CN116747154B - A cerium oxide-based sunscreen material that can resist blue light and its preparation method - Google Patents
A cerium oxide-based sunscreen material that can resist blue light and its preparation method Download PDFInfo
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Abstract
Description
技术领域Technical field
本发明涉及新材料技术领域,特别涉及一种氧化铈基可抵御蓝光的防晒材料及其制备方法。The invention relates to the technical field of new materials, and in particular to a cerium oxide-based sunscreen material that can resist blue light and a preparation method thereof.
背景技术Background technique
短波蓝光是蓝光区的一段可见光波,位于400-450 nm处。其主要来源于自然光与电子显示屏,因电子显示屏辐射所产生不同程度的眼疾病,如视力下降、白内障、失明等,科研人员在对电子屏幕测试中发现屏幕发射的光线中含有大量不规则频率的高能短波蓝光,该蓝光波长短、穿透能力强,可引发氧化应激反应,诱导细胞损伤;“光”还存在积累效应,长时间的接触或暴露于短波蓝光中会降低细胞活性,改变正常细胞的生理形态。因此短波蓝光带来的生理损伤完全不亚于紫外线。Shortwave blue light is a visible light wave in the blue light region, located at 400-450 nm. It mainly comes from natural light and electronic display screens. Due to the radiation from electronic display screens, various degrees of eye diseases are caused, such as vision loss, cataracts, blindness, etc. When testing electronic screens, scientific researchers found that the light emitted by the screen contains a large number of irregularities. High-energy short-wave blue light with a short wavelength and strong penetrating ability can trigger oxidative stress reactions and induce cell damage; "light" also has a cumulative effect. Long-term contact or exposure to short-wave blue light will reduce cell activity. Change the physiological morphology of normal cells. Therefore, the physiological damage caused by short-wave blue light is no less than that of ultraviolet light.
然而,目前在化妆品领域中的防蓝光技术均通过缓解色素沉着、延缓皮肤衰老、细胞通路为主,对于物理吸收辐射方面的开发于研究甚少;同时现有的物理防晒与化学防晒剂均无法过滤、屏蔽短波蓝光,如今常用物理防晒材料如二氧化钛、氧化锌在化妆品使用场景中,常使皮肤假白、易造成皮肤干燥脱皮;而氧化锌也有类似假白且使用粘腻,且由于两者光催化活性强,使用时容易产生自由基,加速细胞衰老。However, the current anti-blue light technologies in the field of cosmetics mainly focus on relieving pigmentation, delaying skin aging, and cell pathways, and there is little research on the development of physical absorption of radiation; at the same time, existing physical sunscreens and chemical sunscreens cannot Filtering and shielding short-wave blue light, physical sunscreen materials such as titanium dioxide and zinc oxide are commonly used today in cosmetics use scenarios, often making the skin false white and easily causing dry and peeling skin; zinc oxide also has similar false whitening properties and is sticky when used, and due to the two It has strong photocatalytic activity and easily generates free radicals when used, which accelerates cell aging.
有鉴于此,基于氧化铈等开发新型复合材料,用于解决人们面临的短波蓝光危害刻不容缓。In view of this, it is urgent to develop new composite materials based on cerium oxide and other materials to solve the short-wave blue light hazards faced by people.
发明内容Contents of the invention
本发明的目的在于,针对现有的上述不足,提供一种氧化铈基可抵御蓝光的防晒材料,具有抵御蓝光、屏蔽紫外线、抑菌,可作为氧化物基复合材料紫外、蓝光屏蔽剂及新型物理防晒剂。The object of the present invention is to provide a cerium oxide-based sunscreen material that can resist blue light in view of the above-mentioned existing deficiencies. It has the functions of resisting blue light, shielding ultraviolet rays, and being antibacterial. It can be used as an oxide-based composite material UV and blue light shielding agent and a new type of sunscreen material. Physical sunscreen.
本发明的目的在于还在于提供前述氧化铈基可抵御蓝光的防晒材料的制备方法。Another object of the present invention is to provide a method for preparing the aforementioned cerium oxide-based sunscreen material that can resist blue light.
本发明为达到上述目的所采用的技术方案是:The technical solutions adopted by the present invention to achieve the above objects are:
一种氧化铈基可抵御蓝光的防晒材料,其包括如下组分制成:聚乙烯亚胺(PEI)、三乙胺(TEA)、六水合硝酸铈(Ce(NO3)3·6H2O)、L-抗坏血酸(L-AC)、硝酸银(SN);所述聚乙烯亚胺PEI与六水合硝酸铈(Ce(NO3)3·6H2O)的摩尔比为2~4:1~10;所述三乙胺TEA与六水合硝酸铈(Ce(NO3)3·6H2O)的摩尔比为5~20:1~200;所述L-抗坏血酸(L-AC)与六水合硝酸铈(Ce(NO3)3·6H2O)的摩尔比为1~2:120~600;所述硝酸银(SN)与六水合硝酸铈(Ce(NO3)3·6H2O)的摩尔比为1~2:100~250。A cerium oxide-based sunscreen material that can resist blue light, which includes the following components: polyethyleneimine (PEI), triethylamine (TEA), cerium nitrate hexahydrate (Ce(NO 3 ) 3 ·6H 2 O ), L-ascorbic acid (L-AC), silver nitrate (SN); the molar ratio of the polyethyleneimine PEI and cerium nitrate hexahydrate (Ce(NO3)3·6H2O) is 2~4:1~10; The molar ratio of the triethylamine TEA and the cerium nitrate hexahydrate (Ce(NO3)3·6H2O) is 5~20:1~200; the molar ratio of the L-ascorbic acid (L-AC) and the cerium nitrate hexahydrate (Ce( The molar ratio of NO3)3·6H2O) is 1~2:120~600; the molar ratio of the silver nitrate (SN) and hexahydrate cerium nitrate (Ce(NO3)3·6H2O) is 1~2:100~250 .
本发明利用三乙胺(TEA)提供碱性环境控制pH,进一步利用六水合硝酸铈(Ce(NO3)3·6H2O)反应,聚乙烯亚胺(PEI)作为模板剂,利用其粘附性使得氧化铈(CeO2)表面富含胺基,得到具有一定抵御蓝光性能的初代改性氧化铈(CeO2-PEI);以硝酸银(NS)为银源,L-抗坏血酸(L-AC)为还原剂,使硝酸银(NS)进一步发生还原反应,与改性氧化铈(CeO2-PEI)表面胺基络合制备出氧化铈基可抵御蓝光的防晒材料。The present invention uses triethylamine (TEA) to provide an alkaline environment to control the pH, further utilizes cerium nitrate hexahydrate (Ce(NO 3 ) 3 ·6H 2 O) to react, polyethyleneimine (PEI) as a template, and utilizes its adhesive The adhesion makes the surface of cerium oxide (CeO 2 ) rich in amine groups, resulting in the first-generation modified cerium oxide (CeO 2 -PEI) with certain resistance to blue light; using silver nitrate (NS) as the silver source, L-ascorbic acid (L- AC) is used as a reducing agent to further reduce silver nitrate (NS) and complex with the surface amine group of modified cerium oxide (CeO 2 -PEI) to prepare a cerium oxide-based sunscreen material that can resist blue light.
本发明的一种上述的氧化铈基可抵御蓝光的防晒材料的制备方法,其包括如下步骤:The preparation method of the above-mentioned cerium oxide-based sunscreen material capable of resisting blue light according to the present invention includes the following steps:
S1,将六水合硝酸铈溶解于无水乙醇中,搅拌充分溶解,得到溶液A;S1, dissolve cerium nitrate hexahydrate in absolute ethanol, stir to fully dissolve, and obtain solution A;
S2,将聚乙烯亚胺溶解于无水乙醇中,搅拌充分溶解,得到溶液B;S2, dissolve polyethyleneimine in absolute ethanol, stir to fully dissolve, and obtain solution B;
S3,将溶液B缓慢加入溶液A中至出现大量白色絮状后,加入三乙胺,反应一定时间t1,经水冷后加入纯水进行水解反应,持续冷却一定时间t2,之后在室温下反应一定时间t3,得到悬浊液C;S3, slowly add solution B to solution A until a large amount of white floc appears, add triethylamine, react for a certain time t1, add pure water after water cooling for a hydrolysis reaction, continue to cool for a certain period of time t2, and then react at room temperature for a certain time At time t3, suspension C is obtained;
S4,将悬浊液C用纯水洗至中性后,再用无水乙醇和纯水进一步离心洗涤,烘干、研磨,得到固体粉末E;S4, wash the suspension C with pure water until neutral, then further centrifuge and wash with absolute ethanol and pure water, dry and grind to obtain solid powder E;
S5,将固体粉末E超声分散于纯水中,滴入2 V/V%氨水,得到浑浊液F;S5, ultrasonically disperse the solid powder E in pure water, and drop in 2 V/V% ammonia water to obtain a turbid liquid F;
S6,将银氨溶液H加入浑浊液F中,避光处理,反应一定时间t4后,高速搅拌下加入L-抗坏血酸水溶液G,改变转速室温反应一定时间t5得到浑浊液I;S6, add the silver ammonia solution H to the turbid liquid F, protect it from light, react for a certain time t4, add L-ascorbic acid aqueous solution G under high-speed stirring, change the rotation speed and react at room temperature for a certain time t5 to obtain the turbid liquid I;
S7,将浑浊液I抽滤,得到灰褐色沉淀,并用无水乙醇和纯水分别洗涤,烘干,得到灰褐色粉末,即得氧化铈基可抵御蓝光的防晒材料。S7, filter the turbid liquid I to obtain a gray-brown precipitate, wash it with absolute ethanol and pure water, and dry it to obtain a gray-brown powder, that is, a cerium oxide-based sunscreen material that can resist blue light is obtained.
优选地,所述的溶液A的浓度为30 W/V%-50 W/V%,无水乙醇的添加量为15 mL。Preferably, the concentration of solution A is 30 W/V%-50 W/V%, and the added amount of absolute ethanol is 15 mL.
优选地,所述的溶液B的浓度为2.5 W/V%-10 W/V%,无水乙醇的添加量为10mL。Preferably, the concentration of solution B is 2.5 W/V%-10 W/V%, and the added amount of absolute ethanol is 10 mL.
优选地,所述的步骤S3中三乙胺TEA称取量为5-15g。Preferably, the weighing amount of triethylamine TEA in step S3 is 5-15g.
优选地,所述的步骤S3中反应时间t1为20-60 min,优选加入纯水为350 ml,持续冷却时间t2为1-15 min,室温下反应时间t3为1-4 h。Preferably, the reaction time t 1 in step S3 is 20-60 min, preferably 350 ml of pure water is added, the continuous cooling time t 2 is 1-15 min, and the reaction time t 3 at room temperature is 1-4 h.
优选地,所述的步骤S5中固体粉末E的浓度为1-10 W/V%,优选地加入纯水10mL。Preferably, the concentration of solid powder E in step S5 is 1-10 W/V%, and 10 mL of pure water is preferably added.
优选地,所述的步骤S6中还包括:将L-抗坏血酸溶解于纯水中,搅拌充分,得到L-抗坏血酸水溶液G,L-抗坏血酸水溶液的浓度为2-5 W/V%,优选地纯水的添加量为0.4 mL。Preferably, the step S6 also includes: dissolving L-ascorbic acid in pure water, stirring thoroughly to obtain L-ascorbic acid aqueous solution G, the concentration of L-ascorbic acid aqueous solution is 2-5 W/V%, preferably pure The amount of water added is 0.4 mL.
优选地,所述的步骤S6中还包括:将硝酸银溶解于纯水中搅拌充分,滴入2 V/V%氨水得到银氨溶液H,银氨溶液H的浓度为0.1-0.5 W/V%,优选地纯水的添加量为5 mL。Preferably, the step S6 also includes: dissolving silver nitrate in pure water, stirring thoroughly, and dripping 2 V/V% ammonia water to obtain a silver ammonia solution H. The concentration of the silver ammonia solution H is 0.1-0.5 W/V. %, preferably the added amount of pure water is 5 mL.
优选地,所述的步骤S6中反应时间t4为10-30 min,高速搅拌为转速1000-2000rad/min、持续时间1-5 min,改变转速为400-600 rad/min下室温反应时间t5为2-10 h。Preferably, the reaction time t 4 in step S6 is 10-30 min, the high-speed stirring is at a rotation speed of 1000-2000 rad/min, the duration is 1-5 min, and the reaction time t at room temperature is changed to 400-600 rad/min. 5 is 2-10 h.
优选地,所述的步骤S4、步骤S7中烘干条件均为在95-115 ℃ 烘干1-3h。Preferably, the drying conditions in step S4 and step S7 are both drying at 95-115°C for 1-3 hours.
本发明利用一定量的聚乙烯亚胺(PEI)作为模板剂对氧化铈CeO2进行表面修饰,修饰后的氧化铈CeO2-PEI表面含有多种胺基,而这类胺基能有效与银粒子络合,此外,该官能团结构中的N原子有着强给电子能力,使得载银后能通过N原子相互作用,可将孤对电子转移至纳米银表面,从而延长复合材料(Ag NPs@CeO2-PEI)的使用寿命。The present invention uses a certain amount of polyethyleneimine (PEI) as a template agent to modify the surface of cerium oxide CeO 2. The surface of the modified cerium oxide CeO 2 -PEI contains a variety of amine groups, and these amine groups can effectively interact with silver. Particle complexation, in addition, the N atoms in the functional group structure have strong electron donating ability, so that after silver is loaded, the lone pair of electrons can be transferred to the nanosilver surface through the interaction of N atoms, thus extending the length of the composite material (Ag NPs@CeO 2 -PEI) service life.
本发明中聚乙烯亚胺是一种高附着性、高吸附性,可降解的分子聚合物,生物相容性与细胞毒性均良好,而负载的纳米银有着良好生物相容性。枝状聚乙烯亚胺(PEI)是一种富含伯胺、仲胺和叔胺基的高附着性、高吸附性聚合物,良好的生物相容性和水溶性的材料。The polyethylenimine in the present invention is a high adhesion, high adsorption, degradable molecular polymer with good biocompatibility and cytotoxicity, and the loaded nanosilver has good biocompatibility. Dendritic polyethyleneimine (PEI) is a highly adhesive and highly absorbent polymer rich in primary, secondary and tertiary amine groups, and has good biocompatibility and water solubility.
本发明利用氧化铈CeO2具独特的4F1电子结构,使其辐射存在光谱选择性,故氧化铈对可见至红外波段能有效屏蔽。The present invention utilizes the unique 4F 1 electronic structure of cerium oxide CeO 2 so that its radiation has spectral selectivity, so cerium oxide can effectively shield the visible to infrared bands.
本发明以L-抗坏血酸(L-AC)作为还原剂,将硝酸银(NS)还原,制备出纳米银,组装附着在改性后的前驱氧化铈(CeO2-PEI)表面,使得最终制备出的氧化铈(Ag NPs@CeO2-PEI)具有纳米银的光学、抗菌性能特点。The present invention uses L-ascorbic acid (L-AC) as a reducing agent to reduce silver nitrate (NS) to prepare nanosilver, which is assembled and attached to the surface of the modified precursor cerium oxide (CeO 2 -PEI), so that the nanosilver is finally prepared. Cerium oxide (Ag NPs@CeO 2 -PEI) has the optical and antibacterial performance characteristics of nanosilver.
本发明不仅对氧化铈CeO2表面进行修饰,还利用硝酸银进行掺杂,使溶液中的银粒子以化学键的方式均匀地负载与前驱氧化铈CeO2-PEI表面,再通过一定浓度的L-抗坏血酸进行还原调控,促进其表面银粒子生长,使得纳米银均匀地成功负载于前驱氧化铈CeO2-PEI表面上,赋予了光学性和抗菌性能,制得氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)。The present invention not only modifies the surface of cerium oxide CeO 2 , but also uses silver nitrate for doping, so that the silver particles in the solution are evenly loaded with the precursor cerium oxide CeO 2 -PEI surface in the form of chemical bonds, and then pass through a certain concentration of L- Ascorbic acid performs reduction control and promotes the growth of silver particles on its surface, so that nanosilver is evenly and successfully loaded on the surface of the precursor cerium oxide CeO 2 -PEI, imparting optical and antibacterial properties, and producing a cerium oxide-based sunscreen material that can resist blue light ( Ag NPs@CeO 2 -PEI).
与现有技术相比,本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
1.本发明的氧化铈基可抵御蓝光的防晒材料,采用简单方便的化学沉淀方法,操作简单、可控、温和,利用聚乙烯亚胺对氧化铈表面进行构建,使其表面富含多种胺基基团,能通过化学键的形式有效与金属元素(如金、银、铜、锌等)进行络合,使其具有给电子能力延长用周期寿命,可作为氧化物基复合材料蓝光、紫外屏蔽剂及新型物理防晒剂,具有优异的抗紫外、抵御蓝光、抑菌及良好的生物相容性,综合性能优异,成本低,应用领域广泛。1. The cerium oxide-based sunscreen material of the present invention that can resist blue light adopts a simple and convenient chemical precipitation method, which is simple, controllable and gentle to operate. It uses polyethyleneimine to construct the cerium oxide surface so that the surface is rich in various The amine group can effectively complex with metal elements (such as gold, silver, copper, zinc, etc.) in the form of chemical bonds, giving it the ability to donate electrons to extend the cycle life. It can be used as an oxide-based composite material for blue light, ultraviolet Shielding agents and new physical sunscreen agents have excellent UV resistance, blue light resistance, bacteriostasis and good biocompatibility. They have excellent comprehensive performance, low cost and a wide range of applications.
2.本发明的氧化铈基可抵御蓝光的防晒材料,选择纳米银作为掺杂金属元素,充分发挥其纳米银本身在其400nm光波左右有紫外特征峰,实现了传统氧化铈在紫外光波区的光防护同时,极大增加综合抵御蓝光性能,当浓度为0.2mg.mL-1时对于短波蓝光400-450nm波长范围内平均透过率为0.24%、UVA与UVB波段280-400nm范围内紫外吸光度平均为2.17,最高吸收峰吸光度约为2.34。2. The cerium oxide-based sunscreen material of the present invention that can resist blue light selects nanosilver as the doping metal element, giving full play to the UV characteristic peak of nanosilver itself around its 400nm light wave, achieving the advantages of traditional cerium oxide in the ultraviolet light wave region. At the same time of photoprotection, it greatly increases the comprehensive performance against blue light. When the concentration is 0.2mg.mL -1 , the average transmittance of short-wave blue light in the wavelength range of 400-450nm is 0.24%, and the ultraviolet absorbance in the UVA and UVB bands of 280-400nm is The average is 2.17, and the highest absorption peak absorbance is about 2.34.
3.本发明解决了短波蓝光给皮肤、眼睛等带来危害等问题,极大解决了现有物理防晒材料因屏蔽波长受限而无法屏蔽短波蓝光带来的光老化的缺陷,还发挥了纳米银本身的抑菌性,减少了相关产品中防腐剂的添加使用,在1.2%(W/V)体系下对革兰氏阳性菌,杀菌率达82.05%,并且在抑菌测试中有着明显抑菌效果。3. The present invention solves the problem of harm caused by short-wave blue light to the skin, eyes, etc., greatly solves the defect of existing physical sunscreen materials that cannot shield the photo-aging caused by short-wave blue light due to the limited shielding wavelength, and also brings into play the advantages of nanotechnology. The antibacterial property of silver itself reduces the use of preservatives in related products. In the 1.2% (W/V) system, the sterilization rate reaches 82.05% against Gram-positive bacteria, and it has obvious inhibitory effects in the antibacterial test. Bacterial effect.
上述是发明技术方案的概述,以下结合附图与具体实施方式,对本发明做进一步说明。The above is an overview of the technical solution of the invention. The invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
附图说明Description of the drawings
图1为实施例的氧化铈(CeO2)、表面修饰的氧化铈(CeO2-PEI)的FTIR红外图谱示意图;Figure 1 is a schematic diagram of the FTIR infrared spectrum of cerium oxide (CeO 2 ) and surface-modified cerium oxide (CeO 2 -PEI) in the embodiment;
图2为实施例的表面修饰的氧化铈(CeO2-PEI)的X-射线衍射示意图;Figure 2 is an X-ray diffraction diagram of the surface-modified cerium oxide (CeO 2 -PEI) of the embodiment;
图3为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)的X-射线能谱图;Figure 3 is the X-ray energy spectrum of the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI) that can resist blue light according to the embodiment;
图4为实施例的不同聚乙烯亚胺(PEI)用量修饰氧化铈后与紫外吸光度的关系示意图;Figure 4 is a schematic diagram of the relationship between cerium oxide modified with different amounts of polyethyleneimine (PEI) and UV absorbance in the embodiment;
图5为实施例的不同用量的L-抗坏血酸(L-AC)所制备氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)与紫外吸光度的关系示意图;Figure 5 is a schematic diagram of the relationship between the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI) prepared by using different amounts of L-ascorbic acid (L-AC) and capable of resisting blue light and ultraviolet absorbance in the embodiment;
图6为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)做成涂层进行可视化防蓝光佐证示意图;Figure 6 is a schematic diagram showing the use of the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI) that can resist blue light as a coating for visual blue light protection according to the embodiment;
图7为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)、CeO2-PEI以及未任何处理的氧化铈,对革兰氏阳性菌杀菌效果对比示意图;Figure 7 is a schematic diagram comparing the bactericidal effects of cerium oxide-based sunscreen materials (Ag NPs@CeO 2 -PEI), CeO 2 -PEI and untreated cerium oxide on Gram-positive bacteria according to the embodiment;
图8为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)、CeO2-PEI以及未任何处理的氧化铈,对革兰氏阳性菌抑菌效果对比示意图;Figure 8 is a schematic diagram comparing the antibacterial effects on Gram-positive bacteria of the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI), CeO 2 -PEI and untreated cerium oxide according to the embodiment;
图9为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)添加至化妆品配方中制备出的防晒产品进行离心稳定性测试示意图;Figure 9 is a schematic diagram of the centrifugal stability test of a sunscreen product prepared by adding the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI) that can resist blue light in the cosmetic formula according to the embodiment;
图10 为实施例的氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)的SEM扫描电镜示意图。Figure 10 is a SEM scanning electron microscope diagram of the cerium oxide-based sunscreen material (Ag NPs@CeO 2 -PEI) that can resist blue light according to the embodiment.
具体实施方式Detailed ways
为了使本发明的目的和技术方案及优点更加清楚明白,以下结合实施例作详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the purpose, technical solutions and advantages of the present invention clearer, detailed descriptions are given below in conjunction with examples. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention.
实施例1Example 1
本实施例提供一种氧化铈基可抵御蓝光的防晒材料,采用包括如下步骤的制备方法制备而成:This embodiment provides a cerium oxide-based sunscreen material that can resist blue light, which is prepared by a preparation method including the following steps:
S1,将5g六水合硝酸铈溶于15ml无水乙醇中,搅拌充分溶解,得到溶液A;S1, dissolve 5g of cerium nitrate hexahydrate in 15ml of absolute ethanol, stir to fully dissolve, and obtain solution A;
S2,将0.25g聚乙烯亚胺溶于10ml无水乙醇中,搅拌充分溶解,得到溶液B;S2, dissolve 0.25g polyethyleneimine in 10ml absolute ethanol, stir to fully dissolve, and obtain solution B;
S3,将溶液B缓慢加入溶液A中至出现大量白色絮状后,加入9.1711g三乙胺,反应一定时间t1即40 min,经水冷加入350ml纯水,持续冷却一定时间t2即5 min,之后在室温下水解反应一定时间t3即1h,得到悬浊液C;S3, slowly add solution B to solution A until a large amount of white floc appears, add 9.1711g triethylamine, react for a certain time t 1 , which is 40 minutes, add 350ml pure water through water cooling, and continue to cool for a certain time t 2 , which is 5 minutes. , and then perform a hydrolysis reaction at room temperature for a certain time t 3 , that is, 1 hour, to obtain suspension C;
S4,将悬浊液C用纯水洗至中性后,再用无水乙醇和纯水进一步离心洗涤3次,105℃烘干2小时,研磨,得到固体粉末E;S4, wash the suspension C with pure water until neutral, then further centrifuge and wash 3 times with absolute ethanol and pure water, dry at 105°C for 2 hours, and grind to obtain solid powder E;
S5,将0.3g固体粉末E超声分散于10ml纯水中,滴入5-6滴2 V/V%氨水,得到浑浊液F;S5, ultrasonically disperse 0.3g solid powder E in 10ml pure water, add 5-6 drops of 2 V/V% ammonia water to obtain turbid liquid F;
S6,将3mg/ml银氨溶液H 5ml加入浑浊液F中,避光处理,反应一定时间t4即15 min后,1200rad/min高速搅拌下快速加入0.1mol/l L-抗坏血酸水溶液G 0.4ml,改变转速540rad/min室温反应一定时间t5即3 小时得到浑浊液I;S6, add 5ml of 3mg/ml silver ammonia solution H into the turbid solution F, protect from light, react for a certain time t 4 , that is, 15 minutes, quickly add 0.1mol/l L-ascorbic acid aqueous solution G 0.4ml under high-speed stirring at 1200rad/min , change the rotation speed to 540rad/min and react at room temperature for a certain time t 5 , that is, 3 hours to obtain turbid liquid I;
S7,将浑浊液I抽滤,得到灰褐色沉淀,并用无水乙醇和纯水分别洗涤3次,105℃烘干2小时,得到灰褐色粉末(Ag NPs@CeO2-PEI),即得氧化铈基可抵御蓝光的防晒材料。S7, filter the turbid liquid I to obtain a gray-brown precipitate, wash it three times with absolute ethanol and pure water, and dry it at 105°C for 2 hours to obtain a gray-brown powder (Ag NPs@CeO 2 -PEI), that is, oxidized Cerium-based sunscreen material that blocks blue light.
由附图1可知,CeO2-PEI在3500-3000cm-1处的宽峰归属于PEI中的伯胺键,该范围宽峰说明CeO2-PEI不仅含有缔合的NH2结构,还有着NH结构;1600cm-1处吸收峰为伯胺及仲胺的NH弯曲振动峰;1140cm-1与1100cm-1处为伯胺及仲胺的C-N的伸缩振动峰,并且处于1050cm-1处的吸收峰说明了CeO2-PEI中存在叔胺结构,红外图谱现象说明了CeO2表面已经富含PEI聚合物,证实了PEI的存在。As can be seen from Figure 1, the broad peaks of CeO 2 -PEI at 3500-3000 cm -1 are attributed to the primary amine bonds in PEI. The broad peaks in this range indicate that CeO 2 -PEI not only contains associated NH 2 structures, but also NH Structure; the absorption peak at 1600cm -1 is the NH bending vibration peak of primary and secondary amines; the 1140cm -1 and 1100cm -1 are the CN stretching vibration peaks of primary and secondary amines, and the absorption peak at 1050cm -1 It shows that there is a tertiary amine structure in CeO 2 -PEI. The infrared spectrum phenomenon shows that the surface of CeO 2 is rich in PEI polymer, confirming the existence of PEI.
由附图2可知,CeO2-PEI在X-射线衍射(XRD)中特征峰减少一半,相对于氧化铈PDF#43-1002标准卡,保留了(111)、(220)、(311)、(331)折射晶面。结合红外图谱可知由于表面富含聚乙烯亚胺导致氧铈表面特有的折射角发生改变,更进一步证实了聚乙烯亚胺成功存在于氧化铈表面。As can be seen from Figure 2, the characteristic peaks of CeO 2 -PEI in X-ray diffraction (XRD) are reduced by half. Compared with the cerium oxide PDF#43-1002 standard card, (111), (220), (311), (331) Refractive crystal plane. Combined with the infrared spectrum, it can be seen that the unique refraction angle of the cerium oxide surface changes due to the rich polyethyleneimine on the surface, which further confirms that polyethyleneimine successfully exists on the cerium oxide surface.
由附图3可知,Ag NPs@CeO2-PEI在X-射线能谱(EDS),出现银元素特征峰证明CeO2-PEI成功通过胺基负载上纳米银。As can be seen from Figure 3, in the X-ray energy spectrum (EDS) of Ag NPs@CeO 2 -PEI, the characteristic peak of silver element appears, proving that CeO 2 -PEI successfully loaded nanosilver through the amine group.
实施例2Example 2
本实施例提供一种氧化铈基可抵御蓝光的防晒材料,采用包括如下步骤的制备方法制备而成,其制备方法与实施例1相比,改变聚乙烯亚胺(PEI)的浓度,具体步骤如下:This embodiment provides a cerium oxide-based sunscreen material that can resist blue light, which is prepared by a preparation method including the following steps. Compared with Example 1, the preparation method changes the concentration of polyethylenimine (PEI). The specific steps are: as follows:
将0.50g聚乙烯亚胺(PEI)溶解于10mL无水乙醇中,搅拌使其充分溶解,得到溶液B;Dissolve 0.50g polyethyleneimine (PEI) in 10mL absolute ethanol, stir to fully dissolve, and obtain solution B;
由附图4可知,展示了不同浓度的聚乙烯亚胺PEI改性后得到的CeO2-PEI紫外吸光度的关系设置5组实验,所用聚乙烯亚胺的浓度分别为2.50%、5.00%、7.50%、10.00%。紫外光谱图均是在相同浓度(0.2 mg∙mL-1)下,测得的由图可知,随着PEI用量的增加,对于450nm短波蓝光处吸收情况呈现先减少后增加的趋势,而在UVA与UVB范围内呈现吸收情况为先增加后减少的趋势,展现出良好的抗紫外、蓝光性能。As can be seen from Figure 4, the relationship between the UV absorbance of CeO2-PEI obtained after modification of polyethyleneimine PEI with different concentrations is shown. Five sets of experiments were set up. The concentrations of polyethyleneimine used were 2.50%, 5.00%, and 7.50% respectively. ,10.00%. The UV spectra are all measured at the same concentration (0.2 mg∙mL -1 ). It can be seen from the figure that as the amount of PEI increases, the absorption of 450nm short-wave blue light shows a trend of first decreasing and then increasing, while in UVA In the UVB range, the absorption trend first increases and then decreases, showing good anti-ultraviolet and blue light properties.
实施例3Example 3
本实施例提供一种氧化铈基可抵御蓝光的防晒材料,采用包括如下步骤的制备方法制备而成,其制备方法与实施例1相比,改变L-抗坏血酸(L-AC)的浓度,具体步骤如下:This embodiment provides a cerium oxide-based sunscreen material that can resist blue light, which is prepared by a preparation method including the following steps. Compared with Example 1, the preparation method changes the concentration of L-ascorbic acid (L-AC), specifically Proceed as follows:
S5,将0.3g固体粉末E超声分散于10ml纯水中,滴入5-6滴2 V/V%氨水,得到浑浊液F;S5, ultrasonically disperse 0.3g solid powder E in 10ml pure water, add 5-6 drops of 2 V/V% ammonia water to obtain turbid liquid F;
S6,将3mg/ml银氨溶液H 5ml加入浑浊液F中,避光处理,反应一定时间t4即15 min后,1200rad/min高速搅拌下快速加入0.1mol/l L-抗坏血酸水溶液G 0.5ml,改变转速540rad/min室温反应一定时间t5即3 小时得到浑浊液I;S6, add 5ml of 3mg/ml silver ammonia solution H into the turbid solution F, protect from light, react for a certain time t 4 , that is, 15 minutes, quickly add 0.1mol/l L-ascorbic acid aqueous solution G 0.5ml under high-speed stirring at 1200rad/min , change the rotation speed to 540rad/min and react at room temperature for a certain time t 5 , that is, 3 hours to obtain turbid liquid I;
S7,将浑浊液I抽滤,得到灰褐色沉淀,并用无水乙醇和纯水分别洗涤3次,105℃烘干2小时,得到灰褐色粉末(Ag NPs@CeO2-PEI),即得氧化铈基可抵御蓝光的防晒材料。S7, filter the turbid liquid I to obtain a gray-brown precipitate, wash it three times with absolute ethanol and pure water, and dry it at 105°C for 2 hours to obtain a gray-brown powder (Ag NPs@CeO 2 -PEI), that is, oxidized Cerium-based sunscreen material that blocks blue light.
由附图5可知,展示了L-AC与CeO2-PEI(PEI:5%)不同质量比,于紫外吸光度的关系设置了设置了7组实验,L-AC的用量分别0.588%、1.174%、1.761%、2.348%、2.935%。紫外光谱图均是在相同浓度(0.2 mg∙mL-1)下测得的,由图可知短波蓝光区吸光度呈现出先增加后减少的趋势,当L-AC用量为2.348%时,对于短波蓝光区来说吸光度最优,并且实验中的L-AC用量为2.348%,改性之后的CeO2短波蓝光吸光度均高于未改性之前的。As can be seen from Figure 5, seven sets of experiments were set up in relation to the relationship between the UV absorbance and the different mass ratios of L-AC and CeO 2 -PEI (PEI: 5%). The dosages of L-AC were 0.588% and 1.174% respectively. , 1.761%, 2.348%, 2.935%. The UV spectra were all measured at the same concentration (0.2 mg∙mL -1 ). It can be seen from the figure that the absorbance in the short-wave blue light region shows a trend of first increasing and then decreasing. When the dosage of L-AC is 2.348%, for the short-wave blue light region The absorbance is optimal, and the amount of L-AC in the experiment is 2.348%. The short-wave blue light absorbance of CeO 2 after modification is higher than that before modification.
由附图6可知,取实施例1所制备的Ag NPs@CeO2-PEI样品,将其做成涂层,图中的4 个字母“GDPU”之上分别覆盖 3 层、2层、1 层和 0 层防晒材料的涂层,利用市面上认可的防蓝光测试卡,进行抵御蓝光可视化证明。可知由Ag NPs@CeO2-PEI所制涂层具有优异抵御蓝光的性能。As can be seen from Figure 6, the Ag NPs@CeO 2 -PEI sample prepared in Example 1 was made into a coating. The four letters "GDPU" in the figure were covered with 3 layers, 2 layers, and 1 layer respectively. And a coating of 0-layer sun protection material, using a commercially recognized anti-blue light test card to visually prove its resistance to blue light. It can be seen that the coating made of Ag NPs@CeO 2 -PEI has excellent performance against blue light.
由附图7可知,取实施例1所制备的Ag NPs@CeO2-PEI样品、与实施例2所制的CeO2-PEI以及未任何处理的氧化铈。通过杀菌实验,可知Ag NPs@CeO2-PEI杀菌性能明显增加,1.2%(W/V)对革兰氏阳性菌杀菌达82.05%,在光协同作用下杀菌率高达100%。As can be seen from Figure 7, the Ag NPs@CeO 2 -PEI sample prepared in Example 1, the CeO 2 -PEI prepared in Example 2, and cerium oxide without any treatment were taken. Through sterilization experiments, it can be seen that the bactericidal performance of Ag NPs@CeO 2 -PEI is significantly increased. 1.2% (W/V) can sterilize 82.05% of Gram-positive bacteria, and the sterilization rate is as high as 100% under the synergistic effect of light.
由附图8可知,取实施例1所制备的Ag NPs@CeO2-PEI样品、与实施例2所制的CeO2-PEI,以及未任何处理的氧化铈。通过抑菌实验,可知Ag NPs@CeO2-PEI样品,载银后对革兰氏阳性菌有着明显的抑菌圈出现,故存在抑菌效果。As can be seen from Figure 8, the Ag NPs@CeO 2 -PEI sample prepared in Example 1, the CeO 2 -PEI prepared in Example 2, and cerium oxide without any treatment were taken. Through the antibacterial experiment, it can be seen that the Ag NPs@CeO 2 -PEI sample has an obvious inhibitory zone against Gram-positive bacteria after loading silver, so it has an antibacterial effect.
该杀菌效果可直接或间接减少化妆品中所使用的部分防腐剂的添加与使用,综合降低成本的同时,提高防腐性能。This bactericidal effect can directly or indirectly reduce the addition and use of some preservatives used in cosmetics, comprehensively reducing costs while improving antiseptic performance.
实施例4Example 4
取实施例1氧化铈基可抵御蓝光的防晒材料样品(Ag NPs@CeO2-PEI)0.6g将其作为1.2%的防晒霜,参考QB/T1857-2013《护肤膏霜》对产品进行3000 rad/min离心速度,30min离心稳定性测试,测试结果如附图9可知,Ag NPs@CeO2-PEI均匀分散在化妆品产品中,未出现分层等情况,说明Ag NPs@CeO2-PEI有着良好复配性,可直接作为新型防晒材料直接添加使用;利用SEM扫描电镜图对实施例1氧化铈基可抵御蓝光的防晒材料样品进行观测,结果显示如附图10可知整体形貌接近球状,具有较高比表面积,可有效将短波蓝光以及紫外线屏蔽。Take 0.6g of the cerium oxide-based sunscreen material sample (Ag NPs@CeO2-PEI) that can resist blue light in Example 1 and use it as a 1.2% sunscreen. Refer to QB/T1857-2013 "Skin Care Cream" to test the product at 3000 rad/ min centrifugal speed, 30 min centrifugal stability test, the test results are shown in Figure 9, Ag NPs@CeO 2 -PEI is evenly dispersed in cosmetic products, and no delamination occurs, indicating that Ag NPs@CeO 2 -PEI has good complexation The cerium oxide-based sunscreen material sample of Example 1 that can resist blue light was observed using SEM scanning electron microscopy images. The results show that as shown in Figure 10, the overall morphology is close to spherical and has a relatively large High specific surface area, can effectively shield short-wave blue light and ultraviolet rays.
本发明具体实施方式以聚乙烯亚胺(PEI)、六水合硝酸铈The specific implementation mode of the present invention uses polyethyleneimine (PEI), cerium nitrate hexahydrate
(Ce(NO3)3·6H2O)、硝酸银(NS),利用三乙胺(TEA)促进沉淀反应发生得到氧化铈(CeO2),以枝状聚乙烯亚胺(PEI)作为模板剂合成,得到初步产物CeO2-PEI,再通过L-抗坏血酸(L-AC)将其银粒子还原,通过络合反应使得CeO2-PEI表面载银,制得氧化铈基可抵御蓝光的防晒材料(Ag NPs@CeO2-PEI)。同时利用SEM观得到的球状形貌有利于光折射与吸收,拥有较高的比表面积更有利于抵御蓝光与紫外线的效果。利用FTIR图、XRD图,证明PEI成功与氧化铈CeO2复合在一起;利用EDS图证实CeO2-PEI成功将银元素负载;利用UV光谱图测得该抵御蓝光防晒材料具有较高的吸光度,从而具有抵御蓝光与抗紫外线的作用;利用市面上认可的防蓝光测试卡进一步证实了材料具有抵御蓝光性能;利用抑菌、杀菌实验数据证明该抵御蓝光防晒材料还具备一定的抗菌作用。(Ce(NO 3 ) 3 ·6H 2 O), silver nitrate (NS), triethylamine (TEA) is used to promote the precipitation reaction to obtain cerium oxide (CeO 2 ), and dendritic polyethylenimine (PEI) is used as a template The preliminary product CeO 2 -PEI is synthesized using L-ascorbic acid (L-AC), and its silver particles are reduced by L-ascorbic acid (L-AC). The surface of CeO 2 -PEI is loaded with silver through a complexing reaction to produce a cerium oxide-based sunscreen that can resist blue light. Material (Ag NPs@CeO 2 -PEI). At the same time, the spherical morphology obtained by SEM observation is conducive to light refraction and absorption, and a higher specific surface area is more conducive to resisting blue light and ultraviolet rays. The FTIR chart and XRD chart were used to prove that PEI was successfully compounded with cerium oxide CeO 2 ; the EDS chart was used to confirm that CeO 2 -PEI successfully loaded the silver element; the UV spectrum chart was used to measure that the blue light sunscreen material has high absorbance. It has the function of resisting blue light and resisting ultraviolet rays; using the anti-blue light test card recognized on the market to further confirm that the material has the ability to resist blue light; using antibacterial and sterilization experimental data to prove that the anti-blue light sunscreen material also has a certain antibacterial effect.
根据上述说明书的揭示和教导,本发明所属领域的技术人员还可以对上述实施方式进行变更和修改,如任意改变组成成分聚乙烯亚胺(PEI)、六水合硝酸铈(Ce(NO3)3·6H2O)、硝酸银(NS)、三乙胺(TEA)等的任意组分配比,形成不同的样品,本发明实施例并未穷尽所有配比,但任何基于本发明实施例中的实验原理进行的任何变形,基于本发明并不局限于上面揭示和描述的具体实施方式,对发明的上述任何一些修改和变更也应当落入本发明的权利要求的保护范围内。Based on the disclosure and teachings of the above description, those skilled in the art of the present invention can also make changes and modifications to the above embodiments, such as arbitrarily changing the composition of polyethylenimine (PEI), cerium nitrate hexahydrate (Ce(NO 3 ) 3 ·6H2O), silver nitrate (NS), triethylamine (TEA), etc., to form different samples. The embodiments of the present invention do not exhaust all the proportions, but any composition based on the experimental principles in the embodiments of the present invention Any modifications made based on the present invention are not limited to the specific embodiments disclosed and described above, and any above-mentioned modifications and changes to the invention should also fall within the protection scope of the claims of the present invention.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11228135A (en) * | 1998-02-17 | 1999-08-24 | Toray Ind Inc | Cerium oxide powder and cosmetic material, coating material and plastic containing the same |
CN102071027A (en) * | 2011-03-01 | 2011-05-25 | 吉林大学 | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof |
WO2014129555A1 (en) * | 2013-02-20 | 2014-08-28 | Kawaguchi Tsunetaka | Cerium oxide composite particles |
CN108077307A (en) * | 2016-11-23 | 2018-05-29 | 韩会义 | A kind of polyethyleneimine embeds colourless nano silver antimicrobials |
CN109289849A (en) * | 2018-11-04 | 2019-02-01 | 扬州大学 | A method for the controllable preparation of novel CeO2/Ag renewable surface-enhanced Raman-active photocatalytic materials |
CN116509756A (en) * | 2023-05-18 | 2023-08-01 | 广东暨纳新材料科技有限公司 | Composite sun-screening emulsion based on cerium oxide clay and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104001491B (en) * | 2014-05-15 | 2016-12-07 | 上海应用技术学院 | A kind of CeO2/TiO2 nanocomposite hollow sphere catalyst and preparation method thereof |
CN108129895B (en) * | 2017-12-01 | 2020-06-12 | 山东新朗华科技有限公司 | Preparation method of nano cerium oxide/silicon dioxide ultraviolet shielding agent |
KR102342903B1 (en) * | 2019-02-28 | 2021-12-24 | 코스맥스 주식회사 | Light screening cosmetic composition comprising cerium oxide |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11228135A (en) * | 1998-02-17 | 1999-08-24 | Toray Ind Inc | Cerium oxide powder and cosmetic material, coating material and plastic containing the same |
CN102071027A (en) * | 2011-03-01 | 2011-05-25 | 吉林大学 | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof |
WO2014129555A1 (en) * | 2013-02-20 | 2014-08-28 | Kawaguchi Tsunetaka | Cerium oxide composite particles |
CN108077307A (en) * | 2016-11-23 | 2018-05-29 | 韩会义 | A kind of polyethyleneimine embeds colourless nano silver antimicrobials |
CN109289849A (en) * | 2018-11-04 | 2019-02-01 | 扬州大学 | A method for the controllable preparation of novel CeO2/Ag renewable surface-enhanced Raman-active photocatalytic materials |
CN116509756A (en) * | 2023-05-18 | 2023-08-01 | 广东暨纳新材料科技有限公司 | Composite sun-screening emulsion based on cerium oxide clay and preparation method thereof |
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