CN110551263A - multi-block polymer, synthesis method thereof and fluorescent probe for tumor detection - Google Patents
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Abstract
The invention discloses a multi-block polymer, a synthesis method thereof and a fluorescent probe for tumor detection, wherein the multi-block polymer is a carbon dioxide stimulus response multi-block polymer, has good supermolecule assembly characteristics and biocompatibility, can form a macromolecular assembly body after absorbing carbon dioxide, generates aggregation induced luminescence phenomenon, and emits bright blue light under the irradiation of high-energy light (such as ultraviolet light); and nitrogen is introduced to restore the size of the supermolecule assembly body formed by the multi-block polymer to the state before carbon dioxide is absorbed, so that blue light disappears. Therefore, the multi-block polymer can be applied to the preparation of a fluorescent probe for tumor detection, and can be used for the fluorescent diagnosis of cancer cells or tissues.
Description
Technical Field
The invention relates to the technical field of biology, in particular to a multi-block polymer, a synthetic method thereof and a fluorescent probe for tumor detection.
background
optical probe imaging has the advantages of high selectivity, high resolution, non-invasive, real-time, etc., and is an important and rapidly developing field of research that encourages continued cooperation among chemists, biologists, and clinicians to further refine optical probes for cancer diagnosis, treatment, and interventional procedures, etc. Carbon dioxide is an important gas molecule metabolite produced by the tricarboxylic acid cycle (energy metabolic pathway of sugar, lipid and amino acid) in the aerobic respiration process of cells, and the carbon dioxide metabolized by the cells directly reflects the activity of the tricarboxylic acid cycle in the cells. Tumor cells have a higher metabolic rate, i.e., a higher rate of carbon dioxide production, than normal cells. Thus, the carbon dioxide content in the tissue and the environment surrounding the cells is an important parameter for identifying cancer cells and cancer tissues.
traditional carbon dioxide measurement methods, such as electrochemistry, infrared, gas chromatography-mass spectrometry and field effect transistors, have been successfully applied in the external environment, in particular in mines, sewers, oil wells, tunnels, ships (submarines) and space capsules for detecting carbon dioxide concentrations. However, these conventional carbon dioxide measurement methods are not suitable as a biological probe responding to stimulation of carbon dioxide due to problems of poor biocompatibility, over-size, and the like.
In recent years, organic carbon dioxide reactive molecular systems have attracted considerable attention. However, it is not sufficient for the biological probe to effectively interact with and collect the substance to be detected. Fast, non-destructive, real-time response signals are also important for cancer diagnosis, treatment, and surgery. Aggregation-induced emission is a promising bioluminescent probe technology, but no aggregation-induced emission bioluminescent probe that can effectively detect cancer cells or tissues in response to carbon dioxide stimulation has been developed.
disclosure of Invention
In order to solve the technical problems, the invention provides a multi-block polymer, a synthetic method thereof and a fluorescent probe for tumor detection.
The technical scheme adopted by the invention is as follows: a multi-block polymer, which is a carbon dioxide stimuli-responsive multi-block polymer having the chemical formula:
Wherein m is an integer of 1 to 50, and n is an integer of 1 to 100; p is an integer of 1-50;
the structural formula of A is:
wherein n 1 is an integer of 1-20;
The structural formula of B is:
the structural formula of C is:
wherein n 2 is an integer of 1-20.
preferably, the number average molecular weight of the multi-block polymer is 20000 to 100000. The molecular weight of the multiblock polymer can be specifically determined by GPC.
the invention also provides a synthesis method of the multi-block polymer, which comprises the following steps:
(1) The synthesis of 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene includes the steps of setting flask containing Zn and tetrahydrofuran in ice water bath, adding TiCl 4 for reflux, adding mixed solution of benzophenone and 4-hydroxybenzophenone, reflux and purification;
(2) synthesizing 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene, which comprises mixing the 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene prepared in the step (1) with Na 2 CO 3, 11-bromo-1-undecanol and potassium iodide, fully reacting at 100-110 ℃, and purifying;
(3) the synthesis of 4-undecoxy tetraphenyl methacrylate vinyl ester comprises the following steps: adding the 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene prepared in the step (2) and methacryloyl chloride into a dichloromethane solution, and fully stirring for reaction; then purifying;
(4) the synthesis of polytetrafluoroethylene comprises the following steps: fully reacting the 4-undecyloxy tetraphenyl methacrylate prepared in the step (3) with 2- (dodecyl thiocarbonylthio) -2-methylpropanoic acid at 50-70 ℃, and then purifying;
(5) Synthesis of a Poly PTPE-b- (4-vinylbenzyl chloride) block polymer comprising: carrying out polymerization reaction on the polytetrafluoroethylene prepared in the step (4) and 4-vinyl benzyl chloride;
(6) Synthesis of a poly PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer, comprising: carrying out polymerization reaction on the PTPE-b- (4-vinylbenzyl chloride) block polymer prepared in the step (5) and a PEO precursor;
(7) synthesizing a poly-PTPE-b- (4-vinylbenzyl azide) -b-PEO block polymer, which comprises mixing the poly-PTPE-b- (4-vinylbenzyl azide) -b-PEO block polymer prepared in the step (6) with NaN 3 for reaction;
(8) the synthesis of N' -propyne-N, N-dimethylacetamide comprises the following steps: mixing and reacting propynylamine and N, N-dimethylacetamide dimethyl acetal;
(9) The synthesis of multi-block polymer poly-PTPE-b-PAD-b-PEO comprises: and (3) carrying out polymerization reaction on the PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer prepared in the step (7) and the N' -propyne-N, N-dimethylacetamide prepared in the step (8).
Preferably, in step (1), the stoichiometric ratio of benzophenone to 4-hydroxybenzophenone is 1: 1;
In the step (2), the stoichiometric ratio of 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene to 11-bromo-1-undecanol and potassium iodide is 1: 1.2: 0.005;
in the step (3), the stoichiometric ratio of 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene to methacryloyl chloride is 4: 1;
in the step (4), the stoichiometric ratio of 4-undecyloxy tetraphenyl vinyl methacrylate to 2- (dodecylthiocarbonylthio) -2-methylpropionic acid is 2.5: 1;
in the step (5), the stoichiometric ratio of polytetrafluoroethylene to 4-vinylbenzyl chloride is 1: 0.135 parts by weight;
in the step (6), the stoichiometric ratio of the poly-PTPE-b- (4-vinylbenzyl chloride) block polymer to the PEO precursor is 1: 4;
In the step (7), the stoichiometric ratio of the PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer to NaN 3 is 1: 11.5;
In the step (8), the chemical equivalent ratio of the propynylamine to the N, N-dimethylacetamide dimethylacetal is 1: 2.4;
In step (9), the stoichiometric ratio of the poly-PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer to N' -propyne-N, N-dimethylacetamide is 1: 1.
Preferably, in the step (1), the step (2) and the step (3), the purification is specifically performed by column chromatography.
preferably, in the step (1), the step (2) and the step (3), before the column chromatography purification, extraction and drying treatment are performed.
Further preferably, the extraction is specifically dichloromethane extraction; the drying treatment used magnesium sulfate as the drying agent.
Preferably, in the step (5), the step (6) and the step (9), the polymerization reaction is performed by a RAFT polymerization method.
preferably, in the step (8), the mixing reaction of the propynylamine and the N, N-dimethylacetamide dimethyl acetal is carried out under the protection of a protective atmosphere.
The multi-block polymer can absorb carbon dioxide to form a supermolecule assembly, and the supermolecule assembly can be excited to generate blue light by ultraviolet irradiation; and nitrogen is introduced to restore the size of the supermolecule assembly body formed by the multi-block polymer to the state before carbon dioxide is absorbed, so that blue light disappears. Because the tumor cells have higher metabolic rate and higher carbon dioxide generation rate than normal cells, the multi-block polymer can be applied to the preparation of fluorescent probes for tumor detection based on the responsiveness of the multi-block polymer to carbon dioxide, and can be used for the fluorescent detection and diagnosis of cancer cells or tissues. Therefore, the invention also provides a fluorescent probe for tumor detection, and the material of the fluorescent probe comprises any one of the multi-block polymers.
In addition, the invention also provides a kit for detecting tumors, which comprises any one of the fluorescent probes for detecting tumors.
The beneficial technical effects of the invention are as follows: the invention provides a multi-block polymer, a synthesis method thereof and a fluorescent probe for tumor detection. The diameter of the multi-block polymer is 50-300 nm under the state of not absorbing carbon dioxide, a supermolecule assembly is formed after absorbing the carbon dioxide, the diameter is 100-500, and nitrogen is introduced to restore the size of the supermolecule assembly formed by the multi-block polymer to the size before absorbing the carbon dioxide. Moreover, the multi-block polymer generates aggregation-induced luminescence after absorbing carbon dioxide, emits bright blue light under the irradiation of high-energy light (such as ultraviolet light), and can make obvious blue light disappear after introducing nitrogen. Therefore, the multi-block polymer can be applied to the preparation of a fluorescent probe for tumor detection, and can be used for the fluorescent diagnosis of cancer cells or tissues.
drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below.
FIG. 1 is a process flow diagram for the synthesis of the multiblock polymer of example 1;
FIG. 2 is a transmission electron micrograph and dynamic light scattering measurements of the multiblock polymer of example 1 before and after response to carbon dioxide;
FIG. 3 is a confocal laser photograph of the supramolecular assembly composed of the multi-block polymer in example 1 applied to fluorescence imaging of tumor.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
a multi-block polymer, as shown in FIG. 1, is synthesized by the following steps:
(1) Synthesis of 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene (TPE-OH) A250 ml flask containing zinc (12.8g) and tetrahydrofuran (200ml) was placed in an ice-water bath to stabilize the system temperature in the range of 0 to 10 ℃ and 10.4ml of TiCl 4 was slowly added with a constant pressure dropping funnel, then the ice-water bath was removed and the resulting mixture was refluxed for 2.5 hours, 4ml of pyridine was slowly added to the flask after the mixture was cooled to room temperature, 2.0g of benzophenone and 2.0g of 4-hydroxybenzophenone were dissolved in 20ml of tetrahydrofuran to obtain a mixed solution, then the mixed solution was slowly added to the flask, the resulting mixture was refluxed and after the mixture was cooled to room temperature, a K 2 CO 3 solution was added to terminate the reaction, the solvent was removed by rotary evaporation, the residue was added to water, extracted twice with dichloromethane and the organic phase was dried with magnesium sulfate, and finally purification was carried out by column chromatography to obtain a white solid (1.20 g).
(2) synthesis of 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene (TPE-11-OH) TPE-OH (1.0g) prepared in step (1), excess Na 2 CO 3, 11-bromo-1-undecanol (1.2 equiv.) and potassium iodide (0.005 equiv.) were dissolved in 6ml DMF, the mixture was reacted at 100 ℃ overnight, after the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, the residue was added to water, extracted twice with dichloromethane and the organic phase was dried over magnesium sulfate, and finally purified by column chromatography to give a white solid (0.55 g).
(3) Synthesis of 4-undecoxy tetraphenyl vinyl methacrylate (PM 1): adding 0.5g of TPE-11-OH (prepared in the step (2)) into a dichloromethane solution (5ml), and dropwise adding 125mg of methacryloyl chloride at 0-5 ℃; subsequently, the mixture was stirred at room temperature overnight; after completion of the reaction, the reaction mixture was added to water, extracted twice with dichloromethane, and the organic phase was dried over magnesium sulfate; finally, purification was performed by column chromatography to obtain a yellow liquid (0.5 g).
(4) synthesis of PTPE: dissolving PM1(0.87g) obtained in step (3) and 2- (dodecylmercaptothiosulfanyl) -2-methylpropanoic acid (21.6mg) in 2.5ml of tetrahydrofuran; subsequently, the mixture was degassed by thawing using a freeze pump and the bottle was sealed under vacuum; then placing the sealed bottle in a preheated oil bath (60 ℃) for 2 hours; finally, the solution was precipitated in methanol to finally obtain 0.8g of a pale yellow solid.
(5) synthesis of a Poly PTPE-b- (4-vinylbenzyl chloride) block Polymer (P2): and (3) polymerizing the PTPE prepared in the step (4) and 4-vinylbenzyl chloride by using a RAFT polymerization method. Specifically, PTPE (2.0g), 4-vinylbenzyl chloride (0.27g) and azobisisobutyronitrile AIBN (1.44mg) were dissolved in 2.0ml of toluene to obtain a mixed solution; subsequently, the mixed solution was degassed by thawing using a freeze pump, and the bottle was sealed under vacuum; placing the sealed bottle in a preheated oil bath at 70 ℃ for 2 h; finally, the solution was precipitated in methanol to finally obtain 2.23g of a pale yellow solid.
(6) Synthesis of Poly-PTPE-b- (4-vinylbenzylchloride) -b-PEO Block Polymer (P3): and (3) polymerizing the P2 and the PEO precursor prepared in the step (5) by using a RAFT polymerization method. Specifically, P2(0.1g), a PEO precursor (0.4 g), and azobisisobutyronitrile AIBN (0.5mg) were dissolved in 5.0ml of toluene to obtain a mixed solution; subsequently, the mixed solution was degassed by thawing using a freeze pump, and the bottle was sealed under vacuum; placing the sealed bottle in a preheated oil bath at 70 ℃ for 2 h; finally, the solution was precipitated in methanol; 0.45g of a pale yellow solid was finally obtained.
(7) Synthesis of Poly-PTPE-b- (4-vinylbenzylazide) -b-PEO Block Polymer (P4) P3(0.2g) and NaN 3 (2.3mg) obtained in step (6) were dissolved in 3.0ml of dry DMF, and the mixture was stirred at room temperature for 24 hours, followed by precipitation of the mixture in excess methanol to finally obtain 0.2002g of a pale yellow solid;
(8) synthesis of N' -propyne-N, N-dimethylacetamide (PDAA) propargylamine (0.5g) was dissolved in anhydrous acetonitrile (4.5ml), and then 1.2 equivalents of N, N-dimethylacetamide dimethylacetal was added to the system by means of a syringe, and the mixture was stirred under nitrogen atmosphere at 65 ℃ for 24 hours, and the solvent was removed by rotary evaporation, and purified by basic Al 2 O 3 chromatography to obtain 0.84g of a yellow liquid.
(9) Synthesis of Poly PTPE-b-PAD-b-PEO: and (3) polymerizing the P4 and the CuBr prepared in the step (7) and the PDAA prepared in the step (8) by using a RAFT polymerization method. Specifically, P4(0.2g), CuBr (0.5mg) and PDAA (0.5mg) were dissolved in 4.5ml of DMF and the mixture was stirred for 2 h; subsequently, the mixture was precipitated in excess methanol to finally obtain a multiblock polymer.
The structural formula of the multi-block polymer is as follows:
wherein m is an integer of 1 to 50, and n is an integer of 1 to 100; p is an integer of 1-50;
The structural formula of A is:
wherein n 1 is an integer of 1-20, and n 1 is specifically 11 in the above embodiment according to the selection of raw materials;
the structural formula of B is:
the structural formula of C is:
wherein n 2 is an integer of 1-20, and n 2 is 10 in the above embodiment according to the selection of raw materials.
the super-assembly characteristics of the prepared carbon dioxide stimulus-responsive multi-block polymer are detected, and a projection electron microscope (TEM) and a dynamic light scattering instrument (DLS) are respectively adopted to obtain a projection electron microscope photo of a super-assembly (in a vesicle structure) formed in water before and after the multi-block polymer responds to carbon dioxide and the relevant assembly size, wherein the obtained result is shown in FIG. 2, the projection electron microscope photo of the multi-block polymer in water before responding to carbon dioxide in FIG. 2 is shown in FIG. 18, (a 1) is a projection electron microscope photo of the multi-block polymer in water before responding to carbon dioxide, (a 2) is size data measured by Dynamic Light Scattering (DLS) of the multi-block polymer before responding to carbon dioxide, (b 1) is a projection electron microscope photo of a super-assembly formed in water after the multi-block polymer responds to carbon dioxide, and (b 2) is size data measured by Dynamic Light Scattering (DLS) of the multi-block polymer after responding to carbon dioxide, as can be seen in FIG. 2, the super-assembly formed in water after responding to carbon dioxide, and the size data is shown in the size of 105nm before assembling.
The prepared multi-block polymer is used for in vitro tumor fluorescence imaging, specifically ultraviolet light radiation is adopted, laser confocal photos are respectively taken at different time (1h, 2h and 5h) after carbon dioxide response, the obtained result is shown in figure 3, and in order to meet the submission requirements of an application document, a, b and c in figure 3 are not colored; in practice, the multi-block polymer absorbs carbon dioxide and generates blue light after being excited by ultraviolet light, and the light intensity of a, b and c in fig. 3 is gradually increased. According to the test result, the multi-block polymer has higher carbon dioxide concentration around the cancer cells, responds to carbon dioxide after absorbing carbon dioxide at the cancer cells, generates aggregation induced luminescence phenomenon, emits bright blue light under the irradiation of high-energy light ultraviolet light, and generates strong fluorescence along with the increase of time, so that the multi-block polymer can be used as a tumor detection fluorescent probe for tumor fluorescence imaging identification and diagnosis. The fluorescent probe for tumor detection can be further applied to the preparation of a kit for tumor detection.
the biocompatibility of the prepared multi-block polymer is tested, and specifically, normal cells are placed in the multi-block polymer solution prepared at a certain concentration, and the activity of the cells is tested after a period of time. The experiment shows that: the cell survival rate of normal cells in the multi-block polymer solution with the concentration of 18 mu g/ml for 48 hours is more than 85 percent. Therefore, the multi-block polymer solution prepared by the method has lower biological toxicity and good biocompatibility.
in addition, the capability of the supermolecular assembly to respond to carbon dioxide stimulation and the fluorescence intensity and the luminescence wavelength generated based on the aggregation-induced emission principle after the assembly is formed can be regulated and controlled by regulating different block ratios of the multi-block polymer and changing the structure of the fluorescent unit. For example, the structure of the fluorescent unit in the a block may be changed to a structural unit that fluoresces red under ultraviolet excitation, so that a red fluorescent probe or the like is formed in fluorescence imaging.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A multi-block polymer, wherein the multi-block polymer is a carbon dioxide stimuli responsive multi-block polymer having the chemical formula:
Wherein m is an integer of 1 to 50, and n is an integer of 1 to 100; p is an integer of 1-50;
the structural formula of A is:
Wherein n 1 is an integer of 1-20;
The structural formula of B is:
The structural formula of C is:
Wherein n 2 is an integer of 1-20.
2. the multiblock polymer according to claim 1, wherein the number average molecular weight of the multiblock polymer is 20000 to 100000.
3. the method of synthesizing a multiblock polymer according to claim 1 or 2, comprising the steps of:
(1) The synthesis of 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene includes the steps of setting flask containing Zn and tetrahydrofuran in ice water bath, adding TiCl 4 for reflux, adding mixed solution of benzophenone and 4-hydroxybenzophenone, reflux and purification;
(2) synthesizing 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene, which comprises mixing the 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene prepared in the step (1) with Na 2 CO 3, 11-bromo-1-undecanol and potassium iodide, fully reacting at 100-110 ℃, and purifying;
(3) The synthesis of 4-undecoxy tetraphenyl methacrylate vinyl ester comprises the following steps: adding the 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene prepared in the step (2) and methacryloyl chloride into a dichloromethane solution, and fully stirring for reaction; then purifying;
(4) The synthesis of polytetrafluoroethylene comprises the following steps: fully reacting the 4-undecyloxy tetraphenyl methacrylate prepared in the step (3) with 2- (dodecyl thiocarbonylthio) -2-methylpropanoic acid at 50-70 ℃, and then purifying;
(5) Synthesis of a Poly PTPE-b- (4-vinylbenzyl chloride) block polymer comprising: carrying out polymerization reaction on the polytetrafluoroethylene prepared in the step (4) and 4-vinyl benzyl chloride;
(6) Synthesis of a poly PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer, comprising: carrying out polymerization reaction on the PTPE-b- (4-vinylbenzyl chloride) block polymer prepared in the step (5) and a PEO precursor;
(7) synthesizing a poly-PTPE-b- (4-vinylbenzyl azide) -b-PEO block polymer, which comprises mixing the poly-PTPE-b- (4-vinylbenzyl azide) -b-PEO block polymer prepared in the step (6) with NaN 3 for reaction;
(8) the synthesis of N' -propyne-N, N-dimethylacetamide comprises the following steps: mixing and reacting propynylamine and N, N-dimethylacetamide dimethyl acetal;
(9) The synthesis of multi-block polymer poly-PTPE-b-PAD-b-PEO comprises: and (3) carrying out polymerization reaction on the PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer prepared in the step (7) and the N' -propyne-N, N-dimethylacetamide prepared in the step (8).
4. The method of synthesizing a multiblock polymer according to claim 3,
in the step (1), the chemical equivalent ratio of the benzophenone to the 4-hydroxybenzophenone is 1: 1;
In the step (2), the stoichiometric ratio of 1- (4-hydroxyphenyl) -1, 2, 2-triphenylethylene to 11-bromo-1-undecanol and potassium iodide is 1: 1.2: 0.005;
in the step (3), the stoichiometric ratio of 1- (4-ethoxyphenyl) -1, 2, 2-triphenylethylene to methacryloyl chloride is 4: 1;
in the step (4), the stoichiometric ratio of 4-undecyloxy tetraphenyl vinyl methacrylate to 2- (dodecylthiocarbonylthio) -2-methylpropionic acid is 2.5: 1;
In the step (5), the stoichiometric ratio of polytetrafluoroethylene to 4-vinylbenzyl chloride is 1: 0.135 parts by weight;
In the step (6), the stoichiometric ratio of the poly-PTPE-b- (4-vinylbenzyl chloride) block polymer to the PEO precursor is 1: 4;
In the step (7), the stoichiometric ratio of the PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer to NaN 3 is 1: 11.5;
in the step (8), the chemical equivalent ratio of the propynylamine to the N, N-dimethylacetamide dimethylacetal is 1: 2.4;
in step (9), the stoichiometric ratio of the poly-PTPE-b- (4-vinylbenzylazide) -b-PEO block polymer to N' -propyne-N, N-dimethylacetamide is 1: 1.
5. the method for synthesizing a multiblock polymer according to claim 3, wherein the purification in step (1), step (2) and step (3) is specifically performed by column chromatography.
6. the method for synthesizing a multiblock polymer according to claim 5, wherein the step (1), the step (2) and the step (3) are subjected to extraction and drying treatments before column chromatography purification.
7. The method for synthesizing a multiblock polymer according to claim 3, wherein in the step (5), the step (6) and the step (9), RAFT polymerization is used as the polymerization reaction.
8. The method for synthesizing a multiblock polymer according to claim 3, wherein the mixing reaction of propynylamine and N, N-dimethylacetamide dimethylacetal in the step (8) is carried out under the protection of a protective atmosphere.
9. a fluorescent probe for tumor detection, characterized in that the material of the fluorescent probe for tumor detection comprises the multiblock polymer according to claim 1 or 2.
10. a kit for tumor detection, comprising the fluorescent probe for tumor detection according to claim 9.
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| CN104263353A (en) * | 2014-09-11 | 2015-01-07 | 华南理工大学 | Ratiometric fluorescent probe for detection of hydrogen sulfide and preparation method of ratio-dependent fluorescent probe |
| WO2015188157A1 (en) * | 2014-06-06 | 2015-12-10 | The Board Of Regents Of The University Of Texas System | Library of ph responsive polymers and nanoprobes thereof |
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| WO2015188157A1 (en) * | 2014-06-06 | 2015-12-10 | The Board Of Regents Of The University Of Texas System | Library of ph responsive polymers and nanoprobes thereof |
| CN104263353A (en) * | 2014-09-11 | 2015-01-07 | 华南理工大学 | Ratiometric fluorescent probe for detection of hydrogen sulfide and preparation method of ratio-dependent fluorescent probe |
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