CN114736209B - Zinc-europium-porphyrin phosphorus cluster material and preparation method and application thereof - Google Patents

Zinc-europium-porphyrin phosphorus cluster material and preparation method and application thereof Download PDF

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CN114736209B
CN114736209B CN202210288425.1A CN202210288425A CN114736209B CN 114736209 B CN114736209 B CN 114736209B CN 202210288425 A CN202210288425 A CN 202210288425A CN 114736209 B CN114736209 B CN 114736209B
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europium
porphyrin
black phosphorus
zinc
phosphorus
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CN114736209A (en
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陈秋云
王军
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Jiangsu University
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Abstract

The invention provides a zinc-europium porphyrin phosphorus cluster material and a preparation method and application thereof, wherein lamellar black phosphorus and europium chloride react with black phosphorus under the noise condition to form europium-doped black phosphorus containing P-Eu and O-Eu bonds; then, reacting tetra (4-carboxyphenyl) porphyrin, zinc acetate and europium-doped black phosphorus by utilizing a solvothermal reaction to obtain a zinc-europium-porphyrin phosphorus cluster material; the material prepared by the invention has better photo-thermal property, and can convert NAD into NAD under the drive of visible light + Reduction to NADH, useful in vivo NAD + The reduction and catalysis of the material are expected to become a novel green bacteria inhibiting material.

Description

Zinc-europium porphyrin phosphorus cluster material and preparation method and application thereof
Technical Field
The invention relates to a zinc-europium porphyrin phosphorus cluster material and a preparation method and application thereof, belonging to the technical field of material preparation and application.
Background
NAD in Normal organisms + the/NADH ratio is always in a state of dynamic equilibrium, and this ratio is a very important index that reflects the redox state of a cell, thereby determining the metabolic activity of a cell and the health of a cell. Nicotinamide Adenine Dinucleotide (NAD) + ) And the reduced NADH thereof are important coenzymes in the life process, and participate in the redox metabolism and other a series of important biochemical processes in the life body. Human body to NAD + And NADH requirements affect the ratio between the two, thereby having various effects on cellular health and biological processes. The research finds that the intervention of mitochondria targeting NADH (reduced state of nicotinamide adenine dinucleotide)/NAD + (Nicotinamide adenine dinucleotide, abbreviated as NAD) + ) The ratio, increasing the amount of NADH, can block the electron transmission of bacteria, thus interfering the expression of cell energy and related genes and reducing the bacterial infection rate.
The treatment of bacterial infection is mainly antibiotics, and the abuse of antibiotics causes the bacteria to generate drug resistance, thereby greatly reducing the curative effect of the antibiotics. The development of low-toxicity high-efficiency green nano antibacterial materials becomes a hot trend of research in recent years, the effect of a nano and biological interface can effectively treat bacterial infection, and the preparation of novel photothermal antibacterial materials by utilizing near infrared light with low phototoxicity on the basis of selecting low-toxicity materials is the current development direction.
Black scale (BP) toolThe metal-modified BP has good biocompatibility, near infrared absorption and good photo-thermal performance, in recent years, the metal-modified BP generates Reactive Oxygen Species (ROS) under the action of near infrared light, and the ROS kills tumors and bacteria, so that the metal-modified BP is a good photodynamic therapeutic agent. However, the black phosphorus has poor stability in air, and the black phosphorus itself can be rapidly degraded when exposed to air and water, thereby seriously affecting the application capability. However, other conventional photothermal antibacterial materials mainly comprise metal sulfides and metal oxides, but these photothermal preparations are degraded slowly, and are easy to cause biological safety problems such as physiological rejection. Thus, the study of NAD + The reduction reagent is expected to be used for regulating cell reduction in the field of biomedicine and becomes a novel compound for resisting infection and activating immunity.
Disclosure of Invention
Aiming at some defects in the prior art, the invention provides a zinc-europium porphyrin phosphorus cluster material (marked as BP @ Eu-TCPP-Zn) and a preparation method and application thereof.
The invention firstly provides a zinc-europium-porphyrin phosphorus cluster material, which is marked as BP @ Eu-TCPP-Zn, the zinc-europium-porphyrin phosphorus cluster material is composed of a lamellar structure with the average width of 1 mu m, the mass percentage content of metal europium and zinc in the zinc-europium-porphyrin phosphorus cluster material is respectively 1.5% and 6.8%, and the zinc-europium-porphyrin phosphorus cluster material contains europium black phosphorus and tetra (4-carboxyphenyl) zinc porphyrin.
The infrared spectrogram is 1650cm -1 Is the stretching vibration peak of C = O in tetracarboxyl porphyrin, and is 1600-1400cm -1 A plurality of absorption peaks at (a) are attributed to the characteristic absorption of the porphyrin; raman spectrum at 683cm -1 And 737cm -1 The absorption peaks of (a) are formed P-Eu bond and O-Eu bond. 2430cm -1 The absorption peak is from the absorption of porphyrin; raman and XPS spectra show P-Eu and P-P bonds.
XPS spectrogram shows that the compound mainly comprises C, N, P, O, zn and Eu elements; wherein trivalent europium is bound to phosphorus in a coordinated fashion and divalent zinc is coordinated to the porphyrin.
The invention also provides a preparation method of the zinc-europium-porphyrin-phosphorus cluster material BP @ Eu-TCPP-Zn, in the invention, lamellar black phosphorus is obtained by a liquid-phase ultrasonic stripping method, and rare earth europium is loaded on the surface of the lamellar black phosphorus by utilizing P-Eu and O-Eu bonds formed by the black phosphorus, surface phosphate radicals and europium ions; then tetra (4-carboxyphenyl) porphyrin and europium are further coordinated, porphyrin is bridged on the surface of black phosphorus, and the absorption capacity and the electron transfer capacity of the black phosphorus to light are improved under the action of a porphyrin photosensitizer; the pyrrole ring at the center of the porphyrin can be combined with transition metal, and the combination of the porphyrin and the metal can obviously improve the photoelectric effect, so that zinc ions which have an inhibiting effect on bacteria are introduced into the center of the porphyrin to obtain the novel zinc-europium porphyrin phosphorus cluster material.
The preparation method of the zinc-europium-porphyrin phosphorus cluster material comprises the following steps:
(1) Adding blocky black phosphorus and N-octylamine into an N-methylpyrrolidinone (NMP) solution, and carrying out ultrasonic stripping in ice bath to obtain the lamellar black phosphorus.
Wherein the dosage proportion of the blocky black phosphorus, the NMP and the n-octylamine is as follows: 100mg:40-120mL:0.1-20mL; preferably, the dosage ratio of the blocky black phosphorus, the NMP and the n-octylamine is as follows: 100mg:90mL:10mL;
the ultrasonic power is 800w, and the ultrasonic time is 5-60 hours, preferably 30 hours.
(2) Respectively dispersing the lamellar black phosphorus and europium trichloride in a DMF (dimethyl formamide) solution, slowly dropwise adding the DMF solution of europium trichloride into the DMF solution of lamellar black phosphorus, uniformly mixing, transferring the mixture into a reaction kettle for reaction, centrifuging after the reaction is finished, washing with DMF and acetonitrile, and drying in vacuum to obtain the europium black phosphorus compound.
Wherein, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1-20;
the reaction temperature is 80-200 ℃, and the reaction time is 5-60 hours; preferably, the reaction temperature is 140 ℃ and the reaction time is 24 hours.
(3) Respectively dispersing the europium black phosphorus compound and tetra (4-carboxyphenyl) porphyrin in a DMF solution, uniformly mixing the two solutions, transferring the mixture into a reaction kettle for reaction, centrifuging after the reaction is finished, washing with DMF and acetonitrile, and drying in vacuum to obtain the europium black phosphorus porphyrin.
Wherein the mass ratio of the europium black phosphorus compound to the tetra (4-carboxyphenyl) porphyrin is 10;
the reaction temperature is 60-200 ℃, the reaction time is 24-60 hours, preferably, the reaction temperature is 140 ℃, and the reaction time is 48 hours.
(4) And dispersing the europium porphyrin black phosphorus compound in a 15mL of DMF solution, adding zinc acetate, heating and refluxing the solution, centrifuging after the reaction is finished, washing with DMF (dimethyl formamide) and acetonitrile, and drying in vacuum to obtain the europium porphyrin phosphorus cluster material.
Wherein the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 10-1; the reaction temperature is 30-150 ℃, the reaction time is 12-60 hours, preferably, the mass ratio is 1.
Further, the preparation process of the material is carried out under the protection of nitrogen.
The novel zinc-europium porphyrin phosphorus cluster material (BP @ Eu-TCPP-Zn) prepared by the invention has stability in aqueous solution, improves the capability of absorbing near infrared light and converting the near infrared light into heat, and has the function of catalyzing NAD (nicotinamide adenine dinucleotide) under sunlight + The reducing property of (2). Compared with the traditional black phosphorus, the porphyrin zinc europium modified black phosphorus has high light conversion capability and can accept light to generate electrons, so that NAD (nicotinamide adenine dinucleotide) + Reduced to NADH, therefore, BP @ Eu-TCPP-Zn is a novel NAD + Light-driven NAD (NAD) with reducing agent BP @ Eu-TCPP-Zn as catalyst + The reduction is different from the traditional NAD + A reducing agent coordinated to the active metal; the modification of hydrophobic porphyrin ensures that BP @ Eu-TCPP-Zn has good stability, can be recycled, and has stability superior to that of the traditional complex NAD + A reducing agent. Therefore, the material of the invention is actually a novel light-driven NAD (nicotinamide adenine dinucleotide) -based material + Reducing agent and its preparation method are provided.
The invention also provides application of the zinc-europium-porphyrin phosphorus cluster material (BP @ Eu-TCPP-Zn), wherein the application is catalytic reduction of NAD + Generating NADH.
The para-NAD + The catalytic reduction method comprises the following steps:
at different light sources(LED blue light, green light, red light and sunlight, preferably sunlight) to irradiate the zinc-europium porphyrin phosphorus cluster material and the NAD + (Add PBS buffer solution, add triethanolamine, every hour using UV spectrophotometer measurements at 340nm UV absorption intensity.
Wherein the zinc europium porphyrin phosphorus cluster material and NAD + The mass ratio of (1): 1, the volume ratio of the PBS buffer solution to the triethanolamine was 4.
The invention has the beneficial effects that:
black scales (BP) has good biocompatibility, near infrared absorption and good photo-thermal performance, and recently, metal modified BP generates Reactive Oxygen Species (ROS) under the action of near infrared light, and kills tumors and bacteria through the ROS, so that the BP is a good photodynamic therapeutic agent. However, the black phosphorus itself is rapidly degraded by exposure to air and water, and the application capability of the black phosphorus is seriously affected. According to the invention, the black phosphorus is modified, so that the stability is improved, and the bacteriostatic ability of the black phosphorus material is improved. The two-dimensional black phosphorus as a nano material consisting of simple substance phosphorus has good near-infrared photo-thermal conversion capability and light absorption capability, and is a good electron transporter. The porphyrin has good hydrophobicity and metal binding capacity, and the stability and the electron transport capacity of the porphyrin-modified black scale can be improved.
The invention reports a preparation method of porphyrin-modified nano material containing metal phosphorus bonds, the prepared zinc-europium-porphyrin-phosphorus cluster material (BP @ Eu-TCPP-Zn) has excellent light absorption effect and near infrared light conversion capability, lone pair electrons of simple substance phosphorus can be coordinated with metal and realize good electron transmission, porphyrin improves the stability of black phosphorus, and the light conversion capability of the enhanced compound can accept light to generate electrons, so that NAD (nicotinamide adenine dinucleotide) can be obtained + Reduction to NADH, BP @ Eu-TCPP-Zn is a novel NAD + Reducing agent, light-driven NAD + The reduction is different from the traditional NAD + The material can be recycled, and the stability of the material is superior to that of the traditional complex NAD + A reducing agent. Thus, the material of the present invention is alsoNovel based on light drive NAD + A reducing agent.
Drawings
FIG. 1 is a schematic structural diagram of a zinc europium porphyrin phosphorus cluster material.
FIG. 2 is a scanning electron microscope and element distribution diagram of the prepared BP @ Eu-TCPP-Zn, wherein a is a scanning diagram of raw material black phosphorus, b is a single scanning diagram of porphyrin zinc europium phosphorus cluster material, C is an EDX element analysis superposition diagram of BP @ Eu-TCPP-Zn, C is an analysis diagram of single element, eu, N, O, P, zn is 1 μm in scale size, and red, yellow, blue, purple, cyan and green fluorescence are respectively shown in the diagram.
FIG. 3 is an infrared spectrum of zinc europium porphyrin phosphorus cluster material BP @ Eu-TCPP-Zn.
FIG. 4 shows photothermal data of zinc europium porphyrin phosphorus cluster materials BP @ Eu-TCPP-Zn and BP in ten minutes, and blank is pure water of the same volume as the reference.
FIG. 5 shows the impedance spectra of BP, BP @ Eu-TCPP and BP @ Eu-TCPP-Zn.
FIG. 6 is a Raman spectrum of BP, BP @ Eu-TCPP.
FIG. 7 is a graph showing the reduction spectrum of BP @ Eu-TCPP-Zn prepared in example 1 on NAD under solar illumination.
FIG. 8 shows the results of the degradation study of BP @ Eu-TCPP-Zn prepared in example 1 and BP as a starting material in an aqueous solution (1 mg/mL).
FIG. 9 is an XPS spectrum of BP @ Eu-TCPP-Zn prepared in Experimental example 1.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following embodiments of the present invention are described in detail, but the following embodiments do not limit the scope of the present invention.
In the examples of the present invention, the experimental methods without specific descriptions of specific conditions were carried out according to the conventional methods and conditions in the art, and the materials used were commercially available in a conventional manner unless otherwise specified.
Reagents and instruments used in the examples of the invention: all solvents used in the reaction were analytically pure, and the reagents used were used without special indication and without any special treatment.
Black scale: nanjing Xiancheng nanomaterial Co., ltd;
n-methylpyrrolidone (NMP), N-Dimethylformamide (DMF): analytically pure, shanghai Pilot plant chemical Co., ltd;
zinc acetate hexahydrate, europium trichloride: analytical grade, shanghai chemical reagents, inc.;
tetra (4-carboxyphenyl) porphyrin (TCPP), n-octylamine: analytically pure, annaiji Co.
Example 1: preparation of zinc-europium porphyrin phosphorus cluster material (marked as BP @ Eu-TCPP-Zn)
In this example, the material preparation process was carried out under nitrogen protection.
(1) Under the protection of nitrogen, 100mg of blocky black phosphorus is ground and dispersed in 90mL of NMP solution, 10mL of n-octylamine is added, and after uniform stirring and mixing, the blocky black phosphorus is ultrasonically stripped for 30 hours by a cell crusher under the condition of 800w of power in an ice bath. And centrifuging at 4000 revolutions after the ultrasonic treatment to obtain an NMP solution containing black scales on the upper layer, centrifuging at 8000 revolutions at a high speed to obtain 90mg of lamellar Black Phosphorus (BP), and storing in dark under nitrogen.
(2) Under the protection of nitrogen, lamellar black phosphorus (32mg, 1mmol) is dispersed in 10mL of DMF solution, europium trichloride (258mg, 1mmol) is dissolved in 10mL of DMF solution, the DMF solution of europium trichloride is slowly dripped into the DMF solution of lamellar black phosphorus, the mixture is stirred for ten minutes at normal temperature, then the mixture is transferred into a reaction kettle to react for 24 hours at 140 ℃,8000 revolutions are carried out after the reaction is finished, the precipitate is centrifugally taken out, DMF is washed for a plurality of times, acetonitrile is used for washing for three times, and vacuum drying is carried out to obtain europium black phosphorus compound (BP @ Eu), 124mg and the compound is stored in a dark place. (in the step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1
(3) Europium black phosphorus compound (100 mg) is dispersed in DMF (20 mL) solution, tetra (4-carboxyphenyl) porphyrin (100 mg) is ultrasonically dissolved in DMF (10 mL) solution, the two are uniformly mixed and stirred for ten minutes at normal temperature, the mixture is transferred into a reaction kettle to react at 140 ℃ for 48h, the reaction kettle is centrifuged at 8000 turns to collect precipitate, the precipitate is washed by DMF for a plurality of times and acetonitrile for three times, and vacuum drying is carried out to obtain europium black phosphorus porphyrin (BP @ Eu-TCPP), 186mg and the precipitate is stored in dark. (in this step, the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 1
(4) Taking a porphyrin europium black phosphorus compound (100 mg) to disperse in a DMF (15 mL) solution, adding zinc acetate hexahydrate (100 mg), reacting at 80 ℃ for 12 hours, centrifuging at 8000 turns, collecting precipitate, washing with DMF for a plurality of times, washing with acetonitrile for three times, and drying in vacuum to obtain a porphyrin zinc europium phosphorus cluster material (BP @ Eu-TCPP-Zn), wherein 164mg is stored in a dark place. (in this step, the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 1
Fig. 1 is a schematic structural view of a zinc-europium porphyrin phosphorus cluster material, wherein a is a schematic structural view and b is a perspective structural view.
FIG. 2 is the scanning electron microscope and element distribution diagram of BP @ Eu-TCPP-Zn prepared in this example, in which a is the scanning diagram of black phosphorus as raw material; the figure b is a scanning image of the zinc europium porphyrin phosphorus cluster material, and the surface of unmodified black phosphorus can be found to be smooth, while the surface of the modified black phosphorus is rough; the figure C is an EDX element analysis overlay chart of BP @ Eu-TCPP-Zn, and the figure C is an analysis chart of Eu, N, O, P and Zn which are single elements. It can be seen from the figure that the compound is a lamellar structure with an average width of 1 micron. Meanwhile, the EDX element analysis finds that the constituent elements of the compound comprise C, N, eu, O, P and Zn.
FIG. 3 is an infrared spectrum of BP @ Eu-TCPP-Zn, which is at 1650cm -1 Is the stretching vibration peak of C = O in tetracarboxyl porphyrin, and is 1600-1400cm -1 The presence of porphyrins in the compound is evidenced by the multiple absorption peaks ascribed to the characteristic absorption of porphyrins.
FIG. 4 shows photothermal data of compounds BP @ Eu-TCPP-Zn and BP in ten minutes (concentration of compound is 100. Mu.g/mL, light source is near infrared light 2 w/cm) 2 ) In the figure, blank is the same volume of pure water as a control. The photo-thermal property of the black phosphorus is maintained by comparing the photo-thermal property of the black phosphorus by timing from illumination. Under the same near-infrared illumination of 10 minutes, the photo-thermal effect of the modified compound is improved compared with that of black phosphorus, so that the photo-thermal antibacterial performance of the compound is further improved.
FIG. 5 is an impedance spectrogram of BP, BP @ Eu-TCPP and BP @ Eu-TCPP-Zn, which shows that the impedance of BP @ Eu-TCPP-Zn is reduced, thus indicating that the modification of europium porphyrin improves the transmission capability of electrons (i.e. the impedance is reduced), and experimental data indicates that europium porphyrin increases the conductivity of black phosphorus, and the ability of the material to generate electrons under illumination is improved, thereby improving the reduction catalysis efficiency.
FIG. 6 is a Raman spectrum of BP and BP @ Eu-TCPP, in which it can be seen that BP @ Eu-TCPP is 683cm in comparison with black phosphorus -1 And 737cm -1 May be formed of P-Eu bonds and O-Eu bonds. 2430cm -1 The absorption peak at (a) is derived from the absorption of the porphyrin, which demonstrates the successful modification of black phosphorus by the porphyrin and Eu.
FIG. 9 is an XPS spectrum of BP @ Eu-TCPP-Zn prepared in Experimental example 1. The modified compound can be found to mainly comprise C, N, P, O, zn and Eu elements. Wherein the P spectrum has P-O bonds and P-P bonds. Wherein europium is bonded to phosphorus in a coordinated fashion, predominantly having a valence of 3, and zinc is coordinated to porphyrin, predominantly having a valence of 2.
Example 2: preparation of zinc-europium-porphyrin phosphorus cluster material (BP @ Eu-TCPP-Zn)
In the present example, the material preparation process was performed under nitrogen protection.
(1) Under the protection of nitrogen, 100mg of blocky black phosphorus is ground and dispersed in 40mL of NMP solution, 0.1mL of n-octylamine is added, and after uniform stirring and mixing, the blocky black phosphorus is ultrasonically stripped for 5 hours by a cell crusher under the condition of 800w of power in an ice bath. And centrifuging at 4000 rpm after the ultrasonic treatment is finished, and taking the upper-layer solution to obtain 15mg of a small amount of lamellar Black Phosphorus (BP), and storing in dark nitrogen.
(2) Under the protection of nitrogen, the sample of the lamellar black phosphorus (3.2 mg, 0.1mmol) prepared in step (1) of example 1 was dispersed in 10mL of DMF solution, europium trichloride (25.8mg, 0.1mmol) was dissolved in 10mL of DMF solution, the DMF solution of europium trichloride was slowly added dropwise to the DMF solution of lamellar black phosphorus, after stirring at room temperature for ten minutes, the mixture was transferred to a reaction kettle to react at 80 ℃ for 24 hours, after the reaction was completed, the precipitate was centrifuged at 8000 rpm, washed with DMF several times, washed with acetonitrile three times, and vacuum-dried to obtain 2.1mg of europium black phosphorus compound (BP @ Eu), which was stored away from light. (in the step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1
(3) And (3) dispersing the europium black phosphorus compound (100 mg) prepared in the step (2) in a DMF (20 mL) solution, ultrasonically dissolving tetra (4-carboxyphenyl) porphyrin (10 mg) in the DMF (5 mL) solution, uniformly mixing the two, stirring for ten minutes at normal temperature, transferring the mixture into a reaction kettle, reacting for 24 hours at 60 ℃, centrifuging at 8000 to collect precipitate, washing with DMF for multiple times, washing with acetonitrile for three times, and drying in vacuum to obtain 5mg of europium black phosphorus porphyrin (BP @ Eu-TCPP), and storing in a dark place. (in this step, the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 10
(4) And (4) dispersing the porphyrin europium black phosphorus compound (100 mg) in the step (3) in a DMF (15 mL) solution, adding zinc acetate hexahydrate (10 mg), reacting at 30 ℃ for 12 hours, centrifuging at 8000 rpm, collecting precipitate, washing with DMF for multiple times, washing with acetonitrile for three times, and drying in vacuum to obtain 6mg of porphyrin zinc europium phosphorus cluster material (BP @ Eu-TCPP-Zn), and storing in a dark place. ( In the step, the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 10:1 )
Example 3: preparation of zinc-europium-porphyrin phosphorus cluster material (BP @ Eu-TCPP-Zn)
In the present example, the material preparation process was performed under nitrogen protection.
(1) Under the protection of nitrogen, 100mg of blocky black phosphorus is ground and dispersed in 120mL of NMP solution, 20mL of n-octylamine is added, and after uniform stirring and mixing, the blocky black phosphorus is ultrasonically stripped for 60 hours by a cell crusher under the condition of 800w of power in an ice bath. And centrifuging 4000 revolutions after the ultrasonic treatment to obtain an upper layer solution to obtain 40mg of lamellar Black Phosphorus (BP), and storing in a dark nitrogen atmosphere.
(2) Under the protection of nitrogen, a sample of the lamellar black phosphorus (32mg, 1mmol) prepared in the step (1) of example 1 is dispersed in 10mL of DMF solution, europium trichloride (516mg, 20mmol) is dissolved in 10mL of DMF solution, the DMF solution of europium trichloride is slowly dripped into DMF of lamellar black phosphorus, the mixture is stirred for ten minutes at normal temperature and then transferred into a reaction kettle to react for 24 hours at 200 ℃,8000 revolutions after the reaction is finished, precipitate is centrifugally taken out, DMF is used for multiple times of washing, acetonitrile is used for three times, and the europium black phosphorus compound (BP @ Eu) is obtained after vacuum drying, 25.2mg is obtained and is stored in a dark place. (in the step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1
(3) And (3) dispersing the europium black phosphorus compound (100 mg) prepared in the step (2) in a DMF (20 mL) solution, ultrasonically dissolving tetra (4-carboxyphenyl) porphyrin (200 mg) in the DMF (20 mL) solution, uniformly mixing the two, stirring for ten minutes at normal temperature, transferring the mixture into a reaction kettle, reacting for 60 hours at 200 ℃, centrifuging at 8000 turns, collecting precipitate, washing with DMF for multiple times, washing with acetonitrile for three times, and drying in vacuum to obtain europium black phosphorus porphyrin (BP @ Eu-TCPP), 65mg and storing in a dark place. (in this step, the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 1
(4) And (3) dispersing the porphyrin europium black phosphorus compound (100 mg) in the step (3) into a DMF (15 mL) solution, adding zinc acetate hexahydrate (200 mg), reacting at 150 ℃ for 10 hours, centrifuging at 8000 turns, collecting precipitate, washing with DMF for multiple times, washing with acetonitrile for three times, and drying in vacuum to obtain the porphyrin europium black phosphorus cluster material (BP @ Eu-TCPP-Zn), wherein the weight of the porphyrin europium black phosphorus cluster material is 60mg and the porphyrin europium black phosphorus cluster material is stored in a dark place. (in this step, the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 1
Example 4:
in the present example, the material preparation process was performed under nitrogen protection.
The europium porphyrin black phosphorus compound (100 mg) in the step (3) in the example 1 is dispersed in DMF (15 mL), zinc acetate hexahydrate (150 mg) is added to react at 100 ℃ for 60 hours, the precipitate is collected by centrifugation at 8000 turns, after being washed by DMF for a plurality of times, acetonitrile is used for washing for three times, and vacuum drying is carried out to obtain zinc europium porphyrin phosphorus cluster (BP @ Eu-TCPP-Zn), 120mg, and the zinc europium porphyrin phosphorus cluster is stored away from light. (in the step, the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 1
Example 5: BP @ Eu-TCPP-Zn vs. NAD + Reduction catalysis experiment of
Respectively preparing aqueous solution of BP @ Eu-TCPP-Zn compound and NAD with concentration of 1mg/mL + Aqueous solution, sodium Phosphate (PBS) buffer solution pH =7.4 was prepared.
300 mul BP @ Eu-TCPP-Zn aqueous solution with concentration of 1mg/mL and NAD are respectively taken + 0.6mL of triethanolamine and 2.34mL of PBS buffer were added to the aqueous solution, and the amount of NADH produced was evaluated by taking the solution every one hour to measure the ultraviolet absorbance at 340nm under the water bath condition at 37 ℃ from the start of the solar irradiation.
FIG. 7 is a graph of BP @ Eu-TCPP-Zn prepared in example 1 vs. NAD under sunlight + The reduction spectrum of (a). The absorption peak at 340nm is the characteristic absorption peak of NADH, and can be seen in the figureBP @ Eu-TCPP-Zn can absorb sunlight to lead NAD to + Reducing to NADH.
Example 6: BP vs. NAD + Reduction catalysis experiment of
Respectively preparing aqueous solution of BP compound with concentration of 1mg/mL and NAD + Aqueous solution, sodium Phosphate (PBS) buffer solution pH =7.4 was prepared.
300. Mu.L of BP and NAD with a concentration of 1mg/mL, respectively + 0.6mL of triethanolamine and 2.34mL of PBS buffer were added to the aqueous solution, and the amount of NADH produced was evaluated by taking the solution every one hour to measure the ultraviolet absorbance at 340nm under the water bath condition at 37 ℃ from the start of the solar irradiation. The experiment shows that no absorption peak appears at 340nm, which indicates that BP can not reduce NAD + 。
Meanwhile, the prepared material BP @ Eu-TCPP-Zn and the raw material BP are tested in the invention for degradation or stability in aqueous solution.
FIG. 8 is a degradation study of BP @ Eu-TCPP-Zn prepared in example 1 and BP as a raw material in an aqueous solution (1 mg/mL). Through testing the three-day degradation condition, the stability of the modified compound BP @ Eu-TCPP-Zn is obviously improved.

Claims (12)

1. The zinc-europium-porphyrin-phosphorus cluster material is characterized by being of a lamellar structure and marked as BP @ Eu-TCPP-Zn, wherein the mass percent of metal europium and zinc in the zinc-europium-porphyrin-phosphorus cluster material are respectively 1.5% and 6.8%, and the zinc-europium-porphyrin-phosphorus cluster material contains europium black phosphorus and tetra (4-carboxyphenyl) zinc porphyrin; the material comprises the following components of C, N, eu, O, P and Zn; raman and XPS spectra show P-Eu and P-P bonds.
2. A method for preparing the material of claim 1, comprising the steps of:
(1) Adding blocky black phosphorus and N-octylamine into an N-methylpyrrolidone (NMP) solution, and carrying out ultrasonic stripping under ice bath to obtain lamellar black phosphorus;
(2) Respectively dispersing lamellar black phosphorus and europium trichloride in a DMF (dimethyl formamide) solution, slowly dropwise adding the DMF solution of europium trichloride into the DMF solution of lamellar black phosphorus, uniformly mixing, centrifuging after the reaction is finished, washing with DMF and acetonitrile, and drying in vacuum to obtain a europium black phosphorus compound;
(3) Respectively dispersing the europium black phosphorus compound and tetra (4-carboxyphenyl) porphyrin in a DMF solution, uniformly mixing the two solutions, reacting, centrifuging after the reaction is finished, washing with DMF and acetonitrile, and drying in vacuum to obtain the europium black phosphorus porphyrin;
(4) And dispersing the europium porphyrin black phosphorus compound in a DMF solution, adding zinc acetate, heating and refluxing the solution, centrifuging after the reaction is finished, washing with DMF and acetonitrile, and drying in vacuum to obtain the europium porphyrin phosphorus cluster material.
3. The method according to claim 2, wherein the ratio of the used amount of the bulk black phosphorus, NMP and n-octylamine in step (1) is as follows: 100mg:40-120mL:0.1-20mL, the ultrasonic power is 800w, and the ultrasonic time is 5-60 hours.
4. The method according to claim 3, wherein the ratio of the black phosphorus, NMP and n-octylamine is as follows: 100mg:90mL of: 10mL, the sonication time was 30 hours.
5. The method according to claim 2, wherein the molar ratio of the lamellar black phosphorus to the europium trichloride in the step (2) is 1-20.
6. The method according to claim 5, wherein the molar ratio of the lamellar black phosphorus to the europium trichloride is 1, the reaction temperature is 140 ℃ and the reaction time is 24 hours.
7. The method of claim 2, wherein the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin in step (3) is 10; the reaction temperature is 60-140 ℃, and the reaction time is 24-60 hours.
8. The method of claim 7, wherein the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin in step (3) is 1; the reaction temperature is 140 ℃ and the reaction time is 48 hours.
9. The method of claim 2, wherein the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate in the step (4) is 10-1.
10. The method of claim 9, wherein the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate in step (4) is 1; the reaction temperature is 80 ℃ and the reaction time is 12 hours.
11. The method of claim 2, wherein the method is performed under a nitrogen blanket.
12. The use of a material according to claim 1 or prepared according to a process according to any one of claims 2 to 11 in the catalytic reduction of NAD in the field of non-disease diagnosis and therapy + Use in the production of NADH.
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