CN106823562A - A kind of artificial pulmonary surfactant is used for the method for removing PM2.5 - Google Patents
A kind of artificial pulmonary surfactant is used for the method for removing PM2.5 Download PDFInfo
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Abstract
本发明涉及一种人工肺表面活性物质用于去除PM2.5的方法,包括丝素蛋白的改性、纤维膜的制备和粉尘的吸附,通过静电纺丝技术将丝素蛋白和人工肺表面活性物质的纺丝液制备成纳米纤维膜,用于去除重金属离子本发明通过静电纺丝制备纳米纤维膜,能有效控制纤维膜的孔隙率,去除不同粒径的PM2.5的颗粒。本发明采用天然的丝素蛋白和人工肺表面活性物质,能有效提高吸附剂与金属离子的接触面积,去除重金属离子。本发明所制备的薄膜应用方便,方法简单,可操作性强。The invention relates to a method for removing PM2.5 by artificial lung surface active substances, including the modification of silk fibroin, the preparation of fiber membranes and the adsorption of dust, and the silk fibroin and artificial lung surface active The spinning solution of the substance is prepared into a nanofiber membrane for removing heavy metal ions. The nanofiber membrane is prepared by electrospinning in the present invention, which can effectively control the porosity of the fiber membrane and remove PM2.5 particles of different particle sizes. The invention adopts natural silk fibroin and artificial lung surface active substance, can effectively increase the contact area between the adsorbent and metal ions, and remove heavy metal ions. The film prepared by the invention has the advantages of convenient application, simple method and strong operability.
Description
技术领域technical field
本发明涉及纳米材料的制备领域,具体地涉及一种人工肺表面活性物质用于去除PM2.5的方法,一种用于吸附重金属离子的纤维膜的制备方法。The invention relates to the field of preparation of nanometer materials, in particular to a method for removing PM2.5 by artificial lung surfactant, and a method for preparing a fiber membrane for absorbing heavy metal ions.
背景技术Background technique
胶原纤维是表面含有氨基、羧基等活性基团的一种高分子材料,还是自然界本就存在的一种物质,可以与金属离子形成螯合物,而我们可以通过对其进行化学改性,增强表面基团的活性程度,改善吸附金属离子的性能。例如,王茹等人利用单宁分子中的酚羟基可与金属离子配位这一原理,将单宁固化于皮胶原纤维上制备新型改性吸附剂,研究结果表明吸附剂与吸附质之间的作用为静电结合,吸附过程符合Freundlich吸附模型。同时,改性胶原纤维对Mo具有选择吸附性,且吸附材料可再生。Collagen fiber is a polymer material with active groups such as amino groups and carboxyl groups on the surface, and it is also a substance that exists in nature. It can form chelates with metal ions, and we can chemically modify it to strengthen it. The degree of activity of the surface groups improves the performance of adsorbing metal ions. For example, Wang Ru et al. used the principle that the phenolic hydroxyl groups in tannin molecules can coordinate with metal ions, and solidified tannin on skin collagen fibers to prepare a new type of modified adsorbent. The research results showed that the relationship between the adsorbent and the adsorbate The role of is electrostatic binding, and the adsorption process conforms to the Freundlich adsorption model. At the same time, the modified collagen fibers have selective adsorption to Mo, and the adsorbed material can be regenerated.
丝素蛋白是从蚕丝中提取的天然高分子纤维蛋白,对细胞的粘附、扩展、分化和生长的作用与胶原相似,且在体内引起的免疫反应要比胶原弱。此外,丝素蛋白价格低廉,来源广泛,且具有极好的生物相容性、出色的力学性能、易加工性,可控的降解性能,已广泛用于组织工程修复材料,如血管修复、皮肤修复、骨组织修复等,以及药物载体材料。丝素富含多种功能基团,通过与其他材料或活性物质复合,能起到对组织结构填充以及功能修复的多重协同作用。Silk fibroin is a natural high-molecular fiber protein extracted from silk. Its effect on cell adhesion, expansion, differentiation and growth is similar to that of collagen, and the immune response caused in the body is weaker than that of collagen. In addition, silk fibroin is cheap, has a wide range of sources, and has excellent biocompatibility, excellent mechanical properties, easy processing, and controllable degradation performance. It has been widely used in tissue engineering repair materials, such as vascular repair, skin Repair, bone tissue repair, etc., as well as drug carrier materials. Silk fibroin is rich in a variety of functional groups, and by compounding with other materials or active substances, it can play multiple synergistic effects on tissue structure filling and functional repair.
肺表面活性物质(PS)是一种存在于支气管及肺泡表面的能降低肺泡表面张力的物质。它由Ⅱ型肺泡细胞产生,主要成分有两部分:脂质和表面活性蛋白。其中脂质的占比接近90%,而脂质中磷脂又占了绝大部分,其他脂质还有:胆固醇,甘油三酯和游离的脂肪酸等。磷脂酰胆碱是表面活性物质中含量最多的成分,占到了所有脂质的70~80%。其中有饱和的磷脂酰胆碱占到了50~70%,主要是二棕榈酸磷脂酰胆碱(DPPC),它是降低肺表面活性物质表面张力的主要成分。此外,磷脂酰甘油含约8%,其他脂质还有:磷脂酰乙醇胺约5%,磷脂酰肌醇约3%,还有少量的磷脂酰丝氨酸、溶血磷脂酰胆碱和鞘磷脂。有研究表明,重金属能与肺泡和上皮细胞表面DPPC相互作用沉积,启动内质网应激,脂质合成基因乙酰辅酶A羧化酶(acetyl-CoA carboxylase,Acaca)表达增加并介导乙酰辅酶A向丙二酰辅酶A转化,促进脂肪酸合成;而甘油二酯酰基转移酶(diglyceride acyltransferase,Dgat)2和激素敏感脂肪酶(Lipe)表达增加促进甘油三酯(triglycerides,TG)合成,这一系列脂肪化从而降低重金属进入体内。但是,到目前为止,未见与DPPC性质相似的人工肺表面活性物质用于重金属离子吸附材料方面的制备。Pulmonary surfactant (PS) is a substance that exists on the surface of the bronchi and alveoli and can reduce the surface tension of the alveoli. It is produced by type II alveolar cells and has two main components: lipids and surfactant proteins. Among them, lipids account for nearly 90%, and phospholipids in lipids account for the vast majority. Other lipids include: cholesterol, triglycerides, and free fatty acids. Phosphatidylcholine is the most abundant component of surface active substances, accounting for 70-80% of all lipids. Among them, saturated phosphatidylcholine accounts for 50-70%, mainly dipalmitate phosphatidylcholine (DPPC), which is the main component that reduces the surface tension of pulmonary surfactant. In addition, phosphatidylglycerol contains about 8%, other lipids include: phosphatidylethanolamine about 5%, phosphatidylinositol about 3%, and a small amount of phosphatidylserine, lysophosphatidylcholine and sphingomyelin. Studies have shown that heavy metals can interact and deposit with DPPC on the surface of alveoli and epithelial cells, initiate endoplasmic reticulum stress, increase the expression of lipid synthesis gene acetyl-CoA carboxylase (Acaca) and mediate acetyl-CoA The conversion to malonyl-CoA promotes the synthesis of fatty acids; while the expression of diglyceride acyltransferase (Dgat) 2 and hormone-sensitive lipase (Lipe) increase to promote the synthesis of triglycerides (triglycerides, TG), this series Fattyization thus reduces the entry of heavy metals into the body. However, so far, no artificial lung surfactants with properties similar to DPPC have been used in the preparation of heavy metal ion adsorption materials.
发明内容Contents of the invention
针对现有技术中的不足,本发明的提供一种人工肺表面活性物质用于去除PM2.5的方法,该方法利用丝素蛋白与人工肺表面活性物质的共同作用,通过静电纺丝技术制备能高效吸附重金属离子的纤维膜,从而大幅度地增强重金属离子的吸附效果。该技术制备方法简单,所得的产品性能明显高于现有市场的产品。Aiming at the deficiencies in the prior art, the present invention provides a method for removing PM2.5 by using artificial lung surfactant. The method utilizes the joint action of silk fibroin and artificial lung surfactant, and is prepared by electrospinning technology. A fiber membrane that can efficiently adsorb heavy metal ions, thereby greatly enhancing the adsorption effect of heavy metal ions. The technical preparation method is simple, and the performance of the obtained product is obviously higher than that of the existing market products.
为了实现这样的目的,在本发明的技术方案中,以丝素蛋白与人工肺表面活性物质为吸附材料,通过静电纺丝技术制备能高效吸附重金属离子的纤维膜;将该纤维膜用于现有分体式口罩的核心芯体,能大幅提高现有口罩的防霾效果。In order to achieve such purpose, in the technical scheme of the present invention, silk fibroin and artificial lung surfactant are used as adsorption materials, and a fibrous membrane capable of efficiently adsorbing heavy metal ions is prepared by electrospinning technology; the fibrous membrane is used in the present The core body of the split mask can greatly improve the haze prevention effect of the existing masks.
本发明的方法包括如下步骤:Method of the present invention comprises the steps:
一种人工肺表面活性物质用于去除PM2.5的方法,其特征在于该方法包括如下步骤:A method for removing PM2.5 by artificial lung surfactant, characterized in that the method comprises the steps:
(1)丝素蛋白的改性(1) Modification of silk fibroin
将丝素蛋白(SF)与DPPC按照摩尔比为10:1-1:1溶解在10mL,0.1M的MES溶液中,MES溶液pH=5.5,吗啉乙磺酸,2小时后加入与DPPC等摩尔比的1-乙基-3-[3-二甲基氨基丙基]碳化二亚胺盐酸化物(EDC)和N-羟基琥珀酰亚胺(NHS),室温搅拌3小时后取出,水洗干燥,最后将丝素蛋白水溶液置于-80℃的冷冻干燥仪器中冻干得到丝素蛋白粉;Dissolve silk fibroin (SF) and DPPC at a molar ratio of 10:1-1:1 in 10mL, 0.1M MES solution, MES solution pH=5.5, morpholineethanesulfonic acid, add DPPC, etc. after 2 hours Molar ratio of 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), stirring at room temperature for 3 hours, taking out, washing and drying , and finally put the silk fibroin aqueous solution in a freeze-drying apparatus at -80°C to freeze-dry to obtain silk fibroin powder;
(2)纤维膜的制备(2) Preparation of fiber membrane
将等质量的丝素蛋白粉和磷脂等配置成3%的水溶液5ml,所得的溶液放入注射器中,采用7号针头,利用已有的静电纺丝设备,设置的仪器参数为:加载电压在10-20 kV,注射器跟接收板距离为7-12 cm,推进速度0.1 ml/h-0.3 ml/h,空气相对湿度35-45%,静电纺丝完成即可得纳米纤维;The same mass of silk fibroin powder and phospholipids are prepared into 5ml of 3% aqueous solution, and the resulting solution is put into a syringe with a No. 7 needle and the existing electrospinning equipment. The instrument parameters are set as follows: the loading voltage is at 10-20 kV, the distance between the injector and the receiving plate is 7-12 cm, the propulsion speed is 0.1 ml/h-0.3 ml/h, the relative humidity of the air is 35-45%, and the nanofibers can be obtained after electrospinning;
(3)粉尘的吸附(3) Dust adsorption
将纤维膜制作成10cm × 10cm,作为分体式口罩的芯体得到新型雾霾口罩,将口罩置于雾霾评价仓中,以柴油机为污染源发生器,通过粉尘检测仪、粉尘成分分析等技术检测口罩对雾霾的治理效果。The fiber membrane is made into 10cm × 10cm, and used as the core body of the split mask to obtain a new type of smog mask. The mask is placed in the smog evaluation chamber, and the diesel engine is used as the pollution source generator to pass dust detectors, dust component analysis and other technical testing. The control effect of masks on smog.
所述的磷脂为大豆卵磷脂、蛋黄卵磷脂、氢化卵磷脂、氢化大豆磷脂酰胆碱、氢化蛋磷脂酰胆碱、二月桂酰磷脂酰胆碱、二肉豆寇酰磷脂酰胆碱、二硬脂酰磷脂酰胆碱、1-肉豆寇酰-2-棕榈酰磷脂酰胆碱、1-棕榈酰-2-硬脂酰磷脂酰胆碱、1-硬脂酰-2-棕榈酰磷脂酰胆碱、1-棕榈酰-2-油酰磷脂酰胆碱、1-硬脂酰-2-亚油酰磷脂酰胆碱或二油酰磷脂酰胆碱中的至少一种。The phospholipids are soybean lecithin, egg yolk lecithin, hydrogenated lecithin, hydrogenated soybean phosphatidylcholine, hydrogenated egg phosphatidylcholine, dilauroylphosphatidylcholine, dimyrisylphosphatidylcholine, di Stearoylphosphatidylcholine, 1-myristoyl-2-palmitoylphosphatidylcholine, 1-palmitoyl-2-stearoylphosphatidylcholine, 1-stearoyl-2-palmitoylphosphatidylcholine At least one of phosphatidylcholine, 1-palmitoyl-2-oleoylphosphatidylcholine, 1-stearoyl-2-linoleoylphosphatidylcholine or dioleoylphosphatidylcholine.
所述的步骤(3)中,加载电压在10-20 kV,优选为12-18 kV。In the step (3), the loading voltage is 10-20 kV, preferably 12-18 kV.
所述的步骤(3)中,注射器跟接收板距离为7-12cm,优选为8-10 cm。In the step (3), the distance between the syringe and the receiving plate is 7-12 cm, preferably 8-10 cm.
所述的步骤优选为(3)中,推进速度0.1 ml/h-0.3 ml/h,优选为0.1 ml/h-0.2ml/h。The step is preferably in (3), the propulsion speed is 0.1 ml/h-0.3 ml/h, preferably 0.1 ml/h-0.2 ml/h.
所述的步骤(3)中,空气相对湿度35-45%,优选为35%-40%。In the step (3), the relative air humidity is 35-45%, preferably 35%-40%.
与现有技术相比,本发明具有如下的有益效果:Compared with the prior art, the present invention has the following beneficial effects:
本发明的优点在于:(1)本发明通过静电纺丝制备纳米纤维膜,能有效控制纤维膜的孔隙率,去除不同粒径的PM2.5的颗粒。(3)本发明采用天然的丝素蛋白和人工肺表面活性物质,能有效提高吸附剂与金属离子的接触面积,去除重金属离子。本发明所制备的薄膜应用方便,方法简单,可操作性强。The advantages of the present invention are: (1) The present invention prepares nanofiber membranes by electrospinning, which can effectively control the porosity of the fiber membranes and remove PM2.5 particles with different particle sizes. (3) The present invention uses natural silk fibroin and artificial lung surfactant, which can effectively increase the contact area between the adsorbent and metal ions, and remove heavy metal ions. The film prepared by the invention has the advantages of convenient application, simple method and strong operability.
具体实施方式detailed description
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1Example 1
a. 丝素蛋白的改性a. Modification of silk fibroin
将1mol,SF与0.5mol,DPPC溶解在10mL,0.1M的MES溶液(pH=5.5,吗啉乙磺酸)中,2小时后加入与DPPC等0.5mol的EDC和NHS,室温搅拌3小时后取出,水洗干燥,最后将丝素蛋白水溶液置于-80℃的冷冻干燥仪器中冻干得到丝素蛋白粉。Dissolve 1mol of SF and 0.5mol of DPPC in 10mL of 0.1M MES solution (pH=5.5, morpholineethanesulfonic acid), add 0.5mol of EDC and NHS such as DPPC after 2 hours, and stir at room temperature for 3 hours Take it out, wash and dry it with water, and finally place the silk fibroin aqueous solution in a freeze-drying apparatus at -80°C to freeze-dry to obtain silk fibroin powder.
b. 纤维膜的制备b. Preparation of fiber membrane
将等质量的丝素蛋白粉和蛋黄卵磷脂等配置成3%的水溶液5ml,所得的溶液放入注射器中,采用7号针头,利用已有的静电纺丝设备,设置的仪器参数为:加载电压在15kV,注射器跟接收板距离为8cm,推进速度0.3ml/h,空气相对湿度40%,静电纺丝完成即可得纳米纤维。Prepare silk fibroin powder of equal mass and egg yolk lecithin into 5ml of a 3% aqueous solution, put the resulting solution into a syringe, use a No. 7 needle, and use the existing electrospinning equipment. The instrument parameters set are: load The voltage is 15kV, the distance between the injector and the receiving plate is 8cm, the advancing speed is 0.3ml/h, and the relative humidity of the air is 40%. Nanofibers can be obtained after electrospinning is completed.
检测结果:除尘率87%,重金属吸附率65%。Test results: the dust removal rate is 87%, and the heavy metal adsorption rate is 65%.
实施例2Example 2
a. 丝素蛋白的改性a. Modification of silk fibroin
将1mol,SF与0.1mol,DPPC溶解在10mL,0.1M的MES溶液(pH=5.5,吗啉乙磺酸)中,2小时后加入与DPPC等0.1mol的EDC和NHS,室温搅拌3小时后取出,水洗干燥,最后将丝素蛋白水溶液置于-80℃的冷冻干燥仪器中冻干得到丝素蛋白粉。Dissolve 1mol of SF and 0.1mol of DPPC in 10mL of 0.1M MES solution (pH=5.5, morpholineethanesulfonic acid), add 0.1mol of EDC and NHS with DPPC after 2 hours, stir at room temperature for 3 hours Take it out, wash and dry it with water, and finally place the silk fibroin aqueous solution in a freeze-drying apparatus at -80°C to freeze-dry to obtain silk fibroin powder.
b. 纤维膜的制备b. Preparation of fiber membrane
将等质量的丝素蛋白粉和1-肉豆寇酰-2-棕榈酰磷脂酰胆碱等配置成3%的水溶液5ml,所得的溶液放入注射器中,采用7号针头,利用已有的静电纺丝设备,设置的仪器参数为:加载电压在18kV,注射器跟接收板距离为10cm,推进速度0.1ml/h,空气相对湿度35%,静电纺丝完成即可得纳米纤维。Prepare equal mass of silk fibroin powder and 1-myristoyl-2-palmitoylphosphatidylcholine into 5ml of 3% aqueous solution, put the resulting solution into a syringe, use a No. 7 needle, and use the existing For the electrospinning equipment, the instrument parameters are set as follows: the loading voltage is 18kV, the distance between the injector and the receiving plate is 10cm, the advancing speed is 0.1ml/h, and the relative air humidity is 35%. Nanofibers can be obtained after electrospinning is completed.
检测结果:除尘率63%,重金属吸附率43%。Test results: the dust removal rate is 63%, and the heavy metal adsorption rate is 43%.
实施例3Example 3
a. 丝素蛋白的改性a. Modification of silk fibroin
将0.5mol,SF与0.5mol,DPPC溶解在10mL,0.1M的MES溶液(pH=5.5,吗啉乙磺酸)中,2小时后加入与DPPC等0.5mol的EDC和NHS,室温搅拌3小时后取出,水洗干燥,最后将丝素蛋白水溶液置于-80℃的冷冻干燥仪器中冻干得到丝素蛋白粉。Dissolve 0.5 mol of SF and 0.5 mol of DPPC in 10 mL of 0.1 M MES solution (pH=5.5, morpholineethanesulfonic acid), add 0.5 mol of EDC and NHS such as DPPC after 2 hours, and stir at room temperature for 3 hours Then take it out, wash and dry it with water, and finally place the silk fibroin aqueous solution in a freeze-drying apparatus at -80°C to freeze-dry to obtain silk fibroin powder.
b. 纤维膜的制备b. Preparation of fiber membrane
将等质量的丝素蛋白粉和二油酰磷脂酰胆碱等配置成3%的水溶液5ml,所得的溶液放入注射器中,采用7号针头,利用已有的静电纺丝设备,设置的仪器参数为:加载电压在15kV,注射器跟接收板距离为8cm,推进速度0.2ml/h,空气相对湿度35%,静电纺丝完成即可得纳米纤维。Equivalent mass of silk fibroin powder and dioleoylphosphatidylcholine etc. are configured into 5ml of 3% aqueous solution, and the resulting solution is put into a syringe with a No. 7 needle, using the existing electrospinning equipment, and the equipment The parameters are: the loading voltage is 15kV, the distance between the injector and the receiving plate is 8cm, the advancing speed is 0.2ml/h, the relative humidity of the air is 35%, and the nanofibers can be obtained after electrospinning.
检测结果:除尘率92%,重金属吸附率85%。Test results: the dust removal rate is 92%, and the heavy metal adsorption rate is 85%.
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