CN101921376A - Chiral three-component polymer with recognition capability, preparation and application thereof - Google Patents
Chiral three-component polymer with recognition capability, preparation and application thereof Download PDFInfo
- Publication number
- CN101921376A CN101921376A CN 201010222860 CN201010222860A CN101921376A CN 101921376 A CN101921376 A CN 101921376A CN 201010222860 CN201010222860 CN 201010222860 CN 201010222860 A CN201010222860 A CN 201010222860A CN 101921376 A CN101921376 A CN 101921376A
- Authority
- CN
- China
- Prior art keywords
- chiral
- preparation
- function monomer
- polymer
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a chiral three-component polymer with recognition capability, preparation and an application thereof. In the invention, a functional monomer based on chiral dipeptide and a thiourea action unit are grafted onto surfaces of Si, SiO2, Au, Ag, Cu, Al, Pt, CuO, Al2O3 or porous silica gel by a method of surface-initiated-atom transfer radical polymerization reaction to obtain a functional surface of the chiral three-component polymer. By adjusting the functional monomer variety, monomer ingredient proportion and grafting surface types, a series of the chiral functional surfaces can be obtained; and the functional polymer shows very good development prospect in chiral recognition and detection, chiral separation and chiral resolution of sugar, amino acid and chiral drugs and other aspects.
Description
Technical field
The present invention relates to chiral three-component polymer, enantioselectivity function monomer, chiral polymer grafting surface, chiral polymer the derive preparation method and the purposes of silica gel.
Background technology
Chirality is the most basic attribute of nature, and chiral material extensively is present in occurring in nature, and the enantiomorph of chiral material (particularly chiral drug) shows marked difference at aspects such as biological activity, drug effect, toxicity and metabolism.Polymeric film with corresponding selection identification and separation function has great importance for the aspects such as detection, Separation of Enantiomers and chiral catalysis of chiral material enantiomeric purity.The current detection that is used for enantiomeric purity mainly depends on isolation technique, particularly uses liquid chromatography, gas-chromatography and the capillary electrophoresis technique etc. of chiral stationary phase.And the core of this technology is the selection and the preparation of chiral stationary phase, the present invention has developed a series of function monomer and thiocarbamide action cell based on the chirality dipeptides, and by the method for surface initiation-atom transfer radical polymerization they are grafted on the various surfaces, obtain the chiral polymer film of tens nanometers.This class chirality film or chirality probe molecule to the identification of monose, amino acid, chiral drug enantiomorph with separate aspect, demonstrate excellent effect, be expected to obtain to use widely at aspects such as the exploitation of enantiomorph detection means, chiral material separation in enormous quantities.
Summary of the invention
Purpose of the present invention aims to provide a kind of chiral three-component polymer and preparation and application with recognition capability.By the preparation method who provides a class to have the function monomer of enantio-selectivity recognition capability, and by surface initiation---the method for atom transfer radical polymerization, at inorganic semiconductor Si or SiO
2, or metal A u, Ag, Cu, Al or Pt, or metal oxide CuO or Al
2O
3Prepare the chiral three-component polymer film Deng, porous silica gel surface grafting.
The object of the invention adopts following proposal to realize:
A kind of three-component polymer is characterized in that, have following P1, P2, P3 or, the molecular structure shown in the P4:
Among P1, P2, P3 and the P4, x:0.01～0.5 y:0.01～0.5
The preparation method of three-component polymer of the present invention utilizes atom transition free radical polymerization reaction mechanism, and three component function copolymer grafted on inorganic semiconductor or metal or metal oxide surface, are obtained the chiral three-component polymer film; Described inorganic semiconductor is Si or SiO
2Described metal is Au, Ag, Cu, Al or Pt; Described metal oxide is CuO or Al
2O
3
The preparation method of three-component polymer of the present invention: three component function multipolymers are derived to be grafted on silica gel or the porous material surface, obtains the chiral three-component polymer film; Described porous material is hydroxyl phosphorus silica or porous alumina.
Three-component polymer of the present invention is applied in chiral recognition, detection and the fractionation field of sugar.
Description of drawings
The surface contact angle value of Fig. 1, chiral three-component polymer surface P1 is with the relation curve of change in concentration.
The chiral polymer surface by being concentration gradient L-or after D-lyxose (lyxose) solution soaking handled, the surface contact angle value of mensuration was with the relation curve of change in concentration.Different variation responding ranges, and the slope of different linear relationships shows that the chiral polymer surface has good chiral selectivity recognition capability to Lyxose, responding ability to D-lyxose obviously is better than L-lyxose, and the significant macroscopic view of simultaneous changes.
Fig. 2, chiral three-component polymer surface P1 are to the identification responding ability of multiple chirality monose
Fig. 2 has shown the P1 polymer surfaces has been immersed in 0.02mol L respectively
-1Various sugar solns in, soak after 10 minutes, the wetting property of measuring the surface changes.The P1 surface has all embodied chirality separating capacity preferably to multiple chirality sugar as we can see from the figure, particularly to Lyxose (lyxose) and Xylose (wood sugar) chiral selectivity obvious difference.Therefore can be as the chirality detection probes of monose, further exploitation can be used for the chiral separation of sugar.
Fig. 3, chiral three-component polymer surface P2 are to the identification responding ability of multiple chirality monose
Fig. 3 has shown three-component polymer surface P2 has been immersed in 0.02mol L respectively
-1Various sugar solns in, soak after 10 minutes, the wetting property of measuring the surface changes.The P2 surface has also embodied chirality separating capacity preferably to multiple chirality sugar as we can see from the figure, particularly to Arabinose (pectinose) and Mannose (seminose) chiral selectivity obvious difference.Therefore also can be as the chirality detection probes of monose, further exploitation can be used for the chiral separation of sugar.
Fig. 4, at the structure iron of silica gel surface grafting three-component polymer.
Embodiment
Raw materials used among the embodiment:
Silicon chip is buied by Silicon Materials Corporation (Germany), and HPLC column chromatography filler silica gel (amido modified) is buied by Shanghai moon rising sun company.N-β-L-aspartyl-L-phenylalanine methyl ester (L-L-aspartyl-L-phenylalanine methylester), CuBr (99.999%), N, N, N ', N ', N "-Pentamethyl-diethylenetriamine (PMDETA); dipyridyl; pyridine, triethylamine, thionyl chloride; N-isopropylacrylamide, acrylate chloride is buied by Sigma-Aldrich company.3,5-Bis (trifluoromethyl) phenylthiourea, 4-(trifluoromethyl) phenylthiourea, phenylthio-urea, acetone, methyl alcohol, DMF, sodium hydroxide, the chirality monose that various tests are used is buied by Alfa company.N-isopropylacrylamide is used the normal hexane recrystallization three times before use, is placed in the vacuum drier standby.Other reagent all use commercially available analytical pure.
1Hand
13C NMR spectra detects at Bruker ARX300 spectrometer and obtains.
Embodiment 1
The preparation of three component P1 polymer surfaces
x：0.01～0.5 y：0.01～0.5
In flask at the bottom of the garden of 25mL, add 0.814g (7.2mmol) N-isopropylacrylamide successively, 0.326g chirality function monomer L-MAP (1) (0.9mmol), 0.308g thiocarbamide function monomer 3 (0.9mmol), material mol ratio are 8: 1: 1, add 3mL H simultaneously
2O, 3mL CH
3OH and 6mL DMF are as polymerization solvent.Under agitation feed nitrogen 40min; after treating that monomer fully dissolves; under nitrogen protection, add Catalysts Cu Br 0.032g and Pentamethyl diethylene triamine (PMDETA) or bipyridine ligand 0.14mL; reaction system vacuumizes-inflated with nitrogen subsequently, and three times fully to remove oxygen remaining in the reaction system so repeatedly.The inorganic semiconductor that bromination was before handled (as Si, SiO
2) or the metallic surface (as Au, Ag, Cu, Al, Pt, CuO, Al
2O
3Deng) immerse the reaction soln configure.The temperature of reaction flask is controlled in the water-bath about 60 ℃ standing and reacting 5-7 hour with this understanding.Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, and the thickness of this polymer surfaces is approximately 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.Use identical method polymerization to obtain three component P1 multipolymer surfaces of different mol ratio example.
Embodiment 2
The preparation of three component P2 polymer surfaces
x：0.01～0.5 y：0.01～0.5
In flask at the bottom of the garden of 25mL, add 0.814g (7.2mmol) N-isopropylacrylamide successively, 0.313g chirality function monomer L-AP (2) (0.9mmol), 0.308g thiocarbamide function monomer 3 (0.9mmol), material mol ratio are 8: 1: 1, add 3mL H simultaneously
2O, 3mL CH
3OH and 4mL DMF are as polymerization solvent.Under agitation feed nitrogen 40min; after treating that monomer fully dissolves; under nitrogen protection, add Catalysts Cu Br 0.032g and Pentamethyl diethylene triamine (PMDETA) or bipyridine ligand 0.14mL; reaction system vacuumizes-inflated with nitrogen subsequently, and three times fully to remove oxygen remaining in the reaction system so repeatedly.The inorganic semiconductor that bromination was before handled (as Si, SiO
2) or the metallic surface (as Au, Ag, Cu, Al, Pt, CuO, Al
2O
3Deng) immerse the reaction soln configure.The temperature of reaction flask is controlled in the water-bath about 60 ℃ standing and reacting 5-7 hour with this understanding.Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, and the thickness of this polymer surfaces is approximately 10-30nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.Use identical method polymerization to obtain three component P2 multipolymer surfaces of different mol ratio example.
Embodiment 3
The preparation of three component P3 polymer surfaces
x：0.01～0.5 y：0.01～0.5
In flask at the bottom of the garden of 25mL, add 0.814g (7.2mmol) N-isopropylacrylamide successively, 0.326g chirality function monomer L-MAP (1) (0.9mmol), 0.246g thiocarbamide function monomer 4 (0.9mmol), material mol ratio are 8: 1: 1, add 3mL H simultaneously
2O, 3mL CH
3OH and 3mL DMF are as polymerization solvent.Under agitation feed nitrogen 40min; after treating that monomer fully dissolves; under nitrogen protection, add Catalysts Cu Br 0.032g and Pentamethyldiethylene triamine (PMDETA) or bipyridine ligand 0.14mL; reaction system vacuumizes-inflated with nitrogen subsequently, and three times fully to remove oxygen remaining in the reaction system so repeatedly.The inorganic semiconductor that bromination was before handled (as Si, SiO
2) or the metallic surface (as Au, Ag, Cu, Al, Pt, CuO, Al
2O
3Deng) immerse the reaction soln configure.The temperature of reaction flask is controlled in the water-bath about 60 ℃ standing and reacting 5-7 hour with this understanding.Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, and the thickness of this polymer surfaces is approximately 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.Use identical method polymerization to obtain three component P3 multipolymer surfaces of different mol ratio example.
Embodiment 4
The preparation of three component P4 polymer surfaces
x：0.01～0.5 y：0.01～0.5
In flask at the bottom of the garden of 25mL, add 0.814g (7.2mmol) N-isopropylacrylamide successively, 0.326g chirality function monomer L-MAP (1) (0.9mmol), 0.185g thiocarbamide function monomer 5 (0.9mmol), material mol ratio are 8: 1: 1, add 3mL H simultaneously
2O, 3mL CH
3OH and 1mL DMF are as polymerization solvent.Under agitation feed nitrogen 40min; after treating that monomer fully dissolves; under nitrogen protection, add Catalysts Cu Br 0.032g and Pentamethyldiethylene triamine (PMDETA) or bipyridine ligand 0.14mL; reaction system vacuumizes-inflated with nitrogen subsequently, and three times fully to remove oxygen remaining in the reaction system so repeatedly.The inorganic semiconductor that bromination was before handled (as Si, SiO
2) or the metallic surface (as Au, Ag, Cu, Al, Pt, CuO, Al
2O
3Deng) immerse the reaction soln configure.The temperature of reaction flask is controlled in the water-bath about 60 ℃ standing and reacting 5-7 hour with this understanding.Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, and the thickness of this polymer surfaces is approximately 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.Use identical method polymerization to obtain three component P4 multipolymer surfaces of different mol ratio example.
Embodiment 5
In the method for silica gel surface grafting three-component polymer,
Cryosel is bathed in the environment, adds silica gel and dry chloroform of 30mL or methylene dichloride that 10g modifies through amino surface in the round-bottomed flask of 50mL, adds 2mL exsiccant pyridine simultaneously.Fully stir and slowly drip 3mL bromo isobutyl acylbromide down, about 30min is added dropwise to complete.Be added dropwise to complete recession deicing salt bath, continued stirring reaction 24 hours.Suction filtration obtains a large amount of white solid powder, several times with the washing of 30mL chloroform; Obtain the silica gel product that bromo is modified after the vacuum-drying.With the P1 copolymer grafted to the silica gel surface as an example, P2～P4 grafted method is similar with it.The collocation method of solution after configuring reaction soln and adding catalyst ligand, drops into the silica gel that the 10g bromo is modified, initiated polymerization before the polymerization in polymerization system shown in example 1.The temperature of reaction flask is controlled in the oil bath pan about 60 ℃, and the mechanical stirring reaction is 24 hours with this understanding.Reaction finishes the pressed powder that the back suction filtration obtains a large amount of oysters, uses DMF, C successively
2H
5OH, CH
3OH respectively washs 2 times, to remove unreacted monomer and catalyzer, part.Vacuum-drying obtains a large amount of white solid powder.Use identical method can prepare varying particle size (comprising the silica gel particle diameter, the aperture), chiral polymer P1～P4 grafted silica gel sample, as the packing material of chiral column.
The structure of enantioselectivity function monomer and synthetic method
For preparing above-mentioned chiral polymer, need synthetic a series of chirality function monomer and Thiourea regulation and control monomer, synthetic method that they are concrete such as following embodiment.
Embodiment 6
The preparation of intermediate M-1 (L-aspartoyl phenylalanine dimethyl ester): bathe in the environment at cryosel, N-β-L-aspartyl-L-phenylalanine methyl ester (L-L-aspartyl-L-phenylalanine methylester) of 2.94g (10mmol) is dissolved in the dry methyl alcohol of 40mL, under the agitation condition, in above-mentioned solution, slowly drip the 6mL thionyl chloride, dropwised in about 30 minutes.Behind the stirring reaction one hour, remove cryosel and bathe, in room temperature environment, continued stirring reaction three hours.After reaction finished, most solvent of pressure reducing and steaming and remaining thionyl chloride obtained a large amount of half oily matter.This half oily matter is dissolved in the dry methyl alcohol of 30mL, and underpressure distillation removes and desolvates once more, and this operation is 3 times repeatedly, removes fully until thionyl chloride.Obtain about 3.38g white solid powder, productive rate 98% by oil pump vacuum-drying.The structure of this product has been undertaken characterizing evaluation by proton nmr spectra, carbon-13 nmr spectra, mass spectrum, and data are as follows:
1H NMR (300MHz, d
6-DMSO): δ (ppm): 2.76-2.80 (m, 2H, CH-Ph), 2.85-2.93 (m, 1H, CHCO), 3.00-3.07 (m, 1H, CHCO), 3.61 (s, 3H, OCH
3), 3.62 (s, 3H, OCH
3), 4.46-4.54 (m, 1H, * H
b), 4.23-4.27 (m, 1H, * H
a), 7.20 (s, 1H, Ph-H), 7.22-7.23 (m, 2H, Ph-H), 7.28 (s, 1H, Ph-H), 7.29-7.20 (m, 2H, Ph-H), 8.39 (s, 2H, NH
2), 8.80 (d, J=6Hz, 1H, CONH);
13C NMR (300MHz, d
6-DMSO): δ (ppm): 34.2,36.7,48.4,51.9,52.6,53.6,126.5,128.2,129.0,136.9,168.3,169.0,171.6; MADLI MS:m/z calcd for C
15H
20N
2O
5: 308.33; Found:309.14[M+H]
+
The preparation of chirality function monomer 1: 1.01g (10mmol) triethylamine and 1.72g (5mmol) N-β-L-aspartyl-L-phenylalanine di-methyl ester (L-aspartoyl phenylalanine dimethyl ester) are dissolved in the dry chloroform of 50mL stirring reaction 10 minutes; At ambient temperature, 0.453g (5mmol) acrylate chloride is dropwise dropped in the above-mentioned mixed solution, continue stirring reaction 24 hours.Reaction is transferred to solution in the separating funnel after finishing, and uses distilled water wash three times, and chloroform spends the night with anhydrous sodium sulfate drying.After the filtration, most solvent is revolved in decompression, and vacuum-drying obtains a large amount of white solid powder, about 1.54g, productive rate 85%, this product need not further separation and purification, the structure of this product has been undertaken characterizing evaluation by nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, mass spectrum, and data are as follows:
1H NMR (300MHz, d
6-DMSO): δ (ppm): 2.56 (d, J=9Hz, 1H, CH-Ph), 2.62 (d, J=6Hz, 1H, CH-Ph), 2.84and 2.88 (d, d, J
1=J
2=9Hz, 1H, CHCO), 2.96and 3.01 (d, d, J
1=J
2=6Hz, 1H, CHCO), 3.57 (s, 3H, OCH
3), 3.58 (s, 3H, OCH
3), 4.41-4.48 (m, 1H, * H
b), 4.58-4.65 (m, 1H, * H
a), 5.60and 5.64 (d, d, J
1=J
2=3Hz, 1H, C=CH
2), 6.05and6.11 (d, d, J
1=J
2=3Hz, 1H, C=CH
2), 6.25and 6.31 (d, d, J
1=12Hz, J
2=9Hz, 1H, CH=C), 7.20 (d, J=1.5Hz, 2H, Ph-H), 7.22-7.23 (m, 1H, Ph-H), 7.25 (s, 1H, Ph-H), 7.26-7.27 (m, 1H, Ph-H), 8.44 (d, J=9Hz, 1H, CONH), 8.49 (d, J=9Hz, 1H, CONH);
13C NMR (300MHz, CDCl
3): δ (ppm): 37.1,37.6,48.9,52.1,52.7,53.6,127.1,127.3,127.6,128.6,129.1,129.2,130.1,130.3,135.8,165.3,169.9,171.4,171.8; MADLI MS:m/z calcd for C
18H
22N
2O
6: 362.38; Found:385.14[M+Na]
+
Embodiment 7
The preparation of chirality function monomer 2:
Bathe in the environment at cryosel, 2.94g (10mmol) N-β-L-aspartyl-L-phenylalanine methyl ester is dissolved in the 10mL 1N NaOH solution, stirring reaction 10 minutes, 0.905g (10mmol) acrylate chloride is dropwise dropped in the above-mentioned solution, dropwised in about 30 minutes.In dripping the process of acrylate chloride, by dripping 2N NaOH solution, the pH value of reaction system is remained at about 11.After dropwising, the pH value of solution is increased to neutrality gradually, continues stirring reaction 2 hours in room temperature environment.Then be adjusted near 2 acidification reaction 20 minutes with the pH value of 2N hydrochloric acid soln with reaction soln.With the above-mentioned reaction solution of 50mL ethyl acetate extraction 4 times, combined ethyl acetate spends the night mutually and with anhydrous sodium sulfate drying.Most of solvent is revolved in filtration, and vacuum-drying obtains the 3.14g white powder, productive rate 90%.The structure of this product has been undertaken characterizing evaluation by nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, mass spectrum, and data are as follows:
1H NMR (300MHz, d
6-DMSO): δ (ppm): 2.55-2.58 (m, 1H, CH-Ph), 2.61-2.64 (m, 1H, CH-Ph), 2.85-2.92 (m, 1H, CHCO), 2.95-3.00 (m, 1H, CHCOO), 3.57 (s, 3H, OCH
3), 4.37-4.44 (m, 1H, * H
b), 4.51-4.58 (m, 1H, * H
a), 5.59and 5.62 (d, d, J
1=J
2=3Hz, 1H, C=CH), 6.04 and 6.10 (d, d, J
1=J
2=3Hz, 1H, C=CH), 6.25 and 6.28 (d, d, J
1=J
2=3Hz, 1H, CH=C), 7.18-7.19 (m, 1H, Ph-H), 7.20-7.21 (m, 2H, Ph-H), 7.24-7.25 (m, 1H, Ph-H), 7.26-7.27 (m, 1H, Ph-H), 8.26 (d, J=3Hz, 1H, CONH), 8.30 (s, 1H, CONH), 12.55-12.65 (br, 1H, COOH);
13C NMR (300MHz, d
6-DMSO): δ (ppm): 36.6,36.7,48.7,51.8,53.6,53.7,125.6,126.5,128.2,129.0,129.4,130.7,131.3,137.4,164.2,169.1,171.8,172.5; MADLI MS:m/z calcd for C
17H
20N
2O
6: 348.35; Found:347.12[M-1]
+..
Embodiment 8
The preparation of thiocarbamide function monomer 3:
In room temperature environment, with 0.505g (5mmol) triethylamine and 1.44g (5mmol) 3,5-Bis (trifluoromethyl) phenyl-thiourea is dissolved in the dry chloroform of 30mL, under the agitation condition, 0.453g (5mmol) acrylate chloride is dropwise dropped in the above-mentioned mixed solution, continue reaction 24 hours.Reaction finish the back with distilled water wash reaction solution 3 times to remove triethylamine hydrochloride, organic phase is spent the night with anhydrous sodium sulfate drying.Filter the back decompression and revolve most solvent, resistates is gone to silicagel column separate, the drip washing solvent polarity is CH
2Cl
2/ CH
3OH (100: 1) separates obtaining the yellow half oily target product of 1.40g, productive rate 82%.The structure of product has been undertaken characterizing evaluation by nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, mass spectrum, and data are as follows:
1H NMR (300MHz, CDCl
3): 5.66-5.73 (m, 1H, CH=C), 6.27-6.32 (m, 2H, C=CH), 7.62 (s, 2H, Ph-H), 7.88 (d, J=9Hz, 1H, Ph-H), 8.03 (d, J=15Hz, 1H, CSNH), 9.73 (s, 1H, CSNH).
13C NMR (300MHz, CDCl
3): δ (ppm): 118.0,121.3,122.1,126.6,131.9,132.1,148.3,153.7,170.3; MADLI MS:m/z calcd for C
12H
8F
6N
2OS:342.26; Found:365.016[M+Na]
+..
Embodiment 9
The preparation of thiocarbamide function monomer 4
The preparation of thiocarbamide function monomer 4: in room temperature environment, 0.505g (5mmol) triethylamine and 1.10g (5mmol) 4-trifluoromethyl phenyl-thiourea are dissolved in the dry chloroform of 30mL, under the agitation condition, 0.453g (5mmol) acrylate chloride is dropwise dropped in the above-mentioned mixed solution, continue reaction 24 hours.Reaction finish the back with distilled water wash reaction solution 4 times to remove triethylamine hydrochloride, organic phase is spent the night with anhydrous sodium sulfate drying.Filter the back decompression and revolve most solvent, resistates is gone to silicagel column separate, the drip washing solvent polarity is CH
2Cl
2/ CH
3OH (150: 1) separates obtaining the yellow half oily target product of 1.27g, productive rate 93%.The structure of product has been carried out the indicator evaluation by nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, mass spectrum, and data are as follows:
1H NMR (300MHz, CDCl
3): 5.73 (d, J=6Hz, 1H ,=CH), 6.31-6.36 (m, 2H ,=CH), 7.01 (d, J=6Hz, 2H, Ph-H), 7.28 (s, 1H, CNHCS), 7.61 (d, J=6.5Hz, 2H, Ph-H), 7.70 (s, 1H, CNHCS);
13C NMR (300MHz, CDCl
3): 115.6,117.2,121.3,122.1,126.4,127.2,132.9,144.4,157.3; MADLI-MS:m/z calcd for C
11H
9F
3N
2OS:274.04; Found:275.046.
The preparation of Thiourea monomer 5
The preparation of thiocarbamide function monomer 5: in room temperature environment, 0.505g (5mmol) triethylamine and 0.76g (5mmol) phenyl-thiourea are dissolved in the dry chloroform of 30mL, under the agitation condition, 0.453g (5mmol) acrylate chloride is dropwise dropped in the above-mentioned mixed solution, continue reaction 24 hours.Reaction finish the back with distilled water wash reaction solution 4 times to remove triethylamine hydrochloride, organic phase is spent the night with anhydrous sodium sulfate drying.Filter the back decompression and revolve most solvent, resistates is gone to silicagel column separate, the drip washing solvent polarity is CH
2Cl
2/ CH
3OH (80: 1) separates obtaining the yellow half oily target product of 0.74g, productive rate 72%.The structure of product has been carried out the indicator evaluation by nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum, mass spectrum, and data are as follows:
1H NMR (300MHz, CDCl
3): 6.00 (d, J=25.5Hz, 1H ,=CH), 6.27 (d, J=27Hz, 1H ,=CH), 6.61 (m, 1H ,=CH), 7.19 (m, 1H, Ph-H), 7.47 (m, 1H, Ph-H), 7.75 (m, 1H, Ph-H), 9.35 (s, 1H, CNHCS), 12.54 (s, 1H, ArNHCS);
13C NMR (300MHz, CDCl
3): 124.9,126.3,129.1,129.2,132.1,138.1,169.8,183.5; MADLI:m/z calcd for C
10H
10N
2OS:206.051; Found:229.1 (M+Na
+).
Application example
Embodiment 11
By the surface wettability method for measuring, estimated the enantioselectivity recognition capability of chiral polymer surface P1 to sugar, L-or D-Lyxose (lyxose) with chirality are example, Fig. 1 has shown chiral polymer surface L-or D-lyxose solution soaking processing back its surface contact angle value of mensuration by being concentration gradient, has obtained the relation curve of contact angle with change in concentration.Accurately dispose the chirality monose solution of different concns before measuring, concentration range is from 1X10
-4Mol L
-1To 0.05mol L
-1Under room temperature (20 ℃) condition, the surface immersion of polymer graft is immersed in respectively in the monose solution that configures, soaks and take out the surface after 10 minutes, dry up with nitrogen gas stream then, place on the contact angle measurement and measure, repeated experiments 3 times is to obtain contact angle numerical value accurately.Different variation responding ranges, and the slope of different linear relationships shows that the chiral polymer surface has good chiral selectivity recognition capability to Lyxose, responding ability to D-lyxose obviously is better than L-lyxose, and the significant macroscopic view of simultaneous changes.This has shown the very outstanding chiral selectivity recognition capability of this type of chiral polymer, has boundless application prospect in chiral recognition, detection, the fractionation field of sugar.
Embodiment 12:
P1 chiral polymer surface is to the identification responding ability test of multiple chirality monose
P1 chiral polymer surface is to the identification responding ability (see figure 2) of multiple chirality monose, and Fig. 2 has shown the P1 polymer surfaces is immersed in 0.02mol L respectively
-1Various sugar solns in, soak after 10 minutes, the wetting property of measuring the surface changes.The P1 surface has all embodied chirality separating capacity preferably to multiple chirality sugar as we can see from the figure, particularly to Lyxose and Xylose chiral selectivity obvious difference.Therefore can be as the chirality detection probes of monose, further exploitation can be used for the chiral separation of sugar.
Embodiment 13:
P2 chiral polymer surface is to the identification responding ability test of multiple chirality monose
P2 chiral polymer surface is to the identification responding ability (see figure 3) of multiple chirality monose, and Fig. 3 has shown the P2 polymer surfaces is immersed in 0.02mol L respectively
-1Various sugar solns in, soak after 10 minutes, the wetting property of measuring the surface changes.The P2 surface has also embodied chirality separating capacity preferably to multiple chirality sugar as we can see from the figure, particularly to Arabinose (pectinose) and Mannose (seminose) chiral selectivity obvious difference.Therefore also can be as the chirality detection probes of monose, further exploitation can be used for the chiral separation of sugar.
Embodiment 14:
P3, P4 chiral polymer surface also has and the similar recognition performance of P1 chiral surfaces, and multiple monose is also had chiral recognition separating capacity preferably.In view of P3, P4 and the P1 surface similarity aspect molecular structure, difference is introducing and the position of substitution on thiocarbamide phenyl ring group of trifluoromethyl group, and the thiocarbamide functional unit is a core cell of adjusting the response of polymkeric substance wetting property, therefore cause P3, the P4 surface is different aspect the interval range of wetting property response.Because the unitary reservation of chirality effect dipeptides, they also have chiral recognition ability preferably to sugar.Dimension P3, P4 chiral polymer surface also can be used in fields such as sugared chiral recognition, fractionation.
Claims (13)
1. a three-component polymer is characterized in that, have following P1, P2, P3 or, the molecular structure shown in the P4:
x：0.01～0.5 y：0.01～0.5
2. the preparation method of the described three-component polymer of claim 1, it is characterized in that: utilize atom transition free radical polymerization reaction mechanism, three component function copolymer grafted on inorganic semiconductor or metal simple-substance or metal oxide surface, are obtained the chiral three-component polymer film; Described inorganic semiconductor is Si or SiO
2Described metal is Au, Ag, Cu, Al or Pt; Described metal oxide is CuO or Al
2O
3
3. the preparation method of the described three-component polymer of claim 1, it is characterized in that: three component function multipolymers are derived to be grafted on silica gel or the porous material surface, obtains the chiral three-component polymer film; Described porous material is hydroxyl phosphorus silica or porous alumina.
4. the preparation method of the described three-component polymer P1 of claim 1, it is characterized in that: in the flask of 25mL, add the 7.2mmol N-isopropylacrylamide successively, the chirality function monomer 1 of 0.9mmol, the thiocarbamide function monomer 3 of 0.9mmol, the material mol ratio is 8: 1: 1, adds 3mL H simultaneously
2O, 3mL CH
3OH and 6mL DMF make solvent; Under agitation feed nitrogen, treat that monomer fully dissolves after, under nitrogen protection, add Catalysts Cu Br 0.032g and PMDETA or bipyridine ligand 0.14mL, reaction system vacuumizes-inflated with nitrogen subsequently, removes oxygen remaining in the reaction system; The Si that bromination was handled,, SiO
2, Au, Ag, Cu, Al, Pt, CuO or Al
2O
3The reaction soln that immersion configures; The temperature of flask was controlled at 60 ℃ of standing and reacting 5-7 hours; Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, obtains three component copolymers P1 surfaces, and the thickness of this polymer surfaces is 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.
5. the preparation method of the described three-component polymer P2 of claim 1, it is characterized in that: in the 25mL flask, add the 7.2mmol N-isopropylacrylamide successively, the chirality function monomer 2 of 0.9mmol, the thiocarbamide function monomer 3 of 0.9mmol, the material mol ratio is 8: 1: 1, adds 3mL H simultaneously
2O, 3mL CH
3OH and 6mL DMF make solvent; Under agitation feed nitrogen, treat that monomer fully dissolves after, under nitrogen protection, add Catalysts Cu Br 0.032g and PMDETA or bipyridine ligand 0.14mL, reaction system vacuumizes-inflated with nitrogen subsequently, removes oxygen remaining in the reaction system; Si, SiO that bromination was handled
2, Au, Ag, Cu, Al, Pt, CuO or Al
2O
3The reaction soln that immersion configures; The temperature of flask was controlled at 60 ℃ of standing and reacting 5-7 hours; Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, obtains three component copolymers P2 surfaces, and the thickness of this polymer surfaces is 10-30nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.
6. the preparation method of the described three-component polymer P3 of claim 1, it is characterized in that: in the flask of 25mL, add the 7.2mmol N-isopropylacrylamide successively, the chirality function monomer 1 of 0.9mmol, the thiocarbamide function monomer 4 of 0.9mmol, the material mol ratio is 8: 1: 1, adds 3mL H simultaneously
2O, 3mLCH
3OH and 3mL DMF are as polymerization solvent; Under agitation feed nitrogen, treat that monomer fully dissolves after, under nitrogen protection, add Catalysts Cu Br 0.032g and PMDETA or bipyridine ligand 0.14mL, reaction system vacuumizes-inflated with nitrogen subsequently, removes oxygen remaining in the reaction system; Si, SiO that bromination was handled
2, Au, Ag, Cu, Al, Pt, CuO or Al
2O
3The reaction soln that immersion configures, controlled temperature was at 60 ℃ of standing and reacting 5-7 hours; Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, obtains three component copolymers P3 surfaces, and the thickness of this polymer surfaces is 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.
7. the preparation method of the described three-component polymer P4 of claim 1 is characterized in that, adds the 7.2mmol N-isopropylacrylamide in the flask of 25mL successively, 0.9mmol chirality function monomer 1,0.9mmol thiocarbamide function monomer 5, the material mol ratio is 8: 1: 1, adds 3mL H simultaneously
2O, 3mLCH
3OH and 1mL DMF are as polymerization solvent; Under agitation feed nitrogen, treat that monomer fully dissolves after, under nitrogen protection, add Catalysts Cu Br 0.032g and PMDETA or bipyridine ligand 0.14mL, reaction system vacuumizes-inflated with nitrogen subsequently, removes oxygen remaining in the reaction system; Si, SiO that bromination was handled
2, Au, Ag, Cu, Al, Pt, CuO or Al
2O
3The reaction soln that immersion configures; Controlled temperature was at 60 ℃ of standing and reacting 5-7 hours; Reaction finishes back DMF, CH
3OH, H
2O is washing copolymer grafting surface successively, obtains three component copolymers P4 surfaces, and the thickness of this polymer surfaces is 20-100nm, and nitrogen dries up the surface and is placed in the vacuum drier standby.
8. the preparation method of chirality function monomer 1 is characterized in that: carries out according to the following procedure,
9. the preparation method of chirality function monomer 2 is characterized in that: carries out according to the following procedure,
10. the preparation method of thiocarbamide function monomer 3 is characterized in that: carries out according to the following procedure,
11. the preparation method of thiocarbamide function monomer 4 is characterized in that: carry out according to the following procedure,
12. the preparation method of thiocarbamide function monomer 5 is characterized in that: carry out according to the following procedure,
13. the application of the described three-component polymer of claim 1 is characterized in that: the chiral recognition, detection and the fractionation field that are applied in sugar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102228601A CN101921376B (en) | 2010-07-06 | 2010-07-06 | Chiral three-component polymer with recognition capability, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102228601A CN101921376B (en) | 2010-07-06 | 2010-07-06 | Chiral three-component polymer with recognition capability, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101921376A true CN101921376A (en) | 2010-12-22 |
| CN101921376B CN101921376B (en) | 2012-04-04 |
Family
ID=43336607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102228601A Expired - Fee Related CN101921376B (en) | 2010-07-06 | 2010-07-06 | Chiral three-component polymer with recognition capability, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101921376B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105181910A (en) * | 2015-10-21 | 2015-12-23 | 武汉理工大学 | Method for measuring enantiomer excess value of monosaccharide |
| CN106749884A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of phosphorylation peptide gathering material and preparation method and application |
| CN106770867A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of method for being enriched with detection phosphorylated protein |
| CN107096504A (en) * | 2017-05-03 | 2017-08-29 | 武汉理工大学 | Compound-modified copper sulfide nano material containing dihydroxy phenyl and its application in glycopeptide enrichment |
| CN108072719A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method of concentration and separation glycopeptide |
| CN111257387A (en) * | 2020-02-19 | 2020-06-09 | 常州大学 | Preparation method of chiral copper oxide-glycine compound modified electrode applicable to electrochemical chiral recognition |
| CN111410768A (en) * | 2020-03-07 | 2020-07-14 | 武汉理工大学 | Three-component intelligent polymer modified porous membrane material and preparation method and application thereof |
| CN111482090A (en) * | 2019-01-25 | 2020-08-04 | 中国科学院大连化学物理研究所 | Intelligent responsive polymer modified porous membrane material and preparation method and application thereof |
-
2010
- 2010-07-06 CN CN2010102228601A patent/CN101921376B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 《J.AM.CHEM.SOC.》 20090603 Guangyan Qing,et al. Nucleotide-responsive wettability on a smart polymer surface 8370-8371 1-13 第131卷, 2 * |
| 《Soft Matter》 20090602 Guangyan Qing,et al. Saccharide-sensitive wettability switching on a smart polymer surface 2759-2765 1-13 第5卷, 2 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105181910A (en) * | 2015-10-21 | 2015-12-23 | 武汉理工大学 | Method for measuring enantiomer excess value of monosaccharide |
| CN106749884A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of phosphorylation peptide gathering material and preparation method and application |
| CN106770867A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of method for being enriched with detection phosphorylated protein |
| CN108072719A (en) * | 2016-11-18 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method of concentration and separation glycopeptide |
| CN107096504A (en) * | 2017-05-03 | 2017-08-29 | 武汉理工大学 | Compound-modified copper sulfide nano material containing dihydroxy phenyl and its application in glycopeptide enrichment |
| CN107096504B (en) * | 2017-05-03 | 2019-10-25 | 武汉理工大学 | Compound-modified copper sulfide nano material containing dihydroxy phenyl and its application in glycopeptide enrichment |
| CN111482090A (en) * | 2019-01-25 | 2020-08-04 | 中国科学院大连化学物理研究所 | Intelligent responsive polymer modified porous membrane material and preparation method and application thereof |
| CN111482090B (en) * | 2019-01-25 | 2021-08-27 | 中国科学院大连化学物理研究所 | Ion-responsive intelligent polymer modified porous membrane material and preparation method and application thereof |
| CN111257387A (en) * | 2020-02-19 | 2020-06-09 | 常州大学 | Preparation method of chiral copper oxide-glycine compound modified electrode applicable to electrochemical chiral recognition |
| CN111257387B (en) * | 2020-02-19 | 2021-11-09 | 常州大学 | Preparation method of chiral copper oxide-glycine compound modified electrode applicable to electrochemical chiral recognition |
| CN111410768A (en) * | 2020-03-07 | 2020-07-14 | 武汉理工大学 | Three-component intelligent polymer modified porous membrane material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101921376B (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921376B (en) | Chiral three-component polymer with recognition capability, preparation and application thereof | |
| CN103301822B (en) | A kind of polar liquid chromatogram filler and preparation method thereof | |
| CN103706341B (en) | Ionic liquid bonding polysiloxane stationary phase and preparation method thereof | |
| CN106770867B (en) | A kind of method for being enriched with detection phosphorylated protein | |
| US5422004A (en) | High performance chiral selector | |
| CN102219800A (en) | Organic substituted boric acid ester, boron affinity functional material using organic substituted boric acid ester as functional monomer as well as preparation and application of organic substituted boric acid ester | |
| CN106749884B (en) | A kind of phosphorylation peptide gathering material and the preparation method and application thereof | |
| EP1269170A1 (en) | Reaction and separation methods | |
| Preinerstorfer et al. | Stereoselective separations of chiral phosphinic acid pseudodipeptides by CEC using silica monoliths modified with an anion‐exchange‐type chiral selector | |
| Alleti et al. | A solanesol-derived scaffold for multimerization of bioactive peptides | |
| CN109705036B (en) | Fluorine-containing quinoline amide folder, preparation method, chiral identification method and application | |
| CN104607163B (en) | A kind of micro- chiral adjusting cellulose chromatography stationary phase, preparation method and applications | |
| CN106946926A (en) | One kind have multiple tooth ammonia carboxylic class dimer chelating agent and preparation method thereof, using and separating medium | |
| JP6083832B2 (en) | Optically active poly (diphenylacetylene) compound, method for producing the same, and use as an optical isomer separating agent | |
| CN103736469A (en) | Ionic liquid bonded polysiloxane stationary phase and preparation method thereof | |
| Villani et al. | Dynamic HPLC of stereolabile iron (II) complexes on chiral stationary phases | |
| CN113372568B (en) | Preparation method of neodymium-based or holmium-based chiral metal-organic porous crystalline material, prepared material and application thereof | |
| CN102335598A (en) | Preparation method of phenothiazine bonded silica gel | |
| CN112881304A (en) | Colored substance rapid detection test paper based on porous metal-organic complex material and detection method and application thereof | |
| Li et al. | Preparation and Characterization of a New Quercetin‐bonded Stationary Phase for High Performance Liquid Chromatography | |
| CN110283087A (en) | Cup [4] squaric amide cyclohexanediamine derivative and its catalysis asymmetric Michael reaction and acetalation tandem reaction method | |
| WO2009066115A1 (en) | Colorimetric sensors for detection of the fluoride anion in solution and gel | |
| CN110372774A (en) | The alpha-acyloxy amides dipeptides analog derivative and synthetic method that isoindolone replaces | |
| CN104876835A (en) | Preparation method and application of Mannich double base | |
| CN112851533B (en) | Chiral fluorescent sensor, preparation method thereof and application thereof in chiral amino acid recognition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120404 Termination date: 20150706 |
|
| EXPY | Termination of patent right or utility model |