CN115558000B - Ruthenium-gadolinium heteronuclear heterometal complex and preparation method and application thereof - Google Patents

Ruthenium-gadolinium heteronuclear heterometal complex and preparation method and application thereof Download PDF

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CN115558000B
CN115558000B CN202211162166.4A CN202211162166A CN115558000B CN 115558000 B CN115558000 B CN 115558000B CN 202211162166 A CN202211162166 A CN 202211162166A CN 115558000 B CN115558000 B CN 115558000B
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唐晓亮
茹嘉喜
陈小芬
刘伟生
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Abstract

The invention belongs to the technical field of coordination chemistry, and particularly relates to a ruthenium-gadolinium heteronuclear metal complex, and a preparation method and application thereof. The invention provides a ruthenium-gadolinium heteronuclear metal complex, which has a structure shown in a formula I, and the ruthenium-gadolinium heteronuclear metal complex not only comprises a ruthenium complex phosphorescence functional unit, but also comprises a rare earth gadolinium chelate magnetic functional unit, has the magnetic-optical dual-functional property, can realize magnetic-optical dual-mode imaging, and can generate singlet oxygen under illumination because the ruthenium-gadolinium heteronuclear metal complex comprises the ruthenium complex phosphorescence functional unit, so that the ruthenium-gadolinium heteronuclear metal complex is used as a photosensitizer in photodynamic therapy.

Description

Ruthenium-gadolinium heteronuclear heterometal complex and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coordination chemistry, and particularly relates to a ruthenium-gadolinium heteronuclear metal complex, and a preparation method and application thereof.
Background
At present, the clinically used cancer treatment method mainly adopts the traditional means such as surgical excision, radiotherapy, chemotherapy and the like. In recent years, with the rapid development of subjects such as chemistry, biology, medicine and the like, various novel cancer diagnosis and treatment methods are continuously emerging, such as cancer immunotherapy, photodynamic therapy, photothermal therapy and the like, and the methods bring new hopes for cancer treatment.
The photodynamic therapy principle is that the photosensitizer is concentrated at the lesion tissue through external application or intravenous administration and is selectively absorbed by the lesion tissue, and the photodynamic reaction occurs under the irradiation of light with specific wavelength to generate free radicals capable of killing the lesion tissue, and normal tissue cells are not damaged; multimode imaging enables the acquisition of useful information about the location, shape, size, etc. of a tumor. Therefore, the accurate treatment under the multi-mode imaging guidance can effectively avoid space-time variability generated in the diagnosis and treatment process, can obviously improve the imaging diagnosis efficiency, increase the treatment effect and reduce the toxic and side effects, and is an effective way for realizing the accurate diagnosis and the efficient treatment of tumors.
In the diagnosis and treatment system applied at present, nano materials are mostly used as drug delivery carriers to load anti-tumor drugs, but the method also faces the problems of low drug loading rate, poor stability, poor repeatability and the like, and lacks of real-time tracing of drug molecules and evaluation and detection of treatment effects. Single molecule diagnostic reagents are another effective strategy for achieving accurate therapy under multi-mode imaging guidance, but due to great difficulty in molecular design and synthesis, few reports are reported at present.
Disclosure of Invention
In view of the above, the invention provides a ruthenium-gadolinium heteronuclear metal complex, which can realize magneto-optical dual-mode imaging and can be used as a photosensitizer in preparation of photodynamic therapy.
In order to achieve the aim of the invention, the invention provides a ruthenium-gadolinium heteronuclear metal complex, which has a structure shown in a formula I:
The M includes Cl -.
Preferably, the M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -.
The invention also provides a preparation method of the ruthenium-gadolinium heteronuclear metal complex, which comprises the following steps:
Dissolving inorganic gadolinium salt and diethylenetriamine pentaacetic acid derivative, and carrying out a first coordination reaction to obtain gadolinium complex;
Dissolving the gadolinium complex and bis (2, 2' -bipyridine) ruthenium dichloride, and performing a second coordination reaction to obtain the ruthenium-gadolinium heteronuclear heterometal complex;
the diethylenetriamine pentaacetic acid derivative has a structure shown in a formula I-1;
the gadolinium complex has a structure shown in a formula I-2;
preferably, the inorganic gadolinium salt comprises one or more of gadolinium nitrate, gadolinium chloride and gadolinium perchlorate.
Preferably, the ratio of the mole number of the inorganic gadolinium salt to the sum of the mole numbers of the inorganic gadolinium salt and the diethylenetriamine pentaacetic acid derivative is 0.2 to 0.8:1.
Preferably, the ratio of the mole number of the gadolinium complex to the sum of the mole numbers of the gadolinium complex and the bis (2, 2' -bipyridine) ruthenium dichloride is 0.3 to 0.7:1.
Preferably, the temperature of the first coordination reaction is 40-60 ℃ and the time is 20-25 h.
Preferably, the temperature of the second coordination reaction is 40-60 ℃ and the time is 22-26 h.
Preferably, when M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -, the replacement method includes: carrying out ion replacement reaction on a product obtained by the second coordination reaction; the reagents for the ion exchange reaction include NH4Br、NaI、NH4NO3、AgBF4、NaSbF6、AgCF3SO3、NH4BPh4 or NH 4PF6.
The invention also provides application of the ruthenium-gadolinium heteronuclear metal complex or the ruthenium-gadolinium heteronuclear metal complex prepared by the preparation method in preparation of a magneto-optical dual-mode imaging agent or a photosensitizer.
The invention provides a ruthenium-gadolinium heteronuclear metal complex, which has a structure shown in a formula I, and the ruthenium-gadolinium heteronuclear metal complex not only comprises a ruthenium complex phosphorescence functional unit, but also comprises a rare earth gadolinium chelate magnetic functional unit, has magnetic-optical dual-functional properties, can be used for preparing an imaging agent in magnetic-optical dual-mode imaging, and can generate singlet oxygen under illumination because the ruthenium-gadolinium heteronuclear metal complex comprises the ruthenium complex phosphorescence functional unit, so that the ruthenium-gadolinium heteronuclear metal complex can be used for preparing a photosensitizer in photodynamic therapy.
Drawings
FIG. 1 is a reaction scheme of ruthenium-gadolinium heteronuclear metal complex prepared in example 1 of the present invention;
FIG. 2 is an electrospray mass spectrum of a ruthenium-gadolinium heteronuclear metal complex prepared in example 1 of the present invention;
FIG. 3 is a photograph of a live cell confocal microscope of ruthenium-gadolinium heteronuclear metal complex prepared in example 1 of the present invention;
FIG. 4 is a magnetic resonance imaging diagram of the ruthenium-gadolinium heteronuclear metal complex prepared in example 1 of the present invention;
FIG. 5 is a graph showing the in vitro photodynamic effect of the ruthenium-gadolinium heteronuclear metal complex prepared in example 1 of the present invention.
Detailed Description
The invention provides a ruthenium-gadolinium heteronuclear heterometal complex, which has a structure shown in a formula I:
The M includes Cl -.
Preferably, the M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -.
The invention also provides a preparation method of the ruthenium-gadolinium heteronuclear metal complex, which comprises the following steps:
Dissolving inorganic gadolinium salt and diethylenetriamine pentaacetic acid derivative, and carrying out a first coordination reaction to obtain gadolinium complex;
Dissolving the gadolinium complex and bis (2, 2' -bipyridine) ruthenium dichloride, and performing a second coordination reaction to obtain the ruthenium-gadolinium heteronuclear heterometal complex;
the diethylenetriamine pentaacetic acid derivative has a structure shown in a formula I-1;
the gadolinium complex has a structure shown in a formula I-2;
according to the invention, an inorganic gadolinium salt and a diethylenetriamine pentaacetic acid derivative are dissolved, and a first coordination reaction is carried out to obtain a gadolinium complex.
In the present invention, the inorganic gadolinium salt includes one or more of gadolinium nitrate, gadolinium chloride and gadolinium perchlorate, more preferably gadolinium nitrate hexahydrate. The ratio of the number of moles of the inorganic gadolinium salt to the sum of the number of moles of the inorganic gadolinium salt and the number of moles of the diethylenetriamine pentaacetic acid derivative is preferably 0.2 to 0.8:1, more preferably 0.5:1.
In the present invention, the reagent for dissolving the inorganic gadolinium salt and the diethylenetriamine pentaacetic acid derivative preferably includes methanol.
In the present invention, the temperature of the first coordination reaction is preferably 40 to 60 ℃, more preferably 50 ℃; the time is preferably 20 to 25 hours; more preferably 24h. In the present invention, the first coordination reaction is preferably performed in a protective atmosphere, which preferably includes helium or nitrogen, more preferably nitrogen.
After gadolinium complex is obtained, the gadolinium complex and bis (2, 2' -bipyridine) ruthenium dichloride are dissolved, and a second coordination reaction is carried out to obtain the ruthenium-gadolinium heteronuclear heterometal complex.
In the present invention, the ratio of the number of moles of the gadolinium complex to the sum of the number of moles of the gadolinium complex and the bis (2, 2' -bipyridine) ruthenium dichloride is preferably 0.3 to 0.7:1, more preferably 0.33:1.
In the invention, the reagent for dissolving the gadolinium complex and the bis (2, 2' -bipyridine) ruthenium dichloride is preferably a mixed solvent of dichloromethane and methanol; the volume ratio of the dichloromethane to the methanol in the mixed solvent is preferably 1:1-2, and more preferably 1:1.5. In the present invention, the temperature of the second coordination reaction is preferably 40 to 60 ℃, more preferably 50 to 55 ℃; the time is preferably 22-26 hours; more preferably 24 to 25 hours. In the present invention, the second coordination reaction is preferably performed in a protective atmosphere, which preferably includes helium or nitrogen, more preferably nitrogen.
In the present invention, when M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -, the replacement method includes: carrying out ion replacement reaction on a product obtained by the second coordination reaction; the reagents for the ion exchange reaction include NH4Br、NaI、NH4NO3、AgBF4、NaSbF6、AgCF3SO3、NH4BPh4 or NH 4PF6.
In the present invention, the method preferably further comprises concentrating the product obtained by the second complexation reaction to dryness, and redissolving the concentrated product with methylene chloride.
In the present invention, the reagent for the ion exchange reaction comprises NaBr, naI, naNO 3 or ammonium hexafluorophosphate, preferably ammonium hexafluorophosphate. In the present invention, the molar ratio of the product obtained by the second coordination reaction to the reagent of the ion replacement reaction is preferably 1:1 to 1.5, more preferably 1:1.2 to 1.3. In the present invention, the temperature of the ion exchange reaction is preferably 20 to 30 ℃, more preferably 25 ℃, and the time is preferably 0.5 to 2 hours, more preferably 1 hour.
The invention preferably further comprises the steps of sequentially carrying out column chromatography separation and concentration on the crude probe product obtained by the ion replacement reaction, wherein the eluent for the column chromatography separation is a mixed solvent of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol in the mixed solvent is 1:1. the concentration is not particularly limited in the present invention, and the solvent in the eluent may be removed by an operation well known to those skilled in the art.
The invention also provides application of the ruthenium-gadolinium heteronuclear metal complex or the ruthenium-gadolinium heteronuclear metal complex prepared by the preparation method in preparation of a magneto-optical dual-mode imaging agent or a photosensitizer.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
122Mg of Gd (NO 3)3·6H2 O, 200mg of diethylenetriamine pentaacetic acid derivative and 20mL of methanol are added into a reaction vessel, under the protection of nitrogen, the first coordination reaction is carried out for 24 hours at 50 ℃, then the product obtained by the first coordination reaction is filtered and the precipitate is collected to obtain gadolinium complex, 200mg of gadolinium complex and 215mg of bis (2, 2' -bipyridine) ruthenium dichloride are added into a mixed solvent of dichloromethane and methanol (the volume ratio of dichloromethane to methanol is 1:1), the second coordination reaction is carried out for 24 hours under the protection of nitrogen at the temperature of 55 ℃, after the reaction is finished, the product obtained by the second coordination reaction is rotationally evaporated to dryness, a small amount of dichloromethane is added for dissolution, and 80mg of ammonium hexafluorophosphate is mixed at room temperature for ion replacement reaction for 1 hour, the product obtained by ion conversion is subjected to column chromatography separation, the eluent is the mixed solvent of dichloromethane and methanol with the volume ratio of 1:1, and the eluent is eluted to concentrate the eluent to remove the solvent, so as to obtain the ruthenium-gadolinium heteronuclear metal complex.
FIG. 1 is a reaction equation for preparing ruthenium-gadolinium heteronuclear heterometallic complex in example 1, as can be seen from FIG. 1: gd (NO 3)3·6H2 O and diethylenetriamine pentaacetic acid derivative are dissolved, a first coordination reaction is carried out to obtain a gadolinium complex, then the obtained gadolinium complex and bis (2, 2' -bipyridine) ruthenium dichloride are dissolved into a mixed solvent of dichloromethane and methanol, a second coordination reaction is carried out, a product obtained by the second coordination reaction is mixed with ammonium hexafluorophosphate, and an ion replacement reaction is carried out to obtain the ruthenium-gadolinium heteronuclear metal complex.
The invention performs electrospray chromatography characterization on the ruthenium-gadolinium heteronuclear mixed metal prepared in the embodiment 1, and the experimental steps are as follows: after the ruthenium-gadolinium heteronuclear heterometallic complex obtained in example 1 was dissolved in acetonitrile, it was characterized by electrospray mass spectrometry, and the results are shown in fig. 2, and it can be seen from fig. 2: the high-resolution mass spectrum measured by the test is consistent with the mass spectrum which is theoretically simulated, whether the molecular weight or the isotope peak type is the same. Molecular formula is C 78H66GdN17O8Ru2, average molecular weight is 1730.26, theoretical simulation molecular weight is 432.3155 due to the fact that the molecular weight is 432.3165 through experiments, and therefore the structure of the complex is correct.
FIG. 3 is an optical image of living cells of the ruthenium-gadolinium heterogeneous polynuclear metal complex prepared in example 1. The experimental steps are as follows: a549 cells in the logarithmic growth phase were divided into confocal 35mm confocal dishes, grown by adherence in 1640 medium containing 10% fetal bovine serum at 37 ℃ for 24 hours, then added with 30 μm ruthenium-gadolinium heterogeneous polynuclear metal complex, incubated for 2 hours, washed with PBS, immediately subjected to confocal microscopy imaging, and experimental results are shown in fig. 3, from which fig. 3: after adding 50 mu M of the ruthenium-gadolinium heteronuclear metal complex, incubating for 1h, and then carrying out confocal laser microscopic imaging, the bright red spots appear in the cells, which shows that the ruthenium-gadolinium heteronuclear metal complex can enter the cells.
The relaxation rate of the ruthenium-gadolinium heterogeneous polynuclear metal complex prepared in the embodiment 1 is measured. The testing process comprises the following steps: the ruthenium-gadolinium heterogeneous polynuclear metal complex prepared in example 1 was prepared into a solution with a total volume of 1.5mL with water at concentrations of 0.4, 0.2, 0.1, 0.05, 0.025 and 0mM, and T1-weighted imaging was performed on the above sample with MesoMR NMR analysis and imaging system (Shanghai N-Mich. Electronic technology Co., ltd.), at a resonance frequency of 23.314MHz, a magnet strength of 0.5T, a coil diameter of 60mM and a magnet temperature of 32.0 ℃. The experimental results are shown in fig. 4, and it can be seen from fig. 4: the concentration of the ruthenium-gadolinium heterogeneous polynuclear metal complex is in direct proportion to the intensity of magnetic resonance imaging signals, the higher the concentration of the complex is, the stronger the signals are, and the better the linear relation is, so that the relaxation rate of the ruthenium-gadolinium heterogeneous polynuclear metal complex can be calculated to be 8.2mM -1s-1, which is far higher than that of commercial magnetic resonance imaging contrast agents.
The invention detects active oxygen generated by illumination on the ruthenium-gadolinium heterogeneous polynuclear metal complex prepared in the embodiment 1. The detection steps are as follows: an aqueous solution containing ruthenium-gadolinium heterogeneous polynuclear metal complex (10 μm) and singlet oxygen probe DPBF (10 μm) was placed in a quartz cuvette, and the absorbance of the solution before and after illumination was detected by an ultraviolet-visible spectrophotometer under a 450nm light source for 1s per radiation. The results are shown in FIG. 5, and as can be seen from FIG. 5: the method is characterized in that 1, 3-diphenyl isobenzofuran (DPBF) is used as a singlet oxygen probe, a ruthenium-gadolinium heteronuclear heterometal complex is mixed with the DPBF, after the mixture is irradiated by light at different time nodes, the change of ultraviolet-visible absorption spectrum is tested by an ultraviolet-visible spectrophotometer, and the gradual decrease of absorption at 410nm along with the increase of irradiation time is found, so that singlet oxygen is generated, and the photodynamic effect is remarkable.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A ruthenium-gadolinium heteronuclear heterometal complex, which is characterized by having a structure shown in a formula I:
M is Cl -.
2. The ruthenium-gadolinium heteronuclear heterometal complex of claim 1, wherein M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -.
3. The method for preparing the ruthenium-gadolinium heteronuclear heterometal complex according to claim 1, comprising the steps of:
Dissolving inorganic gadolinium salt and diethylenetriamine pentaacetic acid derivative, and carrying out a first coordination reaction to obtain gadolinium complex;
Dissolving the gadolinium complex and bis (2, 2' -bipyridine) ruthenium dichloride, and performing a second coordination reaction to obtain the ruthenium-gadolinium heteronuclear heterometal complex;
the diethylenetriamine pentaacetic acid derivative has a structure shown in a formula I-1;
the gadolinium complex has a structure shown in a formula I-2;
4. A method of preparation according to claim 3, wherein the inorganic gadolinium salt comprises one or more of gadolinium nitrate, gadolinium chloride and gadolinium perchlorate.
5. The method according to claim 3, wherein the ratio of the number of moles of the inorganic gadolinium salt to the sum of the number of moles of the inorganic gadolinium salt and the number of moles of the diethylenetriamine pentaacetic acid derivative is 0.2 to 0.8:1.
6. The method according to claim 3, wherein the ratio of the number of moles of the gadolinium complex to the sum of the number of moles of the gadolinium complex and the number of moles of the bis (2, 2' -bipyridine) ruthenium dichloride is 0.3 to 0.7:1.
7. The method according to claim 3 or 5, wherein the temperature of the first coordination reaction is 40 to 60 ℃ for 20 to 25 hours.
8. The method according to claim 3 or 6, wherein the second complexation reaction is carried out at a temperature of 40 to 60 ℃ for 22 to 26 hours.
9. A method of making according to claim 3 wherein M is replaced with Br-、I-、NO3 -、BF4 -、SbF6 -、CF3SO3 - or PF 6 -, the method of replacing comprising: carrying out ion replacement reaction on a product obtained by the second coordination reaction; the reagents for the ion exchange reaction include NH4Br、NaI、NH4NO3、AgBF4、NaSbF6、AgCF3SO3、NH4BPh4 or NH 4PF6.
10. Use of a ruthenium-gadolinium heteronuclear heterometal complex according to claim 1 or 2 or a ruthenium-gadolinium heteronuclear heterometal complex prepared by the preparation method according to any one of claims 3 to 9 in the preparation of a magneto-optical dual-mode imaging agent or in the preparation of a photosensitizer.
CN202211162166.4A 2022-09-23 2022-09-23 Ruthenium-gadolinium heteronuclear heterometal complex and preparation method and application thereof Active CN115558000B (en)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A Heterobimetallic Ruthenium-Gadolinium Complex as a Potential Agent for Bimodal Imaging;Geert Dehaen et al.;《Inorg. Chem.》;20110913;第50卷;摘要,Scheme 2,10008页左栏第2段 *
A novel heterobimetallic Ru(II)–Gd(III) complex-based magnetoluminescent agent for MR and luminescence imaging;Wenbo Shi et al.;《RSC Adv.》;20151104;第5卷;摘要,Scheme 1 *

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