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CN113267492A - Based on CeO2Nano-rod urine glucose test paper and preparation method thereof - Google Patents

Based on CeO2Nano-rod urine glucose test paper and preparation method thereof Download PDF

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CN113267492A
CN113267492A CN202110536590.XA CN202110536590A CN113267492A CN 113267492 A CN113267492 A CN 113267492A CN 202110536590 A CN202110536590 A CN 202110536590A CN 113267492 A CN113267492 A CN 113267492A
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test paper
ceo
nanorods
urine sugar
glucose
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刘勇
陈莹
范曲立
尹维翰
昝佳慧
况培培
黄逾东
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Nanjing University of Posts and Telecommunications
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Abstract

本发明公开一种基于CeO2纳米棒的尿糖试纸及其制备方法,首先将铈盐和无机碱混合后充分搅拌,形成白色悬浮液后移入高压反应釜中,在烘箱中进行水热反应;弃上清,将沉淀物洗涤至中性,干燥后得到CeO2纳米棒;将CeO2纳米棒与显色剂、葡萄糖氧化酶按比例混合制得溶液,将空白试纸浸入溶液中,取出试纸后烘干,即得基于CeO2纳米棒的尿糖试纸。将该试纸置于含有不同浓度葡萄糖的环境中后取出会显色,在低浓度阶段颜色较浅,随着葡萄糖浓度的加深,试纸呈现的颜色也逐步梯度加深,各阶段区别明显,检测灵敏度高;本申请打破了CeO2纳米材料的应用领域局限,有助于进一步拓宽其市场应用范围。

Figure 202110536590

The invention discloses a urine sugar test paper based on CeO2 nanorods and a preparation method thereof. First, a cerium salt and an inorganic base are mixed and fully stirred to form a white suspension, which is then moved into a high-pressure reactor, and subjected to a hydrothermal reaction in an oven; Discard the supernatant, wash the precipitate to neutrality, and dry to obtain CeO 2 nanorods; mix the CeO 2 nanorods with the developer and glucose oxidase in proportion to prepare a solution, immerse the blank test paper in the solution, and take out the test paper. After drying, the urine sugar test paper based on CeO 2 nanorods is obtained. When the test paper is placed in an environment containing different concentrations of glucose, the color will develop. In the low concentration stage, the color is lighter. With the deepening of the glucose concentration, the color of the test paper gradually deepens. The difference between each stage is obvious and the detection sensitivity is high. ; This application breaks the limitation of the application field of CeO 2 nanomaterials and helps to further broaden its market application range.

Figure 202110536590

Description

Based on CeO2Nano-rod urine glucose test paper and preparation thereofMethod
Technical Field
The invention belongs to the technical field of medicinal detection, and particularly relates to a CeO-based reagent2A method for preparing a nanorod test paper for glucose in urine.
Background
Nanoenzymes (also known as nanomimic enzymes) are an extremely important branch of the field of artificial enzymes. In recent decades, researchers have provided different natural enzyme activities by controlling the size and surface functional groups of nanomaterials. Compared with natural enzymes and other mimic enzymes, the nano-enzyme has other properties peculiar to nano-materials such as optics, electrics, magnetics and the like besides catalytic activity, so that the nano-enzyme has double or even multiple functions. In addition, the large specific surface area and abundant surface chemical properties of the nano material enable the nano enzyme to be easy to chemically modify and connect various biomolecules, so that biological probes and sensors can be conveniently constructed. Nano-enzyme based on nano-materials has been widely used in the fields of biosensors, immunoassays, cancer diagnosis and treatment, neuroprotection, contaminant removal, and the like.
CeO2Is a common catalytic material. CeO at the nanoscale due to the presence of surface oxygen vacancies2Ce in (1)3+And Ce4+Being able to reversibly convert to produce a catalytic effect, it is one of the nanoenzymes of great interest. A large number of studies have demonstrated that CeO2Can effectively simulate superoxide dismutase, catalase, peroxidase, oxidase, phosphatase, etc. As a novel nano enzyme, the nano cerium dioxide has high chemical stability and catalytic stability and has wide application prospect under various conditions.
Currently CeO2Mainly focused on catalysis, and in recent years, CeO2The nanometer material plays more and more important roles in the field of catalysis, is applied to catalytic reactions such as CO oxidation, NOx reduction, methanol oxidation and the like, and Chinese patent CN 112516997A discloses CeO2/MnO2The preparation method of the nano-rod has simple process, cerium salt and inorganic base are taken as main raw materials, the obtained nano-rod material has better stability and catalytic performance, and the sewage treatment surface is shownShowing remarkable effect. In chemical mechanical polishing, CeO2The polishing slurry is different from the traditional polishing slurry, can adsorb anions and cations simultaneously under the alkaline polishing condition, is amphoteric, and has better polishing performance. CeO (CeO)2The ultraviolet light absorbing agent has strong absorbing capacity within the range of 300-450 nm, particularly strong absorbing capacity to ultraviolet light, almost zero absorbing capacity to visible light and good light transmittance, can be used as an ultraviolet absorbent, and is applied to the aspects of ultraviolet-proof paint, sunscreen cosmetics, plastics and aging resistance and the like. The material can also be applied to fuel cells, wherein Solid Oxide Fuel Cells (SOFCs) are more researched, and the fuel cells have the advantages of high efficiency, no pollution, long service life, low production cost and the like, and are one of clean fuels. In addition, CeO is used as the cross and infiltration of nanotechnology and modern medicine and biology2Base nanostructure materials are gaining increasing attention in antioxidant biomedicine.
As can be seen from the above, CeO2The nano material is widely applied in many fields, but no technical personnel applying the nano material to test paper research and development are found so far, and if a test paper for detection with low cost, simple flow, easy industrial production and obvious color comparison is researched based on the nano material, the nano material can bring beneficial influence on further widening the market application range.
Disclosure of Invention
The invention aims to provide a CeO-based material2The nanorod test paper for urine glucose and the preparation method thereof have the advantages of simple preparation process, high color development sensitivity and popularization and application value, and can be used for detection in the fields of urine glucose, blood glucose and the like.
The technical scheme of the invention is as follows: based on CeO2The method for preparing the urine glucose test paper by the nano rods specifically comprises the following steps:
(1) mixing cerium salt and inorganic base, and fully stirring to form white suspension;
(2) transferring the white suspension into a high-pressure reaction kettle to perform hydrothermal reaction in an oven;
(3) discarding the supernatant, washing the precipitate to neutrality, and drying to obtainCeO2A nanorod;
(4) the CeO prepared in the step (3) is added2Mixing the nano-rods with a color developing agent and glucose oxidase in proportion to prepare a solution, immersing a blank test paper into the solution, taking out the test paper and drying to obtain the CeO-based test paper2And (3) a urinary sugar test paper of the nano-rod.
Further, in the step (1), the mass ratio of the cerium salt to the inorganic base is 1: 10-1: 20.
Further, in the step (2), the temperature for hydrothermal reaction in the oven is 90-140 ℃, and the reaction time is 7-15 h.
Further, in the step (3), CeO was obtained2The particle size of the nano rod is 70-260 nm.
Further, in the step (4), CeO2The mass ratio of the nanorods to the color developing agent to the glucose oxidase is 1:0.1: 0.1-1: 1: 1.
Further, the cerium salt used in step (1) is selected from the group consisting of cerium nitrate, cerium chloride and cerium sulfate; the range of choice of inorganic base used includes sodium hydroxide, aqueous ammonia and potassium hydroxide.
Further, the selection range of the color developer used in the step (4) includes 2, 2-diaza-bis-3-ethylbenzthiazoline-6-sulfonic acid, o-phenylenediamine and 3,3,5, 5-tetramethylbenzidine.
The test paper prepared by the method is soaked in glucose solutions with different concentrations for 3-5min and then taken out, the test paper shows other colors different from the background color of the test paper, and the color of the test paper tends to deepen in a gradient manner along with the increase of the concentration of glucose.
The basic principle of the preparation of the urine glucose test paper is as follows: since glucose oxidase can react with glucose (main component of urine sugar) to generate hydrogen peroxide and acid (lowering the pH of the system helps the reaction); the hydrogen peroxide reacts with the cerium oxide to generate hydroxyl radicals, which reoxidize color developers (TMB, OPD, etc.) to cause a color development reaction.
Compared with the prior art, the invention has the following advantages:
1. the application provides a CeO-based alloy2Simple and rapid qualitative detection of urine glucose and blood sugar concentration of nano-rodThe test paper is placed in an environment containing glucose with different concentrations and then taken out to be developed, the color is lighter in a low concentration stage, the color presented by the test paper is gradually deepened in a gradient manner along with the increase of the concentration of the glucose, the difference of each stage is obvious, and the detection sensitivity is high;
2. the test paper preparation method disclosed by the application mainly adopts simple inorganic materials as raw materials, is low in price, simple in overall preparation steps and short in preparation period, and is beneficial to large-scale popularization and application;
3. compared with CeO2The application of the nanometer material in the fields of common catalysis, ultraviolet absorption, fuel cells and the like explores a method based on CeO2The new application path of the nano material breaks through the limitation of the conventional field and is beneficial to further widening the market application range of the nano material.
Drawings
FIG. 1 shows CeO prepared in example one2Transmission electron microscopy spectra of the nanorods;
FIG. 2 shows CeO prepared in example II2XRD pattern of the nanorods;
FIG. 3 is a CeO-based alloy prepared in example III2The color development effect of the nanorod test paper for glucose is shown after detecting glucose with different concentrations.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The first embodiment is as follows:
weighing 1g Ce (NO)3)3·6H2Mixing O and 12g NaOH, stirring for 1h at room temperature to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, performing hydrothermal reaction for 9h in a drying oven at 110 ℃, pouring out supernatant, washing precipitate to be neutral, and drying a sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2A nanorod sample; adding CeO2Nanorods with 3,3,5, 5-tetramethylBiphenyl amine (TMB) and glucose oxidase are mixed according to the mass ratio of 1:1:1, mixing and stirring to prepare a solution, soaking the solution in blank test paper (qualitative filter paper, Hangzhou special paper industry Co., Ltd.) for a certain time, taking out the test paper and drying to obtain the CeO-based test paper2A novel urine glucose test paper of a nano rod.
CeO obtained in example2The nanorod samples were microscopically morphologically analyzed by transmission electron microscopy. As a result, as shown in FIG. 1, it was observed that the obtained sample had a uniform rod-like structure and had a particle diameter of 70 to 260 nm.
Example two:
weighing 1g Ce (NO)3)3·6H2Mixing O and 12g NaOH, stirring for 1h at room temperature to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 9h in an oven at 130 ℃, pouring out supernatant, and washing a precipitate to be neutral. Then drying the sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2Nanorod sample, CeO2The mass ratio of the nano rod to TMB and glucose oxidase is 1: 0.5: 1, mixing and stirring to prepare a solution, putting the solution into a blank test paper, soaking for a certain time, taking out the test paper and drying to obtain the CeO-based test paper2A novel urine glucose test paper of a nano rod.
Microscopic morphological analysis is carried out on the sample through a transmission electron microscope, and the obtained sample presents a uniform rod-shaped structure with the grain diameter of 80-240 nm.
CeO obtained in example2Urine glucose test paper, X-ray diffractometer (XRD) on CeO2And (5) carrying out phase structure analysis. As a result, as shown in FIG. 2, it was found that clear CeO was observed2Characteristic peak.
CeO obtained in this example2The test paper for urine glucose was immersed in glucose solutions of 0mmol/L, 5mmol/L, 15mmol/L, 25mmol/L, 35mmol/L and 55mmol/L for five minutes and then taken out with clean tweezers, and the results are shown in FIG. 3, where the test paper immersed in glucose solution of 5mmol/L and taken out to showDifferent from the very light blue color of the test paper of the white control group, the color of the test paper is sequentially deepened along with the increase of the glucose concentration, and the color change has obvious gradient relation, so that the human eye recognition degree is high, and the test paper can be used for detecting urine glucose.
Example three:
weighing 1.2g Ce (NO)3)3·6H2Mixing O and 12g KOH, stirring for 1h at room temperature to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 9h in an oven at 130 ℃, pouring out supernatant, and washing a precipitate to be neutral. Then drying the sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2A nanorod sample. Adding CeO2The nano-rods, 2-dinitro-bis-3-ethylbenzthiazoline-6-sulfonic Acid (ABTS) and glucose oxidase are mixed according to the mass ratio of 1: 0.5: 1, mixing and stirring the solvent to prepare a solution, putting the solution into a test paper, soaking the test paper for a certain time, taking out the test paper and drying the test paper to obtain the CeO-based reagent2And (3) a urinary sugar test paper of the nano-rod.
Microscopic morphological analysis is carried out on the sample through a transmission electron microscope, and the obtained sample presents a uniform rod-shaped structure with the grain diameter of 90-260 nm.
CeO obtained in this example2The urine glucose test paper is used for carrying out a glucose concentration test experiment, the test paper is respectively immersed in glucose solutions with the concentrations of 0mmol/L, 5mmol/L, 15mmol/L, 25mmol/L, 35mmol/L and 55mmol/L, after immersion for five minutes, the test paper is taken out by using a clean forceps, after immersion in the glucose solution with the concentrations of 5mmol/L, the test paper can be taken out to show a very light green color different from that of a white control group, along with the increase of the glucose concentration, the color of the test paper is sequentially deepened, and obvious gradient relation exists in the color change, so that the human eye recognition degree is high, and the test paper can be used for detecting urine glucose.
Example four:
weighing 1g of CeCl3·6H2O and 12g NH3·H2Mixing with O, stirring at room temperature for 1 hr to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, and heating in an oven at 130 deg.C to obtain waterThe reaction was heated for 9h, the supernatant decanted, and the precipitate washed to neutral. Then drying the sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2Nanorod sample, CeO2The nano-rod, o-phenylenediamine (OPD) and glucose oxidase are mixed according to the mass ratio of 1: 0.5: 1, mixing and stirring to prepare a solution, putting the solution into a blank test paper, soaking for a certain time, taking out the test paper and drying to obtain the CeO-based test paper2And (3) a urinary sugar test paper of the nano-rod.
CeO obtained in this example2The urine glucose test paper is used for carrying out a glucose concentration test experiment, the test paper is respectively immersed in glucose solutions with the concentrations of 0mmol/L, 5mmol/L, 15mmol/L, 25mmol/L, 35mmol/L and 55mmol/L, the test paper is taken out by using clean tweezers after being immersed for five minutes, the test paper is taken out after being immersed in the glucose solution with the concentration of 5mmol/L and can show very light yellow different from that of a white control group, the color of the test paper is sequentially deepened along with the increase of the glucose concentration, an obvious gradient relation exists in the color change, the human eye recognition degree is high, and the test paper can be used for detecting urine glucose.
Example five:
weighing 1g Ce (NO)3)3·6H2Mixing O and 12g KOH, stirring for 1h at room temperature to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 9h in an oven at 130 ℃, pouring out supernatant, and washing a precipitate to be neutral. Then drying the sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2Nanorod sample, CeO2The mass ratio of the nano rod to TMB and glucose oxidase is 1: 0.5: 0.5 is mixed and stirred to prepare a solution, the solution is put into test paper to be soaked for a certain time, the test paper is taken out and dried, and the CeO-based test paper is obtained2And (3) a urinary sugar test paper of the nano-rod.
Example six:
weighing 1g Ce (NO)3)3·6H2Mixing O and 12g NaOH, stirring at room temperature for 1h to obtain white suspension, transferring the white suspension into a high-pressure reaction kettle, performing hydrothermal reaction in an oven at 120 ℃ for 10h, pouring out supernatant, and settlingThe precipitate is washed to neutrality. Then drying the sample to constant weight by using a freeze dryer (FD-1D-80, Beijing Bo Yi kang laboratory instrument) at room temperature to obtain CeO2Nanorod sample, CeO2The mass ratio of the nano rod to ABTS and glucose oxidase is 1: 0.5: 0.7 is mixed and stirred to prepare a solution, the solution is put into test paper to be soaked for a certain time, the test paper is taken out and dried, and the CeO-based test paper is obtained2And (3) a urinary sugar test paper of the nano-rod.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1.一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,具体包括如下步骤:1. a method for preparing urine sugar test paper based on CeO nanorod, is characterized in that, specifically comprises the steps: (1)将铈盐和无机碱混合后充分搅拌,形成白色悬浮液;(1) fully stir after mixing cerium salt and inorganic base to form a white suspension; (2)将白色悬浮液移入高压反应釜中在烘箱中进行水热反应;(2) move white suspension into autoclave and carry out hydrothermal reaction in baking oven; (3)弃上清,将沉淀物洗涤至中性,干燥后得到CeO2纳米棒;(3) discard the supernatant, wash the precipitate to neutrality, and obtain CeO nanorods after drying ; (4)将步骤(3)中制得的CeO2纳米棒与显色剂、葡萄糖氧化酶按比例混合制得溶液,将空白试纸浸入溶液中,取出试纸后烘干,即得基于CeO2纳米棒的尿糖试纸。( 4 ) Mix the CeO nanorods prepared in step (3) with the developer and glucose oxidase in proportion to obtain a solution, immerse the blank test paper in the solution, take out the test paper and dry it, to obtain a nanometer based CeO Great urine test strips. 2.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(1)中,铈盐和无机碱的质量比为1:10~1:20。2. a kind of method for preparing urine sugar test paper based on CeO nanorods as claimed in claim 1 , is characterized in that, in step (1), the mass ratio of cerium salt and inorganic base is 1:10~1:20. 3.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(2)中,在烘箱中进行水热反应的温度为90℃-140℃,反应时间为7-15h。3. a kind of method for preparing urine sugar test paper based on CeO nanorod as claimed in claim 1 , is characterized in that, in step (2), the temperature that carries out hydrothermal reaction in oven is 90 ℃-140 ℃, reaction The time is 7-15h. 4.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(3)中,所得CeO2纳米棒的粒径为70-260nm。4. a kind of method for preparing urine sugar test paper based on CeO 2 nanorods as claimed in claim 1, is characterized in that, in step (3), the particle diameter of gained CeO 2 nanorods is 70-260nm. 5.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(4)中,CeO2纳米棒、显色剂和葡萄糖氧化酶的质量比为1:0.1:0.1~1:1:1。5. a kind of based on CeO as claimed in claim 1 The method for preparing urine sugar test paper by nanorod, is characterized in that, in step (4), CeO The mass ratio of nanorod, developer and glucose oxidase is 1 :0.1:0.1~1:1:1. 6.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(1)中所用铈盐的选择范围包括硝酸铈、氯化铈和硫酸铈;所用无机碱的选择范围包括氢氧化钠、氨水和氢氧化钾。6. a kind of based on CeO as claimed in claim 1 The method for preparing urine sugar test paper by nanorod is characterized in that, the selection scope of cerium salt used in step (1) comprises cerium nitrate, cerium chloride and cerium sulfate; The selection of inorganic bases includes sodium hydroxide, ammonia and potassium hydroxide. 7.如权利要求1所述的一种基于CeO2纳米棒制备尿糖试纸的方法,其特征在于,步骤(4)中所用显色剂的选择范围包括2,2-联氮-双-3-乙基苯并噻唑啉-6-磺酸、邻苯二胺和3,3,5,5-四甲基联苯胺。7. a kind of method for preparing urine sugar test paper based on CeO nanorod as claimed in claim 1 , it is characterized in that, in step (4), the selection scope of used chromogenic agent comprises 2,2-azido-bis-3 -Ethylbenzothiazoline-6-sulfonic acid, o-phenylenediamine and 3,3,5,5-tetramethylbenzidine. 8.如权利要求1-7中任一项所述的一种基于CeO2纳米棒制备尿糖试纸的方法制备的尿糖试纸,其特征在于,将试纸浸于不同浓度的葡萄糖溶液中3-5min后取出,试纸显现出区别于试纸底色的其他颜色,且随着葡萄糖浓度的增加,试纸颜色呈梯度加深的趋势。8. a kind of based on CeO as described in any one of claim 1-7 The urine sugar test paper prepared by the method for preparing urine sugar test paper by nanorod is characterized in that, test paper is immersed in the glucose solution of different concentrations 3- Take it out after 5 minutes, the test paper shows other colors that are different from the background color of the test paper, and with the increase of glucose concentration, the color of the test paper shows a trend of gradient deepening.
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