CN102276607A - Imidazole [4,5-f]-1,10-phenanthroline derivatives as well as preparation method and application thereof - Google Patents
Imidazole [4,5-f]-1,10-phenanthroline derivatives as well as preparation method and application thereof Download PDFInfo
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- KCALAFIVPCAXJI-UHFFFAOYSA-N O=C(c1cccnc1-c1ncccc11)C1=O Chemical compound O=C(c1cccnc1-c1ncccc11)C1=O KCALAFIVPCAXJI-UHFFFAOYSA-N 0.000 description 1
- FQHMWPWQKQHOGM-UHFFFAOYSA-N Oc(cc1)ccc1-c1nc(c2c(c3c4cccn3)nccc2)c4[nH]1 Chemical compound Oc(cc1)ccc1-c1nc(c2c(c3c4cccn3)nccc2)c4[nH]1 FQHMWPWQKQHOGM-UHFFFAOYSA-N 0.000 description 1
- RGHHSNMVTDWUBI-UHFFFAOYSA-N Oc1ccc(C=O)cc1 Chemical compound Oc1ccc(C=O)cc1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N c1cnc2c3ncccc3ccc2c1 Chemical compound c1cnc2c3ncccc3ccc2c1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides imidazole [4,5-f]-1,10-phenanthroline derivatives as well as a preparation method and application thereof. The method comprises the following steps: oxidizing 1,10-phenanthroline into 1,10-phenanthroline-5,6-diketone; forming p-hydroxy benzimidazole[4,5-f]phenanthroline with p-hydroxybenzaldehyde in ammonium acetate and glacial acetic acid condition; and forming the imidazole [4,5-f]-1,10-phenanthroline derivatives with 2-dimethylaminoethyl chloride hydrochloride or 1-(2-ethyl) piperidine hydrochloride or 1-(2-ethyl) pyrroline hydrochloride in anhydrous degasified DMF (dimethylformamide) containing NaH. The prepared imidazole [4,5-f]-1,10-phenanthroline derivatives can selectively identify and stabilize telomere G-tetrable helix DNA (deoxyribonucleic acid) in the existence of excessive double helix DNA, and can effectively inhibit growth and propagation of HeLa and HepG2 cancer cells, and can be used for preparing antitumor medicaments.
Description
Technical field
The present invention relates to heterogeneous ring compound, be specifically related to a kind of imidazoles [4,5-f] and 1,10-derivative of phenanthroline and its production and use is particularly as the purposes of antitumor drug.
Background technology
Telomeric dna is non-coding, height repeating sequences, and its structure is double-stranded except 3 ' end is strand district by many G based compositions mostly.The tumor-necrosis factor glycoproteins of the terminal DNA of people's telomere is 5 '-TTAGGG-3 ', and length is about 3-6kb, and its 3 '-end is the strand district of 100-200 base.Crystallography and NMR studies show that, these multiple, is rich in the sequence of G at K
+Perhaps Na
+Exist down, can be folded into G-four chain body structures.
The major function of telomere is to prevent that in the chromosome duplication process disappearance of end of chromosome base pair and end end from merging.There is " end duplicates problem " in telomeric dna in human body cell, and archaeal dna polymerase is the end of duplicated chromosome fully.Therefore, along with cell fission, the base of telomeric dna shortens gradually, and last telomere length reaches threshold value, and it is dead then that cell enters aging.Yet in cancer cells,, constantly increase base, stoped the shortening of telomere length, cause the cancer cells immortality at telomere 3 '-suspension strand by reverse transcriptase of telomere.What is interesting is that expression activity or activity are very not low in normal somatic cell for Telomerase, and activity is very high in the cancer cells of 85-90%.Because the substrate of Telomerase effect is a telomeric dna, stablizes the inhibition that four chain structures cause telomerase activation by small molecules, thereby has stoped the propagation of tumour cell.Therefore, G-four serobila DNA can impel the compound of formation of G-four serobilas or enhanced stability then may the potential therapeutic action be arranged to cancer as the target spot of telomerase inhibitor.
Summary of the invention
The purpose of this invention is to provide a kind of imidazoles [4,5-f] and 1,10-derivative of phenanthroline and its production and use.
A kind of imidazoles provided by the invention [4,5-f] and 1, the 10-derivative of phenanthroline, its structural formula is as follows:
Imidazoles provided by the invention [4,5-f] and 1, the synthetic route of 10-derivative of phenanthroline is as follows:
Imidazoles provided by the invention [4,5-f] and 1, the preparation method of 10-derivative of phenanthroline may further comprise the steps:
(1) with 1,10-phenanthroline preparation 1,10-phenanthroline-5,6-diketone;
(2) with 1,10-phenanthroline-5,6-diketone and p-Hydroxybenzaldehyde prepare para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound;
(3) under the nitrogen protection, the sodium hydride 1: 4 in molar ratio～7 of para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound and mass concentration 25～50% is added among the DMF of the dryings and the degassing, be heated to 110 ℃ of backflow 30-60min; Para hydroxybenzene and imidazoles [4 in molar ratio, 5-f] the phenanthroline compound: 2-dimethylamino monochloroethane hydrochloride=1: 2～5,2-dimethylamino monochloroethane hydrochloride is dissolved among the DMF of the drying degassing, then this solution is dropwise added in the above-mentioned reflux solution, 110 ℃ of reaction 72～96h; The reaction postcooling filters to room temperature, and filtrate boils off solvent and gets solid; This solid is dissolved in methyl alcohol, transfers pH=7.0 with hydrochloric acid and triethylamine, boil off solvent, the gained material separates with column chromatography, obtains imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline.
2-dimethylamino monochloroethane hydrochloride can use 1-(2-chloroethene alkyl) piperidine hydrochlorate or 1-(2-chloroethene alkyl) pyrroles's hydrochloride to replace in the step (3).
Studies show that in the presence of excessive duplex DNA, imidazoles [4,5-f] and 1, the selectivity identification of 10-derivative of phenanthroline energy is also stablized four strands of helical dnas of telomere G-, and can suppress the growth and breeding of HeLa and HepG2 cell, its IC effectively
50Value is about 10 respectively
-6M and 10
-5M proves imidazoles [4,5-f] and 1, and the 10-derivative of phenanthroline can be used in the preparation antitumor drug.
Advantage compared with prior art of the present invention and effect:
The imidazoles that the present invention provides [4,5-f] and 1,10-derivative of phenanthroline synthetic method is simple, the imidazoles of preparation [4,5-f] and 1, the 10-derivative of phenanthroline can be in the presence of 10 times of excessive duplex DNAs, and selectivity identification is also stablized four strands of helical dnas of G-.The imidazoles [4,5-f] and 1 of the present invention's preparation, the 10-derivative of phenanthroline especially can suppress the growth and breeding of HeLa and HepG2 cell, IC effectively
50Value is about 10
-6With 10
-5M, the kill tumor cell is used for preparing anti-tumor medicine effectively.
Description of drawings
Fig. 1 is 1, and the 10-phenanthroline exists down, the FRET (fluorescence resonance energy transfer) melting point curve of four strands of helical dnas of G-, and wherein: 0.2 μ M G-quadruplex DNA (▲) adds 2 μ M 1,10-phenanthroline (●).
Fig. 2 different concns imidazoles [4,5-f] and 1,10-derivative of phenanthroline exist down, the FRET (fluorescence resonance energy transfer) melting point curve of four strands of helical dnas of G-, (A) embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline; (B) embodiment 2 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; (C) embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; Wherein: 0.2 μ MG-quadruplex DNA (▲), add 1 μ M derivative (●), add 2 μ M derivatives (◆), add 3 μ M derivatives
Figure 32 .0 μ M competition duplex DNA is to the influence of the FRET (fluorescence resonance energy transfer) melting point curve of four strands of helical dnas of compound-G-, (A) embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline; (B) embodiment 2 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; (C) embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; Wherein: 0.2 μ MG-quadruplex DNA (▲), add 2.0 μ M derivatives (◆), add 2.0 μ M derivatives and 2.0 μ M duplex DNA (●).
Fig. 4 is hatched the imidazoles [4,5-f] and 1 of different concns after 72 hours, and the 10-derivative of phenanthroline is to the influence of HeLa cell viability, (A) embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline; (B) embodiment 2 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; (C) embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline;
Fig. 5 is hatched the imidazoles [4,5-f] and 1 of different concns after 72 hours, and the 10-derivative of phenanthroline is to the influence of HepG2 cell viability, (A) embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline; (B) embodiment 2 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline; (C) embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline.
Following examples are in order to explanation the present invention
Embodiment 1: imidazoles [4,5-f] and 1, the preparation of 10-derivative of phenanthroline
(1) with (4g, 0.02mol) 1,10-phenanthroline and (4g, 0.03mol) KBr slowly adds respectively in the 30mL vitriol oil of ice bath cooling and stirring successively, the nitrosonitric acid of 15mL mass concentration 86%～97.5% is added in the above-mentioned solution, continue ice bath and stir 30min, reflux 5h afterwards.After the reaction liquid is poured in the 320g frozen water,, used 50mL * 8 dichloromethane extractions then with 10M NaOH neutralization.The extraction liquid anhydrous sodium sulfate drying filters, and boils off solvent, obtains 1,10-phenanthroline-5, and the thick product of 6-diketone, recrystallizing methanol obtains 1,10-phenanthroline-5,6-diketone product;
(2) will (0.26g, 1.25mmol) 1,10-phenanthroline-5,6-diketone, (0.21g, 1.75mmol) p-Hydroxybenzaldehyde and (1.92g, 25mmol) ammonium acetate adds in the 3.5mL glacial acetic acid, reflux 3h.Water washing and precipitating is filtered in reaction back dilute with water, ammoniacal liquor pH=6～7 that neutralize.Collecting precipitation after the vacuum-drying, is used the acetonitrile recrystallization, obtains para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound;
(3) under the nitrogen protection, with (0.20g, 0.7mmol) para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound and (0.13g, 3.4mmol) sodium hydride of mass concentration 25～50% is dissolved among the 20mL DMF of the drying and the degassing, is heated to 110 ℃ of backflow 30min; (0.20g, 1.4mmol) 2-dimethylamino monochloroethane hydrochloride is dissolved among the 40mL DMF of the drying degassing, this solution is dropwise added in the above-mentioned reflux solution 110 ℃ of reaction 72h.The reaction postcooling filters to room temperature, and filtrate boils off solvent and gets solid.This solid is dissolved in methyl alcohol, transfers pH=7.0 with hydrochloric acid and triethylamine, boil off solvent, the gained material separates with column chromatography, and developping agent is a methyl alcohol: chloroform: glacial acetic acid=1: 2: 0.02, obtain imidazoles [4,5-f] and 1, and the 10-derivative of phenanthroline, structural formula is:
Its physical constant and spectroscopic data are as follows:
Pale brown toner end, molecular formula: C
23H
21N
5O;
ESI(+)-MS(m/z)：384.58(100％)，[M+H]
+；789.33(100％)，[2M+Na]
+；
1H-NMR(300MHz，DMSO-d
6)：δ(ppm)9.01(m，4H)，8.29(d，J＝8.4Hz，2H)，7.82(m，2H)，7.14(d，J＝8.4Hz，2H)，4.16(m，2H)，2.67(m，2H)，2.25(m，6H)；
13C-NMR(75MHz，DMSO-d
6)：δ(ppm)160.0，151.9，148.0，143.5，130.6，128.5，123.8，122.4，115.2，66.4，58.1，46.0。
Embodiment 2: imidazoles [4,5-f] and 1, the preparation of 10-derivative of phenanthroline
(1), (2) process is with embodiment 1
(3) under the nitrogen protection, with (0.20g, 0.7mmol) para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound and (0.18g, 4.7mmol) sodium hydride of mass concentration 25～50% is dissolved among the 20mL DMF of the drying and the degassing, is heated to 110 ℃ of backflow 60min; (0.52g, 2.8mmol) 1-(2-chloroethene alkyl) piperidine hydrochlorate is dissolved among the 50mL DMF of the drying degassing, this solution is dropwise added in the above-mentioned reflux solution 110 ℃ of reaction 96h.The reaction postcooling filters to room temperature, and filtrate boils off solvent and gets solid.This solid is dissolved in methyl alcohol, transfers pH=7.0 with hydrochloric acid and triethylamine, boil off solvent, the gained material separates with column chromatography, and developping agent is a methyl alcohol: chloroform: glacial acetic acid=1: 4: 0.02, obtain imidazoles [4,5-f] and 1, and the 10-derivative of phenanthroline, structural formula is:
Its physical constant and spectroscopic data are as follows:
Pale brown toner end, molecular formula: C
26H
25N
5O;
ESI(+)-MS(m/z)：424.50(58％)，[M+H]
+；446.42(64％)，[M+Na]
+；869.33(100％)，[2M+Na]
+；
1H-NMR(300MHz，DMSO-d
6)：δ(ppm)9.12(m，2H)，9.01(m，2H)，8.38(m，2H)，?7.84(m，2H)，7.12(m，2H)，4.17(m，2H)，2.70(m，4H)，1.22-1.51(m，8H)；
13C-NMR(75MHz，DMSO-d
6)：δ(ppm)159.2，151.6，147.3，142.5，130.4，127.9，123.2，121.7，114.4，65.4，57.1，54.2，25.3，23.3。
Embodiment 3: imidazoles [4,5-f] and 1, the preparation of 10-derivative of phenanthroline
(1), (2) process is with embodiment 1
(3) under the nitrogen protection, with (0.20g, 0.7mmol) para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound and (0.13g, 3.4mmol) sodium hydride of mass concentration 25～50% is dissolved among the 20mL DMF of the drying and the degassing, is heated to 110 ℃ of backflow 40min; (0.60g, 3.5mmol) 1-(2-chloroethene alkyl) pyrroles's hydrochloride is dissolved among the 50mL DMF of the drying degassing, this solution is dropwise added in the above-mentioned reflux solution 110 ℃ of reaction 82h.The reaction postcooling filters to room temperature, and filtrate boils off solvent and gets solid.This solid is dissolved in methyl alcohol, transfers pH=7.0 with hydrochloric acid and triethylamine, boil off solvent, the gained material separates with column chromatography, and developping agent is a methyl alcohol: chloroform: glacial acetic acid=1: 3: 0.02, obtain imidazoles [4,5-f] and 1, and the 10-derivative of phenanthroline, structural formula is:
Its physical constant and spectroscopic data are as follows:
Pale brown toner end, molecular formula: C
25H
23N
5O;
ESI(+)-MS(m/z)：410.42(100％)，[M+H]
+；
1H-NMR(300MHz，DMSO-d
6)：δ(ppm)9.05(m，4H)，8.38(d，J＝8.4Hz，2H)，7.84(m，2H)，7.13(d，J＝7.8Hz，2H)，4.17(t，J＝5.7Hz，2H)，2.83(t，J＝5.7Hz，2H)，2.72(m，4H)，1.70(m，4H)；
13C-NMR(75MHz，DMSO-d
6)：δ(ppm)161.9，153.4，149.5，142.5，130.6，126.4，124.6，121.7，117.2，68.9，56.4，31.6，25.5。
Embodiment 4 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the stabilizing power and the Study on Selectivity of four strands of helical dnas of people's telomere G-
We use FRET (fluorescence resonance energy transfer)-fusing point (FRET-melting) experiment, study imidazoles [4,5-f] and 1, and the 10-derivative of phenanthroline is to the identification and the stabilizing power of four strands of helical dnas of G-.For imidazoles [4,5-f] and 1 better are described, the 10-derivative of phenanthroline is to the identification and the stabilization of four strands of helical dnas of G-simultaneously, and we are with 1, and the 10-phenanthroline compares FRET (fluorescence resonance energy transfer)-fusing point experiment of four strands of helical dnas of G-.Used dna sequence dna is 5 '-FAM-GGG (TTAGGG) 3-TAMRA-3 ', i.e. 5 ' and 3 ' terminal people's telomeric sequence 5 '-GGG (TTAGGG) 3-3 ' that uses FAM and TAMRA mark respectively.Buffer system is: 10mM natrium cacodylicum (pH 7.4), 100mM NaCl.The result is shown in Fig. 1, Fig. 2 and table 1.Table 1 has been listed at 2 μ M 1,10-phenanthroline and different imidazoles thereof [4,5-f] and 1, under the 10-derivative of phenanthroline concentration, 1,10-phenanthroline and imidazoles [4 thereof, 5-f] and 1, the 10-derivative of phenanthroline makes melting temperature increased value (the Δ T of four strands of helical dnas of G-
m).The result shows that with 1, the 10-phenanthroline is compared, and imidazoles [4,5-f] and 1,10-derivative of phenanthroline can effectively improve the stability of four strands of helical dnas of the terminal G-of people's telomere.
1 of table 12 μ M concentration, 10-phenanthroline and different concns imidazoles thereof [4,5-f] and 1, the 10-derivative of phenanthroline is to the influence of four strands of helical dna melting temperatures of G-
In order to study imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the selectivity of four strands of relative duplex DNAs of spiral of G-, and we have carried out competition FRET (fluorescence resonance energy transfer)-fusing point (FRET-melting) experiment.Adding in people's telomeric dna experimental system of the above-mentioned mark of 0.2 μ M does not have the chromophoric group mark and excessive 10 times duplex DNA (2.0 μ M), observe the adding of excessive greatly duplex DNA, 2 μ M imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to four gangs of spiral T of G-
mThe influence of value.Wherein, the sequence of competitor dna is 5 '-CAATCGGATCGAATTCGATCCGATTG-3 ', forms duplex DNA from complementation in solution.The result is shown in Fig. 2 and table 2.The result shows, under the condition that 10 times of excessive duplexs exist, imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is influenced hardly or influence is very little to the stability of four strands of helical dnas of G-, and imidazoles [4,5-f] also 1 be described, four strands of helical dnas of the 10-derivative of phenanthroline selectively targeted G-of energy, and can effective as selective identification and four strands of helical dnas of stabilizes telomere G-.
There is imidazoles [4,5-f] and 1 down in table 2 competition duplex DNA, and the 10-derivative of phenanthroline is to the influence of four strands of helical dna melting temperatures of G-
Embodiment 5 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the research of tumor cell activity
In order to study imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the toxicity of tumour cell, we have tested imidazoles [4 with mtt assay, 5-f] and 1, the 10-derivative of phenanthroline is to born of the same parents' toxic action of human cervical carcinoma cell (HeLa cell) and human liver cancer cell (HepG2 cell), and the result respectively as shown in Figure 4 and Figure 5.Find imidazoles [4,5-f] and 1,10-derivative of phenanthroline and HeLa co-culture of cells are after 72 hours, embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline, embodiment 2 imidazoles [4,5-f] and 1,10-derivative of phenanthroline and embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the IC of HeLa cell
50Value is respectively 1.0,0.6 and 0.8 μ M; Imidazoles [4,5-f] and 1,10-derivative of phenanthroline and HepG2 co-culture of cells are after 72 hours, embodiment 1 imidazoles [4,5-f] and 1,10-derivative of phenanthroline, embodiment 2 imidazoles [4,5-f] and 1,10-derivative of phenanthroline and embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the IC of HepG2 cell
50Value is respectively 8.9,8.5 and 18.9 μ M.
More than studies show that in the presence of ten times of duplex DNAs imidazoles [4,5-f] and 1, the selectivity identification of 10-derivative of phenanthroline energy is also stablized four strands of helical dnas of telomere G-, and can suppress the growth and breeding of HeLa and HepG2 cell effectively, cultivate embodiment 1 imidazoles [4,5-f] and 1 after 72 hours altogether, the 10-derivative of phenanthroline, embodiment 2 imidazoles [4,5-f] and 1,10-derivative of phenanthroline and embodiment 3 imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is to the IC of HeLa cell
50Value is respectively 1.0,0.6 and 0.8 μ M, to the IC of HepG2 cell
50Value is respectively 8.9,8.5 and 18.9 μ M, can be used for preparing anti-tumor medicine.
Claims (5)
1. an imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline is characterized in that, structural formula is:
2. a kind of imidazoles according to claim 1 [4,5-f] and 1, the preparation method of 10-derivative of phenanthroline is characterized in that may further comprise the steps:
(1) with 1,10-phenanthroline preparation 1,10-phenanthroline-5,6-diketone;
(2) with 1,10-phenanthroline-5,6-diketone and p-Hydroxybenzaldehyde prepare para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound;
(3) under the nitrogen protection, the sodium hydride 1: 4 in molar ratio～7 of para hydroxybenzene and imidazoles [4,5-f] phenanthroline compound and mass concentration 25～50% is added among the DMF of the dryings and the degassing, be heated to 110 ℃ of backflow 30-60min; Para hydroxybenzene and imidazoles [4 in molar ratio, 5-f] the phenanthroline compound: 2-dimethylamino monochloroethane hydrochloride=1: 2～5,2-dimethylamino monochloroethane hydrochloride is dissolved among the DMF of the drying degassing, then this solution is dropwise added in the above-mentioned reflux solution, 110 ℃ of reaction 72～96h; The reaction postcooling filters to room temperature, and filtrate boils off solvent and gets solid; This solid is dissolved in methyl alcohol, transfers pH=7.0 with hydrochloric acid and triethylamine, boil off solvent, the gained material separates with column chromatography, obtains imidazoles [4,5-f] and 1, the 10-derivative of phenanthroline.
3. a kind of imidazoles according to claim 2 [4,5-f] and 1, the preparation method of 10-derivative of phenanthroline is characterized in that the 2-dimethyl chloride ethane hydrochloride in the described step (3) substitutes with 1-(2-chloroethene alkyl) piperidine hydrochlorate.
4. a kind of imidazoles according to claim 2 [4,5-f] and 1, the preparation method of 10-derivative of phenanthroline is characterized in that the 2-dimethylamino monochloroethane hydrochloride in the described step (3) substitutes with 1-(2-chloroethene alkyl) pyrroles's hydrochloride.
5. a kind of imidazoles according to claim 1 [4,5-f] and 1, the application of 10-derivative of phenanthroline in the preparation antitumor drug.
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| CN106317096A (en) * | 2016-08-19 | 2017-01-11 | 华南师范大学 | Phenanthroline imidazole type rare earth coordination molecule-based probe as well as preparation method and application thereof |
| CN106565713A (en) * | 2016-10-10 | 2017-04-19 | 浙江工业大学 | 2'-pyrazol-1H-imidazole [4,5-f][1,10] phenanthroline derivate and preparing method and application thereof |
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| CN106010502B (en) * | 2015-11-24 | 2019-03-01 | 河北科技大学 | A kind of preparation method of the rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance |
| CN106317096A (en) * | 2016-08-19 | 2017-01-11 | 华南师范大学 | Phenanthroline imidazole type rare earth coordination molecule-based probe as well as preparation method and application thereof |
| CN106565713A (en) * | 2016-10-10 | 2017-04-19 | 浙江工业大学 | 2'-pyrazol-1H-imidazole [4,5-f][1,10] phenanthroline derivate and preparing method and application thereof |
| CN108329317A (en) * | 2018-04-10 | 2018-07-27 | 重庆文理学院 | A kind of derivative of phenanthroline and its preparation method and application |
| CN114671870A (en) * | 2022-03-18 | 2022-06-28 | 广州鲁比生物科技有限公司 | Cinnamic aldehyde derivative and preparation method and application thereof |
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