title: Direct quantitative determination of cyanamide by stable isotope dilution gas chromatography-mass spectrometry.
abstract: Cyanamide is a multifunctional agrochemical used, for example, as a pesticide, herbicide, and fertilizer. Recent research has revealed that cyanamide is a natural product biosynthesized in a leguminous plant, hairy vetch (Vicia villosa). In the present study, gas chromatography-mass spectrometry (GC-MS) equipped with a capillary column for amines was used for direct quantitative determination of cyanamide. Quantitative signals for ((14)N(2))cyanamide, ((15)N(2))cyanamide (internal standard for stable isotope dilution method), and m-(trifluoromethyl)benzonitrile (internal standard for correcting errors in GC-MS analysis) were recorded as peak areas on mass chromatograms at m/z 42 (A(42)), 44 (A(44)), and 171 (A(IS)), respectively. Total cyanamide content, ((14)N(2))cyanamide plus ((15)N(2))cyanamide, was determined as a function of (A(42)+A(44))/A(IS). Contents of ((14)N(2))cyanamide and ((15)N(2))cyanamide were then calculated by multiplying the total cyanamide content by A(42)/(A(42)+A(44)) and A(44)/(A(42)+A(44)), respectively. The limit of detection for the total cyanamide content by the GC-MS analysis was around 1ng. The molar ratio of ((14)N(2))cyanamide to ((15)N(2))cyanamide in the injected sample was equal to the observed A(42)/A(44) value in the range from 0.1 to 5. It was, therefore, possible to use the stable isotope dilution method to quantify the natural cyanamide content in samples; i.e., the natural cyanamide content was derived by subtracting the A(42)/A(44) ratio of the internal standard from the A(42)/A(44) ratio of sample spiked with internal standard, and then multiplying the resulting difference by the amount of added ((15)N(2))cyanamide (SID-GC-MS method). This method successfully gave a reasonable value for the natural cyanamide content in hairy vetch, concurring with the value obtained by a conventional method in which cyanamide was derivatized to a photometrically active compound 4-cyanimido-1,2-naphthoquinone and analyzed with reversed-phase HPLC (CNQ-HPLC method). The determination range of cyanamide in the SID-GC-MS method was almost the same as that in the CNQ-HPLC method; however, the SID-GC-MS method was much simpler than the CNQ-HPLC method.
authors.affiliation: Department of Biological Safety Science, National Institute for Agro-Environmental Sciences, 3-1-3 Kan-nondai, Tsukuba, Ibaraki 305-8604, Japan. hiradate@affrc.go.jp
authors.forename: Syuntaro
authors.initials: S
authors.lastname: Hiradate
authors.forename: Tsunashi
authors.initials: T
authors.lastname: Kamo
authors.forename: Eri
authors.initials: E
authors.lastname: Nakajima
authors.forename: Kenji
authors.initials: K
authors.lastname: Kato
authors.forename: Yoshiharu
authors.initials: Y
authors.lastname: Fujii
mesh_terms: D003484:Cyanamide / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods* / Q000592:standards; D007201:Indicator Dilution Techniques; D007554:Isotopes / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D031306:Vicia / Q000737:chemistry*
chemical_list: D007554:Isotopes; D009570:Nitriles; D003484:Cyanamide; C014356:benzonitrile