CN103254371B - Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic - Google Patents
Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic Download PDFInfo
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- CN103254371B CN103254371B CN201210270478.7A CN201210270478A CN103254371B CN 103254371 B CN103254371 B CN 103254371B CN 201210270478 A CN201210270478 A CN 201210270478A CN 103254371 B CN103254371 B CN 103254371B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000010189 synthetic method Methods 0.000 title claims description 12
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229920001519 homopolymer Polymers 0.000 claims abstract description 8
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 9
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 7
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012987 RAFT agent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000004043 responsiveness Effects 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract 3
- -1 2-benzimidazolyl-beta-naphthyl group Chemical group 0.000 abstract 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 21
- 230000008859 change Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 230000004936 stimulating effect Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
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- 238000000967 suction filtration Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- PAOHHYDZFURJKA-UHFFFAOYSA-N 2-naphthalen-1-yl-1h-benzimidazole Chemical compound C1=CC=C2C(C=3NC4=CC=CC=C4N=3)=CC=CC2=C1 PAOHHYDZFURJKA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a method for synthesizing an amphiphilic block polymer with near-infrared fluorescence characteristics, which comprises the steps of synthesizing a functional monomer VDHBI containing a 2-benzimidazolyl-beta-naphthyl group by the solid-phase reaction of naphthoic acid and o-phenylenediamine, carrying out RAFT polymerization by respectively taking N-isopropylacrylamide (NIPAM) and the VDHBI as monomers and taking alpha-dithionaphthoic acid isobutyronitrile ester (CPDN) as an RAFT reagent to obtain a homopolymer PNIPAM, and carrying out RAFT polymerization by taking the PNIPAM as a macromolecular RAFT reagent and the VDHBVDI as a second monomer to synthesize the amphiphilic block polymer PNIPAM-b-PVDHBI. The scheme of the invention provides a method for preparing a near-infrared fluorescent amphiphilic block polymer with controllable molecular weight and narrow molecular weight distribution and delicate structure by an active/controllable free radical polymerization method, and also provides a novel method for synthesizing the near-infrared fluorescent amphiphilic block polymer with multiple stimulus responsiveness.
Description
Technical field
The invention belongs to high molecular polymer field, be specifically related to a kind of synthetic method having the Amphipathilic block polymer of near-infrared fluorescent characteristic.
Background technology
Stimulating responsive compound becomes the focus that people pay close attention in recent years, mainly a class is under the small stimulus of external environment (as light, temperature, pH, ionic strength, Electric and magnetic fields etc.) effect for it, and the compound of reversible or irreversible change accordingly can occur for some physics of self or chemical property.When these stimulus signals change, self property such as phase, shape, surface energy, speed of reaction, infiltration rate or the recognition performance etc. of compound can change thereupon.Based on the physics and chemistry character behavior of responsiveness compound uniqueness, they play a significant role at detection and sensory field.
The small-molecule chemical sensor of stimulating responsive, have low consumption, high sensitivity and advantage easy and simple to handle, but small-molecule chemical sensor also has many defects, and as poor in poorly water-soluble, structural stability and Post functionalization is more difficult etc.Take amphipathic nature block polymer as the focus that elementary cell obtains that the macromolecular material of stimulating responsive is current research.If the fluorescent signal primitive with sensitive response is incorporated in polymkeric substance, the subtle change of environment then can change the noticeable change of polymer fluorescent signal into, based on this mechanism, just the fluorescence response sensor of microenvironment sensitivity can be constructed, wherein more common to the fluorescence response sensor of temperature, pH, light and metal ion microenvironment sensitivity.
NIPA (NIPAM) molecule is 32
oa minimum critical inversion temperature (Lower Critical Solution Temperature, LCST) is had near C.Lower than this temperature, NIPAM molecule, due to the hydrogen bond action between water molecules, presents wetting ability.Higher than this temperature, hydrogen bond action is destroyed, and NIPAM then presents hydrophobicity.Detect analytical technology relative to other, fluorescence sense technology is combined with the Thermo-sensitive of NIPAM, has more susceptibility and selectivity.The people such as Li (see: Li, C. H.; Liu, S. Y.
j. Mater. Chem. 2010, 20,10716 – 10723) report and obtained close to monodispersed temperature-sensitive nano gel by the letex polymerization of NIPAM, and load can with Hg
2+the fluorescent monomer (NPTUA) of reaction.During room temperature, this nanogel is as just the Hg of proportional-type
2+detector, when temperature is higher than phase transition temperature, Hg
2+the susceptibility detected can be much improved.Jo W. H. etc. (see: Hong S. W., Kim D. Y., Lee J. U., Jo W. H.
macromolecules 2009, 42,2756 – 2761) and use pyrene and C respectively at PNIPAM chain two ends
60fluorescent chromophore is modified, and has synthesized temperature sensing polymer Py-PNIPAM-C
60, when temperature is lower than its critical inversion temperature (LCST), two fluorophors are distant, and cancellation efficiency is lower; And when temperature is higher than LCST, polymer chain occurs folding, Terminal fluorescent group space length reduces, and cancellation efficiency increases greatly, and fluorescence intensity obviously reduces.The people such as Li (see: Li C. H., Zhang Y. X., Hu J.M., Cheng J. J., Liu S. Y.
angew. Chem. Int. Ed. 2010, 49,5120 – 5124) and report stimulating responsive amphiphilic block copolymer based on many chromic systems, this polymkeric substance is proved and can realizes the reversible three grade conversions of fluorescent emission (green, yellow, orange and red) under temperature, pH and illumination.
At biological field, the stimulating responsive polymer containing PNIPAM segment also has good application.The people such as Liu (see: Zhang J. Y., Jiang X., Zhang Y. F., Li Y. T., Liu S. Y.
macromolecules 2007, 9125 – 9132) and the method that reports use shell/core crosslinked obtains the good Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PEO-of structural stability
b-P (NIPAM-
co-NAS)).That this polymkeric substance can carry out the shell core of completely reversibility is crosslinked/separate crosslinked, and have thermal control swelling/deswelling behavior, thus in drug delivery, biological detection, have potential application.
Current use is the many problems of organic fluorescent dye (operation interval is mostly in UV-visible region) for existing during fluoroscopic examination in organism widely, and it is inadequate etc. that the background interference being difficult to enter some composition in biological tissue inside, biological sample as: light makes fluorescence detection efficiency greatly reduce, ultraviolet-visible enters the degree of depth in organism.The existence of these problems makes fluorescence imaging method application in vivo become especially difficulty.But, the fluoroscopic examination near infrared spectrum district (700-900 nm) can avoid self interference of biomolecules, luminous energy penetrates into organization internal and obtains higher sensitivity for analysis, is more applicable to biological tissue's Angiographic, thus carries out biological detection and medical diagnosis on disease.Therefore, based on the responsiveness compound of near-infrared fluorescent mark, be more suitable for biological tissue imaging, at biological field, there is unique advantage.
The advantage of micromolecular near infrared fluorescent probe in biological tissue's radiography clearly, but also also exists many deficiencies, and as the light, heat, unstable chemcial property etc. of these compounds, and kind is few, synthesizes also more difficult.With small molecular phase ratio, near infrared fluorescent probe polymkeric substance has low toxicity, the unique advantage such as good solubility and stability, and by the different water miscible block polymer of synthesis, the self-assembly of polymkeric substance can be implemented, thus regulate and control the chain conformation of polymkeric substance and configuration makes it have response performance widely simple and effectively.Compared with the Small-molecule probe of development relative maturity, detection system based on polymer probe is still in the early stage of development, therefore, the responsive polymer based near infrared fluorescent probe that processability is excellent, futuramic and efficient detection system, to realize accurate detection to glucose, bioactive small molecule and the concentration of other biomacromolecule and the subtle change of gradient and examination, become the important research work that detection and sensory field are paid close attention to.
Summary of the invention
The object of this invention is to provide a kind of synthetic method having the Amphipathilic block polymer of near-infrared fluorescent characteristic.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
There is a synthetic method for the Amphipathilic block polymer of near-infrared fluorescent characteristic, adopt the preparation of RAFT synthetic method to have the Amphipathilic block polymer PNIPAM-of near-infrared fluorescent performance
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bthe molecular weight distribution of-PVDHBI (
m w/
m n) below 1.4, specifically comprise the following steps:
Step 1) by the solid state reaction kinetics 2-benzimidazolyl-of O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
intermediate, then use p-chloromethyl styrene (VBC) and VNBI be obtained by reacting monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
;
Step 2) be monomer with NIPAM, take CPDN as RAFT reagent, obtain homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is Macro RAFT agent with PNIPAM, is that second comonomer carries out RAFT polymerization with VDHBI, synthesizes above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
The building-up reactions formula of step (1), (2), (3):
Further, described intermediate VNBI in described step (1) is when temperature is 180 DEG C by the solid state reaction kinetics of 20 minutes, described homopolymer PNIPAM in described step (2) synthesizes when temperature is 70 DEG C, the Amphipathilic block polymer PNIPAM-in described step (3)
b-PVDHBI synthesizes when 70 DEG C.
The invention has the beneficial effects as follows:
Adopt technical solution of the present invention, provide a kind of by " activity "/controllable free radical polymerization process, prepare the controlled near-infrared fluorescent polymkeric substance with the structure exquisiteness of narrow molecular weight distribution of molecular weight, the CH of the Amphipathilic block polymer of synthesis
2cl
2solution or the aqueous solution all have stronger fluorescent emission at ultraviolet region (near 380nm) and near-infrared region (near 750nm), environmental change to external world simultaneously, as temperature and pH change all have certain responsiveness, also provide a kind of novel method with multiple stimulation responsiveness near-infrared fluorescent Macroscopic single crystal.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, and preferred embodiment of the present invention also coordinates accompanying drawing to be described in detail as follows.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide a further understanding of the present invention, and form a application's part, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is block polymer PNIPAM-in embodiment two
btetrahydrofuran (THF) (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) of-PVDHBI is along with the Fluorescence Increasing collection of illustrative plates (laser wavelength lambda of deionized water adding different ratios
ex =303nm);
Fig. 2 is block polymer PNIPAM-in embodiment two
btetrahydrofuran (THF) (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) of-PVDHBI is along with the Fluorescence Increasing collection of illustrative plates (laser wavelength lambda of deionized water adding different ratios
ex =600nm);
Fig. 3 is block polymer PNIPAM-in embodiment two
btetrahydrofuran (THF) (THF) solution (starting point concentration of polymkeric substance is 0.5mg/mL) of-PVDHBI is along with the Fluorescence Increasing collection of illustrative plates of deionized water and dynamic light scattering (DLS) graphic representation that add different ratios;
Fig. 4 is block polymer PNIPAM-in embodiment three
bthe THF/ aqueous solution (starting point concentration of polymkeric substance is 0.3mg/mL) of-PVDHBI, fluorescent emission collection of illustrative plates (excitation wavelength lambda at various ph values
ex =303nm);
Fig. 5 is block polymer PNIPAM-in embodiment three
bthe THF/ aqueous solution (starting point concentration of polymkeric substance is 0.3mg/mL) of-PVDHBI, exchanges at pH=3 and pH=9 the fluorescence intensity become when replacing and replys figure;
Fig. 6 is the block polymer PNIPAM-of different concns in embodiment four
bthe transmittance variation with temperature collection of illustrative plates of-PVDHBI aqueous solution;
Fig. 7 is the block polymer PNIPAM-of different pH in embodiment four
b((concentration of polymkeric substance is 0.1mg/mL, λ to the fluorescence intensity variation with temperature collection of illustrative plates of-PVDHBI aqueous solution
ex =303nm).
All figure are at block polymer PNIPAM-above
b-PVDHBI's
m n, GPC=14200 g/mol,
m w/
m nproduce when=1.31.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
There is a synthetic method for the Amphipathilic block polymer of near-infrared fluorescent characteristic, adopt the preparation of RAFT synthetic method to have the Amphipathilic block polymer PNIPAM-of near-infrared fluorescent performance
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bthe molecular weight distribution of-PVDHBI (
m w/
m n) below 1.4, specifically comprise the following steps:
Step 1) by the solid state reaction kinetics 2-benzimidazolyl-of O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
intermediate, then use p-chloromethyl styrene (VBC) and VNBI be obtained by reacting monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
;
Step 2) be monomer with NIPAM, take CPDN as RAFT reagent, obtain homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is Macro RAFT agent with PNIPAM, is that second comonomer carries out RAFT polymerization with VDHBI, synthesizes above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
The building-up reactions formula of step (1), (2), (3):
Further, described monomer VNBI in described step (1) is when temperature is 180 DEG C by the solid state reaction kinetics of 20 minutes, described homopolymer PNIPAM in described step (2) synthesizes when temperature is 70 DEG C, the Amphipathilic block polymer PNIPAM-in described step (3)
b-PVDHBI synthesizes when 70 DEG C.
The embodiment of the present embodiment is as follows:
Embodiment one:
1, the synthesis of monomer VDHBI mainly contains two steps:
(1) by O-Phenylene Diamine with
βafter-naphthoic acid mixes, load in 10mL ampere bottle, then add polyphosphoric acid.In the oil bath of about 180 DEG C, vacuumize and react about 30min.Reaction terminates rear naturally cooling, adds DMSO and dissolves.Solution is poured in deionized water, stirs, and occurs precipitation.Suction filtration obtains filter cake, and suction filtration after washing, obtains sterling with dehydrated alcohol recrystallization.
(2) in three neck round-bottomed flasks, DMF is added, intermediate
α-benzimidazolyl-naphthalene, K
2cO
3(grinding is thin), stirs about 20min until all dissolve.Add p-chloromethyl styrene (VBC), be heated to 38 DEG C ~ 42 DEG C, react more than 48h at this temperature.Point plate controls reaction end, and column chromatography is purified.
2, the RAFT method synthesis of polymkeric substance
(1) the RAFT polymerization of PNIPAM
By proportioning [NIPAM]
0: [AIBN]
0: [CPDN]
0=100:1:3, adds NIPAM, CPDN and AIBN, and adds DMF and dissolve, bubbling argon 15 minutes to remove oxygen, then tube sealing.The oil bath that ampere bottle is placed in 70 DEG C is polymerized.Take out after the reaction scheduled time, open sealing after being placed in ice-water bath cooling, with a small amount of THF dissolve polymer, then polymers soln is poured in a large amount of anhydrous diethyl ether and precipitate, collected by suction filter cake.Polymkeric substance is dried to constant weight in 50 DEG C of baking ovens.
(2) PNIPAM-
bthe RAFT polymerization of-PVDHBI
Take VDHBI as monomer, PNIPAM is RAFT reagent, and AIBN is initiator, and RAFT polymerization in DMF solution, the RAFT solution polymerization of its operating process and NIPAM is similar, and typical proportioning is [VDHBI]
0: [AIBN]
0: [PNIPAM]
0=15:1:3.
Table 1. uses gel chromatography (GPC) to test the homopolymer PVDHBI, PNIPAM and the block polymer PNIPAM-that obtain
bthe number-average molecular weight of-PVDHBI (
m n, GPC) and molecular weight distribution (
m w/
m n)
| Sample | M n, GPC (g.mol -1) | M w/ M n |
| PNIPAM | 11620 | 1.16 |
| PNIPAM 102- b-PVDHBI 7 | 14200 | 1.31 |
Embodiment two: block polymer PNIPAM-
bthe self-assembly performance test of-PVDHBI
At block polymer PNIPAM-
bin-PVDHBI structure, VDHBI segment is hydrophobic, and NIPAM segment is hydrophilic.As can be seen from Fig. 1, Fig. 2 and Fig. 3, in the THF solution of block polymer, along with the volume of the water added increases gradually, the fluorescence intensity of polymers soln also strengthens gradually, this is because polymkeric substance there occurs self-assembly in the mixing solutions of water and THF.When the volume of water is 70% of THF volume, fluorescence intensity reaches maximum value.Meanwhile, as can be seen from (Fig. 3) in DLS graphic representation, polymer particle sizes increases along with amount of water and increases, and confirms that polymkeric substance is assembled in the solution.
Embodiment three: block polymer PNIPAM-
bthe pH sensitivity tests of-PVDHBI
Due to nitrogen atom on benzoglyoxaline, when changing the pH of polymkeric substance THF solution, there is significantly change in its fluorescence intensity.As can be seen from Fig. 4 and Fig. 5, block polymer solution is along with the increase of pH or reduction, and its fluorescence intensity change is obvious, and can by by force to weak or grow from weak to strong and repeatedly repeatedly change.When solution becomes alkalescence from neutrality, the change in fluorescence of polymers soln is little.Solution be acidity namely when pH value reduces gradually, the nitrogen-atoms on benzoglyoxaline is protonated gradually, cause the fluorescence emission peak red shift gradually of polymers soln, and fluorescence intensity increases gradually.When pH value is about 3, fluorescence intensity reaches maximum value.
Embodiment four: block polymer PNIPAM-
bthe temperature sensitivity test of-PVDHBI
Due to the Thermo-sensitive of NIPAM, along with the rising of temperature, block polymer PNIPAM-
b-PVDHBI aqueous solution transmittance declines (Fig. 6) gradually.This is because NIPAM segment is in extended configuration when temperature is lower, and is in contraction schedule when temperature is higher.After temperature raises, the hydrogen bond formed between NIPAM segment and water molecules is destroyed, and causes polymkeric substance to be assembled in the solution, thus there occurs phase in version.Therefore, aqueous solutions of polymers becomes muddy gradually due to the scattering of light effect of aggregate.After temperature is returned to room temperature, solution becomes clarification again.
Along with the rising of temperature, the block polymer PNIPAM-under condition of different pH
bthe fluorescence intensity of-PVDHBI the aqueous solution all presents the trend (Fig. 7) first reducing to increase afterwards.As we can see from the figure, when temperature is by 25
oc is heated to 35
oin the process of C, the fluorescence intensity of aqueous solutions of polymers reduces slowly.This may be that PVDHBI is core, PNIPAM is the micella of shell because block polymer defines in aqueous, and NIPAM segment shrinks gradually in temperature-rise period, causes PVDHBI core to be exposed in the larger water of polarity, and polymers soln fluorescence reduces.When temperature is higher than 35
oduring C, the NIPAM segment surrounding PVDHBI core shrinks further and becomes hydrophobic, causes polarity around core to reduce, thus the fluorescence intensity of polymers soln strengthens.
In sum, this patent by reversible addion-fragmentation chain transfer (RAFT) active free radical polymerization obtain on side chain containing 2-benzimidazolyl--
βthe near-infrared fluorescent polymer P NIPAM-of-naphthylene group
b-PVDHBI.The CH of polymkeric substance
2cl
2solution all has stronger fluorescent emission at ultraviolet region (near 380nm) and near-infrared region (near 750nm), and meanwhile, this polymkeric substance is at THF/H
2there is in O mixing solutions aggregation inducing Enhancement of Fluorescence.Owing to benzoglyoxaline containing tertiary N atom, PNIPAM-
b-PVDHBI is at CH
2cl
2fluorescent emission in solution has pH susceptibility.Because NIPAM has responsiveness to temperature, polymer P NIPAM-
bthe fluorescent emission of-PVDHBI in THF/ water mixed solution also can change along with temperature.This patent provides a novel new synthetic method with the near-infrared fluorescent polymkeric substance of multiple stimulation responsiveness.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. there is a synthetic method for the Amphipathilic block polymer of near-infrared fluorescent characteristic, adopt the preparation of RAFT synthetic method to have near-infrared fluorescent performance Amphipathilic block polymer PNIPAM-
b-PVDHBI, the structural formula of described polymkeric substance is:
Described Amphipathilic block polymer PNIPAM-
bthe molecular weight distribution of-PVDHBI (
m w/
m n) below 1.4, specifically comprise the following steps:
Step 1) by the solid state reaction kinetics 2-benzimidazolyl-of O-Phenylene Diamine and naphthoic acid-
β-naphthalene (VNBI)
intermediate, then use p-chloromethyl styrene (VBC) and VNBI be obtained by reacting monomer 1-(4-vinyl benzyl)-2-benzimidazolyl--
β-naphthalene (VDHBI)
;
Step 2) be monomer with NIPAM, take CPDN as RAFT reagent, obtain homopolymer PNIPAM by RAFT active free radical polymerization method;
Step 3) is Macro RAFT agent with PNIPAM, is that second comonomer carries out RAFT polymerization with VDHBI, synthesizes above-mentioned Amphipathilic block polymer PNIPAM-
b-PVDHBI.
2. the synthetic method with the Amphipathilic block polymer of near-infrared fluorescent characteristic according to claim 1, the building-up reactions formula of described step (1), (2), (3):
It is characterized in that: the described intermediate VNBI in described step (1) is when temperature is 180 DEG C by the solid state reaction kinetics of 20 minutes, homopolymer PNIPAM in described step (2) synthesizes when temperature is 70 DEG C, the Amphipathilic block polymer PNIPAM-in described step (3)
b-PVDHBI synthesizes when 70 DEG C.
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