Background technology
Smectite is through for many years clinical practice proof treatment diarrhoeal diseases determined curative effect, the medicine that toxic and side effect is little.Stipulate in the existing montmorillonite powder quality standard that calculate by dry product and should be 95.0~105.0% of labelled amount, content assaying method has following two kinds substantially:
In the montmorillonite powder standard of standard No.: WS-408 (X-352)-99, the smectite content measuring method is: get this product 0.2g, accurately weighed, put in the beaker, add water 25mL, stir evenly, with No. 3 sintered glass crucibles filtrations of constant weight, wash beaker with suitable quantity of water, after washing lotion is incorporated the sintered glass crucible filtration into, be dried to constant weight at 105 ℃, calculate and namely get content.
In the montmorillonite powder standard of standard No.: WS-222 (X-192)-99, the smectite content measuring method is: get the content under the content uniformity item, mix, precision takes by weighing in right amount (being equivalent to approximately smectite 0.4g) and puts in the centrifuge tube, add 50% ethanol 30ml, behind the shake well, centrifugal (3000 rev/mins) 15 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, namely get the weight that contains smectite in the test product.
The smectite content measuring method is several in addition in the montmorillonite preparation quality standard that country promulgates, but just design parameter is different, does not have tangible change.
The deficiency of smectite content measuring method is inaccurate in the existing montmorillonite powder quality standard, reason is, smectite is natural nano level material, have dispersiveness in water, can be dispersed into colloidal state, most particles can reach below the 2um, the part particle can reach nanoscale, when measuring content, put in the centrifuge tube, add 50% ethanol 30ml, behind the shake well, centrifugal, the superfine particle of part can not precipitate fully, and supernatant can not be clarified, discarded during abandoning supernatant, being transferred to content in the evaporating dish of constant weight, is the content of having lost behind the part fines, causes assay inaccurate; Get montmorillonite powder, put in the beaker, add water, stir evenly, filter with No. 3 sintered glass crucibles, the particle that part is superfine can pass through sintered glass crucible, and the residue in the crucible is the residue of having lost behind the part fines, causes assay to be forbidden.
The Accurate Determining effective ingredient content, be one of safety of medicine, effective, quality controllable safeguard measure, smectite content measuring method in the existing montmorillonite preparation quality standard is necessary perfect.
Summary of the invention
The purpose of this invention is to provide the assay method of smectite content in a kind of energy Accurate Determining montmorillonite preparation, realize that montmorillonite preparation is safe, effective, quality controllable.
A kind of montmorillonite preparation content assaying method of the present invention, precision is got montmorillonite preparation, the record quantity of sampling quantity, put in the centrifuge tube, add 50% ethanol or be lower than 50% ethanol or water 20-50ml, the water-soluble salt solution 1-2 that adds 10%-20% drips, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant repeats 1-2 time, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
A kind of montmorillonite preparation content assaying method of the present invention, precision is got the montmorillonite preparation that contains approximately smectite 0.2-0.4g, put in the centrifuge tube, add 50% ethanol or be lower than 50% ethanol or water 30ml, the water-soluble salt solution 1-2 that adds 10%-20% drips, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant, repeat 1-2 time, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
A kind of montmorillonite preparation content assaying method of the present invention, precision is got the montmorillonite preparation that contains approximately smectite 0.2-0.4g, put in the centrifuge tube, add 50% ethanol or be lower than 50% ethanol or water 30ml, the water-soluble salt solution 1-2 that adds 10%-20% drips, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
A kind of montmorillonite preparation content assaying method of the present invention, precision is got the montmorillonite preparation that contains approximately smectite 0.2-0.4g, put in the centrifuge tube, add 50% ethanol or be lower than 50% ethanol or water 30ml, the water-soluble divalent metal ion salt solution 1-2 that adds 10%-20% drips, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
A kind of montmorillonite preparation content assaying method of the present invention, precision is got the montmorillonite preparation that contains approximately smectite 0.2-0.4g, puts in the centrifuge tube, add water 30ml, 1 of the water-soluble divalent metal ion salt solution that adds 10%-20%, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
A kind of montmorillonite preparation content assaying method of the present invention, precision takes by weighing the montmorillonite powder that contains approximately smectite 0.2-0.4g, puts in the centrifuge tube, add water 30ml, add 1 of 10% calcium chloride solution, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.
Water soluble salt of the present invention refers to sodium chloride, sodium nitrate, lime chloride, ammonium chloride, potassium chloride, barium chloride, magnesium chloride, magnesium sulphate.
The divalent metal cation salts such as water soluble salt preferably calcium chloride of the present invention, barium chloride, magnesium chloride, magnesium sulphate.
Divalent metallic ion water soluble salt of the present invention is lime chloride preferably further.
The method of the invention can be measured the smectite content of montmorillonite powder, smectite suspension agent, smectite granule, montmorillonite dispersed tablet and montmorillonite gelling.Dispersing tablet or granule are taken a sample after answering porphyrize in this way.
The concentration of water-soluble salt solution of the present invention is the grams of every 100ml solution containing water-soluble salt.
Precision of the present invention is got montmorillonite preparation, is that precision takes by weighing or measures, and is that solid pharmaceutical preparation takes by weighing with regard to precision, is that liquid preparation is measured with regard to precision.
The salt solusion of 10%-20% adds 1-2 and drips among the present invention, calculate by 20 about 1ml, add approximately 0.05-0.1ml, the about 0.005-0.01g of containing water-soluble salt, add in the liquid of 30ml, the concentration of water soluble salt is 0.017-0.034% (g/ml) approximately, and through test of many times, centrifugal rear supernatant is about 29.5ml, contain the about 0.5ml of Liquid Residue in the precipitation, namely there is approximately the water soluble salt of 0.00008-0.00016g to remain in the precipitation, ignores, do not affect the accuracy of assay.
Through test water soluble salt of the present invention all can obviously improve centrifugal after the clarity of supernatant, but the divalent metal ion salt solution is the most obvious, the analysis reason is, smectite is ion exchanger, 1 valence metal ion that adds, can with smectite in commutative calcium ion generation ion-exchange, form 1 valence metal ion smectite, 1 valence metal ion smectite, especially na-montmorillonite, dispersiveness in water, greater than divalent metallic ion smectite, the clarity of supernatant is good not as the divalent metallic ion when centrifugal.In the divalent metal cation salt, effective, cheap and easy to get through the test calcium chloride solution, so further preferably calcium chloride.
A kind of montmorillonite powder content assaying method of the present invention, through test, put in the centrifuge tube, add 50% ethanol or water 20-50ml, can reach goal of the invention, but add 50% ethanol when centrifugal, the centrifuge tube sidewall has precipitation, and the centrifuge tube sidewall is without precipitation when centrifugal to add water, and it is centrifugal to add water, abandoning supernatant is more easy to operate, so the preferred water of the present invention.
The invention has the advantages that when centrifugal that the supernatant clarification is lost without smectite during abandoning supernatant, assay is more accurate than existing methods.
Further prove advantage of the present invention below by test example.
Test one is pressed WS-408 (X-352)-99 montmorillonite powder content assaying method and is measured smectite content
1, by national standard preparation montmorillonite powder
Take by weighing smectite 300g, glucose 74.9g, saccharin sodium 0.7g, vanillic aldehyde 0.4g, fully mixing makes montmorillonite powder 376g.
2, measure smectite content
Accurately weighed 10 parts of test samples, every part contains smectite 0.2g approximately, puts respectively in the beaker, add water 25mL, stir evenly, with No. 3 sintered glass crucibles filtrations of constant weight, wash beaker with suitable quantity of water, washing lotion is dried to constant weight at 105 ℃ after incorporating the sintered glass crucible filtration into, calculate content, found that filtered solution has opalescence, do not clarify that it is more on the low side than known content to record content, be determined with the lower bound suspicion that feeds intake by the amount of recording, result of determination does not conform to the actual conditions.Assay the results are shown in Table 1:
Table 1 test one 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known smectite amount (g) that contains |
The amount of recording (g) |
Record smectite content (%) |
1 |
0.2501 |
0.1996 |
0.1906 |
95.5 |
2 |
0.2530 |
0.2019 |
0.1940 |
96.1 |
3 |
0.2644 |
0.2110 |
0.2045 |
96.6 |
4 |
0.2514 |
0.2006 |
0.1924 |
95.9 |
5 |
0.2527 |
0.2016 |
0.1966 |
97.5 |
6 |
0.2466 |
0.1968 |
0.1868 |
94.9 |
7 |
0.2786 |
0.2223 |
0.2139 |
96.2 |
8 |
0.2487 |
0.1984 |
0.1895 |
95.5 |
9 |
0.2505 |
0.1999 |
0.1935 |
96.8 |
10 |
0.2766 |
0.2207 |
0.2178 |
98.7 |
Test two is pressed WS-222 (X-192)-99 montmorillonite powder content assaying method and is measured smectite content
10 parts of the montmorillonite powders of preparation in the accurately weighed test one, every part contains smectite 0.4g approximately, puts respectively in the centrifuge tube, adds 50% ethanol 30ml, behind the shake well, centrifugal (3000 rev/mins) 15 minutes, abandoning supernatant repeats 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, namely get the weight that contains smectite in the test product.Found that centrifugate do not clarify, it is more on the low side than known content to record content, is determined with the lower bound suspicion that feeds intake by the amount of recording, and result of determination does not conform to the actual conditions.Assay the results are shown in Table 2:
Table 2 test 2 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known smectite amount (g) that contains |
The amount of recording (g) |
Record smectite content (%) |
1 |
0.5101 |
0.4080 |
0.4007 |
98.2 |
2 |
0.5217 |
0.4163 |
0.3967 |
95.3 |
3 |
0.5016 |
0.4002 |
0.3858 |
96.4 |
4 |
0.4997 |
0.3987 |
0.3816 |
95.7 |
5 |
0.4887 |
0.3899 |
0.3731 |
95.7 |
6 |
0.4969 |
0.3965 |
0.3802 |
96.1 |
7 |
0.5090 |
0.4061 |
0.3959 |
97.5 |
8 |
0.5165 |
0.4121 |
0.3948 |
95.8 |
9 |
0.4884 |
0.3897 |
0.3765 |
96.6 |
10 |
0.4988 |
0.3980 |
0.3781 |
95.0 |
Test three is measured the montmorillonite powder smectite content by the inventive method
10 parts of the montmorillonite powders of preparation in the accurately weighed test one, every part contains smectite 0.4g approximately, puts respectively in the centrifuge tube, add water 30ml, add 1 of 10% calcium chloride solution, behind the shake well, centrifugal (3000 rev/mins) 15 minutes, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight evaporate to dryness, 105 ℃ are dried to constant weight, calculate namely to get the weight that contains smectite in the test product.Found that the centrifugate clarification, content is between 95-105%, and content is accurate, and assay the results are shown in Table 3:
Table 3 test 3 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known smectite amount (g) that contains |
The amount of recording (g) |
Record smectite content (%) |
1 |
0.5159 |
0.4116 |
0.4067 |
98.8 |
2 |
0.5308 |
0.4235 |
0.4197 |
99.1 |
3 |
0.5034 |
0.4017 |
0.4081 |
101.6 |
4 |
0.4486 |
0.3579 |
0.3532 |
98.7 |
5 |
0.5012 |
0.3999 |
0.4015 |
100.4 |
6 |
0.5017 |
0.4003 |
0.4087 |
102.1 |
7 |
0.4674 |
0.3729 |
0.3636 |
97.5 |
8 |
0.4989 |
0.3981 |
0.3993 |
100.3 |
9 |
0.5168 |
0.4124 |
0.4091 |
99.2 |
10 |
0.4853 |
0.3872 |
0.3868 |
99.9 |
For test, convenience of calculation, not by the specification of the montmorillonite powder that goes on the market, carry out packing in the above test example, the known smectite amount (g) that contains obtains according to the montmorillonite powder recipe calculation, and computing formula is:
Smectite recipe quantity=300g in the test example; Montmorillonite powder prescription total amount=376g.
The specification labelled amount of montmorillonite powder of having gone on the market generally is the 3g/ bag, and the formula that smectite content can pass through among the WS-408 (X-352)-99 calculates.
In the table,
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
Taking by weighing labelled amount is the montmorillonite powder 0.2364g of 3g/ bag, puts in the centrifuge tube, adds 50% ethanol 20ml, add 1 of 10% sodium chloride solution, behind the shake well, centrifugal (3000 rev/mins) 25 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.1828g, calculate that smectite content is 96.9% of labelled amount in the test product.
Embodiment 2
Measure labelled amount and be 10% smectite turbid liquor 10ml, put in the centrifuge tube, add water 50ml, add 2 of 20% ammonium chloride, solution, behind the shake well, centrifugal (5000 rev/mins) 15 minutes, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.9814g, calculate that smectite content is 98.1% of labelled amount in the test product.
Embodiment 3
Get the montmorillonite dispersed tablet that labelled amount is the 1g/ sheet, porphyrize takes by weighing 0.5177g, put in the centrifuge tube, add 50% ethanol 30ml, add 2 of 15% magnesium chloride solutions, behind the shake well, centrifugal (4000 rev/mins) 20 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.4263g, calculate that smectite content is 103.2% of labelled amount in the test product.
Embodiment 4
Getting labelled amount is the smectite granule of 3g/ bag, and porphyrize takes by weighing 0.4995g, put in the centrifuge tube, add 30% ethanol 40ml, add 1 of 20% calcium chloride solution, behind the shake well, centrifugal (4000 rev/mins) 10 minutes, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.4002g, calculate that the content of smectite is 100.4% of labelled amount in the test product.
Embodiment 5
Measure labelled amount and be 20% montmorillonite gelling 2ml, put in the centrifuge tube, add water 35ml, add 1 of 10% Adlerika, behind the shake well, centrifugal (3000 rev/mins) 18 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.1992g, calculate that smectite content is 99.6% of labelled amount in the test product.
Embodiment 6
Taking by weighing labelled amount is the montmorillonite powder 0.2530 of 3g/ bag, puts in the centrifuge tube, adds water 25ml, add 1 of 15% barium chloride solution, behind the shake well, centrifugal (3500 rev/mins) 15 minutes, abandoning supernatant, repeat 1 time, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.2061g, calculate that the content of smectite is 102.1% of labelled amount in the test product.
Embodiment 7
Taking by weighing labelled amount is the montmorillonite powder 0.5019 of 3g/ bag, puts in the centrifuge tube, adds water 30ml, add 1 of 10% Klorvess Liquid, behind the shake well, centrifugal (5000 rev/mins) 15 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.3961g, calculate that the content of smectite is 98.9% of labelled amount in the test product.
Embodiment 8
Taking by weighing labelled amount is the montmorillonite powder 0.1920 of 3g/ bag, puts in the centrifuge tube, adds water 30ml, add 1 of 10% sodium nitrate solution, behind the shake well, centrifugal (3000 rev/mins) 15 minutes, abandoning supernatant, repeat 2 times, content is transferred in the evaporating dish of constant weight, evaporate to dryness, 105 ℃ are dried to constant weight, smectite 0.1595g, calculate that the content of smectite is 104.1% of labelled amount in the test product.