CN103342819A - Polyamide-imide dendritic polymer with phosphate radical end group as well as preparation method and application for same - Google Patents
Polyamide-imide dendritic polymer with phosphate radical end group as well as preparation method and application for same Download PDFInfo
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Abstract
The invention belongs to the field of biomineralization materials, and particularly relates to a polymer capable of inducing hydroxyapatite to be remineralized, as well as a preparation method for the same, and an application for the same in the aspect of dental restoration. The polymer has the structural formula defined in the specification, wherein n is the algebra of the polymer. The method disclosed by the invention comprises the following steps of: (1) synthesising a polyamide-imide dendritic polymer with a phosphate ester radical end group; and (2) synthesising a polyamide-imide dendritic polymer with a phosphate radical end group. Experimental results prove that the polymer disclosed by the invention is capable of inducing hydroxyapatite to deposit and crystallize on abrasion dentin blocks and abrasion enamel blocks.
Description
Technical field
The invention belongs to biomineralization material field, the polymkeric substance and preparation method thereof that particularly can induce the hydroxyapatite remineralization with its in the application aspect the tooth reparation.
Background technology
The dental disorder that causes because of demineralization has now become one of important factor that threatens human oral Health, and the clinical technology demand at this type of disease increases sharply at present.Organic substrates such as the dentine phosphorprotein in the human oral cavity and enamel stromatin play an important role in the equilibrium process of the demineralization of tooth and remineralization, are widely used in treating dentistry demineralization disease and simulate the organic substrate materials with function.At present, the simulation organic substrate induces the material of dentine and enamel remineralization to comprise systems such as biomacromolecule, liposome, self-assembled film, micella, gel, but these materials in application process, exist to a certain degree long-lasting poor, easily come off, shortcoming such as curative effect instability, biocompatibility are not good.Therefore, the novel material of exploitation simulation organic substrate function is significant for the treatment of dental disorder.
Summary of the invention
The purpose of this invention is to provide a kind of end group is polyamide-amide type branch-shape polymer of phosphate radical and preparation method thereof, and prove that described end group is that the polyamide-amide type branch-shape polymer of phosphate radical has the function of inducing the hydroxyapatite remineralization, for dental disorders such as treatment or pre-preventing decayed tooth disease, dentin hypersensitiveness provide new medical material.
End group of the present invention is the polyamide-amide type branch-shape polymer of phosphate radical, and its structural formula is as follows:
In the said structure formula, described n is that end group is the algebraically of the polyamide-amide type branch-shape polymer of phosphate radical, n=3,4 or 5.
End group of the present invention is that the synthetic route synoptic diagram of the polyamide-amide type branch-shape polymer of phosphate radical is seen Fig. 1, and end group of the present invention is the preparation method of the polyamide-amide type branch-shape polymer of phosphate radical, and step is as follows:
(1) end group is the synthetic of phosphate-based polyamide-amide type branch-shape polymer
1. prepare first kind of solution
The general is not dissolved in the pure water with highly basic and the tetrahydrofuran (THF) that tetrahydrofuran (THF) reacts under room temperature, normal pressure, namely forms first kind of solution; Described is not a with the hydroxide radical of the highly basic of tetrahydrofuran (THF) reaction and the mol ratio of tetrahydrofuran (THF), 0＜a≤1; Describedly be not limited with the proportioning of highly basic, tetrahydrofuran (THF) and the pure water of tetrahydrofuran (THF) reaction ph=9 ~ 11 with first kind of solution;
2. prepare second kind of solution
Under room temperature, normal pressure, Paraformaldehyde 96 is dissolved in described first kind of solution, namely forms second kind of solution; The proportioning of described Paraformaldehyde 96 and first kind of solution is dissolved fully with Paraformaldehyde 96 and is limited;
3. prepare the third solution
Under room temperature, normal pressure with 3,4 or 5 generation end group for amino polyamide-amide type branch-shape polymer is dissolved in the pure water, namely form the third solution; Described 3,4 or 5 generation end group for the proportioning of amino polyamide-amide type branch-shape polymer and pure water with in the third solution 3,4 or 5 generation end group be that the concentration of the polyamide-amide type branch-shape polymer of amino reaches 1 ~ 2 g/mL and is limited;
4. prepare the 4th kind of solution
Under room temperature, normal pressure, two kinds of solution and the third solution are mixed, namely form the 4th kind of solution; In the 4th kind of solution, the mol ratio 〉=2:1 of the amino of the aldehyde radical in the Paraformaldehyde 96 and polyamide-amide type branch-shape polymer;
5. synthetic
Under nitrogen protection, dimethylphosphite is added drop-wise in the 4th kind of solution, under normal pressure, 60 ℃ ~ 90 ℃ condition, react 12h at least, after reaction times expires, unreacted tetrahydrofuran (THF) is removed in underpressure distillation, through dialysis, filtration, underpressure distillation, lyophilize, namely getting end group is phosphate-based polyamide-amide type branch-shape polymer again;
The proportioning of described the 4th kind of solution and dimethylphosphite is: the mol ratio 〉=2:1 of the amino of the polyamide-amide type branch-shape polymer in dimethylphosphite and the 4th kind of solution;
(2) end group is polyamide-amide type branch-shape polymer synthetic of phosphate radical
End group with step (1) preparation is that phosphate-based polyamide-amide type branch-shape polymer is solute, under normal pressure, room temperature it being dissolved in and namely getting end group in the non-proton property polar solvent is phosphate-based polyamide-amide type branch-shape polymer solution, the proportioning of described solute and non-proton property polar solvent with solute can be in aprotic polar solvent fully dissolving be limited;
With end group be phosphate-based polyamide-amide type branch-shape polymer solution under nitrogen protection in normal pressure; stirring at room is 0.5h at least; add bromotrimethylsilane then and at normal pressure; stir 24h at least under the room temperature; continue after add methyl alcohol and reaction system sealed; at normal pressure; react 24h at least under the room temperature; after reaction times expires; through dialysis; underpressure distillation; lyophilize; namely getting end group is the polyamide-amide type branch-shape polymer of phosphate radical; the add-on of described bromotrimethylsilane is limited with the phosphate-based mol ratio 〉=1:1 in bromotrimethylsilane and the described solution, and the add-on of described methyl alcohol is limited with the mol ratio 〉=1:1 of methyl alcohol and bromotrimethylsilane.
In the aforesaid method, described is not potassium hydroxide, calcium hydroxide, sodium hydroxide or magnesium hydroxide with the highly basic of tetrahydrofuran (THF) reaction.
In the aforesaid method, described non-proton property polar solvent is dimethyl sulfoxide (DMSO), methylene dichloride, trichloromethane, acetonitrile or dimethyl formamide.
In the aforesaid method, described pure water is distilled water or deionized water.
The polyamide-amide type branch-shape polymer that it is phosphate radical that the present invention also provides a kind of described end group is as the application of preparation dentine and enamel original position remineralization inductor.Experiment shows: end group of the present invention be the polyamide-amide type branch-shape polymer of phosphate radical in deionized water, hydroxyapatite is had the good adsorption effect; End group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical can induce hydroxyapatite in wearing and tearing dentine piece and wearing and tearing enamel piece deposition and crystallization in simulate saliva.
Described original position remineralization inductor is that end group of the present invention is the polyamide-amide type branch-shape polymer of phosphate radical and the aqueous solution that deionized water is mixed with, in the described aqueous solution, end group of the present invention is that the concentration of the polyamide-amide type branch-shape polymer of phosphate radical is at least 1000ppm, preferred 4000ppm.
The present invention has following beneficial effect:
1, end group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical is a kind of novel biomineralization material, for biological mineralizing material has increased new kind.
2, experiment shows, end group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical has the function (seeing embodiment 4, embodiment 5) of adsorbing hydroxyapatite and inducing the hydroxyapatite remineralization, thereby can be used as dentine and the application of enamel original position remineralization inductor.
3, end group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical is when using as dentine and enamel original position remineralization inductor, in the short period of time (4 week) induce hydroxyapatite deposition and grow to certain thickness on abrasion dentine piece and abrasion enamel piece, show that it has the good effect of inducing.
4, the method for the invention adopts conventional raw material and equipment to realize, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is that end group of the present invention is the synthetic route synoptic diagram of the polyamide-amide type branch-shape polymer of phosphate radical;
Fig. 2 is the G4-PO of embodiment 1 preparation
3Structural representation, among the figure,
Fig. 3 is the G4-PO of embodiment 1 preparation
3Nucleus magnetic hydrogen spectrum figure;
Fig. 4 is the G4-PO of embodiment 1 preparation
3Infrared spectrum;
Fig. 5 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion dentine piece in embodiment 5 experimental group 2;
Fig. 6 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion enamel piece in embodiment 5 experimental group 2;
Fig. 7 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion dentine piece in embodiment 5 experimental group 3;
Fig. 8 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion enamel piece in embodiment 5 experimental group 3.
Fig. 9 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion dentine piece in embodiment 5 experimental group 1;
Figure 10 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion enamel piece in embodiment 5 experimental group 1;
Figure 11 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion dentine piece in embodiment 5 control groups;
Figure 12 is the stereoscan photograph (a is plane of structure, and b is section) that hydroxyapatite deposits at abrasion enamel piece in embodiment 5 control groups.
Embodiment
Polyamide-amide type branch-shape polymer that end group of the present invention is phosphate radical below by embodiment and preparation method thereof is described further with application.
Present embodiment prepares the 4 generation polyamide-amide type branch-shape polymer (G4-PO that end group is phosphate radical
3), the preparation method is as follows:
1. prepare first kind of solution
Under room temperature, normal pressure, 28 gram potassium hydroxide and 72 gram tetrahydrofuran (THF)s are dissolved in the distilled water, namely form first kind of solution; The hydroxide radical of described potassium hydroxide and the mol ratio of tetrahydrofuran (THF) equal 0.5; The proportioning of described potassium hydroxide, tetrahydrofuran (THF) and distilled water equals 10 with the ph of first kind of solution and is limited;
2. prepare second kind of solution
Under room temperature, normal pressure, 3 gram Paraformaldehyde 96s are dissolved in first kind of solution, namely form second kind of solution; The proportioning of described Paraformaldehyde 96 and first kind of solution is dissolved fully with Paraformaldehyde 96 and is limited;
3. prepare the third solution
Under room temperature, normal pressure the polyamide-amide type branch-shape polymer (G4 PAMAM) of 6.9 grams, 4 generation end group for amino is dissolved in 4 ml distilled waters, namely forms the third solution, the concentration of G4 PAMAM is 1.725 g/mL in the third solution;
4. prepare the 4th kind of solution
Under room temperature, normal pressure, second kind of solution and the third solution are mixed, namely form the 4th kind of solution; In the 4th kind of solution, the mol ratio of the amino of the aldehyde radical in the Paraformaldehyde 96 and polyamide-amide type branch-shape polymer is 3.125;
5. synthetic
Under nitrogen protection, 11 gram dimethylphosphites are added drop-wise in the 4th kind of solution (in dimethylphosphite and the 4th kind of solution 4 generation polyamide-amide type branch-shape polymer the mol ratio of amino be 3.125), in normal pressure, 70 ℃ of oil baths, react 14 h, after reaction times expires, revolve to steam and remove unreacted tetrahydrofuran (THF), be that distilled water, lyophilize are removed in 3500 daltonian dialysis tubings dialysis 1 day, filtration, underpressure distillation with molecular weight cut-off in distilled water, namely getting end group is phosphate-based about 14.7 grams of 4 generation polyamide-amide type branch-shape polymers;
(2) end group is polyamide-amide type branch-shape polymer synthetic of phosphate radical
With 7.3 gram end groups of step (1) preparation be phosphate-based 4 generation polyamide-amide type branch-shape polymer be solute, under normal pressure, room temperature condition, it is dissolved in namely get in 300 milliliters of dimethyl sulfoxide (DMSO) end group be phosphate-based 4 generation polyamide-amide type branch-shape polymer solution;
Described solution is stirred 1h under normal pressure, room temperature, nitrogen protection condition, then to wherein add 9.8 the gram bromotrimethylsilanes and under normal pressure, room temperature condition the stirring velocity with 500 commentaries on classics/min stir 40 h; Phosphate-based mol ratio in bromotrimethylsilane and the described solution is 2:1;
Continue after drip 4.1 gram methyl alcohol (mol ratio of methyl alcohol and bromotrimethylsilane equals 2:1) in the reaction mixture, after methyl alcohol dropwises reaction system is sealed, under normal pressure, room temperature condition, react 40h, after reaction times expires, be 10000 daltonian dialysis tubings dialysis 1 day, underpressure distillation, lyophilize with molecular weight cut-off in distilled water, namely getting end group is 4 generation polyamide-amide type branch-shape polymer (G4-PO of phosphate radical
3).Its structural representation, nucleus magnetic hydrogen spectrum figure and infrared spectrum are respectively as Fig. 2, Fig. 3 and shown in Figure 4.
Present embodiment prepares the 3 generation polyamide-amide type branch-shape polymer (G3-PO that end group is phosphate radical
3), the preparation method is as follows:
1. prepare first kind of solution
Under room temperature, normal pressure, 40 gram sodium hydroxide and 72 gram tetrahydrofuran (THF)s are dissolved in the deionized water, namely form first kind of solution; The hydroxide radical of described sodium hydroxide and the mol ratio of tetrahydrofuran (THF) equal 1, and the proportioning of described sodium hydroxide, tetrahydrofuran (THF) and deionized water is limited with the ph=9 of first kind of solution;
2. prepare second kind of solution
Under room temperature, normal pressure, 0.96 gram Paraformaldehyde 96 is dissolved in first kind of solution, namely forms second kind of solution; The proportioning of described Paraformaldehyde 96 and first kind of solution is dissolved fully with Paraformaldehyde 96 and is limited;
3. prepare the third solution
Under room temperature, normal pressure the polyamide-amide type branch-shape polymer (G3 PAMAM) of 3.2 grams, 3 generation end group for amino is dissolved in 3.2 ml deionized water, namely forms the third solution, the concentration of G3 PAMAM is 1 g/mL in the third solution;
4. prepare the 4th kind of solution
Under room temperature, normal pressure, second kind of solution and the third solution are mixed, namely form the 4th kind of solution; In the 4th kind of solution, the mol ratio of the amino of the aldehyde radical in the Paraformaldehyde 96 and polyamide-amide type branch-shape polymer is 2:1;
5. synthetic
Under nitrogen protection, 3.52 gram dimethylphosphites are joined in the 4th kind of solution (in dimethylphosphite and the 4th kind of solution 3 generation polyamide-amide type branch-shape polymer the mol ratio of amino be 2:1), in normal pressure, 60 ℃ of oil baths, react 12 h, after reaction times expires, revolve to steam and remove unreacted tetrahydrofuran (THF), be that distilled water, lyophilize are removed in 3500 daltonian dialysis tubings dialysis 1 day, filtration, underpressure distillation with molecular weight cut-off in distilled water, namely getting end group is phosphate-based about 7.1 grams of 3 generation polyamide-amide type branch-shape polymers;
(2) end group is polyamide-amide type branch-shape polymer synthetic of phosphate radical
With 3.6 gram end groups of step (1) preparation be phosphate-based 3 generation polyamide-amide type branch-shape polymer be solute, under normal pressure, room temperature condition, it is dissolved in namely get in 200 milliliters of methylene dichloride end group be phosphate-based 3 generation polyamide-amide type branch-shape polymer solution;
Described solution is stirred 0.5h under normal pressure, room temperature, nitrogen protection condition, then to wherein add 2.45 gram bromotrimethylsilanes and under normal pressure, room temperature condition with the stirring velocity of 400 commentariess on classics/min stirring 24h; Phosphate-based mol ratio in bromotrimethylsilane and the described solution is 1:1;
Continue after drip 0.51 gram methyl alcohol (mol ratio of methyl alcohol and bromotrimethylsilane equals 1:1) in the reaction mixture, after methyl alcohol dropwises reaction system is sealed, under normal pressure, room temperature condition, react 24h, after reaction times expires, be 3500 daltonian dialysis tubings dialysis 2 days, underpressure distillation, lyophilize with molecular weight cut-off in distilled water, namely getting end group is 3 generation polyamide-amide type branch-shape polymer (G3-PO of phosphate radical
3).
Embodiment 3
Present embodiment prepares the 5 generation polyamide-amide type branch-shape polymer (G5-PO that end group is phosphate radical
3), the preparation method is as follows:
1. prepare first kind of solution
Under room temperature, normal pressure, 37 gram calcium hydroxides and 72 gram tetrahydrofuran (THF)s are dissolved in (hydroxide radical of described calcium hydroxide and the mol ratio of tetrahydrofuran (THF) equal 1:1) in the distilled water, namely form first kind of solution; The proportioning of described calcium hydroxide, tetrahydrofuran (THF) and distilled water is limited with the ph=11 of first kind of solution;
2. prepare second kind of solution
Under room temperature, normal pressure, 3.84 gram Paraformaldehyde 96s are dissolved in first kind of solution, namely form second kind of solution; The proportioning of described Paraformaldehyde 96 and first kind of solution is dissolved fully with Paraformaldehyde 96 and is limited;
3. prepare the third solution
Under room temperature, normal pressure the polyamide-amide type branch-shape polymer (G5 PAMAM) of 14.2 grams, 5 generation end group for amino is dissolved in 7.1 ml distilled waters, namely forms the third solution, the concentration of G5 PAMAM is 2 g/mL in the third solution;
4. prepare the 4th kind of solution
Under room temperature, normal pressure, second kind of solution and the third solution are mixed, namely form the 4th kind of solution; In the 4th kind of solution, the mol ratio of the amino of the aldehyde radical in the Paraformaldehyde 96 and polyamide-amide type branch-shape polymer is 2:1;
5. synthetic
Under nitrogen protection, 14.08 gram dimethylphosphites are added drop-wise in the 4th kind of solution (in dimethylphosphite and the 4th kind of solution 5 generation polyamide-amide type branch-shape polymer the mol ratio of amino be 2:1), in normal pressure, 90 ℃ of oil baths, react 12 h, after reaction times expires, revolve to steam and remove unreacted tetrahydrofuran (THF), be that distilled water, lyophilize are removed in 3500 daltonian dialysis tubings dialysis 1 day, filtration, underpressure distillation with molecular weight cut-off in distilled water, namely getting end group is phosphate-based about 29.8 grams of 5 generation polyamide-amide type branch-shape polymers;
(2) end group is polyamide-amide type branch-shape polymer synthetic of phosphate radical
With 14.9 gram end groups of step (1) preparation be phosphate-based 5 generation polyamide-amide type branch-shape polymer be solute, under normal pressure, room temperature condition, it is dissolved in namely get in the trichloromethane end group be phosphate-based 5 generation polyamide-amide type branch-shape polymer solution;
Described solution is stirred 0.5h under normal pressure, room temperature, nitrogen protection condition, then to wherein add 9.79 gram bromotrimethylsilanes and under normal pressure, room temperature condition with the stirring velocity of 450 commentariess on classics/min stirring 24h; Phosphate-based mol ratio in bromotrimethylsilane and the described solution is 1:1;
Continue after drip 2.05 gram methyl alcohol (mol ratio of methyl alcohol and bromotrimethylsilane equals 1:1) in the reaction mixture, after dropwising reaction system is sealed, under normal pressure, room temperature condition, react 24h, after reaction times expires, be 14000 daltonian dialysis tubings dialysis 3 days, underpressure distillation, lyophilize with molecular weight cut-off in distilled water, namely getting end group is 5 generation polyamide-amide type branch-shape polymer (G5-PO of phosphate radical
3).
Embodiment 4
Present embodiment is measured the absorption situation of polyamide-amide type branch-shape polymer on hydroxyapatite powder that end group of the present invention is phosphate radical.In the present embodiment, the specification of described hydroxyapatite powder is HA/M30, and its water content is lower than 0.1%.
G4-PO with embodiment 1 preparation
3Solid is dissolved in the deionized water, the G4-PO of 5 concentration gradients of preparation
3The aqueous solution (0.2 g/mL, 0.4 g/mL, 0.6 g/mL, 0.8g/mL and 1g/mL).With the described G4-PO of measurement of ultraviolet-visible spectrophotometer
3The aqueous solution is the absorbance at 281 nm places at wavelength, obtains G4-PO
3Linear relationship between concentration and the absorbance, i.e. typical curve.
G4-PO with embodiment 1 preparation
3Be dissolved in the deionized water G4-PO of 5 concentration gradients of preparation
3The aqueous solution (0.5 g/mL, 1 g/mL, 1.5 g/mL, 2 g/mL and 2.5 g/mL).Getting range and be 10 of the centrifugal PE pipes of 4 mL, is the G4-PO of 0.5 g/mL, 1 g/mL, 1.5 g/mL, 2 g/mL and 2.5 g/mL to wherein adding 25 mg hydroxyapatite powders, getting concentration then respectively respectively
3Each 1mL of the aqueous solution adds the (G4-PO of each concentration gradient in each centrifugal PE pipe
3The aqueous solution arranges 2 centrifugal PE pipes), stir 12 h 37 ℃ of vibrations, then to the mixed solution in each centrifugal PE pipe centrifugal (10000 rev/mins, 3 minutes), get centrifugal gained supernatant liquor respectively and measure G4-PO in the supernatant liquor with ultraviolet spectrophotometer
3Concentration, the reference standard curve can calculate the G4-PO that is adsorbed on the hydroxyapatite powder
3Amount.
Detected result shows, G4-PO
3Saturated adsorptive value on the 25mg hydroxyapatite powder is 0.7g.
Embodiment 5
In the present embodiment, the end group of measuring different concns is that the polyamide-amide type branch-shape polymer aqueous solution of phosphate radical is to the promotion ability of dentine and enamel remineralization.
(1) preparation of abrasion dentine and abrasion enamel piece
Get 15 of normal people's teeth, remove the organic pollutant on normal teeth surface with ethanol, the massfraction that is stored in 4 ℃ after clean with distilled water flushing is standby in 0.05% the thymol aqueous solution.
Adopt aciding to be prepared into abrasion dentine and abrasion enamel piece the people's tooth after the above-mentioned cleaning, operate as follows:
1. on high speed block teeth cutting machine dentine or the enamel part of needs are downcut from people's tooth, being positioned over specification then is 1*1*1(cm
3) emery disc in, and in sand table, water the DMDHE resin, treat its spontaneous curing, resin mass is taken out, on high speed turbine sand paper, it is polished, pay special attention to required dentine or enamel surface are come out from resin.
2. 15 block teeth that are surrounded by the DMDHE resin are placed deionized water, ultrasonic 30 min put into massfraction and are 37% H after the taking-up
3PO
4(aq) soak every tooth of 45 s(in 10 mL phosphoric acid dip), wash 3 (prescriptions of PBS: NaCl 8g, KCl 0.2g, Na with PBS again
2HPO
412H
2O 3.63g, KH
2PO
40.24g, transfer pH to 7.4, and with distilled water diluting to 1000 mL), being placed on then in the deionized water, ultrasonic 5 min preserve the abrasion dentine and the abrasion enamel piece that obtain stand-by in distilled water again.
(2) with the G4-PO of deionized water with embodiment 1 preparation
3Be mixed with G4-PO respectively
3Concentration is the G4-PO of 1000ppm, 4000ppm
3The aqueous solution is with the G3-PO of deionized water with embodiment 2 preparations
3Be mixed with G3-PO
3Concentration is the G3-PO of 4000ppm
3The aqueous solution.
Press following formulated simulate saliva: NaCl 0.4 g, KCl 0.4 g, CaCl
22H
2O 0.795 g, NaH
2PO
42H
2O 0.78 g, Na
2S2H
2O 0. 005 g, urea 1.0 g are with distilled water diluting to 1000 mL.
(3) abrasion dentine piece and the abrasion enamel piece with step (1) preparation is divided into experimental group 1, experimental group 2, experimental group 3 and control group, and abrasion dentine piece and abrasion enamel piece are each 3 in every group.The operation of each group is as follows:
1. the abrasion dentine of experimental group 1 and abrasion enamel piece at room temperature are soaked in the G4-PO of 1000 ppm
3The aqueous solution in, soak time 10min takes out, with 100mM PBS washing; The abrasion dentine of experimental group 2 and abrasion enamel piece at room temperature are soaked in the G4-PO of 4000 ppm
3The aqueous solution in, soak time 10min takes out, with 100mM PBS washing; The abrasion dentine of experimental group 3 and abrasion enamel piece at room temperature are soaked in the G3-PO of 4000 ppm
3The aqueous solution in, soak time 10min takes out, with 100mM PBS washing; With control group abrasion dentine and abrasion enamel piece at room temperature be soaked in the deionized water, soak time 10min takes out, with 100mM PBS washing.
2. dentine and the enamel piece that step is obtained in 1. is soaked in the simulate saliva, preserve in 37 ℃ of constant temperature, simulate saliva was changed once in per 2 days, soaked for 4 weeks, take out, with 100 mM PBS washing, oven dry, wear away deposition and the situation of crystallization, the relatively G4-PO of different concns of dentine piece and abrasion enamel piece surface hydroxyl phosphatic rock then with each group of scanning electron microscopic observation
3The aqueous solution and G3-PO
3The aqueous solution to the promotion ability of dentine and enamel remineralization, experimental result is seen Fig. 5 ~ Figure 12.
Fig. 5 ~ Figure 10 shows, as seen abrasion dentine piece and abrasion enamel piece surface obviously have deposition and the crystallization of certain thickness hydroxyapatite, best results (Fig. 5, Fig. 6) with experimental group 2, and Figure 11, Figure 12 show deposition and the growth that there is no hydroxyapatite on abrasion dentine piece and the abrasion enamel piece, illustrate that thus end group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical can induce hydroxyapatite in abrasion dentine and abrasion enamel piece surface deposition and crystallization.The experimental result of embodiment 4 and embodiment 5 shows that end group of the present invention is that the polyamide-amide type branch-shape polymer of phosphate radical can be used as dentine and enamel original position remineralization inductor is used.
Claims (9)
1. end group is the polyamide-amide type branch-shape polymer of phosphate radical, it is characterized in that structural formula is as follows:
In the said structure formula, described n is that end group is the algebraically of the polyamide-amide type branch-shape polymer of phosphate radical, n=3,4 or 5.
2. the preparation method of the described end group of the claim 1 polyamide-amide type branch-shape polymer that is phosphate radical is characterized in that step is as follows:
(1) end group is the synthetic of phosphate-based polyamide-amide type branch-shape polymer
1. prepare first kind of solution
The general is not dissolved in the pure water with highly basic and the tetrahydrofuran (THF) that tetrahydrofuran (THF) reacts under room temperature, normal pressure, namely forms first kind of solution; Described is not a with the hydroxide radical of the highly basic of tetrahydrofuran (THF) reaction and the mol ratio of tetrahydrofuran (THF), 0＜a≤1; Describedly be not limited with the proportioning of highly basic, tetrahydrofuran (THF) and the pure water of tetrahydrofuran (THF) reaction ph=9 ~ 11 with first kind of solution;
2. prepare second kind of solution
Under room temperature, normal pressure, Paraformaldehyde 96 is dissolved in described first kind of solution, namely forms second kind of solution; The proportioning of described Paraformaldehyde 96 and first kind of solution is dissolved fully with Paraformaldehyde 96 and is limited;
3. prepare the third solution
Under room temperature, normal pressure with 3,4 or 5 generation end group for amino polyamide-amide type branch-shape polymer is dissolved in the pure water, namely form the third solution; Described 3,4 or 5 generation end group for the proportioning of amino polyamide-amide type branch-shape polymer and pure water with in the third solution 3,4 or 5 generation end group be that the concentration of the polyamide-amide type branch-shape polymer of amino reaches 1 ~ 2 g/mL and is limited;
4. prepare the 4th kind of solution
Under room temperature, normal pressure, two kinds of solution and the third solution are mixed, namely form the 4th kind of solution; In the 4th kind of solution, the mol ratio 〉=2:1 of the amino of the aldehyde radical of Paraformaldehyde 96 and polyamide-amide type branch-shape polymer;
5. synthetic
Under nitrogen protection, dimethylphosphite is joined in the 4th kind of solution, under normal pressure, 60 ℃ ~ 90 ℃ condition, react 12h at least, after reaction times expires, unreacted tetrahydrofuran (THF) is removed in underpressure distillation, through dialysis, filtration, underpressure distillation, lyophilize, namely getting end group is phosphate-based polyamide-amide type branch-shape polymer again;
The proportioning of described the 4th kind of solution and dimethylphosphite is: the mol ratio 〉=2:1 of the amino of the polyamide-amide type branch-shape polymer in dimethylphosphite and the 4th kind of solution;
(2) end group is polyamide-amide type branch-shape polymer synthetic of phosphate radical
End group with step (1) preparation is that phosphate-based polyamide-amide type branch-shape polymer is solute, under normal pressure, room temperature it being dissolved in and namely getting end group in the non-proton property polar solvent is phosphate-based polyamide-amide type branch-shape polymer solution, the proportioning of described solute and non-proton property polar solvent with solute can be in aprotic polar solvent fully dissolving be limited;
With end group be phosphate-based polyamide-amide type branch-shape polymer solution under nitrogen protection in normal pressure; stirring at room is 0.5h at least; add bromotrimethylsilane then and at normal pressure; stir 24h at least under the room temperature; continue after add methyl alcohol and reaction system sealed; at normal pressure; react 24h at least under the room temperature; after reaction times expires; through dialysis; underpressure distillation; lyophilize; namely getting end group is the polyamide-amide type branch-shape polymer of phosphate radical; the add-on of described bromotrimethylsilane is limited with the phosphate-based mol ratio 〉=1:1 in bromotrimethylsilane and the described solution, and the add-on of described methyl alcohol is limited with the mol ratio 〉=1:1 of methyl alcohol and bromotrimethylsilane.
3. be the preparation method of the polyamide-amide type branch-shape polymer of phosphate radical according to the described end group of claim 2, it is characterized in that described is not potassium hydroxide, calcium hydroxide, sodium hydroxide or magnesium hydroxide with the highly basic of tetrahydrofuran (THF) reaction.
4. be the preparation method of the polyamide-amide type branch-shape polymer of phosphate radical according to claim 2 or 3 described end groups, it is characterized in that described non-proton property polar solvent is dimethyl sulfoxide (DMSO), methylene dichloride, trichloromethane, acetonitrile or dimethyl formamide.
5. be the preparation method of the polyamide-amide type branch-shape polymer of phosphate radical according to claim 2 or 3 described end groups, it is characterized in that described pure water is distilled water or deionized water.
6. be the preparation method of the polyamide-amide type branch-shape polymer of phosphate radical according to the described end group of claim 4, it is characterized in that described pure water is distilled water or deionized water.
7. the described end group of claim 1 is that the polyamide-amide type branch-shape polymer of phosphate radical is as the application of preparation dentine and enamel original position remineralization inductor.
8. application according to claim 7, it is characterized in that described dentine and enamel original position remineralization inductor are the aqueous solution that the described polymkeric substance of claim 1 and deionized water are mixed with, in the described aqueous solution, the concentration of the described polymkeric substance of claim 1 is at least 1000 ppm.
9. application according to claim 8 is characterized in that in the described aqueous solution that the concentration of the described polymkeric substance of claim 1 is 4000 ppm.
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| CN108852855A (en) * | 2018-07-31 | 2018-11-23 | 成都爱睿康乐医疗器械有限公司 | Biomimetic mineralization repairs desensitizer |
| CN113304055A (en) * | 2021-05-25 | 2021-08-27 | 陕西恒远生物科技有限公司 | Dentin desensitizing paste with bionic remineralization repairing effect and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN103127525A (en) * | 2013-02-27 | 2013-06-05 | 万礼 | Tree-like polymer nanometer drug delivery carrier targeting doxorubicin and its preparation method |
-
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| CN101921233A (en) * | 2010-08-10 | 2010-12-22 | 陕西科技大学 | Tree imidazoline quaternary ammonium salt corrosion inhibitor and preparation method thereof |
| CN103127525A (en) * | 2013-02-27 | 2013-06-05 | 万礼 | Tree-like polymer nanometer drug delivery carrier targeting doxorubicin and its preparation method |
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| CN108852855A (en) * | 2018-07-31 | 2018-11-23 | 成都爱睿康乐医疗器械有限公司 | Biomimetic mineralization repairs desensitizer |
| CN113304055A (en) * | 2021-05-25 | 2021-08-27 | 陕西恒远生物科技有限公司 | Dentin desensitizing paste with bionic remineralization repairing effect and preparation process thereof |
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Application publication date: 20131009 Assignee: Chengdu AI Kangle Medical Equipment Co., Ltd. Assignor: Sichuan University Contract record no.: 2018510000026 Denomination of invention: Polyamide-imide dendritic polymer with phosphate radical end group as well as preparation method and application for same Granted publication date: 20150909 License type: Common License Record date: 20180612 |