技术领域Technical field
本发明属于新型纳米生物医药领域，具体涉及一种具有抗氧化性能的Ce-MOF纳米材料、制备方法及应用。The invention belongs to the field of new nanobiomedicine, and specifically relates to a Ce-MOF nanomaterial with antioxidant properties, a preparation method and application.
背景技术Background technique
干眼（Dry Eye Disease，DED）是由于泪液的量或质或流体动力学异常引起的泪膜不稳定和/或眼表损害，从而引起眼不适症状及视功能障碍的一类疾病。干眼是临床常见的眼表慢性疾病，表现为眼部干涩感、异物感、烧灼感、眼痒、视物模糊、视力波动等，严重干眼可导致角膜上皮缺损及视力下降等，在我国的发病率约为21％～30％，且该数值还将继续上升。DED对患者视觉功能、日常生活能力、专业工作均有不同程度的影响。很多体内和体外的研究证明氧化应激与干眼的发生密不可分。氧化应激可以对角膜及结膜等眼表造成损害，其在干眼的发病中起着重要作用。DED动物模型研究表明，通过降低ROS水平和抑制炎性细胞因子，可以显著减轻氧化应激损伤。因此，用广谱抗氧化剂清除ROS可能是治疗这一类DED的有效方案，即通过降低角膜和结膜上皮细胞的ROS水平来缓解DED。Dry Eye Disease (DED) is a type of disease caused by tear film instability and/or ocular surface damage caused by abnormal tear quantity or quality or fluid dynamics, thereby causing eye discomfort symptoms and visual dysfunction. Dry eye is a common clinical chronic disease of the ocular surface, manifested by dryness, foreign body sensation, burning sensation, eye itching, blurred vision, vision fluctuation, etc. Severe dry eye can lead to corneal epithelial defects and vision loss. In my country, The incidence rate is about 21% to 30%, and this value will continue to rise. DED has varying degrees of impact on patients' visual function, daily living abilities, and professional work. Many in vivo and in vitro studies have proven that oxidative stress is inseparable from the occurrence of dry eye. Oxidative stress can cause damage to ocular surfaces such as the cornea and conjunctiva, and plays an important role in the pathogenesis of dry eye. Studies in DED animal models have shown that oxidative stress damage can be significantly reduced by reducing ROS levels and inhibiting inflammatory cytokines. Therefore, scavenging ROS with broad-spectrum antioxidants may be an effective solution to treat this type of DED, which alleviates DED by reducing ROS levels in corneal and conjunctival epithelial cells.
发明内容Contents of the invention
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种具有抗氧化性能的Ce-MOF纳米材料、制备方法及应用。The purpose of the present invention is to provide a Ce-MOF nanomaterial with antioxidant properties, a preparation method and application in order to overcome the shortcomings and deficiencies of the existing technology.
本发明所采取的技术方案如下：一种具有抗氧化性能的Ce-MOF纳米材料的制备方法，包括以下步骤：以硝酸铈铵和对苯二甲酸为原料，N，N-二甲基甲酰胺和水的混合溶剂体系为反应溶剂，得到反应体系，将反应体系在密封条件下于80-120 ℃下反应0.5-1.5 h，冷却至室温后离心洗涤得到Ce-MOF纳米材料。The technical solution adopted by the present invention is as follows: a preparation method of Ce-MOF nanomaterials with antioxidant properties, including the following steps: using cerium ammonium nitrate and terephthalic acid as raw materials, N, N-dimethylformamide A mixed solvent system with water is used as the reaction solvent to obtain a reaction system. The reaction system is reacted under sealed conditions at 80-120°C for 0.5-1.5 h, cooled to room temperature, and then centrifuged and washed to obtain Ce-MOF nanomaterials.
所述对苯二甲酸溶于N，N-二甲基甲酰胺中，所述硝酸铈铵溶于水中，待二者充分溶解后将二者混合均匀得到反应体系。The terephthalic acid is dissolved in N,N-dimethylformamide, and the ceric ammonium nitrate is dissolved in water. After the two are fully dissolved, the two are mixed evenly to obtain a reaction system.
所述N，N-二甲基甲酰胺和水的体积比为1:1。The volume ratio of N,N-dimethylformamide and water is 1:1.
所述对苯二甲酸与硝酸铈铵的摩尔浓度比值为1:1-1.2。The molar concentration ratio of the terephthalic acid and ceric ammonium nitrate is 1:1-1.2.
所述对苯二甲酸的浓度为10-100mM。该浓度范围制备得到的产物粒径为纳米级的，且均具备抗氧化性能，随着原料浓度的降低，产物粒径也会随之降低，可以轻松实现对所得产物的尺寸的调控。The concentration of terephthalic acid is 10-100mM. The particle size of the products prepared in this concentration range is nanoscale, and they all have antioxidant properties. As the concentration of raw materials decreases, the particle size of the product will also decrease, and the size of the obtained product can be easily controlled.
所述对苯二甲酸的浓度为10-30mM。该浓度范围制备得到的产物为超小Ce-MOF纳米材料，且可以缓解干眼症状。The concentration of terephthalic acid is 10-30mM. The products prepared in this concentration range are ultra-small Ce-MOF nanomaterials and can alleviate dry eye symptoms.
如上所述的具有抗氧化性能的Ce-MOF纳米材料的制备方法制备得到的Ce-MOF纳米材料。Ce-MOF nanomaterials prepared by the above-mentioned preparation method of Ce-MOF nanomaterials with antioxidant properties.
如上所述的Ce-MOF纳米材料在制备缓解干眼症的药物的应用。The application of Ce-MOF nanomaterials as mentioned above in the preparation of drugs for alleviating dry eye syndrome.
本发明的有益效果如下：本发明所提供的方法制备得到的Ce-MOF纳米材料具有显著的抗氧化性能，且通过对原料浓度的控制，可实现对所得产物的尺寸的调控，随着产物粒径的降低，产物的抗氧化能力逐渐增强。在缓解干眼症的应用结果显示，所得Ce-MOF纳米材料在一定程度上可以缓解干眼症状。这对于扩大铈基金属-有机骨架纳米材料在眼科领域里的应用具有重要的研究意义。The beneficial effects of the present invention are as follows: Ce-MOF nanomaterials prepared by the method provided by the present invention have significant antioxidant properties, and by controlling the concentration of raw materials, the size of the obtained product can be controlled. As the diameter decreases, the antioxidant capacity of the product gradually increases. The application results in alleviating dry eye syndrome show that the obtained Ce-MOF nanomaterial can alleviate dry eye symptoms to a certain extent. This has important research significance for expanding the application of cerium-based metal-organic framework nanomaterials in the field of ophthalmology.
附图说明Description of the drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，根据这些附图获得其他的附图仍属于本发明的范畴。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, it is still within the scope of the present invention to obtain other drawings based on these drawings without exerting any creative effort.
图1为本发明制得的三种Ce-MOF纳米材料的XRD图谱；Figure 1 shows the XRD patterns of three Ce-MOF nanomaterials prepared by the present invention;
图2为本发明实例制得的三种Ce-MOF纳米材料的SEM照片及超小Ce-MOF的TEM照片，其中，（a）为Ce-MOF1的SEM照片，（b）为为Ce-MOF2的SEM照片，（c）为为Ce-MOF3的SEM照片，（d）为Ce-MOF3的TEM照片；Figure 2 shows SEM photos of three Ce-MOF nanomaterials prepared by examples of the present invention and TEM photos of ultra-small Ce-MOF, where (a) is a SEM photo of Ce-MOF1, and (b) is Ce-MOF2. SEM photo, (c) is the SEM photo of Ce-MOF3, (d) is the TEM photo of Ce-MOF3;
图3为本发明实例制得的三种Ce-MOF纳米材料的清除H2O2能力的评价。Figure 3 is an evaluation of the H2 O2 scavenging ability of three Ce-MOF nanomaterials prepared in examples of the present invention.
图4为本发明实例制得的三种Ce-MOF纳米材料的清除O2-能力的评价Figure 4 is an evaluation of the O2- scavenging ability of three Ce-MOF nanomaterials prepared in examples of the present invention.
图5为本发明实例制得的三种Ce-MOF纳米材料的细胞内抗氧化性能的评价；Figure 5 is an evaluation of the intracellular antioxidant properties of three Ce-MOF nanomaterials prepared in examples of the present invention;
图6为本发明实例制得的超小Ce-MOF纳米材料（Ce-MOF3）缓解干眼症的评价。Figure 6 is an evaluation of the alleviation of dry eye syndrome by the ultra-small Ce-MOF nanomaterial (Ce-MOF3) prepared in the example of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明作进一步地详细描述。In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail below with reference to the accompanying drawings.
实施例1：Example 1:
将0.708 g H2BDC（终浓度为80.98mM）溶入到24 mL DMF中，2.32 g (NH4)2Ce(NO3)6（终浓度为88.16 mM）溶于24 mL水中，待二者充分溶解后将二者混，继续搅拌10 min。最后将所得混合物转移到50 ml的聚四氟乙烯内衬的反应釜中，密封，在100 ℃ 下反应1 h，自然冷却至室温后离心洗涤即可得到产物一（Ce-MOF1）。Dissolve 0.708 g H2 BDC (final concentration: 80.98mM) into 24 mL DMF, and 2.32 g (NH4 )2 Ce(NO3 )6 (final concentration: 88.16 mM) into 24 mL water. Wait until the two After fully dissolved, mix the two and continue stirring for 10 minutes. Finally, the resulting mixture was transferred to a 50 ml polytetrafluoroethylene-lined reactor, sealed, reacted at 100°C for 1 h, naturally cooled to room temperature, and then centrifuged and washed to obtain product one (Ce-MOF1).
实施例2：Example 2:
将0.304 g H2BDC（终浓度为40.49mM）溶入到24 mL DMF中，1.16g (NH4)2Ce(NO3)6（终浓度为44.08mM）溶于24 mL水中，待二者充分溶解后将二者混，继续搅拌10 min。最后将所得混合物转移到50 ml的聚四氟乙烯内衬的反应釜中，密封，在100 ℃ 下反应1 h，自然冷却至室温后离心洗涤即可得到产物一（Ce-MOF2）。Dissolve 0.304 g H2 BDC (final concentration: 40.49mM) into 24 mL DMF, and 1.16g (NH4 )2 Ce(NO3 )6 (final concentration: 44.08mM) into 24 mL water. Wait until the two After fully dissolved, mix the two and continue stirring for 10 minutes. Finally, the resulting mixture was transferred to a 50 ml polytetrafluoroethylene-lined reactor, sealed, reacted at 100°C for 1 h, naturally cooled to room temperature, and then centrifuged and washed to obtain product one (Ce-MOF2).
实施例3：Example 3:
将0.152g H2BDC（终浓度为20.25mM）溶入到24 mL DMF中，0.58g (NH4)2Ce(NO3)6（终浓度为22.04mM）溶于24 mL水中，待二者充分溶解后将二者混，继续搅拌10 min。最后将所得混合物转移到50 ml的聚四氟乙烯内衬的反应釜中，密封，在100 ℃ 下反应1 h，自然冷却至室温后离心洗涤即可得到产物一（Ce-MOF3）。Dissolve 0.152g H2 BDC (final concentration: 20.25mM) into 24 mL DMF, and 0.58g (NH4 )2 Ce(NO3 )6 (final concentration: 22.04mM) into 24 mL water. Wait until the two After fully dissolved, mix the two and continue stirring for 10 minutes. Finally, the resulting mixture was transferred to a 50 ml polytetrafluoroethylene-lined reactor, sealed, reacted at 100°C for 1 h, naturally cooled to room temperature, and then centrifuged and washed to obtain product one (Ce-MOF3).
以下为对实施例1-3所得产物的相关性能的研究分析结果。The following are the results of research and analysis on the relevant properties of the products obtained in Examples 1-3.
由图1通过调控不同反应物的浓度所得三种Ce-MOF纳米材料的XRD图谱，可以看出所得三种尺寸的Ce-MOF纳米材料的相结构是一致的，反应物浓度的不同对产物相结构的影响不大。From Figure 1, the XRD patterns of three Ce-MOF nanomaterials obtained by adjusting the concentrations of different reactants, it can be seen that the phase structures of the three sizes of Ce-MOF nanomaterials obtained are consistent, and the different concentrations of reactants have an impact on the product phase. The structure has little impact.
由图2通过调控不同反应物的浓度所制备的三种Ce-MOF纳米材料的SEM 照片及超小尺寸Ce-MOF纳米材料的TEM照片，可以看出随着反应物浓度的降低产物的粒径依次降低，从初始的500-1000 nm（Ce-MOF1），到中间产物的50 nm（Ce-MOF2），以及最后的3-5 nm的超小纳米颗粒（SEM 及TEM）（Ce-MOF3）。可以看出通过简单的调节反应物的浓度就可以很好的控制产物的粒径。From Figure 2, SEM photos of three Ce-MOF nanomaterials prepared by adjusting the concentrations of different reactants and TEM photos of ultra-small size Ce-MOF nanomaterials, it can be seen that the particle size of the product decreases as the concentration of the reactants decreases. Decreasing in sequence, from the initial 500-1000 nm (Ce-MOF1), to the 50 nm of the intermediate product (Ce-MOF2), and finally the ultra-small nanoparticles (SEM and TEM) of 3-5 nm (Ce-MOF3) . It can be seen that the particle size of the product can be well controlled by simply adjusting the concentration of the reactants.
由图3三种Ce-MOF纳米材料的清除H2O2能力的评价，可以看出所合成的三种不同尺寸的Ce-MOF纳米材料都具有清除H2O2的能力，并且随着材料粒径的降低，清除能力逐渐增强。From the evaluation of the H2 O2 scavenging ability of the three Ce-MOF nanomaterials in Figure 3, it can be seen that the three synthesized Ce-MOF nanomaterials of different sizes have the ability to scavenge H2 O2 , and as the material particles As the diameter decreases, the scavenging ability gradually increases.
由图4三种Ce-MOF纳米材料的清除O2-能力的评价，可以看出所合成的三种不同尺寸的Ce-MOF纳米材料都具有清除O2-的能力，并且随着材料粒径的降低，清除能力逐渐增强，Ce-MOF2和Ce-MOF3的效能相近。From the evaluation of the O2- scavenging ability of three Ce-MOF nanomaterials in Figure 4, it can be seen that the three synthesized Ce-MOF nanomaterials of different sizes all have the ability to scavenge O2- , and as the material particle size increases decreases, the scavenging ability gradually increases, and the efficiencies of Ce-MOF2 and Ce-MOF3 are similar.
由图5三种Ce-MOF纳米材料的体外细胞内抗氧化性能的评价；可以看出相对于目前常用的阳性对照的N-乙酰-L-半胱氨酸(NAC)，所合成的三种不同粒径的Ce-MOF纳米材料都有一定的抗氧化效果，并且随着材料粒径的降低，抗氧化能力有所增强，视野中绿色明显的更少。From Figure 5, evaluation of the in vitro intracellular antioxidant properties of three Ce-MOF nanomaterials; it can be seen that compared with the commonly used positive control N-acetyl-L-cysteine (NAC), the three synthesized Ce-MOF nanomaterials of different particle sizes have certain antioxidant effects, and as the particle size of the material decreases, the antioxidant capacity increases, and there is obviously less green in the field of view.
由图6超小Ce-MOF纳米材料（Ce-MOF3）在缓解动物干眼症的评价结果显示，相对于PBS组，滴加含有超小Ce-MOF纳米材料的动物干眼症的分值更低，说明干眼症得到了缓解。Figure 6 shows the evaluation results of ultra-small Ce-MOF nanomaterials (Ce-MOF3) in alleviating dry eye syndrome in animals. Compared with the PBS group, the dry eye syndrome scores of animals containing ultra-small Ce-MOF nanomaterials dropped were higher. Low, indicating that dry eye syndrome has been alleviated.
以上所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。What is disclosed above is only the preferred embodiment of the present invention. Of course, it cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope of the present invention.
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| CN202210292346.8ACN114832012B (en) | 2022-03-23 | 2022-03-23 | Ce-MOF nano material with oxidation resistance, preparation method and application |
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