CN115404075A - Magnetic graphene quantum dot and preparation method and application thereof - Google Patents
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 239000002096 quantum dot Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention discloses a magnetic graphene quantum dot and a preparation method and application thereof. The preparation method comprises the following steps: and carrying out hydrothermal reaction on the ferrous ascorbate aqueous solution to obtain the magnetic graphene quantum dots. The preparation method of the magnetic graphene quantum dots provided by the invention can be used for conveniently and rapidly obtaining the magnetic graphene quantum dots, the size of the obtained magnetic graphene quantum dots is 3-10 nm, and the mass ratio of carbon to iron is 3-6: 1-2, can be used for preparing an enhanced imaging contrast agent, shortening imaging time, improving imaging contrast and improving the accuracy of imaging diagnosis, or can be used for preparing a diagnostic probe in vitro and improving the accuracy of in vitro diagnostic technology.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a magnetic graphene quantum dot and a preparation method and application thereof.
Background
The graphene quantum dots serving as a novel graphene nano material have the advantages of nanoscale size, adjustable band gap, excellent dispersibility, good biocompatibility, high fluorescence quantum yield and the like, and can be used as a detection probe for a fluorescence imaging contrast agent and a fluorescence in-vitro diagnosis technology. The graphene quantum dots are used as a contrast agent or a probe for fluorescence imaging due to excellent fluorescence performance, and the magnetic graphene quantum dots can realize nuclear magnetic resonance enhanced imaging and improve the contrast between tissues on the basis of realizing fluorescence enhanced imaging, namely the magnetic graphene quantum dots can be combined with fluorescence imaging and nuclear magnetic resonance imaging to provide more accurate reference for clinical imaging diagnosis and the like. In addition, the magnetic graphene quantum dots can also be used in the field of dual-mode in-vitro diagnosis, and can be used for simultaneously detecting the influence of the marker to be detected on the magnetic signal and the fluorescent signal, and the detection accuracy is improved.
At present, the acquisition of the magnetic graphene quantum dots mainly depends on at least two steps of reactions: the first step is the acquisition of graphene quantum dots, which comprises a bottom-up method and a top-down method, namely respectively polymerizing and carbonizing a small molecule precursor and cutting graphene by using oxidation to obtain the graphene quantum dots; the second step is magnetic modification, in the interface of the graphene quantum dot, the edge atoms are often oxygen (-COOH, -OH, -CHO, etc.) and nitrogen (-NH) 2 , -NH-, etc.) and can realize magnetic modification with magnetic groups through ester bond formation, ether bond formation, amide bond formation or coordination structure generation. The method for obtaining the magnetic graphene quantum dots needs to use various raw materials and carry out multi-step reactionThe method has the advantages of complex steps and low controllability of reaction products.
Therefore, how to design a more convenient and rapid preparation method of magnetic graphene quantum dots is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a convenient and rapid preparation method of the magnetic graphene quantum dots.
The invention also aims to provide the magnetic graphene quantum dot prepared by the preparation method.
The invention further aims to provide application of the magnetic graphene quantum dots.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of magnetic graphene quantum dots comprises the following steps: and carrying out hydrothermal reaction on the ferrous ascorbate aqueous solution to obtain the magnetic graphene quantum dots.
Preferably, the concentration of the ferrous ascorbate aqueous solution is 1-10 mg/mL.
Preferably, the hydrothermal reaction temperature is 120-180 ℃, and the hydrothermal reaction time is 3-24 h.
The magnetic graphene quantum dot is prepared by the preparation method, the size of the magnetic graphene quantum dot is 3-10 nm, the mass ratio of carbon to iron is 3-6: 1 to 2. The relaxation rate of the magnetic graphene quantum dot is 200-500L/(mmol · s), the fluorescence emission wavelength is 300-600 nm, and the magnetic graphene quantum dot not only has magnetism of iron oxide, but also has fluorescence characteristics of the graphene quantum dot.
The invention also provides application of the magnetic graphene quantum dot in preparation of an enhanced imaging contrast agent.
Preferably, the enhanced imaging contrast agent is a dual nuclear magnetic resonance-fluorescence enhanced imaging contrast agent.
The invention also provides application of the magnetic graphene quantum dot in preparation of in-vitro diagnostic probes.
Preferably, the in vitro diagnostic probe is a nuclear magnetic resonance relaxation-fluorescence dual-mode in vitro diagnostic probe.
Preferably, before the magnetic graphene quantum dots are applied to enhanced imaging or in-vitro diagnosis, the magnetic graphene quantum dots are washed and dispersed into a magnetic graphene quantum dot dispersion liquid. Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. the invention provides a convenient and rapid preparation method of magnetic graphene quantum dots, the preparation process only needs one step, only one raw material (namely a precursor) is needed, the reaction conditions are simple and controllable, and the product is simple and easy to purify. The precursor ferrous ascorbate not only contains a carbon source required for synthesizing graphene quantum dots, but also contains an iron source for synthesizing magnetic iron oxide.
2. The relaxation rate of the magnetic graphene quantum dots obtained by the method is 200-500L/(mmol · s), the fluorescence emission wavelength is 300-600 nm, and the magnetic graphene quantum dots not only have the magnetism of iron oxide, but also have the fluorescence characteristics of the graphene quantum dots, and can be used as a nuclear magnetic resonance-fluorescence dual-mode enhanced imaging contrast agent to improve the imaging contrast and improve the accuracy of imaging diagnosis; the probe can also be used as a probe of the nuclear magnetic resonance relaxation-fluorescence dual-mode in-vitro diagnosis technology so as to improve the accuracy and the sensitivity of the in-vitro diagnosis technology.
Drawings
Fig. 1 is a transmission electron micrograph of the magnetic graphene quantum dot dispersion obtained in example 1.
FIG. 2 is a relaxation rate fitting curve, T, measured in an extremely low field magnetic resonance system of the magnetic graphene quantum dot dispersion obtained in example 1 2 Expressed as the nmr transverse relaxation time.
Fig. 3 is a fluorescence emission spectrum of the magnetic graphene quantum dot dispersion obtained in example 1.
Fig. 4 is a nuclear magnetic resonance image of the magnetic graphene quantum dot dispersion obtained in example 1, which is used for nuclear magnetic resonance enhanced imaging of tumor-bearing mice.
Fig. 5 is a fluorescence photograph of the magnetic graphene quantum dot dispersion obtained in example 1 for fluorescence enhanced imaging of tumor-bearing mice.
FIG. 6 is example 2Change curve of relaxation time when the magnetic graphene quantum dot dispersion liquid is used as a nuclear magnetic resonance relaxation sensing technology probe, T 2 Expressed as nmr transverse relaxation time.
FIG. 7 is a graph showing the change of the fluorescence intensity ratio of the magnetic graphene quantum dot dispersion obtained in example 2 when used as a fluorescent probe, wherein F is the fluorescence intensity of the fluorescent probe and streptococcal protein G at different mixing times, and F is the fluorescence intensity of the fluorescent probe and streptococcal protein G at different mixing times 0 Fluorescence intensity of the blank.
FIG. 8 is a relaxation time comparison, T, of markers with different concentrations detected when the magnetic graphene quantum dot dispersion obtained in example 3 is used as a probe in the NMR relaxation sensing technology 2 Expressed as nmr transverse relaxation time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
s1, carrying out a hydrothermal reaction for 3h at 180 ℃ on a ferrous ascorbate aqueous solution of 5mg/mL to obtain the magnetic graphene quantum dot.
S2, centrifuging and washing the magnetic graphene quantum dots, wherein the centrifuging condition is that the rotating speed is 8000rpm/min for 10min, and re-suspending in water to obtain the magnetic graphene quantum dot dispersion liquid.
And (3) characterizing the magnetic graphene quantum dots in the magnetic graphene quantum dot dispersion liquid obtained by the preparation method by using X-ray photoelectron spectroscopy energy spectrum analysis, wherein the carbon content is 30% and the iron content is 20%.
Example 2
the concentration of the ferrous ascorbate aqueous solution is 1mg/mL;
the hydrothermal reaction temperature is 120 ℃, and the time is 24 hours;
the centrifugation condition was 10000rpm/min and the time was 2min.
The carbon content of the magnetic graphene quantum dots in the magnetic graphene quantum dot dispersion liquid obtained by the method is 60%, and the iron content is 10%.
Example 3
the concentration of the ferrous ascorbate aqueous solution is 10mg/mL;
the hydrothermal reaction temperature is 150 ℃, and the time is 12h;
the centrifugation conditions were 3000rpm/min for 4min.
The carbon content of the magnetic graphene quantum dots in the magnetic graphene quantum dot dispersion liquid obtained by the method is 40%, and the iron content is 15%.
Example 4 performance testing of magnetic graphene quantum dots
The magnetic graphene quantum dot dispersion liquids obtained in examples 1 to 3 were observed by a transmission electron microscope for the size of the magnetic graphene quantum dot, and the relaxation rate and the fluorescence emission wavelength were measured by an extremely low field magnetic resonance system.
As shown in fig. 1, the size of the magnetic graphene quantum dot obtained in example 1 was measured to be 5nm under a transmission electron microscope; as shown in fig. 2, the transverse relaxation rate of the magnetic graphene quantum dots in the magnetic graphene quantum dot dispersion obtained in example 1 is 230L/(mmol · s) as measured by fitting a relaxation rate curve measured in a very low field magnetic resonance system; as shown in fig. 3, it was confirmed by fluorescence emission spectroscopy that the maximum fluorescence emission wavelength of the magnetic graphene quantum dot dispersion obtained in example 1 was 427nm.
The size of the magnetic graphene quantum dot in the magnetic graphene quantum dot dispersion liquid obtained in example 2 is 3nm, the transverse relaxation rate is 200L/(mmol · s), and the maximum fluorescence emission wavelength is 600nm.
The size of the magnetic graphene quantum dot in the magnetic graphene quantum dot dispersion liquid obtained in example 3 is 10nm, the transverse relaxation rate is 500L/(mmol · s), and the maximum fluorescence emission wavelength is 300nm.
Example 5 application of magnetic graphene quantum dots in the field of nuclear magnetic resonance-fluorescence dual-mode enhanced imaging
The magnetic graphene quantum dots obtained in example 1 are used as a nuclear magnetic resonance-fluorescence dual-mode enhanced imaging contrast agent. The results were obtained by observing nuclear magnetic resonance images (FIG. 4) and fluorescence images (FIG. 5) of tumor-bearing mice: the magnetic graphene quantum dots obtained in example 1 are used as an imaging enhancement contrast agent, so that the contrast between tumor tissues and normal tissues of tumor-bearing mice is remarkably improved.
Example 6 application of magnetic graphene quantum dots in the field of nuclear magnetic resonance relaxation-fluorescence dual-mode in-vitro diagnosis
The magnetic graphene quantum dots obtained in example 2 are coupled with immunoglobulin G through amide bonds by using EDC/NHS click chemistry reaction (see sens. Activators B chem.:2021,337 129786.) to obtain specific magnetic graphene quantum dots, which are marked as magnetic probes or fluorescent probes and can be specifically combined with streptococcal protein G.
As shown in FIG. 6, in a very low field magnetic resonance system (see biosens. Bioelectron.:2016, 80.). The T.sub.t.sub.p.sub.t.sub.t.sub.661-665.) obtained from the magnetic graphene quantum dots of example 2 increased the mixing time with streptococcal protein G 2 The value gradually increased and stabilized around 470ms at 30min of mixing, indicating that the magnetic probe had fully bound to streptococcal protein G at 30min of mixing. T with blank 2 In contrast, the magnetic probe obtained in example 2 bound to streptococcal protein G for T 2 The variance value is 371ms. Therefore, the T between the blank and the sample to be tested can be determined 2 And (4) judging whether the sample to be detected contains streptococcal protein G or not according to the difference. As shown in FIG. 7, the fluorescent probe obtained by the magnetic graphene quantum dot of example 2 and streptococcal protein G increase in F/F with the increase of mixing time 0 The value gradually decreases when mixedWhen the time reaches 30min, F/F 0 The value tends to be stable, which shows that the fluorescent probe and the streptococcal protein G are fully combined when the mixing time is 30min, and the combination time is consistent with that of the specific magnetic graphene quantum dot serving as a magnetic probe and the streptococcal protein G.
As shown in FIG. 8, the magnetic probe obtained from the magnetic graphene quantum dot of example 3 was mixed with streptococcal protein G of different concentrations, and the T value was measured after the two were sufficiently combined 2 Value by evaluating T 2 The difference between the value and the blank sample shows that the detection sensitivity of the specific magnetic graphene quantum dot for detecting the immunoglobulin G is 0.1ng/mL, and the detection sensitivity is higher.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (8)
1. A preparation method of magnetic graphene quantum dots is characterized by comprising the following steps: and carrying out hydrothermal reaction on the ferrous ascorbate aqueous solution to obtain the magnetic graphene quantum dots.
2. The method of preparing a magnetic graphene quantum dot according to claim 1, comprising at least one of:
the concentration of the ferrous ascorbate is 1-10 mg/mL;
the hydrothermal reaction temperature is 120-180 ℃, and the hydrothermal reaction time is 3-24 h.
3. The magnetic graphene quantum dot is prepared by the preparation method of claim 1 or 2, the size of the magnetic graphene quantum dot is 3-10 nm, and the mass ratio of carbon to iron is 3-6: 1 to 2.
4. Use of the magnetic graphene quantum dots according to claim 4 in the preparation of an enhanced imaging contrast agent.
5. The use of the magnetic graphene quantum dot of claim 1 in the preparation of in vitro diagnostic probes.
6. The use of claim 4, wherein the enhanced imaging contrast agent is a dual MRI-contrast agent.
7. The use according to claim 5, wherein the in vitro diagnostic probe is a dual mode NMR relaxation-fluorescence in vitro diagnostic probe.
8. The use of claim 4 or 5, wherein the magnetic graphene quantum dots are washed and dispersed into a magnetic graphene quantum dot dispersion before use.
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