CN-121823648-B - Water-soluble manganese doped titanium dioxide nanorod and preparation method and application thereof

Abstract

The invention relates to a water-soluble manganese doped titanium dioxide nano rod, a preparation method and application thereof, belonging to the technical field of nano material preparation; the preparation method of the water-soluble manganese-doped titanium dioxide nanorod comprises the steps of adding titanium tetrachloride into oleic acid to prepare a titanium oleate compound precursor, dissolving manganese oleate in oleic acid, adding the titanium oleate compound precursor after ultrasonic treatment, continuing ultrasonic treatment to obtain a titanium oleate and manganese oleate compound precursor, taking the titanium oleate compound precursor, adding a mixed system of oleylamine, oleic acid and octadecene, injecting the titanium oleate and manganese oleate compound precursor to obtain the oil-soluble manganese-doped titanium dioxide nanorod, and carrying out sodium citrate water-soluble surface modification to obtain the water-soluble manganese-doped titanium dioxide nanorod. The nanorod prepared by the invention can be used as an excellent T 1 magnetic resonance molecular image contrast agent, and has important application value and wide application prospect in the biomedical image fields such as tumor detection, vascular imaging and the like.

Inventors

• LIU KUN
• BO CHUNMIN
• WANG CHUNLI
• WANG XINYU
• ZHANG NA
• ZHANG HUAIBIN
• DU KAIMIN
• JIANG JIGANG
• WANG JIAQIAN

Assignees

• 滨州医学院

Dates

Publication Date

20260512

Application Date

20260311

Claims (9)

1. 1. The preparation method of the water-soluble manganese doped titanium dioxide nanorod is characterized by comprising the following steps of: a. Adding titanium tetrachloride into oleic acid, uniformly stirring, and then preserving heat at room temperature to 100 ℃ for 20min to 48h to obtain a compound precursor of titanium oleate, wherein the ratio of the mass of the titanium tetrachloride to the volume of the oleic acid is 0.05 to 1g/mL; b. Adding manganese oleate into oleic acid, carrying out ultrasonic treatment to dissolve the manganese oleate, and then adding the composite precursor of the titanium oleate prepared in the step a, and carrying out ultrasonic treatment to obtain the composite precursor of the titanium oleate and the manganese oleate, wherein the ratio of the manganese oleate to the composite precursor of the titanium oleate is 0.1-5 g to 0.5mL to 0.5-2 mL; c. Adding the compound precursor of the titanium oleate prepared in the step a into a mixture of oleylamine, oleic acid and octadecene, uniformly stirring, then heating to 100-150 ℃, preserving heat for 0.5-2 h to remove water, and heating to 240-320 ℃ under the protection of nitrogen to obtain a reaction solution, wherein the volume ratio of the compound precursor of the titanium oleate, oleic acid, oleylamine and octadecene is 0.5-2:0.5-2:10:10-20; d. C, rapidly injecting the compound precursor of the titanium oleate and the manganese oleate prepared in the step b into the reaction liquid prepared in the step C at the temperature of 240-320 ℃, continuously preserving heat for 0.2-2 hours, and naturally cooling to room temperature to obtain the oil-soluble manganese doped titanium dioxide nanorod, wherein the volume ratio of the compound precursor of the titanium oleate and the manganese oleate to the reaction liquid is 1-5:20; e. And d, carrying out water-soluble surface modification on the oil-soluble manganese-doped titanium dioxide nanorod prepared in the step d by using sodium citrate to obtain the water-soluble manganese-doped titanium dioxide nanorod.
2. 2. The method for preparing the water-soluble manganese-doped titanium dioxide nanorod according to claim 1, wherein the step e specifically comprises the following steps: E1, weighing an oil-soluble manganese doped titanium dioxide nano rod in a container, adding cyclohexane, and uniformly dispersing to obtain a solution E; e2, adding sodium citrate into the flask, then adding water, and uniformly dispersing to obtain a solution F; E3, adding the solution E and ethanol into the solution F, and refluxing and stirring for 2-24 hours at 20-80 ℃ to obtain a reaction solution G; And e4, cooling the reaction solution G to room temperature, using excessive acetone for centrifugal separation, dispersing the obtained precipitate with water, and freeze-drying to obtain a solid, and dispersing the solid in water to obtain the water-soluble manganese-doped titanium dioxide nanorod.
3. 3. The preparation method of the water-soluble manganese-doped titanium dioxide nanorods according to claim 2 is characterized in that in step E1, the ratio of the oil-soluble manganese-doped titanium dioxide nanorods to cyclohexane is 2-20 mg:5-20 mL, in step E2, the ratio of sodium citrate to water is 2-500 mg:5-20 mL, and in step E3, the volume ratio of solution E, solution F and ethanol is 1-2:1-2.
4. 4. A water-soluble manganese-doped titanium dioxide nanorod prepared by the preparation method according to any one of claims 1 to 3.
5. 5. The water-soluble manganese doped titanium dioxide nanorod according to claim 4, wherein the longitudinal molar relaxation rate r 1 of the manganese doped titanium dioxide nanorod is 50.7-69.46 mM -1 S -1 .
6. 6. The water-soluble manganese doped titanium dioxide nanorod according to claim 4, wherein the matrix material of the manganese doped titanium dioxide nanorod is TiO 2 .
7. 7. The water-soluble manganese doped titanium dioxide nanorod according to claim 4, wherein the length of the manganese doped titanium dioxide nanorod is 20-23 nm and the width is 3-6 nm.
8. 8. Use of the water-soluble manganese-doped titanium dioxide nanorod according to any one of claims 4-7 in the field of nuclear magnetic resonance.
9. 9. The use according to claim 8, wherein the water-soluble manganese doped titanium dioxide nanorods are used as a T 1 type magnetic resonance imaging contrast agent.

Description

Water-soluble manganese doped titanium dioxide nanorod and preparation method and application thereof Technical Field The invention relates to a water-soluble manganese doped titanium dioxide nanorod and a preparation method and application thereof, and belongs to the technical field of nanomaterial preparation. Background Currently, the clinical T 1 weighted magnetic resonance imaging is widely applied. The gadolinium chelate based T 1 weighted contrast agents are dominant in the market, such as Gd-DTPA (Ma Genwei display). However, gadolinium-based contrast agents still suffer from a number of problems, such as nephrotoxicity, ease of deposition and low longitudinal relaxation rate r 1. While iron oxide based contrast agents have some limitations on MRI, i.e. are prone to artifacts and dark signals. However, due to the biological properties, high paramagnetism and biocompatibility of manganese-based contrast agents, manganese-based contrast agents have been studied as alternatives to gadolinium-based contrast agents, which have important clinical significance. Chemical Progress (Chemical Industry AND ENGINEERING Progress,2010, volume 29, 6, pages 1071-1074, 1079) reports the synthesis of 12nm sized Mn element doped TiO 2 nanoparticles by dissolving butyl Titanate (TNB) in absolute ethanol, using MnSO 4·H2 O and MnC 2O4·4H2 O as manganese sources, respectively, adding a certain amount of manganese source, stirring strongly until the solution is completely transparent, and adding a certain amount of distilled water and ethanol. After standing and ageing for 24 hours, transferring the mixture into a 180 ℃ high-temperature high-pressure reaction kettle to react for 12h, washing and drying at 110 ℃ to finally obtain Mn-doped TiO 2 nano particles, wherein the two-step method of preparing Mn-doped TiO 2 nano particles is complicated in process, long in reaction time and has the phenomenon of wasting a large amount of solvents, and the Mn-TiO 2 photocatalyst with visible light response is applied and is not a study in the field of living imaging. The us ACS application materials and Interfaces (ACS APPLIED MATERIALS & Interfaces,2023, volume 15, pages 20800-20810) reports that manganese doped hollow titanium dioxide (MHT) is loaded with Rk1, that an rk1@mht sonosensitizer is prepared to enhance the sonodynamic therapeutic effect of tumors, that manganese doping imparts a weighted MRI function to the nanoprobe T 1 (with a relaxation rate ratio of r 2/r1 =1.41), that although the study has application in the magnetic resonance field, the main purpose is to develop around the treatment of tumors, so that the r 1 value is only 6.44mM -1s-1, the longitudinal molar relaxation rate r 1 is relatively not high, and is only 2-3 mM -1s-1 higher than that of the longitudinal molar relaxation rate r 1 of the commercial T 1 magnetic resonance contrast agent Gd-DTPA used clinically, and that the synthesis process is more cumbersome. In conclusion, the existing TiO 2 -based T 1 -type nano magnetic resonance contrast agent is complex in synthesis process, more in solvent waste and not suitable for popularization and use, or the longitudinal molar relaxation rate r 1 of the existing TiO 2 -based T 1 -type nano magnetic resonance contrast agent is not greatly improved compared with a commercial T 1 -type magnetic resonance contrast agent Gd-DTPA used clinically. Disclosure of Invention The invention provides a water-soluble manganese doped titanium dioxide nano rod, a preparation method and application thereof, which are used for solving the technical problems in the prior art. The invention aims to provide a preparation method of a water-soluble manganese-doped titanium dioxide nano rod, which comprises the following steps: a. Adding titanium tetrachloride into oleic acid, uniformly stirring, and then preserving heat at room temperature to 100 ℃ for 20min to 48h to obtain a compound precursor of the titanium oleate; b. adding manganese oleate into oleic acid, carrying out ultrasonic treatment to dissolve the manganese oleate, adding the composite precursor of the titanium oleate prepared in the step a, and carrying out ultrasonic treatment to obtain the composite precursor of the titanium oleate and the manganese oleate; c. adding the compound precursor of the titanium oleate prepared in the step a into a mixture of oleylamine, oleic acid and octadecene, uniformly stirring, then heating to 100-150 ℃, preserving heat for 0.5-2 h to remove water, and heating to 240-320 ℃ under the protection of nitrogen to obtain a reaction solution; d. c, rapidly injecting the compound precursor of the titanium oleate and the manganese oleate prepared in the step b into the reaction liquid prepared in the step C at 240-320 ℃, continuously preserving heat for 0.2-2 h, and naturally cooling to room temperature to obtain the oil-soluble manganese doped titanium dioxide nanorod; e. And d, carrying out water-soluble surface modification on the oil-solub