CN104356380B - ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物及其制备方法与应用 - Google Patents
ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物及其制备方法与应用。该酰胺复合物具有式(I)所示结构,通过ε-多聚赖氨酸和维生素E琥珀酸酯在N,Nˊ-二异丙基碳二亚胺的催化下,发生亲核取代反应后获得。该酰胺复合物既具有较高的抑菌能力,还具有乳化性,解决了现有技术中ε-多聚赖氨酸脂溶性差的问题。
Description
技术领域
本发明涉及生物食品技术领域,具体涉及一种ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物及其制备方法与应用。
背景技术
ε-聚赖氨酸(ε-polylysine,ε-PL)最早由日本学者Shima等人于白色链霉菌培养液中发现。因其良好的水溶性、广谱的抑菌性和在体内可降解为易吸收的赖氨酸等特性而作为天然防腐剂,并于2003年10月被FDA批准为安全食品保鲜剂。
ε-PL为淡黄色粉末,吸湿性强,略有苦味。ε-PL是赖氨酸的直链状聚合物,不受pH值变化的影响,对热稳定(120℃,20min),与盐酸、柠檬酸、苹果酸、甘氨酸和高级脂肪酸甘油酯等合用后,具有增效作用。ε-PL是目前天然防腐剂中具有优良防腐性能和巨大商业潜力的微生物类食品防腐剂。
ε-PL由25~30个赖氨酸聚合而成,其结构式为:其中,分子量在3600~4300之间的ε-PL抑菌活性最好,当分子量低于1300时,ε-PL失去抑菌活性。ε-PL的抑菌谱广,在酸性和微酸性环境中对革兰氏阳性菌、革兰氏阴性菌、酵母菌、霉菌均有较好的抑菌效果。与此同时,ε-PL对其他天然防腐剂不易抑制的革兰氏阴性大肠杆菌、沙门氏菌等抑菌效果也非常好,而且其对耐热性芽孢杆菌和一些病毒也有一定的抑制作用。由于ε-PL为亲水性物质,不能很好地溶解在脂质较多的食品中,所以在食品保鲜方面的应用受到较大局限。
d-α-生育酚琥珀酸酯,又称为维生素E琥珀酸酯(TOS),是改性过的生育酚,分子式C33H54O5,分子量为530.76,不溶于水,溶于丙酮、乙醇、乙醚和植物油,极易溶于氯仿,在乙醇中的最大紫外吸收波长为285nm。TOS不仅具有羧酸和生育酚的生理和药理作用,而且由于在保留其高度生物活性的同时酚羟基被保护起来,使得其稳定性大大提高,从而给生育酚制备的储存、运输等带来了极大的方便。TOS在人体内经消化生成维生素E,是人体一个很好的天然维生素E来源。
目前,为扩大多聚赖氨酸在食品保鲜方面的应用范围,强化多聚赖氨酸的性能,已有大量关于改性多聚赖氨酸的相关研究报道:
(1)中国专利申请CN101348813A公开了具有抑菌性能的纤维素管道的制备方法。该方法将细菌纤维素管放入ε-PL溶液中复合制备,浸泡1~6h后,取出,洗涤,干燥,即得具有抑菌性能的细菌纤维素管。但是该专利在食品保鲜方面应用范围较窄,不能作为食品保鲜剂置于食品当中,只能作为肉制品的肠衣,并且分解后的细菌纤维素管道毒性有无尚不明确。
(2)中国专利申请CN102492162A公开了一种ε-多聚赖氨酸聚乙烯醇复合生物抗菌薄膜及其制备方法。该方法以甘油和乙二醇中的一种或两种为复配增塑剂,采用熔融共混法制备了ε-多聚赖氨酸聚乙烯醇复合高分子聚合膜,ε-PL的加入使薄膜具有了很好的抑菌活性,可作为包装材料使用。但是ε-多聚赖氨酸聚乙烯醇复合物亲水,在脂溶性物质中的应用受到限制,较难添加到亲脂性物质中。
(3)中国专利申请CN102585303A公开了一种壳聚糖/聚赖氨酸原位凝胶及其制备方法。该凝胶是由巯基化壳聚糖溶液和马来酰亚胺化聚赖氨酸溶液按一定比例混合通过原位交联反应得到。该专利中壳聚糖/聚赖氨酸原位凝胶的抑菌效果受温度、pH影响较大,相对不稳定,所以不能添加到过热或过酸的食品中。
虽然上述专利申请在不同程度上对ε-多聚赖氨酸进行了改进,但ε-多聚赖氨酸在脂溶性上的缺陷仍未得到改善,造成其在食品保鲜方面的应用受到较大局限。
发明内容
本发明提供了一种ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物及其制备方法与应用,该酰胺复合物既具有较高的抑菌能力,还具有乳化性,解决了现有技术中ε-多聚赖氨酸脂溶性差的问题。
一种ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物,结构式如式(I)所示:
n=25~30,3≤x≤16。
上述ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物中n与x的值与酰胺复合物的乳化性和抑菌性的关系如下:x的个数越少时(即ε-PL取代度越低时),ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物越表现为亲水性,这时乳化能力较差,当3≤x≤16,ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物的乳化能力较好。ε-聚赖氨酸至少需要有9个赖氨酸残基才具有抗菌性。当x>16时,ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物抑菌活性将丧失。
作为优选,3≤x≤16。该酰胺复合物具有最佳的乳化性和抑菌效果。
所述酰胺复合物的制备方法,包括以下步骤:在催化剂作用下,ε-多聚赖氨酸与维生素E琥珀酸酯发生亲核取代反应,制得所述酰胺复合物。
所述亲核取代反应在无水、无氧的条件下进行,需通入惰性气体,以二甲基甲酰胺为有机溶剂,所述二甲基甲酰胺为经过干燥处理的二甲基甲酰胺,所用的惰性气体不参与合成反应,且对合成反应无影响,通常使用氮气。
所述的催化剂为N,N’-二异丙基碳二亚胺。
所述的亲核取代反应的优选温度为35~40℃,优选时间为18~20小时。温度太低,反应速率较小,温度太高,易有其他副产物生成。优选时间为18~20小时,通过薄层色谱追踪反应进程,在时间为18~20小时,反应最完全。
ε-多聚赖氨酸与维生素E琥珀酸酯的质量比为1:0.7~1.8。ε-多聚赖氨酸与维生素E琥珀酸酯采用上述质量比进行反应,可获得添加量为10~100ppm的酰胺复合物,该酰胺复合物的乳化性和抑菌性更佳,从而实现了ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物在乳化性和抑菌性上的显著提高。
具体的反应方程式如下所示:
所述亲核取代反应过程中,可采用硅胶薄板层析进行反应进程的监控。
亲核取代反应结束后,需经过后处理对产物进行纯化,包括:层析分离、透析提纯、减压旋蒸、冷冻干燥,得到所述的酰胺复合物。上述过程均为本领域常用的技术手段。
本发明中,所述的层析分离采用层析硅胶柱,其中,采用200~300目的硅胶,并且在分离过程中,依次用30~60℃的石油醚、丙酮:甲醇=1:6、甲醇作为洗脱液,洗脱亲核取代反应后得到的反应液。本发明中,将甲醇洗脱液置于1000Da透析袋中用无水乙醇进行透析提纯,可显著提高酰胺复合物的收率。
本发明所述的酰胺复合物可直接作为食品保鲜剂进行使用,也可作为食品保鲜组合物中的一种组成原料。
本发明还公开了一种用于食品保鲜的组合物,该组合物包含所述的酰胺复合物。
将所述酰胺复合物加入上述食品保鲜组合物中,可显著提高食品保鲜剂的抑菌性,且能够将该食品保鲜组合物应用于含脂质较多的各类食品中。
作为优选,所述的组合物中,酰胺复合物的添加量为10~100ppm。
本发明与现有技术相比,具有以下有益效果:
(1)本发明通过ε-多聚赖氨酸和维生素E琥珀酸酯进行亲核取代反应制备酰胺复合物,克服了现有ε-多聚赖氨酸作为食品保鲜剂亲脂能力差的缺陷,获得了兼具乳化性和抑菌性的酰胺复合物,可作为新型食品保鲜剂,扩展了ε-多聚赖氨酸在食品保鲜领域的应用范围;
(2)与现有技术中食品保鲜剂制备方法相比,本发明制备方法反应条件温和,易控制,操作简单,可使反应随时发生,随时停止,简化了保鲜剂的制备工艺,易于推广。
(3)本发明制备得到的酰胺复合物保留了ε-多聚赖氨酸原有的抑菌谱广、抑菌效果好的特点,并且该酰胺复合物水解后可生成具有一定抗氧化能力的天然维生素E,可以防止食品中营养成分被溶解氧化,起到减缓产品氧化的作用,也可供人体吸收,提高食品的营养性。
附图说明
图1为TOS和ε-PL的物理混合物与ε-PL-TOS酰胺复合物的乳液粒径的比较;
图2为ε-多聚赖氨酸的核磁共振图谱;
图3为实施例1制得的ε-PL-TOS酰胺复合物的核磁共振图谱;
图4为实施例2制得的ε-PL-TOS酰胺复合物的核磁共振图谱;
图5为实施例3制得的ε-PL-TOS酰胺复合物的核磁共振图谱。
具体实施方式
下面以具体实施例来对本发明的技术方案做进一步说明,但本发明的保护范围不限于此。
实施例1
两颈圆底烧瓶中,通氮气,加入2.862gε-多聚赖氨酸(ε-PL),3.600g生育酚琥珀酸酯(TOS),10mL无水二甲基甲酰胺(DMF),46.5uL催化剂N,N’-二异丙基碳二亚胺(DIC),搅拌,40℃反应18h,待反应完成后,经过层析分离、透析提纯、减压旋蒸、冷冻干燥,得到ε-PL-TOS酰胺复合物。
实施例2
两颈圆底烧瓶中,通氮气,加入1.208gε-多聚赖氨酸(ε-PL),0.955g生育酚琥珀酸酯(TOS),5mL无水二甲基甲酰胺(DMF),22.5uL催化剂N,N’-二异丙基碳二亚胺(DIC),搅拌,40℃反应20h,待反应完成后,经过层析分离、透析提纯、减压旋蒸、冷冻干燥,得到ε-PL-TOS酰胺复合物。
实施例3
两颈圆底烧瓶中,通氮气,加入2.035gε-多聚赖氨酸(ε-PL),2.275g生育酚琥珀酸酯(TOS),7.5mL无水二甲基甲酰胺(DMF),34.5uL催化剂N,N’-二异丙基碳二亚胺(DIC),搅拌,35℃反应20h,待反应完成后,经过层析分离、透析提纯、减压旋蒸、冷冻干燥,得到ε-PL-TOS酰胺复合物。
实施例4
将500g新鲜猪里脊肉切割成2立方厘米左右的肉丁,放入沸水中煮熟,捞出后浸入500mLε-PL-TOS酰胺复合物溶液(体积比1:10)中5min,再将肉沥干后按50g/袋分别放入保鲜袋中保藏。通过测定菌落总数并结合感官评价衡量保藏效果。结果表明:在4℃下,贮藏11天后,熟里脊肉的菌落总数没有超过国家标准,且无明显异味产生。
实施例5
一、实施例2的抑菌效果实验
采用最小抑菌质量浓度法测定ε-PL-TOS酰胺复合物的抑菌性。将斜面活化菌种,细菌(大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌)在MHB培养基中培养24h,真菌(酵母菌、黑曲霉)在马铃薯葡萄糖肉汤培养基中培养48h,并采用MH(A)(细菌固体培养基)和PDA(真菌固体培养基)的平板计数法得到菌悬液活菌数。将ε-PL-TOS酰胺复合物分别溶于MHB培养基和马铃薯葡萄糖肉汤培养基中,配制成50、40、30、20、10、8、6、4、2μg/mL质量浓度梯度的溶液,并分别向其中接入相应体积的细菌及真菌菌悬液,使菌体浓度达到5×105CFU/mL。细菌在37℃下培养24h,真菌在28℃下培养48h。以培养0h的培养液做阳性对照,于590nm波长处测定其吸光度与空白相同则说明菌体被抑制,其中最小的ε-PL-TOS酰胺复合物质量浓度,即为ε-PL-TOS酰胺复合物最小抑菌质量浓度(MIC),并用同样的方法测定ε-PL的MIC,作为对照。实验重复3次,结果如附表1所示。
表1ε-PL-TOS酰胺复合物的MIC测定结果
二、实施例2的ε-PL-TOS酰胺复合物HLB的测定
采用乳化法测定ε-PL-TOS酰胺复合物的HLB值。乳化法的原理是用表面活性剂来乳化油相介质时,当表面活性剂的HLB值与油相介质所需的HLB值相同时,生成的乳液稳定性最好。使用松节油(所需HLB值为16)和棉籽油(所需HLB值为6)配制一系列需要不同HLB值的油相,每15份油相中加入5份待测ε-PL-TOS酰胺复合物,然后加入80份水,搅拌乳化,其中稳定性最好的试样中油相所需的HLB值就是ε-PL-TOS酰胺复合物表的HLB值。该ε-PL-TOS酰胺复合物的HLB值为11。
三、实施例2的ε-PL-TOS酰胺复合物乳化性的测定
将反应好的ε-PL-TOS酰胺复合物溶于pH7的磷酸缓冲液中,制备成0.6g/100mL的溶液。将溶解好的溶液在高速乳化均质机的搅拌下缓慢加入1.2g油,12000r/min剪切8min,形成粗乳液。粗乳液通过高压均质机进一步均质,采用两级均质阀高压均质机(二级均质压力与总压力的比值为1:10)总压力50MPa,均质温度55℃,循环3次。取均质后的乳液用去离子水稀释1000倍。再将稀释后的溶液放入ZetasizerNano-ZS90激光粒度仪室温条件下进行粒径的测定。以TOS和ε-PL的物理混合物作为参比对照。实验重复3次。
由图1可知,ε-PL-TOS酰胺复合物所得乳液粒径为482nm,TOS和ε-PL的混合物乳液粒径为1620nm。由Stokes公式(式(1))可得,在两相密度和体系黏度确定的情况下,乳液粒径越小,沉降速率越小,乳液越稳定。同时,乳液粒径越小还说明乳化剂的乳化能力越强,即酰胺复合物可更好的乳化油相,使得液滴间不容易碰撞相聚而使乳液粒径增大,因此酰胺复合物乳化性越好。
式中:V为沉降速率/(m/s);R为液滴半径/m;Δp为两相密度差/(kg/m3);g为重力加速度/(m/s2);η为体系黏度/(Pa·s)。
由此可知,通过亲核取代反应后乳液粒径为482nm,ε-PL-TOS酰胺复合物的乳化性逐步提高并远大于TOS和ε-PL的物理混合物的乳化性。这说明,ε-PL和TOS的亲核取代反应很好的改善了ε-PL的乳化性。
Claims (8)
1.一种ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物,其特征在于,结构如式(I)所示:
n=25~30,3≤x≤16。
2.如权利要求1所述ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物的制备方法,包括以下步骤:在催化剂作用下,ε-多聚赖氨酸与维生素E琥珀酸酯发生亲核取代反应,制得所述ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物。
3.如权利要求2所述的制备方法,其特征在于,所述的催化剂为N,N'-二异丙基碳二亚胺。
4.如权利要求2所述的制备方法,其特征在于,ε-多聚赖氨酸与维生素E琥珀酸酯的质量比为1:0.7~1.8。
5.如权利要求2所述的制备方法,其特征在于,反应的温度为35~40℃,时间为18~20小时。
6.如权利要求1所述的ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物作为食品保鲜剂的用途。
7.用于食品保鲜的组合物,其特征在于,包含权利要求1所述的ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物。
8.如权利要求7所述的组合物,其特征在于,所述ε-聚赖氨酸-维生素E琥珀酸酯酰胺复合物的添加量为10~100ppm。
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