CN102590180B - Method for detecting element of Chinese medicine, Chinese medicinal extract, soil or medicinal composition containing Chinese medicinal extract - Google Patents
Method for detecting element of Chinese medicine, Chinese medicinal extract, soil or medicinal composition containing Chinese medicinal extract Download PDFInfo
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Abstract
The invention provides a method for determining an element of a Chinese medicine, a Chinese medicinal extract, soil or a medicinal composition containing the Chinese medicinal extract. By the method, a large amount of samples are determined by a seal and heat preservation primary digestion step and an ultrapure water heat preservation dissolution and volume metering step, so that the effects of complete digestion, accurate detection and high repeatability can be achieved.
Description
Technical field
The invention belongs to the analyzing and testing field of medicine, be specifically related to a kind of Chinese crude drug, Chinese medical extract, soil and containing the determination method of constituent content in the pharmaceutical composition of Chinese medical extract and drug action.
Background technology
Chinese medicine Java brucea is Simarubaceae brucea plant Java brucea
brucea javanica(L.) dry mature fruit of Merr.Gather during fruit maturation autumn, removes impurity, dries.The Java brucea beginning is loaded in the < < A Supplement to the Compendium of Materia Medica > > that Qing Dynasty's Zhao Xuemin is shown.The effect of recording in Pharmacopoeia of People's Republic of China is clearing heat and detoxicating, preventing malaria, and only dysentery, corrodes wart.For dysentery, malaria; Control wart outward, corn.Containing water-soluble composition and vegetable oil two parts in the organic principle of Java brucea, its toxic component is present in water-soluble bitter principle; And oil-soluble composition, brucea fruit oil nontoxicity and result for the treatment of are better, be widely used at present clinical in, brucea fruit oil extract is for the preparation of pharmaceutical preparation, the preparation of commonplace use is Java brucea fruit oil emulsion injection and brucea fruit oil oral latex emulsion.
Many about organic assay and method of quality control in Java brucea medicinal material, extract, preparation, range of control is also more comprehensive, but fewer about the mensuration of constituent content in Java brucea medicinal material, brucea fruit oil and pharmaceutical composition thereof and the research of method of quality control.For example, Sun Weimin etc. analyze constituent content in 14 kinds of anti-tumor Chinese medicines, comprising having analyzed the element in Java brucea by inductivity coupled plasma mass spectrometry (ICP-MS) method, but only analyze to determine, comprise totally 26 kinds of elements such as Be, Na, Mg, Al, K, Ca, V.Employing ICP-AES (ICP-AES) methods such as Zhang little Lin are measured the macro-and microelements in 26 kinds of southern medicines that comprise Java brucea, but have only measured the K in Java brucea, Cr, Zn, Cu, Mn and Fe element.Soup is learnt military affairs etc. in trace elements and health research, adopt ICP-AES, atomic fluorescence spectrometry (AFS), flame atomic absorption spectrometry (FAAS) etc. to analyze rare earth or the non-rare earth that comprises Java brucea medicinal material, but disclose element in concrete sample preparation step, instrument condition, Java brucea, do not detect the detail content such as data.The employing flame atomic absorption spectrometrys (FAAS) such as Han Jin soil are measured totally to comprising 11 kinds of trace elements in 20 kinds of Chinese herbal medicines of Java brucea, have only measured the content of the elements such as Cu, Mg, Mn of Java brucea.
But at present known 92 kinds of natural elements that exist at occurring in nature, except inert gas elements (helium, neon, argon, krypton, xenon, radon) and technetium, francium, actinium, protactinium, astatine etc., other 81 kinds are all present in biosome, and wherein certified indispensable element comprises the trace elements such as 11 kinds of macroelements and iron, iodine, zinc, selenium, fluorine, copper, cobalt, manganese, chromium, vanadium, nickel, tin, strontium, silicon, bromine, arsenic, boron.Be subject at present the restriction of sample treatment and testing conditions, when carrying out element determination, the sampling amount of sample is smaller conventionally, and this causes the detected value of sample in mensuration process very low, some compositions be difficult to detect or error at measurment very large.But when improving the sampling amount of sample, in digestion process, sample often there will be gelatinization, clears up the problems such as inhomogeneous or insufficient, cause measuring be difficult to carry out or error very large.Particularly for Java brucea or its extract or pharmaceutical composition, currently available technology has generally only been measured Java brucea medicinal material or its extract and has been contained the content of Partial Elements in the pharmaceutical composition of extract, lack simultaneously the content limit of element is studied, more lack to Java brucea soil for growth, Chinese crude drug, extract with containing the relevance of the pharmaceutical composition constituent content of extract and study accordingly.
And the current known digestion procedure of sample, as Microwave Digestion, ashing are cleared up, acid is cleared up etc., wherein ashing clears up that efficiency is low, low precision, usually causes element to be measured (as Pb, Hg, As) volatilization.Although micro-wave digestion is convenient, cost is too high, sample size is little, have potential safety hazard, can measure elemental range little.Most widely used is that acid is cleared up, but traditional acid to clear up maximum problem be to clear up not exclusively, the residual excessive acid of digestion solution can affect measurement result, in addition, lacks the unified digestion procedure for vegetable oil, emulsion in prior art.Therefore, need to therefrom set up a set of method for detecting element that is applicable to Chinese crude drug, Chinese medical extract, soil and contains the pharmaceutical composition of Chinese medical extract, it not only can improve the content limit of detection elements, and can adapt to medicinal material, extract and containing the kit detection method of the different associated sample such as pharmaceutical composition constituent content of extract, especially need to set up the digestion procedure that is simultaneously applicable to Java brucea soil for growth, Java brucea medicinal material, brucea fruit oil and 'Brucea fruit oil ' (bruceolic oil emulsion), to increase substantially the element detection level of these samples.
Summary of the invention
The present invention is intended to by carrying out design optimization to Chinese crude drug, Chinese medical extract, soil or containing the method for detecting element of the pharmaceutical composition of Chinese medical extract, the condition of the condition that the digestion procedure major control after optimization is cleared up and final dilution constant volume, that by these controls, can realize sample repeatedly clears up processing, and can realize within the scope of very wide sample weighting amount and all can clear up, and realized clear up completely evenly, not gelatinization, reached detect accurately, the element determination effect of favorable reproducibility.The sample solution obtaining with this digestion procedure can pass through the content of Instrument measuring element.This method providing can be applied to medicinal material soil for growth, Chinese crude drug, Chinese medical extract simultaneously and contain the Specimen eliminating of the pharmaceutical composition of Chinese medical extract.
The present invention is specifically by analyzing to Java brucea medicinal material, brucea fruit oil, soil or containing the detection of the pharmaceutical composition element of brucea fruit oil, detect as far as possible comprehensively element, make the nearly 40 kinds of elements while accurate quantitative analysis wherein comprising, set up a set of reflection Chinese crude drug, Chinese medical extract and contained all analytical approachs of surveying the content of element and investigating the general characteristic of each element in the pharmaceutical composition of extract, and found the relevance of each element in the materials such as medicinal material, the form by the content of each element and limit with finger-print shows.
Particularly, detection method working sample of the present invention is selected from Chinese crude drug, Chinese medical extract, soil or contains the pharmaceutical composition of Chinese medical extract, sample can be anticipated before weighing, processing mode is processed according to common element method for measuring, solids such as Chinese crude drug, soil can carry out pulverization process, in liquid preparation, contain relatively large water, be through dewatered process in advance.Take Java brucea as example, and Java brucea medicinal material, soil can carry out pulverization process; Fructus Bruceae extract is that brucea fruit oil can not carry out extra process; Emulsion of Seed Oils From Brucea Javanica carries out processed.These disposal routes are all the more known methods in this area, according to the common operation in this area.
Detection method comprises the following steps:
sample step: take Chinese crude drug, Chinese medical extract, soil or containing the pharmaceutical composition of Chinese medical extract;
the optional step of clearing up in advance: optionally will sample the sample of step, add digestion solution to soak 2～20 hours;
clear up for the first time step: by the container of clearing up for the first time sample is housed, airtight, the baking oven of putting into 130～210 ℃ is incubated 1～24 hour, cooling after taking out.Container is uncovered, and on 150～210 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling,
The described sample of clearing up is for the first time:
A) clear up in advance after step is soaked and add digestion solution to obtain; Or
B) will sample the sample of step acquisition, add digestion solution to obtain;
dissolve and constant volume step: by being equipped with in the container of the sample after clearing up, add ultrapure water, airtight, put into 100～120 ℃ of baking ovens and be incubated 1～12 hour, cooling after taking out, after thin up constant volume, obtain testing sample;
The sample dissolving and constant volume step obtains is carried out to element determination.
In the research of said method, find to be very crucial in first clearing up middle closed environment and be controlled at 130～210 ℃ of temperature, this be whole clear up react completely, evenly, a key factor of not gelatinization.In final process for preparation, adding ultrapure water to put into 100～120 ℃ of baking oven insulations, be also very crucial in addition.Through experiment showed,, meeting under these two conditions, the accuracy of mensuration, stability and broad spectrum activity are very good.
In said method, the about 0.1 ~ 1g of sample sample weighting amount generally, preferably at 0.35 ~ 1g, 0.5g most preferably.
In addition, after clearing up for the first time, those skilled in the art can select to carry out the follow-up processing of similarly clearing up as required, experimental results show that and carry out secondary or clear up processing for three times substantially meeting testing requirement, and this has further improved the effect of measuring.Certainly at three times, clear up after step, those skilled in the art can carry out as required one or many again and clear up.Considering cost and efficiency factor, two to three times are cleared up is proper.
In said method, after clearing up for the first time, can further comprise that secondary clears up step: will clear up for the first time rear sample and add digestion solution, heating catches up with acid to micro-dry, cooling on 150～210 ℃ of electric hot plates.After secondary is cleared up step, can further include three times and clear up step: in the sample after secondary is cleared up, again add digestion solution, heating catches up with acid to micro-dry, cooling on 150～210 ℃ of electric hot plates.
The present invention is when clearing up step, and preferably on 170～190 ℃ of electric hot plates, heating catches up with acid to micro-dry, more preferably on 180 ℃ of electric hot plates, heats.
In method of operating of the present invention, clear up in advance step and can carry out as required.In Java brucea medicinal material or brucea fruit oil or the element determination containing the pharmaceutical composition of brucea fruit oil, when sample is Java brucea medicinal material, preferably clear up in advance step, more preferably soak 10 hours; When sample is the soil of brucea fruit oil, Java brucea growth, can not need to clear up in advance.
Further, Java brucea medicinal material of the present invention, brucea fruit oil, soil or comprise containing the sample determination method of the pharmaceutical composition of brucea fruit oil:
Sample step: take Java brucea medicinal material, brucea fruit oil, soil or containing the sample of the pharmaceutical composition of brucea fruit oil approximately 0.1 ~ 1g, preferably 0.35g ~ 1g, most preferably 0.5g;
The optional step of clearing up in advance: optionally will sample the sample of step, add digestion solution immersion 2～20 hours; Wherein, when sample is Java brucea medicinal material, preferably soak 10 hours;
Clear up for the first time step: by the container of clearing up for the first time sample is housed, airtight, the baking oven of putting into 130～210 ℃ is incubated 1～24 hour, cooling after taking out, container is uncovered, and on 150～210 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling,
The described sample of clearing up is for the first time:
A) clear up in advance after step is soaked and add digestion solution to obtain; Or
B) will sample the sample of step acquisition, add digestion solution to obtain;
Dissolve and constant volume step: by being equipped with in the container of the sample after clearing up, add ultrapure water, airtight, put into 100～120 ℃ of baking ovens and be incubated 1～12 hour, take out coolingly afterwards, thin up constant volume, shakes up rear to be measuredly, preferably uses plastic bottle constant volume;
The sample that dissolves the acquisition of constant volume step is carried out to element determination.
In said method, after clearing up for the first time, can further comprise that secondary clears up step: will clear up for the first time rear sample and add digestion solution, heating catches up with acid to micro-dry, cooling on 150～210 ℃ of electric hot plates.After secondary is cleared up step, also can further comprise and clear up step three times: in the sample after secondary is cleared up, again add digestion solution, heating catches up with acid to micro-dry, cooling on 150～210 ℃ of electric hot plates.After clearing up step three times, can carry out one or many clears up again.
The digestion solution adding in each step in said method is the general reagent of clearing up in this area, can be selected from nitric acid, hydrogen peroxide, hydrofluorite, perchloric acid, hydrochloric acid, sulfuric acid, potassium persulfate, potassium hydrogen persulfate, sodium peroxydisulfate, hydrogen persulfate sodium, phosphoric acid, hydrobromic acid, or any combination of two or more materials.
In said method, while specifically clearing up step in advance for Java brucea medicinal material, digestion solution is preferably used hydrogen peroxide immersion to clear up in advance, preferably 2ml hydrogen peroxide/0.5g Java brucea medicinal material.
In said method, while clearing up for the first time, brucea fruit oil is cleared up for the first time and can be used nitric acid or hydrogen peroxide, the preferably combination of nitric acid and hydrogen peroxide, and every 0.5g brucea fruit oil is used the effect of 5ml nitric acid and 2ml hydrogen peroxide best; Java brucea soil for growth is cleared up for the first time and can be used nitric acid or hydrofluorite, the preferably combination of nitric acid and hydrofluorite, and the effect of every 0.5g pedotheque 3ml nitric acid and 5ml hydrofluorite is best; Java brucea medicinal material is cleared up for the first time can be according to the use of whether clearing up in advance step and adjust digestion solution, for example: as clear up in advance step digestion solution can directly in the potpourri after clearing up in advance, add digestion solution, preferably use nitric acid, every 0.5g Java brucea medicinal material is used the effect of 5ml nitric acid best, as do not cleared up in advance step, can directly add digestion solution, the preferably combination of nitric acid and hydrogen peroxide, every 0.5g Java brucea medicinal material is used the effect of 5ml nitric acid and 2ml hydrogen peroxide best.
In said method, step and other follow-up clearing up in step, the preferred nitric acid of digestion solution of use are cleared up, cleared up for three times to secondary.The sample that every 0.5g samples adds digestion solution 1～10ml, more preferably 1ml digestion solution.
In said method, the described holding temperature of clearing up for the first time baking oven in step is 180～200 ℃, preferably 190 ℃; Temperature retention time is 10～14 hours, preferably 12 hours.
In said method, clearing up in step on electric hot plate heating described in preferably, to catch up with acid be to heat on 170～190 ℃ of electric hot plates, more preferably on 180 ℃ of electric hot plates, heats.
In said method, in described dissolving and constant volume step, the temperature of baking oven is preferably 105～115 ℃, more preferably 110 ℃; Temperature retention time preferably 3～10 hours, more preferably 4 hours.
constituent content is measured
According to method of the present invention, sample is processed to laggard row element and measure, described assay method can carry out according to the method for conventionally carrying out element determination in this area.
Instrument and the method for measuring at present constituent content mainly contain atomic absorption spectrography (AAS) (AAS), atomic fluorescence spectrometry (AFS), the chromatography of ions (IC), inductively coupled plasma emission spectrography (ICP-AES, ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), By Naa (INAA), x ray fluorescence spectrometry (XRF) etc.Measure in addition the determination of trace element instrument of specific sample and element-specific.In above these assay methods, inductively coupled plasma mass spectrometry have sensitivity the highest, once can measure multiple element, the advantage such as easy to use, the present invention is usingd inductively coupled plasma mass spectrometry as most preferred method, and other instrument and method or its various combinations are as less preferred or supplementary method.
ICP-MS measures preferably measuring by following condition of constituent content: RF power: between 1200w～1600w, preferred 1300w～1400w, cold gas flow velocity: 16L/min, assisted gas flow velocity: 1.0L/min, atomization gas flow velocity: 0.8L/min, sampling depth: 8mm, sampling spiroid aperture: 1.0mm, intercepting taper hole footpath: 0.7mm, sample promotes speed: 0.4ml/min, atomization temperature: 2 ℃.Under these conditions, adopt ICP-MS method, each element in sample is carried out to assay, every duplicate samples replicate determination 3 times, obtains constituent content result.
draw elemental fingerprints collection of illustrative plates
Each constituent content value of measuring is depicted as to elemental fingerprints collection of illustrative plates, and elemental fingerprints collection of illustrative plates comprises 2 kinds of collection of illustrative plates.
The first collection of illustrative plates is safe level finger-print, with the element in measurement result with safe level value, draws 2 curves, safe level curve and mensuration curve.Take element sequence number as horizontal ordinate, and the logarithm value of element limit value of take is ordinate, and the curve of drafting is safe level curve.Take element sequence number as horizontal ordinate, and the logarithm value of constituent content is ordinate, and the curve of drafting is for measuring curve (constituent content is 0ng/g or is meaningless by its logarithm value that measured value is calculated as negative value, counts without exception 0 in this case).Safe level collection of illustrative plates can judge in medicine, whether each element exceeds safe level, require to measure curve completely under safe level typical curve, if two have coincide point or point of crossing to be determined with element between curve, exceed safe level, for defective medicine or need to be applied to conditionally clinical.
The second collection of illustrative plates is constituent content finger-print, with the element of all mensuration, draw a curve, take element sequence number as horizontal ordinate, (constituent content is as 0ng/g or its logarithm value of being calculated as negative value by measured value are as meaningless as ordinate to take the logarithm value of constituent content, count without exception 0 in this case), draw constituent content curve.Constituent content finger-print can intuitive judgment and can be according to the content of each element in medicine, differentiates that the medicinal material true and false is good and bad, distinguishes the effect that the characteristics such as Changing Pattern of Chinese crude drug-extract-preparation are produced in medicinal material and substitute, the discriminating medicinal material place of production, reflection.
What mainly reflect due to chromatographic fingerprints of Chinese materia medica and spectrum fingerprint is the feature of organic compound in Chinese medicine, there is the effect of distinguishing the medicinal material place of production and the medicinal material true and false, but the difference due to the weather in each place of production each year (each crop cycle), rainfall amount, humidity, temperature, season alternation, sunshine-duration, wind direction, wind speed etc., the finger-print of reflection organic compound feature is not exclusively fixing, and spectrum and chromatographic fingerprinting all only have semiquantitative feature, this is a limitation of chromatogram and spectrum fingerprint.But because each micro-content in the earth's crust in each place of production of medicinal material is in a metastable state, in Chinese medicine Java brucea medicinal material, the Fingerprints of each element integral body is mainly subject to the impact in the Java brucea medicinal material place of production, plant the impact of content of the metal elements in soil of Java brucea medicinal material, therefore, reflect that the elemental fingerprints collection of illustrative plates of each place of production medicinal material elemental characteristic can belong to the place of production of medicinal material more accurately, and in elemental fingerprints collection of illustrative plates, the content of each element is accurate quantitative analysis, have the function of independent each constituent content of reflection concurrently, this is the essential thinking of this concept of finger-print: both reflected whole macrofeature, embody again the microscopic feature of each element.
Unknown medicinal material and each known place of production medicinal material, the elemental fingerprints graphs of genunie medicinal materials are carried out to similarity comparison, can judge medicinal material the place of production, whether be genuine piece, whether be genunie medicinal materials.
The more difficult difference of judging between medicinal material quality product and poor products of elemental fingerprints collection of illustrative plates, difference between quality product and poor products is mainly that the drug effect of medicine is good and bad, and the quality control direct relevant with drug effect is generally organic analysis, at this moment can be in conjunction with chromatogram, spectrum fingerprint and elemental fingerprints collection of illustrative plates comprehensive evaluation medicinal material.
the characteristics such as Changing Pattern of Chinese crude drug-extract-preparation are produced in reflection
Chinese crude drug obtains in the process of extract and preparation through steps such as extraction, preparations, in Chinese crude drug, each element there will be the attenuating of content or even disappearance (can't detect), also may occur due to the reason of technique the raising of some constituent contents, and between Study of Traditional Chinese Medicine material-extract-preparation, the Changing Pattern of elemental fingerprints collection of illustrative plates can be used as the means of accurate production control process stabilizing homogeneous.
The production technology of stable uniform must have stable elemental fingerprints collection of illustrative plates Changing Pattern, and this controls the reference that provides important and supplement for the traditional production run of carrying out with reference to quality standard.Also can avoid the element-specific that may exist in Chinese Traditional Medicine to pollute.
advantage of the present invention is:
1, digestion procedure provided by the invention, disturbs less, clears up completely, and accuracy of measurement is high, and applicable sample is extensive, is applicable to soil, medicinal material, extract and preparation thereof.The method has realized the multielement simultaneous determination of sample, by precision, repeatability, accuracy experimental result, has confirmed the content that the method can Accurate Determining 40 multiple elements.
2, of the present invention clear up and final compound method has realized the element of Chinese medical extract and preparation is accurately comprehensively measured, the utilization of the method is for the Changing Pattern of elemental fingerprints collection of illustrative plates between Study of Traditional Chinese Medicine material-extract-preparation, accurately controlling Chinese medicine and produce each link and all play an important role, is to weigh the whether important detection method of stable uniform of Product Process.
3, by the potential safety hazard of element, the form with finger-print accurately shows all sidedly in the present invention, and the safe level of element derives from standards of pharmacopoeia and the industry standard of various countries, can directly control product quality, has guaranteed clinical drug safety.
The similarity comparison of the elemental fingerprints collection of illustrative plates 4, obtaining by the present invention, judge medicinal material the place of production, whether be genuine piece, whether be that genunie medicinal materials are more accurate.
Accompanying drawing explanation
The safe level finger-print of Fig. 1 Java brucea medicinal material
The constituent content finger-print of Fig. 2 Java brucea medicinal material
Embodiment
(1) sample: the Java brucea medicinal material fine powder that takes about 0.5g;
(2) clear up in advance: fine powder is added in the teflon inner tube of high-pressure digestion tank, adds 2ml hydrogen peroxide (top grade is pure), soak 10 hours;
(3) clear up for the first time: by being equipped with in the above-mentioned teflon inner tube of clearing up in advance sample, directly add again 5ml nitric acid (high-grade pure), teflon inner tube is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, and the baking oven of putting into 190 ℃ is incubated 12 hours, cooling after taking out.Teflon inner tube is heated on 180 ℃ of electric hot plates and catch up with acid to micro-dry, cooling.
(4) dissolve and constant volume: by being equipped with, in the teflon inner tube of clearing up rear sample, add 10ml left and right ultrapure water, teflon inner tube is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, put into 110 ℃ of baking ovens and be incubated 4 hours, cooling after taking out, be diluted with water to 25ml.After shaking up, proceed in special plastic sample bottle, number to be measured.
Synchronously with standard substance, do retinue contrast, and do Whole Process blank, with ICP-MS, measure, the results are shown in following table:
Table 1 embodiment 1 element determination result
Massfraction: ng/g (10
-9)
Can't detect: Nd
comparative example 1
Step (1), (2), (4) are with embodiment 1, and step (3) is as follows:
(3) clear up for the first time: the baking oven of unencapsulated high-pressure digestion tank being put into 190 ℃ is incubated 12 hours, cooling after taking out.Teflon inner tube is heated on 180 ℃ of electric hot plates and catch up with acid to micro-dry, cooling.
Experiment, when proceeding to step (3), occurs that sample gelatinization, sample lose and cross pollution in a large number, causes experiment to proceed.
comparative example 2
Step (1), (2), (4) are with embodiment 1, and step (3) is as follows:
(3) clear up for the first time: high-pressure digestion potting is screwed well, and the baking oven of putting into 240 ℃ is incubated 12 hours, cooling after taking out.Teflon inner tube is heated on 180 ℃ of electric hot plates and catch up with acid to micro-dry, cooling.
Synchronously with standard substance, do retinue contrast, and do Whole Process blank, with ICP-MS, measure, the results are shown in following table:
Table 2 comparative example 2 element determination results
Massfraction: ng/g (10
-9)
Can't detect: Nd
comparative example 3
Step (1)～(3) are with embodiment 1, and step (4) is as follows:
(4) dissolve and constant volume: by being equipped with, in the teflon inner tube of clearing up rear sample, add 10ml left and right ultrapure water, teflon inner tube is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, put into 80 ℃ of baking ovens and be incubated 4 hours, cooling after taking out, be diluted with water to 25ml.After shaking up, proceed in special plastic sample bottle, number to be measured.
Synchronously with standard substance, do retinue contrast, and do Whole Process blank, with ICP-MS, measure, the results are shown in following table:
Table 3 comparative example 3 element determination results
Massfraction: ng/g (10
-9)
Can't detect: Nd
Brief summary: by above-mentioned experiment, can be found out, the first digestion procedure that the present invention uses, the basic free of losses of element, determination data is more parallel, and (RSD) is little for relative standard deviation, and result precision is high.
Sample dissolution after clearing up and constant volume process make to measure accurate stable more.
Step (1)～(3) are with embodiment 1, and step (4)～(6) are as follows:
(4) secondary is cleared up: by being equipped with in the teflon inner tube of clearing up for the first time rear sample, add 1ml nitric acid (high-grade pure), on 180 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling.
Clear up for (5) three times: in the sample after secondary is cleared up, again add 1ml nitric acid (high-grade pure), on 180 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling;
(6) dissolve and constant volume: by being equipped with, in the teflon inner tube of clearing up rear sample, add 10ml left and right ultrapure water, teflon inner tube is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, put into 110 ℃ of baking ovens and be incubated 4 hours, cooling after taking out, be diluted with water to 25ml.After shaking up, proceed in special plastic sample bottle, number to be measured.
Synchronously with standard substance, do retinue contrast, and do Whole Process blank, with ICP-MS, measure, the results are shown in following table:
Table 4 embodiment 2 element determination results
Massfraction: ng/g (10
-9)
Can't detect: Nd
Brief summary: owing to containing halogen in sample, these halogens can form a certain amount of halogen acid in digestion process, find that halogen acid has certain infringement to experimental apparatus, in mensuration process after two or three times are cleared up, halogen acid is further removed, and has reduced the infringement to instrument.
In addition, in experiment, also find, although the testing sample that Java brucea is cleared up for the first time is relatively clarified, some other traditional Chinese medicine samples are cleared up for the first time rear testing sample and are clarified not or have an inhomogeneous phenomenon, after two or three times are cleared up, sample can reach the uniform effect of clarification.
(1) sample: take the brucea fruit oil of about 0.5g, be added to the teflon inner tube of high-pressure digestion tank
In, add 5ml nitric acid (high-grade pure), 2ml hydrogen peroxide (top grade is pure);
(2) clear up for the first time: the teflon inner tube that above-mentioned sample is housed is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, the baking oven of putting into 210 ℃ is incubated 20 hours, cooling after taking out; Teflon inner tube is heated on 180 ℃ of electric hot plates and catch up with acid to micro-dry, cooling.
(3) secondary is cleared up: by being equipped with in the teflon inner tube of the sample after clearing up for the first time, add 1ml nitric acid (high-grade pure), on 180 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling;
Clear up for (4) three times: in the sample after secondary is cleared up, again add 1ml nitric acid (high-grade pure), on 180 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling;
(5) dissolve and constant volume: by being equipped with, in the teflon inner tube of clearing up rear sample, add 10ml left and right ultrapure water, teflon inner tube is put into high-pressure digestion tank, high-pressure digestion potting is screwed well, put into 100 ℃ of baking ovens and be incubated 10 hours, cooling after taking out, be diluted with water to 25ml.After shaking up, proceed in special plastic sample bottle, to be measured after numbering (or mark title).
Synchronously with standard substance, do retinue contrast, and do Whole Process blank, with ICP-MS, measure, the results are shown in following table:
Table 5 embodiment 3 element determination results
Massfraction: ng/g (10
-9)
Can't detect: Nd
(ginseng is one of time-honored rare Chinese medicine, and modern Chinese herbal medicine is learned research and shown, polysaccharide is the effective constituent of ginseng, and its pharmacological activity is embodied in many aspects, as antitumor, hypoglycemic, antifatigue, anti-oxidant and immunological regulation etc. to get panaxan.
panaxan be take the effective part extract that the polysaccharide that extracts from ginseng is principal ingredient), according to the step of embodiment 2, carry out element determination, result is as follows:
Table 6 embodiment 4 element determination results
Massfraction: ng/g (10
-9)
Can't detect: Nd
By the element determination result of Java brucea in embodiment 2, draw elemental fingerprints collection of illustrative plates.
The drafting of safe level finger-print: draw 2 curves with the element in measurement result with safe level value, safe level curve and mensuration curve.Take element sequence number as horizontal ordinate, and the logarithm value of element limit value of take is ordinate, and the curve of drafting is safe level curve.Take element sequence number as horizontal ordinate, and the logarithm value of constituent content is ordinate, and the curve of drafting is for measuring curve (constituent content is 0ng/g or is meaningless by its logarithm value that measured value is calculated as negative value, counts without exception 0 in this case).Safe level collection of illustrative plates can judge in medicine, whether each element exceeds safe level, require to measure curve completely under safe level typical curve, if two have coincide point or point of crossing to be determined with element between curve, exceed safe level, for defective medicine or need to be applied to conditionally clinical.
The drafting of constituent content finger-print: draw a curve with the element of all mensuration, take element sequence number as horizontal ordinate, (constituent content is as 0ng/g or its logarithm value of being calculated as negative value by measured value are as meaningless as ordinate to take the logarithm value of constituent content, count without exception 0 in this case), draw constituent content curve.Constituent content finger-print can intuitive judgment and can be according to the content of each element in medicine, differentiates that the medicinal material true and false is good and bad, distinguishes the effect that the characteristics such as Changing Pattern of Chinese crude drug-extract-preparation are produced in medicinal material and substitute, the discriminating medicinal material place of production, reflection.
Claims (30)
1. a method for working sample constituent content, described sample is selected from Chinese crude drug, Chinese medical extract, soil or containing the pharmaceutical composition of Chinese medical extract, said method comprising the steps of:
Sample step: take Chinese crude drug, Chinese medical extract, soil or containing the pharmaceutical composition of Chinese medical extract;
The optional step of clearing up in advance: optionally will sample the sample of step, add digestion solution immersion 2～20 hours;
Clear up for the first time step: by the container of clearing up for the first time sample is housed, airtight, the baking oven of putting into 180～210 ℃ is incubated 10～24 hours, cooling after taking out, container is uncovered, and on 170～190 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling,
The described sample of clearing up is for the first time:
A) clear up in advance after step is soaked and add digestion solution to obtain; Or
B) will sample the sample of step acquisition, add digestion solution to obtain;
Dissolve and constant volume step: by being equipped with in the container of the sample after clearing up, add ultrapure water, airtight, put into 100～115 ℃ of baking ovens and be incubated 3～10 hours, take out coolingly afterwards, after thin up constant volume, obtain testing sample;
The sample dissolving and constant volume step obtains is carried out to element determination.
2. the method for claim 1, is characterized in that, when described working sample is Chinese crude drug, clears up in advance step.
3. the method for claim 1, is characterized in that, described Chinese crude drug, Chinese medical extract or be respectively Java brucea medicinal material or brucea fruit oil or containing the pharmaceutical composition of brucea fruit oil containing the pharmaceutical composition of Chinese medical extract.
4. method as claimed in claim 3, is characterized in that, said method comprising the steps of:
Sample step: take Java brucea medicinal material, brucea fruit oil, soil or containing the sample 0.1 ~ 1g of the pharmaceutical composition of brucea fruit oil;
The optional step of clearing up in advance: optionally will sample the sample of step, add digestion solution immersion 2～20 hours;
Clear up for the first time step: by the container of clearing up for the first time sample is housed, airtight, the baking oven of putting into 180～210 ℃ is incubated 10～24 hours, cooling after taking out, container is uncovered, and on 170～190 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling,
The described sample of clearing up is for the first time:
A) clear up in advance after step is soaked and add digestion solution to obtain; Or
B) will sample the sample of step acquisition, add digestion solution to obtain;
Dissolve and constant volume step: by being equipped with in the container of the sample after clearing up, add ultrapure water, airtight, put into 100～115 ℃ of baking ovens and be incubated 3～10 hours, take out coolingly afterwards, thin up constant volume, shakes up rear to be measured;
The sample that dissolves the acquisition of constant volume step is carried out to element determination.
5. method as claimed in claim 4, is characterized in that, described method takes Java brucea medicinal material, brucea fruit oil, soil or contains the sample 0.35g ~ 1g of the pharmaceutical composition of brucea fruit oil.
6. method as claimed in claim 5, is characterized in that, described method takes Java brucea medicinal material, brucea fruit oil, soil or contains the sample 0.5g of the pharmaceutical composition of brucea fruit oil.
7. method as claimed in claim 4, is characterized in that, described clearing up in advance in step when sample is Java brucea medicinal material, soaks 10 hours.
8. the method as described in claim 1-7 any one, it is characterized in that described dissolving and constant volume step operate in the following manner: add 10ml ultrapure water, put into 100～115 ℃ of baking ovens and be incubated 3～10 hours, cooling after taking out, be diluted with water to 25ml, shake up rear to be measured.
9. method as claimed in claim 8, is characterized in that described dissolving and constant volume step use plastic bottle constant volume.
10. the method as described in claim 1-7 any one, is characterized in that, the described temperature of clearing up for the first time the insulation of step is 180～190 ℃.
11. methods as claimed in claim 10, is characterized in that, the described temperature of clearing up for the first time the insulation of step is 190 ℃.
12. methods as described in claim 1-7 any one, is characterized in that, described to clear up for the first time the time being incubated in step be 10 ~ 14 hours.
13. methods as claimed in claim 12, is characterized in that, described to clear up for the first time the time being incubated in step be 12 hours.
14. methods as described in claim 1-7 any one, is characterized in that, the temperature being incubated in described dissolving and constant volume step is 105～115 ℃.
15. methods as claimed in claim 14, is characterized in that, the temperature being incubated in described dissolving and constant volume step is 110 ℃.
16. methods as described in claim 1-7 any one, is characterized in that, the time of described dissolving and the insulation of constant volume step is 4 hours.
17. methods as described in claim 1-7 any one, is characterized in that, described method is carried out secondary and cleared up step after clearing up for the first time: will clear up for the first time rear sample and add digestion solution, on 170～190 ℃ of electric hot plates, heating catches up with acid to micro-dry, cooling.
18. methods as claimed in claim 17, is characterized in that, described method carries out clearing up step three times after secondary is cleared up step: in the sample after secondary is cleared up, add digestion solution, catch up with acid to micro-dry, cooling on 170～190 ℃ of electric hot plates.
19. methods as claimed in claim 18, is characterized in that, described method is carried out one or many again and cleared up after clearing up step three times.
20. methods as described in claim 1-7 any one claim, is characterized in that, described in clear up in step on electric hot plate heating to catch up with acid be to heat on 180 ℃ of electric hot plates.
21. methods as claimed in claim 4, is characterized in that, clear up in advance step when working sample is Java brucea medicinal material, and the described digestion solution of clearing up in advance step is used hydrogen peroxide immersion to clear up in advance.
22. methods as claimed in claim 21, is characterized in that, adopt 2ml hydrogen peroxide/0.5g Java brucea medicinal material to carry out hydrogen peroxide immersion and clear up in advance.
23. methods as claimed in claim 4, when the described sample of clearing up is for the first time brucea fruit oil, described first digestion solution is nitric acid or hydrogen peroxide; When described sample is the Java brucea medicinal material of clearing up in advance after step, digestion solution is nitric acid.
24. methods as claimed in claim 23, when the described sample of clearing up is for the first time brucea fruit oil, first digestion solution is the combination of nitric acid and hydrogen peroxide, every 0.5g brucea fruit oil is used 5ml nitric acid and 2ml hydrogen peroxide; When described sample is the Java brucea medicinal material of clearing up in advance after step, every 0.5g Java brucea medicinal material is used 5ml nitric acid.
25. methods as claimed in claim 17, is characterized in that, when other after clearing up are for the first time cleared up step, the sample that every 0.5g samples adds 1 to 10ml digestion solution.
26. methods as claimed in claim 25, is characterized in that, when other after clearing up are for the first time cleared up step, the sample that every 0.5g samples adds 1ml digestion solution.
27. methods as claimed in claim 25, is characterized in that, when other after clearing up are for the first time cleared up step, described digestion solution is nitric acid.
28. methods as described in claim 18 or 19, is characterized in that, when other after clearing up are for the first time cleared up step, the sample that every 0.5g samples adds 1 to 10ml digestion solution.
29. methods as claimed in claim 28, is characterized in that, when other after clearing up are for the first time cleared up step, the sample that every 0.5g samples adds 1ml digestion solution.
30. methods as claimed in claim 29, is characterized in that, when other after clearing up are for the first time cleared up step, described digestion solution is nitric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210029994.0A CN102590180B (en) | 2011-10-31 | 2012-02-11 | Method for detecting element of Chinese medicine, Chinese medicinal extract, soil or medicinal composition containing Chinese medicinal extract |
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| CN201110336073.4 | 2011-10-31 | ||
| CN201110336073 | 2011-10-31 | ||
| CN201210029994.0A CN102590180B (en) | 2011-10-31 | 2012-02-11 | Method for detecting element of Chinese medicine, Chinese medicinal extract, soil or medicinal composition containing Chinese medicinal extract |
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| CN109632930B (en) * | 2018-12-29 | 2022-01-25 | 上海微谱化工技术服务有限公司 | Analysis method for compatibility of midazolam and production system |
| CN109632931B (en) * | 2018-12-29 | 2021-07-30 | 上海微谱化工技术服务有限公司 | Analysis method of midazolam preparation |
| CN110412018A (en) * | 2019-09-09 | 2019-11-05 | 华东师范大学 | The detection method of P elements in a kind of plant |
| CN110632162B (en) * | 2019-09-11 | 2021-07-27 | 山西大学 | Method for identifying wild astragalus and cultivated astragalus in ground |
| CN110702773B (en) * | 2019-11-20 | 2020-11-03 | 武汉上谱分析科技有限责任公司 | Method for measuring Pb isotope ratio in sulfide by using MC-ICP-MS |
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