CN103467455A - 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
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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 as shown in 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, with the single photon fluorescence imaging, compare, mostly be near infrared region for the two-photon excitation light wavelength, near infrared has brought many advantages as its excitation light source, as darker light penetration depth, only in focus, in very little volume, occur, make its imaging there is high resolving power, the more important thing is the not damaged almost to biological tissue, lifeless matter background fluorescence interference etc., the performance of above excellence makes the 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 the two-photon luminescent material for biological tissue imaging aspect for the title complex with two-photon activity, with simple organic fluorescence materials, compare, transition metal complex has good photophysical property, as high as quantum yield, the stokes displacement is large, emission peak is narrow, luminescent lifetime is long etc.Particularly utilize their longer luminescent lifetimes, 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 the structure that changes 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, its title complex have 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, title complex (Dalton Trans., 2011 of the Zn (II) of the three pyridine thiodiphenylamine series that 3921-3923.) and in the recent period contriver seminar reports, 40,8170 – 8178), show two-photon behavior preferably, can be used for cell developing.
The contriver has carried out following literature search to the application's theme:
1, www.***.com net result for retrieval: (2013/22/8)
2, CNKI result for retrieval:
Retrieval mode one:
Piece of writing name-there is the terpyridyl title complex of biological tissue developing function without pertinent literature.
Piece of writing name-terpyridyl complex two-photon optical material is without pertinent literature.
Retrieval mode two:
In full-there is the terpyridyl title complex of biological tissue developing function 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 there is 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; the Zn (II) of take again is metal center, have succinctly prepared efficiently terpyridyl Zn complex [the L-Zn-L] [PF had than high-fluorescence quantum yield
6]
2.
The Zn complex two-photon absorbing material that the present invention has the biological tissue developing function is the 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
Add diethylene glycol monomethyl ether 12.0g (0.1mol) in reactor, 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 (0.17mol) of dropping, described 4-toluene sulfonyl chloride drips after being dissolved in the 100mL methylene dichloride in reactor again, drip off rear stirring at normal temperature reaction 20h, separatory after reaction finishes, wash 3-5 time, anhydrous magnesium sulfate drying 8-12h, leave and take filtrate after filtration, revolve and steam except after desolventizing, in-2～-6 ℃ of refrigeration 8-12h, obtaining Compound I-2-(2-methoxy ethoxy)-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, drip 16.70g (0.10mol) carbazole under oil sealing, described carbazole is dissolved in DMF and 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 ℃ of reaction 15h, reaction is poured reaction solution in frozen water into after finishing, 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, leave and take filtrate after filtration, revolve to steam except after desolventizing and obtain purple liquid, (elutriant is CH by volume for column chromatography
2cl
2: CH
3oH=10:1) obtaining the poly-diethylene glycol monomethyl ether carbazole of Compound I I-N-after, is yellow oil,
3) compd A is synthetic
Add 13mL DMF (0.17mol) in reactor, drip 15mL phosphorus oxychloride (0.16mol) under ice-water bath, 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 the 50mL chloroform, be warming up to reflux temperature reaction 12h, reaction is revolved and is steamed except desolventizing after finishing, and adds in frozen water and uses NaHCO
3regulate pH value to 8, stir 5h, (elutriant is ethyl acetate by volume: sherwood oil=1:5), obtaining the poly-diethylene glycol monomethyl ether of compd A-N--3-formyl radical carbazole, is faint yellow solid for filtration, dry rear column chromatography for separation.
4) compd B is synthetic
8.91g (0.030mol) compd A is dissolved in ethanol; add 4mL(0.033mol) the 2-acetylpyridine; then drip the NaOH solution 50mL of mass concentration 2%; stirring reaction 15h under normal temperature; filters and washs after reaction finishes obtain compd B-2 '-pyridyl-3-N-gathers diethylene glycol monomethyl ether carbazyl-cinnamophenone, is yellow solid.
5) Compound C is synthetic
Add 54mL (0.66mol) pyridine and 12.70g (0.10mol) I in reactor
2, be heated to 60 ℃ and stirring and dissolving, then add 3mL (26.78mmol) 2-acetylpyridine, be warming up to 100 ℃ of reaction 1h, reaction is standing cooling after finishing, 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), be warming up to back flow reaction 24h, and reaction is standing cooling after finishing, and solid is separated out, suction filtration, washing dry, and (elutriant is CH by volume for column chromatography for separation
2cl
2: CH
3oH=10:1) obtaining ligand L after, 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, backflow stirring reaction 2h under 70 ℃, reaction is cooled to room temperature after finishing, and after suction filtration, obtains crude product with distilled water, methanol wash vacuum-drying successively, 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 the research title complex develops to the biological tissue two-photon fluorescence, result shows, when 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 the biological tissue developing function, compare and there is larger two photon absorption cross section with other material, excitation energy is low, wavelength is long, the characteristics 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, when the 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]
2the tumor-bearing mice liver cancer tissue is had to high recognition capability, and single two-photon fluorescence developing result shows, when the two-photon excitation wavelength is 750nm, can clearly observe the histocyte (Fig. 3 (b, c)) under the 100 μ m degree of depth; When the one-photon excitation wavelength is 405nm, liver cancer tissue is after three pyridine Zn complex dyeing, the histocyte (Fig. 4 (b)) under the 35 μ m degree of depth can be clearly observed, and, under the 100 μ m degree of depth, corresponding histocyte (Fig. 4 (c)) can't be observed.
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, accompanying drawing explanation
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 part 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, (a) light field action diagram wherein, (b) two-photon action diagram under the 100 μ m degree of depth, be (c) enlarged view of (b).As can be seen from Figure 2, [L-Zn-L] [PF
6]
2can, to the rat liver cancer tissue staining, when the 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, (a) light field action diagram wherein, (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 the rat liver cancer tissue staining, when the one-photon excitation wavelength is 405nm, can clearly observe the histocyte under the 35 μ m degree of depth, but can't observe the histocyte under the 100 μ m degree of depth.
Five, embodiment
Synthesizing of Compound I:
Add diethylene glycol monomethyl ether 12.0g (0.1mol) and be dissolved in the 90mL methylene dichloride in the 500mL round-bottomed flask, the NaOH solution that adds 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 the 100mL methylene dichloride and drops to reaction system, drip off rear stirring at normal temperature reaction 20 hours; Separatory after reaction finishes, wash anhydrous magnesium sulfate drying 8-12h 3-5 time, suction filtration, get filtrate, revolves and steam except desolventizing, obtain Compound I-2-(2-methoxy ethoxy in-2～-6 ℃ of refrigeration 8-12h)-vinyl-4-toluene sulfonic acide methyl esters 24.40g, be 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 the 250mL round-bottomed flask, add subsequently DMF25mL, in being dissolved in appropriate DMF by 16.70g carbazole (0.10mol) and being added drop-wise to flask in the oil sealing situation, drip rear stirring reaction 30min, then add Compound I 30.10g (0.11mol), be warming up to 65 ℃ of reaction 15h, TLC follows the tracks of, reaction is poured reaction solution in frozen water into after finishing, regulate the pH value to 5.5-6.5 with the HCl solution of mass concentration 10%, by ethyl acetate, repeatedly extract, 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) obtaining Compound I I-N-diethylene glycol monomethyl ether carbazole 22.06g after the separation, is yellow oil, productive rate 82%.Characterized, directly carried out next step reaction.
Synthesizing of compd A:
Add 13mL (0.17mol) DMF in the 250mL round-bottomed flask, slowly drip 15mL phosphorus oxychloride (0.16mol) by constant pressure funnel under ice-water bath constant temperature, dropwise rear ice-water bath and continue isothermal reaction 1 hour, obtain white solid, 32.8g Compound I I (0.11mol) is dissolved in the 50mL chloroform and adds in reaction system, slowly be warming up to back flow reaction 12 hours, the some plate tracks to and reacts completely; Reaction boils off solvent by reaction solution and pours in frozen water after finishing, and uses NaHCO
3regulate pH to 8, stir 5 hours, suction filtration is also dry, and (elutriant is ethyl acetate by volume: obtain the poly-diethylene glycol monomethyl ether of compd A-N--3-formyl radical carbazole 22.97g sherwood oil=1:5), be faint yellow solid to chromatography, 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; add 4mL(0.033mol in flask) the 2-acetylpyridine; drip the NaOH solution 50mL of mass concentration 2%; stirring at normal temperature reaction 15h; after reaction finishes, suction filtration is left and taken solid; washing, obtain yellow solid be compd B-2 '-the poly-diethylene glycol monomethyl ether carbazyl-cinnamophenone of pyridyl-3-N-.Characterized, directly carried out next step reaction.
Synthesizing of Compound C:
Add 54mL (0.66mol) pyridine and 12.70g (0.10mol) I in the 250mL flask
2, be heated to 60 ℃ and stirring and dissolving, then add 3mL (26.78mmol) 2-acetylpyridine, be warming up to 100 ℃ of reaction 1h, reaction is standing cooling after finishing, and 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 is standing cooling after finishing, and has solid to separate out, suction filtration, washing dry, (elutriant is CH by volume for column chromatography for separation
2cl
2: CH
3oH=10:1) obtaining ligand L 1.28g after, 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, backflow stirring reaction 2h under 70 ℃, reaction is cooled to room temperature after finishing, and uses successively distilled water after suction filtration, methanol wash is collected solid, 70 ℃ of lower vacuum-dryings, obtain crude product, after ethyl alcohol recrystallization target product [L-Zn-L] [PF
6]
20.18g, be 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 (2)
1. the Zn complex two-photon absorbing material with biological tissue developing function is characterized in that its structural formula is:
2. the preparation method with Zn complex two-photon absorbing material of biological tissue developing function claimed in claim 1 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, after reaction finishes, separate and obtain Compound I;
2) Compound I I's is synthetic
NaH4.80g and solvent DMF are added in reactor, drip the 16.70g carbazole under oil sealing, drip off rear stirring at normal temperature reaction 30min, then add the 30.10g Compound I, be warming up to 65 ℃ of reaction 15h, after reaction finishes, separate and obtain Compound I I;
3) compd A is synthetic
Add 13mL DMF in reactor, drip the 15mL phosphorus oxychloride under ice-water bath, drip off rear continuation isothermal reaction 1h under ice-water bath, add the 32.8g Compound I, be warming up to reflux temperature reaction 12h, after reaction finishes, separate and obtain compd A;
4) compd B is synthetic
The 8.91g compd A is dissolved in ethanol, adds the 4mL2-acetylpyridine, then drip the NaOH solution 50mL of mass concentration 2%, stirring reaction 15h under normal temperature, filter and wash after reaction finishes and obtain compd B;
5) Compound C is synthetic
Add 54mL pyridine and 12.70g I in reactor
2, be heated to 60 ℃ and stirring and dissolving, then add the 3mL2-acetylpyridine, be warming up to 100 ℃ of reaction 1h, separate and obtain Compound C after reaction finishes;
6) ligand L is synthetic
2.00g compd B and 1.63g Compound C are dissolved in methyl alcohol, add 2.31g NH
4oAc, be warming up to back flow reaction 24h, after reaction finishes, separates and obtain ligand L;
7) target product is synthetic
The 0.20g ligand L is dissolved in to CH
2cl
2in, add and be dissolved with 0.07g Zn (PF
6)
2cH
3oH solution, backflow stirring reaction 2h under 70 ℃, separate and obtain target product after reaction finishes.
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| CN104498579A (en) * | 2014-10-22 | 2015-04-08 | 贵州大学 | Fluorescent probe method for monitoring Zn<2+> in cancer cells |
| CN105111458A (en) * | 2015-09-14 | 2015-12-02 | 安徽大学 | Zinc halide terpyridine coordination polymer multifunctional material and preparation method thereof |
| CN105237514A (en) * | 2015-09-14 | 2016-01-13 | 安徽大学 | Carbazole terpyridine zinc coordination compound two-photon fluorescent probe having biological developing function, 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 |
| CN105778890A (en) * | 2016-03-10 | 2016-07-20 | 安徽大学 | Thiophene terpyridyl compound two-photon absorbing material and preparation method thereof |
| CN110407826A (en) * | 2019-05-15 | 2019-11-05 | 安徽大学 | A kind of three-photon fluorescent probe and its preparation method and application with mitochondrial RNA (mt RNA) target function |
| 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 |
| CN111039853A (en) * | 2019-12-26 | 2020-04-21 | 安徽大学 | Iron complex for photoacoustic imaging and photothermal therapy 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 |
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