劉洋 賈文珅 馬潔 梁剛 汪慧華 周巍
摘要:電子鼻因具備操作簡單、能夠快速、無損檢測的特點,滿足人們對肉與肉制品安全指標(biāo)高效和高精確度檢測提出了更高的要求。本文闡述了電子鼻技術(shù)的檢測原理和其在硬件和軟件系統(tǒng)方面的發(fā)展;從肉與肉制品的新鮮度檢測、摻假檢測、風(fēng)味評價、病原微生物污染檢測四個方向,對近年來電子鼻技術(shù)在肉與肉制品檢測的應(yīng)用研究進(jìn)展進(jìn)行了分析,突出了電子鼻技術(shù)應(yīng)用的可行性和先進(jìn)性;指出電子鼻技術(shù)在肉與肉制品檢測中面臨的檢測效果參差不齊,電子鼻儀器體積大、價格高昂,模型通用性和普及性不夠等不足。最后,本文從硬件系統(tǒng)和軟件系統(tǒng)兩方面,對未來電子鼻技術(shù)的發(fā)展及其應(yīng)用前景進(jìn)行了展望,包括硬件系統(tǒng)方面提高電子鼻傳感器陣列電極膜材料的性能,增強(qiáng)電子鼻耐用性和識別氣味的靈敏度;軟件系統(tǒng)方面不斷探索引入新的模式識別算法,使電子鼻技術(shù)實現(xiàn)對氣味更快、更準(zhǔn)確的識別分析。
關(guān)鍵詞:電子鼻;肉與肉制品;高效檢測;質(zhì)量安全;模式識別
中圖分類號: TS207.3;TP29;TP212.9文獻(xiàn)標(biāo)志碼: A文章編號:202011-SA003
引用格式:劉洋, 賈文珅, 馬潔, 梁剛, 汪慧華, 周巍. 電子鼻技術(shù)在肉與肉制品檢測中的研究進(jìn)展和應(yīng)用展望[J].智慧農(nóng)業(yè)(中英文), 2021, 3(4):29-41.
LIU Yang, JIA Wenshen, MA Jie, LIANG Gang, WANG Huihua, ZHOU Wei. Research progress and application prospect of electronic nose technology in the detection of meat and meat products[J]. Smart Agriculture, 2021, 3(4):29-41.(in Chinese with English abstract)
1? 引言
肉與肉制品作為人類獲取蛋白質(zhì)、維生素和礦物質(zhì)等營養(yǎng)成分的重要來源,在人類生活中已不可或缺[1,2],其安全問題也逐漸成為人們關(guān)注的焦點,安全性檢測已成為至關(guān)重要的、關(guān)系民生的工程[3-5]。
食品感官檢測是歷史最悠久、也是最常見的傳統(tǒng)食品檢測方法[6]。官方獸醫(yī)通常通過對宰殺動物時的刀口狀態(tài)、肉的放血程度、血液沉積狀態(tài)、肉尸及皮膚的變化等進(jìn)行觀察分析,來判斷肉與肉制品的品質(zhì)[7]。這種方法雖然可以實現(xiàn)對肉類簡便、快速地鑒別,但是往往主觀性較強(qiáng),易受到人的感官的靈敏度、經(jīng)驗豐富程度、健康狀況或者精神狀態(tài)等因素的影響[8]。隨著科技的發(fā)展,分子生物學(xué)檢測技術(shù)不斷涌現(xiàn),如聚合酶鏈?zhǔn)椒磻?yīng)(Polymerase Chain Reaction ,PCR)技術(shù)[9]、濾膜法[10]、環(huán)介導(dǎo)等溫擴(kuò)增(Loop-Mediated? Isothermal? Amplification , LAMP)技術(shù)[11]、基因芯片法[12]、DNA 檢測技術(shù)[13]等,分子生物學(xué)檢測方法主要是通過生物學(xué)的方法檢測一些大分子的結(jié)構(gòu)與功能,在病原微生物的檢測中應(yīng)用最為廣泛[14]。如今,肉與肉制品在國內(nèi)外高通量的流通,導(dǎo)致對其檢測方法提出了新的要求,即簡單、快速、準(zhǔn)確以及無損[15]。利用分子生物學(xué)檢測方法,雖然可以更加客觀地對樣品進(jìn)行分析檢測,并能夠保證較高的檢測精度,但普遍對樣本制作的要求較高,并且針對某種或者某類病原微生物只能進(jìn)行對應(yīng)的一對一檢測,對儀器以及操作者有較高的專業(yè)技術(shù)要求,當(dāng)樣本數(shù)量比較龐大時候,還需耗費更多的時間、財力和物力,應(yīng)用受到制約。
電子鼻技術(shù)作為將人類的感官特征轉(zhuǎn)移到非生命系統(tǒng)中的熱門技術(shù)之一[16],將人類嗅覺系統(tǒng)轉(zhuǎn)移至電子設(shè)備系統(tǒng),實現(xiàn)通過對待檢測樣品所散發(fā)的氣味進(jìn)行分析、識別和檢測[17, 18]。其操作簡單,對操作者無專業(yè)技術(shù)要求,且不受環(huán)境影響,無需接觸樣品,即可達(dá)到檢測作用。
為綜合報道電子鼻在肉與肉制品檢測中研究進(jìn)展,本文在介紹電子鼻技術(shù)及其檢測原理的基礎(chǔ)上,梳理了近年來電子鼻技術(shù)在肉與肉制品的新鮮度檢測、摻假檢測、風(fēng)味評價、病原微生物污染檢測等方面的應(yīng)用研究進(jìn)展,總結(jié)了電子鼻技術(shù)的檢測原理,以及在當(dāng)前肉與肉制品應(yīng)用中的優(yōu)勢,闡述了電子鼻技術(shù)發(fā)展還將面臨的挑戰(zhàn),同時提出了未來發(fā)展的設(shè)想。
2 電子鼻技術(shù)及檢測原理
電子鼻技術(shù)的發(fā)展從初期的電子模擬嗅覺過程到氣體傳感器陣列,再到如今與計算機(jī)系統(tǒng)相結(jié)合[19],能夠通過氣味快速、準(zhǔn)確地對樣品進(jìn)行檢測,儀器也簡單易操作,實現(xiàn)了官方獸醫(yī)感官評定法和分子生物學(xué)檢測技術(shù)優(yōu)點的融合,同時因為是對氣味進(jìn)行檢測分析,不需要直接接觸樣品,實現(xiàn)了無損檢測。圖1 為電子鼻技術(shù)的發(fā)展歷程及應(yīng)用。上個世紀(jì)60年代,有研究利用氣體在電極上的反應(yīng)模擬嗅覺過程,隨之氣體傳感器[20,21]逐漸問世并得到進(jìn)一步發(fā)展,但未得到重視。直到80年代,Gardner對“電子鼻”概念進(jìn)行了明確定義,即利用氣敏傳感器采集氣味信息,并與模式識別算法[22,23]相結(jié)合的技術(shù),引起了學(xué)術(shù)界廣泛興趣。在此之后,電子鼻技術(shù)得以進(jìn)入快速發(fā)展時期[24]。電子鼻技術(shù)(也稱為電子鼻)是一種通過模擬動物嗅覺系統(tǒng),將傳感器技術(shù)、模式識別技術(shù)以及計算機(jī)技術(shù)等有機(jī)地結(jié)合起來的技術(shù),在若干種混合氣體復(fù)雜的環(huán)境中快速、準(zhǔn)確地識別各種氣味的濃度,并作出定性、定量的分析[25,26]。
圖2為電子鼻系統(tǒng)與人類嗅覺系統(tǒng)對比圖。在電子鼻的發(fā)展前期,傳感器的發(fā)展起到了至關(guān)重要的作用,氣體傳感器陣列相當(dāng)于動物嗅覺系統(tǒng)的嗅感細(xì)胞[27-29]。作為一種檢測裝置,通過傳感器將感受到的被測量信息按一定的規(guī)律轉(zhuǎn)換成其它形式的信息輸出,從而獲取被測樣品的氣味信息。根據(jù)感知功能,可將傳感器分為熱敏、光敏、氣敏、磁敏等類型,在電子鼻中即為氣敏傳感器[30]。隨著技術(shù)的發(fā)展,氣敏傳感器的類型也逐漸增多[31],目前在電子鼻中常用到的類型有:電化學(xué)傳感器[32]、金屬氧化物傳感器[33,34]、固體電解質(zhì)氣敏傳感器[35]等。計算機(jī)相當(dāng)于大腦,而模式識別系統(tǒng)則相當(dāng)于神經(jīng)信號傳遞系統(tǒng)[36,37]。隨著硬件系統(tǒng)的進(jìn)步,軟件系統(tǒng)也越來越受到關(guān)注。在電子鼻系統(tǒng)中,模式識別技術(shù)通過計算機(jī)對來自氣敏傳感器的信息進(jìn)行分析和判讀,從而達(dá)到分析識別的目的[38,39]。目前在電子鼻系統(tǒng)中采用的大多還是主成分分析(PrincipalComponents Analysis ,PCA)、線性判別分析(Linear Discriminant Analysis ,LDA)、函數(shù)判別分析(Functional? Discriminant Analysis , DFA)等傳統(tǒng)的算法。
圖3為電子鼻識別分析氣味過程。電子鼻識別氣味即利用傳感器陣列的氣敏器件對復(fù)雜的混合氣體進(jìn)行識別響應(yīng),將化學(xué)信號轉(zhuǎn)換為電信號,利用模式識別和計算機(jī)技術(shù)對電信號進(jìn)行處理和分析,形成氣味響應(yīng)譜,并對氣味質(zhì)量做出分析與評定[40,41]。
3? 電子鼻技術(shù)在肉與肉制品檢測中研究進(jìn)展
據(jù)《中國統(tǒng)計年鑒2020年》,作為肉類消費大國,雖然近幾年由于豬瘟等食源性疫情的影響,人均豬肉消費量有一定的降低,但中國對肉與肉制品的消費總量并未大幅下降[42]。人們生活水平日益提高,在肉與肉制品的飲食上,純粹的肉類新鮮度等問題已不能滿足人們的需求,對于其成分含量、風(fēng)味評價乃至微生物早期污染狀況等也成為人們在消費過程中重點關(guān)注的問題[43,44]。電子鼻技術(shù)作為新興的仿生嗅覺技術(shù)[45],因其具有簡單、快速、無損檢測的特點,在肉與肉制品的新鮮度、摻假情況、風(fēng)味評價、微生物污染情況等4方面檢測中得到廣泛應(yīng)用。
3.1 新鮮度檢測
新鮮度與肉的品質(zhì)直接相關(guān)。人如果誤食了不新鮮的肉或肉制品,輕則造成腹瀉、嘔吐等腸胃疾病,重則危及生命[46,47]。因此,新鮮度是肉與肉制品品質(zhì)安全的一項重要指標(biāo),快速、準(zhǔn)確、實時檢測肉的新鮮度非常重要[48]。
部分研究團(tuán)隊用電子鼻開展了肉新鮮度檢測的相關(guān)研究。An等[49]以不同劑量電子束照射的鴨肉為研究對象,利用自制的含有6個氣敏傳感器的電子鼻,結(jié)合 PCA 算法,對鴨肉的新鮮度進(jìn)行檢測,結(jié)果表明,電子鼻的氣味數(shù)據(jù)可有效地區(qū)分經(jīng)過不同劑量輻照的鴨肉,低劑量的電子束輻照和真空包裝有利于熏鴨肉的安全性和貨架期延長。Wijaya等[50]針對不同品質(zhì)等級的牛肉,利用自制的含有7個金屬氧化物氣敏傳感器電子鼻,結(jié)合基于小波變換的噪聲濾波和支持向量機(jī)(Support Vector Machine ,SVM)、二次判別分析(Quadratic? Discriminant Analysis , QDA)等算法,研究了通過噪聲濾波處理的電子鼻數(shù)據(jù)信號在不同品質(zhì)等級牛肉分類的效果,進(jìn)而實現(xiàn)預(yù)測牛肉樣品中微生物種群規(guī)模。Mirzaee等[51]針對區(qū)分恒溫冷凍及凍融雞肉,利用自制的含有8個金屬氧化物氣敏傳感器的電子鼻,結(jié)合K近鄰算法(K-Nearest Neighbor ,KNN)進(jìn)行了分類研究,準(zhǔn)確率可達(dá)95.83%。Zheng 等[52]針對脊尾白對蝦,利用自制的含有8個金屬氧化物氣敏傳感器的電子鼻采集氣味數(shù)據(jù)信息,結(jié)合PCA 和隨機(jī)共振(Stochastic Resonance ,SR)方法對數(shù)據(jù)進(jìn)行處理,建立了電子鼻對脊尾白對蝦的品質(zhì)評價模型,并對 PCA 和 SR 的分析結(jié)果進(jìn)行對比,結(jié)果表明,隨著總活菌計數(shù)的增加,對蝦的品質(zhì)會下降,且通過檢測結(jié)果發(fā)現(xiàn),SR 方法對樣本的判別效果優(yōu)于PCA 。Liu等[53]針對牛腰條肉,利用自制的含有8個金屬氧化物氣敏傳感器的電子鼻,結(jié)合 SR 和雙層級聯(lián)序列隨機(jī)共振響應(yīng)進(jìn)行多變量回歸(Multiple Variable Regres‐sion,MVR),分析了利用不同化學(xué)防腐劑對牛腰條肉進(jìn)行處理后的影響,結(jié)果表明,在保證食品食用安全標(biāo)準(zhǔn)的前提下,用4% SL 加2 g/L 乳鏈菌肽處理牛肉,可有效延長樣品的存儲時間,保證了牛肉在貨架期的新鮮度。Wang等[54]對經(jīng)過焦磷酸鈉(SPP)、三聚磷酸鈉(STP)和混合溶液(SPP + STP ,1:1)處理和未經(jīng)過處理的羅非魚魚片為實驗對象,利用PEN3電子鼻結(jié)合線性判別分析算法,提出了一種有效抑制羅非魚魚片在冷藏過程中脂質(zhì)氧化的方法以及簡便的測定方法。Gorska等[55]對新鮮豬肉、冷凍后解凍肉和變質(zhì)肉,利用氣相色譜電子鼻與PCA 、反向傳播神經(jīng)網(wǎng)絡(luò)(Back Propagation Neural Network,BPNN)相結(jié)合,建立了豬肉新鮮度的檢測模型,得到新鮮肉、冷凍后解凍肉和變質(zhì)肉的識別率達(dá)80%以上。
上述研究成果表明,電子鼻在肉的新鮮度檢測中應(yīng)用已經(jīng)相對比較成熟,各種小型的便捷式自制電子鼻在實驗中已經(jīng)得到不錯的試驗效果,但是模型應(yīng)用對象較為單一,適用范圍相對較窄,不能適用于多種肉與肉制品的普適性檢測。
3.2 摻假檢測
為謀取利益,部分商家會用一些平價甚至劣質(zhì)的肉來冒充優(yōu)質(zhì)肉,使消費者經(jīng)濟(jì)利益和健康受損[56]。因此,摻假問題也是肉與肉制品安全的一項重要指標(biāo)。對肉與肉制品摻假檢測是維護(hù)保護(hù)消費者的利益的有效方式。Tian 等[57]利用 PEN2電子鼻檢測羊肉肉糜中摻雜豬肉的含量,結(jié)合偏最小二乘分析(Partial Least Square Analy? sis ,PLS)、多元線性回歸(Multiple Linear Regression ,MLR)和BP神經(jīng)網(wǎng)絡(luò)建立了羊肉肉餡豬肉含量的預(yù)測模型,結(jié)果表明,與 PLS 和 MLR相比,BP神經(jīng)網(wǎng)絡(luò)模型能更準(zhǔn)確地預(yù)測摻假程度。Wang等[58]利用比色傳感器電子鼻,結(jié)合線性判別分析和多層感知器神經(jīng)網(wǎng)絡(luò)分析(Multilayer Perceptron Neural Networks Analysis, MLPN)算法,對羊肉中摻假鴨肉進(jìn)行鑒定,準(zhǔn)確性分別達(dá)到98.2%和 96.5%,且摻假10%即可被檢測出,證明電子鼻技術(shù)對羊肉摻假檢測具有較高的準(zhǔn)確性。Han等[59]利用PEN3電子鼻,分別結(jié)合線性判別分析和極限學(xué)習(xí)機(jī)(Extreme? Learning Machine ,ELM)算法對純牛肉、牛肉- 豬肉混合物和純豬肉進(jìn)行檢測并分析比較,結(jié)果 ELM 模型在訓(xùn)練集和預(yù)測集的識別率分別達(dá)到91.27%和87.5%,優(yōu)于線性判別模型;另又建立 BP 神經(jīng)網(wǎng)絡(luò)模型,對不同摻雜豬肉比例的牛肉進(jìn)行摻假水平的預(yù)測,預(yù)測集相關(guān)系數(shù)為0.85,均方根誤差為0.147,表明基于比色傳感器和化學(xué)計量學(xué)相結(jié)合的電子鼻技術(shù)在快速檢測摻假豬肉的牛肉方面有很大的潛力。Kalinichenko和Ar?????? seniyeva[60]利用石英晶體傳感器電子鼻,結(jié)合 PCA 和概率神經(jīng)網(wǎng)絡(luò)(Probabilistic Neural Network ,PNN),對香腸中大豆蛋白的摻雜情況(0、10%、20%、30%)進(jìn)行分析鑒別,結(jié)果在預(yù)測模型中,電子鼻系統(tǒng)對大豆蛋白4種不同摻雜量的香腸,可實現(xiàn)100%的分類,表明電子鼻在肉制品摻假檢測中的有效性。
上述研究成果表明,對于肉與肉制品摻假的檢測,使用的電子鼻設(shè)備均為大型已成型的儀器,使用低成本自制的便捷式電子鼻的相關(guān)研究極少。主要是由于摻假的成分和種類變化多樣,特征復(fù)雜,因此很難用低成本的自制電子鼻設(shè)備去鎖定其摻假特征,目前主要還是使用大型、復(fù)雜的高成本電子鼻儀器,而自制的便捷式儀器相對很少,推廣難度相對較大。
3.3 風(fēng)味評價
產(chǎn)地、品種、肉源動物飼養(yǎng)狀況、肉源部位、以及烹飪/加工方式會對肉與肉制品風(fēng)味均會有不同程度的影響。人們對飲食的要求越來越精致化,肉與肉制品的風(fēng)味檢測也逐漸引起關(guān)注[61,62]。
3.3.1?? 品種
張賓惠等[63]利用自制的含有16個金屬氧化物氣敏傳感器的電子鼻,結(jié)合化學(xué)計量法提取樣品氣味指紋數(shù)據(jù),并結(jié)合逐步線性判別分析(Stepwise Linear Discriminant Analysis ,S-LDA)和 ANN進(jìn)行數(shù)據(jù)分析,然后利用多層感知器(Multilayer Perceptron ,MLP)和 SVM 對數(shù)據(jù)進(jìn)行分類,從4個品種雞肉(北京油雞、白羽肉雞、海蘭褐蛋雞和蘇禽綠蛋雞)中快速鑒別出北京油雞,識別率高于90%,驗證了電子鼻技術(shù)與化學(xué)計量法結(jié)合識別雞肉種類的可行性。Zhang等[64]針對外觀上難以區(qū)分的白花魚和小黃魚,利用自制的含有18個金屬氧化物氣敏傳感器的電子鼻,結(jié)合 PCA 可對二者氣味特征進(jìn)行較好地區(qū)分。Giovanelli等[65]利用PEN2電子鼻,對3種不同品種的意大利干腌火腿在加工過程中的揮發(fā)性香氣進(jìn)行識別分析,結(jié)果電子鼻可以有效對火腿的品種以及不同加工階段進(jìn)行區(qū)分,表明電子鼻不僅可以用于肉制品品種的識別,還可應(yīng)用于火腿成熟過程的在線監(jiān)測。
3.3.2? 產(chǎn)地
Wang 等[66]利用自制的含有18個金屬氧化物氣敏傳感器的電子鼻和電子舌對產(chǎn)自三個不同地方的中華絨螯蟹風(fēng)味特征進(jìn)行檢測,結(jié)果發(fā)現(xiàn)3種螃蟹的氣味存在一定的差異,表明受環(huán)境等因素影響,來自不同地區(qū)同種動物的肉質(zhì)有所不同。Han等[67]利用氣相色譜電子鼻,結(jié)合PCA、凝聚層次聚類方法(Agglomerative HierarchicalClustering,AHC)和PLS-DA ,對三個不同地區(qū)的肉源豬的水煮豬肉的揮發(fā)性氣味鑒別,成功對3種煮熟的豬肉進(jìn)行了區(qū)分,表明電子鼻可以有效識別不同產(chǎn)地的水煮豬肉。Li等[68]利用氣相色譜電子鼻,結(jié)合PCA ,對4種不同產(chǎn)地的干腌火腿的揮發(fā)性氣味信息進(jìn)行分析識別,結(jié)果發(fā)現(xiàn)產(chǎn)地不同,干腌火腿的香氣特征也有所不同,電子鼻能夠客觀地反映干腌火腿的整體香氣特征,為干腌火腿的分類提供了新的方法。
3.3.3? 肉源動物飼養(yǎng)狀況
Wojtasik等[69]利用HeraclesⅡ電子鼻,對喂養(yǎng)不同飼料的生豬肉進(jìn)行揮發(fā)性氣味分析檢測,結(jié)果通過定性分析發(fā)現(xiàn),喂養(yǎng)豬的飼料中添加抗氧化劑(維生素 E 和硒的結(jié)合物),會使生豬肉的揮發(fā)性化合物成分的分布發(fā)生改變,電子鼻可以有效地對不同飼料喂養(yǎng)的豬肉進(jìn)行區(qū)分。?? 3.3.4? 肉源部位
Ji 等[70]以中華絨螯蟹四個可食性部位(腹部、爪部、腿部和性腺部位)的肉為研究對象,利用氣相色譜電子鼻和感官評價結(jié)合的方式,對其四個不同部位的肉進(jìn)行氣味分析,結(jié)果發(fā)現(xiàn),在腹部、爪部、腿部和性腺部位分別檢測到2 種、7種、7種和10種重要的氣味化合物。張麗萍等[71]以西門塔爾雜交黃牛的五個不同部位的肉(即臀肉、肩肉、黃瓜條、米龍、霖肉)為研究對象,以出品率、嫩度、色澤和感官品質(zhì)等為指標(biāo),利用PEN3電子鼻和電子舌技術(shù)測定、感官評定等方法,研究了牛肉的不同部位的品質(zhì)差異,以米龍制備的黃牛肉干各項指標(biāo)均顯著高于
其他部位所制成的牛肉干。
3.3.5? 烹飪/加工方式
Zhu 等[72]利用 PEN3電子鼻檢測分析雞肉,得到了烹調(diào)過程中雞肉風(fēng)味形成的臨界點:烹飪溫度為80~90℃,烹飪時間為50~60 min ,此時雞肉蛋白質(zhì)降解和蛋白質(zhì)氧化均達(dá)到最大值。 Zhou等[73]針對鰱魚糜,利用氣相色譜電子鼻和感官評價結(jié)合的方法,對經(jīng)過鹽水、弱堿性溶液和水洗滌后的鰱魚糜香味特征進(jìn)行了分析,發(fā)現(xiàn)不同的洗滌方式對氣味的影響程度不同,鹽水和弱堿性洗滌比水洗能除去更多芳香活性成分,且高濃度生理鹽水去除效果更強(qiáng)。
上述研究成果表明,電子鼻對于影響肉與肉制品風(fēng)味的相關(guān)因素的檢測涉獵相對廣泛,將電子鼻應(yīng)用于肉與肉制品風(fēng)味的檢測可以輔助品評師進(jìn)行風(fēng)味評價工作,大幅減少其工作量。相對于其他儀器,電子鼻設(shè)備體現(xiàn)了模擬人類嗅覺的優(yōu)勢,可以更全面地反映肉與肉制品的風(fēng)味特征,綜合反饋人們對肉與肉制品品質(zhì)的感受。
3.4 病原微生物污染檢測
肉類易滋生病菌等微生物,一般高溫即可殺死,但是對于生食肉食品,如果其肉源動物攜帶病原微生物,食用后會對人類健康造成威脅,甚至威脅生命。而目前將電子鼻應(yīng)用于肉類微生物攜帶情況的檢測還處于初步發(fā)展階段[74,75]。
Balasubramanian 等[76]針對接種鼠傷寒沙門氏菌的真空包裝牛肉,利用PEN3電子鼻,結(jié)合PCA 和獨立成分分析(Independent ComponentAnalysis,ICA),并建立線性逐步回歸預(yù)測模型,對其頂部空間氣味的變化進(jìn)行了評估,結(jié)果顯示采用 ICA 的平均預(yù)測精度為82.99%。王丹鳳等[77]針對分別在4℃和20℃條件下保存不同天數(shù)的豬肉,利用氣相色譜電子鼻,結(jié)合 PCA和偏最小二乘回歸分析(PLS -Regression)對其揮發(fā)性氣味的成分進(jìn)行檢測,并通過與微生物數(shù)量變化的比對發(fā)現(xiàn),使用電子鼻檢測的信號信息會隨微生物數(shù)量的變化而發(fā)生變化。Lippolis等[78]以臘腸為研究對象,首先用電子鼻分析培養(yǎng)基培養(yǎng)的青霉菌菌株樣本,并用判別函數(shù)分析(Discrimination Function Analysis ,DFA),得到識別率為82%;然后將菌株接種到臘腸,經(jīng)在實驗室規(guī)模發(fā)酵后,利用PEN3電子鼻采集接種和未接種菌株的臘腸的氣味信息,并結(jié)合DFA 對電子鼻采集的氣味信息數(shù)據(jù)進(jìn)行分析,通過交叉驗證得到模型的平均識別率為88%。上述研究結(jié)果證明了電子鼻技術(shù)可以用來檢測肉類是否攜帶病原微生物,但都局限于對某一種微生物的檢測。
有研究進(jìn)一步探索了電子鼻對多種微生物的檢測及識別情況。例如,Prima等[79]針對胰蛋白酶大豆肉湯(Tryptone Soy Broth ,TSB)培養(yǎng)基中單核細(xì)胞增生性李斯特菌和蠟樣芽孢桿菌,利用自制的電子鼻,并結(jié)合 LDA 、QDA 以及 SVM ,研究了電子鼻對培養(yǎng)基中是否有單核細(xì)胞增生性李斯特菌或蠟樣芽孢桿菌的檢測,準(zhǔn)確率可達(dá)98%,為動物檢疫食品常規(guī)快速檢測中是否存在單核細(xì)胞增生性李斯特菌或蠟樣芽孢桿菌污染提供了理論依據(jù)。
又有研究關(guān)注了如何提升病原微生物污染的肉與肉制品檢測的準(zhǔn)確性。Bonah等[80]針對被沙門氏菌不同污染水平下的豬肉樣品,采用 PEN3電子鼻,結(jié)合PCA 和采用不同優(yōu)化算法的支持向量機(jī)回歸(Support Vector Machine Regression ,SVMR),對沙門氏菌污染豬肉的情況進(jìn)行鑒別,結(jié)果表明電子鼻技術(shù)可用于豬肉污染情況的鑒別,且采用遺傳算法優(yōu)化的 SVMR (Genetic Algorithm - SVMR ,GA-SVMR)的預(yù)測精度最高,模式識別算法的選擇對電子鼻技術(shù)的檢測準(zhǔn)確率具有很大影響。
上述研究成果表明,由于病菌等微生物的代謝產(chǎn)物的含量相對微弱,雖然已經(jīng)有利用電子鼻技術(shù)檢測肉及其制品被病菌等微生物污染狀況的研究,在培養(yǎng)基中的病菌微生物識別率可達(dá)90%以上,而對肉與肉制品病原微生物污染狀況的識別率僅達(dá)80%,檢測精度還不夠高,在未來研究中,考慮利用電子鼻技術(shù)對培養(yǎng)基中的菌落和接種到肉或肉制品中的菌落獨立比較,對病原微生物污染的肉與肉制品的揮發(fā)性氣味信息進(jìn)行充分建模。
4? 目前存在的問題
根據(jù)上述研究,目前,對于電子鼻技術(shù)在肉與肉制品新鮮度、摻假情況、風(fēng)味評價、微生物污染情況等方面所開展的具體研究工作主要是針對特定的某種或者幾種樣本數(shù)據(jù)集,其模式識別算法對應(yīng)于不同的樣本數(shù)據(jù),分析效果也是參差不齊;同時,現(xiàn)階段電子鼻系統(tǒng)的整個裝置相對大型,不利于移動和攜帶,且其使用還處于輔助科研階段,主要應(yīng)用于高校和科研院所,并且,現(xiàn)在所用的已成規(guī)模的電子鼻機(jī)器設(shè)備主要還是國外進(jìn)口,價格昂貴,對于一些小型的元器件只能定制,因此在模型的通用性和普及性方面是電子鼻技術(shù)面臨的最大的問題。
5? 結(jié)論與展望
5.1 結(jié)論
本文對近年來電子鼻技術(shù)在肉與肉制品檢測中的研究進(jìn)行了歸納分析,主要從肉與肉制品的新鮮度、摻假情況、風(fēng)味評價、微生物污染情況等方面的檢測技術(shù)研究進(jìn)行闡述,突出電子鼻技術(shù)應(yīng)用在肉與肉制品全方面檢測的可行性和先進(jìn)性。
在硬件方面,對于肉與肉制品新鮮度和風(fēng)味評價的檢測,相對比較成熟,采用低成本、便捷式的自制電子鼻就可實現(xiàn)較好的檢測效果,而對于肉與肉制品的摻假情況和微生物污染情況,由于樣本揮發(fā)性氣味成分和種類復(fù)雜多樣,目前的研究還是基于大型、復(fù)雜的高成本電子鼻儀器設(shè)備。
在軟件方面,電子鼻模式識別系統(tǒng)對數(shù)據(jù)信息進(jìn)行分析時,多采用的是PCA 、LDA 、ICA等傳統(tǒng)分析方法,隨著算法的發(fā)展、更新,許多新的算法,如MLPN 等,以及傳統(tǒng)算法間的結(jié)合,如GA-SVMR等,也逐漸在肉與肉制品的各方面檢測中得到有效的應(yīng)用驗證。
5.2 展望
電子鼻技術(shù)已成功地應(yīng)用于肉類來源、生產(chǎn)加工到流通儲藏等環(huán)節(jié)的檢測,具有快速、無損、簡便、非侵入式等優(yōu)點,但在通用性和普及性方面仍存在不足處,其性能有待進(jìn)一步完善和提升[81],圖4主要展現(xiàn)了電子鼻傳感器系統(tǒng)和模式識別系統(tǒng)兩方面的改進(jìn)與發(fā)展。
在傳感器系統(tǒng)方面,高敏感度、高性能的材料用于電子鼻傳感器陣列電極膜的制備是重點研究方向,電子鼻是通過氣敏傳感器陣列來模擬人類嗅覺系統(tǒng)從而對不同的氣味進(jìn)行識別,提高對電子鼻傳感器陣列電極膜材料的性能,使其在靈敏度和耐用性上得到提高,數(shù)據(jù)的采集更加快速有效,進(jìn)而對電子鼻的發(fā)展有一定的促進(jìn)作用。
模式識別系統(tǒng)即是模擬大腦,對電子鼻識別的氣味信息進(jìn)行分析,結(jié)合前文研究進(jìn)展,目前在電子鼻模式識別系統(tǒng)中主要采用的還是PCA、 LDA 、DFA 、PLS等的經(jīng)典方法,而計算機(jī)技術(shù)的升級為一些復(fù)雜的算法提供了支撐的平臺,以往需要耗時數(shù)小時,甚至數(shù)天的算法,現(xiàn)在只需要幾分鐘或更短的時間就能得到結(jié)果。所以,不斷有研究對已有的這些算法,如PLS 、LDA 、BP 等進(jìn)行優(yōu)化改進(jìn),根據(jù)其優(yōu)缺點相互結(jié)合使用,提高了模式識別系統(tǒng)的分析率;同時也不斷探索引入新的模式識別算法,如DBN 、CNN等。
總而言之,未來在計算機(jī)提供的快速運算支撐平臺下,通過不斷擴(kuò)充建立訓(xùn)練模型的樣本量,增加樣本訓(xùn)練集,深度對模型進(jìn)行訓(xùn)練,提高電子鼻的識別精度,形成閉環(huán)效應(yīng),使電子鼻技術(shù)能夠更廣泛地應(yīng)用于人們的生產(chǎn)生活。
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Research Progress and Application Prospect of Electronic?? Nose Technology in the Detection of Meat and Meat Products
LIU Yang1, JIA Wenshen1,2,3,4*, MA Jie1, LIANG Gang2,3,4, WANG Huihua5, ZHOU Wei6
(1. School of Automation, Beijing Information Science and Technology University, Beijing 100192, China;2. Instituteof Quality Standard and Testing Technology, Beijing Academy of Agriculture and Forestry Sciences, Beijing 100097,China;3. Department of Risk Assessment LabforAgro-products (Beijing), Ministry of Agriculture and Rural Affairs,Beijing 100097, China;4. Key Laboratory of Urban Agriculture (North China), Ministry of Agriculture and Rural Affairs, Beijing 100097, China;5. Beijing Vocational College of Agriculture, Beijing 102400, China;6. Hebei Food Inspection and Research Institute, Shijiazhuang 050000, China)
Abstract: With the continuous increase of import and export of various countries, people have put forward higher requirements on the efficiency and accuracy of meat and meat products safety indicators detection. Since electronic nose technology is simple to operate and allows rapid and nondestructive testing, it can meet today's need for efficient test of meat and meat products. In this paper, the detection principle of electronic nose technology was introduced firstly, and its development process was described from two aspects of hardware and software system. Then, the application research progress of electronic nose technology in meat and meat products detection in recent years from the aspects of freshness, adulteration, flavor evaluation and microbial contamination of meat and meat products was analyzed. Different electronic nose instruments and equipment or different pattern recognition algorithms result in different analysis results. Therefore, it highlighting the feasibility and advancement of electronic nose technology application in various aspects of meat and meat products detection. At the same time, in view of the application research results of electronic nose technology in the detection of meat and meat products, the paper pointed out the shortcomings of electronic nose technology, for example: The analysis effect of electronic nose technology was uneven, the price of electronic nose equipment was relatively expensive, and the application range of large electronic nose equipment was limited. Therefore, there were still some difficulties and problems of electronic nose technology in the aspects of universality and popularization. Finally, in view of the shortcomings of the current electronic nose technology, the development and application prospects of the electronic nose technology in the future were prospected. In terms of hardware system, with the research and development continuously of new gas sensitive materials, the durability and sensitivity to smell recognition of the electronic nose by improving the performance of the electrode film material of the electronic nose sensor array was enhanced. In terms of software system, with the upgrading continuously of computer systems, a supporting platform for the emerging and complex pattern recognition algorithms was provided. New pattern recognition algorithms in the pattern recognition system of electronic nose technology were explored and introduced, so that electronic nose technology can achieve faster and more accurate recognition and analysis of odors.