CN117945988A - Organic ion salt with electrochemiluminescence effect and preparation method and application thereof - Google Patents
Organic ion salt with electrochemiluminescence effect and preparation method and application thereof Download PDFInfo
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- -1 ion salt Chemical class 0.000 title claims abstract description 63
- 230000000694 effects Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000012984 biological imaging Methods 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 150000003222 pyridines Chemical class 0.000 claims description 11
- GYJBDJGUNDKZKO-UHFFFAOYSA-N 4-(4-bromophenyl)pyridine Chemical compound C1=CC(Br)=CC=C1C1=CC=NC=C1 GYJBDJGUNDKZKO-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229940087646 methanolamine Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- MWBUZYJXQFGQJI-UHFFFAOYSA-N 1,3,5-trihexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC(CCCCCCCCCCCCCCCC)=CC(CCCCCCCCCCCCCCCC)=C1 MWBUZYJXQFGQJI-UHFFFAOYSA-N 0.000 claims 1
- 239000003550 marker Substances 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 231100000086 high toxicity Toxicity 0.000 abstract description 8
- 239000002096 quantum dot Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005349 anion exchange Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 9
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001378 electrochemiluminescence detection Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- MQRWPMGRGIILKQ-UHFFFAOYSA-N sodium telluride Chemical compound [Na][Te][Na] MQRWPMGRGIILKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention discloses a preparation method of organic ion salt with electrochemiluminescence effect. The method comprises the following steps: preparing 1,3, 5-tri (4-pyridylphenylethynyl) benzene, preparing corresponding trivalent pyridinium ion salt, and performing anion exchange to obtain the trivalent pyridinium ion salt with hexafluorophosphate anions. The beneficial effects of the invention are as follows: the preparation method has the advantages of high synthesis yield, stable chemical property, simple preparation method and the like; the prepared organic ion salt has the characteristics of low toxicity and low pollution, and belongs to cathode electrochemiluminescence materials, so that common inorganic quantum dots with high toxicity and high pollution are avoided being used as the cathode electrochemiluminescence materials. The material can be used as a luminescent material for sensing, biological imaging and the like.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to an organic ion salt with an electrochemiluminescence effect, and a preparation method and application thereof.
Background
Electrochemiluminescence, also known as electrochemiluminescence, is a luminescence phenomenon that occurs in a solution electrochemical reaction. In electrochemiluminescence, intermediates generated by an electrochemical process undergo a high-energy-discharge reaction, producing an electron excited state, which then emits light upon relaxation to a lower energy state. This luminescence excitation is a form of chemiluminescence in which one or all of the reactants originate from an electrochemical process on the electrode. Electrochemiluminescence has become one of the research fields of great attention to analytical chemists due to the advantages of low background, high sensitivity, simple equipment, controllable potential and the like. The materials with electrochemiluminescence property which have been developed mostly belong to anode electrochemiluminescence materials, including platinum complexes, iridium complexes, small organic molecules, high molecular nano materials and the like, while materials applied to cathode electrochemiluminescence are limited to quantum dots, such as cadmium sulfide, cadmium selenide, cadmium telluride and the like, but the high toxicity and high pollution limit the application of the materials in biological detection. Therefore, development of novel non-toxic cathode electrochemiluminescence materials with biocompatibility is necessary.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide an organic ion salt with electrochemiluminescence effect, and the structural formula is shown as the formula (A):
it is still another object of the present invention to overcome the deficiencies of the prior art and to provide a method for preparing organic ionic salts having electrochemiluminescence effects.
In order to solve the technical problems, the invention provides the following technical scheme: comprising the steps of (a) a step of,
Weighing 4- (4-bromophenyl) pyridine, 1,3, 5-tri-alkynylbenzene, tetra-triphenylphosphine palladium and cuprous iodide (metal catalyst) under the protection of nitrogen, adding tetrahydrofuran and triethylamine (mixed solvent), magnetically stirring, heating, reacting for 48-60 h, decompressing and removing the solvent, and purifying by using a normal phase chromatographic column to obtain 1,3, 5-tri (4-pyridylphenylethynyl) benzene;
Weighing 1,3, 5-tri (4-pyridylphenylethynyl) benzene and excessive methyl iodide in a pressure-resistant pipe (the excessive methyl iodide can enable the reaction yield of the 1,3, 5-tri (4-pyridylphenylethynyl) benzene to be higher), taking N, N-dimethylformamide as a reaction solvent, magnetically stirring, heating, reacting for 8-12 hours, adding excessive ethyl acetate after the reaction is finished, separating out solids, filtering, continuously washing with ethyl acetate, and drying in vacuum to obtain trivalent pyridine salt;
weighing trivalent pyridine salt and excessive potassium hexafluorophosphate (providing anions and increasing the hydrophobicity of a product), taking an acetonitrile/water mixed solution as a reaction solvent, magnetically stirring, reacting for 0.5-1 h, and distilling under reduced pressure to remove acetonitrile after the reaction is finished, wherein yellow solid is separated out, so that the trivalent pyridine salt with anions of hexafluorophosphate radicals is obtained.
As a preferred embodiment of the method for preparing an organic ion salt having an electrochemiluminescence effect according to the present invention, wherein: the molar ratio of the 4- (4-bromophenyl) pyridine, the 1,3, 5-tri-alkynylbenzene, the tetra-triphenylphosphine palladium and the cuprous iodide is 4.0-4.5:1:0.05:0.05.
As a preferred embodiment of the method for preparing an organic ion salt having an electrochemiluminescence effect according to the present invention, wherein: the volume ratio of the tetrahydrofuran to the triethylamine is 1: 1-1.5,4- (4-bromophenyl) pyridine is dissolved in the mixed solvent at a concentration of 0.05-0.15 mM.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the magnetic stirring speed is 150-200 r/min, the reaction temperature is 60-65 ℃, and the eluent used for purification is dichloromethane, methanol and triethylamine, and the volume ratio is 100:2-3:1-2.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the molar ratio of the 1,3, 5-tri (4-pyridylphenylethynyl) benzene to the methyl iodide is 1:4.0 to 4.5.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the concentration of the 1,3, 5-tri (4-pyridylphenylethynyl) dissolved in N, N-dimethylformamide is 0.01-0.02 mM.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the magnetic stirring speed is 150-200 r/min, and the reaction temperature is 60-70 ℃.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the molar ratio of the trivalent pyridine salt to the potassium hexafluorophosphate is 1:4.0 to 4.5.
As a preferred embodiment of the method for preparing an organic ion salt having electrochemiluminescence effect according to the present invention, wherein: the acetonitrile to water ratio is 1:1 to 2, and the concentration of the trivalent pyridine salt dissolved in the mixed solvent is 0.01mM to 0.02mM.
The invention has the beneficial effects that:
(1) The invention provides a preparation method of organic ion salt with electrochemiluminescence effect, and the prepared organic ion salt has the characteristics of low toxicity and low pollution, belongs to cathode electrochemiluminescence materials, and avoids using common inorganic quantum dots with high toxicity and high pollution as cathode electrochemiluminescence materials. The material can be used as a luminescent material for sensing, biological imaging and the like.
(2) Compared with the prior art, the organic molecule used in the method has the advantages of high synthesis efficiency, simple synthesis method and the like. The molecule has a distinct electrochemiluminescence signal and has a lower physiological toxicity than other electrochemiluminescent substances.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a chemical reaction scheme of an organic ionic salt prepared in example 1 of the present invention;
FIG. 2 is a hydrogen spectrum of an organic ion salt prepared in example 1 of the present invention;
FIG. 3 is a fluorescent chart of the organic ion salt prepared in example 1 of the present invention;
FIG. 4 is an electrochemiluminescence diagram of the organic ion salt prepared in example 1 of the present invention.
FIG. 5 is an electrochemiluminescence diagram of the organic ion salt prepared in example 1 of the present invention at different scan rates.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
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 other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the 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 raw materials used in the invention are all commonly and commercially available without special description.
The organic ion salt prepared by the embodiment of the invention is subjected to fluorescence test according to the following method:
2mg of the organic ion salt synthesized by the method is weighed and dissolved in 1mL of acetonitrile/water mixed solvent (the volume ratio is 3:2), and the prepared solution is diluted to 0.01mg/mL to carry out fluorescence test by using a Edinburgh FLS1000 steady state/transient state fluorescence spectrometer.
The organic ion salt prepared by the embodiment of the invention adopts a Siemens Michael MPI-E electrochemiluminescence detector to carry out electrochemiluminescence determination according to the following method:
2mg of organic ion salt is weighed and dissolved in 1mL of acetonitrile/water mixed solvent (volume ratio is 3:2), 5 mu L of prepared solution is dripped on the surface of an electrode, and the electrode is left to stand and dried. In a 0.1mol/L aqueous LiClO 4 solution (containing 7mmol/L K 2S2O8 as a co-reactant), the voltage range is-1.8-0V, the scanning rate is 200mV/s, and the electrochemiluminescence-potential curve scanning is performed at a photomultiplier high voltage of 650V.
Example 1
The embodiment provides a preparation method of an organic ion salt with electrochemiluminescence effect, which is prepared according to a chemical reaction formula shown in fig. 1, and specifically comprises the following steps:
(1) 4- (4-bromophenyl) pyridine (1.053 g), 1,3, 5-tripyryl benzene (150 mg), tetraphenylphosphine palladium (58 mg) and cuprous iodide (10 mg) were weighed into a three-necked flask, respectively, at this time, the molar ratio of 4- (4-bromophenyl) pyridine, 1,3, 5-tripyryl benzene, tetraphenylphosphine palladium and cuprous iodide was 4.5:1:0.05:0.05. 45mL of mixed solvent of tetrahydrofuran and triethylamine (volume ratio is 1:1) is added under the protection of nitrogen, the reaction temperature is 60 ℃ under the magnetic stirring of 200r/min, the reaction is carried out for 48 hours, after the reaction is finished, the solvent is removed under reduced pressure, the normal phase chromatographic column is used for purification, and the eluent is ethyl acetate, petroleum ether and triethylamine, the volume ratio is 100:3:1, thus obtaining 238mg of 1,3, 5-tri (4-pyridylphenylethynyl) benzene.
(2) 1,3, 5-Tri (4-pyridylphenylethynyl) benzene (200 mg) prepared in the step (1) and excessive methyl iodide (187 mg) are weighed respectively, placed in a pressure-resistant tube, 30mLN and N-dimethylformamide are taken as reaction solvents, and magnetically stirred at a reaction temperature of 60 ℃ for 8 hours, excessive ethyl acetate (100 mL) is added after the reaction is finished, solids are separated out, suction filtration is carried out, washing with ethyl acetate is continued, and vacuum drying is carried out, so that 316mg of trivalent pyridine salt is obtained.
(3) And (3) respectively weighing the trivalent pyridine salt (300 mg) prepared in the step (2) and excessive potassium hexafluorophosphate (215 mg) in a round-bottomed flask, taking 25mL of acetonitrile/water mixed solvent (volume ratio is 1:1) as a reaction solvent, magnetically stirring, reacting for 30min, and after the reaction is finished, distilling under reduced pressure to remove acetonitrile, wherein yellow solid is separated out, thus obtaining 297mg of trivalent pyridine salt with anions of hexafluorophosphate groups, and the yield is 94%.
FIG. 2 is a hydrogen spectrum of the organic ion salt prepared in this example, and the hydrogen spectrum is characterized as follows: 9.06-9.04 (6H, d), 8.57-8.54 (6H, d), 8.21-8.18 (6H, d), 7.94-7.86 (9H, m), 4.35 (9H, s), indicating successful synthesis of the target molecule.
FIG. 3 is a fluorescent chart of the organic ion salt prepared in this example, and it can be seen that the emission wavelength of the organic ion salt is 451nm at the excitation wavelength of 362nm, which indicates that the target molecule has a distinct photo-induced fluorescence signal.
FIG. 4 is a graph of electrochemiluminescence of the organic ion salt prepared in this example, which can be seen to have a distinct electrochemiluminescence response signal at-1.8V, with an intensity of 2520au, indicating that the target molecule has a distinct cathodic electrochemiluminescence response.
FIG. 5 is a graph showing electrochemiluminescence response of organic ion salt prepared in example 1 of the present invention at different scan rates, wherein the electrochemiluminescence response of the organic ion salt is different at 50, 100, 200, 500mV/s, which indicates that the electrochemiluminescence response is affected by different scan rates, and the organic ion salt has the maximum electrochemiluminescence response at a scan rate of 200 mV/s.
Example 2
This example differs from example 1 in that the molar ratio of 4- (4-bromophenyl) pyridine, 1,3, 5-trialkenyl, tetraphenylphosphine palladium, and cuprous iodide was adjusted to 3:1:0.05:0.05, and the remaining preparation processes were the same as in example 1 to obtain an organic ion salt with a yield of 21%.
It can be seen that the modification of the raw material ratio has an effect on the yield of the target molecule, but the purified target molecule has a consistent structure and does not affect the intensity of the electrochemiluminescence response signal of the material. During electrochemiluminescence detection, the scanning rate can affect the electrochemiluminescence response intensity of the target molecule.
Example 3
This example differs from example 1 in that the molar ratio of 4- (4-bromophenyl) pyridine, 1,3, 5-trialkenyl, tetraphenylphosphine palladium, and cuprous iodide was adjusted to 5:1:0.05:0.05, and the remaining preparation processes were the same as in example 1 to obtain an organic ion salt with a yield of 39%.
Comparative example 1
The existing cathode electroluminescent materials comprise cadmium sulfide, cadmium selenide, cadmium telluride and the like. The preparation method comprises the following steps of: thioglycollic acid (15 μl) was added to aqueous cadmium chloride (0.001 mol/L,27 mL) and magnetically stirred for 15min to form a pale blue cloudy solution. Sodium hydroxide (0.01 mol/L) solution was added dropwise to the above solution, and the pH was adjusted to 11. Then, sodium sulfide (0.015 mol/L,1 mL) was added dropwise to the above solution, protected from light, and stirring was continued at room temperature for 1 hour. After the reaction is finished, water is removed by reduced pressure distillation, 30mL of absolute methanol is added, and precipitation and separation are carried out, so that the cadmium sulfide quantum dot is obtained. In the synthesis process, thioglycollic acid and cadmium chloride with high toxicity are needed, wherein the thioglycollic acid has poor stability, burns in the presence of open fire and high heat energy, and emits highly toxic hydrogen sulfide gas.
Comparative example 2
Preparing cadmium selenide quantum dots: thioglycollic acid (15 μl) was added to aqueous cadmium chloride (0.001 mol/L,27 mL) and magnetically stirred for 15min to form a pale blue cloudy solution. Sodium hydroxide (0.01 mol/L) solution was added dropwise to the above solution, and the pH was adjusted to 11. Next, sodium selenide (0.015 mol/L,1 mL) was added dropwise to the above solution, protected from light, and stirring was continued at room temperature for 1 hour. After the reaction is finished, water is removed by reduced pressure distillation, 30mL of absolute methanol is added, and the cadmium selenide quantum dot is obtained by precipitation and separation. In the synthesis process, thioglycollic acid and cadmium chloride with high toxicity are needed, wherein the thioglycollic acid has poor stability, burns in the presence of open fire and high heat energy, and emits highly toxic hydrogen sulfide gas.
Comparative example 3
Preparing cadmium telluride quantum dots: thioglycollic acid (15 μl) was added to aqueous cadmium chloride (0.001 mol/L,27 mL) and magnetically stirred for 15min to form a pale blue cloudy solution. Sodium hydroxide (0.01 mol/L) solution was added dropwise to the above solution, and the pH was adjusted to 11. Next, sodium telluride (0.015 mol/L,1 mL) was added dropwise to the above solution, protected from light, and stirring was continued at room temperature for 1 hour. After the reaction is finished, water is removed by reduced pressure distillation, 30mL of absolute methanol is added, and precipitation and separation are carried out, so that the cadmium telluride quantum dot is obtained. In the synthesis process, thioglycollic acid and cadmium chloride with high toxicity are needed, wherein the thioglycollic acid has poor stability, burns in the presence of open fire and high heat energy, and emits highly toxic hydrogen sulfide gas.
The existing cathode electrochemiluminescence material is generally quantum dots (cadmium sulfide, cadmium selenide and zinc sulfide), belongs to metal-containing inorganic compounds, and has high toxicity. The invention uses organic small molecules, and has the characteristics of low toxicity and low pollution.
In summary, the invention provides a preparation method of organic ion salt with electrochemiluminescence effect, and the prepared organic ion salt has the characteristics of low toxicity and low pollution, and belongs to cathode electrochemiluminescence materials, so that common inorganic quantum dots with high toxicity and high pollution are avoided being used as cathode electrochemiluminescence materials. The material can be used as a luminescent material for sensing, biological imaging and the like. Compared with the prior art, the organic molecule used in the method has the advantages of high synthesis efficiency, simple synthesis method and the like. The molecule has a distinct electrochemiluminescence signal and has a lower physiological toxicity than other electrochemiluminescent substances.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. An organic ionic salt having an electrochemiluminescence effect, characterized in that: the structural formula is shown as formula (A):
2. the method for preparing an organic ion salt with electrochemiluminescence effect according to claim 1, wherein: comprising the steps of (a) a step of,
Adding a mixed solvent of tetrahydrofuran and triethylamine into 4- (4-bromophenyl) pyridine, 1,3, 5-tricetyl benzene, tetraphenylphosphine palladium and cuprous iodide under the protection of nitrogen atmosphere, magnetically stirring, heating, reacting for 48-60 h, removing the solvent under reduced pressure, and purifying by using a normal phase chromatographic column to obtain 1,3, 5-tris (4-pyridylphenylethynyl) benzene;
Adding 1,3, 5-tri (4-pyridylphenylethynyl) benzene and methyl iodide into N, N-dimethylformamide, magnetically stirring, heating, reacting for 8-12 h, adding ethyl acetate for washing, and vacuum drying to obtain trivalent pyridine salt;
Adding trivalent pyridinium and potassium hexafluorophosphate into acetonitrile/water mixed solution, magnetically stirring, reacting for 0.5-1 h, decompressing and distilling to remove acetonitrile, and separating out yellow solid to obtain trivalent pyridinium with anion being hexafluorophosphate, namely organic ion salt with electrochemiluminescence effect.
3. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the molar ratio of the 4- (4-bromophenyl) pyridine, the 1,3, 5-tri-alkynylbenzene, the tetra-triphenylphosphine palladium and the cuprous iodide is 4.0-4.5:1:0.05:0.05.
4. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the volume ratio of the tetrahydrofuran to the triethylamine is 1:1-1.5, and the concentration of the 4- (4-bromophenyl) pyridine dissolved in the mixed solvent is 0.05-0.15 mM.
5. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the magnetic stirring speed is 150-200 r/min, and the reaction temperature is 60-70 ℃.
6. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the eluent used in the purification is dichloromethane, methanol and triethylamine with the volume ratio of 100:2-3:1-2.
7. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the molar ratio of the 1,3, 5-tri (4-pyridylphenylethynyl) benzene to the methyl iodide is 1:4.0 to 4.5; the concentration of the 1,3, 5-tri (4-pyridylphenylethynyl) dissolved in N, N-dimethylformamide is 0.01-0.02 mM.
8. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the mole ratio of the trivalent pyridine salt to the potassium hexafluorophosphate is 1:4.0-4.5.
9. The method for preparing an organic ion salt with electrochemiluminescence effect according to claim 2, wherein: the volume ratio of acetonitrile to water is 1:1-2, and the concentration of trivalent pyridine salt dissolved in the mixed solvent is 0.01-0.02 mM.
10. Use of an organic ionic salt with electrochemiluminescence effect according to claim 1, characterized in that: the organic ion salt is used as an electrochemiluminescence marker and applied to the field of sensing and biological imaging.
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