CN113559262A - Photodynamic nano antibacterial material and preparation method and application thereof - Google Patents
Photodynamic nano antibacterial material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a photodynamic nano antibacterial material and a preparation method and application thereof, wherein the photodynamic nano antibacterial material is prepared byChemical functionalization of MoS on chitosan2And loading a photosensitive material on the substrate. The invention is prepared by mixing chitosan and MoS2After covalent bonding, the photosensitizer Ce6 is physically adsorbed to the surface of M-CS, and the prepared photodynamic nano antibacterial material shows broad-spectrum and high-efficiency antibacterial effect and has wide application prospect in the antibacterial field.
Description
Technical Field
The invention relates to the field of nano materials and microorganisms, in particular to a photodynamic nano antibacterial material and a preparation method and application thereof.
Background
Pathogenic bacteria are important problems which are harmful to human life and health, and along with abuse of antibiotics, the bacteria generate drug resistance, the antibacterial efficiency of the medicine is reduced, the pathogenic bacteria infection is aggravated, and a series of harm is caused. The problem of pathogenic bacteria has increased the need for new antimicrobial agents. The nano material has a unique antibacterial mechanism due to the special size effect and chemical reaction sites, is not easy to cause drug resistance, and becomes a research hotspot of a novel antibacterial agent. Wherein molybdenum disulfide (MoS)2) Compared with metal and photocatalytic nano materials, the material has higher specific surface area, higher loading rate and good biocompatibility; compared with graphene, MoS is found in the experiment2Has better antibacterial performance, can cause damage to bacteria by generating active oxygen and oxidized glutathione, and has great application potential in the antibacterial field. However, MoS2The negative charge on the surface can not be combined with bacteria, and the antibacterial effect can not meet the current antibacterial requirement.
To give full play to MoS2The Chitosan (CS) is used as an alkaline polysaccharide which is rare in nature, amino has positive charge, and can be combined with bacteria with negative charge through electrostatic interaction to destroy cell wall permeability and promote leakage of intracellular bioactive substances. The research at present finds MoS2The antibacterial composite material is combined with an organic antibacterial material in adsorption modes such as mixing, stirring and the like, although the antibacterial activity is improved to a certain extent, the stability of the composite material cannot be ensured, the contact between the composite material and bacteria is reduced, and the material cannot exert an effective antibacterial effect. In addition, due to the difference of cell structures, chitosan has antibacterial advantages on gram-negative bacteria, but has weak antibacterial performance on gram-positive bacteria with thicker cell walls, and the difference causes that the chitosan cannot meet the broad-spectrum antibacterial requirement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a photodynamic nano antibacterial material and a preparation method and application thereof. The invention relates to a method for preparing chitosanAnd MoS2After covalent bonding, the photosensitizer Ce6 is physically adsorbed to the surface of M-CS, and the prepared photodynamic nano antibacterial material shows broad-spectrum and high-efficiency antibacterial effect and has wide application prospect in the antibacterial field.
The technical scheme of the invention is as follows:
the photodynamic nano antibacterial material is prepared by chemically functionalizing MoS on chitosan2And preparing the upper load photosensitive material.
The preparation method of the photodynamic nano antibacterial material comprises the following steps:
(1) adding mercaptoacetic acid to MoS2Adding chitosan into the dispersion liquid after ultrasonic treatment, and performing ultrasonic treatment again to obtain a colloidal solution;
(2) sequentially adding EDC and NHS, performing ultrasonic treatment and stirring, purifying, centrifuging and drying to obtain M-CS powder, and adding water into the M-CS powder to obtain M-CS dispersion liquid;
(3) and (3) adding the Ce6 solution into the M-CS dispersion liquid prepared in the step (2), performing ultrasonic treatment, stirring, centrifuging, and drying to obtain the M-CS-Ce6 photodynamic nano antibacterial material.
Further, in the step (1), the MoS2The preparation method of the dispersion comprises the following steps: mixing MoS2Adding water, and ultrasonically dispersing at 20-25 ℃ for 4-6 hours to prepare MoS with the mass concentration of 1-2 mg/mL2A dispersion liquid; the mercaptoacetic acid and MoS2The volume ratio of the dispersion liquid is 1: 100-150, the temperature of ultrasonic treatment is 20-25 ℃, and the time is 16-24 hours.
Further, in the step (1), the chitosan and MoS are mixed2The mass ratio of (A) to (B) is 1-2: 1; the temperature of the secondary ultrasonic treatment is 20-25 ℃, and the time is 10-20 min.
Further, in step (2), the EDC, NHS and MoS2The mass ratio of (A) to (B) is 2-3:1-1.5: 1; the purity of the EDC is 98-99%; the purity of the NHS is 98-99%.
Further, in the step (2), the temperature of the ultrasonic wave is 20-25 ℃, and the time is 10-15 min; the stirring speed is 600-800 rpm, and the stirring time is 40-60 min.
Further, in the step (2), the specific method for purifying is as follows: using a dialysis bag with 8-14 KDa, adding 1 multiplied by 103～1.5×103Dialyzing with 5-10 mM acetic acid in mL for 1-2 days, and adding 1 × 103～1.5×103Dialyzing with mL ultrapure water for 1-2 days; the speed of the centrifugation is 1 x 104～1.2×104rpm for 15-30 min; the drying is vacuum freeze drying, the temperature is-60 to-70 ℃, and the time is 24 to 48 hours; the mass concentration of the M-CS dispersion liquid is 0.8-1.2 mg/mL.
Further, in the step (3), the mass concentration of Ce6 in the Ce6 solution is 1.8-2.5 mg/mL, and the volume ratio of the Ce6 solution to the M-CS dispersion liquid is 0.4-0.8: 1; the temperature of the ultrasonic wave is 20-25 ℃, and the time is 10-30 min; the stirring speed is 600-800 rpm, and the time is 16-24 hours; the speed of centrifugation is 1-1.2 x 104rpm for 15-30 min; the drying is vacuum freeze drying, the temperature is-60 to-70 ℃, and the time is 24 to 48 hours.
The application of the photodynamic nano antibacterial material is characterized in that the photodynamic nano antibacterial material has antibacterial property on one or two of gram-negative bacteria and gram-positive bacteria.
Further, the gram-positive bacteria are one or two of bacillus cereus and listeria monocytogenes; the gram-negative bacteria are Escherichia coli O157: h7, Salmonella typhimurium, and Yersinia enterocolitica.
The beneficial technical effects of the invention are as follows:
(1) the invention firstly mixes chitosan and MoS2And (3) obtaining M-CS through covalent bonding, and then physically adsorbing the photosensitive material Ce6 on the surface of the M-CS to prepare the M-CS-Ce6 photodynamic nano antibacterial material. By means of covalent bond on MoS2Modifying the surface of chitosan to form stable M-CS composite material, and in the antibacterial process, the M-CS is combined with the surface of bacteria in an electrostatic manner to destroy the permeability of cell membranes and intensify MoS2Oxidative stress and damage of the sheet structure to bacteria, and the antibacterial effect of M-CS is enhanced; meanwhile, the photosensitizer Ce is loaded in an adsorption modeCompared with covalent connection, the Ce6 adsorbed on the surface can be dissociated and released, so that the M-CS composite material is exposed and interacts with the surface of bacteria, meanwhile, singlet oxygen generated by the photodynamic effect can damage the bacterial cells in a short distance, the antibacterial performance on pathogenic bacteria is further improved, the broad-spectrum and efficient antibacterial effect is shown, and the antibacterial material has a wide application prospect in the antibacterial field.
(2) MoS is constructed by loading photosensitizer Ce62The ternary composite nano material/CS/Ce 6 (namely M-CS-Ce6 photodynamic nano antibacterial material) has the advantages that on one hand, the M-CS composite material can destroy the cell wall permeation barrier of gram-negative bacteria, and the photosensitizer Ce6 adsorbed on the surface is released into bacteria cells, so that the action distance of active oxygen is shortened, and the oxidative damage to the gram-negative bacteria is aggravated; on the other hand, the gram-positive bacteria cell wall is provided with a porin channel, and the released small molecule Ce6 can diffuse into cells to play an antibacterial effect on gram-positive bacteria with thicker cell walls. Therefore, the M-CS-Ce6 photodynamic nano antibacterial material not only can exert the photodynamic antibacterial advantage on gram-positive bacteria, but also can enhance the permeability of gram-negative bacteria cell walls so as to enhance the antibacterial effect, thereby achieving the broad-spectrum and high-efficiency antibacterial purpose.
(3) MoS in the invention2The antibacterial material has good biocompatibility, the molybdenum element and the sulfur element are important elements of a human body, the chitosan is a natural antibacterial agent, the two are covalently connected and then load Ce6 in a physical adsorption mode, the broad-spectrum antibacterial efficiency is improved through low load, the cells are not toxic, the safe antibacterial target is realized, and the application range of the M-CS-Ce6 photodynamic nano antibacterial material is widened.
Drawings
FIG. 1 is a schematic diagram of a preparation process and photodynamic antibacterial of an M-CS-Ce6 photodynamic nano antibacterial material.
FIG. 2 is a MoS of comparative example 1 of the present invention2Transmission Electron Micrographs (TEM) of the M-CS prepared in comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1.
FIG. 3 is a MoS of comparative example 1 of the present invention2CS of comparative example 2, Ce6 of comparative example 3, M-And an infrared spectrum (FTIR) of the CS and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1.
FIG. 4 is a MoS of comparative example 1 of the present invention2X-ray diffraction patterns (XRD) of CS of comparative example 2, M-CS prepared in comparative example 5, and M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1.
FIG. 5 is MoS of comparative example 12Thermogravimetric plots (TGA) of CS of comparative example 2, Ce6 of comparative example 3, M-CS prepared in comparative example 5, and M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1.
FIG. 6 is MoS of comparative example 12Zeta potential diagrams of CS of comparative example 2, Ce6 of comparative example 3, M-CS of comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material of example 1.
FIG. 7 is MoS of comparative example 12The ultraviolet-visible spectrum (UV-vis) of Ce6 of comparative example 3, M-CS prepared by comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared by example 1.
Fig. 8 is a singlet oxygen detection diagram of the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1 at different irradiation times.
FIG. 9 is MoS of comparative example 12And the antibacterial effect of CS of comparative example 2, Ce6 of comparative example 3, M-CS prepared by comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared by example 1 on Escherichia coli are shown.
In the figure: a. b is a plate image of the colony of Escherichia coli in the absence of light and at 660nm (5, 10, 20. mu.g/mL); c is the corresponding E.coli survival rate map.
FIG. 10 is MoS of comparative example 12The antibacterial effect of CS of comparative example 2, Ce6 of comparative example 3, M-CS prepared by comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared by example 1 on staphylococcus aureus.
In the figure: a. b is a plate image of the colony of Staphylococcus aureus in the absence of light and at 660nm (5, 10, 20. mu.g/mL); and c is a corresponding survival rate graph of the staphylococcus aureus.
Fig. 11 shows the ratio of the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1 to bacillus cereus, listeria monocytogenes, and escherichia coli O157: h7, Salmonella typhimurium, and Yersinia enterocolitis.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
The preparation process of the M-CS-Ce6 photodynamic nano material and the photodynamic antibacterial schematic diagram thereof are shown in figure 1. As can be seen from fig. 1, the preparation process of the photodynamic nano antibacterial material is as follows: firstly, by using a MoS2The surface is conjugated with thioglycolic acid, carboxyl is covalently connected with amino of chitosan, and then Ce6 is loaded in a mixing and stirring mode, namely, the M-CS-Ce6 composite nano material is prepared through two steps of chemical functionalization and physical adsorption, and the prepared composite nano antibacterial material has an antibacterial effect on gram-negative bacteria and gram-positive bacteria under 660nm illumination.
Example 1
An M-CS-Ce6 photodynamic nano antibacterial material is prepared by the following steps:
firstly 50mg MoS2Dispersed in 25mL of ultrapure water, sonicated at 20 ℃ for 6h, and 200. mu.L volume of thioglycolic acid was added to the above MoS2In the dispersion, ultrasonic treatment is carried out for 24 hours at 25 ℃ to realize that sulfydryl is in MoS2And (4) surface modification. 65mg of chitosan was then added to the mixture and sonicated for 20min to form a homogeneous colloidal suspension.
Gradually adding 150mg EDC and 65mg NHS into the mixed solution, performing ultrasonic treatment at 25 deg.C for 15min, stirring at 600rpm at 25 deg.C for 1h to activate carboxyl group for amide reaction,
the reaction mixture was then transferred to dialysis bags (8-14 KDa) and each was treated with 10mM acetic acid (1.5X 10)3mL) for 2 days with ultrapure water (1.5X 10)3mL) for 2 days. Mixing the mixture at 1.2X 104Centrifuging at rpm for 30min, vacuum freeze drying at-60 deg.C for 48h to obtain M-CS powder, adding water, and ultrasonic dispersing to obtain M-CS dispersion solution with concentration of 1 mg/mL.
37.5mg of Ce6 was dissolved in 20mL of dimethyl sulfoxide (DMSO) to prepare a Ce6 solution, and 25mL of M-CS dispersion (1mg/mL) was addedPerforming ultrasonic treatment at 20 deg.C for 30min to mix well, stirring the mixture at 800rpm in dark for 24 hr, and washing with ultrapure water 1.2 × 10 for the next day4Centrifuging at rpm for 30min, and vacuum freeze-drying at-60 deg.C for 48h to obtain M-CS-Ce6 photodynamic nano antibacterial material.
Example 2
The preparation method of the M-CS-Ce6 photodynamic nano material comprises the following steps:
35mg of MoS2Dispersed in 25mL of ultrapure water, sonicated at 25 ℃ for 5h, and 250. mu.L volume of thioglycolic acid was added to the MoS2In the dispersion, ultrasonic treatment is carried out for 20 hours at 20 ℃ to realize that sulfydryl is in MoS2And (4) surface modification. 70mg of chitosan was then added to the mixture and sonicated for 15min to form a homogeneous colloidal suspension.
70mg of EDC and 55mg of NHS were gradually added to the mixture, sonicated at 20 ℃ for 12min, and stirred at 660rpm at 20 ℃ for 50min to activate the carboxyl group for the amide reaction.
The reaction mixture was transferred to dialysis bags (8-14 KDa) and 5mM acetic acid (1.2X 10) was added thereto3mL) for 1.4 days, and ultrapure water (1.2X 10)3mL) was dialyzed for 1.4 days. Mixing the mixture at a ratio of 1.0X 104Centrifuging at rpm for 20min, vacuum freeze drying at-70 deg.C for 32h to obtain M-CS powder, adding water, and ultrasonic dispersing to obtain M-CS dispersion solution with concentration of 1.2 mg/mL.
30mg of Ce6 was dissolved in 15mL of DMSO, 25mL of M-CS dispersion (1.2mg/mL) was added, sonication was performed at 20 ℃ for 25min to mix well, and then the mixture was stirred in the dark at 700rpm for reaction for 18h, washed 3 times with ultrapure water the next day, 1.2X 104Centrifuging at rpm for 25min, and vacuum freeze-drying at-70 deg.C for 48h to obtain M-CS-Ce6 photodynamic nano antibacterial material.
Example 3
The preparation method of the M-CS-Ce6 photodynamic nano material comprises the following steps:
25mg of MoS2Dispersed in 25mL of ultrapure water, sonicated at 22 ℃ for 4h, and a volume of 167. mu.L of thioglycolic acid was added to the above MoS2In the dispersion, carrying out ultrasonic treatment for 16h at 22 ℃ to realize that sulfydryl is in MoS2And (4) surface modification. Then 25mg of chitosan was added to the mixture and sonicated for 10min to form a homogeneous colloidal suspension.
Gradually adding 60mg EDC and 25mg NHS into the mixture, performing ultrasonic treatment at 22 deg.C for 10min, stirring at 800rpm at 22 deg.C for 40min to activate carboxyl,
the reaction mixture was then transferred to dialysis bags (8-14 KDa) and each was treated with 5mM acetic acid (1.0X 10)3mL) for 1 day with ultrapure water (1.0X 10)3mL) was dialyzed for 1 day. Mixing the mixture at 1.1 × 104Centrifuging at rpm for 15min, vacuum freeze drying at-65 deg.C for 24 hr to obtain M-CS powder, adding water, and ultrasonic dispersing to obtain M-CS dispersion solution with concentration of 0.8 mg/mL.
Dissolving 25mg Ce6 in 10mL DMSO, adding 25mL M-CS dispersion (0.8mg/mL), performing ultrasonic treatment at 22 deg.C for 10min to mix well, stirring the mixture in dark at 600rpm for reaction for 16h, and washing with ultrapure water for the next day, 1.0 × 104Centrifuging at rpm for 15min, and vacuum freeze-drying at-65 deg.C for 30h to obtain M-CS-Ce6 photodynamic nano antibacterial material.
Comparative examples 1 to 3
Comparative examples 1 to 3 are MoS2Chitosan, Ce 6.
Comparative example 4
The preparation method of the CS-Ce6 composite material comprises the following steps:
dissolving 30mg Ce6 in 15mL DMSO to prepare a Ce6 solution with the mass concentration of 2mg/mL, adding 30mg CS into 25mL 0.5% acetic acid for ultrasonic treatment to prepare a 1.2mg/mL CS dispersion, adding 15mLCe6 solution into 25mL CS dispersion, performing ultrasonic treatment at 20 ℃ for 25min to mix uniformly, stirring the mixed solution in the dark at 700rpm for 18h, and washing with ultrapure water for 3 times (1.2 × 10) the next day4Centrifuging at rpm for 25min, and vacuum freeze-drying at-70 deg.C for 48h to obtain CS-Ce6 composite material.
Comparative example 5
An M-CS composite material, the preparation of which comprises the following steps:
firstly 50mg MoS2Dispersing in 25mL of ultrapure water, sonicating at 20 ℃ for 6h, adding 200 μ L of sulfydrylAcetic acid was added to the above MoS2In the dispersion, ultrasonic treatment is carried out for 24 hours at 25 ℃ to realize that sulfydryl is in MoS2And (4) surface modification. 65mg of chitosan was then added to the mixture and sonicated for 20min to form a homogeneous colloidal suspension.
Gradually adding 150mg EDC and 65mg NHS into the mixed solution, performing ultrasonic treatment at 25 deg.C for 15min, stirring at 600rpm at 25 deg.C for 1h to activate carboxyl group for amide reaction,
the reaction mixture was then transferred to dialysis bags (8-14 KDa) and each was treated with 10mM acetic acid (1.5X 10)3mL) for 2 days with ultrapure water (1.5X 10)3mL) for 2 days. Mixing the mixture at 1.2X 104Centrifuging at rpm for 30min, and vacuum freeze drying at-60 deg.C for 48h to obtain M-CS composite material.
Test example 1
And (3) testing the material structure and performance:
MoS in comparative example 1 was verified using TEM at an acceleration voltage of 200KV2The shapes and chemical structures of the raw materials, the M-CS composite material prepared in the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 are shown in FIG. 2, MoS2The composite material presents a smooth single-layer nanosheet structure, while the M-CS composite material prepared in comparative example 5 presents a rough and fuzzy thick nanostructure, which indicates that MoS is caused by chemical modification of macromolecular chitosan2The surface morphology and the roughness of the M-CS-Ce6 photodynamic nano antibacterial material are obviously changed, the surface of the M-CS-Ce6 photodynamic nano antibacterial material prepared by further loading Ce6 is fuzzy and unclear, which is caused by the modification of chitosan, the morphology of the M-CS-Ce6 photodynamic nano antibacterial material is changed, and an irregular sheet structure is shown, so that the preparation method of the embodiment 1 of the invention successfully modifies the chitosan in MoS2A surface.
MoS in comparative example 1 was scanned using FTIR2The CS in the comparative example 2, the Ce6 in the comparative example 3, the M-CS prepared in the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 are 4000-400 cm-1The IR spectrum in the wavelength range is shown in FIG. 3. As can be seen from FIG. 3, new peaks, 2922, 1378, 1151 and 1073cm, appeared in the spectrogram of M-CS prepared in comparative example 5-1Are respectively pairedCorresponding to the C-H, C-N, C-O and C-O-C bonds of chitosan, 1637 and 1572cm-1C ═ O stretching vibration corresponding to the amide I band and N — H bending vibration corresponding to the amide II band, indicating that chitosan was present in MoS2Successful surface modification, and MoS2The surface conjugated thioglycolic acid forms an amide bond; example 1 after Ce6 is loaded, M-CS-Ce6 shows an infrared characteristic peak of Ce6 at 1709cm-1Carboxyl group C ═ O bond assigned to Ce6, 1600, 1218, 1064cm-1The peak is respectively corresponding to N-H and C-N bonds of a pyrrole ring of Ce6, and the result shows that Ce6 is successfully loaded on M-CS, and the M-CS-Ce6 photodynamic nano antibacterial material is successfully prepared.
The MoS of comparative example 1 was scanned using XRD2The diffraction spectra of the CS in the comparative example 2, the M-CS prepared in the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 in the range of 5 degrees to 2 theta to 80 degrees are shown in figure 4, and MoS is shown in figure 42The diffraction peaks of 14.7 °, 33.0 °, 39.8 ° and 58.4 ° appearing in the spectrum of (b) correspond to the (002), (100), (103) and (110) crystal planes (JCPDS 65-1951), respectively; the diffraction peaks of chitosan at 9.7 ° and 18.9 ° correspond to its amorphous structure; MoS appears in M-CS spectrogram2The characteristic peaks of (A) are 14.9 degrees, 33.0 degrees, 40 degrees and 58.9 degrees, and small peaks appear at 9.7 degrees and 18.9 degrees, which are attributed to diffraction peaks of chitosan, and the result shows that the chitosan is successfully modified in MoS2The above step (1); the spectrogram of the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 has no obvious peak value change, and is consistent with the M-CS result prepared in the comparative example 1, which shows that the Ce6 loaded nano antibacterial material has no influence on the crystal form of the composite material.
MoS in comparative example 1 was tested using TGA2And the mass spectrums of the CS in the comparative example 2, the Ce6 in the comparative example 3, the M-CS composite material prepared in the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 are within the temperature range of 50-700 ℃. As can be seen from FIG. 5, the mass of the material gradually changes with temperature, MoS2The mass loss is about 20% at 50-700 ℃, which is caused by the thermal decomposition of residual organic matters in the chemical stripping process; the mass loss of the chitosan is in two stages of 100 ℃ and 250-350 ℃, the first stage is caused by water evaporation, and the second stage is mainly because of the breakage of glycosidic bonds and the depolymerization of polymer units; M-CS toolThe thermal decomposition stage similar to that of chitosan is reduced at 200-350 ℃, which indicates that the chitosan is modified in MoS2A surface; after further loading Ce6, the mass percent of the M-CS-Ce6 composite material gradually decreases with the increase of temperature, the decrease rate is fastest at 150-250 ℃, the decrease rate is consistent with the thermal decomposition curve of Ce6, and the mass loss is more than that of M-CS, which indicates that the mass percent is caused by thermal decomposition of the loaded Ce 6.
MoS in comparative example 1 was tested using a Zeta potentiometer and UV-vis, respectively2The potential and the ultraviolet absorption spectrum of the aqueous dispersion liquid corresponding to the CS in the comparative example 2, the Ce6 in the comparative example 3, the M-CS composite material prepared in the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 are respectively measured. FIG. 6 is MoS of comparative example 12Zeta potential diagrams of aqueous phase dispersions corresponding to the CS of comparative example 2, the Ce6 of comparative example 3, the M-CS composite material prepared in comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1. The test result shows that MoS2Both Ce6 and chitosan carry negative charges, chitosan carries positive charges, and M-CS is converted from negative charges to positive charges due to chemical modification; after further loading Ce6, the potential of the M-CS-Ce6 photodynamic nano antibacterial material is reduced, and the potential change trend of the M-CS-Ce6 photodynamic nano antibacterial material is consistent with the negative charge of Ce6, so that M-CS successfully loads the Ce6 molecule by virtue of electrostatic adsorption. FIG. 7 shows MoS in comparative example 12UV-vis patterns of aqueous dispersions corresponding to Ce6 in comparative example 3, the M-CS composite material prepared in comparative example 5, and the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1. As can be seen from FIG. 7, Ce6 has characteristic absorption peaks at 406 and 686nm, MoS2The wide absorption exists in a near infrared region, the M-CS has no obvious absorption, and after Ce6 is loaded, characteristic peaks of Ce6 appear at 408 nm and 686nm, which indicates that Ce6 is successfully loaded on the M-CS composite material.
Test example 2
And (3) measuring the photodynamic performance of the M-CS-Ce6 composite nano material:
the generation of singlet oxygen under the photodynamic effect is measured by using a 1, 3-diphenyl isobenzofuran (DPBF) singlet oxygen probe, and the probe can react with the singlet oxygen to reduce the absorption of DPBF at 410 nm. Mixing M-CS-Ce6The composite (20. mu.g/mL, 1mL) was mixed with DPBF (10. mu.g/mL, 1mL) using a power density of 100mW/cm2Irradiating the sample for 0-40 min by using 660nm laser, measuring the absorption peak of DPBF at 410nm, and taking the solution of free DPBF as a negative control. FIG. 8 is a singlet oxygen determination diagram of the M-CS-Ce6 photodynamic nano antibacterial material under 660nm illumination for different illumination time. As can be seen from FIG. 8, the singlet oxygen probe DPBF has a characteristic absorption peak at 410nm, when singlet oxygen is generated, it can irreversibly react with singlet oxygen to cause its degradation, and the decrease rate of DPBF absorbance is directly proportional to the generation of singlet oxygen. Compared with a control group of DPBF, the absorbance of the M-CS-Ce6 photodynamic nano antibacterial material is gradually reduced along with the lapse of irradiation time, which shows that Ce6 loaded in an adsorption mode can be continuously released, and singlet oxygen is continuously generated under the irradiation of light, so that the oxidative damage to pathogenic bacteria is aggravated.
Test example 3
And (3) MIC test:
use of the MoS of comparative example 12MIC determination of the target strains for CS of comparative example 2, Ce6 of comparative example 3, CS-Ce6 prepared in comparative example 4, M-CS prepared in comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1.
The MIC of each material in the above examples and comparative examples was investigated by a double gradient dilution method, wherein the concentration of the material was set to 128-1. mu.g/mL, and the OD of the target bacterial liquid600nmThe 96-well plate was irradiated with no light and 660nm laser light for 5min (100 mW/cm) (0.1)2) Taking a bacterial suspension without any material as a control, then culturing for 20h, testing the absorbance of each hole, and calculating the bacteriostasis rate of the material according to the absorbance, wherein the calculation formula is shown as the following formula (1):
MIC can be obtained through the bacteriostasis rate, and the MIC, namely the minimum concentration of the composite material with the antibacterial efficiency of more than 99 percent can be achieved. Table 1 shows MoS of comparative example 12CS of comparative example 2, Ce6 of comparative example 3, CS-Ce6 of comparative example 4, M-CS and realsite of comparative example 5MIC of M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1 to target strain.
TABLE 1
As can be seen from Table 1, the MICs of CS-Ce6 against Escherichia coli and Staphylococcus aureus prepared in comparative example 4 under the action of photodynamic light are 32. mu.g/mL and 8. mu.g/mL respectively, and the antibacterial property of CS-Ce6 against Escherichia coli is found to be weak, while MoS is present2During compounding, namely MICs of the ternary composite nanomaterial M-CS-Ce6 prepared in example 1 to two bacteria are respectively reduced by 16 times and 2 times, namely, the antibacterial activity of the ternary composite nanomaterial on gram-negative bacteria escherichia coli is improved. MICs of the M-CS prepared in the comparative example 5 to a target strain are respectively 4 mug/mL and 32 mug/mL, the antibacterial performance to staphylococcus aureus is weaker, and MICs of the M-CS-Ce6 photodynamic nano antibacterial material to two kinds of bacteria are respectively reduced by 2 times and 8 times after Ce6 is loaded, so that the antibacterial performance of the M-CS to gram-positive bacteria is obviously enhanced. The M-CS-Ce6 photodynamic nano antibacterial material prepared in the embodiment 1 has excellent antibacterial effects on escherichia coli and staphylococcus aureus, and MICs are 2 mug/mL and 4 mug/mL respectively, so that the M-CS-Ce6 ternary photodynamic nano antibacterial material is proved to realize the synergistic effect and the excellent antibacterial effect.
Test example 4
And (3) determining the antibacterial performance of the M-CS-Ce6 photodynamic nano antibacterial material:
taking escherichia coli and staphylococcus aureus as target strains, firstly inoculating the strains in Luria-Bertani (LB) culture medium for resuscitation, carrying out overnight shaking culture at 37 ℃, then taking 20 mu L of cultured bacterial liquid to continue subculture in liquid LB until logarithmic phase and OD (optical density) are reached600nm0.4 (cell concentration 10)8CFU/mL). The precipitate was centrifuged at 8000rpm at 4 ℃ and separated, and the precipitate was washed 3 times with sterile physiological saline (0.85% NaCl), followed by resuspension of the precipitate in physiological saline to obtain a bacterial suspension. Taking the MoS of comparative example 12Adding physiological saline to prepare 5, 10 and 20 mu g/mL dispersion solutions respectively; similarly, CS of comparative example 2 was mixed with physiological saline,Ce6 of comparative example 3, M-CS prepared by comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared by example 1 are respectively prepared into 5, 10 and 20 mu g/mL dispersion liquid. 100 μ L of the bacterial suspension was added to 900 μ L of the dispersions prepared in examples 1, 1 to 3 and 5, which had different concentrations, and the mixture was uniformly mixed and irradiated with 660nm laser for 5min (100 mW/cm)2) And further cultured at 37 ℃ for 5 hours with shaking. Finally, 100 mul of the mixed solution after shaking culture is respectively taken to be coated on an LB solid agar plate and cultured in a constant temperature incubator at 37 ℃ for 16h, and bacterial suspension without any material is taken as a positive control. FIG. 9 is MoS of comparative example 12Comparison of antibacterial effects of CS of comparative example 2, Ce6 of comparative example 3, M-CS prepared in comparative example 5 and M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1 on Escherichia coli in the absence of illumination and 660nm illumination. As can be seen from FIG. 9, MoS was compared with the control group2The antibacterial performance is obviously improved after the chitosan is modified, the specific antibacterial advantage of the chitosan is shown, and the M-CS inhibition rate of 20 mu g/mL reaches 65.2% in the absence of illumination; after the M-CS is further loaded with Ce6, the antibacterial performance is improved, the 10 mu g/mL M-CS-Ce6 photodynamic nano antibacterial material can inhibit the growth of 72.6 percent of escherichia coli, the 20 mu g/mL M-CS-Ce6 photodynamic nano antibacterial material can inhibit 82.5 percent of escherichia coli, after illumination is introduced, the inhibition rate of the 5 mu g/mL M-CS-Ce6 photodynamic nano antibacterial material can reach 99 percent, the inhibition rates of 10 mu g/mL and 20 mu g/mL can reach 100 percent, the antibacterial performance is optimal, and the synergistic antibacterial effect of the ternary composite material is fully exerted. The chitosan can change the permeability of the outer wall of escherichia coli by carrying positive surface charges, and can be used as a chelating agent to deteriorate the permeability of cell walls by chelating metal ions necessary for the growth of microorganisms. Therefore, the small-molecule photosensitizer and singlet oxygen can permeate into the bacteria, so that the oxidation of intracellular components of the bacteria is intensified, and the inhibition rate of escherichia coli is improved.
FIG. 10 is MoS of comparative example 12Comparison of the antibacterial effects of the CS of the comparative example 2, the Ce6 of the comparative example 3, the M-CS prepared by the comparative example 5 and the M-CS-Ce6 photodynamic nano antibacterial material prepared by the example 1 on staphylococcus aureus under no illumination and 660nm illumination. As can be seen from FIG. 10, Ce6 showed an antibacterial advantage against Staphylococcus aureus, stimulated at 660nmAfter light irradiation, the total number of colonies is greatly reduced, 20 mu g/mL of Ce6 can inhibit 80.11% of staphylococcus aureus, the advantage of photodynamic effect on staphylococcus aureus is reflected after M-CS is loaded with Ce6, the inhibition rate of 5 mu g/mL of M-CS-Ce6 can reach 99% under the condition of no light, after the concentration is increased, the inhibition rate of 10 mu g/mL of composite material reaches 100%, no bacterial colony grows on a flat plate, and after 660nm laser irradiation is added, the 5 mu g/mL of M-CS-Ce6 photodynamic nano antibacterial material can inhibit all staphylococcus aureus. Therefore, the M-CS-Ce6 photodynamic nano antibacterial material prepared in the embodiment 1 can completely inhibit escherichia coli and staphylococcus aureus at 5 mu g/mL, and shows the synergistic antibacterial activity of the ternary composite material on a target strain.
Test example 5
And (3) measuring the broad-spectrum antibacterial performance of the M-CS-Ce6 composite nano material:
in addition to target strains of escherichia coli and staphylococcus aureus, 5 strains are selected in the invention, including bacillus cereus, listeria monocytogenes, escherichia coli O157: h7, Salmonella typhimurium and Yersinia enterocolitica, and the broad-spectrum antibacterial ability of the M-CS-Ce6 photodynamic nano antibacterial material is verified by adopting the antibacterial performance test method described in test example 4.
Inoculating the above 5 strains in LB medium, and culturing at 37 deg.C to OD600nm＝0.4(108CFU/mL), 8000rpm, at 4 deg.C for 1min, discarding the supernatant, washing the precipitate with sterile physiological saline for 3 times, and resuspending in physiological saline. 100 mu L of the bacterial suspension is added into 900 mu L of dispersion liquid (2, 5, 10, 20 mu g/mL) prepared by adding physiological saline into the M-CS-Ce6 photodynamic nano antibacterial material prepared in the example 1 with different concentrations. Mixing, irradiating with 660nm laser for 5min (100 mW/cm)2) The culture was performed at 37 ℃ for 5 hours with shaking, 100. mu.L of the mixture was spread on an LB solid agar plate, and the culture was performed at 37 ℃ for 16 hours with a bacterial suspension containing no material as a positive control. FIG. 11 is a flat chart showing the antibacterial effects of the M-CS-Ce6 photodynamic nano antibacterial material prepared in example 1 on the 5 pathogenic bacteria under 660nm illumination. As can be seen from FIG. 11, the antibacterial performance of the M-CS-Ce6 composite material prepared in example 1 appears to be concentratedDegree-dependent, even at lower concentrations of 2 μ g/mL, the number of colonies growing on the plate is low, e.g. listeria monocytogenes, and few colonies grow; with the increase of the concentration of the M-CS-Ce6 photodynamic nano antibacterial material, the colony number on the plate decreases when the concentration is 5 mug/mL; at 10 mu g/mL, the plate diagram can intuitively observe that 5 pathogenic bacteria are completely inhibited without colony growth, which indicates that the M-CS-Ce6 photodynamic nano antibacterial material shows very excellent antibacterial capability to gram-positive bacteria and gram-negative bacteria. Based on the results, the M-CS-Ce6 ternary photodynamic nano antibacterial material prepared by the invention has broad-spectrum, high-efficiency and synergistic photodynamic antibacterial effect.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The photodynamic nano antibacterial material is characterized in that the photodynamic nano antibacterial material is prepared by chemically functionalizing MoS on chitosan2And loading a photosensitive material on the substrate.
2. The photodynamic nano antibacterial material as claimed in claim 1, wherein the preparation of the photodynamic nano antibacterial material comprises the following steps:
(1) adding mercaptoacetic acid to MoS2Adding chitosan into the dispersion liquid after ultrasonic treatment, and performing ultrasonic treatment again to obtain a colloidal solution;
(2) sequentially adding EDC and NHS, performing ultrasonic treatment and stirring, purifying, centrifuging and drying to obtain M-CS powder, and adding water into the M-CS powder to obtain M-CS dispersion liquid;
(3) and (3) adding the Ce6 solution into the M-CS dispersion liquid prepared in the step (2), performing ultrasonic treatment, stirring, centrifuging, and drying to obtain the M-CS-Ce6 photodynamic nano antibacterial material.
3. The photodynamic nano-meter of claim 2Antibacterial material, characterized in that, in step (1), the MoS2The preparation method of the dispersion comprises the following steps: mixing MoS2Adding water, and ultrasonically dispersing at 20-25 ℃ for 4-6 hours to prepare MoS with the mass concentration of 1-2 mg/mL2A dispersion liquid; the mercaptoacetic acid and MoS2The volume ratio of the dispersion liquid is 1: 100-150, the temperature of ultrasonic treatment is 20-25 ℃, and the time is 16-24 hours.
4. The photodynamic nano-antibacterial material as claimed in claim 2, wherein in the step (1), the chitosan and MoS are mixed2The mass ratio of (A) to (B) is 1-2: 1; the temperature of the secondary ultrasonic treatment is 20-25 ℃, and the time is 10-20 min.
5. The photodynamic nano antibacterial material as claimed in claim 2, wherein in the step (2), the EDC, the NHS and the MoS are adopted2The mass ratio of (A) to (B) is 2-3:1-1.5: 1; the purity of the EDC is 98-99%; the purity of the NHS is 98-99%.
6. The photodynamic nano antibacterial material as claimed in claim 2, wherein in the step (2), the ultrasonic temperature is 20-25 ℃ and the ultrasonic time is 10-15 min; the stirring speed is 600-800 rpm, and the stirring time is 40-60 min.
7. The photodynamic nano antibacterial material as claimed in claim 2, wherein in the step (2), the specific purification method comprises the following steps: using a dialysis bag with 8-14 KDa, adding 1 multiplied by 103～1.5×103Dialyzing with 5-10 mM acetic acid in mL for 1-2 days, and adding 1 × 103～1.5×103Dialyzing with mL ultrapure water for 1-2 days; the speed of the centrifugation is 1 x 104～1.2×104rpm for 15-30 min; the drying is vacuum freeze drying, the temperature is-60 to-70 ℃, and the time is 24 to 48 hours; the mass concentration of the M-CS dispersion liquid is 0.8-1.2 mg/mL.
8. The photodynamic nano-antibacterial of claim 2The material is characterized in that in the step (3), the mass concentration of Ce6 in the Ce6 solution is 1.8-2.5 mg/mL, and the volume ratio of the Ce6 solution to the M-CS dispersion liquid is 0.4-0.8: 1; the temperature of the ultrasonic wave is 20-25 ℃, and the time is 10-30 min; the stirring speed is 600-800 rpm, and the time is 16-24 hours; the speed of centrifugation is 1-1.2 x 104rpm for 15-30 min; the drying is vacuum freeze drying, the temperature is-60 to-70 ℃, and the time is 24 to 48 hours.
9. The application of the photodynamic nano antibacterial material as claimed in any one of claims 1 to 8, wherein the photodynamic nano antibacterial material has antibacterial property on one or two of gram-negative bacteria and gram-positive bacteria.
10. The use of claim 9, wherein the gram-positive bacteria is one or both of bacillus cereus, listeria monocytogenes; the gram-negative bacteria are Escherichia coli O157: h7, Salmonella typhimurium, and Yersinia enterocolitica.
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