Voltammetric behaviour of p-nitrophenol and its trace determination in human urine by liquid chromatography with a dual reductive mode electrochemical detection system

被引:56
作者
Honeychurch, Kevin C. [1 ]
Hart, John P. [1 ]
机构
[1] Univ W England, Ctr Res Analyt Mat & Sensors Sci, Fac Sci Appl, Bristol BS16 1QY, Avon, England
关键词
urine; HPLC; dual electrode detection; p-nitrophenol;
D O I
10.1002/elan.200703989
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
The determination of trace p-nitrophenol (PNP) concentrations in human urine has been successfully achieved by high performance liquid chromatography dual electrode detection (LC-DED) in the reduction-reduction mode. Initial cyclic voltammetric studies were undertaken to investigate the electrochemical behavior of PNP at a glassy carbon electrode over a wide pH range; the redox processes giving rise to the signals have been deduced. Further, deductions regarding the behavior in the flow cells were made from hydrodynamic voltammetric data. PNP eluting from the analytical LC column is first reduced to p-hydroxylaminophenol, at the first generator electrochemical cell. This species then undergoes chemical oxidation to give a quinoneimine species which is then detected at the downstream detector electrode using an applied potential of -0.1 V. The optimum chromatographic mobile phase consisted of 40% acetonitrile, 60% water, containing 25 mM o-phosphoric acid, at a flow rate of 0.5 mL/min; this was used in conjunction with a Hypersil C-18 column. Hydrodynamic voltammetric studies were undertaken to investigate the dual electrode behavior of PNP, and an applied potential of -2.0 Vat the generator cell and -0.10 V at the detector cell were found to be optimum. The response was found to be linear over the range 7.0 ng to 500 ng on column, with an associated R-2 value of 0.9981; the limit of detection was found to be 1.0 ng PNP on column. No interferences were seen for a number of common drugs or for the principal electrochemically active components of human urine or serum. The developed assay was successfully applied to the determination of trace concentrations of PNP in human urine samples, exhibiting coefficients of variation of 7.1% (n =7), with a mean recovery of 94.7% for urine fortified at 522 ng mL(-1).
引用
收藏
页码:2176 / 2184
页数:9
相关论文
共 40 条
[1]   Measurement of p-nitrophenol in the urine of residents whose homes were contaminated with methyl parathion [J].
Barr, DB ;
Turner, WE ;
DiPietro, E ;
McClure, PC ;
Baker, SE ;
Barr, JR ;
Gehle, K ;
Grissom, RE ;
Bravo, R ;
Driske, WJ ;
Patterson, DG ;
Hill, RH ;
Needham, LL ;
Pirkle, JL ;
Sampson, EJ .
ENVIRONMENTAL HEALTH PERSPECTIVES, 2002, 110 :1085-1091
[2]   THE REDUCTION OF SOME NITRO-COMPOUNDS AT A STIRRED MERCURY SURFACE [J].
BERGMAN, I ;
JAMES, JC .
TRANSACTIONS OF THE FARADAY SOCIETY, 1954, 50 (01) :60-65
[3]   DETERMINATION OF PHENOL, M-CRESOL, O-CRESOL AND P-CRESOL, P-AMINOPHENOL AND P-NITROPHENOL IN URINE BY HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY [J].
BREGA, A ;
PRANDINI, P ;
AMAGLIO, C ;
PAFUMI, E .
JOURNAL OF CHROMATOGRAPHY, 1990, 535 (1-2) :311-316
[4]   Simultaneous determination of aromatic amines by liquid chromatography coupled with carbon nanotubes/poly (3-methylthiophene) modified dual-electrode [J].
Cao, XN ;
Li, JH ;
Xu, HH ;
Zhan, JR ;
Lin, L ;
Yamamoto, K ;
Jin, LT .
CHROMATOGRAPHIA, 2004, 59 (3-4) :167-172
[5]  
Cordero-Rando MD, 1999, MIKROCHIM ACTA, V132, P7
[6]  
Davies JE, 1997, ANN NY ACAD SCI, V837, P257
[7]   ABSORPTION AND EXCRETION OF PARATHION BY SPRAYMEN [J].
DURHAM, WF ;
WOLFE, HR ;
ELLIOTT, JW .
ARCHIVES OF ENVIRONMENTAL HEALTH, 1972, 24 (06) :381-&
[8]   Rapid and sensitive determination of 4-nitrophenol, 3-methyl-4-nitrophenol, 4,6-dinitro-o-cresol, parathion-methyl, fenitrothion, and parathion-ethyl by liquid chromatography with electrochemical detection [J].
Galeano-Díaz, T ;
Guiberteau-Cabanillas, A ;
Mora-Díez, N ;
Parrilla-Vázquez, P ;
Salinas-López, F .
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 2000, 48 (10) :4508-4513
[9]  
Guidotti M, 1999, HRC-J HIGH RES CHROM, V22, P628, DOI 10.1002/(SICI)1521-4168(19991101)22:11&lt
[10]  
628::AID-JHRC628&gt