CN111170292A - Preparation method and application of fiber-phase red phosphorus nanoparticles - Google Patents
Preparation method and application of fiber-phase red phosphorus nanoparticles Download PDFInfo
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Abstract
The invention relates to the field of novel functional nano materials, and discloses a preparation method and application of fiber-phase red phosphorus nanoparticles, wherein the method comprises the following steps: synthesizing zinc oxide nano particles by a hydrothermal method, depositing a layer of fiber phase red phosphorus on the zinc oxide nano particles by using the zinc oxide nano particles as a template by using a chemical vapor deposition method, washing away the zinc oxide nano particles in a zinc oxide nano particle compound coated by the red phosphorus by using dilute hydrochloric acid, and washing and ultrasonically treating to obtain the fiber phase red phosphorus nano particles. The fiber-phase red phosphorus nanoparticles prepared by the method have good photo-thermal performance, can coordinate antibiotics to efficiently and quickly treat bacterial biofilm infection, and have very good biocompatibility and biodegradability.
Description
Technical Field
The invention relates to the technical field of novel functional nano materials, in particular to a preparation method and application of fiber-phase red phosphorus nanoparticles with good photo-thermal performance.
Background
The escalation of antibiotic resistant bacterial infections poses a huge economic burden and a serious threat to human health care throughout the world. According to the world health organization report, over 200 million people are infected with antibiotic-resistant pathogens, and 2300 die each year. Antibiotic resistant pathogens, as one of the three major threats to human health, cause morbidity and mortality that are expected to outweigh the threat of cancer in the near future. Since conventional antibiotics are becoming less effective and facing the problem of phase-out, the discovery of new effective antibiotics is very urgent. Many new synthetic antibacterial drugs exhibit potent antibacterial properties against antibiotic-resistant pathogens, which shows great potential for infection treatment. Generally, new antibiotics take 10 years or more to use in clinical practice, which costs a lot of manpower and money. However, the time required for the pathogen to develop resistance is less than two weeks. To address the urgent need for antibiotic-resistant bacterial infection treatment, we still rely on conventional antibiotics.
the effectiveness of these antibiotics is eroded by various resistance mechanisms, which can be divided into three categories, (1) production of modifying enzymes, (2) alteration of antibiotic targets, (3) alteration of bacterial membrane permeability and efflux.
We must find a new strategy to re-sensitize antibiotic-resistant pathogens to conventional antibiotics without side effects, thereby extending the life of old drugs. Unlike the use of conventional antibacterial drugs, inhibition of drug resistance mechanism by exogenous strategies (such as low temperature photothermal therapy) has never been reported. Researchers have extensively studied cancer or bacterial infections. Antibiotics such as daptomycin and vancomycin can be used for treating methicillin-resistant staphylococcus aureus infection by combining photothermal effect of Near Infrared (NIR) light, but the antibiotics are low in efficiency. Furthermore, to achieve a lethal photothermal effect, the temperatures used are still above 50 degrees celsius, which may have damaged healthy tissue.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of fiber-phase red phosphorus nanoparticles, wherein the method uses zinc oxide nanoparticles as templates to synthesize the fiber-phase red phosphorus nanoparticles, and has low cost and no pollution to the environment; the obtained fiber-phase red phosphorus nanoparticles have good photo-thermal performance, can efficiently kill drug-resistant bacteria in cooperation with antibiotics, and have very good biocompatibility.
The invention provides a preparation method of fiber-phase red phosphorus nanoparticles, which comprises the following steps:
a preparation method of fiber phase red phosphorus nanoparticles is characterized by comprising the following steps:
s1, synthesis of zinc oxide nanoparticles: weighing zinc nitrate hexahydrate, sodium dodecyl benzene sulfonate and sodium hydroxide, dissolving in ethanol, transferring to a reaction kettle, reacting at 90-110 ℃ for 8-11 h, centrifuging after reaction, washing and drying to obtain zinc oxide nanoparticles;
s2, preparation of fiber-phase red phosphorus zinc oxide compound: putting the zinc oxide nanoparticles obtained in the step S1 and red phosphorus into a crucible, mixing and grinding uniformly, putting into a vacuum tube furnace, heating to 650-700 ℃, keeping for 15-30 min, cooling to 280-300 ℃, keeping for 10-13 h, and cooling to obtain a fiber phase red phosphorus zinc oxide compound;
s3, preparation of fiber-phase red phosphorus nanoparticles: and (4) placing the fiber-phase red phosphorus zinc oxide compound prepared in the step (S2) and dilute hydrochloric acid into a flask to react for 1-3 h, centrifugally collecting a product after the reaction, washing, performing ultrasonic treatment, and performing freeze drying to obtain the fiber-phase red phosphorus nanoparticles.
Preferably, the molar ratio of the zinc nitrate hexahydrate, the sodium dodecyl benzene sulfonate and the sodium hydroxide in the step S1 is 1:1: 20-25.
Preferably, the drying in step S1 is vacuum drying, and the drying temperature is 50 to 65 ℃.
Preferably, the mass ratio of the zinc oxide nanoparticles to the red phosphorus in the step S2 is 1: 1-8.
Preferably, the red phosphorus in step S2 needs to be pretreated, and the pretreatment process specifically includes: putting red phosphorus and deionized water into a reaction kettle, reacting at 180-210 ℃ for 9-13 h, centrifuging after reaction, washing, and drying.
The invention provides application of the prepared fiber-phase red phosphorus nanoparticles in killing drug-resistant bacteria and treating biofilm infection by cooperating with antibiotics.
The invention has the beneficial effects that:
(1) synthesizing zinc oxide nano particles by a hydrothermal method, depositing a layer of fiber phase red phosphorus on the zinc oxide nano particles by using the zinc oxide nano particles as a template by using a chemical vapor deposition method, and then removing the zinc oxide nano particles at normal temperature by using dilute hydrochloric acid.
(2) The commercial red phosphorus is amorphous powder, and the conversion rate of the amorphous red phosphorus powder into fiber-phase red phosphorus nanoparticles can be effectively improved by pretreating the red phosphorus, so that the surface structure of the red phosphorus is presumed to be changed by pretreatment.
(3) The fiber-phase red phosphorus nanoparticles prepared by the method have uniform size and particle size of about 120nm, have good capability of penetrating bacterial biofilms, and can be used for efficiently and quickly treating drug-resistant bacteria and drug-resistant bacterial biofilm infection in cooperation with aminoglycoside antibiotics. Furthermore, the fiber-phase red phosphorus nanoparticles also have good biocompatibility and degradability, can be degraded into phosphoric acid under a biological environment, and have no side effect when being used for treating bacterial infection in cooperation with antibiotics.
(4) The fiber phase red phosphorus nano particle prepared by the invention has the characteristics of good photo-thermal property, high photo-thermal conversion rate, strong repeatability and stable chemical property, and is resistant to heatA photosensitizer for use. Experiments prove that 200 mu g/mL fiber-phase red phosphorus nanoparticles can be irradiated under the near-infrared 808nm illumination (1W/cm)2) The temperature can rise by 64 ℃ in 10 min.
Drawings
FIG. 1 is a TEM image of fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 2 is a Raman absorption spectrum of the fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 3 is a graph of photothermal heating and photothermal cycling of fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 4 is a UV absorption spectrum of the fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 5 shows the cytotoxicity test MTT for fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 6 is a graph of the effect of low temperature photothermal time on fibroblast activity for fiber-phase red phosphorus nanoparticles prepared in example 1;
FIG. 7 is an antibacterial plot of photothermal synergy of the fiber-phase red phosphorus nanoparticles with aminoglycoside antibiotics prepared in example 1;
FIG. 8 shows the photo-thermal synergistic fluorescence staining of fiber-phase red-phosphorus nanoparticles with aminoglycoside antibiotics for biofilm death and survival prepared in example 1.
FIG. 9 is a TEM image of fiber-phase red phosphorus nanoparticles prepared in example 2;
FIG. 10 is a TEM image of the fiber phase red phosphorus zinc oxide composite prepared in example 3;
fig. 11 is a TEM image of the fiber phase red phosphorus nanoparticles prepared in example 4.
Detailed Description
In order that the invention may be better understood, it is further illustrated by the following detailed description, but is not to be construed as being limited thereto.
Example 1
A fiber phase red phosphorus nanoparticle is prepared by the following steps:
(1) synthesizing zinc oxide nano particles: 1.885g of zinc nitrate hexahydrate, 2.185g of sodium dodecylbenzenesulfonate and 6g of sodium hydroxide were dissolved in 60mL of ethanol by a balance. The solution is sonicated until the solute is uniformly dispersed in the solution. And (3) putting the solution after ultrasonic treatment into a 100mL reaction kettle, putting the reaction kettle into a muffle furnace at 100 ℃, and reacting for 9h at high temperature. The solution after the reaction is centrifuged (9000r/min,10min) to collect the zinc oxide nanoparticles. Then, the mixture was centrifuged 3 times with absolute ethanol and then with deionized water 3 times. The centrifuged precipitate was vacuum dried in a vacuum oven at 60 ℃.
(2) Preparation of amorphous pure red phosphorus: weighing commercial amorphous red phosphorus 5.9g, adding into 60mL deionized water, transferring the solution into a 100mL reaction kettle, placing the reaction kettle in a muffle furnace at 200 ℃, and reacting for 13h at high temperature and high pressure. The solution after reaction is centrifuged (5000r/min,5min) to collect amorphous pure red phosphorus. Then, after centrifugation with deionized water for 2 times, the centrifuged precipitate was vacuum-dried in a vacuum oven at 60 ℃.
(3) Preparation of fiber phase red phosphorus zinc oxide compound: after 3g of the amorphous pure red phosphorus prepared in step (2) and 0.5g of the zinc oxide nanoparticles prepared in step (1) were uniformly mixed, ground into a fine powder, preferably having a powder size of about 0.1mm, in a crucible, the powder was put into a tube furnace, which was kept under vacuum and the temperature was raised to 650 ℃ at 10 ℃/min and kept for 15 min. Thereafter, the temperature was lowered to 280 ℃ at 10 ℃/min and held for 10 h. And after the heat preservation is finished, cooling to room temperature at the speed of 5 ℃/min 5 to obtain the fiber phase red phosphorus zinc oxide compound.
(4) Preparing fiber phase red phosphorus nanoparticles: diluting concentrated hydrochloric acid into 1mol/mL diluted hydrochloric acid, mixing 0.5g of fiber-phase red phosphorus zinc oxide compound and 10mL diluted hydrochloric acid together, putting the mixed solution into a 50mL single-neck flask for reaction, stirring for 2h by using a magnetic stirrer, centrifuging the reacted solution (15000r/min,10min) to collect a product, centrifuging for 3 times by using deionized water, carrying out ultrasonic treatment by using a cell crusher, and carrying out freeze drying in a freeze dryer to obtain the fiber-phase red phosphorus nanoparticles.
The preservation conditions of the prepared fiber phase red phosphorus nanoparticles are as follows: keeping the mixture in dark and keeping the mixture in inert gas, wherein the inert gas is preferably argon.
Further, the preparation process of the 1mol/mL diluted hydrochloric acid comprises the following steps: diluting concentrated hydrochloric acid by 12 times, adding 10mL of concentrated hydrochloric acid into 2mL of deionized water to prepare 10mol/mL hydrochloric acid, then adding 1mL of 10mol/mL hydrochloric acid into 9mL of deionized water to obtain 1mol/mL diluted hydrochloric acid.
The prepared fiber phase red phosphorus nanoparticles are detected, and the specific results are as follows:
TEM analysis of the fiber-phase red phosphorus nanoparticles revealed that (a) the diameter of the fiber-phase red phosphorus nanoparticles was about 120nm and the elemental phosphorus in the nanoparticles was confirmed by the energy dispersive optical spectrum of the insertion, as shown in FIG. 1; from (b), it was found that the interplanar spacing of the (400) plane was 2.78 angstroms and the interplanar spacing of the (001) plane was 5.80 angstroms, demonstrating that the fiber phase red phosphorus nanoparticles. The prepared fiber-phase red phosphorus nanoparticles were subjected to raman analysis, as shown in fig. 2, to further prove that the prepared sample was fiber-phase red phosphorus.
200 mu g/mL of fiber-phase red phosphorus nanoparticles are placed under the illumination of near infrared 808nm (1W/cm)2) And recording a temperature rise curve of 10min and a temperature drop curve of 20min by a thermal imager, repeatedly operating for 3 times, and observing the temperature rise and temperature drop trends, wherein the result is shown in figure 3, 200 mu g/mL of fiber-phase red phosphorus nanoparticles can rise to 64 ℃ in 10 minutes, which indicates that the fiber-phase red phosphorus nanoparticles are a durable photosensitizer.
Visible light absorption detection (wavelength is 220-980 nm) is carried out on amorphous red phosphorus (200 mu g/mL) and fiber phase red phosphorus (200 mu g/mL) by using a microplate reader, and the result is shown in figure 4, the fiber phase red phosphorus nanoparticles are dark black, the amorphous red phosphorus is dark red, the dark black red phosphorus is far stronger than the light absorbance of dark red dispersion in the NIR region, and the strong absorption of the photosensitizer is favorable for the very strong photothermal conversion performance of the fiber phase red phosphorus and the fiber phase red phosphorus. Proves that the fiber phase red phosphorus has very excellent photo-thermal conversion performance.
After the cells are cultured for 24h, the fiber-phase red phosphorus nanoparticles are added, and then after the cells are continuously cultured for 24h, the cytotoxicity is detected by using MTT, as shown in figure 5, the cell survival rate of 400 mu g/mL red phosphorus nanoparticles is 90%, and even if the concentration reaches 1.6mg/mL, the cell survival rate can reach 70%, which proves the good biocompatibility of the red phosphorus nanoparticles.
After the cells are cultured for 24h, 200 mu g/mL of fiber-phase red phosphorus nanoparticles are added, and the mixture is irradiated under the near infrared 808nm illumination (1W/cm)2) When the temperature reaches 45 ℃, the incubation is started, the timing is started, and then the death and the survival of the cells are tested by using MTT, and the relationship between the incubation time and the cell survival rate is recorded, and the result is shown in FIG. 6, the survival rate of the cells is 85% under the low-temperature photothermal of 30 minutes, which shows that the low-temperature photothermal of 30 minutes adopted by us has no great influence on the cell activity.
By 107culturing the gentamicin with different concentrations by cfu/mL methicillin-resistant staphylococcus aureus, carrying out photo-thermal treatment on the gentamicin with the concentration of 4 × MIC, and recording the change of bacteria along with time, wherein the photo-thermal treatment is carried out under the illumination of near infrared 808nm (1W/cm)2) And when the temperature reaches 45 ℃, the temperature is preserved for 30 min. The results are shown in FIG. 7: as gentamicin (4 × MIC) content increased, the growth of drug-resistant bacteria remained static until 8 hours; with the addition of low temperature photothermal, the gentamicin (4 × MIC) combination resulted in about a 53-fold reduction in drug-resistant bacterial load compared to gentamicin (4 × MIC) alone; although gentamicin increased to 16 × MIC or 32 × MIC, the antibacterial performance was still much lower than the photothermal treatment + gentamicin (4 × MIC) group, indicating that the combination of gentamicin and photothermal treatment could significantly reduce the abundance of drug-resistant bacteria, which would avoid the side effects of not having to use high concentrations of antibiotics in antibiotic therapy.
After photo-thermal treatment, gentamicin treatment and photo-thermal treatment plus gentamicin treatment, the methicillin-resistant staphylococcus aureus biofilm cultured for 36h was subjected to dead and live fluorescent staining, as shown in fig. 8. Green represents live bacteria and red represents dead bacteria, wherein the colors of non-treated, photothermal treated and gentamicin are green, 3 groups are shown as live bacteria, and the color of the combined group is red, which is shown as dead bacteria. The photothermal synergistic antibiotic is proved to eliminate the infection of the biological membrane.
Example 2
A fiber phase red phosphorus nanoparticle is prepared by the following steps:
(1) synthesizing zinc oxide nano particles: 1.885g of zinc nitrate hexahydrate, 2.185g of sodium dodecylbenzenesulfonate and 4.8g of sodium hydroxide were dissolved in 60mL of ethanol by a balance. The solution is sonicated until the solute is uniformly dispersed in the solution. And (3) putting the solution after ultrasonic treatment into a 100mL reaction kettle, putting the reaction kettle into a muffle furnace at 90 ℃, and reacting for 11h at high temperature. The solution after the reaction is centrifuged (9000r/min,10min) to collect the zinc oxide nanoparticles. Then, the mixture was centrifuged 3 times with absolute ethanol and then with deionized water 3 times. The centrifuged precipitate was dried under vacuum in a vacuum oven at 50 ℃.
Steps (2), (3) and (4) were the same as those in example 1.
Scanning electron microscope detection is carried out on the prepared fiber phase red phosphorus nanoparticles, and the result is shown in figure 9, and the size of the red phosphorus nanoparticles is about 120 nm.
Example 3
A fiber phase red phosphorus nanoparticle is prepared by the following steps:
(1) synthesizing zinc oxide nano particles: 1.885g of zinc nitrate hexahydrate, 2.185g of sodium dodecylbenzenesulfonate and 6g of sodium hydroxide were dissolved in 60mL of ethanol by a balance. The solution is sonicated until the solute is uniformly dispersed in the solution. And (3) putting the solution after ultrasonic treatment into a 100mL reaction kettle, putting the reaction kettle into a muffle furnace at 105 ℃, and reacting at high temperature for 10 h. The solution after the reaction is centrifuged (9000r/min,10min) to collect the zinc oxide nanoparticles. Then centrifuging with anhydrous ethanol for 3 times, then centrifuging with deionized water for 3 times, and vacuum drying the centrifuged precipitate at 65 ℃.
The steps (2), (3) and (4) are the same as those in example 1;
the prepared composite of the zinc oxide nanoparticles and the red phosphorus is detected by a scanning electron microscope, and the result is shown in figure 10, the composite of the zinc oxide nanoparticles and the red phosphorus is in an irregular new appearance, and the red phosphorus is not uniformly deposited on the surfaces of the zinc oxide nanoparticles. Therefore, the zinc oxide nanoparticles are blocked by the rapid drying effect, and are difficult to disperse in the back, so that the compound of the zinc oxide nanoparticles and red phosphorus has irregular appearance.
Example 4
A fiber phase red phosphorus nanoparticle is prepared by the following steps:
steps (1) and (2) were the same as in example 1;
(3) preparation of fiber phase red phosphorus zinc oxide compound: uniformly mixing 1.5g of the amorphous pure red phosphorus prepared in the step (2) and 0.5g of the zinc oxide nano particles prepared in the step (1), grinding the mixture into fine powder in a crucible, putting the powder into a tube furnace, keeping the furnace in vacuum, raising the temperature to 690 ℃ at 10 ℃/min and keeping the temperature for 20 min. Thereafter, the temperature was lowered to 300 ℃ at 10 ℃/min and held for 10 h. And after the heat preservation is finished, cooling to the end at the temperature of 5 ℃ to obtain the fiber phase red phosphorus zinc oxide compound, and finishing the conversion from the amorphous state to the fiber phase.
Step (4) was the same as in example 1.
Scanning electron microscope detection is carried out on the prepared fiber-phase red phosphorus nanoparticles, and the result is shown in fig. 11, and the size of the spherical red phosphorus nanoparticles is about 120 nm.
The above is, of course, only a specific application example of the present invention, and the scope of the present invention is not limited in any way. In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by using equivalent substitutions or equivalent transformations fall within the scope of the present invention.
Claims (6)
1. A preparation method of fiber phase red phosphorus nanoparticles is characterized by comprising the following steps:
s1, synthesis of zinc oxide nanoparticles: weighing zinc nitrate hexahydrate, sodium dodecyl benzene sulfonate and sodium hydroxide, dissolving in ethanol, transferring to a reaction kettle, reacting at 90-110 ℃ for 8-11 h, centrifuging after reaction, washing and drying to obtain zinc oxide nanoparticles;
s2, preparation of fiber-phase red phosphorus zinc oxide compound: putting the zinc oxide nanoparticles obtained in the step S1 and red phosphorus into a crucible, mixing and grinding uniformly, putting into a vacuum tube furnace, heating to 650-700 ℃, keeping for 15-30 min, cooling to 280-300 ℃, keeping for 10-13 h, and cooling to obtain a fiber phase red phosphorus zinc oxide compound;
s3, preparation of fiber-phase red phosphorus nanoparticles: and (4) placing the fiber-phase red phosphorus zinc oxide compound prepared in the step (S2) and dilute hydrochloric acid into a flask to react for 1-3 h, centrifugally collecting a product after the reaction, washing, performing ultrasonic treatment, and performing freeze drying to obtain the fiber-phase red phosphorus nanoparticles.
2. The method for preparing fiber-phase red phosphorus nanoparticles according to claim 1, wherein the molar ratio of the zinc nitrate hexahydrate, the sodium dodecyl benzene sulfonate and the sodium hydroxide in step S1 is 1:1: 20-25.
3. The method for preparing fiber-phase red phosphorus nanoparticles according to claim 1, wherein the drying in step S1 is vacuum drying, and the drying temperature is 50-65 ℃.
4. The method for preparing fiber-phase red phosphorus nanoparticles according to claim 1, wherein the mass ratio of the zinc oxide nanoparticles to the red phosphorus in step S2 is 1: 1-8.
5. The method for preparing fiber-phase red phosphorus nanoparticles according to claim 1 or 4, wherein the red phosphorus in step S2 needs to be pretreated, and the pretreatment process specifically comprises: putting red phosphorus and deionized water into a reaction kettle, reacting at 180-210 ℃ for 9-13 h, centrifuging after reaction, washing, and drying.
6. Use of the fiber-phase red phosphorus nanoparticles prepared according to any one of claims 1 to 5 in killing drug-resistant bacteria and treating biofilm infection in cooperation with antibiotics.
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| CN112919438A (en) * | 2021-04-13 | 2021-06-08 | 北京理工大学 | Controllable preparation method of nano red phosphorus hollow sphere |
| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
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| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
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