Istanbul University, Faculty of Engineering, Department of Chemistry, Avcilar 34320, Istanbul, Turkey.
Analyst. 2010 Aug;135(8):2085-91. doi: 10.1039/b925653a. Epub 2010 Jun 7.
The two members of peroxide-based explosives, triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD), can be manufactured from readily accessible reagents, and are difficult to detect by conventional analytical methods. TATP and HMTD were securely synthesized, taken up with acetone, hydrolyzed with 4 M HCl to hydrogen peroxide, the acidic solution containing H(2)O(2) was neutralized, and assayed by the copper(II)-neocuproine spectrophotometric method. The chromophore of the reaction was the Cu(I)-neocuproine chelate responsible for light absorption at 454 nm. The molar absorptivity (epsilon) of the method for TATP and HMTD was 3.45 x 10(4) and 4.68 x 10(4) L mol(-1) cm(-1), respectively. The TATP recovery from a synthetically contaminated loamy clay soil was 91-99%. The colorimetric method was also applied to a Cu(ii)-neocuproine-impregnated polymeric Nafion membrane sensor developed for the first time in this work for peroxide explosive assay. The absorbance-concentration response was perfectly linear, and the limit of detection (LOD) of the procedure for both TATP and HMTD was approximately 0.2 mg L(-1). Neither common soil ions (Ca(2+), K(+), Cl(-), SO(4)(2-), Mg(2+) and NO(3)(-)) at 100-fold amounts nor military-purpose nitro-explosives of TNT, RDX, and PETN at 10-fold amounts interfered with the proposed assay. Active oxygen constituents of laundry detergents (perborates and percarbonates), which normally interfered with the assay, could easily be separated from the analytes by solubility differences. The method was statistically validated against standard reference methods of TiOSO(4) colorimetry and GC-MS.
基于过氧化物的两种爆炸物，三丙酮三过氧化物（TATP）和六亚甲基三过氧化物二胺（HMTD），可以用易得的试剂制成，并且很难用常规分析方法检测到。TATP 和 HMTD 被安全合成，用丙酮提取，用 4 M HCl 水解生成过氧化氢，将含有 H(2)O(2)的酸性溶液中和，并用铜(II)-邻菲啰啉分光光度法进行测定。反应的生色团是负责在 454nm 处光吸收的 Cu(I)-邻菲啰啉螯合物。该方法对 TATP 和 HMTD 的摩尔吸光率（epsilon）分别为 3.45 x 10(4)和 4.68 x 10(4) L mol(-1) cm(-1)。从合成污染的壤土中回收 TATP 的回收率为 91-99%。该比色法也应用于首次在本工作中开发的 Cu(ii)-邻菲啰啉浸渍聚合物 Nafion 膜传感器，用于过氧化物爆炸物的测定。吸光度-浓度响应呈完全线性，该程序对 TATP 和 HMTD 的检出限（LOD）约为 0.2mgL(-1)。即使在 100 倍量的常见土壤离子（Ca(2+)、K(+)、Cl(-)、SO(4)(2-)、Mg(2+)和 NO(3)(-)）和 10 倍量的军用硝基炸药 TNT、RDX 和 PETN 存在的情况下，该方法也不会受到干扰。通常会干扰测定的洗衣剂中的活性氧成分（过硼酸盐和过碳酸盐）可以通过溶解度差异很容易地与分析物分离。该方法通过 TiOSO(4)比色法和 GC-MS 的标准参考方法进行了统计学验证。
