A sodium carboxymethylcellulose-gelatin-sodium polyvinylsulfonate hydrogel and a method for preparing the same

Abstract

The present application relates to a kind of sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel and its preparation method, by adding hydrophilic polyelectrolyte sodium polyvinyl sulfonate, gently improve the swelling and mechanical properties of hydrogel.The hydrogel of the present application not only has good water absorption swelling performance due to the addition of hydrophilic sodium sulfonate group, but also maintains good mechanical properties due to Hoffmeister effect.The raw materials used, sodium carboxymethyl cellulose, gelatin and sodium polyvinyl sulfonate, have good biocompatibility.

Description

Technical Field

[0001] This invention belongs to the field of hydrogel preparation technology, specifically relating to a sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel and its preparation method. Background Technology

[0002] Both natural and synthetic polymers can form hydrogels. Hydrogels have extremely wide applications in biomedical engineering, such as organ and tissue replacement, drug delivery systems, and embolic agents. Cellulose is a large polysaccharide composed of glucose and is a major component of plant cell walls. Cellulose is abundant in nature, easily degraded, and readily modified; its derivative, sodium carboxymethyl cellulose (CMC-Na), is a commonly used polymer for preparing hydrogels. Collagen is a major structural protein in vertebrates, accounting for 25%-30% of total body protein. Collagen has good biocompatibility, promoting cell adhesion, proliferation, maintaining cell differentiation, and accelerating wound healing. Gelatin is a hydrolysis product of collagen, exhibiting no immune rejection or local inflammatory response, good mechanical properties, and structural support.

[0003] The swelling property of hydrogels refers to their ability to rapidly swell in water and retain a large volume of water without dissolving in this swollen state. Swelling properties are crucial for the application of hydrogels; by adjusting and controlling these properties, various functions and applications can be achieved. However, high water content in hydrogels often results in weak mechanical properties, making it difficult to meet the requirements for replacing load-bearing tissues. For example, as an ideal hernia repair, a hydrogel not only needs good swelling properties but also excellent elasticity similar to soft tissue and the ability to withstand abdominal wall pressure during rapid elastic recovery. The Hoffmeister effect, where ions influence the aggregation of hydrophilic polymer chains by affecting hydrated molecules surrounding them, can significantly improve the mechanical properties of hydrogels. The team led by Cheng Yilong at Xi'an Jiaotong University discovered that polyelectrolytes can improve the mechanical properties of hydrogels through the Hoffmeister effect. Furthermore, compared to inorganic salts, polyelectrolytes also possess excellent biocompatibility (Zhang M, Yang Y, Li M, Shang Q, Cheng Y, et al, Toughening double network hydrogels by polyelectrolytes, Advanced Materials).

[0004] Currently, no hydrophilic polyelectrolyte sodium polyvinyl sulfonate (PVSA) has been found to improve the swelling and mechanical properties of hydrogels. Summary of the Invention

[0005] The present invention aims to provide a sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel, which improves the swelling and mechanical properties of the hydrogel by introducing PVSA.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel.

[0007] The objective of this invention is achieved through the following solution: a sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel, composed of sodium carboxymethyl cellulose, gelatin, and sodium polyvinyl sulfonate; a hydrogel with good swelling and mechanical properties.

[0008] This invention provides a method for preparing sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel, comprising the following steps:

[0009] Step 1: Add CMC-Na and gelatin to a certain amount of ultrapure water at a mass ratio of 1:0.5~5, and stir at 60℃ until completely dissolved;

[0010] Step 2: Add PVSA to the reaction vessel of Step 1 at a mass ratio of 0.5 to 5 with CMC-Na, stir until homogeneous, and obtain the hydrogel precursor solution;

[0011] Step 3: Allow the hydrogel precursor solution from Step 2 to stand for 24-72 h to gel, obtaining sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel.

[0012] In steps (1) and (2), the CMC-Na is preferably of type I, III, or V, and the amount of ultrapure water added is 10 times the total amount of CMC-Na and gelatin. The PVSA is a 30% aqueous solution of sodium polyvinyl sulfonate.

[0013] In step (3), the preferred time for the precursor to stand and gel is 48 h.

[0014] A hydrogel with good swelling and mechanical properties is disclosed, composed of sodium carboxymethyl cellulose, gelatin, and sodium polyvinyl sulfonate. During the swelling process, water absorption in the hydrogel reduces its mechanical properties, making it difficult to meet the weight-bearing requirements of tissues. This invention improves the swelling and mechanical properties of the hydrogel by adding the hydrophilic polyelectrolyte PVSA. The method is mild, and the prepared hydrogel not only exhibits good water absorption and swelling properties due to the addition of hydrophilic sodium sulfonate groups but also maintains good mechanical properties due to the Hoffmeister effect. The raw materials used—CMC-Na, gelatin, and PVSA—have good biocompatibility. Attached Figure Description

[0015] Appendix Figure 1 This is a comparison image of the hydrogel before and after swelling in physiological saline. Detailed Implementation

[0016] The present invention will be further illustrated by the following examples. However, the present invention is not limited to the examples given.

[0017] Example 1

[0018] A sodium carboxymethyl cellulose (CMC)-gelatin-sodium polyvinyl sulfonate (PVSA) hydrogel is prepared according to the following steps: CMC-Na (V-type), gelatin, and PVSA are present in a mass ratio of 1:2:0.5.

[0019] Step 1: Add 1 g CMC-Na (V type) and 2 g gelatin to 30 mL of ultrapure water and stir at 60°C until completely dissolved;

[0020] Step 2: Add 0.5 g of PVSA to the reaction vessel from Step 1 and stir until homogeneous to obtain the hydrogel precursor solution;

[0021] Step 3: Allow the hydrogel precursor solution from Step 2 to stand for 48 h to gel, thereby obtaining sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel.

[0022] The swelling rate of the prepared hydrogel after soaking in physiological saline for 2 hours was 66.8%.

[0023] Example 2

[0024] A sodium carboxymethyl cellulose-gelatin hydrogel is composed of 1 g of type I sodium carboxymethyl cellulose (CMC-Na) and 2 g of gelatin, wherein the mass ratio of type I CMC-Na to gelatin is 1:2. The preparation steps are the same as in Example 1. The swelling rate of the sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel obtained after soaking in physiological saline for 2 h is only 38.7%, as shown in Table 1.

[0025] Example 3

[0026] A sodium carboxymethyl cellulose-gelatin hydrogel is composed of 1 g of V-type sodium carboxymethyl cellulose (CMC-Na) and 2 g of gelatin, wherein the mass ratio of V-type CMC-Na to gelatin is 1:2. The preparation steps are the same as in Example 1. The swelling rate of the sodium carboxymethyl cellulose-gelatin hydrogel obtained after soaking in physiological saline for 2 h is only 45.8%, as shown in Table 1.

[0027] Example 4

[0028] A sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel is composed of 2 g type III sodium carboxymethyl cellulose (CMC-Na), 4 g gelatin, and 1 g sodium polyvinyl sulfonate. The mass ratio of type III CMC-Na:gelatin:PVSA is 1:2:0.5. The preparation steps are the same as in Example 1. The swelling rate of the obtained sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 h is only 53.1%, as shown in Table 1.

[0029] Example 5

[0030] A sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel is prepared by 2 g of V-type sodium carboxymethyl cellulose (CMC-Na), 4 g of gelatin, and 3 g of polyvinyl sulfonate. The mass ratio of V-type CMC-Na:gelatin:PVSA is 1:2:1.5. The preparation steps are the same as in Example 1. The swelling rate of the prepared sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 h is only 84.8%, as shown in Table 1.

[0031] Example 6

[0032] A sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel is prepared by 3 g of V-type sodium carboxymethyl cellulose (CMC-Na), 9 g of gelatin, and 4.5 g of polyvinyl sulfonate. The mass ratio of V-type CMC-Na:gelatin:PVSA is 1:3:1.5. The preparation steps are the same as in Example 1. The swelling rate of the prepared sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 h is only 78.7%, as shown in Table 1.

[0033] Example 7

[0034] A sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel is prepared by 1 g of V-type sodium carboxymethyl cellulose (CMC-Na), 4 g of gelatin, and 1.5 g of polyvinyl sulfonate. The mass ratio of V-type CMC-Na:gelatin:PVSA is 1:4:1.5. The preparation steps are the same as in Example 1. The swelling rate of the prepared sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 h is only 79.4%, as shown in Table 1.

[0035] Example 8

[0036] A sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel is prepared by 1.5g of V-type sodium carboxymethyl cellulose (CMC-Na), 3g of gelatin, and 3g of polyvinyl sulfonate. The mass ratio of V-type CMC-Na:gelatin:PVSA is 1.5:3:3. The preparation steps are the same as in Example 1. The swelling rate of the prepared sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 hours is only 107.4%, as shown in Table 1.

[0037] Example 9

[0038] A sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel is composed of 1 g of V-type sodium carboxymethyl cellulose (CMC-Na), 2 g of gelatin, and 3 g of polyvinyl sulfonate. The mass ratio of V-type CMC-Na:gelatin:PVSA is 1:2:3. The preparation steps are the same as in Example 1. The swelling rate of the obtained sodium carboxymethyl cellulose-gelatin-polyvinyl sulfonate hydrogel after soaking in physiological saline for 2 h is only 233.1%, as shown in Table 1.

[0039] Table 1 shows the swelling rates of sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogels prepared by varying the amounts of CMC-Na, gelatin, and PVSA, and the type of CMC-Na, after soaking in physiological saline for 2 hours. CMC-Na type V hydrogels exhibit stronger absorbency than types I and III. A higher proportion of PVSA significantly increases the swelling rate of the hydrogel while maintaining its morphological integrity.

[0040] .

Claims

1. A sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel, comprising sodium carboxymethyl cellulose (CMC-Na), gelatin, and sodium polyvinyl sulfonate (PVSA), wherein the mass ratio of CMC-Na:gelatin:PVSA is 1:0.5~5:0.5~5, and the CMC-Na is of type I, III, or V.

2. A method for preparing a sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel, characterized in that... The swelling and mechanical properties of hydrogels are gently improved by adding the hydrophilic polyelectrolyte sodium polyvinyl sulfonate, including the following steps: Step 1: Add CMC-Na and gelatin to a certain amount of ultrapure water at a mass ratio of 1:0.5~5, and stir at 60°C until completely dissolved; Step 2: Add PVSA to the reaction vessel from Step 1 at a mass ratio of 0.5~5:1 to CMC-Na, stir until homogeneous, and obtain the hydrogel precursor solution; Step 3: Allow the hydrogel precursor solution from Step 2 to stand for 24-72 h to gel, obtaining sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel.

3. The method for preparing sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel according to claim 2, characterized in that, In steps (1) and (2), the CMC-Na is of type I, III, or V, and the amount of ultrapure water added is 10 times the total amount of CMC-Na and gelatin. The PVSA is a 30% aqueous solution of sodium polyvinyl sulfonate.

4. The method for preparing sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel according to claim 2, characterized in that, In step (3), the precursor is allowed to stand for gelation for 24 to 72 hours.

5. The method for preparing sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel according to any one of claims 2 to 4, characterized in that, The CMC-Na is of type V, with a mass ratio of V-type CMC-Na:gelatin:PVSA of 1:2:0.5, and is prepared according to the following steps: Step 1: Add 1 g of V-type CMC-Na and 2 g of gelatin to 30 mL of ultrapure water and stir at 60°C until completely dissolved; Step 2: Add 0.5 g of PVSA to the reaction vessel from Step 1 and stir until homogeneous to obtain the hydrogel precursor solution; Step 3: Allow the hydrogel precursor solution from Step 2 to stand for 48 h to gel, obtaining sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel.

6. The method for preparing sodium carboxymethyl cellulose-gelatin-sodium polyvinyl sulfonate hydrogel according to claim 5, characterized in that: The V-type CMC-Na:gelatin:PVSA mass ratio is 1:2:1.5; or, The V-type CMC-Na:gelatin:PVSA mass ratio is 1:3:1.5; or, The V-type CMC-Na:gelatin:PVSA mass ratio is 1:4:1.5; or, The V-type CMC-Na:gelatin:PVSA mass ratio is 1:2:2; or, The mass ratio of the V-type CMC-Na: gelatin: PVSA is 1:2:3.

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