CN113292586B - Hybrid material and application thereof in lipoic acid single-molecule quantitative detection - Google Patents
Hybrid material and application thereof in lipoic acid single-molecule quantitative detection Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 235000019136 lipoic acid Nutrition 0.000 title claims abstract description 39
- 229960002663 thioctic acid Drugs 0.000 title claims abstract description 39
- 238000001514 detection method Methods 0.000 title claims abstract description 16
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 title abstract 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 43
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- AGBQKNBQESQNJD-UHFFFAOYSA-N lipoic acid Chemical compound OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 15
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000001448 anilines Chemical class 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 5
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- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
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- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims 1
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
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- 239000007788 liquid Substances 0.000 description 5
- FEUATHOQKVGPEK-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarbaldehyde Chemical compound OC1=CC=C(C=O)C=C1C=O FEUATHOQKVGPEK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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Abstract
The invention discloses a hybrid material and application thereof in lipoic acid single-molecule quantitative detection, wherein the hybrid material is prepared by carrying out esterification reaction on diimine and oil-soluble carbon quantum dots with carboxyl groups on the surface according to the molar ratio of 1: 1; the diimine has the structure shown as follows:
the organic components in the hybrid material fluorescent probe enhance the absorption of the excitation light energy, and transfer the absorbed energy to the carbon quantum dots to enhance the luminous intensity of the carbon quantum dots. The lipoic acid is added into the hybrid material, the disulfide bond and the carboxyl of the lipoic acid can form hydrogen bonds with the hybrid material, the binding force between the hybrid material and lipoic acid molecules is enhanced, the quantitative detection of the lipoic acid is realized, and the lipoic acid has higher sensitivity compared with a high performance liquid chromatography.
Description
Technical Field
The invention relates to the field of fluorescent probes, in particular to a hybrid material and application thereof in lipoic acid single-molecule quantitative detection.
Background
Lipoic acid, also known as alpha-lipoic acid, is a substance essential for the growth of certain bacteria and plants and is called a potato growth factor; lipoic acid has been discovered as early as the 19 th century, and in recent years, the role of lipoic acid in energy, sugar metabolism and health care has been widely noticed by people and applied to the adjuvant treatment of diabetes and complications thereof; in the prior art, lipoic acid is generally quantitatively detected by a high performance liquid chromatography, and in the analysis of actual samples, the high performance liquid chromatography needs a complex sample pretreatment process, is long in time consumption, high in cost, relatively low in sensitivity and low in analysis speed; at present, no method for quantitatively detecting the content of the compound by using a fluorescent probe exists.
The single-molecule fluorescence detection technology has made great progress in recent years and is widely applied to the field of quantitative detection, the single-molecule detection refers to a novel ultra-sensitive detection means for detecting on a single-molecule level, and compared with the traditional fluorescence method, the single-molecule fluorescence detection has the advantages of high sensitivity, less sample consumption, high signal-to-noise ratio and the like, and can detect and image single molecules.
Disclosure of Invention
Aiming at the problems, the invention provides a hybrid material and application thereof in lipoic acid single-molecule quantitative detection.
The invention aims to provide a hybrid material which is prepared by carrying out esterification reaction on diimine and oil-soluble carbon quantum dots containing carboxyl on the surface according to the molar ratio of 1: 1; the diimine has the structure shown as follows:
further, the preparation of the diimine comprises the following steps:
(1) mixing and dissolving 4-hydroxy m-phthalaldehyde and 2- (2-aminobenzene) benzothiazole, carrying out a ketone-ammonia condensation reaction under the action of a catalyst, and carrying out post-treatment to obtain a unilateral substituted imine compound A;
(2) mixing and dissolving the unilateral-substituted imine compound A and the aniline derivative B, carrying out a ketone-ammonia condensation reaction under the action of a catalyst, and carrying out post-treatment to obtain diimine C.
Further, in the step (1), the structure of the one-side substituted imine compound a is as follows:
further, in the step (1), the reaction molar ratio of the 4-hydroxyisophthalaldehyde to the 2- (2-aminobenzene) benzothiazole is 1:1.
Further, in the step (2), the structures of the aniline derivative B and the diimine C are shown as follows:
further, in the step (2), the reaction molar ratio of the mono-substituted imine compound a to the aniline derivative B is 1:1.
Further, the particle size of the oil-soluble carbon quantum dot with the carboxyl on the surface is 1-10 nm.
Further, the preparation of the oil-soluble carbon quantum dots containing carboxyl on the surface comprises the following steps:
dissolving organic carboxylic acid and organic amine in a solvent, adding a catalyst, heating and stirring to obtain the oil-soluble carbon quantum dot with the surface containing carboxyl.
Further, the organic carboxylic acid is one of succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid and 2-methyl-4-ethyl adipic acid.
Further, the organic amine is one of dodecylamine, octadecylamine, o-toluidine, p-butylaniline and p-chloroaniline.
Further, the catalyst is one of triethylamine, pyridine and triethylene diamine.
Further, the solvent is one of toluene, tetrahydrofuran, 1,4 dioxane and ethyl acetate.
Further, the molar ratio of the organic carboxylic acid to the organic amine is 1:1.
The invention also aims to provide a preparation method of the hybrid material, which comprises the following steps:
(1) oil-soluble carbon quantum dots containing carboxyl on the surface and SOCl2Mixing, heating and stirring to obtain solid for later use.
(2) And (3) dropwise adding the dissolved solid prepared in the step (1) and pyridine into diimine, and heating and stirring to obtain the hybrid material.
Further, in the step (1), the oil-soluble carbon quantum dots with carboxyl groups on the surfaces and SOCl2The reaction molar ratio of (a) to (b) is 1: 1.2-2.
Further, in the step (2), the reaction molar ratio of the solid prepared in the step (1) to the diimine is 1:1.
The invention also aims to provide the application of the hybrid material in the single-molecule quantitative detection of lipoic acid.
Further, the steps of applying the hybrid material to the lipoic acid single-molecule quantitative detection are as follows: adding lipoic acid into the hybrid material for fluorescence detection, carrying out fluorescence excitation at 10-400 nm, and recording a fluorescence signal at 400-600 nm.
Further, when the hybrid material is applied to the quantitative detection of the lipoic acid single molecule, the pH value is 6-9.
Preferably, when the hybrid material is applied to the lipoic acid single-molecule quantitative detection, the pH value is 7.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lipoic acid is quantitatively detected by utilizing the hybrid material fluorescent probe, the absorption of the organic components in the hybrid material fluorescent probe on the energy of exciting light is enhanced, the absorbed energy is transferred to the carbon quantum dots, and the luminous intensity of the carbon quantum dots is enhanced.
(2) The lipoic acid is added into the hybrid material, the disulfide bond and the carboxyl of the lipoic acid can form hydrogen bonds with the hybrid material, the binding force between the hybrid material and lipoic acid molecules is enhanced, the quantitative detection of the lipoic acid is realized, and the lipoic acid has higher sensitivity compared with a high performance liquid chromatography.
Drawings
FIG. 1 shows the excitation and emission fluorescence spectra of a mixed solution of the hybrid material prepared in example 14 and dichloromethane.
FIG. 2 is a graph showing the change of fluorescence emission intensity of the hybrid material prepared in example 14 at different concentrations of lipoic acid.
FIG. 3 is a calculated graph of the detection limit of lipoic acid for the hybrid materials prepared in example 14.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 4-hydroxy isophthalaldehyde (5mmol), 2- (2-aminobenzene) benzothiazole (5mmol) and a proper amount of p-toluenesulfonic acid into a 150mL flask with a branch mouth, adding 50mL of toluene, carrying out reflux reaction at 110 ℃ for 12 hours, separating a crude product through a silica gel column, eluting a eluent (petroleum ether/ethyl acetate ═ 10:1), and recrystallizing in ethanol to obtain the unilaterally substituted imine compound A, wherein the yield is 70.3%.
Example 2
Adding a unilaterally substituted imine compound A (5mmol), an aniline derivative B (5mmol) and a proper amount of p-toluenesulfonic acid into a 150mL flask with a branch mouth, adding 50mL of toluene, carrying out reflux reaction at 110 ℃ for 12 hours, separating a crude product through a silica gel column, eluting a eluent (petroleum ether/ethyl acetate 15:1), and recrystallizing with ethanol to obtain a diimine compound C with the yield of 76.4%,1H-NMR(400MHz,CCl3D),δ(ppm):11.23(s,1H,OH),8.59(s,1H,CH),8.57(s,1H,NH),8.43(s,1H,CH),8.27(s,1H,ArH),8.02-7.97(m,2H,ArH),7.79(d,1H,ArH),7.70(m,2H,ArH),7.56-7.44(m,5H,ArH),7.35(d,1H,ArH),7.20(d,1H,ArH),6.99(d,1H,CH),6.92(d,1H,CH),6.81(s,1H,ArH),6.67(d,1H,ArH),6.05-6.03(m,2H,CH),3.69(t,2H,CH2),3.52(m,4H,CH2),2.16(s,6H,CH3),2.10(s,3H,CH3),1.12(t,3H,CH3)。
example 3
Adding 5mol of adipic acid, 5mol of octadecylamine, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing an eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dot with carboxyl on the surface, wherein the particle size is 5 nm.
Example 4
Adding 5mol of phthalic acid, 5mol of octadecylamine, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots with carboxyl on the surface, wherein the particle size is 7 nm.
Example 5
Adding 2-methyl-4-ethyl adipic acid 5mol, octadecylamine 5mol, pyridine 2mL and toluene 20mL into a 50mL pressure-resistant bottle, stirring at 180 ℃ for reaction for 6 hours, separating the crude product through a silica gel column, eluting a liquid (petroleum ether/ethyl acetate is 10:1), removing the eluting liquid by rotary evaporation, and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dot with carboxyl on the surface, wherein the particle size is 6 nm.
Example 6
Adding 5mol of adipic acid, 5mol of o-toluidine, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots with carboxyl on the surface, wherein the particle size is 6 nm.
Example 7
Adding 5mol of phthalic acid, 5mol of o-toluidine, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots with carboxyl on the surface, wherein the particle size is 7 nm.
Example 8
Adding 2-methyl-4-ethyl adipic acid 5mol, o-toluidine 5mol, pyridine 2mL and toluene 20mL into a 50mL pressure-resistant bottle, stirring at 180 ℃ for reaction for 6 hours, separating the crude product through a silica gel column, eluting a liquid (petroleum ether/ethyl acetate is 10:1), removing the eluent by rotary evaporation, and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots containing carboxyl on the surface, wherein the particle size is 8 nm.
Example 9
Adding 5mol of adipic acid, 5mol of parachloroaniline, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots with carboxyl on the surface, wherein the particle size is 5 nm.
Example 10
Adding 5mol of phthalic acid, 5mol of parachloroaniline, 2mL of pyridine and 20mL of toluene into a 50mL pressure-resistant bottle, stirring and reacting for 6 hours at 180 ℃, separating a crude product through a silica gel column, removing eluent by rotary evaporation (petroleum ether/ethyl acetate is 10:1), and drying in vacuum at 45 ℃ to obtain oil-soluble carbon quantum dots with carboxyl on the surface, wherein the particle size is 9 nm.
Example 11
Adding 2-methyl-4-ethyl adipic acid 5mol, p-chloroaniline 5mol, pyridine 2mL and toluene 20mL into a 50mL pressure-resistant bottle, stirring and reacting at 180 ℃ for 6 hours, separating the crude product through a silica gel column, eluting a liquid (petroleum ether/ethyl acetate is 10:1), removing the eluting liquid by rotary evaporation, and drying in vacuum at 45 ℃ to obtain the oil-soluble carbon quantum dots containing carboxyl on the surface, wherein the particle size is 8 nm.
Example 12
Step 1, mixing 5mmol of oil-soluble carbon quantum dots containing carboxyl on the surface prepared in example 3 with 30mL of anhydrous tetrahydrofuran, heating to 65 ℃, and dropwise adding 6mmol of SOCl2And after reacting for 3 hours, carrying out reduced pressure distillation to obtain a solid for later use.
Step 2.N2Under protection, mixing 5mmol of diimine and 30mL of anhydrous toluene, heating to 60 ℃, dropwise adding 1mL of pyridine and 5mmol of solid dissolved in toluene and obtained in the step 1, heating to 75 ℃, cooling the product to room temperature, filtering, and vacuum-drying at 45 ℃ to obtain the hybrid material.
Example 13
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 4, and the rest of the steps are the same as those in example 12.
Example 14
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 5, and the rest of the steps are the same as those in example 12.
Example 15
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 6, and the rest of the steps are the same as those in example 12.
Example 16
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 7, and the rest of the steps are the same as those in example 12.
Example 17
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 8, and the rest of the steps are the same as those in example 12.
Example 18
The oil-soluble carbon quantum dots with surface carboxyl groups prepared in example 3 of example 12 were replaced with the oil-soluble carbon quantum dots with surface carboxyl groups prepared in example 9, and the rest of the procedure was the same as in example 12.
Example 19
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces, which are prepared in example 3 of example 12, are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces, which are prepared in example 10, and the rest of the steps are the same as example 12.
Example 20
The oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 3 of example 12 are replaced by the oil-soluble carbon quantum dots with carboxyl groups on the surfaces prepared in example 11, and the rest of the steps are the same as those in example 12.
Examples 21 to 29
The hybrid materials synthesized in examples 12-20 were mixed with dichloromethane to prepare 5mL of mixed solutions, the concentrations of the hybrid materials were 10mM, and the pH of the mixed solution was 7.
The mixed solutions of the hybrid materials prepared in examples 12 to 20 and dichloromethane were respectively subjected to fluorescence tests, the hybrid materials were excited at an excitation wavelength of 352nm, and the relative fluorescence intensities of the mixed solutions of the hybrid materials prepared in examples 12 to 20 and dichloromethane were recorded, and the results are shown in table 1.
Example 30
Example 14 sensitivity test of the prepared hybrid material fluorescent probe to lipoic acid:
the preparation of the mixed solution of the hybrid fluorescent probe prepared in example 14 is the same as that in example 21, and lipoic acid is gradually added dropwise to the total system to make the concentrations thereof reach 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 8.0, 10.0 and 15.0(μ g/mL) respectively as the total system of the detection reaction; with 352nm as the fluorescence excitation wavelength, as can be seen from fig. 2, the fluorescence intensity at 436nm shows an increasing trend with the increase of the lipoic acid concentration, and when the lipoic acid concentration is increased to 8.0 mug/mL, the fluorescence intensity is saturated and basically remains unchanged; FIG. 3 shows the relationship between the fluorescent intensity of a solution with a lipoic acid concentration less than 3.0 mug/mL at 436nm fluorescence emission and the lipoic acid concentration, and the linear relationship between the fluorescent intensity and the lipoic acid concentration is good (R is a linear relationship between the fluorescent intensity and the lipoic acid concentration)20.9902), the fitted linear equation is y 39550x +2095, which shows that the fluorescent probe has better sensing property to the lipoic acid and can realize the quantitative detection of the lipoic acid.
Comparative examples 1 to 9
And mixing the oil-soluble carbon quantum dots with carboxyl groups on the surfaces, which are prepared in the embodiments 3-11, with dichloromethane to prepare 5mL of mixed solution, wherein the concentrations of the oil-soluble carbon quantum dots with carboxyl groups on the surfaces are respectively 10mM, and the pH of the mixed solution is 7.
Fluorescence tests were performed on the oil-soluble carbon quantum dots containing carboxyl groups on the surfaces prepared in examples 3 to 11 and dichloromethane in a mixed manner, the hybrid material was excited at an excitation wavelength of 352nm, and the relative fluorescence intensity of the mixed solution of the hybrid material prepared in examples 3 to 11 and dichloromethane was recorded, and the results are shown in table 1.
TABLE 1 relative fluorescence intensities for examples 21-29 and comparative examples 1-9.
Finally, it should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the modifications and equivalents of the specific embodiments of the present invention can be made by those skilled in the art after reading the present specification, but these modifications and variations do not depart from the scope of the claims of the present application.
Claims (5)
1. The hybrid material is characterized by being prepared by carrying out esterification reaction on diimine and oil-soluble carbon quantum dots containing carboxyl on the surface according to the molar ratio of 1: 1; the diimine has the structure shown as follows:
the preparation method of the oil-soluble carbon quantum dot with the carboxyl on the surface comprises the following steps:
dissolving organic carboxylic acid and organic amine in a solvent, adding a catalyst, heating and stirring to obtain oil-soluble carbon quantum dots with carboxyl on the surface;
the organic carboxylic acid is one of succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid and 2-methyl-4-ethyl adipic acid;
the organic amine is one of dodecylamine, octadecylamine, o-toluidine, p-butylaniline and p-chloroaniline;
the catalyst is one of triethylamine, pyridine and triethylene diamine;
the solvent is one of toluene, tetrahydrofuran, 1,4 dioxane and ethyl acetate;
the molar ratio of the organic carboxylic acid to the organic amine is 1:1.
2. The hybrid material according to claim 1, wherein the preparation of the diimine comprises the steps of:
(1) mixing and dissolving 4-hydroxy m-phthalaldehyde and 2- (2-aminobenzene) benzothiazole, carrying out a ketone-ammonia condensation reaction under the action of a catalyst, and carrying out post-treatment to obtain a unilateral substituted imine compound A;
(2) mixing and dissolving a unilaterally substituted imine compound A and an aniline derivative B, carrying out a ketoamine condensation reaction under the action of a catalyst, and carrying out post-treatment to obtain diimine C;
the structure of the mono-substituted imine compound a is shown below:
the structures of the aniline derivative B and the diimine C are shown as follows:
3. the hybrid material according to claim 1, wherein the oil-soluble carbon quantum dots having carboxyl groups on the surface have a particle size of 1-10 nm.
4. A method for preparing the hybrid material according to claim 1, comprising the steps of:
(1) oil-soluble carbon quantum dots containing carboxyl on the surface and SOCl2Mixing, heating and stirring to obtain solid for later use;
(2) and (3) dropwise adding the dissolved solid prepared in the step (1) and pyridine into diimine, and heating and stirring to obtain the hybrid material.
5. The use of the hybrid material of claim 1 in the preparation of a lipoic acid single-molecule quantitative detection reagent.
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