CN104311801A - Water-soluble conjugated polymer of benzoselenadiazole and preparation method and application of conjugated polymer - Google Patents
Water-soluble conjugated polymer of benzoselenadiazole and preparation method and application of conjugated polymer Download PDFInfo
- Publication number
- CN104311801A CN104311801A CN201410567169.5A CN201410567169A CN104311801A CN 104311801 A CN104311801 A CN 104311801A CN 201410567169 A CN201410567169 A CN 201410567169A CN 104311801 A CN104311801 A CN 104311801A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- optical sensor
- fluorescent optical
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 5
- TVNJKAZMPQNGGE-UHFFFAOYSA-N 1,2,3-benzoselenadiazole Chemical compound C1=CC=C2[se]N=NC2=C1 TVNJKAZMPQNGGE-UHFFFAOYSA-N 0.000 title abstract 2
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 26
- 230000003287 optical effect Effects 0.000 claims description 68
- 150000001875 compounds Chemical class 0.000 claims description 60
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 25
- 238000010189 synthetic method Methods 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 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 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 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 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 4
- 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 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 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 claims description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims description 2
- 241000545067 Venus Species 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 150000002941 palladium compounds Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 20
- 238000011160 research Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000001514 detection method Methods 0.000 description 31
- 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 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 230000008859 change Effects 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000011133 lead Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- -1 sulfhydryl compound Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 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
- 239000008346 aqueous phase Substances 0.000 description 4
- 229910052802 copper Inorganic materials 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
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011109 contamination Methods 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
- 238000004811 liquid chromatography Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- 238000001556 precipitation Methods 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
- 239000010865 sewage Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 0 S=C1Sc2cc(N=S*3)c3cc2S1 Chemical compound S=C1Sc2cc(N=S*3)c3cc2S1 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
- 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
- 238000003556 assay Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 231100000739 chronic poisoning Toxicity 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
- 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
- 230000036039 immunity Effects 0.000 description 1
- 230000006698 induction Effects 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
- 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
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 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
- 125000004123 n-propyl group Chemical group [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
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a benzoselenadiazole-based conjugated polymer used for detecting heavy metal ions or heavy metal-like ions and a preparation method and application of the conjugated polymer. The polymer has good fluorescent response on certain ions and can serve as a fluorescence sensor. In addition, due to the fluorescent response, the polymer can be used for establishing a molecular logic gate with different guest molecules, so that the polymer has good scientific research values and application potential.
Description
Technical field
The present invention relates to a kind of polymkeric substance that can be used as fluorescent optical sensor for detecting heavy metal ion, relating more particularly to a kind of conjugated polymers based on selenole and preparation method thereof and purposes, belong to compound fluorescent optical sensor field.
Background technology
Along with the development of China's industrialization and urbanization, the problem of environmental pollution that entire society faces becomes increasingly conspicuous, the sewage such as industry, agricultural, life long-term in a large number in line enter river, river water quality goes from bad to worse, particularly contain plurality of heavy metal composition in industrial sewage, as lead, mercury, nickel, copper, cadmium, chromium, iron etc., these heavy metal ion can be amassed by food chain richness in biological tissue, cause the acute or chronic poisoning of human body.Such as, in common heavy metal contamination ion, Hg
2+harm is large especially, and wide-scale distribution, serious environment and social concern can be caused; Fe
3+although be the necessary material of all viable cell, excessive existence also has fatal harm; In addition, lead, nickel, copper, cadmium, chromium also all can cause serious harm to environment especially water body, soil etc.
Along with the raising of entire society's environmental consciousness, the pollution of heavy metal ion in water body, soil also more and more attracts much attention, if the content of heavy metal ion in mensuration environment promptly and accurately, to understanding its pollution level in time, prevent heavy metal contamination, to propose effective treatment process very important.
Detection people for these heavy metal ion have developed multiple method, as plasma emission spectrometry, atomic absorption spectrometry, atomic emissions spectrometry etc., but there are some defects in these methods, for example these method and technologies require high, sample need pre-treatment, detect quick not, use that instrument price is expensive, maintenance cost is high, detect expensive etc., be difficult to widely use.Therefore, in much important application scenario, people in the urgent need to fast, accurately, low cost can the method for optionally these heavy metals of analyzing and testing.
Fluorescent optical sensor is that a class can by molecule, ion identification event by the molecule of fluorescent signal effective expression, because fluorescence spectrophotometer used is simply inexpensive, highly sensitive, easy to operate, thus the fluorescence identifying being widely used in the assays such as positively charged ion, negatively charged ion and neutral molecule by people detects, and is developed rapidly.Conjugated polymers fluorescent optical sensor is due in light activated situation, and energy can be effective along conjugated backbone fast transferring, and amplify transducing signal, this feature causes it to have higher sensitivity compared with small molecule fluorescent sensor.
For this advantage, be developed some polymkeric substance, some in these polymkeric substance relate to selenole skeleton involved in the present invention, such as:
CN102746492A discloses the polygonal line type water-soluble aryleneethynylene of a kind of conjugated main chain doping, and it has following structural formula:
Wherein, between R and two alkynyl lay respectively at phenyl ring three on position; Ar is the one that phenyl, 9,9-bis-replaces in fluorenyl; Ar ' is diazosulfide group, one in selenole group; Polymerization degree n be greater than 1 natural number, 0.7≤x < 1,0 < y≤0.3, and x+y=1; R, R ' and R " be selected from hydrogen atom H, R respectively
1r
2r
3r
4n
+or R
5any one in group.There is FRET (fluorescence resonance energy transfer) by the induction of some ambient conditions in this compound, thus shows multiple light-emitting zone, thus have potential wide application prospect at bio-sensing detection field.
CN103819492A discloses a kind of small molecules electrochemical probe, and it has the following structural formula comprising selenole group:
This compound has sensitive detectivity for sulfhydryl compound, thus can be used as the small molecules electrochemical probe of biological thiol analyzing and testing, has very strong application potential.
CN103951682A discloses a kind of electrochemical probe, and its structural formula is as follows:
This compound can be used as the electrochemical probe detecting sulfhydryl compound, has good detection sensitivity to sulfydryl.
So far, the polymkeric substance being used for detecting heavy metal ion rarely has report, therefore synthesis can detect heavy metal ion, especially can detect the polymkeric substance of contents of many kinds of heavy metal ion or class heavy metal ion (as mercury) simultaneously, also namely alleged fluorescent optical sensor seems very necessary, and has great industrial value and social value.
In addition, Molecular Logic Gates is a concept coming from computer science, and it has merged binary machine language and molecular fluorescence behavior, for the miniaturization of computer industry and microminiaturization are laid a good foundation.The structure of this logical gate, depends on the fluorescent optical sensor compound wherein dominating and produce molecular fluorescence behavior.
Therefore, by exploitation and/or the compound of synthesizing new, the structure of Molecular Logic Gates can be realized on the one hand, be achieved the detection of heavy metal ion on the other hand by this structure, this also just the basic place that is accomplished of the present invention and power lean on.
Summary of the invention
In view of this, to achieve these goals, the present inventor conducts in-depth research for based on the conjugated polymers of selenole and the many aspects such as synthetic method, purposes thereof, after paying a large amount of creative work, thus completes the present invention.
Specifically, the present invention relates to a kind of conjugated polymers based on selenole, its many aspects such as synthetic method, purposes.
More specifically, the present invention relates to following several aspect.
First aspect, the present invention relates to the conjugated polymers based on selenole of a kind of following formula (I), and described polymkeric substance has following structure:
Wherein, L
1, L
2be C independently of one another
1-4alkylidene group;
R
1, R
2, R
3be C independently of one another
1-6alkyl;
A
-for with N
+the negatively charged ion of pairing;
N is the polymerization degree, and n >=5.
In described conjugated polymers of the present invention, C
1-
4the implication of alkylidene group refers to the straight or branched alkylidene group with 1-4 carbon atom, such as can be-CH in non-limiting manner
2-,-(CH
2)
2-,-(CH
2)
3-,-CH
2cH (CH
3)-,-(CH
2)
4-,-(CH
2)
5-,-(CH
2)
6-etc.
In described conjugated polymers of the present invention, C
1-
6the implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
In described conjugated polymers of the present invention, A
-for the negatively charged ion matched with N positively charged ion, such as can be chlorion, bromide anion, iodide ion etc. in non-limiting manner.
In described conjugated polymers of the present invention, n is the polymerization degree, and n is the integer between 5-20, such as, 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 polymers based on selenole of above formula (I), described method comprises the steps:
(1) in organic solvent, under catalyst and promotor exist, there is linked reaction, obtain following formula (II) compound in following formula (IV) compound and following formula (III) compound:
(2) in organic solvent, formula (II) compound and R
3-A reacts, and obtains described formula (I) compound;
Wherein, R
1, R
2, R
3, L
1, L
2, n, A (A namely in formula (I)) definition as above, X is halogen.
In described synthetic method of the present invention, X is halogen, such as can be F, Cl or Br in non-limiting manner.
In described synthetic method of the present invention, the organic solvent in described step (1) is any one in triethylamine, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or any multiple mixture.
In described synthetic method of the present invention, in described step (1), described catalyzer is palladium compound, such as can be Pd (PPh in non-limiting manner
3)
4, palladium acetylacetonate (Pd (acac)
2), acid chloride, palladium trifluoroacetate, Palladous chloride, Na
2pdCl
4, Pd (NH
3)
4cl
2, PdCl
2(dppf), dppePdCl
2, Na
2pdCl
2, PdCl
2(CH
3cN)
2, PdCl
2(PPh
3)
2, Pd (NH
3)
4cl
2, PdCl
2(cod) any one in or any multiple mixture; Preferably, described catalyzer is selected from Pd (PPh
3)
4, palladium acetylacetonate (Pd (acac)
2), any one in acid chloride, palladium trifluoroacetate, Palladous chloride or multiple mixture, most preferably be Pd (PPh
3)
4.
In described synthetic method of the present invention, in described step (1), described promotor is copper compound, such as can be CuI, CuCl, CuBr, Cu (OTf), Cu in non-limiting manner
2sO
4, Cu
2s, CuCl
2, CuBr
2, CuI
2, CuSO
4, venus crystals, acetylacetone copper, Cu (OTf)
2in any one or any multiple mixture; Preferably, described promotor is any one in CuI, CuCl, CuBr or any multiple mixture; Override is CuI.
In 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, such as can be 1:0.5,1:1 or 1:1.5 in non-limiting manner.
In described synthetic method of the present invention, in described step (1), the mol ratio of formula (IV) compound and catalyzer is 1:0.05-0.2, such as can be 1:0.05,1:0.1,1:0.15 or 1:0.2 in non-limiting manner.
In described synthetic method of the present invention, in described step (1), the mol ratio of catalyzer and promotor is 1:1-3, such as can be 1:1,1:1.5,1:2,1:2.5 or 1:3 in non-limiting manner.
In described synthetic method of the present invention, in described step (1), temperature of reaction is 50-100 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C in non-limiting manner.
In described synthetic method of the present invention, in described step (1), the reaction times, there is no particular limitation, such as, detect the residual quantity of raw material by liquid chromatography or TLC how many and determine the suitable reaction times.Normally, the reaction times can be 20-50 hour, such as can be 20 hours in non-limiting manner, 30 hours, 40 hours or 50 hours.
In described synthetic method of the present invention, in described step (2), described organic solvent is tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) or both mixtures.
In described synthetic method of the present invention, in described step (2), formula (II) compound and R
3the mol ratio of-A is 1:2-4, such as can be 1:2,1:2.5,1:3,1:3.5,1:4,1:4.5 or 1:5 in non-limiting manner.
In described synthetic method of the present invention, in described step (2), temperature of reaction is 40-60 DEG C, such as can be 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C in non-limiting manner.
In described synthetic method of the present invention, in described step (2), in described synthetic method of the present invention, in described step (1), reaction times, there is no particular limitation, such as, detect the residual quantity of raw material by liquid chromatography or TLC how many and determine the suitable reaction times.Normally, the reaction times can be 20-60 hour, such as can be 20 hours in non-limiting manner, 30 hours, 40 hours, 50 hours or 60 hours.
3rd aspect, the present invention relates to above-mentioned formula (I) compound and is used as fluorescent optical sensor to detect the purposes of heavy metal ion or class heavy metal ion.
In the purposes of described detection metal ion of the present invention or class heavy metal ion, described heavy metal ion such as can be iron ion, lead ion, nickel ion, cupric ion, cadmium ion, chromium ion, zine ion etc., is preferably iron ion (Fe
3+).
In the purposes of described detection metal ion of the present invention or class heavy metal ion, described class heavy metal ion is preferably mercury ion (Hg
2+).
Contriver is found by research, and described formula (I) compound of the present invention can be used as fluorescent optical sensor, thus realizes the Selective recognition to above-mentioned different kinds of ions, and presents different response modes, such as, to mercury ion (Hg
2+) present the response modes of fluorescent quenching, and to iron ion (Fe
3+) present the response modes of Fluorescence Increasing.
In the purposes of described detection metal ion of the present invention or class heavy metal ion, described fluorescent optical sensor (i.e. formula (I) compound, lower with) can realize mercury ion (Hg
2+) accurate quantification detect, its fluorescence intensity and the mercury ion (Hg added
2+) concentration presents good linear relationship in the scope of 0-40.0 μm of ol/L, limit of detection can reach 2.1 × 10
-7mol/L, and this detection is not subject to Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+, Zn
2+etc. the interference of common metal ion.
In the purposes of described detection metal ion of the present invention or class heavy metal ion, described fluorescent optical sensor can realize iron ion (Fe
3+) detection by quantitative, its fluorescence intensity and the iron ion (Fe added
3+) concentration is linear in the scope of 0-21.7 μm of ol/L, limit of detection can reach 7.9 × 10
-8mol/L, and this detection is not subject to Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+, Zn
2+etc. the interference of common metal ion.
In the purposes of described detection metal ion of the present invention or class heavy metal ion, after detection, ethylenediamine tetraacetic acid (EDTA) (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 described Molecular Logic Gates of the present invention, specifically, can iron ion (Fe
3+) and mercury ion (Hg
2+) be input item, with the fluorescence intensity change of formula (I) compound for output item, and build an INHIBIT Molecular Logic Gates.
In described Molecular Logic Gates of the present invention, specifically, can iron ion (Fe
3+) 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 described Molecular Logic Gates of the present invention, specifically, can mercury ion (Hg
2+) be 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 the purposes of above-mentioned formula (I) compound in structure Molecular Logic Gates.
As mentioned above, described formula (I) compound of the present invention can be used to interact with multiple guest molecule, presents different response forms, thus can build different different kinds of molecules logical gates.
In sum, the invention provides a kind of novel conjugated polymers based on selenole and its production and use, and find that it can be used to build multiple different Molecular Logic Gates, thus at detection field, there is good industrial prospect and market application potential.
Accompanying drawing explanation
Accompanying drawing 1 is fluorescent optical sensor of the present invention (i.e. formula (I) compound, lower with) to the fluorescence response situation of each metal ion species or metalloid ion.
Accompanying drawing 2 is that fluorescent optical sensor of the present invention is to Hg
2+detection by quantitative change in fluorescence figure.
Accompanying drawing 3 is fluorescence intensity and the different concns Hg of fluorescent optical sensor of the present invention
2+linear relationship chart.
Accompanying drawing 4 is that fluorescent optical sensor of the present invention is to Hg
2+anti-interference test result.
Accompanying drawing 5 is that fluorescent optical sensor of the present invention is to Hg
2+the fluorescence detected recovers experimental result.
Accompanying drawing 6 is that fluorescent optical sensor of the present invention is to Fe
3+detection by quantitative change in fluorescence figure.
Accompanying drawing 7 is fluorescence intensity and the different concns Fe of fluorescent optical sensor of the present invention
3+linear relationship chart.
Accompanying drawing 8 is that fluorescent optical sensor of the present invention is to Fe
3+anti-interference test result.
Accompanying drawing 9 is that fluorescent optical sensor of the present invention is to Fe
3+the fluorescence detected recovers experimental result.
Accompanying drawing 10 is to Hg with the fluorescent optical sensor that obtains of the present invention
2+and Fe
3+difference response and build INHIBIT Molecular Logic Gates.
Accompanying drawing 11 is to Fe with fluorescent optical sensor of the present invention
3+with the INHIBIT Molecular Logic Gates that the difference response of EDTA builds.
Accompanying drawing 12 is that fluorescent optical sensor of the present invention is to Hg
2+respond and the IMPLICATION Molecular Logic Gates of structure with the difference of EDTA.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
(1), in being the tetrahydrofuran (THF) of 1:1 and the mixed organic solvents of triethylamine to volume ratio, following formula (IV) compound, formula (III) compound, Pd (PPh is added
3)
4and CuI, thus obtain reaction mixture:
Wherein, the mol ratio of formula (IV) compound and formula (III) compound is 1:1; Formula (IV) compound and Pd (PPh
3)
4mol ratio be 1:0.1; Pd (PPh
3)
4be 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, cool to room temperature, removes palladium black with short column of silica gel, revolve and steam except desolventizing, residue is dissolved in a small amount of trichloromethane, and it is slowly added drop-wise to precipitation precipitation in proper amount of methanol, abundant stirring left standstill after 30 minutes, filtered to obtain red powder, was following formula (II) compound:
Its yield is 78.4%.
Nucleus magnetic resonance:
1h NMR (500MHz, CDCl
3, 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 tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) (both volume ratios are 4:1), add formula (II) compound and the monobromethane of step (1) gained, both mol ratios is 1:4, by the reaction solution of gained stirring reaction 30 hours at 50 DEG C.Reacted rear cool to room temperature, suction filtration obtains pressed powder, is washed by this pressed powder tetrahydrofuran (THF), 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.
Nucleus magnetic resonance:
1h NMR (500Hz, CD
3oD, 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 (PPh
3)
4mol ratio be 1:0.2, Pd (PPh
3)
4be 1:3 with the mol ratio of CuI; The mol ratio of step (2) Chinese style (II) compound and monobromethane is 1:2 ", implement embodiment 2 in the same manner as example 1 outward, 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 (PPh
3)
4mol ratio be 1:0.05, Pd (PPh
3)
4be 1:1 with the mol ratio of CuI; The mol ratio of step (2) Chinese style (II) compound and monobromethane is 1:4 ", implement embodiment 3 in the same manner as example 1 outward, final gained formula (I) compound yield is 89.3%, and other characterization parameter is identical.
Embodiment 4-16
Remove the Pd (PPh in step (1)
3)
4replace 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 see the following form:
As can be seen here, the selection of catalyzer is extremely important, in all Pd compounds, only has Pd (PPh
3)
4just can obtain best catalytic effect, this demonstrate that its catalysis specificity for this reaction.
Embodiment 17-19
Except not adding except CuI in step (1), implement embodiment 17-19 in the same manner as example 1 respectively,
As can be seen here, in synthetic method of the present invention, it is most important whether promotor exists, and when there is not CuI, causing product yield to have and significantly reducing, and this demonstrate that promotor can play significant catalyzing cooperation effect with Pd catalyzer.
Embodiment 20-31
Except other copper promotor replaced with respectively by the CuI in step (1) in following table, implement embodiment 20-31 in the same manner as example 1, copper promotor used, formula (I) compound yield are seen the following form:
As can be seen here, the kind of promotor is selected extremely important, and when using other copper compound, even if CuCl, the CuBr very similar with CuI, product yield still has remarkable reduction.This demonstrate that only have CuI could with Pd (PPh
3)
4produce best catalyzing cooperation effect, the excellent catalytic effect of the catalyst system of this particular combination has unobviousness.
To the detection of different kinds of ions and the structure of logical gate
To the detection of ion
1, accompanying drawing 1 is that the methanol solution (concentration is 10.0 μm of ol/L) of embodiment 1 gained fluorescent optical sensor (i.e. formula (I) compound, lower with) is to the fluorescence response situation of the aqueous solution (concentration is 40.0 μm of ol/L) of each metal ion species or metalloid ion.
As can be seen from this Fig. 1, embodiment 1 gained formula (I) compound is to Hg
2+and Fe
3+show obvious recognition capability, and present different response modes: to Hg
2+present the response modes of fluorescent quenching, and to Fe
3+present the response modes of Fluorescence Increasing, Fluorescence Increasing is to original 1.9 times.Meanwhile, to other ion as Pb
2+, Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+and Zn
2+respond poor, experimental result illustrates that this compound may be used for Hg in aqueous environment
2+and Fe
3+selective recognition.
2, accompanying drawing 2 is that embodiment 1 gained fluorescent optical sensor is to Hg
2+detection by quantitative change in fluorescence situation, detailed process is: the accurately methanol solution of this fluorescent optical sensor of configuration, concentration is 10.0 μm of ol/L, adds Hg gradually wherein
2+the aqueous solution is to Hg
2+concentration is 4 times of fluorescent optical sensor concentration, investigates fluorescent optical sensor to Hg
2+response.
Can find out along with Hg by this figure
2+(concentration is respectively 0,3.3,6.6,10,13,16,20,23,26,30,33,36,40 μm of ol/L, each curve is in fig. 2 these concentration corresponding from top to bottom) add, the fluorescence intensity of sensor reduces gradually, and the change of fluorescence intensity is with the Hg added
2+concentration linear (see Fig. 3).In figure 3, Hg is worked as
2+when concentration changes between 0-40.0 μm of ol/L, linear equation is: F (fluorescence intensity)=5.76 × 10
4-9.90 × 10
8[Hg
2+], limit of detection is 2.1 × 10
-7mol/L, illustrates that this fluorescent optical sensor can with the response modes of fluorescent quenching for Hg
2+trace detection.
3, to embodiment 1 gained fluorescent optical sensor to Hg
2+carried out anti-interference test, detailed process is as follows: first by metal ion Ag soluble in water
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+and Zn
2+(concentration is 40.0 μm of ol/L) joins the methanol solution of embodiment 1 gained fluorescent optical sensor respectively, and (concentration is 1.0 × 10
-5μm ol/L) in, then add Hg wherein
2+(40.0 μm of ol/L), detect the change in fluorescence in this process, experimental result is shown in accompanying drawing 4, found that these metal ions are to Hg
2+interference depart from and be less than 7%, and work as Hg
2+when coexisting with different kinds of ions, as first added Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+and Zn
2+mixture, then add Hg
2+time, embodiment 1 gained fluorescent optical sensor is to Hg
2+detected result be not subject to obvious interference yet, this result illustrates that embodiment 1 gained fluorescent optical sensor is to Hg in aqueous phase
2+detection there is very high immunity from interference, namely not by Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+, Zn
2+etc. the interference of common metal ion.
5, Fig. 5 is that embodiment 1 gained fluorescent optical sensor is to Hg
2+the fluorescence detected recovers experiment, and detailed process is as follows: first by Hg soluble in water
2+(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 adding the aqueous solution (concentration is 80.0 μm of ol/L) of EDTA wherein, detection system change in fluorescence in the process, experimental result is shown in that (1:4 wherein represents described fluorescent optical sensor and Hg to Fig. 5
2+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-Hg
2+the fluorescence intensity of most of cancellation of system, thus described sensor is to Hg in aqueous phase
2+can reuse when detecting.
6, Fig. 6 is embodiment 1 gained fluorescent optical sensor to Fe
3+detection, detailed process is as follows: the accurately methanol solution of the described fluorescent optical sensor of configuration, concentration is 10.0 μm of ol/L, adds Fe gradually wherein
3+the aqueous solution is to Fe
3+concentration is 2.5 times of fluorescent optical sensor concentration, and investigates fluorescent optical sensor fluorescence spectrum to Fe
3+response.
As can be seen from Figure 6 along with Fe
3+(concentration is respectively 0, and 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 is in figure 6 these concentration corresponding from bottom to top) add, the fluorescence intensity of sensor strengthens gradually, and the change of fluorescence intensity is with the Fe added
3+concentration linear (see Fig. 7).Again in Fig. 7, work as Fe
3+when concentration changes between 0-21.7 μm of ol/L, linear equation is: F (fluorescence intensity)=5.98 × 10
4+ 2.66 × 10
9[Fe
3+], limit of detection is 7.9 × 10
-8mol/L, illustrates that described fluorescent optical sensor can with the response modes of Fluorescence Increasing for Fe
3+trace detection.
7, to embodiment 1 gained fluorescent optical sensor to Fe
3+carried out anti-interference test, detailed process is as follows: first by metal ion Ag soluble in water
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+and Zn
2+(concentration is 25.0 μm of ol/L) joins the methanol solution of described fluorescent optical sensor respectively, and (concentration is 1.0 × 10
-5μm ol/L) in, then add Fe wherein
3+(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 Fe
3+interference depart from not quite; And work as Fe
3+when coexisting with different kinds of ions, as first added Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+and Zn
2+mixture, then add Fe
3+time, described fluorescent optical sensor is to Fe
3+interference depart from and be less than 15%.Experimental result illustrates that described fluorescent optical sensor is to Fe in aqueous phase
3+detection there is very high selectivity, not by Ag
+, Cd
2+, Co
2+, Cu
2+, K
+, Mn
2+, Ni
2+, Pb
2+, Zn
2+etc. the interference of common metal ion.
8, Fig. 9 is that embodiment 1 gained fluorescent optical sensor is to Fe
3+the fluorescence detected recovers experiment, and detailed process is as follows: first by Fe soluble in water
3+(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 adding the aqueous solution (concentration is 50.0 μm of ol/L) of EDTA wherein, detection system change in fluorescence in the process, experimental result is shown in that (1:2.5 wherein represents described fluorescent optical sensor and Fe to Fig. 9
3+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-Fe
3+the fluorescence intensity of most of cancellation of system, thus described sensor is to Fe in aqueous phase
3+can reuse when detecting.
The structure of logical gate
1, use embodiment 1 gained fluorescent optical sensor to Fe
3+and Hg
2+difference response structure INHIBIT Molecular Logic Gates, specific as follows: with Hg
2+(concentration is 40.0 μm of ol/L) and Fe
3+(concentration is 21.7 μm of ol/L) as output item as the fluorescence intensity change of input item, described fluorescent optical sensor, builds an INHIBIT Molecular Logic Gates, sees Figure 10.
This logical gate is formed by a NOT door and an AND door merging, is specially: by Fe
3+(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 rusults is " 1 "; In other situation, Output rusults is " 0 ": at " Fe
3+and Hg
2+do not exist " when, " only have Hg
2+exist " when and " Fe
3+and Hg
2+coexist " when, system launches comparatively low Poison, so Output rusults is " 0 ".
At " Fe
3+and Hg
2+coexist " situation in, system fluorescence reduce be due to Hg
2+larger binding constant is had to described fluorescent optical sensor, can by Fe
3+replace from described fluorescent optical sensor.
2, use embodiment 1 gained fluorescent optical sensor to Fe
3+with difference response structure INHIBIT Molecular Logic Gates of EDTA, specific as follows: with Fe
3+(concentration is 21.7 μm of ol/L) and EDTA (concentration is 100.0 μm of ol/L) as output item as the fluorescence intensity change of input item, described fluorescent optical sensor, build an INHIBIT Molecular Logic Gates, see Figure 11.
This logical gate is formed by a NOT door and an AND door merging, is specially: by Fe
3+(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 rusults is " 1 "; In other situation, Output rusults is " 0 ": as " Fe
3+do not exist with EDTA " when, " only having EDTA to exist " when and at " Fe
3+coexist with EDTA " when, system launches comparatively low Poison, so Output rusults is " 0 ".
At " Fe
3+coexist with EDTA " situation in, system fluorescence reduce be because EDTA is to Fe
3+there is larger binding constant, can by Fe
3+replace from described fluorescent optical sensor.
3, use embodiment 1 gained fluorescent optical sensor to Hg
2+with difference response structure IMPLICATION Molecular Logic Gates of EDTA, specific as follows: with Hg
2+(concentration is 40.0 μm of ol/L) and EDTA (concentration is 80.0 μm of ol/L) as output item as the change of input item, described fluorescent optical sensor fluorescence intensity, build an IMPLICATION Molecular Logic Gates, see Figure 12.
This logical gate is formed by a NOT door and an OR door merging, can be regarded as: by Hg
2+(concentration is 1.0 × 10 to join the methanol solution of described fluorescent optical sensor
-5μm ol/L) in, system fluorescent quenching, shows as low fluorescence intensity, and Output rusults is " 0 ", and in other situation, Output rusults is " 1 ": as " Hg
2+do not exist with EDTA " when, " only having EDTA to exist " when and at " Hg
2+coexist with EDTA " when, system launches comparatively hyperfluorescenceZeng Yongminggaoyingguang, so Output rusults is " 1 ".
At " Hg
2+coexist with EDTA " situation in, system fluorescence recover be because EDTA is to Hg
2+there is larger binding constant, can by Hg
2+replace from described fluorescent optical sensor.
As mentioned above, the invention provides a kind of novel conjugated polymers based on selenole, its preparation method and the purposes for detecting 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 only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the conjugated polymers based on selenole of following formula (I), described polymkeric substance has following structure:
Wherein, L
1, L
2be C independently of one another
1-4alkylidene group;
R
1, R
2, R
3be C independently of one another
1-6alkyl;
A
-for with N
+the negatively charged ion of pairing; N is the polymerization degree, and n>=5.
2. the synthetic method of the conjugated polymers based on selenole of formula described in claim 1 (I), described method comprises the steps:
(1) in organic solvent, under catalyst and promotor exist, there is linked reaction, obtain following formula (II) compound in following formula (IV) compound and following formula (III) compound:
(2) in organic solvent, formula (II) compound and R
3-A reacts, and obtains described formula (I) compound;
Wherein, R
1, R
2, R
3, L
1, L
2, n, A definition as above, X is halogen.
3. synthetic method as claimed in claim 2, is characterized in that: described catalyzer is palladium compound, can be Pd (PPh
3)
4, palladium acetylacetonate (Pd (acac)
2), acid chloride, palladium trifluoroacetate, Palladous chloride, Na
2pdCl
4, Pd (NH
3)
4cl
2, PdCl
2(dppf), dppePdCl
2, Na
2pdCl
2, PdCl
2(CH
3cN)
2, PdCl
2(PPh
3)
2, Pd (NH
3)
4cl
2, PdCl
2(cod) any one in or any multiple mixture; Preferably, described catalyzer is selected from Pd (PPh
3)
4, palladium acetylacetonate (Pd (acac)
2), any one in acid chloride, palladium trifluoroacetate, Palladous chloride or multiple mixture, most preferably be Pd (PPh
3)
4.
4. synthetic method as claimed in claim 2 or claim 3, is characterized in that: described promotor is copper compound, can be CuI, CuCl, CuBr, Cu (OTf), Cu
2sO
4, Cu
2s, CuCl
2, CuBr
2, CuI
2, CuSO
4, venus crystals, acetylacetone copper, Cu (OTf)
2in any one or any multiple mixture; Preferably, described promotor is any one in CuI, CuCl, CuBr or any multiple mixture; Override is CuI.
5. the synthetic method as described in any one of claim 2-4, is characterized in that: the mol ratio of formula (IV) compound and formula (III) compound is 1:0.5-1.5.
6. the synthetic method as described in any one of claim 2-5, is characterized in that: the mol ratio of formula (IV) compound and catalyzer is 1:0.05-0.2.
7. the synthetic method as described in any one of claim 2-6, is characterized in that: the mol ratio of catalyzer and promotor is 1:1-3.
8. formula described in claim 1 (I) compound is used as fluorescent optical sensor to detect the purposes of heavy metal ion or class heavy metal ion.
9. use formula (I) compound described in claim 1 and the Molecular Logic Gates that builds.
10. Molecular Logic Gates as claimed in claim, is characterized in that: described Molecular Logic Gates is INHIBIT Molecular Logic Gates or IMPLICATION Molecular Logic Gates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410567169.5A CN104311801B (en) | 2014-10-22 | 2014-10-22 | Soluble conjugated polymer of a kind of selenole and preparation method thereof and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410567169.5A CN104311801B (en) | 2014-10-22 | 2014-10-22 | Soluble conjugated polymer of a kind of selenole and preparation method thereof and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104311801A true CN104311801A (en) | 2015-01-28 |
| CN104311801B CN104311801B (en) | 2016-07-20 |
Family
ID=52367128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410567169.5A Active CN104311801B (en) | 2014-10-22 | 2014-10-22 | Soluble conjugated polymer of a kind of selenole and preparation method thereof and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104311801B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778055A (en) * | 2016-04-28 | 2016-07-20 | 陕西师范大学 | Fe<3+> detection hyperbranched conjugated polymer and preparation method and application thereof |
| CN105778056A (en) * | 2016-04-28 | 2016-07-20 | 陕西师范大学 | Fe<3+> detection porous conjugated polymer and preparation method and application thereof |
| CN106404931A (en) * | 2016-08-25 | 2017-02-15 | 河池学院 | Detection reagent for heavy metal ions and synthesis method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036959A (en) * | 2004-07-28 | 2006-02-09 | Kyoto Univ | Conjugated compound and its polymer |
| WO2007081991A2 (en) * | 2006-01-10 | 2007-07-19 | The Trustees Of The University Of Pennsylvania | Novel conjugated materials featuring proquinoidal units |
| CN102660000A (en) * | 2012-04-13 | 2012-09-12 | 湖南师范大学 | Conjugated polyelectrolyte with ratiometric fluorescence signals, preparation method and application thereof |
| CN102746492A (en) * | 2012-06-25 | 2012-10-24 | 南京邮电大学 | Conjugated backbone doped fold-line water-soluble poly(aryleneethynylene) and preparation method thereof |
| CN103739829A (en) * | 2013-09-06 | 2014-04-23 | 中国科学院上海有机化学研究所 | Acceptor-acceptor type alternated conjugated polymer and preparation method and application thereof |
-
2014
- 2014-10-22 CN CN201410567169.5A patent/CN104311801B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036959A (en) * | 2004-07-28 | 2006-02-09 | Kyoto Univ | Conjugated compound and its polymer |
| WO2007081991A2 (en) * | 2006-01-10 | 2007-07-19 | The Trustees Of The University Of Pennsylvania | Novel conjugated materials featuring proquinoidal units |
| WO2007081991A3 (en) * | 2006-01-10 | 2008-01-10 | Univ Pennsylvania | Novel conjugated materials featuring proquinoidal units |
| CN102660000A (en) * | 2012-04-13 | 2012-09-12 | 湖南师范大学 | Conjugated polyelectrolyte with ratiometric fluorescence signals, preparation method and application thereof |
| CN102746492A (en) * | 2012-06-25 | 2012-10-24 | 南京邮电大学 | Conjugated backbone doped fold-line water-soluble poly(aryleneethynylene) and preparation method thereof |
| CN103739829A (en) * | 2013-09-06 | 2014-04-23 | 中国科学院上海有机化学研究所 | Acceptor-acceptor type alternated conjugated polymer and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778055A (en) * | 2016-04-28 | 2016-07-20 | 陕西师范大学 | Fe<3+> detection hyperbranched conjugated polymer and preparation method and application thereof |
| CN105778056A (en) * | 2016-04-28 | 2016-07-20 | 陕西师范大学 | Fe<3+> detection porous conjugated polymer and preparation method and application thereof |
| CN105778055B (en) * | 2016-04-28 | 2018-01-12 | 陕西师范大学 | It is a kind of to be used to detect Fe3+ hyperbranched conjugated polymer and its preparation method and application |
| CN106404931A (en) * | 2016-08-25 | 2017-02-15 | 河池学院 | Detection reagent for heavy metal ions and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104311801B (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shi et al. | A high selective fluorescent sensor for Cu2+ in solution and test paper strips | |
| Das et al. | Stimuli-responsive discriminative detection of Cu2+ and Hg2+ with concurrent sensing of S2-from aqueous medium and bio-fluids by CN fused azophenine functionalized “smart” hydrogel assay@ A potential biomarker sensor for Wilson’s disease | |
| Shuai et al. | Fluorescent sensors for detection of mercury: From small molecules to nanoprobes | |
| Guo et al. | A highly selective and sensitive dual-mode sensor for colorimetric and turn-on fluorescent detection of cyanide in water, agro-products and living cells | |
| Kumar et al. | Highly sensitive and selective naked-eye detection of Cu2+ in aqueous medium by a ninhydrin–quinoxaline derivative | |
| Che et al. | Ultraselective fluorescent sensing of Hg 2+ through metal coordination-induced molecular aggregation | |
| CN103772318B (en) | A kind of organic compound for measuring metal ion content in water surrounding and application thereof | |
| CN110407717B (en) | P-diethylamino salicylaldehyde modified fluorene fluorescent probe and preparation method thereof | |
| Qazi et al. | Calix [4] arene based chemosensor for selective complexation of Cd (II) and Cu (II) | |
| Vishaka et al. | Paper based field deployable sensor for naked eye monitoring of copper (II) ions; elucidation of binding mechanism by DFT studies | |
| US20100144043A1 (en) | Molecular fluorescence sensor for highly sensitive and selective detection of mercury | |
| CN104311801A (en) | Water-soluble conjugated polymer of benzoselenadiazole and preparation method and application of conjugated polymer | |
| Lee et al. | A thiourea-naphthol based turn-on fluorescent sensor for detecting In3+ and its application | |
| Sadia et al. | Synthesis and evaluation of a schiff-based fluorescent chemosensors for the selective and sensitive detection of Cu 2+ in aqueous media with fluorescence off-on responses | |
| da Silveira Petruci et al. | A new palladium chelate compound for determination of sulfide | |
| Liu et al. | A new “turn-on” fluorescent sensor for highly selective sensing of H2PO4− | |
| Abdel-Rahman et al. | Novel Di-and Tri-azomethine compounds as chemo sensors for th e detection of various metal ions | |
| Sun et al. | A naphthalene based chemosensor for dual channel recognition of Al3+ and relay recognition of Fe3+ in water-bearing system and bioimaging in zebrafish | |
| CN111320585A (en) | Double-colorimetric double-fluorescent phenanthroimidazole probe as well as preparation method and application thereof | |
| Deng et al. | Coumarin-derived Schiff base as a colorimetric and fluorescent dual-channel chemosensor for detecting HSO4− and bioimaging & biosensing in Zebrafish | |
| Fan et al. | A dual-functional chemical sensor for the detection of Cu2+ and Cd2+ based on the photochromic diarylethene | |
| Feng et al. | Selective sensing of Fe3+ based on fluorescence quenching by 2, 6-bis (benzoxazolyl) pyridine with β-cyclodextrin in neutral aqueous solution | |
| CN113121385A (en) | Detectable aquatic Fe3+、Al3+、Cu2+And Zn2+Fluorescent molecular sensor and application | |
| CN113880867B (en) | Detectable Cu in water 2+ 、Zn 2+ Molecular sensor and application | |
| Abdel-Rahman et al. | Design, synthesis and structural inspection of some novel di-and tri-azomethene compounds as chemo sensors for the detection of various metal ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 325035 Zhejiang, Ouhai, South East Road, No. 38, Wenzhou National University Science Park Incubator Applicant after: Wenzhou University Applicant after: Wenzhou Vocational & Technical College Address before: 325035 Zhejiang province Chashan Wenzhou Higher Education Park of Wenzhou University Applicant before: Wenzhou University Applicant before: Wenzhou Vocational & Technical College |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |