CN115590956B - Ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergism and preparation method and application thereof - Google Patents
Ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergism and preparation method and application thereof Download PDFInfo
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 125
- 239000002131 composite material Substances 0.000 title claims abstract description 55
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims description 105
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 32
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 22
- 229910052707 ruthenium Inorganic materials 0.000 claims description 22
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Classifications
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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)
- Chemical & Material Sciences (AREA)
- 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 a ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergism, a preparation method and application thereof. Under illumination, the photo-thermal effect of MXene, the PDT of ruthenium complex and the physical cutting of the ultra-thin MXene nanosheets form a synergistic system of three-in-one of physical cutting, photo-thermal and photodynamic therapy, and high-efficiency sterilization is realized in a short time of 15-30min at a lower energy density of 150mW/cm 2 and a lower concentration of 100 mug/mL. The preparation method utilizes the hydroxyl and carboxyl condensation reaction to carry out bonding, is simple, does not need complex reaction process and harsh reaction conditions, can rapidly separate and purify the product, and meets the industrial production.
Description
Technical Field
The invention belongs to the technical field of photo-thermal and photodynamic materials, and particularly relates to a ruthenium complex modified MXene composite material with photo-thermal and photodynamic cooperations, and a preparation method and application thereof.
Background
In order to address the challenges of bacterial infection and antibiotic resistance, researchers have made many efforts to provide a number of 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 aforementioned several antimicrobial methods have limited their application in wound antimicrobial applications due to their own or application drawbacks. And unlike antibiotics, photodynamic sterilization is performed by generating active oxygen, and photothermal sterilization is performed by good photothermal effect, so that the problem that bacteria are difficult to generate drug resistance is solved, and the drug resistance crisis generated 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 drug resistance and the like, and are recently paid attention to by researchers.
Phototherapy (Photothermal therap% PTT) is a photoinduced method for killing pathogens by converting light energy into heat energy by a photothermal conversion agent to bring the tissue to a temperature to kill microorganisms. Photodynamic therapy (Photodynamic therapy, PDT) is that photodynamic agents generate Reactive Oxygen Species (ROS) with a strong oxidizing power under irradiation of laser light and cause cytotoxicity by virtue of their oxidative reaction with proteins, DNA, leading to deterioration of proteins, DNA and bacterial death. Photodynamic therapy generation is based primarily on the following three points: the interaction of the Photosensitizer (PS), light and oxygen results in the production of Reactive Oxygen Species (ROS). With the continuous development of scientific technology, the preparation of nanoscale photosensitizers or the loading of photosensitizers on nanomaterials for sterilization, which is called nano photodynamic sterilization technology, has received a great deal of 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 meet the application of photodynamic and photothermal in antibiosis and anti-tumor.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide the MXene composite material modified by the ruthenium complex with photo-thermal and photo-dynamic synergy, which has the effects of photo-thermal and photo-dynamic bacteriostasis and killing tumor cells, can realize photo-thermal and photo-dynamic synergy antibacterial and antitumor, and can realize synergy and high-efficiency antibacterial and antitumor through lower energy input.
The second purpose of the invention is to provide a preparation method of the ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergy.
The third purpose of the invention is to provide an application of the ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergy.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
The ruthenium complex modified MXene composite material with the photo-thermal and photo-dynamic coordination comprises a 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 photo-thermal and photo-dynamic coordination ruthenium complex modified MXene composite material.
Further, the ruthenium complex has a structure shown in formula I:
is a 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 a structure represented by formula II:
Wherein R 1、R2、R3、R4、R5 and R 6 are any one of H, alkyl having 1 to 3 carbon atoms, halogen or carboxyl, and at least one of R 1、R2、R3、R4、R5 or R 6 is carboxyl.
Further, the ruthenium complex is
Further, the diameter of the MXene two-dimensional material is smaller than 500nm, and the thickness is 1-5nm.
The second aim of the invention can be achieved by adopting the following technical scheme:
a preparation method of a ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergism comprises the following preparation steps:
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 in an inert gas atmosphere to obtain the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material.
Further, the reaction is carried out under the condition of a catalyst, wherein 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 temperature of the heating reaction is 80-100 ℃.
Further, the preparation method also comprises the preparation steps of the ruthenium complex:
s11, preparing a ruthenium precursor: dissolving substituted or unsubstituted 2,2' -bipyridine, lithium chloride and RuCl 3·3H2 O in DMF, heating to react under 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 the substituted or unsubstituted 2,2' -bipyridine in a second solvent, heating to react under an inert gas atmosphere, regulating the pH value to be alkaline, continuing the reaction, and cooling to room temperature after the reaction is finished, wherein the obtained solid is the ruthenium complex.
Further, the preparation method also comprises the steps of:
the MXene base material is subjected to in-situ etching to obtain a multi-layer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm, and the multi-layer MXene aqueous solution is subjected to ultrasonic oscillation for 0.5-5h to obtain the MXene two-dimensional material.
The third object of the invention can be achieved by adopting the following technical scheme:
Any one of the above devices has photo-thermal and photo-dynamic functions The application of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material prepared by the preparation method of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material or any one of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material in the preparation of photo-thermal and photodynamic synergistic antibacterial or antitumor drugs.
Compared with the prior art, the invention has the beneficial effects that:
1. The photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material provided by the invention is characterized in that the MXene two-dimensional material with photo-thermal effect and the ruthenium complex with photosensitive effect are bonded together through 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 photo-thermal conversion efficiency and photo-thermal stability under illumination, and can be used for photo-thermal antibiosis and anti-tumor; the ruthenium complex can be used as a photosensitizer to generate ROS under illumination, and can be used as an antibacterial and antitumor substance of photodynamic; therefore, the composite material formed by loading the ruthenium complex on the MXene two-dimensional material is antibacterial and anti-tumor in a synergistic way.
2. The preparation method of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material utilizes the rich hydroxyl on the surface of the MXene two-dimensional material to carry out condensation reaction with the carboxyl-containing ruthenium complex to realize bond connection load, has simple preparation method, does not need complex reaction process and harsh reaction conditions, can quickly separate and purify the product, and meets the industrial production.
3. The ruthenium complex modified MXene composite material with the synergy of photo-thermal and photodynamic has the dual effects of photo-thermal and photodynamic, and can realize high-efficiency sterilization in a short time (15-30 min) with lower energy density (150 mW/cm 2) and lower concentration (100 mug/ml), so that the ruthenium complex modified MXene composite material can be applied to the preparation of photo-thermal and photodynamic synergistic antibacterial or antitumor drugs.
Drawings
FIG. 1 is a mass spectrum of the ruthenium complex prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the ruthenium complex prepared in example 1;
FIG. 3 is a TEM image of the MXene two-dimensional material prepared in example 3 and Ru@MXene prepared in example 4;
FIG. 4 is an EDS spectrum of the MXene two-dimensional material prepared in example 3;
FIG. 5 is an EDS spectrum of Ru@MXene prepared in example 4;
FIG. 6 is an XRD pattern of the MXene two-dimensional material prepared in example 3 and the Ru@MXene composite material prepared in example 4;
FIG. 7 is an infrared spectrum of the MXene two-dimensional material prepared in example 3 and the Ru@MXene composite material prepared in example 4;
FIG. 8 is a graph showing the temperature rise of the Ru@MXene aqueous suspension prepared in example 4 at different concentrations with irradiation of a xenon lamp;
FIG. 9 is a graph showing the temperature rise of aqueous suspensions of different samples (water, the MXene two-dimensional material prepared in example 3, the ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4) with irradiation of a xenon lamp;
FIG. 10 is a thermal infrared plot of aqueous suspensions of different samples (water, the MXene two-dimensional material prepared in example 3, the ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4) as irradiated by a xenon lamp;
FIG. 11 is a graph showing the temperature profile of aqueous suspensions of different samples (water, the MXene two-dimensional material prepared in example 3, the ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4) during 5 laser on/off cycles;
FIG. 12 is a graph showing the absorption change at 420nm of a two-dimensional MXene material prepared in example 3, a ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4 mixed with DPBF under illumination;
FIG. 13 is a graph showing the antibacterial effect of the two-dimensional MXene material prepared in example 3, the ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4 on E.coli under dark and light conditions;
FIG. 14 is a graph showing the antibacterial effect of Ru@MXene at different concentrations on E.coli under dark and light conditions;
FIG. 15 is an SEM image of the two-dimensional MXene material prepared in example 3, the ruthenium complex prepared in example 1, and Ru@MXene prepared in example 4 under dark and light conditions.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The MXene two-dimensional material is a novel nano two-dimensional sheet of metal carbonitride, 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.
Unlike antibiotics, the sterilization mechanism of MXene two-dimensional materials mainly depends on physical damage effect and good photo-thermal effect, so that bacteria are difficult to generate drug resistance, and the drug resistance crisis generated by excessive use of antibiotics can be effectively avoided. Particularly, the targeted or specific biological activity modification is carried out on the MXene two-dimensional material, so that the MXene two-dimensional material has other functions such as targeting and loading, 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.
Ru (II) complex has strong visible light absorption capacity and rich excited state property. Among them, ru (II) complexes having long-life triplet excited states exhibit strong redox properties, contributing to intermolecular electron transfer or energy transfer. These properties make them widely used in PDT as photosensitizers.
Ru (II) complexes are widely used in antibacterial and antitumor drugs. The photosensitizer can be combined with the nano material in a covalent or non-covalent combination mode, so that the chemical properties such as solubility of the photosensitizer are controlled, self-quenching among the photosensitizers is avoided, and the generation efficiency of active oxygen is improved; nanomaterials can also alter the in vivo and in vitro behavior, including pharmacokinetics and biodistribution, of photosensitizers by enhancing permeability and retention Effects (EPR) or by modifying their surfaces with targeting ligands.
Therefore, in order to solve the problems of drug resistance of bacteria to antibiotics and poor treatment effect of single photosensitizer or nano material, the ruthenium complex and the MXene two-dimensional material are self-assembled to form a covalent bond through surface functional group reaction, 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 photo-thermal and photo-dynamic coordinated ruthenium complex modified MXene composite material comprises a 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 photo-thermal and photo-dynamic coordinated ruthenium complex modified MXene composite material.
Active oxygen generated by PDT can increase the capture of laser light by photo-thermal agents, and photo-thermal action of PTT can increase oxygen supply to tissues to promote PDT. The system of the photo-thermal treatment and the ruthenium complex photodynamic treatment synergistic antibacterial and antitumor mechanism is formed, so that the MXene composite material can realize PTT and PDT combined treatment simultaneously, and has excellent controllability, minimally invasive property, low toxicity and no drug resistance.
In one embodiment, the ruthenium complex has a structure represented by formula I:
In one of the embodiments of the present invention, Is a compound with 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; the two pyridine rings may also be connected by forming a fused ring with the ring group; wherein three of formula IMay be the same or different, but has at least oneContaining at least one carboxyl group.
Preferably, the method comprises the steps of,Is a substituted or unsubstituted 2,2' -bipyridine, and at least oneIs substituted 2,2' -bipyridine; at least one of the substituted 2,2' -bipyridines has a structure represented by formula II:
wherein R 1-R6 is any one of H, alkyl with 1-3 carbon atoms, halogen and carboxyl, and at least one of R 1-R6 is carboxyl.
The 2,2 '-bipyridine is coordinated with ruthenium, and six N atoms of the three 2,2' -bipyridines are positioned at relatively symmetrical positions, so that the formed ruthenium complex has a relatively compact stable structure, has good stability when being used as a photosensitizer, and can realize relatively good photodynamic force.
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.
The ruthenium complex formed by 2,2 '-bipyridine, wherein two carboxyl groups contained in the 4 and 4' -positions of the 2,2 '-bipyridine are positioned on the same side of the 2,2' -bipyridine, have relatively consistent bond length and bond angle, so that the ruthenium complex has smaller steric hindrance and smaller stress after being condensed with the hydroxyl groups on the surface of the MXene two-dimensional material to form a stable composite structure.
In one embodiment, the ruthenium complex is
In one embodiment, the MXene two-dimensional material has a diameter of less than 500nm and a thickness of 1-5nm.
Wherein the MXene two-dimensional material is a known material; preferably, the MXene two-dimensional material is any one of Ti3C2、Ti2C、Nb2C、V2C、(Ti0.5Nb0.5)2C、(V0.5Cr0.5)3C2、Ti3CN and Ta 4C3. More preferably, the MXene two-dimensional material is Ti 3C2.
The diameter of the MXene two-dimensional material is smaller than 500nm, the thickness is 1-5nm, on one hand, the material can be modified by ruthenium complex, and the material has larger specific surface; on the other hand, after the ruthenium complex is loaded on the MXene two-dimensional material with the size, the material can be transferred in a human body, can be effectively gathered on the surface of bacteria or cells for full contact, and can play a role through photo-thermal and photo-sensitivity.
The invention also provides a preparation method of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material, which comprises the following preparation steps:
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 in an inert gas atmosphere to obtain the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material.
The surface of the MXene two-dimensional material is provided with hydrophilic active groups such as hydroxyl and carbonyl, and the modification of the MXene two-dimensional material can be effectively realized 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 function modification of the MXene two-dimensional material, so that the MXene two-dimensional material is beneficial to being dispersed in a physiological environment.
Therefore, the invention uses the ruthenium complex containing carboxyl, the carboxyl on the ruthenium complex and the hydroxyl on the surface of the MXene two-dimensional material are linked to form a load after condensation reaction, and the reaction is the condensation reaction of carboxyl and hydroxyl into ester, which is conventional in the art, so that the complex process and the harsh reaction condition are not required.
In one embodiment, the reaction is carried out under the condition of a catalyst, wherein 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.
After the carboxyl is activated by the carbodiimide salt, the condensation reaction of the carboxyl and the hydroxyl into ester can be promoted under the catalysis of the catalyst 4-dimethylaminopyridine, and the yield is obviously improved. Preferably, the carbodiimide salt is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI), and can be combined with a water-soluble composite catalyst consisting of 4-Dimethylaminopyridine (DMAP), so that an organic solvent is not required to be introduced, and the post-treatment and composite green chemical requirements are simplified.
In one embodiment, the mass ratio of the ruthenium complex to the MXene two-dimensional material is 1:0.5-2; the reaction temperature is 80-100 ℃.
In one embodiment, the method further comprises the step of preparing a ruthenium complex:
S11, preparing a ruthenium precursor: dissolving substituted or unsubstituted 2,2' -bipyridine, lithium chloride and RuCl 3·3H2 O in DMF, condensing and refluxing for reaction for 8-36h under inert gas atmosphere, cooling to room temperature after the reaction is finished, wherein the solid is the ruthenium precursor; the ruthenium precursor has a structure represented by formula III:
S12, preparing a ruthenium complex: the ruthenium precursor and the substituted or unsubstituted 2,2' -bipyridine are dissolved in a second solvent, heated to react under the atmosphere of inert gas, the pH is regulated to be alkaline, the reaction is continued, the reaction is ended and the temperature is reduced to room temperature, and the obtained solid is ruthenium complex.
In one embodiment, the molar mass ratio of the substituted or unsubstituted 2,2' -bipyridine, lithium chloride and RuCl 3·3H2 O in step S11 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 conditions in step S11 are reflux reaction for 6-24h.
In one embodiment, the molar mass ratio of ruthenium precursor to 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 method further comprises the steps of:
the MXene base material is subjected to in-situ etching to obtain a multi-layer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm, and the multi-layer MXene aqueous solution is subjected to ultrasonic oscillation for 0.5-5h to obtain the MXene two-dimensional material.
The invention also provides an application of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material or the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material prepared by the preparation method of the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite material in preparation of photo-thermal 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 3·3H2 O were dissolved in 10mL of N, N-Dimethylformamide (DMF), and then condensed and refluxed at 140℃for 12 hours under the protection of argon atmosphere. Through suction filtration, recrystallization and vacuum drying, the dark green microcrystal is obtained, and is ruthenium precursor cis- [ Ru (bpy) 2Cl2]·2H2 O;
0.52g of ruthenium precursor cis- [ Ru (bpy) 2Cl2]·2H2 O is dissolved in absolute ethyl alcohol, then 0.3g of 2,2 '-bipyridine-4, 4' -dicarboxylic acid (dcb) is added, the mixture is heated to 80 ℃ for reflux under the protection of argon atmosphere, the pH is regulated to be alkaline by NaOH, the mixture is continuously refluxed for 12 hours after the dissolution, the pH is regulated by HCI after the reaction is finished, the solvent is removed by rotary evaporation under the reduced pressure condition, and the orange-red solid ruthenium complex [ Ru (bpy) 2(dcb)]2+ is obtained.
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 3·3H2 O were dissolved in 30mL of DMF and then condensed under reflux for 6h under the protection of argon atmosphere. Carrying out suction filtration, recrystallization, multiple purification and drying to obtain a ruthenium precursor;
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, regulating pH to alkalinity by NaOH, continuously refluxing for 8 hours after dissolving, regulating pH by HCI after reaction, and removing solvent by rotary evaporation under the condition of reduced pressure to obtain a 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 3·3H2 O were dissolved in 20mL of DMF and then condensed under reflux at 140℃for 24h under argon atmosphere. Carrying out suction filtration, recrystallization and vacuum drying to obtain a ruthenium precursor;
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, regulating pH to alkalinity by NaOH, continuously refluxing for 36 hours after dissolution, regulating pH by HCl after reaction, and removing solvent by rotary evaporation under the condition of reduced pressure to obtain a solid ruthenium complex.
Example 4: MXene two-dimensional material preparation (Ti 3C2Tx)
3G of lithium fluoride powder is weighed, 40mL of 12M concentrated hydrochloric acid is added, 2g of Ti 3AlC2 base material is added after uniform stirring, stirring is carried out for two days at 40 ℃, and pure multi-layer Ti 3C2Tx material is obtained through water washing and ethanol washing. Dispersing the multi-layer Ti 3C2Tx material in a book, vigorously vibrating at room temperature and carrying out ultrasonic treatment for 3 hours to obtain an aqueous suspension of the few-layer Ti 3C2Tx two-dimensional nano material, and carrying out freeze drying to obtain the Ti 3C2Tx two-dimensional nano material.
Example 5: preparation of the Material Ru@MXene
Adding 0.1g of ruthenium complex [ Ru (bpy) 2(dcb)]2+ ] prepared in example 1 into Ti 3C2Tx two-dimensional nano material suspension containing 0.1g, adding 0.005g 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 3h under an inert gas atmosphere at 100 ℃, centrifuging after the reaction is finished, removing supernatant, repeatedly centrifuging and washing residues with deionized water, and freeze-drying to obtain the ruthenium complex modified MXene composite material with the photo-thermal and photo-dynamic synergy, namely Ru@MXene.
Example 6: preparation of composite materials
Adding 0.05g of the ruthenium complex prepared in the example 2 into a Ti 3C2Tx two-dimensional nano material suspension containing 0.1g, 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 in an inert gas atmosphere at 100 ℃, centrifuging after the reaction is finished, removing the supernatant, repeatedly centrifuging and washing residues with deionized water, and freeze-drying to obtain the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite.
Example 7: preparation of composite materials
Adding 0.2g of the ruthenium complex prepared in the example 3 into a Ti 3C2Tx two-dimensional nano material suspension containing 0.1g, adding 0.012g 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 12h in an inert gas atmosphere at 100 ℃, centrifuging after the reaction is finished, removing the supernatant, repeatedly centrifuging and washing residues with deionized water, and freeze-drying to obtain the photo-thermal and photodynamic synergistic ruthenium complex modified MXene composite.
Test example:
1. The ruthenium complex [ Ru (bpy) 2(dcb)]2+ prepared in example 1 was subjected to mass spectrometry and nuclear magnetic resonance analysis, and the results are shown in FIG. 1 and FIG. 2, wherein ESI-MS (CH 3OH)：m/z：329.04[M]2+, M was 658.08, which was almost the same as the relative molecular weight 657.65, and the result of nuclear magnetic resonance analysis was ：1H 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),, which revealed that the ruthenium complex was [ Ru (bpy) 2(dcb)]2+.
2. The two-dimensional material Ti 3C2Tx of MXene prepared in example 4 and Ru@MXene prepared in example 5 were observed under TEM, and TEM images are shown in FIG. 3, wherein the right side image is a TEM image of the two-dimensional material Ti 3C2Tx of MXene prepared in example 4, and the left side image is a TEM image of Ru@MXene prepared in example 5. The EDS energy spectrum is shown in FIG. 4 and FIG. 5, wherein FIG. 4 is the EDS energy spectrum of the MXene two-dimensional material Ti 3C2Tx prepared in example 4, and FIG. 5 is the EDS energy spectrum of Ru@MXene prepared in example 5.
As can be seen from FIG. 3, the MXene two-dimensional material Ti 3C2Tx is in a two-dimensional lamellar shape, and the Ru@MXene material formed by modification of the ruthenium complex is still in a lamellar shape, and the size is about 200 nm.
From FIG. 4, it is clear that the MXene two-dimensional material Ti 3C2Tx contains Ti, O, cl, F, c elements, while the Ru@MXene of FIG. 5 shows new elements N, ru, demonstrating that the MXene surface is successfully loaded by Ru-containing substances.
3. XRD detection is carried out on the MXene two-dimensional material Ti 3C2Tx prepared in the example 4 and Ru@MXene prepared in the example 5, and an XRD pattern is shown in figure 6.
The (002) peak of ru@mxene in fig. 6 is shifted to a lower angle by 0.91 °, corresponding to a significant increase in interlayer space between ru@mxene sheets, is the formation of an ultrathin nanoplatelet structure, favoring the ultrathin nanoplatelets to physically cleave cell membranes, thereby improving antibacterial or antitumor efficiency.
4. The two-dimensional MXene material Ti 3C2Tx prepared in example 4 and Ru@MXene prepared in example 5 were respectively subjected to infrared spectrum test, and an infrared spectrum test chart is shown in FIG. 7.
In fig. 7, the MXene two-dimensional materials Ti 3C2Tx and ru@mxene both show typical characteristic bands at 3431cm -1,1632cm-1 and 562cm -1, corresponding to-OH, c=o and Ti-O stretching vibrations, respectively. The Ru@MXene modified by the ruthenium complex has an absorption band related to ester bonds at 1088cm -1 and 1049cm -1, which shows that the hydroxyl group on the ruthenium complex and the hydroxyl group on the MXene two-dimensional material Ti 3C2Tx are successfully esterified, and the ruthenium complex is loaded on the MXene two-dimensional material Ti 3C2Tx nano-sheet.
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 irradiated using a xenon lamp (laser power density: 1.5 sun), and temperature profiles of Ru@MXene of different concentrations (0. Mu.g/mL, 20. Mu.g/mL, 50. Mu.g/mL, and 100. Mu.g/mL) at the time of irradiation were obtained using a thermal infrared imager, and the temperature profiles are shown in FIG. 8.
As can be seen from FIG. 8, the temperature of the solution can reach 53 ℃ after 15min irradiation under the condition of lower mass concentration (100 mug/mL) of Ru@MXene, which shows that Ru@MXene can be effectively and rapidly subjected to light conversion into heat energy, and meanwhile, the dependency of the photo-thermal property of Ru@MXene on the concentration is also verified.
The aqueous solution of the ruthenium complex prepared in example 1, the aqueous dispersion of the MXene two-dimensional material Ti 3C2Tx prepared in example 4, and the aqueous dispersion of Ru@MXene prepared in example 5 were used in the same volume and the same mass concentration, and irradiated with a xenon lamp (laser power density: 1.5 sun) to obtain a temperature curve using an infrared thermal imager, the temperature curve being shown in FIG. 9, and a thermal infrared image being shown in FIG. 10.
In fig. 9-10, the different samples: under the irradiation of a xenon lamp, the temperature of the aqueous solution of water, the ruthenium complex and the MXene two-dimensional material Ti 3C2Tx and Ru@MXene) is close to 53 ℃ within 15min, and the temperature of the sample water is only 38 ℃, so that the good photo-thermal properties of the MXene two-dimensional material Ti 3C2Tx and the Ru@MXene nano-sheet are demonstrated.
2. Photo-thermal stability:
The aqueous solution of the ruthenium complex prepared in example 1, the aqueous dispersion of the MXene two-dimensional material Ti 3C2Tx prepared in example 4, and the water-soluble Ru@MXene prepared in example 5 were irradiated with the same volume and the same mass concentration using a xenon lamp (laser power density: 1.5 sun), and a temperature profile with an irradiation time of 5 laser on/off cycles was obtained using an infrared thermal imager, and the temperature profile is shown in FIG. 11.
The photo-thermal property of Ru@MXene is not obviously deteriorated in the whole process, which indicates that the Ru@MXene has good photo-thermal stability.
3. In vitro photodynamic activity:
Measuring total ROS generated by a sample under 532nm LED green light irradiation by taking a diphenyl isobenzofuran (DPBF) singlet oxygen indication fluorescent probe as a probe; the samples are respectively: the ruthenium complex prepared in example 1, the MXene two-dimensional material Ti 3C2Tx prepared in example 4, the Ru@MXene prepared in example 5 and water are as follows:
2.97mL of the ruthenium complex prepared in example 1, the MXene two-dimensional material Ti 3C2Tx prepared in example 4, ru@MXene prepared in example 5, water and 30 μl of DMSO solution of DPBF with a concentration of 10mM are mixed in a quartz cuvette; subsequently, the mixture was irradiated with a 20mw 532nm LED green light for a period of 5 minutes. In this process, the absorbance of DPBF at 420nm was recorded using an ultraviolet spectrophotometer at a predetermined time point, and the change curve of absorbance was shown in FIG. 12.
In FIG. 12, when the single ruthenium complex solution was irradiated with 532nm LED green light, the absorbance of DPBF at 420nm was rapidly reduced, producing a large amount of 1O2, while the change in absorbance of DPBF in Ru@MXene solution was not evident for the single ruthenium complex, still producing more 1O2, and little change in absorbance of DPBF in the single MXene two-dimensional material Ti 3C2Tx solution; the Ru@MXene loaded ruthenium complex has a good photodynamic effect.
4. Bactericidal activity of Ru@MXene
(1) Preparing bacterial liquid: e.coli single colony is picked up by an inoculating loop to 10mL of LB culture solution, and the strain is placed in a shaking table at 37 ℃ and 220r/min for culture until the OD600 of the strain is between 0.5 and 0.6, the OD value is measured, and the strain is diluted to 0.01 (the strain concentration is 10 7 CFU/mL) for later use.
(2) Preparing a sample: a mother liquor of 30. Mu.M was prepared, respectively, from the aqueous ruthenium complex of example 1, 5mg/mL of the aqueous dispersion of the MXene two-dimensional material Ti 3C2Tx of example 3, and 5mg/mL of the aqueous dispersion of Ru@MXene of example 4.
Taking a plurality of EP tubes, and preparing each strain 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 liquid, 30. Mu.M of the ruthenium complex solution of example 1 and 200. Mu.L of sterile water were added, 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 3C2Tx of example 3: 50. Mu.L of the bacterial liquid, 5mg/mL of the aqueous dispersion of the MXene two-dimensional material Ti 3C2Tx of example 3 and 440. Mu.L of sterile water are added, and the final concentration of the MXene two-dimensional material Ti 3C2Tx of example 3 in the solution is 100. Mu.g/mL; a500. Mu.L solution containing 50. Mu.L of the bacterial liquid was prepared in the same manner as described above, wherein the final concentration of the MXene two-dimensional material Ti 3C2Tx of example 3 was 20. Mu.g/ml, 50. Mu.g/ml and 200. Mu.g/ml.
Sample 4) bacteria+ru@mxene of example 4: mu.L of the bacterial liquid, 5mg/mL of the Ru@MXene aqueous dispersion of example 4, 10. Mu.L and 440. Mu.L of sterile water were added, and the final concentration of Ru@MXene of example 4 in the solution was 100. Mu.g/mL.
5) Sample 1) bacteria in the configuration; sample 2) bacteria+ruthenium complex of example 1; the MXene two-dimensional material Ti 3C2Tx of example 3 with a final concentration of 100. Mu.g/ml in sample 3); sample 4) bacteria+Ru@MXene of example 4 was the test sample. Each detection sample is simultaneously subjected to two groups of treatment, namely illumination and no illumination; the illumination treatment condition is that a xenon lamp with the wavelength range of 300-2500 nm irradiates for 30min with the light intensity density of 1.50 Sun;
Note that: the light intensity density is 1 sun=100 mw/cm 2.
6) Sample 1) bacteria in the configuration; sample 3) MXene two-dimensional material Ti 3C2Tx of example 3 with a final concentration of 20 μg/ml of bacteria; the MXene two-dimensional material Ti 3C2Tx of example 3 with a final concentration of 50 μg/ml in sample 3); the MXene two-dimensional material Ti 3C2Tx of example 3 with a final concentration of 100. Mu.g/ml in sample 3); the MXene two-dimensional material Ti 3C2Tx of example 3 with a final concentration of 200. Mu.g/ml in sample 3) was used as a test sample. Each detection sample is simultaneously subjected to two groups of treatment, namely illumination and no illumination; the irradiation treatment condition is that a xenon lamp with the wavelength range of 300-2500 nm irradiates for 30min with the light intensity density of 1.50 Sun.
7) Colony plate culture: 100. Mu.L of each set of samples from step 6) were plated on agar plates. Placing in a 37 ℃ incubator, culturing for 18-24 hours, observing the result, and recording data; the results are shown in FIG. 13.
8) Colony plate culture: 100. Mu.L of each set of samples from step 5) were plated on agar plates. Placing in a 37 ℃ incubator, culturing for 18-24 hours, observing the result, and recording data; the results are shown in FIG. 14.
(3) Plate culture results
The illumination of different samples induces the sterilization effect of Ru@MXene.
As shown in FIG. 13, the plate culture result shows that the method has obvious reduction of the concentration of each group of bacteria of the escherichia coli relative to the pure bacteria of the sample 1) under the conditions that the xenon lamp with the light intensity of 1.5Sun is irradiated for 30min,15 mu M of the ruthenium complex of the example 1, 100 mu g/mL of the MXene two-dimensional material Ti 3C2Tx of the example 3 and 110 mu g/mL of the Ru@MXene of the example 4; the Ru@MXene of example 4 was better in sterilization effect than the MXene two-dimensional material Ti 3C2Tx of example 3 alone and the ruthenium complex of example 1 alone.
The results of SEM observation of the above plate-cultured samples are shown in FIG. 15.
As can be seen from the SEM image of FIG. 15, ru@MXene aggregates at the bacterial surface and damages the cell wall. As the ruthenium complex is excited by illumination to generate active oxygen, the cell wall structure is destroyed, meanwhile, ru@MXene converts light energy into heat energy to raise the temperature of tissue in bacteria, the cell content leaks, and the bacteria die finally.
After the function of the MXene two-dimensional material is modified, the water dispersibility of the MXene two-dimensional material can be better improved, and the MXene two-dimensional material is beneficial to being dispersed in physiological environments. In the Ru@MXene composite system, active oxygen generated by the ruthenium complex can increase the capture of a photothermal material MXene on laser, and the photothermal effect of the MXene can increase the oxygen supply of tissues and promote the generation of the ruthenium complex PDT. Ru@MXene simultaneously has ultrathin MXene nanosheets for physically cutting cell membranes, photothermal treatment and ruthenium complex photodynamic treatment, and realizes a three-in-one synergistic antibacterial mechanism.
The Ru@MXene sterilization effect is induced by illumination under different concentrations of Ru@MXene.
As shown in FIG. 14, with the increase of the concentration of Ru@MXene in example 4, the bacterial concentration in dark condition did not change significantly, and the bacterial concentration was in a decreasing trend after illumination irradiation, so that Ru@MXene sterilization of the present invention showed Ru@MXene concentration-dependent effect. When the concentration of Ru@MXene reaches 50 mug/ml, the Ru@MXene shows an obvious inhibition effect on escherichia coli, and along with the increase of the concentration, the inhibition effect is stronger.
In summary, the ruthenium complex and MXene react through the surface functional groups to form covalent bonds, and the ruthenium complex is loaded on the surface of the MXene to form the Ru@MXene nanocomposite. Under illumination, active oxygen generated by the ruthenium complex can increase the capture of the photo-thermal material MXene on laser, and the photo-thermal action of the MXene can increase the oxygen supply of tissues and promote the generation of the ruthenium complex PDT. Meanwhile, the ultrathin MXene nanosheets can also physically cut cell membranes to form a system of three-in-one synergistic antibacterial and antitumor mechanisms of physical cutting, photothermal treatment and ruthenium complex photodynamic treatment, and a new thought is provided for replacing antibiotic treatment and tumor drug treatment.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (7)
1. The ruthenium complex modified MXene composite material with the photo-thermal and photo-dynamic coordination is characterized by comprising a ruthenium complex and a 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 ruthenium complex modified MXene composite material with the photo-thermal and photo-dynamic coordination;
the ruthenium complex is
The MXene two-dimensional material is a Ti 3C2Tx two-dimensional nano material;
The preparation method of the MXene two-dimensional material comprises the following steps: the base material of the MXene is subjected to in-situ etching to obtain a multi-layer MXene aqueous solution with the diameter of 1-10 mu m and the thickness of 10-20nm, the multi-layer MXene aqueous solution is subjected to ultrasonic vibration for 0.5-5h to obtain an aqueous suspension of a few-layer Ti 3C2Tx two-dimensional nano material, and the Ti 3C2Tx two-dimensional nano material is obtained through freeze drying.
2. The ruthenium complex modified MXene composite material with photo-thermal and photo-dynamic coordination according to claim 1, wherein the diameter of the MXene two-dimensional material is less than 500nm, and the thickness is 1-5nm.
3. A method for preparing the ruthenium complex modified MXene composite material with photo-thermal and photo-dynamic synergy according to any one of claims 1-2, comprising the following preparation steps:
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 in an inert gas atmosphere to obtain the ruthenium complex modified MXene composite material with photo-thermal and photo-dynamic cooperations.
4. The method for preparing the ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergy according to claim 3, which is characterized in that,
The reaction is carried out under the condition of a catalyst, wherein 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).
5. The method for preparing the ruthenium complex modified MXene composite material with photo-thermal and photodynamic synergy according to claim 3, which is characterized in that,
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 ℃.
6. The method for preparing a ruthenium complex modified MXene composite material with photo-thermal and photo-dynamic coordination according to claim 3, further comprising the steps of:
S11, preparing a ruthenium precursor: dissolving 2,2' -bipyridine (bpy), lithium chloride and RuCl 3·3H2 O in a first solvent, heating and reacting under an inert gas atmosphere, and cooling to room temperature after the reaction is finished, wherein the obtained solid is the ruthenium precursor cis- [ Ru (bpy) 2Cl2]·2H2 O;
S12, preparing a ruthenium complex: dissolving the ruthenium precursor cis- [ Ru (bpy) 2Cl2]·2H2 O in a second solvent, adding 2,2 '-bipyridine-4, 4' -dicarboxylic acid (dcb), heating to react under an inert gas atmosphere, adjusting pH to be alkaline, continuing the reaction, cooling to room temperature after the reaction is finished, adjusting pH by HCl, and removing the solvent by rotary evaporation under a reduced pressure condition to obtain a solid ruthenium complex [ Ru (bpy) 2(dcb)]2+.
7. Use of a photo-thermal and photo-dynamic ruthenium complex modified MXene composite material with photo-thermal and photo-dynamic synergy according to any one of claims 1-2 or a photo-thermal and photo-dynamic synergy ruthenium complex modified MXene composite material prepared by a preparation method of a photo-thermal and photo-dynamic synergy ruthenium complex modified MXene composite material according to any one of claims 3-6 in preparation of photo-thermal and photo-dynamic synergy anti-escherichia coli drugs.
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