CN112175605B - Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof - Google Patents

Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof Download PDF

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CN112175605B
CN112175605B CN202011075548.4A CN202011075548A CN112175605B CN 112175605 B CN112175605 B CN 112175605B CN 202011075548 A CN202011075548 A CN 202011075548A CN 112175605 B CN112175605 B CN 112175605B
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CN112175605A (en
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张菲
张子彤
李妍
霍建中
张俊华
盛美思
廖亚兰
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Tianjin Normal University
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a near-infrared fluorescence magnetic Fe NCs dual-mode probe and a synthetic method and application thereof. The valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0 valence, the particle size of the magnetic Fe NCs dual-mode probe is 5nm, the iron nano cluster prepared by the stabilizer glutathione to iron ion molar ratio of 1.3073 has excellent near infrared fluorescence emission capability, can effectively avoid interference of biological autofluorescence in a sample, and can be used for high-sensitivity detection of medicine molecule tiopronin a complex detection system. In addition, the probe also has stronger paramagnetic property, and can generate bright T under the action of an external magnetic field 1 The image signal is weighted and is gradually enhanced along with the increase of the probe concentration, and the method has wide application prospect in the aspect of magnetic resonance imaging.

Description

Near-infrared fluorescence magnetic Fe NCs dual-mode probe and synthetic method and application thereof
The invention is supported by a project on national science foundation (No. 21375095), a youth project on Tianjin City science foundation (No. 17JCQNJC05800), an 'inorganic-organic hybrid functional material chemical education department key laboratory' of Tianjin university, an 'Tianjin City functional molecular structure and performance key laboratory' open foundation project and 'future thousand people plan' project (WLQR 201914) of Tianjin university.
Technical Field
The invention belongs to the technical field of chemical synthesis and biological analysis and detection, and relates to a magnetic iron nanocluster with near-infrared fluorescence emission capability and a simple, green and rapid synthesis method thereof.
Background
Metal Nanoclusters (NCs), a nano-luminescent material emerging in recent years, have a particle size close to the fermi wavelength, which not only enables excellent fluorescent properties, but also exhibits properties possessed by molecules such as high water solubility, high dispersibility, and fluorescence tunability. Compared with traditional luminescent materials such as organic fluorescent dyes, semiconductor quantum dots and rare earth up-conversion fluorescent materials, the metal nanoclusters have smaller particle size and better biocompatibility while maintaining excellent fluorescence performance and sensing performance of the nano fluorescent probe, so that the metal nanoclusters are widely applied in relevant fields such as biomedicine, environmental science and the like, and become a hot research and development direction which is concerned in the technical field of domestic and foreign analysis and detection at present. According to different preparation raw materials of the metal nano-cluster fluorescent probe, the metal nano-cluster fluorescent probe can be divided into a noble metal nano-cluster and a common transition metal nano-cluster. The noble metal nanoclusters mainly comprise gold nanoclusters (Au NCs), silver nanoclusters (Ag NCs) and platinum nanoclusters (Pt NCs), and the noble metal nanocluster fluorescent probes are long in development history, so that preparation technologies and processes related to the noble metal nanoclusters are relatively mature, and the preparation and application difficulty is low.
In order to better solve the problem of high cost and difficult popularization of the noble metal nano-cluster fluorescent probe in practical application, in recent years, technologists develop two common transition metal nano-cluster fluorescent probes, namely copper nano-clusters (Cu NCs) and iron nano-clusters (Fe NCs), successively. Because the two transition metal nanoclusters are cheap and easily available in preparation raw materials, heating is not needed in the preparation process, and the reaction time is short, the preparation cost and the use cost are greatly reduced compared with those of the traditional noble metal nanocluster fluorescent probe, the preparation method is very beneficial to large-scale popularization in practical production application, and the preparation method has a wide application prospect.
Among the transition metal nanocluster fluorescent probes, fluorescent Fe NCs also have many unique advantages compared to Cu NCs fluorescent probes that have been widely reported in recent years. Firstly, as for raw materials, the price of iron is obviously lower than that of copper, so that the cost of the Fe NCs probe is much lower than that of the Cu NCs probe, and the Fe NCs probe has more cost advantage in practical production application such as analysis and detection. And secondly, fe NCs have longer fluorescence emission wavelength than Cu NCs, so that interference of biological autofluorescence in a biological sample is avoided, and the sensitivity and accuracy of analysis and detection are improved. More importantly, both the noble metal nanoclusters and the Cu NCs only have fluorescence emission performance and do not have any magnetic performance, the nanoclusters can only be used as a fluorescence probe but not as a fluorescence/magnetic resonance dual-mode probe, and the simultaneous output of a fluorescence signal and a magnetic resonance signal cannot be realized. If a fluorescence/magnetic resonance bimodal nanoprobe is prepared based on the metal nanoclusters, other nanoparticles (such as Fe) with magnetic signal response must be additionally coupled 3 O 4 Etc.), not only additional preparation processes are added, but also the preparation cost is increased. However, the iron element is magnetic, and Fe NCs prepared by using the iron element as a matrix have not only light emission properties but also magnetic properties. If the probe is developed into a fluorescence/magnetic resonance bimodal sensing probe, two signals can be simultaneously output, one material has two purposes, and the application cost is saved. Therefore, the Fe NCs probe undoubtedly has great technical progress as compared with the noble metal nanocluster probe and the Cu NCs probe.
Currently, fluorescent Fe NCs probes are rarely reported in domestic and foreign technical literature because iron element belongs to a metal before hydrogen, and it is difficult to reduce the iron element from cations to 0-valent Fe NCs in a solution compared with metal elements after hydrogen such as gold, silver and copper, and the prepared Fe NCs are also very easy to be oxidized again, so that the product is difficult to store under conventional conditions. At present, only 3 documents are reported internationally for preparing fluorescent Fe NCs, which are: n. goswamine et al, nanoscale, 2014, 6, 1848-1854, n. hashemite et al, microchip.acta, 2018, 185, 60, a. joseet et al, colloid Surface B, 2018, 165, 371-380. Since the preparation of Fe NCs is very difficult, in order to avoid the re-oxidation of the prepared Fe NCs, the above three documents all use hemoglobin (Hb) as an iron source and a preparation template, and they extract iron ions in hemoglobin to the surface of hemoglobin using piperidine and reduce the iron ions to iron atoms with a corresponding reducing agent, thereby preparing Fe NCs fluorescent probes emitting yellow to orange colors (emission wavelength of 580 to 600 nm). The preparation method has the following defects: firstly, whether noble metal nanoclusters or Cu NCs are adopted, metal elements in the nanoclusters are all from metal inorganic salt raw materials, and in the Fe NCs prepared by the method, iron elements are from blood products, namely hemoglobin. As is well known, the price of metal inorganic salt is far lower than that of blood products, and the method adopting hemoglobin as a main raw material for preparing Fe NCs undoubtedly increases the preparation and application cost of the Fe NCs. Secondly, the fluorescence emission capability of the metal nanocluster comes from the transition of excited electrons in metal atoms, the more metal atoms grow and combine on the template molecule, the more the number of electrons excited to generate the transition, and correspondingly, the stronger the fluorescence emission capability of the nanocluster. Generally, 10-100 metal atoms will grow on the surface of one template molecule of the fluorescent metal nanocluster. And the hemoglobin in the preparation method is not only an iron source but also a preparation template, one hemoglobin molecule only contains one iron ion, if the Fe NCs are prepared by the method, only one metal atom can grow on the surface of one template molecule, and the luminous efficiency of the Fe NCs probe is greatly restricted. Meanwhile, the preparation method cannot directly reduce iron ions in hemoglobin, and the iron ions are extracted from the hemoglobin to the surface by using piperidine firstly. Piperidine is a toxic reagent and belongs to an easily prepared toxic chemical, is strictly controlled, and is used as a necessary reagent for preparing Fe NCs, so that great safety and economic risks are faced, and large-scale popularization in actual production is not facilitated.
Aiming at the defects of the prior art, the invention provides a preparation method of a fast, efficient, green and low-cost near-infrared fluorescence magnetic Fe NCs (Fe NCs) bimodal probe. The method uses reduced Glutathione (GSH) as a preparation template and a protective agent, ferrous chloride inorganic salt as an iron source, and sodium borohydride as a reducing agent in aqueous solution to reduce ferrous ions with a valence of +2 into iron atoms with a valence of 0, so as to prepare the Fe NCs with near infrared fluorescence emission performance and paramagnetic performance. The preparation template GSH adopted by the method is a bioactive small molecule (tripeptide) which is widely existed in animals and plants, has wide source and low price, and the rich sulfhydryl group can combine a plurality of iron atoms, thereby ensuring the fluorescence emission efficiency of the prepared Fe NCs. According to the method, sodium borohydride replaces a hydrazine hydrate reducing agent commonly used in the traditional metal nano-cluster synthesis method, toxic reagents such as piperidine are not needed, the preparation process is green, environment-friendly and efficient, and the time is only 15 minutes. The finally formed Fe NCs have stable performance, long preservation time and excellent magnetic resonance response performance, can realize the simultaneous output of fluorescent and magnetic resonance bimodal signals, and has obvious technical progress and wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple aqueous phase room temperature synthesis method of water-soluble non-toxic Fe NCs, the Fe NCs prepared by the method have excellent near infrared fluorescence emission capability and excellent paramagnetic property, can simultaneously have the response capability of two detection signals of fluorescence and Magnetic Resonance Imaging (MRI), namely the response capability of a bimodal signal, and has good application prospect in the aspects of drug molecule detection, MRI imaging application and the like.
In order to realize the purpose, the invention discloses a near-infrared fluorescence magnetic Fe NCs dual-mode probe, which is characterized in that: the valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0 valence, the particle size of the iron element is 5nm, and the molar ratio of a stabilizing agent Glutathione (GSH) to an iron atom is 1;
the Fe NCs probe has near infrared fluorescence emission capacity, the maximum excitation wavelength is located at 515nm, and the maximum emission wavelength is located at 702 nm; and the Fe NCs probe has fluorescent property and obvious paramagnetic property.
The invention further discloses a synthesis method of the near-infrared fluorescence magnetic Fe NCs dual-mode probe, which is characterized by comprising the following steps:
(1) Weighing 0.1000g of reduced Glutathione (GSH) and dissolving in 15mL of high-purity water;
(2) Weighing ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) 0.1988g, dissolving in 10mL of high-purity water to form 0.1M ferrous chloride aqueous solution, transferring 1mL of the above liquid, adding into GSH solution, and stirring thoroughly for 20min;
(3) And adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the Fe NCs probe solution with both magnetism and near-infrared fluorescence emission capability.
The invention further discloses an application of the near-infrared fluorescence magnetic Fe NCs dual-mode probe in the aspect of high-sensitivity detection of medicine molecule tiopronin, and the method comprises the following steps: preparing a detection system by using a certain volume of Fe NCs probe solution, a tiopronin standard solution and high-purity water, determining the quenching quantity (delta F) of a target substance tiopronin on a fluorescence signal of the Fe NCs probe by using the detection system containing the tiopronin standard solutions with different concentrations as a vertical coordinate, drawing a standard curve by using the concentration of the tiopronin standard solution as a horizontal coordinate, determining the concentration of the tiopronin in a sample according to the standard curve, and determining the linear range of the method for detecting the tiopronin to be 0.1-0.6M; the detection limit is: 3.7mM.
The invention also discloses the application of the near infrared fluorescence magnetic Fe NCs dual-mode probe in the aspect of Magnetic Resonance Imaging (MRI), and the method comprises the following steps: taking the Fe NCs probes with different concentrationsLiquid, T in MRI imaging systems for clinical medicine 1 Weighted imaging was performed in the mode in which the T of the Fe NCs probe increased with increasing concentration 1 The MRI signal of the weighted mode is continuously enhanced, the MRI image is brighter and brighter, and the probe can effectively enhance the T of water 1 The MRI images are weighted.
The invention is described in more detail below:
a near-infrared fluorescence magnetic Fe NCs bimodal detection probe is characterized in that: glutathione (GSH) and Fe atom (FeCl as iron source) as protective agents for the Fe NCs probe 2 ·4H 2 Calculated as O) is 1:0.3073; the particle size of the Fe NCs probe is about 5nm, the Fe NCs probe can emit fluorescence in a near infrared region under the excitation of visible light, the maximum excitation wavelength of the Fe NCs probe is 515nm, the maximum emission wavelength of the Fe NCs probe is 702nm, and the Fe NCs probe has obvious T 1 Weighted-mode Magnetic Resonance (MRI) signal response (i.e., MRI images become brighter as probe concentration increases).
The synthesis method of the near-infrared fluorescence magnetic Fe NCs dual-mode probe is characterized by comprising the following steps of:
(1) Weighing 0.1000g of GSH, and dissolving in 15mL of high-purity water;
(2) Weighing 0.1988 gFeCl 2 ·4H 2 O, dissolved in 10mL of high-purity water to form FeCl with the concentration of 0.1M 2 Transferring 1mL of the liquid into the GSH solution, and fully stirring for 20min;
(3) And adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the near-infrared fluorescent magnetic Fe NCs probe solution.
The invention further discloses application of the near-infrared fluorescence magnetic Fe NCs bimodal probe in high-sensitivity detection of a drug molecule tiopronin. The method specifically comprises the steps of preparing a detection system by using a certain volume of Fe NCs probe solution, tiopronin standard solution and high-purity water, measuring the quenching quantity (delta F) of a target substance tiopronin to a fluorescence signal of the Fe NCs probe by using the detection system containing the tiopronin standard solution with different concentrations as a vertical coordinate, drawing a standard curve by using the concentration of the tiopronin standard solution as a horizontal coordinate, and measuring the concentration of the tiopronin in a sample according to the standard curve.
In the detection method, the linear equation is obtained as delta F =415.50648x +27.89188, and delta F = F 0 -F，F 0 Equal to the fluorescence intensity without tiopronin, F is the fluorescence intensity after tiopronin addition, and x is the tiopronin concentration.
In the above detection method, the linear range of detection is 0.1-0.6M, and the detection limit is 3.7mM.
In the detection method, 3.55mL of high-purity water, 0.25mL of Fe NCs dispersion system and 0.20mL of tiopronin solution are adopted.
In the detection method, the fluorescence intensity of the tiopronin solution is detected after the tiopronin solution is added into the high-purity water and Fe NCs dispersion system for 90 min.
The invention further discloses an application of the near-infrared fluorescence magnetic Fe NCs bimodal probe in Magnetic Resonance Imaging (MRI). In particular to a method for taking Fe NCs probe solutions with different concentrations to carry out T in a clinical medical MRI imaging system 1 Weighted imaging was performed in the mode in which the T of the Fe NCs probe increased with increasing concentration 1 The MRI signal of the weighted mode is continuously enhanced, and the MRI image is brighter and brighter.
A typical example of the present invention:
a method for synthesizing a near-infrared fluorescent magnetic Fe NCs dual-mode probe comprises the following steps:
step 1: GSH and FeCl 2 ·4H 2 Dissolving O in high-purity water respectively to obtain stock mother liquor; wherein 0.1000g GSH is dissolved in 15mL high purity water; 0.1988g FeCl 2 ·4H 2 O was dissolved in 10mL high purity water.
Step 2: feCl is added 2 Dropwise adding the stock solution into the GSH solution, and fully stirring at room temperature; specifically transferring 1mL FeCl prepared in step 1 2 The solution was added dropwise to the GSH solution and stirred well for 20 min.
And step 3: adding 0.0190g sodium borohydride into the reaction system obtained in the step 2, fully reacting for 15 min, and obtaining an Fe NCs probe solution when the color of the reaction solution is changed from colorless to light yellow;
and 4, step 4: and (3) centrifuging the Fe NCs probe solution obtained in the step (3) at the rotating speed of 8000 r/min, washing the solution with absolute ethyl alcohol and high-purity water for three times, and drying the solution in a vacuum environment at 60 ℃ for 12 h to obtain the Fe NCs solid product.
Another typical example of the present invention:
step 1: 1.6319 g tiopronin is weighed and dissolved in 10mL high-purity water to prepare 1M tiopronin high-grade solution, and the solution is stored for later use.
Step 2: accurately transferring the tiopronin high-standard solutions prepared in the step 1 with different volumes into a 10mL colorimetric tube, diluting the tiopronin high-standard solutions by using high-purity water to prepare the tiopronin standard solutions with the concentrations of 0.1M, 0.2M, 0.3M, 0.4M and 0.6M in sequence, and storing the tiopronin standard solutions for later use.
And step 3: and (3) accurately transferring 0.20mL of the tiopronin standard solution with each concentration prepared in the step 2 into 5mL centrifuge tubes respectively, adding 0.25mL of Fe NCs probe solution and 3.55mL of high-purity water into each centrifuge tube, uniformly mixing, and measuring the fluorescence intensity of the mixed solution in each centrifuge tube after 90 min.
And 4, step 4: adding 0.25mL of Fe NCs solution into a 5mL centrifuge tube, adding 3.75 mL high-purity water, mixing, standing for 90min, measuring the fluorescence intensity, and recording as F 0 Calculating the fluorescence intensity and F of each detection solution in the step 3 0 Is marked as delta F, and takes the delta F as the ordinate and the concentration of the tiopronin standard solution as the abscissa to draw a standard curve, and the linear equation is obtained as delta F =415.50648x +27.89188, and the linear equation is marked as delta F = F 0 -F，F 0 Equal to the fluorescence intensity without tiopronin, F is the fluorescence intensity after tiopronin addition, and x is the tiopronin concentration.
Yet another exemplary embodiment of the present invention
Step 1: the Fe NCs probe solution with different volumes is transferred and added with high-purity water to be respectively diluted to 0.0045M, 0.00225M, 0.001125M and 0.0009M for storage and standby.
Step 2: accurately transferring the liquid to be tested and pure water (used as comparison) prepared in the step 1 of 2 mL into different hole sites of a detection plate respectively, and performing T-shaped displacement in a clinical medical MRI imaging system 1 Carrying out weighted imaging in a mode, and observing the shadow of the sample in each hole siteThe degree of image brightness.
Compared with the prior art, the near-infrared fluorescence magnetic Fe NCs dual-mode probe and the synthesis method thereof disclosed by the invention have the beneficial effects that:
(1) The Fe NCs prepared by the invention have the advantages of stable optical property, small particle size of synthetic materials, good fluorescence property and the like, the synthetic method is simple and rapid, and complex processes such as heating, pH adjustment, functional modification and the like are not needed in the synthetic process.
(2) The fluorescence emission wavelength of the Fe NCs probe is 702nm, the Fe NCs probe is positioned in a near infrared region, the fluorescence emission peak shape is good, the fluorescence intensity is high, and the Fe NCs probe has good paramagnetism.
(3) The preparation method of the Fe NCs is novel and is not easily interfered by other reasons such as pH, temperature and the like. The sodium borohydride is used as a reducing agent, so that the method is environment-friendly, does not generate by-products harmful to the environment, has high reaction speed, can finish the reaction within 15 min at the fastest speed, is simple in preservation method, and has stable fluorescence and magnetic resonance properties.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of an Fe NCs probe, illustrating that the Fe NCs have a small particle size and are uniform in size;
FIG. 2 is a fluorescence excitation spectrum and an emission spectrum of the Fe NCs probe, which shows that the maximum excitation wavelength is 515nm and the maximum emission wavelength is 702 nm;
FIG. 3 is a standard curve diagram of the detection of tiopronin by Fe NCs probe;
FIG. 4 shows T values of pure water and Fe NCs probe aqueous solutions of different concentrations 1 The MRI images are weighted, which shows that the probe has paramagnetic property and MRI response capability and can enhance the MRI signal of water.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that the invention can be practiced without departing from the spirit or essential characteristics thereofVariations and modifications in the materials and amounts used in the embodiments, within the spirit and scope of the invention, are also contemplated. All the reagents used were analytically pure, and the reagents and manufacturers used were as follows: GSH was purchased from shanghai source, leaf biotechnology limited; sodium borohydride was purchased from tianjin Guangfu chemical research institute; feCl 2 ·4H 2 O was purchased from kyo illinokay technologies ltd. Poly-reduced glutathione, sodium borohydride, ferrous chloride tetrahydrate are commercially available.
Example 1
The preparation of the near-infrared fluorescent magnetic Fe NCs is carried out at room temperature according to the following steps:
(1) Weighing 0.1000g of GSH and dissolving in 15mL of high-purity water;
(2) Weighing 0.1988g FeCl 2 ·4H 2 O, dissolved in 10mL of high-purity water to form FeCl with the concentration of 0.1M 2 Transferring 1mL of the aqueous solution into a prepared GSH solution, and fully stirring for 20min;
(3) And adding 0.0190g of sodium borohydride solid into the reaction mixed solution under the stirring condition, and fully reacting for 15 min under the stirring condition to obtain a final product solution, wherein the color of the reaction solution is changed from colorless to light yellow.
Example 2
(1) Preparation of Fe NCs reference example 1;
(2) Transmission Electron Microscopy (TEM) characterization of Fe NCs:
dispersing the prepared Fe NCs into high-purity water, uniformly dripping the Fe NCs on a special copper net, airing to prepare an observation sample, and observing the appearance of the Fe NCs by using a field emission transmission electron microscope. As shown in FIG. 1, the Fe NCs are approximately spherical in morphology and uniformly dispersed, have small particle size (about 5 nm) and are uniformly distributed.
Example 3
(1) Preparation of Fe NCs reference example 1;
(2) Measurement of fluorescence excitation spectrum and emission spectrum of Fe NCs:
dispersing the prepared Fe NCs into high-purity water, and measuring the fluorescence excitation spectrum and the emission spectrum of the Fe NCs sample by using a fluorescence spectrophotometer, wherein as shown in figure 2, the maximum excitation wavelength of the Fe NCs is 515nm, and the fluorescence emission wavelength of the Fe NCs under the excitation of the maximum excitation wavelength is 702nm and is positioned in a near infrared region, so that the Fe NCs have good near infrared fluorescence emission capability.
Example 4
(1) Preparation of Fe NCs reference example 1;
(2) The application of the Fe NCs probe in the aspect of detecting the medicine molecule tiopronin is as follows:
respectively taking 2 empty centrifuge tubes, numbering (1) and (2), respectively transferring 3.55mL of high purity water into the centrifuge tubes, transferring 250 μ L of Fe NCs probe solution into the centrifuge tubes, mixing uniformly, and continuing to add
Figure 561672DEST_PATH_IMAGE001
And adding 200 mu L of high-purity water into the centrifuge tube to serve as a blank control group, adding 200 mu L of tiopronin solution into the centrifuge tube (2), reacting for 90min to quench fluorescence, and detecting fluorescence emission intensity by using a fluorescence photometer, so that the detection of the tiopronin solution can be realized.
Example 5
(1) Preparation of Fe NCs reference example 1;
(2) The application of the Fe NCs probe in the aspect of detecting the medicine molecule tiopronin is as follows:
adding 3.55mL of high-purity water into a 5mL centrifuge tube, transferring 250 mu L of Fe NCs probe solution, adding into the centrifuge tube, mixing uniformly, respectively adding 200 mu L of tiopronin solutions with different concentrations, reacting for 90min, detecting the fluorescence emission intensity, and performing parallel determination for three times. The linear relationship between the fluorescence quenching amount (delta F) and the concentration of the tiopronin solution (as shown in figure 3) is obtained according to the quenching degree of the tiopronin with different concentrations on the fluorescence of the Fe NCs probe, and the tiopronin is quantitatively detected according to the linear relationship, wherein the linear range of the detection is 0.1-0.6M, and the detection limit is 3.7mM.
Example 6
(1) Preparation of Fe NCs reference example 1;
(2) Paramagnetic characterization of Fe NCs and their use at T 1 Application of weighted MRI imaging:
drying and weighing the prepared Fe NCs probe, dissolving the Fe NCs probe in high-purity water again to prepare probe standard solutions (the serial numbers are 1-5) with the concentrations of 0.0045M, 0.00225M, 0.001125M and 0.0009M in sequence, transferring 2 mL to-be-detected liquid and pure water (for comparison, the serial number is 6) to be respectively transferred to different hole sites of an MRI image detection plate, and performing T imaging in a clinical medical MRI system 1 And carrying out weighted imaging in the mode, and observing the image brightness of the sample in each hole site. As shown in FIG. 4, T of the Fe NCs 1 The weighted magnetic resonance image becomes bright obviously along with the increase of the probe concentration, which indicates that the Fe NCs probe has good paramagnetic property and T 1 Weighted MRI response capability (T is generated if ferromagnetic material is used) 2 Weighted signal, i.e., MRI images become darker as probe concentration increases). In addition, the MRI signal of the Fe NCs probe solution in the hole sites 1-5 is obviously stronger than that of pure water in the hole site 6, which shows that the Fe NCs probe can effectively enhance the MRI signal of a substance without MRI signal response performance like water, and has wide application prospect in MRI imaging.

Claims (3)

1. A near-infrared fluorescence magnetic Fe NCs dual-mode probe is characterized in that: the valence state of the iron element in the magnetic Fe NCs dual-mode probe is 0 valence, the particle size of the iron element is 5nm, and the molar ratio of glutathione serving as a stabilizer to iron atoms is 1; the synthesis method comprises the following steps:
(1) Weighing 0.1000g of reduced Glutathione (GSH) and dissolving in 15mL of high-purity water;
(2) Weighing ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) 0.1988g, dissolving in 10mL of high-purity water to form 0.1M ferrous chloride aqueous solution, transferring 1mL of the above liquid, adding into GSH solution, and stirring thoroughly for 20min;
(3) And adding 0.0190g of sodium borohydride under the stirring condition, fully reacting for 15 min, and changing the color of the solution from colorless to light yellow to obtain the Fe NCs probe solution with both magnetism and near-infrared fluorescence emission capability.
2. The application of the near-infrared fluorescent magnetic Fe NCs dual-mode probe as claimed in claim 1 in the aspect of high-sensitivity detection of medicine tiopronin.
3. Use of the near-infrared fluorescent magnetic Fe NCs bimodal probe of claim 1 in Magnetic Resonance Imaging (MRI).
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