CN104311801B - Soluble conjugated polymer of a kind of selenole and preparation method thereof and purposes - Google Patents
Soluble conjugated polymer of a kind of selenole and preparation method thereof and purposes Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 230000003287 optical effect Effects 0.000 claims abstract description 69
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 60
- 150000002500 ions Chemical class 0.000 claims description 30
- 238000010189 synthetic method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 26
- 238000011160 research Methods 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 43
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 40
- 238000001514 detection method Methods 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 230000008859 change Effects 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 10
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 10
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- -1 sulfhydryl compound Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001880 copper compounds Chemical group 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical group [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical group 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to provide and a kind of can be used to conjugated polymer based on selenole detecting heavy metal ion or class heavy metal ion and preparation method thereof and purposes, some ion is had good fluorescence response by described polymer, can be used as fluorescent optical sensor.Additionally, due to this fluorescence response, this polymer can be used to build Molecular Logic Gates from different guest molecules, thus having good scientific research value and application potential.
Description
Technical field
The present invention relates to a kind of polymer that can be used as fluorescent optical sensor for detecting heavy metal ion, relate more particularly to a kind of conjugated polymer based on selenole and preparation method thereof and purposes, belong to compound fluorescent optical sensor field.
Background technology
Development along with China's industrialization and urbanization, the problem of environmental pollution that entire society faces becomes increasingly conspicuous, the sewage such as industry, agricultural, life for a long time in a large number in line enter river, river water quality goes from bad to worse, particularly containing plurality of heavy metal composition in trade effluent, such as lead, hydrargyrum, nickel, copper, cadmium, chromium, ferrum etc., these heavy metal ion can be amassed by food chain richness in biological tissue, causes human body acute or chronic poisoning.Such as, in common heavy metal pollution ion, Hg2+Harm is big especially, and wide-scale distribution, can cause serious environment and social problem；Fe3+Although material necessary to all living cells, but excessive existence also has fatal harm；Additionally, environment especially water body, soil etc. also all can be caused serious harm by lead, nickel, copper, cadmium, chromium.
Raising along with entire society's environmental consciousness, heavy metal ion pollution in water body, soil also increasingly attracts much attention, if promptly and accurately measure the content of heavy metal ion in environment, to understanding its pollution level in time, prevent heavy metal pollution, to propose effective processing method particularly important.
Detection people for these heavy metal ion have been developed that multiple method, such as plasma emission spectrometry, atomic absorption spectrography (AAS), atomic emissions spectrometry etc., but there are some defects in these methods, such as these method and technologies require height, sample needs pretreatment, detection quick not, used instrument price is expensive, maintenance cost high, detects expensive etc., it is difficult to widely use.Therefore, in much important application scenario, people analyze, in the urgent need to quick, accurate, low cost the property of can select that, the method detecting these heavy metals.
Fluorescent optical sensor is that a class can by molecule, the ion identification event molecule by fluorescence signal effective expression, owing to fluorescence spectrophotometer used is simply inexpensive, highly sensitive, easy to operate, thus the fluorescence identifying being widely used in the analytes such as cation, anion and neutral molecule by people detects, and developed rapidly.Conjugated polymer fluorescent optical sensor is owing to, in light activated situation, energy can be effective along conjugated backbone fast transferring, amplifies transducing signal, and this feature causes that it has higher sensitivity compared with small molecule fluorescent sensor.
For this advantage, being developed some polymer, some in these polymer relate to selenole skeleton involved in the present invention, for instance:
CN102746492A discloses the polygonal line type water-soluble aryleneethynylene of a kind of conjugated main chain doping, and it is structured with formula:
Wherein, R and two alkynyls lay respectively at three of phenyl ring between on position；Ar is the one that phenyl, 9,9-bis-replace in fluorenyl；Ar ' is diazosulfide group, one in selenole group；Polymerization degree n is the natural number more than 1,0.7≤x < 1,0 < y≤0.3, and x+y=1；R, R ' and R " it is respectively selected from hydrogen atom H, R1R2R3R4N+Or R5Any one in group.This compound can be induced by some external condition and FRET (fluorescence resonance energy transfer) occurs, thus showing multiple light-emitting zone, thus having potential wide application prospect at bio-sensing detection field.
CN103819492A discloses a kind of little molecule electrochemical probe, and it has the following structural formula comprising selenole group:
This compound has sensitive power of test for sulfhydryl compound, such that it is able to be used as the little molecule electrochemical probe of biological thiol analysis detection, has very strong application potential.
CN103951682A discloses a kind of electrochemical probe, and its structural formula is as follows:
This compound can serve as the electrochemical probe of detection sulfhydryl compound, and sulfydryl has good detection sensitivity.
So far, the polymer being used for detecting heavy metal ion rarely has report, therefore synthesis can detect heavy metal ion, especially simultaneously contents of many kinds of heavy metal ion or the polymer of class heavy metal ion (such as hydrargyrum) can be detected, namely alleged fluorescent optical sensor seems very necessary, and there is great industrial value and social value.
Additionally, Molecular Logic Gates is a concept coming from computer science, it has merged binary computer language and molecular fluorescence behavior, and miniaturization and microminiaturization for computer industry are laid a good foundation.The structure of this gate, depends on fluorescent optical sensor compound that is wherein leading and that produce molecular fluorescence behavior.
Therefore, by the compound of exploitation and/or synthesizing new, can realizing the structure of Molecular Logic Gates on the one hand, be achieved the detection of heavy metal ion on the other hand by this structure, this basic place that also present invention is accomplished just and power are leaned on.
Summary of the invention
In view of this, to achieve these goals, the present inventor is for conducting in-depth research based on the conjugated polymer of selenole and the many aspects such as synthetic method, purposes thereof, after paying a large amount of creative work, thus completing the present invention.
Specifically, the present invention relates to a kind of conjugated polymer based on selenole, its many aspects such as synthetic method, purposes.
More particularly it relates to following several aspect.
First aspect, the present invention relates to the conjugated polymer based on selenole of a kind of following formula (I), and described polymer is structured with:
Wherein, L1、L2It is each independently C1-4Alkylidene；
R1、R2、R3It is each independently C1-6Alkyl；
A-For with N+The anion of pairing；
N is the degree of polymerization, and n >=5.
In the described conjugated polymer of the present invention, C1-4The implication of alkylidene refers to the straight or branched alkylidene with 1-4 carbon atom, can be such as-CH in non-limiting manner2-、-(CH2)2-、-(CH2)3-、-CH2CH(CH3)-、-(CH2)4-、-(CH2)5-、-(CH2)6-etc..
In the described conjugated polymer of the present invention, C1-6The implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, can be such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
In the described conjugated polymer of the present invention, A-For the anion matched with N cation, can be such as chloride ion, bromide ion, iodide ion etc. in non-limiting manner.
In the described conjugated polymer of the present invention, n is the degree of polymerization, and n is the integer between 5-20, for instance can be 5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20.
Second aspect, the present invention relates to the synthetic method of the conjugated polymer based on selenole of above formula (I), and described method comprises the steps:
(1) in organic solvent, under catalyst and accelerator exist, there is coupling reaction, obtain following formula (II) compound in following formula (IV) compound and following formula (III) compound:
(2) in organic solvent, formula (II) compound and R3-A reacts, and obtains described formula (I) compound；
Wherein, R1、R2、R3、L1、L2, n, A (i.e. A in formula (I)) as defined above, X is halogen.
In the described synthetic method of the present invention, X is halogen, can be such as F, Cl or Br in non-limiting manner.
In the described synthetic method of the present invention, the organic solvent in described step (1) is any or any multiple mixture in triethylamine, dimethyl sulfoxide, oxolane.
In the described synthetic method of the present invention, in described step (1), described catalyst is palladium compound, can be such as Pd (PPh in non-limiting manner3)4, palladium acetylacetonate (Pd (acac)2), acid chloride, palladium trifluoroacetate, Palladous chloride., Na2PdCl4、Pd(NH3)4Cl2、PdCl2(dppf)、dppePdCl2、Na2PdCl2、PdCl2(CH3CN)2、PdCl2(PPh3)2、Pd(NH3)4Cl2、PdCl2(cod) any or any multiple mixture in；Preferably, described catalyst is selected from Pd (PPh3)4, palladium acetylacetonate (Pd (acac)2), acid chloride, palladium trifluoroacetate, any or multiple mixture in Palladous chloride., it is most preferred that for Pd (PPh3)4。
In the described synthetic method of the present invention, in described step (1), described accelerator is copper compound, can be such as CuI, CuCl, CuBr, Cu (OTf), Cu in non-limiting manner2SO4、Cu2S、CuCl2、CuBr2、CuI2、CuSO4, copper acetate, acetylacetone copper, Cu (OTf)2In any or any multiple mixture；Preferably, described accelerator is any or any multiple mixture in CuI, CuCl, CuBr；Override is CuI.
In the described synthetic method of the present invention, in described step (1), the mol ratio of formula (IV) compound and formula (III) compound is 1:0.5-1.5, can be such as 1:0.5,1:1 or 1:1.5 in non-limiting manner.
In the described synthetic method of the present invention, in described step (1), the mol ratio of formula (IV) compound and catalyst is 1:0.05-0.2, can be such as 1:0.05,1:0.1,1:0.15 or 1:0.2 in non-limiting manner.
In the described synthetic method of the present invention, in described step (1), the mol ratio of catalyst and accelerator is 1:1-3, can be such as 1:1,1:1.5,1:2,1:2.5 or 1:3 in non-limiting manner.
In the described synthetic method of the present invention, in described step (1), reaction temperature is 50-100 DEG C, can be such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C in non-limiting manner.
In the described synthetic method of the present invention, in described step (1), the response time, there is no particular limitation, for instance can detect the residual quantity of raw material by liquid chromatograph or TLC how many and determine the suitable response time.Normally, the response time can be 20-50 hour, can be such as 20 hours, 30 hours, 40 hours or 50 hours in non-limiting manner.
In the described synthetic method of the present invention, in described step (2), described organic solvent is oxolane or dimethyl sulfoxide or both mixture.
In the described synthetic method of the present invention, in described step (2), formula (II) compound and R3The mol ratio of-A is 1:2-4, can be such as 1:2,1:2.5,1:3,1:3.5,1:4,1:4.5 or 1:5 in non-limiting manner.
In the described synthetic method of the present invention, in described step (2), reaction temperature is 40-60 DEG C, can be such as 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C in non-limiting manner.
In the described synthetic method of the present invention, in described step (2), in the described synthetic method of the present invention, in described step (1), response time, there is no particular limitation, for instance can detect the residual quantity of raw material by liquid chromatograph or TLC how many and determine the suitable response time.Normally, the response time can be 20-60 hour, can be such as 20 hours, 30 hours, 40 hours, 50 hours or 60 hours in non-limiting manner.
3rd aspect, the present invention relates to above-mentioned formula (I) compound and is used as fluorescent optical sensor to detect heavy metal ion or the purposes of class heavy metal ion.
In the described detection metal ion of the present invention or the purposes of class heavy metal ion, described heavy metal ion can be such as iron ion, lead ion, nickel ion, copper ion, cadmium ion, chromium ion, zinc ion etc., it is preferred to iron ion (Fe3+)。
In the described detection metal ion of the present invention or the purposes of class heavy metal ion, described class heavy metal ion is preferably mercury ion (Hg2+)。
Inventor finds by studying, and described formula (I) compound of the present invention can be used as fluorescent optical sensor, thus realizing the Selective recognition to above-mentioned different kinds of ions, and presents different response modes, for instance to mercury ion (Hg2+) present the response modes of fluorescent quenching, and to iron ion (Fe3+) present the response modes of Fluorescence Increasing.
In the described detection metal ion of the present invention or the purposes of class heavy metal ion, described fluorescent optical sensor (i.e. formula (I) compound, lower same) can realize mercury ion (Hg2+) accurate quantification detection, its fluorescence intensity and affiliated mercury ion (Hg2+) concentration presents good linear relationship in the scope of 0-40.0 μm of ol/L, detectable limit can reach 2.1 × 10-7Mol/L, and this detection is not subject to Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+、Zn2+Interference etc. common metal ion.
In the described detection metal ion of the present invention or the purposes of class heavy metal ion, described fluorescent optical sensor can realize iron ion (Fe3+) detection by quantitative, its fluorescence intensity and affiliated iron ion (Fe3+) concentration is linear in the scope of 0-21.7 μm of ol/L, detectable limit can reach 7.9 × 10-8Mol/L, and this detection is not subject to Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+、Zn2+Interference etc. common metal ion.
In the described detection metal ion of the present invention or the purposes of class heavy metal ion, after detection, ethylenediaminetetraacetic acid (EDTA) can be used to recover the fluorescence activity of described fluorescent optical sensor.
4th aspect, the present invention relates to and use above-mentioned formula (I) compound and the Molecular Logic Gates that builds.
Wherein, described Molecular Logic Gates can be INHIBIT Molecular Logic Gates or IMPLICATION Molecular Logic Gates.
In the described Molecular Logic Gates of the present invention, specifically, it is possible to iron ion (Fe3+) and mercury ion (Hg2+) for input item, with the fluorescence intensity change of formula (I) compound for output item, and build an INHIBIT Molecular Logic Gates.
In the described Molecular Logic Gates of the present invention, specifically, it is possible to iron ion (Fe3+) and EDTA be input item, with the fluorescence intensity change of formula (I) compound for output item, and build an INHIBIT Molecular Logic Gates.
In the described Molecular Logic Gates of the present invention, specifically, it is possible to mercury ion (Hg2+) for input item, with the fluorescence intensity change of formula (I) compound for output item, and build an IMPLICATION Molecular Logic Gates.
5th aspect, the present invention relates to above-mentioned formula (I) compound purposes in structure Molecular Logic Gates.
Different different kinds of molecules gates as it has been described above, described formula (I) compound of the present invention can be used to interact with multiple guest molecule, presents different response forms, thus can be built.
In sum, the invention provides a kind of novel conjugated polymer based on selenole and its production and use, and find that it can be used to build multiple different Molecular Logic Gates, thus there is at detection field good industrial prospect and market application potential.
Accompanying drawing explanation
Accompanying drawing 1 is the fluorescent optical sensor of the present invention (i.e. formula (I) compound, lower same) the fluorescence response situation to each metal ion species or metalloid ion.
Accompanying drawing 2 is that fluorescent optical sensor of the present invention is to Hg2+Detection by quantitative change in fluorescence figure.
Accompanying drawing 3 is fluorescence intensity and the variable concentrations Hg of fluorescent optical sensor of the present invention2+Linear relationship chart.
Accompanying drawing 4 is that fluorescent optical sensor of the present invention is to Hg2+Anti-interference test result.
Accompanying drawing 5 is that fluorescent optical sensor of the present invention is to Hg2+The fluorescence of detection recovers experimental result.
Accompanying drawing 6 is that fluorescent optical sensor of the present invention is to Fe3+Detection by quantitative change in fluorescence figure.
Accompanying drawing 7 is fluorescence intensity and the variable concentrations Fe of fluorescent optical sensor of the present invention3+Linear relationship chart.
Accompanying drawing 8 is that fluorescent optical sensor of the present invention is to Fe3+Anti-interference test result.
Accompanying drawing 9 is that fluorescent optical sensor of the present invention is to Fe3+The fluorescence of detection recovers experimental result.
Accompanying drawing 10 is to Hg with the fluorescent optical sensor that obtains of the present invention2+And Fe3+Different responses and the INHIBIT Molecular Logic Gates that builds.
Accompanying drawing 11 is to Fe with fluorescent optical sensor of the present invention3+The INHIBIT Molecular Logic Gates that different responses with EDTA build.
Accompanying drawing 12 is that fluorescent optical sensor of the present invention is to Hg2+The IMPLICATION Molecular Logic Gates responded with the difference of EDTA and build.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and purpose are only used for enumerating the present invention; not the real protection scope of the present invention is constituted any type of any restriction, more non-protection scope of the present invention is limited thereto.
Embodiment 1
(1) in the mixed organic solvents of the oxolane that volume ratio is 1:1 and triethylamine, following formula (IV) compound, formula (III) compound, Pd (PPh are added3)4And CuI, thus obtaining reaction mixture:
Wherein, formula (IV) compound is 1:1 with the mol ratio of formula (III) compound；Formula (IV) compound and Pd (PPh3)4Mol ratio be 1:0.1；Pd(PPh3)4It is 1:2 with the mol ratio of CuI.By gained reaction mixture under nitrogen atmosphere, stirring reaction 48 hours under 75 DEG C of conditions.After having reacted, it is cooled to room temperature, removes palladium black with short column of silica gel, rotation is evaporated off solvent, dissolves the residue in a small amount of chloroform, and is slowly added dropwise in proper amount of methanol and precipitates out precipitation, stand after being sufficiently stirred for 30 minutes, filter to obtain red powder, be following formula (II) compound:
Its yield is 78.4%.
Nuclear magnetic resonance, NMR:1HNMR (500MHz, CDCl3, δ): 7.71-7.19 (m, 4H), 4.19-4.07 (m, 4H), 3.04-2.96 (m, 4H), 2.68-2.67 (m, 8H), 1.07 (br, 12H)；
Fourier infrared (FT-IR) (KBr, cm-1): 2963,2928,2192,1598,1562,1494,1471,1455,1205.
(2) in the mixed organic solvents of oxolane and dimethyl sulfoxide (both volume ratios are 4:1), add formula (II) compound and the bromoethane of step (1) gained, both mol ratios are 1:4, by the reactant liquor of gained stirring reaction 30 hours at 50 DEG C.Being cooled to room temperature after having reacted, sucking filtration obtains pressed powder, is washed by this pressed powder oxolane, obtains dark red powder, be following formula (I) compound after vacuum drying:
Its yield is 88.9%, weight average molecular weight (Mw)=7980, PDI (polydispersity coefficient)=2.2.
Nuclear magnetic resonance, NMR:1HNMR (500Hz, CD3OD, δ): 7.90-7.39 (m, 4H), 4.66-4.50 (m, 4H), 3.86-3.79 (m, 4H), 3.57-3.51 (m, 10.2H), 1.33 (br, 15.4H)；
Fourier infrared (FT-IR) (KBr, cm-1): 3392,2975,2940,2195,1616,1464,1212.
Embodiment 2-3
Except " mol ratio of step (1) Chinese style (IV) compound and formula (III) compound is 1:0.5, formula (IV) compound and Pd (PPh3)4Mol ratio be 1:0.2, Pd (PPh3)4It is 1:3 with the mol ratio of CuI；The mol ratio of step (2) Chinese style (II) compound and bromoethane is 1:2 " outward, implement embodiment 2 in the same manner as example 1, final gained formula (I) compound yield is 85.8%, and other characterization parameter is identical.
Except " mol ratio of step (1) Chinese style (IV) compound and formula (III) compound is 1:1.5, formula (IV) compound and Pd (PPh3)4Mol ratio be 1:0.05, Pd (PPh3)4It is 1:1 with the mol ratio of CuI；The mol ratio of step (2) Chinese style (II) compound and bromoethane is 1:4 " outward, implement embodiment 3 in the same manner as example 1, final gained formula (I) compound yield is 89.3%, and other characterization parameter is identical.
Embodiment 4-16
Except by the Pd (PPh in step (1)3)4Replacing with respectively outside other palladium catalyst in following table, implement embodiment 4-16 in the same manner as example 1, used catalyst, formula (I) compound yield are shown in following table:
As can be seen here, the selection of catalyst is extremely important, in all of Pd compound, and only Pd (PPh3)4Best catalytic effect could be obtained, this demonstrate that its catalysis specificity for this reaction.
Embodiment 17-19
Except step (1) does not add CuI, implement embodiment 17-19 respectively in the same manner as example 1,
As can be seen here, in the synthetic method of the present invention, it is most important whether accelerator exists, and when being absent from CuI, causes that product yield is greatly lowered, and this demonstrate that accelerator can play significant catalyzing cooperation effect with Pd catalyst.
Embodiment 20-31
Except other copper accelerator replaced with respectively by the CuI in step (1) in following table, implementing embodiment 20-31 in the same manner as example 1, copper accelerator used, formula (I) compound yield are shown in following table:
As can be seen here, the kind of accelerator selects extremely important, and when using other copper compound, even if CuCl, the CuBr very similar with CuI, product yield still has and significantly reduces.This demonstrate that only CuI could with Pd (PPh3)4Producing best catalyzing cooperation effect, the excellent catalytic effect of the catalyst system and catalyzing of this particular combination has unobviousness.
Structure to the detection of different kinds of ions and gate
Detection to ion
1, accompanying drawing 1 is the methanol solution (concentration is 10.0 μm of ol/L) of embodiment 1 gained fluorescent optical sensor (i.e. formula (I) compound, lower same) the fluorescence response situation to the aqueous solution (concentration is 40.0 μm of ol/L) of each metal ion species or metalloid ion.
By this Fig. 1 it can be seen that embodiment 1 gained formula (I) compound is to Hg2+And Fe3+Show obvious identification ability, and present different response modes: to Hg2+Present the response modes of fluorescent quenching, and to Fe3+Presenting the response modes of Fluorescence Increasing, Fluorescence Increasing is to original 1.9 times.Meanwhile, to other ion such as Pb2+、Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+And Zn2+Responding poor, experimental result illustrates that this compound may be used for Hg in aqueous environment2+And Fe3+Selective recognition.
2, accompanying drawing 2 is that embodiment 1 gained fluorescent optical sensor is to Hg2+Detection by quantitative change in fluorescence situation, detailed process is: accurately configuring the methanol solution of this fluorescent optical sensor, concentration is 10.0 μm of ol/L, is gradually added into Hg wherein2+Aqueous solution is to Hg2+Concentration is 4 times of fluorescent optical sensor concentration, investigates fluorescent optical sensor to Hg2+Response.
Be can be seen that along with Hg by this figure2+(concentration is 0,3.3,6.6,10,13,16,20,23,26,30,33,36,40 μm of ol/L respectively, each curve in fig. 2 is these concentration corresponding from top to bottom) addition, the fluorescence intensity of sensor is gradually lowered, and the change of fluorescence intensity is with the Hg added2+Concentration linear (see Fig. 3).In figure 3, Hg is worked as2+When concentration changes between 0-40.0 μm of ol/L, linear equation is: F (fluorescence intensity)=5.76 × 104-9.90×108[Hg2+], detectable limit is 2.1 × 10-7Mol/L, illustrates that this fluorescent optical sensor can with the response modes of fluorescent quenching for Hg2+Trace detection.
3, to embodiment 1 gained fluorescent optical sensor to Hg2+Having carried out anti-interference test, detailed process is as follows: first by metal ion Ag soluble in water+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+And Zn2+(concentration is 40.0 μm of ol/L) is added separately to the methanol solution of embodiment 1 gained fluorescent optical sensor, and (concentration is 1.0 × 10-5μm ol/L) in, then it is added thereto to Hg2+(40.0 μm of ol/L), detects the change in fluorescence in this process, and experimental result is shown in accompanying drawing 4, found that these metal ions are to Hg2+Interference deviate less than 7%, and work as Hg2+When coexisting with different kinds of ions, as being initially charged Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+And Zn2+Mixture, add Hg2+Time, embodiment 1 gained fluorescent optical sensor is to Hg2+Testing result also without being subject to obvious interference, this result illustrate embodiment 1 gained fluorescent optical sensor to Hg in aqueous phase2+Detection there is significantly high capacity of resisting disturbance, namely by Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+、Zn2+Interference etc. common metal ion.
5, Fig. 5 is that embodiment 1 gained fluorescent optical sensor is to Hg2+The fluorescence of detection recovers experiment, and detailed process is as follows: first by Hg soluble in water2+(concentration is 40.0 μm of ol/L) joins the methanol solution of embodiment 1 gained fluorescent optical sensor, and (concentration is 1.0 × 10-5μm ol/L) in, then it being added thereto to the aqueous solution (concentration is 80.0 μm of ol/L) of EDTA, detection system change in fluorescence in the process, experimental result is shown in that (1:4 therein represents described fluorescent optical sensor and Hg to Fig. 52+Molar concentration rate, 1:8 represents the molar concentration rate of described fluorescent optical sensor and EDTA).Fig. 5 illustrates that embodiment 1 gained fluorescent optical sensor has good fluorescence reversibility, and EDTA can recover described fluorescent optical sensor-Hg2+The fluorescence intensity of most of cancellation of system, thus described sensor is to Hg in aqueous phase2+Can reuse when detecting.
6, Fig. 6 is that embodiment 1 gained fluorescent optical sensor is to Fe3+Detection, detailed process is as follows: accurately configuring the methanol solution of described fluorescent optical sensor, concentration is 10.0 μm of ol/L, is gradually added into Fe wherein3+Aqueous solution is to Fe3+Concentration is 2.5 times of fluorescent optical sensor concentration, and investigates fluorescent optical sensor fluorescence spectrum to Fe3+Response.
As can be seen from Figure 6 along with Fe3+(concentration respectively 0,1.67,3.33,5.01,6.68,8.35,10.0,13.4,15.0,18.4,21.7,25.0 μm of ol/L, each curve in figure 6 is these concentration corresponding from bottom to top) addition, the fluorescence intensity of sensor strengthens gradually, and the change of fluorescence intensity is with the Fe added3+Concentration linear (see Fig. 7).Again in Fig. 7, work as Fe3+When concentration changes between 0-21.7 μm of ol/L, linear equation is: F (fluorescence intensity)=5.98 × 104+2.66×109[Fe3+], detectable limit is 7.9 × 10-8Mol/L, illustrates that described fluorescent optical sensor can with the response modes of Fluorescence Increasing for Fe3+Trace detection.
7, to embodiment 1 gained fluorescent optical sensor to Fe3+Having carried out anti-interference test, detailed process is as follows: first by metal ion Ag soluble in water+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+And Zn2+(concentration is 25.0 μm of ol/L) is added separately to the methanol solution of described fluorescent optical sensor, and (concentration is 1.0 × 10-5μm ol/L) in, then it is added thereto to Fe3+(concentration is 25.0 μm of ol/L), detection system change in fluorescence in the process, experimental result is shown in Fig. 8.As can be seen from Fig. 8, these metal ions are to Fe3+Interference deviation little；And work as Fe3+When coexisting with different kinds of ions, as being initially charged Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+And Zn2+Mixture, add Fe3+Time, described fluorescent optical sensor is to Fe3+Interference deviate less than 15%.Experimental result illustrates that described fluorescent optical sensor is to Fe in aqueous phase3+Detection there is significantly high selectivity, by Ag+、Cd2+、Co2+、Cu2+、K+、Mn2+、Ni2+、Pb2+、Zn2+Interference etc. common metal ion.
8, Fig. 9 is that embodiment 1 gained fluorescent optical sensor is to Fe3+The fluorescence of detection recovers experiment, and detailed process is as follows: first by Fe soluble in water3+(concentration is 25.0 μm of ol/L) joins the methanol solution of embodiment 1 gained fluorescent optical sensor, and (concentration is 1.0 × 10-5μm ol/L) in, then it being added thereto to the aqueous solution (concentration is 50.0 μm of ol/L) of EDTA, detection system change in fluorescence in the process, experimental result is shown in that (1:2.5 therein represents described fluorescent optical sensor and Fe to Fig. 93+Molar concentration rate, 1:5 represents the molar concentration rate of described fluorescent optical sensor and EDTA).Fig. 9 illustrates that embodiment 1 gained fluorescent optical sensor has good fluorescence reversibility, and EDTA can recover described fluorescent optical sensor-Fe3+The fluorescence intensity of most of cancellation of system, thus described sensor is to Fe in aqueous phase3+Can reuse when detecting.
The structure of gate
1, with embodiment 1 gained fluorescent optical sensor to Fe3+And Hg2+Different responses build INHIBIT Molecular Logic Gates, specific as follows: with Hg2+(concentration is 40.0 μm of ol/L) and Fe3+(concentration is 21.7 μm of ol/L) as input item, described fluorescent optical sensor fluorescence intensity change as output item, build an INHIBIT Molecular Logic Gates, see Figure 10.
This gate is formed by a NOT gate and an AND-gate merging, particularly as follows: by Fe3+(concentration is 1.0 × 10 to join the methanol solution of described fluorescent optical sensor-5μm ol/L) in, system shows as high fluorescent, and output result is " 1 "；In other situation, output result is " 0 ": at " Fe3+And Hg2+All be absent from " when, " only Hg2+Exist " when and " Fe3+And Hg2+Coexist " when, system launches relatively low Poison, so output result is " 0 ".
At " Fe3+And Hg2+Coexist " situation in, system fluorescence reduce be due to Hg2+Described fluorescent optical sensor there is is bigger binding constant, can by Fe3+Replace from described fluorescent optical sensor.
2, with embodiment 1 gained fluorescent optical sensor to Fe3+Different responses with EDTA build an INHIBIT Molecular Logic Gates, specific as follows: with Fe3+(concentration is 21.7 μm of ol/L) and EDTA (concentration is 100.0 μm of ol/L) as input item, described fluorescent optical sensor fluorescence intensity change as output item, build an INHIBIT Molecular Logic Gates, see Figure 11.
This gate is formed by a NOT gate and an AND-gate merging, particularly as follows: by Fe3+(concentration is 1.0 × 10 to join the methanol solution of described fluorescent optical sensor-5μm ol/L) in, system shows as high fluorescent, and output result is " 1 "；In other situation, output result is " 0 ": such as " Fe3+All be absent from EDTA " when, " only EDTA exist " when and at " Fe3+Coexist with EDTA " when, system launches relatively low Poison, so output result is " 0 ".
At " Fe3+Coexist with EDTA " situation in, system fluorescence reduce be owing to EDTA is to Fe3+There is bigger binding constant, can by Fe3+Replace from described fluorescent optical sensor.
3, with embodiment 1 gained fluorescent optical sensor to Hg2+Different responses with EDTA build an IMPLICATION Molecular Logic Gates, specific as follows: with Hg2+(concentration is 40.0 μm of ol/L) and EDTA (concentration is 80.0 μm of ol/L) as input item, described fluorescent optical sensor fluorescence intensity change as output item, build an IMPLICATION Molecular Logic Gates, see Figure 12.
This gate is formed by a NOT gate and an OR door merging, it will be appreciated that for: by Hg2+(concentration is 1.0 × 10 to join the methanol solution of described fluorescent optical sensor-5μm ol/L) in, system fluorescent quenching, show as low fluorescence intensity, output result be " 0 ", and in other situation, exporting result is " 1 ": such as " Hg2+All be absent from EDTA " when, " only EDTA exist " when and at " Hg2+Coexist with EDTA " when, system launches strong fluorescence, so output result is " 1 ".
At " Hg2+Coexist with EDTA " situation in, system fluorescence recover be owing to EDTA is to Hg2+There is bigger binding constant, can by Hg2+Replace from described fluorescent optical sensor.
As mentioned above, the invention provides a kind of novel based on the conjugated polymer of selenole, its preparation method and for detecting the purposes of different kinds of ions, and use this compound can build multiple Molecular Logic Gates, thus have a good application prospect and industrial value in fluorescence sense field.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the scope of the invention.In addition; it is also contemplated that; after the technology contents having read the present invention, the present invention can be made various change, amendment and/or modification by those skilled in the art, and all these equivalent form of value falls within the application appended claims protection defined equally.
Claims (9)
1. the conjugated polymer based on selenole of following formula (I), described polymer is structured with:
Wherein, L1、L2It is each independently C1-4Alkylidene；
R1、R2、R3It is each independently C1-6Alkyl；
A-For with N+The anion of pairing；N is the degree of polymerization, and n is the integer between 5-20.
2. the synthetic method of the conjugated polymer based on selenole of formula described in claim 1 (I), described method comprises the steps:
(1) in organic solvent, under catalyst and accelerator exist, there is coupling reaction, obtain following formula (II) compound in following formula (IV) compound and following formula (III) compound:
(2) in organic solvent, formula (II) compound and R3-A reacts, and obtains described formula (I) compound；
Wherein, R1、R2、R3、L1、L2, n, A as defined above, X is halogen；
Wherein, described catalyst is Pd (PPh3)4；
Described accelerator is any or any multiple mixture in CuI, CuCl, CuBr.
3. synthetic method as claimed in claim 2, it is characterised in that: described accelerator is CuI.
4. synthetic method as claimed in claim 2 or claim 3, it is characterised in that: the mol ratio of formula (IV) compound and formula (III) compound is 1:0.5-1.5.
5. synthetic method as claimed in claim 2 or claim 3, it is characterised in that: the mol ratio of formula (IV) compound and catalyst is 1:0.05-0.2.
6. synthetic method as claimed in claim 2 or claim 3, it is characterised in that: the mol ratio of catalyst and accelerator is 1:1-3.
7. formula described in claim 1 (I) compound is used as fluorescent optical sensor to detect heavy metal ion or the purposes of class heavy metal ion.
8. the Molecular Logic Gates using formula (I) compound described in claim 1 and build.
9. Molecular Logic Gates as claimed in claim 8, it is characterised in that: described Molecular Logic Gates is INHIBIT Molecular Logic Gates or IMPLICATION Molecular Logic Gates.
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