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Highly sensitive determination of 2,4,6-trinitrotoluene and related byproducts using a diol functionalized column for high performance liquid chromatography.

Gumuscu B, Erdogan Z, Guler MO, Tekinay T - PLoS ONE (2014)

Bottom Line: The detection limits for diol column ranged from 0.78 to 1.17 µg/L for TNT and its byproducts.When compared to C-18 and phenyl-3 columns, solvent usage was reduced up to 64% using diol column and resolution was enhanced approximately two-fold.The sensitivity of diol column was afforded by the hydroxyl groups on polyol layer, joining the formation of charge-transfer complexes with nitroaromatic compounds according to acceptor-donor interactions.

View Article: PubMed Central - PubMed

Affiliation: UNAM, Institute of Materials Science and Nanotechnology, Bilkent University, Ankara, Turkey; MESA+ Institute for Nanotechnology, University of Twente, Enschede, the Netherlands.

ABSTRACT
In this work, a new detection method for complete separation of 2,4,6-trinitrotoluene (TNT); 2,4-dinitrotoluene (2,4-DNT); 2,6-dinitrotoluene (2,6-DNT); 2-aminodinitrotoluene (2-ADNT) and 4-aminodinitrotoluene (4-ADNT) molecules in high-performance liquid-chromatography (HPLC) with UV sensor has been developed using diol column. This approach improves on cost, time, and sensitivity over the existing methods, providing a simple and effective alternative. Total analysis time was less than 13 minutes including column re-equilibration between runs, in which water and acetonitrile were used as gradient elution solvents. Under optimized conditions, the minimum resolution between 2,4-DNT and 2,6-DNT peaks was 2.06. The recovery rates for spiked environmental samples were between 95-98%. The detection limits for diol column ranged from 0.78 to 1.17 µg/L for TNT and its byproducts. While the solvent consumption was 26.4 mL/min for two-phase EPA and 30 mL/min for EPA 8330 methods, it was only 8.8 mL/min for diol column. The resolution was improved up to 49% respect to two-phase EPA and EPA 8330 methods. When compared to C-18 and phenyl-3 columns, solvent usage was reduced up to 64% using diol column and resolution was enhanced approximately two-fold. The sensitivity of diol column was afforded by the hydroxyl groups on polyol layer, joining the formation of charge-transfer complexes with nitroaromatic compounds according to acceptor-donor interactions. Having compliance with current requirements, the proposed method demonstrates sensitive and robust separation.

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Separation of nitroaromatics by C-18 column: (a) self-optimization performance, (b) with the method presented in Table 1.
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pone-0099230-g003: Separation of nitroaromatics by C-18 column: (a) self-optimization performance, (b) with the method presented in Table 1.

Mentions: The separation in C-18 column occurs via hydrophobic interactions. TNT is the most hydrophobic molecule among the tested reagents, thus the TNT peak was observed earlier than the other analytes. The amino group is less polar in 4-ADNT than the nitro group in TNT as a result, 4-ADNT was observed after TNT molecule. 2-ADNT was detected after 4-ADNT because of the methyl group attraction between nitro and amino groups in 2-ADNT. DNTs have two polar groups on the aromatic ring, thus eluted last. Since less prominent steric effects present more powerful hydrophobic interactions, the methyl group bonding on 2,4-DNT with the filling material is stronger than that of the 2,6-DNT isomer, as 2,4-DNT has only one neighboring nitro group (Fig. 3).


Highly sensitive determination of 2,4,6-trinitrotoluene and related byproducts using a diol functionalized column for high performance liquid chromatography.

Gumuscu B, Erdogan Z, Guler MO, Tekinay T - PLoS ONE (2014)

Separation of nitroaromatics by C-18 column: (a) self-optimization performance, (b) with the method presented in Table 1.
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4048276&req=5

pone-0099230-g003: Separation of nitroaromatics by C-18 column: (a) self-optimization performance, (b) with the method presented in Table 1.
Mentions: The separation in C-18 column occurs via hydrophobic interactions. TNT is the most hydrophobic molecule among the tested reagents, thus the TNT peak was observed earlier than the other analytes. The amino group is less polar in 4-ADNT than the nitro group in TNT as a result, 4-ADNT was observed after TNT molecule. 2-ADNT was detected after 4-ADNT because of the methyl group attraction between nitro and amino groups in 2-ADNT. DNTs have two polar groups on the aromatic ring, thus eluted last. Since less prominent steric effects present more powerful hydrophobic interactions, the methyl group bonding on 2,4-DNT with the filling material is stronger than that of the 2,6-DNT isomer, as 2,4-DNT has only one neighboring nitro group (Fig. 3).

Bottom Line: The detection limits for diol column ranged from 0.78 to 1.17 µg/L for TNT and its byproducts.When compared to C-18 and phenyl-3 columns, solvent usage was reduced up to 64% using diol column and resolution was enhanced approximately two-fold.The sensitivity of diol column was afforded by the hydroxyl groups on polyol layer, joining the formation of charge-transfer complexes with nitroaromatic compounds according to acceptor-donor interactions.

View Article: PubMed Central - PubMed

Affiliation: UNAM, Institute of Materials Science and Nanotechnology, Bilkent University, Ankara, Turkey; MESA+ Institute for Nanotechnology, University of Twente, Enschede, the Netherlands.

ABSTRACT
In this work, a new detection method for complete separation of 2,4,6-trinitrotoluene (TNT); 2,4-dinitrotoluene (2,4-DNT); 2,6-dinitrotoluene (2,6-DNT); 2-aminodinitrotoluene (2-ADNT) and 4-aminodinitrotoluene (4-ADNT) molecules in high-performance liquid-chromatography (HPLC) with UV sensor has been developed using diol column. This approach improves on cost, time, and sensitivity over the existing methods, providing a simple and effective alternative. Total analysis time was less than 13 minutes including column re-equilibration between runs, in which water and acetonitrile were used as gradient elution solvents. Under optimized conditions, the minimum resolution between 2,4-DNT and 2,6-DNT peaks was 2.06. The recovery rates for spiked environmental samples were between 95-98%. The detection limits for diol column ranged from 0.78 to 1.17 µg/L for TNT and its byproducts. While the solvent consumption was 26.4 mL/min for two-phase EPA and 30 mL/min for EPA 8330 methods, it was only 8.8 mL/min for diol column. The resolution was improved up to 49% respect to two-phase EPA and EPA 8330 methods. When compared to C-18 and phenyl-3 columns, solvent usage was reduced up to 64% using diol column and resolution was enhanced approximately two-fold. The sensitivity of diol column was afforded by the hydroxyl groups on polyol layer, joining the formation of charge-transfer complexes with nitroaromatic compounds according to acceptor-donor interactions. Having compliance with current requirements, the proposed method demonstrates sensitive and robust separation.

Show MeSH
Related in: MedlinePlus