A kind of paramagnetic fullerene-metal nanocomplex and its preparation method and application

Abstract

The invention discloses a paramagnetic fullerene-metal nano complex, a preparation method and application thereof. The paramagnetic fullerene-metal nano complex is prepared by a chelation reaction between a fullerene-based nano ligand and an inorganic metal salt; the inorganic metal salt is manganese sulfate, manganese nitrate, manganese chloride, carbonic acid One of manganese, manganese acetate, gadolinium sulfate, gadolinium nitrate, and gadolinium chloride; the fullerene-based nano-ligand is connected to the side chain through a nitrogen bridge on the surface of the carbon cage of the fullerene, and each carbon cage has an average 6-18 side chains are linked; the side chains are selected from one of the following. The paramagnetic fullerene-metal nanocomplex of the present invention has good water solubility and excellent paramagnetic properties, can be used as an MRI nanoprobe for MRI imaging contrast enhancement, and has important application prospects in the field of nanodiagnosis and treatment.

Description

technical field

[0001] The invention belongs to the field of carbon nanomaterials, and relates to a class of water-soluble paramagnetic fullerene-metal nanocomplexes and their preparation methods and applications. The water-soluble paramagnetic fullerene-metal nanocomplexes can be used as magnetic resonance Imaging (MRI) probes. Background technique

[0002] MRI relies on nanomaterials to develop high-efficiency and low-toxic paramagnetic MRI nanoprobes to realize malignant tumor diagnosis and / or early image-mediated therapy. one. Among them, among the paramagnetic carbon-based MRI nanoprobes, the most common in the scientific literature is the gadolinium-based metallofullerene MRI nanoprobe. These probes are all Gd@C 82 、Gd 3 N@C 80 、Gd 3 N@C 84 Hydroxylation, amination, and Bingel derivatives of fullerenes such as gadolinium. For example, Gd 3 N@C 80 (OH) 30 (CH 2 CH 2 COOH) 20 、Gd 3 N@C 80 (OH) x (NH 2 ) y 、Gd@C 82 (OH) x (CH 2 CH 2 COOH) y and Gd@...

Examples

Embodiment 1

[0032] Example 1: Preparation C 60 (NCH 2 CH 2 OCH 2 CH 2 Oh) 8 -Mn complex

[0033] 360mg C 60 with liquid N 3 CH 2 CH 2 OCH 2 CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) of 1:100, protected by nitrogen, mechanically stirred, and controlled at a heating rate of 1°C / min, slowly rising to 120°C, keeping the temperature for 24 hours, stopping the reaction, and cooling the product to room temperature Dissolve in 500ml of water, filter, concentrate, dialyze with a molecular weight cut-off 500 dialysis bag, filter again, freeze-dry to obtain solidified fullerene-based nano-ligand 1; mix 0.1544g of fullerene-based nano-ligand 1 with 0.186g of four Hydrated manganese acetate was dispersed in 200ml of methanol according to the molar ratio of 1:10, isolated from the air, refluxed for 12 hours, terminated the reaction, distilled off the methanol and redissolved in water, dialyzed in a dialysis bag with a...

Embodiment 2

[0039] Example 2: Preparation C 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 -Mn complex

[0040] With reference to embodiment 1, 420mg C 70 with liquid N 3 CH 2 CH 2 OCH 2 CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) of 1:100, and the rest of the conditions are the same as in Example 1 of the present invention to obtain the pure fullerene-based nano ligand 2 solid product, and its average molecular formula is characterized by thermogravimetric analysis: C 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 . Further obtain fullerene-manganese nanocomplex 2 product C after the operation chelation according to embodiment 1 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 -Mn.

Embodiment 3

[0041] Example 3: Preparation C 60 (NCH 2 CH(OH)CH 2 Oh) 10 -Mn complex

[0042] With reference to embodiment 1, the 360mg C 60 with liquid N 3 CH 2 CH(OH)CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) 1:100, and the remaining conditions are the same as in Example 1 of the present invention to obtain pure fullerene-based nano-ligand 3 solid product, and its average molecular formula is characterized by thermogravimetric analysis: C 60 (NCH 2 CH(OH)CH 2 Oh) 10 . Further obtain fullerene-manganese nanocomplex 3 product C after the operation chelation according to embodiment 1 60 (NCH 2 CH(OH)CH 2 Oh) 10 -Mn.

technical field

[0001] The invention belongs to the field of carbon nanomaterials, and relates to a class of water-soluble paramagnetic fullerene-metal nanocomplexes and their preparation methods and applications. The water-soluble paramagnetic fullerene-metal nanocomplexes can be used as magnetic resonance Imaging (MRI) probes. Background technique

[0002] MRI relies on nanomaterials to develop high-efficiency and low-toxic paramagnetic MRI nanoprobes to realize malignant tumor diagnosis and / or early image-mediated therapy. one. Among them, among the paramagnetic carbon-based MRI nanoprobes, the most common in the scientific literature is the gadolinium-based metallofullerene MRI nanoprobe. These probes are all Gd@C 82 、Gd 3 N@C 80 、Gd 3 N@C 84 Hydroxylation, amination, and Bingel derivatives of fullerenes such as gadolinium. For example, Gd 3 N@C 80 (OH) 30 (CH 2 CH 2 COOH) 20 、Gd 3 N@C 80 (OH) x (NH 2 ) y 、Gd@C 82 (OH) x (CH 2 CH 2 COOH) y and Gd@...

Examples

Embodiment 1

[0032] Example 1: Preparation C 60 (NCH 2 CH 2 OCH 2 CH 2 Oh) 8 -Mn complex

[0033] 360mg C 60 with liquid N 3 CH 2 CH 2 OCH 2 CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) of 1:100, protected by nitrogen, mechanically stirred, and controlled at a heating rate of 1°C / min, slowly rising to 120°C, keeping the temperature for 24 hours, stopping the reaction, and cooling the product to room temperature Dissolve in 500ml of water, filter, concentrate, dialyze with a molecular weight cut-off 500 dialysis bag, filter again, freeze-dry to obtain solidified fullerene-based nano-ligand 1; mix 0.1544g of fullerene-based nano-ligand 1 with 0.186g of four Hydrated manganese acetate was dispersed in 200ml of methanol according to the molar ratio of 1:10, isolated from the air, refluxed for 12 hours, terminated the reaction, distilled off the methanol and redissolved in water, dialyzed in a dialysis bag with a...

Embodiment 2

[0039] Example 2: Preparation C 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 -Mn complex

[0040] With reference to embodiment 1, 420mg C 70 with liquid N 3 CH 2 CH 2 OCH 2 CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) of 1:100, and the rest of the conditions are the same as in Example 1 of the present invention to obtain the pure fullerene-based nano ligand 2 solid product, and its average molecular formula is characterized by thermogravimetric analysis: C 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 . Further obtain fullerene-manganese nanocomplex 2 product C after the operation chelation according to embodiment 1 70 (NCH 2 CH 2 OCH 2 CH 2 Oh) 10 -Mn.

Embodiment 3

[0041] Example 3: Preparation C 60 (NCH 2 CH(OH)CH 2 Oh) 10 -Mn complex

[0042] With reference to embodiment 1, the 360mg C 60 with liquid N 3 CH 2 CH(OH)CH 2 OH is sequentially fed into the three-necked reaction flask according to the stoichiometric ratio (molar ratio) 1:100, and the remaining conditions are the same as in Example 1 of the present invention to obtain pure fullerene-based nano-ligand 3 solid product, and its average molecular formula is characterized by thermogravimetric analysis: C 60 (NCH 2 CH(OH)CH 2 Oh) 10 . Further obtain fullerene-manganese nanocomplex 3 product C after the operation chelation according to embodiment 1 60 (NCH 2 CH(OH)CH 2 Oh) 10 -Mn.

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