CN102375043A - Detection method for volatile substances in rubber plug - Google Patents
Detection method for volatile substances in rubber plug Download PDFInfo
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- CN102375043A CN102375043A CN2010102636155A CN201010263615A CN102375043A CN 102375043 A CN102375043 A CN 102375043A CN 2010102636155 A CN2010102636155 A CN 2010102636155A CN 201010263615 A CN201010263615 A CN 201010263615A CN 102375043 A CN102375043 A CN 102375043A
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Abstract
The invention provides a detection method for volatile substances in a rubber plug, which comprises the following steps of: 1) constructing a database for volatile substances in the rubber plug; and 2) determining the volatile substances in the rubber plug to be detected. The detection method for the volatile substances in the rubber plug has the advantages that two groups of data can be obtained at the same time when one specimen is detected in one experiment, the test time of qualitative screening is greatly saved and the interference of co-shown peaks can be effectively eliminated; by constructing the database for the volatile substances in the rubber plug, the volatile substances in the rubber plug can be screened rapidly and comprehensively, the database is not limited to specific varieties and the database is a universal database; and moreover, the method provided by the invention is easy to popularize.
Description
Technical field
The present invention relates to the detection method of cartridge bag material component, specifically, relate to the detection method of volatile matter in the plug.
Background technology
Volatile matter in the plug is meant some compositions that in the production run of plug, add for the durability of the usability of improving plug and plug itself.Above-mentioned volatile matter (as: BHT, tygon fat, stearic acid, silicone oil etc.) can evaporate in the use of plug, and particularly the volatile matter in the medical rubber plug can pollute medicine.When if contained above-mentioned volatile matter level is higher than safety value in the medicine, will influences the quality of medicine and human body is produced harm.
The difficult point that volatile matter in the plug is controlled is that the volatile matter in the plug of same breed has uncertainty.This is because different production enterprise can adopt the plug of different prescriptions and production technology production same breed; And the production technology of plug is also constantly changing improvement; Make the volatile matter in the plug constantly change, therefore setting up comprehensively fast, detection system is the trend that the plug volatile matter is measured.
At present; Domestic needleless still is to the detection method of plug volatile matter; Pharmacopeia is used vapor-phase chromatography (GC) always and the residual solvent in the medicine is detected (residual solvent also is volatile; But be different from the volatile matter in the plug), as " detection method of 2010 editions recommendations of Chinese pharmacopoeia is the head space capillary gas chromatography.Qualitative analysis in the vapor-phase chromatography mainly is according to retention time, and this needs to compare with the retention time of known standard substance, still for unknown peak, then is difficult to carry out qualitative analysis.
In addition; When detecting the volatile matter that contains in the plug with conventional vapor-phase chromatography; Because the volatile species in the plug is more, the retention time of different volatile matter on a root chromatogram column maybe be identical or close, and this has all brought difficulty for the qualitative and quantitative test of volatile matter.
Summary of the invention
The object of the present invention is to provide a kind of method that detects volatile matter in the plug efficiently, accurately.
To achieve these goals, the detection method of volatile matter in the plug of the present invention, it comprises the steps:
1) foundation of database
A, with opposite polarity two chromatographic columns the volatile matter of building in the sample of storehouse being carried out gas chromatographic analysis, is reference material with DBPC 2,6 ditertiary butyl p cresol (BHT) then, calculates the relative retention time of each chromatographic peak respectively;
B and then the said volatile matter of building in the sample of storehouse is carried out the gas chromatography mass spectrometry analysis with said opposite polarity two chromatographic columns carries out qualitative analysis to the said volatile matter of building in the sample of storehouse respectively, confirms kind under it;
C, add internal standard compound said building in the sample of storehouse, repeating step a, b, then with on the gas chromatography detector via said opposite polarity two chromatographic peaks that chromatographic column obtains, respectively with mass detector on the peak that obtains carry out the similarity coupling;
D, according to the similarity matching result of step c, set up the peak-to-peak corresponding relation of chromatogram of said opposite polarity two chromatographic columns, and and mass spectrogram between corresponding relation, and sort out, thereby set up database according to mass spectrum;
2) mensuration of volatile matter in the plug to be measured
E, the volatile matter in the plug to be measured is carried out gas chromatographic analysis, and calculate the relative retention time of each chromatographic peak of two chromatographic columns according to step a method with said opposite polarity two chromatographic columns;
F, the relative retention time that step e is obtained are compared with the database of step 1), thus the kind of the volatile matter of confirming to contain in the plug to be measured.
Wherein, the said storehouse sample of building comprises known various plugs such as butyl rubber plug, brominated butyl rubber plug and chlorinated butyl plug; Can also comprise tygon fat, phenolics, stearic acid, brominated butyl rubber plug virgin rubber, the various supplementary materials of existing plugs such as chlorinated butyl plug virgin rubber and Russian glue.
Said internal standard compound is benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol or BHT etc.
Said opposite polarity two chromatographic columns are meant two opposite polarity chromatographic columns of parallel connection in gas chromatography, are preferably nonpolar chromatographic column and polarity chromatographic column.Wherein, said nonpolar chromatographic column comprises that stationary phase is the chromatographic column of polyoxy silane or poly dimethyl silane, like the nonpolar chromatographic column of SPB-1 type of Supelco company production; Said polarity chromatographic column comprises that stationary phase is the chromatographic column that polyglycol-nitro terephthalic acid (TPA) is modified, like the HP-FFAP type polarity chromatographic column of Agilent company production.
The chromatographic condition of gas chromatography is among the step a:
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5: 1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
The gas chromatography mass spectrometry chromatographic condition is among the step b:
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 1.0mL/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
Similarity coupling of the present invention is to use chromatographic fingerprints of Chinese materia medica similarity evaluation system (2004A version; Chinese Pharmacopoeia Commission) carries out similarity analysis; Similarity is at the peak that can think more than 800 to be complementary, and the calculating principle of said similarity analysis is an included angle cosine.
In addition, in order to verify the repeatability of the inventive method, can also after setting up database, increase the step of the time window of confirming every kind of volatile matter.
The inventive method has increased a binary channels or three-channel isocon behind the sampling system of gas chromatography; Each passage has independently its circulation of switch control; At least side by side connect two opposite polarity chromatographic columns behind the isocon; Thereby realized the purpose of two opposite polarity chromatographic columns of parallelly connected use; It can guarantee sample introduction sample and conforming while of sampling condition, and making has the retention time that differs bigger at the volatile matter that retention time is identical or close on the root chromatogram column on opposite polarity chromatographic column.
Specifically, the gas chromatography of using in the inventive method, when using twin-channel isocon, what connect side by side with it is two opposite polarity chromatographic columns; When using three-channel isocon, connect side by side with it except above-mentioned opposite polarity chromatographic column, also have mass spectrometry system, make mass spectrometry system and gas chromatography constitute the analytic system that operates side by side.
Said isocon can be the isocon of operable material preparation in the existing chromatographic apparatuss such as glass tube, stainless-steel tube, to not special restriction such as its shape, size, can select according to the instrument of different model.Said isocon can be applied in the gas chromatography removably; Also can be fixed in gas chromatograph or the gas chromatography mass spectrometry instrument, select different detection system through the switch of controlling each passage this moment, for example is single chromatographic column, two chromatographic column or gas phase and mass spectrum and use detection system.
Detection method of the present invention; Deficiency to prior art; Opposite polarity two chromatographic columns parallel connection is used; Guaranteeing sample introduction sample and conforming while of sampling condition, making has the retention time that differs bigger at the volatile matter that retention time is identical or close on the root chromatogram column on opposite polarity chromatographic column.Retention time and database through after two root chromatogram columns are measured compare, and the result can not have to carry out qualitative analysis under the situation of standard items, tentatively confirm the kind of volatile matter in the medical rubber plug, thereby have avoided unknown peak is carried out the blindness screening.When the unknown chromatographic peak of appearance in the measuring process needs further to confirm, can use the mass spectrometry system parallelly connected to detect simultaneously with chromatogram column system, comprehensive income result confirms.
In addition; Because different with the retention time of a kind of volatile matter on the different chromatographic column of polarity, relative retention time is also different, therefore confirms the retention time of same volatile matter on two kinds of chromatographic columns through the coupling mass spectrum; And connect these two retention times; Form a system of evidence each other, and the structural formula that provides through mass spectral NIST database, and name with the organic compound nomenclature; Thereby volatile matter is sorted out, thereby set up the database of plug volatile matter.
The invention has the advantages that the inventive method can make same sample once obtaining two groups of data simultaneously in the experiment, has saved the test period of qualitative screening greatly, and can effectively get rid of the interference that goes out the peak altogether; Through setting up the database of plug volatile matter, can screen the plug volatile matter all sidedly fast, be not limited to concrete kind, be universal database; In addition, the inventive method is easy to promote.
Description of drawings
Fig. 1 is a binary channels parallel connection chromatogram column system mode chart;
Fig. 2 is a plug volatile matter polarity chromatographic system match collection of illustrative plates;
Fig. 3 is the nonpolar chromatographic system match of a plug volatile matter collection of illustrative plates.
Embodiment
Below further specify the present invention through specific embodiment, but be not used for limiting scope of the present invention.
The foundation of embodiment 1 plug volatile matter database
Instrument and software 1: (gas phase)
Trace GC Ultra (power & light company); Headspace system (power & light company); DAS is Xcalibur data handling system (power & light company); Chromatographic column: the nonpolar chromatographic column of SPB-1 type (30m * 0.32mm * 1um, supelco), HP-FFAP type polarity chromatographic column (30m * 0.32mm * 0.52um, Agilent company), it is as shown in Figure 1 that each parts connects synoptic diagram.
Chromatographic condition 1: (gas phase)
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5: 1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
Instrument and software 2: (gas chromatography mass spectrometry)
Trace GC Ultra-Polaris Q (power & light company); Headspace system (power & light company); DAS is Xcalibur data handling system (power & light company); Chromatographic column: the nonpolar chromatographic column of SPB-1 type (30m * 0.25mm * 0.25um, supelco), HP-FFAP type polarity chromatographic column (30m * 0.25mm * 0.25um, Agilent company).
Chromatographic condition 2: (gas chromatography mass spectrometry)
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 1.0ml/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
The configuration of BHT reference material: precision takes by weighing 5mgBHT, analyzes pure sodium chloride with 50g and in mortar, mixes and develop evenly, processes the reference substance of concentration 0.1 μ g/mg.
Build the storehouse sample: chlorinated butyl rubber bung (Jiangyin Lan Ling, Shandong medicine glass), chlorinated butyl rubber bung (rich medical material incorporated company, Anhui Hua Feng, south, the Chengdu ring of giving birth in Jiangsu), butyl rubber bung (Chongqing San Hai Lan Ling company).
Internal standard compound: benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol and DBPC 2,6 ditertiary butyl p cresol.
Step:
(1) above-mentioned given chromatographic condition 1 time, measure the dead time with methane, measure respectively and build the retention time of volatile matter on polarity and nonpolar chromatographic column (two chromatographic systems) in the sample of storehouse; As reference, calculate the adjustment relative retention time of every kind of volatile matter with the adjustment retention time of BHT, the result sees table 1, wherein T
R(min) be retention time, RART is the adjustment relative retention time;
(2) above-mentioned given chromatographic condition 2 times, with mass detector the volatile matter in the above-mentioned standard model is detected, the result sees table 2;
(3) in standard model, add multiple different internal standard compound; Repeating step (1), (2); Respectively the polarity of parallel connection and nonpolar chromatogram column system are mated at the peak with the volatile matter that on mass detector, obtains, the peak of the volatile matter that obtains on the fid detector then, the result sees table 3～4;
Said coupling is to carry out similarity analysis with chromatographic fingerprints of Chinese materia medica similarity evaluation system (2004A version, Chinese Pharmacopoeia Commission), and similarity is at the peak that can think more than 800 to be complementary;
(4) then according to matching result; Set up the peak-to-peak corresponding relation (as shown in table 5) of the volatile matter of standard model in opposite polarity two chromatographic columns; And and mass spectrogram between corresponding relation; And according to mass spectrum volatile matter is sorted out, thereby setting up volatile matter database in the plug, the result is as shown in table 6;
(5) confirm every kind of volatile matter time window, with the repeatability of checking the inventive method, the result sees table 7.
In table 1 gas phase plug volatile matter retention time and relative retention time
In table 2 gas chromatography mass spectrometry plug volatile matter retention time
The nonpolar system matches result of table 3
Table 4 polar system matching result
Nonpolar system of table 5 and polar system corresponding relation
Classes of compounds under the nonpolar system of table 6 peak of corresponding volatile matter with polar system
Table 7 time window
As stated, table 6 is the plug volatile matter database among the present invention.On this basis; We only need carry out gas chromatographic detection with opposite polarity two chromatographic columns of parallel connection to plug to be measured; The relative retention time and the above-mentioned database of opposite polarity two chromatographic columns that will obtain are then compared; Just can not have standard items, need not carry out under the situation of Mass Spectrometer Method the kind of the volatile matter in the qualitative analysis plug yet.
In addition, after the kind of having known these volatile matter, just can be through analysis to the auxiliary material used in the plug production run; Know the possible source of volatile matter; Come from auxiliary material tygon fat such as straight or branched alkane major part, and straight or branched ketone compounds major part comes from auxiliary material stearic acid or the like, just can affirm the existence of certain compound again through corroborating each other of double-colored spectrum column system; Thereby the prescription of control plug, the quality of grasp plug.
The mensuration of volatile constituent in embodiment 2 chlorinated butyl rubber bungs
The source of test sample: the rich lot number of giving birth in 1 Jiangsu: 09051314
2 Anhui Hua Feng lot number: S090502573
South, 3 Chengdu ring lot number: 090506
The preparation of test sample: an amount of chlorinated butyl rubber bung is shredded, place 20ml head space gas phase bottle, and seal and gland packing with plug to be measured.
The configuration of BHT reference material: precision takes by weighing 5mg BHT, analyzes pure sodium chloride with 50g and in mortar, mixes and develop evenly, processes the reference substance of concentration 0.1 μ g/mg.
Head space condition and chromatographic condition be with embodiment 1, measures the retention time of volatile constituent in retention time and the need testing solution of BHT respectively, compares with the database of embodiment 1 gained then.Measurement result is seen table 8～9; See table 10～12 with the database comparative result.
Table 8SPB-1 chromatographic system result
Annotate: the retention time of methane is that the retention time of 1.623min BHT is 27.741min
Table 9HP-FFAP chromatographic system result
Annotate: the retention time of methane is that the retention time of 1.220min BHT is 23.217min
The result that table 10 is compared with the database of embodiment 1 gained
The result that table 11 is compared with the database of embodiment 1 gained
The result that table 12 is compared with the database of embodiment 1 gained
Can find out by table 8～12, the rich chlorinated butyl rubber bung of producing in Jiangsu, its volatile matter is straight or branched ketone compounds, straight or branched alkane and alkane substituting group phenol; And the chlorinated butyl rubber bung that Anhui Hua Feng produces, its volatile matter is straight or branched ketone compounds, alkane substituting group benzene, straight or branched alkane and silica compounds; And the chlorinated butyl rubber bung that south, Chengdu ring is produced, its volatile matter is straight or branched ketone compounds, straight or branched alkane and enols used.
Therefore; Though can find out and be all one big type of plug; Also maybe be because difference or the difference on the synthesis technique on the prescription cause containing different volatile substance; But the database of setting up through the inventive method can find certain rules in various volatile matter, and feasible refinement to the plug quality control becomes possibility.
Though, with general explanation and embodiment, the present invention has been done detailed description in the preceding text, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (8)
1. the detection method of volatile matter in the plug, it comprises the steps:
1) foundation of database
A, with opposite polarity two chromatographic columns the volatile matter of building in the sample of storehouse being carried out gas chromatographic analysis, is reference material with the DBPC 2,6 ditertiary butyl p cresol then, calculates the relative retention time of each chromatographic peak respectively;
B and then the said volatile matter of building in the sample of storehouse is carried out the gas chromatography mass spectrometry analysis with said opposite polarity two chromatographic columns carries out qualitative analysis to the said volatile matter of building in the sample of storehouse respectively, confirms kind under it;
C, add internal standard compound said building in the sample of storehouse, repeating step a, b, then with on the gas chromatography detector via said opposite polarity two chromatographic peaks that chromatographic column obtains, respectively with mass detector on the peak that obtains carry out the similarity coupling;
D, according to the similarity matching result of step c, set up the peak-to-peak corresponding relation of chromatogram of said opposite polarity two chromatographic columns, and and mass spectrogram between corresponding relation, and sort out, thereby set up database according to the mass spectrum result;
2) mensuration of volatile matter in the plug to be measured
E, the volatile matter in the plug to be measured is carried out gas chromatographic analysis, and calculate the relative retention time of each chromatographic peak of two chromatographic columns according to step a method with said opposite polarity two chromatographic columns;
F, the relative retention time that step e is obtained are compared with the database of step 1), thus the kind of the volatile matter of confirming to contain in the plug to be measured.
2. detection method according to claim 1 is characterized in that, the said storehouse sample of building comprises butyl rubber plug, brominated butyl rubber plug and chlorinated butyl plug.
3. detection method according to claim 1 and 2 is characterized in that, the said storehouse sample of building also comprises tygon fat, phenolics, stearic acid, brominated butyl rubber plug virgin rubber, chlorinated butyl plug virgin rubber and Russian glue.
4. detection method according to claim 1 is characterized in that, said internal standard compound is benzene, toluene, butyl acetate, tetralin, normal butyl alcohol, n-amyl alcohol or DBPC 2,6 ditertiary butyl p cresol.
5. detection method according to claim 1 is characterized in that, said opposite polarity two chromatographic columns are meant two opposite polarity chromatographic columns of parallel connection in gas chromatography.
6. detection method according to claim 5 is characterized in that, said opposite polarity two chromatographic columns are nonpolar chromatographic column and polarity chromatographic column.
7. according to any described detection method of claim 1, it is characterized in that the chromatographic condition of gas chromatography described in the step a is:
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 2.0mL/min; Carrier gas: helium; Split ratio: 5: 1; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
8. according to any described preparation method of claim 1, it is characterized in that the chromatographic condition of gas chromatography mass spectrometry described in the step b is:
Temperature programme: 40 ℃ keep 10min, rise to 170 ℃ and keep 10min with the speed of 10 ℃/min then; Injector temperature: 200 ℃; Constant flow rate: 1.0mL/min; Do not shunt; Detector temperature: 250 ℃; Head space temperature: 150 ℃; The head space time: 30min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108828123A (en) * | 2018-06-26 | 2018-11-16 | 安徽皖维高新材料股份有限公司 | A kind of method of butyraldehyde and para-acetaldehyde content in measurement polyvinyl butyral resin |
| CN111077237A (en) * | 2018-10-22 | 2020-04-28 | 山东省医疗器械产品质量检验中心 | Gas chromatography detection method for medicine compatibility of medicinal butyl rubber plug |
-
2010
- 2010-08-25 CN CN201010263615.5A patent/CN102375043B/en active Active
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| FA ZHANG ETAL: "Structural identification of extractables from rubber closures used for pre-filled semisolid drug applicator by chromatography mass spectrometry, and organic synthesis", 《JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS》 * |
| 刘颖: "药品残留溶剂测定知识库的基础研究与应用", 《中国博士学位论文全文数据库》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108828123A (en) * | 2018-06-26 | 2018-11-16 | 安徽皖维高新材料股份有限公司 | A kind of method of butyraldehyde and para-acetaldehyde content in measurement polyvinyl butyral resin |
| CN108828123B (en) * | 2018-06-26 | 2020-06-02 | 安徽皖维高新材料股份有限公司 | Method for measuring content of butyraldehyde and paraldehyde in polyvinyl butyral resin |
| CN111077237A (en) * | 2018-10-22 | 2020-04-28 | 山东省医疗器械产品质量检验中心 | Gas chromatography detection method for medicine compatibility of medicinal butyl rubber plug |
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