CN116426273B - Preparation method and application of organogel compound with AIE (AIE) property - Google Patents
Preparation method and application of organogel compound with AIE (AIE) property Download PDFInfo
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- CN116426273B CN116426273B CN202310391811.8A CN202310391811A CN116426273B CN 116426273 B CN116426273 B CN 116426273B CN 202310391811 A CN202310391811 A CN 202310391811A CN 116426273 B CN116426273 B CN 116426273B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- -1 1, 10-phenanthroline-2, 9-diyl Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 10
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
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- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- UTCRGEWLQUJXKS-UHFFFAOYSA-N 6-(dodecylcarbamoyl)pyridine-2-carboxylic acid Chemical compound C(CCCCCCCCCCC)NC(=O)C1=CC=CC(=N1)C(=O)O UTCRGEWLQUJXKS-UHFFFAOYSA-N 0.000 claims description 5
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- 230000008569 process Effects 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
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- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 abstract description 33
- 238000001514 detection method Methods 0.000 abstract description 21
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- 238000011896 sensitive detection Methods 0.000 abstract description 3
- 101000999890 Entamoeba histolytica Non-pathogenic pore-forming peptide Proteins 0.000 description 59
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
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- 150000007513 acids Chemical class 0.000 description 9
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 8
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
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- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- ZHGNHOOVYPHPNJ-UHFFFAOYSA-N Amigdalin Chemical compound FC(F)(F)C(=O)OCC1OC(OCC2OC(OC(C#N)C3=CC=CC=C3)C(OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C2OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C(OC(=O)C(F)(F)F)C1OC(=O)C(F)(F)F ZHGNHOOVYPHPNJ-UHFFFAOYSA-N 0.000 description 1
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- 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"
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- 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"
- G01N2021/6432—Quenching
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- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to the technical field of supermolecular chemistry, and discloses a preparation method and application of an organogel compound with AIE properties. The organogel compound of the phenanthroline derivative can form gel in N, N-dimethylformamide/water (V/V, 10/1), dimethyl sulfoxide/water (V/V, 10/1), tetrahydrofuran/water (V/V, 5/1), ethanol and 1, 4-dioxane. The phenanthroline derivative can realize double-mechanism, double-mode and high-sensitivity detection of Hg 2+ by utilizing the AIE property of the phenanthroline derivative; and can realize dual-mode sensitive detection of volatile acid liquid and gas in liquid, film and gel states. The compound designed by the invention has huge potential in fluorescence anti-counterfeiting, higher application value and wide application prospect.
Description
Technical Field
The invention relates to the technical field of supermolecular chemistry, in particular to a preparation method and application of an organogel compound with AIE properties.
Background
The supermolecular gel as one new kind of soft material has the outstanding features of heat reversibility, specific flexibility, easy contact, stimulating response, inclusion, etc. The material is formed by non-covalent bond interactions (such as hydrogen bonds, pi-pi interactions, metal ligand coordination, van der Waals forces, hydrophobic effects), thereby forming a three-dimensional network structure formed by the self-assembly of reversible small molecules. Because the reversible network in the gel structure is formed by weak non-covalent forces, the gel can be made to respond sensitively to external stimuli such as light, heat, pH, biomolecules, ultrasound, metal ions and the like, and cause changes in the optical, electrical, molecular conformation and even chemical properties of the system, thereby enabling the material to have the capability of information storage, transmission and processing.
Mercury is the only metal which is liquid and easy to flow at normal temperature, is mainly used in scientific instruments, mercury boilers, mercury pumps and mercury vapor lamps, is widely applied in medicine, and mercury-containing products are visible everywhere in the life of people for a long time. In general, mercury ions are one of the most common and most stable forms of mercury pollution. The mercury ions have strong affinity for sulfur atom-containing ligands, resulting in thiol blocking of proteins, membranes and enzymes. Dysfunction of the kidneys, gastrointestinal tract, liver and brain is also associated with mercury ions. Because mercury ions are seriously harmful to human health and safety, it is highly desirable to establish a highly sensitive and selective mercury ion detection method.
Volatile acids are also known as gaseous acids, such as hydrochloric acid and trifluoroacetic acid, which are both relatively volatile. Such acids are commonly used as pharmaceutical, pesticide intermediates, biochemical reagents, organic synthesis reagents. Trifluoroacetic acid can be used as a solvent for fluorination, nitration, and halogenation reactions; the organic fluorine compound (pesticide, dye, chemical reagent) is used as material, protecting group for hydroxyl and amino, catalyst for esterification, polymerization and condensation, mineral dressing agent and organic synthesis. However, such acids have a strong irritating effect on the eyes, mucous membranes, respiratory tract and skin and are corrosive. Can cause spasm, inflammation, edema of throat and bronchus, chemical pneumonia, pulmonary edema, and death due to inhalation, and symptoms such as burning sensation, cough, wheezing, short breath, laryngitis, headache, nausea and emesis, and skin burn.
Therefore, the sensitive detection of mercury ions and gaseous acids has important practical significance and also has the value of environmental protection. There are also many fluorescent probes for detecting mercury ions and volatile acids. However, conventional organic fluorescent probes, which are composed of planar and polycyclic pi-conjugated backbones, generally exhibit high efficiency luminescence in dilute solutions. And fluorescence quenching in solid state and aggregation state is an aggregation fluorescence quenching (ACQ) effect, which affects the accuracy of the detection result and limits the application of the detection result in a gel self-assembly system. Aggregation-induced emission (AIE) is a molecule which does not generate fluorescence or has weak fluorescence in a dispersion system, but can generate obvious fluorescence in an aggregation state, and an AIE probe with mercury ion response is developed, so that the high-efficiency and sensitive detection of mercury ions in an aqueous solution can be realized. While the AIE organogel combines the properties of AIE and organogel to provide visual detection of metal ions and volatile acids. In addition, if a new organogel compound can be developed to realize multi-mode detection of mercury ions and volatile acids, the organogel compound has a very good application prospect. If the AIE organogel compound can detect volatile acid through the change of fluorescent signals, the AIE organogel compound can be applied to advanced anti-counterfeiting materials.
Disclosure of Invention
(One) solving the technical problems
In order to overcome the defects in the prior art, the invention provides a preparation method and application of an organogel compound with AIE properties, and solves the problems in the background art.
(II) technical scheme
In order to achieve the above object, the present invention provides the following technical solutions: a process for the preparation of organogel compounds having AIE properties and their use, comprising the steps of: mixing 4,4- (1, 10-phenanthroline-2, 9-diyl) diphenylamine, 6-dodecylcarbamoyl picolinic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and dichloromethane, stirring at normal temperature for 10-13 h, then evaporating dichloromethane under reduced pressure, and purifying the rest products by a column.
Preferably, the molar ratio of the 4,4- (1, 10-phenanthroline-2, 9-diyl) diphenylamine, the 6-dodecylcarbamoyl picolinic acid, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 1-hydroxybenzotriazole is 1:2:4:2.
Preferably, the method comprises the following steps: the organogel compound of the phenanthroline derivative according to claim 1 is obtained by heating an organogel compound in an organic solvent, which is any one of N, N-dimethylformamide/water (V/V, 10/1), dimethyl sulfoxide/water (V/V, 10/1), tetrahydrofuran/water (V/V, 5/1), ethanol, and 1, 4-dioxane, to dissolve and then cooling to room temperature.
Preferably, the organogel compound of the phenanthroline derivative has a critical gel concentration of 22.7mg/ml in N, N-dimethylformamide/water (V/V, 10/1).
Preferably, the organogel compound of the phenanthroline derivative has a critical gel concentration of 9.1mg/ml in dimethyl sulfoxide/water (V/V, 10/1).
Preferably, the organogel compound of the phenanthroline derivative has a critical gel concentration of 20.8mg/ml in a tetrahydrofuran/water (V/V, 5/1) mixed volume ratio.
Preferably, the organogel compound of the phenanthroline derivative has a critical gel concentration in ethanol of 5.6mg/ml.
Preferably, the organogel compound of the phenanthroline derivative has a critical gel concentration in 1, 4-dioxane of 25.0mg/ml.
Preferably, the organogel compound of the phenanthroline derivative is applied to detection of Zn 2+,Cu2+,Hg2+,Fe3+, al 3+ and volatile acid.
(III) beneficial effects
Compared with the prior art, the invention provides a preparation method and application of the organogel compound with AIE property, and the organogel compound has the following beneficial effects:
The organic gel compound of the phenanthroline derivative has pyridine groups and phenanthroline groups, and has metal ion sensing characteristics. The detection of mercury ions by the organogel compound of the phenanthroline derivative is mainly realized by destroying hydrogen bonds and intramolecular charge transfer which inhibit pi-pi accumulation among molecules, so that fluorescence emission spectrum of the organogel compound is quenched. The organogel compound of the phenanthroline derivative can also be used for detecting volatile acid, wherein the detection of the volatile acid is realized by reacting protons in the acid with nitrogen atoms of the phenanthroline to generate quaternary ammonium salt, and when organic amine is added, the color of the solution or the solid is restored to the original appearance through acid-base reaction.
The preparation method and the application of the organogel compound with AIE property can realize the liquid detection of Hg 2+ and volatile acid through the AIE solution of the phenanthroline derivative; the AIE film can realize the gas detection of volatile acid; the organic gel can realize the detection of Zn 2+、Cu2+、Hg2+、Al3+、Fe3+ and volatile acid gas, and the detection method is simple and quick, and can be used for distinguishing without adopting an instrument through naked eyes.
Drawings
FIG. 1 is a 1HNMR spectrum of an organogel compound of a phenanthroline derivative of formula I;
FIG. 2 is a 13CNMR spectrum of an organogel compound of a phenanthroline derivative of formula I;
FIG. 3 is a schematic diagram of the morphology of organogels formed by organogel compounds of phenanthroline derivatives in different solvents;
FIG. 4 is an SEM image of xerogels formed of organogel compounds of phenanthroline derivatives in different solvents;
FIG. 5 is a graph of the spectral change of compound APNP and compound APhen in a mixed solution of tetrahydrofuran and water of varying water content;
FIG. 6 is a graph of fluorescence emission spectra of tetrahydrofuran and water (60%) solutions of compound APNP after addition of various metal ions;
FIG. 7 is a graph of Hg 2+ titration fluorescence emission for a tetrahydrofuran and water (60%) solution of compound APNP and its corresponding linear plot;
FIG. 8 is a graph of Hg 2+ titration ultraviolet absorbance and kinetics of a tetrahydrofuran and water (60%) solution of compound APNP;
FIG. 9 is a schematic representation of tetrahydrofuran/water (V/V, 5/1) gel of compound APNP after addition of various metal ions and fluorescence emission spectra of Cu 2+,Zn2+ and Hg 2+ added;
FIG. 10 is a graph of fluorescence emission spectra of a tetrahydrofuran and water (60%) solution of compound APNP with the addition of various volatile acid liquids;
FIG. 11 is a TFA titration fluorescence emission plot of tetrahydrofuran and water (60%) solution of compound APNP and its corresponding linear plot;
FIG. 12 is a TFA titration ultraviolet absorbance and reaction kinetics plot for a tetrahydrofuran and water (60%) solution of compound APNP;
FIG. 13 is a graph and schematic of fluorescence emission spectra of tetrahydrofuran/water (V/V, 5/1) gel of compound APNP after contact with TFA vapor;
FIG. 14 is a graph showing the fluorescence emission of a tetrahydrofuran and water (60%) film of Compound APNP after contact with TFA and HCl, respectively, and its corresponding change in film emission at 365nm excitation;
FIG. 15 is a graph showing fluorescence emission spectra of a tetrahydrofuran and water (60%) film of Compound APNP after contact with triethylamine;
FIG. 16 is a graph showing the reaction kinetics of a tetrahydrofuran and water (60%) film of compound APNP after contact with TFA and HCl, respectively;
Fig. 17 is a fluorescence photograph of a solution of compound APNP in tetrahydrofuran and water (60%) for anti-counterfeit encryption and information storage applications.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The organogel compound of the phenanthroline derivative has a structure shown in a formula I:
the preparation route of the organogel compound of the phenanthroline derivative is as follows:
the preparation method comprises the following steps:
0.3g (0.828 mmol) of 4,4- (1, 10-phenanthroline-2, 9-diyl) diphenylamine, 0.567g (1.655 mmol) of 6-dodecylcarbamoyl picolinic acid, 0.635g (3.31 mmol) of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.224g (1.66 mmol) of 1-hydroxybenzotriazole are mixed in 100ml of dichloromethane, stirred at room temperature for 12h, then the dichloromethane is distilled off under reduced pressure, the remaining product is purified by a silica gel column with the eluent methanol/dichloromethane (1/30, v/v) to finally obtain a yellow powder, namely the compound shown in the formula I, the yield 70.5％,1H NMR(600MHz,DMSO-d6):δ10.84(s,2H),9.32(s,2H),8.63(d,J＝8.4Hz,4H),8.55(d,J＝8.3Hz,2H),8.39(t,J＝8.0Hz,4H),8.29(t,J＝11.4Hz,2H),8.25(t,J＝7.6Hz,2H),8.16(d,J＝8.5Hz,4H),7.98(s,2H),3.45(d,J＝6.7Hz,4H),1.72–1.64(m,4H),1.44–1.17(m,36H),0.78(t,J＝6.4Hz,6H).13C NMR(150MHz,DMSO-d6):δ149.7,148.5,141.3,135.9,135.2,132.3,125.9,123.8,121.7,114.5,112.6,111.4,108.1,106.1,18.0,16.2,15.2,13.4,8.6.HRMS calculated for C62H74N8O4[M+H]+995.5911,found:995.5930.
The 1 H NMR spectrum of the compound shown in formula I is shown in figure 1, and the 13 CNMR spectrum of the compound shown in formula I is shown in figure 2.
Example 2
The organogel compound of the phenanthroline derivative prepared in example 1 (abbreviated as compound 1) and an organic solvent were heated to about the boiling point of the solvent (80 ℃ or higher) in a sealed vial, and the organogel compound of the phenanthroline derivative was dissolved, then allowed to stand and cool to 25 ℃, and the gel forming ability thereof in different solvents was observed. The gels were all thermodynamically reversible and became flowable sols upon heating, with specific gel properties shown in table 1.
TABLE 1 organogel compounds of phenanthroline derivatives in different solvents in gel form
Annotation: wherein G represents a gel, S represents dissolution, and P represents insolubility; the minimum gel concentration in mg/ml is indicated in brackets.
As is clear from Table 1, the organogel compound of the phenanthroline derivative of the present invention can form organogel in N, N-dimethylformamide/water (V/V, 10/1), dimethylsulfoxide/water (V/V, 10/1), tetrahydrofuran/water (V/V, 5/1), ethanol, 1, 4-dioxane solvent.
Organogel compounds of phenanthroline derivatives have good stability in N, N-dimethylformamide/water (V/V, 10/1), dimethylsulfoxide/water (V/V, 10/1), tetrahydrofuran/water (V/V, 5/1), ethanol, 1, 4-dioxane solvents, are pale yellow opalescence, which can be left for several months, and have the morphology as shown in fig. 3, wherein a) in fig. 3 is an organogel formed in N, N-dimethylformamide/water (V/V, 10/1) solvent, b) is an organogel formed in dimethylsulfoxide/water (V/V, 10/1) solvent, c) is an organogel formed in tetrahydrofuran/water (V/V, 5/1) solvent, d) is an organogel formed in 1, 4-dioxane solvent, e) is an organogel formed in ethanol solvent.
The organic gels thus formed were diluted with the corresponding organic solvents, respectively, and then dispersed on a mica plate, and freeze-dried to form xerogels, and then each was subjected to a scanning electron microscope test, and as shown in fig. 4, the results of which are shown in fig. 4, a), b), c), d), and e) were SEM images of xerogels in N, N-dimethylformamide/water (V/V, 10/1), dimethylsulfoxide/water (V/V, 10/1), tetrahydrofuran/water (V/V, 5/1), ethanol, and 1, 4-dioxane solvents, respectively, and as shown in fig. 4, the compounds were self-assembled into regular microstrip structures having a width of about 10 μm and a length of about tens of micrometers in N, N-dimethylformamide/water (V/V, 10/1) solvents. Irregular micro rods with a width of 0.5-1.2 μm and a length of several micrometers were observed in an organogel formed of dimethyl sulfoxide/water (V/V, 10/1). In FIG. 4c, the membrane structure with some wrinkles is observed from organogels formed from tetrahydrofuran/water (V/V, 5/1) solvents. As shown in fig. 4d and 4e, irregular lamellar structures were observed in organogels formed from solvents of 1, 4-dioxane and ethanol.
Experimental example 1
The fluorescence change of the compound (APNP) of the phenanthroline derivative represented by formula I and the raw material (APhen) of the compound of the phenanthroline derivative represented by formula 2 in tetrahydrofuran of different water contents was studied. As shown in fig. 5a, the emission of solution APNP in THF is weak, probably due to the free and undisturbed rotation of the pyridine groups and good solubility in THF. When the water content was increased from 0 to 70%, the fluorescence intensity was gradually increased, and the maximum fluorescence peak was unchanged. The fluorescence intensity was maximized when the water content reached 70%, and decreased slightly when the water content was further increased. This is probably because rapid aggregation of APNP molecules in the random model resulted in distortion of APNP conformation, which in turn effectively inhibited the pi-pi stacking interactions between APNP molecules. Meanwhile, FIG. 5b records APhen in a mixed solution of tetrahydrofuran and water with different water contents, and the ACQ properties thereof were studied. At a water content of 10%, the intensity at 447nm was reduced by about 80%. When the water content is increased from 10% to 90%, the fluorescence intensity gradually decreases, and when the water content is more than 80%, the fluorescence emission is almost completely extinguished. The maximum emission peak of APhen in the pure tetrahydrofuran solution is shifted from 447nm to APhen nm in the mixed solution of tetrahydrofuran and water with different water contents, which shows that the APhen molecules have stronger pi-pi superposition effect. In summary, ACQ APNP can be perfectly converted to AIE of the target product APNP after appropriate modification to inhibit pi-pi stacking interactions.
Experimental example 2
The detection study of the compound (compound APNP) of the phenanthroline derivative shown in the formula I on metal ions is carried out by respectively selecting Al3+,Ca2+,Cu2+,Cd2+,Co2+,Eu3+,Fe2+,Fe3+,Hg2+,Mg2+,Mn2+,Ni2+,Pb2+,Tb3+ and Zn 2+ for experiment.
To a solution of compound APNP in tetrahydrofuran-water (60%) (c= -5 M) was added the different metal ions Al3 +,Ca2+,Cu2+,Cd2+,Co2+,Eu3+,Fe2+,Fe3+,Hg2+,Mg2+,Mn2+,Ni2+,Pb2+,Tb3+ and Zn 2+, as shown in fig. 6a, and after addition of Hg 2+ the fluorescence of the solution at 415nm was significantly quenched, as can be seen from fig. 6b, compound 1 was selective for Hg 2+.
The ability of compound APNP to detect Hg 2+ was studied by changes in fluorescence emission spectra.
As shown in fig. 7a, the solution of compound APNP had an emission peak at 415nm before Hg 2+ was added, and the fluorescence intensity at 415nm was gradually attenuated as the amount of Hg 2+ added dropwise. The fluorescence intensity of the solution of compound APNP was reduced by about 87.6% after the addition of 1.2 equivalent of Hg 2+. As shown in the inset in fig. 7a, the blue light emitted from the solution is exactly lost at the titration end. As shown in fig. 7b, the fluorescence intensity at 415nM and the addition amount of Hg 2+ are in a linear relationship, the linear coefficient R 2 = 0.9968, and the minimum detection limit of the compound APNP on Hg 2+ is 1.57nM. Subsequently, the kinetics of the reaction between compound APNP and Hg 2+ were verified by time-dependent fluorescence measurements. As shown in fig. 7b, the fluorescence intensity of the compound APNP at 415nm is strong 1.10min before the reaction, and the fluorescence intensity is drastically reduced within 30s after adding Hg 2+, which proves that the compound APNP can realize rapid detection of Hg 2+. During the uv titration of fig. 8a, the absorption band maximum at 380nm also gradually decreases. No significant color change was observed due to the change in the ultraviolet absorption spectrum. But weak absorption at 380nm is the primary cause of emission quenching by Hg 2+. Therefore, the compound APNP is mainly used for detecting mercury ions through coordination with nitrogen atoms of phenanthroline units, and the structure of the compound APNP is changed after the mercury ions are added as follows:
to further demonstrate the selectivity of compound APNP to Hg 2+, compound APNP in tetrahydrofuran/water (V/V, 5/1) organogels and after addition of Al3+,Ca2+,Cu2+,Cd2+,Co2+,Eu3+,Fe2+,Fe3+,Hg2+,Mg2+,Mn2+,Ni2+,Pb2+,Tb3+ and Zn 2+, the results of the changes are shown in fig. 9. Compound APNP after addition of 1.0 equivalent of Fe 3+ to an organogel of tetrahydrofuran/water (V/V, 5/1), the gel changed from pale yellow to bright yellow. When the same equivalent of Al 3+ is added, the gel changes from original blue light to yellow light under the irradiation of a 365nm ultraviolet lamp. After addition of 1.0 equivalent of Zn 2+,Cu2+ and Hg 2+, the gel underwent a macroscopic phase transition, yielding a white precipitate of compound APNP, a purple partial gel and a yellow solution, respectively. As can be seen from fig. 9, fe 3+,Al3+,Zn2+,Cu2+ and Hg 2+ can be separated from the compound 1 by the naked eye. In particular mercury ions, not only undergo a phase transition from gel to solution but also maintain quenching of the fluorescent signal.
Experimental example 3
The organogel compound (compound APNP) of the phenanthroline derivative shown in formula I is used for detecting volatile acid, and trifluoroacetic acid is taken as an example for research.
To a tetrahydrofuran-water (60%) solution of the phenanthroline derivative of formula i (c= -5 M) (compound APNP) was added a different volatile acid solution. As shown in fig. 10, the volatile acid quenches the fluorescence intensity of compound APNP. After addition of 1.0 equivalent of acetic acid, formic acid, HCl and TFA, respectively, the emission intensity of compound APNP at 413nm was reduced by 58.6%, 49.5%, 63.4% and 49.1%, respectively. To examine the detection ability of the compound in a mixed solution of tetrahydrofuran and water having a water content of 60%, a fluorescence titration experiment was performed on a sample represented by TFA. As shown in FIG. 11, with the addition of trifluoroacetic acid, the absorption peak at 413nm gradually decreased by 81.5%. As shown in fig. 11b, the fluorescence intensity at 413nM and the addition amount of trifluoroacetic acid are in a linear relationship, the linear coefficient R 2 = 0.9923, and the lowest detection limit of the compound APNP on the trifluoroacetic acid is 1.47nM. As shown in fig. 12, the reaction kinetics experiments of compound APNP with TFA showed that the reaction time of compound APNP was within 0.5s, indicating that compound APNP could detect liquid volatile acids in real time. With the continuous addition of TFA, the original absorption band was greatly reduced. In particular, at 380nm, the absorbance decreased by about 80%, indicating that the quenching of fluorescence by TFA is due to the decrease in absorbance at 380 nm. The principle of detecting gaseous acid by the compound APNP is as follows: the fluorescence signal of the solution of compound APNP is reduced by the reaction of protons in the acid with the nitrogen atom of the phenanthroline group in compound APNP to form a quaternary ammonium salt.
TFA gas was sprayed onto the tetrahydrofuran/water (V/V, 5/1) organogel surface of the phenanthroline derivative of formula I, as shown in FIG. 13, the pale yellow gel emitted intense blue fluorescence at 415 nm. Upon contact with TFA vapor, the organogel of compound APNP disintegrated within 1min, and after 6min the gel completely turned into a yellow precipitate, exhibiting weak emission at 561 nm.
A solution of the phenanthroline derivative of formula i in tetrahydrofuran-water (60%) was taken (c= -4 M) (compound APNP) and was dropped onto a quartz plate, followed by drying to obtain a thin film of compound APNP. As shown in fig. 14, after exposure to TFA vapor at a concentration of 7.95ppb, the emission intensity of the film rapidly disappeared at 415nm, and a new emission peak appeared at 530 nm. As can be seen from the inset image in fig. 14a, the light emitted by the thin film of compound APNP changes from blue to yellow under 365nm light. When a thin film of compound APNP was exposed to 9.52ppb HCl vapor, the intensity at 415nm was reduced by 81.8% and another peak at 530nm occurred. To verify the protonation of the 1, 10-phenanthroline groups and the reversibility of the film of compound APNP, TEA vapors were added to neutralize the protons of the film. After addition of saturated TEA gas, the fluorescence emission peak at 415nm was recovered and the fluorescence emission peak at 530nm was disappeared. However, the recovery period emission at 415nm cannot reach the original intensity. As can be seen from the inset image in fig. 14, the film emission color of compound APNP returns to blue under UV light. As shown in fig. 15, to exclude the effect of TEA on the experiment, no significant change was observed by exposing a thin film of compound APNP to TEA gas. At the same time the response time of the thin film of compound APNP to TFA was also studied, as shown in fig. 16. TFA quenched the fluorescence of APNP thin films by 79.5% in 5s and the fluorescence at 415nm was completely quenched. For HCl, the response time is reduced to 0.5s, probably due to the stronger acidity of HCl. Therefore, the xerogel film can quantitatively detect volatile acid steam, and has high reaction speed.
The detection of gaseous volatile acid is that the proton in the acid reacts with the nitrogen atom of the phenanthroline serving as a central unit to generate quaternary ammonium salt, a fluorescence signal is changed, and when organic amine is added, the fluorescence signal is converted back through acid-base reaction, wherein the structural change of the compound APNP is shown as follows.
Anti-counterfeiting and secure data storage technologies play an important role in different fields. The potential application of the thin film of the compound APNP in multi-level information encryption is discussed by utilizing the tunable emission of the thin film of the compound APNP under external stimulus. A tetrahydrofuran-water (60%) solution (c= -4 M) of the phenanthroline derivative of formula i was used as an ink to draw a flower on the filter paper (fig. 17). After drying, green plants with no flowers appeared under natural light and 365nm light. Immediately after spraying TFA vapor on the upper pattern, bright yellow flowers stand vividly on the green plants. When the flowers were to disappear again, the flowers disappeared quickly by simply contacting the pattern with TEA gas. The result shows that the phenanthroline derivative shown in the formula I has potential application prospect in the fields of anti-counterfeiting encryption and information storage.
In summary, the preparation method and application of the organogel compound with AIE property have the metal ion sensing characteristic through the existence of pyridine groups and phenanthroline groups in the organogel compound of the phenanthroline derivative. The detection of mercury ions by the organogel compound of the phenanthroline derivative is mainly realized by destroying hydrogen bonds and intramolecular charge transfer which inhibit pi-pi accumulation among molecules, so that fluorescence emission spectrum of the organogel compound is quenched. The organogel compound of the phenanthroline derivative can also be used for detecting volatile acid, wherein the detection of the volatile acid is realized by reacting protons in the acid with nitrogen atoms of the phenanthroline to generate quaternary ammonium salt, and when organic amine is added, the color of the solution or the solid is restored to the original appearance through acid-base reaction.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A process for the preparation of organogel compounds having AIE properties, characterized in that: the method comprises the following steps: mixing 4,4- (1, 10-phenanthroline-2, 9-diyl) diphenylamine, 6-dodecylcarbamoyl picolinic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole and dichloromethane, stirring at normal temperature for 10-13 h, then evaporating dichloromethane under reduced pressure, and purifying the rest products by a column to obtain the catalyst;
The molar ratio of the 4,4- (1, 10-phenanthroline-2, 9-diyl) diphenylamine, 6-dodecylcarbamoyl picolinic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1-hydroxybenzotriazole is 1:2:4:2;
the specific structure of the organogel compound is as follows:
2. An organogel characterized in that: the method comprises the following steps: the organogel compound prepared by the preparation method of claim 1 is heated in an organic solvent to be dissolved, and then cooled to room temperature, wherein the organic solvent is any one of N, N-dimethylformamide/water, V/V=10/1, dimethyl sulfoxide/water, V/V=10/1, tetrahydrofuran/water, V/V=5/1, ethanol and 1, 4-dioxane.
3. An organogel according to claim 2, characterized in that: the organogel compound had a critical gel concentration of 22.7mg/ml in N, N-dimethylformamide/water, V/v=10/1.
4. An organogel according to claim 2, characterized in that: the organogel compound had a critical gel concentration of 9.1mg/ml in dimethylsulfoxide/water, V/v=10/1.
5. An organogel according to claim 2, characterized in that: the organogel compound had a critical gel concentration of 20.8mg/ml in tetrahydrofuran/water, V/v=5/1 mixed volume ratio.
6. An organogel according to claim 2, characterized in that: the organogel compound had a critical gel concentration in ethanol of 5.6mg/ml.
7. An organogel according to claim 2, characterized in that: the organogel compound had a critical gel concentration in 1, 4-dioxane of 25.0mg/ml.
8. Use of organogel compounds with AIE properties prepared according to the preparation process of claim 1, characterized in that: the application of the organogel compound in detecting Zn 2+,Cu2+,Hg2+,Fe3+ and Al 3+ and volatile acid, wherein the volatile acid is acetic acid, formic acid, hydrochloric acid or trifluoroacetic acid.
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| 邻菲罗啉衍生物与人端粒G-四链体DNA的相互作用及细胞活性研究;王立华;文烨;刘洁;张芳芳;魏春英;;山西大学学报(自然科学版);20120815(03);第520-524页 * |
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