MOFs modified PBT leukocyte removal filter material and preparation method and application thereof

Abstract

The present invention relates to the technical field of blood filtration materials, and in particular to MOFs modified PBT leukocyte-removing filter material and its preparation method and application. Take aminoterephthalic acid and dissolve it in N, N-dimethylformamide, then add chitosan and ultrasonically dissolve it to obtain a mixed solution; weigh zirconium tetrachloride and dissolve it in N, N-dimethylformamide to obtain a metal salt solution, add the mixed solution to the metal salt solution and mix it evenly, after the reaction, wash, dry, and obtain UiO-66-NH2@chitosan; Take UiO-66-NH2@chitosan and add it to water to prepare a finishing liquid, take PBT non-woven fabric and immerse it in the finishing liquid, take out the PBT non-woven fabric after immersion and drying, finally wash it with deionized water, and dry it to obtain the MOFs modified leukocyte-removing PBT filter material. The filter material of the present invention has both high leukocyte filtration efficiency, red blood cell and platelet recovery rate and high efficiency antibacterial function.

Description

Technical Field

[0001] The invention relates to the technical field of blood filtration materials, and in particular to a MOFs-modified PBT leukocyte-removing filter material and a preparation method and application thereof. Background Art

[0002] White blood cells are an important component of the human body to resist external bacteria and virus attacks. During blood transfusion, they will attack cells different from the recipient itself, thus causing a series of transfusion side effects such as non-hemolytic fever, adult respiratory distress syndrome, and post-transfusion graft-versus-host disease. Therefore, the removal of white blood cells has become an essential step before clinical blood transfusion.

[0003] At present, the main methods for removing leukocytes are centrifugation, washing, freezing and deglycerolization, ultraviolet or radiation irradiation, and filtration. Among them, filtration is the most effective and economical way to remove leukocytes. Leukocyte-removing filter materials are usually composed of non-woven fabrics made of materials such as PBT, PET, PP, PE, etc. This type of filter material has good biocompatibility and chemical stability, but its hydrophilicity is usually poor, and it often needs to be hydrophilically modified to ensure normal blood infiltration and circulation. In addition, bacterial contamination of blood components is one of the causes of transfusion-related deaths, accounting for more than 10% of transfusion-related deaths. Therefore, the development of a filter material with both high leukocyte removal rate and high antibacterial performance is of great significance to the safety of clinical blood use. Chinese patent CN217163900U discloses a leukocyte-removing antibacterial composite fiber membrane, which is prepared by electrospinning chitosan and PBT. The antibacterial rate of various bacteria can reach 99%, and it has a high leukocyte filtration efficiency, but its red blood cell recovery rate is relatively low, only about 76% to 91%. In addition, electrospinning technology has certain safety issues, low production efficiency and high economic costs. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a MOFs-modified PBT leukocyte-removing filter material and a preparation method and application thereof, so as to at least solve the problems of low leukocyte filtration efficiency and relatively low red blood cell recovery rate existing in the prior art.

[0005] The present invention solves the above technical problems by the following technical means:

[0006] In a first aspect, the present invention provides a method for preparing a MOFs-modified PBT leukocyte removal filter material, comprising the following steps:

[0007] Dissolve aminoterephthalic acid in N,N-dimethylformamide, then add chitosan and dissolve it by ultrasonic for 5 to 10 minutes to obtain a mixed solution;

[0008] Weigh zirconium tetrachloride and dissolve it in N,N-dimethylformamide to obtain a metal salt solution, add the mixed solution into the metal salt solution and mix evenly, then react at 60-150°C for 0.5-24h, wash the obtained reaction product with N,N-dimethylformamide and ethanol for 3-5 times, respectively, and dry to obtain UiO-66-NH2@chitosan;

[0009] Take UiO-66-NH2@chitosan and add it to water to prepare a finishing solution, take a PBT non-woven fabric and immerse it in the finishing solution, take out the immersed PBT non-woven fabric and dry it, finally wash it with deionized water for 3 to 5 times, and dry it at 60 to 120° C. for 6 to 24 hours to obtain the MOFs modified leukocyte-removing PBT filter material.

[0010] Preferably, the molar ratio of zirconium tetrachloride, aminoterephthalic acid and chitosan monomer is 1:(1-6):(1-6).

[0011] Preferably, the drying condition is 60-120° C. for 6-24 hours.

[0012] Preferably, the concentration of UiO-66-NH2@chitosan in the finishing solution is 30-100 g / L.

[0013] Preferably, the drying is carried out in two steps: first pre-baking at 90-120° C. for 5-10 min, and then baking at 150-200° C. for 10-30 min.

[0014] In a second aspect, the present invention provides a MOFs-modified PBT leukocyte removal filter material, which is prepared by the above-mentioned preparation method.

[0015] In a third aspect, the present invention provides the use of the above-mentioned MOFs-modified PBT leukocyte removal filter material in purifying leukocytes in blood.

[0016] The MOFs-modified PBT leukocyte-removing filter material of the present invention has good hydrophilicity, ensures that blood can circulate efficiently, and improves the recovery rate of red blood cells and platelets; the MOFs-modified PBT leukocyte-removing filter material of the present invention utilizes the structural characteristics of large specific surface area of ​​UiO-66-NH2 to enhance its adhesion to leukocytes, thereby improving the leukocyte filtration efficiency; the MOFs-modified PBT leukocyte-removing filter material of the present invention utilizes the excellent antibacterial and antibacterial properties of chitosan to ensure that the blood after filtration is free of bacterial contamination, thereby ensuring the safety of clinical blood use; the MOFs-modified PBT leukocyte-removing filter material of the present invention has a high leukocyte interception rate, good red blood cell protection, and a simple preparation process, and is suitable for industrial promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1This is the plate colony image of Escherichia coli on the filter material prepared in Example 1;

[0018] Figure 2 This is the plate colony image of Escherichia coli on the filter material prepared in Comparative Example 1;

[0019] Figure 3 This is the plate colony image of Escherichia coli on the filter material prepared in Comparative Example 2. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The raw materials, equipment or instruments used, if no manufacturer is specified, are all conventional products that can be obtained commercially.

[0022] The present invention provides a MOFs-modified PBT leukocyte-removing filter material, and a preparation method and application thereof. The hydrophilic 2-aminoterephthalic acid is preferably used as an organic ligand and zirconium tetrachloride is used as a metal salt to synthesize the hydrophilic UiO-66-NH2. At the same time, chitosan with good biocompatibility, hydrophilicity and antibacterial properties is added during the synthesis of UiO-66-NH2 to prepare UiO-66-NH2@chitosan. Finally, UiO-66-NH2@chitosan is used as a finishing agent to treat the PBT melt-blown non-woven fabric by padding to prepare a leukocyte-removing filter material with high leukocyte filtration efficiency, red blood cell and platelet recovery rate, and high antibacterial function. Please refer to the following examples for details:

[0023] Example 1

[0024] The preparation method of the MOFs-modified PBT leukocyte removal filter material of this embodiment is as follows:

[0025] Step (1): 1.81 g of aminoterephthalic acid was dissolved in 180 ml of N, N-dimethylformamide, and then 1.62 g of chitosan was added and dissolved by ultrasonic for 5 min to obtain a mixed solution. 2.33 g of zirconium tetrachloride was weighed and dissolved in 180 ml of N, N-dimethylformamide to obtain a metal salt solution, and the mixed solution was added to the metal salt solution and mixed evenly, and then transferred to a reactor containing a polytetrafluoroethylene liner, reacted at 120°C for 12 h, and the obtained reaction product was washed with N, N-dimethylformamide and ethanol for 5 times, and finally dried at 80°C for 12 h to obtain UiO-66-NH2@chitosan.

[0026] Step (2): PBT non-woven fabric is treated by a padding and baking method, and the steps include dipping, pre-baking, drying, etc. First, a water-soluble finishing solution with a concentration of 75 g / L is prepared by configuring UiO-66-NH2@chitosan in a compound ratio, and the PBT non-woven fabric is dipped and rolled in the finishing solution. Then, the fabric sample is taken out and pre-baked at 110°C for 8 minutes, baked at 175°C for 20 minutes, and finally washed with deionized water for 5 times, and dried at 80°C for 12 hours to obtain a MOFs-modified leukocyte-removing PBT filter material.

[0027] Example 2

[0028] The preparation method of the MOFs-modified PBT leukocyte removal filter material of this embodiment is as follows:

[0029] Step (1): 5.433 g of aminoterephthalic acid was dissolved in 200 ml of N, N-dimethylformamide, and then 4.863 g of chitosan was added and dissolved by ultrasonic for 8 min to obtain a mixed solution. 2.33 g of zirconium tetrachloride was weighed and dissolved in 200 ml of N, N-dimethylformamide to obtain a metal salt solution, and the mixed solution was added to the metal salt solution and mixed evenly, and then transferred to a reactor containing a polytetrafluoroethylene liner, reacted at 150°C for 0.5 h, and then the obtained reaction product was washed with N, N-dimethylformamide and ethanol for 3 times, and finally dried at 60°C for 24 h to obtain UiO-66-NH2@chitosan.

[0030] Step (2): PBT non-woven fabric is treated by padding and baking method, and the steps include dipping, pre-baking, drying, etc. First, a water-soluble finishing solution with a concentration of 30 g / L is prepared by configuring UiO-66-NH2@chitosan in a compound ratio, and the PBT non-woven fabric is dipped and rolled in the finishing solution. Then, the fabric sample is taken out and pre-baked at 90°C for 10 min, baked at 150°C for 30 min, and finally washed with deionized water for 5 times, and dried at 60°C for 24 h to obtain MOFs modified leukocyte-removing PBT filter material.

[0031] Example 3

[0032] The preparation method of the MOFs-modified PBT leukocyte removal filter material of this embodiment is as follows:

[0033] Step (1): 10.884 g of aminoterephthalic acid was dissolved in 300 ml of N, N-dimethylformamide, and then 9.672 g of chitosan was added and dissolved by ultrasonic for 10 min to obtain a mixed solution. 2.33 g of zirconium tetrachloride was weighed and dissolved in 300 ml of N, N-dimethylformamide to obtain a metal salt solution, and the mixed solution was added to the metal salt solution and mixed evenly, and then transferred to a reactor containing a polytetrafluoroethylene liner, reacted at 60°C for 24 h, and then the obtained reaction product was washed with N, N-dimethylformamide and ethanol for 3 times, and finally dried at 120°C for 6 h to obtain UiO-66-NH2@chitosan.

[0034] Step (2): PBT non-woven fabric is treated by a padding and baking method, and the steps include dipping, pre-baking, drying, etc. First, a water-soluble finishing solution with a concentration of 100 g / L is prepared by configuring the compound ratio of UiO-66-NH2@chitosan, and the PBT non-woven fabric is dipped and rolled in the above finishing solution, and then the fabric sample is taken out and pre-baked at 120°C for 5 minutes, baked at 200°C for 10 minutes, and finally washed with deionized water for 3 times, and dried at 120°C for 6 hours to obtain MOFs modified leukocyte-removing PBT filter material.

[0035] Comparative Example 1

[0036] In this example, chitosan was not added during the synthesis of UiO-66-NH2, as follows:

[0037] Step (1): 1.81 g of aminoterephthalic acid was dissolved in 180 ml of N,N-dimethylformamide by ultrasonication for 5 min to fully dissolve to obtain solution A. 2.33 g of zirconium tetrachloride was weighed and dissolved in 180 ml of N,N-dimethylformamide to obtain solution B. Solution A was added to solution B and mixed evenly, and then transferred to a reactor containing a polytetrafluoroethylene liner, reacted at 120° C. for 12 h, and then the obtained reaction product was washed with N,N-dimethylformamide and ethanol for 5 times, respectively, and finally dried at 80° C. for 12 h.

[0038] Step (2): PBT non-woven fabric is treated by padding and baking method, and the steps include dipping, pre-baking, drying, etc. First, a water-soluble finishing solution with a concentration of 75g / L is prepared by configuring UiO-66-NH2 in a compound ratio, and the PBT non-woven fabric is dipped and rolled in the above finishing solution. Then, the fabric sample is taken out and pre-baked at 110°C for 8min, baked at 175°C for 20min, and finally washed with deionized water for 5 times, and dried at 80°C for 12h to obtain the MOFs modified PBT filter material.

[0039] Comparative Example 2

[0040] In this example, chitosan is used as the hydrophilic finishing agent without adding UiO-66-NH2. The details are as follows:

[0041] The PBT non-woven fabric was treated by a padding and baking method, and the steps included dipping, pre-baking, and drying. First, a water-soluble finishing solution with a concentration of 75 g / L was prepared by configuring chitosan in a compound ratio, and the PBT non-woven fabric was dipped and rolled in the finishing solution. Then, the fabric sample was taken out and pre-baked at 110°C for 8 minutes, baked at 175°C for 20 minutes, and finally washed with deionized water for 5 times, and dried at 80°C for 12 hours to obtain the MOFs-modified PBT filter material.

[0042] The performance tests of the modified PBT filter materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 were performed as follows:

[0043] 1. Determination of leukocyte filtration efficiency and red blood cell and platelet recovery rate

[0044] The three groups of filter materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 were loaded into the leukocyte filter, respectively, and 400 ml of whole blood was filtered online. The number of leukocytes and platelets before and after filtration was recorded, and the retention rate of leukocytes and platelets was tested. The test results are shown in Table 1. Among them, the number of leukocytes, platelets and red blood cells before filtration was 3.24×10 9 and 6.42×10 10 and 4.53×10 12 indivual.

[0045] Where N h Leukocyte concentration after filtration, N q is the leukocyte concentration before filtration, V h is the volume of plasma after filtration, V q is the plasma volume before filtration.

[0046] Where P h The concentration of red blood cells after filtration, P q is the red blood cell concentration before filtration, V h is the volume of plasma after filtration, V q is the plasma volume before filtration.

[0047] Where R h Post-filtration platelet concentration, R q is the platelet concentration before filtration, V h is the volume of plasma after filtration, V q is the plasma volume before filtration.

[0048] 2. Hemolysis rate determination

[0049] The relative hemolysis rate of the three groups of filter material samples prepared in Example 1, Comparative Example 1 and Comparative Example 2 was measured. Since hemoglobin has characteristic absorption at 540nm, the absorbance at 540nm can be measured by a spectrophotometer. The relative hemolysis rate is calculated as follows: Relative hemolysis rate (%) = [(A-A0) / (A 100％ -A0)]×100%, where A0 and A are the absorbance of the supernatant (37°C) at 540nm after the red blood cells were in contact with the non-woven fabric surface for 1h before and after modification. 100％ It is the absorbance of the supernatant at 540nm after the red blood cells were incubated in pure water (37°C) for 1 hour. The test results are shown in Table 1.

[0050] Table 1 Leukocyte removal rate and red blood cell and platelet recovery rate

[0051] Example 1 Comparative Example 1 Comparative Example 2 <![CDATA[N h (pcs / L)]]> <![CDATA[0.49×10 5 ]]> <![CDATA[0.18×10 6 ]]> <![CDATA[0.24×10 6 ]]> Leukocyte removal rate (%) 99.999 99.995 99.993 <![CDATA[P h (pcs / L)]]> <![CDATA[4.36×10 12 ]]> <![CDATA[4.28×10 12 ]]> <![CDATA[4.32×10 12 ]]> Red blood cell recovery rate (%) 94.515 92.214 93.266 <![CDATA[R h (pcs / L)]]> <![CDATA[5.82×10 10 ]]> <![CDATA[5.45×10 10 ]]> <![CDATA[5.32×10 10 ]]> Platelet recovery rate (%) 89.022 82.854 81.043 Hemolysis rate (%) 0.48 0.64 0.56

[0052] The data in Table 1 show that the filter material of the present invention has good hydrophilicity, ensures efficient blood circulation, improves the recovery rate of red blood cells and platelets, has a high white blood cell interception rate, good red blood cell protection, and a low hemolysis rate, and is safe to use.

[0053] 3. Antibacterial performance test

[0054] The antibacterial properties of the filter materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 against Escherichia coli, Staphylococcus aureus and Candida albicans were tested according to the national standard GB / T20944.3-2009. The test results are shown in Figure 1-3 .from Figure 1-3 It can be seen that Example 1 exhibits very good antibacterial effects on the three strains, and the antibacterial rates can reach more than 99%.

[0055] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the purpose and scope of the technical solutions of the present invention, which should be included in the scope of the claims of the present invention. The techniques, shapes, and structural parts not described in detail in the present invention are all known technologies.

Claims

1. Application of MOFs-modified PBT leukocyte-removing filter material in purifying leukocytes in blood, and preparation method of MOFs-modified PBT leukocyte-removing filter material, comprising the following steps: Dissolve aminoterephthalic acid in N,N-dimethylformamide, then add chitosan and dissolve it by ultrasonic for 5 to 10 minutes to obtain a mixed solution; Weigh zirconium tetrachloride and dissolve it in N,N-dimethylformamide to obtain a metal salt solution, add the mixed solution into the metal salt solution and mix evenly, then react at 60-150°C for 0.5-24h, wash the obtained reaction product with N,N-dimethylformamide and ethanol for 3-5 times, respectively, and dry to obtain UiO-66-NH2@chitosan; Take UiO-66-NH2@chitosan and add it to water to prepare a finishing solution, take PBT non-woven fabric and immerse it in the finishing solution, take out the immersed PBT non-woven fabric and dry it, finally wash it with deionized water for 3 to 5 times, and dry it at 60 to 120°C for 6 to 24 hours to obtain MOFs modified leukocyte-removing PBT filter material.

2. The use according to claim 1, characterized in that: The molar ratio of zirconium tetrachloride, aminoterephthalic acid and chitosan monomer is 1:(1-6):(1-6).

3. The use according to claim 1, characterized in that: The concentration of UiO-66-NH2@chitosan in the finishing solution is 30-100 g / L.

4. The use according to claim 1, characterized in that: The drying is carried out in two steps: firstly pre-baking at 90-120° C. for 5-10 min, and then baking at 150-200° C. for 10-30 min.

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