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    • 专利摘要:
    The invention relates to a method for identifying the species of oak comprising the following steps: a) A sample of oak wood is available; b) preparing said sample; c) At least one analysis is carried out on the wood sample in order to: - identify: i. between one to three molecules belonging to a 1st category of molecules defined by oleanane triterpenes derivatives derived from a genome of formula C30H48O6, ii. between one to three molecules belonging to a second category of molecules defined by the oleanane triterpenes derivatives derived from a genome of formula C30H46O7, as well as oleanane triterpenes derivatives which are derived from a genome of formula C30H46O8, then - to determine the concentration of the identified molecules; d) a ratio R is determined; e) The species of oak is identified.
    公开号:FR3023618A1
    申请号:FR1456606
    申请日:2014-07-09
    公开日:2016-01-15
    发明作者:Axel Marchal；Denis Dubourdieu
    申请人:Seguin Moreau & C；E Remy Martin and Co；Universite de Bordeaux；Institut Polytechnique de Bordeaux；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method for identifying the oak species of a sample of oak wood. Oaks are hardwood trees. The oak wood has a density of between 0.75 and 0.85 g / cm3. This has the advantage of providing a very strong and hard material for different applications such as cabinet making, carpentry, flooring or cooperage. In addition, oak is particularly popular for its resistance to insects and fungi due to its high tannin content. Of the oak species, sessile oak (Quercus petraea), also known as "oak", and pedunculate oak (Quercus robur) are the two most common surface species found in European forests. Pedunculate oak and sessile wood were used for shipbuilding up to the 19th century and represented the main wood species used in the construction of timber frames in Europe. Today, these oak woods are commonly used in carpentry, flooring, veneer production, as well as cenology. More specifically, with regard to cenology, there are two essential applications of oak wood. First of all, wines and spirit drinks (such as cognac, whiskey, brandy) are aged in oak wood containers called, for example, according to their shape and volume: barrels, barrels and tons. These containers are mostly sessile and pedunculate oak. Indeed, aging is beneficial to the quality of wines and spirits, thanks to the extraction of volatile and non-volatile wood compounds and the complex transformations that take place during the aging in wood. Another oenological application of oak wood is the introduction of pieces of this wood in wines and spirits to enrich them with chemical molecules present in said wood and thus to modify the organoleptic qualities. These products are generally referred to in this technical field as "alternative products" and are used in the form of chips, chips, powders, as well as larger pieces such as sticks. The sessile and pedunculate oak species are therefore used both for the manufacture of containers for cenology and also for the production of the aforementioned alternative products.
    [0002] Because of their respective characteristics, sessile oak is more generally reserved for the production of barrels for wine and pedunculate oak with barrels for spirits. Although these two species of oak sessile and pedunculate have distinct morphological characteristics, for example in the trunk, branches, bark or their foliage, it is difficult to discriminate from one another unambiguously by visual examination. In addition, these two species of oak are often mixed in most forests (eg French forests). Therefore, it is not possible to rely on the forest from which the oak wood comes to determine its species. Indeed, genetic analyzes have shown that in forests known to be populated with sessile oaks, there were also pedunculate oaks in significant quantities. Therefore, the only method of unambiguous identification of the oak species of a sample of oak wood is based on these genetic analyzes. They require to be carried out on fresh wood or, ideally, on leaves, which, from a practical point of view, is not always easy to implement. In addition, these genetic analyzes do not provide an immediate result, but instead require a certain amount of time. Finally, these analyzes are expensive. However, in view of the very different uses due to the variety of beverages that are stored in the oak wood containers, it is essential for the cooper to know precisely and also to guarantee the oak species that is used for the manufacture of its containers. Indeed, in cooperage, the characteristics and the quality of the raw material (that is to say the oak wood) which is used for the storage of alcoholic beverages significantly condition the quality of the finished product, namely the alcoholic drink. It is easily understood that it is essential for the cooper to know exactly the species of oak wood that he has for the manufacture of his 30 wooden containers. To date, the only method of certain identification of an oak species is to implement genetic analyzes which, as recalled above, are long and tedious. The present invention proposes to overcome the above-mentioned disadvantages of genetic analyzes by proposing a new method of identifying the oak species of an oak wood sample.
    [0003] The identification method according to the invention has the advantages of being easy to implement and to obtain the result very quickly. Moreover, the method according to the invention guarantees a perfectly reliable result, and this, in particular, unlike a visual examination of a sample of an element of an oak such as its leaves or its bark, for example . More specifically, the method of identifying the oak species of a sample of oak wood is characterized in that it comprises at least the following steps: a) A sample of oak wood is available; B) The oak wood sample is suitably prepared for a concentration determination analysis of oleanane triterpene derivatives which are present in said oak wood sample; c) At least one analysis is carried out on the oak wood sample thus prepared in step b) so as to: - identify: i. between one to three molecules belonging to an age category of molecules, said one to three molecules being among the three most abundant molecules of all molecules of said 1: 1st category of molecules present in said oak wood sample, said 1: the first category of molecules being defined by the set of oleanane-type triterpene derivatives which are derived from a genin of the empirical formula C30H4806, ii. between one to three molecules belonging to a 21st category of molecules, said one to three molecules being among the three most abundant molecules of all the molecules of said second category of 30 molecules present in said oak wood sample, said 21st category of molecules being defined by all the oleanane triterpenes derivatives which are derived from a genome of the formula C30H4607, as well as oleanane triterpene derivatives which are derived from a genome of the formula C30H4608, and then - to determining the concentration of: - each of said one to three molecules of the class of molecules that have been identified; each of said one to three molecules of the second category of molecules that have been identified; d) determining a ratio R, said ratio R corresponding to the ratio of the concentration or the sum of the concentrations of at least one of said one to three molecules of the first category of molecules which have been identified on the concentration or the sum concentrations of at least one of said one to three molecules of the 2nd class of molecules that have been identified; e) The species of the oak wood sample is identified according to the value of the ratio R determined in step d) as follows: - if the ratio R is less than 0.316, then the sample of oak wood belongs to the pedunculate species, - if the ratio R is greater than 3,162, then the oak wood sample belongs to the sessile species. In the context of the present invention, it is recalled that triterpenes are hydrocarbons with 30 carbon atoms resulting from the condensation of six isoprene molecules. One of the advantages of the method for identifying the species of oak according to the invention lies in the fact that for almost all the oak wood samples which will be analyzed a result will be obtained (namely the determination if this is a sample of sessile oak or pedunculate oak) without any ambiguity. Preferably, the 11th class of molecules is defined by the set of oleanane triterpene derivatives which are derived from arjungenine, seric acid and the isomers of arjungenine and seric acid. Preferably, the second category of molecules is defined by all oleanane-type triterpene derivatives which are derived from bartogenic acid, isomers of bartogenic acid, trachelosperogenin D and isomers of trachelosperogenin. D. The formulas of arjungenine, seric acid, bartogenic acid and trachelosperogenin D are detailed below. The formula (A) below corresponds to arjungenine. (A) Formula (B) below corresponds to seric acid. (B) OH Formula (C) below corresponds to bartogenic acid. HO. ## STR2 ## Formula (D) below corresponds to trachelosperogenin D.
    [0004] In one embodiment of the invention, the class of molecules is defined by the set of molecules of formula (I) as detailed below, wherein X1 represents a glucose group or a hydrogen, X2 represents a gallate group or a hydrogen, X3 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, where X4 represents a hydrogen or a group gallate, of formula (II) as detailed below, wherein X5 represents a glucose group or a hydrogen, where X6 represents a gallate group or a hydrogen, where X7 represents a hydrogen atom; or a glucose group or a gallate group or a glucose-gallate group, where X8 represents a hydrogen or a gallate group. In one embodiment of the invention, the second category of molecules is defined by the set of molecules: of formula (III) as detailed below, Y4-0 Y3-0 0 Y2 Y2 in which: Y1 represents a glucose group or a hydrogen group, Y2 represents a glucose group or a hydrogen group, Y3 represents a hydrogen or a gallate group or a glucose group or a glucose-gallate group, Y4 represents a hydrogen or a gallate group of formula (IV) as detailed below, wherein Y5 is a glucose group or a hydrogen group, Y6 is a glucose group or a hydrogen group, Y7 is hydrogen, or a glucose group or a gallate group or a glucose-gallate group, Y8 represents a hydrogen or a gallate group of formula (V) as detailed below, wherein: Y is a glucose group or a hydrogen, where Y10 represents a glucose or a hydrogen group e, Y11 represents a hydrogen or a gallate group, Y12 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, Y13 represents a hydrogen or a gallate group, of formula (VI) as detailed wherein Y14 represents a glucose group or a hydrogen group, Y15 represents a hydrogen or a gallate group, Y16 represents a glucose group or a hydrogen group, Y17 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, where Y18 represents a hydrogen or a gallate group. In one embodiment of the invention, the first class of molecules is defined by the following set of molecules: quercotriterpenoside I (hereinafter abbreviated QTT I) of formula (VII), quercotriterpenoside II (hereinafter referred to as after abbreviated QTT II) of formula (VIII) and quercotriterpenoside III (hereinafter abbreviated QTT III) of formula (IX), and whose formulas are detailed below. (VIII) HO (IX) HO In one embodiment of the invention, the 2nd class of molecules is defined solely by the 28-glucosyl derivative of bartogenic acid (hereinafter abbreviated Glu-AB) of the formula (X) as detailed below. OH (X) OFF In one embodiment of the invention, the ratio R corresponds to the ratio of the concentration or the sum of the concentrations of at least one of the molecules chosen from the QTT I of formula (VII), the QTT II of formula (VIII) and QTT III of formula (IX) on the concentration of Glu-AB of formula (X). In one embodiment of the invention, the ratio R corresponds to the ratio of the sum of the concentrations of QTT I of formula (VII), of QTT II of formula (VIII) and of QTT III of formula (IX) on concentration. Glu-AB of formula 30 (X). The preparation of the oak wood sample is now more fully described. The oak of the sample to be analyzed for the identification of the oak species may have very varied origins, in particular depending on the application for which the identification method according to the invention is intended. Indeed, it may be, for example, the two oenological applications mentioned above which are: - the identification of the oak species of alternative products; - the identification of the oak species of wooden containers in which wines and spirits are aged. Thus, in the context of the present invention, the oak of the sample can come from a single piece of wood such as a stave or a set of homogeneous pieces of wood such as, for example, a set of staves for the manufacture of a drum or a lot of alternative products. Of course, the examples detailed above which describe the origin of the wood constituting the sample are not limiting of the scope of the invention.
    [0005] Indeed, the identification method according to the invention has the advantage of being implemented on any sample of oak wood, whatever its nature and origin (for example, a piece of wood taken from an oak or from a manufactured wood product such as a stave, a stave, or other equivalent products).
    [0006] Preferably, in step b) of the identification method according to the invention, the oak wood sample is prepared according to a liquid solid extraction. The preparation of the available oak wood sample can be started by cutting it into chips and then allowing the resulting chips to macerate in a liquid for a fixed period of time. Advantageously, the chips are reduced to powder before maceration. In one embodiment of the invention, the oak wood sample is allowed to dry for a few hours (for example at least 6 hours) at room temperature, for example at a temperature of at least 20 ° C. The maceration of the oak wood can be carried out in any suitable liquid, for example water or even a solvent such as an alcoholic solution. It may be an ethanol solution, for example a 12% v / v ethanol solution. The solution may have an acidic pH, for example about 3.5. An example of a solution in which the sample of oak wood is macerated, for example in the form of chips or powder, consists of a 12% v / v ethanol solution containing in addition tartaric acid (for example). example at a concentration of 5 g / L) with a pH of 3.5. The pH of this solution is adjusted with sodium hydroxide, for example at a concentration of 5 mol / L. The concentration of the oak wood sample in this solution can be, for example, 50 g / l.
    [0007] The oak wood sample is macerated in a liquid for several hours, for example for a period of at least 48 hours, and at room temperature (ie about 20 ° C). Preferably, the maceration of the oak wood sample takes place in the dark. This has the advantage of protecting some of the light-sensitive oak wood molecules and thus preventing them from degrading before carrying out the analysis to determine their concentration; which could induce a wrong result of the oak species of the sample. The embodiment of the maceration of the oak wood sample which has been described above is not limiting of the present invention. This is an embodiment that can be envisaged in the context of the present invention for the preparation of said sample for its analysis during step c) of the identification process which, let us recall, consists in identifying and to be assayed (in other words to extract and to quantify) between one to three of the most abundant molecules among the molecules of the 1st category of molecules and the molecules of the 2nd category which have been described above. Indeed, the inventors of the present invention have found that this embodiment of maceration of the oak wood sample was appropriate for carrying out the analysis of step c) because these maceration conditions are quite similar to the conditions of wine aging during which, remember, volatile and non-volatile wood components are extracted. Of course, other conditions of extraction of the most abundant molecules of the 1st category of molecules and the 2nd category of molecules as efficient as those described above could be implemented and are perfectly within the range of the skilled person. Ainisi, in the context of the present invention, the maceration of the wood sample can be carried out under other conditions of time, temperatures than those described above. For example, the maceration can be carried out at temperatures higher than room temperature (for example between about 50 ° C and 80 ° C), and for a shorter time than that specified above (for example a few hours ie between 5 and 10 hours). At the end of the maceration, we obtain a macerate of oak. In one embodiment of the invention, in order to carry out the analysis of step c) of the identification method according to the invention, the macerate of oak wood is diluted, for example by a dilution. 20 times, advantageously in ultrapure water, and then filtered, for example on a PTFE filter (ie the acronym of "polytetrafluoroethylene") with a mesh size of 0.45 μm. This is a feasible embodiment of the finalization of the preparation of the oak wood sample. Other dilutions and other means of filtration can obviously be envisaged in the context of the present invention. They are well known to those skilled in the art. Of course, in the context of the present invention, it should be noted that the dilution of the oak macerate is optional. In other words, step b) of preparing the oak wood sample can be carried out without any dilution step.
    [0008] For example, a dilution will not necessarily be necessary if the initial concentration of the raw oak wood extract of the sample to be analyzed is less than 100 mg / L after filtration. Thus, in this embodiment of the invention, step b) of preparation may consist of a maceration of the oak wood sample (for example in the form of powder) in a mixture of water and ethanol, the concentration of ethanol may be lower than that mentioned above, and for example less than 10% v / v. Of course, the preparation of the oak wood sample is perfectly within the reach of those skilled in the art who will know exactly how to proceed to prepare said sample according to the analyzes it will perform to determine the concentrations of the molecules of the 1 : 1st and 2nd categories of molecules which, remember, have the common feature of being derivatives of triterpenes oleanane type. Thus, the embodiments of the preparation of the oak wood sample described above correspond to exemplary embodiments of step b) which are conceivable in the context of the present invention but do not limit it. however, the scope of the identification method according to the invention. The analysis of step c) of the identification process may consist of at least one chemical analysis allowing the determination of the concentration of the chemical molecules which are derivatives of oleanane type triterpenes. For example, it may be at least one selected from: LC-MS analyzes (ie, liquid chromatography analysis coupled with mass spectrometry analysis), GC-MS analyzes (i.e. gas chromatographic analysis coupled with mass spectrometry analysis), NMR analyzes (ie, nuclear magnetic resonance).
    [0009] Of course, the realization of these chemical analyzes which are detailed above is perfectly within the scope of the skilled person who will implement the appropriate analysis protocol to identify and then determine the concentration of the most abundant molecules of the the category era and the 2nd category of molecules as detailed above. In other words, a person skilled in the art knows how to determine the concentration of oleanane triterpene derivatives present in a sample, and in particular in an oak wood sample, for example after having subjected said sample to a solid extraction. liquid.
    [0010] In particular, with regard to analyzes by liquid and / or gas chromatography, those skilled in the art know how to carry out the appropriate calibration curves, as well as, where appropriate, the ratio of the areas of the chromatograms which are necessary for the determination of the concentrations the most abundant molecules of the 1st category of molecules and the 2nd category of molecules that he has identified in the sample of oak to be analyzed. Preferably, in step e) of the identification process, the logarithm of the ratio R is computed and: if the logarithm of the ratio R thus calculated is greater than 0.5, then the oak wood sample is the sessile oak species; if the decimal logarithm of the R ratio thus calculated is less than -0.5 then the oak wood sample is of the pedunculate oak species. The decimal logarithm is a means of expressing the relative abundance of identified molecules of the 1st and 2nd categories of molecules. The calculation of the logarithm decimal has the advantage of providing an easy-to-read result since the nature of the oak species is linked to the sign of the value thus obtained: if the result is negative, it will be a pedunculate oak and if, on the contrary, the result is positive, it will be a sessile oak.
    [0011] It should be noted that the method of identifying the species of oak wood has the following advantages: the preparation of the oak wood sample can be carried out on fresh wood, but also on wood staves after drying and even after being heated, unlike genetic analyzes that require fresh oak samples; the preparation of the wood sample is simple and the analysis time very short, and this also unlike genetic analyzes. Thus, the use on an industrial scale of the identification process of the oak species according to the invention allows a cooper to certify that its wooden containers (for example barrels, vats, barrels) are made only from sessile oak or pedunculate oak, depending on whether they are intended for the aging of wines and spirits, respectively. The adaptation of the drum to its contents is thus optimized.
    [0012] The identification method according to the invention is a particularly suitable solution for the technical field of the cooperage, because it is simple to implement while being inexpensive and provides a very fast identification result. With the identification method according to the invention, this makes it possible to dispense with genetic analyzes when it is desired to know unambiguously the oak species to which a sample of oak wood belongs. Similarly, the identification method according to the invention is perfectly suitable for identifying the species of oakwood in the context of another oenological application which has been mentioned above, namely the application which concerns alternative products (chips, powders, sticks) introduced in wines and spirit drinks with a view to modifying their organoleptic qualities. Thus, the identification method according to the invention allows an easy and unambiguous determination of the oak species which are made of alternative products. The present invention is in no way limited to the analysis of oak wood samples from these two oenological applications mentioned above. Thus, in the context of the present invention, it is perfectly conceivable to also implement the method for identifying the oak species as described above to identify the species of oak in medical samples and / or pharmaceutical. Indeed, in different medical and / or pharmaceutical applications, it may be necessary to identify the species of oak wood that may contain certain medical and / or pharmaceutical preparations. In this case, those skilled in the art will also be able to perfectly prepare the oak wood sample from these medical and / or pharmaceutical preparations and then identify and dose between one to three of the most abundant molecules of the 1 : 1st and 2nd categories of molecules as defined above. DESCRIPTION OF THE FIGURES FIG. 1 is a diagram of the concentration of QTT I of formula (VII) determined in each of the samples of oak woods A to V. FIG. 2 is a diagram of the concentration of QTT II of formula (VIII ) Figure 3 is a diagram of the QTT III concentration of formula (IX) for each of the A to V wood samples. Figure 4 is a diagram. of the Glu-AB concentration of formula (X) for each of the A to V wood samples. Figure 5 is a diagram of the sum of QTT I, QTT II and QTT concentrations. Figure 6 is a diagram. of the logarithm of the ratio R of each of the samples A to V. An example of implementation of the method of identifying the oak species of an oak wood sample according to the invention is detailed by taking advantage of the experimental part that follows. EXPERIMENTAL PART: Oak samples were taken from 22 trees in 6 French forests, collecting: 25 leaves, for the determination of the oak species by genetic analysis, and wood for the determination of the species of oak according to the identification method according to the invention. Thus, 22 samples referenced A to V were obtained. Each of the 22 Aa samples was subjected to: genetic analysis; the process for identifying the species of oak according to the invention. In the context of this experimental part, the genetic analyzes were used to validate that the identification method according to the invention of the oak species made it possible to identify without error the oak species of these different wood samples. of oak. Indeed, genetic analysis gives a result of the species unambiguously. Thus, genetic analyzes were performed on samples A to V of oak wood.
    [0013] According to the genetic analyzes: samples A to H were samples of the sessile oak species, and samples I to V were samples of the pedunculate oak species.
    [0014] In addition, the oak of each of the 22 samples A to Va was prepared in the following manner: the collected oak was reduced to powder; then, the oak wood powder was added to an aqueous solution containing ethanol (12% v / v) at a concentration of 50 g / L, said aqueous solution further containing tartaric acid (at a concentration of 5g / L) and had a pH of 3.5. The pH of this solution was adjusted with sodium hydroxide (at a concentration of 5mol / L); the solution thus obtained was allowed to macerate for 48 hours in the dark; then, the oak wood macerate thus obtained was diluted 20 times in ultrapure water and then filtered through a PTFE filter with a diameter of 0.45 μm. For each of the 22 samples of oak wood prepared, the concentration of the following molecules was determined: QTT I, QTT II and QTT III, ie molecules belonging to the 1st category of molecules of the identification process according to the invention, and Glu-AB, namely a molecule belonging to the 21st category of molecules of the identification method according to the invention. The determination of these concentrations was carried out by liquid chromatography coupled with Fourier Transform Mass Spectrometry (LC-FTMS). After establishment of calibration lines, the 4 molecules detailed above were assayed simultaneously. The analysis of each of the samples lasted approximately 7.5 minutes.
    [0015] Specifically, the technical characteristics of the liquid chromatrography were as follows: An ultra high performance liquid chromatography platform (Ultra High Performance Liquid Chromatography) comprising a HTC PAL type sample changer (apparatus of the CTC Analytics AG) coupled with an Accela-type pumping system. A C18 type column was used as a stationary phase, said column is marketed by Thermo Fisher Scientific under the trade name Hypersil Gold and has the following dimensions: 2.1 mm x 100 mm and 1.9 μm for the particle size. The mobile phase was a mixture of water and acetonitrile. The flow rate was 600 ulmin and the acetonitrile volume percentage of the mobile phase varied as follows: o Initially: 20% v / v o 30 seconds after the start of the analysis: 20% v / v; o 4 minutes after start of analysis: 50 v / v; o 4.1 minutes after start of analysis: 98% v / v; o 6.1 minutes after start of analysis: 98% v / v; o 6.2 minutes after start of analysis: 20% v / v; o 7.5 minutes after the start of the analysis: 20% v / v. The injection volume was 5 μL. Each sample and each calibration level were injected three times. The ultra-high performance liquid chromatography device described above was coupled to an Exactive mass spectrometer, equipped with an Orbitrap analyzer and equipped with an electronebullization ionization probe. These two devices are marketed by the company Thermo Fisher Scientific.
    [0016] The mass spectrometry data was acquired in 6 minutes in FTMS negative ionization mode (ie the English acronym for "Fourier Transform Mass Spectrometry" which stands for Fourier Transform Mass Spectrometer). The other parameters of the mass spectrometry analysis are detailed in Table 1 below.
    [0017] Parameter FTMS Value Sheath gas flow rate 75 Auxiliary gas flow rate 18 Ionization source temperature 320 ° C Capillary temperature 350 ° C Ionization voltage -3 kV Capillary voltage -95 V Tubular lens voltage (known under the English name: "tube lens") -190 V Voltage of the recuperator (known under the English name: "skim mer") -46 V Fragmentation energy by dissociation in the source 20 eV Scanning range 500 - 1200 Th Resolution 25 000 Value of the automatic gain control 3.106 Table 1 detailing the parameters of the mass spectrometry analysis. In Table 1 above, the gases are dinitrogen and the gas flows are expressed in arbitrary units (i.e., the first two rows of Table 1). In addition, for the fragmentation mode, an energy of 20eV was applied in the source in order to dissociate the possible adducts of the molecules to be quantified with anions of the medium. The resolution is defined as the m / Am ratio at mid-height and is expressed above for an ion of ratio rn / z 200 Th. An external calibration of the spectrometer using a calibration solution "Pierce® ESI Negative Ion Calibration (Thermo Fisher Scientific) was performed before each round of analysis. The data was processed using the Qualbrowser and Quanbrowser applications of the Xcalibur version 2.1 software (Fisher Scientific Thermo 15).
    [0018] The detection of the above 4 molecules was carried out based on their exact theoretical mass, as well as on their respective theoretical retention times. The areas of the peaks were determined by automatic integration and the concentrations of the above-mentioned 4 molecules were determined taking into account the dilution factor (20 times) detailed above. Thus, the concentrations of the above-mentioned four molecules present in the various samples of oak wood A to V prepared in the manner as detailed above were calculated automatically. Table 2 below shows the details of the concentrations of QTT I, QTT II, QTT III for samples A to V, said concentrations being expressed in mg / L and in μg / g (μg / g meaning "microgram / gram "). mg / L ug / g mg / L ug / g mg / L ug / g mg / L ug / g QTT I QTT II QTT III QTT totals A 12.5 249.8 6.0 120.4 17.9 357, 8 36.4 728.0 20.2 403.5 5.1 102.7 30.8 615.0 56.1 1121.2 41.6 832.5 70.9 1418.0 70.4 1408.7 183 , 0 3659.2 23.9 477.9 4.1 82.8 11.8 235.3 39.8 796.0 13.3 265.4 2.2 43.1 6.6 132.5 22.1 441.0 29.0 580.9 6.8 135.2 24.2 484.2 60.0 1200.2 40.7 814.0 66.0 1320.0 70.3 1405.2 177.0 3539, 2 2.8 56.0 1.9 37.5 3.7 74.0 8.4 167.5 0.2 3.1 0.2 4.0 0.2 4.7 0.6 11.7 J 0.1 2.1 0.1 2.1 0.2 3.3 0.4 7.4 K 0.1 1.6 0.5 10.2 0.1 2.9 0.7 14.7 L 0.1 1.3 0.1 1.8 0.1 1.9 0.3 5.0 M 0.1 2.2 0.9 18.8 0.2 4.9 1.3 25.9 N 0.1 1.9 0.1 1.4 0.1 2.0 0.3 5.3 0.2 0.2 0.3 5.9 0.1 2.1 0.6 11.2 P 0.2 4.8 0.1 2.6 0.2 4.3 0.6 11.7 Q 0.1 1.1 0.0 1.0 0.2 3.1 0.3 5.2 R 0.3 5.4 0.3 5.2 0.2 4.8 0.8 15.4 S 0.9 17.3 2.2 44.1 1.3 26.2 4.4 87.7 T 0.5 9.6 0.8 15.3 0.5 10.6 1.8 35.4 U 0.1 2.9 1.4 28.0 0.4 7.2 1.9 38.0 V 0.8 16.3 0.1 3.0 0.2 4.4 1.2 23.7 Table 2 detailing for samples A to V concentrations in me and in ug / of QTT I. QTT II and QTT III, as well as the sum of the concentrations of QTT I. QTT II and QTT III The diagrams of Figures 1 to 3 represent respectively the QTT I, QTT II and QTT III concentrations of the A samples. to V. The diagram of FIG. 5 represents the sum of the concentrations of QTT I, QTT II and QTT III of samples A to V.
    [0019] Table 3 below shows the details of Glu-AB concentrations for samples A to V, said concentrations being expressed in mg / L and in ug / g. mg / L ug / g Glu-AB Oak 0.9 17.6 sessile 0.4 8.2 2.1 42.6 0.3 6.8 0.2 4.1 0.4 8.5 4.9 97.9 0.3 6.5 8.5 160.2 Oak J 5.4 108.2 peduncle K 68.7 1373.5 L 20.5 410.6 M 45.5 910.5 N 1.8 36.0 0 86.7 1733.3 P 18.9 377.1 Q 32.1 641.4 R 34.1 682.8 S 83.8 1676.2 T 23.0 460.2 U 97.6 1952 , 0 V 20.2 403.1 Table 3 detailing for samples A to V the concentrations in mg / L and in μg / g of GLU-AB The diagram of Figure 4 represents the Glu-AB concentration of samples A V. Table 4 below details for samples A to V the ratio R and the logarithm of the ratio R, said ratio R corresponding to the sum of the concentrations of QTT I, QTT II, QTT III on the concentration of Glu-AB.
    [0020] R LOG (R) 41.40 1.62 137.16 2.14 85.94 1.93 116.36 2.07 Oak 108.68 2.04 sessile 141.61 2.15 36.16 1.56 25 , 76 1.41 Oak I 0.07 -1.14, pedunculated J 0.07 -1.16 K 0.01 -1.97 L 0.01 -1.91 M 0.03 -1.55 N 0, 15 -0.84 0 0.01 -2.19 P 0.03 -1.51 0.01 -2.10 R 0.02 -1.65 S 0.05 -1.28 T 0.08 - 1.11 U 0.02 -1.71 V 0.06 -1.23 Table 4 detailing for samples A to V the ratio R and logarithm of the ratio R The diagram in Figure 6 represents the logarithm of the ratio R samples A to V.
    [0021] In view of the values detailed in Table 4 above, it is noted that all sessile oak samples (ie samples A to H) have a R ratio value greater than 3.162 and all pedunculate oak samples (i.e. samples I to V) have a R ratio value of less than 0.316. With respect to, the decimal logarithm of ratio R: the logarithm 10 decimal of the R ratio of all sessile oak samples is greater than 0.5 and the logarithm of the R ratio of all pedunculate oak samples is less than - 0.5. The diagram of FIG. 6 clearly expresses this result of unambiguous differentiation of an oak wood sample of the oak species sessile from that of the pedunculate oak species.
    [0022] Moreover, with regard to tables 2 and 3 and to FIGS. 1 to 5, the samples G and S testify to the whole interest of the method of identifying the oak species of a sample of an oak wood according to the invention, and in particular the absolute necessity of taking into consideration two categories of different molecules which have been described above. Indeed, the sample G (proving to be of the sessile species) has a concentration almost as high in Glu-AB as the sample J which is of the pedunculate species. Similarly, the sample S (proving to be of the pedunculate species) has a significant concentration of QTT I, QTT II and QTT III which, at first glance, could have led to the conclusion that it belonged to the sessile species. Indeed, sessile oak woods have a significant concentration in these molecules of the 1st class of molecules. Thus, these samples show that the identification process according to the invention, thanks to an appropriate selection of two categories of molecules of oleanane-type triterpene derivatives, namely the 1st class of molecules and the second category of molecules which have detailed above, allows unambiguous identification of the oak species of an oak wood. In other words, these samples show that if we consider only the presence in the wood sample of a molecule belonging to either the 1st class of molecules or the 2nd class of molecules, we can conclude that erroneous on the oak species of the analyzed sample.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A method of identifying the oak species of a sample of oak wood, characterized in that it comprises at least the following steps: a) There is a sample of oak wood; b) The oak wood sample is suitably prepared for a concentration determination analysis of oleanane triterpene derivatives which are present in said oak wood sample; c) At least one analysis is carried out on the oak wood sample thus prepared in step b) so as to: - identify: i. between one to three molecules belonging to a 1st category of molecules, said one to three molecules being among the three most abundant molecules of all the molecules of said 1st category of molecules present in said oak wood sample, said 11th class of molecules being defined by the set of oleanane triterpenes derivatives which are derived from a genome of formula C30H4806, ii. between one to three molecules belonging to a second category of molecules, said one to three molecules being among the three most abundant molecules of all the molecules of said second category of molecules present in said oak wood sample, said second category of molecules being defined by the set of oleanane triterpene derivatives which are derived from a genome of formula C30H4607, as well as oleanane triterpene derivatives which are derived from a genome of formula C30H4608, and then - to determine the concentration: of each of said one to three molecules of the class of molecules that have been identified, of each of said one to three molecules of the 2nd class of molecules that have been identified; d) determining a ratio R, said ratio R corresponding to the ratio of the concentration or the sum of the concentrations of at least one of said one to three molecules of the first category of molecules which have been identified on the concentration or the sum concentrations of at least one of said one to three molecules of the 2nd class of molecules that have been identified; e) The species of the oak wood sample is identified according to the value of the ratio R determined in step d) as follows: If the ratio R is less than 0.316, then the wood sample of oak belongs to the pedunculate species, If the ratio R is greater than 3.162, then the oak wood sample belongs to the sessile species.
    [0002]
    2. Identification method according to claim 1, characterized in that the 1st category of molecules is defined by all of the oleanane triterpenes derivatives which are derived from arjungenine, seric acid, as well as isomers of arjungenine and seric acid.
    [0003]
    3. Identification method according to claim 1 or 2, characterized in that the second category of molecules is defined by all the oleanane triterpenes derivatives which are derived from the bartogenic acid, the isomers of the acid. bartogenic, trachelosperogenin D and isomers of trachelosperogenin D. 35
    [0004]
    4. Identification method according to any one of claims 1 to 3, characterized in that the 1st category of molecules is defined by the set of molecules: - of formula (I), (I) X4-0 X3-0 0, wherein X2 o X1 represents a glucose group or a hydrogen, where X2 represents a gallate group or a hydrogen, where X3 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, where X4 represents a hydrogen or a gallate group, of formula (II), X8 -O X7 -0 P wherein X6 o X5 represents a glucose group or a hydrogen, where X6 represents a gallate group or a hydrogen, where X7 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, where X8 represents a hydrogen or a gallate group.
    [0005]
    5. Identification method according to any one of claims 1 to 4, characterized in that the second category of molecules is defined by the set of molecules: - of formula (III), 27 Y4-0 Y3-0 0 in which: Y2 o Y1 represents a glucose group or a hydrogen, where Y2 represents a glucose group or a hydrogen group, Y3 represents a hydrogen or a gallate group or a glucose group or a glucose-gallate group, where Y4 represents a hydrogen group; or a gallate group of formula (IV), wherein: Y6 o Y5 represents a glucose group or a hydrogen, Y6 represents a glucose group or a hydrogen group, Y7 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, Y8 represents a hydrogen or a gallate group, of formula (V), 28 (V) in which: Y9 represents a glucose group or a hydrogen, where Y10 represents a group glucose or a hydrogen, where Y11 represents a hydrogen or a group gallate, Y12 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group, Y13 represents a hydrogen or a gallate group of formula (VI), wherein: Y14 represents a glucose group or a hydrogen, where Y15 represents a hydrogen or a gallate group; Y16 represents a glucose group or a hydrogen group; Y17 represents a hydrogen or a glucose group or a gallate group or a glucose-gallate group; represents a hydrogen or a gallate group.
    [0006]
    6. Identification method according to any one of claims 1 to 5, characterized in that the 1st category of molecules is defined by all of the following molecules: quercotriterpenoside I of formula (VII) Quercotriterpenoside II of formula (VIII), (VIII) OH - quercotriterpenoside III of formula (IX), HO HO
    [0007]
    7. Identification method according to any one of claims 1 to 6, characterized in that the second category of molecules is defined solely by the 28-glucosyl derivative of the bartogenic acid of formula (X): OH
    [0008]
    8. Identification method according to claim 7, characterized in that the ratio R corresponds to the ratio of the concentration or the sum of the concentrations of at least one of the molecules chosen from quercotriterpenoside I of formula (VII), quercotriterpénoside II of formula (VIII) and quercotriterpenoside III of formula (IX) on the concentration of the 28-glucosyl derivative of the bartogenic acid of formula (X).
    [0009]
    9. Identification process according to claim 8, characterized in that the ratio R corresponds to the ratio of the sum of the concentrations of quercotriterpenoside I of formula (VII), quercotriterpenoside II of formula (VIII) and quercotriterpenoside III of formula ( IX) on the concentration of the 28-glucosyl derivative of the bartogenic acid of formula (X).
    [0010]
    10. Identification method according to any one of claims 1 to 9, characterized in that step b), the oak wood sample is prepared according to a liquid solid extraction.
    [0011]
    11. Identification method according to any one of claims 1 to 10, characterized in that in step c), the analysis consists of at least one analysis selected from: liquid chromatography analyzes coupled with an analysis of mass spectrometry, gas chromatographic analyzes coupled with mass spectrometry analysis, nuclear magnetic resonance analyzes.
    [0012]
    12. Identification method according to any one of claims 1 to 11, characterized in that in step e) of the identification method, the decimal logarithm of the ratio R is calculated and: if the logarithm of the ratio R thus calculated is greater than 0.5 then the sample of oak wood is of the sessile species; if the decimal logarithm of the ratio R thus calculated is less than -0.5 then the oak wood sample is of the pedunculate species.
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    同族专利:
    公开号 | 公开日
    FR3023618B1|2016-07-15|
    US20160011166A1|2016-01-14|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1456606A|FR3023618B1|2014-07-09|2014-07-09|METHOD FOR IDENTIFYING OAK SPECIES OF AN OAK WOOD SAMPLE|FR1456606A| FR3023618B1|2014-07-09|2014-07-09|METHOD FOR IDENTIFYING OAK SPECIES OF AN OAK WOOD SAMPLE|
    US14/795,609| US20160011166A1|2014-07-09|2015-07-09|Method for identifying the oak species of an oak wood sample|
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