CN114671898B - Luminescence-enhanced aqueous phase detection Bi 3+ Preparation method of luminescent crystal material - Google Patents
Luminescence-enhanced aqueous phase detection Bi 3+ Preparation method of luminescent crystal material Download PDFInfo
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- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 32
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
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- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
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- 238000000504 luminescence detection Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention provides a luminescence-enhanced aqueous phase detection Bi 3+ Is [ Cd (NDA) (3-L) (H) 2 O)] n The preparation method comprises the steps of adding cadmium chloride, 1, 4-naphthalenedicarboxylic acid and 9-di (3-pyridine) ethylene-fluorene into a mixed solution of water and acetonitrile, stirring to obtain a mixed solution, placing the mixed solution into a closed reaction kettle, heating for reaction, slowly cooling to room temperature, filtering, washing and drying the product to obtain the luminescent crystal material. The invention firstly obtains the high-sensitivity luminescence-enhanced aqueous phase detection Bi 3+ Of (2) a luminescent crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n The synthetic route is simple and easy to control, and is suitable for industrial production, and the obtained material [ Cd (NDA) (3-L) (H) is prepared 2 O)] n The yield can reach 60 percent at most. Enhancement constant K sv ＝‑5.3×10 4 M ‑1 The detection limit is 1.87 multiplied by 10 ‑5 mM。
Description
Technical Field
The invention belongs to the technical field of luminescence detection crystal materials, and particularly relates to luminescence-enhanced aqueous phase detection Bi 3+ The method for preparing a luminescent crystal material of (1).
Background
Trivalent metal bismuth ion (Bi) 3+ ) The compound can be widely applied to the pharmaceutical industry, such as antibacterial agent, anti-HIV agent, anti-ulcer agent, radiotherapeutic agent, etc. However, an excess of Bi 3+ Will pose a threat to human health and the ecological environment. Bi in soil 3+ Concentrations above 0.416g/kg will affect the rate and quantity of earthworms, and thus the soil aeration and soil porosity. And Bi 3+ The half-life is long and may accumulate in the kidney leading to renal disease. Therefore, search forHigh-efficiency detection of Bi 3+ The material of (2) appears to be of great importance.
Current detection of Bi 3+ Has few luminescent materials and sensitive luminescence-enhanced water-phase detection Bi 3+ The luminescent crystal material of (3) has not been reported. Thus developing sensitive luminescence-enhanced aqueous phase detection of Bi 3+ The preparation method and the product of the luminescent crystal material have important significance.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above problems occurring in the prior art.
Therefore, the present invention aims to provide a luminescence-enhanced aqueous phase detection method for Bi 3+ A method for preparing the luminescent crystal material.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: luminescence-enhanced aqueous phase detection Bi 3+ The method for preparing a luminescent crystal material of (1), comprising,
cadmium chloride and 1, 4-naphthalene dicarboxylic acid (H) 2 NDA) and 9-di (3-pyridine) ethylene-fluorene (3-L) are added into a mixed solvent and stirred to prepare a mixed solution;
placing the mixed solution in a closed reaction kettle for heating reaction, slowly cooling to room temperature, filtering, ultrasonically washing, and drying to obtain luminescent crystal material [ Cd (NDA) (3-L) (H) 2 O)] n 。
As the luminescence enhancement water phase of the invention detects Bi 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: the cadmium chloride and the 1, 4-naphthalene dicarboxylic acid (H) 2 NDA) and 9-bis (3-pyridine) ethylene-fluorene (3-L) in a molar ratio of 1:1:0.25 to 0.75.
Luminescence-enhanced aqueous phase detection as described in the present inventionBi 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: the volume ratio of water to acetonitrile in the mixed solvent is 1: 0.5-2.
As the luminescence enhancement water phase of the invention detects Bi 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: the volume of the mixed solvent required by adding 0.1mmol of cadmium chloride is 4-8 mL.
Detection of Bi as the luminescence-enhanced aqueous phase of the invention 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: the heating reaction is carried out at the heating temperature of 130-150 ℃ for 24-72 h.
Detection of Bi as the luminescence-enhanced aqueous phase of the invention 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: the cooling rate of the temperature to the room temperature is 2-5 ℃/h.
Detection of Bi as the luminescence-enhanced aqueous phase of the invention 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: and ultrasonic washing, wherein the volume ratio of washing solvent water to acetonitrile is 1: 0.5-2 of mixture, 50Hz of ultrasonic power and 5-10 min of ultrasonic time. .
Detection of Bi as the luminescence-enhanced aqueous phase of the invention 3+ A preferable embodiment of the method for producing a luminescent crystal material of (1), wherein: and the drying comprises vacuum drying or room temperature drying, wherein the drying temperature is 50-80 ℃, and the drying time is 3-10 min.
As the luminescence enhancement water phase of the invention detects Bi 3+ The material [ Cd (NDA) (3-L) (H) prepared by the preparation method of the luminescent crystal material 2 O)] n Wherein n is not limited in scope.
As the material [ Cd (NDA) (3-L) (H) of the present invention 2 O)] n A preferred embodiment of (1), wherein: the material [ Cd (NDA) (3-L) (H) 2 O)] n Detection of Bi in solution 3+ Has an enhancement constant of-5.3X 10 4 M -1 The detection limit is 1.87 multiplied by 10 -5 mM。
The invention has the beneficial effects that:
the invention provides a luminescence-enhanced aqueous phase detection Bi 3+ Is [ Cd (NDA) (3-L) (H) 2 O)] n Adding cadmium chloride, 1, 4-naphthalene dicarboxylic acid and 9-bis (3-pyridine) ethylene-fluorene into a mixed solution of water and acetonitrile, stirring to prepare a mixed solution, placing the mixed solution into a closed reaction kettle, heating for reaction, slowly cooling to room temperature, filtering, washing and drying the product to obtain the luminescent crystal material. The invention obtains the high-sensitivity luminescence-enhanced aqueous phase detection Bi for the first time 3+ Is [ Cd (NDA) (3-L) (H) 2 O)] n The synthetic route is simple and easy to control, and is suitable for industrial production, and the obtained material [ Cd (NDA) (3-L) (H) is prepared 2 O)] n The yield can reach 60 percent at most. Enhancement constant K sv ＝-5.3×10 4 M -1 The detection limit is 1.87 multiplied by 10 -5 mM。
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 shows a crystal material [ Cd (NDA) (3-L) (H) 2 O)] n Two-dimensional crystal structure diagram (hydrogen atom is omitted);
FIG. 2 shows the crystalline material [ Cd (NDA) (3-L) (H) thus prepared 2 O)] n Powder X-ray diffraction pattern of (a);
FIG. 3 shows 2.5ml of crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n The stimulated emission spectrum of the aqueous suspension of (0.2 g/ml);
FIG. 4 shows 2.5mL of crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n To an aqueous suspension (0.2 mg/mL) of (A) was added Bi in different volumes 3+ The luminous intensity change curve of the aqueous solution (2 mmol/L);
FIG. 5 shows a crystal material [ Cd (NDA) (3-L) (H) 2 O)] n Detection of Bi 3+ The enhancement constant curve of (2);
FIG. 6 shows a crystal material [ Cd (NDA) (3-L) (H) 2 O)] n Detection of Bi 3+ The detection limit curve of (2).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, the references herein to "one embodiment" or "an embodiment" refer to a particular feature, structure, or characteristic that may be included in at least one implementation of the present invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The chemical reagents used in the examples of the present invention are all commercially available analytical reagents unless otherwise specified.
The yield calculation method in the embodiment of the invention comprises the following steps: calculating the yield based on Cd, wherein the calculating steps are as follows:
the 9-bis (3-pyridine) ethylene-fluorene used in the examples is prepared by a laboratory, and the specific preparation process is as follows:
adding 9-fluorenone, carbon tetrabromide and triphenylphosphine into anhydrous dichloromethane, heating to 30-60 ℃ under the protection of nitrogen, reacting for 12-36 hours, cooling after the reaction is finished, obtaining a crude product by adopting a column chromatography method and using normal hexane as an eluent, and finally recrystallizing by using normal hexane to obtain a yellow product, namely 9-dibromoethylene-fluorene;
adding 9-dibromoethene-fluorene, 3-pyridine boric acid, anhydrous sodium carbonate, triphenylphosphine and a palladium acetate catalyst into a mixed solution of 1, 4-dioxane and water, heating to 100-140 ℃ under the protection of nitrogen, reacting for 10-20 hours, extracting for 3 times by using ethyl acetate after the reaction is finished, collecting an organic layer, drying by using anhydrous sodium sulfate, reducing pressure, performing rotary evaporation, and performing column chromatography by using ethyl acetate: petroleum ether (V: V = 1) as eluent gave a crude product which was washed with ethyl acetate to give the light yellow product 9-bis (3-pyridine) etheno-fluorene.
Example 1:
adding 0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.025mmol of 9-bis (3-pyridine) etheno-fluorene to 6mL of water and acetonitrile (V: V = 1) and stirring to prepare a mixed solution;
heating the prepared mixed solution in a closed reaction kettle to 140 ℃ for 72H, slowly cooling to room temperature at the speed of 5 ℃/H, filtering, ultrasonically washing with a mixed solution of acetonitrile and water, and drying in an oven at 60 ℃ for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 40 percent.
Example 2:
adding 0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.05mmol of 9-bis (3-pyridine) ethylene-fluorene into 6mL of water and acetonitrile (V: V = 1) and stirring to prepare a mixed solution;
heating the obtained mixed solution in a sealed reaction kettle to 140 deg.C for 72H, slowly cooling to room temperature at a rate of 5 deg.C/H, filtering, ultrasonically washing with mixed solution of acetonitrile and water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 60 percent.
Example 3:
adding 0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.075mmol of 9-bis (3-pyridine) ethenyl-fluorene to 6mL of water and acetonitrile (V: V = 1) and stirring to prepare a mixed solution;
heating the obtained mixed solution in a closed reaction kettle to 140 deg.C for 72h, slowly cooling to room temperature at a rate of 5 deg.C/h, filtering, and adding acetonitrileUltrasonic washing with water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: and 55 percent.
Example 4:
0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.05mmol of 9-bis (3-pyridine) etheno-fluorene are added to 6mL of water and acetonitrile (V: V = 1) and stirred to prepare a mixed solution;
heating the obtained mixed solution in a sealed reaction kettle to 140 deg.C for 24H, slowly cooling to room temperature at a rate of 5 deg.C/H, filtering, ultrasonically washing with mixed solution of acetonitrile and water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 40 percent.
Example 5:
0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.05mmol of 9-bis (3-pyridine) etheno-fluorene are added to 6mL of water and acetonitrile (V: V = 1) and stirred to prepare a mixed solution;
heating the obtained mixed solution in a sealed reaction kettle to 140 deg.C for 48H, slowly cooling to room temperature at 5 deg.C/H, filtering, ultrasonically washing with mixed solution of acetonitrile and water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 45 percent.
Example 6:
adding 0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.05mmol of 9-bis (3-pyridine) ethylene-fluorene into 6mL of water and acetonitrile (V: V = 1) and stirring to prepare a mixed solution;
heating the obtained mixed solution in a sealed reaction kettle to 130 deg.C for 72H, slowly cooling to room temperature at 5 deg.C/H, filtering, ultrasonically washing with mixed solution of acetonitrile and water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 50 percent.
Example 7:
adding 0.1mmol of cadmium chloride, 0.1mmol of 1, 4-naphthalenedicarboxylic acid and 0.05mmol of 9-bis (3-pyridine) ethylene-fluorene into 6mL of water and acetonitrile (V: V = 1) and stirring to prepare a mixed solution;
heating the obtained mixed solution in a sealed reaction kettle to 150 deg.C for 72H, slowly cooling to room temperature at 5 deg.C/H, filtering, ultrasonically washing with mixed solution of acetonitrile and water at 50Hz for 10min, and drying in oven at 60 deg.C for 5min to obtain [ Cd (NDA) (3-L) (H) 2 O)] n A crystalline material. The calculated yield was: 30 percent.
Bi 3+ Detecting performance: 5mg of the prepared crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n Dispersing in 25 mL of water to obtain a stable suspension, adding different Bi-containing volumes to the suspension 3+ Was measured for its fluorescence intensity under excitation light of 320nm, respectively (2 mmol/L).
The crystal material [ Cd (NDA) (3-L) (H) prepared by the invention 2 O)] n The powder X-ray diffraction pattern is basically consistent with the X-ray diffraction pattern calculated by theory, which shows that the crystal material prepared by the invention has high purity. Soaking in Bi 3+ The powder X-ray diffraction pattern after 24h of the aqueous solution is basically consistent with the X-ray diffraction pattern calculated by theory, which indicates that the crystal material is in Bi 3+ Has good stability in aqueous solution.
FIG. 4 shows 2.5mL of crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n To an aqueous suspension (0.2 mg/mL) of (A) was added Bi in different volumes 3+ Graph showing the change in luminescence intensity of an aqueous solution (2 mmol/L). The fluorescence intensity of an aqueous suspension of the crystalline material was measured at an excitation wavelength of 320nm, and then 2mmol/L of Bi was gradually added dropwise thereto 3+ Aqueous solution with Bi 3+ The quantity is increased gradually, and the luminous intensity of the suspension is increased gradually.
This may be advantageous in Bi 3+ And a pi-cation-pi filling model is formed between the fluorene rings, so that electron transition in a framework is facilitated, and the emission intensity is increased. With Bi 3+ The increase of the concentration, the Pi-cation-Pi filling model generated in the framework is increased continuously, which is beneficial to improving the selection efficiency and correspondingly leading to the increase of the emission intensity.
The invention providesProvides a luminescence enhanced water phase detection Bi 3+ Is [ Cd (NDA) (3-L) (H) 2 O)] n The preparation method comprises the steps of adding cadmium chloride, 1, 4-naphthalenedicarboxylic acid and 9-di (3-pyridine) ethylene-fluorene into a mixed solution of water and acetonitrile, stirring to obtain a mixed solution, placing the mixed solution into a closed reaction kettle, heating for reaction, slowly cooling to room temperature, filtering, washing and drying the product to obtain the luminescent crystal material. The invention obtains the high-sensitivity luminescence-enhanced aqueous phase detection Bi for the first time 3+ Of (2) a luminescent crystalline material [ Cd (NDA) (3-L) (H) 2 O)] n The synthetic route is simple and easy to control, and is suitable for industrial production, and the obtained material [ Cd (NDA) (3-L) (H) is prepared 2 O)] n The yield can reach 60 percent at most. Enhancement constant K sv ＝-5.3×10 4 M -1 The detection limit is 1.87 multiplied by 10 -5 mM。
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. Luminescence-enhanced aqueous phase detection Bi 3+ The preparation method of the luminescent crystal material comprises the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
cadmium chloride and 1, 4-naphthalene dicarboxylic acid (H) 2 NDA) and 9-di (3-pyridine) ethylene-fluorene (3-L) are added into a mixed solvent and stirred to prepare a mixed solution;
placing the mixed solution in a closed reaction kettle for heating reaction, slowly cooling to room temperature, filtering, ultrasonically washing, and drying to obtain luminescent crystal material [ Cd (NDA) (3-L) (H) 2 O)] n 。
2. The luminescence-enhanced aqueous phase assay of claim 1 Bi 3+ The preparation method of the luminescent crystal material is characterized in that: the cadmium chloride and 1, 4-naphthalene dicarboxylic acid (H) 2 NDA) and 9-bis (3-pyridine) ethylene-fluorene (3-L) in a molar ratio of 1:1:0.25 to 0.75.
3. The luminescence-enhanced aqueous phase detection of Bi of claim 1 3+ The preparation method of the luminescent crystal material is characterized in that: the volume ratio of water to acetonitrile in the mixed solvent is 1:0.5 to 2.
4. The luminescence-enhanced aqueous phase assay Bi of claim 1 or 3 3+ The preparation method of the luminescent crystal material is characterized in that: the volume of the mixed solvent required by adding 0.1mmol of cadmium chloride is 4-8 mL.
5. The luminescence-enhanced aqueous phase assay of claim 1 Bi 3+ The preparation method of the luminescent crystal material is characterized in that: and (3) carrying out heating reaction at the temperature of 130-150 ℃ for 24-72 h.
6. The luminescence-enhanced aqueous phase assay of claim 1 Bi 3+ The preparation method of the luminescent crystal material is characterized in that: the cooling rate of cooling to the room temperature is 2-5 ℃/h.
7. The luminescence-enhanced aqueous phase assay of claim 1 Bi 3+ The preparation method of the luminescent crystal material is characterized in that: and ultrasonic washing, wherein the volume ratio of washing solvent water to acetonitrile is 1:0.5 to 2 mixtures, 50Hz of ultrasonic power and 5 to 10min of ultrasonic time.
8. The luminescence-enhanced aqueous phase assay of claim 1 Bi 3+ The preparation method of the luminescent crystal material is characterized in that: and the drying comprises vacuum drying or room temperature drying, wherein the drying temperature is 50 to 80 ℃, and the drying time is 3 to 10min.
9. The luminescence-enhanced aqueous phase detection Bi according to any one of claims 1 to 8 3+ The material [ Cd (NDA) (3-L) prepared by the method)(H 2 O)] n Wherein n is not limited in scope.
10. The material [ Cd (NDA) (3-L) (H) according to claim 9 2 O)] n The method is characterized in that: the material [ Cd (NDA) (3-L) (H) 2 O)] n Detection of Bi in solution 3+ Has an enhancement constant of-5.3X 10 4 M -1 The detection limit is 1.87 multiplied by 10 -5 mM。
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