KR101078256B1 - Water-soluble hyperbranched conjugated polymer for chemical sensors and biosensors, method for producing the same and fluorescent glucose sensor containing the same - Google Patents
Water-soluble hyperbranched conjugated polymer for chemical sensors and biosensors, method for producing the same and fluorescent glucose sensor containing the same Download PDFInfo
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Abstract
The present invention relates to a water-soluble hyperbranched conjugated polymer compound for a chemical sensor and a biosensor having a property of dissolving in water by introduction of a sulfonate or ammonium salt ionic group, and a method of preparing the same. Preferably, the present invention relates to a water-soluble hyperbranched conjugated polymer compound having a large number of receptor groups capable of reacting with a monosaccharide at its end, and used as a chemical sensor and a biosensor, and a method for preparing the same.
The water-soluble hyperbranched conjugated polymer compound according to the present invention is a biosensor material obtained by introducing a receptor capable of selectively reacting with a specific biomaterial, in particular, a sugar such as glucose, at the end thereof. As it is possible to analyze quantitatively and qualitatively, diagnosis, medical research, clinical experiment, chemical analysis, etc. can be widely used.
Description
The present invention relates to a water-soluble hyperbranched conjugated polymer compound for chemical sensors and biosensors having a property of dissolving in water by the introduction of sulfonate or ammonium salt ionic groups, and to a method for preparing the same. The present invention relates to a water-soluble hyperbranched conjugated polymer compound having a large number of receptors that can be used as a chemical sensor and a biosensor, and a method for preparing the same. The present invention also relates to a water-soluble hyperbranched conjugated polymer compound for chemical sensors and biosensors, and to a method for selectively detecting glucose using the same.
In modern society, modern people are exposed to many diseases. As a result, there is a need for rapid and accurate analysis of various diseases. In this analysis, various biosensor materials using materials that are selective for a particular disease are used. The general sensing signal of the sensor uses electrical properties such as electricity, resistance, and potential difference, or optical properties such as color and fluorescence. Among these, color change and fluorescence change can be easily identified by the naked eye, so it is one of the easy methods to measure even without special equipment. In particular, as a sensor showing a change in color and fluorescence, the use of conjugated polymers is generally prominent.
In general, low molecular weight materials are widely used as optical sensors for changing the color and fluorescent colors, and the measurement target material can detect various chemical species such as molecules as well as ions.
Conjugated polymers are capable of converting chemical signals into measurable electrical or optical signals, and in particular, they have increased sensitivity (amplification) when expressing signals in response to interaction with the object under test. And sensor materials such as anion detection and explosive (aromatic nitro compound) detection (DT McQuade, AE Pullen, TM Swager, Chem. Rev. 100, 2537, 2000). In addition, the water-soluble conjugated polymer is widely used as a sensor material for low molecular weight biomaterials, proteins, DNA, etc. by using the advantages of increasing the sensitivity of the conjugated polymer and dissolving in water (C. Li, M. Numata, M. Yu, S. Wang, S. Shinkai, Angew. Chem. Int. Ed. 42, 4803, 2003; I.-B. Kim, JN Wilson, UHF Bunz, Chem. Commun. 10, 1273, 2005; BS Gaylord, AJ Heeger, GC Bazan, Proc. Natl. Acad. Sci. USA 99, 10954, 2002).
Hyperbranched polymers are spotlighted as ideal materials for a wide range of applications due to their unique physical and chemical properties. The most characteristic property is that it has a lower viscosity than similar linear polymers in solution or in the molten state. This phenomenon can be explained by the characteristics of the branching properties of the hyperbranched polymer. Hyperbranched polymers do not take the form of random coils of linear polymers in solution, but take a globular shape. In the case of the linear polymer, the viscosity increases linearly in a certain molecular weight range, but if the limit is exceeded, the viscosity rapidly increases. This is explained by the entanglement of polymer chains, which does not occur in hyperbranched polymers. Thus, hyperbranched polymers have a lower viscosity than linear polymers. The branching properties of these hyperbranched polymers also affect the relative solubility in various solvents. Hyperbranched polymers have higher chemical reactivity and higher solubility than similar linear polymers. Linear polymers have a limited number of terminal groups, whereas hyperbranched polymers have a branching property, which increases the number of terminal groups depending on the degree of branching. The more responsive it is. Superbranched polymers having these characteristics can be utilized as sensor materials through conjugation (J. Feng, Y. Li, M. Yang, J. Polym. Sci., Part A: Polym. Chem. 46, 222, 2008; W.-Y. Lai, R. Xia, Q.-Y. He, PA Levemore, W. Huang, DDC Bradley, Adv. Mater. 20, 1, 2008; R. Kikkeri, I. Garcia-Rubio, PH Seeberger, Chem. Commun. 235, 2009).
The development of a sensor material for detecting monosaccharides is currently attracting much attention, and in particular, the detection of monosaccharides by a change in color or fluorescent color of a sensor material is widely used due to the sensitivity of the detection signal. Among the monosaccharides, the detection of glucose has become a physiologically important factor. Glucose is a causative agent of diabetes, depending on blood levels. Therefore, it is necessary to recognize the cause and risk of diabetes by detecting the concentration of glucose in the human body.
Monosaccharides all have at least two hydroxyl groups and carbonyl groups adjacent thereto. The two hydroxyl groups are composed in three different directions depending on the type of monosaccharide. Among monosaccharides, glucose has two adjacent hydroxyl groups (1,2-diol groups) in the same plane. As such, the hydroxyl groups of glucose react with boronic acid to form boron ester bonds (JP Lorand, JO Edwards, J. Org. Chem., 24, 769, 1959; C. Yu, VW-W. Yam, Chem. Commun. 1347, 2009; C. Shimpuku, R. Ozawa, A. Sasaki, F. Sato, T. Hashimote, A. Yamauchi, I. Suzuki, T. Hayashita, Chem. Commun. 1709. 2009) . When a pigment compound having boronic acid is added to a terminal group in a water-soluble state, glucose and the pigment compound may bind to each other, thereby changing color or fluorescent color.
Efforts to detect proteins with color sensors due to color change due to the characteristics of glucose have been attempted by low molecular weight and high molecular materials. These are known to induce a change in color or fluorescent color through the reaction of the dye compound having boronic acid in the terminal group in the aqueous solution reacts with the hydroxyl group of glucose
Biosensors using linear polymer compounds have limited numbers of boronic acids that can bind to glucose because they can be introduced only at the sock end of the polymer due to their structural properties.In the case of linear polymers, the number of end groups is two per molecule. Because of this, the efficiency is lowered, making it difficult to use as a highly sensitive biosensor.
The present invention is to solve the problems of the prior art as described above, by increasing the number of boronic acid or cyclic boron ester, the end group of the water-soluble conjugated polymer that can react with monosaccharides, in particular glucose, as a chemical sensor and a biosensor An object of the present invention is to provide a water-soluble hyperbranched conjugated polymer compound having an increased sensitivity of and a method for producing the same.
Another object of the present invention is to provide a water-soluble hyperbranched conjugated polymer compound and a method for producing the same, which can be applied to chemical sensors and biosensors that selectively detect monosaccharides, especially glucose, and thus detect a detection signal as a change in fluorescence intensity. do.
The present invention relates to a water-soluble hyperbranched conjugated polymer compound for chemical sensors and biosensors having a property of dissolving in water by the introduction of sulfonate or ammonium salt ionic groups, and to a method for preparing the same. The present invention relates to a water-soluble hyperbranched conjugated polymer compound having a large number of receptors that can be used as a chemical sensor and a biosensor, and a method for preparing the same. The present invention also relates to a water-soluble hyperbranched conjugated polymer compound for chemical sensors and biosensors, and to a method for selectively detecting glucose using the same.
Hereinafter, the present invention will be described in detail.
The water-soluble hyperbranched conjugated polymer compound of the present invention implements a hyperbranched structure in order to introduce a large number of boronic acids or cyclic boron esters that can react with glucose to the conjugated polymer, and at the end of the water-soluble conjugated polymer, It is characterized by containing a boronic acid or a cyclic boron ester as a functional group for the introduction of a receptor for imparting selectivity, and is represented by the following formula (1). In addition, the linear polymer compound for comparing the sensing performance and the hyperbranched polymer compound of Formula 1 containing a plurality of terminal boronic acid or cyclic boron ester in terms of molecular structure is represented by the following formula (2).
[Formula 1]
[In Formula 1,
Ar is (C6-C20) arylene or (C2-C12) heteroarylene containing at least one hetero atom selected from N, O and S;
R 1 and R 2 are each independently a linear or branched C 1 to C 6 alkyl group substituted with sulfonic acid, sulfonic acid salt or tri (C 1 -C 7) alkylammonium salt at each end;
R 3 is
m is an integer from 1 to 30.]
[Formula 2]
[In Formula 2, R 1 , R 2 , Ar, and R 3 are the same as defined in Formula 1, and n is an integer of 5 to 199.]
Terminals of the alkyl groups of R 1 and R 2 may be independently substituted with sulfonic acid, sulfonic acid salt, trimethylammonium salt, ethyldimethylammonium salt, diethylmethylammonium salt, triethylammonium salt, and alkyl groups of R 1 and R 2 Independently of one another, methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, n-pentyl, i-pentyl or n-hexyl, wherein Ar is phenylene or Selected from thienylene.
Although the molecular weight of the water-soluble hyperbranched conjugated polymer compound of Chemical Formula 1 according to the present invention is not limited in principle, the number average molecular weight (Mn) is preferably 3,000 to 100,000, and the range is appropriately adjusted according to the characteristics required for the purpose. Can be used.
Hereinafter, the reaction will be described in detail by taking, for example, a method for producing a water-soluble hyperbranched conjugated polymer compound by Suzuki coupling.
(a) water soluble Second branch Conjugate Preparation of Polymer Compound (Formula 1)
The water-soluble hyperbranched conjugated polymer compound represented by the general formula (1) according to the present invention is a tetrakiss the monomer (III) forming a branch with the water-soluble monomer (I), aromatic monomer (II), as described in Schemes 1 and 2 It is prepared by Suzuki coupling in the presence of a (triphenylphosphine) palladium catalyst.
Scheme 1
Scheme 2
[Scheme 1 and 2,
Ar is (C6-C20) arylene or (C2-C12) heteroarylene containing at least one hetero atom selected from N, O and S;
R 1 and R 2 are each independently a linear or branched C 1 to C 6 alkyl group substituted with sulfonate or tri (C 1 -C 7) alkylammonium salt at the end;
X is Cl, Br or I; R 3 is
In addition, the m value of the water-soluble hyperbranched conjugated polymer compound represented by Chemical Formula 1 may be controlled by the equivalent ratio of the water-soluble monomer (I) and the aromatic monomer (II) to be introduced, and preferably the aromatic monomer (II) 1.2 to 1.4 equivalents of water-soluble monomer (I) are used.
As the aromatic monomer (II), in the embodiment of the present invention, benzene-1,4-diboronic acid was used, and as the monomer (III) forming the branch, hyperbranched conjugated polymer was used by using tris-4-bromophenylamine. Although the compound was prepared, it is not limited thereto, and any monomer may be used as long as it can produce the above water-soluble hyperbranched conjugated polymer compound by Suzuki coupling.
The water-soluble monomer (I) forms a polymer by Suzuki coupling reaction in the presence of 1.2-fold molar number of aromatic monomer (II) and a tetrakis (triphenylphosphine) palladium catalyst (N. Miyaura, A. Suzuki, Chem. Rev. 95, 2457, 1995). The hyperbranched conjugated polymer compound can polymerize a water-soluble monomer and an aromatic monomer having functional groups such as boronic acid or a cyclic boron ester at both terminals by a Suzuki coupling reaction.
(b) Preparation of Linear Water Soluble Conjugated Polymer Compound (Formula 2)
The linear water-soluble conjugated polymer compound represented by the formula (2) has a tetrakis (triphenylphosphine) palladium catalyst containing a water-soluble monomer (I) and a 1.2-fold molar aromatic monomer (II)) as described in Schemes 3 and 4. Under Suzuki coupling.
Scheme 3
Scheme 4
[X, R 1 , R 2 , Ar and R 3 in Schemes 3 and 4 are the same as the definitions in Scheme 1 above.]
The water-soluble hyperbranched conjugated polymer compound of formula (1) having arylene or hetero arylene according to the present invention, or a chemical sensor or biosensor comprising the same, has a monosaccharide that reacts with boron acid or cyclic boron ester at its end. Useful for detection. Utilizing the properties of adjacent hydroxy groups of monosaccharides, it is expected that the hydroxy group in the aqueous solution and the boronic acid or cyclic boron esters containing a large number of hyperbranched polymers react and bind, and thus detect monosaccharides by color and fluorescence changes. can do. In particular, as can be seen in the experimental example it can be used as a use for the selective detection in glucose.
On the other hand, the linear water-soluble conjugated polymer compound of Chemical Formula 2 or chemical sensors and biosensors comprising the same may also be useful for detecting monosaccharides reacting with terminal boronic acid or cyclic boron esters. By taking advantage of the characteristics of the time period, only the hydroxy group in the aqueous solution and only two boronic acids or cyclic boron esters present only at the ends of the linear polymer react and bind, so that the monosaccharides can be detected by the color and fluorescence changes. As can be seen, since the number of functional groups of the end group is small, it can be seen that the detection efficiency and selectivity are inferior.
As mentioned above, the conjugated polymer compound according to the present invention, that is, the water-soluble hyperbranched conjugated polymer compound in which a plurality of receptors (boron acid or cyclic boron ester) that can be easily combined with a monosaccharide (glucose) is introduced into a specific biomaterial It can be used as a cognitive substance, and in particular, it has high selectivity for a specific monosaccharide (glucose), which can be used in various ways as a chemical sensor and a biosensor, and can be widely used for diagnosis, medical research, clinical experiment, and chemical analysis.
In addition, the water-soluble hyperbranched conjugated polymer compound according to the present invention has physical properties corresponding to sensor functions such as responsiveness, stability, and selectivity by the control of guest molecules, etc., and thus may be applied to molecular recognition sensors.
The present invention will be described in detail through the following examples. However, these examples are for illustrative purposes only and the present invention is not limited thereto.
Preparation Example 1 Preparation of 1,4-dibromobenzene-2,5-bis-4-butoxysulfonic acid (1) (R 1 = R 2 = butanesulfonic acid)
8 g (29.9 mmol) of 2,5-dibromohydroquinone and 2.61 g (65.36 mmol) of sodium hydroxide were added to 60 ml ethanol and heated to 80 ° C. To the solution was added 8.9 g (65.36 mmol) of 1,4-butane sultone. After stirring for 20 hours, the mixture was cooled to room temperature and the reaction was filtered. The obtained solid was washed with ethanol and dried to obtain 16.31 g (93.4%) of 1,4-dibromo-2,5-bis (4-sulfonatobutoxy) benzene sodium salt. 5 g of this monomer were dissolved in 130 ml of water, and then 50 ml of 35% hydrochloric acid was slowly added. After stirring for 12 hours the reaction was centrifuged. The obtained solid was dried to obtain 4.2 g (91.3%) of 1,4-dibromobenzene-2,5-bis-4-butoxysulfonic acid.
1 H NMR (300 MHz, D 2 O): delta = 7.43 (2H, aromatic), 4.18 (4H, alkyl group), 3.08 (4H, alkyl group), 2.00 (4H, alkyl group), 1.96 (4H, alkyl group) ppm.
Preparation Example 2 Preparation of 1,4-bis (3-bromopropoxy) -2,5-dibromobenzene (1) (R 1 = R 2 = -CH 2 CH 2 CH 2 Br)
3.52 g (10.00 mmol) of 1,4-bis (3-bromopropoxy) benzene was dissolved in 80 ml of methylene chloride, and 0.01 g (0.18 mmol) of iron was added thereto, followed by stirring at room temperature. 3.43 g (21.4 mmol) of bromine is diluted in 40 ml of methylene chloride and slowly added to the solution. After stirring for 12 hours the reaction was filtered. 50 ml of tertiary distilled water was added to the obtained filtrate and the organic layer was recovered. Magnesium sulfate was added to the collected organic layer, followed by stirring, followed by filtration to obtain a filtrate. After evaporating the obtained filtrate, the obtained solid was separated by column chromatography using a 4: 1 mixed solution of hexane and ethyl acetate using 4.03 g (79%) of 1,4-bis (3-bromopropoxy) -2. , 5-dibromobenzene was obtained.
1 H NMR (300 MHz, CDCl 3 ): δ = 7.14 (2H, aromatic), 4.13 (4H, alkyl group), 3.69 (4H, alkyl group), 2.35 (4H, alkyl group) ppm.
[ Example 1] Water Soluble Second branch Conjugate Polymer compound A (Formula 1, R One = R 2 = -CH 2 CH 2 CH 2 CH 2 S (= O) 2 OH, Ar = 1,4- Phenylene , R 3 = -B ( OH ) 2 Manufacturing
1 g (1.85 mmol) of 1,4-dibromobenzene-2,5-bis-4-butoxysulfonic acid (Preparation Example 1), 0.38 g (2.31 mmol) of 1,4-benzenediboronic acid and tris (4- 0.148 g (0.308 mmol) of bromophenyl) amine, and 0.13 g (0.12 mmol) of tetrakis (triphenylphosphine) palladium catalyst are mixed with 30 mL of DMF and 18 ml of 2M Na 2 CO 3 , dehumidified. Dissolved in and refluxed at 90 ° C. for 40 h. After the reaction, the mixture was cooled to room temperature, poured into acetone to precipitate crystals, and the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water, and then filtered using an osmosis membrane to obtain a water-soluble hyperbranched conjugated polymer compound A having a molecular weight of 12,400 or more.
1 H NMR (300 MHz, D 2 O) δ = 7.7 to 6.8 (8H, aromatic), 4.2 to 3.7 (6H, alkyl group), 3.2 to 2.8 (6H, alkyl group), 2.1 to 1.6 (12H, alkyl group) ppm.
[ Example 2] water soluble Second branch Conjugate Polymer compound B (Formula 1, R One = R 2 = -CH 2 CH 2 CH 2 N (CH 3 ) 3 , Ar = 1,4- Phenylene , R 3 = -B ( OH ) 2 Manufacturing
0.414 g (0.812 mmol) of 1,4-bis (3-bromopropoxy) -2,5-dibromobenzene (Preparation Example 2), 0.36 g (1.08 mmol) of 1,4-benzenediboronic acid and tris ( 0.065 g (0.135 mmol) of 4-bromophenyl) amine, and 0.057 g (0.053 mmol) of tetrakis (triphenylphosphine) palladium catalyst were added with 9 mL of dehumidified toluene and 4.5 ml of 2M Na 2 CO 3 . It was dissolved in the mixed solution and refluxed at 90 ° C. for 48 hours. After the reaction, the mixture was cooled to room temperature and poured into 200 ml of methanol to precipitate crystals. The precipitate was filtered, and the obtained solid was washed with 200 ml of acetone and filtered. The solid obtained by filtration was dissolved in 10 ml of THF, cooled to −78 ° C., and 4 ml of trimethylamine was slowly added thereto. After raising the temperature of the reaction solution to room temperature, the mixture was stirred for 6 hours and poured into 200 ml of acetone to precipitate. The precipitated solid was dissolved in tertiary distilled water and then filtered through an osmosis membrane to obtain a water-soluble hyperbranched conjugated polymer compound B having a molecular weight of 11,000 or more.
1 H NMR (300 MHz, D 2 O) δ = 8.1 to 7.3 (2H, aromatic), 7.2 to 6.7 (2H, aromatic), 4.1 (4H, alkyl group), 3.8 to 3.2 (6H, alkyl group), 2.9 (4H , Alkyl group), 1.7 (4H, alkyl group) ppm.
[Comparative Preparation Example 1] A water-soluble linear conjugated polymer compound C (Formula 2, R 1 = R 2 = -CH 2 CH 2 CH 2 CH 2 S (= O) 2 OH, Ar = 1,4-phenylene, R Preparation of 3 = -B (OH) 2 )
0.5 g (0.825 mmol) of 1,4-dibromobenzene-2,5-bis-4-butoxysulfonic acid (Preparation Example 1), 0.183 g (1.11 mmol) of 1,4-benzenediboronic acid, and tetrakis ( 0.065 g (0.06 mmol) of triphenylphosphine) palladium catalyst was dissolved in a mixed solution of 30 mL of THF and 18 mL of 2M Na 2 CO 3 , which had been dehumidified, and refluxed at 90 ° C. for 48 hours. After the reaction, the mixture was cooled to room temperature, poured into acetone to precipitate crystals, and the precipitate was filtered. The solid obtained by filtration was dissolved in tertiary distilled water and then filtered using an osmosis membrane to obtain a water-soluble linear conjugated polymer compound C having a molecular weight of 10,000 or more.
1 H NMR (300 MHz, D 2 O) δ = 7.7 to 6.8 (8H, aromatic), 4.2 to 3.7 (6H, alkyl group), 3.2 to 2.8 (6H, alkyl group), 2.1 to 1.6 (12H, alkyl group) ppm.
Comparative Preparation Example 2 Aqueous Linear Conjugated Polymer Compound D (Formula 2, R 1 = R 2 = -CH 2 CH 2 CH 2 N (CH 3 ) 3 , Ar = 1,4-phenylene, R 3 =- Preparation of B (OH) 2 )
0.414 g (0.812 mmol) of 1,4-bis (3-bromopropoxy) -2,5-dibromobenzene (Preparation Example 2), 0.36 g (1.08 mmol) of 1,4-benzenediboronic acid, and tetra 0.057 g (0.053 mmol) of a kiss (triphenylphosphine) palladium catalyst were dissolved in a mixed solution of 9 mL of toluene dehumidified and 4.5 ml of 2M Na 2 CO 3 and refluxed at 90 ° C. for 48 hours. After the reaction, the mixture was cooled to room temperature and poured into 200 ml of methanol to precipitate crystals. The precipitate was filtered, and the obtained solid was washed with 200 ml of acetone and filtered. The solid obtained by filtration was dissolved in 10 ml of THF, cooled to −78 ° C., and 4 ml of trimethylamine was slowly added thereto. After raising the temperature of the reaction solution to room temperature, the mixture was stirred for 6 hours and poured into 200 ml of acetone to precipitate. The precipitated solid was dissolved in tertiary distilled water and filtered through an osmosis membrane to obtain a water-soluble linear conjugated polymer compound D having a molecular weight of 12,000 or more.
1 H NMR (300 MHz, D 2 O) δ = 7.8-6.6 (4H, aromatic), 4.1-3.7 (4H, alkyl group), 3.8-3.2 (6H, alkyl group), 2.7 (4H, alkyl group), 1.6 (4H , Alkyl group) ppm.
Experimental Example 1 Performance Evaluation of Prepared Anionic Polymer Glucose Sensor
In order to confirm the biochemical detection ability of the anionic polymer compounds (Compounds A and C) prepared in Example 1 and Comparative Preparation Example 1 with respect to glucose, the polymer compounds were prepared in 0.006 molar concentration of sodium phosphate buffer (pH 7.4). ) And each was adjusted to 8.0 × 10 -8 molarity. The fluorescence change of the solution up to 2.0 × 10 −1 molarity was observed using a fluorophotometer by adding glucose, galactose, and fructose, monosaccharides having a hydroxyl group in the adjacent position.
As a result, it was observed that the anionic hyperbranched conjugated polymer compound A of Example 1 and the anionic linear conjugated polymer compound C of Comparative Preparation Example 1 exhibited different fluorescence changes depending on the monosaccharides tested. In particular, in the case of glucose, the fluorescence intensity of the polymer only before the monosaccharide addition was decreased, showing a different fluorescence intensity before and after the addition of glucose. As a result of measuring the fluorescence with a fluorescence photometer, the anionic hyperbranched conjugated polymer compound A of Example 1 showed a 5% decrease in blue fluorescence at 418 nm due to the addition of galactose, and 418 nm with the addition of fructose. Blue fluorescence at was reduced by 7%. In the case of glucose, unlike the previous two cases, it was found to be significantly reduced than the fluorescence of the polymer before glucose addition. The addition of glucose reduced 52% of the blue fluorescence at 418 nm.
On the other hand, in the anionic linear conjugated polymer compound C of Comparative Preparation Example 1, the blue fluorescence at 418 nm was reduced by 29% by the addition of galactose, and the blue fluorescence at 418 nm was decreased by 29% when fructose was added. It was. In the case of glucose, as in the previous two cases, a 34% decrease was observed, which is slightly decreased than the fluorescence of the polymer before glucose addition.
Experimental Example 2 Performance Evaluation of the Cationic Polymer Prepared by Glucose Sensor
In order to confirm the biochemical detection ability of the cationic polymer compounds (Compounds B and D) prepared in Example 2 and Comparative Preparation Example 2 for glucose, the polymer compounds were prepared in 0.006 molar concentration of sodium phosphate buffer (pH 7.4). ) And each was adjusted to 8.0 × 10 -8 molarity. The fluorescence change of the solution up to 2.0 × 10 −1 molarity was observed using a fluorophotometer by adding glucose, galactose, and fructose, monosaccharides having a hydroxyl group in the adjacent position.
As a result, it was observed that the cationic hyperbranched conjugated polymer compound B of Example 2 and the cationic linear conjugated polymer compound D of Comparative Preparation Example 2 exhibited different fluorescence changes depending on the monosaccharides tested. In particular, in the case of glucose, the fluorescence intensity of the polymer only before the monosaccharide addition was decreased, showing a different fluorescence intensity before and after the addition of glucose. As a result of measuring the fluorescence by a fluorescence photometer, the cationic hyperbranched conjugated polymer compound B of Example 2 showed a 7% decrease in blue fluorescence at 416 nm due to the addition of galactose, and 416 nm when fructose was added. The blue fluorescence at was reduced by 9%. In the case of glucose, unlike the previous two cases, it was found to be significantly reduced than the fluorescence of the polymer before glucose addition. The addition of glucose reduced 51% of blue fluorescence at 416 nm.
On the other hand, in the cationic linear conjugated polymer compound D of Comparative Preparation Example 2, the blue fluorescence at 416 nm was decreased by 28% by the addition of galactose, and the blue fluorescence at 416 nm was reduced by 29% when fructose was added. It was. In the case of glucose, as in the previous two cases, a 32% decrease was observed, which is slightly decreased than the fluorescence of the polymer before glucose addition.
From the results of Experimental Examples 1 and 2, it was confirmed that the prepared polymer compound can be used as a selective biosensor in which the reduction of fluorescence varies depending on the type of monosaccharide, but the linear having a limited number of boronic acids at the terminal In the case of the polymers (compounds C and D prepared in Comparative Preparation Examples 1 and 2), glucose was not selectively detected and thus the fluorescence intensity was not reduced. On the other hand, in the case of hyperbranched polymers (compounds A and B prepared in Examples 1 and 2) containing a large amount of boronic acid in the terminal group, fluorescence was quenched by selectively detecting glucose. Among the polymer compounds prepared based on this, the hyperbranched conjugated polymer having a high end group ratio selectively detects monosaccharides (glucose), as prepared in Examples 1 and 2, whereas it is prepared in Comparative Preparation Examples 1 and 2. It was confirmed that the linear conjugated polymer is inferior in selectivity because of the relatively limited number of end groups.
Claims (10)
[Formula 1]
[In the above formula (1)
Ar is (C6-C20) arylene or (C2-C12) heteroarylene containing at least one hetero atom selected from N, O and S;
R 1 and R 2 are each independently a linear or branched C 1 to C 6 alkyl group substituted with sulfonic acid, sulfonic acid salt or tri (C 1 -C 7) alkylammonium salt at the end;
R 3 is
m is an integer from 1 to 30.]
The terminal of the alkyl group of R 1 and R 2 is independently a water-soluble superbranched conjugated polymer compound, characterized in that substituted with sulfonic acid, sulfonic acid salt, trimethylammonium salt, ethyldimethylammonium salt, diethylmethylammonium salt or triethylammonium salt. .
The alkyl groups of R 1 and R 2 are independently of each other methyl, ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, n-pentyl, i-pentyl or n-hexyl A water-soluble hyperbranched conjugated polymer compound.
Ar is a water-soluble hyperbranched conjugated polymer compound, characterized in that phenylene or thienylene.
The water-soluble hyperbranched conjugated polymer compound is a water-soluble hyperbranched conjugated polymer compound, characterized in that the number average molecular weight of 3,000 to 100,000.
[Reaction Scheme 1]
Scheme 2
[Scheme 1 and 2,
Ar is (C6-C20) arylene or (C2-C12) heteroarylene containing at least one hetero atom selected from N, O and S;
R 1 and R 2 are each independently a linear or branched C 1 to C 6 alkyl group substituted with sulfonate or tri (C 1 -C 7) alkylammonium salt at the end;
X is Cl, Br or I; R 3 is
The sensor is characterized in that the chemical sensor or biosensor.
The sensor is characterized in that for the selective detection of monosaccharides using a fluorophotometer.
The monosaccharide sensor is characterized in that the glucose.
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| KR101529049B1 (en) * | 2013-08-23 | 2015-06-16 | 충남대학교산학협력단 | Method for selective detection of trypsin using complex of fluorescent polymer nanoparticle and graphene oxide |
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| JP2006036664A (en) | 2004-07-23 | 2006-02-09 | Terumo Corp | Saccharide-measuring fluorescent monomer compound, saccharide-measuring fluorescent sensor substance and implantatble saccharide-measuring sensor |
| US20090081803A1 (en) | 2007-07-11 | 2009-03-26 | Glumetrics Inc. | Polyviologen boronic acid quenchers for use in analyte sensors |
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| JP2006036664A (en) | 2004-07-23 | 2006-02-09 | Terumo Corp | Saccharide-measuring fluorescent monomer compound, saccharide-measuring fluorescent sensor substance and implantatble saccharide-measuring sensor |
| US20090081803A1 (en) | 2007-07-11 | 2009-03-26 | Glumetrics Inc. | Polyviologen boronic acid quenchers for use in analyte sensors |
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