CN112920798A - Near-infrared fluorescent probe and preparation method and application thereof - Google Patents
Near-infrared fluorescent probe and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorescent probe preparation and application, and particularly relates to a preparation method of a rare earth ion doped bismuth vanadate substrate near-infrared fluorescent probe and application of the rare earth ion doped bismuth vanadate substrate near-infrared fluorescent probe in bioluminescence imaging. The near-infrared fluorescent probe BiVO4：Re3+With BiVO4Is used as a substrate, rare earth ions are doped into the substrate to be used as a sensitizing agent and an activating agent, bismuth acetate is used as a bismuth source, vanadium acetylacetonate is used as a vanadium source, and an organic solvent is adopted to prepare a precursor solution and be used as a reaction medium. Compared with the prior art, the rare earth ion doped bismuth vanadate substrate fluorescent probe prepared by the invention does not need a nitric acid solution with strong oxidizing property, strong acidity and strong corrosivity as a solvent, and is beneficial to environmental protection and biological application; and water is not used as a solvent, so that the luminescent property of the fluorescent probe is improved. The rare earth ion doped bismuth vanadate substrate fluorescent probe prepared by the invention has good crystallinity and smaller average particle size (less than 150nm), and is more suitable for raw materialsThe application is as follows.
Description
Technical Field
The invention belongs to the technical field of preparation and application of near-infrared fluorescent probes, and particularly relates to a preparation method of a rare earth ion doped bismuth vanadate substrate up-conversion near-infrared fluorescent probe and application of the probe in bioluminescence imaging.
Background
In recent years, the development of rare earth ion doped luminescent materials in combination with biology has become an emerging research field and has received much attention. Although fluorescent dyes, organic fluorescent probes, luminescent quantum dots, etc. have achieved significant success in bioimaging applications, their intrinsic properties limit their further practical applications, such as photobleaching of organic fluorescent probes and dyes, toxicity and poor stability of quantum dots. Compared with the prior art, when the rare earth luminescent material is applied to the field of biomedicine, the rare earth luminescent material has incomparable advantages such as good optical stability, capability of using near infrared light as an excitation light source, narrow emission band and the like. In recent years, research on rare earth doped luminescent materials is mainly focused on NaYF4The patent CN107739603B and the literature of Upconversion luminescence imaging of cells and small animals (Nature Protocols, vol 8,2033-. NaYF, on the other hand4The matrix material has poor chemical stability, is easy to dissociate and release toxic F in a humid environment-Ions, severely limiting their application in the biomedical field.
BiVO4As a typical environment-friendly oxide, the nano-silver/nano. However, due to the limitation of the preparation method, the research on the bismuth vanadate material is mainly focused on the fields of photocatalysis and pigments at present. CN102728342A discloses a sol-gel method for synthesizing Eu3+Doped BiVO4The method is also applied to visible light photocatalyst, and can degrade organic pollutant methyl orange in dye wastewater. CN109021617B discloses the recovery of BiVO from waste water using water as solvent4Raw material, preparation of BiVO with high coloring power4A yellow pigment. So far, the reported preparation of BiVO4The method (A) mainly comprises three methods: high temperature solid phase methods, hydrothermal methods, and sol gel methods. The particle size of the particles prepared by the high-temperature solid phase method is larger, about several micrometers to dozens of micrometers, and the particles are not suitable for being used as fluorescent probes; both the hydrothermal method and the sol-gel method need to use a nitric acid solution with strong oxidizing property, strong acidity and strong corrosivity as a solvent, which is not beneficial to environmental protection and biological application; in addition, water is used as a solvent during synthesis, water molecules have strong polarity, the prepared product is easy to agglomerate, and a large amount of hydroxyl groups exist on the surface of the product, so that fluorescence quenching is caused, and the luminescence property of a sample is influenced.
Patent CN108927140A discloses in 2020 a method for preparing rare earth doped BiVO having both photocatalysis and up-conversion red light emission functions4Material, confirmation of BiVO4Is a good luminescent matrix material. However, the preparation method disclosed by the method adopts a sol-gel method combined with a high-temperature calcination method, adopts conventional bismuth nitrate and ammonium metavanadate as raw materials of bismuth and vanadium, needs to use a nitric acid solution with strong oxidizing property and strong corrosivity as a solvent, is not favorable for environmental protection and further expands BiVO4The new application of the material in the biological field. At present, a simple and 'green' preparation technology is lacked in documents and patent reports to obtain BiVO with a strong emission peak4Near infrared fluorescent probes and make them effectively applied in the biological field.
Disclosure of Invention
In view of the above situation, the present invention provides a method for preparing a rare earth ion doped bismuth vanadate substrate fluorescent probe with high fluorescence efficiency and good biocompatibility, and achieves the purpose of obtaining bright visible light and/or near infrared emission by using a low-power near infrared light source, and the bismuth vanadate substrate near infrared fluorescent probe is applied to the field of bioluminescence imaging.
One of the purposes of the invention is to provide a preparation method of a rare earth doped near-infrared fluorescent probe based on a bismuth vanadate substrate, which comprises the following steps:
1) taking bismuth acetate as a bismuth source, weighing bismuth acetate and rare earth acetate according to the stoichiometric ratio of the structural formula of the fluorescent probe, adding the rare earth acetate comprising sensitizer rare earth acetate and activator rare earth acetate into oleic acid and/or octadecene, wherein the total molar concentration of the bismuth acetate and the rare earth acetate is 0.1-0.3mol/L, heating the mixed solution to 100-130 ℃ until the solution becomes yellow transparent liquid, and then cooling to room temperature to form a solution A;
2) adding vanadium acetylacetonate into a methanol solution by taking vanadium acetylacetonate as a vanadium source, wherein the molar concentration of vanadium acetylacetonate is 0.25-1.2mol/L to form a solution B, dropping the solution B into the solution A, and continuously stirring for 0.5-4h to prepare a solution C;
3) heating the solution C at the temperature of 170-250 ℃ for 8-25h, centrifuging, washing by using absolute ethyl alcohol, drying at the temperature of 70 ℃, and calcining the powder obtained by drying at the temperature of 500-800 ℃ for 1-5h to obtain the target powder.
Furthermore, the doping amount of the activator rare earth ions is 0.1-10%, and the doping amount of the sensitizer rare earth ions is 10-50%.
Further, the molar ratio of the sum of the moles of the bismuth acetate and the rare earth acetate to the moles of the vanadium acetylacetonate is (0.4-1): 1.
further, the rare earth acetate comprises one or more of ytterbium acetate, neodymium acetate, thulium acetate, erbium acetate, praseodymium acetate and holmium acetate.
The second purpose of the invention is to provide a near-infrared fluorescent probe prepared by the preparation method.
By using 980 or 808nm near-infrared laser for irradiation, 455-500nm blue luminescence, 500-570nm green luminescence, 610-720nm red luminescence and 780-900nm near-infrared luminescence with emission spectra in a visible light region can be presented.
The invention also aims to provide application of the near-infrared fluorescent probe.
Applications include bioluminescence imaging, including but not limited to marine microalgal cells, bacteria, fish embryos.
The application steps are as follows: and contacting the organism with the bismuth vanadate near-infrared fluorescent probe, incubating for 5-12 hours, washing by using PBS (phosphate buffer solution) to remove the fluorescent probe which is not combined with the organism, and irradiating by using infrared excitation light to obtain bright bioluminescence imaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) the rare earth ion doped bismuth vanadate substrate fluorescent probe prepared by the invention adopts an organic solvent to prepare a precursor solution and to serve as a reaction medium, and compared with the prior art, the rare earth ion doped bismuth vanadate substrate fluorescent probe does not adopt a nitric acid solution with strong oxidizing property, strong acidity and strong corrosivity as a solvent, is safer and more environment-friendly, and is suitable for biological application; water is not used as a solvent, so that the luminescent property of the fluorescent probe is improved.
(2) The rare earth ion doped bismuth vanadate substrate fluorescent probe prepared by the invention has good biocompatibility, good crystallinity and smaller average particle size (less than 150nm), and is more suitable for biological application.
(3) The near-infrared fluorescence probe prepared by the method is irradiated by a 980 or 808nm near-infrared laser, can show 455-500nm blue luminescence, 500-570nm green luminescence, 610-720nm red luminescence and 780-900nm near-infrared luminescence of an emission spectrum in a visible light region, and can be applied to fluorescence imaging of organisms such as marine microalgae cells, bacteria, fish embryos and the like.
Drawings
FIG. 1 shows the doped and undoped rare earth ion BiVO prepared in example 14Samples and correspondingX-ray diffraction patterns of PDF standard cards.
FIG. 2 is an SEM photograph of the target powder 1(b) prepared in example 1.
FIG. 3 is a plot of the emission spectra of the prepared samples at 980nm excitation, where (a) is the sample prepared in example 2 and (b) is the sample prepared in example 3.
Fig. 4 is a photograph of the head of zebra fish applied to the bioluminescence imaging process in application example 1, wherein (a) is a bright field photograph of incubating zebra fish of 3 days old (total length: 3mm) in a sample of concentration 15mg/mL for 2 hours; (b) fluorescence imaging under 980nm excitation (up-conversion emission signal is collected at 800 nm), and the light-emitting position is the head of the zebra fish;
fig. 5 is a photograph of the abdomen of zebra fish applied to the bioluminescence imaging process in application example 1, wherein (a) is a bright field photograph of incubating zebra fish of 3 days old (total length: 3mm) in a sample of 15mg/mL concentration for 2 hours; (b) fluorescence imaging under 980nm excitation (up-conversion emission signal is collected at 800 nm), and the luminescence position is the abdomen of the zebra fish.
Detailed Description
The following examples are provided to clearly and specifically describe the technical solutions of the present invention, but the present invention is not limited in any way by the examples.
Example 1
BiVO4：20％Yb3+，0.5％Tm3+The preparation method comprises the following steps:
1) weighing bismuth acetate, ytterbium acetate and thulium acetate according to a stoichiometric ratio, adding the weighed bismuth acetate, ytterbium acetate and thulium acetate into 20ml of oleic acid, wherein the total molar concentration of the bismuth acetate, ytterbium acetate and thulium acetate is 0.15mol/L, heating the mixed solution to 120 ℃ until the solution becomes yellow transparent liquid, and then cooling the yellow transparent liquid to room temperature to form a solution A;
2) according to the molar ratio of acetate to vanadium acetylacetonate of 1: 1, dissolving vanadium acetylacetonate in a methanol solution, wherein the molar concentration of the vanadium acetylacetonate is 0.15mol/L to form a solution B, dropwise adding the solution B into the solution A, and continuously stirring for 1h to prepare a solution C;
3) and placing the solution C in a polytetrafluoroethylene-lined reaction kettle, heating for 15 hours at 180 ℃, centrifuging the product, washing the product by using absolute ethyl alcohol, drying the product in a 70 ℃ oven, placing the dried product in a muffle furnace for calcination at 500 ℃, 600 ℃ and 800 ℃ for 5 hours to obtain the target powder 1(a), the target powder 1(b) and the target powder 1 (C).
FIG. 1 is an X-ray diffraction chart of the target powder 1(a), the target powder 1(b) and the target powder 1(c) prepared at different calcination temperatures, from which XRD diffraction peaks and BiVO of the sample can be seen4The monoclinic structure standard card (PDF #14-0688) conformed well. Furthermore, all diffraction peaks of the lanthanide rare earth ion doped sample were shifted to large angles compared to the standard card (PDF # 14-0688). This is due to the small radius of Yb3+And Tm3+Ion doping replaces Bi3+Caused by the contraction of host crystal lattice by ions, the rare earth ions are successfully doped into BiVO4In a matrix.
FIG. 2 is an SEM image of the target powder 1(b), and it can be seen from the image that the prepared rare earth doped bismuth vanadate substrate fluorescent probe has a small average particle size of about 150nm, and is very suitable for application in the biological field.
Example 2
BiVO4：x％Yb3+，0.5％Tm3+The other conditions and procedures were the same as those of the preparation of the target powder 1(b) in example 1 except that the amount of ytterbium acetate added was changed, and table 1 shows samples prepared in example 2.
TABLE 1
| Sample (I) | Sample structural formula |
| Target powder 2(a) | BiVO4：10％Yb3+，0.5％Tm3+ |
| Target powder 3(b) | BiVO4：20％Yb3+，0.5％Tm3+ |
| Target powder 4(c) | BiVO4：30％Yb3+，0.5％Tm3+ |
| Target powder 5(d) | BiVO4：40％Yb3+，0.5％Tm3+ |
FIG. 3 is a graph of the emission spectrum of the near-infrared fluorescent probe prepared in example 2 at 980nm excitation, at low power (20W/cm)2) Under the irradiation of a near-infrared laser with the wavelength of 980nm, the near-infrared fluorescent probe shows 455-500nm blue, 610-720nm red and 780-845nm near-infrared luminescence with emission spectra.
Example 3
BiVO4：30％Yb3+，y％Tm3+The preparation method of (1) was the same as that of the target powder 1(b) in example 1 except that the amounts of ytterbium acetate and thulium acetate added were changed, and table 2 shows samples prepared in example 3.
TABLE 2
| Sample (I) | Sample structural formula |
| Target powder 3(a) | BiVO4：30％Yb3+，0.1％Tm3+ |
| Target powder 3(b) | BiVO4：30％Yb3+，0.5％Tm3+ |
| Target powder 3(c) | BiVO4：30％Yb3+，1％Tm3+ |
| Target powder 3(d) | BiVO4：30％Yb3+，2％Tm3+ |
| Target powder 3(e) | BiVO4：30％Yb3+，4％Tm3+ |
FIG. 3 is a graph of the emission spectrum of the near-infrared fluorescent probe prepared in example 2 at 980nm excitation, at low power (20W/cm)2) Under the irradiation of a near-infrared laser with the wavelength of 980nm, the near-infrared fluorescent probe shows 455-500nm blue, 610-720nm red luminescence and 780-845nm near-infrared emission.
Example 4
BiVO4：30％Er3+，0.8％Tm3+The preparation method comprises the following steps:
1) weighing bismuth acetate, erbium acetate and thulium acetate according to a stoichiometric ratio, adding the bismuth acetate, erbium acetate and thulium acetate into a mixed solution of 10ml of oleic acid and 10ml of octadecene, wherein the total molar concentration of the bismuth acetate, erbium acetate and thulium acetate is 0.2mol/L, heating the mixed solution to 110 ℃ until the solution becomes yellow transparent liquid, and then cooling to room temperature to form a solution A;
2) according to the molar ratio of acetate to vanadium acetylacetonate of 0.4: 1, dissolving a certain amount of vanadium acetylacetonate in a methanol solution, wherein the molar concentration of the vanadium acetylacetonate is 0.5mol/L to form a solution B, dropwise adding the solution B into the solution A, and continuously stirring for 2 hours to prepare a solution C;
3) and (3) placing the solution C in a reaction kettle, treating for 25h at 200 ℃, centrifuging the product, washing with absolute ethyl alcohol, drying, placing the dried powder in a muffle furnace for calcining, and calcining for 5h at 600 ℃ to obtain the target powder 4.
Under the irradiation of a 980nm near-infrared laser, the prepared near-infrared fluorescent probe shows green light with the emission spectrum of 500-570nm, red light with the emission spectrum of 625-700nm and near-infrared emission with the emission spectrum of 780-900 nm.
Example 5
BiVO4：15％Nd3+The preparation method comprises the following steps:
1) weighing bismuth acetate and neodymium acetate according to a stoichiometric ratio, adding the bismuth acetate and neodymium acetate into 20ml of octadecene solution, wherein the total molar concentration of the bismuth acetate and the neodymium acetate is 0.3mol/L, heating the mixed solution to 130 ℃ until the solution becomes yellow transparent liquid, and then cooling to room temperature to form a solution A;
2) according to the molar ratio of acetate to vanadium acetylacetonate of 0.6: 1, dissolving vanadium acetylacetonate in a methanol solution, wherein the molar concentration of vanadium acetylacetonate is 0.5mol/L to form a solution B, dropwise adding the solution B into the solution A, and continuously stirring for 0.5h to prepare a solution C;
3) and (3) placing the solution C in a reaction kettle, treating for 20h at 220 ℃, centrifuging the product, washing with absolute ethyl alcohol, drying, placing the dried powder in a muffle furnace for calcining, and calcining for 5h at 600 ℃ to obtain the target powder 5.
Under the irradiation of a near-infrared laser with the wavelength of 808nm, the prepared near-infrared fluorescent probe shows 850-900nm near-infrared emission with an emission spectrum.
Example 6
BiVO4：20％Yb3+，5％Ho3+The preparation method comprises the following steps:
1) respectively weighing bismuth acetate, ytterbium acetate and holmium acetate according to stoichiometry, adding the bismuth acetate, ytterbium acetate and holmium acetate into 20ml of oleic acid, wherein the total molar concentration of the bismuth acetate, the ytterbium acetate and the holmium acetate is 0.2mol/L, and heating the mixed solution to 100 ℃ until the solution becomes transparent liquid to form a solution A;
2) according to the molar ratio of acetate to vanadium acetylacetonate of 0.8: 1, dissolving vanadium acetylacetonate in a methanol solution, wherein the molar concentration of vanadium acetylacetonate is 0.25mol/L to form a solution B, dropwise adding the solution B into the solution A, and continuously stirring for 4 hours to prepare a solution C;
3) and (3) placing the solution C in a reaction kettle, treating for 8 hours at 250 ℃, centrifuging the product, washing with absolute ethyl alcohol, drying, placing the dried powder in a muffle furnace, calcining for 3 hours at 500 ℃ to obtain the target powder 6.
Under the irradiation of 980nm near-infrared laser, the prepared near-infrared fluorescent probe shows an activator Ho3+The ion is in green emission at 520-570nm and red emission at 620-720 nm.
Example 7
BiVO4：P20％Yb3+，5％Pr3+The preparation method comprises the following steps:
1) respectively weighing bismuth acetate, ytterbium acetate and praseodymium acetate according to the stoichiometric amount, adding the bismuth acetate, the ytterbium acetate and the praseodymium acetate into 20ml of oleic acid, wherein the total molar concentration of the bismuth acetate, the ytterbium acetate and the praseodymium acetate is 0.2mol/L, heating the mixed solution to 100 ℃ until the solution becomes transparent liquid, and forming a solution A;
2) according to the molar ratio of acetate to vanadium acetylacetonate of 0.8: 1, dissolving vanadium acetylacetonate in a methanol solution, wherein the molar concentration of vanadium acetylacetonate is 0.25mol/L to form a solution B, dropwise adding the solution B into the solution A, and continuously stirring for 4 hours to prepare a solution C;
3) and (3) placing the solution C in a reaction kettle, treating for 8 hours at 250 ℃, centrifuging the product, washing with absolute ethyl alcohol, drying, placing the dried powder in a muffle furnace, calcining for 3 hours at 500 ℃, and obtaining the target powder 7.
Under the irradiation of 980nm near-infrared laserThe prepared near-infrared fluorescent probe presents an activator Pr3+The ion is positioned at 470-570 nm blue light emission, 500-570nm green light emission and 580-680nm red light emission.
Application example 1
The target powder 3(d) prepared in example 3 was applied to the bioluminescence imaging process, which specifically included the following steps: the zebra fish larvae (3 days old) are placed in a culture dish for feeding, and before microscopic imaging, the zebra fish larvae and BiVO are firstly carried out4：30％Yb3+，2％Tm3+(15mg/mL) for 5h, washing with PBS buffer to remove fluorescent probes not bound to zebrafish, and imaging zebrafish with a fluorescence inverted microscope at room temperature. As shown in fig. 4 and 5, under the excitation of 980nm, the head and the abdomen of the zebra fish are bright and clearly visible. Illustrates the BiVO prepared4：30％Yb3+，2％Tm3+The fluorescent probe has strong near-infrared fluorescence emission and good biocompatibility, and is an excellent near-infrared fluorescent probe.
Application example 2
The near-infrared fluorescent probe prepared in example 5 was applied to the fluorescence imaging process of microalgae and bacteria. The specific process is as follows: placing crescent rhombus microalgae or bacteria in a culture dish for breeding, and feeding BiVO4：15％Nd3+(15mg/mL) fluorescent probe and culture medium are mixed and then put into a culture dish, and are cultured together with Nitzschia closterium or bacteria for 12h, and the fluorescent probe which is not combined with the microorganism is removed by washing. Fluorescence imaging of Nitzschia closterium and bacteria is obtained under the excitation of 808nm laser.
Claims (8)
1. Near-infrared fluorescent probe BiVO4：Re3+The preparation method is characterized by comprising the following steps: with BiVO4As a substrate, bismuth acetate is used as a bismuth source, vanadium acetylacetonate is used as a vanadium source to prepare BiVO4：Re3+The preparation method comprises the following steps:
1) weighing bismuth acetate and rare earth acetate according to the stoichiometric ratio of the structure formula of the fluorescent probe, wherein the rare earth acetate comprises sensitizer rare earth acetate and activator rare earth acetate, adding the sensitizer rare earth acetate and the activator rare earth acetate into oleic acid and/or octadecene, the total molar concentration of the bismuth acetate and the rare earth acetate is 0.1-0.3mol/L, heating the mixed solution to 100-130 ℃ until the solution becomes yellow transparent liquid, and then cooling to room temperature to form a solution A;
2) adding vanadium acetylacetonate into a methanol solution, wherein the molar concentration of the vanadium acetylacetonate is 0.25-1.2mol/L to form a solution B, dripping the solution B into the solution A, and continuously stirring for 0.5-4h to prepare a solution C;
3) heating the solution C at the temperature of 170-250 ℃ for 8-25h, centrifuging, washing by using absolute ethyl alcohol, drying at the temperature of 70 ℃, and calcining the powder obtained by drying at the temperature of 500-800 ℃ for 1-5h to obtain the target powder.
2. The method of claim 1, wherein: the doping amount of the activator rare earth ions is 0.1-10%, and the doping amount of the sensitizer rare earth ions is 10-50%.
3. The method of claim 1, wherein: the molar ratio of the sum of the molar numbers of the bismuth acetate and the rare earth acetate to the molar number of the vanadium acetylacetonate is (0.4-1): 1.
4. the method of claim 1, wherein: the rare earth acetate comprises one or more of ytterbium acetate, neodymium acetate, thulium acetate, erbium acetate, praseodymium acetate and holmium acetate.
5. A near-infrared fluorescent probe BiVO prepared by the method of any one of claims 1 to 44：Re3+。
6. The near-infrared fluorescent probe according to claim 5, characterized in that: by using 980 or 808nm near-infrared laser for irradiation, 455-500nm blue luminescence, 500-570nm green luminescence, 610-720nm red luminescence and 780-900nm near-infrared luminescence with emission spectra in a visible light region can be presented.
7. The use of the near-infrared fluorescent probe of claim 6, wherein: the applications include bioluminescence imaging, including marine microalgal cells, bacteria, fish embryos.
8. Use according to claim 7, characterized in that: the application steps are as follows: and contacting the organism with the bismuth vanadate infrared fluorescent probe, incubating for 5-12 hours, washing by using PBS buffer solution to remove the fluorescent probe which is not combined with the organism, and irradiating by using infrared excitation light to obtain bright bioluminescence imaging.
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