TWI530681B - Method for analyzing liquid flavor in honey - Google Patents

Description

Method for analyzing liquid fragrance in honey

This invention relates to a method of analyzing liquid fragrances, and more particularly to a method of analyzing liquid fragrances in honey.

Honey production is mainly limited by the climate, such as the abnormal climate of cold and hot or the rainy season when the flowers bloom, the flowers are knocked down, resulting in reduced pollen, causing the bees to collect no pollen, so the yield of honey is greatly reduced. In addition, human factors can also affect the yield of honey. For example, if the agricultural pesticide spray may cause bee poisoning to die, or the bee comes into contact with the pollen with pesticide, return to the nest to feed the young bee. After the young bee eats the pesticide, it will affect the nerve of the young bee. The system reduces the ability to collect honey, which in turn leads to a reduction in honey production. When the production of honey is in short supply, some merchants will mix the honey with high-fructose syrup to add flavor, which has a flavor and taste similar to pure honey, or modify the flavor of honey with spices to extend the shelf life of honey. This blended honey has the same appearance and texture as real honey, so it is impossible to distinguish its authenticity by its appearance and taste.

The current honey detection method is tested by the inspection method specified by the National Standards of the Republic of China CNS1305 and the Stable Carbon Isotope Ratio Analysis (SCIRA) recognized by the International Association of Analytical Chemists (AOAC). The test items of CNS1305 are water <20%, sucrose <2%, sugar (glucose + fructose) >70%, water insolubles <0.1%, acidity <30 (meq H ⁺ /1000g), amylase activity>8schade unit, Hydroxymethyl furfural (HMF) <30mg/kg and no antibiotics can be detected. Among them, high fructose syrup can meet the standards of water, sucrose, sugar (glucose + fructose), water insoluble matter, acidity and hydroxymethylfurfural, and the enzyme is used to achieve the standard of amylase activity. Therefore, it can be very close to real honey. Even manufacturers can add a small amount of pollen to the fake honey to mix the natural honey to make it contain protein, so it is impossible to identify the true and false by analyzing the protein in honey.

Stable carbon isotope ratio analysis is performed by elemental analyzer series stable isotope ratio mass spectrometer (EA-IRMS). The principle is that when plants are photosynthesizing, there are C ₃ , C ₄ and Crassulacean acid metabolism depending on the pathway. CAM) three types. These three types have different carbon isotope differentiation effects due to different pathways, so their stable carbon isotopes are also different. In contrast, C ₄ plants have relatively more ¹³ C isotopes, while C ₃ plants have relatively more ¹² C isotopes. Therefore, the differences in carbon isotope composition are often used to identify photosynthesis pathways. Most of the plants belong to C ₃ plants, such as peanuts, tobacco, spinach, soybeans, rice, wheat, cassava, beetroot, longan, lychee, salty grass, sunflower, etc.; and most of the crops and herbaceous crops belong to C ₄ plants, such as corn, sugar cane, sorghum, etc.; in addition, Bromeliad, Agave, Cactaceae, Sedum, Euphorbiaceae, Liliaceae, Orchidaceae and grape plants mostly belong to CAM plants. The honey-derived honey plant belongs to the C ₃ plant. In general, the C ₃ plant has an isotopic δ ¹³ C value in the range of -8 to -16; the C ₄ plant has an isotopic δ ¹³ C value in the range of -22 to -32. Therefore, if high fructose syrup is mixed with honey, since high fructose syrup is mostly converted from corn starch by enzyme, and corn belongs to C ₄ plant, the measured isotope δ ¹³ C value will be in the range of about -8 to -16. At this point, it can be judged that this is a fake honey mixed with high fructose syrup. However, if the high fructose syrup is converted from tapioca starch, since the source of the tapioca starch is the same as the C ₃ plant, the honey can not be distinguished. Therefore, as long as the C ₃ plant is used as a source to prepare a high fructose syrup, it can be mixed into true honey.

However, true honey has a light floral and fruity aroma, so honey blended with high fructose syrup must be added with a fragrance that gives it a flavor similar to true honey. The appearance of the fragrance is divided into solid fragrance and liquid fragrance. Since the trait of honey is viscous, the solubility and uniformity should be considered when adding the fragrance. Therefore, the selection of the fragrance can only be used with the liquid fragrance. Mixing, while solid flavors (eg, powdered flavors, creamy flavors) are not easily found in addition to being uniformly mixed with blended honey. Perfume can be divided into natural, natural-identical and artificial. The natural flavor is a fragrance completely taken from nature, such as pepper, clove, cinnamon, etc.; the natural flavor is a physical or chemical method, and one of the natural flavors containing a plurality of compounds is separately isolated, also called The fragrance is synthetic; the synthetic fragrance contains a synthetic monomer fragrance such as ethyl maltol, Ethyl vanillin, and the like. Synthetic fragrances are essentially indistinguishable from the equivalent natural fragrances, except for the source.

In addition, in the liquid fragrance, whether it is a natural fragrance, an equivalent natural fragrance, and a synthetic fragrance, it is necessary to dissolve the fragrance monomer in a solvent. Generally, the perfume solvent is mainly propylene glycol (Propylene glycol) or triacetin (Triacetin). However, these solvents do not exist in nature, and thus can be used as one of the analytical basis for judging whether or not honey is added with liquid fragrance.

As described above, the inventors of the present invention have conceived and designed a method for analyzing liquid fragrance in honey. After years of painstaking research, the inventors have made improvements in the absence of the prior art, thereby enhancing the industrial use and utilization.

In view of the above-mentioned problems of the prior art, it is an object of the present invention to provide a method for analyzing liquid fragrance in honey to solve the problem that the conventional method cannot recognize the fake honey.

According to the object of the present invention, a method for analyzing a liquid fragrance in honey is proposed. The method comprises the steps of: preheating the honey at a preheating temperature and a preheating time; using the adsorbing fiber, and adsorbing one of the gas phase volatiles of the honey at an adsorption temperature and an adsorption time, wherein the gas phase volatile matter comprises Ethyl maltitol, ethyl vanillin, propylene glycol, triacetin or a combination thereof; gas phase volatiles are subjected to gas chromatography; and ion fragments for identifying gas phase volatiles are performed.

Preferably, the preheating temperature may be from 70 ° C to 90 ° C.

Preferably, the warm-up time can be from 5 minutes to 25 minutes.

Preferably, the adsorbent fibers may be DVB/CAR/PDMS composite fibers.

Preferably, the adsorption temperature may be from 70 ° C to 90 ° C.

Preferably, the adsorption time can be from 10 minutes to 15 minutes.

Preferably, the mass fraction (m/z) of the ion fragments of the vapor phase volatiles may range from 30 to 350.

Preferably, the step of thermally desorbing the adsorbed fibers is further included.

Preferably, the thermal desorption can be continued at 250 ° C for 30 minutes.

In view of the above, the method of the present invention for analyzing liquid fragrance in honey may have one or more of the following advantages:

(1) The method for analyzing a liquid fragrance in honey according to the present invention, using a DVB/CAR/PDMS composite fiber, and extracting a component to be analyzed from a honey sample by a pretreatment method of headspace solid phase microextraction Come out to reduce the effects of non-analyzed substances or substances that may cause interference on the analyte. In addition to reducing the time required for adsorption, the previously processed method can also increase the accuracy of subsequent analysis and identification results, as well as economic benefits.

(2) The method for analyzing a liquid fragrance in honey according to the present invention, by analyzing whether a gas phase volatile matter of a honey sample contains ethyl maltitol, ethyl vanillin, propylene glycol, triacetin or a combination thereof The basis for judging the true and false honey.

(3) The method for analyzing a liquid fragrance in honey according to the present invention, by using a gas chromatography tandem mass spectrometer to perform gas chromatography and identification of a honey sample, and determining the composition of the liquid fragrance added in the honey sample, This method can also avoid the error of human senses.

S1-S4‧‧‧ steps

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a first embodiment of the method for analyzing liquid fragrance in honey of the present invention.

Figure 2 is a GC/MS total ion chromatogram of pure honey measured according to the first embodiment of the present invention.

Figure 3 is a GC/MS total ion chromatogram of propylene glycol-containing honey measured according to the first embodiment of the present invention.

Figure 4a is a mass spectrum of the ion fragment of the propylene glycol component in Figure 3.

Figure 4b is a mass spectrum of the propylene glycol ion fragment in the NIST11 database.

Figure 5 is a GC/MS total ion chromatogram of honey containing propylene glycol and ethyl maltitol measured according to the first embodiment of the present invention.

Figure 6a is a mass spectrum of the ion fragment of the ethyl maltitol component in Figure 5.

Figure 6b is a mass spectrum of the ion fragment of ethyl maltol in the NIST11 database.

Figure 7 is a graph showing propylene glycol, ethyl maltitol and B as measured according to the first embodiment of the present invention. GC/MS total ion chromatogram of honey with vanillin.

Figure 8a is a mass spectrum of the ion fragment of the ethyl vanillin component in Figure 7.

Figure 8b is a mass spectrum of the ion fragment of ethyl vanillin in the NIST11 database.

Figure 9 is a GC/MS total ion chromatogram of the triacetin-containing honey measured according to the first embodiment of the present invention.

Figure 10a is a mass spectrum of the ion fragment of triacetin in Figure 9.

Figure 10b is a mass spectrum of the ion fragment of triacetin in the NIST11 database.

Figure 11a is a GC/MS total ion chromatogram of pure honey.

Figure 11b is a GC/MS total ion chromatogram of honey containing propylene glycol.

Figure 11c is a GC/MS total ion chromatogram of honey containing both propylene glycol and ethyl maltol.

The technical features, contents, and advantages of the present invention, as well as the advantages thereof, can be understood by the present inventors, and the present invention will be described in detail with reference to the accompanying drawings. The subject matter is only for the purpose of illustration and description. It is not intended to be a true proportion and precise configuration after the implementation of the present invention. Therefore, the scope and configuration relationship of the attached drawings should not be interpreted or limited. First described.

The invention will be further described in detail by the following preferred embodiments and the accompanying drawings. It should be noted that the experimental data disclosed in the following embodiments are for explaining the technical features of the present invention, and are not intended to limit the manner in which they can be implemented.

Please refer to FIG. 1 , which is a method for analyzing liquid fragrance in honey according to the present invention. Flowchart of the first embodiment.

As shown in the figure, the analysis method comprises the following steps: First, in step S1, the honey is preheated at a preheating temperature and a preheating time; secondly, in step S2, the adsorbed fibers are used, and the adsorption is carried out at an adsorption temperature and an adsorption time. a gas phase volatile of honey, wherein the gas phase volatiles comprise Ethyl maltol, Ethyl vanillin, Propylene glycol, Triacetin or a combination thereof; Step S3, gas phase volatiles are subjected to gas chromatography; finally, in step S4, ion fragments for identifying gas phase volatiles are performed.

Specifically, the portion of step S1 is first performed, that is, the honey sample to be analyzed is pretreated. Common pretreatment methods currently include membrane extraction, static headspace sampling, purge and trap, supercritical fluid extraction, and solid phase. Solid phase extraction (SPE), etc., in this embodiment, solid-phase microextraction (SPME) is adopted, which has the advantages of simple instrument, convenient use, short sampling time and good detection limit. In addition, it can reduce analysis time, increase sample analysis speed and reduce human error. Solid phase microextraction can be divided into the following extraction modes: direct solid phase microextraction (direct SPME, DI-SPME), headspace solid phase microextraction (headspace SPME, HS-SPME) and derivatized solid phase micro Derivatization (SPME), and in this example, a headspace solid phase microextraction method was used for the pretreatment step of honey.

Take 5g-10g of honey, put it into 20ml headspace glass bottle, cover it with aluminum cover with PTFE gasket (Silicone Blue/PTFE) and tighten it, about 70°C to about 90°C The preheating temperature is preheated for a preheating period of from about 4 minutes to about 25 minutes. The preheating temperature may be from about 70 ° C to about 90 ° C, and is 85 ° C as an exemplary embodiment in this embodiment, but is not limited thereto. In addition, the preheating time may be from about 5 minutes to about 25 minutes, and in the present embodiment, the pretreatment of the sample is performed in 15 minutes. The amount of honey sampled will affect the results of the analysis. If the sample volume is too small, the concentration will be insufficient. If the sample volume is too much, the adsorbed fiber will be immersed in the honey sample during the headspace solid phase microextraction. Next, the portion of step S2 is carried out, and the honey sample is placed in a pretreatment heating tank at about 85 ° C for about 10 minutes. Thereafter, the adsorption probe containing the DVB/CAR/PDMS composite fiber is inserted into a headspace glass bottle containing the honey sample, and the adsorption fiber is extended to perform adsorption at an adsorption temperature of about 70 ° C to about 90 ° C and The gas phase volatiles of the adsorbed honey sample are subjected to an adsorption time of from about 10 minutes to about 15 minutes. The adsorption fiber of the DVB/CAR/PDMS composite fiber is subjected to headspace extraction, and after a period of time, the gas phase volatiles are distributed and balanced between the DVB/CAR/PDMS composite fiber and the honey sample, that is, the adsorption is completed. A step of. In the adsorption type of probe used in the present embodiment is 50/30 μ M DVB / CAR / PDMS , and the length of DVB / CAR / PDMS composite fibers was 1 cm. The adsorption temperature can be from about 70 ° C to about 90 ° C, and in the present embodiment is controlled at 85 ° C. On the other hand, in the initial stage of adsorbing the gas phase volatiles, the gas phase volatiles to be analyzed are rapidly adsorbed onto the DVB/CAR/PDMS composite fiber, but as time goes on, the adsorption speed becomes It is getting slower and slower. When approaching the equilibrium state, prolonging the adsorption time does not have much influence on the amount of adsorbed gas phase volatiles. Therefore, the adsorption time is generally 30 minutes, and the adsorption time can be about 10 minutes to about 15 minutes. Minutes, but in this embodiment it is controlled for 10 minutes, but not limited to this.

That is to say, the DVB/CAR/PDMS composite fiber of the headspace solid phase microextraction method is not in contact with the honey sample, but is placed above the honey sample solution for the gas phase volatile matter of the headspace extraction honey sample solution. . This method is mainly used to extract volatile or semi-volatile substances. The advantage of using this method is that it can protect the DVB/CAR/PDMS composite fiber from being contaminated and destroyed by the sample during the extraction process, thereby prolonging the service life of the DVB/CAR/PDMS composite fiber and even avoiding the sample matrix (matrix). ) interference.

It is worth mentioning that the DVB/CAR/PDMS composite fiber can be additionally subjected to a thermal desorption step before the adsorption step. Thermal desorption is sustained at a temperature of about 250 ° C 30 minutes. The adsorption fibers for adsorbing vapor phase volatiles are selected according to the principle of "like dissolve like", that is, the adsorption fibers of the polar coating adsorb polar compounds; the adsorption fibers of non-polar coatings are not adsorbed. Polar compound. Further, the longer the adsorbed fiber, the higher the amount of adsorbed gas phase volatiles, but at the same time there is a disadvantage that the adsorbed fibers are easily broken. Therefore, unless otherwise specified, an adsorbent fiber of 1 cm in length is generally used. Secondly, the thicker the coating, the higher the amount of adsorbed gas phase volatiles, but the longer it takes to reach the equilibrium of distribution, which in turn leads to a slower rate of adsorption of vapor phase volatiles.

Next, the steps S3 and S4 are performed. At present, the solid phase microextraction method is mostly combined with a gas chromatograph or a gas chromatography mass spectrometer for post-stage analysis, and the adsorbed fibers adsorbed to the gas phase volatile matter are directly injected into the gas phase. The injection port of the chromatograph is subjected to a thermal desorption step to desorb the gas phase volatiles from the adsorbed fibers to a gas chromatograph for subsequent separation and detection. The gas phase volatile matter of the present embodiment comprises ethyl maltitol, ethyl vanillin, propylene glycol, triacetin or a combination thereof. In the present embodiment, the four substances are used as a basis for judging whether or not the liquid fragrance is added to the honey. As long as it is detected, regardless of the measured concentration, it can be concluded that there is an added liquid fragrance in the honey sample to be tested.

Further, this embodiment uses a gas chromatography mass spectrometry for gas chromatography and identification, wherein the gas chromatograph model is 7890B; the mass spectrometer model is 5977A. (Manufacturer Agilent). The carrier gas of the gas chromatograph must use a chemically inert gas, which may be hydrogen (H ₂ ), nitrogen (N ₂ ) or helium (He). In this embodiment, helium is used as an exemplary aspect. , but not limited to this. In addition, in the present embodiment, the machine setting conditions of the gas chromatograph can be divided into three parts: the conditions of the sample injection port, the capillary column used, and the conditions set by the oven. First, the sample injection port was fully injected (no split), the injection temperature was 250 ° C, the injection pressure was 7.3614 psi, the flow rate was 14 ml/min, and the residue was blown off at 10 ml/min after 2 minutes of injection. kind. Secondly, the capillary column used was an Agilent HP 5MS capillary column (length 30 m, inner diameter 250 μm, film thickness 0.25 μM), the initial sample injection rate in the capillary column was 1 ml/min, and the pressure in the capillary column was 7.3614 psi. Finally, the temperature rise program used in the oven of the vapor deposition tandem mass spectrometer is shown in the following table: The temperature of the capillary main is increased in a continuous or staged manner during the separation to obtain the desired result. First, the starting temperature is 45 ° C for 2 minutes; secondly, it rises to 110 ° C at 2 ° C per minute, the rise time is 32.5 minutes and is maintained for 2 minutes; then, it rises to 220 ° C at 10 ° C per minute, and the rise time is 11 minutes and maintained for 10 minutes, and then, increased to 50 ° C per minute to 250 ° C, the rise time was 0.6 minutes and maintained for 5 minutes; finally, rose to 300 ° C at 10 ° C per minute, the rise time was 5 minutes, and the overall The total time of the process was 68.1 points.

The setting conditions of the mass spectrometer can be divided into the following three parts: (1) entering through the end of the capillary column of the gas chromatograph, and the temperature of the ion source is set to 280 ° C; (2) ionization: EI (electron ionization) The ion is ionized by a voltage of 70 volts, and the temperature of the ion source is controlled at 230 ° C; (3) Quadrupole mass analyzer: the mass-to-charge ratio (m/z) ranges from 30 to 350. The ion fragment is detected by the detector and the temperature of the detector is set to 150 °C.

Specifically, the gas phase volatiles adsorbed by the DVB/CAR/PDMS composite fiber are injected into the injection port of the gas chromatograph, and the gas phase volatiles are removed from the DVB/CAR/PDMS composite fiber due to the high temperature. Attached. The gas chromatograph then uses helium as a carrier gas to carry the vapor phase volatiles into the capillary column of the gas chromatograph. Individual compounds based on capillary columns The affinity of the combination, the compound with strong affinity with the capillary column, the ramification is slower, that is, the residence time is longer; on the contrary, the compound with strong affinity with the capillary column moves faster, that is, the residence time short. The compound after separation by capillary column was analyzed by entering the mass spectrometer through the end of the capillary column, and the temperature of the ion source was set to 280 °C. Next, the mass spectrometer charged the compound with a strong voltage of 70 volts and broke into ion fragments, and the temperature of the ion source was controlled at 230 °C. Finally, the ion fragments are collected by a quadrupole mass analyzer. The collected ion fragments have a mass-to-charge ratio (m/z) ranging from 30 to 350, and are detected by a detector, and the detector is The temperature was set to 150 °C. Qualify the compound by identifying the detected signal. And confirm with the standard product again.

After the honey sample analysis, the following results were obtained: Please refer to Fig. 2, which is a GC/MS total ion chromatography (TIC) of pure honey measured according to the first embodiment of the present invention. .

Please refer to FIG. 3, FIG. 4a and FIG. 4b together, which are respectively GC/MS total ion chromatograms of propylene glycol-containing honey measured according to the first embodiment of the present invention; FIG. An ion fragment mass spectrum of the propylene glycol component; and an ion fragment mass spectrum of propylene glycol in the NIST11 database. As shown in Fig. 3, a peak (Peak) can be found at a position with a retention time of 7.593 minutes, and the peak is analyzed by a mass spectrometer. The result is as shown in Fig. 4a, and the residence time is 7.593 minutes. The main ion fragments of the peaks can be seen as 45.0, 43.0, and 61.0; after comparing the major ion fragments with the NIST11 database, refer to Figure 4b, and identify the most consistent compound by ion fragment alignment. The compound is propylene glycol.

Please refer to FIG. 5, FIG. 6a and FIG. 6b together, which are respectively GC/MS total ion chromatography of honey containing propylene glycol and ethyl maltitol measured according to the first embodiment of the present invention. Fig. 5 is a mass spectrum of the ion fragment of the ethyl maltitol component in Fig. 5; and an ion fragment mass spectrum of ethyl maltol in the NIST11 database. As shown in Figure 5, the residence time is 34.469 A peak was found at the position of the minute, and the peak was analyzed by a mass spectrometer. As shown in Fig. 6a, when the residence time was 34.469 minutes, the main ion fragments of the peak were seen to be 140.0, 139.0, and 97.0; After the main ion fragment is compared with the NIST11 database for the ion fragment, referring to Figure 6b, the most well-matched compound identified by the ion fragment alignment is ethyl maltol.

Please refer to Fig. 7, Fig. 8a and Fig. 8b, respectively, which are GC/ of honey containing propylene glycol, ethyl maltitol and ethyl vanillin, respectively, measured according to the first embodiment of the present invention. MS total ion chromatogram; ion mass spectrogram of ethyl vanillin component in Figure 7; and ion fragment mass spectrum of ethyl vanillin in NIST11 database. As shown in Fig. 7, a peak can be found at a position of 43.712 minutes, and the peak is analyzed by a mass spectrometer. As shown in Fig. 8a, when the residence time is 43.712 minutes, the peak can be seen. The main ion fragments were 137.0, 166.0 and 109.0; after comparing the major ion fragments with the NIST11 database, the compound with the most consistent identity of the compounds was ethyl vanillin by reference to Figure 8b.

Please refer to FIG. 9 , FIG. 10 a and FIG. 10 b , which are respectively GC/MS total ion chromatograms of honey containing triacetin measured according to the first embodiment of the present invention; Figure 9 shows the mass spectrum of the ion fragment of the triacetin component; and the mass spectrum of the ion fragment of triacetin in the NIST11 database. As shown in Fig. 9, a peak can be found at a position with a residence time of 41.981 minutes, and the peak is analyzed by a mass spectrometer. As shown in Fig. 10a, when the residence time is 41.981 minutes, the peak can be seen. The main ion fragments were 43.0, 103.0, and 145.0. After comparing the major ion fragments with the NIST11 database, refer to Figure 10b. The most consistent compound identified by ion block alignment was triacetin.

Finally, please refer to Figures 11a, 11b and 11c, which are respectively GC/MS total ion chromatogram of pure honey, propylene glycol containing honey, and honey containing both propylene glycol and ethyl maltol. First, Figure 11a is a GC/MS total ion chromatogram of pure honey; Figure 11b is a GC/MS total ion chromatogram of honey with a propylene glycol-added fragrance solvent; and Figure 11c is a propylene glycol-added fragrance solvent and GC/MS total ion chromatogram of honey from a monomeric fragrance of ethyl maltol. By comparing the three samples with the total ion chromatogram, the retention time and spectrum of honey can be clearly distinguished between pure honey, honey with propylene glycol, and propylene glycol flavor solvent and ethyl maltitol monomer. difference.

The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims.

S1-S4‧‧‧ steps

Claims (7)

A method for analyzing a liquid fragrance in honey, comprising the steps of: preheating a honey at a preheating temperature and a preheating time; using an adsorbing fiber, and adsorbing at an adsorption temperature and an adsorption time One of the honey vapor phase volatiles, wherein the gas phase volatiles are Propylene glycol, Triacetin or a combination thereof; the adsorbed fibers are subjected to a thermal desorption step at 250 ° C for 30 minutes; The gas phase volatiles obtained by thermal desorption are subjected to gas chromatography; and ion fragments for identifying the gas phase volatiles are subjected. A method of analyzing a liquid fragrance in honey as described in claim 1, wherein the preheating temperature is from 70 ° C to 90 ° C. The method of analyzing the liquid fragrance in honey as described in claim 2, the preheating time is 5 minutes to 25 minutes. A method for analyzing a liquid fragrance in honey as described in claim 1, wherein the adsorbent fiber is a DVB/CAR/PDMS composite fiber. The method for analyzing a liquid fragrance in honey according to the first aspect of the patent application, wherein the adsorption temperature is from 70 ° C to 90 ° C. The method of analyzing the liquid fragrance in honey as described in claim 5, the adsorption time is from 10 minutes to 15 minutes. The method of analyzing the liquid fragrance in honey according to the first aspect of the invention, wherein the ion fragment of the gas phase volatile matter has a mass to charge ratio (m/z) ranging from 30 to 350.