TWI530681B - Method for analyzing liquid flavor in honey - Google Patents
Method for analyzing liquid flavor in honey Download PDFInfo
- Publication number
- TWI530681B TWI530681B TW104101722A TW104101722A TWI530681B TW I530681 B TWI530681 B TW I530681B TW 104101722 A TW104101722 A TW 104101722A TW 104101722 A TW104101722 A TW 104101722A TW I530681 B TWI530681 B TW I530681B
- Authority
- TW
- Taiwan
- Prior art keywords
- honey
- minutes
- analyzing
- liquid fragrance
- adsorption
- Prior art date
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Description
本發明是有關於一種分析液態香料之方法，特別是有關於一種分析蜂蜜中之液態香料之方法。 This invention relates to a method of analyzing liquid fragrances, and more particularly to a method of analyzing liquid fragrances in honey.
蜂蜜產量主要受到氣候的限制，如忽冷忽熱的異常氣候或者花開時遇到雨季，把花朵打落，導致花粉減少，造成蜜蜂採集不到花粉，因此蜂蜜的產量大幅減少。此外，人為因素也會影響蜂蜜的產量，例如果農噴灑農藥可能導致蜜蜂中毒死亡，或者蜜蜂接觸到有農藥的花粉後，回巢餵食幼蜂，幼蜂吃到農藥後，會影響幼蜂的神經系統，降低其採蜜的能力，進而造成蜂蜜產量的減少。當蜂蜜產量供不應求時，部分商人便會以高果糖糖漿添加香料的方式混充真蜂蜜，使其具有類似純蜂蜜的風味及口感，或者以香料修飾且穩定蜂蜜的風味，以延長蜂蜜的保存期限。這種調和蜂蜜的外觀性狀及口感與真實的蜂蜜相同，因此，無法單純以外觀及口感分辨其真實性。 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.
目前的蜂蜜檢測方法以中華民國國家標準CNS1305所規範的檢驗方法以及國際分析化學家協會(AOAC)所公認的穩定碳同位素比值分析(SCIRA)進行檢驗。CNS1305的檢驗項目為水分<20%、蔗糖<2%、糖類(葡萄糖+果糖)>70%、水不溶物<0.1%、酸度<30(meq H+/1000g)、 澱粉酶活性>8schade unit、羥甲基糠醛(Hydroxymethyl furfural，HMF)<30mg/kg及不可驗出抗生素。其中，高果糖糖漿可以符合水分、蔗糖、糖類(葡萄糖+果糖)、水不溶物、酸度及羥甲基糠醛的標準，並且藉由添加酵素來達到澱粉酶活性的標準。因此，可以十分趨近真實的蜂蜜。甚至，廠商也可在假蜂蜜中添加微量的花粉粒(pollen)以混充天然的蜂蜜，使之含有蛋白質，因此無法藉由分析蜂蜜中的蛋白質來辨識真假。 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.
穩定碳同位素比值分析則是利用元素分析儀串聯穩定同位素比值質譜儀(EA-IRMS)進行分析，其原理為植物在行光合作用時，因途徑不同而有C3、C4及Crassulacean acid metabolism(CAM)三種型態。此三種型態由於途徑不同而導致不同的碳同位素分化作用，因此其穩定碳同位素亦有差異。相較來說，C4植物具有相對較多的13C同位素，而C3植物則具有相對較多的12C同位素，因此常利用碳同位素組成的特徵差異去鑑定植物行光合作用的途徑。大部分的植物都是屬於C3植物，例如花生、菸草、菠菜、大豆、水稻、小麥、樹薯、甜菜根、龍眼樹、荔枝樹、咸豐草、向日葵等；而雜糧作物及草本作物大多屬於C4植物，例如玉米、甘蔗、高粱等；另外，鳳梨科、龍舌蘭科、仙人掌科、景天科、大戟科、百合科、蘭科及葡萄科植物大多屬於CAM植物。而蜂蜜來源的蜜原植物屬於C3植物。一般而言，C3植物的同位素δ 13C值約在-8至-16的範圍；C4植物的同位素δ 13C值約在-22至-32的範圍。因此，如果以高果糖糖漿混充蜂蜜時，由於高果糖糖漿大多由玉米澱粉經酵素轉化而來，玉米屬於C4植物，所以測出的同位素δ 13C值會在約-8至-16的範圍，此時便可判斷出這是以高果糖糖漿混充的假蜂蜜。然而，如果高果糖糖漿是以樹薯澱粉轉化而成，由於樹薯澱粉的來源樹薯與蜜源植物同屬C3植物，此時便無法分辨出蜂蜜的真偽。因此，只要以C3植物為來源製備成高果糖糖漿，便可混充成真蜂蜜。 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.
但是，真蜂蜜會帶有淡淡的花果香味，因此以高果糖糖漿所調和之蜂蜜必須添加香料，使其具有近似真蜂蜜的香味。香料的外觀型態分為固態香料及液態香料，由於蜂蜜的性狀為黏稠狀，在添加香料時需考慮到溶解性及均勻性，因此香料的選擇上僅能使用液態香料才容易與調和蜂蜜均勻混合，而固態香料(例如，粉狀香料、膏狀香料)除了無法與調和蜂蜜均勻混合之外，外觀上也容易被發現。香料可分為天然香料(Natural)、等同天然的香料(Natural-identical)及人工合成香料(Artificial)。天然香料為完全取自天然中的香料，如胡椒、丁香、肉桂等；等同天然的香料為使用物理或化學的方法，將含有多種化合物的天然香料中的其中一種化合物單獨分離出來，又稱為單離香料；人工合成香料為香料組成中含有人工合成單體香料，如乙基麥芽醇(Ethyl maltol)、乙基香草醛(Ethyl vanillin)…等。人工合成香料除了來源不同之外，在本質上與等同天然的香料並無區別。 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.
此外，液態香料中無論是天然香料、等同天然的香料及人工合成香料在使用上皆需將香料單體溶解在溶劑中。一般香料溶劑以丙二醇(Propylene glycol)或三乙酸甘油酯(Triacetin)為主。然而，該些溶劑並不存在於自然界，因此可作為判斷蜂蜜是否添加液態香料之分析依據之一。 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.
綜觀前所述，本發明之發明人思索並設計一種分析蜂蜜中之液態香料之方法，經多年潛心研究，以針對現有技術之缺失加以改善，進而增進產業上之實施利用。 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.
有鑑於上述習知技藝之問題，本發明之目的就是在提供一種分析蜂蜜中之液態香料之方法，以解決習知方法無法辨識出假蜂蜜的問題。 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.
根據本發明之目的，提出一種分析蜂蜜中之液態香料之方法， 其包含下列步驟：將蜂蜜以一預熱溫度及一預熱時間進行預熱；使用吸附纖維，並且在一吸附溫度及一吸附時間下進行吸附蜂蜜之一氣相揮發物，其中氣相揮發物包含乙基麥芽醇、乙基香草醛、丙二醇、三乙酸甘油酯或其組合；將氣相揮發物進行氣相層析；以及進行鑑定氣相揮發物之離子片段。 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.
較佳地，預熱溫度可為70℃至90℃。 Preferably, the preheating temperature may be from 70 ° C to 90 ° C.
較佳地，預熱時間可為5分鐘至25分鐘。 Preferably, the warm-up time can be from 5 minutes to 25 minutes.
較佳地，吸附纖維可為DVB/CAR/PDMS複合型纖維。 Preferably, the adsorbent fibers may be DVB/CAR/PDMS composite fibers.
較佳地，吸附溫度可為70℃至90℃。 Preferably, the adsorption temperature may be from 70 ° C to 90 ° C.
較佳地，吸附時間可為10分鐘至15分鐘。 Preferably, the adsorption time can be from 10 minutes to 15 minutes.
較佳地，氣相揮發物之離子片段之質荷比(m/z)範圍可為30至350。 Preferably, the mass fraction (m/z) of the ion fragments of the vapor phase volatiles may range from 30 to 350.
較佳地，更可包含將吸附纖維進行熱脫附之步驟。 Preferably, the step of thermally desorbing the adsorbed fibers is further included.
較佳地，熱脫附可在250℃下持續30分鐘。 Preferably, the thermal desorption can be continued at 250 ° C for 30 minutes.
承上所述，本發明之分析蜂蜜中之液態香料之方法，其可具有一或多個下述優點： 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)本發明之分析蜂蜜中之液態香料之方法，使用DVB/CAR/PDMS複合型纖維，且藉由頂空固相微萃取法的前處理方式，將待分析的成分從蜂蜜樣品中萃取出來，以降低非分析的物質或可能產生干擾的物質對待分析物產生影響。此前處理的方法除了可減短進行吸附所需要的時間，也可增加後續在分析及鑑定結果的準確性，同時也符合經濟效益。 (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)本發明之分析蜂蜜中之液態香料之方法，藉由分析蜂蜜樣品的氣相揮發物是否含有乙基麥芽醇、乙基香草醛、丙二醇、三乙酸甘油酯或其組合，以作為判斷蜂蜜真假的依據。 (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)本發明之分析蜂蜜中之液態香料之方法，藉由使用氣相層析串聯質譜儀，以進行蜂蜜樣品的氣相層析及鑑定，判斷蜂蜜樣品中所添加的液態香料的成分，而此方式也可避免人為感官的誤差。 (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‧‧‧步驟 S1-S4‧‧‧ steps
第1圖係為本發明之分析蜂蜜中之液態香料之方法之第一實施例之流程圖。 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.
第2圖係為根據本發明之第一實施例所測得的純蜂蜜之GC/MS總離子層析圖。 Figure 2 is a GC/MS total ion chromatogram of pure honey measured according to the first embodiment of the present invention.
第3圖係為根據本發明之第一實施例所測得的含丙二醇的蜂蜜之GC/MS總離子層析圖。 Figure 3 is a GC/MS total ion chromatogram of propylene glycol-containing honey measured according to the first embodiment of the present invention.
第4a圖係為第3圖中丙二醇成分之離子片段質譜圖。 Figure 4a is a mass spectrum of the ion fragment of the propylene glycol component in Figure 3.
第4b圖係為NIST11資料庫中丙二醇之離子片段質譜圖。 Figure 4b is a mass spectrum of the propylene glycol ion fragment in the NIST11 database.
第5圖係為根據本發明之第一實施例所測得的含丙二醇及乙基麥芽醇的蜂蜜之GC/MS總離子層析圖。 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.
第6a圖係為第5圖中乙基麥芽醇成分之離子片段質譜圖。 Figure 6a is a mass spectrum of the ion fragment of the ethyl maltitol component in Figure 5.
第6b圖係為NIST11資料庫中乙基麥芽醇之離子片段質譜圖。 Figure 6b is a mass spectrum of the ion fragment of ethyl maltol in the NIST11 database.
第7圖係為根據本發明之第一實施例所測得的含丙二醇、乙基麥芽醇及乙 基香草醛的蜂蜜之GC/MS總離子層析圖。 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.
第8a圖係為第7圖中乙基香草醛成分之離子片段質譜圖。 Figure 8a is a mass spectrum of the ion fragment of the ethyl vanillin component in Figure 7.
第8b圖係為NIST11資料庫中乙基香草醛之離子片段質譜圖。 Figure 8b is a mass spectrum of the ion fragment of ethyl vanillin in the NIST11 database.
第9圖係為根據本發明之第一實施例所測得的含三乙酸甘油酯的蜂蜜之GC/MS總離子層析圖。 Figure 9 is a GC/MS total ion chromatogram of the triacetin-containing honey measured according to the first embodiment of the present invention.
第10a圖係為第9圖中三乙酸甘油酯之離子片段質譜圖。 Figure 10a is a mass spectrum of the ion fragment of triacetin in Figure 9.
第10b圖係為NIST11資料庫中三乙酸甘油酯之離子片段質譜圖。 Figure 10b is a mass spectrum of the ion fragment of triacetin in the NIST11 database.
第11a圖係為純蜂蜜之GC/MS總離子層析圖。 Figure 11a is a GC/MS total ion chromatogram of pure honey.
第11b圖係為含丙二醇的蜂蜜之GC/MS總離子層析圖。 Figure 11b is a GC/MS total ion chromatogram of honey containing propylene glycol.
第11c圖係為含丙二醇及乙基麥芽醇兩者的蜂蜜之GC/MS總離子層析圖。 Figure 11c is a GC/MS total ion chromatogram of honey containing both propylene glycol and ethyl maltol.
為利貴審查員瞭解本發明之技術特徵、內容與優點及其所能達成之功效，茲將本發明配合附圖，並以實施例之表達形式詳細說明如下，而其中所使用之圖式，其主旨僅為示意及輔助說明書之用，未必為本發明實施後之真實比例與精準配置，故不應就所附之圖式的比例與配置關係解讀、侷限本發明於實際實施上的權利範圍，合先敘明。 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.
本發明將藉由下列較佳實施例及其配合之圖式，作進一步之詳細說明。需注意的是，以下各實施例所揭示之實驗數據，係為便於解釋本案技術特徵，並非用以限制其可實施之態樣。 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.
請參閱第1圖，其係為本發明之分析蜂蜜中之液態香料之方法之 第一實施例之流程圖。 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.
如圖所示，此分析方法包含下列步驟：首先，步驟S1，將蜂蜜以預熱溫度及預熱時間進行預熱；其次，步驟S2，使用吸附纖維，並且在吸附溫度及吸附時間下進行吸附蜂蜜之氣相揮發物，其中氣相揮發物包含乙基麥芽醇(Ethyl maltol)、乙基香草醛(Ethyl vanillin)、丙二醇(Propylene glycol)、三乙酸甘油酯(Triacetin)或其組合；接著，步驟S3，將氣相揮發物進行氣相層析；最後，步驟S4，進行鑑定氣相揮發物之離子片段。 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.
具體來說，首先進行步驟S1的部分，也就是將待分析的蜂蜜樣品進行前處理。目前常見的前處理方法有薄膜萃取法(membrane extraction)、靜態上空間採樣法(static headspace sampling)、吹氣捕集法(purge and trap)、超臨界流體萃取法(supercritical fluid extraction)、固相萃取法(solid phase extraction，SPE)等，在本實施例中採用固相微萃取法(solid-phase microextraction，SPME)，其具有儀器裝置簡單、使用方便、採樣時間短、偵測極限佳等優點，此外，更可減少分析時間、提高樣品分析速度及降低人為誤差。而固相微萃取法又可分為下列幾種萃取模式：直接固相微萃取(direct SPME，DI-SPME)、頂空固相微萃取(headspace SPME，HS-SPME)以及衍生化固相微萃取(derivatization SPME)，而在本實施例中採用頂空固相微萃取法進行蜂蜜的前處理步驟。 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.
取5g-10g的蜂蜜，裝入20ml的頂空玻璃瓶中，以附有聚四氟乙烯墊片(Silicone Blue/PTFE)的鋁蓋蓋上並且旋緊後，以約70℃至約90℃的預熱溫度進行預熱約4分鐘至約25分鐘的預熱時間。預熱溫度可為約70℃至約90℃，在本實施例中係以85℃作為示範態樣，但並不以此為限。另外，預熱時間可為約5分鐘至約25分鐘，而在本實施例中係以15分鐘進行樣品的前處理。蜂蜜的取樣量會影響分析的結果，取樣量 太少，會導致濃度不夠；取樣量太多，在頂空固相微萃取的過程中，吸附纖維會浸到蜂蜜樣品。接著進行步驟S2的部分，將蜂蜜樣品放入前處理加熱箱內，在約85℃下持續約10分鐘。之後，將裝有DVB/CAR/PDMS複合型纖維的吸附探針***內含蜂蜜樣品的頂空玻璃瓶中，且伸出吸附纖維以進行吸附，在約70℃至約90℃的吸附溫度且在約10分鐘至約15分鐘的吸附時間的條件下，進行吸附蜂蜜樣品的氣相揮發物。DVB/CAR/PDMS複合型纖維的吸附纖維藉由頂空萃取的方式，待一段時間後使氣相揮發物在DVB/CAR/PDMS複合型纖維與蜂蜜樣品之間達到分配平衡後，即完成吸附的步驟。在本實施例中所使用的吸附探針類型為50/30μM DVB/CAR/PDMS，而DVB/CAR/PDMS複合型纖維的長度為1公分。吸附溫度可為約70℃至約90℃，在本實施例中係控制在85℃。另一方面，在進行吸附氣相揮發物的初始階段時，待分析的氣相揮發物便快速地吸附到DVB/CAR/PDMS複合型纖維上，然而隨著時間增長，吸附的速度卻變得越來越慢，在接***衡狀態時，延長吸附時間對於吸附氣相揮發物的量並無太大影響，因此一般進行吸附的時間會在30分鐘內，吸附時間可為約10分鐘至約15分鐘，而在本實施例中係控制在10分鐘，但並不以此為限。 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.
也就是說，頂空固相微萃取法的DVB/CAR/PDMS複合型纖維並不會與蜂蜜樣品接觸，而是置於蜂蜜樣品溶液的上方，進行頂空萃取蜂蜜樣品溶液的氣相揮發物。此種方式主要用於萃取易揮發或者半揮發性的物質。而採用此方法的好處在於可保護DVB/CAR/PDMS複合型纖維在萃取過程中不會被樣品汙染、破壞，從而延長DVB/CAR/PDMS複合型纖維的使用壽命，甚至可避免樣品基質(matrix)的干擾。 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.
值得一提的是，DVB/CAR/PDMS複合型纖維可在進行吸附步驟之前，再另外進行一熱脫附的步驟。熱脫附係在約250℃的溫度下持續 30分鐘。而進行吸附氣相揮發物的吸附纖維在選擇上則根據「同性相溶(like dissolve like)」的原理，亦即極性塗層的吸附纖維吸附極性化合物；而非極性塗層的吸附纖維吸附非極性化合物。此外，吸附纖維越長，其吸附氣相揮發物的量就越高，但同時也有容易折斷吸附纖維的缺點，因此除非特別指出，一般都使用1公分長的吸附纖維。其次，塗層越厚，其吸附氣相揮發物的量就越高，但達到分配平衡所需的時間也就越長，進而導致吸附氣相揮發物的速度變慢。 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.
接下來進行步驟S3以及步驟S4的部分，目前固相微萃取法大多結合氣相層析儀或氣相層析質譜儀進行後段分析，將已吸附到氣相揮發物的吸附纖維直接注入氣相層析儀的注入口，以進行熱脫附的步驟，將氣相揮發物從吸附纖維上脫附至氣相層析儀，以進行後續的分離及偵測。本實施例的氣相揮發物中包含乙基麥芽醇、乙基香草醛、丙二醇、三乙酸甘油酯或其組合，本實施例以這四樣物質作為判斷蜂蜜中是否添加液態香料的依據，只要有測到，而無論所測得的濃度，皆可斷定待測的蜂蜜樣品中有添加液態香料。 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.
進一步來說，本實施例使用氣相層析串聯質譜儀(Gas chromatography mass spectrometry)進行氣相層析以及鑑定的步驟，其中氣相層析儀的機型為7890B；質譜儀的機型為5977A(廠商Agilent)。氣相層析儀的載流氣體必須使用化學惰性的氣體，其可為氫氣(H2)、氮氣(N2)或氦氣(He)，在本實施例中係以氦氣作為示範態樣，但並不以此為限。另外，在本實施例中，氣相層析儀的機台設定條件可分為樣品注入口的條件、使用的毛細管柱以及烘箱設定的條件三個部分。首先，樣品注入口的條件為全進樣(不分流)，進樣溫度為250℃、進樣壓力為7.3614psi、流速為14ml/分，並且在進樣2分鐘後以10ml/分吹去殘樣。其次，所使用的毛細管柱為Agilent HP 5MS毛細管柱(長度30m，內徑250μm，膜厚0.25
μM)，毛細管柱內的樣品進樣初速為1ml/分、毛細管柱內的壓力為7.3614psi。最後，氣相沉積串聯質譜儀之烘箱所使用的升溫程式如下表所示：
質譜儀的機台設定條件可分為下列3個部分：(1)經由氣相層析儀毛細管柱末端進入，且離子源的溫度設定為280℃；(2)離子化：以EI(electron ionization)將分子藉由70伏特電壓而離子化，且離子源的溫度控制在230℃；(3)四極柱(Quadrupole)質量分析器：收集質荷比(m/z)範圍為30至350之間的離子片段，以偵測器進行偵測，且偵測器的溫度設定為150℃。 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.
具體來說，將DVB/CAR/PDMS複合型纖維所吸附到的氣相揮發物注入氣相層析儀的注入口內，氣相揮發物會因為高溫而自DVB/CAR/PDMS複合型纖維脫附。接著氣相層析儀以氦氣作為載流氣體，攜帶氣相揮發物進入氣相層析儀之毛細管柱。各個化合物依據與毛細管柱 的親和力進行結合，與毛細管柱靜相親和力強的化合物，則沖提較慢，亦即滯留時間長；相反地，與毛細管柱移動相親和力強的化合物，則沖提較快，亦即滯留時間短。經毛細管柱分離之後的化合物，經由毛細管柱末端進入質譜儀中進行分析，且離子源的溫度設定為280℃。接著，質譜儀以70伏特的強力電壓，使化合物帶電並且斷裂成離子片段，且離子源的溫度控制在230℃。最後再以四極柱質量分析器進行離子片段的收集，所收集的離子片段之質荷比(m/z)範圍為30至350之間，並且以偵測器進行偵測，且偵測器的溫度設定為150℃。將偵測到的訊號進行鑑定，即可定性化合物。並且利用標準品再次進行確認。 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.
進行蜂蜜樣品分析之後，得到下列的結果：請參閱第2圖，其係為根據本發明之第一實施例所測得的純蜂蜜之GC/MS總離子層析圖(Total ion chromatography，TIC)。 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. .
請一併參閱第3圖、第4a圖及第4b圖，其係分別為根據本發明之第一實施例所測得的含丙二醇的蜂蜜之GC/MS總離子層析圖；第3圖中丙二醇成分之離子片段質譜圖；以及NIST11資料庫中丙二醇之離子片段質譜圖。如第3圖所示，可在滯留時間為(Retention time)7.593分鐘的位置發現一波峰(Peak)，將該波峰以質譜儀進行分析，結果如第4a圖所示，在滯留時間為7.593分鐘時，可看到波峰的主要離子片段為45.0、43.0及61.0；將該些主要離子片段與NIST11資料庫進行比對離子片段之後，參照第4b圖，經離子片段比對鑑定此化合物最吻合的化合物為丙二醇。 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.
請一併參閱第5圖、第6a圖及第6b圖，其係分別為根據本發明之第一實施例所測得的含丙二醇及乙基麥芽醇的蜂蜜之GC/MS總離子層析圖；第5圖中乙基麥芽醇成分之離子片段質譜圖；以及NIST11資料庫中乙基麥芽醇之離子片段質譜圖。如第5圖所示，可在滯留時間為34.469 分鐘的位置發現一波峰，將該波峰以質譜儀進行分析，結果如第6a圖所示，在滯留時間為34.469分鐘時，可看到波峰的主要離子片段為140.0、139.0及97.0；將該些主要離子片段與NIST11資料庫進行比對離子片段之後，參照第6b圖，經離子片段比對鑑定此化合物最吻合的化合物為乙基麥芽醇。 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.
請一併參閱第7圖、第8a圖及第8b圖，其係分別為根據本發明之第一實施例所測得的含丙二醇、乙基麥芽醇及乙基香草醛的蜂蜜之GC/MS總離子層析圖；第7圖中乙基香草醛成分之離子片段質譜圖；以及NIST11資料庫中乙基香草醛之離子片段質譜圖。如第7圖所示，可在滯留時間為43.712分鐘的位置發現一波峰，將該波峰以質譜儀進行分析，結果如第8a圖所示，在滯留時間為43.712分鐘時，可看到波峰的主要離子片段為137.0、166.0及109.0；將該些主要離子片段與NIST11資料庫進行比對離子片段之後，參照第8b圖，經離子片段比對鑑定此化合物最吻合的化合物為乙基香草醛。 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.
請一併參閱第9圖、第10a圖及第10b圖，其係分別為根據本發明之第一實施例所測得的含三乙酸甘油酯的蜂蜜之GC/MS總離子層析圖；第9圖中三乙酸甘油酯成分之離子片段質譜圖；以及NIST11資料庫中三乙酸甘油酯之離子片段質譜圖。如第9圖所示，可在滯留時間為41.981分鐘的位置發現一波峰，將該波峰以質譜儀進行分析，結果如第10a圖所示，在滯留時間為41.981分鐘時，可看到波峰的主要離子片段為43.0、103.0及145.0；將該些主要離子片段與NIST11資料庫進行比對離子片段之後，參照第10b圖，經離子片段比對鑑定此化合物最吻合的化合物為三乙酸甘油酯。 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.
最後，請參閱第11a圖、第11b圖及第11c圖，其係為分別比 對純蜂蜜、含丙二醇的蜂蜜以及含丙二醇及乙基麥芽醇兩者的蜂蜜之GC/MS總離子層析圖。首先，第11a圖為純蜂蜜之GC/MS總離子層析圖；第11b圖為添加丙二醇的香料溶劑的蜂蜜之GC/MS總離子層析圖；以及第11c圖為添加丙二醇的香料溶劑及乙基麥芽醇的單體香料的蜂蜜之GC/MS總離子層析圖。將這三個樣品進行總離子層析圖譜的比對，可以明顯區分出純蜂蜜、添加丙二醇的蜂蜜以及添加丙二醇香料溶劑及乙基麥芽醇單體香料兩者的蜂蜜之滯留時間與圖譜的差異。 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.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。 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‧‧‧步驟 S1-S4‧‧‧ steps
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104101722A TWI530681B (en) | 2015-01-19 | 2015-01-19 | Method for analyzing liquid flavor in honey |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104101722A TWI530681B (en) | 2015-01-19 | 2015-01-19 | Method for analyzing liquid flavor in honey |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI530681B true TWI530681B (en) | 2016-04-21 |
| TW201627666A TW201627666A (en) | 2016-08-01 |
Family
ID=56361501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104101722A TWI530681B (en) | 2015-01-19 | 2015-01-19 | Method for analyzing liquid flavor in honey |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI530681B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107907600A (en) * | 2017-10-25 | 2018-04-13 | 大连理工大学 | It is a kind of that the method for aflatoxin and flavouring agent in vegetable fat is measured based on liquid-liquid extraction Liquid Chromatography-Tandem Mass Spectrometry at the same time |
| CN114858939A (en) * | 2022-04-27 | 2022-08-05 | 国家烟草质量监督检验中心 | Method for simultaneously determining eugenol, maltol, ethyl maltol, vanillin and ethyl vanillin in novel atomized product |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107677757B (en) * | 2017-09-08 | 2019-11-08 | 大连市食品检验所 | The method for measuring vanillic aldehyde in food, methyl vanillin, Ethyl vanillin simultaneously |
| CN108426968B (en) * | 2018-06-13 | 2021-06-15 | 中国农业科学院蜜蜂研究所 | Classification method of winter honey and Chinese tallow tree honey |
-
2015
- 2015-01-19 TW TW104101722A patent/TWI530681B/en active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107907600A (en) * | 2017-10-25 | 2018-04-13 | 大连理工大学 | It is a kind of that the method for aflatoxin and flavouring agent in vegetable fat is measured based on liquid-liquid extraction Liquid Chromatography-Tandem Mass Spectrometry at the same time |
| CN107907600B (en) * | 2017-10-25 | 2020-04-07 | 大连理工大学 | Method for simultaneously measuring aflatoxin and flavoring agent in vegetable oil based on liquid-liquid extraction-liquid chromatography-tandem mass spectrometry |
| CN114858939A (en) * | 2022-04-27 | 2022-08-05 | 国家烟草质量监督检验中心 | Method for simultaneously determining eugenol, maltol, ethyl maltol, vanillin and ethyl vanillin in novel atomized product |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201627666A (en) | 2016-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Arbulu et al. | Untargeted metabolomic analysis using liquid chromatography quadrupole time-of-flight mass spectrometry for non-volatile profiling of wines | |
| Robinson et al. | Origins of grape and wine aroma. Part 2. Chemical and sensory analysis | |
| TWI530681B (en) | Method for analyzing liquid flavor in honey | |
| Mu et al. | The enantiomeric distributions of volatile constituents in different tea cultivars | |
| CN107941978B (en) | Method for evaluating internal quality stability of bead blasting for cigarettes | |
| Haddad et al. | Perfume fingerprinting by easy ambient sonic‐spray ionization mass spectrometry: nearly instantaneous typification and counterfeit detection | |
| Fraser et al. | Monitoring tea fermentation/manufacturing by direct analysis in real time (DART) mass spectrometry | |
| Li et al. | Direct analysis in real time mass spectrometry: a powerful tool for fast analysis | |
| Avellone et al. | Investigation on the influence of spray-drying technology on the quality of Sicilian Nero d’Avola wines | |
| CN105784862B (en) | One grow tobacco it is middle volatilization and half volatile ingredient analysis method | |
| Verma et al. | Analysis of saffron (Crocus sativus L. Stigma) components by LC–MS–MS | |
| Jones et al. | Investigating sub-2 μm particle stationary phase supercritical fluid chromatography coupled to mass spectrometry for chemical profiling of chamomile extracts | |
| Feng et al. | Gas chromatography for food quality evaluation | |
| CN105929082B (en) | A kind of method of Pyrazine and pyridine substance in separation determination saliva | |
| CN108548877B (en) | Method for measuring volatile components of bead blasting for cigarettes by solid phase microextraction-gas chromatography-mass spectrometry technology | |
| Beltran et al. | Comparison of two quantitative GC–MS methods for analysis of tomato aroma based on purge-and-trap and on solid-phase microextraction | |
| Liberto et al. | Headspace Sampling: An “Evergreen” method in constant evolution to characterize food flavors through their volatile fraction | |
| CN109212066B (en) | Method for determining non-fat organic acid in tobacco and tobacco products | |
| Sánchez-Palomo et al. | Comparison of extraction methods for volatile compounds of Muscat grape juice | |
| CN113049436A (en) | Method for rapidly analyzing consistency of tobacco flavor and fragrance and application thereof | |
| Kimura et al. | Simple and rapid determination of 1‐deoxynojirimycin in mulberry leaves | |
| CN114778728A (en) | Determination method for curcumin compound content | |
| Liberto et al. | Fractionated dynamic headspace sampling in the analysis of matrices of vegetable origin in the food field | |
| Liang et al. | Hydrophilic interaction liquid chromatography for the separation, purification, and quantification of raffinose family oligosaccharides from Lycopus lucidus Turcz | |
| Gao et al. | Headspace solid‐phase microextraction combined with GC× GC‐TOFMS for the analysis of volatile compounds of Coptis species rhizomes |