逐渐减小；两种酶的使用量为3％果胶酶+3％纤维素酶时，番茄红素的浓度最大；反应时间在1-1.5小时内番茄红素浓度呈增加趋势，在1.5小时的时候达到最大，而在2-4小时内番茄红素浓度变化不大，但都呈下降趋势。通过正交试验确定了果胶酶和纤维素酶破壁处理的最佳反应条件。最佳反应条件为：温度40℃、pH值4.4、加酶量为3％果胶酶+3％纤维素酶、反应时间2小时。此反应条件下提取液中番茄红素浓度为2.503μg／mL。2以酶破壁后的番茄粉为原料，超临界萃取番茄红素。研究了萃取压力、萃取温度和萃取时间对番茄红素提取率的影响。当压力达到15Mpa时，番茄红素大部分被提取出来，提取率达到91.3％，继续升高压力，番茄红素的提取率也随之升高，但升高的幅度不大；温度30℃时提取率较低，温度升高，提取率随之升高，在40℃时，提取率已达91％，50℃达到最高，温度升高到60℃提取率反而下降；随着时间的延长，番茄红素的提取率逐渐升高，萃取4h后，提取率达到92％，继续延长时间增加的幅度不大。通过正交试验确定了临界CO₂流体萃取的最佳工艺条件，最佳条件为萃取压力15Mpa，萃取温度40℃，萃取时间4h。3番茄红素油树脂的纯化工艺采用皂化法。较优的工艺条件为，番茄红素油树脂：丙二醇：氢氧化钾：水的比例为3.5：4.5：1.5：1.5，皂化温度为70℃，皂化时间2小时，所得番茄红素的含量为3.4％。提取率为22.48％。4研究了温度、pH值、氧化剂、常见金属离子、还原剂、抗氧化剂、光、防腐剂对番茄红素的稳定性的影响。番茄红素的稳定性实验表明：色素对光、热、酸、金属离子Fe³⁺和Cu²⁺的稳定性差。加入氧化剂略有破坏作用，加入还原剂影响不大；添加抗氧化剂和防腐剂均能起到保护色素的功效。更多还原

【Abstract】 Lycopene is an important carotenoid and has several physiological functions. Lycopene also is apotential functional natural pigment.In 1875, Millardet acquired thick lifted a thing of lycopene from the tomato at the earliest stage,named after solanorubin at that time. In1903, Schunck researched to discover the absorption spectrum ofred within tomato is dissimilarity from carotene, this kind of red pigment named after lycopene. As a fathydrocarbon, lycopene don’t be dissolved in water, it is difficult to dissolve in organic melting agent suchas the methyl alcohol, it can be dissolved in ether, petroleum ether, cetane, acetone, is dissolved inchloroform, carbon disulfide, benzene, grease...etc, easily, color is red, the melting point is 174℃. It ismainly existed in the fruit of the tomato, watermelon, pumpkin, plum, persimmon, pepper fruit, peach,papaya, mango, guava, grape, grapefruit, red raspberry, cloud raspberry, orange etc. and leaf’s slice of thetea and the root of turnip, carrot, rape turnip, cabbage...etc. Among them, the content is the highest in thetomato, and the mature degree is more high, take turns lycopene of the content is more high. Any can causea type of factor that carotene oxidizes, such as the light, temperature, oxygen, pH value and the surface live,all can influence lycopene. Lycopene is more stable in the tomato product and the tomato, but leave a bodythe stability of lycopene is worse.Science research has already confirmed the lycopene has an ability ofanti-oxidize and clearance free radicals, can decelerate an artery gruel kind hardening, keeping low densitycholesterol from oxidizing, can prevent from cardiovascular paroxysm occurrence effectively, it still hasvarious functions such as a repressor gene mutation, prevention malignant tumor, the defer human bodydecrepitude, raise the muscle body immunity etc.Currently health food is more and more valued by people, the growing of market of the health foodmakes the traditional medicine profession face a challenge, the concept which gets sick to take a medicineis suffering with prevent from disease for the main concept pound at. Especially people pay attention to thelive composition of natural plant more the function to the paroxysm prevention nowadays, paying attentionto food more to the healthy importance. Lycopene as a kind of anti-oxidizing agent which has prospectvery much is in the widespread concern which is subjected to people continuously now.The every year of our country tomato yield reaches to more than 10 million tons, now many nationalplaces under way farm crop structure adjust, compress grain to use ground, develop cash crop strongly,therefore take adding tomato as raw material to produce rich function food with the lycopene, health food and food additive is one actually viable important path of comprehensive development of tomatos andmake use of. Although our country takes turns lycopene research and production still in the start, if choosethe tomato of high lycopene content as raw material to carry on processing in the foundation select ofexisting tomato species, adoption advanced technology of supercritical carbon dioxide fluid extraction, willsolve a red industry problem very quickly.This paper mainly dealt with the enzyme assists technology of supercritical CO₂ fluid extraction,purification of lycopene and stability of lycopene. The main contents and concludes were as follows:1 The additive pectolase and cellulase have remarkable function to enhance the lycopene density ofthe extractive fluid. Studied the effects of some single factors such as reaction temperature, pH, thequantity of additive enzyme and reaction time on the function of the pectolase and the cellulase namely thelycopene density of the extractive fluid. The lycopene density presented increment trend when the reactiontemperature was 30-35℃for the pectolase and cellulase. The lycopene density was biggest at 30℃; But thelycopene density varieties all presented to descend trend in 35-60℃; The pH value took turns in 3.2-4.0 thelycopene density was worth with the pH of go up but go up, pH value over 4.0 after, the lycopene densitylet up gradually; Took turns when two kinds of usages of enzymes measured for 3%pectolase+3%cellulosethe density of lycopene was the biggest; the lycopene density presented increment trend when reactiontime within 1-1.5 hours, at 1.5 hour of time attain biggest, but within 2-4 hours the lycopene densitychanged not greatly, but all presented to descend trend.Through orthogonal experiments, the optimum reaction conditions of pectolase and ceilulase wereobtained. The optimum conditions were that reaction temperature:40℃; pH:4.0; the quantity of additiveenzyme:4%pectolase+3%cellulose; reaction time:1.5h. Under these reaction conditions, the lycopenedensity of the extractive fluid is 2.503μg/mL.2 Breaking with tomato powder as raw materials, supercritical extraction of lycopene. Studied theeffects of some single factors such as pressure, temperature and time on the extraction rate of lycopene.When the pressure attained 15Mpa, the lycopene was greatly part of to be withdrawn, the extraction rateattain91.3%, continuing to go up pressure, taking turns the lycopene extraction rate also went upimmediately, but went up of the range was not wide; Temperature30℃the extraction rate lower, thetemperature went up, the extraction rate went up immediately, at 40℃, the extraction rate already91%,50℃attained highest, the temperature went up to 60℃the extraction rate descended on the contrary; Tookturns along with the extension of time the extraction rate of lycopene went up gradually, the extraction rateattained 92% after 4 hours, the range which continues to postpone long time to increase was not wide.Through orthogonal experiments, the optimum reaction conditions of supercritical carbon dioxidefluid extraction were pressure: 15 Mpa; temperature: 40℃; time:4h.3 Lycopene oil resin purification method is saponification. The best technology of purified lycopene oil resin was, lycopene oil resin:Trimethylene glycol:Potassium hydroxide:Water 3.5:4.5:1.5:1.5,saponification temperature 70℃, saponification time 2h. The content of lycopene is 3.4%, extraction rate is22.48%.4 Studied the effects of some factors such as temperature, pH, oxidizer, common metal ions, reducingagent, antioxidant, light, preservative on stability of lycopene. Lycopene stability experiments show that itis sensitive to light, heat, alkali, metal ion Fe³⁺, Cu²⁺, oxidants had destructive effect on lycopene, reducingagents had hardly effect. Antioxidant and preservative had protective effect.更多还原