Background technology
Montmorillonitum is through the proof of clinical practice for many years treatment diarrhoeal diseases determined curative effect, the medicine that toxic and side effects is little.Stipulate in the diffusing quality standard of existing Montmorillonitum that calculate by dry product and should be 95.0~105.0% of labelled amount, content assaying method has following two kinds basically:
In the diffusing standard of the Montmorillonitum of standard No.: WS-408 (X-352)-99, the smectite content measuring method is: get these article 0.2g, the accurate title, decide; Put in the beaker, add water 25mL, stir; With No. 3 sintered glass crucibles filtrations of constant weight, wash beaker with suitable quantity of water, after washing liquid is incorporated the sintered glass crucible filtration into; Be dried to constant weight at 105 ℃, calculate and promptly get content.
The Montmorillonitum of standard No.: WS-222 (X-192)-99 looses in the standard, and the smectite content measuring method is: get the content under the content uniformity item, and mix homogeneously, precision takes by weighing in right amount (being equivalent to Montmorillonitum 0.4g approximately) and puts in the centrifuge tube; Add 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, promptly get the weight that contains Montmorillonitum in the test product.
The smectite content measuring method also has several kinds in the Montmorillonitum preparation quality standard of country's promulgation, but is that concrete parameter is different, does not have the change of essence.
The deficiency of smectite content measuring method is inaccurate in the diffusing quality standard of existing Montmorillonitum, and reason is that Montmorillonitum is a natural nano level material, in water, has dispersibility; Can be dispersed into colloidal state, most granules can reach below the 2um, and the part granule can reach nanoscale, when measuring content; Put in the centrifuge tube, add 50% ethanol 30ml, behind the shake well, centrifugal; The superfine granule of part can not precipitate fully, and supernatant can not be clarified, and is 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 Montmorillonitum and loose, put in the beaker, add water, stir, filter with No. 3 sintered glass crucibles, the granule 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.
Accurately measure effective ingredient content, be one of safety of medicine, effective, quality controllable safeguard measure, smectite content measuring method in the existing Montmorillonitum preparation quality standard is necessary perfect.
Summary of the invention
The purpose of this invention is to provide a kind of assay method that can accurately measure smectite content in the Montmorillonitum preparation, realize Montmorillonitum preparation safety, effective, quality controllable.
A kind of Montmorillonitum preparation content determining method of the present invention, precision is got the Montmorillonitum preparation, and the record quantity of sampling quantity is 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 promptly to get the weight that contains Montmorillonitum in the test product.
A kind of Montmorillonitum preparation content determining method of the present invention, precision is got the Montmorillonitum preparation that contains Montmorillonitum 0.2-0.4g approximately, puts in the centrifuge tube, adds 50% ethanol or is 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 repeats 1-2 time, content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.
A kind of Montmorillonitum preparation content determining method of the present invention, precision is got the Montmorillonitum preparation that contains Montmorillonitum 0.2-0.4g approximately, puts in the centrifuge tube, adds 50% ethanol or is 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 repeats 1 time, content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.
A kind of Montmorillonitum preparation content determining method of the present invention, precision is got the Montmorillonitum preparation that contains Montmorillonitum 0.2-0.4g approximately, puts in the centrifuge tube; Add 50% ethanol or be lower than 50% ethanol or water 30ml, the water solublity 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 repeats 2 times; Content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.
A kind of Montmorillonitum preparation content determining method of the present invention, precision is got the Montmorillonitum preparation that contains Montmorillonitum 0.2-0.4g approximately, puts in the centrifuge tube, adds water 30ml; 1 of the water solublity divalent metal ion salt solution that adds 10%-20%, behind the shake well, centrifugal (3000-5000 rev/min) 10-25 minute; Abandoning supernatant repeats 1 time, content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.
A kind of Montmorillonitum preparation content determining method of the present invention, precision take by weighing the Montmorillonitum that contains Montmorillonitum 0.2-0.4g approximately and loose, and put 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 repeats 1 time, content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.
Water soluble salt according to the invention is meant sodium chloride, Chile saltpeter, calcium chloride, ammonium chloride, potassium chloride, barium chloride, magnesium chloride, magnesium sulfate.
Divalent metal cation salts such as water soluble salt preferably calcium chloride according to the invention, barium chloride, magnesium chloride, magnesium sulfate.
Divalent metal ion water solublity salt according to the invention is calcium chloride preferably further.
The method of the invention can measure that Montmorillonitum looses, the smectite content of smectite suspension agent, Montmorillonitum granule, Montmorillonitum dispersible tablet and montmorillonite gelling.Dispersible tablet or granule are taken a sample after answering porphyrize in this way.
The concentration of water-soluble salt solution according to the invention is the gram number that every 100ml solution contains water solublity salt.
Precision according to the invention is got the Montmorillonitum preparation, is that precision takes by weighing or measures, and is that solid preparation takes by weighing with regard to precision, is that liquid preparation is measured with regard to precision.
The saline solution of 10%-20% adds 1-2 and drips among the present invention, by 20 about 1ml calculating, adds 0.05-0.1ml approximately; Contain the about 0.005-0.01g of water solublity salt, add in the liquid of 30ml, the concentration of water soluble salt is 0.017-0.034% (g/ml) approximately; Through test of many times, centrifugal back supernatant is about 29.5ml, contains the about 0.5ml of debris in the deposition; Promptly there is the water soluble salt of 0.00008-0.00016g to remain in the deposition approximately, ignores, do not influence the accuracy of assay.
Process test water soluble salt according to the invention all can obviously improve the clarity of centrifugal back supernatant, but the divalent metal ion salt solution is the most obvious, analyzes reason to be; Montmorillonitum is an ion-exchanger, 1 valence metal ion of adding, can with the commutative calcium ion generation ion exchange in the Montmorillonitum; Form 1 valence metal ion Montmorillonitum; 1 valence metal ion Montmorillonitum, especially sodium montmorillonite, the dispersibility in water; Greater than divalent metal ion Montmorillonitum, the clarity of supernatant is good not as the divalent metal 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 Montmorillonitum of the present invention content assaying method that looses through test, is 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 deposition, add water when centrifugal the centrifuge tube sidewall do not have deposition, 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 does not have the Montmorillonitum loss during abandoning supernatant, assay is more accurate than existing methods.
Further prove advantage of the present invention through Test Example below.
Test one is pressed the diffusing content assaying method of WS-408 (X-352)-99 Montmorillonitum and is measured smectite content
1, looses by national standard preparation Montmorillonitum
Take by weighing Montmorillonitum 300g, glucose 74.9g, saccharin sodium 0.7g, vanillin 0.4g, fully mixing makes the diffusing 376g of Montmorillonitum.
2, measure smectite content
The accurate title, decided 10 parts of test samples, and every part contains Montmorillonitum 0.2g approximately, puts respectively in the beaker, adds water 25mL; Stir,, wash beaker with suitable quantity of water, after washing liquid is incorporated the sintered glass crucible filtration into No. 3 sintered glass crucibles filtrations of constant weight; Be dried to constant weight at 105 ℃, calculate content, the result finds that filtered solution has opalescence, does not clarify; It is more on the low side than known content to record content, judges that by the amount of recording the lower bound suspicion that feeds intake is arranged, and result of determination does not conform to the actual conditions.The assay result sees table 1:
Table 1 test one 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known Montmorillonitum 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 the diffusing content assaying method of WS-222 (X-192)-99 Montmorillonitum and is measured smectite content
The accurate Montmorillonitum of testing preparation in surely of claiming looses 10 parts, and every part contains Montmorillonitum 0.4g approximately, puts respectively in the centrifuge tube; Add 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, promptly get the weight that contains Montmorillonitum in the test product.The result finds that centrifugal liquid do not clarify, and it is more on the low side than known content to record content, judges that by the amount of recording the lower bound suspicion that feeds intake is arranged, and result of determination does not conform to the actual conditions.The assay result sees table 2:
Table 2 test 2 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known Montmorillonitum 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 diffusing smectite content of Montmorillonitum by the inventive method
The accurate Montmorillonitum of testing preparation in surely of claiming looses 10 parts, and every part contains Montmorillonitum 0.4g approximately, puts respectively in the centrifuge tube, adds water 30ml; Add 1 of 10% calcium chloride solution, behind the shake well, centrifugal (3000 rev/mins) 15 minutes; Abandoning supernatant repeats 1 time, content is transferred in the evaporating dish of constant weight; Evaporate to dryness, 105 ℃ are dried to constant weight, calculate promptly to get the weight that contains Montmorillonitum in the test product.The result finds the centrifugal liquid clarification, and content is between 95-105%, and content is accurate, and the assay result sees table 3:
Table 3 test 3 10 duplicate samples smectite content measuring results
Sequence number |
Sampling amount (g) |
The known Montmorillonitum 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 |
Be test, convenience of calculation, the specification of not loosing by the Montmorillonitum that goes on the market in the above Test Example is carried out packing, and the known Montmorillonitum amount (g) that contains calculates according to the Montmorillonitum powder formula, and computing formula is:
Montmorillonitum recipe quantity=300g in the Test Example; The diffusing prescription of Montmorillonitum total amount=376g.
The specification labelled amount that the Montmorillonitum that gone on the market looses generally is the 3g/ bag, and the formula that smectite content can pass through among the WS-408 (X-352)-99 calculates.
The specific embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
The Montmorillonitum that takes by weighing labelled amount and be the 3g/ bag 0.2364g that looses puts in the centrifuge tube, adds 50% ethanol 20ml, adds 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, Montmorillonitum 0.1828g, calculate that smectite content is 96.9% of a 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, Montmorillonitum 0.9814g, calculate that smectite content is 98.1% of a labelled amount in the test product.
Embodiment 3
Getting labelled amount is the Montmorillonitum dispersible tablet of 1g/ sheet, and porphyrize takes by weighing 0.5177g, puts 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 repeats 2 times, content is transferred in the evaporating dish of constant weight evaporate to dryness; 105 ℃ are dried to constant weight, Montmorillonitum 0.4263g, calculate that smectite content is 103.2% of a labelled amount in the test product.
Embodiment 4
Getting labelled amount is the Montmorillonitum granule of 3g/ bag, and porphyrize takes by weighing 0.4995g, puts 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 repeats 1 time, content is transferred in the evaporating dish of constant weight evaporate to dryness; 105 ℃ are dried to constant weight, Montmorillonitum 0.4002g, calculate that the content of Montmorillonitum 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, Montmorillonitum 0.1992g, calculate that smectite content is 99.6% of a labelled amount in the test product.
Embodiment 6
The Montmorillonitum that takes by weighing labelled amount and be the 3g/ bag looses 0.2530, puts in the centrifuge tube, adds water 25ml, adds 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, Montmorillonitum 0.2061g, calculate that the content of Montmorillonitum is 102.1% of labelled amount in the test product.
Embodiment 7
The Montmorillonitum that takes by weighing labelled amount and be the 3g/ bag looses 0.5019, puts in the centrifuge tube, adds water 30ml, adds 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, Montmorillonitum 0.3961g, calculate that the content of Montmorillonitum is 98.9% of labelled amount in the test product.
Embodiment 8
The Montmorillonitum that takes by weighing labelled amount and be the 3g/ bag looses 0.1920, puts in the centrifuge tube, adds water 30ml, adds 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, Montmorillonitum 0.1595g, calculate that the content of Montmorillonitum is 104.1% of labelled amount in the test product.