CN113831236B - Detect Al 3+ Fluorescent probe of (2), preparation method and application thereof - Google Patents
Detect Al 3+ Fluorescent probe of (2), preparation method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims description 31
- 238000002360 preparation method Methods 0.000 title description 7
- 238000001514 detection method Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012965 benzophenone Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000012264 purified product Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- QAWFLJGZSZIZHO-UHFFFAOYSA-N methyl 4-bromobutanoate Chemical compound COC(=O)CCCBr QAWFLJGZSZIZHO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 34
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000001917 fluorescence detection Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
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- ZSZOSPYBNNWIIN-UHFFFAOYSA-N 4-(1,2,2-triphenylethenyl)phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 ZSZOSPYBNNWIIN-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KQEVIFKPZOGBMZ-UHFFFAOYSA-N methyl 3-bromopropanoate Chemical compound COC(=O)CCBr KQEVIFKPZOGBMZ-UHFFFAOYSA-N 0.000 description 1
- RAVVJKCSZXAIQP-UHFFFAOYSA-N methyl 5-bromopentanoate Chemical compound COC(=O)CCCCBr RAVVJKCSZXAIQP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses a method for detecting Al 3+ The invention takes monohydroxy polytetrastyrene with AIE (aggregation induced emission) property as a fluorophore, reacts with 3-bromomethyl butyrate and hydrolyzes to prepare the para-Al 3+ Fluorescent detection probes with selectivity, specificity and sensitivity. Compared with the fluorescence detection technology in the prior art, the fluorescence detection probe has the advantages of simple synthesis, low cost, high reaction speed and high sensitivity, and can perform real-time in-situ detection.
Description
Technical Field
The invention discloses a method for detecting Al 3+ The fluorescent probe and the preparation method and the application thereof belong to the field of chemical material preparation and analysis detection.
Background
Aluminum is one of the most abundant metals in the crust, is closely related to our life, and aluminum element has been widely applied to industries such as food additives, medicines, water purification and packaging, but any substance has two sides, for example, aluminum-containing silicate minerals are easy to carry out metal from the minerals when being contacted with acid rain, so that the aluminum content in the environment or water is improved, the growth of crops is not facilitated, and the acidification of soil is further aggravated; also, for example, prolonged exposure to aluminum ions or ingestion of excessive amounts of aluminum, people can be susceptible to various diseases due to accumulation of large amounts of aluminum ions in different organs, most commonly resulting in the nervous systemDisease is unified. Thus, for trace amounts of Al in the actual sample 3+ It is important to perform sensitive and selective assays.
There are various methods for detecting aluminum in the prior art, such as atomic absorption spectrometry, plasma atomic generation spectrometry, etc., which are generally time-consuming and expensive, and some probes for detecting aluminum using fluorescence technology are reported at present, but strong hydration of aluminum ions in an aqueous medium generally results in weak coordination ability and is easily interfered by other substances. Compared with the fluorescence detection method in the prior art, the invention uses AIE (aggregation induced emission) compounds to give detection signals through aggregation luminescence, and prepares a fluorescence probe system with high specificity and sensitivity, which can be used for analyzing aluminum ions in real life.
Disclosure of Invention
The invention aims to provide a method for detecting Al 3+ The fluorescent probe and the preparation method and application thereof are used for solving the problem that aluminum ions are easy to be interfered by other substances in the detection of the fluorescent detection method in the prior art. The invention takes monohydroxy tetraphenyl ethylene (TPE-OH) with AIE property as a fluorophore, reacts with 3-bromoalkyl acid methyl ester and hydrolyzes to prepare the para-Al 3+ Fluorescent detection probes with selectivity, specificity and sensitivity. The detection of Al 3+ Has a structure represented by formula (I):
in the formula (I), n is 3, and the fluorescent probe detects Al 3+ Lower detection limit of less than 20nM. Compared with the fluorescence detection technology in the prior art, the fluorescence detection probe has the advantages of simple synthesis, low cost, high reaction speed and high sensitivity, and can perform real-time in-situ detection.
Correspondingly, the invention also provides a preparation method of the fluorescent probe, which comprises the following steps:
step one, synthesizing TPE-OH
Sequentially adding into a two-mouth reaction bottleZinc powder, 4-hydroxybenzophenone, benzophenone and anhydrous tetrahydrofuran are added, and stirred under ice bath to obtain mixed solution; tiCl is added to the mixed solution 4 And after the addition, the ice bath is removed for room temperature reaction, the heating reflux reaction is carried out for 12-24 hours, the heating is stopped, the cooling is carried out to room temperature, the quenching solution is added for quenching, and then the product is collected after silica gel column chromatography and vacuum drying is carried out, so that the TPE-OH is obtained.
Step two, synthesizing TPE-Cn-COOH
DMF, TPE-OH, methyl bromoalkyl acid and K are sequentially added into another two-port reaction bottle 2 CO 3 At N 2 Carrying out normal temperature reaction in atmosphere, purifying by a silica gel column after the reaction is finished, dissolving the purified product in methanol solution, then mixing with alkali, and carrying out stirring reaction under the room temperature condition to obtain white crystals; filtering the white crystals to obtain TPE-Cn-COOH, wherein methyl bromoalkyl acid ester is 4-methyl bromobutyrate.
The synthetic route of the TPE-Cn-COOH is as follows:
n=2, 3,4 in the above synthesis formula.
Preferably, in the first step: before adding the zinc powder, vacuumizing and filling N 2 The method of (2) removes water and oxygen 3 times from the two-port reaction flask.
Preferably, in the first step: the molar ratio of the 4-hydroxybenzophenone to the benzophenone is 1:1-1.5, and the molar mass of the zinc powder is 4-5 times that of the 4-hydroxybenzophenone.
Preferably TiCl is added to the mixed solution 4 The method specifically comprises the following steps:
after 20 minutes of the benzophenone was added to a two-port reaction flask, the TiCl was introduced by syringe 4 Added to the mixed solution.
Preferably, in the first step: the reaction time of the room temperature reaction is 30 minutes, and the heating reflux reactionThe reaction time was 12 hours, the quenching solution was 10% K 2 CO 3 An aqueous solution.
Preferably, in the second step: the molar ratio of the TPE-OH to the methyl 4-bromobutyrate is 1:2-4, and the TPE-OH to the K 2 CO 3 The mol ratio of (2) is 1:4-5, and the reaction time of the normal-temperature reaction is 6-18h.
Preferably, in the second step: the alkali is an aqueous solution of NaOEt, the molar ratio of the purified product to the NaOEt is 1:1-5, and the reaction time of the stirring reaction is 5-10h.
Correspondingly, the invention also provides the use of the fluorescent probe in Al detection 3+ In the application, the fluorescent probe detects Al 3+ The lower limit of detection of (2) is 14nM.
The application synthesizes the fluorescent probes TPE-Cn-COOH with different chain segment lengths based on tetraphenyl ethylene for detecting Al 3+ By comparing the detection efficiency of fluorescent probes of different segment lengths, the results show that when n=3, the fluorescent probe is specific to Al 3+ The detection effect is best, and the Al in the water body can be accurately detected 3+ Has good selectivity, sensitivity and specificity, and the detection lower limit is lower than 20nM.
Drawings
FIG. 1 shows the detection of Al by a fluorescent probe prepared according to various embodiments of the present invention 3+ Is a fluorescent emission spectrum of (2); the abscissa is wavelength (unit: nm), and the ordinate is fluorescence intensity; 1 is example 1,2 is comparative example 1,3 is comparative example 2,4 is comparative example 3.
FIG. 2 is a graph showing the selectivity of fluorescent probe provided in example 1 of the present invention for various metal ions; the abscissa is the metal ion class and the ordinate is the fluorescence intensity.
FIG. 3 shows the detection of different Al by the fluorescent probe according to example 1 of the present invention 3+ A fluorescence emission spectrum change graph at concentration; the abscissa is wavelength (unit: nm), and the ordinate is fluorescence intensity.
FIG. 4 shows the fluorescence probe according to the embodiment 1 of the present invention along with Al 3+ Fitting curves of fluorescence intensities of concentration variations; the abscissa is Al 3+ Concentration (unit: μm), and ordinate is fluorescence intensity.
FIG. 5 shows the fluorescence probe according to example 1 of the present invention at Al 3+ Fluorescence emission spectrum graph coexisting with different metal ions; the abscissa is the metal ion class and the ordinate is the fluorescence intensity.
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific examples:
synthesis of TPE-OH
Preparing a 250mL two-port reaction bottle, vacuumizing and filling N 2 The water and oxygen were removed 3 times from the reaction flask, and then 2.9g (44 mmol) of zinc powder, 2g (10 mmol) of 4-hydroxybenzophenone, 2.184g (12 mmol) of benzophenone, 100mL of anhydrous THF and stirring under ice bath were sequentially added to the reaction flask to obtain a mixed solution. After 20 minutes, 2.5mL (22 mmol) of TiCl was withdrawn with a syringe 4 Slowly adding into the mixed solution, removing ice bath after adding, standing at room temperature for 0.5h, and heating and refluxing overnight. The heating was stopped the next day, cooled to room temperature, and the mixture was quenched with 10% K 2 CO 3 Quenching with water, filtering, spin-drying the filtrate, extracting with diethyl ether and water for 3 times, mixing diethyl ether layers, extracting diethyl ether layer with 5% brine for 2 times, collecting diethyl ether layer, and using anhydrous MgSO 4 And (5) drying. Spin-drying the product, and passing through a column by using a solution chromatography silica gel method. And collecting a product, and drying in vacuum to obtain TPE-OH. The structural formula of the TPE-OH is as follows:
the Nuclear Magnetic Resonance (NMR) spectrum of the TPE-OH is: 1H NMR (400 MHz, DMSO-d 6): delta 9.34 (s, 1H), 7.06-7.14 (m, 9H), 6.93-6.98 (m, 6H), 6.73-6.75 (d, 2H), 6.47-6.52 (d, 2H). Wherein 9.34ppm of the peak is H on OH and 7.14-6.47ppm of the peak is H on benzene ring.
EXAMPLE 1 Synthesis of TPE-C3-COOH
In a two-port reaction flask, 15mL DMF, 0.174g (0.5 mmol) TPE-OH, 181mg (1 mmol) methyl 4-bromobutyrate and 276mg (2 mmol) K were added sequentially 2 CO 3 Introducing N at normal temperature 2 The reaction is carried out for 12 hours, and the product is purified by a silica gel column. The purified product 448mg (1 mmol) was dissolved in methanol solution (10 ml) and then mixed with 103mg (1.5 mmol) of NaOEt aqueous solution and stirred at room temperature for 6h to give white crystals and TPE-C3-COOH was obtained by filtration. The structural formula of the TPE-C3-COOH is as follows:
the Nuclear Magnetic Resonance (NMR) spectrum of the TPE-C3-COOH was: 1H NMR (400 MHz, CD3 OD): delta 7.05 (m, 9H), 6.97 (m, 6H), 6.88 (d, 2H), 6.64 (d, 2H), 3.53 (t, 2H), 1.84 (t, 2H), 1.56 (m, 2H). Wherein the peak of 7.05 to 6.64ppm is hydrogen on the benzene ring, 3.53ppm is H at a, 1.84ppm is H at b, and 1.56ppm is H at c.
Comparative example 1 TPE-C1-COOH synthesized according to Anal. Chem.2015,87,1470-1474
The structural formula of the TPE-C1-COOH is as follows:
the Nuclear Magnetic Resonance (NMR) spectrum of the TPE-C1-COOH was: 1H NMR (400 MHz, CD3 OD): delta 7.05 (m, 9H), 6.98 (m, 6H), 6.88 (d, 2H), 6.66 (d, 2H), 4.43 (s, 2H). Wherein 7.05 to 6.66ppm of the peak is hydrogen on the benzene ring and 4.43ppm is H at a.
Comparative example 2 Synthesis of TPE-C2-COOH
In a two-port reaction flask, 15mL of DMF, 0.174g (0.5 mmol) of TPE-OH, 167mg (1 mmol) of methyl 3-bromopropionate and 276mg (2 mmol) of K were added in this order 2 CO 3 Introducing N at normal temperature 2 The reaction is carried out for 12 hours, and the product is purified by a silica gel column. Purified product 434mg (1 mmol) was dissolved in methanol solution (10 ml), mixed with 103mg (1.5 mmol) of NaOEt aqueous solution and stirred at room temperature for 6h to give white crystals, and TPE-C2-COOH was obtained by filtration. The structural formula of the TPE-C2-COOH is as follows:
the Nuclear Magnetic Resonance (NMR) spectrum of the TPE-C2-COOH was: 1H NMR (400 MHz, CD3 OD): delta 7.03 (m, 9H), 6.95 (m, 6H), 6.86 (d, 2H), 6.63 (d, 2H), 3.82 (t, 2H), 2.26 (t, 2H). Wherein the peak of 7.03-6.63ppm is hydrogen on the benzene ring, 3.82ppm is H at a, and 2.26ppm is H at b.
Comparative example 3 Synthesis of TPE-C4-COOH
In a two-port reaction flask, 15mL DMF, 0.174g (0.5 mmol) TPE-OH, 181mg (1 mmol) methyl 5-bromopentanoate and 276mg (2 mmol) K were added sequentially 2 CO 3 Introducing N at normal temperature 2 The reaction is carried out for 12 hours, and the product is purified by a silica gel column. 462mg (1 mmol) of the purified product were dissolved in methanol solution (10 ml), mixed with 103mg (1.5 mmol) of NaOEt aqueous solution and stirred at room temperature for 6h, after which white crystals were obtained and TPE-C4-COOH was obtained by filtration. The structural formula of the TPE-C4-COOH is as follows:
the Nuclear Magnetic Resonance (NMR) spectrum of the TPE-C4-COOH was: 1H NMR (400 MHz, CD3 OD): delta 7.06 (m, 9H), 6.98 (m, 6H), 6.87 (d, 2H), 6.66 (d, 2H), 3.52 (t, 2H), 1.86 (t, 2H), 1.12-1.46 (m, 4H). Wherein the peak of 7.06-6.66ppm is H on benzene ring, 3.52ppm is H at a, 1.86ppm is H at b, and 1.12-1.46ppm is H at c.
Experimental example 1 responsiveness of different fluorescent probes to Metal ions
Preparation of various metal ions (Ba) with ultrapure water 2+ ,Fe 2+ ,Ca 2+ ,Mg 2+ ,Cr 3+ ,Li + ,Zn 2+ ,Hg 2+ ,Pb 2+ ,Na + ,Ag + ,Fe 3+ ,K + ,Ni 2+ ,Cu 2+ And Al 3+ ) Probe (TPE-Cn-COOH) stock (1 mM) was prepared with DMSO (0.25 m M).
At the time of detection, the probe stock solution 20. Mu. L, al was taken out 3+ 10. Mu.L of stock solution, 455. Mu.L of deionized water and 25. Mu.L of acetonitrile were added to prepare a solution to be tested, and the solution was incubated at room temperatureThe fluorescence emission spectrum (excitation wavelength: 310nm, scanning wavelength range: 350nm-600nm, probe concentration: 40. Mu.M, al) was recorded with a fluorescence spectrometer for 30min 3+ Ion concentration 5 μm).
As a result of the test, as shown in FIG. 1, when the probe was used as the fluorescent probe of example 1, the strongest fluorescence was at 480nm, and the fluorescence intensity was 415; when the probes were used as the fluorescent probes of comparative examples 1 to 3, the strongest fluorescence was at 475nm, and the fluorescence intensities were 105, 66, 60, respectively. From this, it can be seen that the probe pair Al of example 1 3+ Has higher responsiveness. This is probably due to the fluorescent probe of TPE-C3-COOH and Al 3+ Can form more stable complexation and has better dimensional matching.
Selectivity test of probes: 15 representative metal ions with different valence states are respectively selected for carrying out a combination experiment with the probe by taking TPE-C3-COOH synthesized in example 1 as a fluorescent probe, and the probe and Al are examined by fluorescent spectrometry 3+ Selectivity of interaction. In the detection, 20. Mu.L of a probe stock solution, 10. Mu.L of a single metal ion stock solution, 455. Mu.L of deionized water and 25. Mu.L of acetonitrile were taken out to prepare a solution to be detected, and incubated at room temperature for 30 minutes, and fluorescence emission spectra (excitation wavelength: 310nm, scanning wavelength range: 350nm to 600nm, probe concentration: 40. Mu.M, metal ion concentration: 5. Mu.M) were recorded by a fluorescence spectrometer.
The test results are shown in FIG. 2, wherein TPE-C3-COOH synthesized in example 1 is used as a fluorescent probe, and the probe is not responsive to common metal ions and is only responsive to Hg 2+ And Pb 2+ Has weaker response, and thus the probe is resistant to Al 3+ The detection is selective.
Experimental example 2 use of TPE-C3-COOH to Al 3+ Is to be tested
The procedure of example 2 was followed to test for different Al 3+ The experimental results of the fluorescence intensity of the concentration are shown in FIG. 3, and the concentration is shown as Al 3+ The increase in concentration and the continuous increase in fluorescence of the system are probably due to Al 3+ The addition of (2) results in a constant aggregation of the probe, forming hydrophobic aggregates, leading to an increase in fluorescence.
Extraction of Al 3+ The concentration is 0,0.5,1,15, 2. Mu.M, the maximum fluorescence emission intensity of the system at 480nm was corrected to obtain the working curve shown in FIG. 4. The lowest detection lower limit is obtained through the working curve. Lower detection Limit (LOD) =3×s.d./k. Wherein k represents the slope of the curve and S.D represents the value of Al 3+ Standard deviation at concentration 0.
I 480 ＝10+199.8×[Al 3+ ]
Lod=3×0.948/199.8=0.014 μm, so this system Al was obtained 3+ The lower limit of detection of (2) is 14nM, below the lower limit of detection of the known literature.
Experimental example 3 comparative detection experiments of other ion effects.
15 representative metal ions with different valence states and Al are respectively selected by taking TPE-C3-COOH synthesized in example 1 as fluorescent probes 3+ Simultaneously carrying out a combination experiment with the probe, and observing other metal ions to Al through fluorescence spectrum measurement 3+ The effect of the detection. At the time of detection, 20. Mu.L of probe stock solution and 10. Mu. L, al of metal ion stock solution were taken out 3+ 10 mu L of stock solution, 455 mu L of deionized water and 25 mu L of acetonitrile are added to prepare a solution to be tested, the solution is incubated for 30min at room temperature, and a fluorescence emission spectrum (excitation wavelength: 310nm, scanning wavelength range: 350nm-600nm, probe concentration: 40 mu M, other metal ion concentration: 5 mu M, al) is recorded by a fluorescence spectrometer 3+ Concentration 5 μm).
The test results are shown in FIG. 5 (Al 3+ The control group, without other metal ions), shows that TPE-C3-COOH synthesized in example 1 is a fluorescent probe, and the prepared fluorescent probe detects Al in the presence of the metal ions 3+ The fluorescence intensity of the probe has no obvious influence, and the probe has better anti-interference performance.
Experimental example 4 detection of Al by the Probe in tap Water 3+ Is tested by (a)
To examine Al in the actual water sample by the probe pair 3+ Is tested in tap water.
Testing Al in tap water by inductively coupled plasma atomic emission spectrometry 3+ Is 2.1. Mu.M, and the fluorescence synthesized by our example 1The result of the probe detection was 2.07. Mu.M, and the two test results were very close. Adding Al in a known amount 3+ By the detection of the fluorescent probe, the detection result is compared with the test result of the inductively coupled plasma atomic emission spectrometry to obtain the difference between the detection result and the test result, and the experimental result is as follows:
as shown by test results, the prepared probe has higher accuracy and reliability (the recovery rate is between 98.5 and 102.5 percent), the interference of other ions in tap water on the probe is small, and the fluorescent detection is generally higher in accuracy than ICP-AES through calculation of relative standard deviation, so that the accuracy of the fluorescent probe can be comparable to ICP-AES, and the fluorescent probe is convenient to use and can be detected in one step.
The above disclosure is merely illustrative of the embodiments of the present invention and is not intended to limit the invention in any way, and any methods and materials similar or equivalent to those described herein may be used in the methods of the present invention. The preferred methods and materials described herein are illustrative only and the embodiments are not limited thereto, as any person skilled in the art may make modifications or variations to the equivalent embodiments using the teachings disclosed above. The above sequence numbers are merely for description and do not represent advantages or disadvantages of the implementation scenario. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still belongs to the protection scope of the technical solution of the present invention.
Claims (10)
1. Detect Al 3+ Is characterized in thatWherein the fluorescent probe has a structure represented by formula (I):
in the formula (I), n is 3, and the fluorescent probe detects Al 3+ Lower detection limit of less than 20nM.
2. A method of preparing a fluorescent probe according to claim 1, comprising the steps of:
sequentially adding zinc powder, 4-hydroxybenzophenone, benzophenone and anhydrous tetrahydrofuran into a two-port reaction bottle, and stirring under ice bath to obtain a mixed solution; tiCl is added to the mixed solution 4 After the addition, the ice bath is removed for room temperature reaction, then the heating reflux reaction is carried out for 12 to 24 hours, the heating is stopped, the quenching solution is added for quenching after the cooling to room temperature, and then the product is collected after silica gel column chromatography and vacuum drying is carried out, thus obtaining TPE-OH;
sequentially adding DMF, TPE-OH, bromoalkyl acid methyl ester and K into another two-port reaction bottle 2 CO 3 At N 2 Carrying out normal temperature reaction in atmosphere, purifying by a silica gel column after the reaction is finished, dissolving the purified product in methanol solution, then mixing with alkali, and carrying out stirring reaction under the room temperature condition to obtain white crystals; filtering the white crystals to obtain TPE-Cn-COOH, wherein methyl bromoalkyl acid ester is 4-methyl bromobutyrate.
3. The method according to claim 2, wherein in the first step: before adding the zinc powder, vacuumizing and filling N 2 The method of (2) removes water and oxygen 3 times from the two-port reaction flask.
4. The method according to claim 2, wherein in the first step: the molar ratio of the 4-hydroxybenzophenone to the benzophenone is 1:1-1.5, and the molar mass of the zinc powder is 4-5 times that of the 4-hydroxybenzophenone.
5. The process according to claim 2, wherein TiCl is added to the mixed solution 4 The method specifically comprises the following steps:
after 20 minutes of the benzophenone was added to a two-port reaction flask, the TiCl was introduced by syringe 4 Added to the mixed solution.
6. The method according to claim 2, wherein in the first step: the reaction time of the room temperature reaction was 30 minutes, the reaction time of the heated reflux reaction was 12 hours, and the quenching solution was 10% K 2 CO 3 An aqueous solution.
7. The method according to claim 2, wherein in the second step: the molar ratio of the TPE-OH to the methyl 4-bromobutyrate is 1:2-4, and the TPE-OH to the K 2 CO 3 The mol ratio of (2) is 1:4-5, and the reaction time of the normal-temperature reaction is 6-18h.
8. The method according to claim 2, wherein in the second step: the alkali is an aqueous solution of NaOEt, the molar ratio of the purified product to the NaOEt is 1:1-5, and the reaction time of the stirring reaction is 5-10h.
9. A fluorescent probe according to claim 1 for preparing and detecting Al 3+ Is provided.
10. Use according to claim 9, the fluorescent probe detecting Al 3+ The lower limit of detection of (2) is 14nM.
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