色谱 ›› 2022, Vol. 40 ›› Issue (9): 797-809.DOI: 10.3724/SP.J.1123.2022.03003
周智明*(), 李静, 陈张好, 伍英英, 陆土柳, 肖树雄
收稿日期:
2022-03-03
出版日期:
2022-09-08
发布日期:
2022-09-26
通讯作者:
周智明
基金资助:
ZHOU Zhiming*(), LI Jing, CHEN Zhanghao, WU Yingying, LU Tuliu, XIAO Shuxiong
Received:
2022-03-03
Online:
2022-09-08
Published:
2022-09-26
Contact:
ZHOU Zhiming
Supported by:
摘要:
染发类产品中氧化型染料种类多,实际样品测定时干扰多,建立染发类产品中多种常用染料的测定方法,为该类产品的有效监管提供技术手段十分必要。该研究根据染料使用频率分组,采用能够屏蔽硅羟基和金属离子影响的C18柱,优化了《化妆品安全技术规范》(2015年版)中32种染料的高效液相色谱法(HPLC)并建立了高效液相色谱-串联质谱(HPLC-MS/MS)确证方法。样品以10 g/L亚硫酸氢钠水溶液为抗氧化剂,用无水乙醇-水(1∶1, v/v)混合溶液冰浴超声提取10 min。HPLC方法采用甲醇、乙腈和磷酸盐缓冲液为流动相分两个液相色谱条件进行梯度洗脱分离,于280 nm波长下检测,其中一个HPLC条件中的相互干扰组分均在另一个HPLC条件下完全分离,避免了实际样品检测时组分间的干扰,并排除了32种以外的其他15种常用染料的干扰。HPLC-MS/MS方法分别采用5 mmol/L乙酸铵水溶液-乙腈和5 mmol/L乙酸水溶液-乙腈为正离子和负离子模式下的流动相,电喷雾离子模式下用多反应监测(MRM)模式进行定性和定量分析。HPLC和HPLC-MS/MS两个方法中,日内精密度和48 h内稳定性的相对标准偏差(RSD)<10%,回收率为82.6%~114.9%(RSD<10%)。HPLC方法中32种染料在大约10~500 mg/L范围内线性关系良好(r2>0.99),检出限为9.7~40.1 μg/g; HPLC-MS/MS方法中氢醌线性范围为2.0~79.7 mg/L,检出限为8.0 μg/g,其他组分线性范围约为0.1~4 mg/L,检出限为0.01~0.4 μg/g。采用HPLC、HPLC-MS/MS两个方法和《化妆品安全技术规范》方法同时测定实际样品,共检出16种染料,检出含量范围为58~25160 μg/g。3个方法检测结果的RSD为1.9%~10.1%。该研究增加了HPLC-MS/MS确证方法,适应化妆品法定检验中的未知物确认程序;方法简便快速,结果准确,专属性强,具有较好的通用性和可操作性。
中图分类号:
周智明, 李静, 陈张好, 伍英英, 陆土柳, 肖树雄. 32种氧化型染料的高效液相色谱定量及高效液相色谱-串联质谱确证方法[J]. 色谱, 2022, 40(9): 797-809.
ZHOU Zhiming, LI Jing, CHEN Zhanghao, WU Yingying, LU Tuliu, XIAO Shuxiong. Determination of 32 oxidative dyes by high performance liquid chromatography and confirmation by high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(9): 797-809.
HPLC condition 1 | HPLC condition 2 | HPLC-MS/MS condition | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Time/min | φ(A)/% | φ(B)/% | φ(C)/% | Time/min | φ(A)/% | φ(B)/% | Time/min | φ(D)/% | φ(C)/% | |||
0 | 96 | 2 | 2 | 0 | 92 | 8 | 0 | 95 | 5 | |||
15 | 96 | 2 | 2 | 8 | 92 | 8 | 4 | 95 | 5 | |||
22 | 90 | 5 | 5 | 35 | 50 | 50 | 11 | 80 | 20 | |||
35 | 50 | 10 | 40 | 45 | 50 | 50 | 16 | 30 | 70 | |||
50 | 50 | 10 | 40 | 45.1 | 92 | 8 | 17 | 5 | 95 | |||
50.1 | 96 | 2 | 2 | 50 | 92 | 8 | 19 | 5 | 95 | |||
55 | 96 | 2 | 2 | 19.1 | 95 | 5 |
表 1 32种染料的HPLC及HPLC-MS/MS流动相梯度条件
Table 1 Mobile phase gradient conditions of HPLC and HPLC-MS/MS for the 32 dyes
HPLC condition 1 | HPLC condition 2 | HPLC-MS/MS condition | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Time/min | φ(A)/% | φ(B)/% | φ(C)/% | Time/min | φ(A)/% | φ(B)/% | Time/min | φ(D)/% | φ(C)/% | |||
0 | 96 | 2 | 2 | 0 | 92 | 8 | 0 | 95 | 5 | |||
15 | 96 | 2 | 2 | 8 | 92 | 8 | 4 | 95 | 5 | |||
22 | 90 | 5 | 5 | 35 | 50 | 50 | 11 | 80 | 20 | |||
35 | 50 | 10 | 40 | 45 | 50 | 50 | 16 | 30 | 70 | |||
50 | 50 | 10 | 40 | 45.1 | 92 | 8 | 17 | 5 | 95 | |||
50.1 | 96 | 2 | 2 | 50 | 92 | 8 | 19 | 5 | 95 | |||
55 | 96 | 2 | 2 | 19.1 | 95 | 5 |
Dye No. | Dye | Ionization mode | Parent ion (m/z) | Daughter ion (m/z) (collision energy/eV) | tR/min |
---|---|---|---|---|---|
1 | p-phenylenediamine | + | 109.2 | 65.2 (31) | 2.7 |
(p-苯二胺) | 92.1 (26) | ||||
2 | p-aminophenol | + | 110.0 | 65.1 (28) | 3.7 |
(p-氨基苯酚) | 93.0 (38) | ||||
3 | toluene-2,5-diamine sulfate | + | 123.1 | 108.2 (24) | 9.9 |
(甲苯-2,5-二胺硫酸盐) | 77.1 (40) | ||||
4 | m-aminophenol | + | 109.9 | 65.1 (28) | 6.3 |
(m-氨基苯酚) | 92.9 (22) | ||||
5 | o-phenylenediamine | + | 109.0 | 65.2 (33) | 8.0 |
(o-苯二胺) | 92.1 (22) | ||||
6 | 2-chloro-p-phenylenediamine sulfate | + | 143.1 | 108.1 (25) | 9.6 |
(2-氯-p-苯二胺硫酸盐) | 80.1 (36) | ||||
7 | o-aminophenol | + | 110.0 | 65.1 (30) | 9.1 |
(o-氨基苯酚) | 92.1 (22) | ||||
8 | resorcinol | - | 109.1 | 65.0 (17) | 8.9 |
(间苯二酚) | 41.0 (23) | ||||
9 | 2-nitro-p-phenylenediamine | + | 154.0 | 119.1 (22) | 11.0 |
(2-硝基-p-苯二胺) | 135.8 (13) | ||||
10 | toluene-3,4-diamine | + | 123.0 | 77.1 (37) | 13.6 |
(甲苯-3,4-二胺) | 106.0 (22) | ||||
11 | 4-amino-2-hydroxytoluene | + | 124.0 | 109.0 (26) | 13.2 |
(4-氨基-2-羟基甲苯) | 77.1 (35) | ||||
12 | 2-methylresorcinol | - | 123.0 | 55.0 (34) | 10.6 |
(2-甲基雷琐辛) | 79.0 (17) | ||||
13 | 6-amino-m-cresol | + | 124.1 | 106.0 (30) | 14.2 |
(6-氨基-m-甲酚) | 77.1 (36) | ||||
14 | pyrazolone methyl pyrazolone | + | 175.2 | 133.0 (26) | 14.7 |
(苯基甲基吡唑啉酮) | 65.0 (46) | ||||
15 | N,N-diethyltoluene-2,5-diamine hydrochloride | + | 179.1 | 150.0 (23) | 15.2 |
(N,N-二乙基甲苯-2,5-二胺盐酸盐) | 135.1 (36) | ||||
16 | 4-amino-3-nitrophenol | - | 153.2 | 123.0 (14) | 14.1 |
(4-氨基-3-硝基苯酚) | 122.0 (25) | ||||
17 | m-phenylenediamine | + | 109.2 | 65.2 (31) | 4.6 |
(m-苯二胺) | 92.1 (22) | ||||
18 | 2,4-diaminophenoxy ethanol hydrochloride | + | 169.1 | 124.1 (25) | 6.2 |
(2,4-二氨基苯氧基乙醇盐酸盐) | 108.0 (27) | ||||
19 | hydroquinone | - | 109.0 | 108.0 (21) | 5.2 |
(氢醌) | 81.0 (16) | ||||
20 | 4-amino-m-cresol | + | 124.0 | 109.2 (31) | 7.4 |
(4-氨基-m-甲酚) | 77.2 (35) | ||||
21 | 2-amino-3-hydroxypyridine | + | 111.1 | 94.0 (25) | 2.7 |
(2-氨基-3-羟基吡啶) | 66.2 (39) | ||||
22 | N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate | + | 197.1 | 121.1 (36) | 9.4 |
(N,N-双(2-羟乙基)-p-苯二胺硫酸盐) | 152.2 (22) | ||||
23 | p-methylaminophenol sulfate | + | 124.0 | 77.1 (43) | 9.9 |
(p-甲基氨基苯酚硫酸盐) | 109.1 (31) | ||||
24 | 4-nitro-o-phenylenediamine | + | 154.0 | 137.0 (19) | 13.6 |
(4-硝基-o-苯二胺) | 107.0 (28) | ||||
Dye No. | Dye | Ionization mode | Parent ion (m/z) | Daughter ion (m/z) (collision energy/eV) | tR/min |
25 | 2,6-diaminopyridine | + | 110.0 | 66.1 (33) | 4.6 |
(2,6-二氨基吡啶) | 93.0 (30) | ||||
26 | N,N-diethyl-p-phenylenediamine sulfate | + | 165.1 | 121.0 (21) | 14.3 |
(N,N-二乙基-p-苯二胺硫酸盐) | 136.2 (28) | ||||
27 | 6-hydroxyindole | + | 134.0 | 107.1 (28) | 15.7 |
(6-羟基吲哚) | 77.1 (42) | ||||
28 | 4-chlororesorcinol | - | 143.2 | 79.0 (19) | 15.3 |
(4-氯雷琐辛) | 107.0 (16) | ||||
29 | 2,7-naphthalenediol | - | 159.1 | 130.0 (33) | 15.9 |
(2,7-萘二酚) | 102.2 (33) | ||||
30 | N-phenyl-p-phenylenediamine | + | 185.1 | 93.1 (29) | 17.4 |
(N-苯基-p-苯二胺) | 108.1 (31) | ||||
31 | 1,5-naphthalenediol | - | 159.1 | 115.1 (25) | 15.8 |
(1,5-萘二酚) | 131.0 (27) | ||||
32 | 1-naphthol | - | 143.1 | 115.1 (34) | 17.8 |
(1-萘酚) | 41.0 (49) |
表 2 32种染料的电离模式、母离子、子离子、碰撞能及保留时间
Table 2 Ionization modes, parent ions, daughter ions, collision energies, and retention times (tR) of the 32 dyes
Dye No. | Dye | Ionization mode | Parent ion (m/z) | Daughter ion (m/z) (collision energy/eV) | tR/min |
---|---|---|---|---|---|
1 | p-phenylenediamine | + | 109.2 | 65.2 (31) | 2.7 |
(p-苯二胺) | 92.1 (26) | ||||
2 | p-aminophenol | + | 110.0 | 65.1 (28) | 3.7 |
(p-氨基苯酚) | 93.0 (38) | ||||
3 | toluene-2,5-diamine sulfate | + | 123.1 | 108.2 (24) | 9.9 |
(甲苯-2,5-二胺硫酸盐) | 77.1 (40) | ||||
4 | m-aminophenol | + | 109.9 | 65.1 (28) | 6.3 |
(m-氨基苯酚) | 92.9 (22) | ||||
5 | o-phenylenediamine | + | 109.0 | 65.2 (33) | 8.0 |
(o-苯二胺) | 92.1 (22) | ||||
6 | 2-chloro-p-phenylenediamine sulfate | + | 143.1 | 108.1 (25) | 9.6 |
(2-氯-p-苯二胺硫酸盐) | 80.1 (36) | ||||
7 | o-aminophenol | + | 110.0 | 65.1 (30) | 9.1 |
(o-氨基苯酚) | 92.1 (22) | ||||
8 | resorcinol | - | 109.1 | 65.0 (17) | 8.9 |
(间苯二酚) | 41.0 (23) | ||||
9 | 2-nitro-p-phenylenediamine | + | 154.0 | 119.1 (22) | 11.0 |
(2-硝基-p-苯二胺) | 135.8 (13) | ||||
10 | toluene-3,4-diamine | + | 123.0 | 77.1 (37) | 13.6 |
(甲苯-3,4-二胺) | 106.0 (22) | ||||
11 | 4-amino-2-hydroxytoluene | + | 124.0 | 109.0 (26) | 13.2 |
(4-氨基-2-羟基甲苯) | 77.1 (35) | ||||
12 | 2-methylresorcinol | - | 123.0 | 55.0 (34) | 10.6 |
(2-甲基雷琐辛) | 79.0 (17) | ||||
13 | 6-amino-m-cresol | + | 124.1 | 106.0 (30) | 14.2 |
(6-氨基-m-甲酚) | 77.1 (36) | ||||
14 | pyrazolone methyl pyrazolone | + | 175.2 | 133.0 (26) | 14.7 |
(苯基甲基吡唑啉酮) | 65.0 (46) | ||||
15 | N,N-diethyltoluene-2,5-diamine hydrochloride | + | 179.1 | 150.0 (23) | 15.2 |
(N,N-二乙基甲苯-2,5-二胺盐酸盐) | 135.1 (36) | ||||
16 | 4-amino-3-nitrophenol | - | 153.2 | 123.0 (14) | 14.1 |
(4-氨基-3-硝基苯酚) | 122.0 (25) | ||||
17 | m-phenylenediamine | + | 109.2 | 65.2 (31) | 4.6 |
(m-苯二胺) | 92.1 (22) | ||||
18 | 2,4-diaminophenoxy ethanol hydrochloride | + | 169.1 | 124.1 (25) | 6.2 |
(2,4-二氨基苯氧基乙醇盐酸盐) | 108.0 (27) | ||||
19 | hydroquinone | - | 109.0 | 108.0 (21) | 5.2 |
(氢醌) | 81.0 (16) | ||||
20 | 4-amino-m-cresol | + | 124.0 | 109.2 (31) | 7.4 |
(4-氨基-m-甲酚) | 77.2 (35) | ||||
21 | 2-amino-3-hydroxypyridine | + | 111.1 | 94.0 (25) | 2.7 |
(2-氨基-3-羟基吡啶) | 66.2 (39) | ||||
22 | N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate | + | 197.1 | 121.1 (36) | 9.4 |
(N,N-双(2-羟乙基)-p-苯二胺硫酸盐) | 152.2 (22) | ||||
23 | p-methylaminophenol sulfate | + | 124.0 | 77.1 (43) | 9.9 |
(p-甲基氨基苯酚硫酸盐) | 109.1 (31) | ||||
24 | 4-nitro-o-phenylenediamine | + | 154.0 | 137.0 (19) | 13.6 |
(4-硝基-o-苯二胺) | 107.0 (28) | ||||
Dye No. | Dye | Ionization mode | Parent ion (m/z) | Daughter ion (m/z) (collision energy/eV) | tR/min |
25 | 2,6-diaminopyridine | + | 110.0 | 66.1 (33) | 4.6 |
(2,6-二氨基吡啶) | 93.0 (30) | ||||
26 | N,N-diethyl-p-phenylenediamine sulfate | + | 165.1 | 121.0 (21) | 14.3 |
(N,N-二乙基-p-苯二胺硫酸盐) | 136.2 (28) | ||||
27 | 6-hydroxyindole | + | 134.0 | 107.1 (28) | 15.7 |
(6-羟基吲哚) | 77.1 (42) | ||||
28 | 4-chlororesorcinol | - | 143.2 | 79.0 (19) | 15.3 |
(4-氯雷琐辛) | 107.0 (16) | ||||
29 | 2,7-naphthalenediol | - | 159.1 | 130.0 (33) | 15.9 |
(2,7-萘二酚) | 102.2 (33) | ||||
30 | N-phenyl-p-phenylenediamine | + | 185.1 | 93.1 (29) | 17.4 |
(N-苯基-p-苯二胺) | 108.1 (31) | ||||
31 | 1,5-naphthalenediol | - | 159.1 | 115.1 (25) | 15.8 |
(1,5-萘二酚) | 131.0 (27) | ||||
32 | 1-naphthol | - | 143.1 | 115.1 (34) | 17.8 |
(1-萘酚) | 41.0 (49) |
Dye No. | Frequency of dye use/% | Group | Dye No. | Frequency of dye use/% | Group | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Register samples | Supervise sampling samples | Ref. [ | Ref. [ | Ref. [ | Register samples | Supervise sampling samples | Ref. [ | Ref. [ | Ref. [ | ||||
1 | 37.4 | 71.1 | 37.4 | 78.3 | 59.8 | Ⅰ | 17 | - | 0.3 | - | - | - | Ⅱ |
2 | 54.9 | 36.5 | 33.0 | 64.0 | 59.8 | Ⅰ | 18 | 18.7 | 32.2 | 28.6 | 3.9 | 13.4 | Ⅰ |
3 | 29.7 | 25.0 | 32.0 | 44.8 | 36.6 | Ⅰ | 19 | - | - | - | - | - | Ⅱ |
4 | 45.1 | 70.9 | 39.9 | 54.2 | 56.1 | Ⅰ | 20 | 3.3 | 5.0 | 12.3 | 5.4 | 8.5 | Ⅰ |
5 | - | - | - | - | - | Ⅱ | 21 | - | 7.0 | 10.3 | - | 7.3 | Ⅰ |
6 | 5.5 | 0.3 | - | - | - | Ⅰ | 22 | 8.8 | 10.2 | 14.3 | - | 8.5 | Ⅰ |
7 | - | 4.4 | - | 10.8 | 2.4 | Ⅱ | 23 | - | 1.0 | - | - | 1.2 | Ⅱ |
8 | 45.1 | 77.3 | 52.2 | 84.2 | 52.4 | Ⅰ | 24 | - | 0.2 | - | 4.4 | 1.2 | Ⅱ |
9 | - | 0.1 | - | - | - | Ⅰ | 25 | - | 1.0 | - | - | - | Ⅰ |
10 | - | 0.1 | - | - | - | Ⅱ | 26 | - | 0.1 | - | - | - | Ⅱ |
11 | 59.3 | 29.5 | 43.3 | 25.1 | 42.7 | Ⅰ | 27 | - | 1.5 | - | - | - | Ⅰ |
12 | 24.2 | 8.5 | 19.7 | 6.4 | 8.5 | Ⅰ | 28 | - | 6.8 | - | - | 2.4 | Ⅰ |
13 | 3.3 | 0.1 | - | - | 1.2 | Ⅱ | 29 | - | 0.1 | - | - | - | Ⅱ |
14 | 27.5 | 19.2 | 10.8 | - | 1.2 | Ⅰ | 30 | - | - | - | - | - | Ⅱ |
15 | - | 0.1 | - | - | - | Ⅱ | 31 | - | 3.6 | - | - | - | Ⅰ |
16 | 3.3 | 0.1 | - | - | - | Ⅰ | 32 | 15.4 | 10.5 | 10.8 | 3.9 | 6.1 | Ⅰ |
表 3 32种染料的使用频率及分组
Table 3 Application frequency and grouping of the 32 dyes
Dye No. | Frequency of dye use/% | Group | Dye No. | Frequency of dye use/% | Group | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Register samples | Supervise sampling samples | Ref. [ | Ref. [ | Ref. [ | Register samples | Supervise sampling samples | Ref. [ | Ref. [ | Ref. [ | ||||
1 | 37.4 | 71.1 | 37.4 | 78.3 | 59.8 | Ⅰ | 17 | - | 0.3 | - | - | - | Ⅱ |
2 | 54.9 | 36.5 | 33.0 | 64.0 | 59.8 | Ⅰ | 18 | 18.7 | 32.2 | 28.6 | 3.9 | 13.4 | Ⅰ |
3 | 29.7 | 25.0 | 32.0 | 44.8 | 36.6 | Ⅰ | 19 | - | - | - | - | - | Ⅱ |
4 | 45.1 | 70.9 | 39.9 | 54.2 | 56.1 | Ⅰ | 20 | 3.3 | 5.0 | 12.3 | 5.4 | 8.5 | Ⅰ |
5 | - | - | - | - | - | Ⅱ | 21 | - | 7.0 | 10.3 | - | 7.3 | Ⅰ |
6 | 5.5 | 0.3 | - | - | - | Ⅰ | 22 | 8.8 | 10.2 | 14.3 | - | 8.5 | Ⅰ |
7 | - | 4.4 | - | 10.8 | 2.4 | Ⅱ | 23 | - | 1.0 | - | - | 1.2 | Ⅱ |
8 | 45.1 | 77.3 | 52.2 | 84.2 | 52.4 | Ⅰ | 24 | - | 0.2 | - | 4.4 | 1.2 | Ⅱ |
9 | - | 0.1 | - | - | - | Ⅰ | 25 | - | 1.0 | - | - | - | Ⅰ |
10 | - | 0.1 | - | - | - | Ⅱ | 26 | - | 0.1 | - | - | - | Ⅱ |
11 | 59.3 | 29.5 | 43.3 | 25.1 | 42.7 | Ⅰ | 27 | - | 1.5 | - | - | - | Ⅰ |
12 | 24.2 | 8.5 | 19.7 | 6.4 | 8.5 | Ⅰ | 28 | - | 6.8 | - | - | 2.4 | Ⅰ |
13 | 3.3 | 0.1 | - | - | 1.2 | Ⅱ | 29 | - | 0.1 | - | - | - | Ⅱ |
14 | 27.5 | 19.2 | 10.8 | - | 1.2 | Ⅰ | 30 | - | - | - | - | - | Ⅱ |
15 | - | 0.1 | - | - | - | Ⅱ | 31 | - | 3.6 | - | - | - | Ⅰ |
16 | 3.3 | 0.1 | - | - | - | Ⅰ | 32 | 15.4 | 10.5 | 10.8 | 3.9 | 6.1 | Ⅰ |
Compound | tR/min | Disturbed dye Nos. | |||
---|---|---|---|---|---|
Condition 1 | Condition 2 | Condition 1 | Condition 2 | ||
2-Amino-4-hydroxyethyl aminoanisyl ether (2-氨基-4-羟乙氨基茴香醚) | 29.58 | 22.18 | No. 14 | No. 14 | |
Hydroxybenzimoline (羟苯并吗啉) | 29.58 | 21.30 | No. 14 | No. 14 | |
2,6-Dihydroxyethyl aminotoluene (2,6-二羟乙基氨甲苯) | 31.31 | 27.28 | No. 24; No. 16 | No. 13 | |
3-Nitro-p-hydroxyacetaminophen (3-硝基对羟乙氨基酚) | 32.43 | 27.95 | No. 10 | / | |
2-Methyl-5-hydroxyethylaminophenol (2-甲基-5-羟乙氨基苯酚) | 32.65 | 28.81 | / | No. 28 | |
Hydroxyethyl-3,4-methylenedioxyaniline hydrochloride | 33.53 | 30.25 | No. 28 | No. 27 | |
(羟乙基-3,4-亚甲二氧基苯胺盐酸盐) | |||||
4-Hydroxyalanine-3-nitrophenol (4-羟丙氨基-3-硝基苯酚) | 33.88 | 32.24 | No. 28 | No. 31 | |
HC yellow No. 4 (HC黄4号) | 34.792 | 34.29 | No. 27; No. 13 | / | |
5-Amino-6-chloro-o-cresol (5-氨基-6-氯-邻甲酚) | 35.22 | 30.25 | No. 31; No. 29 | No. 27 | |
HC yellow No. 2 (HC黄2号) | 37.21 | 37.95 | / | / | |
5-Amino-4-chloro-o-cresol (5-氨基-4-氯-邻甲酚) | 37.96 | 39.26 | / | / | |
Hydroxyethyl-2-nitro-p-toluidine (羟乙基-2-硝基对甲苯胺) | 39.87 | 45.00 | / | / | |
Disperse violet No. 1 (分散紫1号) | 41.67 | 56.60 | No. 30 | / | |
HC orange No. 1 (HC橙1号) | 48.67 | 59.60 | / | / | |
HC red No. 1 (HC红1号) | 49.47 | 59.07 | / | / |
表 4 其他15种常用染料的HPLC保留时间及可能干扰的32种染料的序号
Table 4 HPLC retention times of 15 other common dyes and interference dye Nos. of the 32 dyes
Compound | tR/min | Disturbed dye Nos. | |||
---|---|---|---|---|---|
Condition 1 | Condition 2 | Condition 1 | Condition 2 | ||
2-Amino-4-hydroxyethyl aminoanisyl ether (2-氨基-4-羟乙氨基茴香醚) | 29.58 | 22.18 | No. 14 | No. 14 | |
Hydroxybenzimoline (羟苯并吗啉) | 29.58 | 21.30 | No. 14 | No. 14 | |
2,6-Dihydroxyethyl aminotoluene (2,6-二羟乙基氨甲苯) | 31.31 | 27.28 | No. 24; No. 16 | No. 13 | |
3-Nitro-p-hydroxyacetaminophen (3-硝基对羟乙氨基酚) | 32.43 | 27.95 | No. 10 | / | |
2-Methyl-5-hydroxyethylaminophenol (2-甲基-5-羟乙氨基苯酚) | 32.65 | 28.81 | / | No. 28 | |
Hydroxyethyl-3,4-methylenedioxyaniline hydrochloride | 33.53 | 30.25 | No. 28 | No. 27 | |
(羟乙基-3,4-亚甲二氧基苯胺盐酸盐) | |||||
4-Hydroxyalanine-3-nitrophenol (4-羟丙氨基-3-硝基苯酚) | 33.88 | 32.24 | No. 28 | No. 31 | |
HC yellow No. 4 (HC黄4号) | 34.792 | 34.29 | No. 27; No. 13 | / | |
5-Amino-6-chloro-o-cresol (5-氨基-6-氯-邻甲酚) | 35.22 | 30.25 | No. 31; No. 29 | No. 27 | |
HC yellow No. 2 (HC黄2号) | 37.21 | 37.95 | / | / | |
5-Amino-4-chloro-o-cresol (5-氨基-4-氯-邻甲酚) | 37.96 | 39.26 | / | / | |
Hydroxyethyl-2-nitro-p-toluidine (羟乙基-2-硝基对甲苯胺) | 39.87 | 45.00 | / | / | |
Disperse violet No. 1 (分散紫1号) | 41.67 | 56.60 | No. 30 | / | |
HC orange No. 1 (HC橙1号) | 48.67 | 59.60 | / | / | |
HC red No. 1 (HC红1号) | 49.47 | 59.07 | / | / |
图 3 采用不同品牌色谱柱时HPLC条件1下Ⅰ组染料的色谱图
Fig. 3 Chromatograms of dye group Ⅰ with different brands of columns under HPLC condition 1 For peak numbers, see Table 2.
Dye No. | HPLC | HPLC-MS/MS | |||||
---|---|---|---|---|---|---|---|
Linear range/(mg/L) | r2 | LOD/(μg/g) | Linear range/(mg/L) | r2 | LOD/(μg/g) | ||
1 | 10.0-499.5 | 0.9999 | 40.0 | 0.1-4.2 | 0.9986 | 0.04 | |
2 | 10.0-499.0 | 0.9999 | 20.0 | 0.1-4.3 | 0.9986 | 0.04 | |
3 | 10.0-500.0 | 0.9998 | 40.0 | 0.1-4.2 | 0.9999 | 0.2 | |
4 | 10.0-501.2 | 0.9979 | 20.0 | 0.1-4.2 | 0.9950 | 0.2 | |
5 | 9.9-495.0 | 1.0000 | 19.8 | 0.1-4.2 | 0.9999 | 0.02 | |
6 | 9.9-497.1 | 0.9996 | 39.9 | 0.1-4.3 | 0.9995 | 0.04 | |
7 | 10.2-509.6 | 1.0000 | 10.2 | 0.1-4.1 | 0.9962 | 0.02 | |
8 | 10.0-501.6 | 1.0000 | 20.0 | 0.1-4.0 | 0.9991 | 0.4 | |
9 | 10.0-500.0 | 1.0000 | 10.0 | 0.1-4.4 | 0.9991 | 0.02 | |
10 | 10.0-501.0 | 1.0000 | 10.0 | 0.1-4.3 | 0.9994 | 0.02 | |
Dye No. | HPLC | HPLC-MS/MS | |||||
Linear range/(mg/L) | r2 | LOD/(μg/g) | Linear range/(mg/L) | r2 | LOD/(μg/g) | ||
11 | 10.0-500.0 | 0.9979 | 19.7 | 0.1-4.1 | 0.9999 | 0.02 | |
12 | 10.0-500.0 | 0.9999 | 40.0 | 0.1-4.2 | 0.9992 | 0.4 | |
13 | 10.0-490.0 | 1.0000 | 19.6 | 0.1-3.8 | 0.9984 | 0.02 | |
14 | 10.0-500.2 | 0.9991 | 19.6 | 0.1-4.2 | 0.9996 | 0.02 | |
15 | 10.0-501.1 | 1.0000 | 40.1 | 0.1-4.2 | 0.9990 | 0.01 | |
16 | 10.0-498.7 | 1.0000 | 20.1 | 0.1-4.2 | 0.9995 | 0.04 | |
17 | 10.0-500.9 | 0.9999 | 10.0 | 0.1-3.7 | 0.9981 | 0.02 | |
18 | 9.8-489.6 | 0.9974 | 39.2 | 0.1-4.0 | 0.9999 | 0.04 | |
19 | 10.0-500.0 | 0.9997 | 10.0 | 2.0-79.7 | 0.9979 | 8.0 | |
20 | 9.9-493.1 | 0.9995 | 19.9 | 0.1-4.0 | 0.9901 | 0.04 | |
21 | 9.9-496.9 | 1.0000 | 39.8 | 0.1-4.2 | 0.9948 | 0.04 | |
22 | 9.7-486.8 | 0.9999 | 39.6 | 0.1-4.2 | 0.9974 | 0.4 | |
23 | 9.9-493.9 | 0.9999 | 39.5 | 0.1-4.5 | 0.9937 | 0.02 | |
24 | 9.9-493.4 | 1.0000 | 9.9 | 0.1-3.8 | 0.9994 | 0.02 | |
25 | 9.9-494.9 | 1.0000 | 19.8 | 0.1-4.3 | 0.9993 | 0.02 | |
26 | 9.9-496.6 | 1.0000 | 39.7 | 0.1-4.0 | 0.9990 | 0.2 | |
27 | 9.8-491.0 | 1.0000 | 9.7 | 0.1-4.3 | 0.9988 | 0.2 | |
28 | 10.0-501.0 | 1.0000 | 9.9 | 0.1-4.3 | 0.9999 | 0.2 | |
29 | 10.1-503.1 | 1.0000 | 10.1 | 0.1-4.4 | 0.9999 | 0.04 | |
30 | 9.9-497.4 | 1.0000 | 9.9 | 0.1-4.6 | 0.9965 | 0.01 | |
31 | 10.1-505.1 | 1.0000 | 10.0 | 0.1-3.8 | 0.9999 | 0.2 | |
32 | 10.0-498.3 | 1.0000 | 10.0 | 0.1-3.8 | 0.9980 | 0.2 |
表 5 HPLC和HPLC-MS/MS方法中32种染料的线性范围、相关系数及检出限
Table 5 Linear ranges, correlation coefficients (r2), and limits of detection (LODs) of the 32 dyes determined using HPLC and HPLC-MS/MS
Dye No. | HPLC | HPLC-MS/MS | |||||
---|---|---|---|---|---|---|---|
Linear range/(mg/L) | r2 | LOD/(μg/g) | Linear range/(mg/L) | r2 | LOD/(μg/g) | ||
1 | 10.0-499.5 | 0.9999 | 40.0 | 0.1-4.2 | 0.9986 | 0.04 | |
2 | 10.0-499.0 | 0.9999 | 20.0 | 0.1-4.3 | 0.9986 | 0.04 | |
3 | 10.0-500.0 | 0.9998 | 40.0 | 0.1-4.2 | 0.9999 | 0.2 | |
4 | 10.0-501.2 | 0.9979 | 20.0 | 0.1-4.2 | 0.9950 | 0.2 | |
5 | 9.9-495.0 | 1.0000 | 19.8 | 0.1-4.2 | 0.9999 | 0.02 | |
6 | 9.9-497.1 | 0.9996 | 39.9 | 0.1-4.3 | 0.9995 | 0.04 | |
7 | 10.2-509.6 | 1.0000 | 10.2 | 0.1-4.1 | 0.9962 | 0.02 | |
8 | 10.0-501.6 | 1.0000 | 20.0 | 0.1-4.0 | 0.9991 | 0.4 | |
9 | 10.0-500.0 | 1.0000 | 10.0 | 0.1-4.4 | 0.9991 | 0.02 | |
10 | 10.0-501.0 | 1.0000 | 10.0 | 0.1-4.3 | 0.9994 | 0.02 | |
Dye No. | HPLC | HPLC-MS/MS | |||||
Linear range/(mg/L) | r2 | LOD/(μg/g) | Linear range/(mg/L) | r2 | LOD/(μg/g) | ||
11 | 10.0-500.0 | 0.9979 | 19.7 | 0.1-4.1 | 0.9999 | 0.02 | |
12 | 10.0-500.0 | 0.9999 | 40.0 | 0.1-4.2 | 0.9992 | 0.4 | |
13 | 10.0-490.0 | 1.0000 | 19.6 | 0.1-3.8 | 0.9984 | 0.02 | |
14 | 10.0-500.2 | 0.9991 | 19.6 | 0.1-4.2 | 0.9996 | 0.02 | |
15 | 10.0-501.1 | 1.0000 | 40.1 | 0.1-4.2 | 0.9990 | 0.01 | |
16 | 10.0-498.7 | 1.0000 | 20.1 | 0.1-4.2 | 0.9995 | 0.04 | |
17 | 10.0-500.9 | 0.9999 | 10.0 | 0.1-3.7 | 0.9981 | 0.02 | |
18 | 9.8-489.6 | 0.9974 | 39.2 | 0.1-4.0 | 0.9999 | 0.04 | |
19 | 10.0-500.0 | 0.9997 | 10.0 | 2.0-79.7 | 0.9979 | 8.0 | |
20 | 9.9-493.1 | 0.9995 | 19.9 | 0.1-4.0 | 0.9901 | 0.04 | |
21 | 9.9-496.9 | 1.0000 | 39.8 | 0.1-4.2 | 0.9948 | 0.04 | |
22 | 9.7-486.8 | 0.9999 | 39.6 | 0.1-4.2 | 0.9974 | 0.4 | |
23 | 9.9-493.9 | 0.9999 | 39.5 | 0.1-4.5 | 0.9937 | 0.02 | |
24 | 9.9-493.4 | 1.0000 | 9.9 | 0.1-3.8 | 0.9994 | 0.02 | |
25 | 9.9-494.9 | 1.0000 | 19.8 | 0.1-4.3 | 0.9993 | 0.02 | |
26 | 9.9-496.6 | 1.0000 | 39.7 | 0.1-4.0 | 0.9990 | 0.2 | |
27 | 9.8-491.0 | 1.0000 | 9.7 | 0.1-4.3 | 0.9988 | 0.2 | |
28 | 10.0-501.0 | 1.0000 | 9.9 | 0.1-4.3 | 0.9999 | 0.2 | |
29 | 10.1-503.1 | 1.0000 | 10.1 | 0.1-4.4 | 0.9999 | 0.04 | |
30 | 9.9-497.4 | 1.0000 | 9.9 | 0.1-4.6 | 0.9965 | 0.01 | |
31 | 10.1-505.1 | 1.0000 | 10.0 | 0.1-3.8 | 0.9999 | 0.2 | |
32 | 10.0-498.3 | 1.0000 | 10.0 | 0.1-3.8 | 0.9980 | 0.2 |
Dye No. | HPLC (10 mg/L) | HPLC (500 mg/L) | HPLC-MS/MS (0.1 mg/L) | HPLC-MS/MS (4 mg/L) | |||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | ||||||||||||||||||||
1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | ||||||||||||
1 | 2.0 | 4.6 | 3.9 | 4.5 | 3.8 | 2.4 | 1.6 | 1.8 | 3.2 | 3.3 | 3.2 | 4.5 | 5.6 | 4.8 | 5.2 | 4.5 | |||||||||||
2 | 3.2 | 3.9 | 4.1 | 4.2 | 2.1 | 3.1 | 2.3 | 2.3 | 6.4 | 7.7 | 2.5 | 3.7 | 8.1 | 9.3 | 3.6 | 3.1 | |||||||||||
3 | 5.0 | 7.5 | 4.0 | 3.8 | 4.8 | 8.0 | 4.9 | 5.5 | 9.3 | 7.4 | 3.9 | 5.5 | 9.8 | 8.7 | 6.1 | 5.1 | |||||||||||
4 | 1.7 | 3.3 | 4.7 | 4.9 | 1.0 | 3.2 | 1.2 | 1.6 | 8.8 | 10 | 4.2 | 8.4 | 9.3 | 8.8 | 5.8 | 6.2 | |||||||||||
5 | 0.7 | 1.2 | 0.8 | 1.0 | 0.1 | 0.3 | 0.2 | 0.4 | 4.1 | 8.1 | 2.0 | 3.7 | 8.1 | 8.1 | 3.7 | 3.2 | |||||||||||
6 | 2.7 | 4.5 | 3.9 | 5.3 | 2.3 | 3.8 | 4.3 | 4.3 | 9.8 | 9.4 | 3.4 | 11 | 9.4 | 8.3 | 5.6 | 5.3 | |||||||||||
7 | 1.2 | 1.8 | 0.9 | 0.9 | 0.1 | 0.3 | 0.1 | 0.3 | 6.5 | 8.0 | 2.6 | 4.9 | 7.6 | 7.2 | 4.2 | 4.3 | |||||||||||
8 | 4.8 | 8.7 | 4.3 | 5.2 | 1.8 | 4.4 | 2.6 | 2.7 | 5.2 | 8.7 | 3.4 | 11 | 8.3 | 8.7 | 4.5 | 7.9 | |||||||||||
9 | 2.5 | 4.2 | 1.0 | 2.6 | 0.2 | 3.4 | 0.9 | 2.8 | 9.2 | 7.6 | 2.4 | 4.6 | 6.1 | 8.5 | 4.6 | 4.6 | |||||||||||
10 | 1.3 | 1.6 | 1.1 | 1.1 | 0.3 | 0.4 | 0.1 | 0.2 | 9.9 | 9.4 | 2.4 | 3.6 | 8.4 | 9.2 | 3.5 | 3.2 | |||||||||||
11 | 2.0 | 5.5 | 4.6 | 4.5 | 0.2 | 4.9 | 0.5 | 1.2 | 4.6 | 4.7 | 2.9 | 4.4 | 5.5 | 5.2 | 4.1 | 3.8 | |||||||||||
12 | 4.2 | 9.2 | 1.9 | 2.8 | 0.7 | 4.8 | 4.0 | 3.8 | 9.3 | 9.2 | 3.0 | 6.5 | 9.3 | 9.6 | 3.1 | 4.0 | |||||||||||
13 | 0.7 | 1.5 | 1.5 | 1.8 | 0.1 | 0.6 | 0.3 | 0.42 | 8.4 | 7.7 | 1.3 | 2.2 | 9.3 | 9.5 | 1.6 | 1.4 | |||||||||||
14 | 1.0 | 6.6 | 1.1 | 3.5 | 0.7 | 9.0 | 3.3 | 5.2 | 2.4 | 8.7 | 2.0 | 8.3 | 3.7 | 8.7 | 1.8 | 5.9 | |||||||||||
Dye No. | HPLC (10 mg/L) | HPLC (500 mg/L) | HPLC-MS/MS (0.1 mg/L) | HPLC-MS/MS (4 mg/L) | |||||||||||||||||||||||
Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | ||||||||||||||||||||
1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | ||||||||||||
15 | 2.8 | 3.3 | 4.8 | 4.5 | 0.2 | 0.5 | 0.2 | 0.2 | 8.8 | 8.7 | 1.1 | 4.6 | 9.1 | 9.2 | 3.4 | 3.8 | |||||||||||
16 | 0.8 | 0.9 | 0.7 | 0.8 | 0.4 | 4.3 | 1.7 | 3.3 | 6.2 | 4.9 | 1.4 | 9.5 | 6.5 | 6.2 | 6.0 | 7.6 | |||||||||||
17 | 0.7 | 1.0 | 1.1 | 1.0 | 0.1 | 1.2 | 1.1 | 1.3 | 7.0 | 5.6 | 2.5 | 4.1 | 6.8 | 6.2 | 3.5 | 3.0 | |||||||||||
18 | 4.5 | 7.3 | 4.3 | 7.4 | 4.7 | 7.8 | 5.0 | 6.1 | 9.5 | 9.9 | 1.8 | 7.4 | 5.5 | 10 | 3.1 | 9.8 | |||||||||||
19 | 4.8 | 10 | 4.1 | 15.5 | 0.1 | 0.2 | 0.1 | 0.1 | 5.2 | 6.3 | 3.9 | 5.9 | 6.9 | 7.5 | 4.9 | 5.8 | |||||||||||
20 | 3.3 | 9.0 | 4.1 | 5.4 | 2.7 | 5.0 | 3.1 | 3.3 | 8.6 | 8.5 | 1.6 | 3.5 | 8.8 | 9.2 | 2.6 | 2.3 | |||||||||||
21 | 2.6 | 2.5 | 4.5 | 4.2 | 1.1 | 1.0 | 0.8 | 0.8 | 8.8 | 8.1 | 2.0 | 4.8 | 8.0 | 6.9 | 4.0 | 3.7 | |||||||||||
22 | 4.4 | 5.2 | 4.2 | 4.0 | 0.2 | 6.8 | 1.0 | 3.8 | 7.2 | 11 | 3.2 | 6.9 | 9.8 | 13 | 4.0 | 8.3 | |||||||||||
23 | 2.1 | 9.8 | 3.5 | 14 | 0.5 | 2.1 | 1.3 | 1.8 | 9.3 | 7.9 | 1.3 | 4.5 | 7.5 | 8.8 | 4.9 | 4.2 | |||||||||||
24 | 0.4 | 0.5 | 0.6 | 0.6 | 0.1 | 0.3 | 0.1 | 0.2 | 6.2 | 6.9 | 1.9 | 7.0 | 8.5 | 7.2 | 1.5 | 4.4 | |||||||||||
25 | 1.5 | 6.1 | 4.4 | 4.3 | 0.4 | 3.5 | 0.5 | 2.5 | 6.1 | 4.3 | 1.7 | 3.4 | 5.8 | 5.5 | 2.6 | 2.8 | |||||||||||
26 | 2.6 | 3.7 | 1.9 | 1.8 | 0.1 | 0.2 | 0.2 | 0.2 | 8.3 | 6.0 | 2.8 | 4.0 | 4.4 | 4.4 | 3.7 | 3.5 | |||||||||||
27 | 1.4 | 0.8 | 1.0 | 1.0 | 0.2 | 0.9 | 0.7 | 1.0 | 8.6 | 8.9 | 2.5 | 5.5 | 8 | 8.2 | 2.2 | 4.9 | |||||||||||
28 | 2.5 | 4.6 | 4.5 | 4.2 | 0.1 | 1.0 | 0.8 | 1.0 | 8.7 | 7.6 | 1.4 | 6.8 | 9.7 | 8.5 | 1.9 | 5.4 | |||||||||||
29 | 0.6 | 0.6 | 0.8 | 0.7 | 0.1 | 0.3 | 0.1 | 0.2 | 5.1 | 7.3 | 2.2 | 3.1 | 5.5 | 7.5 | 4.6 | 4.4 | |||||||||||
30 | 0.5 | 0.6 | 1.2 | 1.1 | 0.1 | 0.4 | 0.1 | 0.3 | 8.6 | 6.1 | 2.5 | 3.3 | 8.8 | 7.6 | 3.1 | 2.9 | |||||||||||
31 | 1.0 | 1.2 | 1.6 | 1.7 | 0.1 | 0.5 | 0.2 | 0.4 | 7.5 | 6.4 | 2.7 | 5.8 | 8.1 | 7.8 | 2.2 | 4.5 | |||||||||||
32 | 1.7 | 1.6 | 3.7 | 3.5 | 0.1 | 0.9 | 0.2 | 0.4 | 6.0 | 9.9 | 2.0 | 6.7 | 9.1 | 9.4 | 3.1 | 5.6 |
表 6 HPLC和HPLC-MS/MS方法中32种染料的精密度(n=6)和稳定性
Table 6 Precisions (n=6) and stabilities of the 32 dyes determined using HPLC and HPLC-MS/MS RSD/%
Dye No. | HPLC (10 mg/L) | HPLC (500 mg/L) | HPLC-MS/MS (0.1 mg/L) | HPLC-MS/MS (4 mg/L) | |||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | ||||||||||||||||||||
1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | ||||||||||||
1 | 2.0 | 4.6 | 3.9 | 4.5 | 3.8 | 2.4 | 1.6 | 1.8 | 3.2 | 3.3 | 3.2 | 4.5 | 5.6 | 4.8 | 5.2 | 4.5 | |||||||||||
2 | 3.2 | 3.9 | 4.1 | 4.2 | 2.1 | 3.1 | 2.3 | 2.3 | 6.4 | 7.7 | 2.5 | 3.7 | 8.1 | 9.3 | 3.6 | 3.1 | |||||||||||
3 | 5.0 | 7.5 | 4.0 | 3.8 | 4.8 | 8.0 | 4.9 | 5.5 | 9.3 | 7.4 | 3.9 | 5.5 | 9.8 | 8.7 | 6.1 | 5.1 | |||||||||||
4 | 1.7 | 3.3 | 4.7 | 4.9 | 1.0 | 3.2 | 1.2 | 1.6 | 8.8 | 10 | 4.2 | 8.4 | 9.3 | 8.8 | 5.8 | 6.2 | |||||||||||
5 | 0.7 | 1.2 | 0.8 | 1.0 | 0.1 | 0.3 | 0.2 | 0.4 | 4.1 | 8.1 | 2.0 | 3.7 | 8.1 | 8.1 | 3.7 | 3.2 | |||||||||||
6 | 2.7 | 4.5 | 3.9 | 5.3 | 2.3 | 3.8 | 4.3 | 4.3 | 9.8 | 9.4 | 3.4 | 11 | 9.4 | 8.3 | 5.6 | 5.3 | |||||||||||
7 | 1.2 | 1.8 | 0.9 | 0.9 | 0.1 | 0.3 | 0.1 | 0.3 | 6.5 | 8.0 | 2.6 | 4.9 | 7.6 | 7.2 | 4.2 | 4.3 | |||||||||||
8 | 4.8 | 8.7 | 4.3 | 5.2 | 1.8 | 4.4 | 2.6 | 2.7 | 5.2 | 8.7 | 3.4 | 11 | 8.3 | 8.7 | 4.5 | 7.9 | |||||||||||
9 | 2.5 | 4.2 | 1.0 | 2.6 | 0.2 | 3.4 | 0.9 | 2.8 | 9.2 | 7.6 | 2.4 | 4.6 | 6.1 | 8.5 | 4.6 | 4.6 | |||||||||||
10 | 1.3 | 1.6 | 1.1 | 1.1 | 0.3 | 0.4 | 0.1 | 0.2 | 9.9 | 9.4 | 2.4 | 3.6 | 8.4 | 9.2 | 3.5 | 3.2 | |||||||||||
11 | 2.0 | 5.5 | 4.6 | 4.5 | 0.2 | 4.9 | 0.5 | 1.2 | 4.6 | 4.7 | 2.9 | 4.4 | 5.5 | 5.2 | 4.1 | 3.8 | |||||||||||
12 | 4.2 | 9.2 | 1.9 | 2.8 | 0.7 | 4.8 | 4.0 | 3.8 | 9.3 | 9.2 | 3.0 | 6.5 | 9.3 | 9.6 | 3.1 | 4.0 | |||||||||||
13 | 0.7 | 1.5 | 1.5 | 1.8 | 0.1 | 0.6 | 0.3 | 0.42 | 8.4 | 7.7 | 1.3 | 2.2 | 9.3 | 9.5 | 1.6 | 1.4 | |||||||||||
14 | 1.0 | 6.6 | 1.1 | 3.5 | 0.7 | 9.0 | 3.3 | 5.2 | 2.4 | 8.7 | 2.0 | 8.3 | 3.7 | 8.7 | 1.8 | 5.9 | |||||||||||
Dye No. | HPLC (10 mg/L) | HPLC (500 mg/L) | HPLC-MS/MS (0.1 mg/L) | HPLC-MS/MS (4 mg/L) | |||||||||||||||||||||||
Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | Precision (n=6) | Stability | ||||||||||||||||||||
1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | 1 d | 3 d | 48 h | 72 h | ||||||||||||
15 | 2.8 | 3.3 | 4.8 | 4.5 | 0.2 | 0.5 | 0.2 | 0.2 | 8.8 | 8.7 | 1.1 | 4.6 | 9.1 | 9.2 | 3.4 | 3.8 | |||||||||||
16 | 0.8 | 0.9 | 0.7 | 0.8 | 0.4 | 4.3 | 1.7 | 3.3 | 6.2 | 4.9 | 1.4 | 9.5 | 6.5 | 6.2 | 6.0 | 7.6 | |||||||||||
17 | 0.7 | 1.0 | 1.1 | 1.0 | 0.1 | 1.2 | 1.1 | 1.3 | 7.0 | 5.6 | 2.5 | 4.1 | 6.8 | 6.2 | 3.5 | 3.0 | |||||||||||
18 | 4.5 | 7.3 | 4.3 | 7.4 | 4.7 | 7.8 | 5.0 | 6.1 | 9.5 | 9.9 | 1.8 | 7.4 | 5.5 | 10 | 3.1 | 9.8 | |||||||||||
19 | 4.8 | 10 | 4.1 | 15.5 | 0.1 | 0.2 | 0.1 | 0.1 | 5.2 | 6.3 | 3.9 | 5.9 | 6.9 | 7.5 | 4.9 | 5.8 | |||||||||||
20 | 3.3 | 9.0 | 4.1 | 5.4 | 2.7 | 5.0 | 3.1 | 3.3 | 8.6 | 8.5 | 1.6 | 3.5 | 8.8 | 9.2 | 2.6 | 2.3 | |||||||||||
21 | 2.6 | 2.5 | 4.5 | 4.2 | 1.1 | 1.0 | 0.8 | 0.8 | 8.8 | 8.1 | 2.0 | 4.8 | 8.0 | 6.9 | 4.0 | 3.7 | |||||||||||
22 | 4.4 | 5.2 | 4.2 | 4.0 | 0.2 | 6.8 | 1.0 | 3.8 | 7.2 | 11 | 3.2 | 6.9 | 9.8 | 13 | 4.0 | 8.3 | |||||||||||
23 | 2.1 | 9.8 | 3.5 | 14 | 0.5 | 2.1 | 1.3 | 1.8 | 9.3 | 7.9 | 1.3 | 4.5 | 7.5 | 8.8 | 4.9 | 4.2 | |||||||||||
24 | 0.4 | 0.5 | 0.6 | 0.6 | 0.1 | 0.3 | 0.1 | 0.2 | 6.2 | 6.9 | 1.9 | 7.0 | 8.5 | 7.2 | 1.5 | 4.4 | |||||||||||
25 | 1.5 | 6.1 | 4.4 | 4.3 | 0.4 | 3.5 | 0.5 | 2.5 | 6.1 | 4.3 | 1.7 | 3.4 | 5.8 | 5.5 | 2.6 | 2.8 | |||||||||||
26 | 2.6 | 3.7 | 1.9 | 1.8 | 0.1 | 0.2 | 0.2 | 0.2 | 8.3 | 6.0 | 2.8 | 4.0 | 4.4 | 4.4 | 3.7 | 3.5 | |||||||||||
27 | 1.4 | 0.8 | 1.0 | 1.0 | 0.2 | 0.9 | 0.7 | 1.0 | 8.6 | 8.9 | 2.5 | 5.5 | 8 | 8.2 | 2.2 | 4.9 | |||||||||||
28 | 2.5 | 4.6 | 4.5 | 4.2 | 0.1 | 1.0 | 0.8 | 1.0 | 8.7 | 7.6 | 1.4 | 6.8 | 9.7 | 8.5 | 1.9 | 5.4 | |||||||||||
29 | 0.6 | 0.6 | 0.8 | 0.7 | 0.1 | 0.3 | 0.1 | 0.2 | 5.1 | 7.3 | 2.2 | 3.1 | 5.5 | 7.5 | 4.6 | 4.4 | |||||||||||
30 | 0.5 | 0.6 | 1.2 | 1.1 | 0.1 | 0.4 | 0.1 | 0.3 | 8.6 | 6.1 | 2.5 | 3.3 | 8.8 | 7.6 | 3.1 | 2.9 | |||||||||||
31 | 1.0 | 1.2 | 1.6 | 1.7 | 0.1 | 0.5 | 0.2 | 0.4 | 7.5 | 6.4 | 2.7 | 5.8 | 8.1 | 7.8 | 2.2 | 4.5 | |||||||||||
32 | 1.7 | 1.6 | 3.7 | 3.5 | 0.1 | 0.9 | 0.2 | 0.4 | 6.0 | 9.9 | 2.0 | 6.7 | 9.1 | 9.4 | 3.1 | 5.6 |
Dye No. | HPLC1) | HPLC2) | HPLC-MS/MS3) | Dye No. | HPLC1) | HPLC2) | HPLC-MS/MS3) | |||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||
1 | 86.0 | 1.6 | 93.8 | 2.3 | 114.0 | 2.9 | 17 | 103.5 | 0.3 | 97.7 | 0.5 | 114.0 | 1.1 | |||||
2 | 104.7 | 1.1 | 96.8 | 1.1 | 114.2 | 3.9 | 18 | 85.1 | 2.6 | 85.3 | 4.1 | 111.0 | 3.4 | |||||
3 | 85.3 | 1.4 | 85.2 | 5.2 | 108.9 | 3.8 | 19 | 105.3 | 0.8 | 87.6 | 0.5 | 98.9 | 6.0 | |||||
4 | 106.2 | 1.7 | 99.8 | 1.4 | 111.8 | 3.0 | 20 | 114.7 | 2.0 | 97.3 | 4.2 | 103.3 | 5.3 | |||||
5 | 103.9 | 1.2 | 98.6 | 0.5 | 111.9 | 2.6 | 21 | 99.9 | 1.3 | 95.1 | 1.0 | 105.3 | 4.3 | |||||
6 | 87.9 | 1.2 | 92.7 | 1.8 | 105.6 | 1.7 | 22 | 100.3 | 2.9 | 87.2 | 4.5 | 104.4 | 8.4 | |||||
7 | 100.6 | 0.6 | 95.2 | 0.5 | 105.6 | 1.4 | 23 | 93.6 | 2.5 | 86.8 | 0.7 | 95.8 | 4.8 | |||||
8 | 98.2 | 1.4 | 99.7 | 5.7 | 107.9 | 2.6 | 24 | 98.1 | 1.1 | 95.4 | 4.2 | 114.5 | 2.4 | |||||
9 | 97.9 | 1.3 | 94.6 | 1.2 | 106.6 | 1.7 | 25 | 90.9 | 1.3 | 90.2 | 2.4 | 114.9 | 1.4 | |||||
10 | 100.4 | 1.1 | 99.2 | 0.5 | 114.4 | 1.5 | 26 | 101.6 | 2.3 | 99.6 | 0.7 | 106.0 | 7.1 | |||||
11 | 89.1 | 1.6 | 109.4 | 3.4 | 100.0 | 1.2 | 27 | 89.9 | 1.8 | 95.0 | 1.8 | 95.8 | 2.0 | |||||
12 | 85.1 | 0.6 | 103.1 | 4.0 | 103.3 | 3.3 | 28 | 97.0 | 1.9 | 95.9 | 1.0 | 98.4 | 2.1 | |||||
13 | 98.1 | 1.3 | 98.7 | 0.4 | 96.5 | 1.4 | 29 | 93.6 | 3.5 | 97.1 | 1.9 | 106.4 | 5.5 | |||||
14 | 85.6 | 2.2 | 93.2 | 1.2 | 112.7 | 3.8 | 30 | 97.6 | 1.2 | 98.4 | 0.5 | 102.2 | 3.8 | |||||
15 | 101.2 | 2.8 | 98.3 | 0.4 | 95.7 | 5.4 | 31 | 89.8 | 3.9 | 86.5 | 3.8 | 96.6 | 9.8 | |||||
16 | 92.7 | 2.1 | 97.8 | 1.1 | 93.5 | 5.8 | 32 | 93.3 | 2.6 | 91.0 | 2.1 | 82.6 | 5.3 |
表 7 HPLC和HPLC-MS/MS方法中32种染料的加标回收率(n=6)
Table 7 Spiked recoveries of the 32 dyes analyzed with HPLC and HPLC-MS/MS (n=6)
Dye No. | HPLC1) | HPLC2) | HPLC-MS/MS3) | Dye No. | HPLC1) | HPLC2) | HPLC-MS/MS3) | |||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | Recovery/ % | RSD/ % | |||||||
1 | 86.0 | 1.6 | 93.8 | 2.3 | 114.0 | 2.9 | 17 | 103.5 | 0.3 | 97.7 | 0.5 | 114.0 | 1.1 | |||||
2 | 104.7 | 1.1 | 96.8 | 1.1 | 114.2 | 3.9 | 18 | 85.1 | 2.6 | 85.3 | 4.1 | 111.0 | 3.4 | |||||
3 | 85.3 | 1.4 | 85.2 | 5.2 | 108.9 | 3.8 | 19 | 105.3 | 0.8 | 87.6 | 0.5 | 98.9 | 6.0 | |||||
4 | 106.2 | 1.7 | 99.8 | 1.4 | 111.8 | 3.0 | 20 | 114.7 | 2.0 | 97.3 | 4.2 | 103.3 | 5.3 | |||||
5 | 103.9 | 1.2 | 98.6 | 0.5 | 111.9 | 2.6 | 21 | 99.9 | 1.3 | 95.1 | 1.0 | 105.3 | 4.3 | |||||
6 | 87.9 | 1.2 | 92.7 | 1.8 | 105.6 | 1.7 | 22 | 100.3 | 2.9 | 87.2 | 4.5 | 104.4 | 8.4 | |||||
7 | 100.6 | 0.6 | 95.2 | 0.5 | 105.6 | 1.4 | 23 | 93.6 | 2.5 | 86.8 | 0.7 | 95.8 | 4.8 | |||||
8 | 98.2 | 1.4 | 99.7 | 5.7 | 107.9 | 2.6 | 24 | 98.1 | 1.1 | 95.4 | 4.2 | 114.5 | 2.4 | |||||
9 | 97.9 | 1.3 | 94.6 | 1.2 | 106.6 | 1.7 | 25 | 90.9 | 1.3 | 90.2 | 2.4 | 114.9 | 1.4 | |||||
10 | 100.4 | 1.1 | 99.2 | 0.5 | 114.4 | 1.5 | 26 | 101.6 | 2.3 | 99.6 | 0.7 | 106.0 | 7.1 | |||||
11 | 89.1 | 1.6 | 109.4 | 3.4 | 100.0 | 1.2 | 27 | 89.9 | 1.8 | 95.0 | 1.8 | 95.8 | 2.0 | |||||
12 | 85.1 | 0.6 | 103.1 | 4.0 | 103.3 | 3.3 | 28 | 97.0 | 1.9 | 95.9 | 1.0 | 98.4 | 2.1 | |||||
13 | 98.1 | 1.3 | 98.7 | 0.4 | 96.5 | 1.4 | 29 | 93.6 | 3.5 | 97.1 | 1.9 | 106.4 | 5.5 | |||||
14 | 85.6 | 2.2 | 93.2 | 1.2 | 112.7 | 3.8 | 30 | 97.6 | 1.2 | 98.4 | 0.5 | 102.2 | 3.8 | |||||
15 | 101.2 | 2.8 | 98.3 | 0.4 | 95.7 | 5.4 | 31 | 89.8 | 3.9 | 86.5 | 3.8 | 96.6 | 9.8 | |||||
16 | 92.7 | 2.1 | 97.8 | 1.1 | 93.5 | 5.8 | 32 | 93.3 | 2.6 | 91.0 | 2.1 | 82.6 | 5.3 |
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