200408803 A7 _ B7 五、發明説明（1 ) 前言： ---------f丨 (請先閱讀背面之注意事項再填巧本頁} 經濟部智毯財產局Β1>νί費合作社印製 揮發性醛類的產生可源自於食品之加工、儲存過程、生活 環境或製造業。例如食用油脂及含油脂食品於加工、貯存 過程的油脂氧化作用（lipid oxidation)即是。在氧化逆境 (oxidative stress)下，食用油脂或含油脂食品於加工、貯存 過程，可因油脂氧化作用而產生有害人體健康的毒性物質 例如：甲醛（formaldehyde)、乙醛、乙二醛、丙醛、丙稀 醛、丙二醛（malonaldehyde)、丁醛、戊醛、己醛、庚酸… 等低分子量揮發性醛類，其中丙二醛是油脂氧化程度的重 要指標。此外，燃燒有機化合物也會產生低分子量揮發性 醛類，因此在吾人生活環境尤其是在飲用水和都市的空氣 中，常可被檢測出微量的甲酸、乙酸、乙二酸、甲基乙二 醛、丙醛、丁醛、丁烯醛、戊醛、己醛、庚醛、苯甲酸… 等揮發性醛類，在這些醛類當中，甲醛廣泛地被應用在製 造業外’也常存在於某些加工食品’因此對於攸關人體健 康的食品與環境安全無疑是一個潛在危害。低分子量揮發 性醛類中的甲醛和丙二醛均具有高度活性，可與生物體中 的親和性劑（nucleophiles)反應，從科學證據顯示其與人體 過敏反應、免疫力降低、細胞老化、心血管疾病、色素生 成、倦怠 '眼睛不適、不孕…等症狀有關。更有甚者，經 由動物試驗證實對細胞具有致突變性與致癌性，而被認為 對人類細胞有致癌的可能。因此對於食品或環境中揮發性 醛類之去除、監控、或檢測方法之改良有其必要性。 表紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐 200408803 經潜部^^¾財產局肖工>/1#合作社9¾ A7 B7 五、發明説明（2) 習用技術及其缺點： 檢測低分子量揮發性醛類有其困難度，通常都須將醛類衍 生化後，再使用精密儀器例如分光光度計或氣、液相層析 儀加以偵測。傳統上以測定硫巴比妥酸反應性物質 (Thiobarbituric acid reactive substances 簡稱 TBARS)的含 量，作為評估油脂氧化程度的指標，此即為以往所稱之 TBA 價（Thiobarbituric acid value)，係測定丙二酸為主的 一群可與TBA反應的揮發性醛類，以丙二醛含量表示；而 傳統上檢測食品或環境中甲醛的方法主要有變色酸 (chromotropic acid)法、乙醯丙酮（acetylacetone)法、對位 玫瑰苯胺（pararosaniline)法、CHD (l，3-cyclo-hexanedione) 法、AHMT (4-amino_3-hydrazino_5-mercapto_l，2,4-triazol) 法、2,4-二瑣基苯月井 （2,4-dinitro-phenyl-hydrazine; 2,4-DNPH)法、2,3,4,5,6·五氟苯基羥胺(2，3，4，5, 6-pentafluorobenzyl)-hydroxylamine; 2, 3, 4, 5, 6-PFBHA) 法以及氮乙基硫醇（CySteamine)衍生法。前述衍生化方法 在檢測過程，或須加熱以促進反應之進行，或須借助氣、 液相層析儀等精密儀器進一步分析，或須用到較為昂貴的 衍生化試劑，因而除汀加熱容易導致衍生化過程檢體之醛 類揮發或產生不必要^副反應，進而影響醛類含量測定之 正確性外，整體而言檢測所需成本包括材料、藥品、儀器 設備均相對較高。 發明目的： 本紙張尺度適用f國國家榡準（CNS ) Λ4規格（21GX 297公釐） (請先閱讀背面之注意事項再填巧本頁) 、·ιτ 200408803 Μ ____Β7 _ 五、發明説明（3) 本發明之目的主要在於開發出較傳統技術更簡便快速且成 本相對低廉的揮發性酸類檢測法’有效地應用於食品及環 境中低分子量揮發性醛類的檢測、監控或去除。 (請先閲讀背面之注意事項再填寫本頁) 圖式部份： 第一圖：聚丙二醇泡棉製備及揮發性醛類檢測流程圖。 ft 第二圖：聚丙二醇泡棉管柱。使空氣或食用油脂（1 )，通 過管柱與聚丙二醇泡棉（2)反應。 第三圖：聚丙二醇泡棉反應試管。抽取待測之空氣檢體 使進入試管（2)，試管中預先放置〇·1Ν鹽酸溶液（3)及聚 丙二醇泡棉（4)。來自空氣檢體之揮發性醛類在〇·丨ν鹽 酸溶液酸性條件下與聚丙二醇泡棉反應呈色。 ^ 第四圖：聚丙二醇泡棉與甲醛標準溶液上部空間（head space)反應呈色後之外觀（甲醛標準色板）。呈色反應所用 甲醛含量為 0，53.9，107.7，215.4，323.1，430.8 I，其 對應之圖示元件符號依序為1，2,3,4,5,6。 經濟部智丛財產局工消費合作社印¾ 第五圖：聚丙二醇泡棉波長385 nm吸光值（Y)與甲醛含量 (X)之檢量線（Y= 0.0002+ 0·075IX ;相關係數R2= 0.9979)。其係將第四圖之聚丙二醇泡棉溶於甲酸後過濾， 測波長385 nm吸光值（Y)對甲醛含量（X)迴歸所得之曲 線。 本發明之運用原理： 以丙二醇（propylene glycol; PG)為單體聚合而成的聚丙二 醇（polypropylene glycol; PPG)，其化學結構上並不含胺基 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200408803 經濟部智丛財產局Μ工消費合作社印製 A7 B7 五、發明説明（4) (aminogroup)，利用化學發泡法，以 Azodicarbonamide 發泡後的聚丙二醇泡棉，在其網狀結構之基質中，分布著 發泡時因發泡劑熱分解所產生之具有醯胺鍵結的固體副產 物例如：Urazol、Biurea、Isocyanuric acid···等化合物。利 用鹽酸適度水解泡棉，可使泡棉基質中具有醯胺鍵結的固 體副產物釋出更多游離胺基和竣基（carboxyl group)。理論_ 上此兩個官能基應該相互靠近，因此在游離羧基就近扮演 質子供應與接受的角色催化下，食品或環境中所存在的揮 發性醛類的醛基，便與游離胺基反應生成亞胺（imine ;又 稱為許夫氏驗，Schiff base)，使泡棉呈色且在其特性波峰 或波長420 nm有吸收。從泡棉顏色深淺，可與標準色板 比色定量外，也可將呈色後的泡棉溶於一定量的甲酸後過 濾、’以分光光度計測其特性波峰或波長420 nm之吸光值， 再由檢量線求出泡棉及檢體之醛類含量。實驗結果顯示， 此一具有活性胺基之聚丙二醇泡棉可與甲醛、乙醛、乙二 搭、甲基乙二盤、丙酸、丙浠酸、丙二酸、丁酸、丁稀酸、 戊醛、戊二醛、己醛、庚醛、苯甲醛、大茴香醛、小茴香 酸…等醛類反應形成共價鍵結，使泡棉變成黃色或褐色， t由FT-IR圖譜分析，證實有許夫氏驗的生成。實驗結果 也發現食用油在模擬油炸過程的TBARS變化量與泡棉所 測之丙二醛變化量相關性很高。故可利用此方法中泡棉顏 色之$成’來快速评估食用油中的TBARS和檢測食品戍 環境中之低分子量揮發性醛類、 ---------mwl——II ^------0Φ. (請先閱讀背面之注意事項再填涔本頁) 夂紙張尺度適用中國國家榡進f rMS ) A4规格f 入格 200408803 A7 B7 五、發明説明（5 ) 本發明所達成之效果…優點陳述： (1) 檢測方法簡便快速，所需成本相對低廉。 (2) 材料之取得與製備皆容易。 (3) 檢測時不需加熱，泡棉呈色穩定。 (4) 在氣相、液相（水相或油相）系統中均可反應。 (5) 可用在包裝食品作為食品品質良窳之參考指標。 (6) 可淨化空氣及食用油。 結語： 存在於食品或環境中之低分子量揮發性醛類，對人體健康 之危害不容忽視，研發出簡便、快速、實用而有效的方法-來檢測、監控或去除食品及環境中之低分子量揮發性醛類 以維護國民健康，是我們努力的目標。綜合上述，本發明 之標的符合專利法之相關規定，爰依此法向鈞局提出專 利申請。惟上述之檢測法為本發明之實施例，舉凡依本發 明申請專利範圍所作之均等變化或等效設計，皆屬於本發 明之專利範圍。 (請先閱讀背面之注意事項再填，«本頁) 、11 線- 經濟部智怂財產局㈢工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）200408803 A7 _ B7 V. Description of the invention (1) Foreword: --------- f 丨 (Please read the precautions on the back before filling out this page} Intellectual Property Bureau of the Ministry of Economic Affairs Β1 > νί co-operative seal The production of volatile aldehydes can originate from food processing, storage, living environment or manufacturing. For example, lipid oxidation of edible oils and fat-containing foods during processing and storage is the case. Under oxidative stress, edible oils or fat-containing foods during processing and storage can produce toxic substances that are harmful to human health due to the oxidation of oils and fats, such as: formaldehyde, acetaldehyde, glyoxal, propanal, and acrylic Low molecular weight volatile aldehydes such as aldehydes, malonaldehyde, butyraldehyde, valeraldehyde, hexanal, heptanoic acid, etc., of which malondialdehyde is an important indicator of the degree of oxidation of fats. In addition, burning organic compounds will also produce low Molecular weight of volatile aldehydes, so in our living environment, especially in drinking water and urban air, trace amounts of formic acid, acetic acid, glyoxylic acid, methylglyoxal, and propane Volatile aldehydes such as aldehydes, butyraldehyde, butenal, valeraldehyde, hexanal, heptaldehyde, benzoic acid, etc. Among these aldehydes, formaldehyde is widely used outside the manufacturing industry, and it is often found in certain processes. Food's is therefore undoubtedly a potential hazard to human health-related food and environmental safety. Both formaldehyde and malondialdehyde in low-molecular-weight volatile aldehydes are highly active and can react with nucleophiles in organisms Scientific evidence shows that it is related to human allergic reactions, decreased immunity, cell aging, cardiovascular disease, pigmentation, burnout, eye discomfort, infertility, etc. What's more, animal experiments have confirmed that it can cause cells to cause Mutagenicity and carcinogenicity are considered to be carcinogenic to human cells. Therefore, it is necessary to improve the removal, monitoring, or detection methods of volatile aldehydes in food or the environment. The paper scales are applicable to Chinese national standards ( CNS) A4 specification (210X297 mm 200408803 Economic Submarine Department ^^ ¾ Property Bureau Xiao Gong > / 1 # Cooperative Society 9¾ A7 B7 V. Description of the invention (2) Conventional technology and its shortcomings Point: The detection of low-molecular-weight volatile aldehydes has its difficulty. Usually, the aldehydes must be derivatized and then detected by a precision instrument such as a spectrophotometer or a gas or liquid chromatography. Traditionally, the sulfur is measured. The content of Thiobarbituric acid reactive substances (TBARS) is used as an indicator to evaluate the degree of oxidation of fats and oils. This is the traditionally known TBA value (Thiobarbituric acid value). Volatile aldehydes that react with TBA are expressed as the content of malondialdehyde. The traditional methods for detecting formaldehyde in food or the environment mainly include chromotropic acid method, acetylacetone method, and para-rosaniline ( (pararosaniline) method, CHD (l, 3-cyclo-hexanedione) method, AHMT (4-amino_3-hydrazino_5-mercapto_l, 2,4-triazol) method, 2,4-diazalylbenzene well (2,4-dinitro -phenyl-hydrazine; 2,4-DNPH) method, 2,3,4,5,6 · pentafluorophenylhydroxylamine (2,3,4,5,6-pentafluorobenzyl) -hydroxylamine; 2, 3, 4, 5, 6-PFBHA) method and CySteamine derivative method. During the detection process of the aforementioned derivatization method, heating may be required to promote the reaction, or further analysis by means of precision instruments such as gas and liquid chromatography, or more expensive derivatization reagents may be used. In the derivatization process, the aldehydes of the specimens volatilize or produce unnecessary side reactions, which affects the accuracy of the aldehyde content determination. On the whole, the cost of the test, including materials, drugs, and equipment is relatively high. Purpose of the invention: The paper size is applicable to the national standard (CNS) Λ4 specification (21GX 297 mm) of the paper (please read the precautions on the back before filling in this page) 、 · τ 200408803 Μ ____ Β7 _ 5. Description of the invention (3 The purpose of the present invention is mainly to develop a volatile acid detection method that is simpler, faster, and relatively cheaper than the traditional technology, and is effectively applied to the detection, monitoring, or removal of low molecular weight volatile aldehydes in food and the environment. (Please read the precautions on the back before filling out this page) Schematic part: The first figure: Flow chart of polypropylene glycol foam preparation and volatile aldehyde detection. ft Figure 2: Polypropylene glycol foam tubing. Air or edible oil (1) is reacted with polypropylene glycol foam (2) through a column. Third figure: Polypropylene glycol foam test tube. The air sample to be tested is drawn into a test tube (2), and a 0.1N hydrochloric acid solution (3) and a polypropylene glycol foam (4) are placed in the test tube in advance. Volatile aldehydes from air specimens reacted with polypropylene glycol foam under acidic conditions of the hydrochloric acid solution. ^ Figure 4: Appearance of polypropylene glycol foam and formaldehyde standard solution head space after reaction (formaldehyde standard swatch). The formaldehyde content used in the color reaction is 0, 53.9, 107.7, 215.4, 323.1, 430.8 I, and the corresponding symbol symbols are 1,2,3,4,5,6. Printed by the Industrial and Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ Figure 5: Calibration curve of absorbance (Y) and formaldehyde content (X) of polypropylene glycol foam at 385 nm (Y = 0.0002+ 0 · 075IX; correlation coefficient R2 = 0.9979). It is a curve obtained by dissolving the polypropylene glycol foam in the fourth figure after dissolving it in formic acid, and measuring the absorption value (Y) of the wavelength at 385 nm versus the formaldehyde content (X). Application principle of the present invention: Polypropylene glycol (PPPG) polymerized by using propylene glycol (PG) as monomer, its chemical structure does not contain amine. The basic paper size is applicable to China National Standard (CNS) A4 specifications. (210X297 mm) 200408803 Printed A7 B7 printed by M Industrial Consumer Cooperative of Zhi Cong Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4) (aminogroup) Polypropylene glycol foam foamed with Azodicarbonamide by chemical foaming method. In the matrix of the network structure, solid by-products such as Urazol, Biurea, Isocyanuric acid, etc., which are produced by the thermal decomposition of the foaming agent during foaming, are distributed. The use of hydrochloric acid to hydrolyze the foam moderately can release more free amine groups and carboxyl groups from the solid by-products of the foam matrix with amidine linkages. Theoretically, these two functional groups should be close to each other. Therefore, under the role of proton supply and acceptance near the free carboxyl group, the aldehyde group of volatile aldehydes present in food or the environment will react with the free amine group to form a subgroup. Amine (imine; also known as Schiff base) makes the foam appear colored and has absorption at its characteristic peak or wavelength of 420 nm. From the color depth of the foam, it can be compared with the standard swatch, and the colored foam can be dissolved in a certain amount of formic acid and filtered, and its characteristic peak or absorbance at 420 nm is measured spectrophotometrically. Then, the aldehyde content of foam and specimen was obtained from the calibration line. Experimental results show that this polypropylene glycol foam with active amine groups can be used with formaldehyde, acetaldehyde, ethylenediamine, methylethylene disc, propionic acid, malonic acid, malonic acid, butyric acid, butyric acid, Valeraldehyde, glutaraldehyde, hexanal, heptaldehyde, benzaldehyde, anisaldehyde, cuminic acid, etc. react to form covalent bonds, making the foam turn yellow or brown. T is analyzed by FT-IR spectrum. It was confirmed that the Schuffer test was generated. The experimental results also found that the TBARS change in edible oil during the simulated frying process was highly correlated with the change in malondialdehyde measured by foam. Therefore, the color of foam color in this method can be used to quickly evaluate TBARS in edible oil and detect low molecular weight volatile aldehydes in food and environment, --------- mwl ---- II ^- ----- 0Φ. (Please read the notes on the back before filling in this page) 夂 The paper size is applicable to China's national advancement f rMS) A4 specification f Included 200408803 A7 B7 V. Description of the invention (5) Achieved effects ... Advantages: (1) The detection method is simple and fast, and the required cost is relatively low. (2) Materials are easy to obtain and prepare. (3) No heating is required during the test, and the color of the foam is stable. (4) It can react in gas phase and liquid phase (water phase or oil phase) system. (5) It can be used as a reference indicator of food quality. (6) It can purify air and cooking oil. Conclusion: Low-molecular-weight volatile aldehydes present in food or the environment cannot harm human health. A simple, fast, practical, and effective method has been developed to detect, monitor, or remove low-molecular-weight volatiles in food and the environment. Sexual aldehydes to protect national health is the goal of our efforts. To sum up, the subject matter of the present invention complies with the relevant provisions of the Patent Law, and submits a patent application to the Bureau in accordance with this law. However, the above-mentioned detection method is an embodiment of the present invention, and any equivalent change or equivalent design made in accordance with the scope of patent application of the present invention belongs to the scope of patent of the present invention. (Please read the notes on the back before filling, «this page）, 11 lines-Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Masonry Consumer Cooperatives. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)