CN115960608A - Fluorescent probe material for exciting near-infrared emission by X-ray and preparation method thereof - Google Patents
Fluorescent probe material for exciting near-infrared emission by X-ray and preparation method thereof Download PDFInfo
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- CN115960608A CN115960608A CN202111179630.6A CN202111179630A CN115960608A CN 115960608 A CN115960608 A CN 115960608A CN 202111179630 A CN202111179630 A CN 202111179630A CN 115960608 A CN115960608 A CN 115960608A
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Abstract
A fluorescent probe material for X-ray excitation near-infrared emission and a preparation method thereof belong to the field of inorganic luminescent materials. The molecular formula is NaLuF 4 Gd, tm, the advantage of this fluorescent probe will emit the strong near infrared light of 800nm under the X-ray excitation, because the X-ray has very strong penetrating quality, and the biological penetrating quality of the near infrared light, this fluorescent probe material has broad application prospects in biological imaging and analytical field. Using Gd 3+ Ion and Tm 3+ Method of ion co-doping to construct Gd 3+ Ion and Tm 3+ Efficient energy transfer process between ions, thereby increasing Tm 3+ Ion emission peak intensity at 800 nm.
Description
Technical Field
The invention belongs to the field of inorganic luminescent materials, and particularly relates to a fluorescent probe material capable of exciting near-infrared emission by X-rays.
Background
The probe has the advantages of rapid response, high spatial resolution, non-contact measurement and the like along with the fluorescent probe, and has wide application prospect in the fields of biological imaging, ion detection, photodynamic therapy and the like. The conventional fluorescent probe mainly utilizes an up-conversion process to detect by using visible light as a signal, wherein the exciting light is usually 980nm, but the visible light is easily absorbed and scattered by biological tissues, so the penetration depth is very limited; in addition, water molecules have strong absorption at 980nm, and long-time irradiation is easy to cause local damage. Therefore, the development of new fluorescent probe materials has important scientific significance.
The X-ray photons have better penetrability in biological tissues and can be detected by deep biological tissues, and the safety of X-rays with proper dosage in medical application is widely accepted clinically. In addition, near-infrared light has a stronger penetrating power in biological tissues than visible light, so that the signal intensity can be remarkably improved. Based on the consideration, the problems of penetration depth of the exciting light, bioluminescence background and thermal effect can be solved by using X rays as the exciting light, and the X-ray fluorescence imaging device can be used for deeper biological detection and imaging by doping appropriate activating ions and regulating and controlling the luminous intensity of the activating ions in a near infrared region. In conclusion, the development of the fluorescent probe material capable of exciting near infrared emission by X rays has very important application value.
Disclosure of Invention
The invention discloses a fluorescent probe material capable of emitting strong near infrared light under the excitation of X rays.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a fluorescent probe material for near-infrared emission excited by X-ray has a molecular formula of NaLuF 4 :Gd,Tm。
Preferably, a fluoride is used as a matrix and Gd is used 3+ Ion regulation of Tm 3+ The ion is at near infrared emission intensity of 800 nm.
A preparation method of a fluorescent probe material capable of emitting near infrared rays through X-ray excitation comprises the following steps:
(1) 10-20% of NaOH,20-30% of oleic acid and 20-30% of ethanol are fully stirred at room temperature according to the molar ratio to obtain white viscous solution.
(2) Under the condition of magnetic stirring, adding 5-15% of NaF and 15-20% of deionized water into the mixture obtained in the step (1) according to the molar ratio, and stirring the mixture until the mixture is a semitransparent solution.
(3) 55-80% Lu (NO) by mol ratio 3 ) 3 ,10-30%Gd(NO 3 ) 3 ,0.1-3%Tm(NO 3 ) 3 And 70-85% deionized water is added into (2) and stirred magnetically for a period of time.
(4) Transferring the mixed solution in the step (3) to a reaction kettle, preserving heat at 200-230 ℃, cooling, cleaning with ethanol and cyclohexane, and centrifuging to obtain a final product.
7. The method for preparing a fluorescent probe material emitting near infrared by X-ray excitation according to claim 3, characterized in that the holding time in the step (3) is 8 to 15 hours.
Preferably, the stirring time in step (1) is 30 to 60 minutes.
Preferably, the stirring time in step (2) is 30 to 60 minutes.
Preferably, the stirring time in step (3) is 60 to 90 minutes.
Preferably, the heat preservation time in step (4) is 8 to 15 hours.
The fluorescent probe material adopting the technical scheme can be used for exciting near infrared emission by X rays, and NaLuF is adopted under the excitation of the X rays 4 Gd, tm can emit stronger 800nm near infrared light 3 H 4 → 3 H 6 ). In NaLuF 4 Gd in the Gd, tm system 6 I 7/2 Energy level and Tm ion 3 P 1 / 3 P 0 Energy level matching, establishing a highly corrected energy transfer process between two Gd-Tm ions, and doping Gd 3+ Ionic NaLuF 4 NaLuF for Tm comparison 4 Gd, the light emission of Tm at 800nm can be improved by 4-5 times. The probe material is used for imaging analysis of deep biological tissues because of the super-strong penetration capability and strong near-infrared light-emitting capability of X-rays. The advantages of the invention include: (1) the synthetic method is simple and easy to operate; (2) Using Gd 3+ The crystal field environment of Tm ions can be adjusted by the ions, so that the near-infrared luminescence performance of the Tm ions can be greatly improved, and high-sensitivity biological imaging and detection application can be realized.
Drawings
FIG. 1 NaLuF in examples 1 and 2 4 X-ray diffraction patterns of Gd, tm;
FIG. 2 example 2NaLuF 4 A near infrared luminescence spectrum of Gd, tm under the excitation of X rays;
FIG. 3 Gd under X-ray excitation of samples of example 1 and example 2 3+ Ion direction Tm 3+ Ion energy transfer and near infrared luminescence.
Detailed Description
The patent is further described with reference to the figures and examples.
Example 1
A fluorescent probe material with the molecular formula of NaLuF for exciting near-infrared emission by X-ray 4 :Gd,Tm。
A preparation method of a fluorescent probe material capable of emitting near infrared rays through X-ray excitation comprises the following steps: (1) Sodium hydroxide 17.5mmol, oleic acid 25mmol and ethanol 10ml are mixed fully at room temperature, and stirred for 45 minutes to obtain white viscous solution; (2) Under the condition of magnetic stirring, adding 7mmol of sodium fluoride and 12ml of deionized water into the solution obtained in the step (1), and stirring for 30 minutes; (3) Adding lutetium nitrate 0.84mmol, gadolinium nitrate 0.24mmol, thulium nitrate 0.0075mmol and 2ml deionized water into the mixture (2) according to the mol ratio, and magnetically stirring for 75 minutes; (4) Transferring the mixed solution in the step (3) to a reaction kettle, preserving heat for 10 hours at 230 ℃, cooling, cleaning with ethanol and cyclohexane, and centrifuging to obtain a final product.
FIG. 1 is the X-ray diffraction pattern of the samples of example 1 and example 2, and it can be seen from the figure that the diffraction peaks and NaYF of the two samples 4 The PDF standard card (JCPDF: 16-0334) is consistent and is pure hexagonal NaYF 4 Phase, free of impurities, may indicate that the samples in both examples have been successfully prepared. FIG. 2 shows NaLuF in example 2 4 Gd, tm sample and NaLuF 4 Gd sample and NaLuF 4 Tm sample near-infrared emission spectrum under X-ray excitation, from which it can be seen that 3+ Under the condition of single ion doping, naLuF 4 Gd sample does not emit light in the near-infrared light emitting region of 800nm, naLuF 4 Luminous intensity of Tm sample in near infrared regionWeaker than Gd 3+ Ion and Tm 3+ When ions are co-doped, naLuF 4 Gd, the luminescence intensity of the Tm sample is NaLuF 4 4.2 times of Tm sample, it can be stated that Gd 3+ The doping of the ions can obviously improve the near infrared luminous intensity of the sample.
Example 2
A fluorescent probe material with the molecular formula of NaLuF for exciting near-infrared emission by X-ray 4 :Gd,Tm。
A preparation method of a fluorescent probe material capable of emitting near infrared rays excited by X rays comprises the following steps: (1) Mixing 15.5mmol of sodium hydroxide, 28mmol of oleic acid and 12ml of ethanol at room temperature, and stirring for 60 minutes to obtain a white viscous solution; (2) Under the condition of magnetic stirring, adding 9mmol of sodium fluoride and 16ml of deionized water into the solution obtained in the step (1), and stirring for 50 minutes; (3) Adding lutetium nitrate 0.74mmol, gadolinium nitrate 0.30mmol, thulium nitrate 0.015mmol and 3ml deionized water into the mixture obtained in the step (2) according to the mol ratio, and magnetically stirring the mixture for 90 minutes; (4) Transferring the mixed solution in the step (3) to a reaction kettle, preserving heat for 12 hours at 220 ℃, cooling, cleaning with ethanol and cyclohexane, and centrifuging to obtain a final product.
FIG. 2 shows NaLuF in example 2 4 Gd, tm sample and NaLuF 4 Gd sample and NaLuF 4 Tm sample near-infrared emission spectrum under X-ray excitation, from which Gd 3+ Under the condition of single ion doping, naLuF 4 Gd sample does not emit light in the near-infrared light emitting region of 800nm, naLuF 4 Tm samples have a weak luminescence intensity in the near infrared region, while Gd is present 3+ Ion and Tm 3+ When ions are co-doped, naLuF 4 Gd, the luminescence intensity of the Tm sample is NaLuF 4 4.2 times of Tm sample. The specific energy transfer process is shown in FIG. 3 when Gd 3+ When the ions are excited by X-rays, energy passes through Gd 3+ Of ions 6 I 7/2 With energy level delivered to Tm ions 3 P 1 / 3 P 0 Energy levels, energy is then transferred to Tm by non-radiative relaxation processes 3+ Of ions 3 H 4 Energy level followed by emission radiation transition process 3 H 4 → 3 H 6 FromWhile emitting near infrared light. Thus, gd is 3+ The doped ions can be used as a bridge for high-energy X-ray energy transfer, and the near-infrared luminous intensity of the sample is obviously improved.
Claims (7)
1. A fluorescent probe material excited by X-ray and emitting near infrared is characterized by its molecular formula of NaLuF 4 Gd, tm, and the molar ratio of the raw materials is as follows: gd (NO) 3 ) 3 10-35% Lu (NO) 3 ) 3 60-80%, tm (NO) 3 ) 3 0.1-3%, naOH 40-60%, and NaF 20-30%.
2. The fluorescent probe material of claim 1, wherein said probe material is fluoride-based and utilizes Gd 3+ The ions regulate the near infrared luminous intensity of the luminous ions.
3. The method for preparing a fluorescent probe material for exciting near-infrared emission by X-rays according to claim 1, characterized by comprising the steps of:
(1) Fully stirring 10-20% of NaOH,20-30% of oleic acid and 20-30% of ethanol at room temperature according to molar ratio to obtain white viscous solution;
(2) Under the condition of magnetic stirring, adding 5-15% of NaF and 15-20% of deionized water into the mixture obtained in the step (1) according to the molar ratio, and stirring the mixture until the mixture is a semitransparent solution;
(3) 55-80% Lu (NO) by mol ratio 3 ) 3 ,10-30%Gd(NO 3 ) 3 ,0.1-3%Tm(NO 3 ) 3 And 70-85% deionized water are added into the (2), and magnetic stirring is carried out for a period of time;
(4) Transferring the mixed solution in the step (3) to a reaction kettle, preserving heat at 200-230 ℃, cooling, cleaning with ethanol and cyclohexane, and centrifuging to obtain a final product.
4. The method for preparing a fluorescent probe material emitting near infrared by X-ray excitation according to claim 3, characterized in that the stirring time in the step (1) is 30 to 60 minutes.
5. The method for preparing a fluorescent probe material emitting near infrared rays by X-ray excitation according to claim 3, wherein the stirring time in the step (2) is 30 to 60 minutes.
6. The method for preparing a fluorescent probe material emitting near infrared by X-ray excitation according to claim 3, characterized in that the stirring time in the step (3) is 60 to 90 minutes.
7. The method for preparing a fluorescent probe material emitting near infrared by X-ray excitation according to claim 3, characterized in that the temperature-keeping time in the step (4) is 8 to 15 hours.
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Citations (3)
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CN107828408A (en) * | 2017-10-12 | 2018-03-23 | 复旦大学 | The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method |
CN111876154A (en) * | 2020-05-15 | 2020-11-03 | 福州大学 | Rare earth doped fluoride long afterglow particle and preparation method and application thereof |
CN112480925A (en) * | 2020-12-23 | 2021-03-12 | 福州大学 | Near-infrared two-region luminous long-afterglow nanoprobe based on X-ray excitation, preparation method and application thereof in living body imaging analysis |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107828408A (en) * | 2017-10-12 | 2018-03-23 | 复旦大学 | The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method |
CN111876154A (en) * | 2020-05-15 | 2020-11-03 | 福州大学 | Rare earth doped fluoride long afterglow particle and preparation method and application thereof |
CN112480925A (en) * | 2020-12-23 | 2021-03-12 | 福州大学 | Near-infrared two-region luminous long-afterglow nanoprobe based on X-ray excitation, preparation method and application thereof in living body imaging analysis |
Non-Patent Citations (1)
Title |
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郑尧,等: "NaLuF4掺杂Tm3+和Er3+的X射线激发发光特性研究", 《中国稀土学报》, vol. 38, pages 602 - 609 * |
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