CN103467455B - Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof - Google Patents
Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof Download PDFInfo
- Publication number
- CN103467455B CN103467455B CN201310422727.4A CN201310422727A CN103467455B CN 103467455 B CN103467455 B CN 103467455B CN 201310422727 A CN201310422727 A CN 201310422727A CN 103467455 B CN103467455 B CN 103467455B
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- add
- compd
- synthetic
- 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.)
- Expired - Fee Related
Links
- 0 COCCOCCN(C1=CC=CCC11)c2c1cc(C1C(*3ncccc3)=NC(c3ncccc3)=C1)cc2 Chemical compound COCCOCCN(C1=CC=CCC11)c2c1cc(C1C(*3ncccc3)=NC(c3ncccc3)=C1)cc2 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a zinc compound two-photon absorption material having a viable tissue development function and a preparation method thereof. A structural formula of the zinc compound two-photon absorption material having the viable tissue development function is shown in the specification. The two-photon absorption section of the zinc compound two-photon absorption material [L-Zn-L] [PF6]2 is obviously larger than that of a corresponding ligand L; at the excitation wavelength of 750 nm, the maximum two-photon absorption section of [L-Zn-L] [PF6]2 reaches up to 240 GM, which is 2.7 times of that of the corresponding ligand L. The zinc compound two-photon absorption material disclosed by the invention is the two-photon absorption material having the viable tissue development function, and has the characteristics of large two-photon absorption section, low excitation energy, long wavelength, strong penetrability, low light damage and the like in contrast with other materials; therefore, the zinc compound two-photon absorption material having the viable tissue development function can be applied to viable tissue detection and has an obvious application value.
Description
One, technical field
The present invention relates to a kind of two-photon absorbing material and preparation method thereof, specifically a kind of Zn complex two-photon absorbing material with biological tissue developing function and preparation method thereof.
Two, background technology
The fields such as two-photon absorbing material is changed on laser, three-dimensional information storage, three-dimensional micro-processing, photodynamic therapy, light amplitude limit and fluorescence imaging have bright application prospect.Wherein, two-photon fluorescence imaging is one of the most practical field of current two-photon absorption technology, compared with single photon fluorescence imaging, mostly be near infrared region for two-photon excitation light wavelength, near infrared has brought many advantages as its excitation light source, as darker light penetration depth, only in the very little volume of focus, occur, make its imaging there is high resolving power, the more important thing is the almost not damaged to biological tissue, lifeless matter background fluorescence interference etc., the performance of above excellence makes two-photon micro-imaging technique be widely used in active somatic cell, the long-time dynamic 3 D imaging of biological tissue.Therefore, the synthetic compound with large two photon absorption cross section of design, as fluorescent probe, is to solve to utilize two-photon fluorescence biological tissue to be developed to the key issue of picture.
At present, people have shown larger interest as two-photon luminescent material for biological tissue imaging aspect for the title complex with two-photon activity, compare with simple organic fluorescence materials, transition metal complex has good photophysical property, as high in quantum yield, stokes displacement is large, emission peak is narrow, luminescent lifetime is long etc.Particularly utilize the luminescent lifetime that they grow, be expected to eliminate the interference of autofluorescence by TIME RESOLVED TECHNIQUE in bio-imaging.Thereby cause the variation of title complex optical physics and other character by changing the structure of part in title complex, realize the simple and effective design of two-photon fluorescence probe.2,2:6 ', 2 " tri-pyridines are the compounds containing many pyridine heterocycles, and transition metal ion is had to stronger coordination ability, and its title complex has good nonlinear optical property (S.M.Brombosz et al.Org.Lett, 2007,9,4519-4522.).Functionalization is carried out in 4 ' position at terpyridyl, by introducing different groups, can further synthesize the part of specific function and advantageous property, and this class part and title complex thereof are widely used in the fields such as biology, chemistry, medical science.The report of zinc terpyridine complex two-photon material aspect was more and more in recent years, wherein representational work is that the people such as X.Zhou in 2011 report one group of Zn title complex (Chem.Commun., 2011,47,3921-3923.) and in the recent period title complex (Dalton Trans., 2011 of the Zn (II) of three pyridine thiodiphenylamine series of contriver seminar report, 40,8170 – 8178), show good two-photon behavior, can be used for cell developing.
Contriver has carried out following literature search to the application's theme:
1, www.google.com net result for retrieval: (2013/22/8)
2, CNKI result for retrieval:
Retrieval mode one:
The terpyridyl title complex of section name-have biological tissue developing function is without pertinent literature.
Section name-terpyridyl complex two-photon optical material is without pertinent literature.
Retrieval mode two:
In full-terpyridyl the title complex with biological tissue developing function is without pertinent literature.
In full-terpyridyl complex two-photon optical material is without pertinent literature.
Three, summary of the invention
The present invention aims to provide a kind of Zn complex two-photon absorbing material with biological tissue developing function and preparation method thereof, technical problem to be solved is to select suitable central ion and part, make it have cell developing function, and there is larger two photon absorption cross section, excitation energy is low, wavelength is long, penetrance is strong, and light injury is little, low toxicity.
The present invention select there is higher reactive behavior, strong coordination ability 2,2:6 ', 2 " tri-pyridines are parent; introduce the carbazole group with ether oxygen chain in 4 ' position; synthesized ligand L; again taking Zn (II) as metal center, have succinctly prepared efficiently terpyridyl Zn complex [the L-Zn-L] [PF having compared with high-fluorescence quantum yield
6]
2.
The Zn complex two-photon absorbing material that the present invention has biological tissue developing function is terpyridyl Zn complex, notes [the PF into [L-Zn-L] by abridging
6]
2, its structural formula is:
The preparation method that the present invention has the Zn complex two-photon absorbing material of biological tissue developing function operates according to the following steps:
1) Compound I is synthetic
In reactor, add diethylene glycol monomethyl ether 12.0g (0.1mol), 0.32g (0.001mol) catalyzer 4-butyl brometo de amonio, the NaOH solution 100mL of mass concentration 30% and methylene chloride 90mL, stir the lower 4-toluene sulfonyl chloride 32.4g of dropping (0.17mol), described 4-toluene sulfonyl chloride drips after being dissolved in 100mL methylene dichloride in reactor again, drip off rear stirring at normal temperature reaction 20h, reaction finishes rear separatory, wash 3-5 time, anhydrous magnesium sulfate drying 8-12h, after filtration, leave and take filtrate, revolve and steam except obtaining Compound I-2-(2-methoxy ethoxy in-2～-6 DEG C of refrigeration 8-12h after desolventizing)-vinyl-4-toluene sulfonic acide methyl esters, for white ice shape solid,
2) Compound I I's is synthetic
NaH4.80g (0.20mol) and solvent DMF 25mL are added in reactor, under oil sealing, drip 16.70g (0.10mol) carbazole, described carbazole is dissolved in and in DMF, drops to reactor again, drip off rear stirring at normal temperature reaction 30min, then add 30.10g Compound I (0.11mol), be warming up to 65 DEG C of reaction 15h, after reaction finishes, reaction solution is poured in frozen water, with the HCl solution adjust pH of mass concentration 10% to 5.5-6.5, be extracted with ethyl acetate rear combining extraction liquid, anhydrous magnesium sulfate drying, after filtration, leave and take filtrate, revolve to steam except after desolventizing and obtain purple liquid, (elutriant is CH by volume for column chromatography
2cl
2: CH
3oH=10:1) after, obtaining the poly-diethylene glycol monomethyl ether carbazole of Compound I I-N-, is yellow oil,
3) compd A is synthetic
In reactor, add 13mL DMF (0.17mol), under ice-water bath, drip 15mL phosphorus oxychloride (0.16mol), drip off rear continuation isothermal reaction 1h under ice-water bath, add 32.8g Compound I I (0.11mol), described Compound I I adds to reactor after being dissolved in 50mL chloroform, be warming up to reflux temperature reaction 12h, after reaction finishes, revolve and steam except desolventizing, add in frozen water and use NaHCO
3regulate pH value to 8, stir 5h, column chromatography for separation (elutriant is ethyl acetate by volume: sherwood oil=1:5) after filtering, being dried, obtains the poly-diethylene glycol monomethyl ether-3-formyl radical carbazole of compd A-N-, is faint yellow solid.
4) compd B is synthetic
8.91g (0.030mol) compd A is dissolved in ethanol; add 4mL(0.033mol) 2-acetylpyridine; then drip the NaOH solution 50mL of mass concentration 2%; stirring reaction 15h under normal temperature; reaction finishes rear filtration and washing obtains the poly-diethylene glycol monomethyl ether carbazyl-cinnamophenone of compd B-2 '-pyridyl-3-N-, is yellow solid.
5) Compound C is synthetic
In reactor, add 54mL (0.66mol) pyridine and 12.70g (0.10mol) I
2, be heated to 60 DEG C and stirring and dissolving, then add 3mL (26.78mmol) 2-acetylpyridine, be warming up to 100 DEG C of reaction 1h, reaction finishes rear standing cooling, and solid is separated out, and suction filtration is also used CH
2cl
2washing, ethyl alcohol recrystallization obtains Compound C-2-acetylpyridine base-pyridinium iodide, is white powder;
6) ligand L is synthetic
2.00g compd B (5.00mmol) and 1.63g Compound C (5.00mmol) are dissolved in 50mL methyl alcohol, add 2.31g NH
4oAc (30mmol), is warming up to back flow reaction 24h, and reaction finishes rear standing cooling, and solid is separated out, and suction filtration, washing are also dry, and (elutriant is CH by volume for column chromatography for separation
2cl
2: CH
3oH=10:1) after, obtaining ligand L, is brown solid;
7) target product [L-Zn-L] [PF
6]
2synthetic
0.20g (0.40mmol) ligand L is dissolved in to 5mL CH
2cl
2in, add and be dissolved with 0.07g (0.20mmol) Zn (PF
6)
2cH
3oH solution 20mL, the stirring reaction 2h that refluxes at 70 DEG C, is cooled to room temperature after reaction finishes, and after suction filtration, obtains crude product successively with distilled water, methanol wash vacuum-drying, obtains target product after ethyl alcohol recrystallization, is faint yellow solid.
The synthetic route of compd A:
The synthetic route of compd B:
The synthetic route of Compound C:
The synthetic route of ligand L:
Using Zn complex two-photon absorbing material of the present invention as two-photon fluorescence probe, by tissue sample being dyeed, cuts, fix, the process such as embedding, section, the characteristic that research title complex develops to biological tissue two-photon fluorescence, result shows, in the time that excitation wavelength is 750nm, can clearly observe the histocyte under the 100 μ m degree of depth.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the synthetic novel zinc terpyridine title complex of the present invention is the two-photon absorbing material that a class has biological tissue developing function, there is larger two photon absorption cross section compared with other material, excitation energy is low, wavelength is long, the features such as penetrance is strong, light injury is little, therefore, can be used for biological tissue and detect, there is obvious using value.
2, terpyridyl Zn complex of the present invention [L-Zn-L] [PF
6]
2two photon absorption cross section apparently higher than corresponding ligand L, in the time of 750nm excitation wavelength, [L-Zn-L] [PF
6]
2maximum two photon absorption cross section reach 240GM (Fig. 2), be 2.7 times of respective ligand.
3, terpyridyl Zn complex of the present invention [L-Zn-L] [PF
6]
2tumor-bearing mice liver cancer tissue is had to high recognition capability, and single two-photon fluorescence developing result shows, in the time that two-photon excitation wavelength is 750nm, can clearly observe the histocyte (Fig. 3 (b, c)) under the 100 μ m degree of depth; In the time that one-photon excitation wavelength is 405nm, liver cancer tissue is after three pyridine Zn complex dyeing, can clearly observe the histocyte (Fig. 4 (b)) under the 35 μ m degree of depth, and under the 100 μ m degree of depth, cannot observe corresponding histocyte (Fig. 4 (c)).
4, by ether oxygen chain substituent, increase the solubleness of compound in the aqueous solution, improved development effect.
5, zinc is human essential elements, and synthetic Zn complex is safe in organism, nontoxic.
Four, brief description of the drawings
Fig. 1 is ligand L of the present invention and [L-Zn-L] [PF
6]
2two photon absorption cross section figure.As can be seen from Figure 1 [L-Zn-L] [PF
6]
2there is the two photon absorption cross section larger than ligand L, there is higher using value.
Fig. 2 is the present invention [L-Zn-L] [PF
6]
2to tumor-bearing mice liver cancer tissue two-photon imaging research result, wherein (a) light field action diagram, (b) two-photon action diagram under the 100 μ m degree of depth, is (c) enlarged view of (b).As can be seen from Figure 2, [L-Zn-L] [PF
6]
2can, to rat liver cancer tissue staining, in the time that two-photon excitation wavelength is 750nm, can clearly observe the histocyte under the 100 μ m degree of depth.
Fig. 3 is the present invention [L-Zn-L] [PF
6]
2to tumor-bearing mice liver cancer tissue single photon image comparative study result, wherein (a) light field action diagram, (b) single photon action diagram under the 35 μ m degree of depth, (c) single photon action diagram under the 100 μ m degree of depth.As can be seen from Figure 3, [L-Zn-L] [PF
6]
2can, to rat liver cancer tissue staining, in the time that one-photon excitation wavelength is 405nm, can clearly observe the histocyte under the 35 μ m degree of depth, but cannot observe the histocyte under the 100 μ m degree of depth.
Five, embodiment
Synthesizing of Compound I:
In 500mL round-bottomed flask, add diethylene glycol monomethyl ether 12.0g (0.1mol) and be dissolved in 90mL methylene dichloride, add the NaOH solution of 0.32g (0.001mol) catalyzer 4-butyl brometo de amonio and 100mL mass concentration 30%, be uniformly mixed, 32.4g (0.17mol) 4-toluene sulfonyl chloride is dissolved in 100mL methylene dichloride and drops to reaction system, drip off rear stirring at normal temperature reaction 20 hours; Reaction finishes rear separatory, washes anhydrous magnesium sulfate drying 8-12h 3-5 time, suction filtration, gets filtrate, revolves and steams except desolventizing, obtain Compound I-2-(2-methoxy ethoxy in-2～-6 DEG C of refrigeration 8-12h)-vinyl-4-toluene sulfonic acide methyl esters 24.40g is white ice shape solid, productive rate 89%.
1H?NMR(CDCl
3,400MHz,ppm)δ(ppm)=2.46(s,3H),3.28（q,3H）,3.42(q,2H),3.53(t,2H),3.67(t,2H),4.28(t,2H),7.49(d,2H),7.83(d,2H).
Compound I I's is synthetic:
NaH4.80g (0.20mol) is joined in 250mL round-bottomed flask, add subsequently DMF25mL, 16.70g carbazole (0.10mol) is dissolved in appropriate DMF and in oil sealing situation and is added drop-wise in flask, drip rear stirring reaction 30min, then add Compound I 30.10g (0.11mol), be warming up to 65 DEG C of reaction 15h, TLC follows the tracks of, after reaction finishes, reaction solution is poured in frozen water, regulate pH value to 5.5-6.5 with the HCl solution of mass concentration 10%, repeatedly extract by ethyl acetate, combining extraction liquid, add anhydrous magnesium sulfate drying, suction filtration, solvent evaporated, obtain purple liquid, (elutriant is CH by volume for column chromatography
2cl
2: CH
3oH=10:1) after separation, obtaining Compound I I-N-diethylene glycol monomethyl ether carbazole 22.06g, is yellow oil, productive rate 82%.Characterize, directly carry out next step reaction.
Synthesizing of compd A:
In 250mL round-bottomed flask, add 13mL (0.17mol) DMF, under ice-water bath constant temperature, slowly drip 15mL phosphorus oxychloride (0.16mol) by constant pressure funnel, dropwise rear ice-water bath and continue isothermal reaction 1 hour, obtain white solid, 32.8g Compound I I (0.11mol) is dissolved in 50mL chloroform and is added in reaction system, slowly be warming up to back flow reaction 12 hours, some plate tracks to and reacts completely; After reaction finishes, reaction solution boiled off to solvent and pour in frozen water, using NaHCO
3regulate pH to 8; stir 5 hours, suction filtration is also dry, obtains the poly-diethylene glycol monomethyl ether-3-formyl radical carbazole 22.97g of compd A-N-after chromatography (elutriant is ethyl acetate by volume: sherwood oil=1:5); for faint yellow solid, productive rate 67%.
1H?NMR(CDCl
3,400MHz,ppm)δ(ppm)=3.30(s,3H),3.42(q,2H),3.53(q,2H),3.92(t,2H),4.56(t,2H),7.35(t,3H),7.51-7.59(m,3H),8.01(d,1H),8.16(d,1H),8.61(s,1H),10.11(s,1H).IR(KBr,cm-1):3433(w),3047(vw),2909(w),1688(vs),1581(s),1474(s),1130(s),1114(m),802(m),726(m).
Synthesizing of compd B:
8.91g (0.030mol) compd A is dissolved in 200mL ethanol and is placed in 500mL flask stirring at normal temperature; in flask, add 4mL(0.033mol) 2-acetylpyridine; drip the NaOH solution 50mL of mass concentration 2%; stirring at normal temperature reaction 15h; reaction finishes rear suction filtration and leaves and takes solid; washing, obtains yellow solid and is the poly-diethylene glycol monomethyl ether carbazyl-cinnamophenone of compd B-2 '-pyridyl-3-N-.Characterize, directly carry out next step reaction.
Synthesizing of Compound C:
In 250mL flask, add 54mL (0.66mol) pyridine and 12.70g (0.10mol) I
2, be heated to 60 DEG C and stirring and dissolving, then add 3mL (26.78mmol) 2-acetylpyridine, be warming up to 100 DEG C of reaction 1h, reaction finishes rear standing cooling, has solid to separate out, and suction filtration is also used CH
2cl
2washing, then by obtaining Compound C-2-acetylpyridine base-pyridinium iodide 6.64g after ethyl alcohol recrystallization, be white powder, productive rate 55%.
Synthesizing of ligand L:
2.00g compd B (5.00mmol) and 1.63g Compound C (5.00mmol) are dissolved in 50mL methyl alcohol, add NH
4oAc2.31g (30mmol), back flow reaction 24h, reaction finishes rear standing cooling, has solid to separate out, and suction filtration, washing are also dry, and (elutriant is CH by volume for column chromatography for separation
2cl
2: CH
3oH=10:1) after, obtaining ligand L 1.28g, is brown solid, productive rate 53%.
1H?NMR(CDCl
3,400MHz,ppm)δ(ppm)=3.34(s,3H),3.45(q,2H),3,56(q,2H),3.93(t,2H),4.57(t,2H),7.31(t,1H),7.39(t,2H),7.51(d,2H),7.60(d,1H),7.91(t,2H),8.07(d,1H),8.23(d,1H),8.68(s,1H),8.73(d,2H),8.79(d,2H),8.89(s,1H).
13C?NMR(CDCl
3,150MHz):δ(ppm)=155.47,155.23,150.38,149.24,140.99,140.80,137.33,128.26,126.09,124.54,124.35,122.95,122.27,120.92,120.78,119.27,118.79,117.88,110.39,109.81;71.23,70.50,69.78,68.80,58.02;IR(KBr,cm-1):3445(m),3063(vw),2918(w),1581(s),1467(s),1123(m),795(m),750(m).MALDI–TOF–MS:m/z,500.2[M
+,100%].
Target product [L-Zn-L] [PF
6]
2synthetic:
0.20g (0.40mmol) ligand L is dissolved in to 5mL CH
2cl
2in solution, add and be dissolved with 0.07g (0.20mmol) Zn (PF
6)
2cH
3oH solution 20mL, the stirring reaction 2h that refluxes at 70 DEG C, is cooled to room temperature after reaction finishes, and uses successively distilled water after suction filtration, methanol wash, collects solid, vacuum-drying at 70 DEG C, obtains crude product, after ethyl alcohol recrystallization target product [L-Zn-L] [PF
6]
20.18g, is faint yellow solid, productive rate 67%.
1H?NMR(d-DMSO,400MHz,ppm)δ(ppm)=9.51(s,2H),9.34(s,1H),9.23(d,2H),8.62(d,1H),8.01(t,3H),7.83(t,3H),7.76(d,2H),7.54(t,4H),7.38(t,1H),4.73(t,2H),3.91(t,2H),3.52(t,2H),3.35(t,2H),3.14(s,3H);
13C?NMR(CDCl
3,150MHz):δ(ppm)=158.03,157.45,152.08,145.28,145.12,139.89,137.20,128.35,125.13,124.26,121.74,121.45,119,87,118.94,118.06,118.02,116.38,110.83,109.61,103.32,71.64,71.21,69.81,59.32,54.90;IR(KBr,cm-1):3423(s),2915(w),2513(w),1796(m)，1472(w),1118(m),874(m),712(m);EI-MS:m/z,cal:1065.37found:532.67[M
2+100%].C
64H
56ZnF
12N
8P
2O
4:Calcd.C56.67,H4.16,N8.26.Found:C56.78,H3.95,N8.28.
Claims (1)
1. a preparation method with the Zn complex two-photon absorbing material of biological tissue developing function, is characterized in that operating according to the following steps:
1) Compound I is synthetic
To the NaOH solution 100mL and the methylene chloride that add diethylene glycol monomethyl ether 12.0g, catalyzer 4-butyl brometo de amonio 0.32g, mass concentration 30% in reactor, stir the lower 4-of dropping toluene sulfonyl chloride 32.4g, drip off rear stirring at normal temperature reaction 20h, reaction finishes rear separation and obtains Compound I;
The structural formula of described Compound I is:
2) Compound I I's is synthetic
NaH4.80g and solvent DMF are added in reactor, drip 16.70g carbazole under oil sealing, drip off rear stirring at normal temperature reaction 30min, then add 30.10g Compound I, be warming up to 65 DEG C of reaction 15h, reaction finishes rear separation and obtains Compound I I;
The structural formula of described Compound I I is:
3) compd A is synthetic
In reactor, add 13mL DMF, drip 15mL phosphorus oxychloride under ice-water bath, drip off rear continuation isothermal reaction 1h under ice-water bath, add 32.8g Compound I, be warming up to reflux temperature reaction 12h, reaction finishes rear separation and obtains compd A;
The structural formula of described compd A is:
4) compd B is synthetic
8.91g compd A is dissolved in ethanol, adds 4mL2-acetylpyridine, then drip the NaOH solution 50mL of mass concentration 2%, stirring reaction 15h under normal temperature, reaction finishes rear filtration and washing obtains compd B;
The structural formula of described compd B is:
5) Compound C is synthetic
In reactor, add 54mL pyridine and 12.70g I
2, be heated to 60 DEG C and stirring and dissolving, then add 3mL2-acetylpyridine, be warming up to 100 DEG C of reaction 1h, reaction finishes rear separation and obtains Compound C;
The structural formula of described Compound C is:
6) ligand L is synthetic
2.00g compd B and 1.63g Compound C are dissolved in methyl alcohol, add 2.31g NH
4oAc, is warming up to back flow reaction 24h, and reaction finishes rear separation and obtains ligand L;
The structural formula of described ligand L is:
7) target product is synthetic
0.20g ligand L is dissolved in to CH
2cl
2in, add and be dissolved with 0.07g Zn (PF
6)
2cH
3oH solution, the stirring reaction 2h that refluxes at 70 DEG C, reaction finishes rear separation and obtains target product;
The structural formula of described target product is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310422727.4A CN103467455B (en) | 2013-09-17 | 2013-09-17 | Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310422727.4A CN103467455B (en) | 2013-09-17 | 2013-09-17 | Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467455A CN103467455A (en) | 2013-12-25 |
| CN103467455B true CN103467455B (en) | 2014-11-26 |
Family
ID=49792530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310422727.4A Expired - Fee Related CN103467455B (en) | 2013-09-17 | 2013-09-17 | Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467455B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498579B (en) * | 2014-10-22 | 2017-06-16 | 贵州大学 | One kind is for Zn in cancer cell2+The fluorescence probe method of monitoring |
| CN105237514B (en) * | 2015-09-14 | 2017-12-22 | 安徽大学 | A kind of carbazole zinc terpyridine complex two-photon fluorescence probe with biological developing function and preparation method thereof |
| CN105111458B (en) * | 2015-09-14 | 2018-07-10 | 安徽大学 | A kind of zinc halide terpyridyl coordination polymer multifunctional material and preparation method thereof |
| CN105154072A (en) * | 2015-10-26 | 2015-12-16 | 安徽大学 | Carbazole derivative, gold and cysteine nano-composite two-photon absorbing material with living cell development function and preparation method thereof |
| CN105778890B (en) * | 2016-03-10 | 2018-05-11 | 安徽大学 | A kind of thiophene terpyridyl compounds two-photon absorbing material and preparation method thereof |
| CN110407826B (en) * | 2019-05-15 | 2022-11-08 | 安徽大学 | Three-photon fluorescent probe with mitochondrial RNA targeting function and preparation method and application thereof |
| CN111039853B (en) * | 2019-12-26 | 2023-02-14 | 安徽大学 | Iron complex for photoacoustic imaging and photothermal therapy and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475581B (en) * | 2009-01-16 | 2011-05-04 | 安徽大学 | Terpyridyl complex two-photon material with cell development and preparation |
| CN102924524B (en) * | 2012-10-29 | 2015-02-04 | 安徽大学 | Manganese complex two-photon absorption material with living cell development function and synthesis method thereof |
-
2013
- 2013-09-17 CN CN201310422727.4A patent/CN103467455B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467455A (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467455B (en) | Zinc compound two-photon absorption material having viable tissue development function and preparation method thereof | |
| Sun et al. | Mitochondria targetable time-gated luminescence probe for singlet oxygen based on a β-diketonate–europium complex | |
| CN111303139B (en) | Compound with aggregation-induced emission performance and preparation method and application thereof | |
| CN103626781B (en) | A kind of target anticancer molecule gefitinib phthalocyanine conjugates and Synthesis and applications thereof | |
| CN102924524B (en) | Manganese complex two-photon absorption material with living cell development function and synthesis method thereof | |
| CN103614135B (en) | Two-photon fluorescent probe as well as preparation method and application thereof | |
| CN108864056B (en) | Near infrared fluorescent compound and its preparation method and application with AIE performance | |
| CN108102408B (en) | A kind of preparation and application of the nir dye based on azepine fluorine borine | |
| CN103709202B (en) | Ruthenium (II) complex and preparation method thereof and its it is used as the application of cell fluorescence dyestuff | |
| Xu et al. | High-efficient carbazole-based photo-bleachable dyes as free radical initiators for visible light polymerization | |
| CN102286213A (en) | Near-infrared aza-BODIPY dye as well as preparation method and application thereof | |
| CN101624520B (en) | Long-wavelength fluorescent probe for detecting zinc ions in water phase, synthesis method thereof and use thereof | |
| WO2013131235A1 (en) | Two-photon fluorescent probe using naphthalene as matrix and preparation method and use thereof | |
| CN103483243B (en) | A kind of sulphonate pyridinium salt biological developing material and preparation method thereof | |
| CN114045045A (en) | Single-photon up-conversion pentamethine cyanine photosensitive dye, preparation method and application thereof | |
| CN102851025B (en) | Intelligent rare-earth luminescent supramolecular device with photocontrollability and preparation thereof | |
| CN102249939B (en) | Lipid-water amphiphilic benzylidene cyclopentanone dye and preparation method and application in photodynamic therapy thereof | |
| CN103936794A (en) | Water-soluble cationic phosphorescent iridium complex, preparation method and application thereof | |
| CN103130837A (en) | Water-soluble cationic phosphorous iridium complex as well as preparation method and application thereof | |
| CN108503673B (en) | Near-infrared azapyrrolidine dye and preparation method and application thereof | |
| CN113024586B (en) | Cell membrane targeted BODIPY type organic photosensitizer and application thereof | |
| CN114907311A (en) | Lipid droplet specific fluorescent probe based on AIE performance, preparation method and application | |
| CN104387790A (en) | Benzindole salt dye containing thiophene group and preparation method and application of benzindole salt dye | |
| CN103467318B (en) | Phenylylidene triphenylamine derivative two-photon absorption material and preparation method thereof | |
| Vasiliu et al. | Complex combinations of some transition metals with new unsymmetrical porphyrins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141126 Termination date: 20150917 |
|
| EXPY | Termination of patent right or utility model |