Numata Masahiko, Kaneko Toshiro, Mi Qiding, Ye Michael, Kawamata Satoshi, Matsuo Mayumi, Yarita Takashi
National Metrology Institute of Japan, AIST, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan.
J Chromatogr A. 2008 Nov 7;1210(1):68-75. doi: 10.1016/j.chroma.2008.09.038. Epub 2008 Sep 16.
In this study, a silica stationary phase modified with sulfoxide group and ammonium-salt was prepared for the separation of polychlorinated biphenyls (PCBs) from mineral oils, and its properties were investigated. Organic sulfide was attached to a diamino (primary and secondary amino) bonded silica surface by an amide bond, and the bonded sulfide groups were oxidized with periodate to afford sulfoxide groups bonded to the stationary phase. The secondary amino groups in the spacer chain were converted to ammonium-salt by the addition of hydrochloric acid. The sulfoxide group and ammonium-salt bonded stationary phase was tested for their suitability as adsorbent for SPE-type preparative short columns and for an analytical HPLC-type separation. The new stationary phase (1.2 mmol of sulfur bonded per gram) separated PCBs from mineral oils (paraffin-based transformer oils) more efficiently than previously reported stationary phases including sulfoxide group or ammonium-salt bonded ones. The quantitative chromatographic parameters for an aliphatic hydrocarbon (eicosane) and some PCB congeners also indicated strong retention of highly chlorinated biphenyls by the sulfoxide and ammonium-salt bonded silica compared with simple aminopropyl, sulfoxide group or ammonium-salt bonded ones. A cleanup procedure was established for simple determination of PCBs in mineral oil samples using sulfoxide group and ammonium-salt bonded silica packed column fractionation. The analytical method, combination of the cleanup procedure, and measurement with a GC-high resolution (magnetic sector) MS or a GC-quadrupole MS were validated using mineral oil certified reference materials.
在本研究中，制备了一种用亚砜基和铵盐改性的硅胶固定相，用于从矿物油中分离多氯联苯（PCBs），并对其性能进行了研究。有机硫化物通过酰胺键连接到二氨基（伯氨基和仲氨基）键合硅胶表面，键合的硫化物基团用过碘酸盐氧化，得到键合到固定相上的亚砜基团。间隔链中的仲氨基通过加入盐酸转化为铵盐。测试了亚砜基和铵盐键合固定相作为SPE型制备短柱吸附剂以及用于分析型HPLC分离的适用性。新的固定相（每克键合1.2 mmol硫）从矿物油（石蜡基变压器油）中分离多氯联苯的效率比先前报道的包括亚砜基或铵盐键合固定相更高。与简单的氨丙基、亚砜基或铵盐键合固定相相比，脂肪烃（二十烷）和一些多氯联苯同系物的定量色谱参数也表明，亚砜基和铵盐键合硅胶对高度氯化的联苯有很强的保留作用。建立了一种使用亚砜基和铵盐键合硅胶填充柱分馏简单测定矿物油样品中多氯联苯的净化方法。使用矿物油标准参考物质对该分析方法、净化方法与气相色谱 - 高分辨率（磁扇形）质谱或气相色谱 - 四极杆质谱测量相结合的方法进行了验证。
