Green synthesis method of antibacterial super-porous hydrogel, product of antibacterial super-porous hydrogel and application of antibacterial super-porous hydrogel to degradation of various pollutants in wastewater treatment

Abstract

Disclosed are a green synthesis method of an antibacterial super-porous hydrogel, a product of the antibacterial super-porous hydrogel and an application of the antibacterial super-porous hydrogel to degradation of various pollutants in wastewater treatment. The super-porous hydrogel based on poly (ionic liquid) is prepared by copolymerization of an imidazole type ionic liquid with double bonds and polyethylene glycol diacrylate (PEGDA) as a cross-linker. In the reaction system, water is a good solvent for the monomer ionic liquid and PEGDA, but a poor solvent for the poly (ionic liquid); when an initial concentration of the ionic liquid is higher than 25%, the phase separation typically proceeds through poly(ionic liquid) formation, interconnected networks with macroporous structure could be obtained by photo-crosslinking.

Claims

1. A green synthesis method of an antibacterial super-porous hydrogel with rapid adsorption and separation of anionic dyes and heavy metal ions, wherein a pore size of the hydrogel is adjustable from 50 m to 200 m, and the method comprises the following steps of: step (1): adding an imidazole ionic liquid and polyethylene glycol diacrylate into deionized water, and magnetically stirring the mixture for a certain time to obtain a uniform solution; and adding a photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate into the solution, and magnetically stirring the mixture for a certain time in the dark until the mixture is completely dissolved, wherein a mass ratio of the imidazole ionic liquid to the deionized water is (0.25 to 0.6):1; and a mass ratio of the imidazole ionic liquid to the polyethylene glycol diacrylate is 1 to 100:0.1 to 10; the imidazole ionic liquid is a vinyl imidazole salt ionic liquid, with a molecular structural formula as follows: ##STR00004## wherein X is one of Cl.sup.?, Br.sup.?, PF.sub.6.sup.?, BF.sub.4.sup.? and CH.sub.3COO.sup.?, and n=2 to 12; step (2): pouring the solution obtained in the step (1) into a mold, and irradiating for a period of time under an ultraviolet lamp with a certain power to initiate polymerization to obtain a poly (ionic liquid)hydrogel; and step (3): soaking the poly (ionic liquid)hydrogel obtained in the step (2) in the deionized water to dialyze for a certain time, and removing an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel; and then freeze-drying the hydrogel at a certain temperature for a certain time to obtain the poly (ionic liquid) super-porous hydrogel.

2. The method according to claim 1, wherein an anion in the imidazole ionic liquid in the step (1) comprises a chloride ion, a tetrafluoroborate ion and a hexafluorophosphate ion.

3. The method according to claim 1, wherein a mass ratio of the imidazole ionic liquid to the photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate in the step (1) is 1 to 100:0.01 to 1.

4. The method according to claim 1, wherein in the step (2), the power of the ultraviolet lamp is 20 W to 200 W, and the irradiating lasts for 1 minute to 200 minutes.

5. The method according to claim 1, wherein in the step (3), the soaking to dialyze lasts for 1 hour to 72 hours, the freeze-drying is carried out at a temperature of ?120? C. to ?60? C., and the freeze-drying lasts for 8 hours to 96 hours.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of preparation of a super-porous hydrogel.

(2) FIG. 2 is an infrared characterization spectrogram of a poly (ionic liquid) super-porous hydrogel (PIL), 1-vinyl-3-butylimidazolium chloride (IL) and polyethylene glycol diacrylate (PEGDA).

(3) FIG. 3A shows a microtopography (SEM image) of the PIL when an initial concentration of the IL is 50% and amounts of the PEGDA are 0.5 g.

(4) FIG. 3B shows a microtopography (SEM image) of the PIL when an initial concentration of the IL is 50% and amounts of the PEGDA are 1 g.

(5) FIG. 3C shows a microtopography (SEM image) of the PIL when an initial concentration of the IL is 50% and amounts of the PEGDA are 0.25 g.

(6) FIG. 3D shows a microtopography (SEM image) of the PIL when the initial concentration of the IL is 10% and the amount of the PEGDA is 0.5 g.

(7) FIG. 4A shows adsorption capacity-time curves for acid orange 7 solutions with different initial concentrations of the PIL.

(8) FIG. 4B shows adsorption capacity-time curves for Cr (VI) solutions with different initial concentrations of the PIL.

(9) FIG. 5A shows fitting results of pseudo-second order adsorption kinetic models for the acid orange 7 solutions with different initial concentrations of the PIL.

(10) FIG. 5B shows fitting results of pseudo-second order adsorption kinetic models for the Cr (VI) solutions with different initial concentrations of the PIL.

(11) FIG. 6A shows adsorption capacities for the acid orange 7 solutions with different pH values of the PIL.

(12) FIG. 6B shows adsorption capacities for the Cr (VI) solutions with different pH values of the PIL.

(13) FIG. 7 shows adsorption capacity-time curves for the acid orange 7 solutions at different temperatures of the PIL.

(14) FIG. 8A shows antibacterial tests (by a plate method) for S. aureus and E. coli of the PIL.

(15) FIG. 8B shows antibacterial tests colony numbers for S. aureus and E. coli of the PIL.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(16) As mentioned above, in view of the defects in the prior art, the inventor of this case put forward the technical solution of the present invention through long-term research and a lot of practice mainly based on at least the followings. (1) Water used in the present invention is a good solvent for the monomer ionic liquid and the PEGDA and a poor solvent for the poly (ionic liquid); phase separation are gradually carried out on a monomer phase rich in the poly (ionic liquid) and water by controlling an initial concentration of the ionic liquid, and a water phase in a hydrogel three-dimensional network structure formed by the poly (ionic liquid) and PEGDA occupies a relatively large space (the microphase separation process is beneficial to formation of interpenetrating channels in the hydrogel network structure); and finally, the unreacted monomer ionic liquid, the PEGDA and the initiator are removed by adopting a pure water dialysis method, and then moisture in the hydrogel is removed by adopting a freeze-drying method to finally obtain the macroporous or super-macroporous hydrogel. (2) According to the present invention, the hydrogel may remove various anionic dyes in sewage through electrostatic adsorption by utilizing the characteristic that an imidazole ring of the monomer ionic liquid carries positive charges; the hydrogel may remove various heavy metal ions in sewage through chelation by utilizing the characteristic that the imidazole ring of the monomer ionic liquid carries N atoms of lone pair electrons; and the hydrogel may kill some microorganisms in a water body by utilizing an excellent antibacterial ability of the ionic liquid.

(17) To make the objects, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail hereinafter with reference to the drawings and the embodiments. It should be understood that specific embodiments described herein are only used for explaining the present invention and are not intended to limit the present invention. In addition, the technical features involved in the implementations of the present invention described hereinafter may be combined with each other as long as they do not conflict with each other.

(18) In one aspect, the present invention provides a preparation method of an antibacterial super-porous hydrogel, a pore size of the hydrogel is adjustable from 50 ?m to 200 ?m, and with reference to FIG. 1, the method comprises the following steps.

(19) In step (1), an imidazole ionic liquid and polyethylene glycol diacrylate are added into deionized water, and magnetically stirred for a certain time to obtain a uniform solution; and a photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate is added into the solution, and magnetically stirred for a certain time in the dark until the mixture is completely dissolved, wherein a mass ratio of the imidazole ionic liquid to the deionized water is (0.25 to 0.6):1; and a mass ratio of the imidazole ionic liquid to the polyethylene glycol diacrylate is 1 to 100:0.1 to 10.

(20) In step (2), the solution obtained in the step (1) is poured into a mold, and irradiated for a period of time under an ultraviolet lamp with a certain power to initiate polymerization to obtain a poly (ionic liquid) gel.

(21) A reaction equation of IL and PEGDA is as follows:

(22) ##STR00002##

(23) In step (3), the poly (ionic liquid)hydrogel obtained in the step (2) is soaked in the deionized water to dialyze for a certain time, and an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel are removed; and then the hydrogel is freeze-dried at a certain temperature for a certain time to obtain the poly (ionic liquid) super-porous hydrogel.

(24) Preferably, the imidazole ionic liquid in the step (1) is an imidazole group-containing vinyl imidazole salt ionic liquid with different alkyl chain lengths and anionic species, with a molecular formula as follows:

(25) ##STR00003## wherein X is one of Cl.sup.?, Br.sup.?, PF.sub.6.sup.?, BF.sub.4.sup.? and CH.sub.3COO.sup.?, and n=2 to 12.

(26) Preferably, an anion in the imidazole ionic liquid in the step (1) comprises, but is not limited to, a chloride ion, a tetrafluoroborate ion and a hexafluorophosphate ion.

(27) Preferably, a molecular weight of the polyethylene glycol diacrylate in the step (1) is 200 to 10,000.

(28) Preferably, a mass ratio of the imidazole ionic liquid to the photoinitiator lithium phenyl (2,4,6-trimethylbenzoyl)phosphinate in the step (1) is 1 to 100:0.01 to 1.

(29) Preferably, in the step (2), the power of the ultraviolet lamp is 20 W to 200 W, and the irradiating lasts for 1 minute to 200 minutes.

(30) Preferably, in the step (3), the soaking to dialyze lasts for 1 hour to 72 hours, the freeze-drying is carried out at a temperature of ?120? C. to ?60? C., and the freeze-drying lasts for 8 hours to 96 hours.

(31) In another aspect, the present invention further provides an application of the antibacterial super-porous hydrogel in wastewater treatment.

(32) Preferably, the above antibacterial super-porous hydrogel is applied to the degradation of anionic dyes and heavy metal ions in wastewater.

(33) FIG. 2 is an infrared characterization spectrogram of a poly (ionic liquid) super-porous hydrogel (PIL), 1-vinyl-3-butylimidazolium chloride (IL) and polyethylene glycol diacrylate (PEGDA).

(34) The technical solution of the present invention is further explained with reference to several preferred embodiments, but the experimental conditions and set parameters should not be regarded as limitations to the basic technical solution of the present invention. Moreover, the scope of protection of the present invention is not limited to the following embodiments.

Comparative Example: Poly (Ionic Liquid) Super-Porous Hydrogel (10% Initial Concentration of Ionic Liquid)

(35) (1) 5 g of 1-vinyl-3-butylimidazolium chloride and 0.5 g of polyethylene glycol diacrylate (with a molecular weight of 600) are added into 50 mL of deionized water, and magnetically stirred for a certain time to obtain a uniform solution (10% initial concentration of ionic liquid); and 0.05 g of photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate is added into the solution, and magnetically stirred for a certain time in the dark until the mixture is completely dissolved.

(36) (2) The solution finally obtained in the step (1) is poured into a mold, and irradiated for 100 minutes under an ultraviolet lamp with a power of 100 W to initiate polymerization to obtain a poly (ionic liquid)hydrogel.

(37) (3) The hydrogel obtained in the step (2) is soaked in the deionized water to dialyze for 12 hours, and an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel are removed. Then, the hydrogel is freeze-dried at ?100? C. for 48 hours to obtain the poly (ionic liquid)hydrogel.

(38) The poly (ionic liquid)hydrogel obtained in the step (3) is detected by a scanning electron microscope, and obtained results are shown in FIG. 3D.

(39) As shown in FIG. 3D, when the initial concentration of the IL is not in the range of 25% to 60%, it is difficult for the ionic liquid monomer to separate from water so as to be difficult to form a stable super-large porous structure after freeze-drying, which is not beneficial to the application in the treatment of anionic dyes and heavy metal ions in sewage.

Embodiment 1: Poly (Ionic Liquid) Super-Porous Hydrogel (50% Initial Concentration of Ionic Liquid)

(40) (1) 5 g of 1-vinyl-3-butylimidazolium chloride and 0.5 g of polyethylene glycol diacrylate (with a molecular weight of 600) were added into 10 mL of deionized water, and magnetically stirred for a certain time to obtain a uniform solution. 0.05 g of photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate was added into the solution, and magnetically stirred for a certain time in the dark until the mixture was completely dissolved.

(41) (2) The solution finally obtained in the step (1) was poured into a mold, and irradiated for 100 minutes under an ultraviolet lamp with a power of 100 W to initiate polymerization to obtain a poly (ionic liquid)hydrogel.

(42) (3) The hydrogel obtained in the step (2) was soaked in the deionized water to dialyze for 12 hours, and an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel were removed. Then, the hydrogel was freeze-dried at ?100? C. for 48 hours to obtain the poly (ionic liquid) super-porous hydrogel.

(43) The poly (ionic liquid) super-porous hydrogel obtained in the step (3) was characterized by an infrared spectrum, and obtained results were shown in FIG. 1.

(44) The poly (ionic liquid) super-porous hydrogel obtained in the step (3) was detected by a scanning electron microscope, and obtained results were shown in FIG. 3A.

Embodiment 2: Poly (Ionic Liquid) Super-Porous Hydrogel (50% Initial Concentration of Ionic Liquid)

(45) (1) 5 g of 1-vinyl-3-butylimidazolium chloride and 1 g of polyethylene glycol diacrylate (with a molecular weight of 600) were added into 10 mL of deionized water, and magnetically stirred for a certain time to obtain a uniform solution. 0.05 g of photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate was added into the solution, and magnetically stirred for a certain time in the dark until the mixture was completely dissolved.

(46) (2) The solution finally obtained in the step (1) was poured into a mold, and irradiated for 100 minutes under an ultraviolet lamp with a power of 100 W to initiate polymerization to obtain a poly (ionic liquid)hydrogel.

(47) (3) The hydrogel obtained in the step (2) was soaked in the deionized water to dialyze for 12 hours, and an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel were removed. Then, the hydrogel was freeze-dried at ?100? C. for 48 hours to obtain the poly (ionic liquid) super-porous hydrogel.

(48) The poly (ionic liquid) super-porous hydrogel obtained in the step (3) was detected by a scanning electron microscope, and obtained results were shown in FIG. 3B.

Embodiment 3: Poly (Ionic Liquid) Super-Porous Hydrogel (50% Initial Concentration of Ionic Liquid)

(49) (1) 5 g of 1-vinyl-3-butylimidazolium chloride and 0.25 g of polyethylene glycol diacrylate (with a molecular weight of 600) were added into 10 mL of deionized water, and magnetically stirred for a certain time to obtain a uniform solution. 0.05 g of photoinitiator lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate was added into the solution, and magnetically stirred for a certain time in the dark until the mixture was completely dissolved.

(50) (2) The solution finally obtained in the step (1) was poured into a mold, and irradiated for 100 minutes under an ultraviolet lamp with a power of 100 W to initiate polymerization to obtain a poly (ionic liquid)hydrogel.

(51) (3) The hydrogel obtained in the step (2) was soaked in the deionized water to dialyze for 12 hours, and an unreacted poly (ionic liquid) monomer and a poly (ionic liquid) homopolymer in the hydrogel were removed. Then, the hydrogel was freeze-dried at ?100? C. for 48 hours to obtain the poly (ionic liquid) super-porous hydrogel.

(52) The poly (ionic liquid) super-porous hydrogel obtained in the step (3) was detected by a scanning electron microscope, and obtained results were shown in FIG. 3C.

Application Embodiment 1: Investigation on Adsorption Capacity of Anionic Dye (Acid Orange 7) in Water

(53) (1) 50 mL of standard solutions of anionic dyes of acid orange 7 with different concentrations of 5 mg/L, 10 mg/L, 15 mg/L, 25 mg/L, 35 mg/L, 45 mg/L and 55 mg/L were prepared respectively. Absorbances of the standard solutions were determined by ultraviolet spectrophotometry, and a standard curve of an acid orange 7 solution was drawn by taking a concentration of the acid orange 7 solution as an abscissa and an absorbance as an ordinate.

(54) (2) 10 mg of the poly (ionic liquid) super-porous hydrogel obtained in Embodiment 1 was put into 50 mL of solutions of anionic dyes of acid orange 7 with concentrations of 10 mg/L, 25 mg/L, 50 mg/L, 75 mg/L, 100 mg/L and 150 mg/L respectively, and placed in a constant temperature water bath shaker for shaking and adsorption at room temperature.

(55) (3) 10 mg of the poly (ionic liquid) super-porous hydrogel obtained in Embodiment 1 was put into 50 mL of acid orange 7 solutions with pH values L; of 2, 4, 6, 8, 10 and 12 respectively, and placed in a constant temperature water bath shaker for shaking and adsorption at room temperature.

(56) (4) 10 mg of the poly (ionic liquid) super-porous hydrogel obtained in Embodiment 1 was put into 50 mL of acid orange 7 solutions with a concentration of 500 mg/L respectively, and placed in a constant temperature water bath shaker for shaking and adsorption at 30? C., 40? C., 50? C. and 60? C. respectively.

(57) (5) The acid orange 7 solution was periodically sucked during shaking in the steps (2), (3) and (4), the absorbance was determined by ultraviolet spectrophotometry, and the concentration of the acid orange 7 in the solution at a moment of solution extraction was calculated by a standard curve, so as to calculate the adsorption capacity for the anionic dye of the acid orange 7 of the polyanionic liquid super-porous hydrogel.

(58) As shown in FIG. 4A, with the increase of the initial concentration of the acid orange 7 solution, the adsorption capacity for the acid orange 7 in the solution of the polyanionic liquid super-porous hydrogel was also increased, wherein a maximum adsorption capacity could reach 724 mg/g at the initial concentration of 150 mg/L, and balance adsorption was approximately reached after 24 hours.

(59) As shown in Table 1, with the increase of the initial concentration of the acid orange 7 solution, the removal rate for the acid orange 7 in the solution of the polyanionic liquid super-porous hydrogel was also increased, wherein the removal rate for the acid orange 7 in the solution could reach 96.56% at the initial concentration of 150 mg/L.

(60) Table 1 Removal rate for acid orange 7 in solution of poly (ionic liquid) super-porous hydrogel

(61) TABLE-US-00001 C.sub.0 (AO7) (mg/L) 10 25 50 75 100 150 Removal rate (%) 70.52 51. 37 94.84 93.26 94.87 96.56

(62) As shown in FIG. 5A and Table 2, an adsorption process for a dye in the acid orange 7 solution of the polyanionic liquid super-porous hydrogel conformed to a pseudo-second order kinetic model, and values of linear fitting correlation coefficients R.sup.2 of the pseudo-second order kinetic models were all higher than 0.997. In the pseudo-second order kinetic model, the adsorption rate was determined by a squared value of remaining adsorption sites on a surface of an adsorbent, the adsorption process was controlled by a chemical adsorption mechanism, and the chemical adsorption related to electron sharing or electron transfer between the adsorbent and an adsorbate. A rate constant k.sub.2 was reduced with the increase of the initial concentration, because effective adsorption sites of the adsorbent were far more than dye molecules of the acid orange 7 at a low initial concentration, and the dye molecules of the acid orange 7 were easily adsorbed. However, with the increase of the initial concentration, the dye molecules of the acid orange 7 were increased, and formed a competitive relationship with each other, resulting in the reduction of the rate constant k.sub.2.

(63) Table 2 Adsorption kinetic parameter for acid orange 7 in solution of poly (ionic liquid) super-porous hydrogel

(64) TABLE-US-00002 Pseudo-second-order C.sub.0 q.sub.e, exp k.sub.2 (g .Math. mg.sup.?1 .Math. q.sub.e, cal (mg/L) (mg/g) min.sup.?1) (mg/g) R.sup.2 10 35.26 4.25 ? 10.sup.?4 35.06 0.99801 25 64.21 3.16 ? 10.sup.?4 63.69 0.99832 50 237.10 2.46 ? 10.sup.?4 237.53 0.99987 75 349.74 2.30 ? 10.sup.?5 358.42 0.99861 100 474.37 1.22 ? 10.sup.?5 495.05 0.99707 150 724. 22 7.73 ? 10.sup.?6 751. 88 0.99727

(65) FIG. 6A shows the adsorption capacities for the acid orange 7 solutions with different pH values of the PIL, and it can be seen that the PIL has the greatest adsorption capacity when pH=4 to 8.

(66) FIG. 7 shows adsorption capacity-time curves for the acid orange 7 solutions at different temperatures of the PIL.

Application Embodiment 2: Investigation on Adsorption Capacity of Heavy Metal Ion Cr(VI) in Water

(67) (1) A Cr(VI) solution with a concentration of 1,000 mg/L was prepared, and a pH value of the solution was adjusted by dropwise adding HNO.sub.3 and NaOH. 10 mg of the poly (ionic liquid) super-porous hydrogel obtained in Embodiment 1 was put into 50 mL of Cr(VI) solutions with pH values of 2, 4, 6, 8, 10 and 12 respectively, and placed in a constant temperature water bath shaker for shaking and adsorption at room temperature.

(68) (2) 10 mg of the poly (ionic liquid) super-porous hydrogel obtained in Embodiment 1 was put into 50 mL of Cr(VI) solutions with concentrations of 25 mg/L, 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L and 300 mg/L respectively, and placed in a constant temperature water bath shaker for shaking and adsorption at room temperature.

(69) (3) The Cr(VI) solution was periodically sucked during shaking in the steps (1) and (2), and the concentration of the Cr(VI) in the solution at a moment of solution extraction was determined by an atomic absorption spectrophotometer, so as to calculate the adsorption capacity for the Cr(VI) of the polyanionic liquid super-porous hydrogel.

(70) As shown in FIG. 4B, with the increase of the initial concentration of the Cr(VI) solution, the adsorption capacity for the Cr(VI) in the solution of the polyanionic liquid super-porous hydrogel was also increased, wherein a maximum adsorption capacity could reach 550 mg/g at the initial concentration of 100 mg/L, and balance adsorption was approximately reached after 24 hours.

(71) FIG. 5B shows fitting results of pseudo-second order adsorption kinetic models for the Cr(VI) solutions with different initial concentrations of the PIL.

(72) FIG. 6B shows adsorption capacities for the Cr(VI) with different pH values of the PIL.

Application Embodiment 3: Investigation on Antibacterial Ability of PIL

(73) (1) 10 ?L of bacterial suspension (1?10.sup.8 CFU/mL) was diluted in a LB culture medium (400 ?L), then the bacterial diluent was transferred to a LB agar plate, and the plate was obliquely shaken to make the bacterial liquid flow over a surface of the whole plate, and horizontally stood for 30 seconds. Then, the plate was obliquely placed for 30 seconds, and excess bacterial liquid was sucked out by a pipette. Then, the plate was horizontally placed for 2 minutes, and then transferred to an incubator for inverted cultivation at 37? C. for 12 hours.

(74) (2) The PIL hydrogel obtained in Embodiment 1 was cut into discs with a diameter of 1 cm, placed in different positions on the bacterial plate, and cultured in a constant temperature incubator for 24 hours.

(75) (3) Subsequently, the PIL hydrogel and the LB solid culture medium covered with the PIL hydrogel were placed in a centrifuge tube filled with the LB culture medium (3 mL), and rapidly shaken at 37? C. for 10 minutes, so that all bacteria adhered to the PIL hydrogel and the LB solid culture medium were dispersed in the culture medium. A proper amount of bacterial suspension (2 ?L) was diluted in the LB culture medium (400 ?L) for dilution. The bacterial diluent was transferred to a LB agar plate, and the plate was obliquely shaken to make the bacterial liquid flow over a surface of the whole plate, and horizontally stood for 30 seconds. Then, the plate was obliquely placed for 30 seconds, and excess bacterial liquid was sucked out by a pipette. Then, the plate was horizontally placed for 2 minutes, and then transferred to an incubator for inverted cultivation at 37? C. for 12 hours, and a colony density was observed.

(76) FIG. 8A shows antibacterial tests (by a plate method) for S. aureus and E. coli of the PIL.

(77) FIG. 8B shows antibacterial tests colony numbers for S. aureus and E. coli of the PIL.

(78) The above embodiments are not intended to restrict the present invention, the present invention is not merely limited to the above embodiments, and so long as it meets the requirements of the present invention, it belongs to the scope of protection of the present invention.