CN104316605B - Ester type compound and homologue thereof and the authentication method of isomer and application - Google Patents
Ester type compound and homologue thereof and the authentication method of isomer and application Download PDFInfo
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Abstract
The invention discloses ester type compound and homologue thereof and the authentication method of isomer and application.The present invention creatively sums up the GC retention time obtaining ester type compound and its Topological Index linear correlation, provide the corresponding relation formula of chromatographic retention T and Topological Index Q, and combine gas chromatogram FID/ infrared spectrum (GC FID/IR) or gaschromatographic mass spectrometry (GC MS), successfully realize the precise Identification of ester type compound and homologue thereof and isomer.The inventive method can be advantageously applied in the complex samples such as essence and flavoring agent ester type compound and homologue thereof and the accurate Analysis and Identification of isomer, and result is accurate, method is simple.
Description
Technical field
The present invention relates to the identification and detection technical field of ester type compound and homologue thereof and isomer, more particularly, to ester type compound and homologue thereof and the authentication method of isomer and the application in terms of essence and flavoring agent Related Component qualification thereof.
Background technology
Development along with Gas chromatographyMass spectrometry (GC-MS), mass spectrum spectrum storage capacity constantly expands, GC-MS has become the conventional means of the numerous areas compound isolation identification such as food, environment, medicine in recent years, and the separation of tobacco chemistry component, essence and flavoring agent and cigarette smoke volatile component is analyzed also based on GC/MS method.While it is true, the different ions mode of mass spectrography and mass separation technology have its limitation, some compound EI(Yu GC often associated with Ionization mode) do not produce molecular ion peak under ionization mode；Utilize library searching typically can only provide the possible matter of matching of certain composition, but the EI mass spectrum of some constitutional isomers is the most similar, rely solely on the result that GC-MS obtains and compound is carried out qualitative the most abundant.
Infrared spectrum has the title of compound " fingerprint ", and its specificity is strong, is provided that abundant molecular structure information, is to identify organic compound and the important tool of structural analysis.But infrared spectrometry is only applicable to pure compound in principle, the most helpless for the qualitative of mixture and identification and analysis.Both technology are taken its chief by gas chromatogram-infrared spectrum (GC-IR) multiple techniques, the high efficiency separation ability of gas chromatogram will combine with the Structural Identification ability of infrared spectrum, have obvious superiority at aspects such as the isolation identification of isomer, unknown material Analysis and Identification.But GC-IR sensitivity is relatively low, and compound functional group can only be sorted out, greatly limit the method and mate the suitability in homologue and isomer analysis and GC-MS method.
Tobacco aromatics using is the product occurred with cigarette industry development, is high, smart, the crystallization of new technique.Tobacco essence is requisite material in production of cigarettes, and the core technology of its formula cigarette enterprise especially is improving the mouthfeel of Medicated cigarette, and prominent Nicotiana tabacum L. style aspect has important effect.Ester perfume compound has extraordinary effect to Medicated cigarette fragrance.Esters conventional in Nicotiana tabacum L. and lactone spice have Ethyl formate, amyl formate, butyl acetate, Cedryl acetate., phenylethyl propionate, C-butyrolactone, C-caprolactone, C-caprylolactone etc..Different ester type compounds is that the fragrance that Medicated cigarette increases is different, and it is fragrant that some ester type compounds can increase cigarette, especially animal perfume and solid sense, fragrant and sweet and the refrigerant fragrance that some increases are strong, flavouring cigarette product can be made to increase fresh and sweet characteristic, and extend the shelf life, have plenty of cigarette flavor precursors etc..So accurately Analysis and Identification ester type compound has great importance.
For ester type compound and homologue thereof and isomer, especially the ester type compound in essence spice for cigarette and homologue thereof and isomer, lack at present and can be combined that carry out, simple and that can accurately realize its identification and analysis technical scheme and relevant technical motivation with methods such as existing conventional GC IR, GC-MS.
Summary of the invention
The purpose of the present invention is based on above-mentioned the deficiencies in the prior art and provides the authentication method of a kind of ester type compound and homologue thereof and isomer, by the judgement to the gas chromatography retention time of ester type compound with its compound structure corresponding relation, be combined with gas chromatography-mass spectrum GC-MS and gas chromatogram-flame ionization ditector/infrared spectrum (GC-FID/IR) method, can corresponding ester type compound in Rapid identification (GC-MS) and GC-FID/IR method, simple, accurately.
Another technical problem that the invention solves the problems that is to provide the application in the complex samples such as essence and flavoring agent in terms of the identification and analysis of ester type compound and homologue and isomer of the described method.
It is an object of the invention to be achieved through the following technical solutions:
The authentication method of a kind of ester type compound and homologue thereof and isomer is provided, comprises the following steps:
S1. the standard sample of ester type compound gas chromatography (GC) is analyzed, obtain the chromatographic retention T of each compound standard sample；
S2. its Topological Index Q is determined according to the structure of ester type compound described in S1；
S3. Criterion sample chromatogram retention time T and the corresponding relation formula of Topological Index Q；
S4. it is calculated the chromatographic retention of ester type compound to be identified in testing sample according to corresponding relation formula, judges to determine ester type compound in conjunction with GC-MS data base and GC-IR functional group；
Wherein, the chromatographic retention T of ester type compound and the corresponding relation formula of Topological Index Q are T=aQ+b, and wherein a, b are constant, are determined with its Topological Index by the retention time of standard sample.
Preferably, the chromatographic retention of described ester type compound is obtained by GC with FID, the detection of IR or MS detector method for combined use.
Preferably, Topological Index Q in described corresponding relation formula is on the basis of non-hydrogen atom point is worth, and the point of definition bonding atom chemistry characteristic is worth δ, and based on Molecular Graphs adjacency matrix, the topological index Q=∑ (δ new by δ constructioni*δj*δk…)0.5, wherein δi=bi(n-1)+∑hij, biBonding electrons number for atom i；N is the principal quantum number of atom i；∑hijFor the hydrogen atom sum being bonded on the atom j that is joined directly together with i.
Preferably, GC-MS analysis condition is: standard specimen concentration 50 mg/L, 10:1 split sampling, sample size 1 μ L；HP-VOC chromatographic column (60 mm × 1.80, m × 0.32 μm)；Carrier gas is He, flow velocity 1 mL/min；Injector temperature 250 DEG C.MS condition: mass spectrometer interface temperature 270 DEG C, ion source temperature 230 DEG C, ionization mode is EI, ion energy 70 eV.Temperature programming method: initial temperature 60 DEG C, is warming up to 230 DEG C with 5 DEG C/min.
Preferably, GC-FID or IR analysis condition is: standard specimen concentration 500 mg/L, 10:1 split sampling, sample size 1 μ L,；HP-VOC chromatographic column (60 mm × 1.80, m × 0.32 μm)；Carrier gas is He, flow velocity 1 mL/min；Injector temperature 260 DEG C, detector temperature 250 DEG C.IR condition: light pipe temperature 270 DEG C, transmission line temperature 270 DEG C, scanning times 8 times, resolution 16 cm-1/ time.
Preferably, described ester type compound and homologue and isomer thereof include but not limited to: ethyl propionate, methyl butyrate, isoamyl acetate, propyl butyrate, isoamyl butyrate, n-pentyl butytate, n-hexyl butyrate, pentyl acetate, ethyl n-butyrate., butyl butyrate, iso-amyl iso-valeriate, ethyl hexanoate or methyl hexadecanoate.
Invention also provides described authentication method preferably to apply, be specifically applied to the identification and analysis aspect of ester type compound and homologue and isomer in essence spice for cigarette.
The method have the advantages that
The present invention sums up according to creative analysis and lot of experiments, take into full account position of functional group and the impact on chromatographic retention of the alkane branched structure thereof of ester type compound, the authentication method of a kind of ester type compound and homologue thereof and isomer is provided, the GC being applicable to different detector and constant temperature, temperature programming different mode analyzes method, the present invention is based on the linear relationship between chromatographic retention and Topological Index, being not related to retention index and other structural parameters, result is accurate, method is simple.The present invention combines GC-MS data base or GC-IR functional group and judges, can be advantageously applied in the complex samples such as essence and flavoring agent ester type compound and homologue thereof and the identification and analysis of isomer.
Accompanying drawing explanation
Fig. 1 is the chromatographic retention-structural relation linear fit curve of alkyl esters compound standard sample.
Fig. 2 is the GC-IR infrared spectrum of 38.859 min correspondence spectral peaks in essence sample.
Detailed description of the invention
The present invention is further illustrated below in conjunction with the accompanying drawings with specific embodiment.Unless stated otherwise, instrument, reagent, equipment and the method that the embodiment of the present invention uses, for instrument commonly used in the art, reagent, equipment and method.The ester type compound illustrated in embodiment the most only illustrates inventive concept, the most therefore limits the scope of the invention.
Embodiment 1
For convenience of description, the following instrument of the present embodiment employing, reagent and instrument working condition:
(1) instrument:
Agilent 6890 gas chromatogram-Nicolet 5790 infrared spectrum combined instrument (GC-FID), Agilent 6890 N gas chromatograph-mass spectrometer (GC-MS).
(2) reagent:
Essence sample for tobacco；Ethyl caprate, ethyl laurate, ethyl myristate, pentadecanoic acid ethyl ester standard sample, other general analysis pure reagents.
(3) instrument working condition:
GC condition: HP-VOC chromatographic column (60 mm × 1.80, m × 0.32 μm), carrier gas is helium, flow 1 mL/min sample size 1 μ L.Vaporizer temperature 250 DEG C；Column temperature: initial temperature 70 DEG C, with 5 DEG C/min temperature programming to 270 DEG C, keeps 10min.
MS condition: mass spectrometer interface temperature 270 DEG C, ion source temperature 230 DEG C, ionization mode is EI, ion energy 70 eV.
GC-IR condition: light pipe temperature 270 DEG C, transmission line temperature 270 DEG C, scanning times 8 times, resolution 16 cm-1。
(4) operation is followed the steps below:
S1. the standard sample of ester type compound gas chromatography (GC) is analyzed, obtain the chromatographic retention T of each compound standard sample；
Standard sample: choose ethyl propionate, methyl butyrate, isoamyl acetate, propyl butyrate, isoamyl butyrate, n-pentyl butytate, n-hexyl butyrate, pentyl acetate, ethyl n-butyrate., butyl butyrate, iso-amyl iso-valeriate, ethyl hexanoate, methyl hexadecanoate for analyze object, be formulated as 100 respectively
Mg/L normal hexane standard solution.
Use GC-FID to analyze method and obtain the chromatographic retention of each standard sample, be shown in Table 1 GC-FID chromatographic retention and Topological Index Q thereof of alkyl esters compound standard sample.
S2. its Topological Index Q is determined according to the structure of ester type compound described in S1；
Topological Index (Q): on the basis of non-hydrogen atom point is worth, the point of definition bonding atom chemistry characteristic is worth δ, and based on Molecular Graphs adjacency matrix, the topological index Q=∑ (δ new by δ constructioni*δj*δk…)0.5, wherein δi=bi(n-1)+∑hij, biBonding electrons number for atom i；N is the principal quantum number of atom i；∑hijFor the hydrogen atom sum being bonded on the atom j that is joined directly together with i.This parameter can reflect molecular volume size.
S3. Criterion sample chromatogram retention time T and the corresponding relation formula of Topological Index Q, and the accuracy of the ester type compound verification method being similar to by structure；
Corresponding relation formula: by GC retention time and each compound molecule topological index (Q) linear fit, obtaining its linear relation is: T=0.86Q-5.30, R2=0.996。
S4. it is calculated the chromatographic retention of ester type compound to be identified in reagent sample according to corresponding relation formula, judges to determine ester type compound in conjunction with GC-MS data base and GC-IR functional group.
2. sample analysis result
As can be seen from Table 2, GC-MS cannot provide accurate structural qualification, especially No. 8 peaks and No. 10 peaks in sample, the mass spectrum matching degree multiple esters homologous compounds more than 80% for the homologue of long-chain ester compounds；
By accompanying drawing 2 it can be seen that GC-IR can pass through functional group (~ 1700 cm-1With 1180
cm-1) determine the type of compounds (esters) of spectral peak, but cannot be distinguished by ester type compound homologous compound；
As can be seen from Table 2, by the calculated retention time of corresponding relation formula, it may be determined that the structure of ester type compound.Determine that compound is pointed out after using standard sample checking errorless.
Knowable to experimental studies results of the present invention, the gas chromatography retention time of ester type compound and its Topological Index have good linear corresponding relation, and this relational expression is applicable to be adapted to the GC of different detector and analyzes method；Be combined with gas chromatogram-infrared spectrum (GC-IR) or gas chromatography-mass spectrum (GC-MS) method by this corresponding relation formula, can be used in the complex samples such as essence and flavoring agent ester type compound and homologue thereof and the identification and analysis of isomer.
Table 1 alkyl esters compound and GC retention time (T) thereof and Topological Index (Q)
Table 2 is GC-MS, GC-IR analysis result of essence sample and according to corresponding relation formula result of calculation
From experimental studies results, ester type compound that the present invention sets up and homologue and the authentication method of isomer, the GC being applicable to different detector and constant temperature, temperature programming different mode analyzes method, the present invention is based on the linear relationship between chromatographic retention and Topological Index, need not relate to retention index and other structural parameters, result is accurate, method is simple.
Claims (3)
1. an ester type compound and homologue thereof and the authentication method of isomer, it is characterised in that include following
Step:
S1. by the gas chromatography analysis of the standard sample of ester type compound, each compound standard sample is obtained
Chromatographic retention T；
S2. its Topological Index Q is determined according to the structure of ester type compound described in S1；
S3. Criterion sample chromatogram retention time T and the corresponding relation formula of Topological Index Q；
When being S4. calculated the chromatograph reservation of ester type compound to be identified in testing sample according to corresponding relation formula
Between, judge to determine ester type compound in conjunction with GC-MS data base and GC-IR functional group；
Wherein, the chromatographic retention T of ester type compound with the corresponding relation formula of Topological Index Q is
T=aQ+b, wherein a, b are constant, true with its Topological Index by the chromatographic retention of standard sample
Fixed；
Described ester type compound and homologue and isomer thereof include but not limited to: ethyl propionate, methyl butyrate,
Isoamyl acetate, propyl butyrate, isoamyl butyrate, n-pentyl butytate, n-hexyl butyrate, pentyl acetate, butanoic acid
Ethyl ester, butyl butyrate, iso-amyl iso-valeriate, ethyl hexanoate or methyl hexadecanoate；
Wherein, described chromatographic retention is detected by GC Yu FID, IR or MS detector method for combined use
Arrive；
The analysis condition of GC with MS detector method for combined use is: standard specimen concentration 50mg/L, 10:1 split sampling,
Sample size 1 μ L；The HP-VOC chromatographic column of 60m × 0.32mm × 1.80 μm；Carrier gas is He, flow velocity 1
mL/min；Injector temperature 250 DEG C；MS condition is: mass spectrometer interface temperature 270 DEG C, ion source temperature
230 DEG C, ionization mode is EI, ion energy 70eV；Temperature programming method: initial temperature 60 DEG C, with 5 DEG C
/ min is warming up to 230 DEG C；
The analysis condition of GC with FID or IR detector method for combined use is: standard specimen concentration 500mg/L, 10:1 divides
Flow to sample, sample size 1 μ L；The HP-VOC chromatographic column of 60m × 0.32mm × 1.80 μm；Carrier gas is He,
Flow velocity 1mL/min；Injector temperature 260 DEG C, detector temperature 250 DEG C；IR condition is: light pipe temperature
270 DEG C, transmission line temperature 270 DEG C, scanning times 8 times, resolution 16cm-1/ time.
Ester type compound and homologue thereof and the authentication method of isomer, its feature the most according to claim 1
Being, Topological Index Q in described corresponding relation formula is on the basis of non-hydrogen atom point is worth, definition
The point of bonding atom chemistry characteristic is worth δ, and based on Molecular Graphs adjacency matrix, the topology new by δ construction refers to
Number Q=∑ (δi*δj*δk…)0.5, wherein δi=bi(n-1)+∑hij, biBonding electrons number for atom i；N is atom i
Principal quantum number；∑hijFor the hydrogen atom sum being bonded on the atom j that is joined directly together with i.
3. the application of authentication method described in claim 1 or 2, it is characterised in that be applied to essence spice for cigarette
The identification and analysis aspect of middle ester type compound and homologue and isomer.
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| 烟用香精的GC-MS指纹图谱;杨虹 等;《分析测试学报》;20040930;第23卷;全文 * |
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