CN105418936A - Lanthanide metal organic framework with polyrotaxane configuration as well as preparation method and application thereof - Google Patents
Lanthanide metal organic framework with polyrotaxane configuration as well as preparation method and application thereof Download PDFInfo
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- CN105418936A CN105418936A CN201510708775.9A CN201510708775A CN105418936A CN 105418936 A CN105418936 A CN 105418936A CN 201510708775 A CN201510708775 A CN 201510708775A CN 105418936 A CN105418936 A CN 105418936A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/007—Polyrotaxanes; Polycatenanes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The present invention relates to a lanthanide metal organic framework with a polyrotaxane configuration as well as a preparation method and application thereof. The adopted technical scheme comprises the following steps: adding Ln(NO3) 3, H2mtpc and solvents such as N,N-dimethylacetamide and water to a container, and stirring the mixture at room temperature; sealing the container and placing the container into an oven for 3 days under the temperature of 300-400K; slowly cooling the container to room temperature to obtain a colorless transparent bulk crystal; and washing the bulk crystal with N,N-dimethylacetamide, filtering and drying the bulk crystal to obtain a target product. The Ln III metal based organic framework prepared by the present invention is used as a fluorescent probe, and nitrobenzene can be efficiently and selectively sensed.
Description
Technical field
The present invention relates to lanthanide series metal organic backbone of a kind of poly-rotaxane configuration and preparation method thereof, specifically, relate to a kind of preparation and the application thereof with the lanthanide series metal organic backbone based on poly-rotaxane configuration of fluorescent probe function.
Background technology
In recent years, metallic organic framework owing to having charming Diversity structure and interesting character (gas adsorption, photoluminescence, magnetic, catalysis etc.), and is subject to extensive concern.The multi-function metal organic backbone with character such as luminescence, magnetic, highly porouies receives special concern because can be used as chemical sensor.By design, selecting organic linker and metal unit to build the metallic organic framework with special construction and function, is also the problem that this area is constantly explored.
Based on safety and environmental problem, nitro arene explosive substance receives much concern.Oil of mirbane is a kind of simple nitro-aromatic compound, is also the important component part of nitro arene explosive substance.In addition, oil of mirbane may cause fearful health problem and become notorious environmental pollutant.Therefore, detect oil of mirbane to be fast and accurately significant to Homeland Security, Military Application, judicial investigation and environment protection.
Summary of the invention
The object of the invention is to utilize two core terbiums bunch as secondary construction structure unit, utilize organic carboxyl acid part as organic ligand, at a certain temperature, utilize the method for solvent thermal to synthesize a kind of lanthanide series metal organic backbone of poly-rotaxane configuration.
The technical solution used in the present invention is: a kind of lanthanide series metal organic backbone of poly-rotaxane configuration, preparation method comprises the steps:
1) by Ln (NO
3)
3, organic carboxyl acid part, N,N-dimethylacetamide, water adds in container, under normal temperature, stirs.
2) put into baking oven by after container sealing, under 300-400K, keep 3-4 days.
3) progressively cool to room temperature, leave standstill 24-30h, obtain crystal.
4) crystal N,N-dimethylacetamide is washed, and filters, dry, obtains the lanthanide series metal organic backbone that target product gathers rotaxane configuration.
The lanthanide series metal organic backbone of above-mentioned poly-rotaxane configuration, the lanthanide series metal organic backbone of described poly-rotaxane configuration, its crystal belongs to oblique system, and spacer is P2/c.
The lanthanide series metal organic backbone of above-mentioned poly-rotaxane configuration, described Ln (NO
3)
3for Tb (NO
3)
3.
The lanthanide series metal organic backbone of above-mentioned poly-rotaxane configuration, described organic carboxyl acid part is v-shaped rigidity bidentate Carboxylic acid ligand, and its preparation method is as follows:
1) get m-xylene in two neck bottles, add iodine, ice-water bath, under lucifuge condition, dropwise add bromine water, reaction 1-1.5h, after at room temperature reacting 15-18h again, add KOH solution, low-grade fever is shaken, and disappears, be cooled to room temperature until yellow, filter, washing, with ethyl alcohol recrystallization, obtains intermediate product A.Preferably, by weight percentage, the concentration of KOH solution is 15-25%.
2) by intermediate product A, 4-methoxycarbonyl phenylo boric acid, tetra-triphenylphosphine palladium and cesium fluoride in two neck bottles, vacuumize logical nitrogen, add dme wherein, under nitrogen protection back flow reaction 70-75h, be cooled to room temperature, add distilled water wherein, mixed solution dichloromethane extraction, organic phase anhydrous magnesium sulfate drying spends the night, filter, except desolventizing, thick product silica column purification, obtains intermediate product C;
3) intermediate product C is dissolved in tetrahydrofuran (THF) and methanol mixed solution, add sodium hydroxide solution again, reflux 10-14h, add water to after mixed solution dissolves completely, reheat backflow 10-14h, cool to room temperature, yellow mercury oxide is obtained with concentrated hydrochloric acid acidifying, filter, be washed to neutrality, obtain target product organic carboxyl acid part.Preferably, tetrahydrofuran (THF) and methanol mixed solution, by volume, tetrahydrofuran (THF): methyl alcohol=1:1.Concentrated hydrochloric acid acidifying, is acidified to PH=1.5-2.5.
The organic carboxyl acid part that the present invention adopts is v-shaped rigidity bidentate Carboxylic acid ligand (H
2mtpc), belong to rigidity bitooth ligand, as organic ligand, coordination mode is flexible, has following structural formula.
The invention has the beneficial effects as follows: the lanthanide series metal organic backbone of the poly-rotaxane configuration prepared by the present invention can be used as multifunctional material and is applied to fluorescent molecular probe field.The lanthanide series metal organic backbone of prepared poly-rotaxane configuration can detect as fluorescent probe p-nitrophenyl.The lanthanide series metal organic backbone preparation method of poly-rotaxane configuration of the present invention is simple, has great application prospect.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 2 is the PXRD figure that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 3 a is the coordination environment schematic diagram that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 3 b is the coordination mode schematic diagram that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 3 c is the two-dimensional layer structural representation that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 4 a is that the lanthanide series metal organic backbone rotaxane that the present invention gathers rotaxane configuration runs through structural representation.
Fig. 4 b is the simulation schematic diagram that lanthanide series metal organic backbone rotaxane that the present invention gathers rotaxane configuration runs through structure.
Fig. 5 is the three-dimensional packed structures schematic diagram that the present invention gathers the lanthanide series metal organic backbone of rotaxane configuration.
Fig. 6 is the fluorescence spectrum figure that the present invention gathers the fluorescence intensity of lanthanide series metal organic backbone in different solvents of rotaxane configuration.
Fig. 7 is the fluorescence spectrum figure of methyl alcohol suspension liquid fluorescence intensity under different nitro phenenyl concentration of the lanthanide series metal organic backbone that the present invention is based on poly-rotaxane configuration.
Fig. 8 is the fluorescence intensity histogram of lanthanide series metal organic backbone in distinct fragrance compound that the present invention is based on poly-rotaxane configuration.
Embodiment
Embodiment 1 gathers the lanthanide series metal organic backbone of rotaxane configuration
(1) v-shaped rigidity bidentate Carboxylic acid ligand (H
2mtpc) preparation
1) get 19.7ml m-xylene in two neck bottles, add 0.2g iodine and dissolve, ice-water bath, dropwise adds 54.6g bromine water under lucifuge condition, reacts 1 hour.After at room temperature reacting 16h again, add 20%KOH solution 20ml, low-grade fever is shaken, and disappear until yellow, be cooled to room temperature, filter, washing, with ethyl alcohol recrystallization, obtains intermediate product A (bromo-2, the 4-dimethyl benzenes of 1,5-bis-).
2) by intermediate product A (2g); 4-methoxycarbonyl phenylo boric acid (3.4g); tetra-triphenylphosphine palladium (0.2g); cesium fluoride (3g) is in two neck bottles; vacuumize logical nitrogen 30min; add anhydrous dimethyl ether (DME) 100ml wherein, back flow reaction 72h under nitrogen protection, is cooled to room temperature; add distilled water 100ml wherein; mixed solution dichloromethane extraction three times, gets organic phase, spends the night with anhydrous magnesium sulfate drying; filter; except desolventizing, thick product silica column purification, obtains intermediate product C.
3) intermediate product C is dissolved in tetrahydrofuran (THF) and methyl alcohol (v/v=1/1) mixing solutions, add 50ml4M sodium hydroxide solution, reflux 12h, add water to mixed solution and dissolve completely, again by mixed solution reflux 12h, cool to room temperature, is acidified to PH=2 with concentrated hydrochloric acid, obtains yellow mercury oxide, filtered water is washed till neutrality, obtain target product, that is, v-shaped rigidity bidentate Carboxylic acid ligand (H
2mtpc).
(2) preparation of the lanthanide series metal organic backbone of poly-rotaxane configuration
By the Tb (NO of 0.033mmol
3)
3, the H of 0.014mmol
2the N,N-dimethylacetamide (DMAC) of mtpc, 1.5ml, it is in the vial of 5ml that the water of 0.5ml adds volume, and normal temperature condition stirs 10 minutes.Vial good seal is put into baking oven.Heating makes the temperature of baking oven reach 358K from room temperature, and temperature rise rate is 5Kmin
-1, and be incubated 72 hours under maintaining the temperature at this condition.With 5Kh
-1rate of temperature fall progressively cool to room temperature, obtain water white transparency bulk crystals; With N, N '-dimethyl ethanamide (DMAC) solution washing, filtration are also dry in atmosphere, and be the lanthanide series metal organic backbone that target product gathers rotaxane configuration, productive rate is 63%.
The PXRD of the lanthanide series metal organic backbone of the poly-rotaxane configuration of the present invention's synthesis detects, result is as Fig. 2, it is fine that the position of the PXRD diffractogram of composite crystals and the relevant peaks of mimic diagram coincide mutually, illustrates that the lanthanide series metal organic backbone of the poly-rotaxane configuration synthesized is pure phase.As shown in Figure 3-Figure 5, drawn by Fig. 3-Fig. 5, this crystalline structure belongs to oblique system to the structure of the lanthanide series metal organic backbone of the poly-rotaxane configuration of synthesis, and spacer is P2/c.Molecular formula is: [Tb (mtpc)
1.5(DMAC) (H
2o)] 2H
2o.This compound is by [Tb
2(COO)
4] as secondary construction unit, by the two-dirnentional structure of dicarboxylates bridging.Each H
2mtpc part and four Tb
3+ion coordination, four Tb
3+ion and eight come from H
2oxygen on mtpc carboxyl and the oxygen from coordinated water and an oxygen coordination from the DMAC of coordination.From Fig. 3-5, this metallic organic framework is the lanthanide series metal organic backbone of poly-rotaxane configuration.
The lanthanide series metal organic backbone that embodiment 2 gathers rotaxane configuration detects oil of mirbane
Oil of mirbane is detected as fluorescent probe using the lanthanide series metal organic backbone of the poly-rotaxane configuration of embodiment 1 preparation.
1) selection of solvent
Get methyl alcohol, DMF, water, ethanol, DMAC, each 4mL of oil of mirbane solvent, add the lanthanide series metal organic backbone crystal 1mg of the uniform poly-rotaxane configuration of grinding respectively, mix under room temperature.Each solution fluorescence intensity is detected with spectrophotofluorometer.As shown in Figure 6, in figure, characteristic peak peak fluorescence intensity is followed successively by the solution of methyl alcohol, DMF, water, ethanol, DMA, oil of mirbane to result from top to bottom.As seen from Figure 6, lanthanide series metal organic backbone crystal fluorescence in methanol solvate of poly-rotaxane configuration is the strongest, and fluorescent quenching in oil of mirbane solvent.This illustrates that the crystal of the lanthanide series metal organic backbone of a kind of poly-rotaxane configuration of the present invention can select methyl alcohol to probe into its luminosity as solvent; Also can be used as fluorescent probe and detect oil of mirbane.
2) crystal getting the lanthanide series metal organic backbone of poly-rotaxane configuration is dissolved in methanol solvate, obtains the lanthanide series metal of poly-rotaxane configuration
Organic backbone crystal concentration is 4 × 10
-4the mixing solutions of M.
Get mixing solutions 5ml, add the oil of mirbane of 0.06 μ l15ppm, 0.3 μ l75ppm, 0.6 μ l150ppm respectively.The change of mixing solutions fluorescence intensity is detected with spectrophotofluorometer.Result as shown in Figure 7, in figure peak value be followed successively by 15 from top to bottom, 75,150ppm.As seen from Figure 7, mixing solutions Tb
3+reduce gradually in the characteristic peak intensity of 545nm.This illustrates that the crystalline structure p-nitrophenyl of the lanthanide series metal organic backbone of a kind of poly-rotaxane configuration of the present invention has good measuring ability.
3) crystal getting the lanthanide series metal organic backbone of poly-rotaxane configuration is dissolved in methanol solvate, obtains the lanthanide series metal of poly-rotaxane configuration
Organic backbone crystal concentration is 4 × 10
-4the mixing solutions of M.
Get mixing solutions 5ml, add aromatic compound benzene, toluene, o-Xylol, phenol, oil of mirbane, chlorobenzene, bromobenzene, the iodobenzene of 150ppm respectively.Tb in mixing solutions is detected with fluorophotometer
3+the change of fluorescence intensity.Result as shown in Figure 8, gets Tb in figure
3+histogram is done at the characteristic peak peak value of 545nm.As seen from Figure 8, Tb in mixing solutions
3+affect by benzene, toluene, o-Xylol, phenol, chlorobenzene, bromobenzene, iodobenzene hardly in the characteristic peak intensity of 545nm, and oil of mirbane causes obvious fluorescent quenching.This illustrates that the crystalline structure p-nitrophenyl of the lanthanide series metal organic backbone of a kind of poly-rotaxane configuration of the present invention has good measuring ability.
Claims (10)
1. a lanthanide series metal organic backbone for poly-rotaxane configuration, is characterized in that: preparation method comprises the steps:
1) by Ln (NO
3)
3, organic carboxyl acid part, N,N-dimethylacetamide, water adds in container, under normal temperature, stirs;
2) put into baking oven by after container sealing, under 300-400K, keep 3-4 days;
3) progressively cool to room temperature, leave standstill 24-30h, obtain crystal;
4) crystal N,N-dimethylacetamide is washed, and filters, dry, obtains the lanthanide series metal organic backbone that target product gathers rotaxane configuration.
2. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 1, is characterized in that: the lanthanide series metal organic backbone of described poly-rotaxane configuration, and its crystal belongs to oblique system, and spacer is P2/c.
3. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 1, is characterized in that: described Ln (NO
3)
3for Tb (NO
3)
3.
4. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 1, is characterized in that: described organic carboxyl acid part is v-shaped rigidity bidentate Carboxylic acid ligand, and preparation method is as follows:
1) get m-xylene in two neck bottles, add iodine, ice-water bath, under lucifuge condition, dropwise add bromine water, reaction 1-1.5h, after at room temperature reacting 15-18h again, add KOH solution, low-grade fever is shaken, and disappears, be cooled to room temperature until yellow, filter, washing, with ethyl alcohol recrystallization, obtains intermediate product A;
2) by intermediate product A, 4-methoxycarbonyl phenylo boric acid, tetra-triphenylphosphine palladium and cesium fluoride in two neck bottles, vacuumize logical nitrogen, add dme wherein, under nitrogen protection back flow reaction 70-75h, be cooled to room temperature, add distilled water wherein, mixed solution dichloromethane extraction, organic phase anhydrous magnesium sulfate drying spends the night, filter, except desolventizing, thick product silica column purification, obtains intermediate product C;
3) intermediate product C is dissolved in tetrahydrofuran (THF) and methanol mixed solution, add sodium hydroxide solution again, reflux 10-14h, add water to after mixed solution dissolves completely, reheat backflow 10-14h, cool to room temperature, yellow mercury oxide is obtained with concentrated hydrochloric acid acidifying, filter, be washed to neutrality, obtain target product v-shaped rigidity bidentate Carboxylic acid ligand.
5. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 4, is characterized in that: by weight percentage, and the concentration of described KOH solution is 15-25%.
6. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 4, is characterized in that: step 3) in, tetrahydrofuran (THF) and methanol mixed solution, by volume, tetrahydrofuran (THF): methyl alcohol=1:1.
7. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 4, is characterized in that: step 3) in, described concentrated hydrochloric acid acidifying, is acidified to PH=1.5-2.5.
8. the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 1 is detecting the application in oil of mirbane as fluorescent probe.
9. application according to claim 8, is characterized in that method is as follows: be dissolved in solvent by the lanthanide series metal organic backbone of poly-rotaxane configuration according to claim 1, then add the solution containing oil of mirbane, carry out fluoroscopic examination.
10. application according to claim 9, is characterized in that: described solvent is methyl alcohol, dimethyl formamide, water, ethanol or N,N-dimethylacetamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106908424A (en) * | 2017-02-09 | 2017-06-30 | 南京大学 | A kind of fluorescent nano probe and preparation method thereof and its application in bio-sensing |
| CN115073762A (en) * | 2022-07-27 | 2022-09-20 | 南京晶立得科技有限公司 | Copper-based coordination polymer pseudopolyrotaxane crystal material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312578A (en) * | 2014-09-22 | 2015-01-28 | 南开大学 | Fluorescent material with high thermal stability and stable to organic solvent |
| CN104447377A (en) * | 2014-11-14 | 2015-03-25 | 天津工业大学 | Application of luminous metal organic framework material in detecting nitro aromatic hydrocarbon pollutant |
| CN104807794A (en) * | 2015-04-29 | 2015-07-29 | 天津工业大学 | Application of transition metal organic zinc complex in trace nitroaromatic pollutant detection |
-
2015
- 2015-10-27 CN CN201510708775.9A patent/CN105418936B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312578A (en) * | 2014-09-22 | 2015-01-28 | 南开大学 | Fluorescent material with high thermal stability and stable to organic solvent |
| CN104447377A (en) * | 2014-11-14 | 2015-03-25 | 天津工业大学 | Application of luminous metal organic framework material in detecting nitro aromatic hydrocarbon pollutant |
| CN104807794A (en) * | 2015-04-29 | 2015-07-29 | 天津工业大学 | Application of transition metal organic zinc complex in trace nitroaromatic pollutant detection |
Non-Patent Citations (2)
| Title |
|---|
| XIAOQING WANG: "Lanthanide metal-organic frameworks containing a novel flexible ligand for luminescence sensing of small organic molecules and selective adsorption", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 赵旭东: "Zn3-MOF用于硝基苯的高效荧光识别", 《化工学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106908424A (en) * | 2017-02-09 | 2017-06-30 | 南京大学 | A kind of fluorescent nano probe and preparation method thereof and its application in bio-sensing |
| CN106908424B (en) * | 2017-02-09 | 2019-12-17 | 南京大学 | Fluorescent nano probe, preparation method thereof and application thereof in biosensing |
| CN115073762A (en) * | 2022-07-27 | 2022-09-20 | 南京晶立得科技有限公司 | Copper-based coordination polymer pseudopolyrotaxane crystal material and preparation method and application thereof |
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