CN101968445B - Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof - Google Patents
Mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and application thereof Download PDFInfo
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- 239000002210 silicon-based material Substances 0.000 title claims abstract description 35
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 10
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- 239000000463 material Substances 0.000 claims abstract description 41
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- 238000003756 stirring Methods 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 239000007777 multifunctional material Substances 0.000 claims description 3
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- 238000010521 absorption reaction Methods 0.000 claims description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010949 copper Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 5
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- 238000000034 method Methods 0.000 abstract description 4
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses mesoporous silicon material immobilized by 1, 8-naphthalimide fluorescent dye and a method of detecting and absorbing copper ions, belonging to the technical field of recognition combination and ion detection and absorbing for optical detection and absorbing of the copper cations. The method takes 4-bromine-5-ntiryl-1, 8- anhydride naphthalene and mesporous silicon (MS) material as raw materials to obtain functionalized hybrid material (MS-P2) after a series of reactions in organic solution. The material can detect copper ions less than 1ppb in a water sample; simultaneously, the material can absorb 80% of copper ions so that the mesporous silicon material has a good application prospect in environmental management. Active tissues and cell fluorescent imaging test proves that the material can quantitatively detect the copper ions in biological bodies so that the functional material can be applied to detoxicant for acute copper toxicity. The material can be recycled after being properly processed.
Description
Technical field
The invention belongs to the identification combination and be used for optical detection and cationic ion detection of absorbing copper and adsorption technology field, specific design utilizes 1, the immobilized mesoporous silicon material of 8-naphthalimide derivative for the identification colour developing in the water with biosome in copper ion fluoroscopic examination and adsorption method.
Background technology
Through the unremitting effort of scientific worker's many decades, the cationic molecule fluorescence probe has been obtained great advance aspect fundamental research, has realized the height selection of specific objective heavy metal ion in the water sample, high-sensitive detection.Especially recent years, the scientific worker to living things system, has realized the molecular probe successful Application to the detection by quantitative of active somatic cell with the interior certain heavy metallic ion of tissue by fluorescence imaging.But the kation probe of the overwhelming majority will really be applied in the real productive life at present, and the scientific worker also need address the problem:
1. micromolecule fluorescence probe detecting operation generally is to carry out in homogeneous phase solution, thereby is unfavorable for separation, extraction and the enrichment of object ion aspect environmental applications, also is unfavorable for the regeneration of probe molecule simultaneously.
When the micromolecule probe when biosome is used, organic molecule can be subjected to the decomposition of biology enzyme in the body, the efficient and the life-span of having reduced probe molecule.
3. the molecular fluorescence probe generally contains dye molecule, therefore when damaging biological tissue and cell when biosome is used.
For addressing the above problem, break and hinder the bottleneck of molecular fluorescence probe aspect environment and biological applications, at present with fluorescent probe molecule immobilized on inorganic material, be an effective way.Aspect the selection of carrier, mesoporous silicon material (mesoporous silica MS) gains a special interest, and this is that it has following advantage because compare with other materials:
1. mesoporous silicon material has orderly duct and relatively large specific surface area, helps guest molecule and enters inside, duct.
Mesoporous silicon material duct inner wall layer contain great amount of hydroxy group (OH), can utilize the silica gel reaction, easily with the organic molecule grafting to inwall, obtain the inorganic-organic hybridization material.
3. because mesoporous silicon material is insoluble to common solvent, therefore, when using, generally in heterogeneous system, carry out, can realize separation, extraction, the enrichment of object easily based on the material of mesoporous silicon.
4. mesoporous silicon material is transparent in the visible region, thereby helps the carrier as fluorescent molecular probe.
5. mesoporous silicon material has good bio-compatibility, therefore at biological field good application prospects is arranged.
6. the chemical property of mesoporous silicon material is stable, physical strength is big, cheap and be easy to recovery, is easy to large-scale develop and utilize.
Based on mesoporous silicon material good character like this, cause concern gradually in the immobilized fluorescence probe field of mesoporous silicon material at present.Jong Hwa Jung (Adv.Mater.2008,20,3229-3234) with Chun Hua Yan (J.Mater.Chem., 2007,17,4492-4498) wait the people that the fluorescence probe micromolecule is immobilized to mesoporous silicon material SBA-15, realized selectivity detection and the adsorptive separation of the fluorescence probe of solid state copper ion.People such as Victor S.-Y.Lin discover that the mesoporous silicon material of functionalization is permeate through cell membranes effectively, realize that medicine ground transmits and the bio-sensing application.Therefore, select the fluorescent probe molecule of function admirable, and then it is immobilized to mesoporous silicon material, the synthetic heavy metal ion that can detect and repair in the water of design, simultaneously can also the quantitative test biological tissue and cell in the multifunctional material of heavy metal ion, will aspect environment and the biological field good application prospects arranged.
Summary of the invention
The objective of the invention is a copper ion probe molecule, N-(3-aminopropyl)-4,5-two [(pyridine-2-methyl) amino]-1, the grafting of 8 naphthalimides (P2) fluorophor is to mesoporous silicon material (MS, as: SBAs, MCMs, HMSs, MSUs is etc. type) the duct inwall, obtain the hybrid material of functionalization, not only can detect with planar water in copper ion, but also apply it in biological living cell and the tissue, by fluorescent microscopic imaging method, the copper ion in the detection by quantitative biosome.Because this functional material has stronger complexing power to copper ion; simultaneously because the mesoporous protection of silicon materials; weakened biology enzyme in the body to the injury of the destruction of molecular probe and probe molecule, thereby this material can also be used for effective toxinicide of acute copper poisoning to living organism.This material is characterised in that: with high selectivity, the immobilized duct inwall to the mesoporous silicon material with good characteristic (MS) of highly sensitive copper ion probe, realized the integration of advantage.
Technical scheme of the present invention is:
In the inner wall surface grafting of the duct of mesoporous silicon material (MS) an efficient copper ion fluorescence probe (P2), synthesized multifunctional material MS-P2, its general formula is as follows:
Wherein reaction raw materials 4-bromo-5-nitro-1,8 naphthalene acid anhydride is to be initiation material reference literature method synthetic (J.Soc.Dyers.Colour 1989,105 for A.T.Peters, Y.S.S.Behesti, 29.) with the acenaphthene.4-bromo-5-nitro-1,8 naphthalene acid anhydride and 3-aminopropyltriethoxywerene werene (APTES) are in absolute ethyl alcohol, and under nitrogen gas protection and the stirring, back flow reaction 4 hours generates N-3-aminopropyl 4-bromo-5-nitro-1,8 naphthalimide (M); And then with the 2-aminomethyl-pyridine in dimethoxy-ethanol, N2 gas shield and stirring down, back flow reaction 12 hours obtains organic probe micromolecule N-(3-aminopropyl)-4,5-two [(pyridine-2-methyl) amino]-1,8 naphthalimide (P2); At last with above-mentioned P2 and mesoporous silicon material (MS) in the dry toluene solvent, under the nitrogen protection, back flow reaction 24 hours is filtered and is obtained target material MS-P2.
Above-mentioned functional material MS-P2 can select to generate following feature structure:
One class is the functional material of carrier with the mesoporous si molecular sieves of SBA series, can have following architectural feature:
One class is the functional material of carrier with the mesoporous si molecular sieves of MCM series, and it has following architectural feature:
One class is the functional material of carrier with the mesoporous si molecular sieves of MSU series, and it has following architectural feature:
One class is the functional material of carrier with the mesoporous si molecular sieves of HMS series, and it has following architectural feature:
This target material MS-P2 can detect and adsorb copper ion.This material because coordination, causes the changes in distribution of electronics in the molecule and variation that fluorescence intensity takes place reaches the purpose that detects copper ion with copper ion interaction fluorescence developing the time.And Hg
2+, Zn
2+, Cd
2+, Pb
2+, Mn
2+, Ni
2+, Co
2+, Ag
+, Cr
3+Variation etc. heavy metal ion can not produce fluorescence intensity with its effect shows that material MS-P2 has high selectivity to copper ion.This material detection limit to copper ion in aqueous systems is 0.65ppb in addition, quotes water quality standard (1ppm) far below up-to-date country.This material can adsorb copper ion in 80% the water simultaneously, and this material can regeneration after EDTA/base handles.Therefore the detection of this material copper ion in Environmental Water has very big application prospect with reparation.
Effect of the present invention and benefit are the simple operations easily of the immobilized mesoporous silicon material reaction of P2, and cost of material is cheap, and the functional material chemical property that obtains is stable, is easy to large scale application.Because the protection in the inner duct of mesoporous material, this material also has very big application prospect at biological field.Zebra fish and mankind mastopathy cell's (MCF-7) fluorescence imaging evidence, this material can detection by quantitative biological tissue and intracellular content of copper ion.And because good bio-compatibility of this material and the complexing power stronger to copper ion, so this material can also be as the toxinicide of acute copper poisoning.
Description of drawings
Fig. 1 is selection, the competition experiments spectrogram of target material MS-P2 to copper ion.
Fig. 2 is the fluorescence intensity response light spectrogram of target material MS-P2 to copper ion concentration.
Fig. 3 is a target material MS-P2 reproducibility spectrogram.
Fig. 4 is the adsorptive power spectrogram of target material MS-P2 to copper ion in the water.
Fig. 5 is that target material MS-P2 detects the copper ion fluorescence imaging figure in the active somatic cell.
Fig. 6 is that target material MS-P2 detects the copper ion fluorescence imaging figure in the biological tissue.
Embodiment
In order to be illustrated more clearly in content of the present invention, be described as follows with specific embodiment, specific embodiment does not limit context of the present invention.
Embodiment 1 (synthesizing of mesoporous silicon material)
(0.642g 2mmol) is dissolved in the 40ml absolute ethyl alcohol to 4-bromo-5-nitro-1,8 naphthalene acid anhydride; then, under the nitrogen protection, dropwise add and contain 3-aminopropyltriethoxywerene werene (0.515ml; 2.2mmol) the 10ml ethanol solution; refluxed 10 hours, and removed solvent under reduced pressure, crude product is purified through silicagel column, and (eluent is; methylene chloride: ethyl acetate=40: 1); get light yellow product N-3-aminopropyl 4-bromo-5-nitro-1,8 naphthalimide (M), productive rate 85%.
1H-NMR(CDCl
3，400MHz)δ0.758(m，Hz，2H；CH
2)，1.212(t，9H；CH
3)，1.634(m，2H；CH
2)，3.812(t，6H；CH
2)，4.163(m，2H；CH
2)，7.925(d，1H；Ar?H)，8.211(d，1H；Ar?H)，8.512(d，1H；Ar?H)，8.704(d，1H；Ar?H).HR-MS(ESI，m/z)：[M
++Na]calcd?for?C
21H
25BrN
2O
7SiNa，547.06；found?547.1。
Embodiment 2 (synthesizing of mesoporous silicon material)
Adding N-3-aminopropyl 4-bromo-5-nitro-1,8 naphthalimide (M) in the 100mL flask (104.8mg, 2mmol); add the 40ml 2-methyl cellosolve, under the nitrogen protection, dropwise adding the 10ml 2-methyl cellosolve solution that contains 2-aminomethyl-pyridine (0.3ml); refluxed 12 hours; remove solvent under reduced pressure, the crude product silicagel column is purified, and (eluent is dichloromethane/ethyl acetate; 20: 1; V/V), get yellow solid P2, productive rate 45%.
1H-NMR(CDCl
3，400MHz)δ0.961(m，2H；CH
2)，1.193(t，9H；CH
3)，1.810(m，2H；CH
2)，3.805(m，6H；CH
2)，4.306(m，2H；CH
2)，4.632(m，4H；CH
2)，6.769(d，2H；Ar)，7.163(t，2H；Ar?H)，7.561(d，2H；Ar?H)，7.529(s，N-H)，7.688(t，2H；Ar?H)，?8.302(d，2H；Ar?H)，8.409(d，2H；Ar?H).HR-MS(ESI，m/z)：[M+H]calcd?for?C
33H
40N
5O
5Si614.27，found?614.3。
Embodiment 3 (synthesizing of mesoporous silicon material)
Add the 40ml dry toluene in the 50mL flask, add P2 (0.245g) and mesoporous silicon material (MS) again (1.0g), N
2Gas shield and stirring down refluxed 24 hours, and cool to room temperature filters, and with toluene and washed with dichloromethane 3 times, vacuum drying had both got target product MS-P2.As shown in Figure 1.Anal.Calcd?for：N，1.801，C，10.96，H?1.416.IR(KBr)：v＝3430(vs；O-H)，2923(w；C-H)，2830(w；C-H)，1635(s；O-H)，1366(w；-C＝C-H)，1090(vs；Si-O-Si)，807(w；SiO-Si)，465(m；Si-O)。
Embodiment 4 (selection competition experiments)
Take by weighing target material MS-P2, be mixed with the standard inventory suspension of the 100ml water of 20ppm, metal cation salt Li, K
+, Na
+, Ca
2+, Mg
2+, Co
2+, Ni
2+, Cu
2+, Mn
2+, Zn
2+, Cd
2+, Ag
+, Pb
2+, and Hg
2+Perchlorate solution, Fe
2+Select sulfate for use, and now with the current.In the ion difference testing experiment, get storing solution 2ml, add the solion of 10 μ M respectively, with the optical excitation of 450nm place, its fluorescence intensity of test changes at the 478nm place.And then in above-mentioned storing solution, add the copper ion solution of equivalent, and excite at 450nm place equally, test its fluorescence intensity variation at 478nm place.The results are shown in accompanying drawing 1.
Embodiment 5 (fluorescence intensity and concentration intensity working curve)
Take by weighing target material MS-P2, be mixed with the standard inventory suspension (1) of the 100ml water of 20ppm, dispose 2 * 10 again
-2The storing solution of the copper ion of M (2).Measure deposit suspension (1) 2ml, add the storing solution (2) of calculated amount, be mixed with standard testing solution.Excite at the 450nm place, test result is seen accompanying drawing 2.
Embodiment 6 (reproducibility of target material MS-P2)
The aqueous suspension of target material MS-P2 (20ppm) adds the copper ion aqueous solution of 10 μ M, and then adds the aqueous solution of the EDTA/ alkali of the glutathione of 10 times of amounts and 5 times of amounts respectively, the variation of observation fluorescence intensity.As accompanying drawing 3.
Embodiment 7 (target material MS-P2 is to the adsorptive power of copper ion in the water)
20mg target material MS-P2 joins the copper ion aqueous solution of 50ml 1pm, stirs 4 hours, filters, and detects the content of copper ion in the water sample of target material MS-P2 absorption front and back with inductively coupled plasma (ICP).As accompanying drawing 4.
Embodiment 8 (application of target material MS-P2 in active somatic cell)
Under 28 ℃, hatched mankind mastopathy cell (MCF-7) 1 hour with the target material MS-P2 of 1ppm, rinse out the particle that adheres to PBS buffer solution, be placed under the fluorescent microscope, with blue-light excited, the fluorescence intensity of observation of cell.With the copper ion solution continuation hatching cell half an hour of 0.2mM, the cell fluorescence intensity that observation adds behind the copper ion changes then.As accompanying drawing 5.
Embodiment 9 (application of target material MS-P2 in biological tissue)
Under 28 ℃, hatch the zebra fish 1 hour of 5 ages in days with the target material MS-P2 of 4ppm, rinse out the particle that adheres to PBS buffer solution, be placed under the fluorescent microscope, with blue-light excited, observe the fluorescence of zebra fish.Copper ion solution with 0.2mM continues to hatch half an hour then, and observation adds the zebra fish change in fluorescence behind the copper ion.As accompanying drawing 6.
Claims (6)
1. the immobilized mesoporous silicon material of 8-naphthalimide fluorescent dye is characterized in that, in the inner wall surface grafting of the duct of mesoporous silicon material (MS) an efficient copper ion fluorescence probe, synthesized multifunctional material MS-P2, its general formula is as follows:
Wherein reaction raw materials 4-bromo-5-nitro-1,8 naphthalene acid anhydride is to be that initiation material is synthetic with the acenaphthene; 4-bromo-5-nitro-1,8 naphthalene acid anhydride and 3-aminopropyltriethoxywerene werene (APTES) are in absolute ethyl alcohol, and under nitrogen gas protection and the stirring, back flow reaction 4 hours generates N-3-aminopropyl 4-bromo-5-nitro-1,8 naphthalimide; And then with the 2-aminomethyl-pyridine in dimethoxy-ethanol, N2 gas shield and stirring down, back flow reaction 12 hours obtains organic probe micromolecule N-(3-aminopropyl)-4,5-two [(pyridine-2-methyl) amino]-1,8 naphthalimide is called for short P2; At last with above-mentioned P2 and mesoporous silicon material (MS) in the dry toluene solvent, under the nitrogen protection, back flow reaction 24 hours is filtered and is obtained target material MS-P2.
2. according to claim 1 a kind of 1, the mesoporous silicon material that 8-naphthalimide fluorescent dye is immobilized is characterized in that above-mentioned functional material is the functional material of carrier with the mesoporous si molecular sieves of SBA series, and it has following architectural feature:
3. according to claim 1 a kind of 1, the mesoporous silicon material that 8-naphthalimide fluorescent dye is immobilized is characterized in that above-mentioned functional material is the functional material of carrier with the mesoporous si molecular sieves of MCM series, and it has following architectural feature:
4. according to claim 1 a kind of 1, the mesoporous silicon material that 8-naphthalimide fluorescent dye is immobilized is characterized in that above-mentioned functional material is the functional material of carrier with the mesoporous si molecular sieves of MSU series, and it has following architectural feature:
5. according to claim 1 a kind of 1, the mesoporous silicon material that 8-naphthalimide fluorescent dye is immobilized is characterized in that above-mentioned functional material is the functional material of carrier with the mesoporous si molecular sieves of HMS series, and it has following architectural feature:
6. the application of claim 1,2,3,4 or 5 described mesoporous silicon materials is characterized in that, this target material MS-P2 is used for detection and the absorption to copper ion.
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