2016年國(guó)內(nèi)外蜂產(chǎn)品質(zhì)量安全研究進(jìn)展（續(xù)）

周金慧 張文文 王欣然 張金振 金玥 楊樹(shù)鵬 趙文 陳蘭珍 問(wèn)亞琴 王鵬 黃京平 劉婷婷 李熠

（中國(guó)農(nóng)業(yè)科學(xué)院蜜蜂研究所農(nóng)業(yè)部蜂產(chǎn)品質(zhì)量監(jiān)督檢驗(yàn)測(cè)試中心，北京100093）

2016年國(guó)內(nèi)外蜂產(chǎn)品質(zhì)量安全研究進(jìn)展（續(xù)）

周金慧 張文文 王欣然 張金振 金玥 楊樹(shù)鵬 趙文 陳蘭珍 問(wèn)亞琴 王鵬 黃京平 劉婷婷 李熠

（中國(guó)農(nóng)業(yè)科學(xué)院蜜蜂研究所農(nóng)業(yè)部蜂產(chǎn)品質(zhì)量監(jiān)督檢驗(yàn)測(cè)試中心，北京100093）

（續(xù)《中國(guó)蜂業(yè)》2017年第3期）

重金屬分析的樣品前處理方法和儀器分析方法也得到了一定的發(fā)展。通過(guò)合成一種螯合樹(shù)脂（MPAEMA-co-DVB-co-AMPS）作為吸附劑來(lái)提取蜂蜜樣品中Cd(II)、Co(II)、Cr(III)、Cu(II)、Fe(III)、Mn(II)、Pb(II)、和Zn (II)離子，然后利用原子熒光光譜法定量分析，檢測(cè)限范圍為0.9～2.2 ng/ml[27]。微波消解-四級(jí)桿-電感耦合等離子體質(zhì)譜也被應(yīng)用于蜂蜜和蜂花粉中Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Dy、Ho、Er、Tm、Lu、Yb、As、Bi、Cd、Pb、Se和In含量分析，通過(guò)調(diào)整四級(jí)桿和質(zhì)譜的參數(shù)能夠極大地減少蜂蜜和蜂花粉基質(zhì)影響，提高準(zhǔn)確度和靈敏度[28]。

蜂蜜主要成分為糖類物質(zhì)，包括果糖和葡萄糖在內(nèi)的所有的糖類物質(zhì)占80%以上，在高糖的環(huán)境下微生物很難存活，但是研究顯示芽孢桿菌因?yàn)槠淠褪艿难挎唧w的存在而廣泛存在于蜂蜜中。基于MALDITOF-MS質(zhì)譜技術(shù)對(duì)蜂蜜中芽孢桿菌的鑒定與分型顯示44株芽孢桿菌中鑒定出蠟樣芽孢桿菌 (B.cereus)31株，短小芽孢桿菌 (B.pumilus)5株，枯草芽孢桿菌(B. subtilis)3株，地衣芽孢桿菌(B.licheniformis)2株，炭疽芽孢桿菌 (B.anthracis)1株，土壤短芽孢桿菌(Brevibacillus agri.)2株。通過(guò)多次重復(fù)試驗(yàn)，表明從同一份樣品或同一品牌蜂蜜樣品中能穩(wěn)定分離到芽孢桿菌，獲得的蛋白指紋圖譜具有極好的穩(wěn)定性[29]。

2.3 溯源分析

蜂產(chǎn)品尤其是蜂蜜的溯源分析是近年來(lái)研究的熱點(diǎn)，其研究主要是基于蜂產(chǎn)品理化性質(zhì)、礦物質(zhì)元素以及黃酮類、酚酸類、氨基酸和芳香類等內(nèi)源性活性組分的靶標(biāo)和非靶標(biāo)數(shù)據(jù)統(tǒng)計(jì)分析構(gòu)建模型，使之可視化的分類。

基于礦物元素含量可進(jìn)行蜂蜜蜜源和產(chǎn)地溯源研究，采用全譜直讀電感耦合等離子體原子發(fā)射光譜法測(cè)定蜜樣礦物元素含量，引進(jìn)啞變量回歸和校正模型，從而建立了蜂蜜產(chǎn)地、蜜源雙目標(biāo)溯源分析方法[30]。基于蜂蜜中的氨基酸種類和含量的不同，應(yīng)用甲醛和乙酰丙酮與蜂蜜中氨基酸發(fā)生熒光衍生反應(yīng)對(duì)源自不同花源的蜂蜜進(jìn)行種類辨別研究。對(duì)衍生后的蜂蜜進(jìn)行三維熒光檢測(cè)，每個(gè)蜂蜜樣品經(jīng)檢測(cè)后得到一個(gè)三維熒光光譜矩陣數(shù)據(jù)，五種蜂蜜共150個(gè)樣品最后得到一個(gè)三維立方數(shù)據(jù)。將檢測(cè)獲得的三維熒光數(shù)據(jù)結(jié)合多維主成分分析、自加權(quán)交替三線性分解法及多維偏最小二乘辨別分析等多維模式識(shí)別方法，進(jìn)行數(shù)據(jù)處理并獲取五種蜂蜜的識(shí)別信息。研究結(jié)果顯示，基于氨基酸熒光衍生的多維模式識(shí)別方法可以用于蜂蜜種類的識(shí)別研究[31]。曹煒等[32]基于高效液相色譜-電化學(xué)檢測(cè)技術(shù)建立一種新的蜂蜜花源鑒別方法，以采自中國(guó)不同地區(qū)的3種單花種蜂蜜為研究對(duì)象，構(gòu)建了3種單花種蜂蜜的液相色譜電化學(xué)檢測(cè)器指紋圖譜，提取圖譜共有峰面積信息并應(yīng)用主成分分析和系統(tǒng)聚類分析進(jìn)行蜂蜜花源分類，并對(duì)完全未參與建模的蜂蜜樣品進(jìn)行驗(yàn)證。此外世界各國(guó)的研究人員還分別利用蜂蜜中的理化指標(biāo)、特征組分尋找、內(nèi)源性組分結(jié)合多種數(shù)據(jù)分析手段對(duì)來(lái)自不同國(guó)家的不同蜜源植物的蜂蜜進(jìn)行了鑒別[33-46]。

先進(jìn)的樣品前處理技術(shù)和儀器分析技術(shù)也用于蜂產(chǎn)品的溯源分析。以鉛筆鉛為機(jī)體的鉍膜電極結(jié)合化學(xué)計(jì)量學(xué)方法，通過(guò)優(yōu)化方波伏安法的參數(shù)，使用Behnken設(shè)計(jì)與期望函數(shù)相結(jié)合，不同的算法如不對(duì)稱最小使用正方形（AsLS）和相關(guān)優(yōu)化變形（COW）來(lái)預(yù)處理原始像數(shù)據(jù)，偏最小二乘法（PLS）和人工神經(jīng)元網(wǎng)絡(luò)（ANN）用來(lái)預(yù)測(cè)樣品中四種金屬的含量。該方法最終用來(lái)鑒別阿根廷不同產(chǎn)地的蜂膠產(chǎn)品[47]。高效液相薄層色譜-熒光檢測(cè)器和實(shí)時(shí)直接分析質(zhì)譜指紋圖譜也用于法國(guó)蜂膠的鑒別，獲得的指紋圖譜數(shù)據(jù)利用模式識(shí)別技術(shù)對(duì)大量數(shù)據(jù)進(jìn)行分析，同時(shí)酚酸類化合物咖啡酸、對(duì)香豆酸、柯茵、短葉松素、3-O-乙酰基短葉松素、高良姜素、莰菲醇和松屬素作為鑒別法國(guó)蜂膠的特征標(biāo)志物[48]。

大氣壓分析探針質(zhì)譜是近兩年出現(xiàn)的又一種環(huán)境大氣壓離子化質(zhì)譜分析技術(shù)，該技術(shù)能夠快速、簡(jiǎn)便分析固體、液體、組織或材料樣品中揮發(fā)性和半揮發(fā)性化合物而無(wú)需樣品制備和分離。探針插放于商品化的質(zhì)譜離子源的源體內(nèi)，熱的氮?dú)饬魇箻悠房焖倜摳街量諝庵校?jīng)電暈放電離子化產(chǎn)生質(zhì)子化(正離子模式)或去質(zhì)子化(負(fù)離子模式)離子，隨后進(jìn)行質(zhì)譜或多級(jí)質(zhì)譜定性、定量分析。不干擾同一源體上的電噴霧(ESI)源或大氣壓化學(xué)電離源（APCI）源的運(yùn)行，互為補(bǔ)充，且切換迅速方便。該離子化方式尤其適用于高端液質(zhì)平臺(tái)，充分展示其多級(jí)質(zhì)譜的選擇性碰撞碎裂能力，進(jìn)行快速鑒定和高靈敏度定量，以及精確質(zhì)量分析能力，實(shí)現(xiàn)復(fù)雜混合物中化合物的快速鑒定和定量分析。該技術(shù)在蜂花粉鑒別種也得到了應(yīng)用，蜂花粉磨碎后借助于微量的水附著于玻璃毛細(xì)管上，然后涂于探針，通過(guò)提高氮?dú)獾臏囟仁够ǚ壑械奈镔|(zhì)至離子源附近，在低碰撞能量條件下的質(zhì)譜中分析，從而通過(guò)分析黃酮類物質(zhì)鑒別花粉的蜜源植物和產(chǎn)地[49]。

2.4 摻假鑒別

目前，世界各國(guó)的蜂產(chǎn)品摻假主要集中于蜂蜜和蜂膠兩個(gè)產(chǎn)品。我國(guó)蜂蜜國(guó)家標(biāo)準(zhǔn)規(guī)定，不得在蜂蜜中添加或混入任何淀粉類、糖類或代糖類物質(zhì)。近年來(lái)，國(guó)內(nèi)和國(guó)際市場(chǎng)對(duì)蜂蜜的需求量不斷增加，在巨大經(jīng)濟(jì)利益的驅(qū)使下不法分子在蜂蜜中加入其他低品質(zhì)的蜂蜜以次充好，或者摻入糖漿等甜味物質(zhì)以假亂真，影響了蜂蜜產(chǎn)品的市場(chǎng)秩序和我國(guó)蜂蜜產(chǎn)品的出口貿(mào)易。而蜂膠被定義為工蜂采集植物樹(shù)脂等分泌物與其上顎腺、蠟腺等分泌物混合形成的膠粘性物質(zhì)。由于其獨(dú)特而廣泛的活性作用，因此市場(chǎng)需求量很大，進(jìn)而也就出現(xiàn)了楊樹(shù)膠混入蜂膠中的造假問(wèn)題。蜂膠來(lái)源于植物樹(shù)脂，尤其是楊樹(shù)蜂膠主要來(lái)源于楊屬植物，因此為鑒別蜂膠和楊樹(shù)膠帶來(lái)了難度。

蜜蜂在采集楊屬植物樹(shù)脂以及蜂巢內(nèi)傳遞這些樹(shù)脂加工成蜂膠的過(guò)程中加入了其腺體分泌的β-葡萄糖苷酶等，將樹(shù)脂中所含有的水楊苷水解，但在楊樹(shù)膠加工過(guò)程中水楊苷能穩(wěn)定存在，因而水楊苷是區(qū)分蜂膠與楊樹(shù)膠的有效指標(biāo)。基于液相色譜-線性離子阱-靜電場(chǎng)軌道阱高分辨質(zhì)譜快速測(cè)定蜂膠中楊樹(shù)膠指標(biāo)性成分水楊苷含量的方法，能夠根據(jù)精確的母離子和子離子質(zhì)荷比進(jìn)行定性和確證，以判斷蜂膠中是否摻雜楊樹(shù)膠[50]。

根據(jù)AOAC 998.12的描述，蜂蜜中C-4糖含量＞7%被認(rèn)定為摻假蜂蜜。但是，按照該方法測(cè)定C-4糖含量＜0%的蜂蜜樣品真實(shí)性的研究較少。使用元素分析儀和液相色譜法電感耦合同位素質(zhì)譜分析蜂蜜及其提取的蛋白質(zhì)和糖（蔗糖，葡萄糖和果糖）中δ13C值，δ2H和δ18O值，以及蔗糖和還原糖含量，進(jìn)而研究C-4糖含量＜0%的蜂蜜樣品的真實(shí)性。研究結(jié)果顯示，與0＜C-4糖含量（%）＜7相比，蜂蜜在-7＜C-4糖含量（%）＜0時(shí)被鑒定為不含C-4糖更加可靠。對(duì)于δ18O值，和其他的蜂蜜相比，C-4糖含量（%）＜-7組值較低為16.30‰，這可以作為一個(gè)鑒別摻假蜂蜜有用參數(shù)。該項(xiàng)研究表明，使用同位素組分和系統(tǒng)偏差能夠可靠的檢測(cè)C-4糖含量＜0%的蜂蜜樣品是否摻假[51]。除了添加糖漿之外，一些不法商販也在蜂蜜中添加防腐劑、甜味劑、色素和香精等外源性添加劑，陳麗娟等[52]將蜂蜜樣品采用甲醇-水溶液提取苯甲酸、山梨酸、安賽蜜、糖精鈉，以乙酸銨溶液和甲醇為流動(dòng)相梯度洗脫，通過(guò)高分辨質(zhì)譜負(fù)離子掃描模式進(jìn)行定性，外標(biāo)法定量，有效考察苯甲酸、山梨酸、安賽蜜和糖精鈉在蜂蜜中添加情況。

3.總結(jié)

2016年已經(jīng)正式出版的文獻(xiàn)主要側(cè)重于蜂產(chǎn)品中待測(cè)物的快速、簡(jiǎn)單的樣品前處理技術(shù)的改進(jìn)和建立高分辨質(zhì)譜技術(shù)的應(yīng)用，進(jìn)而提高待測(cè)物免受基質(zhì)干擾的能力，提高待測(cè)物的靈敏度和準(zhǔn)確度。尤其是電化學(xué)技術(shù)、新材料技術(shù)、免疫膠體金技術(shù)和利用分析化學(xué)技術(shù)在原有質(zhì)譜基礎(chǔ)上的改進(jìn)相結(jié)合的應(yīng)用。

本文僅列舉了部分具有代表性的相關(guān)文獻(xiàn)，以點(diǎn)帶面闡述2016年本領(lǐng)域內(nèi)的研究概況，希望對(duì)以后研究?jī)?nèi)容的范圍和深度都有所幫助。

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[2]于騰輝,劉星星,鄧敏,等.中性解吸電噴霧萃取電離質(zhì)譜法直接檢測(cè)蜂蜜中的敵敵畏[J].分析化學(xué),2016,(09):1432-1436.

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[7]Su Rui,Li Xueyuan,Liu Wenlong,et al.Headspace Microextraction of Sulfonamides from Honey by Hollow Fibers Coupled with Ultrasonic Nebulization [J].Journal of agricultural and food chem－istry,2016,64(7):1627-1634.

[8]Yue Mei-E,Li Qian,Xu Jie,Jiang Ting-Fu.Salt De-Emulsification Dispersive Liquid-Liquid Microextraction and Back-Extraction Combined with Sweeping Micellar Electrokinetic Capillary Chromatography for Detection of Triazine Herbicides in Honey[J]. Food Analytical Methods,2016,9(3):699-705.

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[10]Shirani Mahboube,Haddadi Hedayat,Rezaee Mohammad,et al.Solid-Phase Extraction Combined with Dispersive Liquid–Liquid Microextraction for the Simultaneous Determination of Deltamethrin and Permethrin in Honey by Gas Chromatography–Mass Spectrometry[J].Food Analytical Methods,2016:1-8.

[11]Liu Hsiang Yu,Lin Shu Ling,Fuh Ming Ren.Determination of chloramphenicol,thiamphenicol and florfenicol in milk and honey using modified QuEChERS extraction coupled with polymeric monolith-based capillary liquid chromatography tandem mass spectrometry[J].Talanta,2016,150:233-239.

[12]Shendy Amr H,Al-Ghobashy Medhat A,Alla Sohair a Gad, et al.Development and validation of a modified QuEChERS protocol coupled to LC MS/MS for simultaneous determination of multi-class antibiotic residues in honey [J].Food chemistry,2016,190:982-989.

[13]Calatayud-Vernich Pau,Calatayud Fernando,Simó Enrique, et al.Efficiency of QuEChERS approach for determining 52 pesticide residues in honey and honey bees [J].MethodsX,2016,3: 452-458.

[14]Tette Patrícia Amaral Souza,Da Silva Oliveira Fabiano Aurélio,Pereira Elba Nathália Corrêa,et al.Multiclass method for pesticides quantification in honey by means of modified QuEChERS and UHPLC–MS/MS[J].Food Chemistry,2016,211:130-139.

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