CN111944520A - I-III-VI type quantum dot nano material and preparation method and application thereof - Google Patents
I-III-VI type quantum dot nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an I-III-VI type quantum dot nano material and a preparation method and application thereof. According to the method, IIIA group metal acetate and VIA group nonmetal simple substances are used as precursors and are subjected to ion exchange with IB group metal acetate by a template method to obtain the oil-soluble I-III-VI type quantum dot nano material. The method has the advantages of easily controlled conditions, good repeatability, granular prepared nano material, good dispersibility, uniformity and repeatability and high fluorescence quantum yield. In addition, the adjustment of the size and the emission wavelength of the product can be achieved In a larger range by adjusting the Zn/In ratio or the Cu/In ratio. The oil-soluble I-III-VI type quantum dot nano material prepared by the invention can be further subjected to surface modification to obtain a water-soluble I-III-VI type quantum dot nano material, has strong luminescence and a negative charge surface, and is an ideal material applicable to the fields of biological detection and biological imaging.
Description
Technical Field
The invention belongs to the technical field of fluorescent nano materials, and particularly relates to an I-III-VI type quantum dot nano material as well as a preparation method and application thereof.
Background
Semiconductor nanocrystals (quantum dots) have attracted widespread attention by both domestic and foreign researchers due to their unique optical properties, such as high photoluminescence quantum yield, excellent photostability, and size-dependent emission from the ultraviolet to near-infrared regions. Among semiconductor nanocrystals, the II-VI or IV-VI compound MX (M ═ Cd, Hg, Pb; X ═ S, Se, Te) is the most widely studied. Unfortunately, toxic elements such as Cd, Hg and Pb prevent their further application in the fields of biological detection and biological imaging. As a promising fluorescent nano probe for replacing II-VI semiconductors, the non-toxic I-III-VI quantum dot (such as CuInS)2、CuInSe2、AgInS2) Has become one of the hot spots of research in the last decade. In particular CuInS2Nanocrystals have shown great potential in fluorescent biomarkers. Due to CuInS2The electronic structure and optical properties of nanocrystals depend to a large extent on the [ Cu ] of the material]/[In]Ratio and particle size, and therefore, there is an urgent need for fine control of their composition and morphology.
Generally, CuInS2Nanocrystals were prepared by a direct synthesis method in which three precursors, copper, indium and a sulfur source, were mixed together and reacted by thermal injection or heating (J Am Chem Soc 2008,130, 5620-. By analyzing the methods in the prior art, we found that: when the synthesis is carried out by adopting a conventional high-temperature thermal decomposition method, the obtained reactantThe morphology is not easy to regulate and control, and a large amount of black precipitates can appear in the reaction process without paying attention to the morphology, so that the final luminescence is weakened; when the synthesis is carried out by a hot injection method, reactants need to be injected under the high-temperature condition, so that the method has certain danger and is quick and difficult to control. Both methods cannot accurately control the components and the morphology of the product, and are prone to waste of precursors.
Moreover, although the direct synthesis process is simple, the morphology and compositional control of the final product is limited. The main reason for this is that multiple cationic and anionic precursors exhibit a complex balance between different reactivity during nucleation and growth, which may lead to the formation of intermediate by-products like two-phase nanomaterials or heterostructures (Chem Mater 2015,27, 5949-5956). These by-products may seriously affect CuInS2The fluorescence quantum yield of nanocrystals (Inorg Chem 2011,50, 4065-.
In recent years, the cation exchange strategy has become an attractive approach to design CuInS2The regulation of the morphology, structure and composition of nanocrystals cannot be achieved in the direct synthesis methods (ACS Nano2015,9, 11430-11438). By carefully adjusting the reaction conditions of cation exchange, the final nanocrystal can maintain the morphology of the template nanocrystal. More importantly, by adding the required cation precursor into the template nanocrystal for reaction, the components of the material can be accurately adjusted to synthesize the nanocrystal with high-efficiency luminescence. In the cation exchange reaction, the reasonable design of proper template nanocrystals is a basic premise. To date, most of the reported templates are binary Cu2-xS nanocrystals, but high temperatures or long reaction times are generally required to synthesize CuInS2Nanocrystals (Chem Mater 2015,27, 621-628).
Disclosure of Invention
In order to improve the problems of the prior art, the invention provides a type I-III-VI quantum dot nanomaterial comprising a group IB metal element, a group IIIA metal element and a group VIA nonmetal element, wherein the type I-III-VI quantum dot nanomaterial is prepared from a type III-VI template nanomaterial and has a fluorescence quantum yield of > 2.5%, preferably > 9%, more preferably > 15%, further preferably > 25%, such as 28.76%.
According to the invention, the I-III-VI type quantum dot nano material is a granular nano crystal, belongs to a tetragonal crystal system, and has a grain diameter of 1-50 nm, preferably 1-40 nm, such as 2.2 +/-0.4 nm, 2.6 +/-0.7 nm, 2.5 +/-0.8 nm, 6.5 +/-1.8 nm and 29.6 +/-9.2 nm, wherein, the number behind +/-represents the error of grain diameter statistics, and is obtained by firstly counting the grain diameter of about 200 nano crystals in a TEM picture and then counting the deviation of the grain diameter.
According to the invention, the particle size of the I-III-VI type quantum dot nano material is larger than that of the III-VI type template nano material.
According to the invention, the I-III-VI type quantum dot nano material can be oil-soluble or water-soluble.
According to the invention, the group IB metal element is selected from Cu or Ag, the group IIIA metal element is selected from In or Ga, and the group VIA non-metal element is selected from S or Se.
According to the invention, the chemical composition of the I-III-VI type quantum dot nano material can be CuxInS2yZn, wherein x represents the molar ratio of Cu to In, and y represents the molar ratio of Zn to In.
Preferably, 0< x <2, such as x is 0.057, 0.089, 0.181, 0.379, 0.796, 1.956;
y is more than or equal to 0 and less than or equal to 1, such as y is 0, 0.15, 0.2, 0.33, 0.5 and 1.
Also preferably, 0< x <0.2, 0.3< y ≦ 1.
The invention also provides a preparation method of the I-III-VI type quantum dot nano material, which comprises the following steps: preparing a III-VI type template nano material by adopting a precursor comprising IIIA group metal acetate and VIA group nonmetal simple substances, and then carrying out ion exchange with IB group metal acetate to obtain the oil-soluble I-III-VI type quantum dot nano material.
Wherein, the IB group metal acetate is selected from any one of CuAc and AgAc, and the IIIA group metal acetate is selected from in (Ac)3、Ga(Ac)3Any one of the above, wherein the elemental group VIA nonmetal is selected from elemental sulfur or a single metalSelenium-rich.
Preferably, the preparation method comprises the following steps:
s1, mixing the IIIA group metal acetate, the VIA group nonmetal simple substance and zinc salt with a solvent to obtain a mixed solution, and heating the mixed solution for reaction to obtain a solution of the III-VI type template nanometer material;
s2, cooling the solution of the III-VI type template nano material obtained in the step S1, adding IB group metal acetate into the solution for ion exchange, and performing post-treatment to obtain the oil-soluble I-III-VI type quantum dot nano material.
According to the present invention, in step S1, the solvent is a mixed solvent of dodecanethiol (DDT) and oleylamine; in the mixed solvent, the molar ratio of the dodecyl mercaptan to the oleylamine is (1-10): 1-10, preferably (1-5): 5-10), for example 4: 6.
According to the present invention, the zinc salt in step S1 may be zinc acetate.
According to the invention, in step S1, the molar ratio of the zinc salt to the group IIIA metal acetate may be 0 to 1, for example 0.15, 0.2, 0.33, 0.5, 1.
According to the invention, the molar ratio of the total amount of the zinc salt and the group IIIA metal acetate to the group VIA nonmetal simple substance in the step S1 can be 1 (1-10), preferably 1 (2-6), such as 1: 4.
According to the invention, the concentration of the IIIA group metal acetate in the mixed solution in the step S1 can be 0.01-1 mol/L, preferably 0.01-0.1 mol/L, such as 0.02 mol/L.
According to the invention, the temperature of the reaction in step S1 is in the range of 30 ℃ to 250 ℃, preferably 180 ℃ to 250 ℃, more preferably 200 ℃ to 250 ℃, for example 220 ℃.
According to the present invention, the reaction time in step S1 is 5-60 min, preferably 5-30 min, such as 10 min.
According to the present invention, the reaction in step S1 is performed under an inert atmosphere, which may be any one or more of nitrogen, helium, and argon.
The molar ratio of the group IB metal acetate in step S2 to the group IIIA metal acetate in step S1 may be 0.01 to 2, for example 0.05, 0.1, 0.2, 0.4, 0.8, 2.0.
According to the present invention, the temperature reduction in step S2 may be to 50 to 120 ℃, preferably 80 to 100 ℃.
According to the invention, the preparation method also comprises the step of carrying out surface modification on the oil-soluble I-III-VI type quantum dot nano material so as to obtain the water-soluble I-III-VI type quantum dot nano material.
According to the invention, the step of carrying out surface modification on the oil-soluble I-III-VI type quantum dot nano material comprises the following steps: and carrying out modification reaction on a reaction system comprising the oil-soluble I-III-VI type quantum dot nano material, a nitrogen-containing organic solvent and a modifier, and carrying out post-treatment to obtain the water-soluble I-III-VI type quantum dot nano material.
According to the invention, the water-soluble I-III-VI type quantum dot nano material has a negative charge surface and the potential is (-15) — (-10) mV, such as-13.4 +/-1.5 mV.
According to the present invention, the nitrogen-containing organic solvent may be any one or more of N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide.
According to the invention, the modifier is preferably Glutathione (GSH) or 3-mercaptopropionic acid (MPA).
According to the invention, in the reaction system, the molar ratio of the oil-soluble I-III-VI type quantum dot nano material to the modifier can be 1 (1-5), preferably 1 (1-3), for example 1: 1.8.
According to the invention, in the reaction system, the mass volume ratio of the oil-soluble I-III-VI type quantum dot nano material to the nitrogen-containing organic solvent can be 1g (1-50) mL, preferably 1g (10-40) mL, for example 1g:30 mL.
According to the invention, the temperature of the modification reaction may be between 100 ℃ and 200 ℃, preferably between 100 ℃ and 150 ℃, for example 130 ℃; the reaction time may be 5 to 30min, preferably 10 to 15 min.
The invention further provides the application of the I-III-VI type quantum dot nano material in the field of biotechnology; preferably in biological detection and biological imaging.
According to the invention, the I-III-VI type quantum dot nano material can be used as a fluorescent nano probe to be applied to ATP detection and imaging of normal cells and tumor cells of a human body.
According to the invention, the I-III-VI type quantum dot nano material can be assembled with transition metal ions before being applied to ATP detection, so as to obtain the I-III-VI type quantum dot nano material conjugated by the transition metal ions.
According to the invention, the transition metal ion is preferably Ce3+，Cu2+，Tb3+，Gd3+Any one of them.
The invention has the beneficial effects that:
1) according to the invention, IIIA group metal acetate and VIA group nonmetal simple substances are used as precursors to obtain a III-VI type template, IB group metal acetate is added under mild conditions for ion exchange, and a series of I-III-VI quantum dot nano materials are synthesized.
2) The invention can realize the adjustment of the size and the emission wavelength of the product In a larger range by adjusting the Zn/In ratio or the Cu/In ratio.
3) The water-soluble nano fluorescent probe has stronger luminescence, and is suitable for the biological field or the medical field as a biocompatible nano probe with a negative charge surface, such as the detection and imaging field, in particular to the fluorescence labeling biological detection and biological imaging field.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of template nanomaterials of example 1.1 with different Zn/In ratios;
in FIG. 2, a and b are tetragonal phase Cu prepared In different Zn/In ratios In example 1.2xInS2:ZnyX-ray powder diffraction pattern of nano material and ruler of nano material before and after ion exchangeCun variation chart;
a in FIG. 31-6、b1-6Respectively for the template nano-materials prepared In different Zn/In ratios In example 1, and for the tetragonal phase Cu obtained after ion exchangexInS2:ZnyTransmission electron microscopy images of nanomaterials;
in FIG. 4, a and b are tetragonal phase Cu prepared in example 1.20.057InS2X-ray photoelectron spectrum of Zn nanomaterial and fine spectrum of copper element, and FIG. 4c shows tetragonal phase Cu prepared at different Zn/In ratios In example 1.2xInS2:ZnyEmission spectra of the nanomaterials;
FIG. 5 shows the tetragonal phase Cu prepared at different Cu/In ratios In example 1.3xInS2:ZnyAn X-ray powder diffraction pattern of the nanomaterial;
in FIG. 6a-e are the tetragonal phase Cu prepared at different Cu/In ratios In example 1.3xInS2:ZnyTransmission electron microscopy images and size distribution plots (lower right insert) of the nanomaterials; f. g, h are the tetragonal phase Cu prepared In example 1.3 with different Cu/In ratiosxInS2:ZnyThe absorption spectrum, the emission spectrum and the quantum yield change chart of the nano material;
a in FIG. 7 is for tetragonal phase Cu in example 2xInS2yZn a schematic diagram of surface modification of nano-materials; b. c and d are Cu in example 20.089InS2An infrared spectrogram before and after the surface modification of the Zn nano material, a Zeta potential diagram after the modification and a hydrated particle size distribution diagram;
in FIG. 8, a is Ce obtained in example 23+Conjugated Cu0.089InS2An ATP homogeneous phase analysis schematic diagram with Zn nano material as a probe; b to d are each water-soluble Cu0.089InS2Zn nanomaterial, Ce3+Conjugated Cu0.089InS2Zn nanomaterial and cerium oxide3+Conjugated Cu0.089InS2A transmission electron microscope picture of the Zn nano material added with ATP; e is the addition of Ce in different concentrations3+Obtained Ce3+Conjugated Cu0.089InS2Zn NaAn emission spectrum of the rice material; f. g is to Ce respectively3+Conjugated Cu0.089InS2Adding different amounts of ATP depolymerized emission spectra and AMP calibration curves corresponding to the ATP depolymerized emission spectra into the Zn nano material;
FIG. 9 shows Ce in example 23+Conjugated Cu0.089InS2Zn nanocrystals (0.1mg/mL) were incubated with 10mM ATP, and the fluorescence signal kinetics study was performed with 365nm excitation;
FIG. 10 shows Ce in example 23+Conjugated Cu0.089InS2Specific detection of Zn nanomaterial (0.1mg/mL) and ATP, wherein PBS is phosphate buffered saline, ADP is adenosine diphosphate, AMP is adenosine monophosphate;
FIG. 11 shows HELF cells and Ce in example 33+Conjugated Cu0.089InS2Cell survival rate after incubation of Zn nano material;
in FIG. 12, a, b and c are water-soluble Cu prepared in example 2, respectively0.089InS2Zn nano material and cells HELF, HeLa and HeLa/Ca2+Imaging after culturing;
FIG. 13 shows water-soluble Cu prepared in example 2 of the present invention0.089InS2The synthesis of Zn nano material and the application in the ATP detection and cell imaging fields are shown in the figure;
in the drawings of the specification, "size" is equivalent to "particle diameter", and "quantum yield" is "fluorescence quantum yield".
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The apparatus used in the present invention is as follows:
the X-ray powder diffraction instrument model for testing the nano material is MiniFlex2, the manufacturer is japan ltd, and the radiation wavelength of the copper target is 0.154187 nm.
The transmission electron microscope is JEM-2010 and JEOL.
The model of the instrument for testing the absorption and emission spectra of the nano material is FLS920, the manufacturer is Edinburgh, and the excitation light source is a xenon lamp.
The model of the X-ray photoelectron spectroscopy instrument for testing the nano material is ESCALB 250Xi, and the manufacturer is ThermoFisher.
The infrared spectrometer was identified as VERTEX70 from Bruker Optics.
Hydrated particle size distribution test instrument model no ZS ZEN3600, Malvern dynamic light scattering.
The model of the apparatus for testing the nano material in the aspect of ATP detection is Synergy 4, and the manufacturer is BioTek.
The apparatus for testing nanomaterials for cellular imaging was the model FV1000, manufactured by Olympus.
Example 1
1. Preparing III-VI type template nano materials with different Zn/In ratios: oil soluble In2S3yZn nanocrystalline
(1) In (Ac) was weighed out in a total reaction amount of 0.2mmol (about 0.0584g)3And 0.2mmol (about 0.0361g) of Zn (Ac)2Adding into a three-neck round-bottom flask, and adding 1.6mmol (about 0.051g) of sulfur powder; 6.0mL of Oleylamine (OM) and 4.0mL of dodecanethiol (DDT) were taken with a pipette and added to the round bottom flask. Nitrogen was introduced to the flask to evacuate the air. Heating to about 40 ℃ under stirring, and dissolving the reactants to form colorless transparent liquid; when the solution is heated to 180 ℃, the color of the solution begins to change into orange yellow; heating was continued to 220 ℃ to give a clear orange-yellow solution. Keeping for 10 min. Cooling to room temperature, and centrifuging and washing.
(2) Retention of in (Ac)3And Zn (Ac)2Adding 0.4mmol of the total amount, changing the molar ratio of the two to be 100, 50, 33, 20, 15 and 0 mol%, and synthesizing the III-VI template nano material I under the same conditions as the conditions in the step (1)n2S3yZn nanocrystals with In chemical composition2S3:Zn(Zn/In＝100％)，In2S3:0.50Zn(Zn/In＝50％)，In2S3:0.33Zn(Zn/In＝33％)，In2S3:0.20Zn(Zn/In＝20％)，In2S3:0.15Zn(Zn/In＝15％)，In2S3(Zn/In＝0％)。
As can be seen from FIG. 1, the oil-soluble In obtained2S3yZn nanocrystal has good crystallinity, diffraction peak position and relative intensity and In2S3The PDF standard cards (JCPDS NO.25-0390) are consistent and belong to the tetragonal system.
As shown in figure 3a1-6Shown that the obtained oil-soluble In2S3yZn nanocrystals have good dispersibility and uniform morphology, the particle size gradually decreases with the increase of Zn/In ratio, and the adjustable range is 22.8 + -4.9 nm to 1.7 + -0.7 nm (the number behind "+/-" indicates the error of particle size statistics, which is obtained by firstly counting the particle size of about 200 nanocrystals In a TEM image and then counting the deviation).
2. Preparation of oil-soluble Cu with different Zn/In ratiosxInS2yZn nanometer material
(1) In (Ac) was weighed out in a total reaction amount of 0.2mmol (about 0.0584g)3And 0.2mmol (about 0.0361g) of Zn (Ac)2Adding into a three-neck round-bottom flask, and adding 1.6mmol (about 0.051g) of sulfur powder; 6.0mL of Oleylamine (OM) and 4.0mL of dodecanethiol (DDT) were taken with a pipette and added to the round bottom flask. Nitrogen was introduced to the flask to evacuate the air. Heating to about 40 ℃ under stirring, and dissolving the reactants to form colorless transparent liquid; when the solution is heated to 180 ℃, the color of the solution begins to change into orange yellow; heating was continued to 220 ℃ to give a clear orange-yellow solution.
(2) After 10min, cooling to 80-100 ℃. 0.1mmol of CuAc was weighed and dissolved in 1mL of DDT to prepare a 0.1mol/L solution. And (3) dropwise adding 100 mu L of the CuAc solution into a flask, and continuously stirring for 30-40 min to fully and uniformly mix. Cooling to room temperature, centrifugally washing and drying to obtain oil-soluble Cu0.057InS2Zn nanomaterial in the form of granular nanocrystalThe Cu/In molar ratio In the nanomaterial analyzed by plasma emission spectroscopy (ICP) was 5.7 mol%.
(3) Retention of in (Ac)3And Zn (Ac)2Adding 0.4mmol of Cu In the same conditions as those of (1) and (2), changing the molar ratio of Zn to In to 50, 33, 20, 15 and 0 mol%, respectively0.057InS2:0.50Zn、Cu0.057InS2:0.33Zn、Cu0.057InS2:0.2Zn、Cu0.057InS2:0.15Zn、Cu0.057InS2And (3) nano materials.
As shown in FIG. 2a, the obtained nano material has good crystallinity, and the diffraction peak position and relative intensity of the nano material are compared with those of CuInS2The PDF standard cards (JCPDS NO.65-2732) are consistent and belong to the tetragonal system.
As shown In fig. 2b, the particle size of the obtained nanomaterial gradually decreases with the increase of Zn/In ratio, and the particle size of the nanomaterial after ion exchange slightly increases compared to before;
as shown in fig. 3b1-6The obtained nano material keeps the shape of the template nano material, has good dispersity and uniform shape, the particle size is gradually reduced along with the increase of the Zn/In ratio, and the adjustable range is 29.6 +/-9.2 nm to 2.2 +/-0.4 nm.
As shown in FIGS. 4a-b, it was confirmed that Cu0.057InS2The Zn nano material does contain four elements of Cu, Zn, In and S, and the valence state of Cu In the final product is +1 through a fine spectrum of the Cu element.
As shown In FIG. 4c, under 365nm excitation, the molar ratio of Zn/In was changed to 100, 50, 33, 20, 15, 0 mol%, and the adjustable range of the emission peak was 522-678 nm.
3. Preparation of oil soluble Cu with different Cu/In ratiosxInS2yZn nanometer material
(1) In (Ac) was weighed out in a total reaction amount of 0.2mmol (about 0.0584g)3And 0.2mmol (about 0.0361g) of Zn (Ac)2Adding into a three-neck round-bottom flask, and adding 1.6mmol (about 0.051g) of sulfur powder; 6.0mL of Oleylamine (OM) and 4.0mL of dodecanethiol (DDT) were taken with a pipette and added to the round bottom flask. Nitrogen was introduced to the flask to evacuate the air. In the state of stirringIn the state, when the temperature is heated to about 40 ℃, reactants are dissolved to form colorless transparent liquid; when the solution is heated to 180 ℃, the color of the solution begins to change into orange yellow; heating was continued to 220 ℃ to give a clear orange-yellow solution.
(2) After 10min, cooling to 80-100 ℃. 0.1mmol of CuAc was weighed and dissolved in 1mL of DDT to prepare a 0.1mol/L solution. And (3) dropwise adding 100 mu L of CuAc solution into the flask, and continuously stirring for 30-40 min to fully and uniformly mix. Cooling to room temperature, centrifugally washing and drying to obtain oil-soluble Cu0.057InS2Zn quantum dot nano material is granular nano crystal, and Cu/In molar ratio In the nano material is 5.7 mol% by utilizing plasma emission spectrum (ICP) analysis.
(3) While keeping the Zn/In molar ratio at 100 mol%, varying the amount of CuAc solution added to 200, 400, 800, 1600, 4000. mu.L, respectively, and synthesizing Cu under the same conditions as (1) and (2), respectively0.089InS2:Zn、Cu0.181InS2:Zn、Cu0.379InS2:Zn、Cu0.796InS2:Zn、Cu1.956InS2Zn nano material.
As shown in FIG. 5, the nanomaterial has good crystallinity, and the diffraction peak position and relative intensity of the nanomaterial are the same as those of CuInS2The PDF standard cards (JCPDS NO.65-2732) are consistent and belong to the tetragonal system.
As shown in FIGS. 6a-e, CuxInS2yZn nanometer material has good dispersibility and uniform appearance, the particle size gradually increases with the increase of Cu/In ratio, and the variation range is 2.6 +/-0.7 nm to 6.5 +/-1.8 nm.
As shown In FIG. 6f, as the Cu/In ratio increases, CuxInS2yZn nm has a gradually red-shifted absorption spectrum.
As shown In FIG. 6g, under 365nm light source excitation, the Cu/In ratio increasesxInS2The emission peak of yZn nanometer material gradually red shifts, and the adjustable range is 522-660 nm.
As shown In FIG. 6h, from the graph of the change In fluorescence quantum yield for different Cu/In ratios, it can be seen that the oil-soluble Cu content was at 8.9 mol% for the Cu/In ratio0.089InS2Of Zn nanomaterialsThe quantum yield is the highest and is 28.76%; cu0.181InS2The quantum yield of the Zn nano material is 9.43 percent; cu0.379InS2The quantum yield of the Zn nano material is 6.86 percent; cu0.796InS2The quantum yield of the Zn nano material is 6.79 percent; cu1.956InS2The quantum yield of the Zn nano material is 2.83 percent.
Example 2
Based on fluorescence aggregation induced quenching method, water-soluble Cu is utilizedxInS2yZn nm probe for ATP detection.
1. Preparation of Water-soluble Cu0.089InS2Zn nano material
(1) 0.75mmol (about 0.230g) of GSH and 0.41mmol (about 0.100g) of Cu were weighed out0.089InS2Zn nano material and 3mL of N, N-Dimethylformamide (DMF) are added into a three-neck round-bottom flask to form turbid solution, nitrogen is introduced as protective gas, air is exhausted, and the reactants are stirred uniformly.
(2) Heating to 130 ℃, reacting for 10-15 min, and gradually clearing the solution.
(3) Cooling to room temperature, adding anhydrous ethanol for precipitation, centrifuging at 12000rpm for 5min, dissolving the product with DMF, adding anhydrous ethanol again for precipitation, and centrifuging to obtain final pure product.
(4) 5mg of water-soluble Cu were weighed0.089InS2Zn nanomaterial was dissolved in 5mL of pure water (pH about 7) for subsequent detection, imaging, etc., and the rest of the final product was stored dry.
Shown in FIG. 7a as being for tetragonal phase CuxInS2yZn A schematic diagram of surface modification of nano-materials.
As shown in FIG. 7b, tetragonal phase CuxInS2yZn nano material surface modification front and back infrared spectrum, from 1698cm-1The surface of the modified nano material with known peak indeed realizes the coating of the glutathione.
As shown in FIG. 7c, tetragonal phase Cu0.089InS2The surface of the Zn nano material after water-soluble modification shows negative electricity which is-13.4 +/-1.5 mV.
As shown in FIG. 8b, water-soluble modified Cu0.089InS2The Zn nano material has good dispersibility and uniform appearance. The particle size is not greatly different from that before modification.
As shown in FIG. 7d, tetragonal phase Cu0.089InS2The particle size of the Zn nano material after water-soluble modification has no obvious change and is 2.5 +/-0.8 nm.
2.Cu0.089InS2ATP detection application of Zn nano material
At room temperature, 50mmol/L Ce is prepared3+Diluting the salt solution in a 96-well plate to obtain Ce with different concentrations (0-50mM)3+The volume of the solution was 100. mu.L. Then adding a certain amount of water-soluble Cu0.089InS2Zn quantum dots, shaking at 37 deg.C for 10-20 min to make the quantum dots and Ce3+Mixing uniformly to obtain Ce3+Conjugated Cu0.089InS2Zn nano material to realize aggregation induced luminescence quenching to the maximum extent. Photoluminescence measurement is carried out on the microplate by using a multichannel microplate reader to determine different concentrations of Ce3+Influence on quantum dot luminescence quenching.
Measuring Ce3+Conjugated Cu0.089InS2100 μ L of an aqueous solution (0.5mg/mL) of Zn nanomaterial was mixed with 100 μ L of PBS buffer (pH 7.4, 0.01M), and added to a 96-well microplate containing different amounts of ATP (0 to 50 mM). After incubation for 3h at 37 ℃ the microplate was subjected to photoluminescence measurements with a multichannel microplate reader under 365nm excitation. For comparison, control experiments were performed with either ADP (adenosine diphosphate) or AMP (adenosine monophosphate) under otherwise identical conditions.
As shown in FIG. 8a, Ce3+Conjugated Cu0.089InS2An ATP homogeneous phase analysis schematic diagram with Zn nano material as a probe.
As shown in FIG. 8c, Ce3+Conjugated Cu0.089InS2The Zn nano material is obviously agglomerated, and the grain size is increased.
As shown in FIG. 8d, agglomerated Ce after addition of ATP3+Conjugated Cu0.089InS2The Zn nano material is gradually separated and recovered to a dispersed state.
As shown in FIG. 8e, different concentrations (0-50mM) of Ce were added3+After that, due to the formation of Ce3+Conjugated Cu0.089InS2Zn nano material, the luminescence is gradually weakened.
As shown in FIG. 8f, after adding different concentrations (0-50mM) of ATP, due to ATP and Ce3+Higher conjugation ability of Ce3 +Conjugated Cu0.089InS2The Zn nano material is gradually dissociated and is recovered to a dispersed state, and the luminescence of the nano material is gradually recovered.
As shown in FIG. 8g, a control experiment was performed with AMP under the same conditions, resulting in the calibration curve shown in the figure.
As shown in FIG. 9, Ce3+Conjugated Cu0.089InS2Zn nanomaterials (0.1mg/mL) incubated with 10mM ATP, and the kinetics of PL signal as a function of time upon 365nm excitation were studied. The results show that, with increasing time, Ce3+Conjugated Cu0.089InS2The PL intensity of the Zn nano material is gradually increased and reaches a saturation in 10 min.
As shown in FIG. 10, Ce is used3+Conjugated Cu0.089InS2Zn nanomaterials (0.1mg/mL) were incubated with 10mM PBS, AMP, ADP and ATP to verify the specificity of ATP detection; the experimental result verifies Ce3+Conjugated Cu0.089InS2Zn has higher specificity for detecting ATP compared with interference analogues ADP or AMP.
Example 3
CuxInS2yZn nanomaterial.
1. And (3) biological safety test: as shown in FIG. 11, water-soluble Cu prepared in example 20.089InS2Zn nano material, in the non-illumination and illumination 2 min condition, in the concentration range of 10-200 mug/mL, and is incubated with normal Human Embryonic Lung Fibroblast (HELF) for 24 h, the survival rate of HELF cells which are not treated by the nano material is set as 100%, the cell viability is measured by using MTT method, the result shows that the survival rate of HELF cells is above 85%, and the water-soluble Cu is proved0.089InS2Zn nano-meterThe material has biological safety.
2. Cell imaging effect test: as shown in FIG. 12, water-soluble Cu prepared in example 20.089InS2The Zn nano material can be applied to cell imaging. Water-soluble Cu with concentration of 0.5mg/mL0.089InS2Zn nano material is added into normal Human Embryonic Lung Fibroblast (HELF) and human lung cancer cell (HeLa) and Ca2+Enhancer of human lung cancer cell (HeLa/Ca)2+) After incubation for 2 hours at 37 ℃ the cells were washed with PBS and excited with 408nm light under confocal fluorescence microscopy, and green (520-560 nm) and red (640-680 nm) emissions in the cells were observed.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A type I-III-VI quantum dot nanomaterial comprising a group IB metal element, a group IIIA metal element, a group VIA nonmetal element, characterized in that the type I-III-VI quantum dot nanomaterial is prepared from a type III-VI template nanomaterial with a fluorescence quantum yield > 2.5%, preferably > 9%, more preferably > 15%, still more preferably > 25%, such as 28.76%.
2. The type I-III-VI quantum dot nanomaterial according to claim 1, wherein the type I-III-VI quantum dot nanomaterial is a particulate nanocrystal, belonging to a tetragonal system, having a particle size of 1 to 50nm, preferably 1 to 40nm, such as 2.2 ± 0.4nm, 2.6 ± 0.7nm, 2.5 ± 0.8nm, 6.5 ± 1.8nm, 29.6 ± 9.2 nm;
the particle size of the I-III-VI type quantum dot nano material is larger than that of the III-VI type template nano material;
the I-III-VI type quantum dot nano material is oil-soluble or water-soluble;
the metal element In IB group is selected from Cu or Ag, the metal element In IIIA group is selected from In or Ga, and the nonmetal element In VIA group is selected from S or Se.
3. The type I-III-VI quantum dot nanomaterial of claim 1 or 2, wherein the chemical composition of the type I-III-VI quantum dot nanomaterial is CuxInS2yZn, wherein x represents the mol ratio of Cu to In, and y represents the mol ratio of Zn to In;
preferably, 0< x <2, 0 ≦ y ≦ 1;
also preferably, 0< x <0.2, 0.3< y ≦ 1.
4. A method for preparing a type I-III-VI quantum dot nanomaterial described in any of claims 1-3, comprising the steps of: preparing a III-VI type template nano material by adopting a precursor comprising IIIA group metal acetate and VIA group nonmetal simple substances, and then carrying out ion exchange with IB group metal acetate to obtain an oil-soluble I-III-VI type quantum dot nano material;
wherein, the IB group metal acetate is selected from any one of CuAc and AgAc, and the IIIA group metal acetate is selected from in (Ac)3、Ga(Ac)3Any of the above, wherein the elemental group VIA nonmetal is selected from elemental sulfur or elemental selenium.
5. The method of claim 4, comprising the steps of:
s1, mixing the IIIA group metal acetate, the VIA group nonmetal simple substance and zinc salt with a solvent to obtain a mixed solution, and heating the mixed solution for reaction to obtain a solution of the III-VI type template nanometer material;
s2, cooling the solution of the III-VI type template nano material obtained in the step S1, adding IB group metal acetate into the solution for ion exchange, and performing post-treatment to obtain the oil-soluble I-III-VI type quantum dot nano material.
6. The production method according to claim 5, wherein in step S1, the solvent is a mixed solvent of dodecanethiol (DDT) and oleylamine;
in the mixed solvent, the molar ratio of the dodecanethiol to the oleylamine is (1-10) to (1-10), preferably (1-5) to (5-10);
the zinc salt is zinc acetate;
the molar ratio of the zinc salt to the IIIA group metal acetate is 0-1;
the molar ratio of the total amount of the zinc salt and the IIIA group metal acetate to the VIA group nonmetal simple substance is 1 (1-10), preferably 1 (2-6);
the concentration of the IIIA group metal acetate in the mixed solution is 0.01-1 mol/L, preferably 0.01-0.1 mol/L;
the reaction temperature is 30-250 ℃, preferably 180-250 ℃, and more preferably 200-250 ℃;
the reaction time is 5-60 min, preferably 5-30 min;
the reaction is carried out in an inert atmosphere, wherein the inert atmosphere is any one or more of nitrogen, helium and argon.
7. The method of claim 5, wherein the molar ratio of the group IB metal acetate in step S2 to the group IIIA metal acetate in step S1 is 0.01-2;
in step S2, the temperature is reduced to 50-120 ℃, preferably 80-100 ℃.
8. The preparation method according to claim 4, further comprising a step of performing surface modification on the oil-soluble type I-III-VI quantum dot nanomaterial to obtain a water-soluble type I-III-VI quantum dot nanomaterial: and carrying out modification reaction on a reaction system comprising the oil-soluble I-III-VI type quantum dot nano material, a nitrogen-containing organic solvent and a modifier, and carrying out post-treatment to obtain the water-soluble I-III-VI type quantum dot nano material.
9. The preparation method according to claim 8, wherein the water-soluble type I-III-VI quantum dot nanomaterial has a negatively charged surface with a potential of (-15) — (-10) mV, such as-13.4 ± 1.5 mV;
the nitrogen-containing organic solvent is any one or more of N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide and N, N-diethylacetamide;
the modifier is preferably Glutathione (GSH) or 3-mercaptopropionic acid (MPA);
in the reaction system, the molar ratio of the oil-soluble I-III-VI type quantum dot nano material to the modifier is 1 (1-5), preferably 1 (1-3);
in the reaction system, the mass volume ratio of the oil-soluble I-III-VI type quantum dot nano material to the nitrogen-containing organic solvent is 1g (1-50) mL, preferably 1g (10-40) mL;
the temperature of the modification reaction is 100-200 ℃, and preferably 100-150 ℃;
the reaction time is 5-30 min, preferably 10-15 min.
10. The use of the type I-III-VI quantum dot nanomaterials of any one of claims 1 to 3 in the field of biotechnology;
preferably in biological detection and biological imaging;
more preferably, the I-III-VI type quantum dot nano material is used as a fluorescent nano probe to be applied to ATP detection and human body normal cell and tumor cell imaging.
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