CN117718029A - Efficient uremic toxin adsorbent and preparation method and application thereof - Google Patents

Efficient uremic toxin adsorbent and preparation method and application thereof Download PDF

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CN117718029A
CN117718029A CN202311741202.7A CN202311741202A CN117718029A CN 117718029 A CN117718029 A CN 117718029A CN 202311741202 A CN202311741202 A CN 202311741202A CN 117718029 A CN117718029 A CN 117718029A
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uremic toxin
activated carbon
sodium alginate
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efficient
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CN117718029B (en
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秦广乐
陈大鹏
沙菁
闫烁
李勇
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Jiangsu Jierui Medical Technology Co ltd
Southeast University
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Southeast University
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Abstract

The invention belongs to the field of uremic toxin adsorbent preparation, and particularly discloses a high-efficiency uremic toxin adsorbent and a preparation method thereof, wherein the preparation method comprises the following steps: step (1): dissolving polyvinyl alcohol and modified sodium alginate in deionized water, adding modified coconut shell activated carbon, uniformly stirring and dispersing, and then spreading to form a film; step (2): freezing the film in the step (1), taking out and putting into CaCl 2 The high-efficiency uremic toxin adsorbent is obtained by crosslinking, cleaning and shearing in the saturated boric acid solution, is safe and nontoxic, has a fast adsorption rate to uremic toxin,The adsorption capacity is high, the biocompatibility and the blood compatibility are good, and the method has a good application prospect in the field of wearable artificial kidneys.

Description

一种高效的尿毒症毒素吸附剂及其制备方法与应用An efficient uremic toxin adsorbent and its preparation method and application

技术领域Technical field

本发明涉及一种高效的尿毒症毒素吸附剂及其制备方法与应用,属于尿毒症毒素吸附剂的制备领域。The invention relates to an efficient uremic toxin adsorbent and its preparation method and application, and belongs to the field of preparation of uremic toxin adsorbents.

背景技术Background technique

尿毒症亦称终末期肾病,是慢性肾衰竭终末期的一种临床综合症。Uremia, also known as end-stage renal disease, is a clinical syndrome in the end stage of chronic renal failure.

传统的血液透析方案,可实现对小分子毒素的有效清除,然而对于中大分子毒素的清除能力较弱。组合人工肾治疗方案是指在血液透析器的基础上串联灌流器,通过发挥弥散与吸附作用而达到优势互补,进一步提高血液净化效果,在尿毒症患者治疗中能够对其机体中的毒素实现全面清除,弥补了单一血液透析中无法清除大中分子毒素的缺陷,能够更好的净化患者机体环境。The traditional hemodialysis program can effectively remove small molecule toxins, but its ability to remove medium and large molecule toxins is weak. The combined artificial kidney treatment plan refers to a perfusion device connected in series on the basis of a hemodialyzer, which complements the advantages through dispersion and adsorption, further improves the blood purification effect, and can comprehensively eliminate toxins in the body during the treatment of uremia patients. The removal makes up for the shortcomings of single hemodialysis that cannot remove large and medium molecule toxins, and can better purify the patient's body environment.

目前,我国90%以上的透析患者使用血液透析方法,他们需要频繁地去医院治疗(3次/周,约4h/次),透析期间患者需要一直躺在病床上,这给患者的日常生活造成了极大的不便。可穿戴人工肾的出现能较好地解决这一问题。At present, more than 90% of dialysis patients in our country use hemodialysis method. They need to go to the hospital frequently for treatment (3 times/week, about 4 hours/time). During dialysis, patients need to lie in the hospital bed all the time, which causes problems to the patients' daily life. A huge inconvenience. The emergence of wearable artificial kidneys can better solve this problem.

可穿戴人工肾将设备和人结合在一起,是终末期肾脏替代设备的发展方向,目前是国内外的研究热点。可穿戴人工肾的核心问题是透析液的循环再生,而循环再生透析液的关键是将尿素、肌酐等尿毒症毒素清除,目前国内外常用的方法是用生物酶法、电氧化法和物理吸附法。生物酶法采用生物酶分解尿毒症毒素会产生铵根反应物,其溶于水后生成氨气,对人体伤害很大;电氧化法分解尿毒症毒素能耗很大,不适合可穿戴设备采用;物理吸附法相对安全,通常采用活性炭、Ti3C2Tx、Zn1-xMgxFe2O4等,这些吸附材料对肌酐有一定的吸附能力,但对尿素的吸附效果不够理想。尿素是一种非常不活泼的化合物,在生理pH值下不带电荷,既不非常亲核也不非常亲电,尿素的这些特性造成其较难被去除。此外,一部分吸附材料,如活性炭和沸石等,生物相容性、血液相容性较差,不适合在可穿戴人工肾中应用。Wearable artificial kidneys combine equipment and people, which is the development direction of end-stage kidney replacement equipment. It is currently a research hotspot at home and abroad. The core issue of the wearable artificial kidney is the circulation and regeneration of dialysate. The key to recycling and regenerating dialysate is to remove uremic toxins such as urea and creatinine. Currently, the commonly used methods at home and abroad are biological enzymatic methods, electro-oxidation methods and physical adsorption. Law. The bioenzyme method uses biological enzymes to decompose uremic toxins, which will produce ammonium reactants. When dissolved in water, ammonia gas is generated, which is very harmful to the human body. The electrooxidation method to decompose uremic toxins consumes a lot of energy and is not suitable for wearable devices. ; The physical adsorption method is relatively safe and usually uses activated carbon, Ti 3 C 2 Tx, Zn1-xMgxFe 2 O 4 , etc. These adsorption materials have a certain adsorption capacity for creatinine, but their adsorption effect on urea is not ideal. Urea is a very inactive compound, uncharged at physiological pH, and neither very nucleophilic nor very electrophilic. These properties of urea make it difficult to remove. In addition, some adsorbent materials, such as activated carbon and zeolite, have poor biocompatibility and blood compatibility, and are not suitable for use in wearable artificial kidneys.

因此,针对现有技术存在的不足,开发出生物相容性较高,且对尿毒症毒素具有较好清除效果的吸附剂,应用于可穿戴人工肾具有现实意义。Therefore, in view of the shortcomings of existing technologies, it is of practical significance to develop adsorbents with higher biocompatibility and better removal effects on uremic toxins, and their application in wearable artificial kidneys.

发明内容Contents of the invention

针对尿毒症为患者带来的一系列问题,本发明提供了一种高效的尿毒症毒素吸附剂及其制备方法,将对尿毒症毒素有较高吸附量的改性椰壳活性炭通过交联方式包埋在聚乙烯醇-改性海藻酸钠中,得到高效的尿毒症毒素吸附剂,此吸附剂安全无毒,对尿毒症毒素的吸附速率快、吸附容量高,且有较好的生物相容性和血液相容性。In view of a series of problems that uremia brings to patients, the present invention provides an efficient uremic toxin adsorbent and a preparation method thereof. Modified coconut shell activated carbon with a high adsorption capacity for uremic toxins is cross-linked. Embedded in polyvinyl alcohol-modified sodium alginate, an efficient uremic toxin adsorbent is obtained. This adsorbent is safe and non-toxic, has a fast adsorption rate for uremic toxins, high adsorption capacity, and has good biological phase. capacitance and blood compatibility.

为实现上述目的,本发明采用的技术方案如下:In order to achieve the above objects, the technical solutions adopted by the present invention are as follows:

本发明第一方面提供了一种高效的尿毒症毒素吸附剂的制备方法,具体包括以下步骤:The first aspect of the present invention provides a method for preparing an efficient uremic toxin adsorbent, which specifically includes the following steps:

步骤(1):将聚乙烯醇、改性海藻酸钠溶解在去离子水中,加入改性椰壳活性炭,搅拌分散均匀后平铺,形成薄膜;Step (1): Dissolve polyvinyl alcohol and modified sodium alginate in deionized water, add modified coconut shell activated carbon, stir and disperse evenly, and spread flat to form a film;

步骤(2):将步骤(1)中的薄膜冷冻,取出放入CaCl2的饱和硼酸溶液溶液中交联,洗净、剪碎,得到高效的尿毒症毒素吸附剂。Step (2): Freeze the film in step (1), take it out and put it into a saturated boric acid solution of CaCl 2 for cross-linking, wash and cut into pieces to obtain an efficient uremic toxin adsorbent.

所述步骤(1)中改性海藻酸钠的制备步骤如下:The preparation steps of modified sodium alginate in step (1) are as follows:

步骤S1:将海藻酸钠溶解在盐酸溶液中,水浴加热,得到基础反应体系;Step S1: Dissolve sodium alginate in hydrochloric acid solution and heat in a water bath to obtain a basic reaction system;

步骤S2:使用氮气保护整个步骤S1得到的基础反应体系,将磷酸胆碱缓慢滴加到基础反应体系中,搅拌待其反应;Step S2: Use nitrogen to protect the entire basic reaction system obtained in step S1, slowly add phosphorylcholine dropwise into the basic reaction system, and stir until it reacts;

步骤S3:待步骤S2反应结束后,将反应后所得产物置于去离子水进行透析处理,收集产物,冷冻干燥,得到改性海藻酸钠。Step S3: After the reaction in step S2 is completed, the product obtained after the reaction is placed in deionized water for dialysis treatment, and the product is collected and freeze-dried to obtain modified sodium alginate.

优选地,所述盐酸溶液的质量分数为1-2%,海藻酸钠、磷酸胆碱与盐酸溶液的质量比为(5-10):(1-5):100。Preferably, the mass fraction of the hydrochloric acid solution is 1-2%, and the mass ratio of sodium alginate, phosphorylcholine and hydrochloric acid solution is (5-10):(1-5):100.

进一步优选地,所述盐酸溶液的质量分数为2%,海藻酸钠、磷酸胆碱与盐酸溶液的质量比为9:4:100。Further preferably, the mass fraction of the hydrochloric acid solution is 2%, and the mass ratio of sodium alginate, phosphorylcholine and hydrochloric acid solution is 9:4:100.

申请人发现控制海藻酸钠、磷酸胆碱与盐酸溶液的质量比,既保证了磷酸胆碱和海藻酸钠的充分混合,又可以尽量减少副反应,使改性海藻酸钠的综合性能更好,一方面适量浓度的盐酸作为反应的催化剂,可以加快反应的进行;另一方面大量水的存在不利于反应的发生,适量的水能使海藻酸钠、磷酸胆碱混合均匀,形成流动性较好的体系,加快反应速率,保证改性海藻酸钠的高产率。The applicant found that controlling the mass ratio of sodium alginate, phosphocholine and hydrochloric acid solution not only ensures full mixing of phosphocholine and sodium alginate, but also minimizes side reactions, making the overall performance of modified sodium alginate better. On the one hand, hydrochloric acid of an appropriate concentration can be used as a catalyst for the reaction, which can speed up the reaction; on the other hand, the presence of a large amount of water is not conducive to the occurrence of the reaction. An appropriate amount of water can make sodium alginate and phosphocholine mix evenly, forming a relatively fluid form. A good system can speed up the reaction rate and ensure a high yield of modified sodium alginate.

优选地,所述步骤S1中,所述水浴温度为45-50℃,水浴时长为1-2h。Preferably, in step S1, the water bath temperature is 45-50°C, and the water bath duration is 1-2 hours.

申请人发现控制水浴温度45-50℃、水浴时长为1-2h可以保证反应较好的进行。水浴温度过高或者水浴时间太久会使海藻酸钠溶液的粘度明显下降,粘度下降,会影响交联效果,进而降低吸附剂的吸附效果。The applicant found that controlling the water bath temperature to 45-50°C and the water bath duration to 1-2 hours can ensure better progress of the reaction. If the water bath temperature is too high or the water bath time is too long, the viscosity of the sodium alginate solution will decrease significantly. The decrease in viscosity will affect the cross-linking effect, thereby reducing the adsorption effect of the adsorbent.

优选地,所述尿毒症毒素吸附剂的制备方法步骤(1)中聚乙烯醇、改性海藻酸钠分别为去离子水的4-8wt%、0.6-1.2wt%,聚乙烯醇与改性海藻酸钠的质量比为(5-10):1。Preferably, in step (1) of the preparation method of the uremic toxin adsorbent, polyvinyl alcohol and modified sodium alginate are respectively 4-8wt% and 0.6-1.2wt% of deionized water, and polyvinyl alcohol and modified sodium alginate are respectively The mass ratio of sodium alginate is (5-10):1.

进一步优选地,所述聚乙烯醇为去离子水的6wt%,改性海藻酸钠为去离子水的0.8wt%。Further preferably, the polyvinyl alcohol is 6 wt% of deionized water, and the modified sodium alginate is 0.8 wt% of deionized water.

申请人发现控制聚乙烯醇和改性海藻酸钠的添加量能够使制备的吸附剂更易成型,传质性能、机械性能及生物相容性较好,一方面改性海藻酸钠可以增加吸附剂的抗凝血作用和血液相容性,另一方面改性海藻酸钠与聚乙烯醇通过交联剂产生交联结构,并利用氢键和结晶区产生物理交联结点,从而形成三维立体结构,使内部形成孔隙,有利于提升吸附效果,但若改性海藻酸钠添加量超出限定范围,其会在吸附剂内部对聚乙烯醇分子形成空间位阻,阻碍聚乙烯醇分子间交联的有效范围,会使内部孔隙增多,孔径减小,壁厚减小,导致吸附剂的力学性能和吸附效果下降。The applicant found that controlling the addition amount of polyvinyl alcohol and modified sodium alginate can make the prepared adsorbent easier to shape, with better mass transfer performance, mechanical properties and biocompatibility. On the one hand, modified sodium alginate can increase the adsorbent's Anticoagulant effect and blood compatibility. On the other hand, modified sodium alginate and polyvinyl alcohol produce a cross-linked structure through a cross-linking agent, and use hydrogen bonds and crystallization areas to produce physical cross-linking nodes, thereby forming a three-dimensional structure. Forming pores inside will help improve the adsorption effect. However, if the amount of modified sodium alginate exceeds the limited range, it will form steric hindrance to the polyvinyl alcohol molecules inside the adsorbent, hindering the effective cross-linking of polyvinyl alcohol molecules. range, the internal pores will increase, the pore diameter will decrease, and the wall thickness will decrease, resulting in a decrease in the mechanical properties and adsorption effect of the adsorbent.

优选地,所述尿毒症毒素吸附剂的制备方法步骤(2)中CaCl2为饱和硼酸溶液的3-5wt%,交联时长为18-24h。Preferably, in step (2) of the preparation method of the uremic toxin adsorbent, CaCl 2 is 3-5 wt% of the saturated boric acid solution, and the cross-linking time is 18-24 hours.

进一步优选地,所述步骤(2)中CaCl2为饱和硼酸溶液的4wt%,交联时长为20h。Further preferably, in the step (2), CaCl 2 is 4 wt% of the saturated boric acid solution, and the cross-linking time is 20 h.

本发明中CaCl2的饱和硼酸溶液为交联剂,申请人发现将CaCl2浓度控制为饱和硼酸溶液的4wt%,制备的吸附剂力学性能较好,内部交联程度较好、孔径均匀,使吸附剂具有较好的吸附性能。此外,控制交联时长会使制备的吸附剂具有较好的机械强度,不易破碎。In the present invention, a saturated boric acid solution of CaCl 2 is used as the cross-linking agent. The applicant found that by controlling the CaCl 2 concentration to 4wt% of the saturated boric acid solution, the prepared adsorbent has better mechanical properties, better internal cross-linking degree, and uniform pore size, so that The adsorbent has better adsorption performance. In addition, controlling the cross-linking time will make the prepared adsorbent have better mechanical strength and not easy to break.

优选地,所述改性椰壳活性炭质量与聚乙烯醇、改性海藻酸钠的总质量比为1:(2-4)。Preferably, the total mass ratio of the modified coconut shell activated carbon to polyvinyl alcohol and modified sodium alginate is 1: (2-4).

进一步优选地,所述改性椰壳活性炭质量与聚乙烯醇、改性海藻酸钠的总质量比为1:3。Further preferably, the total mass ratio of the modified coconut shell activated carbon to polyvinyl alcohol and modified sodium alginate is 1:3.

控制改性椰壳活性炭添加量,使其均匀地分布在改性海藻酸钠与聚乙烯醇形成的内部立体孔隙中,且不会堵塞孔隙,有利于吸附剂通过改性椰壳活性炭的活性位点吸附及其负载的玉米须多糖铁与毒素形成的配位键,高效地清除尿毒症毒素。Control the amount of modified coconut shell activated carbon added so that it is evenly distributed in the internal three-dimensional pores formed by modified sodium alginate and polyvinyl alcohol without clogging the pores, which is conducive to the adsorbent passing through the active sites of the modified coconut shell activated carbon. Point adsorption and the coordination bond formed by the loaded corn silk polysaccharide iron and toxins can effectively remove uremic toxins.

优选地,所述改性椰壳活性炭的制备步骤如下:Preferably, the preparation steps of the modified coconut shell activated carbon are as follows:

步骤(1):将椰壳干燥,放入炭化炉,升温、保温炭化,冷却,得到炭化料;Step (1): Dry the coconut shell, put it into a carbonization furnace, heat it up, keep it carbonized, and cool it to obtain carbonized material;

步骤(2):将炭化料破碎,通入氮气、升温,停止通入氮气切换为水蒸气进行活化,停止加热,切断水蒸气通入氮气,冷却至室温,得到活化料,漂洗、干燥,得到活化椰壳活性炭;Step (2): Crush the carbonized material, introduce nitrogen, raise the temperature, stop the nitrogen and switch to water vapor for activation, stop heating, cut off the water vapor and introduce nitrogen, cool to room temperature to obtain the activated material, rinse and dry to obtain activated coconut shell activated carbon;

步骤(3):将活化椰壳活性炭破碎,取破碎后的活性炭加入到硫酸溶液中,恒温振荡后用蒸馏水洗涤至中性,干燥至恒重,得到硫酸改性活性炭;Step (3): Crush the activated coconut shell activated carbon, add the crushed activated carbon to the sulfuric acid solution, shake at a constant temperature, wash with distilled water to neutrality, and dry to constant weight to obtain sulfuric acid modified activated carbon;

步骤(4):称取玉米须,加去离子水,恒温水浴,抽滤,重复上述操作2次,合并滤液,滤液浓缩,在浓缩液中加入无水乙醇,密封,于阴凉处放置,过滤得到固体,洗涤,蒸馏水复溶,流动水透析,醇沉、分离,得到粉末状玉米须多糖,取玉米须多糖、柠檬酸三钠溶解于去离子水中,恒温搅拌,调节pH,滴加三氯化铁溶液,至溶液中有固体出现时,停止滴加,继续加热搅拌,抽滤,滤液中加入等体积的无水乙醇,密封,暗处放置,抽滤,洗涤沉淀,用去离子水透析,醇沉、分离,得到玉米须多糖铁;Step (4): Weigh the corn silk, add deionized water, take a constant temperature water bath, suction filtrate, repeat the above operation twice, combine the filtrate, concentrate the filtrate, add absolute ethanol to the concentrated solution, seal, place in a cool place, and filter Obtain the solid, wash, redissolve in distilled water, dialyze with flowing water, alcohol precipitation and separation to obtain powdered corn silk polysaccharide. Dissolve the corn silk polysaccharide and trisodium citrate in deionized water, stir at constant temperature, adjust the pH, and add trichloride dropwise. Iron solution, when solid appears in the solution, stop dripping, continue heating and stirring, suction filtration, add an equal volume of absolute ethanol to the filtrate, seal, place in a dark place, suction filtration, wash the precipitate, and dialyze with deionized water , alcohol precipitation and separation to obtain corn silk polysaccharide iron;

步骤(5):将玉米须多糖铁溶于乙酸溶液,加入硫酸改性活性炭,水浴搅拌,干燥,得到改性椰壳活性炭。Step (5): Dissolve corn silk polysaccharide iron in an acetic acid solution, add sulfuric acid modified activated carbon, stir in a water bath, and dry to obtain modified coconut shell activated carbon.

通过硫酸对椰壳活性炭的改性,增加椰壳活性炭的总比表面积,打开活性炭内部的封闭孔,同时使许多中孔微孔直接暴露出来,增加吸附位点,提高活性炭对尿毒症毒素的吸附速率;再将玉米须多糖与铁溶液合成玉米须多糖铁负载在硫酸改性椰壳活性炭上,玉米须多糖铁会与尿毒症毒素中的氨基氮原子形成配位键,显著提高了椰壳活性炭对尿毒症毒素的吸附效率。By modifying coconut shell activated carbon with sulfuric acid, the total specific surface area of coconut shell activated carbon is increased, the closed pores inside the activated carbon are opened, and many mesopores are directly exposed, increasing adsorption sites and improving the adsorption of uremic toxins by activated carbon. rate; then corn silk polysaccharide and iron solution are synthesized and the corn silk polysaccharide iron is loaded on the sulfuric acid-modified coconut shell activated carbon. The corn silk polysaccharide iron will form coordination bonds with the amino nitrogen atoms in the uremic toxin, which significantly improves the efficiency of the coconut shell activated carbon. Adsorption efficiency of uremic toxins.

本发明第二方面提供了一种根据上述制备方法得到的高效的尿毒症毒素吸附剂。A second aspect of the present invention provides an efficient uremic toxin adsorbent obtained according to the above preparation method.

本发明第三方面提供了一种根据上述制备方法得到的高效的尿毒症毒素吸附剂在可穿戴人工肾领域的应用。The third aspect of the present invention provides an application of an efficient uremic toxin adsorbent obtained according to the above preparation method in the field of wearable artificial kidneys.

本发明具备的有益效果:The invention has the following beneficial effects:

1、本发明加入的改性椰壳活性炭对尿毒症毒素具有高结合能力、快速动力学特性且不释放毒副产物,可以更快速、高效地吸附尿毒症毒素。1. The modified coconut shell activated carbon added in the present invention has high binding capacity for uremic toxins, fast kinetic properties and does not release toxic by-products, and can absorb uremic toxins more quickly and efficiently.

2、本发明用磷酸胆碱改性海藻酸钠得到改性海藻酸钠,通过聚乙烯醇、改性海藻酸钠交联得到高效的尿毒症毒素吸附剂,改性海藻酸钠可以抵抗血液中蛋白质和细胞粘附,从而提高吸附剂的血液相容性。2. The present invention uses phosphorylcholine to modify sodium alginate to obtain modified sodium alginate, and cross-links polyvinyl alcohol and modified sodium alginate to obtain an efficient uremic toxin adsorbent. The modified sodium alginate can resist the effects of uremic toxins in the blood. Proteins and cells adhere, thereby increasing the hemocompatibility of the adsorbent.

3、本发明使用聚乙烯醇-改性海藻酸钠包埋改性椰壳活性炭,得到生物相容性较好的吸附剂,对尿毒症毒素吸附效果较好,且血液相容性、生物相容性较好,在可穿戴人工肾领域中具有较好的应用前景。3. The present invention uses polyvinyl alcohol-modified sodium alginate to embed modified coconut shell activated carbon to obtain an adsorbent with good biocompatibility, good adsorption effect on uremic toxins, and has hemocompatibility and biocompatibility. It has good capacitance and has good application prospects in the field of wearable artificial kidneys.

具体实施方式Detailed ways

为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。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, the present invention will be further described in detail 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.

为了更好的说明本发明的具体实施方式,下面通过实施例做进一步的举例说明。In order to better illustrate the specific implementation of the present invention, further examples are provided below.

本发明实施例1-8、对比例1中所用改性椰壳活性炭的制备步骤如下:The preparation steps of the modified coconut shell activated carbon used in Examples 1-8 and Comparative Example 1 of the present invention are as follows:

步骤(1):将1kg椰壳干燥,放入炭化炉,升温至650℃、保温炭化3h,冷却,得到炭化料;Step (1): Dry 1kg of coconut shell, put it into a carbonization furnace, raise the temperature to 650°C, maintain carbonization for 3 hours, and cool to obtain carbonized material;

步骤(2):将炭化料破碎,通入氮气25min、升温至850℃,停止通入氮气切换为水蒸气进行活化5h,停止加热,切断水蒸气通入氮气,冷却至室温,得到活化料,漂洗、干燥,得到活化椰壳活性炭;Step (2): Crush the carbonized material, introduce nitrogen for 25 minutes, raise the temperature to 850°C, stop the nitrogen and switch to water vapor for activation for 5 hours, stop heating, cut off the water vapor and introduce nitrogen, cool to room temperature, and obtain the activated material. Rinse and dry to obtain activated coconut shell activated carbon;

步骤(3):将活化椰壳活性炭破碎,取破碎后200目的活性炭加入到6mol/L硫酸溶液中,恒温振荡6h后用蒸馏水洗涤至中性,干燥至恒重,得到硫酸改性活性炭;Step (3): Crush the activated coconut shell activated carbon, add the crushed 200-mesh activated carbon into a 6mol/L sulfuric acid solution, shake at a constant temperature for 6 hours, wash with distilled water to neutrality, and dry to constant weight to obtain sulfuric acid-modified activated carbon;

步骤(4):称取100g玉米须,加入1600mL去离子水,90℃恒温水浴3h,抽滤,重复上述操作2次,合并滤液,滤液浓缩,在浓缩液中加入3倍与浓缩液体积的无水乙醇,密封,于阴凉处放置48h,过滤得到固体,用无水乙醇、丙酮、乙醚各洗涤固体,蒸馏水复溶,流动水透析,醇沉、分离,得棕红色、粉末状玉米须多糖;取10g玉米须多糖、1.0g柠檬酸三钠置于烧杯中,加入50mL去离子水,80℃恒温搅拌,用氢氧化钠溶液调节pH在8-9,滴加1mol·L-1三氯化铁溶液,至溶液中有固体出现时,停止滴加,继续加热搅拌1h,抽滤,滤液中加入等体积的无水乙醇,密封,暗处放置24h,抽滤,沉淀分别用无水乙醇、丙酮洗涤,复溶,去离子水透析,醇沉、分离,得粉末状玉米须多糖铁;Step (4): Weigh 100g of corn silk, add 1600mL of deionized water, hold in a constant temperature water bath at 90°C for 3 hours, filter with suction, repeat the above operation 2 times, combine the filtrate, concentrate the filtrate, and add 3 times the volume of the concentrated solution to the concentrated solution. Absolute ethanol, seal, place in a cool place for 48 hours, filter to obtain a solid, wash the solid with anhydrous ethanol, acetone, and ether, redissolve in distilled water, dialyze with running water, precipitate with alcohol, and separate to obtain brown-red, powdery corn silk polysaccharide. ; Put 10g corn silk polysaccharide and 1.0g trisodium citrate into a beaker, add 50mL deionized water, stir at a constant temperature of 80°C, adjust the pH to 8-9 with sodium hydroxide solution, and add 1mol·L -1 trichloride dropwise Iron solution, when a solid appears in the solution, stop dripping, continue heating and stirring for 1 hour, suction filtration, add an equal volume of absolute ethanol to the filtrate, seal, leave it in a dark place for 24 hours, suction filtration, and use absolute ethanol to precipitate. , acetone washing, redissolution, deionized water dialysis, alcohol precipitation and separation to obtain powdered corn silk polysaccharide iron;

步骤(5):将6g玉米须多糖铁溶于100mL 0.5%乙酸溶液中,加入210g硫酸改性活性炭,30℃水浴搅拌2h,干燥,得到改性椰壳活性炭。Step (5): Dissolve 6g corn silk polysaccharide iron in 100mL 0.5% acetic acid solution, add 210g sulfuric acid modified activated carbon, stir in a 30°C water bath for 2 hours, and dry to obtain modified coconut shell activated carbon.

本发明实施例中所用改性海藻酸钠的制备步骤如下:The preparation steps of modified sodium alginate used in the embodiments of the present invention are as follows:

步骤S1:将9g海藻酸钠溶解在100mL 2%盐酸溶液中,50℃水浴加热1h,得到基础反应体系;Step S1: Dissolve 9g sodium alginate in 100mL 2% hydrochloric acid solution, and heat in a 50°C water bath for 1 hour to obtain a basic reaction system;

步骤S2:使用氮气保护整个步骤S1得到的基础反应体系,将4g磷酸胆碱缓慢滴加到基础反应体系中,搅拌待其反应;Step S2: Use nitrogen to protect the entire basic reaction system obtained in step S1, slowly add 4g of phosphorylcholine dropwise into the basic reaction system, and stir until it reacts;

步骤S3:待步骤S2反应结束后,将反应后所得产物置于去离子水进行透析处理,收集产物,冷冻干燥,得到改性海藻酸钠。Step S3: After the reaction in step S2 is completed, the product obtained after the reaction is placed in deionized water for dialysis treatment, and the product is collected and freeze-dried to obtain modified sodium alginate.

本发明实施例1-8中所用聚乙烯醇为聚乙烯醇124,购自国药化学试剂有限公司。The polyvinyl alcohol used in Examples 1-8 of the present invention is polyvinyl alcohol 124, purchased from Sinopharm Chemical Reagent Co., Ltd.

实施例1Example 1

一种高效的尿毒症毒素吸附剂的制备方法,包括以下步骤:A method for preparing an efficient uremic toxin adsorbent, including the following steps:

步骤(1):将4g聚乙烯醇、0.6g改性海藻酸钠溶解在100mL去离子水中,加入2g改性椰壳活性炭,搅拌分散均匀后平铺,形成薄膜;Step (1): Dissolve 4g polyvinyl alcohol and 0.6g modified sodium alginate in 100mL deionized water, add 2g modified coconut shell activated carbon, stir and disperse evenly, and spread flat to form a film;

步骤(2):将步骤(1)中的薄膜冷冻,取出放入5wt%CaCl2的饱和硼酸溶液溶液中交联18h,洗净、剪碎,得到高效的尿毒症毒素吸附剂。Step (2): Freeze the film in step (1), take it out and put it into a saturated boric acid solution of 5wt% CaCl2 for cross-linking for 18 hours, wash and cut into pieces to obtain an efficient uremic toxin adsorbent.

实施例2Example 2

一种高效的尿毒症毒素吸附剂的制备方法,包括以下步骤:A method for preparing an efficient uremic toxin adsorbent, including the following steps:

步骤(1):将6g聚乙烯醇、0.8g改性海藻酸钠溶解在100mL去离子水中,加入2.3g改性椰壳活性炭,搅拌分散均匀后平铺,形成薄膜;Step (1): Dissolve 6g polyvinyl alcohol and 0.8g modified sodium alginate in 100mL deionized water, add 2.3g modified coconut shell activated carbon, stir and disperse evenly, and spread flat to form a film;

步骤(2):将步骤(1)中的薄膜冷冻,取出放入4wt%CaCl2的饱和硼酸溶液溶液中交联20h,洗净、剪碎,得到高效的尿毒症毒素吸附剂。Step (2): Freeze the film in step (1), take it out and put it into a saturated boric acid solution of 4wt % CaCl2 for cross-linking for 20 hours, wash and cut into pieces to obtain an efficient uremic toxin adsorbent.

实施例3Example 3

一种高效的尿毒症毒素吸附剂的制备方法,包括以下步骤:A method for preparing an efficient uremic toxin adsorbent, including the following steps:

步骤(1):将8g聚乙烯醇、1g改性海藻酸钠溶解在100mL去离子水中,加入3g改性椰壳活性炭,搅拌分散均匀后平铺,形成薄膜;Step (1): Dissolve 8g polyvinyl alcohol and 1g modified sodium alginate in 100mL deionized water, add 3g modified coconut shell activated carbon, stir and disperse evenly, and spread flat to form a film;

步骤(2):将步骤(1)中的薄膜冷冻,取出放入3wt%CaCl2的饱和硼酸溶液溶液中交联24h,洗净、剪碎,得到高效的尿毒症毒素吸附剂。Step (2): Freeze the film in step (1), take it out and put it into a saturated boric acid solution of 3wt % CaCl2 for cross-linking for 24 hours, wash and cut into pieces to obtain an efficient uremic toxin adsorbent.

实施例4Example 4

一种高效的尿毒症毒素吸附剂的制备方法,包括以下步骤:A method for preparing an efficient uremic toxin adsorbent, including the following steps:

步骤(1):将7g聚乙烯醇、0.7g改性海藻酸钠溶解在100mL去离子水中,加入2.6g改性椰壳活性炭,搅拌分散均匀后平铺,形成薄膜;Step (1): Dissolve 7g polyvinyl alcohol and 0.7g modified sodium alginate in 100mL deionized water, add 2.6g modified coconut shell activated carbon, stir and disperse evenly, and spread flat to form a film;

步骤(2):将步骤(1)中的薄膜冷冻,取出放入4wt%CaCl2的饱和硼酸溶液溶液中交联20h,洗净、剪碎,得到高效的尿毒症毒素吸附剂。Step (2): Freeze the film in step (1), take it out and put it into a saturated boric acid solution of 4wt % CaCl2 for cross-linking for 20 hours, wash and cut into pieces to obtain an efficient uremic toxin adsorbent.

实施例5Example 5

此实施例中吸附剂的制备过程与实施例2中制备步骤一致,区别在于步骤(1)中加入了4g改性椰壳活性炭。The preparation process of the adsorbent in this example is the same as that in Example 2, except that 4 g of modified coconut shell activated carbon is added in step (1).

实施例6Example 6

此实施例中吸附剂的制备过程与实施例2中制备步骤一致,区别在于步骤(2)中加入了10g聚乙烯醇。The preparation process of the adsorbent in this example is the same as that in Example 2, except that 10 g of polyvinyl alcohol was added in step (2).

实施例7Example 7

此实施例中吸附剂的制备过程与实施例2中制备步骤一致,区别在于步骤(1)中加入了2g改性海藻酸钠。The preparation process of the adsorbent in this example is the same as that in Example 2, except that 2 g of modified sodium alginate is added in step (1).

实施例8Example 8

此实施例中吸附剂的制备过程与实施例2中制备步骤一致,区别在于步骤(2)中为6wt%CaCl2的饱和硼酸溶液溶液。The preparation process of the adsorbent in this example is consistent with the preparation steps in Example 2, except that step (2) is a saturated boric acid solution of 6 wt% CaCl2 .

对比例1Comparative example 1

此实施例中吸附剂的制备过程与实施例2中制备步骤一致,区别在于使用普通的海藻酸钠代替改性海藻酸钠。The preparation process of the adsorbent in this example is the same as that in Example 2, except that ordinary sodium alginate is used instead of modified sodium alginate.

高效的尿毒症毒素吸附剂的性能测试Performance testing of efficient uremic toxin adsorbents

测定实施例及对比例制备得到的吸附剂的性能,测定方法如下:To measure the performance of the adsorbents prepared in the Examples and Comparative Examples, the measurement method is as follows:

1.机械强度:取大小相似,数量相同质量的上述实施例、对比例制备得到的吸附剂,用滤纸吸干表面水分,称重为W1,将其放入装有超纯水的离心管中超声30min,取出、吸干表面水分,称重为W2,小球机械强度=W2/W1*100%。1. Mechanical strength: Take the adsorbents prepared in the above examples and comparative examples that are similar in size, quantity and mass, use filter paper to absorb the surface moisture, weigh it as W 1 , and put it into a centrifuge tube filled with ultrapure water. Ultrasonicate for 30 minutes, take out and absorb the surface moisture, and weigh it as W 2 . The mechanical strength of the ball = W 2 /W 1 *100%.

2.吸附性能:分别取含尿素、肌酐的血浆溶液10mL,加入上述实施例、对比例制备得到的吸附剂及市售产品的吸附剂各5g,密封,于摇床中37℃震荡吸附2h,吸附完成后,分别测定各毒素的变化,由吸附前后的浓度差异计算吸附剂对各毒素的吸附率,上述实验重复三次取平均值,结果如表1所示;2. Adsorption performance: Take 10 mL of plasma solution containing urea and creatinine respectively, add 5 g each of the adsorbent prepared in the above examples and comparative examples and the adsorbent of commercially available products, seal, and oscillate in a shaker at 37°C for 2 hours. After the adsorption is completed, the changes of each toxin are measured respectively, and the adsorption rate of each toxin by the adsorbent is calculated from the concentration difference before and after adsorption. The above experiment is repeated three times and the average value is taken. The results are shown in Table 1;

3.血液相容性:将吸附剂用生理盐水浸泡30min,砂芯漏斗抽滤干表面水分,称取1g吸附剂加入5mL新鲜志愿者提供的人血,放入37℃水浴中恒温,2h取出于血细胞分析仪测定血细胞变化情况,分别测定实施例及对比例制备得到的吸附剂及市售吸附剂的相容性,上述实验重复三次取平均值,结果见表1。3. Blood compatibility: Soak the adsorbent in physiological saline for 30 minutes, filter out the surface moisture with a sand core funnel, weigh 1g of the adsorbent and add 5mL of human blood provided by fresh volunteers, put it into a 37°C water bath at constant temperature, and take it out after 2 hours. The changes in blood cells were measured on a blood cell analyzer, and the compatibility of the adsorbents prepared in the Examples and Comparative Examples and the commercially available adsorbents were measured respectively. The above experiment was repeated three times and the average value was taken. The results are shown in Table 1.

表1Table 1

由表1结果可知,实施例1-4中制备的吸附剂成型效果、机械性能较好,且对红细胞、白细胞及血小板的黏附均显著下降,不仅提高了血液的相容性,而且对尿毒症患者血液中的尿素、肌酐的吸附率也得到了明显提高,尤其是对尿素具有显著的清除效果,显著高于市售产品对尿素的清除效果。It can be seen from the results in Table 1 that the adsorbent prepared in Examples 1-4 has good molding effect and mechanical properties, and the adhesion to red blood cells, white blood cells and platelets is significantly reduced, which not only improves the compatibility of blood, but also has good effects on uremia. The adsorption rate of urea and creatinine in the patient's blood has also been significantly improved. In particular, it has a significant scavenging effect on urea, which is significantly higher than the scavenging effect of commercially available products on urea.

实施例5中改性椰壳活性炭的添加量较多,造成制备的吸附剂成型困难,且容易堵塞吸附剂的内部孔隙,导致吸附剂对尿素、肌酐的吸附率下降。In Example 5, a large amount of modified coconut shell activated carbon was added, which made it difficult to form the prepared adsorbent and easily blocked the internal pores of the adsorbent, resulting in a decrease in the adsorption rate of urea and creatinine by the adsorbent.

实施例6中聚乙烯醇的添加量过多,实施例7中改性海藻酸钠的添加量过多,导致制备的吸附剂机械强度过高,内部结构中孔隙减小,会降低吸附剂对尿素、肌酐的吸附性能。In Example 6, too much polyvinyl alcohol was added, and in Example 7, too much modified sodium alginate was added, resulting in excessively high mechanical strength of the prepared adsorbent and reduced pores in the internal structure, which would reduce the adsorbent's Adsorption properties of urea and creatinine.

实施例8中所用交联剂中CaCl2的浓度过高,交联过度,造成制备的吸附剂机械强度较高,内部结构中孔隙减小,对尿素、肌酐的吸附性能降低。The concentration of CaCl 2 in the cross-linking agent used in Example 8 is too high and the cross-linking is excessive, resulting in high mechanical strength of the prepared adsorbent, reduced pores in the internal structure, and reduced adsorption performance of urea and creatinine.

对比例1中使用普通的海藻酸钠代替改性海藻酸钠,使制备的吸附剂机械强度较低,易破裂,且对红细胞、白细胞及血小板的黏附较高,血液相容性下降,这说明改性海藻酸钠能够使制备出的吸附剂吸综合性能显著提高。In Comparative Example 1, ordinary sodium alginate was used instead of modified sodium alginate, so that the mechanical strength of the prepared adsorbent was low, easy to break, and the adhesion to red blood cells, white blood cells and platelets was high, and the blood compatibility was reduced. This shows that Modified sodium alginate can significantly improve the comprehensive adsorption performance of the prepared adsorbent.

以上所述,仅是本发明的较佳实施例而已,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于技术方案的范围内。The above are only preferred embodiments of the present invention, and are not intended to limit the present application in any way. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person familiar with the art will , without departing from the scope of the technical solution of the present application, making slight changes or modifications using the technical content disclosed above are equivalent to equivalent implementation examples. Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution.

Claims (10)

1. The preparation method of the efficient uremic toxin adsorbent is characterized by comprising the following steps of:
step (1): dissolving polyvinyl alcohol and modified sodium alginate in deionized water, adding modified coconut shell activated carbon, uniformly stirring and dispersing, and then spreading to form a film;
step (2): cooling the film of step (1)Freezing, taking out and putting into CaCl 2 Cross-linking in the saturated boric acid solution, cleaning, shearing and crushing to obtain the high-efficiency uremic toxin adsorbent.
2. The method for preparing the efficient uremic toxin adsorbent according to claim 1, wherein the preparation steps of the modified sodium alginate are as follows:
step S1: dissolving sodium alginate in hydrochloric acid solution, and heating in water bath to obtain a basic reaction system;
step S2: using nitrogen to protect the basic reaction system obtained in the whole step S1, slowly dripping phosphorylcholine into the basic reaction system, and stirring for reaction;
step S3: and (3) after the reaction in the step (S2) is finished, placing the product obtained after the reaction in deionized water for dialysis treatment, collecting the product, and freeze-drying to obtain the modified sodium alginate.
3. The method for preparing the efficient uremic toxin adsorbent according to claim 1, wherein the mass fraction of the hydrochloric acid solution is 1-2%, and the mass ratio of sodium alginate, phosphorylcholine and the hydrochloric acid solution is (5-10): 1-5): 100.
4. The method for preparing the efficient uremic toxin adsorbent according to claim 1, wherein the polyvinyl alcohol and the modified sodium alginate in the step (1) are respectively 4-8wt% and 0.6-1.2wt% of deionized water.
5. The method for preparing the efficient uremic toxin adsorbent according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the modified sodium alginate in the step (1) is (5-10): 1.
6. The method for preparing a highly potent uremic toxin adsorbent according to claim 1, wherein CaCl in step (2) 2 3-5wt% of saturated boric acid solution, and the crosslinking time is 18-24h.
7. The preparation method of the efficient uremic toxin adsorbent according to claim 1, wherein the total mass ratio of the modified coconut shell activated carbon to the polyvinyl alcohol and the modified sodium alginate is 1 (2-4).
8. The method for preparing the efficient uremic toxin adsorbent according to claim 1, wherein the preparation steps of the modified coconut shell activated carbon are as follows:
step (1): drying coconut shells, putting the coconut shells into a carbonization furnace, heating, preserving heat, carbonizing, and cooling to obtain carbonized materials;
step (2): crushing the carbonized material, introducing nitrogen, heating, stopping introducing nitrogen, switching to steam for activation, stopping heating, cutting off the steam, introducing nitrogen, cooling to room temperature to obtain an activated material, rinsing and drying to obtain activated coconut shell activated carbon;
step (3): crushing activated coconut shell activated carbon, adding the crushed activated carbon into sulfuric acid solution, oscillating at constant temperature, washing with distilled water to neutrality, and drying to constant weight to obtain sulfuric acid modified activated carbon;
step (4): weighing corn silk, adding deionized water, carrying out constant-temperature water bath, carrying out suction filtration, repeating the above operation for 2 times, combining filtrate, concentrating the filtrate, adding absolute ethyl alcohol into concentrated solution, sealing, placing in a shade, filtering to obtain solid, washing, redissolving distilled water, dialyzing with flowing water, precipitating with alcohol, separating to obtain powdery corn silk polysaccharide, dissolving corn silk polysaccharide and trisodium citrate into deionized water, carrying out constant-temperature stirring, regulating pH, dropwise adding ferric trichloride solution until solid appears in the solution, stopping dropwise adding, continuing heating and stirring, carrying out suction filtration, adding equal volume absolute ethyl alcohol into filtrate, sealing, placing in a dark place, carrying out suction filtration, washing precipitate, dialyzing with deionized water, precipitating with alcohol, separating to obtain corn silk polysaccharide iron;
step (5): dissolving corn silk polysaccharide iron in acetic acid solution, adding sulfuric acid modified activated carbon, stirring in water bath, and drying to obtain modified coconut shell activated carbon.
9. A highly effective uremic toxin adsorbent obtainable by the method of any one of claims 1 to 8.
10. Use of a highly potent uremic toxin adsorbent according to claim 9 in the field of wearable artificial kidneys.
CN202311741202.7A 2023-12-18 2023-12-18 Efficient uremic toxin adsorbent and preparation method and application thereof Active CN117718029B (en)

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