CN110204733A - A kind of α-mannose-modified to-receptor type bioabsorbable polymer material and its preparation method and application - Google Patents
A kind of α-mannose-modified to-receptor type bioabsorbable polymer material and its preparation method and application Download PDFInfo
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Abstract
The present invention provide a kind of α-mannose-modified to-receptor type conjugated polymer and preparation method thereof, given by difference, introducings of receptor unit obtains that photophysical property is preferable, polymer of fluorescence emission spectrum wider range.The quasi polymer can target specific recognition α-mannose agglutinin in conjunction with pathogen surface, since variety classes pathogen surface can identify that the type of α-mannose agglutinin and quantity are different, polymer is different from the binding ability of variety classes pathogen, its coherent condition on variety classes pathogen surface is different, so that the transferring efficiency of fluorescence resonance energy of polymeric donor unit to receptor unit is different, by the variation of monitoring polymer fluorescence color, detection can be distinguished to different types of pathogen.The quick visualization differentiating method of this pathogen will food safety, clinical diagnosis and in terms of show potential application value.
Description
Technical field
The invention belongs to filed of functional, be related to a kind of α-mannose-modified to-receptor type boiomacromolecule material
Material and its preparation method and application.
Background technique
In recent years, the infection problems as caused by the pathogens such as bacterium and fungi have become global public health security
Problem.As the Etiological of pathogenic bacterial infection, bacterium and fungal infection normally result in extremely serious consequence, or even can endanger
And the life of patient, so that the death rate of patient is increased [Molecules, 2009,14 (2): 586-597].Pathogenic bacteria is to make
Human infection's food origin disease, syphilis and major reason lungy, and wherein the infection of half is by pathogenic large intestine bar
[J.Clin.Microbiol., 1999,37 (6): 2024-2026 caused by bacterium；Environ.Health Perspect.,1982,
43(FEB):9-19].In clinical practice, the generally existing polymicrobic infection as caused by a variety of pathogens in patient, therefore
The differentiation of pathogen detects [Polymicrobial Diseases.2002] extremely important to the treatment of these diseases.Clinically
Traditional blood sample cultivation is generallyd use to identify pathogenic bacterial infection, but time-consuming, sensitivity is unstable for this method, from
And affect its application efficiency [J.Clin.Microbiol., 1995,33 (4): 978-981 in terms of early diagnosis；
J.Infect.,2008,57(4):307-316].In order to develop more efficiently detection of pathogens technology, research worker is established
PCR method based on specific dna probe, the immunological method for detecting pathogen antigen, DNA microarray method, bio-sensing method
The methods of detection [Biosens.Bioelectron., 2007,22 (7): 1205-1217] are distinguished to pathogen.However, this
The testing cost of a little methods is higher, preparation process is complicated, harsher to instrument requirements, to limit its large-scale application.
2000, Baek research group, California, USA university Lao Lunsi Berkeley National Laboratory was for the first time by sialic acid and sweet
Reveal sugar-modified to the end polythiophene (PT), the change of polymer conjugated degree under acting on by monitoring ligand-receptor specific binding
Change realize influenza virus and Escherichia coli (E.coli) detection [coli.Bioconjugate Chem., 2000,11 (6):
777-788].Then, the identification of this specificity interaction using ligand-receptor and detection method have obtained quick hair
Exhibition, research worker are utilized respectively polyparaphenylene's acetylene (PPE), the α-mannose-modified of α-mannose and three mannose-modifieds
Polyfluorene (PFP) and α-mannose-modified neutral water soluble oligomer containing polyethylene glycol (PEG) side chain etc. realize
Quick, highly sensitive detection [J.Am.Chem.Soc., 2004,126 (41): 13343-13346 of E.coli；
Macromolecules,2008,41(20):7316-7320；J.Mater.Chem.,2010,20(7):1312-1316].This
Outside, it is based on the highly sensitive signal response characteristic of polydiacetylene (PDA), targets identification system relevant to PDA is also used for cause of disease
The detection of bacterium.Then, Ohio State Univ-Columbus USA Wang research group utilizes Gal- α-Isosorbide-5-Nitrae-Gal disaccharides functionalization PDA
The characteristic that Shiga toxin B subunit can be specifically bound in the liquid phase, the variation by monitoring solution colour realize generation will
Congratulate toxin Escherichia coli (E.coli O157) specific detection [Bioorg.Med.Chem.Lett., 2008,18 (2):
700-703].Liquid phase P DA sensor has certain unstability, and in order to overcome the disadvantage, research worker has developed solid phase
PDA senses system.The PDA of Korea Advanced Institute of Science and Technology Park research group designs streptavidin (STA) functionalization is solid
Phase chip, and realize using the system specific detection [Small, 2008,4 (10): 1778-1784] of chlamydia trachomatis.
But the polymer material of existing α-mannose-modified, it is only intended to the detection of specific pathogen bacterium, cannot achieve
The differentiation of variety classes pathogen detects.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of the high to-receptor type biology of α-mannose-modified
Molecular material and application can be realized the visualized distinguishing detection of various pathogenic bacteria.
The present invention is to be achieved through the following technical solutions:
A kind of α-mannose-modified to-receptor type bioabsorbable polymer material, structural formula is as shown in Formulas I or formula II:
In Formulas I and formula II, m and the n integer independent between 1-10 ten thousand；Integer of the k between 0-30；A1、A2、
A3、A6、A7And A8Independent is O, N or S atom；A4For C or N atom；A5For S, O, N or C atom；R is H atom, F atom
Or CN group；R1、R2、R3、R4、R5And R6Independent is the linear chain or branched chain that H atom, F atom or carbon atom number are 1-20
Alkyl.
Preferably, it is any one in following polymer A-H:
Synthetic method of the α-mannose-modified to-receptor type bioabsorbable polymer material, which is characterized in that including
Following steps:
(1) synthesis of conjugated polymer
2,5- dibromo hydroquinone derivative is etherified under the action of the first alkaline matter and additive with compound 1 and obtains
Compound 2；Compound 2 occurs Li-Br with lithium reagent and exchanges to obtain intermediate phenyl lithium, then further different with boric acid pinacol
Propyl ester reacts to obtain compound 3；
Suzuki coupling reaction of the compound 2,3 and 4 by Pd catalysis is obtained to-receptor type conjugated polymer P1；Alternatively,
The alkylation under the effect of the second alkaline matter of 2,7- dibromo fluorenes and compound 1 obtains compound 5, and compound 3,4 and 5 is catalyzed through Pd
The Suzuki coupling reaction of agent catalysis is obtained to-receptor type conjugated polymer P2；
(2) modification of group is targeted
1,2,3,4,6- penta-acetyl-α-mannose reacts under the action of Lewis acid with alkynyl or cyano compound
To compound 6；
SN2 substitution reaction occurs to-receptor type conjugated polymer P1 and Azide reagenl and obtains the polymer P 1- of Azide
1, polymer P 1-1 further occur Click under metallic catalyst catalysis with compound 6 and react, and obtaining end is that acetyl is sweet
Reveal the polymer P 1-2 of sugar, further deacetylate is protected to obtain the compound of Formulas I；
Alternatively, obtaining polymerizeing for Azide with Azide reagenl generation SN2 substitution reaction to-receptor type conjugated polymer P2
Object P2-1, polymer P 2-1 further occur Click under metallic catalyst catalysis with compound 6 and react, and obtaining end is
The polymer P 2-2 of acetylated mannan sugar, further deacetylate are protected to obtain the compound of formula II；
Preferably, in step (1), the first alkaline matter is one of potassium carbonate, potassium hydroxide and KHMDS, additive
It is preced with one of 6 and azepine 18- hat 6 for 18- hat 6, dibenzo 18-, lithium reagent is in n-BuLi, tert-butyl lithium and lithium metal
One kind.
Preferably, in step (1), the second alkaline matter is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, ethyl alcohol
One or more of sodium and potassium tert-butoxide.
Preferably, in step (1), Pd catalyst be acid chloride, tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladiums of dichloro or
(bis- (diphenylphosphine) ferrocene of 1,1'-) palladium chloride.
Preferably, in step (2), Lewis acid is alchlor, titanium tetrachloride, tin tetrachloride, zinc chloride, bismuth trichloride
Or silver trifluoromethanesulfonate；Azide reagenl is sodium azide, potassium azide, TMSN3And TsN3One or more of.
Preferably, in step (2), metallic catalyst is copper-based catalysts, rhodium base catalyst, ruthenium-based catalyst, palladium base are urged
Agent or ferrum-based catalyst.
Preferably, in step (2), reagent used by deacetylate is protected is sodium methoxide, sodium ethoxide and sodium tert-butoxide
One or more of.
α-the mannose-modified is distinguished in variety classes pathogen to-receptor type bioabsorbable polymer material in detection
Application.
Compared with prior art, the invention has the following beneficial technical effects:
A series of α-mannose-modifieds of present invention design synthesis give-receptor type conjugated polymer, are given by difference, receptor
The introducing of unit obtain photophysical property preferably, the polymer of fluorescence emission spectrum wider range.The quasi polymer can target
In conjunction with specific recognition α-mannose agglutinin on pathogen surface, since variety classes pathogen surface can identify that α-is sweet
Type and the quantity for revealing the agglutinin of sugar are different, and polymer is different from the binding ability of variety classes pathogen, not of the same race
The coherent condition on class pathogen surface is different, so that fluorescence resonance energy transfer of the polymeric donor unit to receptor unit
Efficiency is different, by the variation of monitoring polymer fluorescence color, can distinguish detection to different types of pathogen.The party
Method has many advantages, such as easy, quick, visualization, and is not related to any complex instrument, hypertoxic dyestuff and expensive labeled primer
It uses.It is believed that the quick visualization differentiating method of this pathogen will be in food safety, clinical diagnosis and environmental monitoring etc.
Aspect shows potential application value.
The present invention by Suzuki coupling reaction be prepared polymer backbone, by click chemistry to side chain carry out α-it is sweet
Reveal it is sugar-modified be prepared it is a series of to-receptor type bioabsorbable polymer material.
Microorganism detection method based on the functional material has simple, quick, macroscopic, is not related to any complicated instrument
The advantages such as the use of device, hypertoxic dyestuff and expensive labeled primer, have than microorganism detection methods such as existing pathogens more rapidly,
Convenient, inexpensive feature.
Detailed description of the invention
Fig. 1 is the fluorescence emission spectrum after 4 resulting polymers A of embodiment normalization.
Fig. 2 is the fluorescence emission spectrum after 6 resulting polymers C of embodiment normalization.
Fig. 3 is to carry out pathogen using 11 resulting polymers H of embodiment to distinguish testing result figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1: the synthesis of phenyl unit
(1)14,14'-((2,5-dibromo-1,4-phenylene)bis(oxy))bis(1-bromo-3,6,9,12-
Tetraoxa-tetradecane) the preparation of (B-1):
2,5-dibromobenzene-1,4-diol (1.0eq, 10mmol, 2.68g) and 1,14-dibromo-3,6,9,
12-tetraoxatetradecane (5eq, 50mmol, 18.2g) are dissolved in 80mL tetrahydrofuran, and potassium hydroxide is added
(3.0eq, 30mmol, 1.68g) and dibenzo 18- are preced with after 6 (200mg) reaction to the raw material under room temperature to reflux temperature and disappear
Afterwards, 50mL water quenching reaction is added, ethyl acetate extracts, is dry with anhydrous sodium sulfate after merging organic phase.It is obtained after being spin-dried for solvent
To compound B-1.1HNMR(400MHz,CDCl3, δ): 7.21 (s, 2H), 4.42 (t, 4H, J=4.4Hz), 3.90 (t, 4H, J=
3.6Hz), 3.74 (t, 4H, J=4.4Hz), 3.60-3.20 (m, 28H) .C26H42Br4O10:calcd.C37.43,H5.07；
found C 37.48,H 5.04.
(2)2,2'-(2,5-bis((14-bromo-3,6,9,12-tetraoxatetradecyl)oxy)-1,4-
Phenylene) the preparation of bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (B-2):
Compound B-1 (1.0eq, 10mmol, 8.34g) is dissolved in 50mL tetrahydrofuran, is added dropwise just under -78 DEG C of nitrogen protections
After reacting 1-2h at a temperature of this after butyl lithium (2.4eq, 24mmol, 2.5M in hex, 10mL), 2-isopropoxy- is added
4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.2eq, 22mmol, 4.09g, 4.5mL) is simultaneously slowly increased to room
Temperature, is added 50mL saturated ammonium chloride solution quenching reaction, and ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.Rotation
After dry solvent, ethyl alcohol recrystallization obtains compound B-2.1H NMR(400MHz,CDCl3,δ):6.88(s,2H),4.35(t,4H,J
=4.4Hz), 3.92 (t, 4H, J=3.6Hz), 3.76 (t, 4H, J=4.4Hz), 3.62-3.26 (m, 28H), 1.15 (s,
24H).C38H66B2Br2O14:calcd.C 49.16,H 7.17；found C 49.22,H7.14.
(3)20,20'-((2,5-dibromo-3,6-dimethyl-1,4-phenylene)bis(oxy))bis(1-
Bromo-3,6,9,12,15,18-hexaoxaicosane) the preparation of (B-3):
2,5-dibromo-3,6-dimethylbenzene-1,4-diol (1.0eq, 1.0mmol, 296mg) and 1,20-
Dibromo-3,6,9,12,15,18-hexaoxaicosane (5eq, 5.0mmol, 2.26g) are dissolved in 10mL methylene chloride, add
Enter potassium carbonate (3.0eq, 3.0mmol, 414mg) and 18 to be preced with after 6 (0.1eq, 0.1mmol, 26.4mg) in room temperature to reflux temperature
After lower reaction disappears to raw material, 50mL water quenching reaction is added, anhydrous sodium sulfate is dry after ethyl acetate extraction, merging organic phase
It is dry.Compound B-3 is obtained after being spin-dried for solvent.1H NMR(400MHz,CDCl3, δ): 4.35 (t, 4H, J=4.4Hz), 3.85 (t,
4H, J=3.6Hz), 3.70 (t, 4H, J=4.4Hz), 3.55-3.14 (m, 44H), 2.27 (s, 6H) .C36H62Br4O14:
calcd.C 41.64,H 6.02；found C 41.71,H 6.09.
(4)2,2'-(2,5-bis((20-bromo-3,6,9,12,15,18-hexaoxaicosyl)oxy)-3,6-
Dimethyl-1,4-phenylene) the system of bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (B-4)
It is standby:
Compound B-3 (1.0eq, 0.5mmol, 505mg) is dissolved in 10mL tetrahydrofuran, is dripped under -78 DEG C of nitrogen protections
After reaction 1.5h, 2- is added at a temperature of this after adding n-BuLi (2.4eq, 1.2mmol, 2.5M in hex, 0.5mL)
isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2.2eq,1.1mmol,205mg,
0.23mL) and it is slowly increased to room temperature, 15mL saturated ammonium chloride solution quenching reaction is added, ethyl acetate extraction merges organic phase
Anhydrous sodium sulfate is dry afterwards.After being spin-dried for solvent, ethyl alcohol recrystallization obtains compound B-4.1H NMR(400MHz,CDCl3,δ):
4.33 (t, 4H, J=4.4Hz), 3.93 (t, 4H, J=3.6Hz), 3.76 (t, 4H, J=4.4Hz), 3.61-3.22 (m, 44H),
2.31(s,6H),1.17(s,24H).C48H86B2Br2O18:calcd.C 50.90,H 7.65；found C 50.97,H 7.59.
(5)26,26'-((2,5-dibromo-1,4-phenylene)bis(sulfanediyl))bis(1-bromo-3,
6,9,12,15,18,21,24-octaoxahexacosane) the preparation of (B-5):
2,5-dibromobenzene-1,4-dithiol (1.0eq, 10mmol, 3.00g) and 1,26-dibromo-3,6,
9,12,15,18,21,24-octaoxahexacosane (5eq, 50mmol, 27.0g) are dissolved in 10mL methylene chloride, are added
KHMDS (3.0eq, 30mmol, 1.0M, 30mL) and azepine 18, which are preced with after 6 (200mg), to react under room temperature to reflux temperature to raw material
After disappearance, 50mL water quenching reaction is added, ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.After being spin-dried for solvent
Obtain compound B-5.1H NMR(400MHz,CDCl3, δ): 7.18 (s, 2H), 3.92 (t, 4H, J=3.6Hz), 3.78 (t, 4H,
), J=4.4Hz 3.76-3.28 (m, 60H), 3.22 (t, 4H, J=4.4Hz) .C42H74Br4O16S2:calcd.C 41.39,H
6.12；found C 41.45,H 6.19.
(6)2,2'-(2,5-bis((26-bromo-3,6,9,12,15,18,21,24-octaoxahexacosyl)
Thio) -1,4-phenylene) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (B-6) preparation:
Compound B-5 (1.0eq, 0.2mmol, 244mg) is dissolved in 15mL tetrahydrofuran, protects lower be added in room temperature under nitrogen
After lithium metal (10eq, 2.0mmol, 14mg) at 45 DEG C react 1.5h after, be added 2-isopropoxy-4,4,5,5-
Tetramethyl-1,3,2-dioxaborolane (2.2eq, 0.44mmol, 82mg, 0.10mL) are simultaneously slowly increased to room temperature, add
Enter 5mL saturated ammonium chloride solution quenching reaction, ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.It is spin-dried for solvent
Afterwards, ethyl alcohol recrystallization obtains compound B-6.1H NMR(400MHz,CDCl3, δ): 7.21 (s, 2H), 3.90 (t, 4H, J=
3.6Hz), 3.77 (t, 4H, J=4.4Hz), 3.78-3.20 (m, 60H), 3.27 (t, 4H, J=4.4Hz), 1.29 (s, 24H)
.C54H98B2Br2O20S2:calcd.C 49.40,H 7.52；found C 49.52,H 7.61.
(7)20,20'-((2,5-dibromo-3,6-dimethyl-1,4-phenylene)bis(oxy))bis(1-
Bromo-3,6,9,12,15,18-hexaoxaicosane) the preparation of (B-7):
2,5-dibromobenzene-1,4-diamine (1.0eq, 1.0mmol, 2.66g) and 1,20-dibromo-3,
6,9,12,15,18-hexaoxaicosane (5eq, 5.0mmol, 2.26g) are dissolved in 10mL acetone, addition KHMDS (3.0eq,
3.0mmol, 1.0M, 3.0mL) and azepine 18 be preced with 6 (30mg) after under room temperature to reflux temperature reaction to raw material disappear after, be added
50mL water quenching reaction, ethyl acetate extraction merge anhydrous sodium sulfate drying after organic phase.Compound B- is obtained after being spin-dried for solvent
3。1H NMR(400MHz,CDCl3, δ): 9.15 (b, 2H), 6.71 (s, 2H), 3.88 (t, 4H, J=3.6Hz), 3.69 (t, 4H, J
=4.4Hz), 3.78-3.20 (m, 48H) .C34H60Br4N2O12:calcd.C 40.49,H 6.60,N 2.78；found C
40.54,H 6.66,N 2.74.
(8)N1,N4-bis(20-bromo-3,6,9,12,15,18-hexaoxaicosyl)-2,5-bis(4,4,5,5-
Tetra-methyl-1,3,2-dioxaborolan-2-yl) the preparation of benzene-1,4-diamine (B-8):
Compound B-7 (1.0eq, 0.2mmol, 202mg) is dissolved in 6mL tetrahydrofuran, is added dropwise under -78 DEG C of nitrogen protections
After reacting 1.5h at a temperature of this after tert-butyl lithium (4.4eq, 0.88mmol, 1.6M, 0.55mL), 2-isopropoxy- is added
4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.2eq, 0.44mmol, 82mg, 0.1mL) is simultaneously slowly increased to
Room temperature, is added 5mL saturated ammonium chloride solution quenching reaction, and ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.Rotation
After dry solvent, ethyl alcohol recrystallization obtains compound B-8.1H NMR(400MHz,CDCl3,δ):8.94(b,2H),6.47(s,2H),
3.85 (t, 4H, J=3.6Hz), 3.65 (t, 4H, J=4.4Hz), 3.82-3.30 (m, 48H), 1.12 (s, 24H)
.C46H84B2Br2N2O16:calcd.C 50.11,H 7.68,N 2.54；found C 50.17,H 7.71,N 2.51.
Embodiment 2: the synthesis of fluorenyl unit
(1)20,20'-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(1-bromo-3,6,9,12,15,
18-hex-aoxaicosane) the preparation of (F-1):
2,7-dibromo-9H-fluorene (1.0eq, 10mmol, 3.24g) and 1,20-dibromo-3,6,9,12,
15,18-hexaoxaicosane (5eq, 50mmol, 22.6g) are dissolved in 80mL acetone, addition potassium tert-butoxide (3.0eq,
30mmol, 3.4g) and tetrabutylammonium bromide (0.2eq, 2mmol, 644mg) after under room temperature to reflux temperature reaction disappear to raw material
After mistake, 50mL water quenching reaction is added, ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.It is obtained after being spin-dried for solvent
To compound F-1.1H NMR(400MHz,CDCl3, δ): 7.83 (d, 2H, J=8.4Hz), 7.75 (s, 2H), 7.39 (d, 2H, J
=8.0Hz), 3.97 (t, 4H, J=3.6Hz), 3.71-3.16 (m, 48H) 2.13 (t, 4H, J=4.4Hz) .C41H62Br4O12:
calcd.C 46.17,H 5.86；found C 46.21,H 5.89.
(2)26,26'-(2,7-dibromo-9H-fluorene-9,9-diyl)bis(1-bromo-3,6,9,12,15,
18,21,24-octaoxahexacosane) the preparation of (F-2):
2,7-dibromo-9H-fluorene (1.0eq, 10mmol, 3.24g) and 1,20-dibromo-3,6,9,12,
15,18-hexaoxaicosane (5eq, 50mmol, 27.0g) are dissolved in 100mL acetone, addition potassium hydroxide (3.0eq,
30mmol, 1.68g) and tetrabutylammonium bromide (0.2eq, 2mmol, 644mg) after under room temperature to reflux temperature reaction to raw material
After disappearance, 50mL water quenching reaction is added, ethyl acetate extraction merges anhydrous sodium sulfate drying after organic phase.After being spin-dried for solvent
Obtain compound F-2.1H NMR(400MHz,CDCl3, δ): 7.79 (d, 2H, J=8.4Hz), 7.69 (s, 2H), 7.55 (d, 2H,
), J=8.0Hz 3.93 (t, 4H, J=3.6Hz), 3.71-3.16 (m, 64H) 2.11 (t, 4H, J=4.4Hz) .C49H78Br4O16:
calcd.C 47.36,H 6.33；found C 47.42,H 6.38.
The synthesis of embodiment 3: α-mannose group unit
(1)(2R,3R,4S,5S,6S)-2-(acetoxymethyl)-6-(prop-2-yn-1-yloxy)
The preparation of tetrahydro-2H-pyran-3,4,5-triyl triacetate (G-1):
1,2,3,4,6- penta-acetyl-α-mannose (1.0eq, 10mmol, 3.90g) and propargyl alcohol (1.3eq, 13mmol,
It 729mg) is dissolved in 20mL chloroform, is added after tin tetrachloride (1.0eq, 10mmol, 2.61g) under nitrogen protection, -20 DEG C
To being reacted to raw material disappearance at room temperature, 50mL saturated aqueous ammonium chloride quenching reaction is added, chloroform extraction merges organic phase
Anhydrous sodium sulfate is dry afterwards.It is spin-dried for obtaining compound G-1 through column chromatographic purifying after solvent.1H NMR(400MHz,CDCl3,δ):
5.48 (dd, 1H, J=3.4,1.4Hz), 5.37 (dd, 1H, J=10.9,3.4Hz), 5.34 (d, 1H, J=3.6Hz), 5.19
(dd, 1H, J=10.9,3.7Hz), 4.28 (dd, 2H, J=2.4,1.0Hz), 4.27 (m, 1H), 4.13-4.10 (m, 2H),
2.47 (t, 1H, J=2.4Hz), 2.16,2.09,2.06,1.99 (4s, 12H) .C17H22O10:calcd.C 52.85,H 5.74；
found C 52.89,H 5.76.
(2)(2R,3R,4S,5S,6S)-2-(acetoxymethyl)-6-(cyanomethoxy)tetrahydro-2H-
The preparation of pyran-3,4,5-triyl triacetate (G-2):
1,2,3,4,6- penta-acetyl-α-mannose (1.0eq, 10mmol, 3.90g) and 2-
Hydroxyacetonitrile (1.3eq, 13mmol, 742mg) is dissolved in 20mL1, and in 2- dichloroethanes, titanium tetrachloride is added
After (1.0eq, 10mmol, 1.89g) under nitrogen protection, -20 DEG C, to being reacted to raw material disappearance at room temperature, are added 50mL saturation
Aqueous ammonium chloride solution quenching reaction, chloroform extraction merge anhydrous sodium sulfate drying after organic phase.It is spin-dried for chromatographing through column after solvent pure
Change obtains compound G-2.1H NMR(400MHz,CDCl3, δ): 5.67 (dd, 1H, J=3.4,1.4Hz), 5.43 (dd, 1H, J=
), 10.9,3.4Hz 5.39 (d, 1H, J=3.6Hz), 5.25 (dd, 1H, J=10.9,3.7Hz), 4.62-4.54 (m, 2H),
4.35 (dd, 2H, J=2.4,1.0Hz), 4.31 (m, 1H), 2.56 (t, 1H, J=2.4Hz), 2.19,2.11,2.08,2.03
(4s,12H).C16H21NO10:calcd.C 49.61,H 5.64,N 3.62；found C 49.66,H 5.69,N 3.67.
(3)(2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-((cyanomethyl)thio)
The preparation of tetrahydro-2H-pyran-3,4,5-triyl triacetate (G-3):
1,2,3,4,6- penta-acetyl-α-mannose (1.0eq, 10mmol, 3.90g) and 2-
Mercaptoacetonitrile (1.3eq, 13mmol, 950mg) is dissolved in 20mL chloroform, and bismuth trichloride is added
After (1.0eq, 10mmol, 3.15g) under nitrogen protection, -20 DEG C, to being reacted to raw material disappearance at room temperature, are added 50mL saturation
Aqueous ammonium chloride solution quenching reaction, chloroform extraction merge anhydrous sodium sulfate drying after organic phase.It is spin-dried for chromatographing through column after solvent pure
Change obtains compound G-3.1H NMR(400MHz,CDCl3, δ): 5.51 (dd, 1H, J=3.4,1.4Hz), 5.29 (dd, 1H, J=
), 10.9,3.4Hz 5.13 (d, 1H, J=3.6Hz), 4.73 (dd, 1H, J=10.9,3.7Hz), 4.22-4.18 (m, 2H),
4.02 (dd, 2H, J=2.4,1.0Hz), 3.68 (m, 1H), 3.09 (t, 1H, J=2.4Hz), 2.21,2.13,2.10,2.03
(4s,12H).C16H21NO9S:calcd.C 47.64,H 5.25,N 3.47；found C 47.69,H 5.28,N 3.43.
(4)(2R,3R,4S,5S,6S)-2-(acetoxymethyl)-6-(prop-2-yn-1-ylamino)
The preparation of tetrahydro-2H-pyran-3,4,5-triyl triacetate (G-4):
1,2,3,4,6- penta-acetyl-α-mannose (1.0eq, 10mmol, 3.90g) and propargylamine (1.3eq, 13mmol,
It 716mg) is dissolved in 20mL methylene chloride, is added after zinc chloride (1.0eq, 10mmol, 1.36g) under nitrogen protection, -20 DEG C are arrived
It is reacted at room temperature to raw material after disappearing, 50mL saturated aqueous ammonium chloride quenching reaction is added, after chloroform extracts, merges organic phase
Anhydrous sodium sulfate is dry.It is spin-dried for obtaining compound G-4 through column chromatographic purifying after solvent.1H NMR(400MHz,CDCl3,δ):5.27
(dd, 1H, J=9.0,4.0Hz), 5.16 (t, 1H, J=9.4,9.4Hz), 5.05-4.87 (m, 2H), 4.15 (dd, 1H, J=
), 12.0,3.3Hz 4.03 (m, 2H), 3.72 (ddd, 1H, J=9.2,5.0,3.3Hz), 3.31 (d, 2H, J=4.0Hz), 2.99
(s,1H),1.98,1.94,1.91,1.89(4s,12H).C17H23NO9:calcd.C 52.98,H 6.02,N 3.63；found
C 53.01,H 6.04,N 3.61.
(5)(2R,3R,4S,5S,6S)-2-(acetoxymethyl)-6-((cyanomethyl)amino)
The preparation of tetrahydro-2H-pyran-3,4,5-triyl triacetate (G-5):
1,2,3,4,6- penta-acetyl-α-mannose (1.0eq, 10mmol, 3.90g) and 2-
Hydroxyacetonitrile (1.3eq, 13mmol, 729mg) is dissolved in 20mL chloroform, and silver trifluoromethanesulfonate is added
After (1.0eq, 10mmol, 2.57g) under nitrogen protection, -20 DEG C, to being reacted to raw material disappearance at room temperature, are added 50mL saturation
Aqueous ammonium chloride solution quenching reaction, chloroform extraction merge anhydrous sodium sulfate drying after organic phase.It is spin-dried for chromatographing through column after solvent pure
Change obtains compound G-5.1H NMR(400MHz,CDCl3, δ): 5.46 (dd, 1H, J=9.4,3.6Hz), 5.22 (t, 1H, J=
), 9.4,9.4Hz 5.12-4.93 (m, 2H), 4.22 (dd, 1H, J=12.0,3.3Hz), 4.14 (m, 2H), 3.83 (m, 1H),
3.62 (d, 2H, J=3.6Hz), 2.02,1.96,1.94,1.92 (4s, 12H) .C16H22N2O9:calcd.C 49.74,H
5.74,N 7.25；found C 49.77,H 5.75,N 7.23.
Embodiment 4: structural formula is the synthesis of the polymer of A
In N2Under protection, by 3.0mmol boronic acid derivatives B-2,1.5mmol bromobenzene derivative B-1 and 1.5mmol benzo thiophene
Oxadiazole derivative S-1 is added in the three-necked flask being dried in vacuo, and is dissolved in 15mL toluene, and N is led to2It is added after being bubbled 0.5h
The Pd (dba) of 0.03eq2Catalyst is added 2M solution of potassium carbonate and continues the 0.5h that ventilates, then heating reaction 48h.Wait react
After completely, it is cooled to room temperature and is added 30mL water quenching reaction, organic phase is merged after chloroform aqueous phase extracted and uses anhydrous magnesium sulfate
It is dry.The intermediate polymer that end is bromine can be obtained in sedimentation again after Soxhlet extraction.It is dissolved in DMF, is added
The sodium azide of 10eq simultaneously reacts 30h at room temperature.Chloroform dissolution, after washing and drying filtering, needed for sedimentation obtains in methyl alcohol
Intermediate polymer P-A.
Intermediate polymer P-A is dissolved into tetrahydrofuran, and α-mannose group unit and 0.2eq catalysis of 10eq is added
Agent cuprous iodide, and 20h is reacted under nitrogen protection.It is spin-dried for being added in methanol/sodium methoxide system after solvent removing acetyl group
Protection adjusts and extracts reaction solution with chloroform methanol system after pH is 4-5.Merge organic phase, is spin-dried for after anhydrous sodium sulfate is dry molten
Agent.Dialysis removes metal ion and small molecule compound obtains subject polymer A.1H NMR(400MHz,DMSO-d6,δ):
8.10(s,2H),7.73(s,6H),7.12-6.93(m,10H),5.45(b,6H),4.87-4.62(br,20H),4.47(s,
12H),4.32-4.19(m,12H),3.92-2.15(m,132H)。
Embodiment 5: structural formula is the synthesis of the polymer of B
In N2Under protection, by 3.0mmol boronic acid derivatives B-4,1.5mmol bromobenzene derivative B-7 and 1.5mmol benzo thiophene
Oxadiazole derivative S-2 is added in the three-necked flask being dried in vacuo, and is remaining operation reference embodiment of catalyst with acid chloride
4, obtain required intermediate polymer P-B.
Intermediate polymer P-B is dissolved into toluene, and α-mannose group unit and 0.2eq catalyst of 10eq is added
Cp*RuCl(PPh3), and 30h is reacted under nitrogen protection.It is spin-dried for being added in ethyl alcohol/sodium ethoxide system after solvent removing acetyl
Base protection adjusts and extracts reaction solution with chloroform methanol system after pH is 8-9.Merge organic phase, is spin-dried for after anhydrous sodium sulfate is dry
Solvent.Dialysis removes metal ion and small molecule compound obtains subject polymer B.1H NMR(400MHz,DMSO-d6,δ):
7.95(s,6H),7.33(s,4H),6.82(s,2H),5.51(b,6H),4.90-4.60(br,20H),4.52(s,12H),
4.41-4.36(m,12H),3.90-2.10(m,180H),2.32-2.15(m,12H)。
Embodiment 6: structural formula is the synthesis of the polymer of C
In N2Under protection, by 3.0mmol boronic acid derivatives B-6,1.5mmol bromobenzene derivative B-5 and 1.5mmol benzo thiophene
Oxadiazole derivative S-3 is added in the three-necked flask being dried in vacuo, the use of bis- (triphenylphosphine) palladiums of dichloro is catalyst,
TMSN3It is remaining operation reference embodiment 4 of Click catalysts for Azide reagenl, rhodium acetate, obtains required polymer C.1H NMR(400MHz,DMSO-d6,δ):7.78(s,6H),7.42-7.03(m,8H),5.39(b,6H),4.96-4.72(br,
20H),4.29-4.13(m,12H),4.05(s,12H),3.96-2.10(m,228H)。
Embodiment 7: structural formula is the synthesis of the polymer of D
In N2Under protection, by 3.0mmol boronic acid derivatives B-8,1.5mmol bromobenzene derivative B-7 and 1.5mmol benzo thiophene
Oxadiazole derivative S-4 is added in the three-necked flask being dried in vacuo, and uses TsN3It is for Azide reagenl, frerrous chloride
Remaining operation of click catalysts obtains required polymer D referring to embodiment 5.1H NMR(400MHz,DMSO-d6,δ):
9.16(br,6H),7.02-6.85(m,8H),6.22(br,6H),4.76(m,6H),4.96-4.72(br,20H),3.96-
2.10(m,204H)。
Embodiment 8: structural formula is the synthesis of the polymer of E
In N2Under protection, by 3.0mmol boronic acid derivatives B-4,1.5mmol bromobenzene derivative B-5 and 1.5mmol benzo thiophene
Oxadiazole derivative S-4 is added in the three-necked flask being dried in vacuo, and uses (1,1'- bis- (diphenylphosphine) ferrocene) dichloride
Palladium is remaining operation reference embodiment 5 of catalyst, obtains required polymer E.1H NMR(400MHz,DMSO-d6,δ):8.12
(s,2H),7.32-7.21(m,2H),6.91(s,2H),6.31(br,6H),4.81(m,6H),4.91-4.66(br,20H),
4.11-2.54(m,204H),2.35-2.20(m,12H)。
Embodiment 9: structural formula is the synthesis of the polymer of F
In N2Under protection, by 3.0mmol boronic acid derivatives B-6,1.5mmol bromine fluorene derivative F-1 and 1.5mmol benzo thiophene
Oxadiazole derivative S-2 is added in the three-necked flask being dried in vacuo, and the tert-butyl alcohol/sodium tert-butoxide is that deacetylation protects system,
Remaining operation obtains required polymer F referring to embodiment 4.1H NMR(400MHz,DMSO-d6,δ):8.10-7.31(m,
20H),5.43(m,6H),4.81-4.54(m,30H),4.11-2.54(m,240H)。
Embodiment 10: structural formula is the synthesis of the polymer of G
In N2Under protection, by 3.0mmol boronic acid derivatives B-8,1.5mmol bromine fluorene derivative F-2 and 1.5mmol benzo thiophene
Oxadiazole derivative S-5 is added in the three-necked flask being dried in vacuo, remaining operation obtains required polymer referring to embodiment 4
G。1H NMR(400MHz,DMSO-d6,δ):8.91(br,4H),8.09-7.31(m,12H),6.78-6.62(m,2H),4.63
(m,6H),4.89-4.64(m,30H),3.94-2.54(m,174H)。
Embodiment 11: structural formula is the synthesis of the polymer of H
In N2Under protection, by 3.0mmol boronic acid derivatives B-4,1.5mmol bromine fluorene derivative F-1 and 1.5mmol benzo thiophene
Oxadiazole derivative S-3 is added in the three-necked flask being dried in vacuo, remaining operation obtains required polymer referring to embodiment 5
H。1H NMR(400MHz,DMSO-d6,δ):8.12-7.35(m,6H),6.85(s,2H),6.36(br,6H),4.89-4.64
(m,30H),3.94-2.54(m,198H),2.42-2.30(m,12H)。
Fig. 1 is the fluorescence emission spectrum after 4 resulting polymers A of embodiment normalization.Fig. 2 is 6 resulting polymers C of embodiment
Fluorescence emission spectrum after normalization.Since receptor unit introduces electron-withdrawing group F and CN in polymer C, polymer C's is glimmering
Optical emission spectroscopy range broadens.
Fig. 3 is to carry out pathogen using 11 resulting polymers H of embodiment to distinguish testing result figure.Due to strain E.coli,
The type and quantity of the agglutinin that S.aureus, C.albicans contain on surface are different, polymer H respectively in conjunction with them when table
Reveal different coherent conditions, it is different to the effect of the fluorescence resonance energy transfer of-receptor unit, therefore polymer H is different
Launch fluorescence (E.coli, the pink of different colours after strain surface aggregation；S.aureus, purple；C.albicans, it is blue
Purple), to realize the Visual retrieval of variety classes pathogen.
Claims (10)
1. a kind of α-mannose-modified gives-receptor type bioabsorbable polymer material, which is characterized in that its structural formula such as Formulas I or formula
Shown in II:
In Formulas I and formula II, m and the n integer independent between 1-10 ten thousand；Integer of the k between 0-30；A1、A2、A3、A6、
A7And A8Independent is O, N or S atom；A4For C or N atom；A5For S, O, N or C atom；R is H atom, F atom or CN
Group；R1、R2、R3、R4、R5And R6Independent is the linear or branched alkyl group that H atom, F atom or carbon atom number are 1-20.
2. α-mannose-modified according to claim 1 gives-receptor type bioabsorbable polymer material, which is characterized in that its
For any one in following polymer A-H:
3. the synthetic method to-receptor type bioabsorbable polymer material of the described in any item α-mannose-modifieds of claim 1-2,
It is characterized by comprising the following steps:
(1) synthesis of conjugated polymer
2,5- dibromo hydroquinone derivative and compound 1 are etherified under the action of the first alkaline matter and additive obtains chemical combination
Object 2；Compound 2 and lithium reagent occur Li-Br and exchange to obtain intermediate phenyl lithium, then further with boric acid pinacol isopropyl ester
Reaction obtains compound 3；
Suzuki coupling reaction of the compound 2,3 and 4 by Pd catalysis is obtained to-receptor type conjugated polymer P1；Alternatively, 2,7-
The alkylation under the effect of the second alkaline matter of dibromo fluorenes and compound 1 obtains compound 5, and compound 3,4 and 5 is urged through Pd catalyst
The Suzuki coupling reaction of change is obtained to-receptor type conjugated polymer P2；
(2) modification of group is targeted
1,2,3,4,6- penta-acetyl-α-mannose Lewis acid under the action of with alkynyl or cyano compound reaction
Close object 6；
SN2 substitution reaction occurs to-receptor type conjugated polymer P1 and Azide reagenl and obtains the polymer P 1-1 of Azide, it should
Polymer P 1-1 further occurs Click under metallic catalyst catalysis with compound 6 and reacts, and obtaining end is acetylated mannan sugar
Polymer P 1-2, further deacetylate protects to obtain the compound of Formulas I；
Alternatively, SN2 substitution reaction, which occurs, to-receptor type conjugated polymer P2 and Azide reagenl obtains the polymer of Azide
P2-1, polymer P 2-1 further occur Click under metallic catalyst catalysis with compound 6 and react, and obtaining end is second
The polymer P 2-2 of acyl mannose, further deacetylate are protected to obtain the compound of formula II；
4. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (1), the first alkaline matter is one of potassium carbonate, potassium hydroxide and KHMDS, additive be 18- hat 6,
Dibenzo 18- is preced with one of 6 and azepine 18- hat 6, and lithium reagent is one of n-BuLi, tert-butyl lithium and lithium metal.
5. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (1), the second alkaline matter is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium ethoxide and tertiary fourth
One or more of potassium alcoholate.
6. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (1), Pd catalyst is acid chloride, tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladiums of dichloro or (1,1'- is bis-
(diphenylphosphine) ferrocene) palladium chloride.
7. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (2), Lewis acid is alchlor, titanium tetrachloride, tin tetrachloride, zinc chloride, bismuth trichloride or fluoroform
Sulfonic acid silver；Azide reagenl is sodium azide, potassium azide, TMSN3And TsN3One or more of.
8. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (2), metallic catalyst is copper-based catalysts, rhodium base catalyst, ruthenium-based catalyst, palladium-based catalyst or iron
Base catalyst.
9. the synthetic method to-receptor type bioabsorbable polymer material of α-mannose-modified according to claim 3, special
Sign is, in step (2), reagent used by deacetylate is protected is one of sodium methoxide, sodium ethoxide and sodium tert-butoxide
Or it is several.
10. the described in any item α-mannose-modifieds of claim 1-2 are distinguished to-receptor type bioabsorbable polymer material in detection
Application in variety classes pathogen.
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