A kind of biologically active cotton fabric containing protamine and preparation method thereof

Abstract

The present invention belongs to the field of new biological materials, and discloses a bioactive cotton fabric containing protamine and a preparation method thereof. The bioactive cotton fabric is constructed of cotton fabric and protamine. The preparation method of the bioactive cotton fabric containing protamine is as follows: first, the cotton fabric is immersed in an aqueous sodium periodate solution for oxidation, immersed in an ethylene glycol aqueous solution to terminate the oxidation, washed and dried to obtain an oxidized cotton cloth. Secondly, the above-mentioned oxidized cotton fabric is immersed in a protamine aqueous solution, the protamine is connected to the surface of the cotton fiber through a Schiff base, and the antibacterial and antiviral cotton fabric is obtained after rinsing and drying. The preparation method of the present invention has mild conditions and simple steps. The obtained modified cotton fabric not only has high-efficiency and lasting antibacterial and antiviral activity, but also can maintain the inherent properties of the original cotton fiber. The antibacterial agent used is protamine from nature, which is environmentally friendly, green and can be sustainably regenerated, and has great practical value in the field of new textile materials.

Description

Technical Field

[0001] The invention relates to a method for preparing protamine antibacterial and antiviral cotton fabric, belonging to the field of new biological materials. Background Art

[0002] Cotton fabric is one of the most abundant natural fiber clothing fabrics on earth. It is very popular among people because of its excellent performance characteristics such as skin-friendly, soft, breathable, hygroscopic, and non-toxic. However, the good hydrophilicity and moisture retention of cotton fabrics will cause bacteria and viruses in the natural environment to adhere and grow on its surface, thereby reducing the performance of cotton fabrics and making it easy for people to get infected and endanger their lives and health. Bacteria and viruses are everywhere in life. They can attach to textiles in specific environments (such as hospitals, epidemic areas and other high-risk places), and can even spread through droplets from patients talking and coughing and infect the human body. Fiber textiles with good hygroscopicity have become a medium for the spread of bacteria and viruses, causing bacteria and viruses to invade the human body and cause diseases. Therefore, there is an urgent need for a low-cost cotton fabric with antibacterial and antiviral functions to be applied to the textile industry.

[0003] At present, there are three main types of antibacterial finishing for cotton fabrics: inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. Inorganic antimicrobial agents mainly refer to metals such as silver, copper, and zinc or their ions (Pei Zhongyong, Wang Jing. An antimicrobial finishing agent containing nanosilver for cotton fabrics. CN110512416B). This type of antimicrobial agent has the characteristics of good heat resistance, broad antimicrobial spectrum, and long effective antimicrobial period, but has the disadvantages of high cost, complex processing, poor antifungal and mildew effects, and affects the color and comfort of processed products; organic antimicrobial agents mainly include quaternary ammonium salts, guanidines, organic halides, etc. (Ren Xuehong, Liu Ying, etc. A halamine polymer antimicrobial agent containing quaternary ammonium salt groups and its preparation method and application. CN103524652B). This type of antimicrobial agent has a fast sterilization speed and strong sterilization ability, but their heat resistance is relatively poor, the ingredients consume fossil raw materials, and the decomposition products are difficult to be biodegraded in nature, leaving huge potential environmental problems in nature; natural antimicrobial agents refer to chitosan, borneol, betaine, etc. (Tang Jiapeng, Ge Yan, etc. A cotton fabric with antiviral function and its preparation method. CN111254709B) is mainly composed of substances with antibacterial activity, which come from natural extracts. This type of antibacterial agent has the characteristics of high antibacterial efficiency, broad antibacterial spectrum, green environmental protection, safety and non-toxicity, but has disadvantages such as difficult processing and poor heat resistance.

[0004] Protamine is a protein mainly composed of polycationic peptides. It exists in the mature testicular tissue of various male animals in the form of nuclear protamine. The molecular weight of protamine is relatively small. It is usually composed of only about 30 amino acids, mainly arginine. In recent years, there have been many reports on protamine at home and abroad. As a natural and easy-to-extract protein with high nutritional value and functionality, it is not only safe, but also has strong antibacterial and antiviral activity. It also has the advantages of applicability and thermal stability in a wide pH range. As an environmentally friendly cationic polymer, protamine has a large amount of positive charge on the surface. It can adsorb bacteria and viruses with negatively charged membranes through electrostatic action, and then destroy their cell membranes and cause the outflow of substances such as cytoplasm, thereby killing bacteria and viruses. Protamine from nature has strong bactericidal and antiviral activity, and is environmentally friendly, recyclable, safe and non-toxic. It is mainly used in the food field as a natural antibacterial agent. However, there is no report on the use of protamine for antibacterial and antiviral treatment of cotton fabrics.

[0005] Therefore, the present invention uses sodium periodate to perform oxidation treatment on the surface of cotton fabric to generate aldehyde functional groups, and reacts with the amino groups of protamine to produce Schiff base, so as to chemically graft protamine to the surface of cotton fabric to obtain efficient and durable antibacterial and antiviral properties. The modified cotton fabric obtained by the present invention not only has efficient and durable antibacterial and antiviral properties, but also has all natural ingredients and good biocompatibility, does not cause harm to human health, and also maintains the physical properties of the original cotton fiber such as air permeability, softness, and hygroscopicity.

[0006] In summary, cotton fabric has good flexibility, good water absorption, good air permeability, good biocompatibility and the characteristics of being cheap and easy to obtain, and has unique advantages as a biomaterial. However, its antibacterial rate is low, and its hygroscopicity is good, which makes it easy for bacteria and viruses to breed on the surface, thus affecting people's life and health, and also hinders its further application and development. The present invention obtains a modified cotton fabric with high-efficiency antibacterial and antiviral properties by oxidizing cotton fabric and chemically grafting protamine molecules. The experimental process is simple and easy, the reaction conditions are mild, the experimental materials are green and safe, and no harmful by-products are generated. In addition, the modified cotton fabric has good washability and maintains the mechanical properties of the original cotton fiber. Summary of the invention

[0007] In view of this, the object of the present invention is to provide a method for preparing a protamine bioactive cotton fabric with high antibacterial and antiviral properties and good wash resistance. The present invention is to graft protamine molecules onto the surface of cotton fabric through Schiff base reaction to obtain a high-efficiency antibacterial effect, and the functional groups of cotton fabric and protamine form a stable chemical bond link, which significantly improves the wash resistance of the antibacterial and antiviral cotton fabric. The present invention has the characteristics of low cost, simple operation, high antibacterial and antiviral activity, stable wash resistance, safety and environmental protection. It is a method for preparing antibacterial and antiviral cotton fabric that is beneficial to the sustainable development of the ecological environment. In order to achieve the above purpose, the specific technical scheme of the present invention is as follows:

[0008] A biologically active cotton fabric containing protamine, wherein the protamine is covalently linked to the surface of cotton fibers via a Schiff base, and the content of the protamine is 100-200 g / kg of the cotton fabric. The cotton fabric has excellent antibacterial and antiviral activities and good washability.

[0009] Further, the following steps are included:

[0010] 1) Soak the cotton fabric in 0.01-0.1 mol / L sodium periodate solution and stir for 1-4 hours at 25°C in the dark;

[0011] 2) Immerse the cotton fabric oxidized by sodium periodate solution in 0.01 mol / L ethylene glycol solution for 30-60 min, wash with water and dry at 80 °C for 4 h;

[0012] 3) The cotton fabric is immersed in a 1-20 wt% protamine aqueous solution, stirred at 25°C for 1-4 h, washed with water and dried at 40°C for 24 h.

[0013] Furthermore, the weight of the wet cloth increased by 80-120%.

[0014] Furthermore, in step 3), the stirring reaction is preferably performed for 2 hours.

[0015] The present invention achieves the following effects:

[0016] First, the cotton fabric surface was oxidized with sodium periodate, and then ethylene glycol was used to terminate the oxidation reaction. Finally, protamine molecules were grafted onto the cotton fabric surface using the Schiff base reaction to obtain antibacterial and antiviral cotton fabric. The original cotton fabric had almost no inhibitory effect on Escherichia coli, Staphylococcus aureus and T7 bacteriophage. The oxidized cotton fabric had an antibacterial rate of only 50.0% on these two bacteria and no inhibitory effect on T7 bacteriophage. The antibacterial and antiviral cotton fabric obtained by grafting protamine molecules had an antibacterial rate of up to 100% on these two bacteria and a virus inactivation rate of up to 100% on T7 bacteriophage. After washing 50 times, the antibacterial cotton fabric still had an antibacterial rate and virus inactivation rate of more than 99.9%. DETAILED DESCRIPTION

[0017] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0018] Example 1

[0019] In the first step, the cotton fabric raw material was immersed in 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C.

[0020] The prepared cotton fabric is made of cotton fabric and sodium periodate, the concentration of sodium periodate solution is 0.01 mol / L, the antibacterial and antiviral cotton fabric has an inhibition rate of only 50.0% against Escherichia coli and Staphylococcus aureus, and after 50 strict washing cycles, the inhibition rate is below 30.0%. The obtained antibacterial and antiviral cotton fabric has no inactivation effect on T7 bacteriophage.

[0021] Example 2

[0022] In the first step, the cotton fabric raw material was immersed in a 10 wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0023] The prepared cotton fabric is constructed of cotton fabric and protamine, the concentration of the protamine solution is 10 wt %, and the obtained cotton fabric has no obvious killing effect on Escherichia coli, Staphylococcus aureus and T7 phage.

[0024] Example 3

[0025] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0026] The obtained antibacterial and antiviral cotton fabric is composed of cotton fabric, sodium periodate and protamine, the concentration of sodium periodate solution is 0.01 mol / L, the concentration of protamine solution is 10 wt%, the obtained antibacterial and antiviral cotton fabric has an antibacterial rate of 100% against Escherichia coli and Staphylococcus aureus, and after 50 strict washing cycles, the antibacterial rate is more than 99.9%. The obtained antibacterial and antiviral cotton fabric has an inactivation rate of 100% against T7 bacteriophage, and after 50 strict washing cycles, the inactivation rate is more than 99.9%.

[0027] Example 4

[0028] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred for 1 h at 25 °C in the dark, and then immersed in a 0.01 mol / L ethylene glycol solution for 30 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred for 2 h at 25 °C, washed, and dried at 40 °C.

[0029] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 85.9%, and after 50 strict washing cycles, the antibacterial rate is more than 80.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 50%, and after 50 strict washing cycles, the inactivation rate is only 20%.

[0030] Example 5

[0031] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred for 0.5 h at 25 °C in the dark, then immersed in a 0.01 mol / L ethylene glycol solution for 30 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred for 2 h at 25 °C, washed, and dried at 40 °C.

[0032] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 77.0%, and after 50 strict washing cycles, the antibacterial rate is more than 70.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 50%, and after 50 strict washing cycles, the inactivation rate is only 20%.

[0033] Example 6

[0034] In the first step, the raw cotton fabric was immersed in a 0.001 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 30 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0035] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.001 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 59.9%, and after 50 strict washing cycles, the antibacterial rate is more than 50.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 30%, and after 50 strict washing cycles, the inactivation rate is only 10%.

[0036] Example 7

[0037] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 0.1wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0038] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 0.1 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 65.0%, and after 50 strict washing cycles, the antibacterial rate is more than 60.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 30%, and after 50 strict washing cycles, the inactivation rate is only 10%.

[0039] Example 8

[0040] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 1 wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0041] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 1 wt%. The obtained modified cotton fabric has an antibacterial rate of more than 75.9% against Escherichia coli and Staphylococcus aureus, and after 50 strict washing cycles, the antibacterial rate is more than 70.0%. The obtained modified cotton fabric has an inactivation rate of 50% against T7 phage, and after 50 strict washing cycles, the inactivation rate is only 20%.

[0042] Example 9

[0043] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 20wt% protamine solution, stirred at 25 °C for 2 h, washed, and dried at 40 °C.

[0044] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 20 wt%. The obtained modified cotton fabric has an antibacterial rate of up to 100% against Escherichia coli and Staphylococcus aureus, and after 50 strict washing cycles, the antibacterial rate is above 99.9%. The obtained modified cotton fabric has an inactivation rate of 100% against T7 phage, and after 50 strict washing cycles, the inactivation rate is above 99.9%.

[0045] Example 10

[0046] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred at 25 °C for 0.5 h, washed, and dried at 40 °C.

[0047] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 80.0%, and after 50 strict washing cycles, the antibacterial rate is more than 78.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 50%, and after 50 strict washing cycles, the inactivation rate is only 20%.

[0048] Embodiment 11

[0049] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10 wt% protamine solution, stirred at 25 °C for 1 h, washed, and dried at 40 °C.

[0050] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 90.0%, and after 50 strict washing cycles, the antibacterial rate is more than 85.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 70%, and after 50 strict washing cycles, the inactivation rate is only 50%.

[0051] Example 12

[0052] In the first step, the raw cotton fabric was immersed in a 0.01 mol / L sodium periodate solution, stirred at 25 °C in the dark for 4 h, then immersed in a 0.01 mol / L ethylene glycol solution for 60 min, washed, and dried at 80 °C. The cotton fabric obtained above was immersed in a 10wt% protamine solution, stirred at 25 °C for 4 h, washed, and dried at 40 °C.

[0053] The prepared modified cotton fabric is composed of cotton fabric, sodium periodate and protamine. The concentration of sodium periodate solution is 0.01 mol / L, and the concentration of protamine solution is 10 wt%. The antibacterial rate of the obtained modified cotton fabric against Escherichia coli and Staphylococcus aureus is more than 95.0%, and after 50 strict washing cycles, the antibacterial rate is more than 90.0%. The inactivation rate of the obtained modified cotton fabric against T7 phage is 90%, and after 50 strict washing cycles, the inactivation rate is more than 70%.

[0054] The summary of the above embodiments is shown in Table 1:

[0055]

[0056] Table 1 Experimental results of various embodiments.

Claims

1. A method for preparing a protamine-containing bioactive cotton fabric, characterized in that: Protamine is covalently linked to the surface of cotton fiber via Schiff base, and the content is 100-200 g protamine / kg cotton fabric; the preparation method comprises the following steps: 1) Soak the cotton fabric in 0.01-0.1 mol / L sodium periodate solution and stir for 1-4 h at 25 ℃ in the dark; 2) Immerse the cotton fabric oxidized by sodium periodate solution in 0.01 mol / L ethylene glycol solution for 30-60 min, wash with water and dry at 80 °C for 4 h; 3) Immerse the above cotton fabric in a 1-20 wt% protamine aqueous solution, stir and react at 25°C for 1-4 h, wash with water and dry at 40°C for 24 h; the weight of the wet fabric increases by 80-120%.

2. The method for preparing the protamine-containing bioactive cotton fabric according to claim 1, characterized in that: In step 3), the reaction was stirred for 2 h.

Images