气相色谱法测定染发剂中13种染料及杂质

提出了应用气相色谱法同时测定染发剂中苯酚、邻苯二胺、间苯二胺、对苯二胺、邻苯二酚、间苯二酚、对苯二酚、间氨基苯酚、对氨基苯酚、2,6-二氨基吡啶、2-甲基雷琐辛、5-氨基-2-甲基苯酚、3,4-二氨基甲苯等13染料含量的方法。染发剂样品经乙酸乙酯超声萃取15min,经AgilentHP-5(30m×0.32mm,0.25μm)毛细管柱分离,用氢火焰离子化检测器检测。13种染料的质量浓度均在10～500mg.L-1范围内呈线性,方法的检出限(3S/N)均小于1mg.L-1。在50,100,200mg.L-1等3个添加水平下,13种染料的回收率在85.4%～103.5%之间,测定值的相对标准偏差(n=6)在1.2%～5.2%之间。     

反相液相色谱法同时检测染发剂中4种合成染料的研究

应用超高效液相色谱(UPLC),建立了一套同时分析染发剂中酸性紫6B、罗丹明B、甲基紫2B、结晶紫4种染料类化合物的方法。该方法用V(乙腈):V(水)=30:70萃取染发剂中的染料类成分,定容后用作UPLC检测。经CapcellPakC18色谱柱分离,检测器波长560nm。4种染料类物质的检出限均不高于0.01μg/mL,定量限均不高于0.05μg/mL。用外标法定量,3个添加水平下,4种物质回收率在74.60%～109.15%之间,RSD(n=6)在0.67%～12%之间。方法可用于染发剂中合成染料类物质的快速检测。     

韭菜中吡虫啉和啶虫脒残留的微波处理-逆固相分散法净化及液相色谱检测

建立了韭菜中两种烟碱类农药吡虫啉和啶虫脒残留的快速检测方法.韭菜样本用微波炉加热处理,使酶钝化消除含硫基质干扰,然后用乙腈提取、逆固相分散净化,用反相高效液相色谱-二极管阵列检测器检测.在0.05～2.0 mg/kg添加水平范围内,吡虫啉的平均添加回收率在95.2%～105.3%之间;相对标准偏差在0.8%～7.8%之间;啶虫脒的平均添加回收率在97.4%～108.8%之间;相对标准偏差在1.3%～8.3%之间.本方法对吡虫啉的检出限(LOD)为0.0078 mg/kg,定量检出限(LOQ)为0.026 mg/kg;对啶虫脒的检出限为0.0075 mg/kg,定量检出限为0.025 mg/kg.     

超高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查染发剂中32种染料成分

建立了超高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查和分析染发剂中32种禁限用染料的分析方法。样品经甲醇-2 g/L抗坏血酸水溶液溶解提取,正己烷净化,用ZORBAX Eclipse Plus C_(18)(3.0 mm×100 mm,1.8μm)色谱柱分离,以甲醇-5 mmol/L乙酸铵水溶液为流动相进行梯度洗脱,采用正、负离子切换同时测定了32种染料成分,显著提高了检测通量。以全扫描模式下提取的保留时间和一级母离子精确质量数以及同位素丰度比,实现对染发剂中多种染料成分的快速筛查;以自动触发采集的二级碎片离子精确质量数进行确证。32种染料在相应的质量浓度范围内线性关系良好,相关系数(r~2)均大于0.99;定量下限(LOQ)为0.2～40μg/g,回收率为81.0%～110%,相对标准偏差(RSD)为3.3%～9.9%。该方法简单、准确、快速,适用于染发剂中多种禁限用染料成分的高通量快速定性筛查和定量分析。     

QuEChERS/超高效液相色谱-串联质谱法测定茶叶中17种氨基甲酸酯类农药及其代谢物残留

建立了检测茶叶中灭多威等17种氨基甲酸酯类农药残留的超高效液相色谱-串联质谱(UPLC-MS/MS)方法。详细讨论了加水对茶叶中氨基甲酸酯类农药提取效率的影响。茶叶样品加水后,用乙腈提取,经QuEChERS方法净化,C18色谱柱分离,三重四极杆电喷雾质谱检测,基质外标法定量。17种氨基甲酸酯类农药残留在各自质量浓度范围内线性关系良好,相关系数(R~2)均大于0. 99。方法检出限(S/N=3)为0. 001～0. 02 mg/kg,定量限(S/N=10)为0. 002～0. 05 mg/kg。在0. 05,0. 5,5. 0 mg/kg 3个添加水平下,17种农药残留平均加标回收率在82. 1%～119. 2%之间,相对标准偏差均小于8. 5%。     

MSPD-RRLC-UV/MS法同时检测果蔬中9种三嗪类除草剂残留量

基于基质固相分散萃取(MSPD)-快速高分离液相色谱紫外和质谱检测法, 测定了果蔬中9种三嗪类除草剂的残留量. 以浓度与色谱峰面积之间的线性关系定量, 保留时间结合质谱信息进行定性. 9种待测物在0.02～4.0 mg/kg范围内峰面积与浓度具有良好的线性关系, 相关系数(r2)在0.9996～0.9998之间; 方法的最低检出限(LOD)为0.002 mg/kg; 低、中和高3个浓度点的加标回收率介于75.2%～95.6%之间, 相对标准偏差(RSD)小于11%.     

超声辅助-固相分散溶液提取离子色谱法测定染发剂中的9种染料中间体

建立了提取和清洗整合成一步的超声辅助-固相分散溶液提取离子色谱法测定染发剂中的9种染料中间体的方法。样品基质经分散后,测定组分进入溶液,油脂溶解在正己烷中,干扰化合物被分散剂吸附。在振荡、超声和加热的协同作用下,9min内快速完成提取,具有高的样品处理效率。用离子色谱法测定商业染发剂中的中间体以确定方法的提取效率。方法的线性范围为0.2～100mg/L,检出限0.019～0.048mg/L,回收率85.0%～107.0%,相对标准偏差0.3%～3.7%。实验结果表明,方法简单、可靠,适用于大批量样品的常规分析。     

超高效液相色谱-串联质谱法同时测定染发剂中6种染料

建立了同时测定染发剂中4,4'-二氨基二苯胺硫酸盐和2,4-二氨基苯酚硫酸盐等6种染料的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法.以水为提取剂进行超声提取,用Waters BEH-C₁₈柱(100 mm×2.1 mm, 1.7 μm)分离,以10 mmol/L的乙酸铵和乙腈为流动相进行梯度洗脱.在电喷雾正离子模式下,采用多反应监测(MRM)模式进行定性和定量分析.6种染料在相应的质量浓度范围内线性关系良好,线性相关系数(R²)均大于0.99,检出限为0.26~4.6 mg/kg,回收率为83.0%~92.2%,相对标准偏差为5.4%~11.2%.方法精密度、准确度、回收率和基质效应均符合染发剂样品测定的要求,用于实际样品测定,结果满意.本方法准确、简便、快速,适用于染发剂中6种染料的分析测定.     

超高效液相色谱-电喷雾串联四极杆质谱法检测果汁和葡萄酒中的27种工业染料

建立了以超高效液相色谱-电喷雾串联四极杆质谱(UPLC-MS/MS)检测果汁和葡萄酒中27种工业染料的方法。样品经乙腈振荡提取,在盐析作用下分层,目标化合物转移至乙腈层中。目标化合物在梯度洗脱条件下经C18柱分离后采用多反应监测(MRM)模式进行检测。其中24种工业染料使用正离子模式检测,流动相为乙腈和0.1%的甲酸水溶液;其余3种工业染料则采用负离子模式检测,流动相为乙腈和水。结果表明: 果汁中27种工业染料的定量限(LOQ)为0.1～50 μg/kg,回收率为57.0%～117.7%,相对标准偏差为2.4%～17.7%。葡萄酒中的LOQ为0.2～50 μg/kg,回收率为40.8%～109.4%,相对标准偏差为1.6%～17.9%。该方法操作简单,灵敏度高,实现了不同种类的工业染料的同时提取,适合于软饮料中非法添加工业染料的快速检测。     

微液液提取或固相萃取法净化、气相色谱-质谱联用检测葡萄酒中19种农药多残留

建立了红葡萄酒中19种农药多残留的气相色谱-质谱联用选择离子模式进行监测的检测方法,比较了固相萃取(SPE)和微液液提取(MLLE)两种前处理方法并考察了基质效应。两种方法在0.01~10 mg/L范围内线性关系良好,相关系数大于0.997。在0.01~1.0 mg/kg添加水平范围内,SPE法的平均添加回收率在77.8%~109.1%之间(四螨嗪为137.5%);MLLE法的平均添加回收率在83.3%~116.7%之间(四螨嗪为43%)。SPE法的最低检出限(LOD)0.001~0.01 mg/kg之间,定量检出限(LOQ)为0.005~0.05 mg/kg,相对标准偏差小于10%;MLLE法为LOD在0.02~0.10 mg/kg,LOQ为0.06~0.30 mg/kg,相对标准偏差小于14%。所有目标化合物均存在基质增强效应,可用基质匹配标准溶液来减少其对测定结果的影响。     

Determination of dye intermediates in oxidative hair dyes by fused-silica capillary gas chromatography

A fused-silica capillary gas chromatographic method is described for the determination of dye intermediates in oxidative hair dyes. An appropriate amount of hair dye sample is dissolved in 10 ml of methanol containing 0.25 g of ammonium thioglycolate and an appropriate amount of 2-amino-4-methylphenol as an internal standard. This solution is directly injected into a gas chromatograph. A fused-silica capillary column with cross-linked methyl silicone OV-1 or SE-54 as a liquid phase yields excellent resolution of dye intermediates. Some factors affecting the quantitation of dye intermediates are discussed. The proposed method gave good recoveries and reproducibilities, and permits simultaneous determination of various types of dye intermediates without any pretreatment. The use of a nitrogen-phosphorus detector allows the selective detection of nitrogen-containing dye intermediates. This simple and versatile method is applicable for the determination of dye intermediates in commercial hair dyes.     

Simultaneous determination of p-phenylenediamines and aminophenols in hair dye products: interlaboratory study

An isocratic HPLC method routinely used in the National Laboratory for Food and Drug Analysis of Taiwan was validated for the simultaneous determination of six aminophenols and phenylenediamines in commercial hair dyes. After extraction of the commercial hair dye product, the dye intermediates were determined by HPLC. Recoveries from the extraction were between 91.6 and 96.5%. The method was then evaluated in an interlaboratory collaborative study according to AOAC guidelines. Five laboratories in Taiwan participated in the study that analyzed the test product, which was preanalyzed by two laboratories to ensure acceptable homogeneity. The RSD(r) and RSD(R) values of the measurements obtained for the dye intermediates in the product were < or = 3.75 and < or = 5.95%, respectively. The method demonstrated acceptable reproducibility, as evidenced by HorRat values of 0.82- 0.97. The applicability of the method to the determination of oxidative hair dye components was further demonstrated in analyses of two different products. The method is thus proposed to be used by manufacturers and laboratories to evaluate the quality of commercial hair dyes containing the six aminophenols and phenylenediamines.     

高效液相色谱法同时测定氧化型染发产品中33种染发剂

建立了高效液相色谱同时测定氧化型染发产品中33种禁限用染发剂含量的分析方法。采用Waters Atlantis^® T3 MV Kit色谱柱（250 mm×4.6 mm，5 μm），以磷酸盐缓冲液-乙腈为流动相，梯度洗脱，流速为1.0 mL/min，柱温为25℃；采用二极管阵列检测器（DAD），检测波长为235及280 nm，进样量为5 μL。结果表明，各成分在线性范围内线性关系良好，相关系数均高于0.999，各成分精密度实验相对标准偏差（RSDs）均小于2%；四氨基嘧啶硫酸盐和2，4-二氨基苯氧基乙醇盐酸盐在12 h内稳定性实验RSDs小于5%，其余31种成分在24 h内稳定性实验RSDs均小于5%；各成分在3个浓度水平下的加标回收率为77.6%~116.3%。该方法简便、快速、准确，适用于氧化型染发产品中多种染发剂的检测。     

Effect of hair dyes and bleach on the hair protein patterns as revealed by isoelectric focusing

The effect of hair dyes, i.e., temporary, semi-permanent, or permanent hair dyes, or hair bleach on the isoelectric focusing (IEF) hair protein patterns was studied. A permanent hair dye (metallic, alkaline oxidative, or acidic oxidative) and hair bleach induced changes in the IEF hair protein patterns and in the intensity of hair protein bands. The changes in the IEF patterns, caused by the alkaline oxidative dye or the bleach, are considered to result from the combined effect of an alkaline agent and an oxidative agent in the alkaline oxidative dye and in the hair bleach.     

高效液相色谱法测定氧化型染发产品中40种染发剂

氧化型染发产品中的多种染发剂具有不同程度的致敏性及其他毒性,建立快速、准确检测多种染发剂的方法,为该类产品监管提供有效的技术手段,十分必要。该研究建立了氧化型染发类产品中40种染发剂的高效液相色谱测定方法。染发产品经含70%乙醇的亚硫酸氢钠水溶液涡旋、超声提取,并经亚硫酸氢钠水溶液稀释后,以0.02 mol/L乙酸铵水溶液(含4%乙腈)和乙腈为流动相,采用Waters Atlantis^® T3 MV Kit色谱柱(250 mm×4.6 mm, 5 μm)分离,配合柱温变化进行梯度洗脱,二极管阵列检测器检测,检测波长为235 nm和280 nm,外标法定量。结果表明,40种染发剂在各自范围内线性关系良好,相关系数均大于0.999; 40种染发剂的检出限为5~168 μg/g,定量限为16~504 μg/g;各染发剂在3个添加水平下的平均回收率为81.4%~109.6%, RSD均小于5%;各染发剂标准溶液在24 h内稳定性良好,RSD为0.2%~2.2%。与现行标准检验方法相比,该方法较大程度地增加了单一液相色谱条件下可测定的染发剂,特别是准用染发剂种类(36种),提高了检测效率,并可保证检测结果的灵敏度与准确性,适用于氧化型染发产品中多种染发剂的检测分析。     

Separation and determination of basic dyes formulated in hair care products by capillary electrophoresis

A capillary electrophoretic (CE) method for analyzing five basic dyes (Basic Red 76, Basic Brown 16, Basic Yellow 57, Basic Brown 17 and Basic Blue 99) sold under the trade name Arianor, which are commonly used in hair care products, has been established. A buffer of 100 mM acetic acid-ammonium acetate (50:50) containing 90% (v/v) methanol was employed in a fused-silica capillary of 40.0 cm x 50 microm I.D. with a bubble cell arrangement. Washing the capillary end immediately after injection was effective in preventing peak tailing of the basic dyes, which was due to their adsorption onto the outer wall of the capillary during the injection. Under these optimized conditions, acceptable results for reproducibility, limit of detection and quantitation, and linearity were obtained for the five authentic dyes tested. The recoveries of five authentic basic dyes spiked to three commercial hair care products also provided with acceptable results. This optimized CE method is useful for the analysis of mixed basic dyes in hair care products.     

32种氧化型染料的高效液相色谱定量及高效液相色谱-串联质谱确证方法北大核心CSCD

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C_(18)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(r^(2)>0.99),检出限为9.7~40.1μg/g;HPLC-MS/MS方法中氢醌线性范围为2.0~79.7 mg/L,检出限为8.0μg/g,其他组分线性范围约为0.1~4 mg/L,检出限为0.01~0.4μg/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58~25160μg/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。     

Capillary zone electrophoresis in the analysis of dyes and other compounds employed in the dye-manufacturing and dye-using industries

High resolution separation of several dyes and related intermediates, as well as other compounds employed in the dye-manufacturing and dye-using industries, has been achieved using capillary zone electrophoresis (CZE).

The analysis of anionic dyes and some non-coloured anionic intermediates has been achieved using 10 mM Na₂B₄O₇−40 mM sodium dodecyl sulphate (SDS) buffer; high-resolution separations of water soluble anionic, neutral and cationic intermediates were also achieved using this micellar buffer. Micellar electrokinetic capillary chromatography (MECC) has also been developed for the analysis of aqueous insoluble, electrically neutral compounds by incorporating a co-solvent, acetonitrile, into a micellar buffer. In addition, MECC has been used successfully for following all the major steps involved in the synthesis of a disperse dye.     

Simultaneous determination of dihydroxybenzenes, aminophenols and phenylenediamines in hair dyes by high-performance liquid chromatography on hypercross-linked polystyrene

The retention of polar organic molecules such as dihydroxybenzenes, aminophenols and phenylenediamines on a 250 x 4.6 mm id column packed with 5 microns hypercross-linked polystyrene Chromalite 5HGN (Purolite) was studied. The influence of separation parameters such as concentration of acetonitrile, buffer (citrate, phosphate) concentration, ionic strength and pH of the eluent on their retention was investigated. Under optimum conditions [acetonitrile-0.3 mol l-1 ammonium phosphate, pH 5.15 (30:70 v/v)], eight substances generally used as dye intermediates in hair colouring compositions could be separated within 20 min. An HPLC method with spectrophotometric detection is proposed for the simultaneous determination of pyrocatechol, resorcinol, hydroquinone, o-, m- and p-aminophenols and p-phenylenediamine in commercial haircolour products. The detection limits of these compounds are in the range 0.05-0.16 microgram ml-1. The suitability of the method is demonstrated by the analysis of three different permanent hair dyes.