技术领域Technical field
本发明属于食品检测领域，具体涉及一种胺敏感型食品新鲜度指示标签及其制备方法。The invention belongs to the field of food testing, and specifically relates to an amine-sensitive food freshness indication label and a preparation method thereof.
背景技术Background technique
随着社会的不断发展，人们对于生活品质的不断提高，食品安全问题也越来越受到重视。食品经过运输、储存、加工和销售过程中不可避免的受到外界环境和微生物的污染，食品中丰富的营养成分，极易导致微生物迅速生长繁殖，在自身酶解和微生物的分解作用下，使得食品的感官品质和理化品质发生变化，最终导致食品新鲜度下降，从而可能损害人们的身体健康。因此，及时监测食品新鲜度是非常重要的，而新鲜度指示标签是目前食品包装的主要趋势，可以直观地表达食品内部信息，方便人们了解食品新鲜度情况。With the continuous development of society and the continuous improvement of people's quality of life, food safety issues have also received more and more attention. Food is inevitably contaminated by the external environment and microorganisms during transportation, storage, processing and sales. The rich nutrients in food can easily cause the rapid growth and reproduction of microorganisms. Under the action of their own enzymatic and microbial decomposition, the food The sensory quality and physical and chemical quality of food will change, ultimately leading to a decrease in food freshness, which may harm people's health. Therefore, it is very important to monitor the freshness of food in a timely manner, and freshness indicator labels are the main trend in food packaging at present. They can intuitively express internal information of food and facilitate people to understand the freshness of food.
目前已知的检测食品新鲜度的方法主要有感官分析和理化分析，感官分析主要依靠研究人员的主观感受，分析误差大。传统的理化检测，需要借助仪器并破坏被测样品的完整性，耗时较长，不够便携。Currently known methods for testing food freshness mainly include sensory analysis and physical and chemical analysis. Sensory analysis mainly relies on the subjective feelings of researchers, and the analysis error is large. Traditional physical and chemical testing requires the use of instruments and destroys the integrity of the sample being tested, which is time-consuming and not portable enough.
食品腐败过程中，尤其是水产品及虾，微生物通过分解蛋白质会产生有机胺气体，可以通过对有机胺的监测以此来分析食品的新鲜度变化情况。姜黄素是常见的天然色素，在不同酸碱条件下，自身结构会发生转变，从而呈现不同的颜色变化，然而使用姜黄素监测新鲜度时颜色变化对比度不高，影响监测结果，因此，需要可以产生对比度高的颜色变化的食品新鲜度指示标签，且便携、监测方便。During the food spoilage process, especially aquatic products and shrimp, microorganisms will produce organic amine gases by decomposing proteins. The changes in the freshness of food can be analyzed by monitoring organic amines. Curcumin is a common natural pigment. Under different acid-base conditions, its own structure will change, thus showing different color changes. However, when using curcumin to monitor freshness, the color change contrast is not high, which affects the monitoring results. Therefore, it is necessary to It produces food freshness indication labels with high contrast color changes, which are portable and easy to monitor.
发明内容Contents of the invention
针对上述现有技术存在的问题，提供一种胺敏感型食品新鲜度指示标签及其制备方法，通过颜色变化检测包装内食品的新鲜度，实现食品在运输、贮藏、加工和销售过程中新鲜度的实时监测。In view of the problems existing in the above-mentioned existing technologies, an amine-sensitive food freshness indication label and a preparation method thereof are provided, which detect the freshness of the food in the package through color changes, and realize the freshness of the food during transportation, storage, processing and sales. real-time monitoring.
本发明的目的是通过以下技术方案来实现的，The object of the present invention is achieved through the following technical solutions:
第一方面，本发明提供一种胺敏感型食品新鲜度指示标签的制备方法，所述方法包括如下步骤：In a first aspect, the present invention provides a method for preparing an amine-sensitive food freshness indication label, which method includes the following steps:
步骤1、新鲜度指示剂的制备：称取姜黄素和栀子蓝溶解于丙酮和水的混合溶剂中，搅拌均匀得到新鲜度指示剂；Step 1. Preparation of freshness indicator: Weigh curcumin and gardenia blue and dissolve them in a mixed solvent of acetone and water, stir evenly to obtain a freshness indicator;
步骤2、混合纺丝溶液的制备：称取1788型聚乙烯醇和1799型聚乙烯醇分别溶解于蒸馏水中，分别得到1788型聚乙烯醇溶液和1799型聚乙烯醇溶液；将1788型聚乙烯醇溶液和1799型聚乙烯醇溶液混合均匀，得到混合聚乙烯醇溶液；将混合聚乙烯醇溶液和步骤1中制备的新鲜度指示剂混合，搅拌均匀得到混合纺丝溶液；Step 2. Preparation of mixed spinning solution: Weigh 1788-type polyvinyl alcohol and 1799-type polyvinyl alcohol and dissolve them in distilled water to obtain 1788-type polyvinyl alcohol solution and 1799-type polyvinyl alcohol solution respectively; add 1788-type polyvinyl alcohol Mix the solution and the 1799 type polyvinyl alcohol solution evenly to obtain a mixed polyvinyl alcohol solution; mix the mixed polyvinyl alcohol solution and the freshness indicator prepared in step 1, stir evenly to obtain a mixed spinning solution;
步骤3、纳米纤维膜的制备：将混合纺丝溶液采用滚筒接收装置制备厚度均匀的复合纳米纤维膜，将接收器上的复合纳米纤维膜取下，放置在戊二醛溶液和三氟乙酸溶液蒸汽中熏蒸，制备完成聚乙烯醇纳米纤维膜，即得到食品新鲜度指示标签。Step 3. Preparation of nanofiber membrane: Use the mixed spinning solution to use a roller receiving device to prepare a composite nanofiber membrane with uniform thickness. Remove the composite nanofiber membrane on the receiver and place it in glutaraldehyde solution and trifluoroacetic acid solution. After fumigation in steam, the polyvinyl alcohol nanofiber membrane is prepared, and the food freshness indicator label is obtained.
优选的，步骤1中所述的新鲜度指示剂中姜黄素与栀子蓝的质量比为0.5～5:1；丙酮与水的体积比为1:1；所述新鲜度指示剂的溶液浓度为0～40mg/mL。Preferably, the mass ratio of curcumin to gardenia blue in the freshness indicator described in step 1 is 0.5-5:1; the volume ratio of acetone to water is 1:1; the solution concentration of the freshness indicator It is 0~40mg/mL.
优选的，步骤2中，1788型聚乙烯醇溶解于蒸馏水中，溶解温度为40～60℃，时间为1～2h；1799型聚乙烯醇溶解于蒸馏水中，溶解温度为95～100℃，时间为4～6h。Preferably, in step 2, type 1788 polyvinyl alcohol is dissolved in distilled water, the dissolving temperature is 40-60°C, and the time is 1-2 hours; the type 1799 polyvinyl alcohol is dissolved in distilled water, the dissolving temperature is 95-100°C, and the time is 1-2 hours. It is 4~6h.
优选的，1788型聚乙烯醇溶液的质量百分浓度为10％，1799型聚乙烯醇溶液的质量百分浓度为10％。Preferably, the mass percentage concentration of the 1788 type polyvinyl alcohol solution is 10%, and the mass percentage concentration of the 1799 type polyvinyl alcohol solution is 10%.
优选的，步骤2中所述的1788型聚乙烯醇溶液、1799型聚乙烯醇溶液与新鲜度指示剂的体积比为2：2：1。Preferably, the volume ratio of the 1788-type polyvinyl alcohol solution, the 1799-type polyvinyl alcohol solution and the freshness indicator described in step 2 is 2:2:1.
优选的，步骤3中，调节推进泵与滚筒之间的距离为10～20cm，推进泵与接收器之间的电源电压为5～10kv，调节推进泵流速为1～2mL/h。Preferably, in step 3, the distance between the propelling pump and the drum is adjusted to 10-20cm, the power supply voltage between the propelling pump and the receiver is 5-10kv, and the flow rate of the propelling pump is adjusted to 1-2mL/h.
优选的，步骤3中，戊二醛溶液的质量分数为25～50％；三氟乙酸溶液的质量分数为1％。Preferably, in step 3, the mass fraction of glutaraldehyde solution is 25-50%; the mass fraction of trifluoroacetic acid solution is 1%.
优选的，步骤3中，熏蒸时间为12h。Preferably, in step 3, the fumigation time is 12 hours.
第二方面，本发明提供一种胺敏感型食品新鲜度指示标签，所述食品新鲜度指示标签是利用所述胺敏感型食品新鲜度指示标签的制备方法制得。In a second aspect, the present invention provides an amine-sensitive food freshness indication label, which is prepared by using the preparation method of the amine-sensitive food freshness indication label.
将食品新鲜度指示标签应用与虾检测中，包括以下步骤：Applying food freshness indicator labels to shrimp detection includes the following steps:
S1、虾的新鲜度检测S1. Shrimp freshness detection
将制备得到的食品新鲜度指示标签粘贴在待检测样品的空间内，经过不同时间贮藏后，利用智能手机拍照，获取空间内指示标签的颜色变化图。Paste the prepared food freshness indicator label in the space of the sample to be tested. After storage for different times, use a smartphone to take photos to obtain a color change diagram of the indicator label in the space.
S2、不同贮藏时间虾的TVB-N值S2. TVB-N values of shrimp at different storage times
通过凯氏定氮法检测不同贮藏时间虾的TVB-N值，作为判断虾的新鲜度的依据，将不同贮藏时间下虾的TVB-N值范围对应步骤S1中不同贮藏时间下指示标签的颜色变化，得到不同的颜色对应不同的新鲜度。The TVB-N value of shrimp at different storage times is detected by Kjeldahl method. As a basis for judging the freshness of shrimp, the TVB-N value range of shrimp at different storage times corresponds to the color of the indicator label at different storage times in step S1. Change to get different colors corresponding to different freshness.
本发明具有以下有益效果：(1)本发明采用复合新鲜度指示染料，通过筛选确定姜黄素和栀子蓝的比例，产生对比度高的颜色变化的指示标签，呈现最优的显色效果，而且方便快捷，易于观察，能够克服传统新鲜度指示染料颜色不明显的缺点，且制备的新鲜度指示标签成分安全，可应用于食品新鲜度检测；通过1788型聚乙烯醇溶液和1799型聚乙烯醇溶液混合得到混合聚乙烯醇纺丝溶液再与新鲜度指示剂混合制备得到的聚乙烯醇纳米纤维膜，可以有效增加纳米纤维膜的机械强度，通过戊二醛和三氟乙酸进行交联，可以有效增加聚乙烯醇静电纺丝膜的耐水性和稳定性。The present invention has the following beneficial effects: (1) The present invention uses a composite freshness indicator dye, determines the ratio of curcumin and gardenia blue through screening, produces an indicator label with high contrast color changes, and presents an optimal color development effect; and It is convenient, fast, and easy to observe. It can overcome the shortcomings of traditional freshness indicating dyes that the color is not obvious. The prepared freshness indicating label has safe ingredients and can be used for food freshness testing; it has passed the 1788 type polyvinyl alcohol solution and the 1799 type polyvinyl alcohol. The solution is mixed to obtain a mixed polyvinyl alcohol spinning solution and then mixed with a freshness indicator to prepare a polyvinyl alcohol nanofiber membrane, which can effectively increase the mechanical strength of the nanofiber membrane. Cross-linking through glutaraldehyde and trifluoroacetic acid can Effectively increase the water resistance and stability of polyvinyl alcohol electrospinning membrane.
(2)静电纺丝制备的纳米纤维膜具有高表面积，结构致密和小孔隙率的优点，使得其可以负载活性物质。将姜黄素和栀子蓝色素通过静电纺丝技术负载在聚乙烯醇纳米纤维膜上，制备成智能指示标签，实现对食品新鲜度的可视化监测。(2) The nanofiber membrane prepared by electrospinning has the advantages of high surface area, dense structure and small porosity, allowing it to load active substances. Curcumin and gardenia blue pigments were loaded on polyvinyl alcohol nanofiber membranes through electrospinning technology to prepare intelligent indicator labels to achieve visual monitoring of food freshness.
(3)传统测定有机胺气体的方法操作繁琐，消耗时间长，本发明中的胺敏感型食品新鲜度智能指示标签能够直观可视化产品的新鲜度，成本较低，消费者易于识别，对于各个环节保障食品安全具有重要意义。(3) The traditional method of measuring organic amine gas is cumbersome and time-consuming. The amine-sensitive food freshness intelligent indicator label in the present invention can intuitively visualize the freshness of the product, has low cost, and is easy for consumers to identify. For each link Ensuring food safety is of great significance.
附图说明Description of drawings
图1为实施例一中实施例1.1和1.2的指示标签颜色总色差曲线图；Figure 1 is a graph of the total color difference curve of the indicator label color in Examples 1.1 and 1.2 in Example 1;
图2为实施例一中实施例1.2-1.6的指示标签在不同浓度的氨水中模拟对胺响应的颜色变化图；Figure 2 is a diagram showing the color change of the indicator label of Examples 1.2-1.6 in Example 1 in different concentrations of ammonia water to simulate the response to amine;
图3为实施例一种实施例1.2-1.6的指示标签在不同浓度的氨水中模拟对胺响应的颜色总色差曲线图；Figure 3 is a graph of the total color difference of the color of the indicator label of Example 1.2-1.6 in different concentrations of ammonia water simulating the response to amine;
图4为实施例二中实施例2.1与2.2、2.3交联前后指示标签亲水性测定图；Figure 4 is a measurement chart of the hydrophilicity of the indicator label before and after cross-linking of Examples 2.1, 2.2, and 2.3 in Example 2;
图5为实施例三中指示标签在不同贮存条件下虾的新鲜度的颜色变化图和TVB-N值图；Figure 5 is a color change diagram and a TVB-N value diagram of the shrimp freshness indicator label under different storage conditions in Example 3;
图6为实施例三中制备的指示标签图。Figure 6 is a diagram of the indicator label prepared in Example 3.
具体实施方式Detailed ways
以下结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂盒材料，如无特殊说明，均可从商业途径获得。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention. The test methods described in the following examples are all conventional methods unless otherwise specified; the kit materials, unless otherwise specified, can be obtained from commercial sources.
实施例一、食品新鲜度指示标签颜色变化Example 1. Color changes of food freshness indicator labels
1.1、不添加栀子蓝的食品新鲜度指示标签1.1. Food freshness indication labels without adding gardenia blue
(1)新鲜度指示染料的制备：(1) Preparation of freshness indicating dye:
称取36mg姜黄素粉于50ml离心管中，加入30ml丙酮溶解混合均匀，得到天然色素指示染料。Weigh 36 mg of curcumin powder into a 50 ml centrifuge tube, add 30 ml of acetone, dissolve and mix evenly to obtain a natural pigment indicator dye.
(2)混合纺丝溶液的制备：(2) Preparation of mixed spinning solution:
称取6.0g 1788型聚乙烯醇，加入60ml蒸馏水，50℃水浴搅拌至聚乙烯醇颗粒全部溶解，静置消泡，得到1788型聚乙烯醇溶液；称取6.0g 1799型聚乙烯醇，加入60ml蒸馏水，95℃加热搅拌4h以上至聚乙烯醇颗粒完全溶解，得到1799型聚乙烯醇溶液；将1788型聚乙烯醇溶液和1799型聚乙烯醇溶液混合均匀，得到混合聚乙烯醇溶液；Weigh 6.0g of 1788 type polyvinyl alcohol, add 60 ml of distilled water, stir in a 50°C water bath until all the polyvinyl alcohol particles are dissolved, and leave to defoaming to obtain a 1788 type polyvinyl alcohol solution; weigh 6.0g of 1799 type polyvinyl alcohol, and add 60ml distilled water, heat and stir at 95°C for more than 4 hours until the polyvinyl alcohol particles are completely dissolved to obtain a 1799 type polyvinyl alcohol solution; mix the 1788 type polyvinyl alcohol solution and the 1799 type polyvinyl alcohol solution evenly to obtain a mixed polyvinyl alcohol solution;
将混合聚乙烯醇溶液和步骤(1)制备的天然色素指示染料混合，搅拌均匀得到混合纺丝溶液。Mix the mixed polyvinyl alcohol solution and the natural pigment indicating dye prepared in step (1), and stir evenly to obtain a mixed spinning solution.
(3)纳米纤维膜的制备：(3) Preparation of nanofiber membrane:
将混合纺丝溶液从针筒后倒入，固定在推进泵上，接入高压电电源，采用滚筒接收装置接收均匀的复合纳米纤维膜，调节推进泵与滚筒之间的距离为10～20cm，推进泵与接收器之间的电源电压为5～10kv，调节推进泵流速为1～2mL/h，环境温度控制在25℃，相对湿度为50％；纺丝完成后，将接收器上的纳米纤维膜取下，室温下放置1～2d，使溶剂完全挥发，得到聚乙烯醇纳米纤维膜。Pour the mixed spinning solution from the back of the syringe, fix it on the propeller pump, connect it to the high-voltage power supply, use the roller receiving device to receive the uniform composite nanofiber membrane, and adjust the distance between the propeller pump and the roller to 10-20cm , the power supply voltage between the propulsion pump and the receiver is 5~10kv, adjust the propulsion pump flow rate to 1~2mL/h, the ambient temperature is controlled at 25°C, and the relative humidity is 50%; after the spinning is completed, remove the Remove the nanofiber membrane and place it at room temperature for 1 to 2 days to completely evaporate the solvent to obtain a polyvinyl alcohol nanofiber membrane.
1.2、姜黄素与栀子蓝的质量比为5:1的食品新鲜度指示标签1.2. Food freshness indication label with a mass ratio of curcumin to gardenia blue of 5:1
与1.1不同的是步骤(1)新鲜度指示剂的制备：分别称取30mg姜黄素粉和6mg栀子蓝粉末于50ml离心管中，加入15ml蒸馏水与15ml丙酮溶解，混合均匀，得到新鲜度指示剂；其他与1.1相同。The difference from 1.1 is the preparation of step (1) freshness indicator: weigh 30 mg curcumin powder and 6 mg gardenia blue powder respectively in a 50 ml centrifuge tube, add 15 ml distilled water and 15 ml acetone to dissolve, mix evenly, and obtain the freshness indicator. agent; others are the same as 1.1.
1.3、姜黄素与栀子蓝的质量比为2:1的食品新鲜度指示标签1.3. Food freshness indication label with a mass ratio of curcumin to gardenia blue of 2:1
与1.1不同的是步骤(1)新鲜度指示剂的制备：分别称取24mg姜黄素粉和12mg栀子蓝粉末于50ml离心管中，加入15ml蒸馏水与15ml丙酮溶解，混合均匀，得到新鲜度指示剂；其他与1.1相同。The difference from 1.1 is the preparation of step (1) freshness indicator: weigh 24 mg curcumin powder and 12 mg gardenia blue powder respectively in a 50 ml centrifuge tube, add 15 ml distilled water and 15 ml acetone to dissolve, mix evenly, and obtain the freshness indicator. agent; others are the same as 1.1.
1.4姜黄素与栀子蓝的质量比为1:2的食品新鲜度指示标签1.4 Food freshness indication label with a mass ratio of curcumin to gardenia blue of 1:2
与1.1不同的是步骤(1)新鲜度指示剂的制备：分别称取12mg姜黄素粉和24mg栀子蓝粉末50ml离心管中，加入15ml蒸馏水与15ml丙酮溶解，混合均匀，得到新鲜度指示剂；其他与1.1相同。The difference from 1.1 is step (1) preparation of freshness indicator: weigh 12 mg curcumin powder and 24 mg gardenia blue powder into 50 ml centrifuge tubes, add 15 ml distilled water and 15 ml acetone to dissolve, mix evenly, and obtain the freshness indicator ;Others are the same as 1.1.
1.5、姜黄素与栀子蓝的质量比为1:1的食品新鲜度指示标签1.5. Food freshness indication label with a mass ratio of curcumin to gardenia blue of 1:1
与1.1不同的是步骤(1)新鲜度指示剂的制备：分别称取18mg姜黄素粉和18mg栀子蓝粉末于50ml离心管中，加入15ml蒸馏水与15ml丙酮溶解，混合均匀，得到新鲜度指示剂；其他与1.1相同。The difference from 1.1 is the preparation of step (1) freshness indicator: weigh 18 mg curcumin powder and 18 mg gardenia blue powder respectively in a 50 ml centrifuge tube, add 15 ml distilled water and 15 ml acetone to dissolve, mix evenly, and obtain the freshness indicator. agent; others are the same as 1.1.
1.6、姜黄素与栀子蓝的质量比为1:5的食品新鲜度指示标签1.6. Food freshness indication label with a mass ratio of curcumin to gardenia blue of 1:5
与1.1不同的是步骤(1)新鲜度指示剂的制备：分别称取6mg姜黄素粉和30mg栀子蓝粉末于50ml离心管中，加入15ml蒸馏水与15ml丙酮溶解，混合均匀，得到新鲜度指示剂；其他与1.1相同。The difference from 1.1 is the preparation of step (1) freshness indicator: weigh 6 mg curcumin powder and 30 mg gardenia blue powder respectively in a 50 ml centrifuge tube, add 15 ml distilled water and 15 ml acetone to dissolve, mix evenly, and obtain the freshness indicator. agent; others are the same as 1.1.
如图1所示，在实施例1.1与1.2中，对两种静电纺丝膜进行胺响应颜色测定，测定方法采用ΔE法，在室温下，将聚乙烯醇纳米纤维膜(1cm×1cm)切割并粘贴在氨溶液(0,10,20,50,100,200,500,1000ppm，10mL)上方的培养皿(5cm)上。使用相机记录不同胶片的颜色变化，并定期记录颜色变化。每1分钟拍摄一次胶片的图像和色度数据，持续6分钟。使用以下公式计算总色差：As shown in Figure 1, in Examples 1.1 and 1.2, the amine response color of the two electrospun membranes was measured. The measurement method was the ΔE method. The polyvinyl alcohol nanofiber membrane (1cm × 1cm) was cut at room temperature. And paste it on the petri dish (5cm) above the ammonia solution (0,10,20,50,100,200,500,1000ppm, 10mL). Use a camera to record color changes on different films, and record color changes regularly. Image and colorimetric data of the film were captured every 1 minute for 6 minutes. Calculate the total color difference using the following formula:
其中L0，a0，b0是0分钟测定的初始色差值，L，a，b是不同浓度水条件下的测定值。Among them, L0 , a0 , and b0 are the initial color difference values measured at 0 minutes, and L, a, and b are the measured values under different concentrations of water conditions.
通过色差值变化可以发现，栀子蓝粉末的加入，标签的颜色变化区域有了明显的增加，更加易于观察和辨别。Through the changes in color difference values, it can be found that the addition of gardenia blue powder significantly increases the color change area of the label, making it easier to observe and identify.
将实施例1.2-1.6进行氨气响应测定：将聚乙烯醇纳米纤维膜裁剪成大小均一的指示标签，将其粘贴在培养皿皿盖内侧，在培养皿中倒入5ml不同浓度的氨水，浓度分别为0ppm，50ppm，100ppm，200ppm，500ppm，1000ppm，并盖上皿盖，用保鲜膜密封，保证其密封性。在自然光下用智能手机拍摄不同浓度氨水下复合天然色素指示标签的颜色变化，如图2所示，计算总色差值，如图3所示，优选姜黄素：栀子蓝为5:1，1:1，1:2，2:1，最优为5:1。Conduct ammonia response measurement in Examples 1.2-1.6: Cut the polyvinyl alcohol nanofiber membrane into uniformly sized indicator labels, paste them on the inside of the Petri dish lid, pour 5 ml of ammonia water of different concentrations into the Petri dish, the concentration They are 0ppm, 50ppm, 100ppm, 200ppm, 500ppm, and 1000ppm respectively. Cover the container with a lid and seal it with plastic wrap to ensure its tightness. Use a smartphone to photograph the color changes of the composite natural pigment indicator label under different concentrations of ammonia under natural light, as shown in Figure 2. Calculate the total color difference value, as shown in Figure 3. The preferred curcumin:gardenia blue ratio is 5:1. 1:1, 1:2, 2:1, the optimal is 5:1.
实施例二、食品新鲜度指示标签亲水性测定Example 2. Determination of hydrophilicity of food freshness indication labels
2.1、聚乙烯醇纳米纤维膜未熏蒸2.1. Polyvinyl alcohol nanofiber membrane is not fumigated
(1)新鲜度指示剂的制备：(1) Preparation of freshness indicator:
分别称取30mg姜黄素粉和6mg栀子蓝粉末于50ml离心管中，加入15mL蒸馏水与15mL丙酮的混合溶剂进行溶解，混合均匀，得到新鲜度指示剂。Weigh 30 mg curcumin powder and 6 mg gardenia blue powder respectively into a 50 ml centrifuge tube, add a mixed solvent of 15 mL distilled water and 15 mL acetone to dissolve, and mix evenly to obtain a freshness indicator.
(2)混合纺丝溶液的制备：(2) Preparation of mixed spinning solution:
称取6.0g 1788型聚乙烯醇，加入60mL蒸馏水，50℃水浴搅拌至聚乙烯醇颗粒全部溶解，静置消泡，得到1788型聚乙烯醇溶液；称取6.0g 1799型聚乙烯醇，加入60mL蒸馏水，95℃加热搅拌4h以上至聚乙烯醇颗粒完全溶解，得到1799型聚乙烯醇溶液；将1788型聚乙烯醇溶液和1799型聚乙烯醇溶液混合均匀，得到混合聚乙烯醇溶液。Weigh 6.0g of 1788 type polyvinyl alcohol, add 60 mL of distilled water, stir in a 50°C water bath until all the polyvinyl alcohol particles are dissolved, and leave to defoaming to obtain a 1788 type polyvinyl alcohol solution; weigh 6.0g of 1799 type polyvinyl alcohol, and add Heat and stir 60 mL of distilled water at 95°C for more than 4 hours until the polyvinyl alcohol particles are completely dissolved to obtain a 1799 type polyvinyl alcohol solution; mix the 1788 type polyvinyl alcohol solution and the 1799 type polyvinyl alcohol solution evenly to obtain a mixed polyvinyl alcohol solution.
将混合聚乙烯醇溶液和步骤(1)中制备的新鲜度指示剂混合，搅拌均匀得到混合纺丝溶液。Mix the mixed polyvinyl alcohol solution and the freshness indicator prepared in step (1), and stir evenly to obtain a mixed spinning solution.
(3)纳米纤维膜的制备：(3) Preparation of nanofiber membrane:
将混合纺丝溶液从针筒后倒入，固定在推进泵上，接入高压电电源，采用滚筒接收装置接收厚度均匀的复合纳米纤维膜，调节推进泵与滚筒之间的距离为10～20cm，推进泵与接收器之间的电源电压为5～10kv，调节推进泵流速为1～2mL/h，环境温度控制在25℃，相对湿度为50％。纺丝完成后，将接收器上的纳米纤维膜取下，室温下放置1～2d，使溶剂完全挥发，得到聚乙烯醇纳米纤维膜。Pour the mixed spinning solution from the back of the syringe, fix it on the propeller pump, connect it to the high-voltage electric power supply, use the roller receiving device to receive the composite nanofiber membrane with uniform thickness, and adjust the distance between the propeller pump and the roller to 10~ 20cm, the power supply voltage between the propulsion pump and the receiver is 5~10kv, adjust the propulsion pump flow rate to 1~2mL/h, the ambient temperature is controlled at 25°C, and the relative humidity is 50%. After the spinning is completed, remove the nanofiber membrane from the receiver and place it at room temperature for 1 to 2 days to allow the solvent to completely evaporate to obtain a polyvinyl alcohol nanofiber membrane.
2.2、聚乙烯醇纳米纤维膜在25％戊二醛溶液和1％三氟乙酸溶液下熏蒸2.2. The polyvinyl alcohol nanofiber membrane is fumigated under 25% glutaraldehyde solution and 1% trifluoroacetic acid solution.
与2.1不同的是步骤(3)纳米纤维膜的制备：The difference from 2.1 is the preparation of nanofiber membrane in step (3):
将制备完成的聚乙烯醇纳米纤维膜裁剪成小片，粘贴在培养皿皿盖内侧，在培养皿中加入25％戊二醛溶液和1％三氟乙酸溶液，通过蒸汽熏蒸12h，使纳米纤维膜交联，完成聚乙烯醇纳米纤维膜的制备，即得到食品新鲜度指示标签。Cut the prepared polyvinyl alcohol nanofiber membrane into small pieces and paste them on the inside of the Petri dish lid. Add 25% glutaraldehyde solution and 1% trifluoroacetic acid solution to the Petri dish, and fumigate with steam for 12 hours to make the nanofiber membrane After cross-linking, the preparation of the polyvinyl alcohol nanofiber membrane is completed, and the food freshness indicator label is obtained.
2.3、聚乙烯醇纳米纤维膜在50％戊二醛溶液和1％三氟乙酸溶液下熏蒸2.3. The polyvinyl alcohol nanofiber membrane is fumigated under 50% glutaraldehyde solution and 1% trifluoroacetic acid solution.
与2.1不同的是步骤(3)纳米纤维膜的制备：将制备完成的聚乙烯醇纳米纤维膜裁剪成小片，粘贴在培养皿皿盖内侧，在培养皿中加入50％戊二醛溶液和1％三氟乙酸溶液，通过蒸汽熏蒸12h，使纳米纤维膜交联，完成聚乙烯醇纳米纤维膜的制备，即得到食品新鲜度指示标签。The difference from 2.1 is the preparation of the nanofiber membrane in step (3): cut the prepared polyvinyl alcohol nanofiber membrane into small pieces, paste them on the inside of the Petri dish cover, add 50% glutaraldehyde solution and 1 % trifluoroacetic acid solution, steam fumigation for 12 hours to cross-link the nanofiber membrane, complete the preparation of the polyvinyl alcohol nanofiber membrane, and obtain the food freshness indicator label.
如图4所示，对2.1制备的指示比标签(a、d)与2.2制备的指示标签(b、e)、2.3制备的指示标签(c、f)进行亲水性测定，将三种静电纺丝膜放入水中，观察溶解情况，图4a为未进行交联的静电纺丝膜，图4b、图4c为经过交联的静电纺丝膜，结果显示的是经过戊二醛与三氟乙酸交联后，标签的亲水性有了明显的降低，稳定性增加；图4d、图4e和图4f是对交联前后的静电纺丝膜的扫描电镜图，对静电纺丝膜的结构进行表征，结果表明交联后的静电纺丝膜纤维直径增加，耐水性以及稳定性更好，且在50％戊二醛溶液和1％三氟乙酸溶液熏蒸交联条件下的耐水性和稳定性最好，可以利用与标签在实际新鲜度检测中的应用。As shown in Figure 4, the hydrophilicity of the indicator labels prepared in 2.1 (a, d), the indicator labels prepared in 2.2 (b, e), and the indicator labels prepared in 2.3 (c, f) were measured. The three types of electrostatic Put the spinning membrane into water and observe the dissolution. Figure 4a shows the electrospinning membrane that has not been cross-linked. Figure 4b and Figure 4c show the electrospinning membrane that has been cross-linked. The results show that after glutaraldehyde and trifluoride After cross-linking with acetic acid, the hydrophilicity of the label is significantly reduced and the stability is increased; Figure 4d, Figure 4e and Figure 4f are scanning electron microscope images of the electrospun membrane before and after cross-linking, and the structure of the electrospun membrane Characterization was carried out and the results showed that the fiber diameter of the cross-linked electrospun membrane increased, the water resistance and stability were better, and the water resistance and stability were better under fumigation cross-linking conditions of 50% glutaraldehyde solution and 1% trifluoroacetic acid solution. The best performance can be used with the application of tags in actual freshness detection.
实施例三、食品新鲜度指示标签在虾的新鲜度检测中的应用Example 3. Application of food freshness indicator labels in shrimp freshness detection
(1)新鲜度指示剂的制备：(1) Preparation of freshness indicator:
分别称取30mg姜黄素粉和6mg栀子蓝粉末于50ml离心管中，加入15mL蒸馏水与15mL丙酮的混合溶剂进行溶解，混合均匀，得到新鲜度指示剂。Weigh 30 mg curcumin powder and 6 mg gardenia blue powder respectively into a 50 ml centrifuge tube, add a mixed solvent of 15 mL distilled water and 15 mL acetone to dissolve, and mix evenly to obtain a freshness indicator.
(2)混合纺丝溶液的制备：(2) Preparation of mixed spinning solution:
称取6.0g 1788型聚乙烯醇，加入60mL蒸馏水，50℃水浴搅拌至聚乙烯醇颗粒全部溶解，静置消泡，得到1788型聚乙烯醇溶液；称取6.0g 1799型聚乙烯醇，加入60mL蒸馏水，95℃加热搅拌4h以上至聚乙烯醇颗粒完全溶解，得到1799型聚乙烯醇溶液；将1788型聚乙烯醇溶液和1799型聚乙烯醇溶液混合均匀，得到混合聚乙烯醇溶液。Weigh 6.0g of 1788 type polyvinyl alcohol, add 60 mL of distilled water, stir in a 50°C water bath until all the polyvinyl alcohol particles are dissolved, and leave to defoaming to obtain a 1788 type polyvinyl alcohol solution; weigh 6.0g of 1799 type polyvinyl alcohol, and add Heat and stir 60 mL of distilled water at 95°C for more than 4 hours until the polyvinyl alcohol particles are completely dissolved to obtain a 1799 type polyvinyl alcohol solution; mix the 1788 type polyvinyl alcohol solution and the 1799 type polyvinyl alcohol solution evenly to obtain a mixed polyvinyl alcohol solution.
将混合聚乙烯醇溶液和步骤(1)中制备的新鲜度指示剂混合，搅拌均匀得到混合纺丝溶液。Mix the mixed polyvinyl alcohol solution and the freshness indicator prepared in step (1), and stir evenly to obtain a mixed spinning solution.
(3)纳米纤维膜的制备：(3) Preparation of nanofiber membrane:
将混合纺丝溶液从针筒后倒入，固定在推进泵上，接入高压电电源，采用滚筒接收装置接收厚度均匀的复合纳米纤维膜，调节推进泵与滚筒之间的距离为10～20cm，推进泵与接收器之间的电源电压为5～10kv，调节推进泵流速为1～2mL/h，环境温度控制在25℃，相对湿度为50％。纺丝完成后，将接收器上的纳米纤维膜取下，室温下放置1～2d，使溶剂完全挥发，得到聚乙烯醇纳米纤维膜。Pour the mixed spinning solution from the back of the syringe, fix it on the propeller pump, connect it to the high-voltage electric power supply, use the roller receiving device to receive the composite nanofiber membrane with uniform thickness, and adjust the distance between the propeller pump and the roller to 10~ 20cm, the power supply voltage between the propulsion pump and the receiver is 5~10kv, adjust the propulsion pump flow rate to 1~2mL/h, the ambient temperature is controlled at 25°C, and the relative humidity is 50%. After the spinning is completed, remove the nanofiber membrane from the receiver and place it at room temperature for 1 to 2 days to allow the solvent to completely evaporate to obtain a polyvinyl alcohol nanofiber membrane.
将制备完成的聚乙烯醇纳米纤维膜裁剪成小片，粘贴在培养皿皿盖内侧，在培养皿中加入50％戊二醛溶液和1％三氟乙酸溶液，通过蒸汽熏蒸12h，使纳米纤维膜交联，完成聚乙烯醇纳米纤维膜的制备，即得到食品新鲜度指示标签。Cut the prepared polyvinyl alcohol nanofiber membrane into small pieces and paste them on the inside of the Petri dish lid. Add 50% glutaraldehyde solution and 1% trifluoroacetic acid solution to the Petri dish, and fumigate with steam for 12 hours to make the nanofiber membrane After cross-linking, the preparation of the polyvinyl alcohol nanofiber membrane is completed, and the food freshness indicator label is obtained.
(4)虾的新鲜度的检测(4) Detection of shrimp freshness
将新鲜虾放置于培养皿中，将大小为1cm×2cm的长方形指示标签粘贴在培养皿盖内侧，并盖上皿盖，用保鲜膜密封，保证其密封性。在自然光下用只能手机拍摄新鲜虾0，1，3，5，7天时间贮存条件下标签的颜色响应情况，如图5所示，不同贮存时间下指示标签颜色最开始的绿色逐渐变成黄色，可以明显看出指示标签颜色的变化。Place the fresh shrimp in a petri dish, stick a 1cm × 2cm rectangular indicator label on the inside of the petri dish lid, cover the lid, and seal it with plastic wrap to ensure its tightness. Under natural light, use a mobile phone to photograph the color response of fresh shrimp labels under storage conditions for 0, 1, 3, 5, and 7 days. As shown in Figure 5, the initial green color of the indicator label gradually turns to green under different storage times. Yellow, you can clearly see the change in color of the indicator label.
不同贮存时间下指示标签颜色从最开始的绿色逐渐变成紫色，表明虾随着贮存时间的延长，新鲜度下降，生物胺的释放逐渐增多，而复合的天然色素姜黄素和栀子蓝色素对胺的响应敏感，从而使得指示标签的颜色发生变化。国标中规定新鲜鱼虾挥发性盐基氮值小于20mg/100g视为新鲜，大于等于20mg/100g则视为变质，通过对挥发性盐基氮值TVB-N进行测定，发现标签颜色变化与挥发性盐基氮值相对应，可以很好地检测虾新鲜度的变化。The color of the indicator label gradually changed from green to purple at different storage times, indicating that as the storage time increases, the freshness of the shrimp decreases and the release of biogenic amines gradually increases, while the compound natural pigments curcumin and gardenia blue pigments The amine response is sensitive, causing the color of the indicator label to change. The national standard stipulates that the volatile base nitrogen value of fresh fish and shrimp is less than 20mg/100g as fresh, and if it is greater than or equal to 20mg/100g, it is considered spoiled. By measuring the volatile base nitrogen value TVB-N, it is found that the color change of the label is related to volatilization Corresponding to the basic nitrogen value, changes in shrimp freshness can be well detected.
以上所述仅是本发明的优选实施方式，并不用于限制本发明，在本发明的前提下，对其进行优化、组合、替代等一系列改进，均在本发明的权利要求范围内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Under the premise of the present invention, a series of improvements such as optimization, combination, and substitution are within the scope of the claims of the present invention.
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