CN110819345B - Quantum dot for magnetic resonance and fluorescence imaging and preparation method thereof - Google Patents
Quantum dot for magnetic resonance and fluorescence imaging and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a quantum dot for magnetic resonance and fluorescence imaging and a preparation method thereof, belonging to the technical field of semiconductor nano material preparation and medical materials3The surface ligand of the quantum dot is oleylamine, oleic acid and mercaptan; the preparation method comprises the following steps: firstly, copper acetate, zinc acetate, ferric chloride, gadolinium chloride and oleic acid are subjected to vacuum treatment, dodecyl mercaptan is added, the temperature is raised to 150-210 ℃, an oleylamine solution of sulfur is injected, and the Gd element doped Zn-Cu-FeS is prepared after reaction for 5 minutes3And finally adding acetone or ethanol to cause the quantum dots to precipitate, and further dispersing into a chloroform or hexane solvent. The synthetic method is simple and rapid, and the prepared Gd @ Zn-Cu-FeS3The quantum dots are green and nontoxic, can be used as a nuclear magnetic resonance imaging contrast agent, and realize adjustable fluorescence spectrum and stable chemical properties.
Description
Technical Field
The invention belongs to the technical field of semiconductor nano material preparation and medical materials, and particularly relates to a fluorescent quantum dot for magnetic resonance imaging and a preparation method thereof.
Background
The nuclear magnetic resonance imaging is to detect the generated electromagnetic waves by a gradient magnetic field according to different attenuation degrees caused by different energy in internal structure environments of a substance by utilizing the nuclear magnetic resonance principle, so as to judge the position and the type of object nuclei and draw a structural image of the object. Medically, the technology is used for imaging the internal structure of the human body, is a revolutionary medical diagnosis tool, and can provide good anatomical information based on soft tissue contrast and functional information of a non-invasive real-time detection mode. The proper nuclear magnetic resonance imaging contrast agent can change the relaxation time of partial water molecules around human tissues, thereby improving the sensitivity and accuracy of MRI detection.
The fluorescence characteristic of the quantum dot has important application in the aspects of biological probes and active imaging, and gadolinium ions have 7 unpaired electrons and are metal ions with strong paramagnetism, so that the T1 relaxation time of the gadolinium ions can be obviously shortened, the nuclear magnetic resonance signal intensity is influenced, and an enhanced signal is shown. And doping the gadolinium ions with quantum dots, thereby realizing the function of magnetic resonance imaging.
Nuclear magnetic resonance contrast agents are primarily administered intravenously, requiring that the contrast agent be either slightly or non-toxic. The rare earth element Gd complex is a component of the mainstream contrast agent, but a large amount of Gd element has certain harm to human body. How to efficiently utilize Gd element to obtain stable contrast agent materials is a challenging issue for synthesis.
Disclosure of Invention
The invention aims to solve the technical problem of compounding Gd element with fluorescent quantum dots without heavy metal components, provides a simple, convenient, green and environment-friendly synthesis method, and prepares a quantum dot material which can be used as a contrast agent raw material for magnetic resonance imaging and used for fluorescence labeling detection.
The technical problem of the invention is solved by the following technical scheme:
the quantum dot for magnetic resonance and fluorescence imaging is characterized in that the quantum dot is ZnCuFeS doped with Gd element3The doping amount of the quantum dots is that the molar ratio of Gd to Zn elements is 1: 10-100; the particle size of the quantum dots is 4.5-8 nanometers; the surface ligand is oleylamine, oleic acid and thiol.
Preferably, the molar ratio of Gd to Zn elements is 1: 10; the particle size of the quantum dots is 5.5 nanometers.
A preparation method of quantum dots for magnetic resonance and fluorescence imaging comprises the steps of firstly, carrying out vacuum treatment on copper acetate, zinc acetate, ferric chloride, gadolinium chloride and oleic acid, then adding dodecyl mercaptan, heating to 150-210 ℃, injecting an oleylamine solution of sulfur, and reacting for 5 minutes to obtain Gd element doped Zn-Cu-FeS3Finally adding acetone or ethanol to the quantum dots to cause the quantum dots to precipitate, and further dispersing the quantum dots into chloroform or hexane solvent to obtain the purified quantum dots Gd @ Zn-Cu-FeS for magnetic resonance and fluorescence imaging3(ii) a The molar ratio of the copper acetate to the zinc acetate to the ferric chloride is 1:1, the molar ratio of Gd element contained to Zn element contained in the zinc acetate is 1: 10-100, the dosage of sulfur is in accordance with the stoichiometric ratio, and the dosages of oleic acid and dodecyl mercaptan as ligands are in accordance with the stoichiometric ratio.
The concentration of the oleylamine solution of sulphur is preferably 1mmol/mL, and the amount of octadecene is preferably 50mL per millimole of Zn element.
Furthermore, the invention can regulate and control the size of the prepared quantum dots by controlling the thermal injection temperature, specifically, the oleylamine solution of sulfur is injected when the temperature of the system is raised to 150 ℃, and Gd @ Zn-Cu-FeS with the particle size of 4.5nm is finally obtained3Quantum dots; injecting sulfur into oleylamine solution at 180 ℃ to finally obtain Gd @ Zn-Cu-FeS with the particle size of 5.5nm3Quantum dots; injecting sulfur into oleylamine solution at 210 ℃ to finally obtain Gd @ Zn-Cu-FeS with the particle size of 8.0nm3And (4) quantum dots.
Gd @ Zn-Cu-FeS is synthesized by a high-temperature thermal injection method3And (4) quantum dots. Quantum dots with different sizes are obtained by controlling the reaction temperature, the adjustment of the fluorescence peak position is realized, and GdCl is regulated and controlled3The dosage of the Gd @ Zn-C-uFeS with different doping concentrations is obtained3And (3) preparing the quantum dots. Gd @ Zn-Cu-FeS3The quantum dot can be used as a contrast agent for nuclear magnetic resonance imaging, the doping concentration is related to the relaxation time, the synthesis method is simple and rapid, and the quantum dot has low biological toxicity and high chemical stability.
The quantum dots are green quantum dots without heavy metals, the prepared quantum dots are uniform in size, and the optical luminescence wavelength is 620-775 nanometers by regulating and controlling the size of the quantum dots. In summary, the invention has the following advantages:
1. the obtained quantum dots can be used as a nuclear magnetic resonance imaging contrast agent material and also has the fluorescence adjustable property with a wider range.
2. Compared with the existing nuclear magnetic resonance contrast agent, the magnetic resonance contrast agent has good cell compatibility, can carry out nondestructive and non-invasive analysis and detection on organisms in vivo, and has stable material structure and chemical properties.
3. The doping amount of Gd can be regulated and controlled through a simple feed ratio.
4. The quantum dots are uniform in size.
Description of the drawings:
FIG. 1 is Gd @ Zn-Cu-FeS with a particle size of 4.5nm prepared at a temperature of 150 ℃ in example 13Of quantum dotsAnd (5) transmission electron microscope photographs.
FIG. 2 is Gd @ Zn-Cu-FeS with a particle size of 5.5nm prepared at a temperature of 180 ℃ in example 23Transmission electron microscope photographs of quantum dots.
FIG. 3 is Gd @ Zn-Cu-FeS with a particle size of 8.0nm prepared at a temperature of 210 ℃ in example 33Transmission electron microscope photographs of quantum dots.
FIG. 4 shows the results of X-ray powder diffraction analysis of quantum dots of different sizes prepared in examples 1 to 3. The particle sizes of the quantum dots are respectively 4.5nm, 5.5nm and 8.0nm from bottom to top, and the reaction temperatures are respectively 150 ℃, 180 ℃ and 210 ℃.
FIG. 5 is a graph of Gd @ Zn-Cu-FeS of different sizes prepared at different temperatures in examples 1-33Absorption spectra of quantum dots. The particle sizes of the quantum dots corresponding to the 3 pairs of curves from bottom to top are respectively 4.5nm, 5.5nm and 8.0nm, and the reaction temperatures are respectively 150 ℃, 180 ℃ and 210 ℃.
FIG. 6 is a graph of Gd @ Zn-Cu-FeS of different sizes prepared at different temperatures in examples 1-33Fluorescence spectra of quantum dots. The particle sizes of the quantum dots corresponding to the 3 pairs of curves from left to right are respectively 4.5nm, 5.5nm and 8.0nm, and the reaction temperatures are respectively 150 ℃, 180 ℃ and 210 ℃.
FIG. 7 is an in vitro magnetic resonance imaging (T) using the product of the invention as a contrast agent1Weighted image), corresponding to Gd @ Zn-Cu-FeS having doping ratios (Gd/Zn) of 0, 1:100, 1:50 and 1:10 in the order from left to right in the figure3The quantum dot solution is used as a contrast agent.
The specific implementation mode is as follows:
example 1:
firstly, adding 5ml of octadecene, 0.1mmol of copper acetate, 0.1mmol of zinc acetate, 0.1mmol of ferric chloride, 0.01mmol of gadolinium chloride and 1mmol of oleic acid into a reaction bottle, performing vacuum treatment at 100 ℃, adding 1mmol of dodecyl mercaptan, heating the solution to 150 ℃, dissolving 0.3mmol of elemental sulfur in 0.3ml of oleylamine, rapidly injecting the solution into the reaction solution, and keeping the solution for 5 minutes to obtain Gd @ Zn-Cu-FeS with the particle size of 4.5nm and the ratio of Gd to Zn being 1:103And (4) quantum dots. The transmission electron micrograph of the product is shown in FIG. 1, and the X-ray powder diffraction analysis result is shown in FIG. 4 (lower).
Example 2:
firstly, adding 5ml of octadecene, 0.1mmol of copper acetate, 0.1mmol of zinc acetate, 0.1mmol of ferric chloride, 0.002mmol of gadolinium chloride and 1mmol of oleic acid into a reaction bottle, carrying out vacuum treatment at 100 ℃, adding 1mmol of dodecyl mercaptan, heating the solution to 180 ℃, dissolving 0.3mmol of elemental sulfur in 0.3ml of oleylamine, rapidly injecting the solution into the reaction solution, and keeping the solution for 5 minutes to obtain Gd @ Zn-Cu-FeS with the particle size of 5.5nm and the ratio of Gd to Zn being 1:503And (4) quantum dots. The transmission electron micrograph of the product is shown in FIG. 2, and the X-ray powder diffraction analysis result is shown in FIG. 4 (middle).
Example 3:
firstly, adding 5ml of octadecene, 0.1mmol of copper acetate, 0.1mmol of zinc acetate, 0.1mmol of ferric chloride, 0.001mmol of gadolinium chloride and 1mmol of oleic acid into a reaction bottle, performing vacuum treatment at 100 ℃, adding 1mmol of dodecyl mercaptan, heating the solution to 210 ℃, dissolving 0.3mmol of elemental sulfur in 0.3ml of oleylamine, rapidly injecting the solution into the reaction solution, and keeping the solution for 5 minutes to obtain Gd and Zn of 1:100, and Gd @ Zn-Cu-FeS of 8.0nm in size3And (4) quantum dots. The transmission electron micrograph of the product is shown in FIG. 3, and the X-ray powder diffraction analysis result is shown in FIG. 4 (upper).
The results of the absorption spectrum and fluorescence spectrum measurements on the products prepared in examples 1-3 are shown in FIG. 5 and FIG. 6, respectively.
Example 4:
firstly, adding 50ml of octadecene, 1mmol of copper acetate, 1mmol of zinc acetate, 1mmol of ferric chloride, 0.02mmol of gadolinium chloride and 10mmol of oleic acid into a reaction bottle, performing vacuum treatment at 100 ℃, adding 10mmol of dodecyl mercaptan, heating the solution to 180 ℃, dissolving 3mmol of elemental sulfur in 3ml of oleylamine, rapidly injecting the oleylamine into the reaction solution, and keeping the solution for 5 minutes to obtain Gd @ Zn-Cu-FeS with the Gd: Zn being 1:50 and the size being 5.5nm3And (4) quantum dots. When the feeding is expanded by 10 times in equal proportion, the same product can still be prepared.
On the basis of the above conditions, the charging amount of gadolinium chloride is changed from 0.02mmol to 0.01mmol and 0.1mmol, so that Gd @ Zn-Cu-FeS with Gd: Zn of 1:100 and 1:10 and the size of 5.5nm are respectively prepared3And (4) quantum dots. For 3 different feed ratiosThe product of (a) was subjected to elemental analysis, and the results are shown in Table 1.
TABLE 1 results of elemental analysis of products prepared with different Gd/Zn charge ratios
Example 5:
the quantum dot prepared in example 3 is calibrated by near infrared fluorescent dye IR-125, and the specific steps are as follows:
the Gd @ ZnCuFeS prepared in example 3 is taken3Dissolving quantum dots (emission peak is 775nm) in n-hexane solution at 20 deg.C, diluting to make absorbance value at 602nm in absorption spectrum 0.13, dissolving fluorescent dye IR-125 in methanol at 20 deg.C, intersecting absorption spectrum at 602nm, and making absorbance value 0.13; then exciting the two diluted solutions at the wavelength of 602nm to respectively obtain fluorescence spectra, and calculating to obtain Gd @ Zn-Cu-FeS3The integral area ratio of the quantum dots to the dye is 7.32, Gd @ Zn-Cu-FeS3The fluorescence quantum efficiency of the quantum dots is calculated by the formula
Φx＝Φs(nx/ns)2(As/Ax)(Fx/Fs)
Wherein phi is fluorescence quantum efficiency, n represents refractive index of solvent at test temperature, A is absorbance value of solution at excitation wavelength position, F is integral area of fluorescence spectrum, subscript x of each parameter represents Gd @ Zn-Cu-FeS to be tested3Quantum dots, subscript S, standard substance fluorescent dye IR-125.
Substituting the result into a fluorescence quantum efficiency calculation formula to calculate the absorbance value A of the two solutions at the excitation wavelength of 715nmsAnd AxAre all 0.13; refractive index n of methanol at 20 DEG CsIs 1.44, n-hexane has a refractive index n of 20 DEG CxIs 1.388; the integral area ratio Fx/Fs obtained by measurement is 7.32, and the fluorescence quantum efficiency phi of the fluorescent dye IR-125 in methanolsThe content was 4%. The Gd @ Zn-Cu-FeS is prepared by calculation3The quantum efficiency of the quantum dots is 29 percent, and the quantum dots have high fluorescence efficiencyThe quantum dot material prepared by the invention has high fluorescence quantum efficiency.
Example 6:
taking the same amount of Gd @ Zn-Cu-FeS with the feeding Gd elements of which the proportions are 0, 1:100, 1:50 and 1:10 in sequence and the granularity is 5.5nm3The quantum dot solutions were subjected to the nmr radiography test so that the Gd element concentrations in the samples were 0mM, 0.01mM, 0.02mM, and 0.1mM, respectively, and the results are shown in fig. 7. The signal was significantly enhanced with the increase of the Gd doping concentration.
Claims (5)
1. The quantum dot for magnetic resonance and fluorescence imaging is characterized in that the quantum dot is ZnCuFeS doped with Gd element3The doping amount of the quantum dots is that the molar ratio of Gd to Zn elements is 1: 10-100; the particle size of the quantum dots is 4.5-8 nanometers; the surface ligand is oleylamine, oleic acid and thiol.
2. The quantum dot for magnetic resonance and fluorescence imaging according to claim 1, wherein the molar ratio of Gd to Zn elements is 1: 10; the particle size of the quantum dots is 5.5 nanometers.
3. The preparation method of the quantum dot for magnetic resonance and fluorescence imaging according to claim 1, comprising the steps of firstly, carrying out vacuum treatment on octadecene, copper acetate, zinc acetate, ferric chloride, gadolinium chloride and oleic acid, then adding dodecyl mercaptan, heating to 150-210 ℃, injecting an oleylamine solution of sulfur, and reacting for 5 minutes to obtain Gd element doped Zn-Cu-FeS3Finally adding acetone or ethanol to the quantum dots to cause the quantum dots to precipitate, and further dispersing the quantum dots into chloroform or hexane solvent to obtain the purified quantum dots Gd @ Zn-Cu-FeS for magnetic resonance and fluorescence imaging3(ii) a The molar ratio of the copper acetate to the zinc acetate to the ferric chloride is 1:1, the molar ratio of Gd element contained to Zn element contained in the zinc acetate is 1: 10-100, the dosage of sulfur is in accordance with the stoichiometric ratio, and the dosages of oleic acid and dodecyl mercaptan as ligands are in accordance with the stoichiometric ratio.
4. The method of claim 3, wherein the concentration of the solution of sulfur in oleylamine is 1mmol/mL, and the amount of octadecyl amine is 50mL per mmol of Zn element.
5. The preparation method of the quantum dot for magnetic resonance and fluorescence imaging according to claim 3, wherein the size of the prepared quantum dot is regulated and controlled by controlling the thermal injection temperature, and sulfur oleylamine solution is injected when the temperature of the system is raised to 150 ℃, so that Gd @ Zn-Cu-FeS with the particle size of 4.5nm is finally obtained3Quantum dots; or injecting sulfur into oleylamine solution at 180 deg.C to obtain Gd @ Zn-Cu-FeS with particle size of 5.5nm3Quantum dots; or injecting sulfur into oleylamine solution at 210 ℃ to finally obtain Gd @ Zn-Cu-FeS with the particle size of 8.0nm3And (4) quantum dots.
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