Jiang Ruoke, Ding Xiaojing
1. School of Public Health,Capital Medical University,Beijing 100069,China;2. Beijing Center for Disease Control and Prevention,Beijing Research Center for Preventive Medicine,Beijing 100013,China.
Se Pu. 2023 Feb;41(2):168-177. doi: 10.3724/SP.J.1123.2022.06016.
Triclosan (TCS), triclocarban (TCC), and -chloro--xylenol (PCMX) are some of the most widely used antibiotics because of their broad-spectrum and highly-efficient bactericidal effects. In the context of disinfection, the National Standard GB 38598-2020 stipulates that the contents of the effective ingredients present in a disinfectant must be specified, wherein their range must fall within 90%-110% of the specified central value. To ensure a suitable product quality, analysis by high performance liquid chromatography (HPLC) is recommended by both the GB/T 27947-2020 and GB/T 34856-2017. However, the results analyzed according to the National Standard method often exceed the declared contents, thereby indicating the necessity to establish a new method based on a completely different principle (e. g., capillary electrophoresis), especially since it was not possible to analyze TCS, TCC, and PCMX in a single injection using the National Standard method. Moreover, using this method, large amounts of methanol were consumed, which could be potentially harmful to both operators and the environment. In terms of their water solubilities, this decreases in the order of PCMX>TCS>TCC, wherein TCC is insoluble in water. As such, the use of nonaqueous capillary electrophoresis (NACE) based on running buffer solutions prepared in pure organic solvents (e. g., methanol or acetonitrile) is necessary. In this paper, a new NACE approach combined with an ultraviolet detection method was developed for the simultaneous analysis of TCS, TCC, and PCMX in disinfectants, personal care products, and ointments. For this purpose, an uncoated fused silica capillary (20 cm×50 μm, total length=30.2 cm) was used as the separation column with a separation buffer composed of 14 mmol/L sodium borate, 2 g/L polyethylene glycol (PEG) 20000, and 0.5 mmol/L dodecyltrimethylammonium bromide (DTAB) in methanol. Following optimization of the separation parameters, the complete and simultaneous separation of TCS, TCC, and PCMX was achieved when the sample solution was prepared using 5 g/L PEG 20000 in methanol-acetonitrile (50∶50, v/v). It was possible to directly inject the sample into the analysis system after a simple dilution with the sample medium, and no interference was observed in any of the sample electropherograms when a separation voltage and detection wavelength of -12 kV and 214 nm were employed, respectively. Furthermore, TCS, TCC, and PCMX showed good linear relationships with their corrected peak areas within a mass concentration range of 1-100 mg/L, and the correlation coefficients () were all greater than 0.99. Moreover, the limits of detection (LODs, =3) and limits of quantification (LOQs, =10) were determined to be 0.2 and 1 mg/L, respectively. The spiked recoveries ranged from 94.5% to 104.4% with relative standard deviations of ≤4.8% in all cases. Subsequently, the established method was used to analyze 31 commercial samples, including hand sanitizer, disinfectant, baby powder, and antibacterial cream. A comparative analysis of HPLC, the developed NACE method, and our previously reported micellar electrokinetic chromatographic (MEKC) method was also carried out for the quantitative determination of TCS, TCC, and PCMX. Although no statistically significant differences were observed among the three methods, the results determined for 16 out of the 31 samples did not match the claimed contents. These results therefore indicate the necessity to further control the compositions of disinfectant products. Our results indicate that the newly established NACE method can be an important alternative to HPLC for routine laboratory analyses, especially considering that it minimizes waste generation, requires only a simple sample pretreatment process, and exhibits a good selectivity to the target compounds. It is therefore hoped that the NACE method will be incorporated into the National Standard method in the near future.
三氯生(TCS)、三氯卡班(TCC)和对氯间二甲苯酚(PCMX)是一些应用最为广泛的抗菌剂,因其具有广谱、高效的杀菌作用。在消毒领域,国家标准GB 38598-2020规定,必须明确消毒剂中有效成分的含量,其范围必须在规定中心值的90%-110%以内。为确保合适的产品质量,GB/T 27947-2020和GB/T 34856-2017均建议采用高效液相色谱法(HPLC)进行分析。然而,按照国家标准方法分析的结果往往超过宣称的含量,因此有必要基于完全不同的原理(如毛细管电泳)建立一种新方法,特别是因为采用国家标准方法无法一次进样分析TCS、TCC和PCMX。此外,使用该方法会消耗大量甲醇,这可能对操作人员和环境都有潜在危害。就它们的水溶性而言,顺序为PCMX>TCS>TCC,其中TCC不溶于水。因此,有必要使用基于纯有机溶剂(如甲醇或乙腈)配制的运行缓冲溶液的非水毛细管电泳(NACE)。本文建立了一种新的NACE方法,并结合紫外检测法,用于同时分析消毒剂、个人护理产品和药膏中的TCS、TCC和PCMX。为此,使用未涂层熔融石英毛细管(20 cm×50 μm,总长=30.2 cm)作为分离柱,分离缓冲液由14 mmol/L硼酸钠、2 g/L聚乙二醇(PEG)20000和0.5 mmol/L十二烷基三甲基溴化铵(DTAB)的甲醇溶液组成。在优化分离参数后,当样品溶液用甲醇-乙腈(50∶50,v/v)中的5 g/L PEG 20000配制时,实现了TCS、TCC和PCMX的完全同时分离。样品用样品介质简单稀释后可直接进样到分析系统中,当分别采用-12 kV的分离电压和214 nm的检测波长时,在任何样品电泳图中均未观察到干扰。此外,TCS、TCC和PCMX在1-100 mg/L的质量浓度范围内与其校正峰面积呈现良好的线性关系,相关系数(r)均大于0.99。而且,检测限(LODs,n=3)和定量限(LOQs,n=10)分别确定为0.2和1 mg/L。加标回收率在94.5%至104.4%之间,所有情况下相对标准偏差均≤4.8%。随后,使用所建立的方法分析了31种商业样品,包括洗手液、消毒剂、婴儿爽身粉和抗菌乳膏。还对HPLC、所建立的NACE方法以及我们之前报道的胶束电动色谱法(MEKC)进行了比较分析,以定量测定TCS、TCC和PCMX。虽然三种方法之间未观察到统计学上的显著差异,但31个样品中有16个样品的测定结果与宣称的含量不相符。因此,这些结果表明有必要进一步控制消毒产品的成分。我们的结果表明,新建立的NACE方法可成为HPLC用于常规实验室分析的重要替代方法,特别是考虑到它能减少废物产生,仅需简单的样品预处理过程,并且对目标化合物具有良好的选择性。因此,希望NACE方法在不久的将来能纳入国家标准方法。