CN108169373B - GC-MS (gas chromatography-Mass spectrometer) method for rapidly identifying dalbergia odorifera and dalbergia odorifera - Google Patents
GC-MS (gas chromatography-Mass spectrometer) method for rapidly identifying dalbergia odorifera and dalbergia odorifera Download PDFInfo
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- CN108169373B CN108169373B CN201711406063.7A CN201711406063A CN108169373B CN 108169373 B CN108169373 B CN 108169373B CN 201711406063 A CN201711406063 A CN 201711406063A CN 108169373 B CN108169373 B CN 108169373B
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Abstract
The invention discloses a GC-MS (gas chromatography-Mass spectrometer) method for rapidly identifying dalbergia odorifera and dalbergia odorifera. The method sequentially comprises the following steps: sampling and preprocessing a wood sample, extracting essential oil, analyzing essential oil composition, qualitatively judging characteristic components and the like. The method well avoids the problem of similarity of dalbergia odorifera and dalbergia odorifera wood in physical properties, makes full use of the difference of the compositions of essential oil of the heartwood of the dalbergia odorifera and the dalbergia odorifera, and thoroughly solves the problem that the dalbergia odorifera and the dalbergia odorifera are difficult to accurately and rapidly identify by the traditional method or means. The method has the advantages of simple operation, small sampling amount, accuracy, rapidness, high efficiency, environmental protection, strong applicability and suitability for wood powder, and is particularly suitable for the material identification of some undamaged finished furniture and high-grade artware. The method provides an efficient, reliable and rapid identification method for wood trading markets, dealers, consumers, public security organs, customs, scientific research institutions and the like, and has strong application value and application prospect.
Description
Technical Field
The invention belongs to the technical field of wood identification, relates to a method for identifying dalbergia odorifera and dalbergia odorifera, and particularly relates to a gas chromatography-mass spectrometry method for rapidly identifying dalbergia odorifera and dalbergia odorifera.
Background
The genus Dalbergia (Dalbergia) is a pan-tropical distribution of the Papilionoceae family (Papilionaceae), distributed mainly in Central and south America, Africa and southern Asia. Many arbor species of the genus Dalbergia are called as species of rosewood species due to their special wood texture, excellent material quality, unique flavor, special use, etc., such as Dalbergia odorifera (Dalbergia odorifera) called as rosewood, Dalbergia odorifera (D.cochinchinensis) called as Tahitian red wood, and Dalbergia odorifera (D.sisoo) called as Indian red wood. Different mangrove species have great economic value due to the differences of wood properties, structural characteristics, component compositions and the like. However, these redwoods have many similarities in appearance, wood color, density and structure, and many low-grade woods are often seen in the market to serve as high-grade wood products, and phenomena of counterfeiting, inferior filling, fish and dragon mixing and the like exist, for example, when the cross-toe sandalwood is used as dalbergia odorifera wood, consumers and even part of professional appraisers are difficult to accurately identify through naked eyes, so that the consumers and operators can suffer great economic loss.
At present, the identification technology of dalbergia odorifera and dalbergia odorifera wood is not researched much, and identification is mainly carried out through some microscopic anatomical structures of the wood, such as growth wheel types, core material colors, axial thin-walled tissue forms, structures, aroma and the like. Some characteristics of the two woods are briefly distinguished in the national standard GB/T18107-2000 Redwood (national quality and technology supervision agency, 2000), however, in the actual identification process, the characteristic differences are often difficult to define accurately, and the requirements on the professional technical level of an identifier are very high, so that the most of Redwood in the existing wood identification institutions or scientific research institutions in China can only be identified to belong to or class, specific species names are difficult to determine, and the defect can be overcome by adopting an analysis method of chemical components.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a GC-MS method for rapidly identifying dalbergia odorifera and dalbergia odorifera.
The essential oil components of the heartwood of the two congeneric rosewood species are respectively extracted and analyzed by adopting a gas-mass combination method based on the composition difference of the essential oil components of the heartwood of the dalbergia odorifera and the dalbergia odorifera, qualitative and quantitative analysis is carried out, and the two woods are accurately identified by comparing the types and the relative content ranges of the main characteristic components of the heartwood of the two tree species. The main characteristic components of the dalbergia odorifera and the dalbergia odorifera heartwood essential oil are obviously different, and the two redwood woods can be effectively distinguished.
The purpose of the invention is realized by the following technical scheme:
a GC-MS method for rapidly identifying dalbergia odorifera and dalbergia odorifera sequentially comprises the following steps:
A. sampling and pretreating wood samples: respectively cutting lignum Dalbergiae Odoriferae and lignum Dalbergiae Odoriferae samples with a sampler, pulverizing, and sieving;
B. extraction of essential oil components: placing the sieved sample into an extraction bottle for extraction, and taking supernatant for component composition analysis;
C. composition analysis of essential oil components: detecting the supernatant with a gas chromatography-mass spectrometer (GC-MS) on a computer to obtain total ion current chromatogram and mass spectrum data of the essential oil components, and performing matching retrieval with a standard mass spectrum library (NIST11, Willey);
D. qualitative judgment of characteristic components: performing map matching retrieval to obtain main characteristic components, calculating the relative content of the main characteristic components by using an area normalization method, and identifying dalbergia odorifera and dalbergia odorifera according to the types and relative content ranges of the main characteristic components;
preferably, in the step A, the sampler is a utility knife or a woodworking chisel, 2-5 g of dalbergia odorifera and dalbergia odorifera samples are respectively chiseled by the utility knife or the woodworking chisel, the samples are crushed by a micro crusher, and then the samples are sieved by a sieve of 50-80 meshes.
Preferably, in step a, the sampling site of the sample is a heartwood.
Preferably, in the step B, the sieved sample is placed into an extraction bottle, 20-50 mL of ethyl acetate is added, a cover is fastened, the extraction is carried out in an ultrasonic extractor at normal temperature, the extraction frequency is 37-45 kHz, the extraction time is 30-60 min, and after the extraction is finished, the filtration is carried out to obtain the liquid to be detected.
Preferably, in step C, the chromatographic detection and analysis conditions are as follows: a chromatographic column: HP-5 weak polar column (specification: 30m × 0.25mm × 0.25 μm); sample inlet temperature: 250 ℃; temperature programming: the initial temperature of the column box is 70 ℃, the column box is kept for 1min, then the temperature is raised to 250 ℃ at the speed of 8 ℃/min, and the column box is kept for 15 min; carrier gas and flow rate: he, 1 mL/min. Mass spectrum conditions: ion source temperature: 280 ℃; an ionization mode: an EI source; ionization voltage: 70 eV; mass spectrum scanning range: 35 to 450 amu.
Preferably, step D comprises the steps of:
a. judging dalbergia odorifera: the main characteristic components are trimethyl cyclohexanol, santalin, nerolidol and trans-nerolidol; wherein the trimethylcyclohexanol is Cyclonol, and the CAS number is 116-02-9; the pterocarpin is medicalin, and the CAS number is: 32383-76-9; nerolidol is Nerolidol with CAS number: 7212-44-4; trans-Nerolidol is trans-Nerolidol with CAS number 40716-66-3: detecting the four main characteristic components, and judging as dalbergia odorifera when the proportion of the four main characteristic components in the total amount of the total essential oil components exceeds 30%;
b. judging the wingceltis odorata: the main characteristic components are 2, 6-dimethoxyphenyl-beta-phenylpropionic acid and N- (2-methoxy-4-nitrophenyl) -hydrocinnamamide; wherein the 2, 6-Dimethoxyphenyl-beta-phenylpropionic acid is 2, 6-Dimethoxyphenyl-beta-phenylpropionate, and the CAS number is as follows: 40123-34-0; n- (2-methoxy-4-nitrophenyl) -phenylacrylamide is N- (2-methoxy-4-nitrophenyl) -benzanepropanamide; detecting the two main characteristic components, and judging as the pteroceltis indicus when the proportion of the total essential oil components exceeds 50 percent.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides a gas chromatography-mass spectrometry method for rapidly identifying dalbergia odorifera and dalbergia odorifera, which well avoids the problem of similarity of dalbergia odorifera and dalbergia odorifera in physical properties, makes full use of the difference of the compositions of essential oil of heartwood of dalbergia odorifera and dalbergia odorifera, and thoroughly solves the problem that the dalbergia odorifera and the dalbergia odorifera are difficult to accurately and rapidly identify by using the traditional wood dissection means. Compared with the traditional anatomical identification means, the method has the advantages of simple and convenient operation, less sampling amount, short time consumption, high accuracy, high efficiency, environmental protection and the like, is suitable for not only complete wood samples, but also wood powder samples, and is particularly suitable for identifying the wood types of undamaged finished furniture and high-grade artware. The invention provides a high-efficiency and reliable method for quickly identifying dalbergia odorifera and dalbergia odorifera for wood trading markets, wood dealers, consumers, public security organs, customs and scientific research institutions and the like, and has strong application value and wide application prospect.
Drawings
FIG. 1 is a total ion flow chromatogram of heartwood essential oil components of sample 1; wherein, 1: trans-Nerolidol; 2: (ii) Cyclonol; 3: nerolidol; 4: medicarpin; 5: gamma-Thujaplicin.
FIG. 2 is a total ion flux chromatogram of essential oil components of heartwood of sample 2; wherein, 1: n- (2-methoxy-4-nitrophenyl) -benzanepropanamide; 2: 2, 6-Dimethoxyphenyl-beta-phenylproprionate.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
And (3) taking 2 samples 1 and 2 of the dalbergia odorifera or dalbergia odorifera wood, and identifying the authenticity. The identification is carried out according to the steps of the invention, which comprises the following steps:
1. sampling and pretreating wood samples: cutting 2g of core material samples of the sample 1 and the sample 2 respectively by using an art designer, crushing by using a micro crusher, and sieving by using a 50-mesh sieve;
2. extraction of essential oil components: respectively placing the sieved samples into 100mL extraction bottles, injecting 20mL ethyl acetate, fastening a cover, placing the extraction bottles in an ultrasonic extractor for normal-temperature extraction at the extraction frequency of 37kHz for 30min, filtering after extraction is finished, and taking supernatant for component composition analysis;
3. composition analysis of essential oil components: and (3) detecting the filtered supernatant by using a gas chromatography-mass spectrometer (GC-MS) on a machine, wherein the chromatographic detection analysis conditions are as follows: a chromatographic column: HP-5 weak polar column (specification: 30m × 0.25mm × 0.25 μm); sample inlet temperature: 250 ℃; temperature programming: the initial temperature of the column box is 70 ℃, the column box is kept for 1min, then the temperature is raised to 250 ℃ at the speed of 8 ℃/min, and the column box is kept for 15 min; carrier gas and flow rate: he, 1 mL/min. Mass spectrum conditions: ion source temperature: 280 ℃; an ionization mode: an EI source; ionization voltage: 70 eV; mass spectrum scanning range: 35 to 450 amu. Obtaining total ion current chromatogram (shown in figure 1 and figure 2) and mass spectrum data of the essential oil components after detection, and performing matching retrieval with a standard mass spectrum library (NIST11, Willey);
4. qualitative judgment of components: and (3) obtaining main characteristic components of the heartwood essential oil according to matching retrieval of mass spectrum, and calculating the relative percentage (namely the relative percentage content) of each peak area by an area normalization method. Through searching, the main component names and corresponding relative contents of the heartwood essential oil of the sample 1 are trimethylcyclohexanol Cyclonol (18.18%), gamma-thujaplicin (9.04%), santalin medicinarpin (13.14%), trans-Nerolidol (6.49%), Nerolidol (2.11%), wherein the sum of the relative contents of four main characteristic components of trimethylcyclohexanol, mendysantalin, trans-Nerolidol and Nerolidol is 30.78% and more than 30%, and the heartwood essential oil can be judged to be dalbergia odorifera.
The essential oil of heartwood of sample 2 was characterized mainly by 2,6-Dimethoxyphenyl- β -phenylpropionate (48.03%) and N- (2-methoxy-4-nitrophenyl) -phenylacrylamide N- (2-methoxy-4-nitrophenyl) -benzanepropamide (25.56%), wherein the sum of the relative contents of 2,6-Dimethoxyphenyl- β -phenylpropionate and N- (2-methoxy-4-nitrophenyl) -phenylamide was 73.59% > 50%, and was judged as "yellow sandalwood".
And (3) identification result: sample 1 is dalbergia odorifera and sample 2 is dalbergia odorifera.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made in the claims of the present invention should be covered by the claims of the present invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A combined use method for rapidly identifying the gas and the quality of dalbergia odorifera and dalbergia odorifera is characterized by sequentially comprising the following steps:
A. sampling and pretreating wood samples: respectively cutting lignum Dalbergiae Odoriferae and lignum Dalbergiae Odoriferae samples with a sampler, pulverizing, and sieving;
B. extraction of essential oil components: placing the sieved sample into an extraction bottle, adding ethyl acetate for extraction, and taking supernatant for component composition analysis;
C. composition analysis of essential oil components: detecting the supernatant with a gas chromatography-mass spectrometer to obtain total ion current chromatogram and mass spectrum data of the essential oil components, and performing matching retrieval with a standard mass spectrum library;
D. qualitative judgment of characteristic components: performing map matching retrieval to obtain main characteristic components, calculating the relative content of the main characteristic components by using an area normalization method, and identifying dalbergia odorifera and dalbergia odorifera according to the types and relative content ranges of the main characteristic components;
in the step C, the chromatographic detection and analysis conditions are as follows: a chromatographic column: HP-5 weak polar column, specification: 30 m.times.0.25 mm.times.0.25 μm; sample inlet temperature: 250 ℃; temperature programming: the initial temperature of the column box is 70 ℃, the column box is kept for 1min, then the temperature is raised to 250 ℃ at the speed of 8 ℃/min, and the column box is kept for 15 min; carrier gas and flow rate: he, 1 mL/min; mass spectrum conditions: ion source temperature: 280 ℃; an ionization mode: an EI source; ionization voltage: 70 eV; mass spectrum scanning range: 35-450 amu;
in step D, the following steps are included:
a. judging dalbergia odorifera: the main characteristic components are trimethyl cyclohexanol, santalin, nerolidol and trans-nerolidol; when the proportion of the four main characteristic components in the total amount of the total essential oil components is detected to exceed 30 percent, the rosewood is judged to be dalbergia odorifera;
b. judging the wingceltis odorata: the main characteristic component is 2,6-dimethoxyphenyl-β-Phenylpropionic acid and N- (2-methoxy-4-nitrophenyl) -hydrocinnamamide; when the proportion of the two main characteristic components in the total amount of the total essential oil components is detected to exceed 50 percent, the cross toe yellow sandalwood is judged.
2. The method for rapidly identifying the combination of qi and the quality of dalbergia odorifera and dalbergia odorifera according to claim 1, which comprises the following steps:
in the step A, the sampler is a utility knife or a woodworking chisel, 2-5 g of dalbergia odorifera and dalbergia odorifera samples are respectively chiseled by the utility knife or the woodworking chisel, the samples are crushed, and then the samples are sieved by a sieve of 50-80 meshes.
3. The method for rapidly identifying the combination of qi and the quality of dalbergia odorifera and dalbergia odorifera according to claim 1 or 2, which comprises the following steps:
in step A, the sampling part of the sample is heartwood.
4. The method for rapidly identifying the combination of qi and the quality of dalbergia odorifera and dalbergia odorifera according to claim 1 or 2, which comprises the following steps:
and step B, placing the sieved sample into an extraction bottle, adding 20-50 mL of ethyl acetate, fastening a cover, placing the extraction bottle into an ultrasonic extractor for normal-temperature extraction, wherein the extraction frequency is 37-45 kHz, the extraction time is 30-60 min, and filtering after extraction is finished to obtain the liquid to be detected.
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| CN110780014B (en) * | 2019-10-24 | 2022-07-19 | 莆田市家具产品质量监督检验中心 | Method for identifying gall-containing wood by gas chromatography-mass spectrometry technology |
| CN111948329A (en) * | 2020-06-01 | 2020-11-17 | 上海市质量监督检验技术研究院 | Method for identifying pteroceltis tatarinowii and pteroceltis tenuipes |
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| CN103308637B (en) * | 2013-05-10 | 2014-11-26 | 浙江省林产品质量检测站 | Gas chromatography-mass spectrometry method for identifying dalbergia odorifera and dalbergia tonkinensi |
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