1333062 九、發明說明： 【發明所屬之技術領威】 本發明係有關-種以感測電位測試魚肉新鮮度之方法及裝 置，尤指-種以二氧化鈦修飾電極（Ti/TiQ2)飾作為感測電極， 相對於Ag/AgGl作為參考電極，對魚死後之魚肉進〃ΤΡΗ值的感 測，配合所建立的魚肉pH值對應時間的線性方魟式，计异出魚 死的時間，而便於判斷出魚肉的新鮮度。 【先前技術】 隨健康意識的抬頭，人們對食物、營養的攝取相當重視。 魚肉本身除了具有其他肉質的營養成分外，還含有高蛋白質、 維生素及礦物質，是人類理想的高級營養食品’但判斷魚肉新 鮮度對消費者及業者是相當重要的課題，最常見的方法係以肉 眼判斷魚鰓顏色，此方法誤差相當大且容易造假，先後有研發 許多方法，直接量測的像是使用攜帶式電子鼻、以金屬氧化物 半導体、三甲胺氣壓探針評估魚肉中的TMA ;非破壞性方法以螢 光光譜儀分析魚肉中核酸、色氨基酸、蛋白質之特有光譜闵； 破壞性的量測方法有利祕酸染料置於魚肉巾以紫外光分析 光4。基於以上所述，本發明似簡單、快速、非破壞的方式 對…、肉進盯新鮮度的量測。以陽極處理修飾鈦電極，形成 Ti/tw電極’湘此Tl/TiQ2為感測電極，相對於㈣^為參 考電極對魚死後魚肉巾的H+濃度進行錢與監控，已知魚死後 魚肉p H值會下降，藉由此現象，利用線性回歸法，得P H值-死後 時間的線性方程式。應用此以[_感測電極去量測魚肉的ΡΗ P可判斷出,#、肉的新鮮度’也可作為魚冷來保鮮實用或為魚 加工飼料用之選料依據。 【發明内容】 本=明之第-目的，在於提供一種魚肉新鮮度檢測方法， • ^於提供—Ti/TiG2感測電極，以Ag/AgCl為相對參考電極， 士”、、死後進行魚肉pH值的感測進而得到魚肉讪值—死亡時間 的關係’應用此關係，由直接量測魚肉p H值，得知魚死亡時間， 即可知魚肉的新鮮度。 本發明之第二目的，在於提供魚肉新鮮度之裝置，其包括 有 盛裴有鹽水的容器，供一待測魚置入其内；一針狀之一 ^鈦仏飾電極（Τι/Τι〇2)係為感測電極，供插入該待測备肉 ’以感測該待測魚肉中的r濃度，並產生一訊號；—Ag/⑽丄 =為參考電極’供置人該容器_鹽水中；及—魏處理模組， 其分別與該感測電極及該參考電極電性連接，用以依據該感測 電極所產生之該说號而產生該待測魚肉 中的pH值。 【實施方式】 I .本發明的技術概念 本發明主要的技術概念，係針對魚死後其肌肉通過解糖反 應生成乳酸及肌肉細胞中ATP酶促使ATP分解出磷酸而產生 . 1 1333062 I t ' H+，進而導致魚肉中蛋白質變性，使魚肉尚失了原有的鮮味， 利用Ti/Ti〇2感測電極上的二氧化鈦膜對H+之高敏感度，藉此 對魚肉中之H+作感測及監控並觀察其變化，進而得知魚肉的新 鮮度。 Π.本發明所採用的裝置 i.本發明製作二氧化鈦修飾電極之裝置 請參看圖一所示，為本發明中，製作二氧化鈦修飾電極 • (Ti/Ti0〇 (即感測電極）之裝置的示意圖。由該圖可知，本 發明之該裝置，係包括有一陽極處理槽（6)，其内裝有陽極處理 之電解液（4)。加工時，係將一鈦線（2)以及不繡鋼電極（5)置於 陽極處理槽（6)之相對的兩端，以一可程式直流電源供應器（1) 施以陽極處理，鈦線（2)表面經陽極處理後，表面會形成一層二 氧化鈦薄膜，進而得到二氧化鈦修飾電極。 I ii.本發明測試魚肉新鮮度之裝置 請參看圖二所示，本發明基本操作方式，係將針狀的二氧 化鈦修飾電極以一定深度插入待測魚肉中，而Ag/AgC 1參考電極 置於待測魚旁邊的水中，分別將其連接至一pH值處理模組，即 可對待測魚肉進行量測。 請參看圖二所示，本發明量測魚肉新鮮度之裝置的具體實 施例，係包括有： 一容器（11)，其内盛裝有鹽水（9)，供一待測魚（10)置入 1333062 其内； 一針狀之二氧化鈦修飾電極（Ti/Ti〇2)係為感測電極（8)， 供插入該待測魚（10)肉中’以感測該待測魚（10)肉中的矿濃 - 度，並產生一訊號； • 一銀/氣化銀修飾電極（Ag/AgCl)作為參考電極（7)，供置 入該待測魚（10)旁邊的鹽水（9)中；及 一pH值處理模組（12)，其經由導線（15)而分別與該感測電 #極（8)及該參考電極電性（7)連接，用以依據該感測電極（8)所產 生之該訊號而產生該待測魚（10)肉中的pH值。其中，該pH值處 理模組（12)可包括有一電腦（13)及一數位電錶（14)。 5月參看圖二所示，本發明一種較佳實施例，可加設有一警 示裝置（16)，該警示裝置（16)與該pH值處理模組（12)電性連 接’於pH值處理模組⑽預設一pH基準值，當待測魚的pH值低 #於_基準值時，控制該警示裝置（16)發出不新鮮的警示訊 號。其中’該警示訊㈣選自音頻訊號及光訊號之中至少一種， 该音頻訊號的實現係於該警示裝置包括有蜂鳴器，而光訊號的 實現則於該警示展置包括有發光二極體（LED)。 Π ·本發明的基本方法步称 本發月應用陽極處理方法，先製作二氧化欽修飾電極 (Ti/Ti〇2) 乂作為pH感測電極，將針狀之感測電極固定深度刺 入待測”、、肉+ ’相對於銀/氣化銀（Ag/AgCi)參考電極，而對待 8 進行T i /T i ΟφΗ電位變化量測。從侍測魚肉pH值與死後 ，之關係可判斷出魚肉的新鮮度，也可做為魚肉冷凍保鮮食 用或做飼料用之選料依據。 IV.本發明之實驗例 纸列舉以下實驗例，以更加詳細說明及驗證本發明之可行 性。 I實例一，為本發明之Ti/Ti〇2感測電極製作方法 本發明之實例，係以長度與直徑分別為0.1mm X 75mm之 線進行以下步驟’置於去離子水（Di-Water)中，以超音波 震盪機；丨眘、、Φ $ 无之，再以丙酮清洗鈦線，將洗淨之鈦線置於圖一之 曰處理槽（6)的電解液（4)中，陽極為鈦線，陰極為不鏽鋼電 藉由可程式直流電源供應器提供定電壓於電解液（4)(本實 %例之電解液為90vol% DMSO + lOvol% H3P〇4溶液）中，進行陽 極處理時間約120sec。 11.實例二，為本發明之以氧化鈦修飾電極測試魚肉新鮮度 本發明利用實例一所製作出之二氧化鈦修飾電極對魚死後 魚肉中H+濃度的變化進行感測及監控，其包括有（a)建立魚死亡 後魚肉的P Η值與時間之線性關係，及（b)測試該待測魚死亡的時 間。其具體實施例之裝置及方法如圖二所示，將針狀之Ti/Ti〇2 感測電極（8)固定深度刺入魚（10)肉中，以銀/氯化銀（Ag/AgC1) 為參考電極（7)置於魚（10)旁邊的鹽水（9)中，讓魚（1〇)於空氣 1333062 中漸漸窒息而死，並以二氧化鈦感測電極（8)對魚（1 〇)肉中的H+ 濃度做至少七小時的感測及監控，本實驗例係做十二小時以上 的感測及監控’獲得結果如圖四所示。圖四為魚肉中pH值-時間 之變化關係圖，其中’由於本實例是讓魚於空氣中慢慢窒息而 死，因此一開始會有一呈現弱鹼之現象，魚完全死後，因呼吸 停止而使體内缺少氧氣，原本需要氧氣能量的醣類代謝進而轉 憂成缺氧狀態的分解作用’而產生了乳酸，同時肌肉細胞中帶 _有咼濃度之三磷酸腺苷（Adenosine iripHospHate，ATP)也分解 產生了峨酸。酸使得肌肉中的pH值降至酸性。因在酸性環境之 下而使得肌肉纖維中粗與細肌肉纖維相互吸引及肌節的收縮， 進而使得肌肉呈現僵硬狀態。由於在一大氣壓、室溫下不使用 任何冷凍裝置下進行，魚死後約20〜30分鐘則開始呈現僵硬現 象’當魚肉呈現僵硬狀態時，肌肉細胞中三磷酸腺苷（ATP)仍然 φ 繼續分解出磷酸而使得肌肉中的pH值繼續往下降。魚肉發生僵 硬後約5〜6小時後便開始軟化。從魚肉僵硬至軟化過程中可發現 其pH值變化與時間呈現線性關係，魚肉軟化時，使其邱值回升， 兹因電極表面所接觸的肌肉中一些較粗糙難溶解的結締組織吸 水膨脹而軟化，進而使得氧化鈦修飾電極表面所吸附H+濃度下 降’且也因在酸性環境下肌肉纖維破裂而釋放出一些弱酸性電 解質’在酸性環境下它們呈現鹼性，故pH值才會有所上升。再 經過約1〜2小時後，因肌肉中的結締組織配分解而破裂使得被吸 s 10 1333062 收之r再賴釋放吨缺修㈣極表面，使得祕快速地下 降因肌肉...田胞令的二磷酸腺芽（Ατρ)仍然繼續分解出鱗酸，故 使得肌肉中的_持續地往下降。經過約7〜8小時後，此時备肉 已腐敗’由於有大量的腐敗細料微生物生長繁殖，因微生物 的活動及它們的產物而使得ρΗ值回升，此時魚肉已轉換為有毒 有臭味之物»，而失去魚肉原本財的肌岐織、顏色、味道 及外觀。如圖五所示，是由圖四中2〜7小時之間線性關係，直接 放大判斷出，湘線性回歸方式即可得到線性方程式十 -0.0987χ + 5.2842、“.9413,因此將可以簡單的以此線性 方程式計算得知纽亡的相，進而得知魚肉_鮮度，也可 做為魚要冷凍保鮮食用或做飼料用之選料依據。 V.結論1333062 IX. Description of the Invention: [Technical Leading Technology of the Invention] The present invention relates to a method and a device for testing the freshness of fish meat by sensing potential, in particular, a titanium dioxide modified electrode (Ti/TiQ2) is used for sensing. The electrode, relative to Ag/AgGl as a reference electrode, senses the sputum value of the fish after the death of the fish, and cooperates with the established linear formula of the pH value of the fish corresponding to the time, and calculates the time of the fish to die, and is convenient for judging The freshness of the fish. [Prior Art] With the rise of health awareness, people attach great importance to the intake of food and nutrition. In addition to other meaty nutrients, the fish itself contains high protein, vitamins and minerals, which is an ideal high-grade nutritious food for humans. But judging the freshness of fish is a very important issue for consumers and the industry. The most common method is The color of the fish gill is judged by the naked eye. This method is quite error-prone and easy to falsify. Many methods have been developed. The direct measurement is like using a portable electronic nose to evaluate the TMA in fish meat with a metal oxide semiconductor and a trimethylamine gas pressure probe. Non-destructive method to analyze the characteristic spectrum of nucleic acid, color amino acid and protein in fish meat by fluorescence spectrometer; Destructive measurement method is advantageous for the acid dye to be placed on fish flakes to analyze light by ultraviolet light. Based on the above, the present invention appears to be a simple, fast, non-destructive way to measure the freshness of meat. The titanium electrode was modified by anodization to form a Ti/tw electrode, and the Tl/TiQ2 was used as a sensing electrode. The H+ concentration of the fish meat towel after fish death was compared with (4)^ as the reference electrode. The value will decrease, and by this phenomenon, the linear equation of PH value - post-mortem time is obtained by linear regression method. Applying this to [_ sensing the electrode to measure the fish's ΡΗ P can be judged, #, meat freshness' can also be used as a basis for selecting fish for cold storage or for fish processing feed. SUMMARY OF THE INVENTION The purpose of the present invention is to provide a fish meat freshness detecting method, which is provided by a Ti/TiG2 sensing electrode, with Ag/AgCl as a relative reference electrode, and a fish meat pH value after death. The second sensor aims to provide fish meat by directly measuring the p H value of the fish and knowing the fish death time by using the relationship of the fish devaluation-death time. a freshness device comprising a container containing salt water for placing a fish to be tested therein; a needle-shaped one of titanium enamel electrodes (Τι/Τι〇2) is a sensing electrode for insertion The meat to be tested is used to sense the concentration of r in the fish to be tested, and generates a signal; - Ag / (10) 丄 = is the reference electrode 'storage container _ brine; and - Wei processing module, And electrically connecting the sensing electrode and the reference electrode to generate a pH value in the fish meat to be tested according to the number generated by the sensing electrode. [Embodiment] I. Technical Concept of the Invention The main technical concept of the invention is directed to the fish after its death. Meat is produced by thawing sugar to produce lactic acid and ATPase in muscle cells causes ATP to decompose out of phosphoric acid. 1 1333062 I t 'H+, which leads to protein denaturation in fish, which makes the fish taste the original umami, using Ti/Ti 〇2 senses the high sensitivity of the titanium dioxide film on the electrode to H+, thereby sensing and monitoring the H+ in the fish meat and observing the change, thereby knowing the freshness of the fish. Π. The device used in the present invention i The apparatus for preparing a titanium dioxide modified electrode according to the present invention is shown in Fig. 1. In the present invention, a schematic diagram of a device for preparing a titanium dioxide modified electrode (Ti/Ti0〇 (i.e., a sensing electrode) is shown in the present invention. The device comprises an anode treatment tank (6), which is provided with an anode-treated electrolyte (4). During processing, a titanium wire (2) and a stainless steel electrode (5) are placed in the anode treatment tank. (6) The opposite ends are anodized by a programmable DC power supply (1), and after the surface of the titanium wire (2) is anodized, a titanium dioxide film is formed on the surface to obtain a titanium dioxide modified electrode. Ii. Ben The device for testing the freshness of fish meat is shown in Figure 2. The basic operation mode of the present invention is to insert the needle-shaped titanium dioxide modified electrode into the fish to be tested at a certain depth, and the Ag/AgC 1 reference electrode is placed beside the fish to be tested. The water in the water is connected to a pH processing module to measure the fish to be tested. Referring to Figure 2, the specific embodiment of the device for measuring the freshness of the fish of the present invention includes: a container (11) containing saline (9) for placing a fish to be tested (10) into 1333062; a needle-shaped titanium dioxide modified electrode (Ti/Ti〇2) is a sensing electrode (8) For inserting the fish to be tested (10) in the meat to sense the concentration of the ore in the meat of the fish to be tested (10) and generating a signal; • a silver/vaporized silver modified electrode (Ag/AgCl) As a reference electrode (7) for being placed in the brine (9) beside the fish (10) to be tested; and a pH processing module (12) respectively connected to the sensing electricity via the wire (15) The pole (8) and the reference electrode are electrically connected (7) for generating according to the signal generated by the sensing electrode (8) Tested fish (10) pH value of the meat. The pH processing module (12) may include a computer (13) and a digital meter (14). Referring to FIG. 2, a preferred embodiment of the present invention may be provided with a warning device (16), and the warning device (16) is electrically connected to the pH processing module (12) for pH processing. The module (10) presets a pH reference value, and when the pH of the fish to be tested is low #__ reference value, the warning device (16) is controlled to emit a fresh warning signal. Wherein the warning message (4) is selected from at least one of an audio signal and an optical signal, the audio signal is implemented in the warning device including a buzzer, and the optical signal is implemented in the warning display including the light emitting diode Body (LED). Π · The basic method of the present invention is called the application of the anode treatment method in this month, firstly preparing a dioxide-modified electrode (Ti/Ti〇2) 乂 as a pH sensing electrode, and puncturing the needle-shaped sensing electrode to a fixed depth Measure ", meat + 'relative to the silver / gasified silver (Ag / AgCi) reference electrode, and treat T 8 / T i Ο φ Η potential change measurement. From the test of the pH value of the fish and the relationship between death, can be judged The freshness of the fish meat can also be used as the basis for the selection of the fish frozen food or for the feed. IV. Experimental Examples of the Invention The following experimental examples are listed to illustrate and verify the feasibility of the present invention in more detail. First, the Ti/Ti〇2 sensing electrode manufacturing method of the present invention is an example of the present invention, which is carried out in a deionized water (Di-Water) by a line having a length and a diameter of 0.1 mm X 75 mm, respectively. Ultrasonic vibration machine; 丨 caution, Φ $ No, then clean the titanium wire with acetone, place the cleaned titanium wire in the electrolyte (4) of the treatment tank (6) in Figure 1, the anode is titanium Line, the cathode is stainless steel, and the constant voltage is supplied by the programmable DC power supply. In the electrolyte (4) (the electrolyte solution of the present example is 90 vol% DMSO + 10 vol% H3P 〇 4 solution), the anodic treatment time is about 120 sec. 11. Example 2, the test of the fish meat with the titanium oxide modified electrode of the present invention Freshness The present invention uses the titanium dioxide modified electrode prepared in Example 1 to sense and monitor the change in H+ concentration in the fish after fish death, which includes (a) establishing a linear relationship between the P Η value of the fish and the time after the death of the fish, And (b) testing the time of death of the fish to be tested. The device and method of the specific embodiment are shown in Figure 2, and the needle-shaped Ti/Ti〇2 sensing electrode (8) is inserted into the fish at a fixed depth (10). In the meat, silver/silver chloride (Ag/AgC1) is used as the reference electrode (7) in the salt water (9) next to the fish (10), and the fish (1〇) gradually suffocates in the air 1333602 and dies. The titanium dioxide sensing electrode (8) was used to sense and monitor the H+ concentration in the fish (1 〇) meat for at least seven hours. This experiment was performed for more than 12 hours of sensing and monitoring. Figure 4. Figure 4 shows the relationship between pH and time in fish, where 'because this example is let The fish slowly suffocate and die in the air, so there will be a phenomenon of weak alkali at the beginning. After the fish is completely dead, the body lacks oxygen due to the stop of breathing, and the sugar metabolism that originally needs oxygen energy turns into anoxic state. The decomposition of 'produces' lactic acid, and the adenosine iripHospHate (ATP) in the muscle cells is also decomposed to produce tannic acid. The acid makes the pH in the muscles acidic. Because of the acidic environment The muscle fibers are attracted to the muscle fibers and the muscle fibers are contracted, which makes the muscles stiff. Since it is carried out at atmospheric pressure and room temperature without using any freezing device, the fish begins to show stiffness after about 20 to 30 minutes after the death of the fish. When the fish is in a stiff state, the adenosine triphosphate (ATP) in the muscle cells continues to decompose the phosphoric acid. The pH in the muscle continues to drop. After the fish is stiff, the softening begins after about 5 to 6 hours. From the stiffness of the fish to the softening process, it can be found that the pH value changes linearly with the time. When the fish softens, the Qi value rises. Because of the coarser and more difficult connective tissue in the muscle contacted by the electrode surface, the water is swollen and softened. In addition, the H+ concentration of the surface of the titanium oxide modified electrode is decreased, and some weakly acidic electrolytes are released due to the breakage of muscle fibers in an acidic environment. In an acidic environment, they are alkaline, so the pH value will increase. After about 1~2 hours, the rupture of the connective tissue in the muscle is broken, so that the sucked s 10 1333062 receives the r and then releases the ton of the missing (four) pole surface, so that the secret rapidly drops due to the muscle... The bismuth diphosphate bud (Ατρ) continues to decompose scaly acid, so that the _ in the muscle continues to decrease. After about 7~8 hours, the meat has been spoiled at this time. Due to the large amount of spoilage microbial growth and reproduction, the microbial activity and their products have caused the value of ρΗ to rise. At this time, the fish has been converted into toxic and odor. The object», and lose the muscle texture, color, taste and appearance of the original fish. As shown in Figure 5, it is determined by the linear relationship between 2 and 7 hours in Figure 4. The linear regression equation can be obtained by linear regression equations of -10987χ + 5.2842, ".9413, so it will be simple. Calculate the phase of death in this linear equation, and then learn the fish_freshness. It can also be used as the basis for the selection of the fish for frozen or fresh food or for feed. V. Conclusion
在本發明以氧化祕輕測電極賴魚肉崎度中，最主 要的特點如下： ，此方法直接、簡單、 1.本發明所使用之測試方法為感測電位法 快速、精確。 2. 本發明所使用之Ti/Ti〇2_電極製作法為陽極處理法簡 單、無毒性及感測性佳，可用於直接量㈣ 3. 本發明利用Η™感測電極對魚肉PH值-時間1現線性關 係，藉此得到魚肉之新鮮度。 以上所ϋ ’僅林_之彳·為可行實齡丨，並非用以限 11 ΐ： 5 > ^本發明之專利範圍’凡舉依據下列中請專利範圍所述之内 ♦特徵以及其精神為之其他變化等m含於本發明之專 利範圍内。 ^综上所述，本發明所具體界定於申請專利範圍之技術特 &未見於同_技術而具新穎性，且較已知技術具進步性，並 ^ 業充伤利用，已符合發明專利要件，依法具文提出申請，In the present invention, the most important features of the oxidized light measuring electrode are as follows: This method is straightforward and simple. 1. The test method used in the present invention is fast and accurate by the sensing potential method. 2. The Ti/Ti〇2_electrode used in the invention has the advantages of simple anode treatment, no toxicity and good sensing property, and can be used for direct amount (4). 3. The invention utilizes ΗTM sensing electrode to measure the pH value of fish- Time 1 is now linear, in order to get the freshness of the fish. The above ϋ 'only forest _ 彳 彳 为 为 可行 为 为 为 为 为 为 丨 丨 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Other changes such as m are included in the patent of the present invention. In summary, the technical scope of the present invention specifically defined in the scope of the patent application is not found in the same technology, but is more novel than the known technology, and is more advanced than the known technology, and has been used in the invention. Essentials, apply in accordance with the law,
謹請韵局依法核予專利，以維護本巾請人合法之權益。 【圖式簡單說明】 圖為本發明製作二氧化鈦電極力口工之示意圖； 圖一為本發明魚肉新鮮度測試之裝置示意圖·； 圖二為本發明加設有警示裝置之實施例示意圖； 圖四為本發明實驗例之魚肉中pH值-時間變化關係圖；及 圖五為本發明實驗例之魚肉中值—時間變化之線性關係圖。I would like to ask the rhyme to approve the patent in accordance with the law in order to protect the legal rights of the person who requested it. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a device for testing the freshness of fish meat according to the present invention; FIG. 2 is a schematic view showing an embodiment of a warning device provided with the present invention; The pH-time relationship diagram of the fish meat of the experimental example of the present invention; and FIG. 5 is a linear relationship diagram of the median-time change of the fish meat of the experimental example of the present invention.
【主要元件符號說明】 (1)可程式電源供應器（2)鈦線 (3)鈦原子 (5)不銹鋼電極 (4)陽極處理之電解液 (6)處理槽 (7)Ag/AgCl參考電極 （8)二氧化鈦修飾電極 (9)鹽水 （1〇)魚 (11)容器 (13)電腦 (12)pH處理模組 (14)數位電錶 12 5 1333062 (15)導線 （16)警示裝置[Main component symbol description] (1) Programmable power supply (2) Titanium wire (3) Titanium atom (5) Stainless steel electrode (4) Anode treated electrolyte (6) Treatment tank (7) Ag/AgCl reference electrode (8) Titanium dioxide modified electrode (9) Saline (1〇) fish (11) Container (13) Computer (12) pH processing module (14) Digital electric meter 12 5 1333062 (15) Conductor (16) warning device
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