CN116478687A - Long afterglow material based on MOF template method and preparation method and application thereof - Google Patents
Long afterglow material based on MOF template method and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000004033 porphyrin derivatives Chemical class 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- OYINILBBZAQBEV-UWJYYQICSA-N (17s,18s)-18-(2-carboxyethyl)-20-(carboxymethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18,22,23-tetrahydroporphyrin-2-carboxylic acid Chemical compound N1C2=C(C)C(C=C)=C1C=C(N1)C(C)=C(CC)C1=CC(C(C)=C1C(O)=O)=NC1=C(CC(O)=O)C([C@@H](CCC(O)=O)[C@@H]1C)=NC1=C2 OYINILBBZAQBEV-UWJYYQICSA-N 0.000 claims description 4
- UJKPHYRXOLRVJJ-MLSVHJFASA-N CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C Chemical compound CC(O)C1=C(C)/C2=C/C3=N/C(=C\C4=C(CCC(O)=O)C(C)=C(N4)/C=C4\N=C(\C=C\1/N\2)C(C)=C4C(C)O)/C(CCC(O)=O)=C3C UJKPHYRXOLRVJJ-MLSVHJFASA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229960003569 hematoporphyrin Drugs 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 150000001845 chromium compounds Chemical group 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
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- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
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- 206010027476 Metastases Diseases 0.000 description 1
- 241000699666 Mus <mouse, genus> Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
- C09K11/682—Chalcogenides with zinc or cadmium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a long afterglow material based on a MOF template method, and a preparation method and application thereof. The preparation method of the invention comprises the following steps: (1) preparing a MOF template: uniformly mixing porphyrin derivatives and a metal source in a solvent, and performing hydrothermal reaction to obtain an MOF template; (2) preparing a precursor: dispersing the MOF template obtained in the step (1) in the solvent again, adding a chromium source, mixing for a period of time, separating to obtain a precipitate, and freeze-drying to obtain the precursor; (3) And (3) under the air atmosphere, carrying out high-temperature treatment on the precursor obtained in the step (2) to obtain the long afterglow material. According to the invention, MOF is used as a precursor, and the spatial distribution and the element proportion of metal ions can be well arranged, so that a long afterglow material with more regular crystal form and more uniform element distribution is obtained in the calcination process, and the formation of lattice defects in the system is facilitated, so that the brightness and the afterglow duration of the afterglow material are improved.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a long afterglow material based on a MOF template method, and a preparation method and application thereof.
Background
Tumor surgical treatment procedures include preoperative tumor localization, intraoperative focal resection, and postoperative efficacy assessment. Surgical navigation is helpful for determining the boundary of tumor tissues and finding micro tumor (metastasis) in surgery, and the postpatient is reduced to the greatest extent. Tumor imaging detection equipment such as Magnetic Resonance Imaging (MRI), CT and the like which are clinically used at present is huge, has low signal to noise ratio and cannot be used for imaging navigation in operation. At present, the operation is mainly carried out by the experience judgment of doctors, and the problems of inaccurate boundary determination and unclean excision of tiny focuses exist. Therefore, if the real-time imaging navigation with high signal-to-noise ratio in operation can be realized, the method has important significance for improving the tumor resection accuracy.
The long afterglow material is a material which can be excited by ultraviolet or visible light and can continuously emit light (afterglow) for a plurality of hours after a light source is removed for a period of time. Since no external light source (by afterglow) is needed in the light emitting process, the autofluorescence of biological tissues is not caused, and the imaging signal to noise ratio can be improved, so that researchers in recent years are used as the research of biological imaging, and no clinical report is available. The afterglow generated by the material can be conveniently detected and collected by using a CCD camera, so that the operation cost is greatly reduced, real-time imaging in operation can be realized, and the guiding effect of imaging on operation is improved. The problem to be solved at present is to improve the afterglow duration and luminous intensity of the material.
Researchers in China have made a lot of valuable work in the aspect of long afterglow materials for in vivo imaging or detection. Although the fluorescence brightness and afterglow duration of the long afterglow material are both increased, most materials still have the problem of fast fluorescence intensity decay (generally, the fluorescence brightness is reduced by at least one order of magnitude after 30 min), and the recovered fluorescence signal intensity after secondary excitation is limited. The injection dose is increased in order to obtain sufficient signal strength, thus also presenting a potential safety hazard. These long afterglow materials currently cannot meet the requirements of surgical navigation.
Therefore, how to reduce the particle size and improve the water phase stability of the inorganic long afterglow material while having excellent luminous property is the key for obtaining the long afterglow surgical guidance material through the structural design.
While inorganic long afterglow materials have incomparable potential advantages in surgical navigation, they face two major contradictions in application: 1. the long afterglow material prepared by the existing method has excellent fluorescent brightness and afterglow duration, but has larger granularity (tens of micrometers) and uneven granularity, the quantity of traps and electrons of a matrix is inevitably lost by reducing the granularity, and meanwhile, the depth of the traps is reduced, so that the fluorescent intensity and afterglow duration are reduced. 2. The stability in water environment is poor, and the operation navigation can not be realized by means of intravenous injection.
Disclosure of Invention
The invention provides a preparation method of a long afterglow material, which comprises the following steps:
(1) Preparing a MOF template: uniformly mixing porphyrin derivatives and a metal source in a solvent, and performing hydrothermal reaction to obtain an MOF template;
(2) Preparing a precursor: dispersing the MOF template obtained in the step (1) in the solvent again, adding a chromium source, mixing for a period of time, separating to obtain a precipitate, and freeze-drying to obtain the precursor;
(3) And (3) under the air atmosphere, carrying out high-temperature treatment on the precursor obtained in the step (2) to obtain the long afterglow material.
According to an embodiment of the invention, the porphyrin-like derivative is selected from amino-or carboxyl-containing porphyrin-like derivatives. Illustratively, the porphyrin-like derivative is selected from the group consisting of tetracarboxylic phenyl porphyrin (TCPP), tetraaminophenyl porphyrin (TAPP), hematoporphyrin monomethyl ether (HMME), chlorin e6 (Ce 6). In the invention, porphyrin derivatives and metal ions (such as zinc ions and gallium ions) are coordinated to form MOF for determining the metal ion ratio, so that the metal ions are assembled according to a certain proportion and space positions, the space regularity of the metal ions is improved, the possibility of forming lattice defects in the calcining process is improved, the number of defects is increased, and finally the afterglow brightness and time of the afterglow material are improved.
According to an embodiment of the present invention, in step (1), the molar ratio of the porphyrin-based derivative to the metal source is (0.05-0.07): (0.1-0.6), for example 0.05:0.2, 0.05:0.3, 0.05:0.4, 0.05:0.5, 0.07:0.2, 0.07:0.3, 0.07:0.4, 0.07:0.5, 0.06:0.1, 0.06:0.2, 0.06:0.3, 0.06:0.4, 0.06:0.5, 0.06:0.6.
preferably, the metal source is selected from at least one of nitrate, acetate, chloride, sulfate of a metal. Preferably, the metal is at least one of zinc, gallium and germanium, preferably zinc and gallium.
Illustratively, the metal source includes Zn (OAc) 2 And Ga (NO) 3 ) 3 ，Zn(OAc) 2 And Ga (NO) 3 ) 3 The molar ratio of (2) is 0.1-0.3:0.2-0.3.
According to an embodiment of the invention, in step (1), the solvent is selected from water, for example deionized water. The amount of the solvent used in the present invention is not particularly limited as long as the porphyrin derivative and the metal source are dissolved. Illustratively, the solvent is used in an amount of 10-20mL.
According to an embodiment of the present invention, in step (1), the mixing is performed uniformly at room temperature.
According to an embodiment of the present invention, in step (1), the conditions for uniform mixing may be selected from methods known in the art, such as vigorous stirring for 3 hours.
According to an embodiment of the invention, in step (1), the hydrothermal process is carried out in a reaction vessel known in the art.
According to an embodiment of the present invention, in step (1), the hydrothermal conditions include: the reaction is carried out at 150-200℃for 10-24 hours, for example at 180℃for 10-24 hours.
According to an embodiment of the invention, in step (1), the MOF template is further washed and/or dried. Preferably, the washing and drying may be performed using methods known in the art. Preferably, the washing is washing with the solvent and a volatile organic solvent. Further, the drying is, for example, drying at 50-80 ℃.
According to an embodiment of the invention, in step (1), the MOF template is a solid, for example a dark brown solid. Illustratively, when the metal source includes Zn (OAc) 2 And Ga (NO) 3 ) 3 In the obtained MOF template, ga reacts with a functional group outside the porphyrin derivative, and Zn is chelated inside a porphyrin ring of the porphyrin derivative.
According to an embodiment of the invention, in step (2), the chromium source is selected from a compound of chromium, for example a nitrate of chromium.
According to an embodiment of the invention, in step (2), the mass ratio of the chromium source to the MOF template is (0.000288-0.00864): 1
According to an embodiment of the invention, in step (2), the mixing may be performed by methods known in the art, for example stirring for 1 hour at room temperature.
According to an embodiment of the invention, in step (2), the lyophilization conditions are lyophilization at 0 ℃ to-50 ℃ for 1-48 hours, for example, lyophilization at-50 ℃ for 24 hours.
According to an embodiment of the present invention, in step (3), the conditions of the high temperature treatment include: the reaction is carried out at 800℃to 1000℃for 1 to 10 hours, for example at 900℃for 4 hours.
According to an embodiment of the invention, in step (3), the long persistence material is a solid powder, preferably a white solid powder.
The invention also provides a long afterglow material which is prepared by the preparation method.
According to an embodiment of the invention, the long persistence material comprises Cr 3+ Doped zinc gallate, designated ZnGa 2 O 4 :Cr 3 + 。
According to an embodiment of the present invention, in the long afterglow material, cr 3+ The doping amount of (c) is more than 0.001%, preferably not more than 1%, for example, 0.1% to 0.6%, and for example, 0.5%.
According to an embodiment of the invention, the long persistence material has an average particle size in the range of 10 to 1000nm, for example 170nm.
According to an embodiment of the invention, the long persistence material has a regular crystalline form. Preferably, the long afterglow material is in the 111 crystal form, and the crystal lattice of the long afterglow material is 0.48nm.
According to an embodiment of the invention, the long persistence material has a signal to noise ratio 541 after irradiation at 254nm for 10 minutes.
According to an embodiment of the invention, the long persistence material has water stability.
The invention also provides application of the long afterglow material in the field of biological imaging.
Advantageous effects
According to the invention, MOF is used as a precursor, and the spatial distribution and the element proportion of metal ions can be well arranged, so that a long afterglow material with more regular crystal form and more uniform element distribution is obtained in the calcination process, and the formation of lattice defects (traps) in the system is facilitated, so that the brightness and the afterglow duration of the afterglow material are improved.
According to the invention, a removable high molecular template is utilized, MOF prepared by using porphyrin derivatives can be used for accurately regulating and controlling the proportion and space position of metal elements in the template, for example, ga and functional groups outside the porphyrin derivatives react, zn is chelated in porphyrin rings of the porphyrin derivatives, and inorganic long afterglow materials are induced to grow according to the size of the template, so that expected nanoparticles can be obtained; make up for the reduction of electron number, trap concentration and depth in the crystal caused by the reduction of granularity, thereby effectively improving the fluorescence brightness and duration of the material. Finally, the nano long afterglow material with high purity and excellent performance is obtained, and the precise navigation is provided for the biological imaging field (such as tumor excision).
Drawings
FIG. 1 is a schematic diagram of a process for preparing a long afterglow material of the present invention;
FIG. 2 shows the morphology characterization result of ZGC-1 prepared in example 1.
FIG. 3 shows the afterglow performance test result of ZGC-1 obtained in example 1.
FIG. 4 shows the afterglow stability test results of ZGC-1 obtained in example 1.
Fig. 5 is an evaluation result in a living animal of application example 1.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
In the following examples, the porphyrin derivatives are selected from the group consisting of tetraphenylporphyrin tetracarboxylic acid (TCPP), tetraphenylporphyrin (TAPP), hematoporphyrin monomethyl ether (HMME), chlorin e6 (Ce 6).
Example 1
The preparation method of the long afterglow material comprises the following steps:
1. synthesis of Zn-Ga-TMOF (ZGT)
0.06mmol of phenyl porphyrin tetracarboxylic acid (TCPP), 0.2mmol of Zn (OAc) were weighed out 2 0.2mmol of Ga (NO) 3 ) 3 Dissolved in 20mL of deionized water and vigorously stirred at room temperature for 6 hours. Then transferred to a 45mL polytetrafluoroethylene reaction kettle and reacted at 180 ℃ for 18 hours. Cooled to room temperature to give a dark brown solid. Washing 3 times with deionized water and ethanol, and oven drying at 60deg.C to obtain 20mg of ZGT-1 solid powder.
2. Synthesis of Zn-Ga-TMOF-Cr (ZGTC)
Redispersing the ZGT-1 obtained in the step 1 in 10mL of deionized water, and dripping 200uL of Cr (NO) 3 ) 3 Solution (2 mg/mL) into the system, ZGT-1 and Gr (NO) 3 ) 3 Is 1:0.02 and stirred at room temperature for 1 hour. The precipitate was centrifuged and washed 3 times with deionized water and lyophilized to give 20mg of dark brown ZGTC-1.
3. Preparation of ZGC-1 nanoparticles
And (3) placing the black brown ZGTC-1 obtained in the step (2) in a tube furnace, and reacting for 4 hours at 900 ℃ in an air atmosphere. Then naturally cooled to room temperature, a white ZGC-1 solid powder was obtained in 40% yield. As a result of the test, the doping amount of Cr in ZGC-1 prepared in example 1 was 0.5%.
Test example 1
Morphology characterization of ZGC-1
As shown in fig. 2 a-e, the ZGC-1 prepared in example 1 has a regular rod-like structure, and the hydrated particle size is about 170nm. As shown in f of FIG. 2, high resolution TEM confirmed that the ZGC-1 material has high crystallinity, its lattice is 0.48nm, and it accords with the 111 crystal form of ZGC.
Afterglow characterization of ZGC-1
ZGC-1 obtained in example 1 was dissolved in water to obtain a ZGC-1 suspension (3 mg/mL) to obtain a ZGC-1 sample in water. After irradiation of the ZGC-1 sample and the solid ZGC-1 sample in water with a 254nm uv lamp for 10min, the uv lamp was turned off and the afterglow intensity was recorded for 60 min. The afterglow intensity of the sample was recorded using IVIS imaging system and an afterglow decay curve was plotted.
As shown in FIG. 3, the ZGC-1 obtained in example 1 maintains high afterglow performance even in water. The afterglow intensity of ZGC-1 in water was reduced by about 22% from the initial value, but still remained at a higher level. Although the afterglow intensity of ZGC-1 in water at the early stage decreases faster, the decay rate at the later stage is basically the same as that of the solid ZGC-1. It is found by calculation that the average life of ZGC-1 in water is prolonged by tau avg Average life extension τ of ZGC-1 solids at 192 seconds avg 216s, indicating water to ZGC preparedThe afterglow lifetime has little effect.
As shown in fig. 4 a, solid ZGC-1 exhibited good reproducibility and photostability with no significant signal decay over three excitation periods.
Afterglow stability characterization of ZGC-1
The afterglow stability test conditions are basically the same as those of the afterglow performance characterization, and the afterglow stability test conditions are as follows: the ZGC-1 solid powder obtained in example 1 was taken to obtain a ZGC-1 sample in water. After irradiating the solid ZGC-1 sample with a 5000lm light emitting diode for 10min, the LED was turned off and the afterglow intensity was recorded for 5min, recorded as one cycle. The above procedure was repeated 4 times and the afterglow intensities of four excitation periods were recorded. The afterglow intensity of the sample was recorded using IVIS imaging system and an afterglow decay curve was plotted.
The NIR PL of the ZGC-1 powder was able to recover the initial afterglow without significant fluctuations over at least four cycles of irradiation with a 5,000lm light emitting diode, as shown in FIG. 4 b, thereby confirming that the ZGC-1 powder had good excitation repeatability. The high afterglow stability of ZGC-1 can greatly extend imaging time and is sufficient for in vivo bioimaging and molecular fluorescence guided surgery.
Example 2
The preparation procedure of this example is substantially the same as in example 1, except that:
in step 1, tetraphenylporphyrin tetracarboxylic acid (TCPP) is replaced by Tetraphenylporphyrin (TAPP), TAPP, zn (OAc) 2 And Ga (NO) 3 ) 3 The molar ratio of (C) was the same as in example 1 to give 20mg of ZGT-2 solid powder;
in step 2, ZGT-1 is replaced by ZGT-2, ZGT-2 and Gr (NO) 3 ) 3 The mass ratio of (2) is the same as in example 1; lyophilizing to obtain 20mgZGTC-2;
in step 3, ZGTC-2 was placed in a tube furnace and reacted at 900℃for 4 hours under an air atmosphere. Then naturally cooled to room temperature, a white ZGC-2 solid powder was obtained in 35% yield.
As a result of the test, the doping amount of Cr in ZGC-1 prepared in example 2 was 0.5%.
Example 3
The preparation procedure of this example is substantially the same as in example 1, except that:
in step 1, tetraphenylporphyrin tetracarboxylic acid (TCPP) was replaced with hematoporphyrin monoethyl ether (HMME), HMME, zn (OAc) 2 And Ga (NO) 3 ) 3 The molar ratio of (C) was the same as in example 1 to give 20mg of ZGT-3 solid powder;
in step 2, ZGT-1 is replaced by ZGT-3, ZGT-3 and Gr (NO) 3 ) 3 The mass ratio of (2) is the same as in example 1; lyophilizing to obtain 20mgZGTC-3;
in step 3, ZGTC-3 was placed in a tube furnace and reacted at 900℃for 4 hours under an air atmosphere. Then naturally cooled to room temperature, a white ZGC-3 solid powder was obtained in 40% yield.
As a result of the test, the doping amount of Cr in ZGC-1 prepared in example 3 was 0.5%.
Example 4
The preparation procedure of this example is substantially the same as in example 1, except that:
in step 1, the tetracarboxylic phenyl porphyrin (TCPP) is replaced by chlorin e6 (Ce 6), ce6, zn (OAc) 2 And Ga (NO) 3 ) 3 The molar ratio of (C) was the same as in example 1 to give 20mg of ZGT-4 solid powder;
in step 2, ZGT-1 is replaced by ZGT-4, ZGT-4 and Gr (NO) 3 ) 3 The mass ratio of (2) is the same as in example 1; lyophilizing to obtain 20mgZGTC-4;
in step 3, ZGTC-4 was placed in a tube furnace and reacted at 900℃for 4 hours under an air atmosphere. Then naturally cooled to room temperature, a white ZGC-4 solid powder was obtained in 40% yield.
As a result of the test, the doping amount of Cr in ZGC-1 prepared in example 4 was 0.5%.
Application example 1
24-hour afterglow attenuation experiment and mouse imaging experiment
After irradiating the solid ZGC-1 sample with 254nm uv light for 10min, the uv light was turned off and PL pictures were captured over 24 hours using the IVIS imaging system. In the absence of any external illumination, the charge-coupled device (CCD) camera still clearly detects the NIR PL after 24 hours. After 24 hours, the signal-to-noise ratio (SNR) drops from the original 2,567 to 541.
PL characteristics of ZGC prepared in example 1 were also evaluated in living animals. The ZGC suspension (3 mg/mL) was subcutaneously injected into mice after 10 minutes of excitation with an ultraviolet lamp (254 nm, 6W). High luminescence was observed at 5 minutes after injection, at which time the SNR was 134.
The above results demonstrate the potential for application in bioimaging of long afterglow materials (PLNPs) prepared using MOF templates as precursors.
The above description of exemplary embodiments of the invention has been provided. However, the scope of protection of the present application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing a long afterglow material, which is characterized by comprising the following steps:
(1) Preparing a MOF template: uniformly mixing porphyrin derivatives and a metal source in a solvent, and performing hydrothermal reaction to obtain an MOF template;
(2) Preparing a precursor: dispersing the MOF template obtained in the step (1) in the solvent again, adding a chromium source, mixing for a period of time, separating to obtain a precipitate, and freeze-drying to obtain the precursor;
(3) And (3) under the air atmosphere, carrying out high-temperature treatment on the precursor obtained in the step (2) to obtain the long afterglow material.
2. The method according to claim 1, wherein the porphyrin derivative is selected from the group consisting of amino group-containing and carboxyl group-containing porphyrin derivatives.
Illustratively, the porphyrin-like derivative is selected from the group consisting of tetraphenylporphyrin, hematoporphyrin monomethyl ether, chlorin e6.
3. The method according to claim 1 or 2, wherein in step (1), the molar ratio of the porphyrin derivative to the metal source is (0.05-0.07): (0.1-0.6).
Preferably, the metal source is selected from at least one of nitrate, acetate, chloride, sulfate of a metal. Preferably, the metal is at least one of zinc, gallium and germanium.
4. A process according to any one of claims 1 to 3, wherein in step (1) the solvent is selected from water.
Preferably, in step (1), the hydrothermal conditions include: reacting at 150-200 deg.c for 10-24 hr.
Preferably, in step (1), the MOF template is further washed and/or dried.
5. The method according to any one of claims 1 to 4, wherein in step (2), the chromium source is selected from chromium compounds.
Preferably, in step (2), the mass ratio of the chromium source to the MOF template is (0.000288-0.00864) 1
Preferably, in step (2), the lyophilization conditions are lyophilization at 0 ℃ to-50 ℃ for 1-48 hours.
6. The method according to any one of claims 1 to 5, wherein in the step (3), the conditions of the high-temperature treatment include: reacting at 800-1000 deg.c for 1-10 hr.
Preferably, in step (3), the long persistence material is a solid powder.
7. A long afterglow material, characterized in that it is produced by the production method according to any one of claims 1 to 6.
8. The long persistence material of claim 7, wherein the long persistence material comprises Cr 3+ Doped zinc gallate, designated ZnGa 2 O 4 :Cr 3+ 。
9. The long persistence material of claim 7 or 8, wherein Cr in the long persistence material 3+ The doping amount of (2) is more than 0.001%.
Preferably, the average particle size of the long persistence material is in the range of 10-1000nm.
Preferably, the long persistence material has a regular crystalline form. Preferably, the long afterglow material is in the 111 crystal form, and the crystal lattice of the long afterglow material is 0.48nm.
Preferably, the long persistence material has a signal to noise ratio of 541 after irradiation at 254nm for 10 minutes.
Preferably, the long persistence material is water stable.
10. Use of a long persistence material as recited in any one of claims 7-9 in the field of bioimaging.
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