CN104257517B - A kind of modified hydroxylapatite and preparation method thereof and purposes - Google Patents
A kind of modified hydroxylapatite and preparation method thereof and purposes Download PDFInfo
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- CN104257517B CN104257517B CN201410487169.4A CN201410487169A CN104257517B CN 104257517 B CN104257517 B CN 104257517B CN 201410487169 A CN201410487169 A CN 201410487169A CN 104257517 B CN104257517 B CN 104257517B
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Abstract
The invention belongs to biological medicine and commodity technical field, and in particular to a kind of modified hydroxylapatite and preparation method thereof and the purposes in preparing with the hydroxyapatite chitosan plural gel for improving gingivitis effect.There is preferable improvement to the gum redness caused by gingivitis and bleeding gums symptom by toothpaste prepared by modified hydroxylapatite of the present invention, there is certain mitigation to oral peculiar smell, without obvious adverse reaction, also have to stomatocace and have some improvement and therapeutic action.
Description
Technical field
The invention belongs to biological medicine and commodity technical field, and in particular to a kind of modified hydroxylapatite and its preparation
Method and the purposes in preparing with the hydroxyapatite-chitosan plural gel for improving gingivitis effect.
Background technology
Vertebrate sclerous tissues (such as bone and tooth) be it is a kind of be made up of organic and inorganic nano-hybrid body it is compound
Thing, wherein inorganic matter are mainly nano-grade hydroxy apatite [Ca10(PO4)6(OH)2, Hydroxyapatite, abbreviation HA], people's
The content of hydroxyapatite is more than 95% in enamel.Artificial synthesized hydroxyapatite is due to excellent bio-compatible
Property, there is certain inducing action to new bone growth, so as to showing one's talent in numerous artificial synthesized bone substitutes, by looking steadily
Mesh.In addition, hydroxyapatite has the effect such as certain remineralization, desensitization and whitening to oral health, applied to toothpaste
Through there are many reports, there are launch products in the country such as Japan, America and Europe.
Simple HA has high-crystallinity, and easily biological-degradable, absorption and remineralization do not act on the deficiencies of slower, medical real
In trampling, in terms of bond strength of the based materials between rate of dissolution, bioactivity and coating and matrix also there is
Some problems, it drastically influence the long-time stability of implant.In order to develop and explore the Bone Defect Repari more suitable for clinical practice
With oral health material, improve the performance of hydroxyapatite has turned into a focus of research.Since the 1980s, permitted
Study from hydroxyapatite molecular structure and bionics angularly more, using artificial synthesized hydroxyapatite as matrix, adopt
With ion exchange, organic or inorganic is material doped, compound the methods of, to the physical and mechanical properties of hydroxyapatite, surface and whole
Body bioactivity is improved.However, artificial synthesized hydroxyapatite is used for sclerous tissues's displacement and oral health is also present
Some shortcomings, such as the problems such as physical and mechanical properties is undesirable, fragility is big, bone inductive effect is weak.From bionics angle, it is desirable to
It is in nm regime to keep HA in bone substitute, to avoid HA agglomerate grains as far as possible, so the ceramic post sintering that tradition uses
HA particles in body, generally in micron dimensions above, are greatly differed from each other with the size of natural osteolith, made due to crystallinity height
It must apply and be restricted, therefore the non-sintered bodies of HA or HA slurries can only be typically selected when preparing bone renovating material.But therewith
And the problem of coming is, HA products only could obtain preferable mechanical property by sintering, and simple HA powders or slurry are present
Forming difficulty, bear external force and ability extreme difference that liquid washes away, and to cannot act as the repair materials of load-bearing bone tissue etc. many
Problem.
In skeleton, in addition to calcium orthophosphate base material, the also trace element of numerous species, such as Mg2+、Mn2+、Zn2 +、Na+Deng.These ions are played very heavy due to directly related with more than 200 kinds of biology enzyme of participation metabolism in human body
The effect wanted.Therefore, hydroxyapatite molecular structure is improved based on bionic principle turns into the focus of research.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of modification hydroxyl more suitable for Clinical mouth healthcare applications
Base apatite, and further disclose its preparation method and purposes.
In order to solve the above technical problems, the present invention is achieved through the following technical solutions：
A kind of modified hydroxylapatite of the present invention, the modified hydroxylapatite are that hydroxyapatite adulterates Al3+、Na+、K+
And Mg2+Carry out the complex of depth mineralising.
The above-mentioned modified hydroxylapatite of the present invention, is prepared by the following raw material：Hydroxyapatite 100-300 parts by weight, hydrogen-oxygen
Change aluminium 1-5 parts by weight, sodium chloride 20-70 parts by weight, potassium chloride 2-10 parts by weight, magnesium chloride 20-70 parts by weight.
The above-mentioned modified hydroxylapatite of the present invention, is prepared by the following raw material：The parts by weight of hydroxyapatite 200, aluminium hydroxide 2
Parts by weight, the parts by weight of sodium chloride 45, the parts by weight of potassium chloride 6, the parts by weight of magnesium chloride 45.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, comprises the following steps：
(1) hydroxyapatite, the aluminium hydroxide of selected parts by weight are weighed, adds concentrated nitric acid, stirring makes to being completely dissolved, obtained
A liquid；
(2) sodium chloride, potassium chloride, magnesium chloride of selected parts by weight are weighed, adds water to stir to being completely dissolved, filters to obtain B liquid；
(3) the A liquid and B liquid are mixed, and it is >=10 to adjust pH value, obtains white suspension；
(4) suspension is stirred completely, and it is still aging at room temperature, filter and taking precipitate washs to filtrate and is
Neutrality, drying, is produced.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, in the step (3), using 5%-25% hydroxide
Sodium solution adjusts pH value >=10.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, in the step (1), the mass concentration of the concentrated nitric acid
For 65-70%, and preferably 68%；The addition of the concentrated nitric acid and the hydroxyapatite and the weight ratio of aluminium hydroxide total amount
For 2-4：1.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, in the step (2), the addition of the water with it is described
Sodium chloride, the weight ratio of potassium chloride and magnesium chloride total amount be 2-5：1.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, in the step (4), by the white suspension in
20-50rpm persistently stirs 2-6 hours to stirring completely, and the time of the still aging step is 12-48 hours.
The preparation method of the above-mentioned modified hydroxylapatite of the present invention, in the step (4), in addition to by described in after drying
Modified hydroxylapatite is ground into the step that particle diameter is 200-400 mesh.
The above-mentioned modified hydroxylapatite of the present invention is being prepared with the hydroxyapatite-chitosan for improving gingivitis effect
Purposes in plural gel.
Modified hydroxylapatite of the present invention adulterates Al with hydroxyapatite3+、Na+、K+And Mg2+It is made, based on bionical
Principle is improved to hydroxyapatite molecular structure, can be with due to the addition of on the basis of hydroxyapatite property is kept
Directly affect the Mg of the calcification process of bone2+, help to influence or even control the crystallization of area of new bone mineral and formed
Journey, the bioactivity of the modified hydroxylapatite material of synthesis have important medical value.With the modified hydroxylapatite
The gel toothpaste of preparation is red and swollen to the gum caused by gingivitis and bleeding gums symptom has preferable improvement, different to oral cavity
Taste has certain mitigation, no obvious adverse reaction, also has to stomatocace and has some improvement and therapeutic action.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, specific embodiment and combination below according to the present invention
Accompanying drawing, the present invention is further detailed explanation, wherein：
Fig. 1 is experimental group and the comparison of control group periodontal items index baseline values in experimental example 1；
Fig. 2 is experimental group and control group PLI comparison, * in experimental example 1：Compared with baseline, P ＜ 0.05；#：With 2 weeks ratios
Compared with P ＜ 0.05；◎：Compared with control group, P ＜ 0.05；
Fig. 3 is experimental group and control group BI comparison, * in experimental example 1：Compared with baseline, P ＜ 0.05；#：With 2 weeks ratios
Compared with P ＜ 0.05；◎：Compared with control group, P ＜ 0.05；
Fig. 4 is experimental group and control group GI comparison, * in experimental example 1：Compared with baseline, P ＜ 0.05；#, with 2 weeks ratios
Compared with P ＜ 0.05；◎：Compared with control group, P ＜ 0.05.
Experimental example
Experimental example 1
Clinical verification of the hydroxyl apatite-chitosan plural gel efficacy factor toothpaste to improvement gingivitis
First, materials and methods
In order to verify that hydroxyapatite-chitosan plural gel containing modified hydroxylapatite of the present invention contains (HA/
SHA/CS) plural gel efficacy factor toothpaste improves the effect of gingivitis, and we cooperate with front three stomatological hospital, uses
Double-blind study, after patient's use with gingivitis problem, oral cavity inspection is carried out by the Dentist that technology is really up to the mark, qualification is deeper
Look into, and statistical analysis is carried out to result of the test.
1st, case selection
Choose the patient that clinical diagnosis is gingivitis, inclusive criteria：Whole body health in order and simultaneously examine on time by cooperation
Look into；At least retain 20 teeth in oral cavity；Gingival index >=1.0；It also is expected to complete this experiment and is ready to keep away in tested period
Exempt from using other toothpaste and take antibiotic, without using other oral hygiene measures (dental floss, mouthwash etc.)；Oral hygiene is protected
Strong product is without allergies.
Exclusion standard：Current long-term use of chemicals；There is the systemic disease oral mucosa such as digestive tract ulcer in need
The ulcer of the focus for the treatment of or serious recurrent exerbation；Dentures repai wears orthodontic appliance person, bad repair be present in oral cavity
Complex person；Take used antibiotic orally or carried out periodontal treatment within 2 weeks before baseline inspection；Diabetes, hepatitis B, tuberculosis or other
Infection or metabolic disease patient；There is allergies person to oral cavity health care product；Need to use that any to be likely to cause gum anti-
The medicine person answered；Pregnancy women.
Before all clinical trials start, volunteer signs informed consent form and provides medical history taking.
2nd, test specimen
Outward appearance sign is consistent, is marked with A, B printed words respectively.A is containing (HA/SHA/CS) plural gel efficacy factor toothpaste, B
For without (HA/SHA/CS) plural gel efficacy factor toothpaste.
The preparation of 2.1 (HA/SHA/CS) plural gel efficacy factor toothpaste
Raw material：Glycerine 5%, sorbierite 20%, sodium carboxymethylcellulose (CMC) l%, sodium lauryl sulfate 2%, titanium dioxide
Silicon 15%, calcium monohydrogen phosphate 25%, hydroxyapatite-chitosan plural gel prepared by embodiment 4 are (HA/SHA/CS) compound solidifying
Glue 2%, saccharin sodium 0.2%, essence l%, water surplus.
According to above composition of raw materials, using the toothpaste manufacturing process of routine, can be made containing (HA/SHA/CS) plural gel
Efficacy factor toothpaste.
Above-mentioned toothpaste presses defined quality examination condition and examination cycle, is observed through high/low temperature, normal temperature, lotion outward appearance is just
Often, obvious change does not occur for color, taste, and every physical and chemical index reaches the requirement of toothpaste standard GB/T 8372.
2.2 toothbrush
All subjects use 360 ° of toothbrushes that Guangzhou Colgate-Palmolive Co., Ltd produces.
3rd, test method
3.1 experiment principles
The experiment is in accordance with random, double blinding, control experiment principle.
3.2 observational techniques and index
3.2.1 change of the chief complaint (such as bleeding gums and oral peculiar smell) of patient before and after toothpaste use is recorded
1) oral peculiar smell：Being divided into often has, and occasionally has, and no Three Estate is come the change that is recorded in before and after toothpaste use.
2) bleeding gums：Being divided into often has, and occasionally has, and no Three Estate is come the change that is recorded in before and after toothpaste use.
Z：Hematostaxis (saliva is told from morning bloodstain)
C：Bleeding (brushing teeth or sting hard thing bleeding, suck bleeding) after stimulation
3.2.2 periodontal training observation index
3.2.2.1 gingival index (gingival index, GI)
0=gums healthies；1=gum mild inflammations：The color and luster of gum has mild change and examined not with Mild edema, spy
Bleeding；2=gum moderate inflammations：Gum color is red, oedema is bright, and bleeding is examined in spy；3=gum extensive inflammations：Gum is substantially red and swollen
Or have ulcer, there is automatic hemorrhagic tendency.
Inspection method：Williams periodontal probes are put into gingival edge gingival sulcus opening, and gently slided along gum edge, tooth
Gum tissue is only involved by slight.
3.2.2.2 plaque index (plaque index, PLI)
0=facings are without bacterial plaque；At the nearly gum edge of 1=mottled bacterial plaque is dispersed on facing；Have at the nearly gum edge of 2=on facing thin
Bacterial plaque continuously become band, width is no more than 1mm；3=bacterial plaques colored band is more than 1mm but the area of coverage is less than the neck 1/3 of corona；4
=bacterial plaque the area of coverage is between the 1/3~2/3 of corona；The 5=bacterial plaques area of coverage is the 2/3 of corona or more than 2/3.
Inspection method：Plaque disclosing agent is coated on facing, and Germ distribution of the bacterial plaque in facing of coloring is reexamined after gargling
And scope.
3.2.2.3 bleeding index (bleeding index, BI)
Inspection method：Williams periodontal probes gently probe into gingival sulcus, take out probe after 30 seconds, observation whether there is bleeding and bleeding
Degree.
Scored with 0 to 5 grade：0=gums healthies, no inflammation and bleeding；1=gingiva colors have inflammation to sexually revise, and spy is examined not
Bleeding；2=spies have petechial hemorrhage after examining；3=spies are examined bleeding and spread along gingival margin；4=, which goes out blood flow, to expire and overflows gingival sulcus；5=is certainly
Dynamic bleeding.
3.2.2.4 experiment process
Check tooth position be Ramfjord indexes tooth (check 16,21,24,36,41,44 representatives arranged as dental pattern, if
1 index anodontia, will be replaced by its remote middle adjacent teeth 17,11,25,37,42 or 45), when checking BI and GI, each index tooth inspection
Look into 6 sites：Nearly middle buccal surface, buccal surface center, remote middle buccal surface, nearly middle lingual surface, lingual surface center and remote middle lingual surface, record react most
The position of weight.When checking PLI, the buccal labial surface and tongue palatal surface of each index tooth, the most heavy position of record are checked.
3.2.3 while each periodontal checks, oral soft tissue situation is checked, to evaluate toothpaste oral cavity soft tissue
Effect.
3.3 experimental method
Screening meets inclusive criteria and exclusion standard person, is divided into two groups, two groups of A (experimental group), B (control group) by random table
It is essentially identical in health, the periodontal disease order of severity, age, sex ratio.Patient is uniformly had using Guangzhou Colgate-Palmolive
360 ° of toothbrushes of limit company production, and teach and brushed teeth using Bass brushings, once in the morning and once at night, each dosage is about 2g
(extrusion toothpaste is about 1.5cm), brushes teeth 3 minutes every time.To the clinical indices of subject according to baseline during the 2nd, 4 week in experiment
The program of inspection is reevaluated.During inspection respectively by 2 stomatological medical doctors check respectively for gingivitis indices, plaque index,
Bleeding index.Examiner has carried out itself replica test, unified checking tool and every inspection before experiment and in experiment
Indication.Gingival index and bleeding index inspection are estimated after visiting tactile gingival sulcus using Williams periodontal probes.Plaque index is in gum
Carried out after index and bleeding index detection, reading after being dyed with plaque indicator agents (basic fuchsin).
3.4 statistical analysis
4th week and the 2nd week index variation situation after being tested using independent samples t test assay each group.
4th, experimental result
The person 258 that meets inclusive criteria is collected in this experiment altogether, due to part research object when 2 weeks or 4 weeks it is in succession lost to follow-up,
In final 135 research objects for including research, experimental group 69, control group 66.
4.1 periodontal training observation index
4.1.1 the comparison of experimental group, control group periodontal items index baseline values
Experimental result is as shown in figure 1, during baseline, three clinical indices of experimental group and control group：Plaque index (PLI), tooth
Oulorrhagia index (BI), gingival index (GI) there was no significant difference (P>0.05).As a result show, two groups of tools of experimental group and control group
There is comparativity.
4.1.2 baseline and the comparison using toothpaste experimental group, control group periodontal items index after 2 weeks, 4 weeks
4.1.2.1PLI
Experimental result as shown in Fig. 2 experimental group and control group after baseline, experiment 2 weeks, testing 4 weeks, as toothpaste uses
The extension of time, compare between three time points, PLI values gradually reduce, and difference is respectively provided with statistical significance.In baseline, experiment 2
When week and 4 weeks, there are no significant for PLI differences between experimental group and control group.
4.1.2.2BI
Experimental result is as shown in figure 3, experimental group and control group in baseline, are tested 2 weeks, after testing 4 weeks, between three time points
Compare, BI values gradually reduce, and difference is respectively provided with statistical significance.When testing 2 weeks, there is aobvious BI values between experimental group and control group
Sex differernce is write, experimental group BI values substantially reduce compared with control group.When testing 4 weeks, BI values are in two group differences without conspicuousness.
4.1.2.3GI
Experimental result is as shown in figure 4, control group in baseline, experiment 2 weeks, after testing 4 weeks, compares, GI between three time points
Value gradually reduces, and difference has statistical significance.After experimental group baseline, experiment 2 weeks, experiment 4 weeks, the gradual reduction of GI values, base
Difference has a statistical significance between line and experiment 2 weeks, but no significant difference between testing 2 weeks and testing 4 weeks.In experiment 2
Zhou Shi, GI differences have conspicuousness between experimental group and control group, and experimental group GI values substantially reduce compared with control group；When testing 4 weeks, GI
In two group differences, there are no significant.
4.2 chief complaint
4.2.1 after baseline, experiment 2 weeks and 4 weeks, the chief complaint of patient describes (including oral cavity between experimental group and control group
Peculiar smell and bleeding gums) no significant difference.
4.2.2 the comparison between three time points of experimental group and control group
4.2.2.1 oral peculiar smell
When testing 2 weeks, compared with before experiment, the oral peculiar smell of two groups of patients is not improved.When testing 4 weeks, with experiment
Before compare, two groups of patient's oral peculiar smells mitigate, and difference is statistically significant.After 4 weeks, experimental group and control group obtain
The ratio that oral peculiar smell improves is respectively 73% and 55%.4.2.2.2 bleeding after stimulating
Bleeding has been alleviated before relatively being tested when testing 2 weeks, testing 4 weeks after the stimulation of two groups of patients, and difference
It is statistically significant.
4.2.2.3 hematostaxis
The hematostaxis symptom of two groups of patients difference between three time points is not statistically significant.
4.3 adverse reaction
132 study subjects do not find obvious adverse reaction during experiment, to oral mucosa and the sense of taste without obvious shadow
Ring, most study subjects think toothpaste mouthfeel " good ".
2nd, conclusion
By gingival index (GI), gingival sulcus bleeding index (BI), plaque index (plaque index, PLI) test mark
Standard, the efficacy factor toothpaste containing (HA/SHA/CS) plural gel is used to gingivitis patient, observe the outer of subject's gingivitis
See change.
Pass through this clinical test, it can be deduced that to draw a conclusion：
1st, under this experiment condition, containing (HA/SHA/CS) plural gel efficacy factor toothpaste to the gum caused by gingivitis
Red and swollen and bleeding gums symptom has preferable improvement.
2nd, under this experiment condition, have containing (HA/SHA/CS) plural gel efficacy factor toothpaste to oral peculiar smell certain
Mitigation.
3rd, under this experiment condition, using containing (HA/SHA/CS) plural gel efficacy factor toothpaste without obvious adverse reaction,
Oral mucosa and the sense of taste are had no significant effect, most study subjects think toothpaste mouthfeel " good ".
The plural gel of experimental example 2 is to cavy oral cavity gingivitis therapeutic effect research experiment
First, experimental method
Cavy is divided into 6 one group, male and female half and half.No. 5 syringe needles for only exposing 1mm at syringe needle are held together with 6, are stabbed
At gum among two lower front tooths of cavy, and pick n-butyric acie with cotton swab and smear wound, inflammation is photographed to record after 24 hours, is tried
Test group and smear sample 100mg at inflammation for every daily, control group does not process, and is recorded by gingival index (GI) standard grading scorching
Disease situation.
Gingival index (GI) standard grading：0 grade：No inflammation；1 grade：Slight inflammation, gum color is rubescent, and light micromodification becomes, no
Bleeding；2 grades：Moderate inflammation, gum is rubescent, bleeding is touched in loose, spy；3 grades：Severe inflammation, gum is rubescent, oedema, hypertrophy, burst
Ulcer, hematostaxis.
2nd, experimental result
The gingival index that table 1 records daily
| Test group | Control group | |
| First day | 3±0 | 3±0 |
| Second day | 3±0 | 3±0 |
| 3rd day | 2.87±0.84 | 3±0 |
| 4th day | 2.4±0.49 | 3±0 |
| 5th day | 2.17±0.37* | 2.83±0.37 |
| 6th day | 1.83±0.37* | 2.67±0.47 |
| 7th day | 1.5±0.5* | 2.4±0.49 |
| 8th day | 1.17±0.37* | 2.33±0.75 |
| 9th day | 0.67±0.47** | 2.17±0.37 |
| Tenth day | 0.17±0.37** | 2±0.63 |
*p<0.05, * * p<0.01
The healing days of table 2
| Test group | Control group | |
| Healing days | 10.3±1.7** | 16.8±2.5 |
*p<0.05, * * p<0.01
From the data of table 1 and 2, the toothpaste of the present invention containing hydroxyapatite-chitosan gel rubber factor can have
Effect improves gum symptom, shortens the healing time of gum illness.
Embodiment
For a more detailed description to the present invention with embodiment below, following examples are only to the optimal embodiment party of the present invention
The description of formula, does not have any restrictions to the scope of the present invention.
Embodiment 1
The preparation method of modified hydroxylapatite described in the present embodiment comprises the following steps：
(a) hydroxyapatite 200kg, aluminium hydroxide 2kg are weighed, it is about 68% to add 2.5 times of weight amount mass concentrations
Concentrated nitric acid (commercially available product), stirring make to be completely dissolved, and obtain A liquid；
(b) sodium chloride 45kg, potassium chloride 6kg, magnesium chloride 45kg are weighed to mix, adds 3 times of weight amount purified waters, stirring makes
It is completely dissolved, filters, obtain B liquid；
(c) above-mentioned A liquid and B liquid are mixed, adds 10% sodium hydroxide solution and adjust its pH value >=10, it is suspended to form white
Liquid；
(d) after the suspension persistently being stirred into 3 hours under 30rpm rotating speeds, stirring is stopped, material is quiet at room temperature
Ageing 24 hours, compression filtration filtering are put, it is neutrality that taking precipitate, which is washed with deionized to filtrate, and in 105 ± 2 DEG C of bakings
It is dry, smash, cross 325 mesh sieves, produce.
Embodiment 2
The preparation method of modified hydroxylapatite described in the present embodiment comprises the following steps：
(a) weigh hydroxyapatite 100kg, aluminium hydroxide 5kg, add 4 times of weight amount mass concentrations be about 68% it is dense
Nitric acid (commercially available product), stirring make to be completely dissolved, and obtain A liquid；
(b) sodium chloride 20kg, potassium chloride 2kg, magnesium chloride 20kg are weighed, adds 5 times of weight amount purified waters, stirring makes completely
Dissolving, filtering, obtains B liquid；
(c) above-mentioned A liquid and B liquid are mixed, it is >=10 to add 25% sodium hydroxide solution and adjust its pH value, and it is outstanding to form white
Turbid；
(d) after the suspension persistently being stirred into 2 hours under 50rpm rotating speeds, stirring is stopped, material is quiet at room temperature
Ageing 48 hours, compression filtration filtering are put, it is neutrality that taking precipitate, which is washed with deionized to filtrate, and in 105 ± 2 DEG C of bakings
It is dry, smash, cross 400 mesh sieves, produce.
Embodiment 3
The preparation method of modified hydroxylapatite described in the present embodiment comprises the following steps：
(a) weigh hydroxyapatite 100kg, aluminium hydroxide 1kg, add 2 times of weight amount mass concentrations be about 68% it is dense
Nitric acid (commercially available product), stirring make to be completely dissolved, and obtain A liquid；
(b) sodium chloride 70kg, potassium chloride 10kg, magnesium chloride 70kg are weighed, adds 2 times of weight amount purified waters, stirring has made
Fully dissolved, filtering, obtains B liquid；
(c) above-mentioned A liquid and B liquid are mixed, it is >=10 to add 5% sodium hydroxide solution and adjust its pH value, and it is outstanding to form white
Turbid；
(d) after the suspension persistently being stirred into 6 hours under 20rpm rotating speeds, stirring is stopped, material is quiet at room temperature
Ageing 12 hours, compression filtration filtering are put, it is neutrality that taking precipitate, which is washed with deionized to filtrate, and in 105 ± 2 DEG C of bakings
It is dry, smash, cross 200 mesh sieves, produce.
Embodiment 4
The preparation method of modified hydroxylapatite described in the present embodiment comprises the following steps：
(a) hydroxyapatite 300kg, aluminium hydroxide 2kg are weighed, it is about 68% to add 2.5 times of weight amount mass concentrations
Concentrated nitric acid (commercially available product), stirring make to be completely dissolved, and obtain A liquid；
(b) sodium chloride 45kg, potassium chloride 6kg, magnesium chloride 45kg are weighed to mix, adds 3 times of weight amount purified waters, stirring makes
It is completely dissolved, filters, obtain B liquid；
(c) above-mentioned A liquid and B liquid are mixed, adds 10% sodium hydroxide solution and adjust its pH value >=10, it is suspended to form white
Liquid；
(d) after the suspension persistently being stirred into 3 hours under 30rpm rotating speeds, stirring is stopped, material is quiet at room temperature
Ageing 24 hours, compression filtration filtering are put, it is neutrality that taking precipitate, which is washed with deionized to filtrate, and in 105 ± 2 DEG C of bakings
It is dry, smash, cross 325 mesh sieves, produce.
Embodiment 5
Raw material：Modified hydroxylapatite 35kg, chitosan 30kg prepared by hydroxyapatite 35kg, embodiment 1.
The preparation method of hydroxyapatite-chitosan plural gel comprises the following steps described in the present embodiment：
(1) hydroxyapatite and modified hydroxylapatite are weighed, adds 20 times of weight amount purified waters, stirring makes to form suspension
Liquid, the concentrated nitric acid (commercially available product) that mass concentration is about 68% is added while stirring and adjusts pH of suspension to 2, must clarify A liquid；
(2) chitosan is weighed, the acetic acid solution of 60 times of weight amount 0.5% is added, stirs to chitosan and be completely dissolved, is filtered,
Obtain B liquid；
(3) A liquid is well mixed with B liquid, adds 10% sodium hydroxide solution regulation pH >=10；
(4) after continuing stirring 12 hours, stirring is stopped, material is aged 24 hours at room temperature, is filtered, and taking precipitate is spent
Ion water washing to filtrate is neutrality；
(5) pH7.0 PBS 2000kg is prepared, sediment is mixed with PBS, mixing speed 50rpm,
Open 3000rpm homogeneous 20 minutes simultaneously, stop homogeneous, continue stirring 2 hours, stop stirring, discharging, obtain plural gel.
The gel addition customary adjuvant is taken, toothpaste is made using common process.
Embodiment 6
Raw material：Modified hydroxylapatite 20kg, chitosan 50kg prepared by hydroxyapatite 40kg, embodiment 2
The preparation method of hydroxyapatite-chitosan plural gel comprises the following steps described in the present embodiment：
(1) hydroxyapatite and modified hydroxylapatite are weighed, adds 25 times of weight amount purified waters, stirring makes to form suspension
Liquid, the concentrated nitric acid (commercially available product) that mass concentration is about 68% is added while stirring and adjusts pH of suspension to 2, must clarify A liquid；
(2) chitosan is weighed, the acetic acid solution of 80 times of weight amount 0.3% is added, stirs to chitosan and be completely dissolved, is filtered,
Obtain B liquid；
(3) A liquid is well mixed with B liquid, adds 20% sodium hydroxide solution regulation pH >=10；
(4) after continuing stirring 12 hours, stirring is stopped, material is aged 12 hours at room temperature, is filtered, and taking precipitate is spent
Ion water washing to filtrate is neutrality；
(5) pH7.5 PBS 2500kg is prepared, sediment is mixed with PBS, mixing speed 80rpm,
Open 4000rpm homogeneous 15 minutes simultaneously, stop homogeneous, continue stirring 4 hours, stop stirring, discharging, obtain plural gel.
The gel addition customary adjuvant is taken, tooth patch is made using common process.
Embodiment 7
Raw material：Modified hydroxylapatite 10kg, chitosan 20kg prepared by hydroxyapatite 50kg, embodiment 3
The preparation method of hydroxyapatite-chitosan plural gel comprises the following steps described in the present embodiment：
(1) hydroxyapatite and modified hydroxylapatite are weighed, adds 30 times of weight amount purified waters, stirring makes to form suspension
Liquid, the concentrated nitric acid (commercially available product) that mass concentration is about 68% is added while stirring and adjusts pH of suspension to 2, must clarify A liquid；
(2) chitosan is weighed, the acetic acid solution of 50 times of weight amount 1.0% is added, stirs to chitosan and be completely dissolved, is filtered,
Obtain B liquid；
(3) A liquid is well mixed with B liquid, adds 25% sodium hydroxide solution regulation pH >=10；
(4) after continuing stirring 12 hours, stirring is stopped, material is aged 48 hours at room temperature, is filtered, and taking precipitate is spent
Ion water washing to filtrate is neutrality；
(5) pH6.0 PBS 1000kg is prepared, sediment is mixed with PBS, mixing speed 40rpm,
Open 2000rpm homogeneous 30 minutes simultaneously, stop homogeneous, continue stirring 3 hours, stop stirring, discharging, obtain plural gel.
The gel addition customary adjuvant is taken, spray is made using common process.
Embodiment 8
Raw material：Modified hydroxylapatite 40kg, chitosan 10kg prepared by hydroxyapatite 20kg, embodiment 1
The preparation method of hydroxyapatite-chitosan plural gel comprises the following steps described in the present embodiment：
(1) hydroxyapatite and modified hydroxylapatite are weighed, adds 15 times of weight amount purified waters, stirring makes to form suspension
Liquid, the concentrated nitric acid (commercially available product) that mass concentration is about 68% is added while stirring and adjusts pH of suspension to 2, must clarify A liquid；
(2) chitosan is weighed, the acetic acid solution of 100 times of weight amount 0.4% is added, stirs to chitosan and be completely dissolved, is filtered,
Obtain B liquid；
(3) A liquid is well mixed with B liquid, adds 5% sodium hydroxide solution regulation pH >=10；
(4) after continuing stirring 12 hours, stirring is stopped, material is aged 36 hours at room temperature, is filtered, and taking precipitate is spent
Ion water washing to filtrate is neutrality；
(5) pH6.5 PBS 1500kg is prepared, sediment is mixed with PBS, mixing speed 60rpm,
Open 5000rpm homogeneous 10 minutes simultaneously, stop homogeneous, continue stirring 2 hours, stop stirring, discharging, obtain plural gel.
The gel addition customary adjuvant is taken, film is made using common process.
Embodiment 9
Raw material：Modified hydroxylapatite 50kg, chitosan 40kg prepared by hydroxyapatite 10kg, embodiment 3
The preparation method of hydroxyapatite-chitosan plural gel comprises the following steps described in the present embodiment：
(1) hydroxyapatite and modified hydroxylapatite are weighed, adds 20 times of weight amount purified waters, stirring makes to form suspension
Liquid, the concentrated nitric acid (commercially available product) that mass concentration is about 68% is added while stirring and adjusts pH of suspension to 2, must clarify A liquid；
(2) chitosan is weighed, the acetic acid solution of 70 times of weight amount 0.8% is added, stirs to chitosan and be completely dissolved, is filtered,
Obtain B liquid；
(3) A liquid is well mixed with B liquid, adds 15% sodium hydroxide solution regulation pH >=10；
(4) after continuing stirring 12 hours, stirring is stopped, material is aged 24 hours at room temperature, is filtered, and taking precipitate is spent
Ion water washing to filtrate is neutrality；
(5) pH7.0 PBS 3000kg is prepared, sediment is mixed with PBS, mixing speed 30rpm,
Open 3000rpm homogeneous 25 minutes simultaneously, stop homogeneous, continue stirring 1 hour, stop stirring, discharging, obtain plural gel.
The gel and filmogen and other customary adjuvants are taken, gel is made using common process.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. a kind of modified hydroxylapatite, it is characterised in that the modified hydroxylapatite is prepared by the following raw material：Hydroxy-apatite
Stone 100-300 parts by weight, aluminium hydroxide 1-5 parts by weight, sodium chloride 20-70 parts by weight, potassium chloride are 2-10 parts by weight, magnesium chloride
20-70 parts by weight；
Its preparation method, comprise the following steps：
(1) hydroxyapatite, the aluminium hydroxide of selected parts by weight are weighed, adds concentrated nitric acid, stirring makes to being completely dissolved, and obtains A liquid；
(2) sodium chloride, potassium chloride, magnesium chloride of selected parts by weight are weighed, adds water to stir to being completely dissolved, filters to obtain B liquid；
(3) the A liquid and B liquid are mixed, and it is >=10 to adjust pH value, obtains white suspension；
(4) suspension is stirred completely, and it is still aging at room temperature, filter and taking precipitate is washed in being to filtrate
Property, drying produces.
2. modified hydroxylapatite according to claim 1, it is characterised in that prepared by the following raw material：Hydroxyapatite
200 parts by weight, the parts by weight of aluminium hydroxide 2, the parts by weight of sodium chloride 45, the parts by weight of potassium chloride 6, the parts by weight of magnesium chloride 45.
3. a kind of preparation method of the modified hydroxylapatite of claim 1 or 2, it is characterised in that comprise the following steps：
(1) hydroxyapatite, the aluminium hydroxide of selected parts by weight are weighed, adds concentrated nitric acid, stirring makes to being completely dissolved, and obtains A liquid；
(2) sodium chloride, potassium chloride, magnesium chloride of selected parts by weight are weighed, adds water to stir to being completely dissolved, filters to obtain B liquid；
(3) the A liquid and B liquid are mixed, and it is >=10 to adjust pH value, obtains white suspension；
(4) suspension is stirred completely, and it is still aging at room temperature, filter and taking precipitate is washed in being to filtrate
Property, drying produces.
4. the preparation method of modified hydroxylapatite according to claim 3, it is characterised in that in the step (3), adopt
PH value >=10 are adjusted with 5%-25% sodium hydroxide solution.
5. the preparation method of the modified hydroxylapatite according to claim 3 or 4, it is characterised in that the step (1)
In, the mass concentration of the concentrated nitric acid is 65-70%, the addition of the concentrated nitric acid and the hydroxyapatite and aluminium hydroxide
The weight ratio of total amount is 2-4：1.
6. the preparation method of modified hydroxylapatite according to claim 5, it is characterised in that in the step (2), institute
The weight ratio for stating the addition and described sodium chloride, potassium chloride and magnesium chloride total amount of water is 2-5：1.
7. the preparation method of the modified hydroxylapatite according to claim 3,4 or 6, it is characterised in that the step (4)
In, the white suspension is persistently stirred into 2-6 hours in 20-50rpm and extremely stirs complete, the time of the still aging step
For 12-48 hours.
8. the preparation method of modified hydroxylapatite according to claim 7, it is characterised in that in the step (4), also
Including the modified hydroxylapatite after drying is ground into the step that particle diameter is 200-400 mesh.
9. the modified hydroxylapatite of claim 1 or 2 is being prepared with the hydroxyapatite-shell for improving gingivitis effect
Purposes in glycan plural gel.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0029332A1 (en) * | 1979-11-15 | 1981-05-27 | Dental Chemical Co., Limited | Dentifrice compositions |
| EP0389713A1 (en) * | 1989-03-29 | 1990-10-03 | Kyoto University | Process for coating a substrate with a bioactive hydroxyapatite film |
| CN101703797A (en) * | 2009-12-07 | 2010-05-12 | 上海交通大学 | Fluorine-substituted apatite coating on surface of biologic medical magnesium or alloy thereof and preparation method |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0029332A1 (en) * | 1979-11-15 | 1981-05-27 | Dental Chemical Co., Limited | Dentifrice compositions |
| EP0389713A1 (en) * | 1989-03-29 | 1990-10-03 | Kyoto University | Process for coating a substrate with a bioactive hydroxyapatite film |
| CN101703797A (en) * | 2009-12-07 | 2010-05-12 | 上海交通大学 | Fluorine-substituted apatite coating on surface of biologic medical magnesium or alloy thereof and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| Synthesis, characterization and high temperature analysis of Al-containing hydroxyapatites;I. Mayer等;《Journal of crystal growth》;19971231;第172卷;第220页左栏第2段 * |
| 介孔羟基磷灰石研究进展;赵森林;《有色金属》;20090531;第61卷(第2期);第55页第1段 * |
| 微量元素对羟基磷灰石晶体结构的影响;刘飚等;《济南大学学报》;20060731;第20卷(第3期);第193-194页 * |
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