CN115590956A - MXene composite material modified by ruthenium complex with photo-thermal and photodynamic synergism, and preparation method and application thereof - Google Patents
MXene composite material modified by ruthenium complex with photo-thermal and photodynamic synergism, and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
Abstract
The invention discloses an MXene composite material modified by a ruthenium complex with photo-thermal and photodynamic synergism, and a preparation method and application thereof. Under the irradiation of light, MXene photothermal effect, ruthenium complex PDT and ultra-thin MXene nanosheet physical cutting cell membrane form a three-in-one synergistic system of physical cutting, photothermal and photodynamic therapy, and the realization of the synergistic system is realized at 150mW/cm 2 Low energy density, low concentration of 100 mug/mL and high-efficiency sterilization within a short time of 15-30 min. The preparation method utilizes the condensation of hydroxyl and carboxylThe synthetic reaction is bonded and loaded, the preparation method is simple, complex reaction processes and harsh reaction conditions are not needed, and products can be quickly separated and purified, so that the industrial production is met.
Description
Technical Field
The invention belongs to the technical field of photo-thermal and photo-dynamic materials, and particularly relates to an MXene composite material modified by a ruthenium complex with photo-thermal and photo-dynamic synergy and a preparation method and application thereof.
Background
In response to the challenge of bacterial infections and antibiotic resistance, researchers have made many efforts to provide many viable options. At present, the novel antibacterial mode comprises an antibacterial agent, a low-temperature plasma technology, photocatalytic degradation, photodynamic antibacterial, photothermal antibacterial and the like. The above antibacterial methods have defects in themselves or in application, and limit the application of the antibacterial method to wound. And different from antibiotics, photodynamic sterilization depends on generation of active oxygen, photothermal sterilization depends on good photothermal effect, and bacteria hardly generate drug resistance, so that the drug resistance crisis caused by excessive use of antibiotics can be effectively avoided. Therefore, photodynamic antibiosis and photothermal antibiosis have the advantages of safety, high efficiency, capability of avoiding bacteria from generating antibiotic resistance and the like, and are concerned by researchers recently.
Photothermal therapy (Photothermal therapy% PTT) is a light-induced method for killing pathogens by converting light energy into heat energy by a Photothermal converter to bring cell tissues to a certain temperature and thus kill microorganisms. Photodynamic therapy (PDT) is that a Photodynamic reagent generates Reactive Oxygen Species (ROS) with strong oxidizing power under irradiation of laser, and causes cytotoxicity by virtue of oxidation reaction with protein and DNA, so that the protein and DNA deteriorate to cause bacterial death. The photodynamic therapy plays a role mainly based on the following three points: photosensitizer (PS), light and oxygen, the interaction of these three components leading to the generation of Reactive Oxygen Species (ROS). With the continuous development of scientific technology, the preparation of nano-scale photosensitizer or the loading of photosensitizer on nano material for sterilization is called nano photodynamic sterilization technology, which has received wide attention in recent years. However, the existing photosensitizer is loaded on the nano material, and only depends on the photosensitizer for sterilization, so that the sterilization effect is not obvious. Therefore, the existing PDT material and PTT material can not fully satisfy the application of photodynamic and photothermal in antibiosis and antitumor.
Disclosure of Invention
In order to overcome the defects of the prior art, the first object of the invention is to provide an MXene composite material modified by a ruthenium complex with photo-thermal and photodynamic synergism, which has the effects of photo-thermal and photodynamic bacteriostasis and tumor cell killing, can realize photo-thermal and photodynamic synergism of antibiosis and tumor resistance, and can realize synergetic and efficient antibiosis and tumor resistance through lower energy input.
The second purpose of the invention is to provide a preparation method of the MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergy.
The third purpose of the invention is to provide an application of the MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergy.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic coordination comprises the ruthenium complex and an MXene two-dimensional material, wherein the ruthenium complex is loaded on the surface of the MXene two-dimensional material through a covalent bond to form the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic coordination.
Further, the ruthenium complex has a structure shown in formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R 6 Is any one of H, alkyl with 1-3 carbon atoms, halogen or carboxyl, and R 1 、R 2 、R 3 、R 4 、R 5 Or R 6 At least one is a carboxyl group.
Further, the ruthenium complex is
Further, the MXene two-dimensional material has the diameter of less than 500nm and the thickness of 1-5nm.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a method for preparing MXene composite material modified by ruthenium complex with photo-thermal and photodynamic synergy, the preparation method comprises the following preparation steps:
and dispersing the MXene two-dimensional material into water to form a dispersion liquid, adding the ruthenium complex into the dispersion liquid, and heating and reacting under an inert gas atmosphere to obtain the MXene composite material modified by the ruthenium complex and cooperated with photo-thermal and photodynamic.
Further, the reaction is carried out under the action of a catalyst, the catalyst is a composite catalyst of carbodiimide salt and 4-dimethylaminopyridine, and the mass ratio of the carbodiimide salt to the 4-dimethylaminopyridine is 1: (0.5-2).
Further, the mass ratio of the ruthenium complex to the MXene two-dimensional material is 1: (0.5-2); the heating reaction temperature is 80-100 ℃.
Further, the method also comprises the following preparation steps of the ruthenium complex:
s11, ruthenium precursor preparation: mixing 2,2' -bipyridine, lithium chloride and RuCl 3 ·3H 2 Dissolving O in DMF, heating to react under the atmosphere of inert gas, and cooling to room temperature after the reaction is finished, wherein the obtained solid is the ruthenium precursor; the ruthenium precursor has a structure represented by formula III:
s12, ruthenium complex preparation: and dissolving the ruthenium precursor and substituted or unsubstituted 2,2' -bipyridine in a second solvent, heating to react under the atmosphere of inert gas, adjusting the pH value to be alkaline, continuing to react, and cooling to room temperature after the reaction is finished to obtain a solid ruthenium complex.
Further, the preparation steps of MXene two-dimensional material are also included:
obtaining a multilayer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm by the MXene base material through in-situ etching, and ultrasonically oscillating the multilayer MXene aqueous solution for 0.5-5h to obtain the MXene two-dimensional material.
The third purpose of the invention can be achieved by adopting the following technical scheme:
any one of the above mentioned devices is photo-thermal and photo-dynamic
The MXene composite material modified by the ruthenium complex with the synergetic effect or the MXene composite material modified by the ruthenium complex with the synergetic photo-thermal and photo-dynamic effects, which is prepared by the preparation method of the MXene composite material modified by the ruthenium complex with the synergetic photo-thermal and photo-dynamic effects, is applied to preparation of photo-thermal and photo-dynamic synergetic antibacterial or antitumor drugs.
Compared with the prior art, the invention has the beneficial effects that:
1. the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic synergism, disclosed by the invention, has the advantages that the MXene two-dimensional material with the photo-thermal effect and the ruthenium complex with the photo-sensitive effect are bonded together through a condensation reaction of carboxyl and hydroxyl, so that the ruthenium complex is loaded on the surface of the MXene two-dimensional material. The MXene two-dimensional material has good near infrared absorption, good photothermal conversion efficiency and photothermal stability under illumination, and can be used as photothermal antibacterial and antitumor agents; the ruthenium complex is taken as a photosensitizer to generate ROS under illumination, and can be taken as a photodynamic antibacterial and antitumor substance; therefore, the MXene two-dimensional material is supported by the ruthenium complex to form the composite material which is antibacterial and antitumor in a synergistic manner.
2. The preparation method of the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic synergism, disclosed by the invention, has the advantages that the bonding load is realized by utilizing rich hydroxyl groups on the surface of the MXene two-dimensional material and performing condensation reaction on the MXene two-dimensional material and the ruthenium complex containing carboxyl, the preparation method is simple, no complex reaction process or harsh reaction conditions are required, the product can be quickly separated and purified, and the industrial production is met.
3. The MXene composite material modified by the photo-thermal and photodynamic synergistic ruthenium complex has the dual functions of photo-thermal and photodynamic, and can realize the low energy density (150 mW/cm) 2 ) The sterilization is carried out with high efficiency in a short time (15-30 min) and at a lower concentration (100 mu g/ml), so the sterilization can be applied to the preparation of photo-thermal and photodynamic synergistic antibacterial or antitumor drugs.
Drawings
FIG. 1 is a mass spectrum of a ruthenium complex prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the ruthenium complex prepared in example 1;
FIG. 3 is a TEM image of MXene two-dimensional material prepared in example 3 and Ru @ MXene prepared in example 4;
FIG. 4 is an EDS energy spectrum of MXene two-dimensional material prepared in example 3;
FIG. 5 is the EDS energy spectrum of Ru @ MXene prepared in example 4;
FIG. 6 is the XRD patterns of MXene two-dimensional material prepared in example 3 and Ru @ MXene composite prepared in example 4;
FIG. 7 is an infrared spectrum of MXene two-dimensional material prepared in example 3 and Ru @ MXene composite material prepared in example 4;
FIG. 8 is a graph of the temperature rise of aqueous suspension of Ru @ MXene prepared in example 4 at various concentrations as a function of xenon lamp irradiation;
FIG. 9 is a graph of the temperature rise of aqueous suspensions of different samples (water, MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1 and Ru @ MXene prepared in example 4) as a function of xenon lamp irradiation;
FIG. 10 is a thermal infrared plot of aqueous suspensions of different samples (water, MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1, and Ru @ MXene prepared in example 4) as a function of xenon lamp exposure;
FIG. 11 is a temperature profile of aqueous suspensions of different samples (water, MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1 and Ru @ MXene prepared in example 4) over 5 laser on/off cycles;
FIG. 12 is the absorption change curve at 420nm of mixed DPBF under light conditions of MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1 and Ru @ MXene prepared in example 4;
FIG. 13 is a graph showing the antibacterial effect of MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1, and Ru @ MXene prepared in example 4 on E.coli in dark and light conditions;
FIG. 14 is a graph showing the antibacterial effect of Ru @ MXene in different concentrations on E.coli under dark and light conditions;
FIG. 15 is an SEM image of E.coli under dark and light conditions for MXene two-dimensional material prepared in example 3, ruthenium complex prepared in example 1 and Ru @ MXene prepared in example 4.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments. It is to be understood that the described embodiments are merely some, and not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The MXene two-dimensional material is a novel metal carbonitride nano two-dimensional sheet layer, has the advantages of good photo-thermal conversion efficiency, photo-thermal stability and the like compared with nano antibacterial materials such as nano metal particles (such as nano silver and the like) and photosensitive nano materials (such as ZnO) and the like, and has great application prospects in the aspects of photo-thermal treatment, drug carriers and the like.
Different from antibiotics, the sterilization mechanism of the MXene two-dimensional material mainly depends on physical injury effect and good photo-thermal effect, so that the problem of drug resistance of bacteria is difficult to generate, and the drug resistance crisis caused by excessive use of antibiotics can be effectively avoided. Particularly, the MXene two-dimensional material is subjected to targeted or specific bioactivity modification, so that the MXene two-dimensional material has other functions such as targeting and load, the biocompatibility of the MXene two-dimensional material can be improved, and the application of the MXene two-dimensional material in the biomedical field such as the anti-tumor field is expanded.
The Ru (II) complex has strong visible light absorption capacity and abundant excited state properties. Among them, the Ru (II) complex having a long-life triplet excited state exhibits a strong redox property, contributing to intermolecular electron transfer or energy transfer. These properties make them widely used as photosensitizers in PDT.
Ru (II) complexes are widely applied to antibacterial and antitumor drugs. The photosensitizer can be combined with the nano material in a covalent or non-covalent combination mode, the chemical properties of the photosensitizer such as solubility are controlled, self-quenching between the photosensitizers is avoided, and the generation efficiency of active oxygen is improved; the nanomaterials can also alter the in vitro and in vivo behavior of the photosensitizer, including pharmacokinetics and biodistribution, enhancing the selectivity of the photosensitizer by enhancing the permeability and retention Effect (EPR) or by modifying its surface with a targeting ligand.
Therefore, in order to solve the problems of drug resistance of bacteria to antibiotics and poor treatment effect of a single photosensitizer or a nano material, the ruthenium complex and the MXene two-dimensional material are reacted and self-assembled through surface functional groups to form covalent bonds, so that the ruthenium complex is loaded on the surface of the MXene two-dimensional material to form a Ru @ MXene nano composite system.
The MXene composite material modified by the photo-thermal and photodynamic cooperative ruthenium complex comprises the ruthenium complex and an MXene two-dimensional material, wherein the ruthenium complex is loaded on the surface of the MXene two-dimensional material through a covalent bond to form the MXene composite material modified by the photo-thermal and photodynamic cooperative ruthenium complex.
Active oxygen generated by PDT can increase the capture of laser light by a photothermal agent, and the photothermal effect of PTT can increase the oxygen supply of tissues to promote PDT. A system of a photothermal therapy and ruthenium complex photodynamic therapy synergistic antibacterial and antitumor mechanism is formed, so that the MXene composite material can realize PTT and PDT combined therapy at the same time, and has excellent controllability, minimally invasive property, low toxicity and no drug resistance.
In one embodiment, the ruthenium complex has the structure of formula I:
in one of the embodiments, the first and second electrodes are,
is a compound with a pi conjugated structure and containing two substituted or unsubstituted pyridine rings, wherein the two pyridine rings can be directly connected; the two pyridine rings may be connected by an element containing a lone pair of electrons; two pyridine rings may also be joined by forming fused rings with the ring groups; wherein three in the formula I
May be the same or different, but at least one
Containing at least one carboxyl group.
Preferably, the first and second liquid crystal materials are,
is substituted or unsubstituted 2,2' -bipyridine, and at least one
Is substituted 2,2' -bipyridine; at least one of the substituted 2,2' -bipyridines has the structure shown in formula II:
wherein R is 1 -R 6 Is any one of H, alkyl with 1-3 carbon atoms, halogen and carboxyl, and R 1 -R 6 At least one of which is a carboxyl group.
5363 Zxft 5363 '-bipyridine is coordinated with ruthenium, six N atoms of three 2,2' -bipyridine are located at relatively symmetrical positions, therefore, the formed ruthenium complex has a compact stable structure, has good stability when being used as a photosensitizer, and can realize better photodynamic.
In one embodiment, the number of carboxyl groups in the ruthenium complex is two, located at the 4 and 4 'positions of the same 2,2' -bipyridine.
2,2 '-bipyridine, wherein the 2,2' -bipyridine contains two carboxyl groups at the 4 and 4 'positions, which are located at the same side of 2,2' -bipyridine, and have consistent bond length and bond angle, so that the ruthenium complex has less steric hindrance after condensation with hydroxyl on the surface of MXene two-dimensional material, and forms a stable composite structure with less stress.
In one embodiment, the ruthenium complex is
In one embodiment, the MXene two-dimensional material has a diameter less than 500nm and a thickness of 1-5nm.
Wherein, MXene two-dimensional material is known material; preferably, the MXene two-dimensional material is Ti 3 C 2 、Ti 2 C、Nb 2 C、V 2 C、(Ti 0.5 Nb 0.5 ) 2 C、(V 0.5 Cr 0.5 ) 3 C 2 、Ti 3 CN and Ta 4 C 3 Any one of them. More preferably, the MXene two-dimensional material is Ti 3 C 2 。
The MXene two-dimensional material has the diameter less than 500nm and the thickness of 1-5nm, can be subjected to load modification by a ruthenium complex, and has a larger specific surface; on the other hand, after the MXene two-dimensional material with the size is loaded with the ruthenium complex, the MXene two-dimensional material can be transferred in a human body, can be effectively and fully contacted with bacteria or cell surfaces in an aggregation manner, and can play a role in photo-thermal and photosensitive actions.
The invention also provides a preparation method of the MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergism, which comprises the following preparation steps:
and dispersing the MXene two-dimensional material into water to form a dispersion liquid, adding the ruthenium complex into the dispersion liquid, and heating and reacting under an inert gas atmosphere to obtain the MXene composite material modified by the ruthenium complex and cooperated with photo-thermal and photodynamic.
The surface of the MXene two-dimensional material is provided with hydrophilic active groups such as hydroxyl groups, carbonyl groups and the like, the MXene two-dimensional material can be effectively modified by carrying out chemical reaction or physical adsorption on the active groups, and the water dispersibility of the MXene two-dimensional material can be better improved after the MXene two-dimensional material is functionally modified, so that the MXene two-dimensional material is favorably dispersed in a physiological environment.
Therefore, the ruthenium complex containing the carboxyl is used, the carboxyl on the ruthenium complex is bonded to form the load after condensation reaction with the hydroxyl on the surface of the MXene two-dimensional material, the reaction is the reaction of condensation of the carboxyl and the hydroxyl into ester, which is conventional in the field, and complex processes and harsh reaction conditions are not needed.
In one embodiment, the reaction is carried out in the presence of a catalyst, wherein the catalyst is a composite catalyst of a carbodiimide salt and 4-dimethylaminopyridine, and the mass ratio of the carbodiimide salt to the 4-dimethylaminopyridine is 1: (0.5-2).
After carboxyl is activated by carbodiimide salt, the reaction of condensation of carboxyl and hydroxyl to form ester can be promoted under the catalysis of 4-dimethylaminopyridine serving as a catalyst, and the yield is remarkably improved. Preferably, the carbodiimide salt is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI), and can be used as a water-soluble composite catalyst consisting of 4-Dimethylaminopyridine (DMAP), so that an organic solvent is not required to be introduced, and the requirements of post-treatment and composite green chemistry are simplified.
In one embodiment, the mass ratio of the ruthenium complex to the MXene two-dimensional material is 1 to (0.5-2); the reaction temperature is 80-100 ℃.
In one embodiment, the method further comprises the step of preparing the ruthenium complex:
s11, ruthenium precursor preparation: reacting 2,2' -bipyridine with lithium chloride and RuCl 3 ·3H 2 Dissolving O in DMF, carrying out condensation reflux reaction for 8-36h under the atmosphere of inert gas, cooling to room temperature after the reaction is finished, wherein the obtained solid is the ruthenium precursor; the ruthenium precursor has a structure represented by formula III:
s12, preparing a ruthenium complex: and dissolving the ruthenium precursor and substituted or unsubstituted 2,2' -bipyridine in a second solvent, heating to react in an inert gas atmosphere, adjusting the pH value to be alkaline, continuing to react, and cooling to room temperature after the reaction is finished to obtain a solid ruthenium complex.
In one embodiment, the substituted or unsubstituted 2,2' -bipyridine, lithium chloride and RuCl of step S11 3 ·3H 2 The molar mass ratio of O is (1.7-2.2) to (2.2-3.5) to 1; the first solvent is DMF, and the volume of the DMF is 10-30mL; the reaction condition in the step S11 is reflux reaction for 6-24h.
In one embodiment, the molar mass ratio of the ruthenium precursor and the substituted or unsubstituted 2,2' -bipyridine in step S12 is 1: (1.2-2); the second solvent is absolute ethyl alcohol; the volume of the absolute ethyl alcohol is 50mL; the reaction condition in the step S12 is reflux reaction for 8-36h; the pH was adjusted to alkaline with NaOH.
In one embodiment, the inert gas atmosphere is nitrogen or argon, preferably argon.
In one embodiment, the preparation steps of MXene two-dimensional material are also included:
obtaining a multilayer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm by the MXene base material through in-situ etching, and ultrasonically oscillating the multilayer MXene aqueous solution for 0.5-5h to obtain the MXene two-dimensional material.
The invention also provides an application of the photothermal and photodynamic synergistic ruthenium complex modified MXene composite material or the photothermal and photodynamic synergistic ruthenium complex modified MXene composite material prepared by the preparation method of the photothermal and photodynamic synergistic ruthenium complex modified MXene composite material in preparation of photothermal and photodynamic synergistic antibacterial or antitumor drugs.
Example 1: preparation of ruthenium complexes
1.8g of 2,2' -bipyridine (bpy), 0.7g of lithium chloride and 1.56g of RuCl 3 ·3H 2 O was dissolved in 10mL of N, N-Dimethylformamide (DMF) and then condensed at reflux for 12h at 140 ℃ under an argon atmosphere. Filtering, recrystallizing, and vacuum drying to obtain dark green microcrystal as ruthenium precursor cis- [ Ru (bpy) 2 Cl 2 ]·2H 2 O；
0.52g of the ruthenium precursor cis- [ Ru (bpy) 2 Cl 2 ]·2H 2 Dissolving O in absolute ethyl alcohol, adding 0.3g of 2,2 '-bipyridine-4,4' -dicarboxylic acid (dcb), heating to 80 ℃ under the protection of argon atmosphere for reflux, adjusting the pH value to be alkaline by NaOH, continuously refluxing for 12h after dissolving, adjusting the pH value by HCI after the reaction is finished, and removing the solvent by rotary evaporation under the reduced pressure condition to obtain an orange-red solid which is a ruthenium complex [ Ru (bpy) 2 (dcb)] 2+ 。
Example 2: preparation of ruthenium complexes
2.5g of 2,2 '-bipyridine-4,4' -dimethyl, 0.9g of lithium chloride and 1.56g of RuCl 3 ·3H 2 O is dissolved in 30mL of DMF and then condensed at reflux for 6h under an argon atmosphere. Obtaining a ruthenium precursor through suction filtration, recrystallization, multiple purification and drying;
dissolving 0.52g of ruthenium precursor in absolute ethyl alcohol, adding 0.22g of 2,2-bipyridine-4,4' -dicarboxylic acid, heating to reflux under the protection of argon atmosphere, adjusting the pH to be alkaline by using NaOH, continuously refluxing for 8 hours after dissolving, adjusting the pH by using HCI after the reaction is finished, and removing the solvent by rotary evaporation under the reduced pressure condition to obtain the solid ruthenium complex.
Example 3: preparation of ruthenium complexes
1.62g of 2,2' -bipyridine, 0.57g of lithium chloride and 1.56g of RuCl 3 ·3H 2 O was dissolved in 20mL of DMF and then condensed at reflux for 24h at 140 ℃ under an argon atmosphere. Obtaining a ruthenium precursor through suction filtration, recrystallization and vacuum drying;
dissolving 0.52g of ruthenium precursor in absolute ethyl alcohol, adding 0.33g of 2,2-bipyridine-4-carboxylic acid, heating to reflux under the protection of argon atmosphere, adjusting the pH value to be alkaline by using NaOH, continuously refluxing for 36h after dissolving, adjusting the pH value by using HCl after the reaction is finished, and removing the solvent by rotary evaporation under the reduced pressure condition to obtain a solid ruthenium complex.
Example 4: MXene two-dimensional Material preparation (Ti) 3 C 2 T x )
Weighing 3g of lithium fluoride powder, adding 40mL of 12M concentrated hydrochloric acid, stirring uniformly, and adding 2g of Ti 3 AlC 2 Stirring the base material for two days at 40 ℃, and obtaining pure multilayer Ti by water washing and ethanol washing 3 C 2 T x A material. A plurality of layers of Ti 3 C 2 T x Dispersing the material in a book, violently shaking at room temperature and carrying out ultrasonic treatment for 3 hours to obtain few layers of Ti 3 C 2 T x Two-dimensional nano-material water suspension, freezing and drying to obtain Ti 3 C 2 T x Two-dimensional nanomaterials.
Example 5: preparation of material Ru @ MXene
To contain 0.1g of Ti 3 C 2 T x To the two-dimensional nanomaterial suspension was added 0.1g of the ruthenium complex [ Ru (bpy) prepared in example 1 2 (dcb)] 2+ Then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP) in a mass ratio of 1: 1 to form a water-soluble composite catalyst0.005g of oxidant is uniformly mixed, the mixture reacts for 3 hours at the temperature of 100 ℃ in the atmosphere of inert gas, the mixture is centrifuged after the reaction is finished, the supernatant is removed, the residue is repeatedly centrifuged and washed by deionized water, and the MXene composite material modified by the ruthenium complex with the cooperation of photo-thermal and photodynamic is obtained by freeze drying and is marked as Ru @ MXene.
Example 6: preparation of composite Material
To contain 0.1g of Ti 3 C 2 T x Adding 0.05g of the ruthenium complex prepared in the example 2 into a two-dimensional nano material suspension, adding 0.01g of a water-soluble composite catalyst consisting of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP) in a mass ratio of 1: 1, uniformly mixing, reacting for 1h at 100 ℃ in an inert gas atmosphere, centrifuging after the reaction is finished, removing a supernatant, repeatedly centrifuging and washing residues with deionized water, and freeze-drying to obtain the photothermal and photodynamic synergistic ruthenium complex modified MXene composite material.
Example 7: preparation of composite Material
To contain 0.1g of Ti 3 C 2 T x Adding 0.2g of ruthenium complex obtained in the example 3 into a two-dimensional nano material suspension, adding 0.012g of water-soluble composite catalyst consisting of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP) in a mass ratio of 1: 1, uniformly mixing, reacting for 12 hours at 100 ℃ in an inert gas atmosphere, centrifuging after the reaction is finished, removing a supernatant, repeatedly centrifuging and washing residues with deionized water, and freeze-drying to obtain the photothermal and photodynamic synergistic ruthenium complex modified MXene composite material.
Test example:
1. the ruthenium complex [ Ru (bpy) prepared in example 1 was reacted 2 (dcb)] 2+ The results of mass spectrometry and nuclear magnetic analysis are shown in FIGS. 1 and 2, in which ESI-MS (CH) 3 OH)：m/z：329.04[M] 2+ From this, M was 658.08, which almost coincided with the relative molecular weight 657.65. The results obtained from nuclear magnetic analysis were: 1 H NMR(400MHz，DMSO)δ8.85(d，J＝8.2Hz，4H)，8.79(s，2H)，8.15(dd，J＝13.0，6.6Hz，4H)，7.74(d，J＝5.4Hz，6H) 7.66 (d, J =5.7Hz, 2H), 7.53 (t, J =6.7Hz, 4H), the resulting ruthenium complex was confirmed to be [ Ru (bpy) 2 (dcb)] 2+ 。
2. MXene two-dimensional material Ti prepared in example 4 3 C 2 T x Ru @ MXene prepared in example 5 was observed under TEM (FIG. 3), wherein the right image is the MXene two-dimensional material Ti prepared in example 4 3 C 2 T x The left side of the TEM image of Ru @ MXene prepared in example 5. EDS energy spectra are shown in FIGS. 4 and 5, wherein FIG. 4 is MXene two-dimensional material Ti prepared in example 4 3 C 2 T x FIG. 5 is the EDS energy spectrum of Ru @ MXene prepared in example 5.
As can be seen from FIG. 3, MXene two-dimensional material Ti 3 C 2 T x The Ru @ MXene material is in a two-dimensional flake shape, is modified by the ruthenium complex and still is in a flake shape, and the size is about 200 nm.
From FIG. 4, MXene two-dimensional material Ti can be seen 3 C 2 T x Contains Ti, O, cl, F and c elements, while Ru @ MXene of FIG. 5 shows new elements N and Ru, which proves that MXene surface is successfully loaded by Ru-containing substance.
3. MXene two-dimensional material Ti prepared in example 4 3 C 2 T x And Ru @ MXene prepared in example 5 were subjected to XRD detection, and an XRD pattern is shown in FIG. 6.
In the figure 6, the (002) peak value of Ru @ MXene deviates 0.91 degrees towards a lower angle, and the obvious increase of the interlayer space between the Ru @ MXene sheet layer and the sheet layer is corresponding to the formation of an ultrathin nanosheet structure, so that the physical cutting of the cell membrane by the ultrathin nanosheets is facilitated, and the antibacterial or anti-tumor efficiency is improved.
4. MXene two-dimensional material Ti prepared in example 4 3 C 2 T x And Ru @ MXene prepared in example 5 were subjected to infrared spectroscopic measurements, the infrared spectroscopic measurements being shown in FIG. 7.
MXene two-dimensional material Ti in FIG. 7 3 C 2 T x And Ru @ MXene were both shown at 3431cm -1 ，1632cm -1 And 562cm -1 The typical characteristic bands of (a) correspond to stretching vibrations of-OH, C = O and Ti-O, respectively. Wherein the Ru @ MXene modified by the ruthenium complex is 1088cm -1 And 1049cm -1 The absorption band related to ester bond appears, which indicates that hydroxyl on the ruthenium complex and MXene two-dimensional material Ti 3 C 2 T x The hydroxyl is successfully esterified, and the MXene two-dimensional material Ti is loaded by the ruthenium complex 3 C 2 T x And (4) nano-chips.
Test example:
1. photo-thermal heating efficiency:
ru @ MXene prepared in example 5 was dispersed in water to prepare dispersions of different mass concentrations, and irradiation was performed using a xenon lamp (laser power density: 1.5 sun) to obtain temperature profiles of Ru @ MXene at different concentrations (0. Mu.g/mL, 20. Mu.g/mL, 50. Mu.g/mL, and 100. Mu.g/mL) upon irradiation with an infrared thermal imager, the temperature profiles being shown in FIG. 8.
As can be seen from FIG. 8, the Ru @ MXene can reach 53 ℃ after being irradiated for 15min at a lower mass concentration (100 mug/mL), which indicates that the Ru @ MXene can be effectively and rapidly photo-converted into heat energy, and simultaneously verifies the dependency of the photo-thermal performance of the Ru @ MXene on the concentration.
The same volume of the aqueous solution of the ruthenium complex prepared in example 1 and the MXene two-dimensional material Ti prepared in example 4 with the same mass concentration are taken 3 C 2 T x The aqueous dispersion of (1), the aqueous dispersion of Ru @ MXene obtained in example 5, and water were irradiated with a xenon lamp (laser power density: 1.5 sun), and a temperature curve was obtained with an infrared thermograph, the temperature curve being shown in FIG. 9, and a thermal infrared image being shown in FIG. 10.
In fig. 9-10, different samples: water, ruthenium complex and MXene two-dimensional material Ti 3 C 2 T x Ru @ MXene) under xenon lamp irradiation, wherein MXene two-dimensional material Ti 3 C 2 T x And Ru @ MXene reaches a solution temperature close to 53 ℃ within 15min under the irradiation of a xenon lamp, while the temperature of sample water is only 38 ℃, which proves that the MXene two-dimensional material Ti is 3 C 2 T x And Ru @ MXene nanoflakesHave good photo-thermal properties.
2. Photo-thermal stability:
the same volume of the aqueous solution of the ruthenium complex prepared in example 1 and the MXene two-dimensional material Ti prepared in example 4 with the same mass concentration are taken 3 C 2 T x The aqueous dispersion of (E), the aqueous dispersion of Ru @ MXene obtained in example 5 and water were irradiated with a xenon lamp (laser power density: 1.5 sun), and a temperature profile of 5 laser on/off cycles was obtained using an infrared thermal imager, as shown in FIG. 11.
The photothermal performance of Ru @ MXene is not obviously deteriorated in the whole process, which indicates that the composite material has good photothermal stability.
3. In vitro photodynamic activity:
measuring total ROS generated by a sample under the irradiation of a 532nm LED green lamp by taking a diphenyl isobenzofuran (DPBF) singlet oxygen indication fluorescent probe as a probe; the samples were: ruthenium complex prepared in example 1, MXene two-dimensional material Ti prepared in example 4 3 C 2 T x The Ru @ MXene and water prepared in example 5 were as follows:
2.97mL of the ruthenium complex prepared in example 1 and the MXene two-dimensional material Ti prepared in example 4 with different mass concentrations were placed in a quartz cuvette 3 C 2 T x Ru @ MXene prepared in example 5 and water were mixed with 30. Mu.L of a 10mM DPBF DMSO solution, respectively, under stirring; followed by illumination with a 532nm LED green lamp at 20mw for a 5min illumination period. In this process, at a predetermined time point, the absorbance of DPBF at 420nm was recorded using an ultraviolet spectrophotometer, and the change curve of the absorbance is shown in fig. 12.
In FIG. 12, when a ruthenium complex solution alone was irradiated with 532nm LED green light, the absorbance of DPBF at 420nm rapidly decreased, resulting in a large amount of 1 O 2 While the DPBF absorbance change in the Ru @ MXene solution is not obvious than that of the single ruthenium complex, more DPBF absorbance changes 1 O 2 MXene two-dimensional material Ti alone 3 C 2 T x DPBF Absorbance in solutionAlmost no change; the Ru @ MXene is shown to have a good photodynamic effect after loading the ruthenium complex.
4. Bactericidal activity of Ru @ MXene
(1) Preparing bacterial liquid: inoculating the single colony of colibacillus to 10mL LB culture solution, culturing in a shaking table at 37 deg.C and 220r/min until OD600 of bacteria solution is 0.5-0.6, measuring OD value, and diluting to 0.01 (bacteria solution concentration is 10) 7 CFU/mL) for use.
(2) Preparing a sample: preparing 30 mu M of mother liquor of the ruthenium complex aqueous solution of the embodiment 1 and 5mg/mL of the MXene two-dimensional material Ti of the embodiment 3 3 C 2 T x Aqueous dispersion and 5mg/mL of the aqueous dispersion of Ru @ MXene of example 4.
Taking a plurality of EP tubes, and preparing each bacterium according to the following mode:
sample 1) bacteria: adding 50 mu L of bacterial liquid and 450 mu L of sterile water;
sample 2) bacteria + ruthenium complex of example 1: mu.L of the bacterial suspension, 30. Mu.M of the ruthenium complex solution of example 1 (250. Mu.L) and sterile water (200. Mu.L) were added thereto, and the final concentration of the ruthenium complex of example 1 in the solution was 15. Mu.M.
Sample 3) bacteria + MXene two-dimensional material Ti of example 3 3 C 2 T x : adding 50 μ L of bacterial liquid and 5mg/mL of MXene two-dimensional material Ti of example 3 3 C 2 T x 10 μ L of aqueous dispersion and 440 μ L of sterile water in solution of MXene two-dimensional material Ti of example 3 3 C 2 T x The final concentration is 100 mug/ml; MXene two-dimensional Material Ti of example 3 was prepared in the same manner 3 C 2 T x The final concentration was 20. Mu.g/ml, 50. Mu.g/ml, 200. Mu.g/ml of 500. Mu.L solution containing 50. Mu.L of the bacterial suspension.
Sample 4) bacteria + ru @ mxene of example 4: 50 μ L of the bacterial suspension, 5mg/mL of the aqueous dispersion of Ru @ MXene of example 4 (10 μ L) and 440 μ L of sterile water were added thereto, and the final concentration of Ru @ MXene of example 4 in the solution was 100 μ g/mL.
5) The prepared sample 1) is inoculated; sample 2) bacteria + ruthenium complex of example 1; MXene two-dimensional Material Ti from example 3 with a final concentration of bacteria + in sample 3) of 100. Mu.g/ml 3 C 2 T x (ii) a Sample 4) bacteria + implementationRu @ MXene of example 4 was the test sample. Each detection sample is simultaneously treated with light and without light; irradiating a xenon lamp with the light intensity density of 1.50Sun for 30min under the illumination treatment condition of the wavelength range of 300-2500 nm;
note: light intensity density 1Sun =100mw/cm 2 。
6) The prepared sample 1) is inoculated; sample 3) MXene two-dimensional material Ti of example 3 with a final concentration of 20. Mu.g/ml of bacteria + 3 C 2 T x (ii) a MXene two-dimensional Material Ti of example 3 with a final concentration of bacteria + in sample 3) of 50. Mu.g/ml 3 C 2 T x (ii) a Sample 3) MXene two-dimensional material Ti of example 3 with final concentration of bacteria + 100. Mu.g/ml 3 C 2 T x (ii) a Sample 3) MXene two-dimensional material Ti of example 3 with a final concentration of 200. Mu.g/ml of bacteria + 3 C 2 T x To test the sample. Each detection sample is simultaneously treated with light and without light; the xenon lamp with the light irradiation condition of 300-2500 nm is irradiated for 30min with the light intensity density of 1.50 Sun.
7) And (3) colony plate culture: 100 μ L of each set of samples from step 6) was spread on agar plates. Placing in an incubator at 37 ℃, culturing for 18-24 hours, observing results, and recording data; the results are shown in FIG. 13.
8) And (3) colony plate culture: 100 μ L of each set of samples from step 5) was spread on agar plates. Placing in an incubator at 37 ℃, culturing for 18-24 hours, observing results, and recording data; the results are shown in FIG. 14.
(3) Results of plate culture
The different samples are irradiated by light to induce the sterilization effect of Ru @ MXene.
As shown in FIG. 13, the plate culture results showed that the method irradiated 30min under a xenon lamp with a light intensity of 1.5Sun with 15. Mu.M of the ruthenium complex of example 1 and 100. Mu.g/mL of the MXene two-dimensional material Ti of example 3 3 C 2 T x Under the condition of 110 mu g/mL Ru @ MXene of example 4, the concentration of each group of bacteria of the Escherichia coli is obviously reduced relative to that of the pure bacteria of the sample 1); while the Ru @ MXene of example 4 compares with the MXene two-dimensional material Ti of example 3 3 C 2 T x Single action group, ruthenium Complex of example 1The sterilization effect of the single action group of the substance is good.
The results of SEM observation of the plate-cultured samples are shown in FIG. 15.
As can be seen from the SEM image of FIG. 15, ru @ MXene accumulated on the surface of the bacteria and disrupted the cell wall. The ruthenium complex is excited by illumination to generate active oxygen to destroy a cell wall structure, and meanwhile, ru @ MXene converts light energy into heat energy to raise the temperature of tissues in a bacterial body, so that cell contents are leaked, and finally the bacterial death is caused.
The MXene two-dimensional material can be better improved in water dispersibility after being subjected to functional modification, and is favorable for being dispersed in a physiological environment. In the Ru @ MXene composite system, active oxygen generated by the ruthenium complex can increase capture of the photothermal material MXene to laser, and the photothermal effect of MXene can increase oxygen supply of tissues and promote PDT (PDT) of the ruthenium complex. Ru @ MXene has ultra-thin MXene nanosheet physics cutting cell membrane simultaneously, and photo-thermal treatment and ruthenium complex photodynamic treatment realize trinity synergistic antibiotic mechanism.
The sterilization effect of the Ru @ MXene is induced by light under different concentrations of the Ru @ MXene.
As shown in FIG. 14, the concentration of Ru @ MXene in example 4 was increased, the concentration of bacteria in dark condition did not change significantly, and the concentration of bacteria after light irradiation tended to decrease, so the concentration dependent effect of Ru @ MXene was shown by the Ru @ MXene sterilization of the present invention. When the concentration of Ru @ MXene reaches 50 mu g/ml, the Ru @ MXene of the invention has obvious inhibition effect on Escherichia coli, and the inhibition effect is stronger along with the increase of the concentration.
In conclusion, the ruthenium complex and MXene react through the surface functional group to form a covalent bond, and the ruthenium complex is loaded on the MXene surface to form the Ru @ MXene nanocomposite. Under the irradiation of light, active oxygen generated by the ruthenium complex can increase the capture of laser by the photothermal material MXene, and the photothermal effect of MXene can increase the oxygen supply of tissues and promote the generation of PDT (photodynamic therapy) of the ruthenium complex. Meanwhile, the ultrathin MXene nanosheets can also physically cut cell membranes to form a three-in-one system of a synergistic antibacterial and anti-tumor mechanism of physical cutting, photothermal therapy and ruthenium complex photodynamic therapy, and a new idea is provided for replacing antibiotic therapy and tumor drug therapy.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergy is characterized by comprising the ruthenium complex and an MXene two-dimensional material, wherein the ruthenium complex is loaded on the surface of the MXene two-dimensional material through a covalent bond to form the MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergy.
2. The MXene composite material modified by the photothermal and photodynamic cooperative ruthenium complex according to the claim 1,
the ruthenium complex has a structure shown in formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R 6 Is any one of H, alkyl with 1-3 carbon atoms, halogen or carboxyl, and R 1 、R 2 、R 3 、R 4 、R 5 Or R 6 At least one is a carboxyl group.
3. The MXene composite material modified by the photothermal and photodynamic cooperative ruthenium complex according to claim 1 or 2, wherein the ruthenium complex is
4. The MXene composite material modified by the photothermal and photodynamic synergistic ruthenium complex as claimed in claim 1, wherein the MXene two-dimensional material has a diameter of less than 500nm and a thickness of 1-5nm.
5. The preparation method of the MXene composite material modified by the photothermal and photodynamic synergistic ruthenium complex as claimed in any one of claims 1 to 4, is characterized by comprising the following preparation steps: and dispersing the MXene two-dimensional material into water to form a dispersion liquid, adding the ruthenium complex into the dispersion liquid, and heating and reacting under an inert gas atmosphere to obtain the MXene composite material modified by the ruthenium complex with photo-thermal and photodynamic synergism.
6. The method for preparing the MXene composite material modified by the ruthenium complex with photo-thermal and photo-dynamic synergy as claimed in claim 5, wherein the ruthenium complex is a mixture of ruthenium complex and MXene complex,
the reaction is carried out under the catalyst which is a composite catalyst of carbodiimide salt and 4-dimethylaminopyridine, and the mass ratio of the carbodiimide salt to the 4-dimethylaminopyridine is 1: 0.5-2.
7. The method for preparing the MXene composite material modified by the ruthenium complex with photo-thermal and photo-dynamic synergy according to claim 5,
the mass ratio of the ruthenium complex to the MXene two-dimensional material is 1: 0.5-2; the temperature of the heating reaction is 80-100 ℃.
8. The method for preparing the MXene composite material modified by the ruthenium complex with photo-thermal and photo-dynamic synergy as claimed in claim 5, further comprising the step of preparing the ruthenium complex:
s11, ruthenium precursor preparation: mixing 2,2' -bipyridine, lithium chloride and RuCl 3 Dissolving 3H2O in a first solvent, heating to react under an inert gas atmosphere, and cooling to room temperature after the reaction is finished, wherein the obtained solid is the ruthenium precursor; the ruthenium precursor has a structure represented by formula III:
s12, preparing a ruthenium complex: and dissolving the ruthenium precursor and substituted or unsubstituted 2,2' -bipyridine in a second solvent, heating to react under the atmosphere of inert gas, adjusting the pH value to be alkaline, continuing to react, and cooling to room temperature after the reaction is finished to obtain a solid ruthenium complex.
9. The method for preparing the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic coordination function as claimed in claim 5, further comprising the steps of:
the MXene two-dimensional material is obtained by carrying out in-situ etching on a base material of the MXene to obtain a multilayer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm, and carrying out ultrasonic oscillation on the multilayer MXene aqueous solution for 0.5-5 h.
10. An application of the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic coordination function as defined in any one of claims 1 to 4 or the MXene composite material modified by the ruthenium complex with the photo-thermal and photodynamic coordination function as defined in any one of claims 5 to 9 in preparation of a photo-thermal and photodynamic coordination antibacterial or antitumor drug.
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