WO2018137272A1

WO2018137272A1 - Dynamically adjustable discoloring material and preparation method therefor

Info

Publication number: WO2018137272A1
Application number: PCT/CN2017/075237
Authority: WO
Inventors: 张超; 田子健; 郭占云
Original assignee: 北京镧彩科技有限公司
Priority date: 2017-01-25
Filing date: 2017-02-28
Publication date: 2018-08-02
Also published as: CN106940312B; CN106940312A

Abstract

The present invention relates to a self-evolving discoloring indicator, a preparation method therefore and a use method thereof. The self-evolving discoloring indicator comprises the following components: a) a metal nanomaterial, b) water-insoluble silver halide, c) a reducing agent, d) one, two or more cationic surfactants containing halide ions, e) water, and f) an optional acidity regulator.

Description

一种动力学可调节的变色材料及其制备方法Dynamically adjustable color changing material and preparation method thereof

技术领域Technical field

本发明涉及一种变色指示技术及相关材料，具体涉及一种用来指示易变质产品品质状态的自演化变色指示剂，及其制备和使用方法。The invention relates to a color change indication technology and related materials, in particular to a self-evolving color change indicator for indicating the quality state of a perishable product, and a preparation and use method thereof.

背景技术Background technique

食品和药品等易变质产品的安全问题一直是人们关注的焦点。为了避免此类产品由于微生物繁殖或有效成分的劣化而不宜食用或不能达到其应有的效果，通常通过标明保质期(或有效期等)来提示其处于质量合格阶段的时间期限。然而，此类保质期(或有效期等)通常是基于若干过于简化的因素(包括确定的温度、湿度、气氛、包装等)预估出来的，实际中常常由于储存条件改变，尤其是温度升高，而不能保证在标定期限内食品和药品的安全性。例如，需要低温冷藏保存的食品或药品，可能会由于产品在运输、储藏、销售过程中不可避免地经历升高的温度，而导致其在标定期限内即发生变质。因此，现阶段产品包装上所标示的保质期(或有效期)并不具有充分的可信度，而这一问题可能会对公众健康安全产生巨大威胁。The safety of perishable products such as foods and medicines has always been the focus of attention. In order to prevent such products from being ingested or failing to achieve their desired effects due to microbial growth or deterioration of active ingredients, the time period for which the quality is qualified is usually indicated by indicating the shelf life (or expiration date, etc.). However, such shelf life (or expiration date, etc.) is usually estimated based on a number of oversimplified factors (including defined temperature, humidity, atmosphere, packaging, etc.), in practice often due to changes in storage conditions, especially temperature rise, The safety of food and medicine within the calibration period cannot be guaranteed. For example, foods or medicines that require cryopreservation may be subject to deterioration during the calibration period due to the inevitable experiencing of elevated temperatures during transportation, storage, and sale. Therefore, the shelf life (or expiration date) indicated on the product packaging at this stage is not sufficiently credible, and this problem may pose a huge threat to public health and safety.

为了致力于解决这一问题，目前已研发出一些技术来真实记录产品所经历的温度历程，例如时间-温度指示剂(Time-Temperature Indicator,TTI)。一种主要类型的TTI是基于电子的数据记录器和射频识别芯片。它们可以跟踪并记录产品所经历的温度变化，但这些技术往往成本较高，且难以完全覆盖产品“从生产商到消费者”的整个过程，而且消费者很难直观读取其中所记录的信息。另一种类型的TTI基于物理化学反应，例如染料扩散，酶催化水解和聚合等。然而此类TTI常常由于其体积较大、颜色变化单一、动力学可调节范围差、成本高等限制了其使用。In order to solve this problem, some techniques have been developed to truly record the temperature history experienced by the product, such as Time-Temperature Indicator (TTI). One major type of TTI is an electronic based data logger and a radio frequency identification chip. They can track and record the temperature changes experienced by the product, but these techniques are often costly and difficult to fully cover the entire process of the product “from producer to consumer”, and it is difficult for consumers to visually read the information recorded therein. . Another type of TTI is based on physicochemical reactions such as dye diffusion, enzymatic hydrolysis and polymerization. However, such TTIs often limit their use due to their large size, single color change, poor kinetic range, and high cost.

由于现有的电子和化学TTI的局限性，需要研发出一种通用的、统一的、廉价的和简便易行的新型TTI，来追踪并记录每个单一产品的温度历程，并将涉及产品的品质状态的有关信息直接地呈现给消费者。 Due to the limitations of existing electronic and chemical TTIs, a new, uniform, inexpensive, and easy-to-use new TTI needs to be developed to track and record the temperature history of each individual product and will involve the product. Information about the quality status is presented directly to the consumer.

发明内容Summary of the invention

本发明研发出一种新型TTI，其可用于跟踪、模拟、指示易变质产品的变质过程，以及冷链物流过程中温度随时间的累积效应。The present invention develops a novel TTI that can be used to track, simulate, and indicate the metamorphic process of a perishable product, as well as the cumulative effect of temperature over time during cold chain logistics.

本发明的自演化变色指示剂对二元金属纳米晶体的形状和组成的表面等离子共振极度灵敏，具有前所未有的大范围动力学可调节性，因而可以将易变质产品中的细菌生长或有效成分变质的动力学与之匹配，从而将产品品质变化对消费者可视化。The self-evolving color change indicator of the invention is extremely sensitive to the surface plasmon resonance of the shape and composition of the binary metal nanocrystal, and has an unprecedented wide range of kinetic adjustability, thereby deteriorating bacterial growth or active ingredients in the perishable product. The dynamics are matched to visualize product quality changes to consumers.

本发明采用的自演化变色指示剂具有颜色变化丰富、体积较小、成本低、无毒等优势。而且，其动力学可调节范围大且容易调节，可覆盖大多数易变质产品的变质动力学参数。The self-evolving color change indicator used in the invention has the advantages of rich color change, small volume, low cost and no toxicity. Moreover, its kinetic range is large and easy to adjust, covering the metamorphic kinetic parameters of most perishable products.

在一方面，本发明涉及一种自演化变色指示剂，其中包含以下成分：In one aspect, the invention relates to a self-evolving color change indicator comprising the following components:

a)金属纳米材料，a) metallic nanomaterials,

b)水不溶性卤化银，b) water insoluble silver halide,

c)还原剂，c) reducing agent,

d)一种、两种或多种含卤素离子的阳离子型表面活性剂，d) one, two or more cationic surfactants containing halogen ions,

e)水，以及，e) water, and,

f)任选地，酸度调节剂，f) optionally, an acidity regulator,

其中，among them,

所述金属纳米材料在380nm至780nm的波长范围内有消光且单质银可在其表面外延生长，The metal nanomaterial has extinction in a wavelength range of 380 nm to 780 nm and an elemental silver can be epitaxially grown on the surface thereof.

所述卤素离子选自氯离子、溴离子和碘离子，The halogen ion is selected from the group consisting of chloride ion, bromide ion and iodide ion.

所述一种、两种或多种含卤素离子的阳离子型表面活性剂在指示剂中的浓度不小于0.01mM，并且The concentration of the one, two or more halogen-containing cationic surfactants in the indicator is not less than 0.01 mM, and

水不溶性卤化银选自氯化银、溴化银或碘化银。The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.

在该方面的一个优选实施方案中，所述自演化变色指示剂还包含：In a preferred embodiment of this aspect, the self-evolving color change indicator further comprises:

g)含溴离子的物质、含碘离子的物质、含硫离子的物质、含硫氢离子的物质、硫醇和硫醚中的一种或多种。g) one or more of a bromide-containing substance, an iodide-containing substance, a sulfur ion-containing substance, a sulfur-hydrogen ion-containing substance, a mercaptan, and a thioether.

优选地，当所述自演化变色指示剂还包含含溴离子的物质时，其中溴离子与构成金属纳米材料的金属原子的比例大于0.005:1。优选地，当自演化变色指示剂还包含含碘离子的物质时，其中碘离子与构成金属纳米材料的金属原子的比例大于0.0005:1。更优选地，含溴离子的物质或含碘离子的物质选自溴化钠、溴化钾、溴化铵、十六烷基三甲基溴化铵等水溶性溴化物，或碘化钠、碘化钾、碘化铵、十六烷基三甲基碘化铵等水溶性碘化物。Preferably, when the self-evolving color change indicator further comprises a bromide ion-containing substance, a ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1. Preferably, when the self-evolving color change indicator further comprises a substance containing an iodide ion, wherein the iodide ion and the metal constituting the metal nanomaterial The ratio of atoms is greater than 0.0005:1. More preferably, the bromide ion-containing substance or the iodide-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide. A water-soluble iodide such as potassium iodide, ammonium iodide or cetyltrimethylammonium iodide.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的水不溶性卤化银由含卤素离子的阳离子型表面活性剂溶液与可溶性银盐溶液制得，并且其中卤素元素与银元素的物质的量的比值大于1。优选地，所述可溶性银盐选自硝酸银、乙酸银、三氟乙酸银、高氯酸银、氟硼酸银等水溶性银盐。In another preferred embodiment of this aspect, the water-insoluble silver halide in the self-evolving color change indicator is prepared from a halogen ion-containing cationic surfactant solution and a soluble silver salt solution, and wherein the halogen element and the silver element The ratio of the amount of matter is greater than one. Preferably, the soluble silver salt is selected from the group consisting of water-soluble silver salts such as silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, and silver fluoroborate.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的金属纳米材料为贵金属的纳米材料。优选地，所述金属纳米材料为金、银、铂、钯中任一种的纳米材料，或金、银、铂、钯中任两种、任三种或全部四种的合金的纳米材料。更优选地，所述金属纳米材料为金的纳米材料。In another preferred embodiment of this aspect, the metal nanomaterial in the self-evolving color change indicator is a nanomaterial of a noble metal. Preferably, the metal nanomaterial is a nano material of any one of gold, silver, platinum, palladium, or an alloy of any two of gold, silver, platinum, palladium, any three or all of four alloys. More preferably, the metallic nanomaterial is a nanomaterial of gold.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的金属纳米材料具有选自下列的结构：纳米球、纳米棒、纳米板、纳米笼等，及以上纳米结构的混合物。优选地，所述金属纳米材料具有纳米棒的结构。优选地，所述金属纳米材料具有直径小于20nm且长度不限的纳米棒的结构。更优选地，所述金属纳米材料具有直径小于10nm且长度不限的纳米棒的结构。In another preferred embodiment of this aspect, the metal nanomaterial in the self-evolving color change indicator has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocages, and the like, and mixtures of the above nanostructures. Preferably, the metal nanomaterial has a structure of nanorods. Preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length. More preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三乙基氯化铵、十六烷基三乙基溴化铵、十六烷基三乙基碘化铵、十八烷基三乙基氯化铵、十八烷基三乙基溴化铵、十八烷基三乙基碘化铵等。优选地，所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵或十六烷基三甲基溴化铵。In another preferred embodiment of this aspect, the halogen ion-containing cationic surfactant in the self-evolving color change indicator is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide,hexadecane Triethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethyl bromide Ammonium, octadecyltriethylammonium iodide, and the like. Preferably, the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的还原剂选自抗坏血酸、异抗坏血酸或其衍生物。优选地，所述还原剂选自(异)抗坏血酸或其水溶性盐、卤代(异)抗坏血酸及其水溶性盐。更优选地，所述还原剂选自(异)抗坏血酸、(异)抗坏血酸钠、(异)抗坏血酸钾、(异)抗坏血酸铵、(异)抗坏血酸钙等水溶性盐。In another preferred embodiment of this aspect, the reducing agent in the self-evolving color change indicator is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof. Preferably, the reducing agent is selected from the group consisting of (iso)ascorbic acid or a water-soluble salt thereof, a halogenated (iso)ascorbic acid, and a water-soluble salt thereof. More preferably, the reducing agent is selected from the group consisting of water-soluble salts such as (iso)ascorbic acid, (iso)ascorbate, (iso)ascorbate, (iso)ammonium ascorbate, (iso)calcium ascorbate.

在该方面的另一个优选实施方案中，所述自演化变色指示剂中的酸度调节剂为水溶性弱酸或其盐。优选地，所述酸度调节剂选自甲酸、乙酸、乳酸、柠檬酸、草酸、葡萄糖酸及其钠盐、钾盐、铵盐、钙盐等水溶性盐。 In another preferred embodiment of this aspect, the acidity modifier in the self-evolving color change indicator is a water soluble weak acid or a salt thereof. Preferably, the acidity adjusting agent is selected from the group consisting of water-soluble salts such as formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid and sodium, potassium, ammonium, calcium salts thereof.

在该方面的另一个优选实施方案中，所述自演化变色指示剂还包含基于变色指示剂总质量计大于等于1％、小于等于60％的防冻剂。优选地，所述防冻剂选自乙二醇、丙二醇、丙三醇等。In another preferred embodiment of this aspect, the self-evolving color change indicator further comprises an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator. Preferably, the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.

在该方面的另一个优选实施方案中，所述自演化变色指示剂还包含基于变色指示剂总质量计大于等于0.01％、小于等于60％的黏度调节剂。优选地，所述黏度调节剂选自卡波姆、黄原胶等。In another preferred embodiment of this aspect, the self-evolving color change indicator further comprises a viscosity modifier greater than or equal to 0.01% and less than or equal to 60% based on the total mass of the color change indicator. Preferably, the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.

在该方面的另一个优选实施方案中，所述自演化变色指示剂还包含基于变色指示剂总质量计大于等于0.01％、小于等于10％的成胶剂。优选地，所述成胶剂为水溶性成胶剂。更优选地，所述成胶剂选自琼脂、明胶、琼脂糖、***胶、海藻酸钙、卡拉胶等。In another preferred embodiment of this aspect, the self-evolving color change indicator further comprises a gelling agent in an amount of 0.01% or more and 10% or less based on the total mass of the color changing indicator. Preferably, the gelling agent is a water soluble gelling agent. More preferably, the gelling agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.

在该方面的另一个优选实施方案中，所述自演化变色指示剂通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度、表面活性剂的浓度，实现改变由最初颜色变为最终颜色所需要的时间及变色过程的表观活化能。In another preferred embodiment of this aspect, the self-evolving color change indicator achieves a change by adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity adjuster, the concentration of the reducing agent, and the concentration of the surfactant. The time required to change from the initial color to the final color and the apparent activation energy of the color change process.

在该方面的更具体的优选实施方案中，所述自演化变色指示剂包含以下成分：In a more specific preferred embodiment of this aspect, the self-evolving color change indicator comprises the following components:

a)具有直径小于10nm且长度不限的金纳米棒，a) a gold nanorod having a diameter of less than 10 nm and an unlimited length,

b)氯化银，b) silver chloride,

c)抗坏血酸，c) ascorbic acid,

d)十六烷基三甲基氯化铵，d) cetyltrimethylammonium chloride,

e)水，e) water,

f)乙酸，以及，f) acetic acid, and,

g)十六烷基三甲基溴化铵，g) cetyltrimethylammonium bromide,

其中所述十六烷基三甲基氯化铵在指示剂中的浓度不小于0.01mM。Wherein the concentration of the cetyltrimethylammonium chloride in the indicator is not less than 0.01 mM.

在另一方面，本发明涉及一种自演化变色指示剂的制备方法，其步骤包括：In another aspect, the present invention is directed to a method of preparing a self-evolving color change indicator, the steps of which include:

1)将金属纳米材料溶液、含第一卤素离子的第一阳离子型表面活性剂溶液、还原剂、任选地酸度调节剂充分混合，以制备胶体溶液；1) thoroughly mixing a metal nanomaterial solution, a first cationic surfactant solution containing a first halogen ion, a reducing agent, and optionally an acidity adjuster to prepare a colloidal solution;

2)将含第二卤素离子的第二阳离子型表面活性剂溶液与可溶性银盐溶液混合，形成卤化银悬浊液，并且其中卤素元素与银元素的物质的量的比值大于1；或者，将含第二卤素离子的第二阳离子型表面活性剂溶液与水不溶性卤化银的悬浊液混合，得到卤化银悬浊液；以及2) mixing a second cationic surfactant solution containing a second halogen ion with a soluble silver salt solution to form a silver halide suspension, and wherein the ratio of the amount of the halogen element to the silver element is greater than 1; or, The second cationic surfactant solution containing the second halogen ion is insoluble with water a suspension of silver halides to obtain a silver halide suspension;

3)将上述胶体溶液与卤化银悬浊液以及水混合，以获得自演化变色指示剂；3) mixing the above colloidal solution with a silver halide suspension and water to obtain a self-evolving color change indicator;

其中，among them,

所述含第一卤素离子的第一阳离子型表面活性剂和含第二卤素离子的第二阳离子型表面活性剂可相同或不同，并且它们在指示剂中的总浓度不小于0.01mM，The first cationic surfactant containing the first halogen ion and the second cationic surfactant containing the second halogen ion may be the same or different, and their total concentration in the indicator is not less than 0.01 mM,

第一卤素和第二卤素可相同或不同，且独立地选自氯离子、溴离子和碘离子，并且The first halogen and the second halogen may be the same or different and are independently selected from the group consisting of chloride ion, bromide ion, and iodide ion, and

在该方面的一个优选实施方案中，所述制备方法中还加入含溴离子的物质、含碘离子的物质、含硫离子的物质、含硫氢离子的物质、硫醇和硫醚中的一种或多种作为抑制剂。优选地，当所述抑制剂为含溴离子的物质时，其中溴离子与构成金属纳米材料的金属原子的比例大于0.005:1。优选地，当所述抑制剂为含碘离子的物质时，其中碘离子与构成金属纳米材料的金属原子的比例大于0.0005:1。更优选地，所述含溴离子或碘离子的物质选自溴化钠、溴化钾、溴化铵、十六烷基三甲基溴化铵等水溶性溴化物，或碘化钠、碘化钾、碘化铵、十六烷基三甲基碘化铵等水溶性碘化物。In a preferred embodiment of this aspect, the preparation method further comprises adding one of a bromide ion-containing substance, an iodide ion-containing substance, a sulfur ion-containing substance, a sulfur-hydrogen ion-containing substance, a mercaptan, and a thioether. Or a variety of inhibitors. Preferably, when the inhibitor is a bromide-containing substance, the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1. Preferably, when the inhibitor is an iodide-containing substance, the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1. More preferably, the bromide ion or iodide ion-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide or potassium iodide. A water-soluble iodide such as ammonium iodide or cetyltrimethylammonium iodide.

在该方面的另一个优选实施方案中，所述制备方法中的金属纳米材料为贵金属的纳米材料。优选地，所述金属纳米材料为金、银、铂、钯中任一种的纳米材料，或金、银、铂、钯中任两种、任三种、或全部四种的合金的纳米材料。更优选地，所述金属纳米材料为金的纳米材料。In another preferred embodiment of this aspect, the metal nanomaterial in the method of preparation is a nanomaterial of a noble metal. Preferably, the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or an alloy of any two, any three, or all four of gold, silver, platinum, and palladium. . More preferably, the metallic nanomaterial is a nanomaterial of gold.

在该方面的另一个优选实施方案中，所述制备方法中的金属纳米材料具有下列结构：纳米球、纳米棒、纳米板、纳米笼。优选地，所述金属纳米材料具有纳米棒的结构。优选地，所述金属纳米材料具有直径小于20nm且长度不限的纳米棒的结构。更优选地，所述金属纳米材料具有直径小于10nm且长度不限的纳米棒的结构。In another preferred embodiment of this aspect, the metal nanomaterial in the preparation method has the following structure: nanospheres, nanorods, nanoplates, nanocage. Preferably, the metal nanomaterial has a structure of nanorods. Preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length. More preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.

在该方面的另一个优选实施方案中，所述制备方法中的含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三乙基氯化铵、十六烷基三乙基溴化铵、十六烷基三乙基碘化铵、十八烷基三乙基氯化铵、十八烷基三乙基溴化铵、十八烷基三乙基碘化铵等。优选地，所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵或十六烷基三甲基溴化铵。In another preferred embodiment of this aspect, the halogen ion-containing cationic surfactant in the preparation method is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethylammonium bromide. Ten Hexacyclotrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, cetyltriethylethyl Ammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide, eighteen Alkyl triethyl ammonium iodide or the like. Preferably, the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.

在该方面的另一个优选实施方案中，所述制备方法中的还原剂选自抗坏血酸、异抗坏血酸或其衍生物。优选地，所述还原剂选自(异)抗坏血酸或其水溶性盐、卤代(异)抗坏血酸及其水溶性盐。更优选地，所述还原剂选自(异)抗坏血酸、(异)抗坏血酸钠、(异)抗坏血酸钾、(异)抗坏血酸铵、(异)抗坏血酸钙等水溶性盐。In another preferred embodiment of this aspect, the reducing agent in the method of preparation is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof. Preferably, the reducing agent is selected from the group consisting of (iso)ascorbic acid or a water-soluble salt thereof, a halogenated (iso)ascorbic acid, and a water-soluble salt thereof. More preferably, the reducing agent is selected from the group consisting of water-soluble salts such as (iso)ascorbic acid, (iso)ascorbate, (iso)ascorbate, (iso)ammonium ascorbate, (iso)calcium ascorbate.

在该方面的另一个优选实施方案中，所述制备方法中的酸度调节剂为水溶性弱酸或其盐。优选地，所述酸度调节剂选自甲酸、乙酸、乳酸、柠檬酸、草酸、葡萄糖酸及其钠盐、钾盐、铵盐、钙盐等水溶性盐。更优选地，所述可溶性银盐选自硝酸银、乙酸银、三氟乙酸银、高氯酸银、氟硼酸银等水溶性银盐。In another preferred embodiment of this aspect, the acidity regulator in the preparation method is a water-soluble weak acid or a salt thereof. Preferably, the acidity adjusting agent is selected from the group consisting of water-soluble salts such as formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid and sodium, potassium, ammonium, calcium salts thereof. More preferably, the soluble silver salt is selected from the group consisting of water-soluble silver salts such as silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, and silver fluoroborate.

在该方面的另一个优选实施方案中，所述制备方法中还加入基于变色指示剂总质量计大于等于1％、小于等于60％的防冻剂。优选地，所述防冻剂选自乙二醇、丙二醇、丙三醇等。In another preferred embodiment of this aspect, the preparation method further comprises an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator. Preferably, the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.

在该方面的另一个优选实施方案中，所述制备方法中还加入基于变色指示剂总质量计大于等于0.01％、小于等于60％的黏度调节剂。优选地，所述黏度调节剂选自卡波姆、黄原胶等。In another preferred embodiment of this aspect, the preparation method further comprises a viscosity modifier greater than or equal to 0.01% and less than or equal to 60% based on the total mass of the color change indicator. Preferably, the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.

在该方面的另一个优选实施方案中，所述制备方法中还加入基于变色指示剂总质量计大于等于0.01％、小于等于10％的成胶剂。优选地，所述成胶剂为水溶性成胶剂。更优选地，所述成胶剂选自琼脂、明胶、琼脂糖、***胶、海藻酸钙、卡拉胶等。In another preferred embodiment of this aspect, the preparation method further comprises a gelling agent in an amount of 0.01% or more and 10% or less based on the total mass of the color changing indicator. Preferably, the gelling agent is a water soluble gelling agent. More preferably, the gelling agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.

在该方面的另一个优选实施方案中，所述制备方法中通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度、表面活性剂的浓度，实现改变由最初颜色变为最终颜色所需要的时间。In another preferred embodiment of this aspect, the preparation method achieves the change by initially adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity regulator, the concentration of the reducing agent, and the concentration of the surfactant. The time it takes for the color to change to the final color.

在又一方面，本发明涉及一种易变质产品保质期的变色指示方法，其包括以下步骤：In still another aspect, the present invention is directed to a color change indicating method for a shelf life of a perishable product, comprising the steps of:

1)测量易变质产品在不同温度下特定质量参数随时间变化情况，得到相应温度下的产品变质所需时间；1) Measuring the variation of specific quality parameters of a perishable product at different temperatures over time, The time required for the product to deteriorate at the corresponding temperature;

2)提供技术方案1-30中任一项的自演化变色指示剂，并通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度和表面活性剂的浓度中的一项或多项，使相应温度下易变质产品由最初颜色变为最终颜色所需要的时间与产品变质所需要的时间相等；2) The self-evolving color change indicator of any one of the technical solutions 1-30, wherein the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity adjuster, the concentration of the reducing agent, and the concentration of the surfactant are adjusted. One or more times, the time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3)根据易变质产品变色过程，得到溶液颜色与产品的变质程度对应关系，指示易变质产品保质期。3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.

在该方面的一个优选实施方案中，所述变色指示方法的特征在于，变质产品特定质量参数为：菌群数量、有效成份含量、有害成份含量。In a preferred embodiment of this aspect, the color change indicating method is characterized in that the specific quality parameter of the deteriorated product is: the number of the flora, the content of the active ingredient, and the content of the harmful component.

本发明所述的自演化变色指示剂具有以下优点：The self-evolving color change indicator of the present invention has the following advantages:

1.本发明所述的自演化变色指示剂可跟踪并记录易变质产品所经历的温度变化历程，模拟待指示产品的变质过程，并通过颜色直观地指示产品质量和保质期；1. The self-evolving color change indicator of the present invention can track and record the temperature change history experienced by the perishable product, simulate the deterioration process of the product to be indicated, and visually indicate the product quality and shelf life by color;

2.本发明所述的自演化变色指示剂在变色过程中呈现出可分辨的颜色变化，其可实现从红、橙、黄、绿、蓝、紫、红、橙色这样丰富的颜色变化；2. The self-evolving color change indicator of the present invention exhibits a resolvable color change during the color change process, which can achieve rich color changes such as red, orange, yellow, green, blue, purple, red, and orange;

3.本发明所述的自演化变色指示剂的变色速率可调节，使得在特定温度(例如室温(25℃)时，指示剂由最初颜色变为最终颜色所经历的时间在数分钟到数月范围之内，也可使得同样的自演化变色指示剂在不同温度时表现出由最初颜色变为最终颜色所经历的时间不同(在低温显著慢于在室温)；3. The rate of discoloration of the self-evolving color change indicator of the present invention can be adjusted such that the time elapsed from the initial color to the final color at a specific temperature (e.g., room temperature (25 ° C) is from several minutes to several months Within the scope, the same self-evolving color change indicator can exhibit different time from the initial color to the final color at different temperatures (significantly slower than room temperature at low temperatures);

4.本发明所述的自演化变色指示剂可以呈溶液状态，也可以呈水凝胶状态，便于不同的实际需求；4. The self-evolving color change indicator of the present invention may be in a solution state or in a hydrogel state, which is convenient for different practical needs;

5.本发明所述的自演化变色指示剂的用量低，以肉眼可分辨其颜色变化为下限，其中金、银的试剂用量低于10μg·mL^-1，其它辅助试剂均为常用品添加剂，具有安全无毒、成本低的特点；5. The self-evolving color change indicator of the present invention has a low dosage, and the color change can be distinguished by the naked eye as a lower limit, wherein the amount of gold and silver reagent is less than 10 μg·mL ^-1 , and other auxiliary reagents are common additives. It is safe, non-toxic and low cost;

6.本发明所述的自演化变色指示剂的制备过程完全在水相环境中进行，无需高温高压等苛刻条件，制备过程安全、简便，并且可以在食品和药品包装期间由生产厂家自行配制。6. The preparation process of the self-evolving color change indicator according to the present invention is completely carried out in an aqueous phase environment, and does not require harsh conditions such as high temperature and high pressure, and the preparation process is safe and simple, and can be prepared by the manufacturer during the packaging of food and medicine.

附图说明DRAWINGS

附图1：实施例1的自演化变色指示剂在35℃恒温环境中的变色过程。Figure 1: The process of discoloration of the self-evolving color change indicator of Example 1 in a constant temperature environment of 35 °C.

附图2：实施例2的自演化变色指示剂在5℃恒温环境中的变色过程，其表明环境温度降低时，自演化变色指示剂的自演化变色过程减慢。Figure 2: The color change process of the self-evolving color change indicator of Example 2 in a constant temperature environment of 5 ° C, It shows that the self-evolving color change process of the self-evolving color change indicator slows down when the ambient temperature decreases.

附图3：实施例3的自演化变色指示剂在35℃恒温环境中的变色过程，其表明还原剂浓度降低时，自演化变色指示剂的自演化变色过程减慢。Figure 3: The discoloration process of the self-evolving color change indicator of Example 3 in a constant temperature environment at 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the concentration of the reducing agent is lowered.

附图4：实施例4的自演化变色指示剂在35℃恒温环境中的变色过程，其表明表面活性剂浓度升高时，自演化变色指示剂的自演化变色过程减慢。Figure 4: The discoloration process of the self-evolving color change indicator of Example 4 in a constant temperature environment of 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the surfactant concentration is increased.

附图5：实施例5的自演化变色指示剂在35℃恒温环境中的变色过程，其表明加入酸度调节剂时，自演化变色指示剂的自演化变色过程减慢。Figure 5: Discoloration process of the self-evolving color change indicator of Example 5 in a constant temperature environment at 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the acidity adjuster is added.

附图6：实施例6的自演化变色指示剂在35℃恒温环境中的变色过程，其表明卤化银的加入量不足时，自演化变色指示剂的自演化变色过程不能达到最终颜色。Figure 6: The color change process of the self-evolving color change indicator of Example 6 in a constant temperature environment of 35 ° C, which indicates that the self-evolving color change process of the self-evolving color change indicator cannot reach the final color when the amount of silver halide added is insufficient.

附图7：实施例7的自演化变色指示剂在35℃恒温环境中的变色过程，其表明不加入抑制剂对自演化变色指示剂的自演化变色过程的影响，具体表现在光谱蓝移速率减慢，指示剂颜色偏淡偏暗，饱和度低。Figure 7: The discoloration process of the self-evolving color change indicator of Example 7 in a constant temperature environment at 35 ° C, which shows the effect of no addition of an inhibitor on the self-evolving color change process of the self-evolving color change indicator, specifically in the spectral blue shift rate Slow down, the indicator color is lighter and darker, and the saturation is low.

附图8：实施例8的自演化变色指示剂在-5℃恒温环境中的变色过程，其表明加入防冻剂后，含水的自演化变色指示剂能在零度以下正常工作。Figure 8: The color change process of the self-evolving color change indicator of Example 8 in a constant temperature environment of -5 ° C, which indicates that the aqueous self-evolving color change indicator can work normally below zero after the addition of the antifreeze.

附图9：实施例9的自演化变色指示剂在35℃恒温环境中的变色过程，其表明加入黏度调节剂后，可以有效地抑制纳米颗粒因重力而导致的沉降，使胶体溶液体系更均匀。Figure 9 is a diagram showing the discoloration process of the self-evolving color change indicator of Example 9 in a constant temperature environment of 35 ° C, which shows that after the addition of the viscosity modifier, the sedimentation of the nanoparticles due to gravity can be effectively suppressed, and the colloidal solution system is more uniform. .

附图10：实施例10的自演化变色指示剂在25℃恒温环境中的详细变色过程，其中成胶剂使体系呈凝胶态。Figure 10: Detailed color change process of the self-evolving color change indicator of Example 10 in a constant temperature environment at 25 ° C, wherein the gelling agent renders the system in a gel state.

附图11：在温度为35℃与5℃时，本发明的自演化变色指示剂的颜色变化与微生物繁殖倍数的函数关系示意图。Figure 11 is a graphical representation of the color change of the self-evolving color change indicator of the present invention as a function of microbial multiplication at temperatures of 35 ° C and 5 ° C.

实施方式Implementation

以下结合具体的实施方式，对本发明所述的自演化变色指示剂及其制备方法进行详细描述，目的是为了公众更好的理解所述的技术内容，而不是对所述技术内容进行限制，事实上，在以相同或近似的原理对所述材料及其制备方法进行的改进，都在本发明所要求保护的权利要求范围之内。The self-evolving color change indicator and the preparation method thereof according to the present invention are described in detail below in conjunction with specific embodiments, and the purpose is to better understand the technical content of the public, rather than limiting the technical content. Modifications to the materials and methods of making the same, in the same or similar principles, are within the scope of the appended claims.

自演化变色指示剂Self-evolving color change indicator

本发明的自演化变色指示剂包含以下成分：The self-evolving color change indicator of the present invention comprises the following components:

a)金属纳米材料， a) metallic nanomaterials,

b)水不溶性卤化银，b) water insoluble silver halide,

c)还原剂，c) reducing agent,

e)水，以及，e) water, and,

f)任选地，酸度调节剂。f) optionally, an acidity regulator.

此外，在优选的技术方案中，本发明的自演化变色指示剂还包含以下成分的一种或多种：抑制剂、防冻剂、黏度调节剂和成胶剂。Further, in a preferred embodiment, the self-evolving color change indicator of the present invention further comprises one or more of the following components: an inhibitor, an antifreeze, a viscosity modifier, and a gel former.

发明原理Principle of invention

本发明基于以下原理：卤化银的还原反应生成单质银，后者沉积在金属纳米材料(作为晶种)上，并随沉积层厚度增加逐渐改变金属纳米材料的颜色。The invention is based on the principle that the reduction reaction of silver halide produces elemental silver which is deposited on the metal nanomaterial (as a seed crystal) and gradually changes the color of the metal nanomaterial as the thickness of the deposited layer increases.

以金纳米棒为例，当卤化银随时间逐渐还原为单质银后，银不断在金纳米棒上外延生长，形成银壳包裹金核。随着银壳的增厚，纵向的等离子基元共振的消光带逐渐向短波方向移动，因而将胶体溶液的颜色改变。Taking gold nanorods as an example, when the silver halide is gradually reduced to elemental silver with time, the silver is continuously epitaxially grown on the gold nanorods to form a silver shell-wrapped gold core. As the silver shell thickens, the matte band of the longitudinal plasma element resonance gradually moves toward the short wave direction, thereby changing the color of the colloidal solution.

金属纳米材料与颜色变化Metal nanomaterials and color changes

首先需要说明的是，金属纳米材料没有特殊限制，只要其在380nm至780nm的波长范围内有消光且单质银可在其表面外延生长即可。First, it should be noted that the metal nanomaterial is not particularly limited as long as it has extinction in a wavelength range of 380 nm to 780 nm and elemental silver can be epitaxially grown on the surface thereof.

满足此条件的一种典型的金属纳米材料为贵金属的纳米材料，所述贵金属包括但不限于金、银、铂、钯等，也可以使用两种、三种、四种或更多种贵金属的合金。在一个优选实施方案中，金的纳米材料是特别优选的。A typical metal nanomaterial satisfying this condition is a noble metal nanomaterial, including but not limited to gold, silver, platinum, palladium, etc., and two, three, four or more precious metals may also be used. alloy. In a preferred embodiment, gold nanomaterials are particularly preferred.

金属纳米材料的形状也是多种多样的。在具体实施方案中，金属纳米材料具有选自下列的结构：纳米球、纳米棒、纳米板、纳米笼，以及这些纳米结构的混合物。在一个优选实施方案中，金属纳米材料具有纳米棒的结构。The shape of metal nanomaterials is also varied. In a particular embodiment, the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocages, and mixtures of these nanostructures. In a preferred embodiment, the metal nanomaterial has the structure of a nanorod.

金属纳米材料的最初颜色与组成元素、尺寸、形状等因素有关。例如：The initial color of metal nanomaterials is related to factors such as compositional elements, size, and shape. E.g:

□元素不同时：同是直径10nm的纳米球，金球呈红色，银球呈黄色；□ When the elements are different: the same is a nanosphere with a diameter of 10 nm, the golden sphere is red, and the silver sphere is yellow;

□尺寸不同时：同是金纳米球，直径10nm时颜色为红色，直径50nm时颜色为紫色；□ When the size is different: the same is a gold nanosphere, the color is red when the diameter is 10nm, and the color is purple when the diameter is 50nm;

□形状不同时：同是直径10nm的金纳米棒，长径比为2:1时呈蓝色，长径比为5:1时呈橙红色。□ When the shape is different: the same is a gold nanorod with a diameter of 10 nm. The aspect ratio is blue when the aspect ratio is 2:1, and the orange-red color when the aspect ratio is 5:1.

随着银壳逐渐沉积在金属纳米结构上，金属纳米材料的元素组成、尺寸和形状发生改变，因此其颜色也相应发生变化。因此，不同的金属纳米结构，其颜色变化也可能不一样。例如： As the silver shell gradually deposits on the metal nanostructures, the composition, size and shape of the metal nanomaterials change, so the color changes accordingly. Therefore, different metal nanostructures may have different color variations. E.g:

□以直径10nm、长度50nm的金纳米棒为晶种时，随银壳生长，颜色依次为红、橙、黄、绿、蓝、紫、红、橙；□ When a gold nanorod with a diameter of 10 nm and a length of 50 nm is used as a seed crystal, the color is followed by silver, orange, yellow, green, blue, purple, red, and orange.

□以厚度2nm、边长40nm的钯六边形纳米板为晶种时，随银壳生长，颜色依次为灰、绿、蓝、紫、棕；□ When a palladium hexagonal nanoplate with a thickness of 2 nm and a side length of 40 nm is used as a seed crystal, the color is gray, green, blue, purple, and brown in accordance with the growth of the silver shell;

□以直径10nm的单晶金纳米球为晶种时，随银壳生长，颜色依次为红、橙、黄。□ When a single crystal gold nanosphere with a diameter of 10 nm is used as a seed crystal, the color is followed by red, orange, and yellow.

因此，在一个优选实施方案中，优选使用直径小于20nm，尤其10nm的金纳米棒，其变色变化可实现从红、橙、黄、绿、蓝、紫、红、橙依次改变。Thus, in a preferred embodiment, gold nanorods having a diameter of less than 20 nm, especially 10 nm, are preferably used, the change in color change of which can be changed sequentially from red, orange, yellow, green, blue, purple, red, and orange.

银源和表面活性剂Silver source and surfactant

待被还原成单质银的银化合物是本发明的自演化变色指示剂的另一重要成分。理论上，一切可以被还原剂还原为单质银的银化合物都可以用于此目的，例如，水溶性银盐和水不溶性卤化银。水溶性银盐包括但不限于硝酸银、乙酸银、高氯酸银、氟化银、三氟乙酸银、氟硼酸银等水溶性银盐等；水不溶性卤化银可以选自氯化银、溴化银或碘化银。The silver compound to be reduced to elemental silver is another important component of the self-evolving color change indicator of the present invention. In theory, all silver compounds which can be reduced to elemental silver by a reducing agent can be used for this purpose, for example, water-soluble silver salts and water-insoluble silver halides. The water-soluble silver salt includes, but is not limited to, silver nitrate, silver acetate, silver perchlorate, silver fluoride, silver trifluoroacetate, silver fluoroborate, and the like; the water-insoluble silver halide may be selected from silver chloride and bromine. Silver or silver iodide.

然而，本发明人惊奇地发现，在本发明的自演化变色指示剂中使用不溶性卤化银可以取得更高重复性的优异效果，因为若使用可溶性银盐，体系中的卤素离子与还原剂都与银离子反应，两者形成竞争，使体系中银离子浓度不稳定，进而使变色过程的重复性变差。当使用水不溶性卤化银时则避免了该竞争反应。However, the inventors have surprisingly found that the use of insoluble silver halide in the self-evolving color change indicator of the present invention can achieve superior reproducibility, because if a soluble silver salt is used, both the halide ion and the reducing agent in the system The silver ion reaction, the two form a competition, the concentration of silver ions in the system is unstable, and the repeatability of the discoloration process is deteriorated. This competitive reaction is avoided when water insoluble silver halide is used.

因此，除了直接使用水不溶性卤化银来配制本发明的自演化变色指示剂外，也可以原位配制水不溶性卤化银。例如将水溶性银盐与含有卤素离子(氯离子、溴离子或碘离子)的阳离子表面活性剂优先反应，形成悬浊液(其中卤素元素与银元素的物质的量的比值大于1，以确保所有银离子均转换为沉淀)，然后再加入还原剂。Thus, in addition to the direct use of water insoluble silver halide to formulate the self-evolving color change indicator of the present invention, water insoluble silver halide can also be formulated in situ. For example, a water-soluble silver salt is preferentially reacted with a cationic surfactant containing a halogen ion (chloride ion, bromide ion or iodide ion) to form a suspension (in which the ratio of the amount of the halogen element to the silver element is greater than 1, to ensure All silver ions are converted to precipitates, and then a reducing agent is added.

由上可知，表面活性剂优选为阳离子型表面活性剂，且更优选含卤素离子的阳离子型表面活性剂，其包括但不限于：十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三乙基氯化铵、十六烷基三乙基溴化铵、十六烷基三乙基碘化铵、十八烷基三乙基氯化铵、十八烷基三乙基溴化铵、十八烷基三乙基碘化铵等。特别优选十六烷基三甲基氯化铵或十六烷基三甲基溴化铵。此外，阳离子型表面活性剂在指示剂中的总浓度不小于0.01mM是特别有利的。From the above, the surfactant is preferably a cationic surfactant, and more preferably a halogen ion-containing cationic surfactant including, but not limited to, cetyltrimethylammonium chloride, cetyltrimethyl Ammonium methyl bromide, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, Cetyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethyl Ammonium bromide, octadecyltriethylammonium iodide, and the like. Particularly preferred is cetyltrimethyl chloride Ammonium or cetyltrimethylammonium bromide. Further, it is particularly advantageous that the total concentration of the cationic surfactant in the indicator is not less than 0.01 mM.

还原剂reducing agent

理论上，还原剂没有特别限制，只要能将银化合物还原为单质银即可。本发明人发现，抗坏血酸、异抗坏血酸或其衍生物可以很好地实现本发明的目的，例如(异)抗坏血酸或其水溶性盐、卤代(异)抗坏血酸或其水溶性盐。具体包括但不限于(异)抗坏血酸、(异)抗坏血酸钠或(异)抗坏血酸钾、(异)抗坏血酸铵、(异)抗坏血酸钙等水溶性盐。Theoretically, the reducing agent is not particularly limited as long as the silver compound can be reduced to elemental silver. The present inventors have found that ascorbic acid, isoascorbic acid or a derivative thereof can well achieve the object of the present invention, for example, (iso)ascorbic acid or a water-soluble salt thereof, halogenated (iso)ascorbic acid or a water-soluble salt thereof. Specifically, but not limited to, (iso) ascorbic acid, (iso) sodium ascorbate or (iso) potassium ascorbate, (iso) ammonium ascorbate, (iso) calcium ascorbate and other water-soluble salts.

抑制剂Inhibitor

本发明人发现，若使银只沿纳米棒的直径方向长，不往长度方向长时，会得到更丰富的颜色变化，并且使得颜色鲜艳，饱和度高。本发明人出乎意料地发现，以下与金属纳米材料表面有强亲合性的抑制剂均可以实现此目的：含溴离子的物质、含碘离子的物质、含硫离子的物质、含硫氢离子的物质、硫醇和硫醚。当使用含溴离子的物质时，其中溴离子与构成该金属纳米材料的金属原子的比例大于0.005:1是特别优选的。当使用含碘离子的物质时，其中碘离子与构成该金属纳米材料的金属原子的比例大于0.0005:1是特别优选的。所述含溴离子的物质或含碘离子的物质选自溴化钠、溴化钾、溴化铵、十六烷基三甲基溴化铵等水溶性溴化物，或碘化钠、碘化钾、碘化铵、十六烷基三甲基碘化铵等水溶性碘化物。The present inventors have found that if silver is made long only in the diameter direction of the nanorods and not long in the longitudinal direction, a richer color change is obtained, and the color is bright and the saturation is high. The present inventors have unexpectedly found that the following inhibitors having strong affinity with the surface of the metal nanomaterial can achieve this purpose: a substance containing bromide ions, a substance containing iodide ions, a substance containing sulfur ions, and a sulfur-containing hydrogen. Ionic materials, mercaptans and thioethers. When a substance containing a bromide ion is used, a ratio of a bromide ion to a metal atom constituting the metal nanomaterial of more than 0.005:1 is particularly preferable. When a substance containing an iodide ion is used, a ratio of the iodide ion to the metal atom constituting the metal nanomaterial is more than 0.0005:1 is particularly preferable. The bromide-containing substance or the iodide-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide or potassium iodide. A water-soluble iodide such as ammonium iodide or cetyltrimethylammonium iodide.

酸度调节剂与动力学调节Acidity regulator and kinetic regulation

可以有多种方式改变本发明的自演化变色指示剂的动力学，例如金属纳米材料的浓度、卤素离子的浓度、还原剂的浓度、表面活性剂的浓度等。此外，还可以通过加入酸度调节剂最简便地调节自演化变色指示剂的动力学。所酸度调节剂为水溶性弱酸或其盐，例如有机弱酸或无机弱酸。酸度调节剂的实例包括但不限于甲酸、乙酸、乳酸、柠檬酸、草酸和葡萄糖酸及其钠盐、钾盐、铵盐、钙盐等水溶性盐。The kinetics of the self-evolving color change indicator of the present invention can be varied in various ways, such as the concentration of the metal nanomaterial, the concentration of the halide ions, the concentration of the reducing agent, the concentration of the surfactant, and the like. In addition, the kinetics of the self-evolving color change indicator can be adjusted most simply by the addition of an acidity regulator. The acidity regulator is a water-soluble weak acid or a salt thereof, such as an organic weak acid or an inorganic weak acid. Examples of acidity regulators include, but are not limited to, water-soluble salts of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, and gluconic acid, and sodium, potassium, ammonium, calcium, and the like.

其他成分Other ingredients

本发明的自演化变色指示剂还可以包含一种或多种其他成分，以进一步改善其理化性质便于实际需要。这些其他成分包括防冻剂、黏度调节剂或成胶剂。The self-evolving color change indicator of the present invention may also contain one or more other ingredients to further improve its physicochemical properties for practical needs. These other ingredients include antifreeze, viscosity modifiers or gelling agents.

防冻剂可以降低体系的凝固点，使其可以在0摄氏度以下工作。基于变色指示剂总质量计大于等于1％且小于等于60％的防冻剂是特别优选的。防冻剂的实例包括但不限于乙二醇、丙二醇和丙三醇等。Antifreeze can lower the freezing point of the system, allowing it to work below 0 degrees Celsius. Based on change An antifreeze agent having a total mass of 1% or more and 60% or less of the color indicator is particularly preferable. Examples of antifreeze agents include, but are not limited to, ethylene glycol, propylene glycol, glycerol, and the like.

黏度调节剂可以增加体系的黏度，避免卤化银发生沉降导致的体系内成分分布不均匀。因而加入黏度调节剂后，本发明的自演化变色指示剂变色更加均匀。基于变色指示剂总质量计大于等于0.01％且小于等于60％的黏度调节剂是特别优选的。黏度调节剂的实例包括但不限于卡波姆和黄原胶等。The viscosity modifier can increase the viscosity of the system and avoid uneven distribution of components in the system caused by the precipitation of silver halide. Thus, the self-evolving color change indicator of the present invention is more uniform in color after the addition of the viscosity modifier. A viscosity modifier which is 0.01% or more and 60% or less based on the total mass of the color change indicator is particularly preferable. Examples of viscosity modifiers include, but are not limited to, carbomer and xanthan gum.

成胶剂可以实现两方面目的：一方面与黏度调节剂类似，抑制由于氯化银沉降导致的不均匀性；另一方面，可以将变色体系由液态变为固态，可能对后续的加工有利。基于变色指示剂总质量计大于等于0.01％且小于等于10％的成胶剂是特别优选的。优选的成胶剂为水溶性成胶剂。成胶剂的实例包括但不限于琼脂、明胶、琼脂糖、***胶、海藻酸钙和卡拉胶等。The gelling agent can achieve two purposes: on the one hand, similar to the viscosity modifier, inhibiting the unevenness due to the sedimentation of the silver chloride; on the other hand, the color changing system can be changed from a liquid state to a solid state, which may be advantageous for subsequent processing. A gelling agent having a total mass of 0.01% or more and 10% or less based on the total mass of the color changing indicator is particularly preferred. Preferred gelling agents are water soluble gelling agents. Examples of gelling agents include, but are not limited to, agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan, and the like.

指示剂变色过程与易变质产品变质过程的关联技术Correlation technology between indicator color change process and metamorphic product deterioration process

测量易变质产品在不同温度(T₁，T₂)下特定质量参数(如菌群数量、有效成份含量、有害成份含量等)随时间的变化情况，得到相应温度下的产品变质所需要的时间(t₁与t₂)。调节变色反应的动力学参数(如金属纳米材料、还原剂、弱酸的浓度等)，使其在相应温度下由最初颜色变为最终颜色的所需要的时间(t_1’与t_2’)分别与t₁与t₂相等。由此可知，溶液的颜色与产品的变质程度呈一一对应的关系，即溶液的颜色可以指示产品的质量：当溶液呈最初颜色时，表示产品远未达到过期标准；当溶液呈中间颜色时，表示产品保质期过半；当溶液呈最终颜色时，即表示产品已过期。以溶液最大消光峰位蓝移程度(或其它与颜色相关的参数，如色坐标等)为横轴，以产品质量参数为纵轴作图，即可得到指示剂变色过程与易变质产品变质过程在不同温度下的相关性函数曲线。Measure the time-dependent changes of specific quality parameters (such as the number of bacteria, the content of active ingredients, the content of harmful components, etc.) of perishable products at different temperatures (T ₁ , T ₂ ), and obtain the time required for product deterioration at the corresponding temperature. (t ₁ and t ₂ ). Adjusting the kinetic parameters of the color change reaction (such as metal nanomaterials, reducing agents, concentrations of weak acids, etc.), respectively, to the time required to change from the initial color to the final color at the corresponding temperature (t _{1 '} and t _{2 '} ) Equal to t ₁ and t ₂ . It can be seen that the color of the solution has a one-to-one correspondence with the degree of deterioration of the product, that is, the color of the solution can indicate the quality of the product: when the solution is in the original color, it means that the product is far from the expiration standard; when the solution is in the middle color , indicating that the product has a shelf life of more than half; when the solution is in the final color, the product has expired. The degree of blue shift of the maximum extinction peak position of the solution (or other color-related parameters, such as color coordinates, etc.) is plotted on the horizontal axis, and the product quality parameter is plotted on the vertical axis to obtain the indicator color change process and the metamorphic product deterioration process. Correlation function curves at different temperatures.

实施例Example

实施例1Example 1

使用以下配方和操作，制备自演化变色指示剂。Self-evolving color change indicators were prepared using the following formulations and procedures.

配方：formula:

注1：标准浓度的金纳米棒溶液由金纳米棒分散于十六烷基三甲基氯化铵溶液(0.010M)中制得，其消光峰位在508nm和825nm，其中508nm处的光学密度为10.000cm^-1，825nm处的光学密度44.000cm^-1。下同。Note 1: The standard concentration of gold nanorod solution is prepared by dispersing gold nanorods in cetyltrimethylammonium chloride solution (0.010M) with extinction peaks at 508 nm and 825 nm, of which optical density at 508 nm. It is 10.000 cm ^-1 and the optical density at 825 nm is 44.000 cm ^-1 . The same below.

注2：标准浓度的氯化银悬浊液由等质量的十六烷基三甲基氯化铵溶液(浓度为0.116M)和硝酸银(浓度为0.100M)溶液混合得到。下同。Note 2: A standard concentration of silver chloride suspension is obtained by mixing an equal mass of a solution of cetyltrimethylammonium chloride (concentration: 0.116 M) and silver nitrate (concentration of 0.100 M). The same below.

操作：operating:

1)在35℃的反应温度，将金纳米棒溶液(标准浓度,0.4000g)、十六烷基三甲基氯化铵(0.100M,0.5000g)、十六烷基三甲基溴化铵(0.001M,0.4000g)、抗坏血酸(0.100M,0.1000g)充分混合，制得胶体溶液；1) Gold nanorod solution (standard concentration, 0.4000 g), cetyltrimethylammonium chloride (0.100 M, 0.5000 g), cetyltrimethylammonium bromide at a reaction temperature of 35 °C (0.001M, 0.4000g), ascorbic acid (0.100M, 0.1000g) was thoroughly mixed to prepare a colloidal solution;

2)将等质量的十六烷基三甲基氯化铵(0.116M)与硝酸银(0.100M)溶液混合，形成卤化银悬浊液；2) mixing equal amounts of cetyltrimethylammonium chloride (0.116 M) with silver nitrate (0.100 M) to form a silver halide suspension;

3)将上述胶体溶液与卤化银悬浊液(0.1350g)以及超纯水(3.4650g)混合，得到自演化变色指示剂。3) The above colloidal solution was mixed with a silver halide suspension (0.1350 g) and ultrapure water (3.4650 g) to obtain a self-evolving color change indicator.

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图1A和1B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 1A and 1B.

由光谱结果可知，35℃时溶液的自演化变色过程在4h内完成，终点时消光峰位蓝移至558nm左右。It can be seen from the spectral results that the self-evolving discoloration process of the solution is completed within 4 h at 35 ° C, and the extinction peak position is blue-shifted to about 558 nm at the end point.

实施例2Example 2

使用与实施例1相同的配方和操作，在5℃的反应温度配制自演化变色指示剂。Using the same formulation and procedure as in Example 1, a self-developing color change indicator was formulated at a reaction temperature of 5 °C.

将配制得到的自演化变色指示剂置于5℃恒温环境中，每隔24h测量其消光光谱，结果如图2A和2B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 5 ° C, and its extinction spectrum was measured every 24 hours, and the results are shown in FIGS. 2A and 2B.

由光谱结果可知，与实施例1相比，当环境温度降低时(由35℃降低至5℃)，自演化变色指示剂的自演化变色过程减慢。 From the spectral results, it is known that the self-evolving color change process of the self-evolving color change indicator is slowed down when the ambient temperature is lowered (from 35 ° C to 5 ° C) as compared with Example 1.

实施例3Example 3

使用以下配方和与实施例1相同的操作，制备自演化变色指示剂。A self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.

配方：formula:

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图3A和3B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 3A and 3B.

由光谱结果可知，与实施例1相比，当抗坏血酸浓度降低时(使用量由0.1000g降低至0.0500g)，自演化变色指示剂的自演化变色过程减慢。From the spectral results, it was found that the self-evolving color change process of the self-evolving color change indicator was slowed down when the ascorbic acid concentration was lowered (the amount used was decreased from 0.1000 g to 0.0500 g) as compared with Example 1.

实施例4Example 4

配方：formula:

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图4A和4B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 4A and 4B.

由光谱结果可知，与实施例1相比，当十六烷基三甲基氯化铵浓度升高时(使用量由0.5000g增加至2.0000g)，自演化变色指示剂的自演化变色过程减慢。From the spectral results, it is known that when the concentration of cetyltrimethylammonium chloride is increased (the amount used is increased from 0.5000 g to 2.000 g) as compared with Example 1, the self-evolving color change indicator self-evolving color change The process slows down.

实施例5Example 5

使用以下配方和与实施例1相同的操作(除了在步骤1)中加入乙酸)，制备自演化变色指示剂。A self-evolving color change indicator was prepared using the following formulation and the same procedure as Example 1 except that acetic acid was added in step 1.

配方：formula:

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图5A和5B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in Figs. 5A and 5B.

由光谱结果可知，与实施例1相比，当加入酸度调节剂时，自演化变色指示剂的自演化变色过程减慢。From the spectral results, it was found that the self-evolving color change process of the self-evolving color change indicator was slowed down when the acidity adjuster was added as compared with Example 1.

实施例6Example 6

配方：formula:

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图6A和6B所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in Figs. 6A and 6B.

由光谱结果可知，与实施例1相比，当氯化银的加入量降低时(由0.1350g降低至0.0350g)，自演化变色指示剂的自演化变色过程于1h内基本完成，终点时消光峰位蓝移至660nm左右。From the results of the spectroscopy, compared with Example 1, when the amount of silver chloride added was decreased (from 0.1350 g to 0.0350 g), the self-evolving color change process of the self-evolving color change indicator was substantially completed within 1 h, and extinction at the end point. The peak position is blue shifted to around 660 nm.

实施例7Example 7

配方：formula:

将配制得到的自演化变色指示剂置于35℃恒温环境中，每隔1.0h测量其消光光谱，结果如图7A至7D所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 7A to 7D.

由图7A和7B所示的光谱结果可知，与实施例1相比，当不加入溴离子(抑制剂)时，自演化变色指示剂的自演化变色过程也发生变化，具体表现在光谱蓝移速率减慢。具体而言，随着光谱蓝移，使用实施例1或7的金纳米棒溶液配制的自演化变色指示剂将呈现以下颜色变化：红、橙、黄、绿、蓝、紫、红、橙。当加入溴离子抑制剂时，实施例1的自演化变色指示剂在2h和4h时，颜色分别由橙红色变为蓝绿色再变为红色；当不加入溴离子抑制剂时，实施例7的自演化变色指示剂在2h和4h时，颜色分别由橙红色变为淡绿色再变为蓝灰色(详见图7C)。由此可见，溴离子抑制剂减慢了自演化变色指示剂的变色过程。From the spectral results shown in FIGS. 7A and 7B, it is known that the self-evolving color change process of the self-evolving color change indicator also changes when bromide ions (inhibitors) are not added, as shown in the spectral blue shift. The rate is slowed down. In particular, as the spectrum is blue shifted, the self-evolving color change indicator formulated using the gold nanorod solution of Example 1 or 7 will exhibit the following color changes: red, orange, yellow, green, blue, purple, red, orange. When the bromide ion inhibitor was added, the self-evolving color change indicator of Example 1 changed from orange red to blue green to red again at 2 h and 4 h; when the bromide inhibitor was not added, the case of Example 7 At 2h and 4h, the self-evolving color-changing indicator changed from orange-red to light-green to blue-gray (see Figure 7C for details). Thus, the bromide ion inhibitor slows down the discoloration process of the self-evolving color change indicator.

此外，当不加入溴离子时，自演化变色指示剂的消光值升高，表现出颜色偏淡偏暗(饱和度低)，不及实施例1得到溶液颜色鲜艳，详见图7C。从透射电子显微镜照片来看，当不加入溴离子时，银在金纳米棒的侧面、两端均有沉积，得到对称的纳米结构(投影为矩形)；当加入适量溴离子时，银在金纳米棒的两端几乎没有沉积，而几乎只在某个侧面沉积，得到不对称的纳米结构(投影为船形)，详见图7D。因此，溴离子抑制剂的加入还使得观察自演化变色指示剂的颜色演变更加方便、清晰。In addition, when no bromide ions were added, the extinction value of the self-evolving color change indicator increased, indicating that the color was lighter and darker (slow saturation), and the color of the solution obtained in Example 1 was not as bright as shown in Fig. 7C. From the transmission electron micrograph, when no bromide ions are added, silver is deposited on the side and both ends of the gold nanorods to obtain a symmetrical nanostructure (projected as a rectangle); when a proper amount of bromide ions is added, silver is in gold. There are almost no deposits on both ends of the nanorods, and almost only on one side, resulting in asymmetric nanostructures (projected as a boat), as shown in Figure 7D. Therefore, the addition of a bromide ion inhibitor also makes it easier and clearer to observe the color evolution of the self-developing color change indicator.

实施例8Example 8

配方：formula:

将配制得到的自演化变色指示剂置于-5℃恒温环境中，每隔7天测量其消光光谱，结果如图8所示。The prepared self-evolving color change indicator was placed in a constant temperature environment of -5 ° C, and its extinction spectrum was measured every 7 days. The results are shown in FIG.

由光谱结果可知，当溶液配方中加入适量1,2-丙二醇(作为防冻剂)，溶液可在低于0℃的温度下保持液态，且仍具有自演化变色性能。From the spectral results, it can be seen that when an appropriate amount of 1,2-propanediol (as an antifreeze) is added to the solution formulation, the solution can remain liquid at a temperature below 0 ° C and still have self-evolving discoloration properties.

实施例9Example 9

配方：formula:

注1：卡波姆溶液由卡波姆粉末与适量水混合搅拌后得到均一透明溶液。Note 1: The carbomer solution is mixed with carbomer powder and an appropriate amount of water to obtain a uniform transparent solution.

将配制得到的自演化变色指示剂置于35℃环境中，5h后得到红色溶液，并将适量红色溶液转移至比色皿中。同时取实施例1得到的自演化变色指示剂静置48h后红色溶液，将适量红色溶液转移至另一比色皿中。结果如图9所示。The prepared self-evolving color change indicator was placed in an environment of 35 ° C, and after 5 hours, a red solution was obtained, and an appropriate amount of the red solution was transferred to a cuvette. At the same time, the self-evolving color change indicator obtained in Example 1 was allowed to stand for 48 hours, and then the red solution was transferred to another cuvette. The result is shown in Figure 9.

由照片可知，与实施例1相比，当溶液配方中加入卡波姆(黏度调节剂)后，可以有效地抑制纳米颗粒因重力而导致的沉降，使胶体溶液体系更均匀。As can be seen from the photograph, when carbomer (viscosity modifier) is added to the solution formulation, the sedimentation of the nanoparticles due to gravity can be effectively suppressed, and the colloidal solution system is more uniform.

实施例10Example 10

配方：formula:

注1：琼脂溶液由琼脂粉末与适量水混合加热后得到均一透明溶液，由于该溶液冷却后可能发生相变形成凝胶，须趁热与其它组分溶液混合均匀，得到的溶液迅速冷却至5℃左右，待形成凝胶后使用。Note 1: The agar solution is heated by mixing agar powder with an appropriate amount of water to obtain a uniform transparent solution. Since the solution may form a gel after cooling, it must be mixed with other component solutions evenly, and the obtained solution is rapidly cooled to 5 About °C, to be used after forming a gel.

将配制得到的自演化变色指示剂切作小块，置于25℃环境中，随时间记录其颜色，结果如图10所示。图10表示的是12个小时内自演化变色指示剂的变色过程。具体而言，从12点钟方向的起始颜色(红色)，按顺序从1点钟方向的颜色逐渐变为11点钟方向的颜色，依次为：红色、橙色、黄色、绿色、绿色、蓝绿色、蓝色、蓝紫色、紫色、***、红色、红色。The prepared self-evolving color change indicator was cut into small pieces, placed in a 25 ° C environment, and its color was recorded over time, and the results are shown in FIG. Figure 10 shows the color change process of the self-evolving color change indicator within 12 hours. Specifically, the starting color (red) from the 12 o'clock direction gradually changes from the 1 o'clock direction color to the 11 o'clock direction color, in order: red, orange, yellow, green, green, blue Green, blue, blue-violet, purple, magenta, red, red.

由图10可知，当溶液配方中加入适量琼脂后(作为成胶剂)，体系呈凝胶态，且仍具有自演化变色性能。 It can be seen from Fig. 10 that when an appropriate amount of agar is added to the solution formulation (as a gelling agent), the system is in a gel state and still has self-evolving discoloration properties.

实施例11Example 11

1)测量易变质产品在不同温度下特定质量参数(菌群数量、有效成份含量、有害成分含量)随时间变化情况，得到相应温度下的产品变质所需时间；1) Measure the time-dependent changes of specific quality parameters (bacterial quantity, active ingredient content, and harmful component content) of perishable products at different temperatures, and obtain the time required for product deterioration at the corresponding temperature;

2)通过调节含氯离子或溴离子的表面活性剂水溶液、可溶性抗坏血酸盐水溶液、可溶性弱酸或弱酸盐水溶液和金纳米棒溶液浓度，使相应温度下易变质产品由红色变为绿色所需要的时间与产品变质所需要的时间相等；2) by adjusting the concentration of aqueous solution of surfactant containing chloride or bromide, aqueous solution of soluble ascorbate, soluble weak acid or weak acid salt solution and gold nanorod solution, so that the perishable product at the corresponding temperature is changed from red to green. Time is equal to the time required for product deterioration;

3)根据易变质产品变色过程，得到溶液颜色与产品的变质程度对应关系，指示易变质产品保质期，如图11所示，两者几乎完全重合。3) According to the discoloration process of the perishable product, the relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product, as shown in Fig. 11, the two are almost completely coincident.

本发明所述的变色指示技术是利用化学反应动力学对温度的敏感性来模拟易变质产品变质过程对温度的依赖性。通过调节试剂用量，可以模拟易变质产品的变质过程，并指示产品质量和保质期。本发明申请所述的变色指示剂具有变色对比鲜明、操作简便、成本低廉、安全性高等特点，可以用来跟踪并记录产品在运输、储藏、销售过程中经历的温度变化，模拟产品的变质过程，通过指示剂自身的颜色变化直观地指示产品质量和保质期。The color change indicating technology of the present invention utilizes the sensitivity of chemical reaction kinetics to temperature to simulate the temperature dependence of the metamorphic product deterioration process. By adjusting the amount of reagents, it is possible to simulate the deterioration process of a perishable product and indicate the quality and shelf life of the product. The color change indicator described in the application of the invention has the characteristics of clear color contrast, simple operation, low cost and high safety, and can be used for tracking and recording the temperature change experienced by the product during transportation, storage and sales, and simulating the deterioration process of the product. The product quality and shelf life are visually indicated by the color change of the indicator itself.

虽然本发明以前述的实施例公开如上，然其并非用以限定本发明。本发明所属技术领域中的技术人员，在不脱离本发明的精神和范围内，当可做些许之更改与润饰。因此本发明的保护范围以权利要求书为准。 Although the invention is disclosed above in the foregoing embodiments, it is not intended to limit the invention. Those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the claims.

Claims

一种自演化变色指示剂，其中包含以下成分：A self-evolving color change indicator comprising the following components:

a)金属纳米材料，a) metallic nanomaterials,

b)水不溶性卤化银，b) water insoluble silver halide,

c)还原剂，c) reducing agent,

d)一种、两种或多种含卤素离子的阳离子型表面活性剂，d) one, two or more cationic surfactants containing halogen ions,

e)水，以及，e) water, and,

f)任选地，酸度调节剂，f) optionally, an acidity regulator,

其中，among them,

所述金属纳米材料在380nm至780nm的波长范围内有消光且单质银可在其表面外延生长，The metal nanomaterial has extinction in a wavelength range of 380 nm to 780 nm and an elemental silver can be epitaxially grown on the surface thereof.

所述卤素离子选自氯离子、溴离子和碘离子，The halogen ion is selected from the group consisting of chloride ion, bromide ion and iodide ion.

所述一种、两种或多种含卤素离子的阳离子型表面活性剂在指示剂中的浓度不小于0.01mM，并且The concentration of the one, two or more halogen-containing cationic surfactants in the indicator is not less than 0.01 mM, and

水不溶性卤化银选自氯化银、溴化银或碘化银。The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.
如权利要求1所述的自演化变色指示剂，其还包含：The self-evolving color change indicator of claim 1 further comprising:

g)含溴离子的物质、含碘离子的物质、含硫离子的物质、含硫氢离子的物质、硫醇和硫醚中的一种或多种。g) one or more of a bromide-containing substance, an iodide-containing substance, a sulfur ion-containing substance, a sulfur-hydrogen ion-containing substance, a mercaptan, and a thioether.
如权利要求1所述的自演化变色指示剂，其还包含：The self-evolving color change indicator of claim 1 further comprising:

g)含溴离子的物质，其中溴离子与构成所述金属纳米材料的金属原子的比例大于0.005:1。g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
如权利要求1所述的自演化变色指示剂，其还包含：The self-evolving color change indicator of claim 1 further comprising:

g)含碘离子的物质，其中碘离子与构成所述金属纳米材料的金属原子的比例大于0.0005:1。g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
如权利要求3或4的自演化变色指示剂，其中所述含溴离子的物质或含碘离子的物质选自溴化钠、溴化钾、溴化铵、十六烷基三甲基溴化铵等水溶性溴化物，或碘化钠、碘化钾、碘化铵、十六烷基三甲基碘化铵等水溶性碘化物。A self-evolving color change indicator according to claim 3 or 4, wherein said bromide ion-containing substance or iodide-containing substance is selected from the group consisting of sodium bromide, potassium bromide, ammonium bromide, cetyltrimethyl bromide. A water-soluble bromide such as ammonium or a water-soluble iodide such as sodium iodide, potassium iodide, ammonium iodide or cetyltrimethylammonium iodide.
如权利要求1-5中任一项所述的自演化变色指示剂，其中水不溶性卤化银由含卤素离子的阳离子型表面活性剂溶液与可溶性银盐溶液制得，并且其中卤素元素与银元素的物质的量的比值大于1。The self-evolving color change indicator according to any one of claims 1 to 5, wherein the water-insoluble silver halide is prepared from a solution of a cationic surfactant containing a halogen ion and a solution of a soluble silver salt, and The ratio of the amount of the halogen element to the silver element is greater than 1.
如权利要求6所述的自演化变色指示剂，其中所述可溶性银盐选自硝酸银、乙酸银、三氟乙酸银、高氯酸银、氟硼酸银等水溶性银盐。The self-evolving color change indicator according to claim 6, wherein the soluble silver salt is selected from the group consisting of water-soluble silver salts such as silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, and silver fluoroborate.
如权利要求1-7中任一项所述的自演化变色指示剂，其中构成所述金属纳米材料的金属为贵金属。The self-evolving color change indicator according to any one of claims 1 to 7, wherein the metal constituting the metal nanomaterial is a noble metal.
如权利要求8所述的自演化变色指示剂，其中所述金属纳米材料为金、银、铂、钯中任一种的纳米材料，或金、银、铂、钯中任两种、任三种或全部四种的合金的纳米材料。The self-evolving color change indicator according to claim 8, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium, and any three Nanomaterials of all or all four alloys.
如权利要求9所述的自演化变色指示剂，所述金属纳米材料为金的纳米材料。The self-evolving color change indicator of claim 9, the metal nanomaterial being a gold nanomaterial.
如权利要求1-10中任一项所述的自演化变色指示剂，其中所述金属纳米材料具有选自下列的结构：纳米球、纳米棒、纳米板、纳米笼等，及以上纳米结构的混合物。The self-evolving color change indicator according to any one of claims 1 to 10, wherein the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and the above nanostructures mixture.
如权利要求11所述的自演化变色指示剂，其中所述金属纳米材料具有纳米棒的结构。The self-evolving color change indicator according to claim 11, wherein the metal nanomaterial has a structure of nanorods.
如权利要求12所述的自演化变色指示剂，其中所述金属纳米材料具有直径小于20nm且长度不限的纳米棒的结构。The self-evolving color change indicator according to claim 12, wherein the metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length.
如权利要求12所述的自演化变色指示剂，其中所述金属纳米材料具有直径小于10nm且长度不限的纳米棒的结构。The self-evolving color change indicator according to claim 12, wherein the metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.
如权利要求1-14中任一项所述的自演化变色指示剂，其中所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三乙基氯化铵、十六烷基三乙基溴化铵、十六烷基三乙基碘化铵、十八烷基三乙基氯化铵、十八烷基三乙基溴化铵、十八烷基三乙基碘化铵等。The self-evolving color change indicator according to any one of claims 1 to 14, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and hexadecyltrimethyl. Ammonium bromide, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, ten Hexyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethyl Ammonium bromide, octadecyltriethylammonium iodide, and the like.
如权利要求15所述的自演化变色指示剂，其中所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵或十六烷基三甲基溴化铵。The self-evolving color change indicator according to claim 15, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.
如权利要求1-16中任一项所述的自演化变色指示剂，其中所述还原剂选自抗坏血酸、异抗坏血酸或其衍生物。The self-evolving color change indicator according to any one of claims 1 to 16, wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
如权利要求17所述的自演化变色指示剂，其中所述还原剂选自抗坏血酸或其水溶性盐、异抗坏血酸或其水溶性盐、卤代抗坏血酸或其水溶性盐、卤代异抗坏血酸或其水溶性盐。The self-evolving color change indicator according to claim 17, wherein the reducing agent is selected from the group consisting of ascorbic acid or a water-soluble salt thereof, erythorbic acid or a water-soluble salt thereof, halogenated ascorbic acid or a water-soluble salt thereof, Halogenated ascorbic acid or a water soluble salt thereof.
如权利要求17所述的自演化变色指示剂，其中所述还原剂选自抗坏血酸、异抗坏血酸、抗坏血酸钠、异抗坏血酸钠、抗坏血酸钾、异抗坏血酸钾、抗坏血酸铵、异抗坏血酸铵、抗坏血酸钙、异抗坏血酸钙等水溶性盐。The self-evolving color change indicator according to claim 17, wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid, sodium ascorbate, sodium erythorbate, potassium ascorbate, potassium erythorbate, ammonium ascorbate, ammonium erythorbate, calcium ascorbate, and the like. A water-soluble salt such as calcium ascorbate.
如权利要求1-19中任一项所述的自演化变色指示剂，其中所述酸度调节剂为水溶性弱酸或其盐。The self-evolving color change indicator according to any one of claims 1 to 19, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
如权利要求20所述的自演化变色指示剂，其中所述酸度调节剂选自甲酸、乙酸、乳酸、柠檬酸、草酸、葡萄糖酸及其钠盐、钾盐、铵盐、钙盐等水溶性盐。The self-evolving color change indicator according to claim 20, wherein the acidity adjuster is selected from the group consisting of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid, and sodium, potassium, ammonium, calcium salts thereof and the like. salt.
如权利要求1-21中任一项所述的自演化变色指示剂，其还包含基于变色指示剂总质量计大于等于1％、小于等于60％的防冻剂。The self-evolving color change indicator according to any one of claims 1 to 21, further comprising an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator.
如权利要求22所述的自演化变色指示剂，其中所述防冻剂选自乙二醇、丙二醇、丙三醇等。The self-evolving color change indicator according to claim 22, wherein the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerin, and the like.
如权利要求1-23中任一项所述的自演化变色指示剂，其还包含基于变色指示剂总质量计大于等于0.01％、小于等于60％的黏度调节剂。The self-evolving color change indicator according to any one of claims 1 to 23, further comprising a viscosity modifier of 0.01% or more and 60% or less based on the total mass of the color change indicator.
如权利要求24所述的自演化变色指示剂，其中所述黏度调节剂选自卡波姆、黄原胶等。A self-evolving color change indicator according to claim 24, wherein said viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.
如权利要求1-25中任一项所述的自演化变色指示剂，其还包含基于变色指示剂总质量计大于等于0.01％、小于等于10％的成胶剂。The self-evolving color change indicator according to any one of claims 1 to 25, further comprising a gelling agent of 0.01% or more and 10% or less based on the total mass of the color change indicator.
如权利要求26所述的自演化变色指示剂，其中所述成胶剂为水溶性成胶剂。A self-evolving color change indicator according to claim 26, wherein said gel forming agent is a water soluble gel forming agent.
如权利要求26所述的自演化变色指示剂，其中所述成胶剂选自琼脂、明胶、琼脂糖、***胶、海藻酸钙、卡拉胶等。The self-evolving color change indicator according to claim 26, wherein the gel forming agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.
如权利要求1-28中任一项所述的自演化变色指示剂，其中通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度、表面活性剂的浓度，可以实现改变由最初颜色变为最终颜色所需要的时间及变色过程的表观活化能。The self-evolving color change indicator according to any one of claims 1 to 28, wherein the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity adjuster, the concentration of the reducing agent, the concentration of the surfactant, The time required to change the initial color to the final color and the apparent activation energy of the color change process can be achieved.
一种自演化变色指示剂，其中包含以下成分：A self-evolving color change indicator comprising the following components:

a)具有直径小于10nm且长度不限的金纳米棒，a) a gold nanorod having a diameter of less than 10 nm and an unlimited length,

b)氯化银，b) silver chloride,

c)抗坏血酸或异抗坏血酸， c) ascorbic acid or isoascorbic acid,

d)十六烷基三甲基氯化铵，d) cetyltrimethylammonium chloride,

e)水，e) water,

f)乙酸，以及，f) acetic acid, and,

g)十六烷基三甲基溴化铵，g) cetyltrimethylammonium bromide,

其中所述十六烷基三甲基氯化铵在指示剂中的浓度不小于0.01mM。Wherein the concentration of the cetyltrimethylammonium chloride in the indicator is not less than 0.01 mM.
一种自演化变色指示剂的制备方法，其步骤包括：A method for preparing a self-evolving color change indicator, the steps comprising:

1)将金属纳米材料溶液、含第一卤素离子的第一阳离子型表面活性剂溶液、还原剂、任选地酸度调节剂充分混合，以制备胶体溶液；1) thoroughly mixing a metal nanomaterial solution, a first cationic surfactant solution containing a first halogen ion, a reducing agent, and optionally an acidity adjuster to prepare a colloidal solution;

2)将含第二卤素离子的第二阳离子型表面活性剂溶液与可溶性银盐溶液混合，形成卤化银悬浊液，并且其中卤素元素与银元素的物质的量的比值大于1；或者，将含第二卤素离子的第二阳离子型表面活性剂溶液与水不溶性卤化银的悬浊液混合，得到卤化银悬浊液；以及2) mixing a second cationic surfactant solution containing a second halogen ion with a soluble silver salt solution to form a silver halide suspension, and wherein the ratio of the amount of the halogen element to the silver element is greater than 1; or, a second cationic surfactant solution containing a second halogen ion is mixed with a suspension of water-insoluble silver halide to obtain a silver halide suspension;

3)将上述胶体溶液与卤化银悬浊液以及水混合，以获得自演化变色指示剂；3) mixing the above colloidal solution with a silver halide suspension and water to obtain a self-evolving color change indicator;

其中，among them,

所述金属纳米材料在380nm至780nm的波长范围内有消光且单质银可在其表面外延生长，The metal nanomaterial has extinction in a wavelength range of 380 nm to 780 nm and an elemental silver can be epitaxially grown on the surface thereof.

所述含第一卤素离子的第一阳离子型表面活性剂和含第二卤素离子的第二阳离子型表面活性剂可相同或不同，并且它们在指示剂中的总浓度不小于0.01mM，The first cationic surfactant containing the first halogen ion and the second cationic surfactant containing the second halogen ion may be the same or different, and their total concentration in the indicator is not less than 0.01 mM,

第一卤素和第二卤素可相同或不同，且独立地选自氯离子、溴离子和碘离子，并且The first halogen and the second halogen may be the same or different and are independently selected from the group consisting of chloride ion, bromide ion, and iodide ion, and

水不溶性卤化银选自氯化银、溴化银或碘化银。The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.
如权利要求31所述的自演化变色指示剂的制备方法，其中还加入含溴离子的物质、含碘离子的物质、含硫离子的物质、含硫氢离子的物质、硫醇和硫醚中的一种或多种作为抑制剂。The method for preparing a self-evolving color change indicator according to claim 31, wherein a substance containing a bromide ion, a substance containing an iodide ion, a substance containing a sulfur ion, a substance containing a sulfur ion, a mercaptan and a thioether are further added. One or more of them act as inhibitors.
如权利要求32所述的自演化变色指示剂的制备方法，其中所述抑制剂为含溴离子的物质，并且溴离子与构成所述金属纳米材料的金属原子的比例大于0.005:1。A method of producing a self-evolving color change indicator according to claim 32, wherein said inhibitor is a bromide ion-containing substance, and a ratio of a bromide ion to a metal atom constituting said metal nanomaterial is greater than 0.005:1.
如权利要求32所述的自演化变色指示剂的制备方法，其中所述抑制剂为含碘离子的物质，并且碘离子与构成所述金属纳米材料的金属原子的比例大于0.0005:1。A method of producing a self-evolving color change indicator according to claim 32, wherein said inhibitor is a substance containing an iodide ion, and a ratio of iodide ion to a metal atom constituting said metal nanomaterial The example is greater than 0.0005:1.
如权利要求33或34所述的自演化变色指示剂的制备方法，其中所述含溴离子或碘离子的物质选自溴化钠、溴化钾、溴化铵、十六烷基三甲基溴化铵等水溶性溴化物，或碘化钠、碘化钾、碘化铵、十六烷基三甲基碘化铵等水溶性碘化物。The method for producing a self-evolving color change indicator according to claim 33 or 34, wherein the bromide ion or iodide ion-containing substance is selected from the group consisting of sodium bromide, potassium bromide, ammonium bromide, and cetyltrimethyl group. A water-soluble bromide such as ammonium bromide or a water-soluble iodide such as sodium iodide, potassium iodide, ammonium iodide or cetyltrimethylammonium iodide.
如权利要求31-35中任一项所述的自演化变色指示剂的制备方法，其中构成所述金属纳米材料的金属为贵金属。The method of producing a self-evolving color change indicator according to any one of claims 31 to 35, wherein the metal constituting the metal nanomaterial is a noble metal.
如权利要求36所述的自演化变色指示剂的制备方法，其中所述金属纳米材料为金、银、铂、钯中任一种的纳米材料，或金、银、铂、钯中任两种、任三种、或全部四种的合金的纳米材料。The method for preparing a self-evolving color change indicator according to claim 36, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium. Nanomaterials of any three or all four alloys.
如权利要求37所述的自演化变色指示剂的制备方法，其中所述金属纳米材料为金的纳米材料。A method of producing a self-evolving color change indicator according to claim 37, wherein said metal nanomaterial is a gold nanomaterial.
如权利要求31-38中任一项所述的自演化变色指示剂的制备方法，其中所述金属纳米材料具有下列结构：纳米球、纳米棒、纳米板、纳米笼。The method of producing a self-evolving color change indicator according to any one of claims 31 to 38, wherein the metal nanomaterial has the following structure: nanospheres, nanorods, nanoplates, nanocage.
如权利要求39所述的自演化变色指示剂的制备方法，其中所述金属纳米材料具有纳米棒的结构。A method of producing a self-evolving color change indicator according to claim 39, wherein said metal nanomaterial has a structure of nanorods.
如权利要求40所述的自演化变色指示剂的制备方法，其中所述金属纳米材料具有直径小于20nm且长度不限的纳米棒的结构。A method of producing a self-evolving color change indicator according to claim 40, wherein said metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length.
如权利要求40所述的自演化变色指示剂的制备方法，其中所述金属纳米材料具有直径小于10nm且长度不限的纳米棒的结构。A method of producing a self-evolving color change indicator according to claim 40, wherein said metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.
如权利要求31-42中任一项所述的自演化变色指示剂的制备方法，其中所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、十六烷基三甲基碘化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、十二烷基三甲基碘化铵、十六烷基三乙基氯化铵、十六烷基三乙基溴化铵、十六烷基三乙基碘化铵、十八烷基三乙基氯化铵、十八烷基三乙基溴化铵、十八烷基三乙基碘化铵等。The method for producing a self-evolving color change indicator according to any one of claims 31 to 42, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and hexadecane. Trimethylammonium bromide, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethyl iodide Ammonium, cetyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyl Triethylammonium bromide, octadecyltriethylammonium iodide, and the like.
如权利要求43所述的自演化变色指示剂的制备方法，其中所述含卤素离子的阳离子型表面活性剂选自十六烷基三甲基氯化铵或十六烷基三甲基溴化铵。A method of producing a self-evolving color change indicator according to claim 43, wherein said halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethyl bromide. Ammonium.
如权利要求31-44中任一项所述的自演化变色指示剂的制备方法，其中所述还原剂选自抗坏血酸、异抗坏血酸或其衍生物。 The method of producing a self-evolving color change indicator according to any one of claims 31 to 44, wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
如权利要求45所述的自演化变色指示剂的制备方法，其中所述还原剂选自抗坏血酸或其水溶性盐、异抗坏血酸或其水溶性盐、卤代抗坏血酸及其水溶性盐、卤代异抗坏血酸及其水溶性盐。A method of producing a self-evolving color change indicator according to claim 45, wherein said reducing agent is selected from the group consisting of ascorbic acid or a water-soluble salt thereof, erythorbic acid or a water-soluble salt thereof, halogenated ascorbic acid and a water-soluble salt thereof, and halogenated Ascorbic acid and its water-soluble salts.
如权利要求45所述的自演化变色指示剂的制备方法，其中所述还原剂选自抗坏血酸、异抗坏血酸、抗坏血酸钠、异抗坏血酸钠、抗坏血酸钾、异抗坏血酸钾、抗坏血酸铵、异抗坏血酸铵、抗坏血酸钙、异抗坏血酸钙等水溶性盐。A method of producing a self-evolving color change indicator according to claim 45, wherein said reducing agent is selected from the group consisting of ascorbic acid, erythorbic acid, sodium ascorbate, sodium erythorbate, potassium ascorbate, potassium erythorbate, ammonium ascorbate, ammonium erythorbate, ascorbic acid. Water-soluble salts such as calcium and calcium ascorbate.
如权利要求31-47中任一项所述的自演化变色指示剂的制备方法，其中所述酸度调节剂为水溶性弱酸或其盐。The method for producing a self-evolving color change indicator according to any one of claims 31 to 47, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
如权利要求48所述的自演化变色指示剂的制备方法，其中所述酸度调节剂选自甲酸、乙酸、乳酸、柠檬酸、草酸、葡萄糖酸及其钠盐、钾盐、铵盐、钙盐等水溶性盐。The method according to claim 48, wherein the acidity adjusting agent is selected from the group consisting of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid, and sodium, potassium, ammonium, calcium salts thereof Water soluble salts.
如权利要求31-49中任一项所述的自演化变色指示剂的制备方法，其中所述可溶性银盐选自硝酸银、乙酸银、三氟乙酸银、高氯酸银、氟硼酸银等水溶性银盐。The method for producing a self-evolving color change indicator according to any one of claims 31 to 49, wherein the soluble silver salt is selected from the group consisting of silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, silver fluoroborate, and the like. Water soluble silver salt.
如权利要求31-50中任一项所述的自演化变色指示剂的制备方法，其中还加入基于变色指示剂总质量计大于等于1％、小于等于60％的防冻剂。The method for producing a self-evolving color change indicator according to any one of claims 31 to 50, wherein an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator is further added.
如权利要求51所述的自演化变色指示剂的制备方法，其中所述防冻剂选自乙二醇、丙二醇、丙三醇等。The method of producing a self-evolving color change indicator according to claim 51, wherein the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerin, and the like.
如权利要求31-52中任一项所述的自演化变色指示剂的制备方法，其中还加入基于变色指示剂总质量计大于等于0.01％、小于等于60％的黏度调节剂。The method for producing a self-evolving color change indicator according to any one of claims 31 to 52, wherein a viscosity modifier greater than or equal to 0.01% and less than or equal to 60% based on the total mass of the color change indicator is further added.
如权利要求53所述的自演化变色指示剂的制备方法，其中所述黏度调节剂选自卡波姆、黄原胶等。A method of producing a self-evolving color change indicator according to claim 53, wherein said viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.
如权利要求31-54中任一项所述的自演化变色指示剂的制备方法，其中还加入基于变色指示剂总质量计大于等于0.01％、小于等于10％的成胶剂。The method for producing a self-evolving color change indicator according to any one of claims 31 to 54, wherein a gelling agent of 0.01% by mass or more and 10% or less based on the total mass of the coloring indicator is further added.
如权利要求55所述的自演化变色指示剂的制备方法，其中所述成胶剂为水溶性成胶剂。A method of producing a self-evolving color change indicator according to claim 55, wherein said gel forming agent is a water-soluble gel forming agent.
如权利要求55所述的自演化变色指示剂的制备方法，其中所述成胶剂选自琼脂、明胶、琼脂糖、***胶、海藻酸钙、卡拉胶等。A method of preparing a self-evolving color change indicator according to claim 55, wherein said gelation The agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.
如权利要求31-57中任一项所述的自演化变色指示剂的制备方法，其中通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度、表面活性剂的浓度，可以实现改变由最初颜色变为最终颜色所需要的时间。The method for producing a self-evolving color change indicator according to any one of claims 31 to 57, wherein the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity adjuster, the concentration of the reducing agent, and the surfactant are adjusted. The concentration can be changed to the time required to change from the initial color to the final color.
一种易变质产品保质期的变色指示方法，其包括以下步骤：A color change indication method for a shelf life of a perishable product, comprising the following steps:

1)测量易变质产品在不同温度下特定质量参数随时间变化情况，得到相应温度下的产品变质所需时间；1) Measuring the variation of specific quality parameters of a perishable product at different temperatures with time, and obtaining the time required for product deterioration at the corresponding temperature;

2)提供权利要求1-30中任一项的自演化变色指示剂，并通过调节金属纳米材料的浓度、卤素离子的浓度、酸度调节剂的浓度、还原剂的浓度和表面活性剂的浓度中的一项或多项，使相应温度下易变质产品由最初颜色变为最终颜色所需要的时间与产品变质所需要的时间相等；2) Providing the self-evolving color change indicator of any one of claims 1 to 30, and by adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity regulator, the concentration of the reducing agent, and the concentration of the surfactant One or more times, the time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3)根据易变质产品变色过程，得到溶液颜色与产品的变质程度对应关系，指示易变质产品保质期。3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.
如权利要求59所述的易变质产品保质期的变色指示方法，其特征在于，变质产品特定质量参数为：菌群数量、有效成份含量、有害成份含量。 The method for indicating discoloration of a perishable product according to claim 59, wherein the specific quality parameter of the deteriorating product is: the number of the flora, the content of the active ingredient, and the content of the harmful component.