CN116063193B - Preparation method and application of castor oil-based multicolor fluorescent compound - Google Patents
Preparation method and application of castor oil-based multicolor fluorescent compound Download PDFInfo
- Publication number
- CN116063193B CN116063193B CN202211224118.3A CN202211224118A CN116063193B CN 116063193 B CN116063193 B CN 116063193B CN 202211224118 A CN202211224118 A CN 202211224118A CN 116063193 B CN116063193 B CN 116063193B
- Authority
- CN
- China
- Prior art keywords
- castor oil
- fluorescent compound
- multicolor fluorescent
- chloride
- based multicolor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004359 castor oil Substances 0.000 title claims abstract description 85
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 85
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 85
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 iron ions Chemical class 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001263 acyl chlorides Chemical group 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 3
- 150000003141 primary amines Chemical group 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 2
- 229940100684 pentylamine Drugs 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 17
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000010943 off-gassing Methods 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FWQHRZXEQNUCSY-UHFFFAOYSA-N tert-butyl N-[2-(ethoxycarbonylamino)-5-[(4-fluorophenyl)methyl-prop-2-ynylamino]phenyl]carbamate Chemical compound CCOC(=O)NC1=C(C=C(C=C1)N(CC#C)CC2=CC=C(C=C2)F)NC(=O)OC(C)(C)C FWQHRZXEQNUCSY-UHFFFAOYSA-N 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- MGQPJLWKFQNTOZ-UHFFFAOYSA-N n,n-bis(prop-2-enyl)carbamoyl chloride Chemical compound C=CCN(C(=O)Cl)CC=C MGQPJLWKFQNTOZ-UHFFFAOYSA-N 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- MZFGYVZYLMNXGL-UHFFFAOYSA-N undec-10-enoyl chloride Chemical compound ClC(=O)CCCCCCCCC=C MZFGYVZYLMNXGL-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 229940039407 aniline Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000001893 coumarin derivatives Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229960001669 kinetin Drugs 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- 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"
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Immunology (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
本发明公开了一种蓖麻油基多色荧光化合物的制备方法及其应用。带有π电子的酯键和孤对(n)电子的胺基等非常规发色团通过大量的分子内和分子间氢键形成高浓度簇，从而引起电子云重叠和构象刚性化。这种行为使非辐射能量损失最小化并最大化它们的辐射跃迁概率。且其对Fe3+具有灵敏的荧光猝灭效应，可用于检测水体中残留铁离子。制作过程原料易得，操作简单，条件温和。
The invention discloses a preparation method and application of a castor oil-based multicolor fluorescent compound. Unconventional chromophores such as ester bonds with π electrons and amine groups with lone pairs of (n) electrons form high-concentration clusters through a large number of intramolecular and intermolecular hydrogen bonds, thereby causing electron cloud overlap and conformational rigidification. This behavior minimizes non-radiative energy losses and maximizes their radiative transition probabilities. It has a sensitive fluorescence quenching effect on Fe 3+ and can be used to detect residual iron ions in water. The raw materials of the production process are easily available, the operation is simple, and the conditions are mild.
Description
Technical Field
The invention belongs to the technical field of polymer material preparation, and particularly relates to a preparation method and application of a castor oil-based multicolor fluorescent compound
Background
The traditional dye or fluorescent molecule, such as oxadiazole and derivatives thereof, triazole and derivatives thereof, rhodamine and derivatives thereof, coumarin derivatives thereof and the like, has stronger intermolecular acting force due to the conjugated plane structure in the structure, and causes fluorescence quenching phenomenon when the dye or fluorescent molecule is in an aggregation state due to the intramolecular electronic transition dipole moment phenomenon generated by the conjugated plane structure.
However, it has now been found that many chromophore-free synthetic compounds and natural biopolymers emit abnormal luminescence in the aggregated state, which is known as aggregation-induced emission (AIE). Tang Benzhong institutes have opened up investigation and explanation of AIE and further developed The Space Conjugation (TSC) mechanism. This mechanism suggests that at low concentrations, electron clouds are less likely to overlap, resulting in weak or no light emission. In contrast, unconventional chromophores with pi and lone pair (n) electrons form clusters at high concentrations through a large number of intramolecular and intermolecular hydrogen bonds, resulting in electron cloud overlap and conformational rigidification. This behavior minimizes non-radiative energy losses and maximizes the probability of its radiative transitions. The AIE material has wide application prospect in the fields of three-dimensional high-density information storage, organism three-dimensional imaging, fluorescent marking, fluorescent probe and the like. However, the molecule related to AIE is usually complex in structural design, poor in solubility, and mainly uses petroleum-based raw materials, so that raw materials for preparing bio-based sources are easy to obtain, the operation is simple, and multicolor fluorescent compounds with mild conditions are still difficult in the prior art.
Disclosure of Invention
The invention provides a preparation method and application of a castor oil-based multicolor fluorescent compound. Unconventional chromophores such as amine groups with pi-electron ester bonds and lone pair (n) electrons form high concentration clusters through a large number of intramolecular and intermolecular hydrogen bonds, thereby causing electron cloud overlap and conformational rigidification. The compound has good solubility and processability, and can be applied to detecting Fe 3+ in water.
The preparation method of the castor oil-based multicolor fluorescent compound comprises the following steps:
(1) Adding castor oil, an acid binding agent, a polymerization inhibitor and a solvent into a reaction container, dropwise adding an allyl acyl chloride compound at 0-5 ℃, reacting for 4-8 hours at room temperature after the dropwise adding is finished, washing with deionized water until the pH value is neutral after the reaction is finished, collecting an organic phase, removing water with anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester;
(2) Adding castor oil allyl ester and primary amino compound into a reaction vessel, adding a solvent and a catalyst, magnetically stirring at room temperature for reaction for 12-72 hours, adding deionized water after rotary evaporation to wash until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and performing suction filtration to obtain the castor oil-based multiple fluorescent compound.
In the step (1), the allyl chloride compound is acryloyl chloride, methacryloyl chloride, diallyl carbamoyl chloride or 10-undecylenoyl chloride.
In the step (1), the molar ratio of hydroxyl groups of castor oil to acyl chloride groups of allyl acyl chloride compounds is 1:2-2.5.
In the step (1), the acid binding agent is triethylamine, the polymerization inhibitor is hydroquinone, and the solvent is ethyl acetate or tetrahydrofuran.
In the step (1), the mol ratio of the allyl acyl chloride compound to the acid binding agent is 1:1-1.2, and the dosage of the acid binding agent is 0.2wt.%.
In the step (2), the primary amino compound is any one of diethylenetriamine, pentylamine, aniline, 2-furanmethanamine, cyclopentylamine, ethylamine, tert-butylamine, dopamine and methyl l-dopamine.
In the step (2), the catalyst is anhydrous ferric chloride, anhydrous aluminum chloride, N-bromosuccinimide or sodium methoxide, and the solvent is tetrahydrofuran, ethyl acetate or dichloromethane.
In the step (2), the molar ratio of allyl groups to primary amine groups in the castor oil allyl ester is 1:1-2, and the addition amount of the catalyst is 0.2wt.%.
The castor oil-based multicolor fluorescent compound prepared by the preparation method is applied to detection of Fe 3+ in water.
The method has the beneficial effects that no synthetic method for preparing the multicolor fluorescent compound by taking castor oil as a raw material is reported at present, the method is initiated, and the unconventional chromophores such as ester bonds with pi electrons, amino groups with lone pair (n) electrons and the like form high-concentration clusters through a large number of intramolecular and intermolecular hydrogen bonds, so that electron cloud superposition and conformational rigidification are caused. This behavior minimizes non-radiative energy losses and maximizes their radiative transition probabilities. The compound has a sensitive fluorescence quenching effect on Fe 3+, has good solubility and processability, and can be used for detecting residual iron ions in water. The product of the invention has excellent photophysical property, the optimal excitation is 425nm, and the maximum polychromatic fluorescence emission wavelength is 515nm. The invention takes castor oil as raw material, has abundant raw material sources and low production cost, accords with the concept of green environmental protection and sustainable development, and has simple synthesis process, strong operability and easy implementation.
Drawings
FIG. 1 is a schematic diagram of the light emitting principle of the present invention;
FIG. 2 is a nuclear magnetic spectrum of the castor oil-based multicolor fluorescence compound obtained in example 1 of the present invention;
FIG. 3 fluorescence emission spectra of the castor oil-based multicolor fluorescence compound obtained in example 1 under different excitation lights;
FIG. 4 shows the fluorescence emission spectrum at 425nm of the castor oil-based multicolor fluorescence compound obtained in example 1 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some embodiments of the present invention, but not all embodiments.
The preparation method of the castor oil-based multicolor fluorescent compound comprises the following steps of (1) synthesizing castor oil allyl ester, namely adding castor oil, an acid binding agent, a polymerization inhibitor and a solvent into a four-neck flask, dropwise adding an allyl acyl chloride compound at the temperature of 0-5 ℃, and reacting for 4-8 hours at room temperature after the dropwise adding is finished. The molar ratio of the hydroxyl group to the acyl chloride group of the castor oil is 1 (2-2.5). The mol ratio of the allyl acyl chloride compound to the acid binding agent is 1 (1-1.2). The polymerization inhibitor was added in an amount of 0.2wt.%. After the reaction is finished, washing with deionized water until the pH is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester. (2) The synthesis of castor oil-based polyamine comprises the steps of adding castor oil allyl ester and primary amino compound into a conical flask, adding a solvent and 0.2wt.% of catalyst, wherein the molar ratio of allyl in the castor oil allyl ester to primary amino is 1 (1-2), and magnetically stirring and reacting for 12-72 hours at room temperature. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the castor oil base multicolor fluorescent compound.
Preferably, in the step (1), the allyl acyl chloride compound is acryloyl chloride, methacryloyl chloride, diallyl carbamoyl chloride or 10-undecylenoyl chloride, and the molar ratio of hydroxyl groups of castor oil to acyl chloride groups of the allyl acyl chloride compound is 1:2.2.
Preferably, in the step (1), the acid-binding agent is triethylamine, and the molar ratio of the allylic acid chloride compound to the acid-binding agent is 1:1.1. The polymerization inhibitor is hydroquinone, the amount of which is 0.2wt.%. The solvent is ethyl acetate or tetrahydrofuran.
Preferably, in the step (2), the molar ratio of allyl groups to primary amine groups in the castor oil allyl ester is 1:1.5. The primary amino compound is any one of diethylenetriamine, pentanediamine, aniline, 2-furanmethylamine, cyclopentylamine, ethylamine and tert-butylamine.
Preferably, in the step (2), the catalyst is anhydrous ferric chloride, anhydrous aluminum chloride, N-bromosuccinimide (NBS) or sodium methoxide, and the addition amount is 0.2wt.%. The solvent is tetrahydrofuran, ethyl acetate or dichloromethane.
The castor oil-based multicolor fluorescent compound prepared by the synthesis method.
The castor oil-based multicolor fluorescent compound is applied to detecting Fe 3+ in water.
Example 1
(1) Synthesis of allyl Castor oil 100g of Castor oil, 36g of triethylamine, 0.22g of hydroquinone and 300ml of ethyl acetate are added into a four-necked flask, 29.1g of acryloyl chloride is added dropwise at 0 ℃, and the reaction is carried out for 6h at room temperature after the dropwise addition is finished. After the reaction is finished, washing with deionized water until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid acrylic castor oil.
(2) Synthesis of Castor oil-based multicolor fluorescent Compound 10g of acrylated castor oil and 4.4g of diethylenetriamine were added to a conical flask, 0.003g of anhydrous ferric chloride was added, and the reaction was magnetically stirred at room temperature for 24 hours. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the diethylenetriamine castor oil-based fluorescent compound I.
(3) The application of the castor oil-based multicolor fluorescent compound in detecting Fe 3+ in water body is that 1mg/ml of diethylenetriamine castor oil-based fluorescent compound I solution is added with 1mol/l to 1X 10 -15mol/l Fe3+ solution, and the solution is subjected to ultrasonic treatment for 30s. Photoluminescence (excitation and emission) spectra were studied on a CARY ECLIPSE fluorescence spectrometer from agilent. The excitation and emission slits were 5nm and 10nm wide, respectively. Under excitation of a xenon discharge lamp, measurement was performed with a quartz cell of a 2mm path, and the scanning wavelength rate was 1200nm/min. Fluorescence spectra of different Fe 3+ solutions were obtained without outgassing at 425nm of incident light. When the concentration of Fe 3+ reaches 10 -8 mol/l, the fluorescence intensity is reduced sensitively, and when the concentration of Fe 3+ reaches 10 -3 mol/l, the fluorescence is quenched substantially completely.
Example 2
(1) Synthesis of allyl Castor oil 100g of Castor oil, 36g of triethylamine, 0.22g of hydroquinone and 300ml of ethyl acetate are added into a four-necked flask, 29.1g of acryloyl chloride is added dropwise at 0 ℃, and the reaction is carried out for 6h at room temperature after the dropwise addition is finished. After the reaction is finished, washing with deionized water until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid acrylic castor oil.
(2) Synthesis of Castor oil-based multicolor fluorescent Compound 10g of acrylated castor oil and 4.15g of furfuryl amine were added to a conical flask, 0.003g of anhydrous ferric chloride was added, and the reaction was magnetically stirred at room temperature for 24 hours. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the castor oil base multicolor fluorescent compound.
(3) The application of the castor oil-based multicolor fluorescent compound in detecting Fe 3+ in water body is that 1mg/ml solution of the furfuryl amine castor oil-based fluorescent compound is added with 1mol/l to 1X 10 -15mol/l Fe3+ concentration solution, and ultrasonic is carried out for 30s. Photoluminescence (excitation and emission) spectra were studied on a CARY ECLIPSE fluorescence spectrometer from agilent. The excitation and emission slits were 5nm and 10nm wide, respectively. Under excitation of a xenon discharge lamp, measurement was performed with a quartz cell of a 2mm path, and the scanning wavelength rate was 1200nm/min. Fluorescence spectra of the solutions were obtained without degassing. Fluorescence spectra of different Fe 3+ solutions were obtained without outgassing at 425nm of incident light. When the concentration of Fe 3+ reaches 10 -6 mol/l, the fluorescence intensity is reduced, and when the concentration of Fe 3+ reaches 10 -1 mol/l, the fluorescence is almost completely quenched.
Example 3
(1) Synthesis of Castor oil allyl ester Castor oil 100g, triethylamine 36g, hydroquinone 0.22g and ethyl acetate 300ml were added to a four-necked flask, and 36.96g of methacryloyl chloride was added dropwise at 0℃and reacted at room temperature for 6 hours after the completion of the addition. After the reaction is finished, washing with deionized water until the pH is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester.
(2) Synthesis of Castor oil-based multicolor fluorescent Compound 10g of Castor oil allyl ester and 3.66g of diethylenetriamine were added to a conical flask, 0.003g of anhydrous ferric chloride was added, and the reaction was magnetically stirred at room temperature for 24 hours. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the diethylenetriamine castor oil-based fluorescent compound II.
(3) The application of the castor oil-based multicolor fluorescent compound in detecting Fe 3+ in water body is that 1mg/ml of diethylenetriamine castor oil-based fluorescent compound II solution is added with 1mol/l to 1X 10 -15mol/l Fe3+ solution, and the solution is subjected to ultrasonic treatment for 30s. Photoluminescence (excitation and emission) spectra were studied on a CARY ECLIPSE fluorescence spectrometer from agilent. The excitation and emission slits were 5nm and 10nm wide, respectively. Under excitation of a xenon discharge lamp, measurement was performed with a quartz cell of a 2mm path, and the scanning wavelength rate was 1200nm/min. Fluorescence spectra of the solutions were obtained without degassing. Fluorescence spectra of different Fe 3+ solutions were obtained without outgassing at 425nm of incident light. When the concentration of Fe 3+ reaches 10 -7 mol/l, the fluorescence intensity is reduced sensitively, and when the concentration of Fe 3+ reaches 10 -2 mol/l, the fluorescence is quenched substantially completely.
Example 4
(1) Synthesis of Castor oil allyl ester Castor oil 100g, triethylamine 36g, hydroquinone 0.22g and ethyl acetate 300ml were added to a four-necked flask, and then 39.96g of methacryloyl chloride was added dropwise at 0℃and reacted at room temperature for 6 hours after the completion of the addition. After the reaction is finished, washing with deionized water until the pH is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester.
(2) Synthesis of Castor oil-based multicolor fluorescent Compound 10g of Castor oil allyl ester and 3.3g of aniline were added to a conical flask, 0.003g of anhydrous ferric chloride was added, and the reaction was magnetically stirred at room temperature for 24 hours. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the castor oil base multicolor fluorescent compound.
(3) The application of the castor oil-based multicolor fluorescent compound in detecting Fe 3+ in water body is that 1mg/ml solution of the aniline castor oil-based fluorescent compound is added with 1mol/l to 1X 10 -15mol/l Fe3+ concentration solution, and ultrasonic is carried out for 30s. Photoluminescence (excitation and emission) spectra were studied on a CARY ECLIPSE fluorescence spectrometer from agilent. The excitation and emission slits were 5nm and 10nm wide, respectively. Under excitation of a xenon discharge lamp, measurement was performed with a quartz cell of a 2mm path, and the scanning wavelength rate was 1200nm/min. Fluorescence spectra of the solutions were obtained without degassing. Fluorescence spectra of different Fe 3+ solutions were obtained without outgassing at 425nm of incident light. When the concentration of Fe 3+ reaches 10 -9 mol/l, the fluorescence intensity is reduced sensitively, and when the concentration of Fe 3+ reaches 10 -3 mol/l, the fluorescence is quenched substantially completely.
Example 5
(1) Synthesis of allyl Castor oil 100g of Castor oil, 36g of triethylamine, 0.22g of hydroquinone and 300ml of ethyl acetate are added into a four-necked flask, 56.42g of diallyl carbamoyl chloride is added dropwise at 0 ℃, and the reaction is carried out for 6h at room temperature after the dropwise addition is finished. After the reaction is finished, washing with deionized water until the pH is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester.
(2) Synthesis of Castor oil-based multicolor fluorescent Compound 10g of Castor oil allyl ester and 3.56g of diethylenetriamine were added to a conical flask, 0.1g of anhydrous ferric chloride was added, and the reaction was magnetically stirred at room temperature for 24 hours. And (3) adding deionized water to wash until the pH value is neutral after rotary evaporation, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the diethylenetriamine castor oil-based fluorescent compound III.
(3) The application of the castor oil-based multicolor fluorescent compound in detecting Fe 3+ in water body is that 1mg/ml of diethylenetriamine castor oil-based fluorescent compound III solution is added with 1mol/l to 1X 10 -15mol/l Fe3+ concentration solution, and ultrasonic treatment is carried out for 30s. Photoluminescence (excitation and emission) spectra were studied on a CARY ECLIPSE fluorescence spectrometer from agilent. The excitation and emission slits were 5nm and 10nm wide, respectively. Under excitation of a xenon discharge lamp, measurement was performed with a quartz cell of a 2mm path, and the scanning wavelength rate was 1200nm/min. Fluorescence spectra of the solutions were obtained without degassing. Fluorescence spectra of different Fe 3+ solutions were obtained without outgassing at 425nm of incident light. When the concentration of Fe 3+ reaches 10 -10 mol/l, the fluorescence intensity is reduced sensitively, and when the concentration of Fe 3+ reaches 10 -2 mol/l, the fluorescence is quenched substantially completely.
The foregoing examples are provided to illustrate the technical spirit and features of the present invention and are only for those skilled in the art to understand the contents of the present invention and to implement the same, and are not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. A method for preparing a castor oil-based multicolor fluorescent compound, which is characterized by comprising the following steps:
(1) Adding castor oil, an acid binding agent, a polymerization inhibitor and a solvent into a reaction container, dropwise adding an allyl chloride compound at 0-5 ℃, reacting for 4-8 hours at room temperature after the dropwise adding is finished, washing with deionized water until the pH value is neutral after the reaction is finished, collecting an organic phase, removing water with anhydrous magnesium sulfate, and carrying out suction filtration to obtain oily liquid castor oil allyl ester;
(2) The synthesis of the castor oil-based polyamine comprises the steps of adding castor oil allyl ester and primary amino compound into a reaction vessel, adding a solvent and a catalyst, magnetically stirring at room temperature for reaction for 12-72 hours, adding deionized water after rotary evaporation to wash until the pH value is neutral, collecting an organic phase, removing water by using anhydrous magnesium sulfate, and carrying out suction filtration to obtain the castor oil-based multiple fluorescent compound, wherein the primary amino compound is any one of diethylenetriamine, pentylamine, aniline, 2-furanmethylamine, cyclopentylamine, ethylamine, tert-butylamine and dopamine, and the catalyst is anhydrous ferric chloride or anhydrous aluminum chloride.
2. The method for preparing the castor oil-based multicolor fluorescent compound according to claim 1, wherein in the step (1), the molar ratio of hydroxyl groups of castor oil to acyl chloride groups of the allyl acyl chloride compound is 1:2-2.5.
3. The method for preparing the castor oil-based multicolor fluorescent compound according to claim 1, wherein in the step (1), the acid binding agent is triethylamine, the polymerization inhibitor is hydroquinone, and the solvent is ethyl acetate or tetrahydrofuran.
4. The method for preparing the castor oil-based multicolor fluorescent compound according to claim 1, wherein in the step (1), the molar ratio of the allylic acid chloride compound to the acid-binding agent is 1:1-1.2, and the amount of the acid-binding agent is 0.2 wt%.
5. The method for producing a castor oil-based multicolor fluorescent compound according to claim 1, wherein in the step (2), the solvent is tetrahydrofuran, ethyl acetate or methylene chloride.
6. The method for preparing the castor oil-based multicolor fluorescent compound according to claim 1, wherein in the step (2), the molar ratio of allyl groups to primary amine groups in the castor oil allyl ester is 1:1-2, and the addition amount of the catalyst is 0.2 wt%.
7. Use of the castor oil-based multicolor fluorescent compound prepared by the preparation method of any one of claims 1-6 for detecting Fe 3+ in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211224118.3A CN116063193B (en) | 2022-10-08 | 2022-10-08 | Preparation method and application of castor oil-based multicolor fluorescent compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211224118.3A CN116063193B (en) | 2022-10-08 | 2022-10-08 | Preparation method and application of castor oil-based multicolor fluorescent compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116063193A CN116063193A (en) | 2023-05-05 |
| CN116063193B true CN116063193B (en) | 2025-02-07 |
Family
ID=86168904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211224118.3A Active CN116063193B (en) | 2022-10-08 | 2022-10-08 | Preparation method and application of castor oil-based multicolor fluorescent compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116063193B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675989A (en) * | 2018-04-25 | 2018-10-19 | 中国科学院生物物理研究所 | Fe3+Molecular fluorescence test agent and preparation method thereof |
| CN109776552A (en) * | 2019-03-29 | 2019-05-21 | 南京林业大学 | Preparation and application of a rhodamine B-type Fe3+ fluorescent sensor based on 1-naphthoyl chloride |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012177021A2 (en) * | 2011-06-24 | 2012-12-27 | Lg Chem, Ltd. | Polymeric fluorescent material |
| CN110627756B (en) * | 2019-10-10 | 2023-03-17 | 中国科学院新疆理化技术研究所 | Colorimetric-fluorescent probe for detecting hypochlorite and preparation method and application thereof |
-
2022
- 2022-10-08 CN CN202211224118.3A patent/CN116063193B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675989A (en) * | 2018-04-25 | 2018-10-19 | 中国科学院生物物理研究所 | Fe3+Molecular fluorescence test agent and preparation method thereof |
| CN109776552A (en) * | 2019-03-29 | 2019-05-21 | 南京林业大学 | Preparation and application of a rhodamine B-type Fe3+ fluorescent sensor based on 1-naphthoyl chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116063193A (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Studies on preparation, structure and fluorescence emission of polymer-rare earth complexes composed of aryl carboxylic acid-functionalized polystyrene and Tb (Ⅲ) ion | |
| Abd-El-Aziz et al. | Aggregation enhanced excimer emission (AEEE) with efficient blue emission based on pyrene dendrimers | |
| CN111875811B (en) | A kind of supramolecular polymer and its preparation method and application | |
| CN101735216B (en) | Europium complex silicon dioxide fluorescent nano particles and preparation method thereof | |
| CN106674028A (en) | Benzylidene indandione compound and preparation thereof and application in specific imaging of lipid droplet | |
| CN105860583A (en) | Preparation and application of pH-response type rhodamine grafted lignin-based fluorochrome | |
| CN107312536B (en) | Red luminescent rare earth composite material, preparation method and application | |
| Lin et al. | From simple Katritzky salts to AIEgens: mechanochromic luminescence and heparin detection | |
| Mo et al. | Chlorination vs. fluorination: A study of halogenated benzo [c][1, 2, 5] thiadiazole-based organic semiconducting dots for near-infrared cellular imaging | |
| CN101205416A (en) | Pyrromethine fluorescent dyes and their synthesis method and application | |
| CN102876319A (en) | Spirofluorene pyridine fluorescent material and preparation method thereof | |
| CN116063193B (en) | Preparation method and application of castor oil-based multicolor fluorescent compound | |
| CN104448254A (en) | Phosphorescence conjugated polyelectrolyte photoelectric material containing porphyrin platinum complex as well as preparation method and application of phosphorescence conjugated polyelectrolyte photoelectric material | |
| CN105131024A (en) | Preparation method for novel rare-earth fluorescent gel adopting PVA as main body and application thereof | |
| Kong et al. | Dynamic photo-enhanced polyacrylic acid-based room temperature phosphorescence materials with persistent long-wavelength and even near-infrared luminescence via Förster resonance energy transfer | |
| CN108314636A (en) | A kind of polyaryl sulphur oscillation luminescent material and its preparation method and application | |
| CN112341462A (en) | Rare earth dysprosium cryptate ether fluorescent complex and preparation method thereof | |
| Ohishi et al. | A Versatile Synthetic Method for Photophysically and Chemically Stable [5] Rotaxane‐Type Fluorescence Dyes of Various Colors by Using a Cooperative Capture Strategy | |
| CN107151555A (en) | A kind of controllable luminous carbon nano-particles and preparation method and application | |
| CN109020828B (en) | A kind of Schiff alkali copper complex and its preparation method and application | |
| CN114874145B (en) | A water-soluble trityl radical material and its preparation method and application | |
| CN115010833A (en) | A Fluorescent Polymer Responsive to Acid-Base Stimuli and Its Application in Optical Encryption | |
| CN112500515B (en) | Luminous polymer containing aromatic unit cluster and preparation method thereof | |
| CN111334279A (en) | Composite material and preparation method thereof | |
| Russegger et al. | Fluorescent 1-hydroxy-10-alkylacridin-9 (10H)-one BF2-chelates: Large Stokes shift and long emission decay times |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |