編制說(shuō)明-畜禽肉中食源性興奮劑和孕激素的測(cè)定 液相色譜-串聯(lián)質(zhì)譜法

1畜禽肉中食源性興奮劑和孕激素的測(cè)定液相色譜-串聯(lián)質(zhì)譜法2 4 4 4 4 52.1標(biāo)準(zhǔn)編制的必要性 52.2標(biāo)準(zhǔn)編制的預(yù)期效果 7 7 7 7 8 8 10 10 11 115.3.2混合標(biāo)準(zhǔn)儲(chǔ)備液的配制 115.3.3外標(biāo)混合標(biāo)準(zhǔn)中間液的配制 12 12 12 12 12 13 13 133 13 13 13 15 15 21 21 22 23 23 23 24 24 34 35 36 49 49 49 49 514為保障冬奧食品安全，特別是對(duì)畜禽肉供應(yīng)保障PXM2020_178305_000007），52標(biāo)準(zhǔn)制定的必要性和預(yù)期效果2.1標(biāo)準(zhǔn)編制的必要性發(fā)布的《2021年禁用清單》中明確規(guī)定β2-激動(dòng)劑、蛋白同化制劑、糖皮質(zhì)激素類、6食源性興奮劑等激素物質(zhì)檢測(cè)方法主要有色譜-質(zhì)譜法、酶聯(lián)免疫法、生物芯片等技術(shù)，目前色譜-質(zhì)譜因?yàn)槠錅?zhǔn)確度高、靈敏度高、檢測(cè)通量高等優(yōu)勢(shì)是食源性興奮劑等激素的主要檢測(cè)手段。然而食源性興奮劑檢測(cè)依然面臨較大挑戰(zhàn)，主要有以（5）SN/T4744-2017進(jìn)出口法（7）GB31658.22-2022食品7品過(guò)兩種凈化柱，耗時(shí)較長(zhǎng)，需要18種內(nèi)標(biāo)物，檢測(cè)成本較高。其他2.2標(biāo)準(zhǔn)編制的預(yù)期效果孕激素共六大類化合物為研究對(duì)象，結(jié)合QuEChERS樣品前處理技術(shù)，完成了《畜同時(shí)測(cè)定45個(gè)化合物，實(shí)現(xiàn)了高通量和高效率，該標(biāo)準(zhǔn)方法能夠?yàn)榇笮腕w育賽事運(yùn)3標(biāo)準(zhǔn)制定的原則和依據(jù)在實(shí)施過(guò)程中，本項(xiàng)目組按照《實(shí)驗(yàn)室質(zhì)量控制規(guī)范4主要技術(shù)內(nèi)容的論據(jù)無(wú)8表1被測(cè)化合物及對(duì)應(yīng)9種內(nèi)標(biāo)的名稱、CAS號(hào)、供應(yīng)來(lái)源、純度/濃度序號(hào)目標(biāo)化合物英文名稱CAS供應(yīng)商純度/濃度克倫特羅21898-19-1Dr.Ehrenstorfer99.3%2.妥布特羅41570-61-0TorontoResearchChemicals97.0%班布特羅81732-46-9Dr.Ehrenstorfer98.6%4.克倫丙羅38339-11-6Dr.Ehrenstorfer98.0%噴布特羅28163-36-2WITEGALaboratorienBerlin-AdlershofGmbH99.7%克倫塞羅1435934-75-0WITEGALaboratorienBerlin-AdlershofGmbH99.8%7.馬布特羅54240-36-7Dr.Ehrenstorfer90.6%溴布特羅41937-02-4WITEGALaboratorienBerlin-AdlershofGmbH99.5%9.西馬特羅54239-37-1TorontoResearchChemicals98.0%氯丙那林6933-90-0Dr.Ehrenstorfer98.0%奧西那林5874-97-5Dr.Ehrenstorfer99.2%沙丁胺醇18559-94-9Dr.Ehrenstorfer99.9%119520-06-8WITEGALaboratorienBerlin-AdlershofGmbH99.6%萊克多巴胺90274-24-1StanfordAnalyticalChemicalsInc.95.8%沙美特羅89365-50-4Dr.Ehrenstorfe99.4%阿替洛爾Atenolol29122-68-7Dr.Ehrenstorfer99.0%普萘洛爾318-98-9Dr.Ehrenstorfer99.6%美托洛爾56392-17-7Dr.Ehrenstorfer98.0%98.39.40.氨苯喋啶螺內(nèi)酯坎利酮睪酮諾龍去氫甲睪酮勃地酮群勃龍雄烯二酮脫氫表雄酮甲基睪酮美睪酮美雄諾龍司坦唑醇地塞米松氫化可的松波尼松龍可的松波尼松醋酸氟輕松氟氫可的松倍氯米松Triamterene396-01-0SpironolactoneCanrenone976-71-6Testosterone58-22-0Nortestosterone434-22-0Methandienone72-63-9Boldenone846-48-0Trenbolone10161-33-84-Androstene-363-5-8Prasterone53-43-0Methyltestosterone58Mesterolone1424-00-6Mestanolone521-11-9Stanozolol10418-03-8Dexamethasone50-02-2Hydrocortisone50-23-7Prednisolone50-24-8Cortisone53-06-5Prednisone53-03-267-73-2AcetonideFludrocortison127-31-1Beclomethasone4419-39-0TorontoResearchChemicalsStanfordAnalyticalChemicalsInc.TorontoResearchChemicalsDr.EhrenstorferDr.EhrenstorferStanfordAnalyticalChemicalsInc.Dr.EhrenstorferDr.EhrenstorferTorontoResearchChemicalsDr.EhrenstorferDr.EhrenstorferAChemtekInc.Dr.EhrenstorferDr.EhrenstorferDr.EhrenstorferDr.EhrenstorferDr.EhrenstorferDr.EhrenstorferDr.EhrenstorferTorontoResearchChemicalsTorontoResearchChemicalsTorontoResearchChemicals98.0%99.5%98.0%99.3%96.7%99.3%98.8%96.3%99.7%99.3%97.7%99.0%97.8%99.9%99.2%99.3%99.8%99.8%98.0%99.3%99.3%41.孕酮57-83-0Dr.Ehrenstorfer99.7%42.醋酸美倫孕酮2919-66-6Dr.Ehrenstorfer99.0%43.醋酸甲羥孕酮71-58-9Dr.Ehrenstorfer99.2%44.17α-羥孕酮604-09-1Dr.Ehrenstorfer99.2%45.甲地孕酮3562-63-8Dr.Ehrenstorfer99.4%I-1克倫特羅-D9129138-58-5StanfordAnalyticalChemicalsInc.99.7%I-2萊克多巴胺-D590274-24-1AChemtekInc.95.0%I-3沙丁胺醇-D31219798-60-3AChemtekInc.98.5%I-4去甲烏藥堿-D4Methyltestosterone-2249814-83-1FirstStandard100μg/mLI-5睪酮-D377546-39-5TorontoResearchChemicals100μg/mLI-6勃地酮-D3361432-76-0AChemtekInc.99.2%I-7孕酮-D915775-74-3TorontoResearchChemicals95.0%I-8氫化可的松-D3115699-92-8AChemtekInc.10μg/mLI-9地塞米松-D5358731-91-6TorontoResearchChemicals98.0%國(guó)藥集團(tuán)試劑公司；N-丙基乙二胺鍵合固相吸附材料（PSA，40-60μm鍵合硅膠吸附材料（C18，40-60μm）、氨基吸附劑（NH2，40-60μm）均購(gòu)于博納艾ACQUITYUPLC超高效液相色譜儀、XevoTQ-S四級(jí)桿串聯(lián)質(zhì)譜儀，美國(guó)瑞誠(chéng)儀器有限公司；渦旋混合器：vortex-genie2，美國(guó)s），5.3.2混合標(biāo)準(zhǔn)儲(chǔ)備液的配制序號(hào)化合物儲(chǔ)備液濃度(μg/mL)中間液濃度(μg/mL)組別序號(hào)化合物儲(chǔ)備液濃度(μg/mL)中間液濃度(μg/mL)組別1克倫特羅128脫氫表雄酮22002妥布特羅129甲基睪酮22003班布特羅130美睪酮82004克倫丙羅220031美雄諾龍22005噴布特羅132司坦唑醇22006克倫塞羅133地塞米松44007馬布特羅220034氫化可的松44008溴布特羅135波尼松龍44009西馬特羅220036可的松4400氯丙那林137波尼松4400奧西那林138醋酸氟輕松4400沙丁胺醇139氟氫可的松4400齊帕特羅140倍氯米松4400萊克多巴胺141孕酮2200序號(hào)化合物儲(chǔ)備液濃度(μg/mL)中間液濃度(μg/mL)組別序號(hào)化合物儲(chǔ)備液濃度(μg/mL)中間液濃度(μg/mL)組別沙美特羅142醋酸美倫孕酮2200阿替洛爾143醋酸甲羥孕酮2200普萘洛爾14417α-羥孕酮2200美托洛爾145甲地孕酮2200氨苯喋啶2200克倫特羅-D9120螺內(nèi)酯2200I-2萊克多巴胺-D5121坎利酮2200I-3沙丁胺醇-D3122睪酮2200I-4甲基睪酮-D3220023諾龍2200I-5睪酮-D3220024去氫甲睪酮2200I-6勃地酮-D3220025勃地酮2200I-7孕酮-D9220026群勃龍2200I-8氫化可的松-D3440027雄烯二酮2200I-9地塞米松-D544005.3.3外標(biāo)混合標(biāo)準(zhǔn)中間液的配制稱取不含被測(cè)物的陰性雞肉樣品5.0g，不加內(nèi)標(biāo)，按照上述方法進(jìn)行前處理，表3HPLC梯度洗脫條件時(shí)間（min）A（%）B（%）流速（mL/min）09550.30.59550.3900.36.030700.38.0200.39.000.300.39550.39550.3）；）；表4目標(biāo)分析物及9種內(nèi)標(biāo)的保留時(shí)間及主要質(zhì)譜參數(shù)編號(hào)目標(biāo)化合物保留時(shí)間(min)母離子(m/z)定量離子（m/z）（碰撞能）（碰撞能）碎裂電壓(V)克倫特羅4.56277.4342.妥布特羅4.97228.4班布特羅368.772.2(34)294.4(20)4.克倫丙羅2.83263.326噴布特羅7.31292.5236.3(14)74.2(20)72克倫塞羅3.81319.4203.1(20)367.馬布特羅5.02311.4217.2(24)237.2(14)20溴布特羅4.96367.4132.3(46)26西馬特羅2.64220.4143.2(24)氯丙那林4.51214.3118.9(26)奧西那林2.20212.3125.2(20)22沙丁胺醇2.86240.4齊帕特羅2.82262.4185.2(24)202.2(18)萊克多巴胺4.21302.5107.2(26)26沙美特羅7.31416.791.2(38)25阿替洛爾2.87267.4145.2(26)74.2(22)20普萘洛爾5.94260.4美托洛爾4.75268.5氨苯喋啶4.43254.4104.2(38)20.螺內(nèi)酯7.10341.5107.2(26)91.1(48)4821.坎利酮341.5107.2(28)22.睪酮7.49289.5109.2(22)4823.諾龍7.20275.5109.2(28)239.3(16)224.去氫甲睪酮7.31301.52625.勃地酮7.06287.53026.群勃龍6.98271.4199.2(22)165.3(44)6227.雄烯二酮7.19287.597.2(20)109.2(24)34編號(hào)目標(biāo)化合物保留時(shí)間(min)母離子(m/z)定量離子（m/z）（碰撞能）（碰撞能）碎裂電壓(V)28.脫氫表雄酮7.49289.5253.3(10)213.3(18)629.甲基睪酮7.75303.6109.2(24)3230.美睪酮8.33305.5269.4(16)95.6(32)31.美雄諾龍8.45305.6269.4(14)105.2(20)32.司坦唑醇8.33329.633.地塞米松6.78393.5373.4(8)34.氫化可的松6.42363.54435.波尼松龍6.42361.5325.4(8)2436.可的松6.19361.6163.2(24)121.2(36)37.波尼松359.52838.醋酸氟輕松6.82453.5121.2(28)433.4(8)39.氟氫可的松6.34381.5239.3(24)91.2(58)3840.倍氯米松6.81409.5373.4(8)121.2(42)641.孕酮8.40315.5109.2(22)42.醋酸美倫孕酮8.30397.2279.2(22)243.醋酸甲羥孕酮8.25387.2123.0(32)244.17α-羥孕酮7.58331.297.0(26)109.2(30)445.甲地孕酮7.87343.12I-1克倫特羅-D94.54286.4133.0(28)6I-2萊克多巴胺-D54.19307.5I-3沙丁胺醇-D32.85243.532I-4去甲烏藥堿-D43.28276.5108.3（20）164.3（18）I-5睪酮-D37.49292.597.2(24)90I-6勃地酮-D37.05290.6121.2(22)I-7孕酮-D98.35324.6113.2(24)26I-8氫化可的松-D36.42366.6121.2(22)I-9地塞米松-D56.78398.6378.5(8)在最佳碎裂電壓下確認(rèn)目標(biāo)化合物的母離子（m/z）值，然后進(jìn)行二級(jí)質(zhì)譜優(yōu)化，通本試驗(yàn)被測(cè)物在正離子模式監(jiān)測(cè)下具有較強(qiáng)的信號(hào)值大部分被測(cè)物可獲得較高征離子信號(hào)重現(xiàn)性好，可滿足監(jiān)測(cè)要求，因用乙腈-水、乙腈-水（含0.1%甲酸）、甲醇-水、甲醇-水（含0.1%甲酸）、甲醇-水在ESI+模式下很容易得到準(zhǔn)分子離子，在改善峰形之余，提高了分離效果，而甲酸本試驗(yàn)考察了5cm和10cm的色譜柱，發(fā)現(xiàn)5cm無(wú)法將分異構(gòu)體美睪酮為了提高采用負(fù)離子掃描的3種化合物的檢測(cè)靈敏度，試驗(yàn)采用單獨(dú)乙腈-水體圖2基質(zhì)標(biāo)的MRM色譜圖時(shí)，隨著甲醇在乙腈體系中的比例增大，其蛋白沉淀效果越來(lái)越β2-激動(dòng)劑、β-阻斷劑類、蛋白同化激素在酸度超過(guò)0.5%時(shí)，有基質(zhì)干擾，回收率有降低的趨勢(shì)；糖皮質(zhì)激素、孕酮和利尿劑對(duì)提取液中乙酸的比例不敏感。當(dāng)采用含0.5%乙酸的乙腈溶液作為取溶劑時(shí)，所有被測(cè)物的回收率均大于50%，確定為最優(yōu)單獨(dú)采用NH2時(shí)，大約有45%的化合物回收率比使用其他3種凈化劑時(shí)低，且進(jìn)一步采用以下4種組合方案：①PSA250mg采用組合②或③時(shí)，蛋白同化激素和糖皮質(zhì)激素收率較高，但對(duì)β2-興奮劑類和孕激綜合以上多重因素，本試驗(yàn)最終采用組合④作為最終凈化劑。其中PSA可以去除肉中的脂肪酸類和糖類干擾，C18則對(duì)脂肪和非極性化合物的吸附效果比較明顯，圖4采用不同凈化條件時(shí)不同回收率范圍的目標(biāo)物個(gè)數(shù)占被測(cè)物總個(gè)數(shù)的比例圖根據(jù)流動(dòng)相和各目標(biāo)化合物的溶解性能，考察了三種復(fù)溶溶劑：①乙腈/水（含0.1%甲酸1/9，v/v②甲醇/水（含0.1%甲酸1/9，v/v③甲醇/水（含察了目標(biāo)物在基質(zhì)中的信號(hào)增強(qiáng)或抑制的程度(signalsuppression/enhancement,增強(qiáng)效應(yīng)，當(dāng)其低于80%時(shí)顯示基質(zhì)抑制效應(yīng)，見(jiàn)表5。檢測(cè)發(fā)現(xiàn)，美托洛爾、倍方法靈敏度以檢出限（LimitofDetection,LOD）和定量限（LimitofQuantitation,LOQ）來(lái)衡量。制備不同濃度的添加樣品，采用本方法測(cè)定后，以定性離子對(duì)的3倍信號(hào)噪聲比（S/N=3）對(duì)應(yīng)的定量濃度作為檢出限，10倍信號(hào)噪聲），表5被測(cè)物的線性范圍、相關(guān)系數(shù)（R2）、檢出限（LOD）、定量限（LOQ）及對(duì)應(yīng)內(nèi)標(biāo)化合物序號(hào)目標(biāo)化合物SSE值線性范圍(μg/L)線性方程相關(guān)系數(shù)（R2）LOD(μg/kg)LOQ(μg/kg)1克倫特羅克倫特羅-D997%y=1.259x+0.09820.99940.030.12妥布特羅克倫特羅-D9y=1.008x+0.01270.99920.030.13班布特羅克倫特羅-D9y=0.415x-0.05480.99950.030.14克倫丙羅克倫特羅-D90.2~20y=0.725x+0.05770.99920.070.25噴布特羅克倫特羅-D9y=4.360x+0.2590.99610.030.16克倫塞羅克倫特羅-D980%y=1.324x+0.1320.99850.030.17馬布特羅克倫特羅-D90.2~20y=0.116x+0.009520.99910.070.28溴布特羅克倫特羅-D9y=0.137x-0.003380.99930.030.19西馬特羅克倫特羅-D90.2~20y=1.042x+0.05990.99960.070.2氯丙那林克倫特羅-D9y=0.752x+0.02530.99970.030.1奧西那林克倫特羅-D9y=2.046x-0.07250.99930.030.1沙丁胺醇沙丁胺醇-D3y=0.432x+0.04940.99710.030.1齊帕特羅沙丁胺醇-D385%y=0.921x+0.1630.99750.030.1萊克多巴胺萊克多巴胺-D592%y=1.121x+0.3900.99890.030.1沙美特羅萊克多巴胺-D5y=0.339x-0.04200.99800.030.1阿替洛爾克倫特羅-D9y=1.789x+0.3330.99590.030.1序號(hào)目標(biāo)化合物SSE值線性范圍(μg/L)線性方程相關(guān)系數(shù)（R2）LOD(μg/kg)LOQ(μg/kg)普萘洛爾克倫特羅-D987%y=1.761x+0.07140.99960.03美托洛爾克倫特羅-D975%y=1.137x+0.01710.99990.03氨苯喋啶萊克多巴胺-D50.2~50y=0.998x+1.4740.99930.070.220螺內(nèi)酯勃地酮-D30.2~50y=0.980x+0.1120.99920.070.221坎利酮睪酮-D399%0.2~50y=0.0116x+0.00230.99720.070.222睪酮睪酮-D398%0.2~50y=0.0428x+0.00980.99660.070.223諾龍睪酮-D30.2~50y=0.0158x+0.01050.99630.070.224去氫甲睪酮睪酮-D395%0.2~50y=0.022x+0.01110.99510.070.225勃地酮勃地酮-D385%0.2~50y=3.571x+0.9230.99710.070.226群勃龍勃地酮-D30.2~50y=2.423x+1.2300.99510.070.227雄烯二酮勃地酮-D399%0.2~50y=0.642x+0.02480.99950.070.228脫氫表雄酮勃地酮-D30.2~50y=0.135x+0.1750.99820.070.229甲基睪酮甲基睪酮-D390%0.2~50y=0.737x+0.1750.99570.070.230美睪酮甲基睪酮-D30.2~50y=0.0284+0.01520.99660.250.831美雄諾龍甲基睪酮-D395%0.2~50y=0.0274x-0.03030.99570.070.232司坦唑醇孕酮-D90.2~50y=1.858x-0.1380.99870.070.233地塞米松地塞米松-D594%0.5~200y=2.269x+0.1700.99950.160.4序號(hào)目標(biāo)化合物SSE值線性范圍(μg/L)線性方程相關(guān)系數(shù)（R2）LOD(μg/kg)LOQ(μg/kg)34氫化可的松氫化可的松-D399%0.5~100y=0.630x+0.0440.99910.160.435波尼松龍氫化可的松-D385%0.5~200y=0.131x+0.0.0380.99640.160.436可的松氫化可的松-D382%0.5~100y=0.894x+0.0560.99860.160.437波尼松氫化可的松-D391%0.5~100y=0.272x-0.002030.99960.160.438醋酸氟輕松氫化可的松-D380%0.5~100y=0.446x+0.05870.99340.160.439氟氫可的松氫化可的松-D381%0.5~100y=0.218x-0.006610.99990.160.440倍氯米松氫化可的松-D360%0.5~100y=0.0535x+0.01150.99920.160.441孕酮孕酮-D989%0.2~50y=0.556x+0.08870.99830.070.242醋酸美倫孕酮孕酮-D90.2~50y=0.0538x+0.00160.99980.070.243醋酸甲羥孕酮孕酮-D90.2~50y=0.0671x-0.01760.99870.070.24417α-羥孕酮睪酮-D30.2~50y=0.158x-0.05870.99400.070.245甲地孕酮甲基睪酮-D30.2~50y=0.0298x+0.00620.99760.070.2表6雞肉加標(biāo)測(cè)定結(jié)果、回收率、相對(duì)標(biāo)準(zhǔn)偏差（n=6）化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）123456克倫特羅000.080.1090.1980.430.380.450.430.440.427.3妥布特羅0.10.090.090.100.0993.37.00.40.360.440.330.420.330.410.3895.3班布特羅0.350.380.320.380.320.350.3587.77.7克倫丙羅620.380.340.380.410.380.3792.070.810.870.800.870.800.844.5噴布特羅070.180.1784.080.340.260.300.260.340.3074.7克倫塞羅0020.420.460.420.460.430.434.8馬布特羅0.40.420.450.440.440.420.460.430.920.800.930.830.900.876.2溴布特羅0化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）1234560.40.420.420.430.440.390.440.424.4西馬特羅60.230.1930.420.420.420.440.420.430.780.800.800.770.730.7796.04.3氯丙那林0.380.410.350.410.360.380.3895.7奧西那林0.10.080.080.080.070.060.070.0760.130.1500.2563.39.9沙丁胺醇0.10.090.090.100.090.090.100.09090.2098.000.420.410.450.390.440.425.3齊帕特羅0.10.060.070.060.060.060.060.0765.35.030.130.1366.000.290.280.300.270.300.2972.74.5萊克多巴胺000.40.410.420.420.430.420.450.423.4沙美特羅80.070.090.100.090.0950.270.320.270.310.270.300.2973.07.7阿替洛爾0.10.090.090.090.0950.150.270.260.250.260.250.270.2665.34.2化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）123456普萘洛爾000.190.300.330.270.340.290.340.3178.09.9美托洛爾0.370.380.360.380.340.350.3690.73.6氨苯喋啶90.180.1994.010.310.310.300.320.300.320.690.670.700.700.710.6885.54.8螺內(nèi)酯80.200.1892.060.390.420.380.360.430.3998.030.860.880.820.830.820.843.0坎利酮80.190.200.320.370.380.320.380.380.360.700.730.740.730.700.770.7390.83.5睪酮60.130.1340.380.340.350.310.340.350.840.740.750.800.770.780.7897.54.8諾龍80.200.190.390.400.330.410.380.370.3895.000.680.710.770.710.740.7290.04.3去氫甲睪酮0.430.470.390.430.380.410.420.900.860.940.920.820.904.9勃地酮50.180.1888.7化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）1234560.40.340.340.420.340.340.320.3587.040.920.880.770.810.840.846.3群勃龍090.200.190.390.380.430.380.390.420.4099.76.00.80.870.910.900.890.820.870.883.4雄烯二酮00.40.470.420.450.390.460.340.420.80.940.930.970.920.920.900.932.6脫氫表雄酮0.390.460.460.430.460.380.450.850.850.830.860.870.85甲基睪酮50.380.380.360.350.410.410.380.750.810.880.860.740.800.816.9美睪酮0.80.520.560.510.480.470.580.5265.08.0274.14.842.552.702.622.672.742.622.6566.32.5美雄諾龍0.40.440.360.420.460.470.380.420.80.810.720.730.700.650.690.7289.57.4司坦唑醇80.210.1994.00.40.340.410.360.420.380.350.380.870.730.850.860.770.860.827.1地塞米松0.40.570.460.410.460.460.400.460.80.850.770.730.820.810.830.805.5化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）12345693.88.2氫化可的松0.40.320.300.340.290.320.340.320.650.730.740.780.800.800.7593.77.884.53.6波尼松龍80.330.290.260.340.2980.610.620.580.580.670.6176.05.98.8可的松0.40.410.440.430.430.440.440.490.890.620.670.740.620.6986.092.26.8波尼松0.40.340.310.380.380.360.390.360.530.660.600.630.570.560.5973.893.14.3醋酸氟輕松0.40.320.380.440.390.400.380.3910.710.610.670.630.630.6480.56.385.74.9氟氫可的松0.40.400.390.440.410.410.420.450.760.720.780.780.660.7390.78.093.35.6倍氯米松0.40.340.330.360.390.380.320.3588.00.80.840.790.810.720.730.760.7796.891.8孕酮60.160.1892.00.40.340.330.300.320.330.350.3382.06.00.80.710.710.770.700.620.660.7087.27.0化合物加標(biāo)水平(μg/kg)重復(fù)數(shù)平均值(μg/kg)回收率（%）RSD（%）123456醋酸美倫孕酮00.470.400.410.420.400.500.400.760.770.820.930.810.838.4醋酸甲羥孕酮30.270.300.260.290.400.390.3310.830.930.940.870.930.904.717α-羥孕酮0.440.470.470.470.380.430.470.700.820.880.740.780.808.9甲地孕酮0.450.470.400.420.380.380.440.680.730.700.790.770.7594.07.9按照本方法測(cè)定了9個(gè)肉樣品，并采用國(guó)家標(biāo)準(zhǔn)方法《GB/T用國(guó)標(biāo)方法驗(yàn)證了20個(gè)與本研究一致的化合物：群勃龍、勃地酮、諾龍、雄烯表7肉類樣品采用本方法檢測(cè)結(jié)果及國(guó)標(biāo)法驗(yàn)證結(jié)果樣品名稱本方法檢測(cè)結(jié)果(μg/kg）國(guó)標(biāo)方法檢測(cè)結(jié)果(μg/kg）氫化可的松可的松雄烯二酮?dú)浠傻乃煽傻乃尚巯┒凹猓ㄘi肉）4.90-5.21-瘦肉（豬肉）7.74-8.07-后尖（豬肉）5.600.96-6.71-雞胸------雞翅中------鴨肉------牛腿肉5.960.42-6.320.45-牛腱子3.800.263.44-牛腩5.762.36-5.74-定量限(μg/kg）注：表中“-”代表低于定量限。標(biāo)方法過(guò)程繁瑣，消耗試劑耗材多，方法測(cè)定時(shí)間長(zhǎng)，表8兩種方法差值的統(tǒng)計(jì)學(xué)分析樣品名稱d值（d=C1-C2）氫化可的松可的松豬肉1-0.310豬肉2-2.00-0.33豬肉3-0.42牛肉1-0.36-0.03牛肉20.360.17牛肉30.020.37-0.57-0.04差值標(biāo)準(zhǔn)差（Sdi）0.860.30差值平均標(biāo)準(zhǔn)差（S=Sdi/“）0.350.33采用本方法檢測(cè)了12個(gè)牛肉樣品，結(jié)果檢出4個(gè)化合物，結(jié)果見(jiàn)表9。表9牛肉樣品的檢測(cè)結(jié)果樣品名稱檢測(cè)結(jié)果(μg/kg)氫化可的松可的松雄烯二酮睪酮牛腿肉1號(hào)牛2.0-0.8牛腿肉2號(hào)牛22.6--牛腿肉3號(hào)牛22.22.0--牛腿肉4號(hào)牛-牛腿肉5號(hào)牛-牛腿肉6號(hào)牛3.3---牛腿肉7號(hào)牛3.3---牛腿肉8號(hào)牛5.5---牛腿肉9號(hào)牛7.6---牛腿肉10號(hào)牛7.6--霖肉（牛）0.6牛前部肉0.62家參與驗(yàn)證的機(jī)構(gòu)分別為北京市疾病預(yù)防控制中心（A）和北京市延慶區(qū)疾病預(yù)防控制中心（B）。驗(yàn)證結(jié)果如下。）；表10實(shí)驗(yàn)室A的驗(yàn)證結(jié)果化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值1.克倫特羅0.10.080.100.080.090.080.090.0960.1888.00.40.400.440.420.530.420.530.462.妥布特羅0070.420.390.510.380.500.433.班布特羅0.40.420.410.350.490.350.470.424.克倫丙羅0.430.380.420.370.420.340.398.660.740.740.890.720.900.7998.85.噴布特羅090.340.260.360.270.380.3279.76.克倫塞羅00.420.380.400.440.400.450.416.07.馬布特羅20.400.400.340.370.400.397.660.880.830.920.820.940.885.78.溴布特羅60.090.090.060.090.0879.883.3化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值0.40.420.440.400.460.350.420.429.29.西馬特羅30.380.410.420.430.410.410.80.690.780.810.820.820.840.796.899.010.氯丙那林0.40.380.410.340.460.350.450.4011.奧西那林0.10.080.070.060.060.090.060.0772.066.040.220.270.220.290.2562.012.沙丁胺醇0.10.0005.396.0096.500.420.390.510.390.500.4413.齊帕特羅0.10.070.080.060.060.070.070.078.530.139.868.00.40.290.300.270.340.270.340.309.875.014.萊克多巴胺0000.440.420.480.430.480.447.215.沙美特羅0574.00.40.260.320.280.380.260.400.3279.316.阿替洛爾90.080.100.090.0976.00.40.270.280.250.370.250.350.2973.7化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值17.普萘洛爾00.100.006.264.00.40.280.340.290.400.300.430.3484.718.美托洛爾00.40.380.410.370.460.370.470.4119.氨苯喋啶80.170.1680.070.250.280.260.290.270.2700.670.640.820.660.740.6986.020.螺內(nèi)酯00.180.1892.040.400.340.350.370.380.376.350.740.730.780.800.840.775.396.721.坎利酮80.180.1888.060.340.330.340.330.370.344.986.00.80.680.600.620.710.700.660.666.783.022.睪酮20.420.410.420.450.410.400.80.690.740.710.700.740.740.723.389.823.諾龍30.320.340.360.320.360.345.580.580.550.670.590.660.618.375.724.去氫甲睪酮10.190.270.450.420.370.480.420.430.860.790.850.740.820.7897.825.勃地酮50.167.778.70.2化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值0.40.410.350.380.360.430.340.3895.00.80.780.800.740.900.780.900.828.426.群勃龍40.380.410.370.420.340.379.270.760.660.800.690.860.759.794.327.雄烯二酮90.130.390.270.340.320.380.330.3460.650.660.860.770.820.7593.828.脫氫表雄酮60.150.190.440.420.340.360.460.410.400.80.740.860.720.830.780.860.807.899.729.甲基睪酮60.340.330.320.290.330.300.325.710.790.860.920.690.900.8330.美睪酮0.80.840.900.880.740.790.890.847.30.822.332.292.182.0943.662.793.293.133.079.531.美雄諾龍20.220.200.290.260.240.269.365.00.80.700.620.700.820.660.780.7189.032.司坦唑醇0.40.420.410.430.380.450.420.460.890.830.740.830.780.826.433.地塞米松40.260.250.290.280.270.780.820.820.540.800.790.7695.0化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值7.234.氫化可的松0.40.270.260.260.270.250.350.280.650.490.500.500.360.500.5062.585.835.波尼松龍0.40.340.300.290.340.340.370.330.850.820.860.840.780.860.833.96.791.736.可的松0.40.450.420.370.340.500.390.440.900.900.710.740.930.822.837.波尼松0.40.370.340.290.300.420.350.350.620.810.860.720.710.870.7695.56.938.醋酸氟輕松0.40.290.340.290.250.260.290.290.610.560.560.540.560.620.575.271.881.139.氟氫可的松0.40.310.280.260.250.310.250.280.770.880.660.670.690.870.7694.791.940.倍氯米松0.40.300.330.330.350.380.370.348.70.670.660.620.650.620.630.643.580.396.741.孕酮80.430.420.390.410.380.4040.780.660.830.690.780.758.593.3化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值42.醋酸美倫孕酮0.40.440.420.370.450.400.380.418.00.80.580.620.630.660.700.690.657.280.843.醋酸甲羥孕酮10.20.460.440.470.380.430.380.440.910.870.860.950.900.913.844.17α-羥孕酮60.180.190.340.410.370.300.440.360.3730.760.580.740.790.770.7188.845.甲地孕酮60.420.330.320.420.390.3970.740.730.760.930.940.83表11實(shí)驗(yàn)室B的驗(yàn)證結(jié)果化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值1.克倫特羅00.420.430.480.440.470.450.455.02.妥布特羅0093.240.380.350.440.400.420.399.697.03.班布特羅070.360.340.440.380.460.3998.04.克倫丙羅0.40.380.320.420.370.420.380.389.995.00.80.800.790.770.870.860.800.814.95.噴布特羅0.10.080.090.100.080.100.080.0988.060.1380.340.280.380.320.380.3382.76.克倫塞羅0.10.080.100.080.090.1020.360.420.410.460.380.418.77.馬布特羅10.180.190.380.320.370.360.420.460.3896.00.80.800.900.740.900.870.940.868.58.溴布特羅00.070.090.070.0990.70.1化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值094.00.40.380.420.340.450.420.460.419.西馬特羅0.40.390.430.470.440.450.400.437.00.80.710.710.720.820.830.760.767.395.010.氯丙那林0.40.380.390.370.460.420.450.418.711.奧西那林0880.270.230.290.260.300.278.368.012.沙丁胺醇0.10.000.100.090.094.480.196.400.440.410.470.420.480.447.813.齊帕特羅0.10.070.060.080.060.070.060.079.435.664.00.40.290.310.280.380.290.380.3280.314.萊克多巴胺00.450.440.420.510.430.500.467.915.沙美特羅30.139.470.00.40.330.340.300.450.290.430.3689.316.阿替洛爾70.070.080.090.080.0881.30.1化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值50.157.070.00.40.220.280.310.2869.017.普萘洛爾0.10.00030.1330.330.300.440.280.400.3586.718.美托洛爾0.10.060.380.380.430.390.450.408.699.719.氨苯喋啶30.1568.040.240.290.260.270.260.267.265.00.80.620.640.620.690.620.680.645.080.520.螺內(nèi)酯00.480.350.340.340.340.330.3691.00.80.660.780.780.700.780.700.736.891.521.坎利酮10.320.320.290.360.300.328.079.00.80.660.830.770.740.670.660.729.690.522.睪酮0.300.300.350.380.340.390.3470.740.660.730.690.720.704.487.723.諾龍59.60.270.300.350.320.270.280.3040.780.860.720.800.780.786.597.524.去氫甲睪酮化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值0.40.470.390.440.440.400.500.400.750.890.860.740.850.838.525.勃地酮88.040.350.420.410.400.380.4030.860.870.900.870.800.864.026.群勃龍80.180.160.370.340.370.400.420.350.378.010.900.760.910.750.8527.雄烯二酮0.440.460.460.470.450.420.490.940.940.940.890.940.922.828.脫氫表雄酮00.320.300.270.420.390.350.3410.650.580.670.660.750.659.381.729.甲基睪酮30.330.330.320.320.320.300.323.740.780.740.860.790.830.796.098.730.美睪酮0.80.550.570.530.560.510.510.544.667.30.828.088.743.083.193.653.533.083.277.681.931.美雄諾龍0.20.270.20.40.350.350.370.420.340.370.30.630.660.590.710.700.630.656.881.732.司坦唑醇30.260.210.2化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值0.40.340.390.380.380.360.420.387.395.00.80.790.740.680.750.700.720.735.491.533.地塞米松90.280.260.300.220.270.630.660.510.620.620.620.618.576.57.784.134.氫化可的松20.340.350.310.410.330.660.620.550.720.540.540.6175.74.735.波尼松龍0.40.450.350.420.340.350.390.3896.070.720.700.660.680.730.692.736.可的松0.40.420.440.420.470.370.460.40.580.800.730.890.790.860.7796.74.937.波尼松0.40.380.360.320.330.390.440.370.660.820.780.780.710.850.7695.54.595.838.醋酸氟輕松0.40.260.260.340.290.370.340.30.490.500.520.560.580.660.5569.27.539.氟氫可的松0.40.460.380.450.460.360.420.480.610.620.640.620.580.614.375.87.340.倍氯米松0.40.260.360.260.279.466.30.4化合物加標(biāo)水平(μg/kg)測(cè)定結(jié)果(μg/kg)RSD（%）回收率（%）定量限(μg/kg)123456平均值0.80.540.580.500.510.570.530.545.867.33.269.841.孕酮10.20.360.340.300.300.260.320.3178.00.80.820.870.740.890.730.880.828.942.醋酸美倫孕酮0.450.340.410.310.360.460.3997.00.80.620.680.620.700.710.630.666.482.743.醋酸甲羥孕酮00.150.1890.040.350.420.390.400.330.379.980.900.940.930.900.860.903.344.17α-羥孕酮60.170.1574.090.360.390.340.320.400.3520.910.820.900.840.890.874.745.甲地孕酮00.260.360.420.330.400.3620.790.730.830.810.860.797.098.76采用國(guó)際標(biāo)準(zhǔn)的程度與水平的簡(jiǎn)要說(shuō)明無(wú)7標(biāo)準(zhǔn)涉及的專利及相關(guān)知識(shí)產(chǎn)權(quán)說(shuō)明本標(biāo)準(zhǔn)涉及一個(gè)發(fā)明專利，該專利已通過(guò)初審，專8重大意見(jiàn)分歧的處理經(jīng)過(guò)和依據(jù)無(wú)9與現(xiàn)行法律法規(guī)和強(qiáng)制性標(biāo)準(zhǔn)的關(guān)系《食品安全國(guó)家標(biāo)準(zhǔn)食品中獸藥最大殘留限量》（GB），表12《體育局反興奮劑字[2021]584食源性興奮劑防控工作指南清單》中附錄“建議檢測(cè)的各類藥物名單”及本方法的檢出限藥物名控制限量參考檢驗(yàn)方法*參考檢出限**(μg/kg）本方法檢出限(μg/kg)1.克侖特羅不得檢出SN/T1924-2011《進(jìn)出口動(dòng)物源食品中克侖特羅、萊克多巴胺、沙丁胺醇和特布他林殘留量的測(cè)定液相色譜-質(zhì)譜/質(zhì)譜法》0.050.032.沙丁胺醇不得檢出物源性食品中β-受體激動(dòng)劑殘留檢測(cè)液相色譜-串聯(lián)質(zhì)譜法》0.250.033.萊克多巴胺不得檢出0.250.034.妥布特羅不得檢出0.250.035.噴布特羅不得檢出0.250.036.西馬特羅不得檢出0.250.077.沙美特羅不得檢出0.50.038.克侖丙羅不得檢出0.20.079.普萘洛爾不得檢出SN/T2624-2010《動(dòng)物源性食品中多種堿性藥物殘留量的檢測(cè)方法液相色譜-質(zhì)譜/質(zhì)譜法》0.50.0310.阿替洛爾不得檢出0.0311.美托洛爾不得檢出0.50.03不得檢出農(nóng)業(yè)部1031號(hào)公告-1-2008《動(dòng)物源性食品中11種激素殘留檢測(cè)液相色譜-串聯(lián)質(zhì)譜法》0.10.0713.司坦唑醇不得檢出0.10.07不得檢出0.10.07不得檢出0.50.0716.勃地酮不得檢出0.40.0717.群勃龍不得檢出0.50.07≤2μg/kg0.0719.脫氫表雄酮≤2μg/kgGB/T21981-2008《動(dòng)物源食品中激素多殘留檢測(cè)方法液相色譜-質(zhì)譜/質(zhì)譜法》2.00.220.齊帕特羅不得檢出SN/T2624-2010《動(dòng)物源性食品中多種堿性藥物殘留量的檢測(cè)方法液相色譜-質(zhì)譜/質(zhì)譜法》0.50.0321.潑尼松不得檢出農(nóng)業(yè)部1031號(hào)公告-2-2008《動(dòng)物源性食品中糖皮質(zhì)激素類藥物多殘留檢測(cè)液相色譜-串聯(lián)質(zhì)譜法；GB/T21981-2008《動(dòng)物源食品中激素多殘留檢測(cè)方法液相色譜-質(zhì)譜/質(zhì)譜法》0.50.222.潑尼松龍不得檢出0.50.223.地塞米松不得檢出0.50.224.氟氫可的松不得檢出0.225.倍氯米松不得檢出0.226.氫化可的松≤30μg/kg2.00.227.可的松≤30μg/kg0.40.228.坎利酮不得檢出5.00.229.螺內(nèi)酯不得檢出5.00.230.氨苯蝶啶不得檢出5.00.21.ProhibitedList(effective1January2021)[S]，WorldAnti-DopingAgency，internationalstandard2.GB31650-2019食品安全國(guó)家標(biāo)準(zhǔn)食品中獸藥最大殘留限量[S],中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn)3.GB/T21981-2008動(dòng)物源食品中激素多殘留檢測(cè)方法液相色譜-質(zhì)譜-質(zhì)譜法[S],中華人民共和國(guó)國(guó)家標(biāo)準(zhǔn)4.徐佳，液相色譜-串聯(lián)質(zhì)譜法檢測(cè)雞肉中7種糖皮質(zhì)激素殘留量[J],福建分析測(cè)試,2015，24(2)5.張?jiān)儆?等.通過(guò)式固相萃取-超高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定豬肉和牛肉中9種類固醇激素[J].肉類研究,2020,34(7)6.馮月超，等.超高效液相色譜-質(zhì)譜聯(lián)用法檢測(cè)魚(yú)肉中23種性激素殘留量[J]，食品安全質(zhì)量檢測(cè)學(xué)報(bào)，2018,9(16)7.李凱華，等.超高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定魚(yú)肉中多種雄性激素和孕激素[J]，食品安全質(zhì)量檢測(cè)學(xué)報(bào)，2020,11(15)8.崔秀棟，肉類食品中激素殘留的檢測(cè)技術(shù)[J]，現(xiàn)代畜牧科技，2020,70(10)9.徐偉，等.高效液相色譜-串聯(lián)質(zhì)譜法同時(shí)檢測(cè)豬肉中125種獸藥殘留[J]，天津農(nóng)業(yè)科學(xué)，2020,26(2)10.楊兆甜，等.高效液相色譜-串聯(lián)質(zhì)譜法檢測(cè)豬肉中多獸藥殘留[J]，食品與生物技術(shù)學(xué)報(bào)，2020,39(7)11.貝峰，等.QuEChERS-液相色譜串聯(lián)質(zhì)譜儀檢測(cè)豬肉中102種農(nóng)獸藥殘留及非法添加物方法的研究[J]，山東畜牧獸醫(yī)，2020,41(2)12.晏利芝，等.超高效液相色譜-串聯(lián)質(zhì)譜法同時(shí)測(cè)定豬肉中β-受體激動(dòng)劑、喹諾酮類和磺胺類獸藥殘留量[J]，分析試驗(yàn)室，2011,30(1)13.王洪利,等.食源性興奮劑防控與運(yùn)動(dòng)員飲食安全管理研究[J].遼寧體育科技,2013,35(6)14.張貽豪,等.膳食補(bǔ)充劑中蛋白同化雄性類固醇檢測(cè)研究進(jìn)展[J],中國(guó)運(yùn)動(dòng)醫(yī)學(xué)雜志,2021,40(1)15.AbirKhaled,VaroonSingh,JanuszPawliszyn.ComparisonofSolid-PhaseMicroextractiontoSolventExtractionandQuEChERSforQuantitativeAnalysisofVeterinaryDrugResiduesinChickenandBeefMatrices[J].JournalofAgriculturalandFoodChemistry,2019,67(46)16.吳平谷,等.同時(shí)檢測(cè)動(dòng)物肌肉中26種β2-興奮劑和激素殘留[J],分析化學(xué),2008,36(11)17.徐錦忠，等.高效液相色譜-串聯(lián)質(zhì)譜法同時(shí)檢測(cè)雞肉和雞蛋中合成類固醇類激素和糖皮質(zhì)激素[J]，分析化學(xué)，2009,37(3)18.高潔，等.通過(guò)式固相萃取-超高效液相色譜-串聯(lián)質(zhì)譜法快速測(cè)定豬肉中52種同化激素[J]，中國(guó)衛(wèi)生檢驗(yàn)雜志，2018,28(12)19.李笑曼,等.國(guó)內(nèi)外食源性興奮劑誤服事件分析與法規(guī)標(biāo)準(zhǔn)現(xiàn)狀[J]．食品科學(xué)，2019，40(21)20.徐成鋼,等.高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定牛肉中18種β-受體興奮劑[J]，食品研究與開(kāi)發(fā),2016,37(4)21.吳敏，等.超高效液相色譜-串聯(lián)質(zhì)譜測(cè)定豬肉中地塞米松、倍他米松和倍氯米松[J]，理化檢驗(yàn)(化學(xué)分冊(cè)).2010,46(11)22.劉萍，等.人血漿中螺內(nèi)酯及其代謝物坎利酮的LC-MS測(cè)定[J]，中國(guó)醫(yī)藥工業(yè)雜志，2008,23.薛穎，等.超高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定雞肉和豬肉中利尿劑殘留量[J]，食品工業(yè)科技，2021,42(3)24.楊旺火，高效液相色譜串聯(lián)質(zhì)譜法測(cè)定飼料中8種利尿劑藥物[J]．糧食與飼料工業(yè)，2019(4)25.許文佳，等.HPLC-MS/MS法同時(shí)測(cè)定育發(fā)化妝品中的13種違禁成分[J]，藥物分析雜志.2019,39(08)26.Chung,StephenW.C.Lam,Chi-Ho.Developmentofa15-classmultiresiduemethodforanalyzing78hydrophilicandhydrophobicveterinarydrugsinmilk,eggandmeatbyliquidchromatography-tandemmassspectrometry[J].Analyticalmethods.2015,7(16)27.方從容,等.QuEChERS-超高效液相色譜-串聯(lián)質(zhì)譜法測(cè)定雞蛋中125種獸藥殘留[J],色譜,2018,36(11)28.JianZhou，Jiao-JiaoXu，Jin-MiCong，ect.Optimizationforquick,easy,cheap,effective,ruggedandsafeextractionofmyco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