CN102952539A - Molecular sensor with Cu2＋ recognition function and preparation method thereof - Google Patents
Molecular sensor with Cu2＋ recognition function and preparation method thereof Download PDFInfo
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- CN102952539A CN102952539A CN201210422759XA CN201210422759A CN102952539A CN 102952539 A CN102952539 A CN 102952539A CN 201210422759X A CN201210422759X A CN 201210422759XA CN 201210422759 A CN201210422759 A CN 201210422759A CN 102952539 A CN102952539 A CN 102952539A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HDBQZGJWHMCXIL-UHFFFAOYSA-N 3,7-dihydropurine-2-thione Chemical compound SC1=NC=C2NC=NC2=N1 HDBQZGJWHMCXIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- CWHJIJJSDGEHNS-MYLFLSLOSA-N Senegenin Chemical compound C1[C@H](O)[C@H](O)[C@@](C)(C(O)=O)[C@@H]2CC[C@@]3(C)C(CC[C@]4(CCC(C[C@H]44)(C)C)C(O)=O)=C4[C@@H](CCl)C[C@@H]3[C@]21C CWHJIJJSDGEHNS-MYLFLSLOSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000003068 molecular probe Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000009871 tenuigenin Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000016397 Methyltransferase Human genes 0.000 description 1
- 108060004795 Methyltransferase Proteins 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000008844 regulatory mechanism Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a Cu-containing alloy2+Molecular sensor with recognition function and preparation method thereof, wherein Cu is contained2+The structural formula of the molecular sensor (TMP) with the recognition function is as follows:
TMP of the invention as Cu2+The sensor has good selectivity and high sensitivity (detection limit of 10)-5M) and can be used for Cu by different spectroscopic means2+And realizing the unity identification.
Description
One, technical field
The present invention relates to a kind of molecule sensor and preparation method thereof, specifically a kind of have a Cu
2+Molecule sensor of recognition function and preparation method thereof.
Two, background technology
Molecular recognition is widespread in nature, and especially plays very important effect in the vital movement process, such as the specificity of enzyme, the formation of protein.Molecular recognition is by utilizing the selective binding of non covalent bond to realize between host molecule (receptor molecule) and the guest molecule (substrate molecule), and produces the process of certain specific function.Usually can selectivity to guest molecule (substrate molecule) host molecule (receptor molecule) of identification be called molecule sensor (moleeularsensor) or molecular probe (molecularprobe).Sensor or probe can be for detection of the target molecules (or ion) in various clinical, the environmental samples.
Transition metal ion plays an important role in environment and life science.In recent years, synthetic part (receptor) molecule to the selective recognition function of transition metal ion of design receives much concern.Copper is essential a kind of trace heavy metal element in the animal and plant body, and body has very strict regulatory mechanism for the content of cupric ion in the cell, and the superfluous or shortage of copper all can cause disease.In addition, cupric ion also is one of heavy metal ion to environment.Therefore, how to detect rapidly and sensitively cupric ion, all have great significance for life science, environmental science.At present a lot of to the detection method of cupric ion, mainly contain atomic absorption spectrometry, atomic emission spectrometry and electrochemical method etc.In recent years, owing to advantages such as highly sensitive, the selectivity of fluorescence detection method inherence are good, and sampling amount is few, can detect in real time, the fluorescence sense method develops in molecular recognition rapidly, and making the design fluorescent probe detect cupric ion becomes a new study hotspot.
Three, summary of the invention
The present invention aims to provide a kind of Cu of having
2+Molecule sensor of recognition function and preparation method thereof, technical problem to be solved are to obtain good, the highly sensitive identification Cu of selectivity by molecular designing
2+Part, and can identify by fluoroscopic examination.
The present invention has Cu
2+The molecule sensor of recognition function is called for short TMP, and structural formula is as follows:
The present invention has Cu
2+The preparation method of the molecule sensor of recognition function is characterized in that operating according to the following steps:
Under the room temperature, potassium tert.-butoxide is placed dry mortar grinding powder, then add N, N-diethylbenzaldehyde and thiopurine methyltransferase-4, the 6-dimethyl pyrimidine continues to grind 20-40min, thin-layer chromatography (TLC) is followed the tracks of, reaction is poured the reactant in the mortar in the methyl alcohol into after finishing, and reflux 1-3 hour, obtains faint yellow crystallite TMP after filtration, methanol wash and the drying; Thiopurine methyltransferase-4,6-dimethyl pyrimidine, N, the ratio of the amount of substance of N-diethylbenzaldehyde and potassium tert.-butoxide is 1:1.5-1.8:5-6.
Synthetic route of the present invention is as follows:
The present invention with pyrimidine group with higher reactive behavior, strong coordination ability and good biocompatibility as main body, with the N with D – π-A conjugated structure, the reaction of N-diethylbenzene vinyl, succinct pyridine derivatives 2-thiopurine methyltransferase with the pi-conjugated system-4-methyl-6 (4-N that prepared efficiently, N-diethylbenzene vinyl) pyrimidine (TMP), it is identified the metal ion activity screening, and the result shows that the TMP molecule has single identification Cu in the ultraviolet-visible district
2+Character, and identification before and after two photon absorption cross section larger variation is arranged, cell experiment shows, probe can permeates cell membranes, shows red fluorescence in tenuigenin, can be used for qualitative detection liver cancer cell, the discovery of this result of study is significant for the life science direction.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, TMP of the present invention is as Cu
2+Good, the highly sensitive (detectability 10 of sensor selectivity
-5And can be by different spectroscopy means to Cu M),
2+The identification of realization unicity.
In acetonitrile solution, add Cu
2+After, the Single Photon Absorption intensity of TMP weakens rapidly, a new absorption peak (Fig. 2) appears in the long wave position simultaneously, the single photon fluorescent emission intensity weakens (Fig. 3), maximum two photon absorption cross section is increased to 2884GM (Fig. 4) from 307GM, and other ion does not all have above phenomenon.
2, TMP of the present invention and Cu
2+In conjunction with after have good cell permeability, during take 820nm as excitation wavelength, observe its two-photon fluorescence developing result (Fig. 5), the light of this low-lying excitation high energy emission has the characteristics little to cell injury.
3, introduce dimethyl sulfide among the TMP of the present invention, can increase solvability and the biocompatibility of compound, be convenient to the application aspect the trace element detection in animal and plant body.
4, the preparation of TMP of the present invention is to make raw material with pyrimidine, and raw material is easy to get, and cost is low, and synthesis step is simple, and productive rate is high.
Four, description of drawings
Fig. 1 is the crystalline structure figure of TMP of the present invention.
Fig. 2 is TMP of the present invention impact on metal ion Single Photon Absorption spectrum in acetonitrile solution, as can be seen from the figure can realize that by absorption spectrum TMP is to Cu
2+Single identification.
Fig. 3 is TMP of the present invention impact on metal ion single photon fluorescence spectrum in acetonitrile solution, as can be seen from the figure can realize also that by fluorescence spectrum TMP is to Cu
2+Single identification.
Fig. 4 be TMP of the present invention in acetonitrile solution to Cu
2+Two photon absorption cross section before and after the identification, as can be seen from the figure the variation by two photon absorption cross section can realize that equally TMP is to Cu
2+Single identification.
Fig. 5 is that TMP of the present invention adds Cu
2+After two-photon fluorescence hepatoma Hep G 2 cells imaging research result, a two-photon action diagram wherein, b light field action diagram, c stacking diagram.As can be seen from the figure TMP can pass cytolemma, enters cell, uniform coloring tenuigenin.
Five, embodiment
The present invention has Cu
2+The molecule sensor of recognition function is called for short TMP, and structural formula is as follows:
The present invention has Cu
2+The preparation method of the molecule sensor of recognition function is as follows:
Under the room temperature, the 50mmol potassium tert.-butoxide is placed dry mortar grinding powder, then add 15mmol N, N-diethylbenzaldehyde and 10mmol thiopurine methyltransferase-4,6-dimethyl pyrimidine, continue to grind 20min, thin-layer chromatography (TLC) is followed the tracks of, and reaction is poured the reactant in the mortar in the 150mL methyl alcohol into reflux 1 hour after finishing, obtain faint yellow crystallite TMP after filtration, methanol wash and the drying, productive rate 81%.
Employing human hepatocellular HepG2 cell, DMEM culture medium culturing 24 hours is washed three times to remove substratum with PBS before the dyeing, adds the anhydrous DMSO solution (1 * 10 of TMP of 40 μ L in cultivating capsule behind the PBS of adding 200 μ L
-3Mol/L).After lucifuge is hatched 15 minutes, with liquid-transfering gun sucking-off solution.Carry out behind the PBS solution washing three times two-photon fluorescence micro-with imaging (two-photon absorption excitation wavelength 820nm, emission wavelength are 500～600nm, scal bar=50 μ m).
Claims (2)
1. one kind has Cu
2+The molecule sensor of recognition function is characterized in that its structural formula is as follows:
2. one kind claimed in claim 1ly has a Cu
2+The preparation method of the molecule sensor of recognition function is characterized in that:
Potassium tert.-butoxide is placed dry mortar grinding powder, add N, N-diethylbenzaldehyde and thiopurine methyltransferase-4, the 6-dimethyl pyrimidine, normal temperature griding reaction 20-40min, reaction is poured the reactant in the mortar in the methyl alcohol into after finishing, and reflux 1-3 hour, namely gets target product after filtration, washing and the drying; Thiopurine methyltransferase-4,6-dimethyl pyrimidine, N, the material of N-diethylbenzaldehyde and potassium tert.-butoxide amount than being 1:1.5-1.8:5-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210422759.XA CN102952539B (en) | 2012-10-29 | 2012-10-29 | Molecular sensor with Cu2＋ recognition function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210422759.XA CN102952539B (en) | 2012-10-29 | 2012-10-29 | Molecular sensor with Cu2＋ recognition function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952539A true CN102952539A (en) | 2013-03-06 |
| CN102952539B CN102952539B (en) | 2014-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210422759.XA Expired - Fee Related CN102952539B (en) | 2012-10-29 | 2012-10-29 | Molecular sensor with Cu2＋ recognition function and preparation method thereof |
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| Country | Link |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440965A (en) * | 2003-01-23 | 2003-09-10 | 安徽大学 | Pyridine salt derivative as strong two-photon absorbing material and its prepn process |
-
2012
- 2012-10-29 CN CN201210422759.XA patent/CN102952539B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440965A (en) * | 2003-01-23 | 2003-09-10 | 安徽大学 | Pyridine salt derivative as strong two-photon absorbing material and its prepn process |
Non-Patent Citations (2)
| Title |
|---|
| JESSIE SANDOSHAM ET AL.: "Syntheses of 5-Alkenylpyrimidines by Organotin Reactions", 《ACTA CHEMICA SCANDINAVICA B》 * |
| 马健等: "一种新型吡啶衍生物的合成及其光谱性质研究", 《安徽大学学报(自然科学版)》 * |
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| CN102952539B (en) | 2014-11-26 |
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