CN111825863A - 一种二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜及其制备方法 - Google Patents

一种二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜及其制备方法 Download PDF

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CN111825863A
CN111825863A CN201910312618.4A CN201910312618A CN111825863A CN 111825863 A CN111825863 A CN 111825863A CN 201910312618 A CN201910312618 A CN 201910312618A CN 111825863 A CN111825863 A CN 111825863A
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李德富
邓磊
葛黎明
杨蝶
易丽
赵喜
穆畅道
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Abstract

本发明提供一种二硫键交联的明胶/ε‑聚赖氨酸活性食品包装膜及其制备方法。本发明首先将巯基化合物化学共价接枝于明胶分子链骨架上制备得到巯基化改性明胶,然后向巯基化改性明胶溶液中加入ε‑聚赖氨酸,将上述溶液均匀混合后倒入模具,于室温下干燥以制备二硫键交联的明胶/ε‑聚赖氨酸活性食品包装膜。本发明通过接枝的巯基在空气中氧化形成二硫键和添加抗菌多肽ε‑聚赖氨酸的方法,制备得到的明胶基活性食品包装膜具有较高机械强度、良好紫外线阻隔能力、可生物降解、较强的抗菌性能和有效的抗氧化性能。因此,本发明提供的二硫键交联的明胶/ε‑聚赖氨酸活性食品包装膜在食品包装材料领域具有广阔的应用前景。

Description

一种二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜及其制 备方法
技术领域
本发明涉及食品包装材料技术领域,具体而言涉及一种具有广谱抗菌性、抗氧化性、较高机械强度、较强耐水性能、良好紫外线阻隔能力和可生物降解的可食性活性食品包装膜及其制备方法。
背景技术
基于石油为原料制备的合成高分子塑料包装材料,由于其具有机械强度高和使用便捷等特性,在人们的日常生活中得到了广泛应用。但是,由于合成高分子塑料一次性使用和不可环境降解等特点,其大量使用造成了日趋严重的环境污染。截止2015年,全球共产生63亿吨的塑料垃圾,到2050年,预计将达到1.2万亿吨。而且,全球能源危机也为合成塑料的发展敲响了警钟。此外,微生物、自由基和紫外线等是引起食品腐败变质的主要元凶。因此,通过抑制或杀灭微生物、清除自由基和阻隔紫外线等方法可以有效延长食品的保存时间和保持食品的质量。基于此,以广泛来源于动物和植物的多糖和蛋白质等天然高分子为原材料,通过引入抗菌和抗氧化等活性质制备具有可生物降解、良好紫外线阻隔能力、广谱抗菌和有效抗氧化性能的活性食品包装材料在食品包装材料领域具有广阔的应用前景。
明胶(Gelatin)是广泛来源于哺乳动物跟腱、皮肤和软骨等组织的胶原经热变性或物理/化学降解后的产物,其三股螺旋结构几乎完全被破坏,由单条链或多链组成的多肽聚合物。明胶具有原材料来源广泛、安全可食、较高的阻气和阻油性、可生物降解性和良好的成膜性等特点,在可食性食品包装材料领域具有显著的应用优势。但是,明胶基材料较低的机械强度、较差的耐水性和易被微生物污染等缺陷需要通过化学交联改性和添加抗菌剂等方法加以克服。二硫键(S-S)是比较稳定的共价键,在蛋白质分子中起着稳定肽链空间结构的作用。蛋白质分子中二硫键含量越多,其抵抗外界因素影响的稳定性就越强。通过将巯基化学共价接枝于明胶分子链上,利用巯基氧化形成二硫键的方法可以实现明胶分子的化学交联。该方法能够有效提高明胶基材料的机械强度、耐水性能和紫外线阻隔性能等,而且可以避免因引入甲醛和戊二醛等醛类交联剂所引起的细胞毒性和钙化作用。此外,巯基化改性明胶中未被完全交联的巯基能够有效清除自由基,表现出较强的抗氧化性能。纯明胶膜不具备抑制和杀灭微生物的能力,因此需要通过添加抗菌剂的方法以赋予明胶基材料良好的抗菌性能。ε-聚赖氨酸是由25~35个赖氨酸残基形成聚阳离子多肽,相对分子质量为4000左右。ε-聚赖氨酸具有高水溶性、高热稳定性和高安全性,对革兰氏阳性菌、革兰氏阴性菌、酵母菌和霉菌等均具有高效广谱抗菌活性。2003年,ε-聚赖氨酸被美国食品药品监督管理局(FDA)认定为安全的食品添加剂,其被广泛用作为抗菌食品添加剂。
基于此,本发明通过将巯基化合物共价接枝于明胶分子链骨架上,然后引入ε-聚赖氨酸,利用巯基在空气中氧化形成二硫键的方法实现明胶分子的共价交联,制备得到具有较高机械强度、较强耐水性能、良好紫外线阻隔能力、可生物降解、广谱抗菌和有效抗氧化性能的明胶/ε-聚赖氨酸活性食品包装膜。
发明内容
本发明提供了一种二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜及其制备方法。本发明首先在催化剂的作用下将巯基化合物共价接枝于明胶分子链骨架上制备得到巯基化改性明胶,然后将ε-聚赖氨酸加入到巯基化改性明胶溶液中,于室温下干燥制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜,其具体制备方法如下:
(1) 将1质量份明胶溶解于50体积份去离子水中,然后加入0.2~0.5质量份的1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.1~0.4质量份的N-羟基琥珀酰亚胺,搅拌30 min,之后向混合溶液中加入0.1~1质量份巯基化合物,将上述混合溶液的pH调为3~7后于氮气保护和避光条件下反应4~24 h,之后将混合溶液透析2~4天,冷冻干燥以制备得到巯基化改性明胶;
(2) 将1质量份巯基化改性明胶溶解于25体积份去离子水中,然后加入0.02~0.4质量份的ε-聚赖氨酸,搅拌2~8 h后,加入0.2~0.4质量份增塑剂,搅拌20~40 min,最后将混合溶液倒入模具中,于室温下鼓风干燥48~72 h,即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。
上述制备方法中,所述巯基化合物为L-半胱氨酸、L-半胱氨酸盐酸盐一水合物、L-半胱氨酸甲酯盐酸盐、L-半胱氨酸乙酯盐酸盐、D-半胱氨酸盐酸盐一水物和DL-半胱氨酸中的任意一种或几种混合物。
上述制备方法中,所述增塑剂为甘油、山梨醇、木糖醇、果糖和甘露糖醇中的任意一种或几种混合物。
本发明与已有的食品包材料相比,具有如下优点:
(1) 本发明通过将巯基化合物共价接枝于明胶分子链骨架上,利用巯基氧化形成二硫键的方法实现明胶分子的化学共价交联,其不仅有效避免了因引入甲醛和戊二醛等交联剂所带来的毒性问题,而且可以显著提高明胶基膜的机械强度、耐水性能和紫外线阻隔能力等;
(2) 巯基化改性明胶分子中未被交联的巯基能够有效清除自由基,因此以巯基化改性明胶为原材料制备的明胶基活性食品包装膜具有较强的抗氧化性能,无需额外添加抗氧化试剂;
(3) 聚阳离子多肽ε-聚赖氨酸具有高效且广谱的抗菌性,安全无毒害,允许食品添加,以ε-聚赖氨酸为抗菌剂制备的明胶基可食性活性食品包装膜能够有效延长食品的货架寿命并保持食品的质量;
(4) 本发明的操作简单易行,工艺条件易于控制,制备明胶/ε-聚赖氨酸活性食品包装膜具有透明度高、可环境降解和可食性等特点,其不仅能够节约化石资源,而且可以部分缓解因大量使用几乎不可环境降解的合成塑料而引起的环境污染和土壤退化等生态问题。
具体实施方式
下面给出本发明的4个实施例,通过实施例对本发明进行具体描述。有必要指出的是,实施例只用于对本发明做进一步的说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可根据本发明的内容做出一些非本质的改进和调整。
实施例1
将1质量份明胶溶于50体积份去离子水中,加入0.5质量份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.4质量份N-羟基琥珀酰亚胺,搅拌30 min后加入0.3质量份L-半胱氨酸,将混合溶液的pH值调为4后在氮气保护和避光下反应5 h,之后将混合溶液透析4天,冷冻干燥后得到巯基化改性明胶;将1质量份巯基化改性明胶溶解于25体积份去离子水中,加入0.2质量份ε-聚赖氨酸,将混合溶液搅拌4 h后加入0.2质量份甘油,继续搅拌20 min,最后将混合液倒入模具中于室温下鼓风干燥48 h即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。
实施例2
将1质量份明胶溶于50体积份去离子水中,加入0.4质量份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.1质量份N-羟基琥珀酰亚胺,搅拌30 min后加入0.8质量份L-半胱氨酸盐酸盐一水合物,将混合溶液的pH值调为6后在氮气保护和避光下反应5 h,之后将混合溶液透析3天,冷冻干燥后得到巯基化改性明胶;将1质量份巯基化改性明胶溶解于25体积份去离子水中,加入0.1质量份ε-聚赖氨酸,将混合溶液搅拌4 h后加入0.2质量份山梨醇,继续搅拌35 min,最后将混合液倒入模具中于室温下鼓风干燥54 h即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。
实施例3
将1质量份明胶溶于50体积份去离子水中,加入0.4质量份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.3质量份N-羟基琥珀酰亚胺,搅拌30 min后加入0.75质量份D-半胱氨酸盐酸盐一水合物,将混合溶液的pH值调为5后在氮气保护和避光下反应18 h,之后将混合溶液透析3天,冷冻干燥后得到巯基化改性明胶;将1质量份巯基化改性明胶溶解于25体积份去离子水中,加入0.04质量份ε-聚赖氨酸,将混合溶液搅拌4 h后加入0.3质量份木糖醇,继续搅拌25 min,最后将混合液倒入模具中于室温下鼓风干燥40 h即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。
实施例4
将1质量份明胶溶于50体积份去离子水中,加入0.4质量份1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.4质量份N-羟基琥珀酰亚胺,搅拌30 min后加入0.6质量份DL-半胱氨酸,将混合溶液的pH值调为4后在氮气保护和避光下反应15 h,之后将混合溶液透析3天,冷冻干燥后得到巯基化改性明胶;将1质量份巯基化改性明胶溶解于25体积份去离子水中,加入0.1质量份ε-聚赖氨酸,将混合溶液搅拌4 h后加入0.4质量份果糖,继续搅拌40 min,最后将混合液倒入模具中于室温下鼓风干燥40 h即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。

Claims (3)

1.一种二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜,其特征在于首先将巯基化合物共价接枝于明胶分子链骨架上制备得到巯基化改性明胶,然后将ε-聚赖氨酸加入到巯基化改性明胶溶液中,于室温下干燥以制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜,其具体制备方法如下:
(1) 将1质量份明胶溶解于50体积份去离子水中,然后加入0.2~0.5质量份的1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和0.1~0.4质量份的N-羟基琥珀酰亚胺,搅拌30 min,之后向混合溶液中加入0.1~1质量份巯基化合物,将上述混合溶液的pH值调为3~7后于氮气保护和避光条件下反应4~24 h,之后将混合溶液透析2~4天,冷冻干燥以制备得到巯基化改性明胶;
(2) 将1质量份巯基化改性明胶溶解于25体积份去离子水中,然后加入0.02~0.4质量份的ε-聚赖氨酸,搅拌2~8 h后加入0.2~0.4质量份增塑剂,搅拌20~40 min,最后将混合溶液倒入模具中于室温下鼓风干燥48~72 h,即制备得到二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜。
2.根据权利要求1所述的二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜,其特征在于步骤(1)中所述巯基化合物为L-半胱氨酸、L-半胱氨酸盐酸盐一水合物、L-半胱氨酸甲酯盐酸盐、L-半胱氨酸乙酯盐酸盐、D-半胱氨酸盐酸盐一水物和DL-半胱氨酸中的任意一种或几种混合物。
3.根据权利要求1所述的二硫键交联的明胶/ε-聚赖氨酸活性食品包装膜,其特征在于步骤(2)中所述增塑剂为甘油、山梨醇、木糖醇、果糖和甘露糖醇中的任意一种或几种混合物。
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CN107540849A (zh) * 2017-09-11 2018-01-05 常州百瑞吉生物医药有限公司 明胶化学改性方法及其交联材料和用途
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705270A (en) * 1991-10-29 1998-01-06 Vivorx, Inc. Microcapsules prepared from crosslinkable polysaccharides, polycations and/or lipids and use therefor
US20140288190A1 (en) * 2011-09-07 2014-09-25 Prolynx Llc Hydrogels with biodegradable crosslinking
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