Alnajjar Ahmed O, El-Zaria Mohamed E
Department of Chemistry, College of Science, King Faisal University, P.O. Box 380, 31982 Hofuf, Saudi Arabia.
Eur J Med Chem. 2008 Feb;43(2):357-63. doi: 10.1016/j.ejmech.2007.03.034. Epub 2007 Apr 14.
A new simple and fast spectroscopic method was presented as a new marker for heroin use. Novel azo-morphine derivatives with spectroscopic absorption peaks ranging from 330-470 nm, were synthesized by the coupling of morphine (M) and 6-acetyl morphine (6-AM) with freshly prepared diazonium salt of aniline hydrochloride at 0 degrees C. However, no reaction was observed with codeine under the same reaction conditions. Separation of azo dyes was performed by TLC using tetrahydrofuran and dichloromethane in the ratio 1:1. The chemical structure of the products was established by their microanalysis, NMR, IR, UV-vis, and mass spectroscopies. Electronic absorption and excitation spectra of the dyes were measured in solvents of different polarities. The dyes exhibited positive solvatochromism, i.e., a bathochromic band shift as the solvent polarity is increased. Also, the fluorescence quantum yield was sensitive to the polarity and the pH of the medium. The UV-vis spectroscopy of spiked compounds in human urine samples was also reported. The drugs (M, 6-AM and mixture of both) were coupled with freshly prepared diazonium salt even at very low concentration of the drugs 10(-9)M.
提出了一种新的简单快速的光谱方法作为海洛因使用的新标志物。通过吗啡（M）和6-乙酰吗啡（6-AM）与新制备的盐酸苯胺重氮盐在0℃下偶联，合成了具有330 - 470nm光谱吸收峰的新型偶氮吗啡衍生物。然而，在相同反应条件下，可待因未观察到反应。使用四氢呋喃和二氯甲烷按1:1比例的薄层色谱法对偶氮染料进行分离。通过微量分析、核磁共振、红外、紫外可见和质谱对产物的化学结构进行了确证。在不同极性的溶剂中测量了染料的电子吸收和激发光谱。这些染料表现出正溶剂化显色性，即随着溶剂极性增加，吸收带发生红移。此外，荧光量子产率对介质的极性和pH敏感。还报道了人尿液样品中加标化合物的紫外可见光谱。即使在药物浓度非常低（10⁻⁹M）时，药物（M、6-AM以及两者的混合物）也能与新制备的重氮盐偶联。
