CN114015022B - Cationic conjugated polymer, ratio-type fluorescent probe based on cationic conjugated polymer, preparation method and application - Google Patents

Cationic conjugated polymer, ratio-type fluorescent probe based on cationic conjugated polymer, preparation method and application Download PDF

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CN114015022B
CN114015022B CN202111355665.0A CN202111355665A CN114015022B CN 114015022 B CN114015022 B CN 114015022B CN 202111355665 A CN202111355665 A CN 202111355665A CN 114015022 B CN114015022 B CN 114015022B
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conjugated polymer
fluorescent probe
serum albumin
dichloromethane
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CN114015022A (en
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萨米尔·侯赛因
田雪蒙
陈曦
王悦
高瑞霞
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Xian Jiaotong University
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Abstract

The invention discloses a ratiometric fluorescent probe for selectively and quantitatively detecting serum albumin, and a preparation method and application thereof. The ratiometric fluorescent probe is a novel self-assembly system of cation conjugated polymer and sodium dodecyl sulfate, and has the characteristic of enhancing reverse fluorescence resonance energy transfer in polymer chains and among molecules. The ratio type fluorescent probe has specific obviously-enhanced color response to the concentration of the serum albumin, can eliminate the interference of other biomolecules in a complex matrix environment, and realizes selective quantitative detection of the serum albumin; the ratio type fluorescent probe can greatly reduce the instability of instruments, the interference of the change of measurement conditions and probe concentration on detection results, and is high in sensitivity, high in accuracy, convenient and quick to operate and suitable for field detection.

Description

Cationic conjugated polymer, ratiometric fluorescent probe based on cationic conjugated polymer, preparation method and application
Technical Field
The invention belongs to the technical field of fluorescent probes, and relates to a cation conjugated polymer, a ratiometric fluorescent probe based on the cation conjugated polymer, a preparation method and application of the ratiometric fluorescent probe, in particular to a novel cation conjugated polymer, a ratiometric fluorescent probe based on the cation conjugated polymer and capable of selectively and quantitatively detecting serum albumin, and a preparation method and application of the ratiometric fluorescent probe.
Background
Serum albumin is the most abundant protein in the human body's internal circulation system, it has the physiological functions of combining and transporting endogenous and exogenous substances, maintaining the blood colloid osmotic pressure, eliminating free radicals, inhibiting platelet aggregation and anticoagulation, etc., and has important significance in the life process. Since serum albumin is involved in many important biological functions in the human body, the serum albumin content in human body fluids such as serum and urine is generally considered as an index for evaluating human health. A large number of clinical studies indicate that abnormal levels of serum albumin in these biological matrices are directly related to prognosis or diagnosis of various human health diseases, and may indicate chronic hepatitis, liver cirrhosis, even liver failure, diabetes and other diseases. Therefore, serum albumin is considered as an important biomarker for clinical evaluation of various diseases, and has great application potential in clinical and biological analysis aspects. However, accurate measurement and selective analysis of serum albumin remains a major challenge to researchers due to interference of multiple biomolecules present in complex biological matrices.
At present, the detection methods of serum albumin mainly comprise an electrophoresis method, an immunoassay method and a dye binding method. The methods have the defects of large equipment investment, long time consumption, complex sample pretreatment and the like, so that the application of the methods in conventional analysis is limited. The fluorescence detection technology has the advantages of fast signal response time, simplicity, high sensitivity and the like, and shows good potential in the field of protein detection. Conjugated Polymers (CPs) are novel fluorescent organic materials, have a special molecular wire effect, promote excitons generated by light or electric excitation to rapidly migrate in and among CPs chains, amplify sensed response signals hundreds of times under the condition of not changing the binding constant of functional groups and recognition molecules, effectively improve detection sensitivity and reduce the lower limit of detection, and are widely applied to the fields of biosensing, imaging, treatment, photoelectron and the like. However, most of the existing CPs fluorescent probes detect by monitoring the enhancement or quenching of a single fluorescent signal, are influenced by autofluorescence, instrument fluctuation or environment, and are difficult to ensure the accuracy of detection results. The ratio type fluorescent probe is an analysis method for determining a target object by measuring a ratio of fluorescence intensities at two different wavelengths as a signal, and can avoid the influence of instruments and environments and improve the sensitivity and stability of the probe. In addition, the currently reported CPs system is used for protein detection, and is often easily interfered by other proteins due to the existence of nonspecific electrostatic or hydrophobic interaction force, and the selectivity is poor. Therefore, the design of the ratio type fluorescent probe which can effectively eliminate the interference of other proteins in the biological matrix and realize accurate, rapid and selective detection of serum-coated albumin has important significance for clinical diagnosis and biomedical research.
Disclosure of Invention
In order to overcome the technical defects, the invention aims to provide a cationic conjugated polymer, a ratiometric fluorescent probe based on the cationic conjugated polymer, a preparation method and application, which can realize selective recognition of serum albumin in a complex matrix.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a cation conjugated polymer, which is characterized by containing a polyfluorene fluorophore and a dithienyl benzothiadiazole fluorophore, and has the following structural general formula:
Figure BDA0003357489270000021
the invention also discloses a preparation method of the cationic conjugated polymer, which comprises the following steps:
1) mixing 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene and 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole, and adding a tetrahydrofuran solution to obtain a solution 1;
2) mixing potassium carbonate and ultrapure water, adding the obtained mixed solution into the solution 1, degassing for 30min, adding a catalyst of tetrakis (triphenylphosphine) palladium, introducing nitrogen for 30min, heating and refluxing, carrying out a polymerization reaction, and after the polymerization reaction is finished, carrying out separation and purification to obtain a precursor polymer;
3) and mixing the precursor polymer, 1-methylimidazole and dichloromethane, reacting at room temperature, and then separating and purifying to obtain the novel cationic conjugated polymer.
Preferably, in the step 1), the using ratio of the 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene, the 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene, the 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole and the tetrahydrofuran solution is (0.1-1.0 g): (0.1-1.2) g: (0.1-1.0) g: (25-100) mL.
Preferably, in the step 2), the ratio of the potassium carbonate to the ultrapure water is (0.5-5) g: (1-10) mL; the dosage of the added tetrakis (triphenylphosphine) palladium catalyst is 0.005 g-0.020 g; the reaction temperature of the heating reflux is 45-120 ℃, and the reaction time is 6-72 h.
Preferably, in step 2), the separation and purification steps are: after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane to extract an organic phase, drying by using anhydrous sodium sulfate, and filtering; the organic solvent was removed by rotary evaporation.
Preferably, in the step 3), the amount ratio of the precursor polymer, 1-methylimidazole and dichloromethane is (10-100) mg: (1-10) mL: (1-20) mL; the reaction time at room temperature is 12-96 h.
Preferably, in step 3), the separation and purification steps are: after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washed three times with dichloromethane and the organic solvent removed by rotary evaporation.
The invention discloses a ratiometric fluorescent probe capable of selectively and quantitatively detecting serum albumin, which is a self-assembly system consisting of the cationic conjugated polymer and sodium dodecyl sulfate.
The invention also discloses a preparation method of the ratiometric fluorescent probe for selectively and quantitatively detecting serum albumin, which comprises the following steps of mixing the novel cationic conjugated polymer and sodium dodecyl sulfate in a ratio of (5-50) mu M: (5-100) mu M, mixing and self-assembling to obtain the ratiometric fluorescent probe capable of selectively and quantitatively detecting the serum albumin.
The ratiometric fluorescent probe capable of selectively and quantitatively detecting serum albumin disclosed by the invention can exclude interference of other biomolecules in a complex biological environment to selectively identify the serum albumin.
Compared with the prior art, the invention has the following beneficial effects:
the novel cationic conjugated polymer (PF-DBT-Im) is subjected to Suzuki cross-coupling polymerization, is adjustable in color, is represented as a nano aggregate in a dilute aqueous solution, has weak interchain fluorescence resonance energy transfer (interchain-FRET) and is represented as purple luminescence.
The invention relates to a ratiometric fluorescent probe (PF-DBT-Im/SDS) capable of selectively and quantitatively detecting serum albumin, which is a self-assembly system of a novel cationic conjugated polymer (PF-DBT-Im) and sodium dodecyl sulfate.
Compared with the traditional ratiometric fluorescent probe, the ratiometric fluorescent probe (PF-DBT-Im/SDS) for selectively and quantitatively detecting the serum albumin has the advantages that the intermolecular reverse fluorescence resonance energy transfer (intermolecular reverse-FRET) from the serum albumin to the ratiometric fluorescent probe (PF-DBT-Im/SDS) occurs due to the synergistic effect of electrostatic interaction, hydrophobic interaction and higher intrinsic quantum yield of the serum albumin, so that the color change of the fluorescent probe is realized, and the interference of other biomolecules in a complex biological environment can be eliminated, so that the serum albumin can be selectively identified.
The invention realizes the high-selectivity quantitative detection of serum albumin in an aqueous medium by adopting a conjugated polymer-surfactant self-assembly system for the first time. Compared with the traditional fluorescent probe with single signal output, the ratiometric fluorescent probe (PF-DBT-Im/SDS) for selectively and quantitatively detecting the serum albumin can greatly reduce the instability of instruments, the interference of the change of measurement conditions and probe concentration on detection results, and is high in sensitivity, high in accuracy, convenient and quick to operate and suitable for field detection.
Drawings
FIG. 1 is a scheme showing the synthesis of the novel cationic conjugated polymer PF-DBT-Im in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the novel cationic conjugated polymer PF-DBT-Im in example 1 of the present invention;
FIG. 3 is a graph showing fluorescence response spectra of PF-DBT-Im/SDS to Human Serum Albumin (HSA) at various concentrations in example 7 of the present invention;
FIG. 4 is a graph showing the relationship between the ratio of the fluorescence intensity at 645nm and 420nm of PF-DBT-Im/SDS and the concentration of human serum albumin in example 7 of the present invention;
FIG. 5 is a bar graph of the selectivity test of PF-DBT-Im/SDS against serum albumin in example 8 of the present invention, i.e., the relationship between the response of PF-DBT-Im/SDS and various potential interferents.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1:
taking 0.1g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 0.1g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), 0.1g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) in a three-necked flask, adding 25mL of tetrahydrofuran solution to obtain solution 1; mixing 0.5g of potassium carbonate and 1mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.005g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing at 45 ℃ for 6h, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; and removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br. Mixing 10mg of PF-DBT-Br, 1mL of 1-methylimidazole and 1mL of dichloromethane, and reacting at room temperature for 12 hours; after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with dichloromethane for three times, and performing rotary evaporation to remove the organic solvent to obtain a novel cationic conjugated polymer PF-DBT-Im; mixing 5 mu M PF-DBT-Im and 5 mu M Sodium Dodecyl Sulfate (SDS), and self-assembling to obtain a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin.
PF-DBT-Im was characterized by NMR, and the results are shown in FIG. 2. Proton signature peaks can be assigned from the test results of fig. 2: 1 H NMR(400MHz,d6-DMSO):δ9.65–9.55(b,N＝CH–N),δ9.30–9.01(b,N–CH＝CH–N),δ8.30–6.70(b,aromatic backbone),4.15–4.04(b,N–CH 2 –(CH 2 ) 5 ),3.90-3.70(b,N–CH 3 ),2.25–0.40(b,N–CH 2 –(CH 2 ) 5 ) And determining that the synthesized product is PF-DBT-Im.
Example 2:
taking 0.8g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 0.4g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), 0.3g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) in a three-necked flask, adding 75mL of tetrahydrofuran solution to obtain solution 1; mixing 1.38g of potassium carbonate and 5mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.009g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing at 60 ℃ for 24h, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br; mixing 50mg of PF-DBT-Br, 5mL of 1-methylimidazole and 8mL of dichloromethane, and reacting at room temperature for 48 hours; after the room temperature reaction is finished, removing dichloromethane through rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with dichloromethane for three times, and removing the solvent by rotary evaporation to obtain a novel cationic conjugated polymer PF-DBT-Im; mixing 25 mu M PF-DBT-Im and 25 mu M Sodium Dodecyl Sulfate (SDS), self-assembling to obtain a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin.
The characterization of the fluorescent compound obtained in this example is the same as the characterization result in example 1.
Example 3:
taking 0.2g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 0.6g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), 0.9g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) in a three-necked flask, adding 35mL of tetrahydrofuran solution to obtain solution 1; mixing 2.5g of potassium carbonate and 3.5mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.017g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing for 32h at 100 ℃, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; and removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br. Mixing 30mg of PF-DBT-Br, 6mL of 1-methylimidazole and 12mL of dichloromethane, and reacting at room temperature for 72 hours; after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with dichloromethane for three times, and removing the organic solvent by rotary evaporation to obtain the novel cationic conjugated polymer PF-DBT-Im. The 20 mu M PF-DBT-Im and 40 mu M Sodium Dodecyl Sulfate (SDS) are mixed and self-assembled to obtain a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin.
The characterization of the fluorescent compound obtained in this example is the same as the characterization result in example 1.
Example 4:
0.6g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 0.2g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), 0.6g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) were put in a three-necked flask, and 60mL of tetrahydrofuran solution was added to obtain solution 1; mixing 3.7g of potassium carbonate and 7mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.012g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing at 80 ℃ for 48h, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br; mixing 60mg of PF-DBT-Br, 8mL of 1-methylimidazole and 15mL of dichloromethane, and reacting at room temperature for 54 h; after the room temperature reaction is finished, removing dichloromethane through rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with DCM for three times, and removing the solvent by rotary evaporation to obtain a novel cationic conjugated polymer PF-DBT-Im; a ratiometric fluorescent probe PF-DBT-Im/SDS capable of selectively and quantitatively detecting serum albumin is obtained by self-assembly after mixing 30 mu M PF-DBT-Im and 60 mu M Sodium Dodecyl Sulfate (SDS).
The characterization of the fluorescent compound obtained in this example is the same as the characterization result in example 1.
Example 5:
0.9g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 0.8g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), and 0.4g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) were put in a three-necked flask, and 45mL of tetrahydrofuran solution was added to obtain solution 1; mixing 4.75g of potassium carbonate and 8mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.006g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing at 75 ℃ for 54h, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br; mixing 80mg of PF-DBT-Br, 3mL of 1-methylimidazole and 5mL of dichloromethane, and reacting at room temperature for 36 hours; after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with dichloromethane for three times, and removing the solvent by rotary evaporation to obtain a novel cationic conjugated polymer PF-DBT-Im; a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin is obtained by self-assembly after 40 mu M PF-DBT-Im and 70 mu M Sodium Dodecyl Sulfate (SDS) are mixed.
The characterization of the fluorescent compound obtained in this example is the same as the characterization result in example 1.
Example 6:
1.0g of 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene (M1), 1.2g of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromoethyl) fluorene (M2), 1.0g of 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole (M3) were put in a three-necked flask, and 100mL of tetrahydrofuran solution was added to obtain solution 1; mixing 5g of potassium carbonate and 10mL of ultrapure water, adding the mixture into the solution 1 by using an injector, degassing for 30min, adding 0.02g of tetrakis (triphenylphosphine) palladium as a catalyst, introducing nitrogen for 30min, heating and refluxing at 120 ℃ for 72h, and carrying out polymerization reaction; after the polymerization reaction is finished, removing the organic solvent by using a rotary evaporator, adding water and dichloromethane for extraction, taking an organic phase, drying by using anhydrous sodium sulfate, and filtering; removing the organic solvent by rotary evaporation to obtain a precursor polymer PF-DBT-Br; mixing 100mg of PF-DBT-Br, 10mL of 1-methylimidazole and 20mL of dichloromethane, and reacting at room temperature for 96 hours; after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding 1mL of methanol for dissolution, transferring into a dialysis bag with the molecular weight of 2.5kDa, and dialyzing for 2 days; washing with dichloromethane for three times, and performing rotary evaporation to remove the organic solvent to obtain a novel cationic conjugated polymer PF-DBT-Im; a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin is obtained by self-assembly after mixing 50 mu M PF-DBT-Im and 100 mu M Sodium Dodecyl Sulfate (SDS).
The characterization of the fluorescent compound obtained in this example is the same as the characterization result in example 1.
Example 7:
the invention discloses a fluorescence detection of a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin on human serum albumin with different concentrations. The concentration of PF-DBT-Im/SDS was always kept at 25. mu.M and the concentration of HSA was 0. mu.g mL at the time of the test -1 、100μg mL -1 、200μg mL -1 、300μg mL -1 、400μg mL -1 、500μg mL -1 、600μg mL -1 、700μg mL -1 、800μg mL -1 、900μg mL -1 、1000μg mL -1 (ii) a The total amount of the test system was 1mL, the test temperature was 25 ℃ and the excitation wavelength was 380nm, and the measured fluorescence spectrum was shown in FIG. 3, in which the fluorescence intensity at 420nm and 645nm gradually increased with the increase in the HSA concentration. This shows that under the excitation of ultraviolet lamp, the simultaneous change of two emission peaks can realize ratiometric calculation, reduce the instability from the instrument, and the interference of the change of measurement condition and probe concentration to the detection result; but also causes the color of the solution to change from dark red to pink, thereby realizing the naked eye detection of the serum albumin. FIG. 4 shows example 1The ratio of the fluorescence intensity at 645nm to the fluorescence intensity at 420nm of the fluorescent probe (I) 645 /I 420 ) FIG. 4 shows that the ratio of the fluorescence intensity to the HSA concentration has a high R 2 And the value shows good linear correlation, which indicates that the data obtained in the detection analysis has high accuracy, small measurement error and strong reliability of the detection result.
Example 8:
the invention relates to a selective test of a ratiometric fluorescent probe PF-DBT-Im/SDS for selectively and quantitatively detecting serum albumin on Human Serum Albumin (HSA) in the presence of different potential interferents. The complex system with potential interferents was subjected to fluorescence detection using a PF-DBT-Im/SDS ratiometric fluorescent probe at a concentration of 25. mu.M. The test system consisted of the analytes alanine (Ala), histidine (His), isoleucine (Isoleu), cysteine (Cys), valine (Val), Glucose (Glucose), hemoglobin (Hb), cytochrome c (CytC), ribonuclease (RNase), Pepsin (Pepsin), Trypsin (Trypsin), horseradish peroxidase (HRP), lysozyme (Lyz), Human Serum Albumin (HSA) and Bovine Serum Albumin (BSA), each at a concentration of 1000. mu.g mL –1 The total amount of the test system is 1mL, the test temperature is 25 ℃, the excitation wavelength is 380nm, the measured fluorescence spectrum is shown in figure 5, and figure 5 shows that the ratiometric fluorescent probe for selectively and quantitatively detecting serum albumin has excellent selectivity on serum protein. Table 1 shows isoelectric points and intrinsic quantum yields of various enzymes and proteins, and it can be seen from table 1 that serum albumin has higher intrinsic quantum yield (table 1) compared with other proteins, and under the synergistic effect of electrostatic interaction and hydrophobic interaction, intermolecular reverse fluorescence resonance energy transfer (intermolecular reverse-FRET) from serum albumin to the ratiometric fluorescent probe (PF-DBT-Im/SDS) can occur, resulting in a strong color change, thereby achieving highly selective detection of serum albumin.
TABLE 1 isoelectric points and intrinsic Quantum yields of various enzymes and proteins
Figure BDA0003357489270000111
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (9)

1. A cationic conjugated polymer, comprising a polyfluorene fluorophore and a dithienothiadiazole fluorophore, having the following structural formula:
Figure FDA0003659845180000011
2. the method of claim 1, comprising the steps of:
1) mixing 2, 7-dibromo-9, 9-di (6-bromohexyl) fluorene, 2, 7-di (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-di (6-bromohexyl) fluorene and 4, 7-di (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole, adding a tetrahydrofuran solution, and uniformly mixing to obtain a solution 1;
2) mixing potassium carbonate and ultrapure water, adding the mixture into the solution 1, degassing, adding a catalyst of tetrakis (triphenylphosphine) palladium, introducing nitrogen, heating and refluxing, carrying out polymerization reaction, and separating and purifying to obtain a precursor polymer;
3) and mixing the precursor polymer, 1-methylimidazole and dichloromethane, reacting at room temperature, and then separating and purifying to obtain the cation conjugated polymer.
3. The method of claim 2, wherein in the step 1), the amount ratio of the 2, 7-dibromo-9, 9-bis (6-bromohexyl) fluorene, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -9, 9-bis (6-bromohexyl) fluorene, 4, 7-bis (5-bromothien-2-yl) benzo [ c ] [1,2,5] thiadiazole, and the tetrahydrofuran solution is (0.1 to 1.0 g): (0.1-1.2) g: (0.1-1.0) g: (25-100) mL.
4. The method for preparing a cationic conjugated polymer according to claim 2, wherein in the step 2), the ratio of the amount of potassium carbonate to ultrapure water is (0.5-5) g: (1-10) mL; the dosage of the added tetrakis (triphenylphosphine) palladium catalyst is 0.005 g-0.020 g; the reaction temperature of the heating reflux is 45-120 ℃, and the reaction time is 6-72 h.
5. The method for preparing the cationic conjugated polymer according to claim 2, wherein the step of separating and purifying in step 2) comprises: after the polymerization reaction, the organic solvent was removed by a rotary evaporator, the organic phase was extracted with water and dichloromethane, dried over anhydrous sodium sulfate, filtered, and the organic solvent was removed by rotary evaporation.
6. The method of claim 2, wherein in the step 3), the ratio of the precursor polymer, 1-methylimidazole and dichloromethane is (10-100) mg: (1-10) mL: (1-20) mL; the reaction time at room temperature is 12-96 h.
7. The method for preparing the cationic conjugated polymer according to claim 2, wherein in the step 3), the separation and purification steps are: after the room temperature reaction is finished, removing dichloromethane by rotary evaporation; adding methanol for dissolving, transferring into a dialysis bag with molecular weight of 2.5kDa, and dialyzing for 2 days; washed three times with dichloromethane and the organic solvent removed by rotary evaporation.
8. A ratiometric fluorescent probe capable of selectively and quantitatively detecting serum albumin, which is a self-assembled system consisting of the cationic conjugated polymer according to claim 1 and sodium dodecyl sulfate.
9. The method of claim 8, wherein the ratio-type fluorescent probe is prepared by mixing the cationic conjugated polymer and sodium dodecyl sulfate in a ratio of (5-50) μ M: (5-100) mu M, mixing and self-assembling to obtain the ratiometric fluorescent probe capable of selectively and quantitatively detecting the serum albumin.
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