JP4609943B2 - Method and apparatus for continuous evaluation of volatile components - Google Patents

Description

  The present invention is an apparatus for fractionating components separated by gas chromatography in aroma of animal and plant raw materials. And a method for evaluating the influence of volatile components separated by gas chromatography on aroma or flavor.

  Conventionally, by separating volatile components separated by gas chromatograph, more precise analysis and evaluation of separated components have been performed. Since the conventional fractionation apparatus is generally assumed to be used for instrumental analysis, a method of condensing volatile components by introducing and cooling the gas discharged from the gas chromatograph into a fractionation container is adopted ( Patent Document 1).

  Non-Patent Document 2 describes a method for collecting and collecting volatile components separated by gas chromatography into water in “Development of Coffee Flavor”.

  On the other hand, smell sniffing GC (GC-O) (GC-O) is used as a method for retrieving trace aromatic components from animal and plant raw materials. That is, it is generally performed by searching for a trace component that is not detected by GC-MS by smelling the component separated and discharged at the GC column outlet. Such perfume analysis technology is introduced in, for example, “Utilization of Gas Chromatography and Mass Spectrometer in Perfume Analysis” (Non-Patent Document 1). In addition, for the flavor role of the aromatic component in the liquid sample of the animal and plant raw materials, a method of adding and evaluating the isolated or concentrated component to the liquid sample of the animal and plant raw materials is used.

Patent Document 2 proposes a method for continuously evaluating the influence of a separated volatile component on aroma by mixing a volatile component separated by a gas chromatograph and a component volatilized from a sample.
Japanese Examined Patent Publication No. 6-64035 JP 2003-107067 A Fragrance Journal, 1997-6, 12, 1997 Soft Drink Technical Document, 2002 No.1, 67-83

  In the conventional sorting apparatus, the method in which the separated volatile component is introduced into the sorting container together with the carrier gas and cooled and condensed is performed in a vented state in order to discharge the carrier gas. Or low boiling point components are difficult to collect.

  On the other hand, as an evaluation method of the aroma component, the evaluation of the aroma component using the above-described GC-O only expresses the characteristics of the component in the gas phase. The interaction with can not be evaluated at all. In addition, when aroma components are isolated, concentrated and added to a liquid sample of animal and plant raw materials for evaluation, enormous labor is required for isolation and concentration. In addition, the evaluation method described in Patent Document 2 evaluates the influence of each component in a state where it is volatilized in the atmosphere, and evaluates the influence of the volatile component on the aroma and the deodorizing effect. However, it is difficult to accurately predict the influence of the components present in the liquid.

  In addition, the method described in Non-Patent Document 2 is a method of introducing and bubbling volatile components discharged together with the carrier gas into water, so that the gas-liquid contact area and the contact time can be made constant. It was difficult. In addition, this method has a problem in that the operation becomes complicated because a plurality of containers into which water for introducing a volatile component is charged are prepared and sequentially replaced.

  That is, an object of the present invention is to provide a method and an apparatus for simply evaluating the contribution of volatile components in a liquid.

  The inventors of the present application overcome the drawbacks and limitations of the conventional GC-O analysis method and evaluation method of aroma components as described above, and the method of adding each aroma component to a liquid sample of animal and plant raw materials. As a result of intensive research aimed at faithful reproduction of aroma and development of functionality, volatile components separated by gas chromatography and liquid samples of animal and plant raw materials are continuously mixed and evaluated. A new aroma collection method was developed and the present invention was completed.

  The novel aroma evaluation method developed by the present inventors is an aroma evaluation method in which a volatile component separated by a gas chromatograph is continuously mixed with a liquid sample.

  Since the present invention can easily and sensuously evaluate the mixed liquid of the separated volatile component and the liquid sample for evaluation, it is very useful for evaluation of fragrance components in which fragrance components such as masking and enhancement interact with each other. It is a technique.

  The fractionation device of the present invention is characterized in that a volatile component separated by a gas chromatograph is absorbed by a liquid solvent, a gas channel connected to an exhaust channel of the gas chromatograph, a liquid container, It has a flow path for passing a liquid from a liquid container, a flow path for joining a gas flow path and a liquid flow path, and includes means for separating the solution discharged from the flow path after the merge.

  In the present invention, the liquid container can be heated or cooled as necessary depending on the liquid to be used or the purpose of sorting. As a method of adjusting the temperature in the sample container, a known method such as a method of installing a heater outside the container or a method of attaching a jacket to the container and passing a temperature adjusting fluid can be used. In addition, a temperature measuring instrument can be installed inside or on the outer surface of the container, and means for adjusting the temperature by the output of the measuring device can be applied. The material of the container is preferably a material that does not itself release volatile components such as odor and does not adsorb volatile components, and a glass container or the like is usually used.

  As the liquid flow method, any method such as a gravity drop method or pump liquid feed can be selected, but liquid feed by a pump is preferable because the flow rate can be controlled more easily and accurately. Furthermore, when passing the sample solution for evaluation, it is more preferable to use a tube pump that can easily exchange the flow path in order to avoid the influence of residual aromatic components and taste components in the flow path. .

  In the present invention, the fractionation device may constitute an apparatus separately from the gas chromatograph, or may constitute an apparatus integrated with the gas chromatograph. When configured as an apparatus separate from the gas chromatograph, there are provided a gas flow path, a flow path for passing the liquid in the container, a flow path for merging the gas flow path and the flow path for the sample solution. A means for separating the solution discharged from the flow path after the merging is arranged, and a means for connecting to the exhaust flow path of the gas chromatograph is provided at the end of the gas flow path. When the apparatus is integrated with the gas chromatograph, in order to avoid the influence of heating by the column oven, the liquid sample container, the liquid flow path, and the sorting apparatus are independently arranged outside the column tank.

  In the present invention, the components separated by the gas chromatograph are divided into a combined flow path of the flow path to the detector and the liquid from the liquid container, or are guided to the combined flow path after passing through the detector. When the detector of the gas chromatograph may cause a change in volatile components due to heating or the like, it is preferable to divide the flow path to the detector after column separation.

  In the present invention, the volatile component and the liquid separated by the gas chromatograph are mixed in the merging path, and discharged from the path in a state where the volatile component is absorbed by the liquid sample. The discharged liquid mixture is collected every time or every detection peak of the gas chromatogram. In the case of a system that sorts by time, the time setting in the fraction collector is the sampling switching time. In addition, when sorting for each detection peak, for example, based on a signal from a detector, the time point when the numerical change ΔT changes from a negative value to 0 or a positive value is detected as a peak change point, and the gas chroma is detected. The time difference between the detection time of the graph and the discharge time of the liquid mixture containing the component is added to obtain the sampling switching time.

  In the present invention, a fraction collector is usually used as a method for separating a mixed solution. The fraction collector used in the present invention only needs to have a general function, and can be integrated with a fractionation device.

  In the volatile component evaluation method of the present invention, the gas chromatograph fractionation apparatus is used. That is, an apparatus comprising means for separating essential oils composed of multiple components into each component, means for continuously mixing the separated volatile components and the liquid sample for evaluation test, and means for separating the mixed solution Is used. In the present invention, the mixed liquid of the separated volatile component and the liquid sample for evaluation is sensorially evaluated. At the same time, each component can be easily associated with the evaluation by the chromatogram.

  In the volatile component evaluation method of the present invention, a sample solution containing a volatile component and / or a taste component is charged into the liquid container in the gas chromatograph fractionation apparatus, and the volatile component separated from the sample solution is obtained. A solution obtained by mixing and separating the sex components is used for evaluation. Sample solutions for evaluation tests include, for example, a solution in which a volatile component and / or a taste component is dissolved or dispersed in a solvent such as water, alcohol, propylene glycol, or a mixed solvent thereof, milk, milk beverage, taste beverage, Liquids such as alcoholic beverages, fruit juices, liquid seasonings, and the like, solvent extracts of animal and plant raw materials, steam distilled water, essential oils, or dilutions with these solvents. The type of solvent used as the extraction solvent or dilution solvent used for preparing the liquid sample may be liquid such as water, ethyl alcohol, propylene glycol, oils and fats, but preferably has a low viscosity and does not solidify at room temperature. Is preferred.

  The mixed liquid of the separated volatile component and the liquid sample for evaluation can be subjected to component analysis by GC or GC-MS by a known method.

  FIG. 1 shows an example of a conceptual diagram of the simplest apparatus used in the present invention, but the present invention is not limited to this drawing.

(Figure 1)

Examples of the present invention are shown below.
Example 1
The coffee aroma concentrate obtained by steam distillation is introduced into the gas chromatograph, and at the same time, the coffee extract is passed through a sample container provided outside the gas chromatograph path to obtain a mixed liquid with the effluent gas from the gas chromatograph. The mixture was evaluated. The gas chromatograph used in the experiment was HP 5890, the detector was TCD, the column used was HP-1 (length 30 m, inner diameter 0.53 mm, film thickness 1.5 μm), and the gas chromatograph carrier gas was helium. The gas flow was 4.4 ml / min, and the temperature was raised from 40 ° C. to 230 ° C. at a rate of 3 ° C./min. As a sorting method, 1 ml of coffee extract is passed through a metering pump per minute, and the coffee extract and gas effluent from the gas chromatograph are brought into contact with each other at the portion where the liquid passage and the gas passage meet. A liquid mixture was obtained, and the liquid mixture was fractionated using a fraction collector. Sampling switching time in the fraction collector was 1 minute, and 1 ml was sampled.

  As a panelist, three flavorists performed sensory evaluation under the above-mentioned conditions. As a result, it was possible to evaluate the influence on the coffee flavor of each fraction, which cannot be understood from the evaluation by GC-O.

  By the continuous evaluation method of the present invention and the apparatus used therefor, it is possible to more accurately and simply evaluate the contribution of the volatile components dissolved in the liquid to the aroma, or the effect of suppressing the generation of malodor, etc. It can be used for blending and selection of deodorant components.

Claims (5)

A gas channel connected to the exhaust channel of the gas chromatograph, a liquid container, a channel through which the liquid from the liquid container flows, and a channel that merges the gas channel and the liquid flow channel; A volatile component fractionating device comprising means for fractionating a solution discharged from the flow path. A gas chromatograph having a column for separating a volatile component, a sample container for continuously passing a liquid sample, and a flow path where a liquid from the sample container and a flow path for an outflow gas from the column merge. Volatilization characterized by continuously mixing a volatile component separated by gas chromatography and a liquid sample containing a volatile component and / or a taste component using the apparatus according to claim 1 or 2. Evaluation method of sex component. 4. The method for evaluating a volatile component according to claim 3, wherein the sample introduced into the sample container is a squeezed liquid or extract of an animal or plant material. The method for evaluating a volatile component according to claim 3 or 4, wherein the sample introduced into the sample container provided outside the gas chromatograph path is a liquid containing a malodorous substance.