CN105199114B - A kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light - Google Patents
A kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light Download PDFInfo
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- CN105199114B CN105199114B CN201510713329.7A CN201510713329A CN105199114B CN 105199114 B CN105199114 B CN 105199114B CN 201510713329 A CN201510713329 A CN 201510713329A CN 105199114 B CN105199114 B CN 105199114B
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 102
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000017 hydrogel Substances 0.000 title claims abstract description 56
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000012456 homogeneous solution Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000037048 polymerization activity Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229940117958 vinyl acetate Drugs 0.000 abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 238000012660 binary copolymerization Methods 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000090 biomarker Substances 0.000 abstract 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 230000010148 water-pollination Effects 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- -1 dimethyl methyls Acid amides Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
A kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light, belongs to the synthesis field of polymer luminescent material.This method carries out binary copolymerization using the monomer of labile coordination compound containing europium containing olefinic double bonds and vinylacetate and prepares the polymer containing europium, further above-mentioned polymer water solution has been obtained good biocompatibility by the invention has the photism polyvinyl alcohol of visible ray lighting function again, and the hydrogel material that can light has been obtained by dissolving the method freezed repeatedly, it is still observed that good illumination effect through skin.This technology is compared with tradition is using fluorescein technology, the fluorescent quenching that can be prevented fluorescent material from assembling again with fine biocompatibility and produce, and the material can be directly used in processing as body phase material, it need not be coated on other base materials, it is luminous uniform, it may be reused and reduce cost, the hydrogel polymer material containing europium of the luminescence generated by light can be applied to biomarker, the association area such as biology sensor.
Description
Technical field
The present invention relates to a kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light, belong to polymer light-emitting
The synthesis field of material.
Background technology
Mix europium hydrogel light-emitting materials it is emerging be applied to biomedicine field material, due to Eu3+With big Si Tuo
The advantage of gram this displacement, narrow feux rouges discharge and long fluorescence lifetime, and can be with beta-diketon class, aromatic rings class, heterocyclic, the big ring of armed
Class or multiamide type part react, and generate a series of organic coordination compound containing europium that structures are novel, species is abundant.These parts
All there is low molecule amount and height can be formed to electron delocalization degree, the effective energy that improves is from part to central Eu3+The biography of ion
Pass, so as to improve luminous efficiency.And be mostly to be doped in organic phase at present for the application of Orgnic RE complex
In (such as polymer), include the mode of physical doping and in-situ polymerization.But these methods can cause the scattered inequality of rare earth compounding
Or occur reuniting and causing the phenomenons such as fluorescent quenching in process.Active group is introduced in complex, passes through active group
Group carries out copolymerization with polymerisable monomer and forms the high molecular polymer containing rare earth compounding group, and feasible efficiently solves this
A little problems.
Hydrogel be it is a kind of can be swelled in water but a water insoluble class hydrophily highland molecular material, it
Flexibility is good, and water content is high, so the conformability to surrounding tissue is good, is more suitable for being used for compared with other types of synthetic material
Do bio-medical material.Polyvinyl alcohol is the water miscible macromolecule polymer material of only one in nature, and its source is rich
It is richness, good hydrophilic property, cheap.Polyvinyl alcohol is exactly polyvinyl acetate ground hydrolysate, rather than directly direct with monomer
Polymer formed by polymerization.There is very good solvent resistance to also have very excellent filming performance for it, and it can be formed
That surface unusual light also has very tough but also tear-resistant film.It is even more to have excellent biocompatibility, and
To human body without what toxic side effect, in addition polyalcohol hydrogel be containing water three-dimensional crosslinked network, polyalcohol hydrogel it is excellent
It is benign further to expand its potential application, the backing material of different biology sensors can be done.
Polyalcohol hydrogel containing europium is that complex and the polymeric material of europium carry out copolymerization in molecular level, it is to avoid due to
Split-phase caused by polymerization is uneven makes the fluorescent quenching that rare earth compounding density unevenness is caused.The luminous efficiency and complex structure of europium
Relation it is quite close, i.e. complexes system conjugate planes, rigid structure degree is bigger, and complex middle rare earth luminous efficiency is also
It is higher, because this structural stability is big, luminous energy loss can be substantially reduced.Methacrylic acid containing europium draws in complex
Enter carbon-carbon double bond, the free-radical polymerized formation polymer of double bond is carried out with vinylacetate, then hydrolyze to form required sample.
Sample forms hydrogel by way of physical crosslinking, and novel hydrogels can substitute the material of some other fluorescence class in biology
Application medically, can effectively evade and relatively low fluorescence output is run into extremely sensitive fluoroscopic examination, and pH is sensitive, light drift
It is white and form non-fluorescence product.Polyalcohol hydrogel containing europium can be detected with the naked eye after by light source activation, convenient,
Fast.In addition, using polyvinyl alcohol as backing material, because it has good hydrophily, biocompatibility and the transparency,
The novel hydrogels being polymerized can be used as good bio-medical material, and not had for the fluorescent effect of europium complex
There is obvious influence.
The content of the invention
It can not be combined with each other performance for the hydrogel material of polymer luminescent material containing europium at present and good biocompatibility
Both excellent performances, and the main present situation based on physical doping of the polymer luminescent material containing europium, the present invention provide one
Plant and the light-emitting materials of polyalcohol hydrogel containing europium are synthesized by the method for radical polymerization, this method, which should be used, contains olefinic double bonds
Carry out binary copolymerization containing europium complex and vinylacetate and prepare can carry out the polymer visible ray containing europium of alcoholysis and light material
Material, after hydrolysis, the luminous hydrogel material of the good visible ray of pliability is obtained with sol-gel process.
The technical solution adopted by the present invention is：A kind of synthetic method bag of the polymer hydrogel materials containing europium of luminescence generated by light
Include following steps：
1. a kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light, it is characterised in that：Including following step
Suddenly：
The synthesis of step 1, the organic coordination compound containing europium with polymerization activity
The dibenzoyl methane of 0.1802g phenanthroline and 0.4485g is added in 30mL ethanol solutions, in 50-
Dissolving is heated in 80 DEG C of waters bath with thermostatic control complete；0.0947g methacrylic acid is instilled in this solution, is poured into and is placed on 30-
In three-necked flask in 60 DEG C of constant temperature oil baths, and it is 7.0-8.0 that 1mol/L sodium hydrate aqueous solution regulation pH value, which is added dropwise, leads to nitrogen
Gas is simultaneously stirred, and the ethanol solution 20mL for the Europium chloride that concentration is 0.05mol/L is slowly added dropwise after 30-60min with separatory funnel, and
The sodium hydrate aqueous solution regulation pH value that 1mol/L is added dropwise is 7.0-8.0, continues constant temperature stirring reaction 20h；Reaction solution is at a high speed
Centrifuge is separated, and gained solid phase is repeatedly washed with ethanol, and 25-35 DEG C of vacuum drying 12h obtains containing europium complex；
The synthesis of step 2, polymer containing europium complex
0.1778g-the 3.0361g that step 1 is obtained contain europium complex, 10.3308g vinylacetates, 5mL dimethyl methyls
Acid amides is added in 100mL three-necked flasks, is led to after nitrogen gas stirring half an hour, adds 0.035g azodiisobutyronitriles, and 50-70 DEG C anti-
4-6h is answered to obtain copolymer solution, copolymer solution water sedimentation, again with methanol dissolving after drying, repeated precipitation purification is multiple,
25-35 DEG C of vacuum drying 24-48h obtains the polymer containing europium complex；
The alcoholysis of step 3, polymer containing europium complex
Take the polymer 5g containing europium complex in step 2 to be dissolved in 4-40mL methanol solution, pour into and be placed on 30-60 DEG C
Stirred in three-necked flask in constant temperature oil bath, be passed through after nitrogen half an hour, 4-15mL 1mol/L sodium hydroxide is slowly added dropwise
Ethanol solution, reaction 1-5h obtains hydrogel containing europium, and reaction solution is separated with supercentrifuge, adds 20-30mL's in sediment
Deionized water is poured into the three-necked flask being placed in 80-100 DEG C of constant temperature oil bath, is stirred 30 minutes and is dissolved, again with methanol precipitation
Out, centrifuge, it is repeated multiple times untill pH value reaches 7, by the product being centrifugally separating to obtain in 25-35 DEG C of vacuum drying；
The synthesis of step 4, the hydrogel containing europium
Hydrolysates of the 2g containing europium complex is taken to add 20mL deionized waters, the heating stirring at 90 DEG C, until polymer
It is completely dissolved, forms homogeneous solution, homogeneous solution is positioned over after -20 DEG C of freezing 4-8h, homogeneous solution is taken out and solves at room temperature
Freeze 2-4h, freeze-thaw repeatedly, finally obtains hydrogel containing europium repeatedly.
The beneficial effects of the invention are as follows：The method of this synthesis visible ray light-emitting materials of polyalcohol hydrogel containing europium passes through
Polymerization is combined luminescent material in the polymer and alcohol takes off the carboxyl in polymer, obtains a kind of good water-setting of hydrophily
Glue material, the Material cladding is avoided because the uneven caused split-phase of doping makes rare earth compounding density unevenness cause fluorescence sudden
Go out.Material emission and biocompatibility are combined together by the invention well, the hydrogel obtained with sol-gel process
Through Skin observing to good illumination effect.
Brief description of the drawings
Fig. 1 is the synthetic route chart containing europium complex.
Fig. 2 is the nuclear magnetic spectrogram containing europium complex.
Fig. 3 is the Macroscopic single crystal route map containing europium complex.
Fig. 4 is the polymeric infrared light spectrogram containing europium complex.
Fig. 5 is the polymer nuclear magnetic spectrogram containing europium complex.
Fig. 6 is the infrared spectrogram of hydrogel containing europium.
Fig. 7 is the nuclear magnetic spectrogram of hydrogel containing europium.
Fig. 8 is hydrogel containing europium (Eu=0.5wt%) fluorescence spectra.
Fig. 9 is the polymer hydrophilicity picture of (a) containing europium complex and (b) hydrogel containing europium hydrophily picture.
Embodiment
Following embodiments can make one of ordinary skill in the art that the present invention is more fully understood, but not in any way
The limitation present invention.
Embodiment 1
The phenanthroline of 0.4485g dibenzoyl methane and 0.1802g is added in 30mL ethanol solutions, at 60 DEG C
Dissolving is heated in water bath with thermostatic control complete；0.0947g methacrylic acid is instilled in this solution, is poured into and is placed on 50 DEG C of constant temperature
In three-necked flask in oil bath, and it is 7.0-8.0 that 1mol/L sodium hydrate aqueous solution regulation pH value, which is added dropwise, and logical nitrogen is simultaneously stirred
Mix, the ethanol solution 20mL for the Europium chloride that concentration is 0.05mol/L is slowly added dropwise after 30min with separatory funnel, and 1mol/ is added dropwise
L sodium hydrate aqueous solution regulation pH value is 7.0-8.0, continues constant temperature stirring reaction 20h；Reaction solution supercentrifuge point
From gained solid phase is repeatedly washed with ethanol, and 30 DEG C of vacuum drying 12h obtain the complex containing europium；
Complexs of the 0.2998g containing europium is taken, 10.3308g vinylacetates, 5mL dimethylformamides are added to 100mL tri-
In mouth flask, lead to after nitrogen gas stirring half an hour, add 0.035g azodiisobutyronitriles, 65 DEG C of reaction 4h obtain copolymer solution.
Again with methanol dissolves after copolymer solution water sedimentation, precipitation, and cyclic washing is multiple.48h is dried in vacuo at 30 DEG C, obtains containing europium
The polymer of complex；
Take polymer of the 5g containing europium complex to be dissolved in 40mL methanol solution, pour into and be placed in 40 DEG C of constant temperature oil baths
Stirred in three-necked flask.It is passed through after nitrogen half an hour, 5mL 1mol/L sodium hydroxide ethanol solution is slowly added dropwise, reacts 2h
Obtain hydrogel containing europium.Reaction solution is separated with supercentrifuge, and addition 30mL deionized water, which is poured into, in sediment is placed on 90
In three-necked flask in DEG C constant temperature oil bath, stir 30 minutes and dissolve, again with methanol is precipitated out, centrifuge.It is repeated multiple times until PH
Untill value reaches 7.30 DEG C of vacuum drying obtain sediment；
Hydrolysates of the 2g containing europium complex is taken to add 20mL deionized waters, the heating stirring at 90 DEG C, until polymer
It is completely dissolved to form homogeneous solution.Homogeneous solution is positioned over after -20 DEG C of freezing 6h, taking-up is thawed 2h at room temperature, repeatedly 6
It is secondary, finally obtain hydrogel containing europium.
Embodiment 2
All reaction raw materials and operating method be the same as Example 1 used, difference is the addition containing europium complex
It is 0.3wt% hydrogels containing europium to obtain europium content for 0.1778g.
Embodiment 3
All reaction raw materials and operating method be the same as Example 1 used, difference is the addition containing europium complex
It is 1wt% hydrogels containing europium to obtain europium content for 0.6182g.
Fig. 1 is the synthetic route chart containing europium complex.
Fig. 2 is the nuclear magnetic spectrogram containing europium complex.
Fig. 3 is the Macroscopic single crystal route map containing europium complex.
Fig. 4 is the polymeric infrared light spectrogram containing europium complex.As seen from the figure, passed through certainly containing europium complex and vinylacetate
After base copolymerization, the resulting polymer containing europium complex is in 1731cm-1Place is the characteristic absorption peak of C=O double bonds；1597 Hes
1515cm-1It is the characteristic absorption peak of phenyl ring；2926cm-1Locate as-CH2Absworption peak；1032cm-1Locate as C-O absworption peak.IR
(KBr,cm-1)：γ (C=O)=1731cm-1, γ (Caromatic)=1597 and 1515cm-1, γ (- CH2)=2926cm-1,
γ (C-O)=1032cm-1。
Fig. 5 is the polymer nuclear magnetic spectrogram containing europium complex.As seen from the figure：At chemical shift δ=8.01-7.50ppm
Characteristic peak correspondence containing the hydrogen (1,2,3,4 in figure) in phenanthroline on europium complex, the characteristic peak correspondence at 7.55ppm places is containing europium
On complex in dibenzoyl methane=CH-on hydrogen (5 in figure), the characteristic peak correspondence at 7.52-6.90ppm contains europium complex
Characteristic peak in upper dibenzoyl methane at benzene ring hydrogen (6,7,8 in figure), 4.87ppm is on emergencing copolymer carbon carbon long-chain
- OCH on characteristic peak correspondence vinylacetate at hydrogen (12 in figure) in HC-COO, 2.03ppm3In hydrogen (13 in figure),
Characteristic peak at 1.77ppm is to H on emergencing copolymer carbon carbon long-chain2Feature at hydrogen (11 in figure) in C-C, 1.26-1.13ppm
Peak correspondence is containing the hydrogen (9,10 in figure) in methacrylic acid on europium complex.
1H NMR(400MHz,CDCl3,δ):8.01(m,2H,),7.99(m,2H,),7.56
(m,2H,),7.50(m,2H,), 7.55 (s, 1H ,=CH -), 7.52 (m, 8H ,-Ph), 7.48 (m,
4H,–Ph),6.90(m,8H,–Ph),4.87(s,1H,–COOCH3),2.03(s,3H,–OCH3),1.77(s,2H,–
CH–COOCH3),1.26(s,2H,–C–CH3),1.13(s,3H,H2C–C–) Fig. 6 is the infrared spectrum of hydrogel containing europium
Figure.There is figure to understand, polymer containing europium is after hydrolyzing decarboxylize, and resulting hydrogel containing europium is in 3263cm-1Place is-OH spy
Levy absworption peak；1422cm-1It is the characteristic absorption peak of phenyl ring；2922cm-1Locate as-CH2Absworption peak；1085cm-1Locate as C-O's
Absworption peak；In 1731cm-1There is the characteristic absorption peak of the C=O double bonds of very little at place.Illustrate that the polymer containing europium has been hydrolyzed into contain
The hydrogel of europium, an only seldom part is not hydrolyzed.IR(KBr,cm-1)：γ (- OH)=3263cm-1, γ (n)=
1422cm-1, γ (- CH2)=2922cm-1, γ (C-O)=1085cm-1.Fig. 7 is the nuclear magnetic spectrogram of hydrogel containing europium.As seen from the figure：
At chemical shift δ=8.16-7.52ppm characteristic peak correspondence containing in phenanthroline on europium complex hydrogen (1 in figure, 2,3,
4), at 7.75ppm characteristic peak correspondence containing in dibenzoyl methane on europium complex=CH-on hydrogen (5 in figure), 7.61-
Characteristic peak correspondence at 6.14ppm is containing benzene ring hydrogen (6,7,8 in figure), 4.12ppm in dibenzoyl methane on europium complex
Characteristic peak correspondence at hydrogen (13 in figure) after the characteristic peak correspondence decarboxylize of polymer containing europium at place in-OH, 3.75ppm polymerize
Characteristic peak correspondence at hydrogen (12 in figure) on thing carbon carbon long-chain in HC-O, 2.33ppm is containing in methacrylic acid on europium complex
Hydrogen (9 in figure), the characteristic peak at 1.80ppm is to H on emergencing copolymer carbon carbon long-chain2Hydrogen (11 in figure) in C-C-O,
Characteristic peak correspondence at 1.30ppm is containing the hydrogen (10 in figure) in methacrylic acid on europium complex.
1H NMR(400MHz,DMSO-d6,d):8.16(m,2H,),8.08(m,2H,),
7.81(m,2H,),7.52(m,2H,), 7.75 (s, 1H ,=CH -), 7.61 (m, 8H ,-Ph), 6.43
(m,4H,–Ph),6.14(m,8H,–Ph),4.12(s,1H,OH),3.75(s,1H,–OH),2.33(s,2H,–C–
CH3),1.80(s,2H,–CH–OH),1.30(s,3H,H2C–C–).
Fig. 8 is hydrogel containing europium (Eu=0.5wt%) luminescent spectrum figure, and hydrogel has very strong glimmering as seen from the figure
Light.
Fig. 9 is the polymer hydrophilicity picture of (a) containing europium complex and (b) hydrogel containing europium hydrophily picture.Can by figure
Know：Polymer containing europium complex obtains europium hydrogel after alcoholysis, and the contact angle of the hydrogel after alcoholysis significantly decreases,
The hydrophily of hydrogel very well, for synthesized hydrogel containing europium in biological field with providing guarantee.
Application examples 1
The cladding cock skin of polyalcohol hydrogel containing europium that embodiment 1 is obtained carries out UV light permeability：Embodiment 1 is obtained
Hydrogel containing europium, which is fitted into specific bottle, is heated to 90 DEG C of dissolvings with pure water, then passes through the method for freeze-thaw repeatedly
Polyalcohol hydrogel is made, bottled hydrogel is inverted, and cock skin is coated in the outer surface of bottle, (wavelength is with 5W uviol lamp
The hydrogel of parcel cock skin 375nm) is excited, and hydrogel is inverted without cladding cock skin and is contrasted.Hydrogel containing europium is inverted small
Do not flowed in bottle, and hydrogel can observe feux rouges under the irradiation of uviol lamp through cock skin, it may be said that bright water-setting containing europium
Glue has good crosslinking and fluorescent effect.
Claims (1)
1. a kind of synthetic method of the polymer hydrogel materials containing europium of luminescence generated by light, it is characterised in that：Comprise the following steps：
The synthesis of step 1, the organic coordination compound containing europium with polymerization activity
The dibenzoyl methane of 0.1802 g phenanthroline and 0.4485 g is added in 30 mL ethanol solutions, in 50-
Dissolving is heated in 80 DEG C of waters bath with thermostatic control complete；0.0947 g methacrylic acid is instilled in this solution, is poured into and is placed on
In three-necked flask in 30-60 DEG C of constant temperature oil bath, and it is 7.0- that 1 mol/L sodium hydrate aqueous solution regulation pH value, which is added dropwise,
8.0, logical nitrogen is simultaneously stirred, and the ethanol for the Europium chloride that concentration is 0.05 mol/L is slowly added dropwise after 30-60 min with separatory funnel
The mL of solution 20, and it is 7.0- 8.0 that 1 mol/L sodium hydrate aqueous solution regulation pH value, which is added dropwise, continues constant temperature stirring reaction 20
h；Reaction solution is separated with supercentrifuge, and gained solid phase is repeatedly washed with ethanol, and 35 DEG C of 12 h of vacuum drying of 25- obtain containing europium
Complex；
Step 2, the Macroscopic single crystal containing europium complex
0.1778 g -3.0361 g that step 1 is obtained contain europium complex, 10.3308 g vinylacetates, 5 mL diformazans
Base formamide is added in 100 mL three-necked flasks, is led to after nitrogen gas stirring half an hour, adds 0.035 g azodiisobutyronitriles,
50-70 DEG C of reaction 4-6 h obtains copolymer solution, copolymer solution water sedimentation, again with methanol dissolving, repeated precipitation after drying
Purification is multiple, and 35 DEG C of vacuum drying 24-48 h of 25- obtain the polymer containing europium complex；
The alcoholysis of step 3, polymer containing europium complex
Take the g of polymer 5 containing europium complex in step 2 to be dissolved in 4-40 mL methanol solution, pour into and be placed on 30-60 DEG C
Stirred in three-necked flask in constant temperature oil bath, be passed through after nitrogen half an hour, 4-15 mL 1 mol/L hydroxide is slowly added dropwise
Sodium ethoxide solution, reaction 1-5 h obtain hydrogel containing europium, and reaction solution is separated with supercentrifuge, 20-30 will be added in sediment
ML deionized water, is subsequently poured into and is placed in the three-necked flask of 80-100 DEG C of constant temperature oil bath, stirs 30 minutes and dissolves, then uses first
Alcohol is precipitated out, centrifugation, repeated multiple times untill pH value reaches 7, by the product being centrifugally separating to obtain in 35 DEG C of vacuum of 25-
Dry；
The synthesis of step 4, the hydrogel containing europium
Polymer of the 2g containing europium complex is taken to add 20 mL deionized waters, the heating stirring at 90 DEG C, until polymer is complete
Dissolving, forms homogeneous solution, and homogeneous solution is positioned over after -20 DEG C of freezing 4-8 h, takes out homogeneous solution and thaws at room temperature 2-
4 h, freeze-thaw is multiple repeatedly, finally obtains hydrogel containing europium.
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| CN109400916B (en) * | 2018-09-29 | 2021-01-12 | 青岛大学 | SiO (silicon dioxide)2Luminous hydrogel material of grafted polymer and preparation method thereof |
| CN109513039B (en) * | 2019-01-08 | 2021-05-14 | 大连工业大学 | Antibacterial hydrogel dressing containing imidazole bromide salt and preparation method and application thereof |
| CN109777015B (en) * | 2019-01-22 | 2021-04-13 | 青岛大学 | Preparation method of PEG (polyethylene glycol) grafted polymer luminescent hydrogel material |
| CN113801148B (en) * | 2020-06-15 | 2022-11-22 | 北京大学 | Europium-doped macrocyclic complex and application thereof as electroluminescent material |
| CN112342012B (en) * | 2020-11-05 | 2023-03-21 | 常州晶丽光学科技有限公司 | Photochromic material, preparation method thereof and contact lens |
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