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市场监管总局关于发布《食品中那非类物质的测定》食品补充检验方法的公告

市场监管总局 samr

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市场监管总局关于发布《食品中 那非类物质的测定》食品补充检验方法的公告 〔2018年第14号〕 按照《食品补充检验方法工作规定》有关规定，《食品中那非类物质的测定》食品补充检验方法已经国家市场监督管理总局批准，现予发布。 特此公告。 附件：食品中那非类物质的测定（BJS 201805） 市场监管总局 2018年7月2日 附件：食品中那非类物质的测定（BJS 201805） 附件 食品中那非类物质的测定 （BJS 201805） 1 范围 本标准规定了食品（含保健食品）基质中90种那非类物质的超高效液相色谱-串联质谱测定方法。 标准中方法一超高效液相色谱-三重四极杆串联质谱法，适用于饮料、果冻、蛋白粉、牡蛎粉、饼干、糖果、酒类及咖啡等食品（含与上述基质相同的保健食品及片剂、胶囊、软胶囊等剂型）中90种那非类物质的定性和定量测定。 标准中方法二超高效液相色谱-串联高分辨质谱法，适用于饮料、果冻、蛋白粉、牡蛎粉、饼干、糖果、酒类及咖啡等食品（含与上述基质相同的保健食品及片剂、胶囊、软胶囊等剂型）中90种那非类物质的筛查和定性确证。 方法一超高效液相色谱-三重四极杆串联质谱法 2原理 试样经甲醇超声提取，过滤后，滤液供超高效液相色谱—三重四极杆串联质谱仪测定，外标法定量。 3试剂和材料 注：水为GB/T 6682规定的一级水。 3.1 试剂 3.1.1 甲醇（CH3OH）：质谱级。 3.1.2 甲酸（HCOOH）：质谱级。 3.1.3 乙酸乙酯（C4H8O2）：分析纯。 3.1.4 盐酸（HCl）：分析纯。 3.2 试剂配制 3.2.1 0.1%甲酸水溶液：取甲酸1mL用水稀释至1000mL，用滤膜（4.3）过滤后备用。 3.2.2 盐酸甲醇溶液（1+99）：取盐酸1mL用甲醇稀释至100mL。 3.2.3 甲醇水溶液（1+1）：将甲醇与水等体积混合。 3.3 标准品 西地那非等90种物质标准品的中文名称、英文名称、CAS登录号、分子式、相对分子量见附录A表A.1，纯度≥98%。 3.4 标准溶液配制 3.4.1标准储备液（200 μg/mL）：分别精密称取Lodenafil carbonate（46罗地那非碳酸酯）、Sildenafil dimer impurity（63西地那非二聚体杂质）、Vardenafil dimer（69伐地那非二聚体）标准品（3.3）各10mg，用盐酸甲醇溶液（1+99）溶解并稀释至50mL，摇匀；分别精密称取其余87种标准品（3.3）各10 mg，用甲醇溶解并稀释至50mL，摇匀，制成浓度为200 μg/mL标准储备液。-20 ℃避光贮存，有效期3个月。 3.4.2 混合标准中间工作溶液（1 μg/mL）：分别准确吸取标准储备液（200 μg/mL）（3.4.1）各0.1 mL，用甲醇稀释至20mL，摇匀，制成1 μg/mL的混合标准工作溶液。临用新制。根据化合物保留时间适当分组。 3.4.3 混合标准工作溶液：分别准确吸取混合标准中间工作液（1 μg/mL）（3.4.2）适量，用甲醇水溶液（1+1）（3.2.3）稀释，摇匀，作为系列混合标准工作溶液，浓度依次为各化合物2 μg/L、5 μg/L、10 μg/L、20 μg/L、50 μg/L，临用新制或依仪器响应情况配制适当浓度的混合标准工作溶液。或根据需要采用空白基质提取液（5.1.4），配制适当浓度的基质混合标准工作溶液。 4 仪器和设备 4.1高效液相色谱-串联质谱仪，配电喷雾（ESI）离子源。 4.2天平：感量分别为0.01 mg和0.1 mg。 4.3微孔滤膜：0.22µm，有机相型。 离心机：转速≥4 000 r/min。 4.5 超声波清洗器。 5 分析步骤 5.1 试样制备 5.1.1 固态或半固态试样 取固态试样（蛋白粉、牡蛎粉、饼干、糖果、咖啡及含与上述基质相同的保健食品及片剂、胶囊等剂型）适量混匀，研细，或取半固态试样（果冻）适量混匀，精密称取1g（精确至0.001 g）置于50 mL容量瓶中，加甲醇（3.1.1）适量，超声提取15 min，放冷至室温，用甲醇（3.1.1）定容，转移至50 mL离心管中，4 000 r/min离心5 min，上清液经微孔滤膜过滤（4.3），取续滤液，根据实际浓度用甲醇水溶液（1+1）（3.2.3）适当稀释至线性范围内，备用。 5.1.2 液态试样 取试样（饮料、酒）适量摇匀，准确吸取1mL置于50 mL容量瓶中，加甲醇（3.1.1）适量，超声提取15 min，放冷至室温，用甲醇（3.1.1）定容，经微孔滤膜（4.3）过滤，取续滤液，根据实际浓度用甲醇水溶液（1+1）（3.2.3）适当稀释至线性范围内，备用。 5.1.3 油脂基质（软胶囊）试样 取试样（软胶囊）适量混匀，精密称取1g（精确至0.001 g）置于50 mL容量瓶中，加乙酸乙酯5mL，振摇，使其分散，加甲醇（3.1.1）适量，超声提取15 min，放冷至室温，用甲醇（3.1.1）定容，转移至50 mL离心管中，4 000 r/min离心5 min，上清液经微孔滤膜过滤（4.3），取续滤液，根据实际浓度用甲醇水溶液（1+1）（3.2.3）适当稀释至线性范围内，备用。 5.1.4 空白基质提取液 称取空白试样适量，与试样同法处理，制得空白基质提取液。 5.1.5 空白溶液 不加试样，与试样同法处理，制得空白溶液。 5.2仪器参考条件 5.2.1色谱条件 a）色谱柱：Agilent Eclipse Plus C18 （3.0×150 mm， 1.8 µm），或性能相当者。 b）流动相：A为0.1%甲酸水溶液（3.2.1），B为甲醇（3.1.1），梯度洗脱程序见表1。 c）流速：400 μL/min。 d）柱温：35℃。 e）进样量：5 μL。 表1 梯度洗脱程序表 梯度时间/min 流动相A/% 流动相B/% 0 90 10 1 50 50 16 35 65 19 2 98 22 2 98 22.1 90 10 25 90 10 5.2.2 质谱条件 a）离子源：电喷雾离子源（ESI源）。 b）检测方式：多反应离子监测（MRM）。 c）碰撞气为高纯氮气，干燥气、雾化气、鞘气等均为氮气或其他合适气体，使用前应调节相应参数使质谱灵敏度达到检测要求，毛细管电压、干燥气温度、鞘气温度、鞘气流量、喷嘴电压、碰撞能量、碎裂电压等参数应优化至最佳灵敏度，监测离子对和定量离子对等信息详见附录B。 5.3 定性测定 按照超高效液相色谱-三重四极杆串联质谱条件测定试样和标准工作溶液，记录试样和标准溶液中各化合物的色谱保留时间，当试样中检出与某标准品色谱峰保留时间一致的色谱峰（变化范围在±2.5%之内），并且试样色谱图中所选择的监测离子对的相对丰度比与相当浓度标准溶液的离子相对丰度比（k）的偏差不超过表2规定的范围，可以确定试样中检出相应化合物。 表2 定性确证时相对离子丰度的最大允许偏差 相对离子丰度（%） k＞50% 50%≥k＞20% 20%≥k＞10% k≤10% 允许的最大偏差（%） ± 20 ± 25 ± 30 ± 50 5.4定量测定 5.4.1标准曲线的制作 将混合标准工作溶液（3.4.3）分别按仪器参考条件（5.2）进行测定，得到相应的标准溶液的色谱峰面积。以混合标准工作溶液的浓度为横坐标，以定量离子的色谱峰的峰面积为纵坐标，绘制标准曲线。 5.4.2试样溶液的测定 将试样溶液（5.1.1-5.1.3）按仪器参考条件（5.2）进行测定，得到样品溶液中对应组分的色谱峰面积。根据标准曲线得到待测液中组分的浓度，平行测定次数不少于两次。 对照品色谱图参见附录D。 5.4.3空白溶液的测定 空白溶液（5.1.5）同试样溶液测定步骤操作。 6 结果计算 将液相色谱-质谱测得浓度代入下式计算含量： EMBED Equation.3 …………………………………………（1） 式中： X — 试样中各待测物的含量，单位为毫克每千克或毫克每升（mg/kg或mg/L）； c — 从标准曲线中读出的供试品溶液中各待测物的浓度，单位为微克每升（μg/L）； V — 样液最终定容体积，单位为毫升（mL）； m —试样溶液所代表的质量，单位为克（g或L）； f— 稀释倍数。 计算结果以重复性条件下获得的两次独立测定结果的算术平均值表示，结果保留三位有效数字。 7 精密度 在重复性条件下获得的两次独立测定结果的绝对差值不得超过算术平均值的20%。 8 其他 当称样量为1 g（精确至0.001g）或1mL，定容体积为50mL时，本方法中90种那非类物质的检出限均为为0.05~1mg/kg或0.05~0.25 mg /L，定量限为0.1~2.5mg/kg或0.1~0. 5mg /L。详见附录C表C.1。 空白试验应无干扰。 方法二超高效液相色谱-串联高分辨质谱法 2 原理 试样经甲醇超声提取，过滤后，滤液供高效液相色谱-串联高分辨质谱测定，比较供试品与标准品的保留时间、一级质谱图和二级质谱图进行筛查和定性确证。 3 试剂和材料 注：水为GB/T 6682规定的一级水。 3.1 试剂 3.1.1乙腈（C2H3N）：质谱级。 3.1.2 甲酸（HCOOH）：质谱级。 3.1.3 甲醇（CH3OH）：分析纯。 3.1.4 乙酸乙酯（C4H8O2）：分析纯。 3.1.5 盐酸（HCl）：分析纯。 3.2试剂配制 3.2.1 0.1%甲酸水溶液：取甲酸1mL用水稀释至1000mL，用滤膜（4.3）过滤后备用。 3.3标准品 同方法一3.3标准品项下。 3.4 标准溶液配制 3.4.1标准储备液（200 μg/mL）：同方法一3.4.1标准储备液项下。 3.4.2 混合标准工作溶液（1 μg/mL）：同方法一3.4.2混合标准中间工作溶液项下。或依仪器响应情况配制至适当浓度。根据化合物保留时间和仪器扫描速度适当分组。 4仪器和设备 4.1高效液相色谱-串联高分辨质谱仪，配有电喷雾（ESI）离子源。 4.2天平：感量分别为0.1 mg和1 mg。 4.3滤膜：0.22µm，有机相型。 4.4 超声波发生器。 5分析步骤 5.1试样制备 5.1.1 试样处理 同方法一试样制备5.1.1～5.1.3项下，根据实际浓度适当稀释，备用。 5.1.2 空白溶液制备 同方法一空白溶液制备5.1.5项下。 5.2 仪器参考条件 5.2.1 色谱条件 a）色谱柱：Agilent Poroshell 120 SB-C18 （3.0×75 mm， 2.7µm），或性能相当者。 b）流动相：A为0.1%甲酸水溶液（3.2.1），B为乙腈（3.1.1），梯度洗脱程序见表3。 c）流速：0.4mL/min。 d）柱温：30℃。 e）进样量：1μL。 表3 梯度洗脱程序表 梯度时间/min 流动相A/% 流动相B/% 0 95 5 15 2 98 17 2 98 17.5 95 5 20 95 5 5.2.2 质谱条件 a）离子源：电喷雾离子源（ESI源）。 b）干燥气、雾化气、鞘气、碰撞气等均为高纯氮气或其他合适气体，使用前应调节相应参数使质谱灵敏度达到检测要求，毛细管电压、干燥气温度、鞘气温度、鞘气流量、喷嘴电压、碰撞能量、碎裂电压等参数应优化至最佳灵敏度，母离子及碎片离子等参考信息详见附录E表E.1。 6定性判定 按照超高效人液相色谱-串联高分辨质谱条件测定试样（5.1.1）和混合标准工作溶液（3.4.2），记录试样和混合标准工作溶液中各化合物的色谱峰保留时间及多级质谱图，当试样中检出与某标准品色谱峰（或由标准品建立的谱库）保留时间一致的色谱峰，并且与标准品母离子精确分子量误差不超过百万分之五，主要碎片离子精确分子量误差不超过百万分之十，即可以确定试样中检出相应化合物。 7 检测方法的灵敏度和专属性 7.1 灵敏度 当取样量为1 g或1 mL，定容体积为50 mL时，本方法中90种化合物的检出限为0.1~70mg/kg或0.1~50mg/L，详见附录F表F.1。 7.2 专属性 取空白溶液（5.1.2）进样测定，应无干扰。 取混合标准工作溶液（3.4.2）进样测定，各化合物之间应无互相干扰，同分异构体应可通过保留时间或二级质谱图进行区分。 附录A 西地那非等90种化合物相关信息 表A.1 90种化合物英文名称、中文名称、分子式、CAS号、相对分子质量 序号 英文名 中文名 分子式 CAS号 分子量 1 Sildenafil 西地那非 C22H30N6O4S 139755-83-2 474.6 2 Tadalafil 他达拉非 C22H19N3O4 171596-29-5 389.4 3 Imidazosagatriazinone 脱硫伐地那非 C17H20N4O2 139756-21-1 312.4 4 Gendenafil 庆地那非 C19H22N4O3 147676-66-2 354.4 5 Acetil acid 那非乙酰酸 C18H20N4O4 147676-78-6 356.4 6 Xanthoanthrafil 苯酰胺那非 C19H23N3O6 1020251-53-9 389.4 7 Aminotadalafil 氨基他达拉非 C21H18N4O4 385769-84-6 390.4 8 Chloropretadalafil 他达拉非甲基氯化物 C22H19ClN2O5 171489-59-1 426.8 9 Piperiacetildenafil 苯噻啶红地那非 C24H31N5O3 147676-50-4 437.5 10 Noracetildenafil 那红地那非 C24H32N6O3 949091-38-7 452.5 11 Carbodenafil 卡巴地那非 C24H32N6O3 944241-52-5 452.5 12 Pseudovardenafil 伪伐地那非 C22H29N5O4S 224788-34-5 459.6 13 Norneosildenafil 那莫西地那非 C22H29N5O4S 371959-09-0 459.6 14 N-Desethylvardenafil N-去乙基伐地那非 C21H28N6O4S 448184-46-1 460.6 15 N-Desmethylsildenafil N-去甲基西地那非 C21H28N6O4S 139755-82-1 460.6 16 Acetildenafil 红地那非 C25H34N6O3 831217-01-7 466.6 17 Hydroxyacetildenafil 羟基红地那非 C25H34N6O4 147676-56-0 482.6 18 Avanafil 阿伐那非 C23H26ClN7O3 330784-47-9 484.0 19 Aildenafil 艾地那非 C23H32N6O4S 496835-35-9 488.6 20 Homosildenafil 豪莫西地那非 C23H32N6O4S 642928-07-2 488.6 21 Vardenafil 伐地那非 C23H32N6O4S 224785-90-4 488.6 22 Thiosildenafil 硫代西地那非 C22H30N6O3S2 479073-79-5 490.6 23 Thiohomosildenafil 硫代豪莫西地那非 C23H32N6O3S2 479073-80-8 504.7 24 Hydroxyvardenafil 羟基伐地那非 C23H32N6O5S 224785-98-2 504.6 25 Hydroxyhomosildenafil 羟基豪莫西地那非 C23H32N6O5S 139755-85-4 504.6 26 Udenafil 乌地那非 C25H36N6O4S 268203-93-6 516.7 27 Hydroxythiohomosildenafil 羟基硫代豪莫西地那非 C23H32N6O4S2 479073-82-0 520.7 28 Norneovardenafil 那莫伐地那非 C18H20N4O4 358390-39-3 356.4 29 Nitrodenafil 硝地那非 C17H19N5O4 147676-99-1 357.4 30 Nortadalafil 去甲基他达拉非 C21H17N3O4 171596-36-4 375.4 31 Chlorodenafil 氯地那非 C19H21ClN4O3 1058653-74-9 388.8 32 Hydroxychlorodenafil 羟基氯地那非 C19H23ClN4O3 1391054-00-4 390.9 33 N-Butyltadalafil N-丁基他达拉非 C25H25N3O4 171596-31-9 431.5 34 Desmethylcarbodenafil 去甲基卡巴地那非 C23H30N6O3 147676-79-7 438.5 35 Descarbonsildenafil 去碳西地那非 C21H30N6O4S 1393816-99-3 462.6 36 Dimethylacetildenafil 二甲基红地那非 C25H34N6O3 1290041-88-1 466.6 37 Dithio-desmethylcarbodenafil 二硫代去甲基卡巴地那非 C23H30N6OS2 1333233-46-7 470.7 38 Oxohongdenafil 酮红地那非 C25H32N6O4 1446144-70-2 480.6 39 N-Octylnortadalafil N-辛基去甲他达拉非 C29H33N3O4 1173706-35-8 487.6 40 Dioxohongdenafil 双酮红地那非 C25H30N6O5 1609405-33-5 494.5 41 Hydroxythiovardenafil 羟基硫代伐地那非 C23H32N6O4S2 912576-30-8 520.7 42 Cyclopentynafil 环戊那非 C26H36N6O4S 1173706-34-7 528.7 43 Propoxyphenyl thiohydroxyhomosildenafil 丙氧苯基硫代羟基豪莫西地那非 C24H34N6O4S2 479073-90-0 534.7 44 Benzylsildenafil 苄西地那非 C28H34N6O4S 1446089-82-2 550.7 45 Cinnamyldenafil 桂地那非 C32H38N6O3 1446089-83-3 554.7 46 Lodenafil carbonate 罗地那非碳酸酯 C47H62N12O11S2 398507-55-6 1035.2 47 Propoxyphenylsildenafil 丙氧苯基西地那非 C23H32N6O4S 877777-10-1 488.6 48 Depiperazinothiosildenafil 脱哌嗪基硫代西地那非 C17H20N4O4S2 1353018-10-6 408.5 49 Acetaminotadalafil 乙酰胺基他达拉非 C23H20N4O5 1446144-71-3 432.4 50 2-Hydroxypropylnortadalafil 2-羟丙基去甲他达拉非 C24H23N3O5 1353020-85-5 433.5 51 Acetylvardenafil 乙酰伐地那非 C25H34N6O3 1261351-28-3 466.6 52 Propoxyphenyl hydroxyhomosildenafil 丙氧苯基羟基豪莫西地那非 C24H34N6O5S 139755-87-6 518.6 53 Propoxyphenyl thioaildenafil 丙氧苯基硫代艾地那非 C24H34N6O3S2 856190-49-3 518.7 54 Yohimbine 育亨宾 C21H26N2O3 146-48-5 354.4 55 Dapoxetine 达泊西汀 C21H23NO 119356-77-3 305.4 56 N-Desethylacetildenafil N-去乙基红地那非 C23H30N6O3 147676-55-9 438.5 57 Desmethylthiosildenafil 去甲基硫代西地那非 C21H28N6O3S2 479073-86-4 476.6 58 N-Boc-N-desethyl acetildenafil N-叔丁氧羰基-N-去乙基红地那非 C28H38N6O5 1246820-46-1 538.6 59 N-Ethyltadalafil N-乙基他达拉非 C23H21N3O4 1609405-34-6 403.4 60 O-Desethylsildenafil O-去乙基西地那非 C20H26N6O4S 139755-91-2 446.5 61 Pyrazole N-desmethylsildenafil 吡唑N-去甲基西地那非 C21H28N6O4S 139755-95-6 460.6 62 Isobutylsildenafil 异丁基西地那非 C23H32N6O4S 1391053-95-4 488.6 63 Sildenafil dimer impurity 西地那非二聚体杂质 C38H46N10O8S2 1346602-67-2 835.0 64 Vardenafil oxopiperazine 伐地那非哌嗪酮 C21H26N6O5S 448184-58-5 474.5 65 Sildenafil N-oxide 西地那非N-氧化物 C22H30N6O5S 1094598-75-0 490.6 66 Vardenafil N-oxide 伐地那非N-氧化物 C23H32N6O5S 448184-48-3 504.6 67 2-Hydroxyethylnortadalafil 2-羟乙基去甲他达拉非 C23H21N3O5 385769-94-8 419.4 68 Vardenafil acetyl analogue 伐地那非乙酰基类似物 C24H31N5O3 / 437.5 69 Vardenafil dimer 伐地那非二聚体 C38H46N10O8S2 1255919-03-9 835.0 70 Mirodenafil 米罗那非 C26H37N5O5S 862189-95-5 531.7 71 Mutaprodenafil 亚硝地那非 C27H35N9O5S2 1387577-30-1 629.8 72 Thioquinapiperfil 硫喹哌非 C24H28N6OS 220060-39-9 448.6 73 Aminosildenafil 氨基西地那非 C18H23N5O4S 319491-68-4 405.5 74 Desethylcarbodenafil 去乙基卡巴地那非 C22H28N6O3 1027192-92-2 424.5 75 Didescarbonsildenafil 双去碳西地那非 C20H28N6O4S 466684-88-8 448.5 76 N-Phenylpropenyltadalafil N-苯丙烯基他达拉非 C30H24N4O4 2064212-00-4 504.5 77 N-Desethyl-N-methylvardenafil N-去乙基-N-甲基伐地那非 C22H30N6O4S 224785-87-9 474.6 78 Thioaildenafil 硫代艾地那非 C23H32N6O3S2 856190-47-1 504.7 79 Dichlorodenafil 双氯地那非 C19H20Cl2N4O2 1446089-84-4 407.3 80 Piperazonifil 哌唑那非 C25H34N6O4 1335201-04-1 482.6 81 Propoxyphenyl thiosildenafil 丙氧苯基硫代西地那非 C23H32N6O3S2 479073-87-5 504.7 82 Propoxyphenyl thiohomosildenafil 丙氧苯基硫代豪莫西地那非 C24H34N6O3S2 479073-88-6 518.7 83 Dithiodesethyl carbodenafil 二硫代去乙基卡巴地那非 C22H28N6OS2 1610830-81-3 456.6 84 Hydroxythioacetildenafil 羟基硫代红地那非 C25H34N6O3S 1159977-47-5 498.7 85 Tadalafil dichloro impurity 他达拉非二氯代杂质 C22H18Cl2N2O5 1598416-08-0 461.3 86 Sildenafil impurity 12 西地那非杂质12 C25H34N6OS2 / 498.7 87 Demethylpiperaziny sildenafil sulfonic acid 去甲基哌嗪基西地那非磺酸 C17H20N4O5S 1357931-55-5 392.1 88 Propoxyphenyl aildenafil 丙氧苯基艾地那非 C24H34N6O4S 1391053-82-9 502.6 89 Sildenafil impurity 14 西地那非杂质14 C24H32N6OS2 2146091-79-2 484.7 90 Propoxyphenylisobutyl aildenafil 丙氧苯基异丁基艾地那非 C25H36N6O4S 1621873-33-3 516.7 注： 68 Vardenafil acetyl analogue 伐地那非乙酰基类似物 C24H31N5O3 86 Sildenafil impurity 12 西地那非杂质12 C25H34N6OS2 附录B 超高效液相-三重四极杆串联质谱参考条件 质谱参考条件 离子源：电喷雾离子源（ESI）； 检测方式：多反应监测（MRM）； 扫描方式：正、负离子模式； 毛细管电压：3.5kV； 干燥气温度：325℃； 干燥气流量：7L/min； 雾化气压力：40psi； 鞘气温度：350℃ ；鞘气流量：11L/min； 喷嘴电压：正离子： 0V；负离子：1000V； 其他质谱参数见表B.1。 表B.1 化合物定性、定量离子和质谱分析参数 序号 化合物 母离子（m/z） 子离子（m/z） 碎裂电压 （V） 碰撞能量 （V） 离子化模式 保留时间 （min） 1 Sildenafil 475.2 283.1 170 46 + 6.42 475.2 100.1* 170 30 + 2 Tadalafil 390.2 268* 120 10 + 11.47 390.2 135 120 26 + 3 Imidazosagatriazinone 313.2 285. 1* 145 26 + 19.98 313.2 256 145 34 + 4 Gendenafil 355.2 327.1* 160 26 + 17.81 355.2 285 160 34 + 5 Acetil acid 357.2 329.1* 170 26 + 15.38 357.2 285.1 170 34 + 6 Xanthoanthrafil 390.2 151* 105 10 + 9.39 390.2 107 105 74 + 7 Aminotadalafil 391.1 269* 130 10 + 9.05 391.1 204 130 66 + 8 Chloropretadalafil 427.1 274 145 34 + 15.57 427.1 135* 145 18 + 9 Piperiacetildenafil 438.2 297.1 165 42 + 6.01 438.2 98.1* 165 34 + 10 Noracetildenafil 453.3 166 210 58 + 5.78 453.3 97.1* 210 34 + 11 Carbodenafil 453.3 339.1* 160 26 + 4.80 453.3 311.1 160 38 + 12 Pseudovardenafil 460.2 312.1 215 42 + 19.13 460.2 151* 215 50 + 13 Norneosildenafil 460.2 299.1 210 42 + 19.80 460.2 282.9* 210 42 + 14 N-Desethylvardenafil 461.2 312.1 195 38 + 5.85 461.2 151* 195 58 + 15 N-Desmethylsildenafil 461.2 311.1 180 34 + 6.45 461.2 283* 180 42 + 16 Acetildenafil 467.3 127.1 190 34 + 5.82 467.3 111.1* 190 34 + 17 Hydroxyacetildenafil 483.3 143.1 205 38 + 5.58 483.3 127.1* 205 34 + 18 Avanafil 484.2 375.1* 175 30 + 5.66 484.2 155 175 46 + 19 Aildenafil 489.2 113.1* 190 34 + 7.06 489.2 99.1 190 38 + 20 Homosildenafil 489.2 113.1* 180 30 + 6.48 489.2 72.2 180 50 + 21 Vardenafil 489.2 312.1 200 46 + 6.24 489.2 151* 200 54 + 22 Thiosildenafil 491.2 299 165 42 + 14.26 491.2 100.1* 165 30 + 23 Thiohomosildenafil 505.2 299 170 46 + 14.32 505.2 113.1* 170 34 + 24 Hydroxyvardenafil 505.2 312.1 190 46 + 6.48 505.2 151* 190 54 + 25 Hydroxyhomosildenafil 505.2 129.1 190 42 + 6.85 505.2 99.1* 190 42 + 26 Udenafil 517.3 283* 200 50 + 7.89 517.3 112.1 200 38 + 27 Hydroxythiohomosildenafil 521.2 129.1 190 34 + 14.12 521.2 99.1* 190 38 + 28 Norneovardenafil 357.2 329.1 175 26 + 12.73 357.2 151* 175 34 + 29 Nitrodenafil 358.2 330.1* 160 26 + 19.45 358.2 284.1 160 34 + 30 Nortadalafil 376.1 254 105 10 + 9.56 376.1 204* 105 70 + 31 Chlorodenafil 389.1 361.1* 170 30 + 18.89 389.1 285 170 38 + 32 Hydroxychlorodenafil 391.2 313.1* 180 38 + 18.37 391.2 285.1 180 34 + 33 N-Butyltadalafil 432.2 310.1* 130 14 + 19.36 432.2 135 130 30 + 34 Desmethylcarbodenafil 439.2 339.1* 165 22 + 4.67 439.2 311.1 165 34 + 35 Descarbonsildenafil 463.2 311.1 165 34 + 5.65 463.2 283.1* 165 42 + 36 Dimethylacetildenafil 467.3 166 195 58 + 6.93 467.3 127.1* 195 34 + 37 Dithio-desmethylcarbodenafil 471.2 371.1* 165 22 + 15.62 471.2 343.1 165 38 + 38 Oxohongdenafil 481.3 297.1 165 50 + 12.09 481.3 410.2* 165 34 + 39 N-Octylnortadalafil 488.3 169 135 50 + 20.71 488.3 366.2* 135 14 + 40 Dioxohongdenafil 495.2 311.1 190 46 + 11.03 495.2 127.1* 190 42 + 41 Hydroxythiovardenafil 521.2 167* 215 70 + 11.27 521.2 99.1 215 38 + 42 Cyclopentynafil 529.3 461.2* 175 30 + 7.43 529.3 98.1 175 42 + 43 Propoxyphenyl thiohydroxyhomosildenafil 535.2 299.1 185 42 + 17.01 535.2 99.1* 185 42 + 44 Benzylsildenafil 551.2 377.1* 185 30 + 11.29 551.2 134.1 185 42 + 45 Cinnamyldenafil 555.3 117* 175 30 + 12.40 555.3 115.1 175 80 + 46 Lodenafil carbonate 518.3 230.2* 151 38 + 19.65 518.3 112.2 151 38 + 47 Propoxyphenylsildenafil 489.2 283.1 170 42 + 8.24 489.2 166.2* 170 30 + 48 Depiperazinothiosildenafil 407.1 378.1 155 22 - 9.15 407.1 314* 155 34 - 48 Depiperazinothiosildenafil 409.1 381.1 165 30 + 9.15 409.1 167.1* 165 40 + 49 Acetaminotadalafil 433.2 135 135 22 + 9.2 433.2 204* 135 74 + 50 2-Hydroxypropylnortadalafil 434.2 312.1* 150 14 + 11.4，12.18 434.2 135 150 26 + 51 Acetylvardenafil 467.3 151 195 54 + 5.26 467.3 111.1* 195 34 + 52 Propoxyphenyl hydroxyhomosildenafil 519.2 283 175 46 + 8.22 519.2 99.1* 175 42 + 53 Propoxyphenyl thioaildenafil 519.2 299* 160 38 + 17.98 519.2 113.1 160 34 + 54 Yohimbine 355.2 212 155 26 + 3.24 355.2 144* 155 34 + 55 Dapoxetine 306.2 157* 105 26 + 9.21 306.2 127 105 62 + 56 N-Desethylacetildenafil 439.2 166 160 58 + 4.96 439.2 99.1* 160 34 + 57 Desmethylthiosildenafil 477.2 327.1 175 30 + 14.13 477.2 299.1* 175 42 + 58 N-Boc-N-desethyl acetildenafil 539.3 439.2* 125 18 + 12.89 539.3 99.1 125 46 + 59 N-Ethyltadalafil 404.2 282.1* 120 10 + 13.70 404.2 135 120 26 + 60 O-Desethylsildenafil 447.2 299.1 155 34 + 8.45 447.2 283* 155 30 + 61 Pyrazole N-desmethylsildenafil 461.2 269 165 42 + 4.15 461.2 100.1* 165 30 + 62 Isobutylsildenafil 489.2 297.1* 170 46 + 8.24 489.2 100.1 170 34 + 63 Sildenafil dimer impurity 835.2 283.1* 225 78 + 19.94 835.2 299 225 66 + 64 Vardenafil oxopiperazine 475.2 312.1 160 42 + 9.76 475.2 151* 160 58 + 65 Sildenafil N-oxide 491.2 404.1 185 30 + 7.01 491.2 99.1* 185 38 + 66 Vardenafil N-oxide 505.2 477.2 130 22 + 5.96 505.2 151* 130 74 + 67 2-Hydroxyethylnortadalafil 420.2 298.1* 120 10 + 9.88 420.2 169 120 46 + 68 Vardenafil acetyl analogue 438.2 98.1* 190 34 + 5.39 438.2 151 190 54 + 69 Vardenafil dimer 833.3 805.1 165 42 - 19.92 833.3 282* 165 66 - 69 Vardenafil dimer 835.3 312.1 250 70 + 19.92 835.3 151.1* 250 80 + 70 Mirodenafil 532.3 296.1* 220 46 + 11.72 532.3 99.1 220 46 + 71 Mutaprodenafil 630.2 312.1 160 46 + 9.99 630.2 141.9* 160 30 + 72 Thioquinapiperfil 449.2 204* 145 22 + 7.26 449.2 186 145 42 + 73 Aminosildenafil 406.2 364.1* 165 26 + 12.10 406.2 299.1 165 38 + 74 Desethylcarbodenafil 425.2 339.1* 135 22 + 4.63 425.2 311.1 135 34 + 75 Didescarbonsildenafil 449.2 311.1 170 30 + 5.54 449.2 283.1* 170 42 + 76 N-Phenylpropenyltadalafil 503.2 262.3* 150 20 - 20.91 503.2 232.2 150 50 - 76 N-Phenylpropenyltadalafil 505.2 383.0* 145 15 + 20.91 505.2 261.9 145 30 + 77 N-Desethyl-N-methylvardenafil 475.2 312.1 200 46 + 5.64 475.2 151* 200 50 + 78 Thioaildenafil 505.2 113.1* 170 34 + 14.53 505.2 99.1 170 42 + 79 Dichlorodenafil 407.1 379* 185 30 + 21.02 407.1 350 185 34 + 80 Piperazonifil 483.2 166 166 58 + 6.81 483.2 436.2* 166 34 + 81 Propoxyphenyl thiosildenafil 505.2 313.1 175 42 + 17.18 505.2 299* 175 42 + 82 Propoxyphenyl thiohomosildenafil 519.2 299* 175 42 + 17.21 519.2 113.1 175 34 + 83 Dithiodesethyl carbodenafil 457.2 371.1* 165 26 + 14.93 457.2 343 165 38 + 84 Hydroxythioacetildenafil 499.2 127.1 189 34 + 12.74 499.2 143.1* 189 34 + 85 Tadalafil dichloro impurity 461.1 204* 150 78 + 18.54 461.1 135 150 22 + 86 Sildenafil impurity 12 499.2 371.1 160 26 + 16.44 499.2 343* 160 42 + 87 Demethylpiperaziny sildenafil sulfonic acid 393.1 365.1* 175 30 + 5.50 393.1 256 175 42 + 88 Propoxyphenyl aildenafil 503.2 283* 185 38 + 9.02 503.2 113.2 185 34 + 89 Sildenafil impurity 14 485.2 371.1* 165 26 + 16.53 485.2 343 165 38 + 90 Propoxyphenylisobutyl aildenafil 517.3 297.3* 200 42 + 11.21 517.3 113.1 200 34 + *定量离子。 备注：1.本方法提供质谱条件为推荐质谱方法条件。可根据实际情况，选择响应信号强且无干扰的离子对进行检测，质谱参数亦可根据实际可达到最优灵敏度的条件进行设定。 2.48、69、76三种化合物分别给出了正负质谱条件，可根据实际响应选择正/负模式进行检测。 3.50、63、69三种化合物包含手性异构体，为双峰，以峰面积之和定量。 4.47与62号化合物为同分异构体，保留时间一致。如实际样品中有检出，应以方法二超高效液相-串联高分辨质谱确证。 附录C 超高效液相-三重四极杆串联质谱检出限及定量限 表C.1 90种那非类物质在11种基质中的检出限及定量限 序号化合物片剂饮料糖果咖啡软胶囊果冻蛋白粉酒胶囊饼干牡蛎粉检出限（μg/kg）定量限（μg/kg）检出限（μg/L）定量限（μg/L）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）检出限（μg/L）定量限（μg/L）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）检出限（μg/kg）定量限（μg/kg）1Sildenafil501005010050100501005010050100501005010050100501001002502Tadalafil501005010050100501005010050100501005010050100501001002503Imidazosagatriazinone50100501005010050100501005010050100501005010050100501004Gendenafil50100501005010050100501005010050100501005010050100501005Acetil acid50100501005010050100501005010050100501005010050100501006Xanthoanthrafil50100501005010050100501005010050100501005010050100501007Aminotadalafil501005010050100501005010050100501005010050100501001002508Chloropretadalafil50100501005010050100501005010050100501005010050100501009Piperiacetildenafil501005010050100//5010050100501005010050100501005010010Noracetildenafil501005010050100//5010050100501005010050100501005010011Carbodenafil501005010050100501005010050100501005010050100501005010012Pseudovardenafil501005010050100501005010050100501005010050100501005010013Norneosildenafil501005010050100501005010050100501005010050100501005010014N-Desethylvardenafil501005010050100501005010050100501005010050100501005010015N-Desmethylsildenafil501005010050100501005010050100501005010050100501005010016Acetildenafil5010050100501005010050100501005010050100100250501005010017Hydroxyacetildenafil501005010050100//50100501005010050100100250501005010018Avanafil501005010050100501005010050100501005010050100501005010019Aildenafil5010050100501005010050100501005010050100501005010010025020Homosildenafil5010050100501005010050100501005010050100501005010010025021Vardenafil501005010050100501005010050100501005010050100501005010022Thiosildenafil5010050100501005010050100501005010050100501005010010025023Thiohomosildenafil501005010050100501005010050100501005010050100501005010024Hydroxyvardenafil501005010050100501005010050100501005010050100501005010025Hydroxyhomosildenafil501005010050100501005010050100501005010050100501005010026Udenafil501005010050100501005010050100501005010050100501005010027Hydroxythiohomosildenafil5010050100501005010050100501005010050100501005010010025028Norneovardenafil501005010050100501005010050100501005010050100501005010029Nitrodenafil501005010050100501005010050100501005010050100501005010030Nortadalafil501005010050100501005010050100501005010050100501005010031Chlorodenafil501005010050100501005010050100501005010050100501005010032Hydroxychlorodenafil501005010050100501005010050100501005010050100501005010033N-Butyltadalafil5010050100501005010050100501005010050100501005010010025034Desmethylcarbodenafil501005010050100501005010050100501005010050100501005010035Descarbonsildenafil501005010050100501005010050100501005010050100501005010036Dimethylacetildenafil5010050100501005010050100501005010050100100250501005010037Dithio-desmethylcarbodenafil5010050100501005010050100501005010050100501005010010025038Oxohongdenafil5010050100501005010050100501005010050100501005010010025039N-Octylnortadalafil501005010050100501005010050100501005010050100501005010040Dioxohongdenafil501005010050100501005010050100501005010050100501005010041Hydroxythiovardenafil5010050100501005010050100501005010050100501005010010025042Cyclopentynafil501005010050100501005010050100501005010050100501005010043Propoxyphenyl thiohydroxyhomosildenafil5010050100501005010050100501005010050100501005010010025044Benzylsildenafil501005010050100501005010050100501005010050100501005010045Cinnamyldenafil501005010050100//50100501005010050100250750501005010046Lodenafil carbonate5010050100501005010050100501005010050100501005010010025047Propoxyphenylsildenafil501005010050100501005010050100501005010050100501005010048Depiperazinothiosildenafil5010050100501005010050100501005010050100501005010010025049Acetaminotadalafil5010050100501005010050100501005010050100501005010050100502-Hydroxypropylnortadalafil501005010050100501005010050100501005010050100501005010051Acetylvardenafil501005010050100501005010050100501005010010002500501005010052Propoxyphenyl hydroxyhomosildenafil50100501005010050100501005010050100501005010050100//53Propoxyphenyl thioaildenafil501005010050100501005010050100501005010050100501005010054Yohimbine501005010050100501005010050100501005010050100501005010055Dapoxetine501005010050100501005010050100501005010050100501005010056N-Desethylacetildenafil501005010050100501005010050100501005010025075050100//57Desmethylthiosildenafil501005010050100501005010050100501005010050100501005010058N-Boc-N-desethyl acetildenafil501005010050100//5010050100501005010050100501005010059N-Ethyltadalafil501005010050100501005010050100501005010050100501005010060O-Desethylsildenafil501005010050100501005010050100501005010050100501005010061Pyrazole N-desmethylsildenafil50100501005010050100501005010050100501005010050100//62Isobutylsildenafil501005010050100501005010050100501005010050100501005010063Sildenafil dimer impurity50100501005010050100501005010050100100250501005010010025064Vardenafil oxopiperazine501005010050100501005010050100501005010050100501005010065Sildenafil N-oxide501005010050100501005010050100501005010050100501005010066Vardenafil N-oxide5010050100501005010050100501005010050100501005010050100672-Hydroxyethylnortadalafil501005010050100501005010050100501005010050100501005010068Vardenafil acetyl analogue501005010050100////501005010050100100250501005010069Vardenafil dimer5010050100501005010050100501005010050100501005010010025070Mirodenafil501005010050100501005010050100501005010050100501005010071Mutaprodenafil501005010050100501005010050100501005010050100501005010072Thioquinapiperfil5010050100501005010050100501005010050100501005010010025073Aminosildenafil501005010050100501005010050100501005010050100501005010074Desethylcarbodenafil5010050100501005010050100501005010050100501005010010025075Didescarbonsildenafil501005010050100501005010050100501005010050100501005010076N-Phenylpropenyltadalafil501005010050100501005010050100501005010050100501005010077N-Desethyl-N-methylvardenafil501005010050100501005010050100501005010050100501005010078Thioaildenafil501005010050100501005010050100501005010050100501005010079Dichlorodenafil5010025050050100501005010050100501005010050100501005010080Piperazonifil501005010050100501005010050100501005010050100501005010081Propoxyphenyl thiosildenafil50100501005010050100501005010050100501002501000501005010082Propoxyphenyl thiohomosildenafil501005010050100501005010050100501005010050100501005010083Dithiodesethyl carbodenafil501005010050100501005010050100501005010025010005010010025084Hydroxythioacetildenafil501005010050100//5010050100501005010050100501005010085Tadalafil dichloro impurity501005010050100501005010050100501005010050100501005010086Sildenafil impurity 125010050100501005010050100501005010050100501005010010025087Demethylpiperaziny sildenafil sulfonic acid501005010050100501005010050100501005010050100501005010088Propoxyphenyl aildenafil501005010050100501005010050100501005010050100501005010089Sildenafil impurity 145010050100501005010050100501005010050100501005010010025090Propoxyphenylisobutyl aildenafil50100501005010050100501005010050100501005010050100100250 备注：1.针对胶囊基质中10、16、17、36、45、51、56、68、81、83号化合物，软胶囊基质中69、76、84号化合物，本方法适用于定性检测。如定量检测，需折算回收率进行测定。 2.本方法不适用于咖啡基质中9、10、17、45、56、68、84号化合物，软胶囊基质中68号化合物，牡蛎粉基质中52、56、61号化合物的检测。 附录D 超高效液相-三重四极杆串联质谱标准品 色谱图 图D. 90种那非物质标准品的提取离子色谱叠加图 附录E 超高效液相-串联高分辨质谱参考条件 离子源：电喷雾离子源（ESI） 扫描方式：正离子MS/MS模式 毛细管电压：正离子模式：5000V 离子源温度：325℃ 干燥气流量：12L/min 雾化气压力：50psi 鞘气温度：375℃；鞘气（N2）流量：12L/min 表E.1化合物英文名称、分子式、准分子离子、保留时间、碰撞电压及主要碎片离子 序号 英文名 分子式 准分子离子（m/z） 保留时间（min） 碰撞电压（V） 主要碎片离子（m/z） 1 Sildenafil C22H30N6O4S 475.2122 6.2 40 311.1503,283.1195,100.0995,99.0917,58.0651 2 Tadalafil C22H19N3O4 390.1448 7.5 20 268.1081,262.0862,250.0863,240.1131,169.0760,135.0441 3 Imidazosagatriazinone C17H20N4O2 313.1659 10.1 40 285.1346,256.0955,241.0720,166.0975,120.0444 4 Gendenafil C19H22N4O3 355.1765 8.7 40 327.1452,313.1659,298.1061,285.1346,256.0955,166.0975 5 Acetil acid C18H20N4O4 357.1557 7.5 40 329.1244,311.1139,300.0853,285.1346,256.0955,166.0975 6 Xanthoanthrafil C19H23N3O6 390.1660 7.7 10 151.0754,107.0491 7 Aminotadalafil C21H18N4O4 391.1401 6.9 20 269.1033,263.0941,262.0849,169.0760,135.0441 8 Chloropretadalafil C22H19ClN2O5 427.1055 9.6 20 334.1074,302.0812,274.0862,262.0862,135.0441 9 Piperiacetildenafil C24H31N5O3 438.2500 6.1 40 341.1608,325.1322,313.1295,297.1346,166.0975,98.0964 10 Noracetildenafil C24H32N6O3 453.2609 5.6 40 341.1608,325.1295,297.1346,166.0975,113.1073,70.0651 11 Carbodenafil C24H32N6O3 453.2609 5.3 20 339.1452,311.1139,166.0975,147.0077,113.1073 12 Pseudovardenafil C22H29N5O4S 460.2013 8.9 40 312.1581,299.1139,284.1268,256.0955,151.0866 13 Norneosildenafil C22H29N5O4S 460.2013 10.6 40 312.1581,299.1139,283.1195,256.0955,84.0808 14 N-Desethylvardenafil C21H28N6O4S 461.1966 5.4 40 331.0852,312.1581,299.1139,284.1268,151.0866 15 N-Desmethylsildenafil C21H28N6O4S 461.1966 6.1 40 377.1278,311.1503,299.1139,283.1195,85.0760 16 Acetildenafil C25H34N6O3 467.2765 5.8 40 341.1608,325.1322,297.1346,166.0975,127.1230,111.0917,84.0808 17 Hydroxyacetildenafil C25H34N6O4 483.2714 5.5 40 396.2030,341.1608,311.1430,297.1346,143.1179,127.0866,97.0760 18 Avanafil C23H26ClN7O3 484.1858 6.2 20 375.1205,357.1099,233.1020,221.1033,155.0258 19 Aildenafil C23H32N6O4S 489.2279 6.5 40 377.1271,311.1503,283.1195,113.1073,99.0917 20 Homosildenafil C23H32N6O4S 489.2279 6.4 40 311.1503,283.1195,113.1073,99.0917,72.0808 21 Vardenafil C23H32N6O4S 489.2279 5.5 40 376.1067,312.1581,299.1139,284.1268,151.0866,113.1073 22 Thiosildenafil C22H30N6O3S2 491.1894 8.2 40 341.1424,327.1274,299.0961,100.0995,99.0917,58.0651 23 Thiohomosildenafil C23H32N6O3S2 505.2050 8.4 40 355.1581,327.1274,299.0961,113.1073,99.0917,72.0808,58.0651 24 Hydroxyvardenafil C23H32N6O5S 505.2228 5.4 40 376.1054,312.1581,299.1139,151.0866,99.0917 25 Hydroxyhomosildenafil C23H32N6O5S 505.2228 6.1 40 487.2122,311.1503,283.1195,129.1022,99.0917 26 Udenafil C25H36N6O4S 517.2592 6.8 40 474.2170,325.1653,299.1139,283.1195,191.0849,112.1121,84.0808 27 Hydroxythiohomosildenafil C23H32N6O4S2 521.1999 8.0 40 503.1894,327.1274,299.0961,129.1022,99.0917 28 Norneovardenafil C18H20N4O4 357.1557 6.0 40 329.1244,300.0853,151.0866,123.0917 29 Nitrodenafil C17H19N5O4 358.1510 9.7 40 330.1197,284.1268,256.0955,136.0505 30 Nortadalafil C21H17N3O4 376.1292 7.1 20 302.0812,263.0901,262.0862,233.0835,254.0924,169.076,135.0441 31 Chlorodenafil C19H21ClN4O3 389.1375 9.5 40 361.1062,311.1139,285.1346,256.0968,166.0975 32 Hydroxychlorodenafil C19H23ClN4O3 391.1531 8.5 40 363.1219,313.1295,285.1346,256.0955,166.0975 33 N-Butyltadalafil C25H25N3O4 432.1918 9.3 40 310.1550,282.1601,262.0862,197.0709,169.07690,135.0441 34 Desmethylcarbodenafil C23H30N6O3 439.2452 5.2 40 339.1452,311.1139,283.1190,255.1240,166.0975 35 Descarbonsildenafil C21H30N6O4S 463.2122 5.8 40 418.1544,312.1542,311.1503,283.1183,72.0808,58.0651 36 Dimethylacetildenafil C25H34N6O3 467.2765 5.8 40 410.2187,353.1846,325.1587,297.1346,166.0975,127.1230 37 Dithio-desmethylcarbodenafil C23H30N6OS2 471.1995 8.4 20 414.1417,371.0995,343.0682 38 Oxohongdenafil C25H32N6O4 481.2558 6.3 40 410.2187,396.2030,325.1619,297.1346,72.0808 39 N-Octylnortadalafil C29H33N3O4 488.2544 11.8 20 366.2176,338.2200,262.0862,169.0760,135.0441 40 Dioxohongdenafil C25H30N6O5 495.2350 7.1 40 311.1139,166.0975,127.0866 41 Hydroxythiovardenafil C23H32N6O4S2 521.1999 6.9 40 328.1352,315.0910,299.0961,167.0638,129.1022,99.0917 42 Cyclopentynafil C26H36N6O4S 529.2592 7.0 40 461.1966,377.1278,311.1503,283.1195,112.1121,98.0964 43 Propoxyphenyl thiohydroxyhomosildenafil C24H34N6O4S2 535.2156 8.6 40 315.0910,299.0961,271.0985,129.1022,99.0917 44 Benzylsildenafil C28H34N6O4S 551.2435 7.7 40 459.1775,377.1271,312.1574,134.0964,91.0542 45 Cinnamyldenafil C32H38N6O3 555.3078 7.9 20 437.2296,355.1765,117.0699 46 Lodenafil carbonate C47H62N12O11S2 1035.4175 10.0 40 487.2109,112.0995 47 Propoxyphenylsildenafil C23H32N6O4S 489.2279 6.7 40 325.1659,299.1139,283.1195,100.0995,99.0917,58.0651 48 Depiperazinothiosildenafil C17H20N4O4S2 409.0999 5.6 40 381.0686,292.0387,212.0818,167.0638,99.0137 49 Acetaminotadalafil C23H20N4O5 433.1506 6.9 20 391.1401,311.1139,263.0914,262.0849,135.0441 50 2-Hydroxypropylnortadalafil C24H23N3O5 434.1710 7.2 20 312.1343,284.1393,262.0862,169.0760,135.0427 51 Acetylvardenafil C25H34N6O3 467.2765 5.0 40 396.2030,355.1765,341.1608,325.1295,297.1346,151.0866,127.1230, 111.0917 52 Propoxyphenyl hydroxyhomosildenafil C24H34N6O5S 519.2384 6.6 40 501.2279,325.1619,299.1152,283.1195,129.1022,99.0917 53 Propoxyphenyl thioaildenafil C24H34N6O3S2 519.2207 9.3 40 341.1424,315.0910,299.0955,113.1073,99.0917,71.0730 54 Yohimbine C21H26N2O3 355.2016 4.9 20 294.1489,224.1281,212.1281,194.1176,144.0808 55 Dapoxetine C21H23NO 306.1852 7.7 10 261.1274,233.0961,183.0804,157.1648,117.0699 56 N-Desethylacetildenafil C23H30N6O3 439.2452 5.3 40 353.1608,341.1608,325.1295,311.1430,297.1346,166.0975,99.0917 57 Desmethylthiosildenafil C21H28N6O3S2 477.1737 8.1 40 393.1016,327.1274,299.0961,271.0985,85.0760 58 N-Boc-N-desethyl acetildenafil C28H38N6O5 539.2976 7.5 40 439.2452,353.1568,339.1816,297.1346,99.0917 59 N-Ethyltadalafil C23H21N3O4 404.1605 8.0 10 282.1237,262.0862,250.0822,135.0441 60 O-Desethylsildenafil C20H26N6O4S 447.1809 6.4 20 347.0808,299.1139,283.1195,101.1073,99.0917 61 Pyrazole N-desmethylsildenafil C21H28N6O4S 461.1966 5.2 40 297.1139,269.1027,100.0995,99.0917,58.0651 62 Isobutylsildenafil C23H32N6O4S 489.2279 6.7 40 325.1653,297.1339,100.0995,99.0917,58.0651 63 Sildenafil dimer impurity C38H46N10O8S2 835.3014 11.1 80 312.1581,299.1139,283.1195,255.1202,166.0975,85.0760 64 Vardenafil oxopiperazine C21H26N6O5S 475.1758 6.0 40 312.1581,299.1139,284.1268,151.0866 65 Sildenafil N-oxide C22H30N6O5S 491.2071 6.4 40 404.1387,312.1554,311.1503,283.1195,99.0917 66 Vardenafil N-oxide C23H32N6O5S 505.2228 5.7 20 477.1915,377.1271,312.1581,151.0866,113.1271 67 2-Hydroxyethylnortadalafil C23H21N3O5 420.1554 6.9 40 298.1186,270.1237,262.0862,197.0709,169.076,135.0441 68 Vardenafil acetyl analogue C24H31N5O3 438.2500 5.2 40 341.1608,325.1295,297.1346,151.0866,98.0964 69 Vardenafil dimer C38H46N10O8S2 835.3014 9.3 80 312.1581,299.1134,284.1268,283.1195,151.0866 70 Mirodenafil C26H37N5O5S 532.2588 7.6 40 404.1632,312.1336,296.1387,129.1022,99.0917 71 Mutaprodenafil C27H35N9O5S2 630.2275 7.8 20 487.2109,377.1267,312.1574,142.0070,113.1073 72 Thioquinapiperfil C24H28N6OS 449.2118 5.7 20 258.0808,204.1383,186.1277 73 Aminosildenafil C18H23N5O4S 406.1544 7.6 40 364.1074,299.1139,283.1195,256.0968,255.1214,166.0975 74 Desethylcarbodenafil C22H28N6O3 425.2296 5.1 20 339.1452,311.1139,166.0975 75 Didescarbonsildenafil C20H28N6O4S 449.1966 5.6 40 312.1542,311.1503,299.1139,283.1195,166.0975,58.0651 76 N-Phenylpropenyltadalafil C30H24N4O4 505.1870 10.0 20 383.1502,262.0849,250.0849,159.0917,135.0441 77 N-Desethyl-N-methylvardenafil C22H30N6O4S 475.2122 5.4 40 376.1067,312.1581,299.1139,284.1268,151.0866 78 Thioaildenafil C23H32N6O3S2 505.2050 8.6 40 327.1274,315.0910,299.0961,113.1073,99.0917,71.0730 79 Dichlorodenafil C19H20Cl2N4O2 407.1036 12.4 40 379.0723,363.0410,350.0332,343.0956,280.0955,166.0975,136.0505 80 Piperazonifil C25H34N6O4 483.2714 5.5 40 465.2609,436.2231,297.1346,203.1179,166.0975,127.0866 81 Propoxyphenyl thiosildenafil C23H32N6O3S2 505.2050 8.8 40 355.1553,341.1431,329.1033,315.0910,313.1118,299.0961,271.1012,99.0917,58.0651 82 Propoxyphenyl thiohomosildenafil C24H34N6O3S2 519.2207 9.0 40 327.1274,315.0910,299.0961,113.1073,99.0917,72.0808,58.0651 83 Dithiodesethyl carbodenafil C22H28N6OS2 457.1839 8.2 20 371.0995,343.0682 84 Hydroxythioacetildenafil C25H34N6O3S 499.2486 8.1 40 341.1174,327.1240,313.1112,143.1173,127.0862 85 Tadalafil dichloro impurity C22H18Cl2N2O5 461.0666 10.4 20 349.1183,334.1074,302.0812,274.0862,263.0914,262.0862,135.0441 86 Sildenafil impurity 12 C25H34N6OS2 499.2308 8.8 20 468.1886,428.1573,371.0995,343.0682,72.0808 87 Demethylpiperaziny sildenafil sulfonic acid C17H20N4O5S 393.1227 5.0 40 365.0914,336.0523,285.1319,269.1006,256.0955,166.0975,136.0505 88 Propoxyphenyl aildenafil C24H34N6O4S 503.2435 7.1 40 325.1653,299.1139,283.1195,115.1230,113.1073,99.0917,71.0730 89 Sildenafil impurity 14 C24H32N6OS2 485.2152 8.7 20 468.1886,428.1573,371.0995,343.0682 90 Propoxyphenylisobutyl aildenafil C25H36N6O4S 517.2592 7.6 40 339.1809,313.1295,297.1339,113.1073,99.0917,71.0730 注：可根据实际情况，选择响应信号强且碎片离子稳定且丰富的准分子离子进行检测。 附录F 超高效液相-串联高分辨质谱检出限 表F.1 90种那非类物质在11种基质中的检出限 序号英文名片剂饮料糖果咖啡软胶囊果冻蛋白粉酒胶囊饼干牡蛎粉检出限（mg/kg）检出限（mg/L）检出限（mg/kg）检出限（mg/kg）检出限（mg/kg）检出限（mg/kg）检出限（mg/kg）检出限（mg/L）检出限（mg/kg）检出限（mg/kg）检出限（mg/kg）1Sildenafil2.02.02.04.02.04.02.02.08.02.05.02Tadalafil10.010.010.040.010.010.010.010.040.010.010.03Imidazosagatriazinone0.10.10.22.00.10.10.10.20.50.10.14Gendenafil2.00.50.52.00.50.50.50.50.50.52.55Acetil acid2.02.02.04.02.02.02.02.02.02.05.06Xanthoanthrafil4.04.04.08.04.04.04.04.04.04.01.07Aminotadalafil20.020.020.040.020.020.020.020.020.020.010.08Chloropretadalafil6.06.06.06.06.06.06.06.06.06.01.09Piperiacetildenafil0.10.10.240.00.50.10.20.140.00.10.510Noracetildenafil0.50.55.040.00.52.00.50.540.00.10.511Carbodenafil2.00.55.02.00.50.50.50.52.00.50.512Pseudovardenafil0.50.10.24.00.10.10.20.14.00.10.513Norneosildenafil0.50.54.00.54.04.04.04.04.00.52.514N-Desethylvardenafil0.20.55.010.05.01.00.50.510.00.21.015N-Desmethylsildenafil0.52.02.02.02.02.00.52.010.00.50.516Acetildenafil0.50.51.040.01.00.50.50.540.00.50.117Hydroxyacetildenafil0.50.55.040.02.01.00.50.540.00.52.518Avanafil0.10.10.12.00.10.10.10.11.00.10.519Aildenafil0.50.20.22.00.50.20.50.22.00.52.020Homosildenafil1.01.02.05.02.05.00.50.52.02.010.021Vardenafil0.50.55.010.010.00.50.52.02.00.52.522Thiosildenafil10.010.010.010.010.010.010.010.010.010.010.023Thiohomosildenafil4.04.04.04.04.04.04.04.010.04.05.024Hydroxyvardenafil0.50.52.02.02.04.00.52.02.00.52.525Hydroxyhomosildenafil2.010.010.010.02.02.010.02.04.02.01.026Udenafil0.10.20.22.50.10.20.20.10.50.21.027Hydroxythiohomosildenafil5.05.05.05.05.05.05.05.05.05.05.028Norneovardenafil0.10.10.12.50.10.10.10.10.50.12.529Nitrodenafil2.02.02.04.02.02.02.02.02.02.00.530Nortadalafil20.020.020.040.020.020.020.020.040.020.010.031Chlorodenafil1.01.01.02.04.04.04.01.01.01.05.032Hydroxychlorodenafil1.01.01.02.01.01.01.01.04.01.05.033N-Butyltadalafil5.05.05.05.05.05.05.05.05.05.05.034Desmethylcarbodenafil0.40.42.02.00.40.42.00.44.02.05.035Descarbonsildenafil0.50.50.52.51.01.00.50.50.51.02.536Dimethylacetildenafil2.00.50.54.02.02.02.02.020.00.15.037Dithio-desmethylcarbodenafil8.08.08.08.08.08.08.08.020.08.010.038Oxohongdenafil2.01.02.010.02.02.02.02.02.02.00.539N-Octylnortadalafil4.04.04.04.04.04.04.04.04.04.05.040Dioxohongdenafil0.52.00.52.02.00.50.52.02.02.02.541Hydroxythiovardenafil2.02.02.02.04.02.02.02.02.02.00.542Cyclopentynafil0.10.20.22.50.50.20.10.210.00.51.043Propoxyphenyl thiohydroxyhomosildenafil4.04.020.040.020.020.020.020.020.020.020.044Benzylsildenafil1.01.04.02.01.01.01.01.01.01.00.145Cinnamyldenafil0.50.50.240.01.01.00.20.140.00.50.146Lodenafil carbonate50.050.050.050.050.050.050.050.050.050.050.047Propoxyphenylsildenafil2.02.02.02.02.02.02.02.02.02.02.048Depiperazinothiosildenafil1.01.04.020.04.04.04.04.050.04.05.049Acetaminotadalafil8.08.08.08.08.08.08.08.032.08.010.0502-Hydroxypropylnortadalafil6.06.06.040.06.06.06.06.06.06.01.051Acetylvardenafil8.08.08.020.08.08.08.08.010.08.010.052Propoxyphenyl hydroxyhomosildenafil2.02.05.02.52.02.02.02.010.02.00.553Propoxyphenyl thioaildenafil5.05.05.05.05.05.05.05.05.05.05.054Yohimbine0.20.10.12.50.10.10.10.10.50.10.555Dapoxetine0.50.10.12.50.10.10.20.10.50.10.156N-Desethylacetildenafil5.01.04.010.04.01.01.01.040.00.51.057Desmethylthiosildenafil20.020.020.020.020.04.020.020.040.020.05.058N-Boc-N-desethyl acetildenafil1.01.04.040.02.02.01.01.040.04.00.559N-Ethyltadalafil5.05.05.020.05.05.020.05.020.05.05.060O-Desethylsildenafil20.01.020.020.01.01.01.01.020.01.010.061Pyrazole N-desmethylsildenafil1.01.04.02.04.01.04.01.04.01.00.562Isobutylsildenafil0.40.40.48.02.00.40.40.40.50.40.563Sildenafil dimer impurity8.08.08.08.08.08.08.08.08.08.010.064Vardenafil oxopiperazine0.51.00.52.51.00.50.50.510.00.52.565Sildenafil N-oxide0.20.80.84.00.81.00.20.84.00.81.066Vardenafil N-oxide0.20.55.010.02.02.00.20.21.00.21.0672-Hydroxyethylnortadalafil6.024.024.040.06.024.06.06.040.06.01.068Vardenafil acetyl analogue3.03.05.070.020.05.03.03.040.03.00.569Vardenafil dimer1.01.01.060.01.01.01.04.01.01.01.070Mirodenafil2.02.02.02.02.02.02.02.02.02.00.571Mutaprodenafil3.03.03.03.03.03.03.03.03.03.00.572Thioquinapiperfil8.04.04.08.04.04.04.08.04.04.05.073Aminosildenafil2.02.02.02.02.02.02.02.05.02.05.074Desethylcarbodenafil3.03.05.012.04.03.03.03.012.03.00.575Didescarbonsildenafil2.02.02.02.02.02.02.02.010.02.00.576N-Phenylpropenyltadalafil4.04.04.04.04.04.04.04.05.04.00.577N-Desethyl-N-methylvardenafil0.50.50.56.00.54.00.51.01.00.50.178Thioaildenafil8.04.08.04.08.02.02.02.08.08.05.079Dichlorodenafil2.00.40.42.02.02.02.00.45.00.42.580Piperazonifil2.02.02.04.02.02.02.02.010.02.02.581Propoxyphenyl thiosildenafil4.04.04.04.04.04.04.04.04.04.05.082Propoxyphenyl thiohomosildenafil8.04.08.08.08.08.08.08.08.08.05.083Dithiodesethyl carbodenafil8.04.08.08.08.08.08.08.08.08.05.084Hydroxythioacetildenafil2.02.02.04.02.02.02.02.08.02.02.585Tadalafil dichloro impurity20.020.020.020.020.020.020.020.020.020.05.086Sildenafil impurity 1210.010.010.010.010.010.010.010.010.010.010.087Demethylpiperaziny sildenafil sulfonic acid5.05.05.020.05.05.020.05.020.05.010.088Propoxyphenyl aildenafil0.50.42.00.80.40.40.40.41.00.42.589Sildenafil impurity 144.04.04.04.04.04.04.04.020.04.01.090Propoxyphenylisobutyl aildenafil1.01.01.02.01.01.01.01.01.01.00.5附录G 超高效液相-串联高分辨质谱标准色谱图 图G. 90种那非标准品的提取离子色谱叠加图 本方法负责起草单位：中国食品药品检定研究院、上海市食品药品检验所。 方法验证单位：四川省食品药品检验检测院、广东省食品检验所、中国肉类食品综合研究中心、广西-东盟食品药品安全检验检测中心、山西省食品药品检验所。 方法一主要起草人：金绍明、宁霄、高文超、曹进、李道霞、陈煜。 方法二主要起草人：胡青、于泓、孙健、张颖颖、王立亚、韦环。 —— PAGE \* MERGEFORMAT2 — — PAGE \* MERGEFORMAT1 —— —— PAGE \* MERGEFORMAT18 — — PAGE \* MERGEFORMAT33 —— —— PAGE \* MERGEFORMAT34 — — PAGE \* MERGEFORMAT34 ——

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Publisher	市场监管总局
Site	samr
Date	2024-05-07
CMS Category	总局文件
Keywords	食品,市场,总局,中,发布

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unkn 食品补充检验方法工作规定	named

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