CN104004125B - A kind of two fluorescent functional polymer nano-microspheres of pH response and the application in tumor tissues detects thereof - Google Patents
A kind of two fluorescent functional polymer nano-microspheres of pH response and the application in tumor tissues detects thereof Download PDFInfo
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Abstract
Two fluorescent functional polymer nano-microspheres of pH response and the application in tumor tissues detects thereof, belong to technical field of polymer materials.First synthesize the emulsion microballoon of a kind of composite fluorescence molecule A, adopt the method for seeded emulsion polymerization, the polymkeric substance with pH response function is incorporated into the shell of microballoon, prepares the emulsion microballoon of nucleocapsid structure.Further fluorescence molecule B is compound in the shell of microballoon, obtains the functional polymer Nano microsphere of two fluorescent emission with pH response.This microballoon presents different fluorescence intensities and fluorescence color under the different pH condition from acidity to alkalescence.Based on the pH response function of Nano microsphere photoluminescent property, be applied in tissue detection, healthy tissues (pH ~ 7.4) presents purple fluorescence, tumor tissues (pH & lt; 6.5) present pink fluorescence, it may be used for preparing fluorescent material, thus has broad application prospects at tumour cell and the field such as tissue detection, medicament slow release.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to two fluorescent functional polymer nano-microspheres that a kind of pH responds and the fluorescent material applied in detecting for the preparation of tumor tissues thereof.
Background technology
Intelligent material be to environment have can perception, can respond and there is the type material of function ability of discovery.Mainly contain temperature sensitive, pH responsive, electric sensitivity, light, magnetic and biological susceptibility hydrogel material.Although the history of intelligent material research, exploitation is not long, because the performance of its uniqueness is not only widely applied in industrial and agricultural production and daily life, and developing high-tech is played an important role.In recent years, the research work of intelligent material is unprecedentedly active, and novel high polymer and the hydrogel thereof wherein with intelligent behavior are with the fastest developing speed.This family macromolecule energy perception goes out ambient environmental conditions, as changes such as temperature, acidity, pressure, sound wave, electric field, magnetic field, light waves, produces performance change simultaneously.Therefore, have a good application prospect in fields such as chemical sensor, convertor, switchette, artificial-muscle, medicament slow release, immobilized enzyme.
Decades in the past, the development of cell labeling technique receives much concern, and at present, multiple injectable materials in the research of cell marking, comprising: organic molecule, fluorescin and inorganic-quantum-dot.But they self also exist certain limitation, the molar absorption coefficient of organic molecule is lower, the less stable of fluorescin, and inorganic-quantum-dot is owing to having very high bio-toxicity containing a large amount of heavy metal elements in its structure, these factors all limit the application of these materials in cell marking.There is response function, fluorescent stabilization, and bio-toxicity is subject to the attention of investigator gradually compared with low Poison polymer materials, and plays an important role in cell marking.
Main in the detection of conventional fluorescent mark what adopt is the image forming material with single fluorescence color, and under coenocorrelation, background fluorescence signal has interference to a great extent to it, causes Detection results easily to occur error.In order to address this problem, the image forming material constructing two fluorescent emission is necessary.Particularly for tumor tissues and healthy tissues, pH value is the important physical signs of both differences.In tumor tissues, pH is acid state (pH<6.5), and the pH of healthy tissues is neutral state (pH ~ 7.4).Therefore, prepare a kind of fluorescent nanometer microsphere with the two emission function of pH responsiveness, difference imaging is carried out to normal cell and tumour cell, and then realize carrying out to cancer the target that Diagnosis and Treat is medical circle and a region of chemistry Worth Expecting.
Summary of the invention
An object of the present invention is to provide two fluorescent emission Nano microspheres that a kind of pH responds.
First the present invention synthesizes the emulsion microballoon of a kind of composite fluorescence molecule A, then with the emulsion microballoon obtained for seed, adopt the method for seeded emulsion polymerization, the polymkeric substance with pH response function be incorporated into the shell of microballoon, prepare the emulsion microballoon of nucleocapsid structure.Further fluorescence molecule B is compound in the shell of microballoon, obtains the functional polymer Nano microsphere of two fluorescent emission with pH response.The effect of the fluorescence molecule B and polymkeric substance that are compounded in shell is subject to the regulation and control of environment pH, and photoluminescent property changes; And the photoluminescent property being assembled in the fluorescence molecule A in core is not subject to the impact of pH, keep photoluminescent property constant.Different fluorescence intensities and fluorescence color is presented under causing the different pH condition of polyalcohol nucleocapsid Nano microsphere from acidity to alkalescence.Under the condition of neutral and alkalescence, the stratum nucleare fluorescence molecule A (ruddiness) of Nano microsphere and shell fluorescence molecule B (blue light) is luminescence simultaneously, and entirety presents the two composite fluorescence (purple); Along with pH reduces, under acidic conditions, the fluorescence of shell fluorescence molecule B weakens gradually, and the fluorescence molecule A luminescence (ruddiness) of Nano microsphere stratum nucleare is constant; Based on the pH response function of Nano microsphere photoluminescent property, be applied in tissue detection, healthy tissues (pH ~ 7.4) presents purple fluorescence, tumor tissues (pH<6.5) presents pink fluorescence, it may be used for preparing fluorescent material, thus has broad application prospects at tumour cell and the field such as tissue detection, medicament slow release.
Two fluorescent emission polymer nano-microspheres with pH response of the present invention, it is prepared by following steps:
(1) the N-isopropylacrylamide NIPAM monomer taking 2-10mmol is dissolved in the deionized water of 100-200mL, then adds the polymerization single polymerization monomer 1,1 × 10 of 10-50mmol
-6-5 × 10
-6the fluorescence molecule A of mol, under room temperature and nitrogen protection, mechanical stirring 30-60min; Then be warming up to 60-70 DEG C gradually, add the aqueous solution of 5-15mL containing 0.3-0.6mmol initiator, initiated polymerization, after reaction 12-24h, obtain the polymer seeds microballoon containing fluorescence molecule A; Finally by the impurity such as unconverted monomer, initiator in high speed centrifugation removing liquid phase, the more centrifugal polymer seeds microballoon containing fluorescence molecule A obtained is dissolved in 50-100mL deionized water stand-by;
(2) polymer microballoon of step (1) is proceeded seeded emulsion polymerization: in the polymer seeds microspheres solution of step (1), add the polymerization single polymerization monomer 1 of 10-60mmol and the pH responsiveness polymerization single polymerization monomer 2 of 1-5mmol, under room temperature and nitrogen protection, mechanical stirring 30-60min, then 70-85 DEG C is warming up to gradually, add the aqueous solution of 15mL containing 0.5 – 1.5mmol initiator, initiated polymerization, obtains the polymer nano-microspheres of nucleocapsid structure after reaction 12-24h; Finally by the impurity such as unconverted monomer, initiator in high speed centrifugation removing liquid phase, the more centrifugal nucleocapsid structure polymer nano-microspheres obtained is dissolved in 50-100mL deionized water stand-by;
(3) measure the core-shell nano microballoon emulsion that 10-30mL step (2) obtains, the fluorescence molecule B taking 2-10 μm of ol joins in this core-shell nano microballoon emulsion, at 30-40 DEG C, under the condition of nitrogen protection, reacts 3-8h under magnetic agitation; Finally by the fluorescence molecule B of the non-compound of high speed centrifugation removing liquid phase, obtain two fluorescent core shell polymeric Nano microspheres of fluorescence molecule A and B compound.
The object of the invention is two are to provide a kind of fluorescent material applied in tumor tissues detects, and it is for major ingredient prepares with foregoing pair of fluorescent core shell polymeric Nano microsphere.
Inoculated tumour cell (Tca8113 cells, cervical cancer cell) in the subcutis of nude mice, after 7 days, cell is after diffusion propagation forms tumor tissues, two fluorescent core shell polymeric Nano microspheres step (3) obtained are mixed with the aqueous solution that concentration is 1-5mg/mL, measure 10-40 μ L and be injected into the tumor tissues of nude mice and normal subcutis respectively, carry out slicing treatment respectively after 24h, then carry out imaging by laser confocal microscope.
In aforesaid method, polymerization single polymerization monomer 1 is vinylbenzene (St), fluorostyrene (F-St), methyl methacrylate (MMA) or glycidyl methacrylate (GMA);
In aforesaid method, pH responsiveness polymerization single polymerization monomer 2 is vinylformic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methacrylic acid are received (NaMA) or dimethylaminoethyl methacrylate (DMAEMA);
In aforesaid method, initiator is Potassium Persulphate (K
2s
2o
8), ammonium persulphate ((NH
4)
2s
2o
8), Sodium peroxoborate (NaBO
34H
2o), Sodium Persulfate (Na
2s
2o
8) or azo-bis-isobutyl cyanide (AIBN);
In aforesaid method, fluorescence molecule A can be rare earth compounding RaXnYm, and its Rare Earth Ion Ra can be: europium (Eu), terbium (Tb), thulium (Tm) lanthanum (La), erbium (Er), ytterbium (Yb); First X ligand can be: thenoyltrifluoroacetone (TTA), methyl ethyl diketone (acac), diphenylpropane-1,3-dione(DPPO) (DBM), Whitfield's ointment (sal), the integer of n=1 ~ 3, represents the number of part; Ligands Y can be 1,10-phenanthroline (Phen), the integer of m=0 ~ 1, represents the number of part; Fluorescence molecule A can also be semiconductor nano (CdTe, CdSe, CdS, PbS, PbSe, PbTe, Ag
2s), rhodamine B (RhB), metal nanometre cluster (Au, Ag nano-cluster) etc.;
In aforesaid method, fluorescence molecule B is bromination (N, N, N-triethyl-3-(4-(1, 2-phenylbenzene-2-(4-(2-triethylamine) oxyethyl group) vinyl) vinyl) phenyl) propyl group amine (TAPE), bromination 2, 2 ', 2 ' '-(4, 4 ', 4 ' '-(2-(4-(3-s triethylamine) propyl group) phenyl) 1, 1, 2-triphenyl vinyl three oxygen) three (N, N, N-triethyl ethamine) (TTAPE) or hexaphenyl thiophene cough up (HPS), Silole (silacyclopentadiene) and derivative 1 thereof, 1-bis-[p-(diethylaminomethyl) benzene]-2, 3, 4, 5-tetra-benzo Silole (A
2hPS), 3-(4-(1,2-phenylbenzene-2-(4-sulfo group oxyethyl group) phenyl) vinyl) propyl group-1-sodium sulfonate (TPE).
Tool of the present invention has the following advantages: 1, the Nano microsphere of this pair of fluorescent emission function has sensitive pH response function.Its fluorescence intensity and fluorescence color are with environment pH intelligent control.2, the size of this responsiveness fluorescent nanometer microsphere is little of nano level, is applicable to being applied to multiple detection; 3, the grain size of this responsiveness fluorescent nanometer microsphere can be controlled in 100-500 nanometer; 4, the pH responding range that prepared pH responds fluorescent nanometer microsphere is that 4.0-7.6 presents different fluorescence color; 5, this pH response fluorescent nanometer microsphere has good response function within the scope of wider pH, is the optics that a kind of novel pH detects; 6. this pH responds fluorescent nanometer microsphere and can detect normal and cancer cell tissue by photoluminescent property differentiation, obtains biological detecting function and application.
Accompanying drawing explanation
Fig. 1: be the stereoscan photograph of EuPS/PNIPAM-PAA/TAPE nuclear shell structure nano microballoon prepared by embodiment 1; Nano microsphere uniform particle sizes is approximately 252nm.
Fig. 2: the EuPS/PNIPAM-PAA/TAPE core-shell nano microballoon prepared for embodiment 1 is at the fluorescence spectrum figure of pH:4-7.6 range; Microballoon has excellent fluorescent emission performance at wavelength 468nm and 613nm place, along with pH value reduces, at the fluorescence kept stable at 613nm place, reduces gradually in the fluorescence intensity at 468nm place.
Fig. 3: the EuPS/PNIPAM-PAA/TAPE core-shell nano microballoon prepared for embodiment 1 reduces gradually with pH:7.6-4, presents the fluorescence color that purple, cyan, pink colour, redness etc. are different respectively.Show that this fluorescent nanometer microsphere has sensitive pH responsiveness.
Fig. 4: the EuPS/PNIPAM-PAA/TAPE core-shell nano microballoon prepared for embodiment 1 is at the confocal microscope photo of healthy tissues and tumor tissues (Dendritic cell tissue).Present purple fluorescence in healthy tissues, and present pink colour fluorescence at tumor tissues.
Embodiment
Embodiment 1:
(1) the NIPAM monomer taking .4.42mmol is dissolved in 185mL deionized water, joins in the three-necked bottle of 500mL, adds 1.4 × 10
-6the rare earth compounding Eu (TTA) of mol
3the vinylbenzene (St) of Phen, 5mL, under room temperature and nitrogen protection; mechanical stirring (400rpm) 30min; then be warming up to 70 DEG C gradually, add the aqueous solution of 15mL containing initiator potassium persulfate (KPS) 0.3mmol in system, initiated polymerization.Reaction is carried out 12h and is terminated.Obtain the polymer seeds microballoon containing rare earth compounding.Remove the impurity such as unconverted monomer, initiator in liquid phase by high speed centrifugation (18500r/min), then be dissolved in 100mL deionized water stand-by.
(2) the seed microspheres solution that step (1) obtains slowly is poured in the three-necked bottle of 500mL; as seed; by seeded emulsion polymerization synthesis EuPS/PNIPAM-PAA core-shell particles; 40mmolNIPAM is added, the AA of 3mmol, under room temperature and nitrogen protection in system; mechanical stirring (300rpm) 30min; then be warming up to 70 DEG C gradually, add the aqueous solution of 15mL containing initiator potassium persulfate (KPS) 0.3mmol in system, initiated polymerization.Reaction is carried out 12h and is terminated, and obtains the nucleocapsid structure polymer nano-microspheres containing rare earth compounding.Remove the impurity such as liquid phase unconverted monomer, initiator by high speed centrifugation (18800r/min), be dissolved in 100mL deionized water stand-by.
(3) measuring the EuPS/PNIPAM-PAA Nano microsphere that 10mL step (2) obtains pours in the three-necked bottle of 100mL; the TAPE molecule 5.2 μm of ol taking trace put into core-shell nano microballoon emulsion; at 35 DEG C, under the condition of nitrogen protection, magnetic agitation reaction 3h.By high speed centrifugation process, the TAPE molecule in the non-compound of removing liquid phase, obtains fluorescence molecule TAPE and Eu (TTA)
3two fluorescence nucleocapsid Nano microspheres of Phen compound.The fluorescent nanometer microsphere obtained is dissolved in 25mL water.
(4) in the subcutis of nude mice, Tca8113 cells is inoculated, after 7 days, cell is after diffusion propagation forms tumor tissues, two fluorescent core shell polymeric Nano microspheres step (3) obtained are mixed with the solution that concentration is 2mg/mL, measure 20 μ L and inject the tumor tissues of the nude mice of tumour and normal subcutis respectively, carry out slicing treatment respectively after 24h, then carry out imaging by laser confocal microscope.
Embodiment 2:
(1) the NIPAM monomer taking 5mmol is dissolved in 100mL deionized water, joins in the three-necked bottle of 500mL, adds 1.5 × 10
-6the fluorostyrene (F-St) of the CdTe of mol, 5mL, under room temperature under nitrogen protection, mechanical stirring (400rpm) 30min, is then warming up to 70 DEG C gradually, adds 10mL containing initiator Sodium Persulfate (Na
2s
2o
8) aqueous solution of 0.3mmol is in system, initiated polymerization, reaction is carried out 12h and is terminated.The polymer seeds microballoon containing CdTe obtained removes the impurity such as unconverted monomer, initiator in liquid phase by high speed centrifugation (18500r/min), then is dissolved in 100mL deionized water stand-by.
(2) the seed microballoon emulsion that step (1) obtains slowly is poured in the three-necked bottle of 500mL; as seed; by seeded emulsion polymerization synthesis CdTe-PFS/PNIPAM-PMAA core-shell particles; 45mmolNIPAM is added in system; the MAA of 3.5mmol, under room temperature and nitrogen protection, mechanical stirring (300rpm) 30min; then be warming up to 70 DEG C gradually, add 15mL containing initiator Sodium Persulfate (Na
2s
2o
8) aqueous solution of 0.6mmol in system, initiated polymerization.Reaction is carried out 12h and is terminated, and obtains the nucleocapsid structure polymer nano-microspheres containing CdTe.Remove the impurity such as liquid phase unconverted monomer, initiator by high speed centrifugation (18800r/min), be dissolved in 100mL deionized water stand-by.
(3) measuring the CdTe-PFS/PNIPAM-PMAA Nano microsphere that 10mL step (2) obtains pours in the three-necked bottle of 100mL; the d-TPE molecule 5.2 μm of ol taking trace put into core-shell nano microballoon emulsion; at 35 DEG C, under the condition of nitrogen protection, magnetic agitation reaction 5h.By high speed centrifugation process, in removing liquid phase, the HPS molecule of non-compound, obtains two fluorescent core shell structure polymer nano-microspheres of fluorescence molecule HPS and CdTe compound.The fluorescent nanometer microsphere obtained is dissolved in 350mL water.
(4) in the subcutis of nude mice, Tca8113 cells is inoculated, after 7 days, cell is after diffusion propagation forms tumor tissues, two fluorescent core shell polymeric Nano microspheres step (3) obtained are mixed with the solution that concentration is 3mg/mL, measure 30 μ L and inject the tumor tissues of the nude mice of tumour and normal subcutis respectively, carry out slicing treatment respectively after 24h, then carry out imaging by laser confocal microscope.
Embodiment 3:
(1) the NIPAM monomer taking 5mmol is dissolved in 190mL deionized water, joins in the three-necked bottle of 500mL, adds 2 × 10
-6the RhB of mol; the vinylbenzene (St) of 5mL; under room temperature and nitrogen protection; mechanical stirring (400rpm) 30min; then 70 DEG C are warming up to gradually; add the aqueous solution of 10mL containing initiator ammonium persulfate (APS) 0.3mmol in system, initiated polymerization, reaction is carried out 12h and is terminated.The polymer seeds microballoon containing RhB obtained.Remove the impurity such as liquid phase unconverted monomer, initiator by high speed centrifugation (18500r/min), then be dissolved in 100mL deionized water stand-by.
(2) the seed microspheres solution that step (1) obtains slowly is poured in the three-necked bottle of 500mL; and as seed; by seeded emulsion polymerization synthesis RhB-PS/PNIPAM-PMAA core-shell particles; 40mmolNIPAM is added in system; the MAA of 3.2mmol; under room temperature and nitrogen protection; mechanical stirring (300rpm) 30min; then 70 DEG C are warming up to gradually; add the aqueous solution of 15mL containing initiator ammonium persulfate (APS) 0.6mmol in system, initiated polymerization.Reaction is carried out 12h and is terminated, and obtains the nucleocapsid structure polymer nano-microspheres containing RhB.Remove the impurity such as liquid phase unconverted monomer, initiator by high speed centrifugation (18800r/min), be dissolved in 100mL deionized water stand-by.
(3) measuring the RhB-PS/PNIPAM-PMAA Nano microsphere that 10mL step (2) obtains pours in the three-necked bottle of 100mL; the d-TPE molecule 5.2 μm of ol taking trace put into core-shell nano microballoon emulsion; at 35 DEG C, under the condition of nitrogen protection, magnetic agitation reaction 5h.By high speed centrifugation process, the TTAPE molecule of the non-compound of removing liquid phase, obtains two fluorescent core shell polymeric Nano microspheres of fluorescence molecule TTAPE and RhB compound.The fluorescent nanometer microsphere obtained is dissolved in 30mL water.
(4) in the subcutis of nude mice, cervical cancer cell is inoculated, after 7 days, cell is after diffusion propagation forms tumor tissues, two fluorescent core shell polymeric Nano microspheres step (3) obtained are mixed with the solution that concentration is 5mg/mL, measure 10 μ L and inject the tumor tissues of the nude mice of tumour and normal subcutis respectively, carry out slicing treatment respectively after 24h, then carry out imaging by laser confocal microscope.
Claims (5)
1. two fluorescent emission polymer nano-microspheres for pH response, is characterized in that: prepared by following steps:
(1) the N-isopropylacrylamide NIPAM monomer taking 2-10mmol is dissolved in the deionized water of 100-200mL, then adds the polymerization single polymerization monomer 1,1 × 10 of 10-50mmol
-6-5 × 10
-6the fluorescence molecule A of mol, under room temperature and nitrogen protection, mechanical stirring 30-60min; Then be warming up to 60-70 DEG C gradually, add the aqueous solution of 5-15mL containing 0.3-0.6mmol initiator, initiated polymerization, after reaction 12-24h, obtain the polymer seeds microballoon containing fluorescence molecule A; Comprise unconverted monomer, initiator at interior impurity finally by high speed centrifugation removing liquid phase, the more centrifugal polymer seeds microballoon containing fluorescence molecule A obtained is dissolved in 50-100mL deionized water stand-by;
(2) in the polymer seeds microspheres solution of step (1), the polymerization single polymerization monomer 1 of 10-60mmol and the pH responsiveness polymerization single polymerization monomer 2 of 1-5mmol is added, under room temperature and nitrogen protection, mechanical stirring 30-60min, then 70-85 DEG C is warming up to gradually, add the aqueous solution of 15mL containing 0.5 – 1.5mmol initiator, initiated polymerization, obtains the polymer nano-microspheres of nucleocapsid structure after reaction 12-24h; Comprise unconverted monomer, initiator at interior impurity finally by high speed centrifugation removing liquid phase, the more centrifugal nucleocapsid structure polymer nano-microspheres obtained is dissolved in 50-100mL deionized water stand-by;
(3) measure the core-shell nano microballoon emulsion that 10-30mL step (2) obtains, the fluorescence molecule B taking 2-10 μm of ol joins in this core-shell nano microballoon emulsion, at 30-40 DEG C, under the condition of nitrogen protection, reacts 3-8h under magnetic agitation; Finally by the fluorescence molecule B of the non-compound of high speed centrifugation removing liquid phase, obtain two fluorescent core shell polymeric Nano microspheres of fluorescence molecule A and B compound;
Wherein, polymerization single polymerization monomer 1 is vinylbenzene, fluorostyrene, methyl methacrylate or glycidyl methacrylate; PH responsiveness polymerization single polymerization monomer 2 is vinylformic acid, methacrylic acid, methyl acrylate, sodium methacrylate or dimethylaminoethyl methacrylate;
Fluorescence molecule A is rare earth compounding RaXnYm, semiconductor nano, rhodamine B or metal nanometre cluster; Wherein, Ra is europium, terbium, thulium, lanthanum, erbium or ytterbium; First X ligand is thenoyltrifluoroacetone, methyl ethyl diketone, diphenylpropane-1,3-dione(DPPO) or Whitfield's ointment, n=1-3; Ligands Y is 1,10-phenanthroline, m=0-1;
Fluorescence molecule B is bromination (N, N, N-triethyl-3-(4-(1, 2-phenylbenzene-2-(4-(2-triethylamine) oxyethyl group) vinyl) vinyl) phenyl) propyl group amine, bromination 2, 2 ', 2 "-(4, 4 ', 4 "-(2-(4-(3-s triethylamine) propyl group) phenyl) 1, 1, 2-triphenyl vinyl three oxygen) three (N, N, N-triethyl ethamine), hexaphenyl thiophene is coughed up, Silole, 1, 1-bis-[p-(diethylaminomethyl) benzene]-2, 3, 4, 5-tetra-benzo Silole or 3-(4-(1, 2-phenylbenzene-2-(4-sulfo group oxyethyl group) phenyl) vinyl) propyl group-1-sodium sulfonate.
2. two fluorescent emission polymer nano-microspheres of a kind of pH response as claimed in claim 1, is characterized in that: semiconductor nano is CdTe, CdSe, CdS, PbS, PbSe or PbTe.
3. two fluorescent emission polymer nano-microspheres of a kind of pH response as claimed in claim 1, is characterized in that: metal nanometre cluster is Au nano-cluster or Ag nano-cluster.
4. two fluorescent emission polymer nano-microspheres of a kind of pH response as claimed in claim 1, is characterized in that: initiator is Potassium Persulphate K
2s
2o
8, ammonium persulphate (NH
4)
2s
2o
8, Sodium peroxoborate NaBO
34H
2o, Sodium Persulfate Na
2s
2o
8or Diisopropyl azodicarboxylate AIBN.
5. the fluorescent material applied in detecting for the preparation of tumor tissues of two fluorescent emission polymer nano-microspheres of a kind of pH response of Claims 1 to 4 described in any one.
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