CN106432341A - Hyperbranched CTP-TPY (Cyclotriphosphazene Terpyridyl), preparation method and recognition method of metal ions - Google Patents
Hyperbranched CTP-TPY (Cyclotriphosphazene Terpyridyl), preparation method and recognition method of metal ions Download PDFInfo
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- CN106432341A CN106432341A CN201610817500.3A CN201610817500A CN106432341A CN 106432341 A CN106432341 A CN 106432341A CN 201610817500 A CN201610817500 A CN 201610817500A CN 106432341 A CN106432341 A CN 106432341A
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- China
- Prior art keywords
- ctp
- tpy
- hyperbranched
- terpyridyl
- tripolyphosphazene
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000002189 fluorescence spectrum Methods 0.000 claims abstract description 8
- 238000004448 titration Methods 0.000 claims abstract description 8
- 230000004044 response Effects 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000008267 milk Substances 0.000 claims description 6
- 210000004080 milk Anatomy 0.000 claims description 6
- 235000013336 milk Nutrition 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011835 investigation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims 1
- -1 rare earth europium ions Chemical class 0.000 abstract description 21
- 229910052693 Europium Inorganic materials 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 6
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical class PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 2
- ZHBOFZNNPZNWGB-UHFFFAOYSA-N 9,10-bis(phenylethynyl)anthracene Chemical compound C1=CC=CC=C1C#CC(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C#CC1=CC=CC=C1 ZHBOFZNNPZNWGB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000009576 somatic growth Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
-
- 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"
- G01N2021/6443—Fluorimetric titration
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
Abstract
The invention relates to Hyperbranched CTP-TPY (Cyclotriphosphazene Terpyridyl), a preparation method and a recognition method of metal ions, and belongs to the field of luminescent materials. Firstly, a CTP-TPY multi-core ligand is compounded; then, fluorescence spectrum titration on various metal ions by a cyclotriphosphazene derivative and a hyperbranched triphosphazene derivative is researched, ultraviolet and fluorescent responses of the cyclotriphosphazene derivative and the hyperbranched triphosphazene derivative on different metal ions are detected, and a result verifies that rare earth europium ions and zinc ions can be well recognized by CTP-TPY. The hyperbranched CTP-TPY disclosed by the invention has better photoluminescence performance and electroluminescence performance, high stability, good solubility and low cost; the preparation method is relatively low in cost, simple in operation, low in risks and easy to promote and use. The hyperbranched CTP-TPY has six coordination sites, so that metal Eu<3+> and Zn<2+> can be more effectively recognized, the selective recognition ability is high, and response is rapid.
Description
Technical field
The present invention relates to field of light emitting materials is and in particular to hyperbranched tripolyphosphazene terpyridyl and its synthetic method and right
The recognition methodss of metal ion.
Background technology
Supramolecular chemistry can imitate out the more special function of many of the material that nature has existed, and is formed
New material, has been developed as merging with the subject crossing such as life sciences, material science, nano science, information science now
Supermolecule science, supermolecule device, supermolecular biosome material, supermolecule capsule, liquid crystal material, tissue or organ substitute
The aspects such as thing, nano material, new polymerss and LB membrane material suffer from being widely applied prospect, are 21 century new material and height
The important development of technology.In the process of development supramolecular materials, how to make good use of the peculiar property of supramolecular materials, develop
Abundanter, the material of more top time, to be applied in wider field.
The ligancy of rare earth ion is high, and it is interchangeable that polypodand has the characteristics that structure can be in harmonious proportion function terminal groups, can obtain
There is the hyperbranched coordination compound of novel structure, enable rare earth material to obtain the application of more areas.The part of oversubscription subclass utilizes
The hyperbranched coordination compound that multi-functional part and rare earth central ion pass through the effect formation such as hydrogen bond, coordinate bond has become material
Hot fields in chemistry, Coordinative Chemistry and supramolecular chemistry research, have the joining of hyperbranched rare earth compounding of novel structure
Body is the focus of illumination field research in recent years.Rare earth ion chemical property is similar, and detection rare earth ion just becomes
A great problem.In view of metal ion the content in human body and on physiology and pathology role, design and
Development can be used for biological internal identification metal-ion fluorescent sensor and is particularly important.
Fluorescence sense technology is because it has the feasibility of the exchange of " wireless " remote control between high sensitivity, each molecule, special
Wide dynamic response time and using more convenient the advantages of enjoy researchers favor.The design mesh of fluorescence chemical sensor
Predominantly detect various aniones, cation and molecule, have simple, economical, can be than photoresponse in larger concentration range
The advantages of.Zn2+It is trace element needed by human, be widely distributed in the body fluid of human body and intracellular, the direct participant of zinc ion
In the vital metabolic such as somatic growth, growth, tissue repair, reproduction, vital movement plays very important effect.Zinc
In ion fluorescence sensor, the more commonly used carrier is mostly pyridine derivatives such as BPA, BPEA and TPEA, the knowledge of these parts
Other site is single, and identification ability is weaker.Compared to pyridine derivatives such as BPA, BPEA and TPEA, it is super that this Patent design synthesizes
Branched tripolyphosphazene terpyridyl CTP-TPY has six recognition sites, not only to Zn2+There is higher selection identification ability,
And can be to rare earth Eu3+Effectively identified.
Content of the invention
For deficiencies of the prior art, the invention provides a kind of photoluminescence performance and electroluminescent properties
Excellent, good stability, dissolubility hyperbranched tripolyphosphazene terpyridyl excellent and with low cost.
Another object of the present invention is to providing the preparation method of above-mentioned hyperbranched tripolyphosphazene terpyridyl.
It is still another object of the present invention to provide the selectivity to metal ion for the above-mentioned hyperbranched tripolyphosphazene terpyridyl
Recognition methodss.
Solve above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of hyperbranched tripolyphosphazene terpyridyl
CTP-TPY it is characterised in that：Its structural formula is：
Wherein, reaction is carried out at room temperature with CTP-CHO and 2-acetopyridine and obtains hyperbranched tripolyphosphazene terpyridyl,
Its synthetic route is：
Concrete steps include：
The preparation of (1) six (4- formaldehyde phenoxyl) ring three phosphonitrile (CTP-CHO)：
The hexachlorocyclotriph,sphazene of 1 equivalent, the hydroxy benzaldehyde (para hydroxybenzene of 6 equivalents is sequentially added in single-necked flask
Methyl formate) and 6 equivalents potassium carbonate, with 200ml oxolane dissolving, heated and stirred at 66 DEG C, condensing reflux 40-48h；
It is changed to distilling apparatus, distilling off solvent oxolane after reaction completely, then product is added in 1000ml distilled water, stirring
30min, static obtain white precipitate, sucking filtration, with distilled water wash three times, be placed in 60 DEG C of dryings in vacuum drying oven；Use acetic acid
Ethyl ester is recrystallized to give six (4- formaldehyde phenoxyl) ring three phosphonitrile (CTP-CHO)；
(2) preparation of hyperbranched tripolyphosphazene terpyridyl CTP-TPY：
CTP-CHO, the 2-acetopyridine of 12 equivalents and the 500ml dehydrated alcohol of 1 equivalent is added in there-necked flask, completely molten
Lurid solution is obtained after solution；It is subsequently adding potassium hydroxide KOH, the ammonia of 12 equivalents of 12 equivalents, stir under room temperature, solution
Become light brown, stopped reaction after reacting 12 hours；Remove solvent with Rotary Evaporators revolving, obtain a large amount of milk yellow precipitations,
Filter, then with 500～1000ml absolute ethanol washing 2-3 time, obtain milk yellow powder；The product obtaining is placed vacuum drying
60 DEG C of dried in vacuum overnight in case, obtain final product hyperbranched tripolyphosphazene terpyridyl CTP-TPY.
The present invention is mainly hyperbranched tripolyphosphazene terpyridyl CTP-TPY should identify for metalloform-selective
With.
Hyperbranched tripolyphosphazene terpyridyl CTP-TPY is used for the Selective recognition method to metal ion, and its feature exists
In comprising the steps：
(1) prepare 1x10 with volumetric flask-4The hyperbranched tripolyphosphazene terpyridyl CTP-TPY solution of mol/L, solvent is four
Hydrogen furan, chloroform, N, one or more of N '-dimethyl Methanamide, dimethyl sulfoxide；
(2) prepare 1x10 respectively with volumetric flask-2Mol/L metal cation ethanol solution；Described metal cation is Zn2+、
Ni2+、K+、Mg2+、Na+、Fe3+、Ca2+、Ba2+、Pd2+、Hg+、Cu2+、Li+、Co2+、Eu3+Or Tb3+Deng 15 kinds of metal cations.
(3) all of fluorescence titration experiment is all carried out under the conditions of 25 ± 0.5 DEG C, quantitative master used by each titration experiments
Body (CTP-TPY) is 3ml, and metal cation solution is instilled by 5ul, 10ul, 20ul, 30ul, 60ul incremented by successively, instills every time
Carry out fluorometric investigation with 3 minutes after dropper mix homogeneously more afterwards；
Record metal cation solution fluorescence spectrum is simultaneously analyzed.
Compared to existing technology, the present invention has the advantages that：
1st, for compared to the conventional organic ligand only with a coordination site, hyperbranched poly phosphonitrile of the present invention
Terpyridyl CTP-TPY has six coordination sites, can more effectively with metal Eu3+And Zn2+It is identified, select identification energy
Power is high and is swift in response.Selective recognition especially to europium soil ion.
2nd, the present invention provide preparation method relative inexpensiveness, simple to operate, risk low it is easy to promote the use of.
Brief description
Fig. 1 is six (4- formaldehyde phenoxyl) ring tripolyphosphazene infrared spectrum (potassium bromide pressure of the embodiment of the present invention 1 gained
Piece).
Fig. 2 is the infrared spectrum (bromination of the hyperbranched tripolyphosphazene terpyridyl CTP-TPY of the embodiment of the present invention 2 gained
Potassium tabletting).
Fig. 3 is the fluorescent exciting spectrogram of the hyperbranched tripolyphosphazene terpyridyl CTP-TPY of the embodiment of the present invention 2 gained
(launch wavelength：415nm, slit 5nm, DMF dissolve).
Fig. 4 is the thermogravimetric analysiss spectrogram of the hyperbranched tripolyphosphazene terpyridyl CTP-TPY of the embodiment of the present invention 2 gained.
Fig. 5 is the fluorescent emission spectrogram with the interaction of europium ion for the CTP-TPY part of the embodiment of the present invention 3 gained
(excitation wavelength：365nm, slit 5nm, DMF dissolve).
Fig. 6 is CTP-TPY part and the Zn of the embodiment of the present invention 3 gained2+The fluorescent emission spectrogram of interaction (excite
Wavelength：365nm, slit 5nm, DMF dissolve).
Fig. 7 is the fluorescent emission with the interaction of other metal ions for the part CTP-TPY of the embodiment of the present invention 3 gained
Spectrogram (excitation wavelength：365nm, slit 5nm, DMF dissolve).
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1：The preparation of six (4- formaldehyde phenoxyl) ring phosphonitrile (CTP-CHO)：
Oxolane 100ml, hexachlorocyclotriph,sphazene 2.50g (7.19mmol) is sequentially added in 250ml single-necked flask, right
Hydroxy benzaldehyde 6.30g (51.59mmol), potassium carbonate 11.38g (82.30mmol), heated and stirred under 66 degree, condensing reflux
48h.
It is changed to distilling apparatus, distilling off solvent oxolane after reaction completely, then product is added to 1000ml distillation
Water, stirs half an hour, static obtain white precipitate, sucking filtration, with distilled water wash three times, be placed in vacuum drying oven 60 degree dry
Dry.Obtain product six (4- formaldehyde phenoxyl) ring phosphonitrile (CTP-CHO) with re-crystallizing in ethyl acetate.Reaction equation is as follows：
As accompanying drawing 1 mid-infrared spectrogram can be seen that 2820cm-1And 2740cm-1For the upper C-H characteristic absorption peak of-CHO；
1700.4cm-1It is the characteristic absorption peak of the upper C=O of-CHO；1590.8cm-1、1500cm-1、1590.8cm-1、1500.0cm-1With
1430.0cm-1The absorption band at place is the skeletal vibration absorption band of phenyl ring；832.1cm-1Strong absorption be para-orientation benzene feature
Absworption peak；1010.0cm-1And 961.8cm-1Locate the absworption peak for P-O-C；1160.7cm-1And 1270.3cm-1Absorption for P=N
Peak；891.4cm-1Absworption peak for P-N.Compare with the infrared spectrum of hexachlorocyclotriph,sphazene, 518cm-1, 605cm-1The absorption at place
The basic stretching vibration absorption disappearing, there's almost no P-Cl, illustrates that most chlorine is all substituted, has synthesized target product
For six (4- formaldehyde phenoxyl) ring phosphonitrile.
Embodiment 2：The preparation of hyperbranched poly phosphonitrile terpyridyl CTP-TPY：
Six (4- formaldehyde phenoxyl) ring phosphonitrile 4.04g (4.14mmol), 2- acetyl pyrrole is added in the there-necked flask of 500ml
Pyridine 7.18g (55.68mmol), adds dehydrated alcohol 120ml, oxolane 200ml, obtains lurid molten after being completely dissolved
Liquid, is subsequently adding potassium hydroxide KOH 3.894g (55.68mmol), ammonia 90ml, stirs under room temperature, solution becomes light brown,
Stopped reaction after reacting 12 hours, removes oxolane with Rotary Evaporators revolving, obtains a large amount of milk yellows precipitations, filters, then
With substantial amounts of absolute ethanol washing 2-3 time, obtain milk yellow powder, put in vacuum drying oven 60 DEG C and be dried overnight.Reacted
Journey is as follows：
As accompanying drawing 2 mid-infrared spectrogram can be seen that in 3050cm-1Place, is the stretching vibration absworption peak of C-H, 1598cm-1、
1580cm-1And 1500cm-1The absorption band at place is the skeletal vibration absorption band of phenyl ring, 1160cm-1It is the stretching vibration absorption of C-N
Band, 960cm-1Locate the absworption peak for P-O-C.Compare with the infrared spectrum of six (4- formaldehyde phenoxyl) ring tripolyphosphazene ,-CHO
The characteristic absorption peak 1700cm of upper C=O-1Basic disappearance, above results proved that and successfully synthesize target product hyperbranched poly phosphorus
Nitrile terpyridyl CTP-TPY.
As in accompanying drawing 3, fluorescence spectrum can be seen that the hyperbranched tripolyphosphazene terpyridyl CTP-TPY of synthesis, exciting
In the presence of light, send blue green light, 415nm is the scope of blue light.
As in accompanying drawing 4, thermogravimetric spectrogram can be seen that the liter with temperature for the hyperbranched tripolyphosphazene terpyridyl CTP-TPY
Height, water, solvent molecule start to volatilize, and the P-O key that the tripolyphosphazene ring at center was connected with para-position phenyl ring later starts chain rupture and decomposes
This process is continued until 510 DEG C, and after this, the rigid radical such as phenyl ring starts slowly to decompose.
Embodiment 3：The Selective recognition to each metal ion species for the hyperbranched tripolyphosphazene terpyridyl CTP-TPY, fluorescence
Titration process is as follows：
1st, the volumetric flask using 50ml prepares supermolecule tripolyphosphazene terpyridyl CTP-TPY solution, and solvent is oxolane,
Solution concentration is 1 × 10-4mol/L.
2nd, prepare Zn respectively with the volumetric flask of 50ml again2+、Ni2+、K+、Mg2+、Na+、Fe3+、Ca2+、Ba2+、Pd2+、Hg+、Cu2 +、Li+、Co2+、Eu3+、Tb3+Deng 15 kinds of metal cation ethanol solution, solution concentration is 1 × 10-2mol/L.
3rd, all of fluorescence titration experiment is all carried out under the conditions of 25 ± 0.5 DEG C, the main body used by each titration experiments
(CTP-TPY) it is 3mL, metal cation solution is instilled by 5ul, 10ul, 20ul, 30ul, 60ul incremented by successively, after instilling every time
Carry out fluorometric investigation with 3 minutes after dropper mix homogeneously again.With object (metal cation solution) addition fluorescence spectrum by
Gradually it is recorded.
As accompanying drawing 5 fluorescence spectrum can be seen that the characteristic light spectral line of europium ion, at 590nm it is5D0→7F1, position
Main emission peak at 618nm be5D0→7F2Transition display HONGGUANG, at 655nm be5D0→7F3, positioned at 704nm
Place is5D0→7F4.With the increase of europium ion, launching peak intensity is also increasing, and after adding the europium ion solution of 90ul, sends out
Penetrate peak intensity and reach maximum, continuously add europium ion solution to 150ul, launch peak intensity and have dropped on the contrary, this is also in that surpass
The reaction of branched tripolyphosphazene terpyridyl CTP-TPY and europium ion has reached saturation, has a small amount of flocculent deposit in solution
Generate.It should be noted that with the addition of europium ion, indigo plant at 415nm for the hyperbranched tripolyphosphazene terpyridyl CTP-TPY
Green light peak at photopeak and 503nm gradually weakens, and after adding the europium ion of 90ul, the green light peak at 503nm is wholly absent.This
A little results all show, europium ion and hyperbranched tripolyphosphazene terpyridyl CTP-TPY there occurs coordination, and CTP-TPY will inhale
The energy efficient received has been delivered to the europium ion centre of luminescence.
It is issued by the light blue green light of comparison as accompanying drawing 6 fluorescence spectrum can be seen that in itself, hyperbranched tripolyphosphazene three
Pyridine CTP-TPY, with Zn2+Increase, the intensity of blue light characteristic peak and green glow characteristic peak all declining, last green glow characteristic peak
There's almost no.Zn is described2+Addition, with part interact, the fluorescent quenching of system can be made.
When can be seen that addition europium ion as accompanying drawing 7 fluorescence spectrum, red emission peak intensity strengthens, when adding zinc ion,
The blue light peak intensity of part script and green glow peak intensity all decline, but when adding the metal ion of other same concentrations, part
Emission spectra characteristic peak change all very littles, this demonstrate that part hyperbranched tripolyphosphazene terpyridyl CTP-TPY pair of synthesis
Eu3+And Zn+2There is selectivity, especially to rare earth Eu3+There is high selectivity, so hyperbranched tripolyphosphazene terpyridyl
CTP-TPY is expected to become europium ion high selectivity sensor in following development.
The Selective recognition principle of other metal ions is identical, does not make tired stating.
Finally illustrate, above example only in order to technical scheme to be described and unrestricted, although with reference to relatively
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, the objective without deviating from technical solution of the present invention and scope, and it all should be covered at this
In the middle of the right of invention.
Claims (5)
1. a kind of hyperbranched tripolyphosphazene terpyridyl CTP-TPY it is characterised in that：Its structural formula is：
2. as claimed in claim 1 hyperbranched tripolyphosphazene terpyridyl CTP-TPY preparation method it is characterised in that with
CTP-CHO and 2-acetopyridine carry out reaction at room temperature and obtain hyperbranched tripolyphosphazene terpyridyl, and its synthetic route is：
Concrete steps include：
The preparation of (1) six (4- formaldehyde phenoxyl) ring three phosphonitrile (CTP-CHO)：
The hexachlorocyclotriph,sphazene of 1 equivalent, the hydroxy benzaldehyde (P-hydroxybenzoic acid of 6 equivalents is sequentially added in single-necked flask
Methyl ester) and 6 equivalents potassium carbonate, with 200ml oxolane dissolving, heated and stirred at 66 DEG C, condensing reflux 40-48h；Reaction
It is changed to distilling apparatus, distilling off solvent oxolane after completely, then product is added in 1000ml distilled water, stirring
30min, static obtain white precipitate, sucking filtration, with distilled water wash three times, be placed in 60 DEG C of dryings in vacuum drying oven；Use acetic acid
Ethyl ester is recrystallized to give six (4- formaldehyde phenoxyl) ring three phosphonitrile (CTP-CHO)；
(2) preparation of hyperbranched tripolyphosphazene terpyridyl CTP-TPY：
Add CTP-CHO, the 2-acetopyridine of 12 equivalents and the 500ml dehydrated alcohol of 1 equivalent in there-necked flask, after being completely dissolved
Obtain lurid solution；It is subsequently adding potassium hydroxide KOH, the ammonia of 12 equivalents of 12 equivalents, stirs under room temperature, solution becomes
Light brown, stopped reaction after reacting 12 hours；Remove solvent with Rotary Evaporators revolving, obtain a large amount of milk yellow precipitations, filter,
Again with 500～1000ml absolute ethanol washing 2-3 time, obtain milk yellow powder；The product obtaining is placed in vacuum drying oven
60 DEG C of dried in vacuum overnight, obtain final product hyperbranched tripolyphosphazene terpyridyl CTP-TPY.
3. as claimed in claim 2 hyperbranched tripolyphosphazene terpyridyl CTP-TPY preparation method it is characterised in that：Step
(1) reaction is nucleophilic substitution, response time 48h.
4. hyperbranched tripolyphosphazene terpyridyl CTP-TPY is in the application identifying for metalloform-selective.
5. hyperbranched tripolyphosphazene terpyridyl CTP-TPY be used for the Selective recognition method of metal ion it is characterised in that
Comprise the steps：
(1) prepare 1x10 with volumetric flask-4The hyperbranched tripolyphosphazene terpyridyl CTP-TPY solution of mol/L, solvent is tetrahydrochysene furan
Mutter, chloroform, N, one or more of N '-dimethyl Methanamide, dimethyl sulfoxide；
(2) prepare 1x10 respectively with volumetric flask-2Mol/L metal cation ethanol solution；
(3) all of fluorescence titration experiment is all carried out under the conditions of 25 ± 0.5 DEG C, quantitative main body used by each titration experiments
(CTP-TPY) it is 3ml, metal cation solution is instilled by 5ul, 10ul, 20ul, 30ul, 60ul incremented by successively, after instilling every time
Carry out fluorometric investigation with 3 minutes after dropper mix homogeneously again；
Record metal cation solution fluorescence spectrum is simultaneously analyzed.
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| CN114164431A (en) * | 2021-12-03 | 2022-03-11 | 菏泽学院 | Hyperbranched organic ionic liquid metal corrosion inhibitor and preparation method thereof |
| CN114164431B (en) * | 2021-12-03 | 2024-02-20 | 菏泽学院 | Hyperbranched organic ion liquid metal corrosion inhibitor and preparation method thereof |
| CN114539497A (en) * | 2022-04-02 | 2022-05-27 | 南昌航空大学 | Cyclotriphosphazene-acylhydrazone covalent organic polymer material and preparation method and application thereof |
| CN114539497B (en) * | 2022-04-02 | 2023-03-10 | 南昌航空大学 | Cyclotriphosphazene-acylhydrazone covalent organic polymer material and preparation method and application thereof |
| CN116706237A (en) * | 2023-08-07 | 2023-09-05 | 浙江华宇钠电新能源科技有限公司 | Quick ion conductor additive, mixed electrolyte, sodium ion battery and vehicle |
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