CN102133154A - Root apex filling material and preparation method thereof - Google Patents
Root apex filling material and preparation method thereof Download PDFInfo
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- CN102133154A CN102133154A CN2011100560512A CN201110056051A CN102133154A CN 102133154 A CN102133154 A CN 102133154A CN 2011100560512 A CN2011100560512 A CN 2011100560512A CN 201110056051 A CN201110056051 A CN 201110056051A CN 102133154 A CN102133154 A CN 102133154A
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Abstract
The invention relates to a root apex filling material which comprises the following components in mass percent: 35%-44% of natural hydroxyapatite, 35%-44% of tetracaicium phosphate of which the particle size is 0-50mu m and the mean particle size is 2-8mu m, 7%-9% of polyacrylic acid of which the mean molecular weight is 30000-50000, 1.5%-2.5% of citric acid and 1.5%-2.5% of sodium citrate. The natural hydroxyapatite, the tetracaicium phosphate, the polyacrylic acid, the citric acid and the sodium citrate are mixed, ground and sieved by a 200-mesh sieve to form the root apex filling material. The preparation method comprises the following concrete steps of: mixing, grinding and sieving the natural hydroxyapatite, the tetracaicium phosphate, the polyacrylic acid, the citric acid and the sodium citrate by a 200-mesh sieve to obtain the root apex filling powder, preserving the root apex filling powder in a dry place for later use; using ionized water, polyethylene glycol (PEG) 400 or glycerol as a liquid phase, mixing the prepared powder with the liquid phase in a mass ratio of (4-5):1, and filling into a mold to prepare the root apex filling material.
Description
Technical field
The present invention relates to a kind of preparation hard tissue repairing material and method thereof, relate in particular to a kind of root of the tooth tip of a root filler and preparation method thereof.
Background technology
Dental pulp disease, periapical disease are not only the oral medicine clinical common diseases, also are the oral diseases that causes that the patient has an intense pain.If they can not get diagnosis and treatment timely or malpractice, can cause having an intense pain of patient, cause suffering from pulling out of tooth, influence chewing and aesthetic function etc. of patient; Even also can become oral focus, cause subacute bacterial endocarditis, rheumatic or rheumatoid arthritis, glomerulonephritis etc., thereby patient's physical and mental health is brought huge misery.
(root canal therapy RCT) is a kind of method of treatment dental pulp disease and periapical disease to root canal therapy, and its successful effective percentage is to generally acknowledge both at home and abroad at present to preserve the best Therapeutic Method of suffering from tooth more than 85%.But some case only adopts root canal therapy to be difficult to cure, and must be aided with surgical operation, and the treatment technology that tooth is suffered from these preservations that combined by two kinds of methods claims root pipe surgical operation (endodontic surgery).The U.S. just had 5,300,000 patients will carry out the treatment of dental pulp disease in 1999 approximately according to estimates, wherein had the patient more than 5.5% will carry out root pipe surgical operation approximately.In China, because people make this treatment technology be subjected to scholars' extensive concern day by day, so root pipe surgical operation have crucial research prospect and clinical value to the rapid raising of oral cavity health care consciousness and oral medicine treatment level.
The apicoectomy and the tip of a root fall plombage be the most frequently used, most important the pipe surgical operation.For simple root canal therapy, its clinical manipulation complexity, and the plain significantly increase of prognosis uncertain therapeutic efficacy determining cause.One of its success rate is not only closely related with factors such as trouble tooth situation, modus operandis, and the key factor of the above-mentioned often operation success of the selection of tip of a root filler.Because tip of a root filler not only will seal the hole shape of tip of a root preparation, play the sealing process of physical property, and ideal tip of a root filler can also promote cementum at its surface deposition, reach the effect of physiological and the dual sealing of physical property.
Ideal tip of a root filler should possess: tissue of tooth is had caking property, and can three-dimensionally seal the tip of a root broken ends of fractured bone; Preferably can bacteria growing inhibiting; Volume stability, and be not subjected to the influence of factors such as humidity; The periapical tissue tolerance, reaction can not cause inflammation; Harmless to body; Stimulate the regeneration of normal root periapical tissue; Corrosion-resistant; Do not make the dyeing of tooth body or periapical tissue; The resistance of X line is penetrated, and is convenient to differentiate; Holding time is long, easy operating etc.The tip of a root filler kind that adopts clinically is numerous at present, tip of a root filler wherein comparatively commonly used has: silver amalgam, zinc oxide, glass-ion cement spit of fland, composite resin and MTA etc., but there are some significant disadvantage in the equal tool of these tip of a root fillers.For example: silver amalgam is because the toxicity of hydrargyrum and relatively poor biocompatibility have now belonged to the material that will eliminate; Though materials such as zinc oxide, glass-ion cement spit of fland, composite resin have better biocompatibility and physicochemical property, can form the hole shape of the sealing root pipe surgery preparation of better physical, but their common defects is not possess biological activity, can not promote cementum at its surface deposition, can not reach the effect of physiological sealing tip of a root end; Though MTA is a kind of comparatively ideal bioactive materials, have moisture-curable, good remarkable advantages such as closure, biocompatibility and biological activity, but also there is big (pH value: 10-12),, defectives such as price high (about 800 yuan/gram), full imported material little to tissue of tooth caking property of hardening time long (3h), alkalescence in it.Therefore, up to the present, also there is not a kind of ideal tip of a root filler to occur.
Summary of the invention
The present invention seeks to be to provide a kind of root of the tooth tip of a root filler and preparation method thereof, molded material of the present invention has the comprcssive strength height, and anti-rare diffusing property is good, hydrophilic and bio-compatible performance, and X-ray display performance well and the advantage that can not absorb.
Technical scheme of the present invention is:
A kind of root of the tooth tip of a root filler of the present invention, comprise: natural hydroxyapatite, particle diameter are that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is 30,000～50,000 polyacrylic acid, citric acid and sodium citrate, its mass percent is 35%～44%:35%～44%:7%～9%:1.5%～2.5%:1.5%～2.5%, and described natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate form root of the tooth tip of a root filler through mixing, grinding and after crossing 200 mesh sieves.
The optimisation technique scheme of root of the tooth tip of a root filler of the present invention is: described root of the tooth tip of a root filler is that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is that 30,000～50,000 polyacrylic acid, citric acid, sodium citrate and barium sulfate are formed by natural hydroxyapatite, particle diameter, and the addition of barium sulfate is that natural hydroxyapatite, particle diameter are that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is 0%～20% of 30,000～50,000 polyacrylic acid, citric acid and sodium citrate gross mass.
The preparation method of a kind of root of the tooth tip of a root filler of the present invention,
Further optimisation technique measure of the present invention is: mix, grind and mistake 200 mesh sieves add barium sulfate in natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate after.
The present invention has following advantage:
(hydroxyapatite is the main inorganic composition of sclerous tissueses such as skeleton and tooth HA) to hydroxyapatite, and safety non-toxic has the good biological activity, is considered to the most promising artificial tooth and artificial bone replacing material.As far back as 1976, the blue or green wood of Japan and the Jarcho of the U.S. respectively synthetic hydroxyapatite, the frontier of having started the research of hydroxylapatite biology medical material and having used; Tokyo medical university of tooth section began to be applied to the hydroxyapatite artificial dental root clinical in 1980.At present, the ceramic material of hydroxyapatite, metal coating layer material and become hard tissue repair materials such as most important clinically tooth, skeleton with organic composite.But defectives such as hydroxyapatite also exists, and bone inductive effect is weak, forming ability is poor, fragility is big, processing difficulties, the easy displacement of granular pattern hydroxyapatite.In order to overcome the shortcoming of above-mentioned hydroxyapatite, thereby this seminar has good physicochemical performance and biocompatibility with compound preparing of material such as itself and polyacrylic acid, tetracalcium phosphate, citric acids, can be used as that tip of a root filler, tooth floor of pulp chamber are worn, root pipe side is worn patching material and direct or indirect lid marrow material.
(Polyacrylic acid PAA) is faintly acid to polyacrylic acid, is one of main component of tooth section cement (polycarboxylate cement and glass-ion cement spit of fland, molecular weight is generally about 50,000) consolidation liquid.Though hydroxyapatite can not with polyacrylic acid generation acid-base reaction, polyacrylic carbonyl (COOH) with hydroxyapatite in Ga2+ carry out ligand complex, thereby strengthen the mechanical strength of its material.But the acid pair cell of polyacrylic acid has certain toxic action, for example Umemo Kozo etc. shows polyacrylic Study of cytotoxicity: concentration does not influence the growth of people's pulp cells less than 0.1% polyacrylic acid solution, but when its concentration reached 0.2%, its cytotoxicity significantly increased.
In order to reduce the acidity of composite, this problem in composite, add tetracalcium phosphate (tetracalciumphosphate, TTCP).Tetracalcium phosphate is one of important component of calcium phosphate bone cement, is alkalescence, has very strong biological activity, can generate hydroxyapatite and calcium hydroxide behind the chance water, and these two kinds of products and tetracalcium phosphate all have excellent biological compatibility.Tetracalcium phosphate is incorporated in this material the polyacrylic acidity that can neutralize on the one hand, reaction speed, determine the hardening time of material, in addition, tetracalcium phosphate is met water cure, the material that we are developed has moisture-curable, is beneficial to the application clinically of this material.
The calcium polyacrylate (CPA) water soluble that tetracalcium phosphate and polyacrylic acid generation acid-base reaction generate, but so material degradation in vivo.In order to overcome this defective, we add an amount of citric acid and hydrochlorate thereof in the material compatibility, reaction speed, the dissolubility of reduction material.
1) main component behind hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler curing reaction is that hydroxyapatite and calcium carboxylates calcium salt are formed, and along with the prolongation of hardening time, and unreacted tetracalcium phosphate completely gradates and is hydroxyapatite.
2) good anti-rare diffusing performance: hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies in PBS liquid, does not have chip around the material and occurs, and does not see disintegration phenomenon.
3) comparatively ideal hardening time: be 11.03 ± 0.78min hydroxyapatite/tetracalcium phosphate/polyacrylic hardening time, is suitable for the medical procedure on mouth requirement.
4) comprcssive strength is higher, reaches the requirement of tip of a root filler: after hydroxyapatite/tetracalcium phosphate/polyacrylic acid solidified 1d, its comprcssive strength promptly reached 30.96 ± 6.57MPa; After solidifying 7d, its comprcssive strength reaches 57.46 ± 12.77MPa respectively, reaches the comprcssive strength requirement of tip of a root filler substantially;
5) pH value is alkalescence, is suitable for body and is implanted into: hydroxyapatite/tetracalcium phosphate/polyacrylic pH value is alkalescence between 6.13～8.37, close with the pH value of human teeth and skeletal tissue.
6) less contact angle: hydroxyapatite/tetracalcium phosphate/polyacrylic contact angle is about 21.55 ± 2.65 °, points out this material to have hydrophilic preferably, is beneficial to the adhesion of cell at material surface.
7) excellent biological compatibility: we are according to the cell growth inhibition assay of recommending among the GB/T 16886-ISO 10993, adopt two kinds of colorimetrys such as MTT and crystal violet to detect the cytotoxicity of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler, the cytotoxicity of the equal signify hydroxy apatite/tetracalcium phosphate of these two kinds of colorimetry results/polyacrylic acid tip of a root filler is rated 0 grade, cell growth condition is good, does not have significant difference with negative control group; Morphological observation result shows that the L-929 cell can be good in hydroxyapatite/tetracalcium phosphate/polyacrylic acid specimen material superficial growth.Above-mentioned experimental result all points out this material to have excellent biological compatibility.
8) main component after hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies is a hydroxyapatite, performance is penetrated in its X line resistance and dentin layer is close, in material solid phase powder body component, add 0～20% barium sulfate, performance is penetrated in the X-line resistance that can significantly improve this material, easily differentiates mutually with tissue of tooth.
9) this material solid phase powder body and PEG400 or glycerol by solid-liquid mutually the ratio of quality be to mix, transfer mix at 4～5: 1, can prepare two kinds of premixing hydroxyapatite/tetracalcium phosphates/polyacrylic acid tip of a root filler, its have mix homogeneously, arbitrarily moulding, anti-rare diffusing property, save operating time, meet better clinical operating performances such as water cure.
10) multiple use: except that being mainly used in tip of a root filler, hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler can be used for also that the tooth floor of pulp chamber is worn, root pipe side is worn patching material, direct or indirect lid marrow material etc.
11) production cost is low: the raw material preparing that the present invention proposes is simple, the source is abundant, cheap; It is simple that hydroxyapatite/tetracalcium phosphate/production of polyacrylic acid tip of a root filler has technology, do not need special equipment, the with low cost significant advantage of Denging.
Description of drawings
Fig. 1 is that the SEM of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler powder body characterizes (* 5000).
Fig. 2 is the SEM sign (* 5000) that hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies the rear surface.
Fig. 3 is that the FTIR of hydroxyapatite, polyacrylic acid, tetracalcium phosphate and hydroxyapatite/tetracalcium phosphate/materials such as polyacrylic acid tip of a root filler characterizes.
Fig. 4 is that the XRD before and after hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies characterizes (H: hydroxyapatite, T: tetracalcium phosphate).
Fig. 5 is the anti-rare diffusing Journal of Sex Research result of hydroxyapatite/tetracalcium phosphate/tip of a root fillers such as polyacrylic acid, and wherein (a) is hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler, (b) is the glass-ion cement spit of fland, (c) is Portland Cement.
Fig. 6 is hydroxyapatite/tetracalcium phosphate/tip of a root filler contact angles such as polyacrylic acid, and wherein (a) is hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler, (b) is the glass-ion cement spit of fland, (c) is Portland Cement.
Fig. 7 is that the hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler lixiviating solution and the L-929 of variable concentrations cultivates 72h group cell photo.(a) negative control group (the DMEM culture fluid of 10%FBS); (b) 12.5% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (c) 25% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (d) 50% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (e) 100% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (f) positive controls (0.7% polyacrylamide amine monomers).
Fig. 8 is that the hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler lixiviating solution and the L-929 of variable concentrations cultivates 72h group violet staining cell photo.(a) negative control group (the DMEM culture fluid of 10%FBS); (b) 12.5% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (c) 25% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (d) 50% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (e) 100% hydroxyapatite/tetracalcium phosphate/polyacrylic acid group; (f) positive controls (0.7% polyacrylamide amine monomers).
Fig. 9 be cell hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample surfaces growth 3d situation (a: the blank group, b: hydroxyapatite/tetracalcium phosphate/polyacrylic acid, 100 *).
Figure 10 be cell hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample surfaces growth 5d situation (a: the blank group, b: hydroxyapatite/tetracalcium phosphate/polyacrylic acid, 100 *).
Figure 11 is that the FTIR of glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler characterizes.
Figure 12 is that the FTIR of PEG premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler characterizes.
Figure 13 is the anti-rare diffusing Journal of Sex Research result of glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler.
Figure 14 is the anti-rare diffusing Journal of Sex Research result of PEG premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler.
The specific embodiment
The present invention is further described with accompanying drawing in conjunction with the embodiments.
The preparation method of embodiment 1 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
1) preparation of solid phase part: accurately take by weighing the natural hydroxy apatite powder of 0.435 gram, 0.435 (particle diameter is 0～50 μ m to the gram tetracalcium phosphate, mean diameter is 2～8 μ m), 0.87 gram polyacrylic acid (mean molecule quantity is 50,000), 0.215 gram citric acid, 0.215 gram sodium citrate place in the mortar and fully grind, cross 200 mesh sieves, preserve every wet, standby
2) preparation of liquid phase part: be the 0.2mL deionized water;
3) preparation method of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler: ambient temperature is 23 ± 1 ℃, ratio by solid-liquid phase quality is 5: 1, the material of above-mentioned solid phase and liquid phase part is placed respectively on the exsiccant glass plate of cleaning, adopting plastics to transfer to mix cutter fully to transfer mixes evenly, the mediation time is 60～90 seconds, doughy hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is filled in the mould of definite shape, and tooth section plugger pressurized filling is shaped.
4) SEM characterizes: observe pattern behind the powder body of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler and the solidified sample metal spraying under scanning electron microscope.Fig. 1 shows: hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler powder body mainly contains the material of different-grain diameter to be formed, and big particle diameter can reach 2-8 μ m, and little particle diameter only reaches about 0.5 μ m; Fig. 2 shows: the surface of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidified sample is honeycomb, coralliform, and space not of uniform size is arranged, and the material granule of visible different-grain diameter is distributed in wherein in polyacrylic acid forms the substrate of homogeneous comparatively.
5) FTIR characterizes: get an amount of novel tip of a root filler, mixed with potassium bromide by 1: 150, fully grind the back tabletting, the test infrared spectrum.Fig. 3 shows: in wave number is 3568.7cm
-1, 1088.5cm
-1, 1052.1cm
-1, 628.1cm
-1, 571.1cm
-1The place has presented the characteristic peak of hydroxyl that hydroxyapatite had and phosphate radical; At 1458.4cm
-1, 1415.5m
-1The place is CO
3 2-Characteristic absorption peak, at 1567.3cm
-1The flexible characteristic peak of antisymmetry that carboxylate radical in the polyacrylic acid occurs.This results suggest hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler mainly contains hydroxyapatite and the carboxylic acid calcium salt is formed.
6) XRD characterizes: with the powder body and the sample of different hardening times (material immerses dehydrated alcohol and stops its curing reaction) of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler, wear into fine powder with agate mortar, again sample is pressed into the sample platform, on the X-diffractometer, carry out the powder body (0min) of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler then, the XRD that solidifies specimen materials such as 30min, 2h, 10h, 1d, 7d characterizes the change procedure of the composition of test sample.Fig. 4 shows that the powder body of this material mainly contains hydroxyapatite and tetracalcium phosphate is formed (characteristic peak that hydroxyapatite and tetracalcium phosphate mainly occur), but prolongation along with hardening time, the characteristic peak of tetracalcium phosphate reduces gradually, and the hydroxyapatite characteristic peak strengthens gradually, this results suggest hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is along with the prolongation of hardening time, and tetracalcium phosphate gradates and is hydroxyapatite.
Anti-rare diffusing property detection of embodiment 2 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
Press embodiment 1 method, hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is fully mixed by suitable powder liquor ratio (5: 1), after accent is mixed 1 minute, place immediately in the PBS liquid container that contains 10mL, after leaving standstill 10 minutes, observation sample resists rare diffusing implementations.Fig. 5 shows that hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies in PBS liquid, do not have chip around the material and occur, and does not see disintegration phenomenon, points out this material to have good anti-rare diffusing property.
The detection of the hardening time of embodiment 3 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler:
Table 1 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler testing result hardening time
The detection of the comprcssive strength of embodiment 4 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler:
Press embodiment 1 method, hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is fully mixed by suitable powder liquor ratio (5: 1), after mixing, accent inserts in the mould of comprcssive strength, adopt tooth section cement filling instrument slicing and filling, after making it exceed mould slightly, place on the metal base plate and pressurization, remove unnecessary material.Cover metallic plate and compress, then comprcssive strength is moved into 1 ℃ of 37 ℃ of scholar with whole assembly, relative humidity is not less than in 30% the climatic chamber, will be in climatic chamber maintenance the sample of 1d and 7d take out, it is 6mm that length is made at the grinding two ends, diameter is the cylindrical sample of 4mm, comprcssive strength with universal testing machine (newly think carefully in Shenzhen) working sample, promptly under drying regime, standard specimen is placed on the test machine for mechanism, axial pressure is measured comprcssive strength, loading velocity is 1mm/min, the curvilinear motion of record pressure-deformation, the compression strength value of calculation sample.Experimental result shows:
1) after hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidified 1d, its comprcssive strength promptly reached 30.96 ± 6.57MPa; After solidifying 7d, its comprcssive strength reaches 57.46 ± 12.77MPa respectively, reaches the comprcssive strength requirement of tip of a root filler;
2) comprcssive strength of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is along with the prolongation of hardening time, comprcssive strength strengthens gradually, the specimen material comprcssive strength of solidifying 7d is significantly higher than the comprcssive strength of material cured 1d, and difference has significance meaning (p＜0.05) (seeing Table 2).
The comprcssive strength testing result of table 2 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
The pH value of embodiment 5 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler detects:
Table 3 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler pH value testing result
The contact angle detection of embodiment 6 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler:
Table 4 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler contact angle detection result
The biocompatibility of embodiment 7 hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler detects:
1) the MTT colorimetry detects the cytotoxicity (ISO 10993-12:2002 standard) of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
Press embodiment 1 method, hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is fully mixed by suitable powder liquor ratio (5: 1), placing and being prepared into diameter in the mould is 5mm, (37 ℃ of high 2mm sheet samples, solidify 24h under 100% humidity), after handling, ultraviolet radiation 12h puts into sterile test tube, according to the ISO10993-12:2002 standard, determine required lixiviating solution volume according to the surface area of experiment material, according to 1.25cm
2/ mL ratio adds and contains 10% the aloof from politics and material pursuits sugared DMEM culture fluid of calf blood, is statically placed in incubator, at 37 ℃, 5%CO
2Humidity is preserved for 95% time, collects the lixiviating solution of experiment material behind the 72h.We adopt the cell growth inhibition assay of recommending among the GB/T16886-ISO 10993 (MTT colorimetry), cytotoxicity to hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample is estimated, and with inverted phase contrast microscope the influence of material lixiviating solution pair cell (L-929) form is observed.The result shows: the lixiviating solution of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample variable concentrations is at 24h, and 48h, the relative rate of increase of the cell during 72h are between 83.19%～110.74%, and cytotoxicity is rated 0 grade (seeing Table 5); Fig. 7 shows that the lixiviating solution group cell of variable concentrations is fusiformis or polygon, and cell growth condition is good, does not have significant difference with negative control group.MTT colorimetry cytotoxicity experiment proves that tentatively this material has excellent biological compatibility.
Table 5 MTT colorimetry detects the relative rate of increase of cell and the toxicity grading result of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
2) the crystal violet colorimetry detects the cytotoxicity (ISO 10993-12:2002 standard) of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
We are according to MT reconnaissance T colorimetry experimental program, adopt the crystal violet colorimetry that the cytotoxicity of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample is estimated, and the influence of material lixiviating solution pair cell (L-929) form is observed with inverted phase contrast microscope.The result shows: the variable concentrations lixiviating solution of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample is at 24h, and all between 92.22%～104.90%, its cytotoxicity is rated 0 grade (seeing Table 6) for 48h, the relative rate of increase of the cell during 72h; Fig. 8 shows the lixiviating solution group cell of variable concentrations through violet staining, and it is blue that nucleus is, the Cytoplasm pinkiness, and variable concentrations lixiviating solution experimental group cell and negative control group do not have significant difference.Crystal violet colorimetry cytotoxicity experiment proves that tentatively this material has excellent biological compatibility.
Table 6 crystal violet colorimetry detects the relative rate of increase of cell and the toxicity grading result of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
3) morphological observation:
The L-929 cell suspension inoculation in containing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler surface, is cultivated 3d and 5d under the normal condition, acridine orange dyeing, the cellular morphology that fluorescence microscope is observed material surface down.Fig. 9-10 shows: visible cell does not have significant difference at hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample surfaces well-grown with matched group under the fluorescence microscope.
Hydroxyapatite/the tetracalcium phosphate of embodiment 8 barium sulfate-containings/polyacrylic acid tip of a root filler preparation method
1) carry out solid phase preparation partly by embodiment 1 scheme, and add 5%, 10%, 15,20% quality respectively than barium sulfate, place in the mortar and fully grind, cross 200 mesh sieves, preserve every wetting at the solid phase powder body material, standby.
2) preparation of liquid phase part: deionized water;
3) preparation method of the hydroxyapatite/tetracalcium phosphate of barium sulfate-containing/polyacrylic acid tip of a root filler: mix, be shaped by the accent that embodiment 1 carries out material.
4) detect the cytotoxicity of different barium sulfate content hydroxyapatite/tetracalcium phosphates/polyacrylic acid tip of a root filler by the MTT colorimetry of embodiment 7, the result shows: the lixiviating solution of different content barium sulfate hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler sample is at 24h, 48h, all between 82.85%～100.33%, its cytotoxicity is rated 0 grade (seeing Table 7) to the relative rate of increase of cell during 72h; The prompting above-mentioned material has excellent biological compatibility.
Table 7MTT colorimetry detects the relative rate of increase of cell and the toxicity grading result of different content barium sulfate hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
Embodiment 9 premixing hydroxyapatite/tetracalcium phosphates/polyacrylic acid tip of a root filler preparation method
1) carries out solid phase preparation partly by embodiment 1 scheme.
2) preparation of liquid phase part: PEG400 or glycerol.
3) premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler preparation method: mixing, be shaped by the accent that embodiment 1 carries out material, is 4～5: 1 by the ratio of solid-liquid phase quality.
4) FTIR that carries out hydroxyapatite/tetracalcium phosphate/polyacrylic acid solidified sample by embodiment 1 scheme characterizes, and Figure 11 shows that PEG400 or glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler mainly be made up of hydroxyapatite and carboxylic acid calcium salt.
5) carry out anti-rare diffusing property detection of PEG400 or glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler by embodiment 2, Figure 12 shows, hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidifies in PBS liquid, not having chip around the material occurs, do not see disintegration phenomenon, point out this material to have good anti-rare diffusing property.
6) carry out the detection of the comprcssive strength of PEG400 or glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler by embodiment 4, the result shows that the comprcssive strength of glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler reaches 14.24MPA, the comprcssive strength that is higher than premixed calcium phosphate bone cement (about 10MPa) document in the document, the comprcssive strength of PEG400 premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler also reaches 5.85MPA (seeing Table 8).
The comprcssive strength of table 8 PEG400 or glycerol premixing hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler
The present invention (is the main component of MTA with glass-ion cement spit of fland (main component of its liquor is a polyacrylic acid) and Portland Cement, but it is cheap, be expected to become the substitution material of MTA) etc. material as hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler contrast material, its physicochemical property and biology performance are studied.
A kind of root of the tooth tip of a root filler, comprise: natural hydroxyapatite, particle diameter is that 0～50 μ m and mean diameter are the tetracalcium phosphate of 2～8 μ m, mean molecule quantity is 30,000～50,000 polyacrylic acid, citric acid and sodium citrate, its mass percent is 35%～44%: 35%～44%: 7%～9%: 1.5%～2.5%: 1.5%～2.5%, described natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate are through mixing, form root of the tooth tip of a root filler after grinding and cross 200 mesh sieves, present embodiment can be selected: particle diameter is that 0.1 μ m and mean diameter are the tetracalcium phosphate of 2 μ m, mean molecule quantity is 30,000 polyacrylic acid, citric acid and sodium citrate, its mass percent are 35%: 35%: 7%: 1.5%: 1.5%; Also can select: particle diameter is that 50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 8 μ m is 50,000 polyacrylic acid, citric acid and sodium citrate, and its mass percent is 44%: 44%: 9%: 2.5%: 2.5%; Perhaps select: particle diameter is that 30 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 5 μ m is 40,000 polyacrylic acid, citric acid and sodium citrate, and its mass percent is 40%: 4244%: 8%: 2%: 2.1%.
Embodiment 11
A kind of root of the tooth tip of a root filler, by natural hydroxyapatite, particle diameter is that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is that 30,000～50,000 polyacrylic acid, citric acid, sodium citrate and barium sulfate are formed, and the addition of barium sulfate is that natural hydroxyapatite, particle diameter are that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is 0%～20% of 30,000～50,000 polyacrylic acid, citric acid and sodium citrate gross mass.
Embodiment 12
A kind of preparation method of root of the tooth tip of a root filler,
In the present embodiment, in natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate, mix again, grind behind the adding barium sulfate and mistake 200 mesh sieves.Anti-rare diffusing property detection of Comparative Examples 1 glass-ion cement spit of fland and Portland Cement
Carry out the preparation of materials such as glass-ion cement spit of fland and Portland Cement by Comparative Examples 1 method, carry out the material cured time detecting by embodiment 3.Experimental result shows: be 4.49 ± 0.39min the hardening time in glass-ion cement spit of fland; Reach 171.93 ± 6.72min the hardening time of Portland Cement, similar hardening time to MTA, and do not meet the requirement of desirable tip of a root filler, be it as one of the major defect of tip of a root filler (seeing Table 9).
Testing result hardening time of table 9 glass-ion cement spit of fland and Portland Cement
The detection of the comprcssive strength of Comparative Examples 3 glass-ion cement spits of fland and Portland Cement
Carry out the preparation of materials such as glass-ion cement spit of fland and Portland Cement by Comparative Examples 1 method, carry out the detection of the comprcssive strength of material by embodiment 4.Experimental result shows: after 1d was solidified in the glass-ion cement spit of fland, its comprcssive strength promptly reached 63.86 ± 11.44MPa; After solidifying 7d, its comprcssive strength reaches 107.24 ± 22.62MPa, reaches the comprcssive strength requirement of tip of a root filler; After Portland Cement solidified 1d, its comprcssive strength promptly reached 28.11 ± 8.15MPa; After solidifying 7d, its comprcssive strength reaches 61.48 ± 16.23MPa, and is similar to MTA comprcssive strength, and the comprcssive strength that reaches tip of a root filler requires (seeing Table 10).
The comprcssive strength testing result of table 10 glass-ion cement spit of fland and Portland Cement
The pH value of Comparative Examples 4 glass-ion cement spits of fland and Portland Cement detects
Carry out the preparation of materials such as glass-ion cement spit of fland and Portland Cement by Comparative Examples 1 method, the pH value that carries out material by embodiment 5 detects.Experimental result shows: the pH value in glass-ion cement spit of fland is faintly acid between 3.96～5.25; And the pH value of Portland Cement is similar to the pH value of MTA between 12.04～12.61, is strong basicity (seeing Table 11).
Table 11 hydroxyapatite/tetracalcium phosphate/tip of a root filler pH value testing results such as polyacrylic acid
The contact angle detection of Comparative Examples 5 glass-ion cement spits of fland and Portland Cement
Carry out the preparation of materials such as glass-ion cement spit of fland and Portland Cement by Comparative Examples 1 method, carry out the contact angle detection of material by embodiment 6.Experimental result shows: the contact angle in glass-ion cement spit of fland is about 78.17 ± 1.91 °, and Portland Cement contact angle is about 10.25 ± 0.95 °.PortlandCement is similar for this results suggest, has stronger hydrophilic, and the hydrophilic in glass-ion cement spit of fland weak (see Table 12 and Fig. 6).
Table 12 hydroxyapatite/tetracalcium phosphate/tip of a root filler contact angle detection results such as polyacrylic acid
The result of study contrast of embodiment and Comparative Examples
1) embodiment 2 shows with Comparative Examples 1 experimental result: the anti-rare diffusing property of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is better than glass-ion cement spit of fland and Portland Cement;
2) embodiment 3 shows with Comparative Examples 2 experimental results: be 11.03 ± 0.78min the hardening time of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler, (4.49 ± 0.39min) length hardening time than the glass-ion cement spit of fland, than hardening time of Portland Cement, (171.93 ± 6.72min) is short, is more suitable for clinical requirement;
3) embodiment 4 shows with Comparative Examples 3 experimental results, and after hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler solidified 1d, its comprcssive strength promptly reached 30.96 ± 6.57MPa; After solidifying 7d, its comprcssive strength reaches 57.46 ± 12.77MPa respectively, reaches the comprcssive strength requirement of tip of a root filler substantially; The comprcssive strength and the PortlandCement of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler are close, there is not significance meaning (p＞0.05) with the comprcssive strength difference of Portland Cement, but all less than the comprcssive strength in glass-ion cement spit of fland, difference has significance (p＜0.05) to both comprcssive strength;
4) embodiment 5 and Comparative Examples 4 experimental results show: the pH value of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is alkalescence between 6.13～8.33; The pH value in glass-ion cement spit of fland is faintly acid between 3.96～5.25; And the pH value of Portland Cement is between 12.04～12.61; Therefore the pH value of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is fit to clinical practice more.
Embodiment 6 shows with Comparative Examples 5 experimental results: the contact angle of hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is about 21.55 ± 2.65 °, the contact angle in glass-ion cement spit of fland is about 78.17 ± 1.91 °, and the PortlandCement contact angle is about 10.25 ± 0.95 °.This results suggest hydroxyapatite/tetracalcium phosphate/polyacrylic acid tip of a root filler is similar to Portland Cement, has stronger hydrophilic, and the hydrophilic in glass-ion cement spit of fland a little less than.
Claims (4)
1. root of the tooth tip of a root filler, it is characterized in that, comprise: natural hydroxyapatite, particle diameter are that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is 30,000～50,000 polyacrylic acid, citric acid and sodium citrate, its mass percent is 35%～44%:35%～44%:7%～9%:1.5%～2.5%:1.5%～2.5%, and described natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate form root of the tooth tip of a root filler through mixing, grinding and after crossing 200 mesh sieves.
2. root of the tooth tip of a root filler according to claim 1, it is characterized in that, described root of the tooth tip of a root filler is that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is that 30,000～50,000 polyacrylic acid, citric acid, sodium citrate and barium sulfate are formed by natural hydroxyapatite, particle diameter, and the addition of barium sulfate is that natural hydroxyapatite, particle diameter are that 0～50 μ m and mean diameter are that tetracalcium phosphate, the mean molecule quantity of 2～8 μ m is 0%～20% of 30,000～50,000 polyacrylic acid, citric acid and sodium citrate gross mass.
3. the preparation method of the described root of the tooth tip of a root of claim 1 filler is characterized in that,
Step 1 is mixed natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate, grind and obtains root of the tooth tip of a root packet powder behind 200 mesh sieves excessively, preserves every wet, and is standby;
Step 2 is a liquid phase with ionized water, PEG400 or glycerol, the powder body of step 1) preparation and liquid phase are transferred according to the mass ratio of 4～5:1 mix, the filling mould, prepare root of the tooth tip of a root filler.
4. according to the preparation method of the described root of the tooth tip of a root of claim 3 filler, it is characterized in that, in natural hydroxyapatite, tetracalcium phosphate, polyacrylic acid, citric acid and sodium citrate, mix again, grind behind the adding barium sulfate and mistake 200 mesh sieves.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1403069A (en) * | 2001-08-30 | 2003-03-19 | 陈瑾惠 | Process for producing slurry from calcium cementing agent |
| US20030216777A1 (en) * | 2002-05-16 | 2003-11-20 | Yin-Chun Tien | Method of enhancing healing of interfacial gap between bone and tendon or ligament |
| WO2007067561A2 (en) * | 2005-12-06 | 2007-06-14 | Etex Corporation | Porous calcium phosphate bone material |
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| CN1403069A (en) * | 2001-08-30 | 2003-03-19 | 陈瑾惠 | Process for producing slurry from calcium cementing agent |
| US20030216777A1 (en) * | 2002-05-16 | 2003-11-20 | Yin-Chun Tien | Method of enhancing healing of interfacial gap between bone and tendon or ligament |
| WO2007067561A2 (en) * | 2005-12-06 | 2007-06-14 | Etex Corporation | Porous calcium phosphate bone material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105686960A (en) * | 2014-11-24 | 2016-06-22 | 好来化工(中山)有限公司 | Tooth sensitivity prevention composition |
| CN105686960B (en) * | 2014-11-24 | 2018-10-02 | 好来化工(中山)有限公司 | Tooth antiallergic composition |
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