Aminopyrenes, determination

In the PO-CL system, the compounds showing native fluorescence or that fluoresce after chemical derivatization can be detected. As examples of the PO-CL detection of native fluorescence compounds, dipyridamole and benzydamine in rat plasma [57] and fluphenazine [58] have been reported in the former method, the detection limits of dipyridamole and benzydamine were 345 pM and 147 nM in plasma, respectively. Diamino- and aminopyrenes were sensitively determined using TCPO and their detection limits were in the sub-fmol range [59], Carcinogenic compounds such as 1- nitropyrene and its metabolites, can also be determined by the HPLC-PO-CL system. Nonfluorescent nitropyrenes were converted into the corresponding fluorescent aminopyrenes by online reduction on a Zn column followed by detection 2-50-fmol detection limits were achieved in the determination of ethanol extracts from airborne particulates (Fig. 13) [60],... 

HPLC on a Cosmosil 5 Cis column, using a perchloric acid-acetonitrile eluent (pH 7.6), followed by CLD in the presence of hydrogen peroxide and bis(2,4,6-trichlorophenyl) oxalate (42), was applied to the determination of 1-aminopyrene (43a) and various diaminopyrenes (43b-d). Ascorbic acid was added to avoid oxidative degradation of the aminopyrenes in the presence of metals LOD in the sub-fmol range (SNR 3)147. A fast (less than 10 min) HPLC-ELCD method was proposed for determination of dopamine (19b) and its metabolites in microdialysates, using packed fused silica capillary columns LOD 0.05 Xg/L of dopamine in a 2 XL sample, RSD 3% (n = 10)148. 

Hayakawa K, Kitamura R, Butoh M, Imaizumi N, Miyazaki M. Determination of diamino- and aminopyrenes by high performance liquid chromatography with chemiluminescence detection. Anal Sci 1991 573-7. 

Zhu et al. proposed more complicated biosensor construction for selective binding of rhodamine B and 1-aminopyrene [119]. To do this, first GO is electrochemically reduced on the surface of the GCE and then iV-acetylaniline is polymerized on top of it. After this, -CD was covalently attached to the composite surface by electrooxidation. This sensor was used for voltammetric determination of 1-aminopyrene, an electrochemically active polycyclic aromatic hydrocarbon deleterious for living organisms. The authors show that -CD binds rhodamine B selectively, but in the presence of 1-aminopyrene, the rhodamine B molecules are displaced by 1-aminopyrene. This displacement results in a decreased oxidation peak current of rhodamine B and the appearance of an oxidation peak current for 1-aminopyrene. The current is linearly dependent on the 1-aminopyrene concentration between 10-260 nM. 

Weller [21-23] has pointed out the competition between the rates of proton transfer and the deactivation in the excited state. In fact, it has been shown that proton-induced fluorescence quenching competitive with the proton-transfer reaction is present in the excited state of naphthylamines, that is, simple acid-base equilibrium cannot be accomplished in the excited state of aromatic amines, and that a dynamic analysis containing the quenching process is, therefore, needed in order to obtain the correct values [32,33]. The dynamic analyses by means of nanosecond time-resolved spectroscopy with fluorimetry have been applied to 1-aminopyrene [34,35], 1-aminoanthracene [36], phenanthrylamine [37,38], and naphthols [39]. This method to determine the values of naphthylamines has been used by Hafner et al. [40], and similar experiments for excited naphthols have been carried out by Harris and Selinger [41]. On the other hand, establishment of prototropic equilibrium has been reported in the case of 2-hydroxynaphthalene-6,8-disulfonate [42]. 

The dynamic analysis method with nanosecond time-resolved flnorimetry has been applied to determine the pK values for 1-aminopyrene [34,35], 1-aminophenanlhrene [36], phenanthrylamines [37], and naphthols [39]. The Smttgart gronp has supported this method to determine the pK values of naphthylamines [40]. The detailed Idnelics of proton transfer reaction of 1-naphthol in H O and D O have been investigated by using picosecond time-resolved fluorescence spectroscopy [48]. 

Ferancova A, Buckova M, Korgova E, Korbut O, Griindler P, Wiimmark 1, Mepan R, Barek J, Zima J, Labuda J (2005) Association interaction and voltammetric determination of 1-aminopyrene and 1-hydroxypyrene at cyclodextrin and DNA based electrochemical sensors. Bioelectrochemistry 67(2) 191-197. doi 10.1016/j.bioelechem.2004.06.007... 

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