CN117069615A - Near infrared fluorescent probe capable of identifying and detecting palladium through naked eyes and preparation method and application thereof - Google Patents
Near infrared fluorescent probe capable of identifying and detecting palladium through naked eyes and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 71
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 21
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 12
- VKTMDTZJPKSAKH-UHFFFAOYSA-N 5-(diethylamino)-2-ethenylphenol Chemical compound CCN(CC)c1ccc(C=C)c(O)c1 VKTMDTZJPKSAKH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- MTZNODTZOSBYJW-UHFFFAOYSA-N 3-amino-5,5-dimethylcyclohex-2-en-1-one Chemical compound CC1(C)CC(N)=CC(=O)C1 MTZNODTZOSBYJW-UHFFFAOYSA-N 0.000 claims description 7
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000000862 absorption spectrum Methods 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 5
- 101150003085 Pdcl gene Proteins 0.000 description 28
- 239000000523 sample Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001917 fluorescence detection Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- SQEQNZJGQVHATH-UHFFFAOYSA-N 2,4,4-trimethyl-6-oxocyclohexene-1,3-dicarbonitrile Chemical compound CC1=C(C#N)C(=O)CC(C)(C)C1C#N SQEQNZJGQVHATH-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000012632 fluorescent imaging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material 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
- 238000003947 neutron activation analysis Methods 0.000 description 1
- 230000007084 physiological dysfunction Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
- C07C255/43—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
Abstract
The invention discloses a near infrared fluorescent probe capable of detecting palladium through naked eye recognition and a preparation method and application thereof, relates to the technical field of fluorescent probe preparation, provides a specific structural formula of the near infrared fluorescent probe, and simultaneously provides a preparation method of the near infrared fluorescent probe and application thereof in palladium detection. The fluorescent probe takes allyl carbonate as a response group, and after palladium is added, the absorption spectrum is subjected to red shift, so that various types of palladium can be detected with high sensitivity and high selectivity, and the palladium can be quantitatively detected through off-on type fluorescent reaction, thereby effectively solving the problems that complicated and high-equipment detection is required, the consumed time is long, naked eye identification cannot be performed and the like in the prior art.
Description
Technical Field
The invention relates to the technical field of fluorescent probe preparation, in particular to a near infrared fluorescent probe capable of detecting palladium through naked eye identification, and a preparation method and application thereof.
Background
Palladium (Pd) is widely used in various fields of chemistry, biology, environmental science, and materials science. The palladium-containing catalyst has the advantages of high catalytic activity, strong selectivity, small dosage, wide application field and the like, and plays an important role in chemical industrial production. The popularization of automobiles leads to the use of a large amount of palladium-containing catalysts in an exhaust gas treatment system, which causes an increase in the palladium content in the air and environmental pollution. Platinum group elements (PGM) are widely used in tumor therapy, and palladium-based complexes and nanomaterials have been used in clinical applications in anticancer drugs and radiotherapy due to their similar chemical properties. In addition, palladium is also used in the fields of jewelry, electrical equipment, dental materials, fuel cells, aerospace, and the like. Palladium used in scientific research and industrial production is discharged into air, rivers and soil, is enriched in organisms, easily enters into human bodies to attack biomacromolecules such as amino acid containing sulfhydryl, protein, DNA and the like, and interferes with cell signal transduction, thereby causing physiological dysfunction. The development of the palladium detection strategy is simple, economical and efficient, and has important practical significance.
Currently known palladium detection methods such as atomic absorption spectrometry, atomic emission spectrometry, electrochemical methods, inductively coupled plasma mass spectrometry, neutron Activation Analysis (NAA), X-ray fluorescence spectrometry, high performance liquid chromatography and the like, but have the disadvantages of requiring professional technicians, being complex and expensive, having complicated preparation and treatment processes in the early stage, having complex experimental processes, being long in consumed time and the like; in addition, in daily production and life, detection by an actual precision instrument is difficult, and development of a fluorescent probe capable of quantitatively detecting palladium according to naked eye identification of color change is recently reported.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a near infrared fluorescent probe capable of detecting palladium by naked eye recognition, and a preparation method and application thereof.
The technical scheme for solving the technical problems is as follows: the near infrared fluorescent probe capable of identifying and detecting palladium through naked eyes is provided, and has the structural formula:
the preparation method of the near infrared fluorescent probe capable of identifying and detecting palladium by naked eyes comprises the following steps of:
(1) Sequentially adding malononitrile, sodium acetate and ethanol into a flask at room temperature, stirring for 10-30min, then adding 3-amino-5, 5-dimethyl-2-cyclohexene-1-one (compound 1), stirring for 20h under a nitrogen atmosphere at 40-60 ℃, sequentially cooling, evaporating and removing a solvent, finally dissolving in dichloromethane, extracting with water, concentrating an organic phase, and purifying by a silica gel chromatographic column to obtain 2- (3, 5-trimethylcyclohex-2-ene-1-subunit) malononitrile (compound 2);
(2) Mixing the 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile obtained in the step (1) with a solution of 4 (diethylamino) -2-hydroxybenzaldehyde (compound 3) and piperidine in ethanol, heating at 90-110 ℃ for 12h, then sequentially cooling, evaporating, concentrating and drying, dissolving in methylene chloride, extracting with water, concentrating the organic phase, and purifying by a silica gel chromatographic column to obtain (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile (compound 4);
(3) Tetrabutylammonium chloride, 1M sodium hydroxide solution, methylene chloride and (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile obtained in the step (2) are mixed, stirred at 0 ℃ for 10-20min, then allyl carbonate is added, stirred for 2-4h in a nitrogen atmosphere at room temperature, and finally extracted and purified to obtain a near infrared fluorescent probe (compound 5) capable of detecting palladium by naked eye recognition, namely (E) -allyl (2- (2- (3- (dicyano-methylene) -5, 5-dimethylcyclohex-1-enyl) vinyl) -5- (diethylamino) phenyl) carbonate.
Further, in the step (1), the molar volume ratio of malononitrile, sodium acetate, 3-amino-5, 5-dimethyl-2-cyclohexen-1-one and ethanol is 24 to 25mmol:12-13mmol:21-22mmol:50mL.
Further, in the step (1), the molar volume ratio of malononitrile, sodium acetate, 3-amino-5, 5-dimethyl-2-cyclohexen-1-one and ethanol was 24.9mmol:12.2mmol:21.7mmol:50mL.
Further, in the step (2), the molar volume ratio of 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile, 4 (diethylamino) -2-hydroxybenzaldehyde, piperidine and ethanol is 11-12mmol:12-14mmol:0.4-0.6mL:150mL.
Further, in the step (2), the molar volume ratio of 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile, 4 (diethylamino) -2-hydroxybenzaldehyde, piperidine and ethanol was 11.8mmol:13mmol:0.5mL:150mL.
Further, in the step (3), tetrabutylammonium chloride, (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile, allyl carbonate, sodium hydroxide solution and methylene chloride are in a molar volume ratio of 0.05 to 0.06mmol:8-9mmol:12-13mmol:3.3mL:20mL.
Further, in the step (3), tetrabutylammonium chloride, (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile, allyl carbonate, sodium hydroxide solution and methylene chloride were in a molar volume ratio of 0.0581mmol:8.3mmol:12.5mmol:3.3mL:20mL.
Further, in step (3), extraction with methylene chloride is performed, and the organic phase is concentrated and purified by silica gel chromatography.
The near infrared fluorescent probe capable of detecting palladium through naked eye recognition is applied to palladium detection.
The invention has the following beneficial effects:
1. the fluorescent probe takes allyl carbonate as a response group, and after palladium is added, the absorption spectrum is subjected to red shift, so that various types of palladium can be detected with high sensitivity and high selectivity, quantitative detection can be carried out on palladium through off-on fluorescent reaction, low-concentration palladium can be rapidly detected with high sensitivity and specificity, and palladium can be rapidly detected in a naked eye contrast mode under the condition of lack of instruments and equipment, and the like; the problems that complicated and high equipment is required to detect, the consumed time is long, naked eye identification cannot be carried out and the like in the prior art are effectively solved.
2. The invention designs and synthesizes the near infrared fluorescent probe capable of detecting palladium by naked eye recognition based on Tsuji-Trost reaction, has the advantages of simple structure, easy synthesis from cheap commercial raw materials, high sensitivity and selectivity, excellent sensibility and the like, and can carry out qualitative and quantitative analysis on palladium according to the color change trend before and after the reaction. In view of good fluorescence response of near infrared fluorescence probes capable of detecting palladium through naked eye recognition to 0,2 and 4-valent palladium, and PdCl 2 Stable chemical property, low price compared with other palladium-containing compounds, and PdCl 2 As a representative, the fluorescence properties of the probes were studied, which exhibited palladium (Pd) at room temperature in DMSO-PBS buffer (100 mM, pH= 7.4,3/2, v/v) 2+ ) The concentration was increased, a linear increase in Near Infrared (NIR) fluorescence intensity occurred, and the detection was rapid (30 min), with a lower limit of detection (lod=714 nM). Through the selective and anti-interference capability detection of palladium, the probe has good fluorescence properties in neutral and alkaline environments, and provides a new design thought and fluorescence detection method for palladium detection.
3. The fluorescent start probe for identifying palladium by naked eyes with dicyanoisophorone as a mother nucleus can be used for quantitative detection of palladium in the environment, and has the following characteristics: the fluorescent probe has simple synthesis steps, low cost of synthesis raw materials, easy obtainment, high yield of target products and easy separation and purification; the dye emits in a red light area, has good structural stability, and can be used for detecting palladium under neutral and alkaline conditions; in addition, the palladium ion concentration has a good linear relationship in the range of 0-100 mu M. The palladium ion fluorescent probe compound has strong anti-interference performance, has no obvious fluorescent response to other 25 interference metal cations, only has selective response to palladium ions, and is suitable for palladium ion fluorescent imaging and tracing in a complex biological system.
Drawings
FIG. 1 is CDCl 3 Of the compound Probe1 1 H NMR spectrum.
FIG. 2 is CDCl 3 Of the compound Probe1 13 C NMR spectrum.
FIG. 3 shows the PdCl for near infrared fluorescent probe 2 Is a result of the absorption spectrum test of (a);
FIG. 4 shows the PdCl for near infrared fluorescent probe 2 Is a fluorescent spectrum of (2);
FIG. 5 shows the addition of PdCl to near infrared fluorescent probes 2 A change curve of the fluorescence intensity with time;
FIG. 6 shows the near infrared fluorescence probe along with PdCl 2 Fluorescence intensity profile with increasing concentration;
FIG. 7 shows a near infrared fluorescent probe and 0-100. Mu.M PdCl 2 Linearly fitting the fluorescence intensity after the solution reaction;
FIG. 8 shows near infrared fluorescent probes and PdCl concentrations 2 Color change under visible light after reaction;
FIG. 9 shows the PdCl for near infrared fluorescent probe 2 Selectivity and competition experiments of (a);
FIG. 10 is a graph showing the fluorescence response of near infrared fluorescent probes to a common palladium-containing catalyst;
FIG. 11 shows the near infrared fluorescence probe pair PdCl under different pH conditions 2 Is a fluorescent response of (a).
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The near infrared fluorescent probe capable of identifying and detecting palladium by naked eyes comprises the following steps:
(1) Malononitrile (1.3 g,1.1 eq, 24.9 mmol), sodium acetate (1 g,0.7 eq, 12.2 mmol) and ethanol (50 mL) were added sequentially to the flask at room temperature and stirred for 20min, then 3 amino-5, 5-dimethyl-2-cyclohexen-1-one (compound 1,3g,1.0 eq, 21.7 mmol) was added, stirred under nitrogen atmosphere at 50 ℃ for 20h, then cooled, evaporated and the solvent removed sequentially, finally dissolved in dichloromethane and extracted with water, the organic phase concentrated and purified by silica gel chromatography column (petroleum ether/ethyl acetate=10:1) to give 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile (compound 2,2.2g,60% yield); the reaction process is as follows:
(2) 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile (2.2 g,1.0 eq, 11.8 mmol) obtained in step (1) was mixed with a solution of 4 (diethylamino) -2-hydroxybenzaldehyde (compound 3,2.5g,1.1 eq, 13 mmol) and piperidine (0.5 mL) in ethanol (150 mL), heated at 100 ℃ for 12h, then successively cooled, evaporated, concentrated and dried, redissolved in dichloromethane and extracted with water, the organic phase concentrated and purified by silica gel chromatography (petroleum ether/ethyl acetate=3:1) to give (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile (compound 4,3.0g,70% yield);
1 H NMR(400MHz,CDCl 3 )δ7.43–7.31(m,2H),6.89(d,J＝15.9Hz,1H),6.72(s,1H),6.31(dd,J＝8.9,2.0Hz,1H),6.06–6.00(m,1H),5.40(s,1H),3.38(q,J＝7.1Hz,4H),2.55(s,2H),2.47(s,2H),1.20(t,J＝7.0Hz,6H),1.05(s,6H). 13 C NMR(101MHz,CDCl 3 )δ169.4,156.5,156.3,150.5,133.3,129.5,124.1,120.8,114.6,113.9,111.1,105.8,97.8,74.3,44.6,43.1,39.1,32.0,28.1,12.7.
HRMS(ESI Positive):calc.for C 23 H 27 N 3 O + ；[M] + 362.2206
the reaction process is as follows:
(3) Tetrabutylammonium chloride (TBAC, 16.2mg,0.007 eq, 0.0581 mmol), 1M sodium hydroxide solution (3.3 mL), methylene chloride (20 mL) and (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile (3 g,1.0 eq, 8.3 mmol) obtained in step (2), were mixed, stirred at 0deg.C for 15min, then allyl carbonate (1.5 g,1.5 eq, 12.5 mmol) was added, stirred for 3h in a nitrogen atmosphere at room temperature, finally extracted with methylene chloride, the concentrated organic phase was purified by silica gel chromatography column (Petrol/ethyl acetate=5:1) to give a near infrared fluorescent probe (compound 5,1.9g,51% yield) capable of detecting palladium by naked eye recognition, i.e. (E) -allyl (2- (2- (3- (dicyano-methylene) -5, 5-dimethylcyclohex-1-enyl) vinyl) -5- (diethylamino) phenyl) carbonate.
1 H NMR(400MHz,CDCl 3 )δ7.51(d,J＝9.0Hz,1H),7.06(d,J＝15.9Hz,1H),6.80(d,J＝16.0Hz,1H),6.74(s,1H),6.57(dd,J＝9.0,2.6Hz,1H),6.40(d,J＝2.6Hz,1H),6.08–5.96(m,1H),5.51–5.41(m,1H),5.35(d,J＝10.5Hz,1H),4.77(d,J＝5.8Hz,2H),3.39(q,J＝7.0Hz,4H),2.57(s,2H),2.41(s,2H),1.20(t,J＝7.1Hz,6H),1.06(s,6H). 13 C NMR(101MHz,CDCl 3 )δ169.1,155.1,153.2,151.2,149.9,131.1,130.6,128.4,125.7,122.0,119.7,114.9,113.3,110.1,104.4,69.3,44.7,43.1,39.1,32.0,28.1,12.6.
HRMS(ESI Positive):calc.for C 27 H 31 N 3 O 3 + ；[M] + 446.2420
The reaction process is as follows:
the probe1 was synthesized with the hydroxyl group on (E) -2- (3- (4- (diethylamino) -2-hydroxyphenyl) -5, 5-dimethylcyclohexyl-2-en-1-ethyl) malononitrile as the capture site for palladium and allyl carbonate as the recognition group for palladium. In order to better realize the invention, the reaction condition of the invention is DMSO-PBS buffer solution (100 mM, pH= 7.4,3/2, v/v), the reaction is carried out for 30 minutes at room temperature, the excitation wavelength of fluorescence detection is 670nm, the emission wavelength is 700nm, and the slit width is 5nm.
Experimental example 1
Obtaining near-infrared fluorescent Probe (Probe 1) pair PdCl obtained in example 1 and capable of detecting palladium by naked eye recognition 2 The absorption spectrum and fluorescence spectrum of (2) are shown in FIGS. 3-4, respectively; then pair PdCl 2 Time response experiments, concentration titration experiments and limit of detection experiments were performed as shown in figures 5-7, respectively.
As can be seen from FIG. 3, near infrared fluorescent probe (10. Mu.M) capable of detecting palladium by naked eye recognition has an absorption peak at 520nm in DMSO-PBS buffer (100 mM, pH= 7.4,3/2, v/v) at room temperature. PdCl was added to the probe (10. Mu.M) 2 After (100. Mu.M), the absorption peak at 520nm in the absorption spectrum is red shifted to 670nm, so 670nm is selected as the excitation wavelength.
As can be seen from FIG. 4, the probe (10. Mu.M) emits almost no fluorescence at around 700nm under 670nm excitation; adding PdCl 2 After incubation for 30 minutes (100. Mu.M), the fluorescence intensity was significantly enhanced.
As can be seen from FIG. 5, the control probe solution (10. Mu.M) showed almost no fluorescence at λex=670 nm and λem=700 nm, and 100. Mu.M PdCl was added to the 10. Mu.M probe solution 2 The fluorescence intensity gradually increased, and the fluorescence intensity tended to be saturated steadily at about 30min of reaction. Because ofHere, 30min was chosen as the reaction time for all experiments.
As can be seen from FIG. 6, the probe (10. Mu.M) was followed by PdCl 2 Fluorescence intensity profile with increasing concentration (0,5,10,20,30,40,50,60,70,80,90,100,150,200,300,400,500,700,1000 μm). λex=670 nm, λem=700 nm; it can be seen that when PdCl 2 When the concentration reaches 700 mu M, the fluorescence intensity reaches the maximum value, pdCl 2 The fluorescence intensity tends to decrease in excess of 700. Mu.M when the concentration is too high.
As can be seen from FIG. 7, pdCl was added with the fluorescence intensity at 700nm obtained by the concentration titration experiment as the ordinate 2 The concentration was plotted as the abscissa, and the obtained points were subjected to straight line fitting with a linear coefficient of 0.9962. By testing the fluorescence intensity at 700nm of the five blank controls, the following formula: lod=3σ/k was measured, where σ is the standard deviation of 10 blank controls and k is the slope in fig. 7. The probe pair PdCl can be calculated 2 The limit of detection of (2) is 714nM. It can be seen that the probe has a high sensitivity for palladium detection.
Experimental example 2
The near infrared fluorescent probe and PdCl which can be used for detecting palladium and can be identified and detected by naked eyes and are obtained in the embodiment 1 2 The color change before and after the reaction was performed, and the result is shown in FIG. 8; for PdCl 2 The results of the selectivity and competition experiments of (2) are shown in FIG. 9; the fluorescence response to a common palladium-containing catalyst is shown in fig. 8; pdCl under different pH conditions 2 The results of the fluorescence response of (2) are shown in FIG. 11.
As can be seen from FIG. 8, when PdCl is present at different concentrations 2 (0, 5,10, 15, 20,30,40,50,60, 80, 100,150,200, 250, 300,400,500,700,1000, 2000, 4000. Mu.M) was added to a 10. Mu.M probe solution, and after incubation for 30 minutes at room temperature, a gradual change in the solution from pink, violet, green to blue was observed, demonstrating that the probe was not only highly sensitive to palladium, but also rapidly characterized and quantified by a macroscopic color change over a wide concentration range. The internal filtering effect is an unavoidable disadvantage of the fluorescence detection method, while the near infrared fluorescence probe of the invention can be identified by naked eyes without the help of instrument conditionsThe method can rapidly, simply and intuitively detect palladium, and makes up the limitations of the instrument detection method.
As can be seen from FIG. 9, the probe (10. Mu.M) was present or absent PdCl in DMSO-PBS buffer (100 mM, pH= 7.4,3/2, v/v) 2 (100. Mu.M) the fluorescence intensity of the solution after addition of various metal ions (100. Mu.M) for 30min, black in the figure represents the selectivity test (left column of each set of data) and red represents the competitiveness test (right column of each set of data, high). Numbers 1 to 25 respectively represent Co 2+ 、Cr 2+ 、Cr 3+ 、Cs + 、Fe 2+ 、Fe 3+ 、Rh 3+ 、Ru 3+ 、Ag + 、Ba 2+ 、Ca 2+ 、Cd 2+ 、Cu 2+ 、Pt 2+ 、K + 、Mg 2+ 、Mn 2+ 、Na + 、Ni 2+ 、Pb 2+ 、Sr 2+ 、Li + 、Zn 2+ And Pd (Pd) 2+ . λex=670 nm, λem=700 nm. As can be seen from the results, the probe has no response to other metal ions, but has stronger response to metal palladium in the presence of PdCl 2 The addition of various metal ions to the solution of (a) also has extremely high fluorescence response. It is illustrated that the probe has good selectivity and anti-interference capability to metallic palladium.
As can be seen from FIG. 10, pd (PPh) was added to the probe (10. Mu.M) solution 3 ) 4 (0-valent palladium), pdCl 2 、Pd(OAc) 2 (2-valent palladium), K 2 PdCl 6 After each (100. Mu.M) of (4-valent palladium), the fluorescence intensity in DMSO-PBS buffer (100 mM, pH= 7.4,3/2, v/v); λex=670 nm, λem=700 nm. From the results, the probe can have good fluorescence response to various types of palladium-containing catalysts.
As can be seen from fig. 11, at different pH values (ph= 4.0,5.0,6.0,7.0,7.4,8.0,9.0, 10.0), the probe (10 μm) was in the presence or absence of Pd 2+ (100. Mu.M), fluorescence intensity after incubation at room temperature for 30 min; and λex=670 nm, λem=700 nm. From the results, it can be seen that the probe has a good fluorescent response to palladium under neutral and alkaline conditions.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The near infrared fluorescent probe capable of identifying and detecting palladium by naked eyes is characterized by comprising the following structural formula:
2. the method for preparing the near infrared fluorescent probe capable of detecting palladium by naked eye recognition according to claim 1, which is characterized by comprising the following steps:
(1) Sequentially adding malononitrile, sodium acetate and ethanol into a flask at room temperature, stirring for 10-30min, then adding 3-amino-5, 5-dimethyl-2-cyclohexene-1-one, stirring for 20h under a nitrogen atmosphere at 40-60 ℃, sequentially cooling, evaporating and removing the solvent, finally dissolving in dichloromethane, extracting with water, concentrating the organic phase, and purifying by a silica gel chromatographic column to obtain 2- (3, 5-trimethylcyclohex-2-ene-1-subunit) malononitrile;
(2) Mixing the 2- (3, 5-trimethylcyclohex-2-ene-1-subunit) malononitrile obtained in the step (1) with an ethanol solution of 4 (diethylamino) -2-hydroxybenzaldehyde and piperidine, heating for 12 hours at a temperature of 90-110 ℃, then sequentially cooling, evaporating, concentrating and drying, dissolving in dichloromethane, extracting with water, concentrating an organic phase, and purifying by a silica gel chromatographic column to obtain (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-ene-1-subunit) malononitrile;
(3) Tetrabutylammonium chloride, 1M sodium hydroxide solution, methylene dichloride and (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile obtained in the step (2) are mixed, stirred at the temperature of 0 ℃ for 10-20min, then allyl carbonate is added, stirred for 2-4h in a nitrogen environment at room temperature, and finally the near infrared fluorescent probe capable of detecting palladium by naked eye recognition is obtained through extraction and purification.
3. The method for preparing a near infrared fluorescent probe capable of detecting palladium by naked eye recognition according to claim 1, wherein in the step (1), the molar volume ratio of malononitrile, sodium acetate, 3-amino-5, 5-dimethyl-2-cyclohexen-1-one and ethanol is 24-25mmol:12-13mmol:21-22mmol:50mL.
4. The method for preparing a near infrared fluorescent probe for detection of palladium by naked eye recognition according to claim 1 or 3, wherein in the step (1), the molar volume ratio of malononitrile, sodium acetate, 3-amino-5, 5-dimethyl-2-cyclohexen-1-one and ethanol is 24.9mmol:12.2mmol:21.7mmol:50mL.
5. The method for preparing a near infrared fluorescent probe for detecting palladium by naked eye recognition according to claim 1, wherein in the step (2), the molar volume ratio of 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile, 4 (diethylamino) -2-hydroxybenzaldehyde, piperidine and ethanol is 11 to 12mmol:12-14mmol:0.4-0.6mL:150mL.
6. The method for preparing a near infrared fluorescent probe for detection of palladium by naked eye recognition according to claim 1 or 5, wherein in the step (2), the molar volume ratio of 2- (3, 5-trimethylcyclohex-2-en-1-ylidene) malononitrile, 4 (diethylamino) -2-hydroxybenzaldehyde, piperidine and ethanol is 11.8mmol:13mmol:0.5mL:150mL.
7. The method for preparing a near infrared fluorescent probe for detection of palladium by naked eye recognition according to claim 1, wherein in the step (3), the molar volume ratio of tetrabutylammonium chloride, (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile, allyl carbonate, sodium hydroxide solution and methylene chloride is 0.05 to 0.06mmol:8-9mmol:12-13mmol:3.3mL:20mL.
8. The method for preparing a near infrared fluorescent probe for detection of palladium by naked eye recognition according to claim 1 or 7, wherein in the step (3), the molar volume ratio of tetrabutylammonium chloride, (E) -2- (3- (4- (diethylamino) -2-hydroxystyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile, allyl carbonate, sodium hydroxide solution and methylene chloride is 0.0581mmol:8.3mmol:12.5mmol:3.3mL:20mL.
9. The method for preparing near infrared fluorescent probe for detecting palladium by naked eye recognition according to claim 1, wherein in the step (3), dichloromethane is used for extraction, and the organic phase is concentrated and purified by silica gel chromatography.
10. The use of a near infrared fluorescent probe capable of detecting palladium by naked eye recognition according to claim 1 in palladium detection.
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