Abstract
Fluorescamine is a non-fluorescent reagent widely used for the quantitative determination of primary amines by fluorescence spectroscopy as it reacts readily with primary amines to form a fluorescent product. In this work, a new sensitive voltammetric method for the detection of ammonia in aqueous solution by the reaction with fluorescamine has been developed. First, the electrochemical behaviour of fluorescamine in the absence and presence of ammonia was investigated in 0.1 mol L-1 borate buffer solution (pH 9.0) by cyclic voltammetry using a glassy carbon (GC) electrode. As for fluorescamine itself, a well-defined irreversible oxidation peak could be observed at ca. 0.70 V vs. SCE. When ammonia was added to the fluorescamine solution, another irreversible oxditaion peak corresponding to the oxidation of the reaction product formed between fluorescamine and ammonia could be observed at ca. 0.46 V vs. SCE. Upon the addition of ammonia, the oxidation peak of fluorescamine became smaller while the oxidation peak of the reaction product formed increased in height, due to the stoichiometric chemical consumption of fluorescamine by ammonia and the formation of the product during the reaction, respectively. These two anodic peaks corresponding to the oxidation of fluorescamine and its fluorescent product formed were then used for the quantitative detection of ammonia, explored by square wave voltammetry and by fluorescence spectroscopy. The square wave voltammetric response of the reaction product formed showed a linear response over ammonia concentration range of 0 to 60 μmol L-1. The limits of detection (LOD) was found to be 0.71 μmol L-1 and 3.17 μmol L-1 determined based upon Signal/Noise (S/N) = 3 and 3σ, respectively. These limits of detection are similar to those obtained with the fluorometric method.
Graphical Abstract
Keywords
electrochemical detection, cyclic voltammetry, square wave voltammetry, fluorescence spectroscopy, ammonia, fluorescamine
Publication Date
2012-10-28
Online Available Date
2012-08-30
Revised Date
2012-08-27
Received Date
2012-06-26
Recommended Citation
Panchompoo Janjira, G. Compton Richard.
Electrochemical Detection of Ammonia in Aqueous Solution using Fluorescamine: A Comparison of Fluorometric Versus Voltammetric Analysis[J]. Journal of Electrochemistry,
2012
,
18(5): Article 6.
DOI: 10.61558/2993-074X.2614
Available at:
https://jelectrochem.xmu.edu.cn/journal/vol18/iss5/6
References
[1] Timmer B, Olthuis W, van den Berg A. Ammonia sensors and their applications—a review[J]. Sensors and Actuators B: Chemical, 2005, 107(2): 666-677.
[2] Huszár H, Pogány A, Bozóki Z, et al. Ammonia monitoring at ppb level using photoacoustic spectroscopy for environmental application[J]. Sensors and Actuators B: Chemical, 2008, 134(2): 1027-1033.
[3] Valentini F, Biagiotti V, Lete C, et al. The electrochemical detection of ammonia in drinking water based on multi-walled carbon nanotube/copper nanoparticle composite paste electrodes[J]. Sensors and Actuators B: Chemical, 2007, 128(1): 326-333.
[4] Waich K, Mayr T, Klimant I. Fluorescence sensors for trace monitoring of dissolved ammonia[J]. Talanta, 2008, 77(1): 66-72.
[5] Pal T, Pal A, Miller G H, et al. Analytica Passive dosimeter for monitoring ammonia vapor[J]. Analytica Chimica Acta, 1992, 263(1/2): 175-178.
[6] “Occupational health guideline for ammonia” by U.S. Occupational Safety and Health Administration (OSHA), to be found under http://www.cdc.gov/niosh/
[7] “Safety and health topics: Ammonia”, to be found under http://www.osha.gov
[8] “Criteria for a recommended standard: Occupational exposure to ammonia”, to be found under http://www.cdc.gov/niosh/
[9] Cellk M S, Ozdemir B, Turan M, et al. Removal of ammonia by natural clay minerals using fixed and fluidized bed column reactors[J]. Water Science and Technology: Water Supply, 2001, 1: 81-88.
[10] Rahmani A R, Mahvi A H, Mesdaghinia A R, et al. Investigation of ammonia removal from polluted waters by clinoptilolite zeolite[J]. International Journal of Environmental Science and Technology, 2004, 1: 125-133.
[11] Gaspard M, Neveu A, Martin G. Clinoptilolite in drinking water treatment for ammonium ion removal[J]. Water Research, 1983, 17: 279-288.
[12] Winquist F, Spetz A, Lundstr?m I, et al. Determination of ammonia in air and aqueous samples with a gas-sensitive semiconductor capacitor[J]. Analytica Chimica Acta, 1984, 164(0): 127-138.
[13] Danielson N D, Conroy C M. Fluorometric determination of hydrazine and ammonia separately or in mixtures[J]. Talanta, 1982, 29(5): 401-404.
[14] Need A, Karmen C, Sivakoff S, et al. Specific detection of nitrogen in gas—liquid chromatographic effluents by fluorescent detection of ammonia[J]. Journal of Chromatography A, 1978, 158: 153-160.
[15] Rapsomanikis S, Wake M, Kitto A M N, et al. Analysis of atmospheric ammonia and particulate ammonium by a sensitive fluorenscence method[J]. Environmental Science and Technology, 1988, 22: 948-52.
[16] Sahasrabuddhey B, Jain A, Verma K K. Determination of ammonia and aliphatic amines in environmental aqueous samples utilizing pre-column derivatization to their phenylthioureas and high performance liquid chromatography[J]. Analyst, 1999, 124(7): 1017-1021.
[17] Imai K, Toyo'oka T, Miyano H. Fluorigenic reagents for primary and secondary amines and thiols in high-performance liquid chromatography. A review[J]. Analyst, 1984, 109(11): 1365-1373.
[18] Blau K, Halket J M. Handbook of derivatives for chromatography[M]. 2nd ed. 1993, Chichester; New York: Wiley.
[19] Stein S, B?hlen P, Udenfriend S. Studies on the kinetics of reaction and hydrolysis of fluorescamine[J]. Archives of Biochemistry and Biophysics, 1974, 163(1): 400-403.
[20] De Bernardo S, Weigele M, Toome V, et al. Studies on the reaction of fluorescamine with primary amines[J]. Archives of Biochemistry and Biophysics, 1974, 163(1): 390-399.
[21] Chen Y, Zhang Y. Fluorescent quantification of amino groups on silica nanoparticle surfaces[J]. Analytical and Bioanalytical Chemistry, 2011, 399(7): 2503-2509.
[22] Wilson R, Schiffrin D J. Use of fluorescamine for the spectrofluorimetric investigation of primary amines on silanized glass and indium tin oxide-coated glass[J]. Analyst, 1995, 120(1): 175-178.
[23] Castell J V, Cervera M, Marco R. A convenient micromethod for the assay of primary amines and proteins with fluorescamine. A reexamination of the conditions of reaction[J]. Analytical Biochemistry, 1979, 99(2): 379-391.
[24] Miedel M C, Hulmes J D, Pan Y C E. The use of fluorescamine as a detection reagent in protein microcharacterization[J]. Journal of Biochemical and Biophysical Methods, 1989, 18(1): 37-52.
[25] Djozan D M A, Farajzadeh M A. The use of fluorescamine (Fluram) in fluorimetric trace analysis of primary amines of pharmaceutical and biological interest[J]. Journal of Pharmaceutical and Biomedical Analysis, 1992, 10(10/12): 1063-1067.
[26] Udenfriend S, Stein S, Bohlen P, et al. Fluorescamine: A reagent for assay of amino acids, peptides, proteins, and primary amines in the picomole range[J]. Science, 1972, 178: 871-872.
[27] Settle F A. Handbook of instrumental techniques for analytical chemistry[M]. 1997, Upper Saddle River, NJ: Prentice Hall PTR.
[28] Panchompoo J, Aldous L, Baker M, et al. One-step synthesis of fluorescein modified nano-carbon for Pd(ii) detection via fluorescence quenching[J]. Analyst, 2012, 137(9): 2054-2062.
[29] Lakowicz J R, Principles of fluorescence spectroscopy[M]. 2nd ed. 1999, New York, London: Kluwer Academic/Plenum.
[30] Ware W R. Oxygen quenching of fluorescence in solution: An experimental study of the diffusion process[J]. The Journal of Physical Chemistry, 1962, 66(3): 455-458.
[31] ArIk M, ?elebi N, Onganer Y. Fluorescence quenching of fluorescein with molecular oxygen in solution[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2005, 170(2): 105-111.
[32] Bates R G, Pinching G D. Dissociation constant of aqueous ammonia at 0 to 50° from E. m. f. studies of the ammonium salt of a weak acid[J]. Journal of the American Chemical Society, 1950, 72(3): 1393-1396.
[33] Weast R C. CRC handbook of chemistry and physics[M]. 1st Student ed. 1988, Boca Raton, FL: CRC Press.
[34] Al-Kady A S, Gaber M, Hussein M M, et al. Structural and fluorescence quenching characterization of hematite nanoparticles[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2011, 83(1): 398-405.
[35] Thomsen, V, Schatzlein D, Mercuro D. Limits of detection in spectroscopy[J]. Spectroscopy, 2003, 18(12): 112-114.
[36] Panchompoo J, Aldous L, Downing C, et al. Facile synthesis of Pd nanoparticle modified carbon black for electroanalysis: Application to the detection of hydrazine[J]. Electroanalysis, 2011, 23(7): 1568-1578.
[37] Bard A J, Faulkner L R. Electrochemical methods: Fundamentals and applications[M]. 1980, New York, Chichester: Wiley.
[38] Compton R G, Banks C E. Understanding voltammetry[M]. 2nd ed. 2011, London: Imperial College Press.
[39] Osteryoung J G, Osteryoung R A. Square wave voltammetry[J]. Analytical Chemistry, 1985, 57: 101A-110A.
[40] Helfrick J C, Bottomley L A. Cyclic square wave voltammetry of single and consecutive reversible electron transfer reactions[J]. Analytical Chemistry, 2009, 81(21): 9041-9047.