CN116218236A - 一种基于绿原酸纳米颗粒的功能性食品包装膜 - Google Patents
一种基于绿原酸纳米颗粒的功能性食品包装膜 Download PDFInfo
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Abstract
本发明属于食品包装技术领域,具体涉及一种基于绿原酸纳米颗粒的功能性食品包装膜。所公开的包装膜的制备原料包括明胶、普鲁兰多糖、甘油和绿原酸纳米颗粒;所述绿原酸纳米颗粒的制备方法包括:制备绿原酸、鼠李糖脂和壳聚糖混合溶液,之后向混合溶液中加入或滴入三聚磷酸钠溶液进行离子交联反应;反应物经冷冻干燥得绿原酸纳米颗粒。本发明制备的添加绿原酸纳米颗粒的薄膜显示出理想的抗菌活性和抗氧化能力,可以有效延长食品的保质期。
Description
技术领域
本发明属于食品包装技术领域,涉及一种基于绿原酸纳米颗粒的功能性食品包装膜。
背景技术
长期以来,环境可降解的包装材料一直是众多科学家关注的焦点。世界正面临着日益严重的塑料污染问题,目前,塑料的广泛使用已导致了小型塑料碎片在生活环境和食物链中的积累,对人类的健康造成了威胁。因此,急需开发绿色环保的包装材料。世界卫生组织(WHO)表示,当食物被细菌、病毒、化学品或寄生虫污染时就会被丢弃,这些污染物还可能会诱发200多种疾病,所以,在从农场到餐桌的整个供应链中,确保食品安全和尽量减少食品损失也是至关重要的。天然可降解的活性包装材料就为解决这些问题提供了一个可行的方案。
绿原酸是植物在有氧呼吸过程中经莽草酸途径形成的苯丙素类化合物,具有抗菌、清除自由基等生理功能。绿原酸因其良好的生物活性被广泛应用于食品领域。但含有绿原酸的食品包装膜抗菌性和抗氧化性效果不够理想。
发明内容
针对现有技术的缺陷或不足,本发明提供了一种基于绿原酸纳米颗粒的功能性食品包装膜。
为此,本发明所提供的包装膜的制备原料包括明胶、普鲁兰多糖、甘油和绿原酸纳米颗粒;所述绿原酸纳米颗粒的制备方法包括:制备绿原酸、鼠李糖脂和壳聚糖混合溶液,之后向混合溶液中加入或滴入三聚磷酸钠溶液进行离子交联反应;反应物经冷冻干燥得绿原酸纳米颗粒。
可选的方案中,所述明胶、普鲁兰多糖、甘油和绿原酸纳米颗粒的质量配比范围为:30:10:(8-10):(1-2)。
可选的方案中,所述绿原酸、鼠李糖脂、壳聚糖、三聚磷酸钠的质量配比范围是:(1-2):1:1:(0.25-0.33)。
可选的方案中,所述制备绿原酸、鼠李糖脂和壳聚糖混合溶液包括:将绿原酸溶解于鼠李糖脂水溶液中的第一混合液,之后将第一混合液滴入到壳聚糖乙酸溶液中。
可选的方案中,制备过程中的溶液均经0.4-0.5μm膜过滤器过滤。
本发明同时提供了上述食品包装膜的制备方法。所述方法包括:
先对明胶、普鲁兰多糖和甘油在70℃±5℃的条件下进行混合加热熔化混合得到基础膜液;待基础膜液温度降至45℃±5℃时加入绿原酸纳米颗粒混匀后得到制膜液;之后利用制膜液制膜。
本发明制备了绿原酸纳米颗粒,将其添加到成膜基质(明胶-普鲁兰多糖)中后,薄膜的透光率明显增加;此薄膜不仅具有高透明度,而且还表现出卓越的紫外线屏蔽能力,可以保护食品免受紫外线辐射带来的脂质氧化等影响,避免不良风味的形成,从而维持食品质量;并且本发明的包装膜在紫外光下会发出强烈的蓝绿色荧光,其出色的荧光特性还可用于食品包装的防伪;更显著的是,本发明制备的添加绿原酸纳米颗粒的薄膜显示出理想的抗菌活性和抗氧化能力,可以有效延长食品的保质期。
附图说明
图1是为对比例和实施例1所制包装膜的电镜图,其中:(a)对比例3中所制备的RL/CGA纳米颗粒的TEM图,(b)对比例4中所制备的纳米颗粒的TEM图,(c)实施例1中所制备的绿原酸纳米颗粒的TEM图;
图2是对比例1-4及实施例1表面及截面的扫描电镜图;
图3是对比例1-4及实施例1的包装膜光学性能效果对比;其中:(a)透光率,(b)每种薄膜的UVA阻隔效率,(c)L*、a*和b*值,(d)总色差ΔE*值,(e)明胶、普鲁兰多糖和CF的红外光谱图;(f)实施例1和对比例2-4所制薄膜的红外光谱图,(g)紫外线照射(365nm)下的图像,(h)实施例1的在紫外线照射(365nm)下的荧光防伪性能图。
图4是对比例1-4及实施例1的抗菌、抗氧化效果图;(a)薄膜的抗菌效果图(平板涂布法),(b)大肠杆菌和金黄色葡萄球菌的存活率(%),(c)薄膜对DPPH·清除效果的紫外光谱图,(d)对DPPH·清除效果的紫外光谱图,(e)对DPPH·和ABTS+的清除率(%)。
图5是本发明实施例包装膜在食品保鲜中的应用效;其中(a)无涂层和有涂层的香蕉在室温下储存7天期间的照片;(b)无包装和有包装的鸡肉在储存1、3和5天后的细菌总数(CFU/2克)。
具体实施方式
除非有特殊说明,本文中的科学与技术术语根据相关领域普通技术人员的认识理解。
下面结合附图和具体实施方式对本发明进行详细说明。
以下实施例的绿原酸、壳聚糖、鼠李糖脂、明胶、普鲁兰多糖和甘油均为现有材料,其中绿原酸(CGA,纯度≥95%)从阿拉丁生化技术有限公司购买。壳聚糖(CS,Mw:800-1000,纯度≥98%)从上海麦克林生化有限公司购买,鼠李糖脂(RL,纯度≥95%)从陕西先锋生物技术有限公司购买,明胶从索莱宝科技有限公司购买,普鲁兰多糖从北京伊诺凯科技有限公司购买。
本发明各指标的检测方法如下:
透光率反映薄膜的透明度,透光率的检测方法为:通过紫外分光光度计测试200至800nm范围内膜的透光率,将空的测试池设置为空白对照。
UVA屏蔽能力体现薄膜对紫外线的屏蔽效果,UVA屏蔽能力根据下面的公式计算:
其中,T(λ)是薄膜透光率的平均值,dλ是带宽,λ是波长。
薄膜的颜色通过色差仪进行测量,以标准白板为色差参比,L*、a*、b*和ΔE*值表征薄膜的颜色,L*与亮度相关,数值范围为0(黑色)到100(白色);a*的数值范围为-80(绿色)到100(红色);b*的数值范围为-80(蓝色)到70(黄色),总色差ΔE*通过下面的公式进行计算:
红外光谱图反映分子间相互作用力;紫外灯照射下表现出薄膜的荧光特性。
包装膜的抗菌性能通过平板涂布法进行了测定,具体测定方法如下:首先,用紫外光对薄膜表面(2cm×2cm)照射杀菌;然后,将薄膜放入六孔板中,100μL细菌溶液(1×105CFU mL-1)分散在两张膜之间,所有样品在25℃和90%RH下孵育24小时后,每个孔中加入3mL生理盐水;最终,吸取100μL的混合溶液并涂布在琼脂平板上,37℃下培养24小时。具体以大肠杆菌和金黄色葡萄球菌的存活率来表征包装膜的抗菌效果。
抗氧化性能通过对DPPH·和ABTS+的自由基清除率进行了评估:
其中A0和Ai分别表示空白对照组(超纯水)和样品的吸光度。
食品包装效果测试:
新鲜的香蕉和鸡肉购自当地的超市(中国杨凌);
将新鲜香蕉浸入不同成膜溶液中2分钟,然后自然干燥并在室温下观察7天;同时以未涂层香蕉作为对照组;每天采集香蕉的图像;第七天,香蕉被剥皮,以观察其内部腐烂情况。
鸡肉样品(2g)用测试薄膜(市售保鲜膜、CF、F/CGA、F/RC、F/CR和F/CRC)包装,其中市售保鲜膜为对照;然后将其在4℃下储存5天;在第1天、第3天和第5天检测鸡肉样本的细菌总数。
实施例1:
本实施例为基于绿原酸纳米颗粒的功能性食品包装膜的制备方法,包括如下步骤:
步骤1,绿原酸纳米颗粒的制备:
(1)将壳聚糖(CS)溶于乙酸溶液(质量百分比浓度为0.5%)中制备壳聚糖乙酸溶液,鼠李糖脂(RL)溶于去离子水中制备鼠李糖脂水溶液(RL溶液),壳聚糖乙酸溶液与鼠李糖脂水溶液的溶液浓度均为0.5mg mL-1;
然后使用0.45μm的膜过滤器分别过滤壳聚糖乙酸溶液与鼠李糖脂水溶液,用0.22μm的膜过滤器过滤0.5mg mL-1TPP溶液;
(2)将30mg绿原酸(CGA)超声分散到30mL 0.5mg mL-1的RL溶液中,持续超声30min得RC NPs水溶液;之后用0.45μm膜过滤器过滤RC NPs水溶液;
随后,将30mL的RC NPs水溶液逐滴添加到30mL的0.5mg mL-1的壳聚糖乙酸溶液中得混合溶液,再将7.5mL的0.5mg mL-1TPP溶液(TPP:CS=1:4,w/w)逐滴添加到此混合溶液中,进行离子交联反应;具体在700rpm、25℃下搅拌24h进行反应,所得反应物经冷冻干燥后得绿原酸纳米颗粒CRC NPs。所得绿原酸纳米颗粒的电镜图如图1(c)所示。
步骤2,成膜液的制备:
0.45g明胶、0.15g普鲁兰多糖、0.15g甘油和15mL去离子水混合,在70℃下搅拌至溶解,再添加0.15g甘油,继续搅拌30min至混合均匀,停止加热;
为保护绿原酸纳米颗粒的活性,当冷却到45℃时,再添加15mg的CRC NPs并在45℃继续搅拌30min,然后停止搅拌,保温消泡后得到成膜液。
步骤3,食品包装膜的制备:
量取15mL所述成膜液浇注铺展到培养皿中(直径为9cm),成膜温度为25±0.5℃,湿度为50±3%,成膜时间为24-48h,然后手动揭下得到食品包装膜。
经电镜观察及测试,参图2和3所示,实施例1所制备的食品包装膜(F/CRC),外观无色透明,表面光滑(图2),透明度高,其在可见光范围内的透光率约为90%(图3a),同时其UVA屏蔽率也达到89.06%(图3b)。
在紫外光下,实施例1所制备的食品包装膜会发出强烈的蓝绿色荧光(图3g),其突出的荧光特性也可用于食品包装的防伪(图3h);
另外,参见图4所示,F/CRC还显示出理想的抗菌活性和抗氧化能力(图4),其对S.aureus的抑菌率为98.72%,对大肠杆菌的抑菌率为92.14%;对ABTS的清除率为100%。
参见图5所示,与对比例1-4相比,实施例1制备的成膜液对香蕉进行涂层后,在第7天时,褐变程度最低。由实施例1包装的鸡肉样品在第五天时,其上的菌落数最少。
对比例1:
对比例1与实施例1不同的是:成膜液中未添加绿原酸纳米颗粒。
通过扫描电镜对该实施例制备的薄膜(CF)表面及横截面的显微结构进行观察(图2);经测试,相比于实施例1,该对比例制备的薄膜透光率较低(图3a);在紫外灯下,相比于实施例1,该对比例1所制备的包装膜荧光较弱(图3g);相比于实施例1,对比例1制备的膜不具备抗菌和抗氧化活性(图4)。
对比例2:
该对比例与实施例1不同的是:在成膜液中直接添加绿原酸,即当冷却到45℃时,添加15mg的绿原酸制备成膜液。
经电镜观察及测试,参图2和3所示,与实施例1相比,对比例2制得的食品包装膜(F/CGA)透明度较低(图3a)。
并且,参见图4所示,F/CGA对大肠杆菌和金黄色葡萄球菌的抑制率为85.64%和90.22%。
对比例3:
该对比例与实施例1不同的是:在制备绿原酸纳米颗粒RC NPs时没有交联壳聚糖。具体制备过程为:将30mg CGA超声分散到30mL 0.5mg mL-1的RL溶液中,持续超声30min,冷冻干燥12h获得RL/CGA纳米颗粒(RC NPs)。
经电镜观察及测试,参图2和3所示,与实施例1相比,对比例3制得的基于RC NPs的功能性食品包装膜(F/RC)透明度、抑菌性及对ABTS的清除率均差于实施例1。
对比例4:
该对比例与实施例1不同的是:步骤1中不加入绿原酸,直接将RL溶液滴加至壳聚糖乙酸溶液中,其余操作通实施例1。
经电镜观察及测试,参图2和3所示,与实施例1相比,对比例4制得的功能性食品包装膜(F/CR)紫外屏蔽性能较弱(图3a),并且在紫外灯下对比例4所制备的包装膜没有很强的荧光效果(图3g),抗菌性和抗氧化性效果均较差。
上述实施例和对比例的包装膜效果对比见表1所示。
表1
结合表1所示,与空白膜(对比例1)相比,本发明的包装膜的透光率明显增加,且还表现出卓越的紫外线屏蔽能力,可以保护食品免受紫外线辐射带来的脂质氧化等影响,避免不良风味的形成,从而维持食品质量;同时本发明的包装膜在紫外光下会发出强烈的蓝绿色荧光,其出色的荧光特性还可用于食品包装的防伪。更重要的是,本发明的包装膜表现出理想的抗菌活性和抗氧化能力。
进一步经食品包装测试,本发明的食品包装膜可以延长香蕉和鸡肉样品的保质期。
Claims (6)
1.一种基于绿原酸纳米颗粒的功能性食品包装膜,其特征在于,所述包装膜的制备原料包括明胶、普鲁兰多糖、甘油和绿原酸纳米颗粒;
所述绿原酸纳米颗粒的制备方法包括:制备绿原酸、鼠李糖脂和壳聚糖混合溶液,之后向混合溶液中加入或滴入三聚磷酸钠溶液进行离子交联反应;反应物经冷冻干燥得绿原酸纳米颗粒。
2.如权利要求1所述的基于绿原酸纳米颗粒的功能性食品包装膜,其特征在于,所述明胶、普鲁兰多糖、甘油和绿原酸纳米颗粒的质量配比范围为:30:10:(8-10):(1-2)。
3.如权利要求1所述的基于绿原酸纳米颗粒的功能性食品包装膜,其特征在于,所述绿原酸、鼠李糖脂、壳聚糖、三聚磷酸钠的质量配比范围是:(1-2):1:1:(0.25-0.33)。
4.如权利要求1所述的基于绿原酸纳米颗粒的功能性食品包装膜,其特征在于,所述制备绿原酸、鼠李糖脂和壳聚糖混合溶液包括:将绿原酸溶解于鼠李糖脂水溶液中的第一混合液,之后将第一混合液滴入到壳聚糖乙酸溶液中。
5.如权利要求4所述的基于绿原酸纳米颗粒的功能性食品包装膜,其特征在于,制备过程中的溶液均经0.4-0.5μm膜过滤器过滤。
6.权利要求1所述食品包装膜的制备方法,其特征在于,所述方法包括:
先对明胶、普鲁兰多糖和甘油在70℃±5℃的条件下进行混合加热熔化混合得到基础膜液;
待基础膜液温度降至45℃±5℃时加入绿原酸纳米颗粒混匀后得到制膜之后利用制膜液制膜。
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