CN115475244A - Metal organic framework nano composite and preparation method and application thereof - Google Patents
Metal organic framework nano composite and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of antibacterial materials, and particularly relates to a metal organic framework nano composite, a preparation method and application thereof. In order to improve the accuracy of the antibacterial treatment of the nano material, the invention uses UiO-66 as a carrier to load TMB and HRP to form H 2 O 2 And NIR light cascade response characteristics, and exhibits excellent photothermal bacterial inactivation characteristics.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a metal organic framework nano composite as well as a preparation method and application thereof.
Background
Bacterial infections are a serious threat to human life health. Antibiotics, as a traditional drug for the treatment of bacterial infections, save countless lives. However, when antibiotics are used, bacterial resistance can also be caused, which greatly reduces the therapeutic effect of the antibiotics and even makes the antibiotics ineffective. The development of bacterial resistance has also been accelerated by the abuse of antibiotics in recent years. Unfortunately, the rate at which we develop new antibiotics is far slower than the rate at which bacterial resistance develops. According to the World Health Organization (WHO) report, about 70 million people die of drug-resistant bacterial infections every year worldwide. If no effective measures are taken, it is expected that 1000 million people die annually from drug-resistant bacterial infections by the year 2050. In the face of such severe situations, on one hand, the development of antibiotics is to be accelerated while avoiding the abuse of antibiotics; on the other hand, new antibacterial strategies are urgently needed.
Nanoparticle-mediated physical stimulation therapy is a promising strategy for bacterial therapy that can partially replace antibiotics. The strategy is to convert a physical stimulation signal into forms of heat energy or free radicals and the like by taking nano particles as a medium to inactivate bacteria. For example, most of noble metal nanoparticles, nano carbon materials, magnetic nano materials, some nano polymers and the like can be heated under light, magnetism and ultrasonic waves or be subjected to other physical stimulation to generate high temperature so as to achieve the aim of sterilization; photosensitizer and nano semiconductor material (such as titanium dioxide, bismuth vanadate, quantum dot and the like) can generate free radicals under the irradiation of light, X rays and even ultrasonic waves for inactivating bacteria. Among these strategies, the photothermal strategy has the obvious advantages of easy acquisition of light source, high bacterial inactivation efficiency, low toxic and side effects, and the like. In addition, photothermal therapy does not readily cause bacterial resistance. Therefore, photothermal antibacterial therapy has received much attention in recent years and has made great progress in this field. The realization of efficient antibiosis is no longer the main problem of a photo-thermal method, and the improvement of the treatment accuracy is based on the development trend of the photo-thermal antibacterial treatment research field. Although the modification of targeting molecules such as antibodies and antibacterial peptides can improve the accuracy of nano photothermal therapy to a certain extent, the modification also faces the problems of high cost and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a metal organic framework nano composite, which is used for forming H by loading TMB and HRP (Tetramethylbenzidine) by using UiO-66 as a carrier to improve the accuracy of nano material antibacterial treatment 2 O 2 And NIR light cascade response characteristics, and exhibits excellent photothermal bacterial inactivation characteristics.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a metal organic framework nano-composite takes metal organic framework MOF as a nano-carrier and is loaded with tetramethylbenzidine TMB and horseradish peroxidase HPR.
The metal-organic framework nanocomposite has H 2 O 2 And NIR light cascade response characteristics.
The metal organic framework nano composite has the photo-thermal antibacterial effect
The preparation method of the metal organic framework nano composite comprises the following steps:
and 2, incubating and synthesizing the UiO-66, TMB and HRP to obtain the metal organic framework nano-composite.
The metal organic framework nano composite is used in the antibacterial field,
the metal organic framework nano composite is used in the field of wound treatment, and particularly used in the field of skin wound infection treatment.
From the above description, it can be seen that the present invention has the following advantages:
1. in order to improve the accuracy of the antibacterial treatment of the nano material, the invention uses UiO-66 as a carrier to load TMB and HRP to form H 2 O 2 And NIR light cascade response characteristics, and exhibits excellent photothermal bacterial inactivation characteristics.
2. In the using process, the nano carrier can be triggered to perform enzyme catalytic reaction by the high oxidation state of the bacterial infection microenvironment, so that a charge transfer compound with a near-infrared thermal effect is generated, and the carrier has near-infrared photo-thermal antibacterial activity.
Drawings
FIG. 1 is a representation of the UiO-66 and supported TMB and HRP (UiO-66 @ TMB-HRP, UTH) prepared in the examples; wherein a) TEM of MOF (UiO-66), b) XRD of UiO-66D, c) size distribution of MOF and of the obtained nanocomposite UiO-66@ TMB-HRP (UTH), D) zeta potential of MOF and of the obtained nanocomposite UiO-66@ TMB-HRP (UTH).
FIG. 2 is the nanocomposite pair H of example 1 2 O 2 In which a) UTH and H 2 O 2 Absorption spectra before and after incubation; b) UTH-H 2 O 2 The change in absorbance at 650nm in the system with time.
FIG. 3 is the photothermal effect of the nanocomposite material of example 1, wherein a) 0.2mg/mLUTH (i), 0.05mg/mLUTH +1mMH 2 O 2 (ii)、0.1mg/mLUTH+1mMH 2 O 2 (iii) And 0.2mg/mLUTH +1mMH 2 O 2 (iv) Photothermal effect under 900nm NIR light irradiation. b) a corresponding thermal imaging map. c) 0.2mg/mLUTH +1mMH 2 O 2 The "on-off" temperature change under 900nm light illumination. d) Linear cooling time data,. Tau.s =172.63933s, with negative natural logarithm of-Ln (θ) to driving force temperature.
FIG. 4 is a photograph of colonies of E.coli and S.aureus from the nanocomposite obtained in example 1 irradiated under different conditions at 900nm (0.4 mg/mLUTH +1 mMH) 2 O 2 )。
FIG. 5 shows the bacteriostatic activity of the nanocomposites of example 1, wherein a) H under 900nm light irradiation 2 O 2 Photographs of colonies of E.coli and S.aureus treated with UTH at a concentration of 1 mM. b) The corresponding bacterial survival rate was obtained by (a) counting. c) Under 900nm light irradiation in H 2 O 2 Fluorescence images of E.coli before (left) and after (right) treatment with UTH in the presence (staining with SYTO9 and PI).
FIG. 6 is a graph showing the therapeutic effects of the nanocomposites prepared in example 1 on wound infection (caused by Staphylococcus aureus) in mice under various conditions.
Detailed Description
An embodiment of the present invention is described in detail with reference to fig. 1 to 6, but the present invention is not limited in any way by the claims.
Example 1
A metal organic framework nano-composite takes metal organic framework MOF as a nano-carrier and is loaded with tetramethylbenzidine TMB and horseradish peroxidase HPR.
The preparation method of the metal organic framework nano composite comprises the following steps:
And 2, preparing the nano composite, namely adsorbing TMB in the pore channel through the porous characteristic of the UiO-66 and pi bond interaction, and adsorbing the HRP on the surface of the UiO-66 through the nano surface effect of the UiO-66 and the action of the HRP. The method comprises the following specific steps: adding TMB into 5mL of solution with the concentration of 5mg/mLUiO-66 to obtain TMB with the final concentration of 0.5mM, incubating for 3h, adding 25UHRP, and continuously stirring at 4 ℃ for 8h; then, the above-mentioned product was centrifuged and washed several times with water, and finally dispersed in water to obtain a nanocomposite wherein TMB and HRP were contained at final concentrations of 0.5mM and 10U/mL, respectively, and the appearance of the solution was still a white milky solution.
And (3) performance detection:
the prepared UiO-66 is milk white, and has better stability and dispersibility in water. As shown in FIG. 1a, TEM characterization results show that the UiO-66 size is around 100nm and good dispersibility; as shown in fig. 1b, the crystalline and phase information was studied by powder X-ray diffraction (XRD), and the appearance of a sharp peak in the XRD pattern indicated that uo-66 had good crystallinity. As shown in FIGS. 1c and 1d, of the size and zeta potential of UiO-66 and the UiO-66 supporting TMB and HRP (UiO-66 @ TMB-HRP, UTH), uiO-66 predominant size was around 110nm, and after TMB and HRP supporting, the resulting nanocomposite UTH showed a larger size around 210 nm. In addition, uiO-66 has a positive zeta potential of 26.3mV, which increases to 46.1mV after TMB and HRP loading. The changes in size and zeta potential clearly indicate the successful preparation of nanocomposite UTH.
As shown in fig. 2, nanocomposite pair H 2 O 2 With response characteristics, the nanocomposite UTH contains an enzyme (HRP) and a substrate (TMB) in H 2 O 2 In the presence of HRP, it will catalyze H 2 O 2 Producing an intermediate that can oxidize TMB to a colored state. As shown in fig. 2a, the color of the nanocomposite solution changed from light milky to dark turquoise, while the uv absorption spectrum clearly indicates the production of TMB oxidation products; warp H 2 O 2 After the treatment, two strong absorption peaks appeared around 650nm and around 900 nm. The intensity of the absorption peak increases with increasing concentration of the nanocomposite. As shown in FIG. 2b, H 2 O 2 The concentration of (A) is as low as 0.1mM, and the discoloration of the nano composite material can be obviously caused in a short time, which shows that the nano composite material is used for H 2 O 2 Has high responsiveness. Meanwhile, the photothermal effect of the nano-material is often closely related to the intensity of the absorption peak, which means that the oxidized nano-composite material is likely to generate a strong photothermal effect under the irradiation of near infrared light (900 nm).
As shown in fig. 3, the nanocomposite has excellent photothermal effect, and as shown in fig. 3a and 3b, the temperature increase of 0.2mg/ml luth solution was very slight under 900nm light irradiation. However, in the presence of 1mMH 2 O 2 In the case of (2), even a low concentration of UTH (0.05 mg/mL) is rapidly heated by irradiation with 900nm light. Rate of temperature rise and maximum temperature dependence of nanocompositeThe concentration increases. 0.2mg/mLUTH and 1mMH 2 O 2 The temperature of the solution can reach more than 45 ℃ within 3min under the irradiation of 900nm light, and the excellent photo-thermal effect is obviously shown. It should be noted that H in the region of bacterial infection 2 O 2 The concentration is usually around 1 mM. Furthermore, during light irradiation, the local temperature of the nanoparticle surface is much higher than the solution temperature. These indicate that the nanoparticles are the infected region pair H 2 O 2 The sensitive reaction and the high-efficiency antibiosis provide necessary foundation. The photothermal efficiency was calculated by measuring the heating and cooling rates, as shown in FIGS. 3c and 3d, and the results showed that the nanocomposite UTH was at H 2 O 2 The photothermal efficiency in the presence reaches 18%.
The nano-composite has a photo-thermal antibacterial effect. Coli and staphylococcus aureus were selected as gram-negative and gram-positive bacterial models, respectively, to study the cascade antibacterial efficiency (the antibacterial efficiency was determined by plate counting). As shown in FIG. 4, the results indicate that only H is present 2 O 2 (1 mM) or UTH, NIR light irradiation does not lead to significant antibacterial activity.
At H 2 O 2 In the presence of both UTH and near-infrared radiation, significant bacteriostatic activity may be induced, with bacteriostatic activity increasing with increasing UTH concentration. As shown in fig. 5a and 5b, when H is 2 O 2 At a concentration of 1mM, the IC50 of UTH for E.coli and S.aureus was about 150 and 450. Mu.g/mL, respectively, under NIR light irradiation; this shows that it has significant antibacterial effect on both gram-positive and gram-negative bacteria, indicating that the cascade nano-system has broad-spectrum antibacterial property. LIVE/DEAD staining was performed using LIVE/DEAD bacterial viability kit to explore the antibacterial mechanism of the nanosystems. In this process, green fluorescence (SYTO 9 dye) indicates live bacteria and red fluorescence (PI dye) indicates dead bacteria with damaged cell walls. As shown in fig. 5c, most of the treated bacteria had strong red fluorescence, indicating that the cascade of nanosystems can cause damage to the cell wall and kill the bacteria.
In the mouse skin infection model, hair was removed from a back portion area of a mouse with depilatory cream, and a small piece of back skin was cut out to construct a wound model. The infection was performed by instilling 10 μ LOD600 of 1 s.aureus solution into the wound. 10 μ LUTH was dripped into an infected wound once a day for the first three days, and then irradiated with 900nm light for 5 minutes. The wounds were photographed daily and changes were recorded. As shown in fig. 6, after the treatment of near infrared irradiation or UTH, the skin wound of the mice infected with staphylococcus aureus was significantly suppurative and the like, and the wound was slowly healed. Ten days later, the wound was still visibly dented. However, after treatment with UTH and NIR light, the wound is less prone to suppurative symptoms and heals more quickly. After ten days, the wound was substantially healed. These results indicate that the cascade nanosystems have a good therapeutic effect on skin wound infections.
In conclusion, the compound prepared by the technical scheme has H 2 O 2 And the MOF nano composite material with the NIR light cascade response characteristic has excellent photo-thermal antibacterial activity. Nanocomposite pair H 2 O 2 The reaction is sensitive and rapid. Color of the nanocomposite at H 2 O 2 The nano composite material turns into dark turquoise color in the presence of the ultraviolet light, and simultaneously, a strong absorption peak appears in a near-infrared region near 900nm, and the oxidized nano composite material can convert near-infrared photons into heat energy with the efficiency of 18%. The nano system has strong inactivation effect on gram-negative bacteria and gram-positive bacteria. At 1mM hydrogen peroxide and 0.5W/cm 2 Under NIR light intensity conditions, the IC50 of the MOF nanocomposite on Escherichia coli and Staphylococcus aureus is 150 and 450 mug/mL respectively. The cascade reaction nano-drug also shows strong therapeutic action on a mouse skin wound infection model.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be understood by those skilled in the art that the present invention may be modified and equivalents substituted for elements thereof to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (7)
1. A metal-organic framework nanocomposite, characterized by: the MOF is used as a nano carrier, and is loaded with TMB and HPR.
2. The metal-organic framework nanocomposite as claimed in claim 1, wherein: the metal-organic framework nanocomposite has H 2 O 2 And NIR light cascade response characteristics.
3. The metal-organic framework nanocomposite as claimed in claim 1, wherein: the metal organic framework nano composite has a photo-thermal antibacterial effect.
4. The metal-organic framework nanocomposite as claimed in claim 1, wherein: the preparation method of the metal organic framework nano composite comprises the following steps:
step 1, uniformly mixing zirconium propoxide solution, DMF and acetic acid, keeping the temperature for stirring for 2 hours when the temperature is 130 ℃ due to oil bath, and then cooling to room temperature to change the color of the solution from colorless to yellow; finally, adding 1, 4-dicarboxybenzene for ultrasonic dispersion, stirring for 18h at room temperature, and then centrifugally washing to obtain a UiO-66 carrier; the UiO-66 carrier is dispersed in water;
and 2, incubating and synthesizing the UiO-66, TMB and HRP to obtain the metal organic framework nano-composite.
5. The metal-organic framework nanocomposite as claimed in claim 1, wherein: the metal organic framework nano composite is used in the antibacterial field.
6. The metal-organic framework nanocomposite as claimed in claim 1, wherein: the metal-organic framework nanocomposite is used in the field of wound therapy.
7. The metal-organic framework nanocomposite according to claim 6, wherein: the metal organic framework nano composite is used in the field of skin wound infection treatment.
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