CN114736209A - 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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CN114736209A
CN114736209A CN202210288425.1A CN202210288425A CN114736209A CN 114736209 A CN114736209 A CN 114736209A CN 202210288425 A CN202210288425 A CN 202210288425A CN 114736209 A CN114736209 A CN 114736209A
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europium
porphyrin
black phosphorus
zinc
phosphorus
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CN114736209B (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+Reducing to NADH, and can be used for 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, which is a very important index that can reflect the redox state of the cell, thereby determining the metabolic activity of a cell and the health of the 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 demand, can affect the ratio between the two, thereby having various effects on cellular health and biological processes. Line of research discovery and interventionMitochondrially targeted NADH (reduced form 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 in recent research, the effect of a nano interface and a biological interface can effectively treat bacterial infection, and the preparation of novel photo-thermal antibacterial materials by utilizing near infrared light with low toxicity on the basis of selecting low-toxicity materials is the current development direction.
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 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, 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-1Is the stretching vibration peak of C ═ O in the tetracarboxylporphyrin, 1600-1400cm-1A plurality of absorption peaks at (a) are attributed to the characteristic absorption of the porphyrin; raman spectrum at 683cm-1And 737cm-1The absorption peaks of (a) are formed P-Eu bond and O-Eu bond. 2430cm-1The absorption peak at (A) is from the absorption of the 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 the 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-methylpyrrolidone (NMP) solution, and ultrasonically 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: 100 mg: 40-120 mL: 0.1-20 mL; preferably, the dosage ratio of the blocky black phosphorus, the NMP and the n-octylamine is as follows: 100 mg: 90mL of: 10 mL;
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 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 1-20:10-1, preferably 1: 1;
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 10:1-1:2, preferably, the mass ratio of the europium black phosphorus compound to the tetra (4-carboxyphenyl) porphyrin is 1: 1;
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 10:1-1: 2; the reaction temperature is 30-150 ℃, the reaction time is 12-60 hours, preferably, the mass ratio is 1:1, the reaction temperature is 80 ℃, and the reaction time is 12 hours.
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 acceptLight generates electrons to thereby make NAD+Reduced to NADH, therefore, BP @ Eu-TCPP-Zn is a novel NAD+Light-driven NAD (nicotinamide adenine dinucleotide) 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 better stability than the traditional complex NAD+A reducing agent. Therefore, the material of the invention is actually a novel NAD based light drive+Reducing agent and its preparation method are provided.
The invention also provides an application of the zinc-europium-porphyrin phosphorus cluster material (BP @ Eu-TCPP-Zn), wherein the application is the catalytic reduction of NAD+Generating NADH.
The para-NAD+The catalytic reduction method comprises the following steps:
under the irradiation of different light sources (LED blue light, green light, red light and sunlight, optimally sunlight), the zinc-europium porphyrin phosphorus cluster material and NAD are mixed+(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: 1.
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 when exposed 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 porphyrin-modified black scale can improve the stability and the electron transmission capacity of the porphyrin-modified black scale.
The invention reports a preparation method of a porphyrin-modified nano material containing a metal phosphorus bond, 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, the porphyrin improves the stability of black phosphorus, and the light conversion capability of a compound is enhanced and 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. Therefore, the material of the invention is also a novel light-driven NAD (nicotinamide adenine dinucleotide) -based material+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 a porphyrin zinc-europium phosphorus cluster material, C is an EDX element analysis superposition diagram of the BP @ Eu-TCPP-Zn, C is an analysis diagram of single elements of Eu, N, O, P and Zn, the scale sizes in the diagram are all 1 μm, 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 over ten minutes for zinc europium porphyrin phosphorus cluster materials BP @ Eu-TCPP-Zn and BP, where blank is the same volume of pure water as a control.
FIG. 5 is an impedance spectrum of BP, BP @ Eu-TCPP and BP @ Eu-TCPP-Zn.
FIG. 6 shows a Raman spectrum of BP, BP @ Eu-TCPP.
FIG. 7 is a graph of the reduction spectrum of BP @ Eu-TCPP-Zn prepared in example 1 in sunlight on NAD.
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 were carried out according to the conventional methods and conditions in the art, and the materials used were commercially available in the 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 corporation.
Example 1: preparation of zinc-europium-porphyrin phosphorus cluster material (marked as 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 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, sheet-layer 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 sheet-layer black phosphorus, after stirring for ten minutes at normal temperature, the mixture is transferred into a reaction kettle to react for 24 hours at 140 ℃, 8000 turns to centrifuge after the reaction is finished, precipitates are obtained, DMF is used for washing 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 of europium black phosphorus compound is stored in a dark place. (in the step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1:1)
(3) And (2) dispersing the europium black phosphorus compound (100mg) in a DMF (20mL) solution, ultrasonically dissolving tetra (4-carboxyphenyl) porphyrin (100mg) in the DMF (10mL) solution, uniformly mixing the two solutions, stirring for ten minutes at normal temperature, transferring the mixture into a reaction kettle, reacting for 48 hours at the temperature of 140 ℃, centrifuging at 8000 rpm, 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), 186mg and storing in the dark. (in this step, the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 1:1)
(4) And (2) dispersing a porphyrin europium black phosphorus compound (100mg) in a DMF (15mL) solution, adding zinc acetate hexahydrate (100mg), reacting at 80 ℃ for 12 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 a zinc europium porphyrin 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 1:1)
Fig. 1 is a schematic structural diagram of a zinc europium porphyrin phosphorus cluster material, fig. a is a schematic structural diagram, and fig. b is a perspective structural diagram.
FIG. 2 is a scanning electron microscope and element distribution diagram of BP @ Eu-TCPP-Zn prepared in this example, wherein FIG. a is a scanning diagram of raw material black phosphorus; fig. b is a scanning image of a zinc europium porphyrin phosphorus cluster material, and it can be found that the unmodified black phosphorus has a smooth surface, and the modified black phosphorus has a rough surface; FIG. C is an EDX elemental analysis overlay chart of BP @ Eu-TCPP-Zn, and FIG. C is an analysis chart of Eu, N, O, P, Zn as a single element. 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-1Is a stretching vibration peak of C ═ O in tetracarboxylporphyrin, 1600-1400cm-1The 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 the compounds BP @ Eu-TCPP-Zn and BP in ten minutes (concentration of the 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 the control. The compound BP @ Eu-TCPP-Zn maintains the photo-thermal property of the black phosphorus by comparing the photo-thermal property of the black phosphorus when the timing is started 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, and it can be found that the impedance of BP @ Eu-TCPP-Zn is reduced, which indicates 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 conductive capability of black phosphorus, and improves the capability of the material to generate electrons under illumination, thereby improving the reduction catalysis efficiency.
FIG. 6 is a Raman spectrum of BP @ Eu-TCPP, showing that BP @ Eu-TCPP is 683cm in comparison with black phosphorus-1And 737cm-1The absorption peaks of (A) may be formed of P-Eu bonds and O-Eu bonds. 2430cm-1The absorption peak at (a) is due to 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. Wherein, the modified compound mainly comprises C, N, P, O, Zn and Eu elements. Wherein the P spectrum has P-O bonds and P-P bonds. Wherein europium is bound to phosphorus in a coordinated fashion, predominantly 3 valent, and zinc is coordinated to porphyrin, predominantly 2 valent.
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, 3.2mg of lamellar black phosphorus (BP @ Eu) of the sample prepared in the step (1) in the example 1 is dispersed in 10mL of DMF solution, europium trichloride (25.8mg and 0.1mmol) 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 and then transferred into a reaction kettle to react for 24 hours at 80 ℃, after the reaction is finished, the DMF solution is centrifuged to take precipitate, the precipitate is washed for multiple times, the precipitate is washed for three times by acetonitrile, and the precipitate is dried in vacuum to obtain 2.1mg of europium black phosphorus compound (BP @ Eu), and the europium black phosphorus compound is protected from light. (in the step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1:1)
(3) And (3) dispersing the europium black phosphorus compound (100mg) prepared in the step (2) in a DMF (20mL) solution, ultrasonically dissolving tetra (4-carboxyphenyl) porphyrin (10mg) in the DMF (5mL) solution, uniformly mixing the two, stirring for ten minutes at normal temperature, transferring the mixture into a reaction kettle, reacting for 24 hours at the temperature of 60 ℃, performing 8000-rotation centrifugation, collecting precipitate, washing with DMF for multiple times, washing with acetonitrile for three times, performing vacuum drying 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 10:1)
(4) And (3) dispersing the porphyrin europium black phosphorus compound (100mg) in the step (3) into a DMF (15mL) solution, adding zinc acetate hexahydrate (10mg), reacting at 30 ℃ for 12 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 6mg of porphyrin europium black phosphorus cluster material (BP @ Eu-TCPP-Zn), and storing in a dark place. (in this 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 at 4000 rpm after the ultrasonic treatment to obtain an upper layer solution to obtain 40mg of lamellar Black Phosphorus (BP), and storing in dark under nitrogen.
(2) Under the protection of nitrogen, the sample of lamellar black phosphorus (32mg, 1mmol) prepared in 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 turns after the reaction is finished, centrifugation is carried out to obtain precipitate, the precipitate is washed by DMF for multiple times, acetonitrile is used for washing for three times, vacuum drying is carried out to obtain europium black phosphorus compound (BP @ Eu), and 25.2mg is protected from light. (in this step, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1:20)
(3) And (3) dispersing the europium black phosphorus compound (100mg) prepared in the step (2) in a DMF (20mL) solution, ultrasonically dissolving tetra (4-carboxyphenyl) porphyrin (200mg) in the DMF (20mL) 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), wherein 65mg is stored in a dark place. (in this step, the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 1:2)
(4) And (3) dispersing the porphyrin europium black phosphorus compound (100mg) in the step (3) into a DMF (15mL) solution, adding zinc acetate hexahydrate (200mg), 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 1:2)
Example 4:
in the present example, the material preparation process was performed under nitrogen protection.
The europium porphyrin black phosphorus compound (100mg) in the step (3) in the example 1 is dispersed in DMF (15mL), zinc acetate hexahydrate (150mg) 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 the zinc europium porphyrin phosphorus cluster (BP @ Eu-TCPP-Zn) is obtained by vacuum drying and is stored in dark place at 120 mg. (in this step, the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate is 1:1.5)
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+An aqueous solution was prepared as a pH 7.4 sodium Phosphate (PBS) buffer solution.
Respectively taking 300 mu L of BP @ Eu-TCPP-Zn aqueous solution with the concentration of 1mg/mL and NAD+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 the comparison of BP @ Eu-TCPP-Zn prepared in example 1 with respect to NAD under sunlight+The reduction spectrum of (a). The absorption peak at 340nm is the characteristic absorption peak of NADH, and the graph shows that BP @ Eu-TCPP-Zn can absorb sunlight to lead NAD+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+An aqueous solution was prepared as a pH 7.4 sodium Phosphate (PBS) buffer solution.
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 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 starting material in an aqueous solution (1 mg/mL). The degradation condition of three days is tested, and the stability of the modified compound BP @ Eu-TCPP-Zn is obviously improved.

Claims (10)

1. The zinc-europium-porphyrin-phosphorus cluster material is characterized by having a lamellar structure and being marked as BP @ Eu-TCPP-Zn, wherein the mass percentages 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: 100 mg: 40-120 mL: 0.1-20mL, wherein the ultrasonic power is 800w, and the ultrasonic time is 5-60 hours; preferably, the dosage ratio of the blocky black phosphorus, the NMP and the n-octylamine is as follows: 100 mg: 90mL of: 10mL, the sonication time was 30 hours.
4. The method according to claim 2, wherein the molar ratio of the lamellar black phosphorus to the europium trichloride in the step (2) is 1-20:10-1, the reaction temperature is 80-200 ℃, and the reaction time is 5-60 hours; preferably, the molar ratio of the lamellar black phosphorus to the europium trichloride is 1:1, the reaction temperature is 140 ℃, and the reaction time is 24 hours.
5. The method of claim 2, wherein the europium black phosphorus compound and tetrakis (4-carboxyphenyl) porphyrin in step (3) are present in a mass ratio of 10:1 to 1: 2; the reaction temperature is 60-200 ℃, and the reaction time is 24-60 hours.
6. The method of claim 5, wherein in step (3) the mass ratio of the europium black phosphorus compound to tetrakis (4-carboxyphenyl) porphyrin is 1: 1; the reaction temperature was 140 ℃ and the reaction time was 48 hours.
7. 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 10:1-1:2, the reaction temperature is 30-150 ℃, and the reaction time is 12-60 hours.
8. The method of claim 7, wherein the mass ratio of the europium porphyrin black phosphorus compound to the zinc acetate in step (4) is 1: 1; the reaction temperature is 80 ℃ and the reaction time is 12 hours.
9. The method of claim 2, wherein the method is performed under a nitrogen blanket.
10. Use of a material according to claim 1 or prepared according to a process according to any one of claims 2 to 9 in the catalytic reduction of NAD+Use in the production of NADH.
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