Nanocomposite bacteriostatic material and a preparation method and an application thereof

Abstract

The present invention discloses a novel nano-composite antibacterial material and a preparation method and an application thereof, and belongs to the technical field of preservative materials. The novel nano-composite antibacterial material disclosed by the present invention is prepared by mixing a dimethylimidazole solution, deionized water and a zinc nitrate solution to prepare a metal-organic framework carrier, compositing with nisin to form a nano antibacterial composite material, separating out from a solution in a precipitate form, centrifuging, removing a supernatant, cleaning and re-suspending with the deionized water. The novel nano-composite antibacterial material prepared by the present invention has an antibacterial effect superior to nisin having a same concentration. The present invention prominently improves an antibacterial activity and thermostability of the nisin under neutral and slightly alkaline conditions, effectively promotes antibacterial property and a usable range of the nisin, and further expands an application field of the metal-organic framework carrier.

Claims

1. A method for preparing a nano-composite antibacterial material, comprising the following steps: (1) preparing a nisin solution having a concentration of 1-30 g/L, a solvent being water; (2) adding a 0.5-1.0 mol/L dimethylimidazole solution, deionized water and a 0.1-0.8 mol/L zinc nitrate solution in sequence according to a volume ratio of (5-20):1:1 for mixing, stirring for 30-60 min, centrifuging to take a precipitate, and cleaning to obtain a metal-organic framework carrier; and (3) adding the nisin solution to the metal-organic framework carrier, stirring for 1-2 h, centrifuging a reacted sample, removing a supernatant, cleaning a precipitate, and adding deionized water to be subjected to vortex suspension to obtain a nano-composite antibacterial material suspension having a concentration of 10-15 g/L.

2. The method for preparing the nano-composite antibacterial material according to claim 1, wherein the titer of the nisin in the step (1) is (0.9-1.3)*10.sup.6 IU/g.

3. The method for preparing the nano-composite antibacterial material according to claim 1, wherein the concentration of the dimethylimidazole solution in the step (2) is 0.8-1.0 mol/L.

4. The method for preparing the nano-composite antibacterial material according to claim 1, wherein the concentration of the zinc nitrate solution in the step (2) is 0.3-0.5 mol/L.

5. The method for preparing the nano-composite antibacterial material according to claim 1, wherein the volume ratio of the dimethylimidazole solution to the deionized water to the zinc nitrate solution in the step (2) is (8-15):(1-3):(1-3).

6. The method for preparing the nano-composite antibacterial material according to claim 5, wherein the volume ratio of the dimethylimidazole solution to the deionized water to the zinc nitrate solution in the step (2) is (11-15):(1-2):(1-2).

7. The method for preparing the nano-composite antibacterial material according to claim 1, wherein in the step (2), a stirring rotational speed is 8000-12000 rpm, and stirring time is 5-10 min.

8. The method for preparing the nano-composite antibacterial material according to claim 1, wherein in the step (3), a volume ratio of an added amount of the nisin solution to the dimethylimidazole solution in the step (2) is 1:(1-2).

9. A nano-composite antibacterial material prepared with the preparation method according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a measurement diagram of thermostability of a nano-composite antibacterial material according to Experimental example 4, where the (a) shows antibacterial circles corresponding to experimental group 1 and control groups 1, 3, wherein 1-embodimental group 1 (composite material), 2-control group 1 (empty carrier), and 3-control group 3 (free nisin, having a concentration of 10 g/L); and the (b) shows antibacterial circles corresponding to experimental group 2, and control groups 2, 4, wherein 1-experimental group 2 (composite material), 2-control group 2 (empty carrier), and 3-control group 4 (free nisin, having a concentration of 30 g/L).

(2) FIG. 2 shows a micromorphological structure of a metal-organic framework carrier under a scanning electron microscope, where the (a) is the metal-organic framework carrier prepared from a zinc nitrate solution having a concentration of 0.4 mol/L, and the (b) is the metal-organic framework carrier prepared from a zinc nitrate solution having a concentration of 0.7 mol/L, the amplification factor being 13,000 times.

DESCRIPTION OF THE EMBODIMENTS

(3) The present invention is described below through specific embodiments. Unless otherwise specified, the technical means used in the present invention are all methods known to those skilled in the art. In addition, the embodiments should be understood as being illustrative, rather than limiting the scope of the present invention. The essence and scope of the present invention are only defined by the claims. For those skilled in the art, without departing from the essence and scope of the present invention, various changes or modifications to the material composition and amount used in these embodiments also belong to the protection scope of the present invention. The present invention is further described below in combination with specific embodiments.

Embodiment 1 Preparation of Nisin Nano-Composite Antibacterial Material

(4) The nisin nano-composite antibacterial material obtained by adsorption of nisin by the metal-organic framework carrier is prepared by the following steps:

(5) (1) 10 mg of nisin having a molecular weight of about 3500 Da was dissolved in 10 mL of deionized water to prepare a nisin solution having a concentration of 1 g/L, the titer of the nisin being 0.9*10.sup.6 IU/g.

(6) (2) 11 mL of 1.0 mol/L dimethylimidazole solution was added to a conical flask and placed onto a magnetic stirrer, then 2 mL of deionized water was added, 2 mL of 0.4 mol/L zinc nitrate solution was added, the mixed solution reacted at 20-30° C., was stirred for 30 min and was centrifuged at 8000 rpm for 10 min, a supernatant was removed, and the deionized water was used for cleaning to obtain a metal-organic framework carrier.

(7) (3) The metal-organic framework carrier was placed into a conical flask and stirred uniformly on the magnetic stirrer; and then, 11 mL of nisin solution having the concentration of 1 g/L was added, and stirred for adsorption reaction with reference to an experimental method in which the carrier absorbs an enzyme. A reacted sample was centrifuged, a supernatant was removed, and after a precipitate was cleaned with the deionized water, the deionized water was added continuously for vortex suspension to prepare a milk white suspension having a concentration of 10 g/L, and obtain a nisin nano-composite antibacterial material suspension, a pH of the suspension being measured as 8.5.

Embodiment 2 Preparation of Nisin Nano-Composite Antibacterial Material

(8) The nisin nano-composite antibacterial material obtained by adsorption of nisin by the metal-organic framework carrier is prepared by the following steps:

(9) (1) 100 mg of nisin having a molecular weight of about 3500 Da was dissolved in 10 mL of deionized water to prepare a nisin solution having a concentration of 10 g/L, the titer of the nisin being 1.1*10.sup.6 IU/g.

(10) (2) 12 mL of 0.8 mol/L dimethylimidazole solution was added to a conical flask and placed onto a magnetic stirrer, then 2 mL of deionized water was added, 1 mL of 0.3 mol/L zinc nitrate solution was added, the mixed solution reacted at 20-30° C., was stirred for 45 min and was centrifuged at a stirring rotational speed of 12000 rpm for 6 min, a supernatant was removed, and the deionized water was used for cleaning to obtain a metal-organic framework carrier.

(11) (3) The metal-organic framework carrier was placed into the conical flask and stirred uniformly on the magnetic stirrer; and then, 10 mL of nisin solution having the concentration of 10 g/L was added, and stirred for adsorption reaction with reference to an experimental method in which the carrier absorbs an enzyme. A reacted sample was centrifuged, a supernatant was removed, and after a precipitate was cleaned with the deionized water, the deionized water was added continuously for vortex suspension to prepare a milk white suspension having a concentration of 15 g/L, and obtain a nisin nano-composite antibacterial material suspension, a pH of the suspension being measured as 8.16.

Embodiment 3 Preparation of Nisin Nano-Composite Antibacterial Material

(12) The nisin nano-composite antibacterial material obtained by adsorption of nisin by the metal-organic framework carrier is prepared by the following steps:

(13) (1) 300 mg of nisin having a molecular weight of about 3500 Da was dissolved in 10 mL of deionized water to prepare a nisin solution having a concentration of 30 g/L, the titer of the nisin being 1.0*10.sup.6 IU/g.

(14) (2) 12 mL of 1.0 mol/L dimethylimidazole solution was added to a conical flask, the conical flask was placed onto a magnetic stirrer, 1 mL of deionized water was added, then 1 mL of 0.4 mol/L zinc nitrate solution was added, the mixed solution reacted at 20-30° C., was stirred for 60 min and was centrifuged at a stirring rotational speed of 9000 rpm for 8 min, a supernatant was removed, and the deionized water was used for cleaning to obtain a metal-organic framework carrier.

(15) (3) The metal-organic framework carrier was placed into the conical flask and stirred uniformly on the magnetic stirrer; and then, 12 mL of nisin solution having the concentration of 30 g/L was added, and stirred for adsorption reaction with reference to an experimental method in which the carrier absorbs an enzyme. A reacted sample was centrifuged, a supernatant was removed, and after a precipitate was cleaned with the deionized water, the deionized water was added continuously for vortex suspension to prepare a milk white suspension having a concentration of 15 g/L, and obtain a nisin nano-composite antibacterial material suspension, a pH of the suspension being measured as 7.66.

Embodiment 4 Preparation of Nisin Nano-Composite Antibacterial Material

(16) The nisin nano-composite antibacterial material obtained by adsorption of nisin by the metal-organic framework carrier is prepared by the following steps:

(17) (1) A nisin solution having a concentration of 30 g/L was prepared, the titer of the nisin being 1.0*10.sup.6 IU/g.

(18) (2) 0.8 mol/L dimethylimidazole solution, deionized water and 0.4 mol/L zinc nitrate solution were added to a conical flask in sequence according to a volume ratio of (11-12):(1-2):(1-2), the conical flask was placed onto a magnetic stirrer for mixing, the mixed solution reacted at 20-30° C., was stirred for 60 min, and was centrifuged at a stirring rotational speed of 8000-9000 rpm for 5-10 min, a supernatant was removed, and the deionized water was used for cleaning to obtain a metal-organic framework carrier.

(19) (3) The metal-organic framework carrier was placed into the conical flask and uniformly stirred on the magnetic stirrer, and then the nisin solution having the concentration of 30 g/L was added, a volume ratio of an added amount of the nisin solution to the dimethylimidazole solution in the step (2) being 1:(1-2). The mixed solution was stirred for adsorption reaction with reference to an experimental method in which the carrier adsorbs an enzyme. A reacted sample was centrifuged, a supernatant was removed, and after a precipitate was cleaned with the deionized water, the deionized water was added continuously for vortex suspension to prepare a milk white suspension having a concentration of 14-15 g/L, and obtain a nisin nano-composite antibacterial material suspension.

Experimental Example 1 Comparison of Antibacterial Property of Nano-Composite Antibacterial Material (the Adsorbent Concentration of Nisin is 1 g/L)

(20) In order to measure an antibacterial activity of the nisin nano-composite antibacterial material obtained by adsorption of nisin by the metal-organic framework carrier in Embodiment 1, a series of antibacterial tests are carried out:

(21) Bacillus subtilis was selected as a strain for the antibacterial test. The Bacillus subtilis was cultured for overnight in a shake flask first, and a bacteria solution having a concentration of 10.sup.8 CFU/mL was selected as a seed solution for later use. Multiple 100 mL triangular flasks provided with 30 mL of LB liquid medium were taken, and sterilized for 20 min at 121° C. The triangular flasks were divided into four groups, three triangular flasks in each group for parallel test. 1 mL of suspension of the carrier adsorbed with nisin, 1 mL of empty carrier suspension, 1 mL of nisin solution and 1 mL of sterilized ultrapure water were added respectively to each group.

(22) The Bacillus subtilis solution having the concentration of 10.sup.8 CFU/mL was inoculated to the above four groups as per an inoculum size of 2% (v/v), and respectively cultured for 4 h, 8 h, 12 h, 24 h and 28 h on a shaker, where a culture condition was 37° C. and 180 r/min. Then, a sample at every timing was taken, and a viable count in each shake flask was measured via a dilution spread plate method to embody the antibacterial activity.

(23) The experiment was divided into four groups.

(24) No-treatment Control group: 1 mL of sterilized ultrapure water and bacteria solution were added to an LB liquid culture medium, an initial pH value of the culture medium after the addition being 6.85.

(25) Control group 1: 1 mL of metal-organic framework carrier obtained in step (2) of Embodiment 1 was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.08.

(26) Control group 2: 1 mL of nisin solution having a concentration of 1 g/L was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 6.80.

(27) Experimental group: 1 mL of nano-composite antibacterial material suspension prepared in Embodiment 1 of the present invention was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.16.

(28) TABLE-US-00001 TABLE 1 Comparison of antibacterial property of nano-composite antibacterial material (the added concentration of nisin was 1 g/L) Antibacterial agent Control group 1 Experimental group No-treatment Metal-organic Control group 2 Nano-composite Control group framework Nisin material Colony pH value of Colony pH value of Colony pH value of Colony pH value of Culture count bacteria count bacteria count bacteria count bacteria time (h) (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution 4

(29) Measured results show that when the concentration of viable bacteria in the shake flask is higher, the antibacterial effect is poorer. When the concentration of viable bacteria in the shake flask is lower, it is indicated that the antibacterial effect of the antibacterial agent is better. As can be seen from data, the concentration of viable bacteria in the shake flask added with the nisin at 4 h in culture reaches to 10.sup.4 CFU/mL or more, that in the shake flask added with the nano-composite material is 10.sup.3 CFU/mL, that in the shake flask added with the empty carrier is 10.sup.5 CFU/mL, and the No-treatment Control group is up to a level of 10.sup.7 CFU/mL. Therefore, it can be seen that the nano-composite material has a better antibacterial effect than other antibacterial agents. At 8-12 h in culture, a content of bacteria in the shake flask added with the nisin reaches to 10.sup.7 CFU/mL or more, which indicates that the nisin has lost bacteriostatic action at 8 h. However, the concentration of bacteria in the flasks added with the nano-composite material and the empty carrier are respectively keeps at 10.sup.3 CFU/mL and 10.sup.5 CFU/mL, which indicates that the nano-composite material still has a high antibacterial activity. At 24-28 h, the concentration of bacteria in the shake flask added with the empty carrier is up to 10.sup.8 CFU/mL or more, and similar to the colony count of the No-treatment Control group, which indicates that the empty carrier has basically lost an antibacterial characteristic at this time. However, the concentration of bacteria after the nano-composite material is added still keeps at 10.sup.3 CFU/mL, which indicates that the nano-composite material still has the high antibacterial activity at 28 h, excellent antibacterial property to the Bacillus subtilis and a slow-release effect to the nisin, and may keep a long-acting antibacterial function of the nisin.

Experimental Example 2 Comparison of Antibacterial Property of Nano-Composite Antibacterial Material (the Adsorbent Concentration of Nisin is 10 g/L)

(30) In order to measure an antibacterial activity of the metal-organic framework carrier adsorbing nisin nano-composite antibacterial material in Embodiment 2, a series of antibacterial tests are carried out:

(31) Bacillus subtilis was selected as a strain for the antibacterial test. The Bacillus subtilis was cultured for overnight in a shake flask first, and a bacteria solution having a concentration of 10.sup.8 CFU/mL was selected as a seed solution for later use. Multiple 100 mL triangular flasks provided with 30 mL of LB liquid medium were taken, and sterilized for 20 min at 121° C. The triangular flasks were divided into four groups, three triangular flasks in each group for parallel test. 1 mL of suspension of the carrier adsorbed with nisin, 1 mL of empty carrier suspension, 1 mL of nisin solution and 1 mL of sterilized ultrapure water were added respectively to each group.

(32) The Bacillus subtilis solution having the concentration of 10.sup.8 CFU/mL was inoculated to the above four groups as per an inoculum size of 2% (v/v), and respectively cultured for 4 h, 8 h, 12 h, 24 h and 28 h on a shaker, where a culture condition was 37° C. and 180 r/min, for sampling. Then, a sample was taken, and a viable count in each shake flask at every moment was measured via a dilution spread plate method to embody the antibacterial activity.

(33) The experiment was divided into four groups.

(34) No-treatment Control group: same as the No-treatment Control group in the experimental example 1

(35) Control group 1: 1 mL of metal-organic framework carrier obtained in the step (2) of Embodiment 2 was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.04.

(36) Control group 2: 1 mL of nisin solution having a concentration of 10 g/L was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 6.82.

(37) Experimental group: 1 mL of nano-composite antibacterial material suspension prepared in Embodiment 2 of the present invention was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.14.

(38) The experimental data are as follows:

(39) TABLE-US-00002 TABLE 2 Comparison of antibacterial property of nano-composite antibacterial material (the added concentration of nisin was 10 g/L) Culture Antibacterial agent time (h) No-treatment Control group 1 Control group 2 Experimental group Control group Metal-organic Nisin Nano-composite framework material Colony pH value of Colony pH value of Colony pH value of Colony pH value of count bacteria count bacteria count bacteria count bacteria (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution

(40) Experimental results show that when the concentration of the nisin is improved to 10 g/L, the antibacterial effect of the nano-composite material is further improved. At 16 h, the antibacterial activity of the nisin having a same concentration has been greatly reduced, and the antibacterial effect of the empty carrier has basically lost. However, the antibacterial activity of the nano-composite antibacterial material is still notable.

Experimental Example 3 Comparison of Antibacterial Property of Nano-Composite Antibacterial Material (the Adsorbent Concentration of Nisin is 30 g/L)

(41) In order to measure an antibacterial activity of the metal-organic framework carrier adsorbing nisin nano-composite antibacterial material in Embodiment 3, a series of antibacterial tests are carried out:

(42) Bacillus subtilis was selected as a strain for the antibacterial test. The Bacillus subtilis was cultured for overnight in a shake flask first, and a bacteria solution having a concentration of 10.sup.8 CFU/mL was selected as a seed solution for later use. Multiple 100 mL triangular flasks provided with 30 mL of LB liquid medium were taken, and sterilized for 20 min at 121° C. The triangular flasks were divided into four groups, three triangular flasks in each group for parallel test. 1 mL of suspension of the carrier adsorbed with nisin, 1 mL of empty carrier suspension, 1 mL of nisin solution and 1 mL of sterilized ultrapure water were added respectively to each group.

(43) The Bacillus subtilis solution having the concentration of 10.sup.8 CFU/mL was inoculated to the above four groups as per an inoculum size of 2% (v/v), and respectively cultured for 4 h, 8 h, 12 h, 24 h and 28 h on a shaker, where a culture condition was 37° C. and 180 r/min, for sampling. Then, a sample was taken, and a viable count in each shake flask at every moment was measured via a dilution spread plate method to embody the antibacterial activity.

(44) The experiment was divided into four groups.

(45) No-treatment Control group: same as the No-treatment Control group in the experimental example 1

(46) Control group 1: 1 mL of metal-organic framework carrier obtained in the step (2) of Embodiment 3 was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.01.

(47) Control group 2: 1 mL of nisin solution having a concentration of 30 g/L was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 6.79.

(48) Experimental group: 1 mL of nano-composite antibacterial material suspension prepared in Embodiment 3 of the present invention was added to an LB liquid culture medium, and a bacteria solution was added, an initial pH value of the culture medium after the addition being 7.15.

(49) The experimental data are as follows:

(50) TABLE-US-00003 TABLE 3 Comparison of antibacterial property of nano-composite antibacterial material (the added concentration of nisin was 30 g/L) Culture Antibacterial agent time (h) No-treatment Control group 1 Control group 2 Experimental group Control group Metal-organic Nisin Nano-composite framework material Colony pH value of Colony pH value of Colony pH value of Colony pH value of count bacteria count bacteria count bacteria count bacteria (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution (CFU/mL) solution

(51) Experimental results show that when the absorbent concentration of the nisin is improved to 30 g/L, the viable count in previous 12 h is further reduced, and the antibacterial activity of the nisin nano-composite antibacterial material prepared in the present invention is further improved.

(52) It is to be noted that the nisin nano-composite antibacterial material prepared in Embodiment 4 of the present invention has a similar technical effect with Embodiment 3 in antibacterial property.

Experimental Example 4 Measurement of Thermostability of Nano-Composite Material

(53) In order to measure the thermostability of the nano-composite material prepared in the present invention under a neutral condition, the material is subjected to heat treatment under the neutral condition, to measure antibacterial property.

(54) The following groups were provided: experimental group 1: nano-composite material prepared via steps (1), (2) and (3) of Embodiment 2.

(55) Experimental group 2: nano-composite material prepared via steps (1), (3) and (3) of Embodiment 3.

(56) Control group 1: empty carrier prepared via step (2) of Embodiment 2.

(57) Control group 2: empty carrier prepared via step (2) of Embodiment 3.

(58) Control group 3: nisin prepared via step (1) of Embodiment 2 (having a concentration of 10 g/L)

(59) Control group 4: nisin prepared via step (1) of Embodiment 3 (having a concentration of 30 g/L)

(60) The pH value of each material in the above groups was regulated to 7 with HCl and subjected to the heat treatment at 60° C. for 30 min; and with the use of an antibacterial circle experimental method, the antibacterial effect was determined according to a diameter of an antibacterial circle.

(61) Bacillus subtilis was cultured for overnight in a shake flask, and a bacteria solution having a concentration of 10.sup.8 CFU/mL was selected as a seed solution for later use. The seed solution was inoculated as per 2% of inoculum size to an LB semi-solid culture medium sterilized at about 50° C. under a sterile condition, and mixed quickly and uniformly to pour into a culture dish, 20 mL being poured into each culture dish. Upon solidification, three holes were punched on the culture dish by a puncher, and different antibacterial samples were respectively added to each hole, an added amount of each group being 150 μL. Upon the completion, each culture dish was placed into a constant temperature incubator at 37° C., and cultured for 16 h to observe and measure a size of the antibacterial circle. FIG. 1 shows the picture of an experiment result of an antibacterial circle method.

(62) TABLE-US-00004 TABLE 4 Diameter of antibacterial circle for measurement of thermostability of nano-composite antibacterial material (Unit: mm) Antibacterial Antibacterial Antibacterial Group circle (mm) Group circle (mm) Group circle (mm) Experi - Control Control mental group 1 group 3 group 1 Experi- Control Control mental group 2 group 4 group 2

(63) It can be seen from the antibacterial experiment that the composite material prepared in the present invention has notable thermostability. Compared with free nisin that is easily inactivated with high-temperature treatment under the neutral condition, by treating the nisin with the method of the present invention to prepare the nano-composite material or a composite biological preservative, the stability under neutral and alkaline conditions may be improved (experimental groups 1, 2). Although the empty carrier in the control groups 1, 2 also has the antibacterial property, it can also be seen that the experimental groups 1, 2 are obviously higher than the control groups 1, 2 in antibacterial property.

(64) It is to be noted that the nisin nano-composite antibacterial material prepared in Embodiment 4 of the present invention has a similar technical effect with Embodiment 3 (experimental group 2) in antibacterial property.

Experimental Example 5 Influence of Zinc Nitrate on Carrier Form

(65) The form of the metal-organic framework carrier has an important influence on an adsorbing capacity of the nisin, and the concentration of the zinc nitrate has a certain influence on a carrier form. Hence, the following groups were provided:

(66) Experimental group 1: 0.4 mol/L zinc nitrate solution.

(67) Experimental group 2: 0.7 mol/L zinc nitrate solution.

(68) The specific preparation method is as follows:

(69) 10 mL of 1.0 mol/L dimethylimidazole solution was respectively added to conical flasks, the conical flasks were placed onto a magnetic stirrer, then 1 mL of deionized water was added, 1 mL of 0.4 mol/L zinc nitrate solution and 1 mL of 0.7 mol/L zinc nitrate solution were added respectively. The mixed solution reacted at 20-30° C., was stirred for 30 min and was centrifuged. A supernatant was removed, and the deionized water was used for cleaning to obtain two metal-organic framework carriers. Referring to FIG. 2, the picture a is a photo of the metal-organic framework carrier, prepared with the 0.4 mol/L zinc nitrate solution, under a scanning electron microscope, and the picture b is a photo of the metal-organic framework carrier, prepared with the 0.7 mol/L zinc nitrate solution, under the scanning electron microscope. The amplification factor is 13000 times.

(70) As can be seen from the figure, particle sizes of the two carriers are basically the same and are about 1 μm. For the experimental group 1, the metal-organic framework carrier prepared with the zinc nitrate solution having the concentration of 0.4 mol/L is of a square shape, has a plump form and a large specific surface area, may adsorb more nisin under the condition of a same concentration, and has an adsorbing capacity superior to the experimental group 2. For the experimental group 2, the metal-organic framework carrier prepared with the zinc nitrate solution having the concentration of 0.7 mol/L is of a cruciate flower shape and a slightly small specific surface area but may also adsorb the nisin.

(71) The above are only preferred embodiments of the present invention. It should be pointed out that the person of ordinary skill in the art may further make multiple improvements and modifications without departing from the principle of the present invention, and those improvements and modifications are also should be considered as the protection scope of the present invention.