CN116790248B - A zinc-nitrogen doped carbon dot and its preparation method and application - Google Patents

A zinc-nitrogen doped carbon dot and its preparation method and application Download PDF

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CN116790248B
CN116790248B CN202310661429.4A CN202310661429A CN116790248B CN 116790248 B CN116790248 B CN 116790248B CN 202310661429 A CN202310661429 A CN 202310661429A CN 116790248 B CN116790248 B CN 116790248B
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陈龙
徐昊
何旷
田耀旗
缪铭
金征宇
周星
邹益东
陈冠雄
徐振林
孟嫚
谢正军
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Abstract

本发明公开了一种锌氮掺杂碳点及其制备方法和应用,属于纳米碳材料和新材料技术领域。本发明的制备具有高荧光强度的新型金属掺杂型碳点的方法,是将类儿茶酚胺类物质与金属盐溶液混合发生自组装金属多酚配位反应,形成一体化碳源、氮源和金属源的金属多酚复合前驱体溶液;再采用水热反应一步法制备具有高荧光量子产率和发光强度的新型金属掺杂型碳点。本发明成本低、方法简单、无污染,副产物少,所制备的碳点稳定且具有高荧光量子产率(78%),可以用于铁离子的检测,适合用于食品质量检测、环境监测和食品智能包装等方面。

The invention discloses a zinc-nitrogen doped carbon dot and its preparation method and application, and belongs to the technical field of nanocarbon materials and new materials. The method of the present invention for preparing new metal-doped carbon dots with high fluorescence intensity is to mix catecholamine-like substances and metal salt solutions to undergo a self-assembled metal-polyphenol coordination reaction to form an integrated carbon source, nitrogen source and metal The source metal polyphenol composite precursor solution is used; and then a one-step hydrothermal reaction method is used to prepare new metal-doped carbon dots with high fluorescence quantum yield and luminescence intensity. The method has low cost, simple method, no pollution, and few by-products. The prepared carbon dots are stable and have high fluorescence quantum yield (78%). They can be used for the detection of iron ions and are suitable for food quality detection and environmental monitoring. and food smart packaging.

Description

一种锌氮掺杂碳点及其制备方法和应用A zinc-nitrogen doped carbon dot and its preparation method and application

技术领域Technical field

本发明涉及一种锌氮掺杂碳点及其制备方法和应用,尤其涉及一种具有高荧光量子产率的锌氮元素掺杂碳点及其制备方法和应用,属于纳米碳材料和新材料技术领域。The invention relates to a zinc-nitrogen doped carbon dot and its preparation method and application, in particular to a zinc-nitrogen doped carbon dot with high fluorescence quantum yield and its preparation method and application, which belongs to nanocarbon materials and new materials. technical field.

背景技术Background technique

碳点也称为碳量子点或碳纳米点,2004年,Xu等人在制备单壁碳纳米管的过程中首次发现并报道了具有荧光性质的碳量子点。碳点的发现开创了荧光纳米材料的新的发展方向,随着对碳点的深入研究发现,碳点是一类具有良好荧光光学性能的零维碳纳米材料,它通常由分散的、尺寸低于10nm的碳纳米颗粒组成。同时,更多的研究发现,碳点不仅具有与半导体量子点相媲美的荧光性能,而且还具有高稳定性,低毒性以及较好的生物相溶性等优点。在生产中,碳点原料成本低,制备方法简单,因此,容易实现大规模生产。这些优点使得碳点在生物标记、医学成像、医疗诊断、环境监测、食品分析检测、智能食品包装等领域具有广阔的应用前景。特别是在金属离子监测方面,例如饮用水或饮料中铁超标容易导致身体各脏器功能损害,并引发严重的毒性反应,而土壤中铁超标除了对人体伤害外,还严重降低植物光合作用,影响植物的生长发育,而在医疗诊断中则可通过监测铁离子浓度或追踪含铁蛋白来监测人体健康或进行病理研究。Carbon dots are also called carbon quantum dots or carbon nanodots. In 2004, Xu et al. first discovered and reported carbon quantum dots with fluorescent properties during the preparation of single-walled carbon nanotubes. The discovery of carbon dots has created a new development direction for fluorescent nanomaterials. With in-depth research on carbon dots, it has been found that carbon dots are a type of zero-dimensional carbon nanomaterials with good fluorescent optical properties. They are usually composed of dispersed, low-size carbon dots. Composed of 10nm carbon nanoparticles. At the same time, more research has found that carbon dots not only have fluorescence properties comparable to semiconductor quantum dots, but also have the advantages of high stability, low toxicity, and good biocompatibility. In production, the cost of carbon dot raw materials is low and the preparation method is simple. Therefore, large-scale production is easy to achieve. These advantages make carbon dots have broad application prospects in the fields of biomarkers, medical imaging, medical diagnosis, environmental monitoring, food analysis and testing, smart food packaging and other fields. Especially in terms of metal ion monitoring, for example, excessive iron in drinking water or beverages can easily cause damage to the functions of various organs of the body and cause severe toxic reactions. In addition to harming the human body, excessive iron in soil can also seriously reduce plant photosynthesis and affect plants. growth and development, and in medical diagnosis, human health or pathological research can be monitored by monitoring iron ion concentration or tracking iron-containing protein.

然而,根据原料的不同,大多数制备出的碳点不具有荧光发光性质或者荧光较弱难以用于进一步应用,而且,部分荧光较强的碳纳米点的原料具有毒性和化学危险性,例如间二苯酚、对苯二酚等是较强的致癌物质,这些都限制了碳点在生物、医疗和食品领域的进一步广泛应用。有比如,CN 105131948A中公开了一种具有高荧光量子产率的金属掺杂碳点及其制备方法和应用,其使用了柠檬酸钠和氯化亚铜作为原料,虽然其制备的碳点具有较强的荧光强度和70%的荧光量子产率,并可以用于检测铁离子,但是该方案存在如下问题,所用原料氯化亚铜是一种强还原性物质,在使用过程中具有强腐蚀性,存在极大的使用安全风险,其还原后残留的铜离子是常见的有毒金属离子,对人体和环境具有显而易见的毒性,应用受限较大,另外,该专利提及氯化亚铜和/硫酸铜,但并未证明是亚铜离子还是铜离子形成的优势碳点,但显而易见的是,铜离子外层电子轨道特性并不适用于制备高荧光量子产率的碳点,而该专利也最终选择了亚铜离子作为原料,因此可以推断的是,亚铜离子是该专利的主要铜源,但如前所述,亚铜离子极不稳定,尤其在水中易被氧化,因此在制备过程中需时刻保持亚铜离子电子轨道状态,例如通氮气或在其它无氧状态下,其步骤复杂,所需实验条件苛刻。而形成的亚铜离子碳点也存在显而易见的易失电子还原反应,这容易导致所得碳点在使用期间稳定性差的问题。因此,通过选择无毒的原料,并进行合理的结构调控设计来提高碳点的发光性能和生物相溶性是一种拓宽其应用范围的有效途径。However, depending on the raw materials, most of the prepared carbon dots do not have fluorescent properties or have weak fluorescence and are difficult to use for further applications. Moreover, the raw materials of some highly fluorescent carbon nanodots are toxic and chemically dangerous, such as metabolites. Diphenol, hydroquinone, etc. are strong carcinogens, which limit the further widespread application of carbon dots in the biological, medical and food fields. For example, CN 105131948A discloses a metal-doped carbon dot with high fluorescence quantum yield and its preparation method and application. It uses sodium citrate and cuprous chloride as raw materials, although the carbon dots prepared have It has strong fluorescence intensity and 70% fluorescence quantum yield, and can be used to detect iron ions. However, this solution has the following problems. The raw material used, cuprous chloride, is a strongly reducing substance and has strong corrosion during use. It is highly toxic and poses great safety risks. The copper ions remaining after its reduction are common toxic metal ions, which are obviously toxic to the human body and the environment, and their applications are greatly limited. In addition, the patent mentions cuprous chloride and / copper sulfate, but it has not been proven whether cuprous ions or copper ions form the dominant carbon dots, but it is obvious that the outer electron orbital characteristics of copper ions are not suitable for preparing carbon dots with high fluorescence quantum yield, and this patent Cuprous ions were finally chosen as the raw material, so it can be inferred that cuprous ions are the main source of copper for this patent. However, as mentioned above, cuprous ions are extremely unstable and are easily oxidized especially in water. Therefore, during the preparation During the process, the electron orbital state of cuprous ions must be maintained at all times, such as by flowing nitrogen or other oxygen-free conditions. The steps are complicated and the experimental conditions required are harsh. The formed cuprous ion carbon dots also have obvious volatile electron reduction reactions, which easily leads to the problem of poor stability of the obtained carbon dots during use. Therefore, improving the luminescence performance and biocompatibility of carbon dots by selecting non-toxic raw materials and conducting reasonable structural control design is an effective way to broaden their application scope.

目前,现有的方法和技术中,对碳点进行元素掺杂是一种常用方法,但目前大多数元素掺杂都集中在氮、硫、磷、硼等元素的单掺杂或双掺杂,而原料则选择柠檬酸钠或对苯二胺为碳源,硼酸、硫酰胺或氨基酸作为硼源、硫源和氮源,所需原料多,具有化学危险性,成本高,荧光量子产率较低,这使得碳点的进一步应用依然受限。例如,《基于氨基酸分子制备聚合物碳点的荧光机理和应用研究》文献中公开了利用丝氨酸和色氨酸为原料结合200℃水热法制备氮掺杂碳点的方案,该方案制备的碳点荧光量子产率最高仅为46.83%,对Fe3+具有选择性,但仅具有一定的猝灭响应,并没有详细的最低检测限。而在《基于元素、官能团和空间构象传递策略的荧光碳点的制备及其细胞成像应用》文献中公开了一种利用对苯二胺、3-甲酰基苯基硼酸和乙醇为原料的180℃水热24h制备氮、硼掺杂型碳点,该碳点荧光强度仅为55左右,而且不具有Fe3+检测性能,同时,该碳点所用原料对苯二胺已被列为致癌物,具有可燃性,是一种危险化学品;在该论文中同样公开了另一种利用半胱氨酸和柠檬酸为原料在200℃下水热反应60min制备的碳点材料,该碳点荧光量子产率仅为68%,并不具备Fe3+检测性能。另外,在《基于葡萄糖酸盐制备的金属离子掺杂碳点及其结构与性能研究》文献中,公开了一种利用葡萄糖酸锌为原料,在N2气氛下,160℃经1h煅烧所得的锌离子掺杂型碳点,该碳点荧光量子产率仅为13.98%,强度仅为450左右,该碳点仅可以检测Zn2+,然而葡萄糖酸锌成本高,该碳点制备方法较危险和复杂,需通入N2稳定反应。Currently, among the existing methods and technologies, element doping of carbon dots is a common method, but most of the current element doping focuses on single or double doping of nitrogen, sulfur, phosphorus, boron and other elements. , and the raw materials are sodium citrate or p-phenylenediamine as the carbon source, and boric acid, sulfamide or amino acid as the boron source, sulfur source and nitrogen source. Many raw materials are required, which are chemically dangerous, high cost and low fluorescence quantum yield. Lower, which still limits the further application of carbon dots. For example, the document "Research on Fluorescence Mechanism and Application of Polymer Carbon Dots Prepared Based on Amino Acid Molecules" discloses a plan to prepare nitrogen-doped carbon dots using serine and tryptophan as raw materials combined with a 200°C hydrothermal method. The carbon dots prepared by this plan The highest point fluorescence quantum yield is only 46.83%, which is selective for Fe 3+ , but only has a certain quenching response and no detailed minimum detection limit. In the document "Preparation of Fluorescent Carbon Dots Based on Elements, Functional Groups and Spatial Conformation Transfer Strategies and Their Application in Cell Imaging", a 180℃ method using p-phenylenediamine, 3-formylphenylboronic acid and ethanol as raw materials is disclosed. Nitrogen- and boron-doped carbon dots were prepared by hydrothermal treatment for 24 hours. The fluorescence intensity of the carbon dots is only about 55, and it does not have Fe 3+ detection performance. At the same time, the raw material used for the carbon dots, p-phenylenediamine, has been listed as a carcinogen. It is flammable and is a dangerous chemical; the paper also disclosed another carbon dot material prepared by hydrothermal reaction at 200°C for 60 minutes using cysteine and citric acid as raw materials. The carbon dot fluorescence quantum product The rate is only 68% and does not have Fe 3+ detection performance. In addition, in the document "Research on Metal Ion-Doped Carbon Dots Prepared Based on Gluconate and Their Structure and Properties", a method using zinc gluconate as raw material and calcined at 160°C for 1 hour under N2 atmosphere is disclosed. Zinc ion-doped carbon dots have a fluorescence quantum yield of only 13.98% and an intensity of only about 450. This carbon dot can only detect Zn 2+ . However, the cost of zinc gluconate is high and the preparation method of this carbon dot is dangerous. and complex, N 2 needs to be introduced to stabilize the reaction.

另一些研究中运用了多巴胺作为碳点制备原料,例如,Qu等人公开了一种单独以多巴胺为原料,在180℃水热反应6h制备了多巴胺基碳点,尽管多巴胺无毒,但其制备的碳点荧光性质极弱,荧光强度仅为650左右,而且尺寸难以控制,在重复该实验后发现,该多巴胺基碳点由于表面伯氨基和酚羟基的氧化聚合,容易形成不均匀的聚集体,从而导致荧光猝灭,稳定性差,特别是随着储存时间的延长,聚集程度会更大,无法进一步有效应用。另外Kang等人公开了一种以多巴胺和邻苯二胺为原料,在180℃下水热6h所制备的碳点,该碳点荧光强度仅为3700左右,在乙醇溶液中的荧光量子产率仅为28%,而且该碳点所用原料有邻苯二胺,其风险如前所述。与本发明相比,上述已公开的碳点及其制备方法无论是从安全性还是效果都不够理想。In other studies, dopamine was used as a raw material for the preparation of carbon dots. For example, Qu et al. disclosed a method to prepare dopamine-based carbon dots using dopamine alone as a raw material and a hydrothermal reaction at 180°C for 6 hours. Although dopamine is non-toxic, its preparation The fluorescence properties of the carbon dots are extremely weak, the fluorescence intensity is only about 650, and the size is difficult to control. After repeating the experiment, it was found that the dopamine-based carbon dots tend to form uneven aggregates due to the oxidative polymerization of surface primary amino groups and phenolic hydroxyl groups. , resulting in fluorescence quenching and poor stability. Especially as the storage time is extended, the degree of aggregation will be greater and further effective application cannot be achieved. In addition, Kang et al. disclosed a carbon dot prepared using dopamine and o-phenylenediamine as raw materials and hydrothermal treatment at 180°C for 6 hours. The fluorescence intensity of the carbon dot was only about 3700, and the fluorescence quantum yield in ethanol solution was only It is 28%, and the raw material used in this carbon dot contains o-phenylenediamine, and its risks are as mentioned above. Compared with the present invention, the above disclosed carbon dots and their preparation methods are not ideal in terms of safety or effect.

因此,亟需开发一种具有高荧光量子产率、高发光强度、原料和产物无毒的能够用于铁离子检测的新型碳点,这对于拓宽碳点应用领域,尤其在高效食品危害物分析检测、医学精准成像、环境监测以及可视化食品智能包装技术等领域具有重要的技术价值和经济社会意义。Therefore, there is an urgent need to develop a new type of carbon dots that can be used for iron ion detection with high fluorescence quantum yield, high luminescence intensity, non-toxic raw materials and products, which will help expand the application fields of carbon dots, especially in efficient food hazard analysis. The fields of detection, medical precision imaging, environmental monitoring, and visual food intelligent packaging technology have important technical value and economic and social significance.

发明内容Contents of the invention

[技术问题][technical problem]

现有碳点,荧光强度弱、量子产率低、原料多或原料危险性大或不可用于铁离子的检测,导致其应用受限。Existing carbon dots have weak fluorescence intensity, low quantum yield, many raw materials or dangerous raw materials, or cannot be used for the detection of iron ions, resulting in limited applications.

[技术方案][Technical solutions]

为了解决上述至少一个问题,本发明利用金属多酚复合物以作为碳点的碳源、氮源和金属源,并通过简单的一步水热法制备具有高荧光量子产率和高发光强度的金属和氮元素双掺杂的新型碳点,特别提供了一种锌氮掺杂碳点及其制备方法。该方法简单、绿色、无污染、反应速度快、原料用量少、低成本,用于检测铁离子的检测限比较低。目前还没有利用金属多酚网络制备的碳点,而与现有的碳点相比,本发明制备的锌氮掺杂碳点具有更高的荧光量子产率和发光强度。In order to solve at least one of the above problems, the present invention utilizes metal polyphenol complexes as carbon sources, nitrogen sources and metal sources of carbon dots, and prepares metals with high fluorescence quantum yield and high luminescence intensity through a simple one-step hydrothermal method. New carbon dots doubly doped with nitrogen elements, in particular, a zinc-nitrogen doped carbon dot and a preparation method thereof are provided. The method is simple, green, pollution-free, has fast reaction speed, uses less raw materials, is low-cost, and has a relatively low detection limit for detecting iron ions. At present, there are no carbon dots prepared using metal polyphenol networks. Compared with existing carbon dots, the zinc-nitrogen-doped carbon dots prepared by the present invention have higher fluorescence quantum yield and luminescence intensity.

本发明的第一个目的是提供一种制备锌氮掺杂碳点的方法,包括如下步骤:The first object of the present invention is to provide a method for preparing zinc-nitrogen-doped carbon dots, which includes the following steps:

(1)碳源和氮源溶液:(1) Carbon source and nitrogen source solution:

将类儿茶酚胺类物质溶解于去离子水中,调节酸碱度得到类儿茶酚胺类物质碳源和氮源溶液;Dissolve catecholamine-like substances in deionized water and adjust the pH to obtain a carbon source and nitrogen source solution of catecholamine-like substances;

(2)金属多酚配位复合物前驱体溶液:(2) Metal polyphenol coordination complex precursor solution:

将类儿茶酚胺类物质溶液与金属盐溶液混合制备金属多酚复合物前驱体溶液;所述金属盐溶液中的金属为锌;A metal polyphenol complex precursor solution is prepared by mixing a catecholamine-like substance solution and a metal salt solution; the metal in the metal salt solution is zinc;

(3)水热反应制备锌氮掺杂碳点。(3) Hydrothermal reaction to prepare zinc-nitrogen-doped carbon dots.

在本发明的一种实施方式中,步骤(1)所述的类儿茶酚胺类物质溶液是将类儿茶酚胺类物质溶解在去离子水中得到,浓度为5-60mg/mL。In one embodiment of the present invention, the catecholamine-like substance solution in step (1) is obtained by dissolving the catecholamine-like substance in deionized water, with a concentration of 5-60 mg/mL.

在本发明的一种实施方式中,步骤(1)所述的类儿茶酚胺类物质溶液的酸碱度调节为1-4。In one embodiment of the present invention, the pH of the catecholamine-like substance solution described in step (1) is adjusted to 1-4.

在本发明的一种实施方式中,步骤(1)所述的类儿茶酚胺类物质包括3,4-二羟基氢肉桂酸、5,6-二羟基吲哚、L-多巴胺、儿茶酚胺、盐酸多巴胺或多巴胺中的一种。多巴胺中存在的氨基结构和酚羟基结构在本发明的金属配位作用中起到至关重要的作用,特别是在碳点合成过程中,通过氨基和羟基与锌离子的配位反应,容易将锌元素引入聚合物碳点体系,并一步生成荧光碳点,因此含有氨基或易开环的吲哚基团以及羟基的儿茶酚胺类物质理论上都能作为该碳点合成的原料。In one embodiment of the present invention, the catecholamine-like substances described in step (1) include 3,4-dihydroxyhydrocinnamic acid, 5,6-dihydroxyindole, L-dopamine, catecholamine, dopamine hydrochloride or A type of dopamine. The amino structure and phenolic hydroxyl structure present in dopamine play a vital role in the metal coordination of the present invention. Especially in the carbon dot synthesis process, through the coordination reaction of amino and hydroxyl groups with zinc ions, it is easy to Zinc element is introduced into the polymer carbon dot system and generates fluorescent carbon dots in one step. Therefore, catecholamines containing amino groups or easily ring-opening indole groups and hydroxyl groups can theoretically be used as raw materials for the synthesis of carbon dots.

在本发明的一种实施方式中,步骤(2)所述的金属盐溶液是将金属盐溶解于去离子水中得到的,浓度为1-30mg/ml。In one embodiment of the present invention, the metal salt solution in step (2) is obtained by dissolving the metal salt in deionized water, with a concentration of 1-30 mg/ml.

在本发明的一种实施方式中,步骤(2)所述的金属盐和类儿茶酚胺类物质的质量比为0.1:1~3:1。In one embodiment of the present invention, the mass ratio of the metal salt and the catecholamine-like substance in step (2) is 0.1:1 to 3:1.

在本发明的一种实施方式中,步骤(2)所述的反应是200-400rpm、20-25℃下反应1-10min。In one embodiment of the present invention, the reaction in step (2) is carried out at 200-400 rpm and 20-25°C for 1-10 min.

在一种实施方式中,所述步骤(3)包括:将前驱体溶液加入水热高压反应釜中反应一定时间、然后自然冷却至45℃得到粗碳点分散液。In one embodiment, the step (3) includes: adding the precursor solution into a hydrothermal high-pressure reactor to react for a certain period of time, and then naturally cooling it to 45°C to obtain a crude carbon dot dispersion.

在本发明的一种实施方式中,步骤(3)所述的水热高压反应釜为具有聚四氟乙烯内衬的不锈钢法兰高压釜并配备温控加热炉。In one embodiment of the present invention, the hydrothermal high-pressure reactor described in step (3) is a stainless steel flange autoclave lined with polytetrafluoroethylene and equipped with a temperature-controlled heating furnace.

在本发明的一种实施方式中,步骤(3)所述的水热反应温度为115-205℃,压力为1MPa,优选为140-180℃,反应时间为1.5-8h,优选为4-6h。In one embodiment of the present invention, the hydrothermal reaction temperature in step (3) is 115-205°C, the pressure is 1MPa, preferably 140-180°C, and the reaction time is 1.5-8h, preferably 4-6h .

在一种实施方式中,所述方法还包括步骤(4)纯化分离;可选地,具体是:将粗碳点分散液利用微滤膜初步分离得到二级碳点分散液,并将二级碳点分散液置于透析袋中透析得到碳点溶液。In one embodiment, the method further includes step (4) purification and separation; optionally, specifically: preliminarily separating the crude carbon dot dispersion liquid using a microfiltration membrane to obtain a secondary carbon dot dispersion liquid, and converting the secondary carbon dot dispersion liquid into The carbon dot dispersion is placed in a dialysis bag and dialyzed to obtain a carbon dot solution.

在本发明的一种实施方式中,步骤(4)所述的透析袋截留分子量为1kDa、2kDa、3.5kDa、20kDa或50kDa中的任意一种或至少两种组合。In one embodiment of the present invention, the molecular weight cutoff of the dialysis bag in step (4) is any one or a combination of at least two of 1kDa, 2kDa, 3.5kDa, 20kDa or 50kDa.

在本发明的一种实施方式中,步骤(4)所述的透析时间为8-72h。In one embodiment of the present invention, the dialysis time in step (4) is 8-72 hours.

在一种实施方式中,所述方法还包括步骤((5)浓缩干燥;可选地,具体是将碳点溶液置于圆底烧瓶中浓缩并冷冻干燥或高温烘干得到所述铁氮掺杂碳点。In one embodiment, the method further includes step (5) concentrating and drying; optionally, specifically placing the carbon dot solution in a round-bottomed flask, concentrating and freeze-drying or drying at high temperature to obtain the iron-nitrogen-doped solution. Miscellaneous carbon dots.

在本发明的一种实施方式中,步骤(5)所述的浓缩温度为80-100℃。In one embodiment of the present invention, the concentration temperature in step (5) is 80-100°C.

在本发明的一种实施方式中,步骤(5)所述的冷冻干燥在真空条件下进行,温度为-100~-40℃,干燥时间为12-48h,烘箱干燥在常压下进行,温度为70-100℃,干燥时间为12-24h。In one embodiment of the present invention, the freeze-drying in step (5) is performed under vacuum conditions, the temperature is -100~-40°C, the drying time is 12-48h, and the oven drying is performed under normal pressure, and the temperature The temperature is 70-100℃ and the drying time is 12-24h.

本发明的第二个目的是本发明所述的方法制备得到的一种锌氮掺杂碳点。The second object of the present invention is a zinc-nitrogen doped carbon dot prepared by the method of the present invention.

本发明的第三个目的是本发明所述的锌氮掺杂碳点在食品检测、环境监测或包装领域中的应用,用于铁离子(或含铁物质,比如铁蛋白)的检测。The third object of the present invention is the application of the zinc-nitrogen-doped carbon dots of the present invention in the fields of food testing, environmental monitoring or packaging, for the detection of iron ions (or iron-containing substances, such as ferritin).

可选地,所述应用是指在金属离子监测方面;例如饮用水或饮料中铁超标容易导致身体各脏器功能损害,并引发严重的毒性反应;而土壤中铁超标除了对人体伤害外,还严重降低植物光合作用,影响植物的生长发育;在医疗诊断中则可通过监测铁离子浓度或追踪含铁蛋白来监测人体健康或进行病理研究。Optionally, the application refers to metal ion monitoring; for example, excessive iron in drinking water or beverages can easily lead to functional damage to various organs of the body and trigger severe toxic reactions; while excessive iron in soil, in addition to causing serious harm to the human body, can also seriously It reduces plant photosynthesis and affects the growth and development of plants; in medical diagnosis, it can be used to monitor human health or conduct pathological research by monitoring iron ion concentration or tracking iron-containing protein.

本发明的第四个目的是提供一种食品检测材料,其含有本发明所述的一种锌氮掺杂碳点。可选地,将含有本发明所述碳点的检测试纸浸润食品提取液或流体食品样品液,浸润后,利用荧光分光光度计检测试纸荧光强度。The fourth object of the present invention is to provide a food testing material, which contains a zinc-nitrogen-doped carbon dot according to the present invention. Optionally, the detection test paper containing the carbon dots of the present invention is infiltrated into the food extract liquid or the fluid food sample liquid. After infiltration, a fluorescence spectrophotometer is used to detect the fluorescence intensity of the test paper.

本发明的第五个目的是提供一种环境监测材料,其含有本发明所述的一种锌氮掺杂碳点。可选地,在水环境中可以通过在样品水溶液中添加该碳点,并直接通过荧光分光光度计检测该样品溶液荧光强度。进一步地,可以根据荧光强度来判断铁离子浓度。The fifth object of the present invention is to provide an environmental monitoring material, which contains a zinc-nitrogen doped carbon dot according to the present invention. Alternatively, in a water environment, the carbon dots can be added to the sample aqueous solution, and the fluorescence intensity of the sample solution can be directly detected using a fluorescence spectrophotometer. Furthermore, the iron ion concentration can be determined based on the fluorescence intensity.

本发明的第六个目的是提供一种包装材料,其含有本发明所述的一种锌氮掺杂碳点。可选地,针对流体食品包装材料,该材料中可以复合含有本发明所述碳点的标签材料,如果食品中金属离子超标,可以通过包装材料的上的碳点荧光标签的发光程度来判断铁离子含量。The sixth object of the present invention is to provide a packaging material containing a zinc-nitrogen-doped carbon dot according to the present invention. Optionally, for liquid food packaging materials, label materials containing carbon dots of the present invention can be compounded into the materials. If the metal ions in the food exceed the standard, the iron content can be judged by the luminescence degree of the carbon dot fluorescent labels on the packaging materials. ion content.

[有益效果][beneficial effect]

(1)本发明是基于自组装金属多酚配位反应优先制备一体化碳源、氮源和金属源的金属多酚复合物碳点前驱体,通过氮元素和金属铁的电子轨道排布的改变和能级跃迁,大大提高多巴胺碳点的荧光量子产率和荧光强度,通过调节酸碱度来控制金属多酚网络配体结构可以实现金属掺杂碳点的性能定量调控,并借助金属多酚网络外富含的氨基和羟基等亲水性基团(该类基团可与蛋白、水分子或同样富含羟基的溶液相互作用从而提高相溶性),赋予该碳点亲水性、生物相溶性、高荧光强度、无毒、无污染的有益效果。(1) The present invention is based on the self-assembly metal polyphenol coordination reaction to preferentially prepare a metal polyphenol composite carbon dot precursor that integrates carbon source, nitrogen source and metal source, and is arranged through the electron orbits of nitrogen element and metal iron. Changes and energy level transitions greatly improve the fluorescence quantum yield and fluorescence intensity of dopamine carbon dots. By adjusting the pH to control the ligand structure of the metal polyphenol network, quantitative control of the performance of metal doped carbon dots can be achieved, and with the help of the metal polyphenol network The carbon dots are rich in hydrophilic groups such as amino groups and hydroxyl groups (such groups can interact with proteins, water molecules or solutions also rich in hydroxyl groups to improve compatibility), giving the carbon dots hydrophilicity and biocompatibility. , high fluorescence intensity, non-toxic, non-polluting beneficial effects.

(2)本发明选用食品级硫酸锌、食品级聚乙二醇和无毒的盐酸多巴胺,原料安全,无制备风险,无环境污染风险,无人体健康风险。另外,本发明所用锌离子具有稳定性,同时借助金属离子配位反应形成更稳定的配合物,在不需要通氮气或其它无氧状态下,能够稳定并一步掺杂形成高荧光碳点,本发明制备方法简单,而且效果明显。(2) The present invention uses food-grade zinc sulfate, food-grade polyethylene glycol and non-toxic dopamine hydrochloride. The raw materials are safe and there are no preparation risks, no environmental pollution risks, and no human health risks. In addition, the zinc ions used in the present invention are stable and can form more stable complexes through metal ion coordination reactions. They can be stably and doped to form highly fluorescent carbon dots in one step without the need for nitrogen or other oxygen-free conditions. The preparation method of the invention is simple and has obvious effects.

(3)本发明制备的金属掺杂碳点稳定且无毒,其量子产率可达78%;可用于检测铁离子,使得铁离子检测的最低限可以达到2.95μM。(3) The metal-doped carbon dots prepared by the present invention are stable and non-toxic, and their quantum yield can reach 78%; they can be used to detect iron ions, so that the lowest limit for iron ion detection can reach 2.95 μM.

(4)本发明适合应用于水污染监测、食品饮料中金属离子监测等,也具有监测体内金属离子的潜在优势;本发明在食品质量检测、食品智能包装、医学成像等方面具有广阔应用前景。(4) The present invention is suitable for water pollution monitoring, metal ion monitoring in food and beverages, etc., and also has the potential advantage of monitoring metal ions in the body; the present invention has broad application prospects in food quality detection, food intelligent packaging, medical imaging, etc.

附图说明Description of the drawings

图1为实施例1~5和对比例1~6所制备的碳点的荧光强度对比图。Figure 1 is a comparison chart of the fluorescence intensity of carbon dots prepared in Examples 1 to 5 and Comparative Examples 1 to 6.

图2为实施例1~5和对比例1~6所制备的碳点的荧光量子产率对比图。Figure 2 is a comparison chart of the fluorescence quantum yield of carbon dots prepared in Examples 1 to 5 and Comparative Examples 1 to 6.

图3为实施例1所制备的碳点不同激发波长下的发射光谱图。Figure 3 shows the emission spectra of the carbon dots prepared in Example 1 at different excitation wavelengths.

图4为对比例1所制备的碳点不同激发波长下的发射光谱图。Figure 4 shows the emission spectra of the carbon dots prepared in Comparative Example 1 under different excitation wavelengths.

具体实施方式Detailed ways

以下对本发明的优选实施例进行说明,应当理解实施例是为了更好地解释本发明,不用于限制本发明。Preferred embodiments of the present invention are described below. It should be understood that the embodiments are for the purpose of better explaining the present invention and are not intended to limit the present invention.

测试方法:Test Methods:

1、荧光量子产率测试:采用荧光光谱仪通过参比法分析测试金属掺杂碳点和参比溶液的荧光信号参数以计算其荧光量子产率。1. Fluorescence quantum yield test: Use a fluorescence spectrometer to analyze and test the fluorescence signal parameters of metal-doped carbon dots and reference solutions through the reference method to calculate their fluorescence quantum yield.

具体操作步骤如下:配制适宜浓度的硫酸奎宁溶液,测定其紫外吸收光谱,记录其在350nm处的吸光度(A2),确保该吸光度值小于0.05;然后以350nm为其激发波长,获取其在380–620nm范围内的荧光发射光谱,记录其荧光积分峰面积(S2);同样地,配制一定浓度的碳点溶液,重复以上步骤,记录其吸光度(A1)和荧光积分峰面积(S1);按如下公式计算金属掺杂碳点的荧光量子产率。The specific steps are as follows: Prepare a quinine sulfate solution of appropriate concentration, measure its UV absorption spectrum, record its absorbance (A2) at 350nm, and ensure that the absorbance value is less than 0.05; then use 350nm as its excitation wavelength to obtain its absorbance at 380nm. Fluorescence emission spectrum in the range of –620nm, record its fluorescence integrated peak area (S2); similarly, prepare a certain concentration of carbon dot solution, repeat the above steps, record its absorbance (A1) and fluorescence integrated peak area (S1); press The following formula is used to calculate the fluorescence quantum yield of metal-doped carbon dots.

Y1=Y2(S1/S2)(A2/A1)(n1/n2)Y 1 =Y 2 (S 1 /S 2 )(A 2 /A 1 )(n 1 /n 2 )

2、荧光强度测试:采用荧光光谱仪,利用荧光分析法,对分析物质进行荧光强度测定。2. Fluorescence intensity test: Use a fluorescence spectrometer and fluorescence analysis method to measure the fluorescence intensity of the analyzed substance.

3、铁离子检测限的测试:采用荧光光谱仪,利用荧光分析法,对梯度稀释的铁离子溶液进行测试,每个浓度测试3-5次,得到斜率值σ,并对空白样进行11次测试得出空白样检测值标准差S,利用如下公式进行计算:LOD=3σ/S。3. Testing of the iron ion detection limit: Use a fluorescence spectrometer and fluorescence analysis method to test the gradient diluted iron ion solution. Each concentration is tested 3-5 times to obtain the slope value σ, and the blank sample is tested 11 times. The standard deviation S of the blank sample detection value is obtained and calculated using the following formula: LOD=3σ/S.

实施例1:一种制备锌氮掺杂碳点的方法Example 1: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为3的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

实施例2:一种制备锌氮掺杂碳点的方法Example 2: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为3的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应6h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 6 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

实施例3:一种制备锌氮掺杂碳点的方法Example 3: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为3的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate, dissolve them in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix evenly with ultrasonic (100W, 5 min) And react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应5h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 5 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

实施例4:一种制备锌氮掺杂碳点的方法Example 4: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为1的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 1 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

实施例5:一种制备锌氮掺杂碳点的方法Example 5: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为4的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 4 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

实施例6:一种制备锌氮掺杂碳点的方法Example 6: A method of preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和300mg七水合硫酸锌,溶解于10mL,pH为3的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 300 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应5h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 5 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。对比例1:一种制备不掺杂锌碳点的方法The concentrated solution was placed in a freeze dryer and freeze-dried for 48 hours, and the powder was collected to obtain zinc ion-doped carbon dot solid powder. Comparative Example 1: A method of preparing zinc-free carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,溶解于10mL蒸馏水中,用10mL聚乙二醇-200混合,制得碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride, dissolve it in 10 mL of distilled water, and mix with 10 mL of polyethylene glycol-200 to prepare a carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应6h得到碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 6 hours to obtain a crude carbon dot solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the above carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution into a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours. Change to new distilled water every 24 hours for dialysis. The carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain carbon dot solid powder.

对比例2:一种锌氮掺杂型碳点的制备方法Comparative Example 2: A method for preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为7的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate, dissolve them in 10 mL of distilled water with a pH of 7 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix evenly with ultrasonic (100W, 5 min) And react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。对比例3:一种锌氮掺杂型碳点的制备方法The concentrated solution was placed in a freeze dryer and freeze-dried for 48 hours, and the powder was collected to obtain zinc ion-doped carbon dot solid powder. Comparative Example 3: A method for preparing zinc-nitrogen doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,和200mg七水合硫酸锌,溶解于10mL,pH为9的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 200 mg of zinc sulfate heptahydrate, dissolve them in 10 mL of distilled water with a pH of 9 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix evenly with ultrasonic (100W, 5 min) And react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。对比例4:一种铁掺杂型碳点的制备方法The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder. Comparative Example 4: A method for preparing iron-doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,和200mg六水合三氯化铁,溶解于10mL,pH为3的蒸馏水中制得三氯化铁和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg dopamine hydrochloride and 200 mg ferric chloride hexahydrate, dissolve it in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of ferric chloride and dopamine, mix it with 10 mL polyethylene glycol-200, and pass it through ultrasonic (100W, 5min), mix evenly and react for 10min to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到铁离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a crude iron ion-doped carbon dot solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述铁离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the above crude solution of iron ion doped carbon dots through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得铁离子掺杂碳点固体粉末。对比例5:一种铁掺杂型碳点的制备方法The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain iron ion-doped carbon dot solid powder. Comparative Example 5: A method for preparing iron-doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取200mg盐酸多巴胺,和100mg六水合三氯化铁,溶解于10mL,pH为3的蒸馏水中制得三氯化铁和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 100 mg of ferric chloride hexahydrate, dissolve it in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of ferric chloride and dopamine, mix it with 10 mL of polyethylene glycol-200, and pass it through ultrasonic (100W, 5min), mix evenly and react for 10min to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到铁离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a crude iron ion-doped carbon dot solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述铁离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the above crude solution of iron ion doped carbon dots through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得铁离子掺杂碳点固体粉末。对比例6:一种铁掺杂型碳点的制备方法The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain iron ion-doped carbon dot solid powder. Comparative Example 6: A method for preparing iron-doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

称取50mg盐酸多巴胺,和150mg六水合三氯化铁,溶解于10mL,pH为3的蒸馏水中制得三氯化铁和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 50 mg of dopamine hydrochloride and 150 mg of ferric chloride hexahydrate, dissolve it in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of ferric chloride and dopamine, mix it with 10 mL of polyethylene glycol-200, and pass it through ultrasonic (100W, 5min), mix evenly and react for 10min to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应7h得到铁离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 7 hours to obtain a crude iron ion-doped carbon dot solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述铁离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the above crude solution of iron ion doped carbon dots through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得铁离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain iron ion-doped carbon dot solid powder.

如图1和表1所示,为各实施例和对比例获得的碳点的荧光强度;如图2和表1所示,为各实施例和对比例获得的碳点的荧光量子产率;如表1所示,为各实施例和对比例获得的碳点的铁离子检测限。As shown in Figure 1 and Table 1, it is the fluorescence intensity of the carbon dots obtained in each embodiment and comparative example; as shown in Figure 2 and Table 1, it is the fluorescence quantum yield of the carbon dots obtained in each embodiment and comparative example; As shown in Table 1, it is the iron ion detection limit of the carbon dots obtained in each example and comparative example.

对比例7:一种制备锌氮掺杂碳点的方法Comparative Example 7: A method of preparing zinc-nitrogen-doped carbon dots

(1)碳点前驱体溶液制备:(1) Preparation of carbon dot precursor solution:

分别称取200mg盐酸多巴胺,和10mg七水合硫酸锌,溶解于10mL,pH为3的蒸馏水中制得硫酸锌和多巴胺水溶液,用10mL聚乙二醇-200混合,通过超声(100W,5min)混合均匀并反应10min,得到碳点前驱体溶液;Weigh 200 mg of dopamine hydrochloride and 10 mg of zinc sulfate heptahydrate respectively, dissolve them in 10 mL of distilled water with a pH of 3 to prepare an aqueous solution of zinc sulfate and dopamine, mix with 10 mL of polyethylene glycol-200, and mix by ultrasonic (100W, 5 min) Evenly and react for 10 minutes to obtain the carbon dot precursor solution;

(2)高压反应制备碳点粗溶液:(2) Preparation of carbon dot crude solution through high-pressure reaction:

将上述前驱体溶液置于聚四氟乙烯管中,并放置于高压反应釜内,在180℃下反应5h得到锌离子掺杂碳点粗溶液;Place the above precursor solution in a polytetrafluoroethylene tube, place it in a high-pressure reactor, and react at 180°C for 5 hours to obtain a zinc ion-doped carbon dot crude solution;

(3)精制碳点:(3) Refined carbon dots:

通过0.22微米滤膜过滤上述锌离子掺杂碳点粗溶液,将过滤后所得溶液加入1000Da透析袋中,并将该透析袋放置于pH为3的蒸馏水中透析48h,每24h换新的蒸馏水透析,将透析后的碳点溶液经旋转蒸发获得浓缩液;Filter the zinc ion-doped carbon dot crude solution through a 0.22 micron filter membrane, add the filtered solution to a 1000Da dialysis bag, and place the dialysis bag in distilled water with a pH of 3 for dialysis for 48 hours, and replace it with new distilled water every 24 hours. , the dialyzed carbon dot solution is rotary evaporated to obtain a concentrated solution;

(4)冷冻干燥:(4) Freeze drying:

将该浓缩液置于冷冻干燥机中经48h冻干,并收集粉末,获得锌离子掺杂碳点固体粉末。The concentrated solution was placed in a freeze dryer for 48 hours to be freeze-dried, and the powder was collected to obtain zinc ion-doped carbon dot solid powder.

将实施例1-6和对比例1-7所制备的碳点,进行荧光量子产率测试、荧光强度测试、铁离子检测限测定,结果如表1所示。The carbon dots prepared in Examples 1-6 and Comparative Examples 1-7 were subjected to fluorescence quantum yield testing, fluorescence intensity testing, and iron ion detection limit testing. The results are shown in Table 1.

表1Table 1

应用实施例1:锌氮掺杂碳点在食品检测中的应用Application Example 1: Application of zinc-nitrogen doped carbon dots in food testing

一种食品检测材料,其为检测试纸,含有实施例1所述的锌氮掺杂碳点。A food testing material, which is a testing paper containing the zinc-nitrogen-doped carbon dots described in Embodiment 1.

具体检测时,将含有检测试纸浸润食品提取液或流体食品样品液,浸润后,利用荧光分光光度计检测试纸荧光强度。During specific testing, the test paper containing the test paper is infiltrated into the food extract liquid or fluid food sample liquid. After infiltration, a fluorescence spectrophotometer is used to detect the fluorescence intensity of the test paper.

应用实施例2:锌氮掺杂碳点在食品检测中的应用Application Example 2: Application of zinc-nitrogen doped carbon dots in food testing

一种环境监测材料,含有实施例2所述的锌氮掺杂碳点。An environmental monitoring material containing the zinc-nitrogen-doped carbon dots described in Embodiment 2.

具体检测时,在水环境中可以通过在样品水溶液中添加含有实施例2所述的锌氮掺杂碳点的环境监测材料,并直接通过荧光分光光度计检测该样品溶液荧光强度。For specific detection, in a water environment, the environmental monitoring material containing the zinc-nitrogen-doped carbon dots described in Example 2 can be added to the sample aqueous solution, and the fluorescence intensity of the sample solution can be directly detected by a fluorescence spectrophotometer.

进一步地,可以根据荧光强度来判断铁离子浓度。Furthermore, the iron ion concentration can be determined based on the fluorescence intensity.

应用实施例3:锌氮掺杂碳点在包装材料检测中的应用Application Example 3: Application of zinc-nitrogen doped carbon dots in packaging material detection

一种流体食品包装材料,该材料中可以复合含有实施例3所述的锌氮掺杂碳点的标签材料。A liquid food packaging material, in which the label material containing the zinc-nitrogen-doped carbon dots described in Example 3 can be compounded.

具体监测时,如果食品中金属离子超标,可以通过包装材料的上的碳点荧光标签的发光程度来判断是否含有铁离子;进一步地,也可以根据荧光强度来确认铁离子含量。During specific monitoring, if the metal ions in the food exceed the standard, the luminescence degree of the carbon dot fluorescent label on the packaging material can be used to determine whether it contains iron ions; further, the iron ion content can also be confirmed based on the fluorescence intensity.

虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed above in terms of preferred embodiments, they are not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention should be defined by the claims.

Claims (12)

1.一种制备锌氮掺杂碳点的方法,其特征在于,所述方法包括如下步骤:1. A method for preparing zinc-nitrogen doped carbon dots, characterized in that the method includes the following steps: (1)碳源和氮源溶液:(1) Carbon source and nitrogen source solution: 将类儿茶酚胺类物质溶解于去离子水中,调节酸碱度得到类儿茶酚胺类物质碳源和氮源溶液;其中,所述的类儿茶酚胺类物质包括5,6-二羟基吲哚、L-多巴胺、儿茶酚胺、盐酸多巴胺或多巴胺中的一种;Dissolve catecholamine-like substances in deionized water, adjust the pH to obtain a carbon source and nitrogen source solution of catecholamine-like substances; wherein, the catecholamine-like substances include 5,6-dihydroxyindole, L-dopamine, catecholamine, Dopamine hydrochloride or one of the dopamines; (2)金属多酚配位复合物前驱体溶液:(2) Metal polyphenol coordination complex precursor solution: 将类儿茶酚胺类物质溶液与金属盐溶液混合制备金属多酚复合物前驱体溶液;所述金属盐溶液中的金属为锌;A metal polyphenol complex precursor solution is prepared by mixing a catecholamine-like substance solution and a metal salt solution; the metal in the metal salt solution is zinc; (3)水热反应制备锌氮掺杂碳点。(3) Hydrothermal reaction to prepare zinc-nitrogen-doped carbon dots. 2.根据权利要求1所述的方法,其特征在于,所述步骤(1)所述的类儿茶酚胺类物质溶液的酸碱度调节为1-4。2. The method according to claim 1, characterized in that the pH of the catecholamine-like substance solution in step (1) is adjusted to 1-4. 3.根据权利要求1所述的方法,其特征在于,步骤(2)所述的金属盐和类儿茶酚胺类物质的质量比为0.1:1~3:1。3. The method according to claim 1, characterized in that the mass ratio of the metal salt and catecholamine-like substances in step (2) is 0.1:1 to 3:1. 4.根据权利要求1所述的方法,其特征在于,步骤(1)所述的类儿茶酚胺类物质溶液是将类儿茶酚胺类物质溶解在去离子水中得到,浓度为5-60mg/mL。4. The method according to claim 1, wherein the catecholamine-like substance solution in step (1) is obtained by dissolving the catecholamine-like substance in deionized water, with a concentration of 5-60 mg/mL. 5.根据权利要求1所述的方法,其特征在于,步骤(2)所述的金属盐溶液是将金属盐溶解于去离子水中得到的,浓度为1-30mg/ml。5. The method according to claim 1, characterized in that the metal salt solution in step (2) is obtained by dissolving the metal salt in deionized water, with a concentration of 1-30 mg/ml. 6.根据权利要求1所述的方法,其特征在于,所述方法还包括步骤(4)纯化分离和/或步骤(5)浓缩干燥。6. The method according to claim 1, characterized in that the method further comprises step (4) purification and separation and/or step (5) concentration and drying. 7.权利要求1-6任一所述的方法制备得到的锌氮掺杂碳点。7. Zinc-nitrogen-doped carbon dots prepared by the method of any one of claims 1-6. 8.权利要求7所述的锌氮掺杂碳点在食品检测、环境监测或包装领域中的应用。8. Application of the zinc-nitrogen-doped carbon dots according to claim 7 in the fields of food testing, environmental monitoring or packaging. 9.根据权利要求8所述的应用,其特征在于,所述应用是对含铁物质的检测。9. The application according to claim 8, characterized in that the application is the detection of iron-containing substances. 10.一种能够用于检测含铁物质的食品检测材料,其特征在于,所述材料含有权利要求7所述的锌氮掺杂碳点。10. A food testing material that can be used to detect iron-containing substances, characterized in that the material contains the zinc-nitrogen-doped carbon dots described in claim 7. 11.一种能够用于检测含铁物质的环境监测材料,其特征在于,所述材料含有权利要求7所述的锌氮掺杂碳点。11. An environmental monitoring material capable of detecting iron-containing substances, characterized in that the material contains the zinc-nitrogen-doped carbon dots of claim 7. 12.一种能够用于检测含铁物质的包装材料,特征在于,所述材料含有权利要求7所述的锌氮掺杂碳点。12. A packaging material capable of detecting iron-containing substances, characterized in that the material contains the zinc-nitrogen-doped carbon dots of claim 7.
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