Streicher R P, Arnold J E, Ernst M K, Cooper C V
Department of Health and Human Services, U.S. Public Health Service, National Institute for Occupational Safety and Health, Cincinnati, OH 45226, USA.
Am Ind Hyg Assoc J. 1996 Oct;57(10):905-13. doi: 10.1080/15428119691014413.
Analytical reference standards generally are not available for non-monomeric isocyanate species, making accurate identification and quantitation by high-performance liquid chromatography (HPLC) difficult. A successful derivatizing reagent must react rapidly with all isocyanate groups, the derivatized isocyanate must be detectable selectively and at very low levels, and the detector used for quantitation must give a response proportional to the number of derivatized isocyanate groups present. A novel derivatizing reagent, 1-(9-anthracenylmethyl)piperazine (MAP), was prepared in an attempt to achieve these goals. Derivatives were prepared by reacting five mono- and difunctional isocyanates with MAP and three other established isocyanate derivatizing reagents. These reagents included 1-(2-methoxyphenyl)piperazine (MOPP),9-(methylaminomethyl)anthracene (MAMA), and tryptamine (TRYP). The relative reactivities of MAP, MOPP, TRYP, and MAMA with phenyl isocyanate were found to be 100, 88, 30, and 25, respectively. Average molar absorptivities at the absorbance maxima +/- compound-to-compound variabilities were, for MAP: 1.47 x 10(5) +/- 3.50%; MAMA: 1.38 x 10(5) +/- 7.07%: and TRYP: 3.98 x 10(4) +/- 13.1%. Average fluorescence responses were, for MAP: 100 +/- 32.6%; MAMA: 41.0 +/- 58.8%; and TRYP: 2.27 +/- 15.6%. A comparison of MAP and MOPP ureas by HPLC/ultraviolet (UV)/electrochemical (EC) gave average responses for UV, EC, and EC/UV for MAP: 117 +/- 7.3%, 52.1 +/- 6.6%, and 0.447 +/- 10.7%, respectively; for MOPP: 24.3 +/- 62.5%, 76.7 +/- 28.5%, and 4.28 +/- 59.1%, respectively. The favorable performance of MAP warrants its further study as a reagent for the determination of total isocyanate group in air.
对于非单体异氰酸酯类物质，通常没有分析参考标准品，这使得通过高效液相色谱法（HPLC）进行准确鉴定和定量变得困难。一种成功的衍生试剂必须能与所有异氰酸酯基团快速反应，衍生后的异氰酸酯必须能被选择性地检测到且检测限要非常低，并且用于定量的检测器给出的响应必须与存在的衍生异氰酸酯基团的数量成正比。为了实现这些目标，制备了一种新型衍生试剂1-(9-蒽甲基)哌嗪（MAP）。通过使五种单官能和双官能异氰酸酯与MAP以及其他三种已有的异氰酸酯衍生试剂反应来制备衍生物。这些试剂包括1-(2-甲氧基苯基)哌嗪（MOPP）、9-(甲氨基甲基)蒽（MAMA）和色胺（TRYP）。发现MAP、MOPP、TRYP和MAMA与苯基异氰酸酯的相对反应活性分别为100、88、30和25。在最大吸收波长处的平均摩尔吸光系数±化合物间的变化率，对于MAP为：1.47×10⁵±3.50%；对于MAMA为：1.38×10⁵±7.07%；对于TRYP为：3.98×10⁴±13.1%。平均荧光响应，对于MAP为：100±32.6%；对于MAMA为：41.0±58.8%；对于TRYP为：2.27±15.6%。通过HPLC/紫外（UV）/电化学（EC）对MAP和MOPP脲进行比较，MAP的UV、EC和EC/UV的平均响应分别为：117±7.3%、52.1±6.6%和0.447±10.7%；对于MOPP分别为：24.3±62.5%、76.7±28.5%和4.28±59.1%。MAP的良好性能保证了其作为测定空气中总异氰酸酯基团的试剂值得进一步研究。
