CN1190453C - Polymer of aromatic amine-2,3-pyridine diketone, its preparing method and usage - Google Patents
Polymer of aromatic amine-2,3-pyridine diketone, its preparing method and usage Download PDFInfo
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- CN1190453C CN1190453C CNB031135536A CN03113553A CN1190453C CN 1190453 C CN1190453 C CN 1190453C CN B031135536 A CNB031135536 A CN B031135536A CN 03113553 A CN03113553 A CN 03113553A CN 1190453 C CN1190453 C CN 1190453C
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- 238000013019 agitation Methods 0.000 claims description 9
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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Abstract
The present invention relates to an aromatic-amine-2, 3-pyridine diketone polymer, a method for the preparation of the polymer, the preparation of the nanometer particles of the polymer, the preparation of the assembling structure of the nanometer particles, and the application of the nanometer particles and the assembling structure of the nanometer particles, and the polymer is disclosed in the structural general formula 1. The definition of the R#-[1] in the formula 1 is disclosed in the specification.
Description
Technical field
The present invention relates to a class and contain aromatic amine-2, polymkeric substance of 3-pyridine diketone repeated structural unit and preparation method thereof, and the preparation and the application of this polymkeric substance in biochip material and biomacromolecule immobilization material of the preparation of such polymer nano granules dispersed system, nano particle packaging assembly.
Background technology
Closely during the last ten years, along with people to the structure of matter and performance, and the going deep into of the theoretical investigation of the level ordered structure of biomacromolecule the biological function complicated relation with it, preparation has the material of level ordered structure and the character of these material uniquenesses, and the research of the performance of discerning mutually and acting on biomolecules such as protein and DNA caused widely and to have paid attention to, and makes remarkable progress.Organic polymer with nanostructure is because in biomedicine, the potential use of Materials science aspect, the focus of people's research especially.
Summary of the invention
The purpose of this invention is to provide a class and contain aromatic amine-2, polymkeric substance of 3-pyridine diketone repeated structural unit and preparation method thereof, and the preparation method of such polymer nano granules dispersed system, nano particle packaging assembly preparation method and this polymkeric substance are as the application of biochip and biomacromolecule immobilization material.
Aromatic amine of the present invention-2,3-pyridine two ketone polymers are as (to be designated hereinafter simply as formula 1 polymkeric substance) shown in the following formula 1:
Formula 1
Wherein, R
1Optional from one of following group I-VIII:
The molecular weight of formula 1 polymkeric substance of the present invention is usually in the 1000-15000 scope.
Formula 1 polymkeric substance of the present invention can be by 2, and the 3-dihydroxy-pyridine is oxidized to 2,3 pyridine diketone, makes by addition reaction with aromatic diamines again.Its synthetic reaction process is as shown in Equation 2:
Formula 2
Concrete preparation method is:
(1) with 2, the 3-dihydroxy-pyridine is dissolved in the solvent, is made into the solution that concentration is 0.1～0.4mol/L, adds oxygenant then, stirring at room 5～30min.
(2) dripping concentration under the stirring is the aromatic diamines solution (being dissolved in the identical solvent) of 0.1～0.4mol/L, stirred overnight at room temperature.
(3) after reaction is finished, filter, and, be washed till elutant with ethanol-water mixed solvent and dehydrated alcohol respectively again and be colourless, promptly obtain required aromatic amine-2 after the drying, 3-pyridine two ketone polymers with the inorganic salt in the distilled water flush away product.
In the aforesaid method, used oxygenant is I
2, KIO
4, KIO
3, NaIO
4, NaIO
3, NaClO, Ca (ClO)
2, FeCl
3Or active MnO
2, wherein preferred KIO
3Or NaIO
3Used solvent is for being selected from a kind of of ethanol, methyl alcohol, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), or the aqueous solution of above-mentioned solvent; The most frequently used solvent is the dimethyl formamide (DMF) of 30-90% or the aqueous solution of dimethyl sulfoxide (DMSO) (DMSO); R in used aromatic diamines and formula 1 polymkeric substance
1Group I-VIII is corresponding; The mol ratio of used each composition is: 2, and 3-dihydroxy-pyridine: oxygenant: aromatic diamines=1: 2～4: 0.7～1.5.
Formula 1 polymkeric substance that above method makes is a powdery product.
Can make the colloidal solid and the dispersion system thereof of formula 1 polymkeric substance of the present invention by the following method, concrete steps are: compound concentration is the formula 1 polymkeric substance DMF solution of 20mg/mL, is diluted to 2,2 * 10 then
-1, 2 * 10
-2, 2 * 10
-3With 2 * 10
-4The serial solution for later use of mg/mL; Get the polymkeric substance DMF solution after the above-mentioned dilution, dropwise add or disposable joining in the distilled water under ultrasonic oscillation, the DMF solution of above-mentioned polymkeric substance and the volume ratio of distilled water are that the concentration of 1: 10～300 final dispersed systems is 2 * 10
-1～2 * 10
-6Between the mg/mL; Continue concussion 0.5～2h again; Obtain the colloidal dispersion system of the nano particle that formula 1 polymkeric substance forms in water.
Can make the various nano particle packaging assemblies of formula 1 polymkeric substance of the present invention by the following method respectively:
(1) preparation method of the nano particle cube packaging assembly of formula 1 polymkeric substance, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system aqueous solution of claim 6 0.1～2mL, put under the room temperature and treat solvent evaporates, promptly obtain cube packaging assembly of formula 1 described polymer beads.
(2) preparation method of the nano particle ball-type packaging assembly of formula 1 polymkeric substance, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system solution of claim 6 0.1～5mL, at the centrifugal 0.5～6h of 5000～21000rpm, carefully remove supernatant liquor then; Add 0.1～5mL methyl alcohol in precipitation, ultrasonic oscillation 2～6h makes methyl alcohol-polymer nano granules dispersion system, and the concentration of final dispersed system is 2 * 10
-2～2 *
-6Between the mg/mL; Get methyl alcohol-polymer nano granules dispersion system 0.1～2mL,, put under the room temperature and treat solvent evaporates, promptly obtain the ball-type packaging assembly of formula 1 described polymer beads.
(3) preparation method of the membranaceous packaging assembly of nano particle of formula 1 polymkeric substance, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system solution of claim 6, clean slide glass is vertically inserted in the dispersed system solution, slowly lift out solution then, put under the room temperature and treat solvent evaporates, promptly obtain the membranaceous packaging assembly that formula 1 polymer nano granules forms on sheet glass.
The structure of formula 1 polymkeric substance of the present invention, MS, UV, IR and ultimate analysis data acknowledgement.
The contriver discovers that by experiment by 2,3-pyridine cyclohexadione compounds and aromatic diamines have outstanding feature by formula of the present invention 1 polymkeric substance that Michael addition obtains.Contain aromatic amine-2, in the molecule of 3-pyridine diketone repeated structural unit polymkeric substance, except containing the polymer backbone that constitutes by aromatic ring and quinone ring, also contain highdensity carbonyl (hydrogen acceptor) and amino groups such as (hydrogen donors), and the combination of these groups is suitable for forming hydrogen bond with protein, enzyme or DNA.Quinone ring in the oligomer molecule links to each other by the singly-bound that can rotate freely with aromatic ring structure, can form helical conformation.Appliance computer simulating polymer molecular model has also confirmed aromatic amine-2, and 3-pyridine diketone polymeric chain can form the supposition of spirane structure in the space.These constitutional featuress help identification and the absorption (mainly by hydrogen bond, π-delocalized bond, hydrophobic bond and Van der Waals force etc.) of polymkeric substance and protein, enzyme and DNA.We also find, use suitable synthetic technology, can prepare to have different molecular weight, have the polymer beads of nano-scale or their packaging assembly.The new polymkeric substance of this class is met as the requirement that protein, enzyme and DNA is had multidigit point and big area recognition performance.Therefore, the nano particle of formula 1 polymkeric substance of the present invention can be used as biochip material and the application of biomacromolecule immobilization material.
The contriver finds that also the membranaceous packaging assembly of nano particle of formula 1 polymkeric substance of the present invention can be used as inorganic nano material ordered structure template applications.
Dispersions of nanoparticles (colloid) feature of formula 1 polymkeric substance of the present invention, the field emission scanning electron microscope photo confirms (accompanying drawing 1).
Formula 1 polymer nano granules dispersed system of the present invention and cube, spherical or membranaceous packaging assembly feature, field scan electron micrograph (accompanying drawing 2,3,4,5) confirms.
Formula 1 polymer nano granules dispersed system of the present invention to the molecular recognition effect of DNA biosensor assay result (accompanying drawing 6) confirm.
Formula 1 polymkeric substance of the present invention is touched the plate possibility of its application as the inorganic nano material ordered structure, confirms (embodiment 13) by correlation test.
Formula 1 polymkeric substance of the present invention confirms (embodiment 14-15) by correlation test as the biochip material possibility of its application of protein and DNA etc.
Description of drawings
Fig. 1: aromatic amine-2, the field emission scanning electron microscope photo of 3-pyridine diketone polymeric colloid dispersed system.
Take a morsel by 4 of embodiment 9 preparations, 4 '-methylene dianiline (MDA)-2,3-pyridine diketone polymer latex liquid solution is applied on the slide glass vacuum-drying.Before the test sample being carried out the Au-Ag vacuum evaporating handles.Take electromicroscopic photograph with JEOL FEM-6330F type field scan electron microscope.
Fig. 2 and Fig. 3: 4,4 '-methylene dianiline (MDA)-2,3-pyridine diketone polymer nano granules cube packaging assembly field scan electron micrograph.
Prepare polymer nano granules cube packaging assembly by embodiment 10 methods, take electromicroscopic photograph with JEOL FEM-6330F type field scan electron microscope.
Fig. 4: 4,4 '-methylene dianiline (MDA)-2,3-pyridine diketone polymer nano granules ball-type packaging assembly field scan electron micrograph.
Prepare polymer nano granules ball-type packaging assembly by embodiment 11 methods, take electromicroscopic photograph with JEOL FEM-6330F type field scan electron microscope.
Fig. 5: 4,4 '-methylene dianiline (MDA)-2, the membranaceous packaging assembly field scan of 3-pyridine diketone polymer nano granules electron micrograph.
Prepare the membranaceous packaging assembly of polymer nano granules by embodiment 12 methods, take electromicroscopic photograph with JEOL FEM-6330F type field scan electron microscope.
Fig. 6: applying biological sensor determination 2,6-diamino-pyridine-2,3-pyridine two ketone polymers are to the collection of illustrative plates of DNA identification;
Press embodiment 14 methods, with 2,6-diamino-pyridine-2,3-pyridine two ketone polymers are connected on the substrate (containing carboxyl) of sample pool by amido linkage, adding base sequence is the single stranded DNA of 5 '-GCAAAGATGTGCCCTGTATT-3 ', measures the recognition reaction of polymkeric substance to DNA with Affinity sensorsIAsys.
Embodiment
The invention will be further described by the following examples.(I～VIII) is the R of expression and corresponding formula 1 polymkeric substance of this aromatic diamine compound respectively for numeral among each embodiment in the bracket of aromatic diamine compound title back
1Group (I～VIII).
Embodiment 1. 4,4 '-methylene dianiline (MDA)-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL DMF/ water mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 4,4 '-methylene dianiline (MDA) (I) solution [0.02mol is dissolved in the 100mL ethanol/water mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has a large amount of reddish brown precipitations to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings promptly get 5.5g red-brown polymkeric substance.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.IR (KBr): 3429.0,3352.2,3237.0,1722.5,1652.3,1607.0cm
-1 1H-NMR δ 10.05 (=NH), 9.44 (=NH), 6.49～7.30 (Ar-H), 5.94 (pyridine ring C-H), 4.80 (NH
2).
13C-NMR δ 174.4 (C=O), 156.9 (C=O), 100.69 (pyridine ring C-H), 39.82 (CH
2-).Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 2100～15000.
Embodiment 2. 4,4 '-ethyl pentanoic-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL DMSO/ water mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 4,4 '-ethyl pentanoic (II) solution [0.02mol is dissolved in the 100mL ethanol/water mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has red precipitate to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get the 4.5g red polymer.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.IR (KBr): 3435.0,3349.2,3286.0,1721.5,1652.4,1607.3cm
-1 1H-NMR δ 10.60 (=NH), 9.46 (=NH), 6.50～7.50 (Ar-H), 5.96 (pyridine ring C-H), 5.00 (NH
2).
13C-NMR δ 173.6 (C=O), 156.6 (C=O), 100.65 (pyridine ring C-H), 37.10 (CH
2-), 36.36 (CH
2-).Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 1350～12000.
Embodiment 3. 3,3 '-two fluoro-4,4 '-di-aniline-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mLDMF/ water mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 3,3 '-two fluoro-4,4 '-p-diaminodiphenyl (III) solution [0.02mol is dissolved in 100ml acetone mixed solvent].Stir 6h down at 50 ℃ then.Reaction finishes, and has yellow mercury oxide to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get, and get the 3g yellow polymer.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 1,400～6000.
Embodiment 4. 4,4 '-diaminobenzene sulfone-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL methanol mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 4,4 '-diaminobenzene sulfone (IV) solution [0.02mol is dissolved in 100ml methanol mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has brown precipitate to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get, and get 3.5g red-brown polymkeric substance.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is more than 2,500～13000.
Embodiment 5. 4,4 '-vinyl pentanoic-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mLDMF/ water mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 4,4 '-vinyl base pentanoic (V) solution [0.02mol is dissolved in 100mL methanol mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has the scarlet precipitation to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get 5g scarlet polymkeric substance.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 2,100～7800.
Embodiment 6. 3,9-proflavin-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL methanol mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 3,9-proflavin (VI) solution [0.02mol is dissolved in 100mL acetone mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has a large amount of red precipitates to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get, and get the 4g red polymer.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 2,400～9300.
Embodiment 7. 3,6-proflavin-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL methanol mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 3,6-proflavin (VII) solution [0.02mol is dissolved in 100mL acetone mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has a large amount of salmon precipitations to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get, and promptly get 3.5g red-brown polymkeric substance.Product structure is IR,
1H-NMR and
13The C-NMR analytical data confirms.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 2,600～11600.
Embodiment 8. 2,6-diamino-pyridine-2,3-pyridine two ketone polymers synthetic
Get 2.2g (0.02mol) 2, the 3-dihydroxy-pyridine is dissolved in the 100mL methanol mixed solvent, adds 8.6g (0.04mol) sodium iodate (NaIO
3), stirring at room 5～30min.Under agitation condition, drip 2,6-diamino-pyridine (VIII) solution [0.02mol is dissolved in 100mL acetone mixed solvent].Stirred overnight at room temperature.Reaction finishes, and has the red-purple precipitation to generate.Filter, and with the inorganic salt in the distilled water flush away product.Be washed till elutant with 50% ethanol-water mixed solvent and dehydrated alcohol respectively then and be colourless.50 ℃ of vacuum-dryings get, and get 4.5g red-purple polymkeric substance.Product structure is IR,
1H-NMR and
13C-NMR analyses data acknowledgement.Use matrix auxiliary laser desorption ionization flight time mass spectrum technology, the molecular weight distribution that records polymkeric substance is 650～3, and 200.
Embodiment 9. 4,4 '-methylene dianiline (MDA)-2, the preparation of 3-pyridine diketone polymer nano granules and dispersion system thereof
Can make the nano particle and the dispersed system thereof of formula 1 polymkeric substance of the present invention by the following method, concrete steps are: get 4,4 '-methylene dianiline (MDA)-2, the DMF solution 1mL of 3-pyridine two ketone polymers, under ultrasonic concussion dropwise or disposable joining in the 100mL distilled water.The concentration of final dispersed system is 2 * 10
-3Mg/mL.Continue ultrasonic concussion 0.5h, obtain required formula 1 polymer beads colloidal dispersion system (colloid).The above-mentioned colloidal solution that takes a morsel is applied on the slide glass, is used for the electron microscopic observation (see figure 1).
Embodiment 10. 4,4 '-methylene dianiline (MDA)-2, the preparation of 3-pyridine diketone polymer nano granules cube packaging assembly
Get embodiment 9 polymer nano granules dispersion system 0.5mL, put under the room temperature and treat solvent evaporates, obtain the nano particle cube packaging assembly of formula 1 described polymkeric substance.Small amount of sample is transferred on the slide glass, is used for electron microscopic observation.(see Fig. 2, Fig. 3).
Get embodiment 9 polymer nano granules dispersion system 1mL, centrifugation (15000rpm) 4h, collecting precipitation is deposited in ultrasonic concussion 2h in the methyl alcohol, obtains methyl alcohol-polymer nano granules dispersion system.The dispersion system of above-mentioned preparation is placed under the room temperature, treat solvent evaporates, obtain the nano particle ball-type packaging assembly of formula 1 described polymkeric substance.Take a morsel sample on slide glass, be used for electron microscopic observation.(see figure 4).
Embodiment 12. 4,4 '-methylene dianiline (MDA)-2, the preparation of the membranaceous packaging assembly of 3-pyridine diketone polymer nano granules
Get embodiment 9 polymer nano granules dispersion system 100mL, clean slide is vertically inserted in the colloidal solution, again slide is slowly vertically lifted out liquid level from solution.Slide glass is placed under the room temperature, treat to be used for electron microscopic observation after the solvent evaporates.(see figure 5).
Embodiment 13. 4,4 '-methylene dianiline (MDA)-2, and the membranaceous packaging assembly of 3-pyridine diketone polymer nano granules prepares three oxidations two as template
The iron ordered structure
The surface is scribbled 4 of embodiment 12 preparations, 4 '-methylene dianiline (MDA)-2, it is solution 4h that the slide of the membranaceous packaging assembly of 3-pyridine diketone polymer nano granules places the ferric oxide nano-dispersed.Take out slide, use the distilled water thorough washing.The two-dimensional arrangements structure of ferric oxide nano particle formation rule on sheet glass.
Embodiment 14. 2,6-diamino-pyridine-2, and 3-pyridine two ketone polymers are to the recognition reaction of DNA
With 2 of embodiment 8 preparations, 6-diamino-pyridine-2,3-pyridine two ketone polymers are connected on the substrate (containing carboxyl) of sample pool by amido linkage, behind buffered soln flush away condensing agent, adding base sequence is the single stranded DNA of 5 '-GCAAAGATGTGCCCTGTATT-3 ', measures recognition reaction (Fig. 6) with Affinity sensors Iasys.As can be seen from the figure, polymkeric substance has very strong identification and adsorption to the DNA with this base sequence.
Embodiment 15. 2,6-diamino-pyridine-2, and 3-pyridine two ketone polymers are as the application of biochip material
Press embodiment 8 preparations 2,6-diamino-pyridine-2,3-pyridine two ketone polymers.With the polymkeric substance that this method obtains, end group mostly is free amino.By this free amino, can be connected with the carrier that carboxyl or active halogen are contained in the surface.
With 2 of above-mentioned preparation, 6-diamino-pyridine-2,3-pyridine two ketone polymers are connected to the surface and contain on the slide glass of carboxymethyl.The slide glass that obtains after handling with this method can be discerned and adsorbs multiple different polypeptide, oligonucleotide and drug molecule.Identification and adsorption property can be used mensuration such as UV, biosensor.Since 2,6-diamino-pyridine-2, and 3-pyridine two ketone polymers are undertaken by non covalent bond the adsorption of biomolecules or drug molecule, can carry out wash-out under suitable condition, thereby can use repeatedly.
Obviously, according to the present embodiment similar methods, use different diamines raw material and operational condition, can prepare other aromatic amine-2,3-pyridine diketone polymer biological chip.
Claims (9)
1. aromatic amine-2 as shown in Equation 1,3-pyridine two ketone polymers, the molecular-weight average of this polymkeric substance are 1000～15000:
Formula 1
Wherein, R
1Be one of following group I to VIII:
2. the preparation method of described formula 1 polymkeric substance of claim 1 is characterized in that concrete steps are:
(1) with 2, the 3-dihydroxy-pyridine is dissolved in the solvent, is made into the solution that concentration is 0.1～0.4mol/L, adds oxygenant then, stirring at room 5～30min;
(2) under the agitation condition, dripping the concentration that is dissolved in the solvent is the aromatic diamines solution of 0.1～0.4mol/L, at room temperature stirs then and spends the night;
(3) after reaction is finished, filter, and, be washed till elutant with ethanol-water mixed solvent respectively again and be colourless, promptly obtain required aromatic amine-2 after the drying, 3-pyridine two ketone polymers with the inorganic salt in the distilled water flush away product;
Used oxygenant is I
2, KIO
4, KIO
3, NaIO
4, NaIO
3, NaClO, Ca (ClO)
2, FeCl
3Or active MnO
2Used solvent is for being selected from a kind of of ethanol, methyl alcohol, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), or the aqueous solution of above-mentioned solvent; R in used aromatic diamines and formula 1 polymkeric substance
1One of group I to VIII is corresponding; The mol ratio of used each composition is: 2, and 3-dihydroxy-pyridine: oxygenant: aromatic diamines=1: 2～4: 0.7～1.5.
3. according to the preparation method of described formula 1 polymkeric substance of claim 3, it is characterized in that used solvent is 30～90% ethanol, dimethyl sulfoxide (DMSO) or the dimethyl formamide aqueous solution.
4. according to the preparation method of claim 3 or 4 described formula 1 polymkeric substance, it is characterized in that used oxygenant is KIO
3Or NaIO
3
5. the preparation method of the nanometer colloid particles dispersed system of described formula 1 polymkeric substance of claim 1, concrete steps are: compound concentration is the formula 1 polymkeric substance DMF solution of 20mg/mL, is diluted to 2,2 * 10 then
-1, 2 * 10
-2, 2 * 10
-3With 2 * 10
-4The serial solution for later use of mg/mL; Get polymkeric substance DMF solution, dropwise add or disposable joining in the distilled water under ultrasonic oscillation, the DMF solution of above-mentioned polymkeric substance and the volume ratio of distilled water are 1: 10～300; The concentration of final dispersed system is 2 * 10
-1～2 * 10
-6Between the mg/mL; Continue concussion 0.5～2h again; Obtain the colloidal dispersion system of the nano particle that formula 1 polymkeric substance forms in water.
6. the preparation method of the nano particle cube packaging assembly of described formula 1 polymkeric substance of claim 1, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system aqueous solution of claim 6 01～2mL, put under the room temperature and treat solvent evaporates, promptly obtain cube packaging assembly of formula 1 described polymer beads.
7. the preparation method of the nano particle ball-type packaging assembly of described formula 1 polymkeric substance of claim 1, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system solution of claim 6 0.1～5mL, at the centrifugal 0.5～6h of 5000～21000rpm, carefully remove supernatant liquor then; Add 0.1～5mL methyl alcohol in precipitation, ultrasonic oscillation 2～6h makes methyl alcohol-polymer nano granules dispersion system, and the concentration of final dispersed system is 2 * 10
-2～2 *
-6Between the mg/mL: get methyl alcohol-polymer nano granules dispersion system 0.1～2mL, put under the room temperature and treat solvent evaporates, promptly obtain the ball-type packaging assembly of formula 1 described polymer beads.
8. the preparation method of the membranaceous packaging assembly of nano particle of described formula 1 polymkeric substance of claim 1, concrete steps are: get according to the described formula 1 polymer nano granules dispersion system solution of claim 6, clean slide glass is vertically inserted in the dispersed system solution, slowly lift out solution then, put under the room temperature and treat solvent evaporates, promptly obtain the membranaceous packaging assembly that formula 1 polymer nano granules forms on sheet glass.
9. described formula 1 polymkeric substance of claim 1 is as the application as inorganic nano material ordered structure template of biochip material, biomacromolecule immobilization material and the membranaceous packaging assembly of nano particle.
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