CN110731377B - 一种羧甲基壳聚糖基褪黑素双层自组装膜及其应用方法 - Google Patents
一种羧甲基壳聚糖基褪黑素双层自组装膜及其应用方法 Download PDFInfo
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Abstract
本发明公开了一种羧甲基壳聚糖基褪黑素双层自组装膜及其在抑制鲜切果蔬叶绿素降解的应用,属于食品保鲜技术领域,所述羧甲基壳聚糖基褪黑素双层自组装膜,包括:羧甲基壳聚糖在包埋褪黑素后形成羧甲基壳聚糖基褪黑素纳米颗粒分散液与壳聚糖乙酸溶液组成;所述羧甲基壳聚糖基褪黑素纳米颗粒分散液中羧甲基壳聚糖的负电荷与壳聚糖的正电荷通过分子间氢键和静电作用,形成羧甲基壳聚糖基褪黑素双层自组装膜。本发明制备的羧甲基壳聚糖基褪黑素双层自组装涂膜,对鲜切蔬菜具有良好的防止黄化、阻水、抑菌等性能,有效地延长了鲜切蔬菜的货架期。
Description
技术领域
本发明涉及食品保鲜技术领域,具体涉及一种羧甲基壳聚糖基褪黑素双层自组装膜以及在抑制鲜切蔬菜叶绿素降解方面的应用方法。
背景技术
褪黑素(melatonin,MLT),化学名为N-乙酰基-5-甲氧基色胺,在植物中是普遍都具有的一类天然内源吲哚胺,褪黑素参与了植物的多个发育过程,比如发芽、幼苗生长和衰老过程,同时,也主要通过中和自由基;加强酶和非酶的抗氧化能力;防止抗氧化酶的钝化;抑制自由基的产生,实现抗氧化作用,降低植物的氧化损伤。此外,褪黑素具有抑制采后乙烯合成,调控叶片中叶绿素的降解,延缓植物衰老的功能,能够有效的延长蔬菜的货架期,具有极高的开发利用价值。
壳聚糖(chitosan,CS),化学名聚(1,4)-2-氨基-2-脱氧-β-D-葡萄糖,是通过甲壳素脱乙酰基得到的天然多糖类高分子化合物,壳聚糖具有优良的广谱抗菌性、良好的成膜性,并且还有环保、易降解、无毒无污染等优点。
羧甲基壳聚糖(Carboxymethyl chitosan,CMCS),由壳聚糖改性而来,具有较好的生物降解性、抗菌性、良好的生物相容性、吸湿保湿性、延缓细胞衰老、促进皮肤伤口愈合等优点。
鲜切蔬菜是目前新兴的水果加工制品,具有新鲜、营养、方便等特点,随着国民生活水平的提高,人们对鲜切蔬菜的需求不断增大,它们的安全性越来越受到重视,鲜切蔬菜由于组织和形态被破坏极易败坏,以羧甲基壳聚糖为基质的褪黑素和壳聚糖的双层自组装涂膜,对鲜切蔬菜具有较佳的阻水、防止黄化和抑菌等性能。
公开号为CN103275358A公开了一种壳聚糖基复合保鲜膜或涂层的制备方法,属于食品保鲜技术领域,将壳聚糖溶于乙酸水溶液,然后加入含有抗氧化和抗菌功能的天然活性物质水溶液,经加热搅拌及超声波脱泡,得到壳聚糖基复合保鲜膜或涂层膜液,将壳聚糖基复合保鲜膜或涂层膜液流延干燥,得到壳聚糖基复合保鲜膜;将壳聚糖基复合保鲜膜或涂层膜液涂敷在食品表面得到壳聚糖基复合保鲜涂层。
公开号为CN108835249A公开了一种壳聚糖基芒果保鲜液的制备方法,包括以下步骤:(1)将壳聚糖溶解于乙酸的蒸馏水溶液中,溶解均匀形成壳聚糖膜液;(2)加入改性剂;(3)加入溶菌酶,再加入TBHQ与槐糖脂的混合液,得到该壳聚糖基芒果保鲜液。
发明内容
本发明提供了一种羧甲基壳聚糖基褪黑素双层自组装膜及其在抑制鲜切果蔬叶绿素降解的应用方法,所述羧甲基壳聚糖基褪黑素双层自组装涂膜对鲜切果蔬具有良好的抑菌、阻水、防止黄化等作用。
一种羧甲基壳聚糖基褪黑素双层自组装膜,包括:羧甲基壳聚糖乙醇溶液在包埋褪黑素后形成羧甲基壳聚糖基褪黑素纳米颗粒分散液,加入壳聚糖乙酸溶液后通过分子间作用力,形成羧甲基壳聚糖基褪黑素双层自组装膜。
优选的,所述羧甲基壳聚糖基褪黑素纳米颗粒分散液中,由于羧甲基壳聚糖乙醇溶液对蔬菜具有较好黏着性和保水性,所述羧甲基壳聚糖乙醇溶液的质量浓度为3-13mg/L;由于褪黑素具有抗氧化,延缓叶绿素降解,延缓衰老的作用,所述褪黑素乙醇溶液质量浓度为30-100mg/L。
优选的,壳聚糖乙酸溶液的质量浓度为6-20mg/L-1。
优选的,所述羧甲基壳聚糖基褪黑素纳米颗粒分散液与壳聚糖乙酸溶液的体积比为1:1-3。
本发明还提供了一种羧甲基壳聚糖基褪黑素双层自组装膜的应用方法,包括:
步骤1:将配制好的褪黑素乙醇溶液与羧甲基壳聚糖乙醇溶液,通过超声辅助抗溶剂沉淀法制备羧甲基壳聚糖基褪黑素纳米颗粒分散液;
步骤2:将果蔬切块处理;
步骤3:将步骤2中的果蔬切块在羧甲基壳聚糖基褪黑素纳米颗粒分散液中浸渍,晾干;
步骤4:配置壳聚糖(Chitosan,CS)乙酸溶液;
步骤5:将步骤3中处理后的果蔬切块,在壳聚糖乙酸溶液中浸渍,晾干,贮藏。
由于,所述羧甲基壳聚糖所带的亲水基团,使得羧甲基壳聚糖具有良好的生物相容性、水溶性和成膜性的作用;羧甲基壳聚糖在包埋生物大分子药物后,可以增大生物大分子药物的透膜能力,使其生物粘附性和生物降解性得到提高,促进生物体对生物大分子药物的吸收,这一特性使得羧甲基壳聚糖可作为药物载体,起到药物缓释的作用。
所述的羧甲基壳聚糖乙醇溶液在包埋褪黑素后形成羧甲基壳聚糖基褪黑素纳米颗粒分散液,先将果蔬切块浸渍其中,使得羧甲基壳聚糖与褪黑素能够够好的附着在果蔬切块的表面,并控制褪黑素的释放速率,起到缓释的作用。
由于,壳聚糖仅溶于某些酸性介质的特性,限制了其应用范围,但是壳聚糖作为天然的阳离子高分子多糖可与羧甲基壳聚糖基褪黑素纳米颗粒分散液中带有负电荷的羧甲基壳聚糖通过分子间氢键、静电作用形成生成羧甲基壳聚糖基褪黑素双层自组装膜。
优选的,为显著缩短浸渍时间,所述浸渍方式为真空脉冲浸渍,浸渍时间为15-45s。
为了使果蔬切块能够浸渍在溶液中,步骤3中,所述果蔬切块的质量与羧甲基壳聚糖褪黑素纳米颗粒分散液的质量比为1:3-5。
优选的,步骤5中,所述步骤3中处理后的蔬菜切块的质量与壳聚糖乙酸溶液的质量比为1:3-5。
优选的,步骤5中,将步骤3中经过处理的果蔬切块,置于壳聚糖乙醇溶液中浸渍后,晾干,使得羧甲基壳聚糖基褪黑素双层自组装膜能更加稳定。
本发明的有益效果是:
本发明公开的羧甲基壳聚糖基褪黑素双层自组装膜具有广谱抗菌性、延缓细胞衰老、抑制果蔬中乙烯合成,调控叶片中叶绿素的降解的功能,从而有效的延长蔬菜的货架期。
附图说明:
图1为本发明实施例1中西兰花表面的羧甲基壳聚糖基褪黑素双层自组装膜的扫描电镜结构示意图;其中,A图为经扫描电镜放大1000倍的结构示意图;B图为经扫描电镜放大10000倍的结构示意图。
具体实施方式
下面通过实施例对本发明做进一步的详细说明,其目的在于更为具体、清晰地阐述本发明的内容而非限制本发明的保护范围。
实施例1
步骤1:配制50mg/L褪黑素乙醇溶液,12.8mg/L的羧甲基壳聚糖乙醇溶液,将褪黑素乙醇溶液以1:9的体积比例加入羧甲基壳聚糖乙醇溶液中,通过自下而上反溶剂沉淀法形成羧甲基壳聚糖基褪黑素纳米颗粒分散液;
步骤2:将西兰花清洗沥干切成3cm×3cm×4cm的小块;
步骤3:将步骤2中处理好的西兰花在羧甲基壳聚糖基褪黑素纳米颗粒分散液中真空脉冲浸渍20s,晾干;
步骤4:配置19.2mg/L的壳聚糖乙酸溶液;
步骤5:将步骤3中处理过的西兰花在壳聚糖乙酸溶液中真空脉冲浸渍20s后,自然晾干,再次浸渍20s后晾干,在西兰花的表面形成羧甲基壳聚糖基褪黑素双层自组装膜,最后置于PVC餐盒中,贮藏。
以蒸馏水、实施例1配置的羧甲基壳聚糖乙醇溶液和壳聚糖乙酸溶液浸渍的西兰花切块作为对照,羧甲基壳聚糖基褪黑素双层自组装膜浸渍的西兰花块作为实验组,实验结果表明,羧甲基壳聚糖基褪黑素双层自组装膜能显著降低水分流失、减缓西兰花的软化、抑制叶绿素a,叶绿素b含量的下降(p<0.05),维持西兰花的感官品质。
如表1所示,经过蒸馏水中浸渍过的西兰花块的硬度、叶绿素a和叶绿素b下降速度最快,由于蒸馏水不具有果蔬保湿作用,所以西兰花的失重率最大为29.55%±7.48%a;由于带负电荷的羧甲基壳聚糖具有较好的亲水性,能更好的附着在西兰花块表面形成保鲜膜,所以经过羧甲基壳聚糖乙醇溶液浸渍过的西兰花块的硬度、叶绿素a和叶绿素b都有较好的保持,由于羧甲基壳聚糖所形成的保护膜具有保湿作用,经过处理的西兰花块失重率相较于蒸馏水处理后的失重率低,仅为21.43%±0.98%b;由于壳聚糖的亲水性较差,仅溶解于部分酸中,所以经过壳聚糖乙酸溶液浸渍的西兰花块的硬度、叶绿素a、叶绿素b和失重率下降比较大;经过本发明制备的羧甲基壳聚糖基褪黑素双层自组装膜的浸渍后的西兰花块,其硬度、叶绿素a、叶绿素b和失重率都是损失最少的,这说明本发明所制备的羧甲基壳聚糖基褪黑素双层自组装膜具有调控西兰花中叶绿素的降解的功能,有效延长了西兰花的货架期。
表1西兰花涂膜保鲜第2天的品质指标
组别 | 硬度/g | 叶绿素a/mg·L<sup>-1</sup> | 叶绿素b/mg·L<sup>-1</sup> | 失重率% |
对照 | 67.43±12.48<sup>c</sup> | 2.93±0.13<sup>c</sup> | 2.54±0.23<sup>c</sup> | 29.55%±7.48%<sup>a</sup> |
羧甲基壳聚糖 | 309.72±19.76<sup>b</sup> | 3.46±0.21<sup>b</sup> | 2.98±0.54<sup>b</sup> | 21.43%±0.98%<sup>b</sup> |
壳聚糖 | 342.83±35.36<sup>b</sup> | 4.01±011<sup>b</sup> | 3.02±0.49<sup>b</sup> | 23.79%±2.65%<sup>ab</sup> |
双层自组装膜 | 410.27±26.26<sup>a</sup> | 5.45±0.12<sup>c</sup> | 4.72±0.84<sup>a</sup> | 20.22%±1.32%<sup>b</sup> |
注:不同字母代表显著性差异,p<0.05;表格中的双层自组装膜即为本发明所制备的羧甲基壳聚糖基褪黑素双层自组装膜。
如图1所示,A图为本实施例中西兰花表面的羧甲基壳聚糖基褪黑素双层自组装膜在扫描电镜放大1000倍的结构示意图;B图为放大10000的结构示意图,从图中可以看出,羧甲基壳聚糖在包埋褪黑素后与壳聚糖乙酸溶液后通过分子间作用力,形成羧甲基壳聚糖基褪黑素双层自组装膜,两层膜的分层现象并不明显,并且两者之间存在紧密的相互作用,从而形成复杂的网状结构。
实施例2
步骤1:配制100mg/L褪黑素乙醇溶液、9.6mg/L的羧甲基壳聚糖乙醇溶液,将褪黑素乙醇溶液以1∶5的体积比加入羧甲基壳聚糖膜溶液中,通过自下而上反溶剂沉淀法形成羧甲基壳聚糖基褪黑素(CMCS-MLT)纳米颗粒分散液;
步骤2:将黄瓜清洗沥干后,切成3cm×3cm×4cm左右小块;
步骤3:将处理好的黄瓜在CMCS-MLT纳米颗粒分散液中真空脉冲浸渍30s,晾干;
步骤:4:配置12.8mg/L的壳聚糖乙酸溶液;
步骤5:将步骤3中处理好的黄瓜在壳聚糖乙酸溶液中真空脉冲浸渍30s后,自然晾干,再次浸渍30s后晾干,最后置于PVC餐盒中,贮藏。
以蒸馏水、实施例1配置的羧甲基壳聚糖乙醇溶液和壳聚糖乙酸溶液浸渍的西兰花切块作为对照,羧甲基壳聚糖基褪黑素双层自组装膜浸渍的黄瓜切块作为实验组,实验结果表明,羧甲基壳聚糖基褪黑素双层自组装膜能显著降低水分流失、减缓黄瓜的软化、维持糖酸比和叶绿素a,叶绿素b含量(p<0.05)维持黄瓜的感官品质。
如表2所示,经过蒸馏水浸渍后的黄瓜切块失重率高,黄瓜软化明显,其截面果实与截面髓心的硬度变化较大,糖酸比作为评价果蔬新鲜程度的重要指标,其数值越大表示果实越新鲜,其中经过蒸馏水浸渍的黄瓜切块酸糖比下明显,叶绿素a与叶绿素b的含量下降明显;由于羧甲基壳聚糖具有较好的亲水性,能在黄瓜切块的表面形成保鲜膜,相较于亲水性差的壳聚糖,经过羧甲基壳聚糖浸渍过的黄瓜切块的失重率较小,黄瓜截面果实与截面髓心的硬度变化小,酸糖比,叶绿素a与叶绿素b的含量变化不明显;经过本发明制备的羧甲基壳聚糖基褪黑素双层自组装膜的浸渍后的黄瓜切块,其硬度、叶绿素a、叶绿素b和失重率都是损失最少的,这说明本发明所制备的羧甲基壳聚糖基褪黑素双层自组装膜具有调控黄瓜中叶绿素的降解的功能,降低了黄瓜的失重率,防止软化,有效延长了西兰花的货架期。
表2黄瓜涂膜保鲜第3天的品质指标
注:不同字母代表显著性差异,p<0.05;表格中的双层自组装膜即为本发明所制备的羧甲基壳聚糖基褪黑素双层自组装膜。
Claims (8)
1.一种羧甲基壳聚糖基褪黑素双层自组装膜,其特征在于,包括:羧甲基壳聚糖乙醇溶液与褪黑素乙醇溶液形成羧甲基壳聚糖基褪黑素纳米颗粒分散液,加入壳聚糖乙酸溶液,通过分子间作用力,形成羧甲基壳聚糖基褪黑素双层自组装膜。
2.根据权利要求1所述的羧甲基壳聚糖基褪黑素双层自组装膜,其特征在于,所述羧甲基壳聚糖基褪黑素纳米颗粒分散液中,褪黑素乙醇溶液的质量浓度为30-100 mg/L;羧甲基壳聚糖乙醇溶液的质量浓度为3-13 mg/L。
3.根据权利要求1所述的羧甲基壳聚糖基褪黑素双层自组装膜,其特征在于,所述壳聚糖乙酸溶液的质量浓度6-20 mg/L。
4.根据权利要求3所述的羧甲基壳聚糖基褪黑素双层自组装膜,其特征在于,所述羧甲基壳聚糖基褪黑素纳米颗粒分散液与壳聚糖乙醇溶液的体积比为1:1-3。
5.一种根据权利要求1-4任一项所述的羧甲基壳聚糖基褪黑素双层自组装膜的应用方法,其特征在于,包括:
步骤1:将配制好的褪黑素乙醇溶液与羧甲基壳聚糖乙醇溶液,通过超声辅助抗溶剂沉淀法,制备羧甲基壳聚糖基褪黑素纳米颗粒分散液;
步骤2:将果蔬切块处理;
步骤3:将步骤2中的果蔬切块在羧甲基壳聚糖基褪黑素纳米颗粒分散液中浸渍,晾干;
步骤4:配置壳聚糖乙酸溶液;
步骤5:将步骤3中处理后的果蔬切块,在壳聚糖乙酸溶液中浸渍,晾干,贮藏。
6.根据权利要求5所述的羧甲基壳聚糖基褪黑素双层自组装膜的应用方法,其特征在于,所述浸渍方式为真空脉冲浸渍;所述浸渍时间为15-45s。
7.根据权利要求5所述的羧甲基壳聚糖基褪黑素双层自组装膜的应用方法,其特征在于,步骤3中,所述果蔬切块的质量与羧甲基壳聚糖褪黑素纳米颗粒分散液的质量比为1:3-5。
8.根据权利要求5所述的羧甲基壳聚糖基褪黑素双层自组装膜的应用方法,其特征在于,步骤5中,所述步骤3中处理后的果蔬切块的质量与壳聚糖乙酸溶液的质量比为1:3-5。
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