Malaysian
Journal of Analytical Sciences Vol 20 No 2 (2016): 288 - 295
POLYVINYLPYRROLIDONE
AS A NEW FLUORESCENT SENSOR FOR NITRATE ION
(Polivinilpirolidon Sebagai Sensor Pendafluor Baru Bagi Ion
Nitrat)
Ing Hua Tang1,
Rita Sundari2, Hendrik O. Lintang3, Leny Yuliati3*
1Department of Chemistry, Faculty of Science,
Universiti
Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
2The Research Center of Private Universities
Coordination, 13360 Jakarta, Indonesia
3Centre for Sustainable Nanomaterials,
Ibnu
Sina Institute for Scientific and Industrial Research,
Universiti
Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia
*Corresponding author: leny@ibnusina.utm.my
Received: 9
December 2014; Accepted: 9 October 2015
Abstract
In this study, non-conjugated
polyvinylpyrrolidone(PVP) was investigated for the first time as the potential
polymeric material to sense nitrate ions by fluorescence spectroscopy. The PVP
was diluted into various concentrations (3-10%) and they were used to sense the
nitrate ions in different concentrations (0.1-100 mM). The PVP showed two
excitation peaks at 285 and 330 nm due to the presence of C=O and N-C groups,
respectively. One strong emission at 400 or 408 nm was observed with the
excitation at 285 or 330 nm. The higher value of quenching constant at
excitation wavelength of 285 nm indicated that C=O site was more favored for NO3-
ions sensing than the N-C site. The PVP 7% gave the highest quenching constant;
where the KSV value was 9.89 × 10-3 mM-1 and
2.44 × 10-3 mM-1 for excitation at 285 and 330 nm,
respectively. The sensing capability was evaluated in the presence of
interference ions (SO42-, HCO3-, Cl-,
and OH-). It was observed that the interference ions interacted strongly
with the C=O, but weakly with the N-C. Therefore, in the presence of the
interference ions, the PVP would be a potential fluorescent sensor when it is
excited at 330 nm.
Keywords:
polyvinylpyrrolidone; fluorescent sensor; nitrate ions; quenching
Abstrak
Dalam
kajian ini, polivinilpirolidon (PVP) yang bersifat bukan konjugat dikaji untuk
kali pertama sebagai bahan polimer yang berpotensi untuk mengesan ion nitrat
dengan spektroskopi pendaflour. PVP dicairkan kepada kepekatan yang berlainan
(3-10%) dan digunakan untuk mengesan ion nitrat dalam kepekatan yang berbeza
(0.1-100 mM). PVP menunjukkan dua puncak pengujaan pada 285 and 330 nm dengan
kewujudan C=O dan N-C masing-masing. Satu puncak pemancaran yang tinggi pada
400 atau 408 nm diperolehi dengan pengujaan pada 285 atau 330 nm. Pemalar
pelidap kejutan dengan nilai yang lebih tinggi pada puncak pengujaan 285 nm
menunjukkan bahawa tapak C=O lebih cenderung untuk mengesan ion NO3-
daripada tapak N-C. PVP 7% memberi pemalar pelidap kejutan yang paling tinggi,
dengan nilai KSV 9.89 × 10-3 mM-1 and 2.44 ×
10-3 mM-1 untuk puncak pengujaan pada 285 dan 330 nm
masing-masing. Kemampuan pengesanan dinilai dengan kehadiran ion gangguan (SO42-,
HCO3-, OH-, and Cl-). Hasil kajian
menunjukkan bahawa ion gangguan berinteraksi kuat dengan C=O, tetapi lemah
dengan N-C. Oleh itu, dengan kehadiran ion gangguan, PVP berpotensi menjadi
pendafluor sensor pada tapak pengujaan 330 nm.
Kata
kunci: polivinilpirolidon;
pengesan pendaflour, ion nitrat, pelidap kejutan
References
1.
Bourlinos,
A. B., Georgakilas, V., Zboril, R., Steriotis, T. A., Stubos, A. K. and
Trapalis, C. (2009). Aqueous-phase exfoliation of graphite in the presence of
polyvinylpyrrolidone for the water-soluble graphenes. Solid State Communications,
149 (47-48): 2172-2176.
2.
Harsányi,
G. (2000). Polymer films in sensor applications: A review of
present uses and future possibilities. Emerald Insight, 20 (2): 98-105.
3.
Chen,
G., Lin, Y. and Wang, J. (2006). Monitoring environmental pollutants by
microchip capillary electrophoresis with electrochemical detection. Talanta, 68 (3): 497-503.
4.
Ozaydin-Ince,
G., Coclite, A. M. and Gleason, K. K. (2012). CVD of polymeric thin films:
applications in sensors, biotechnology, microelectronics/organic electronics,
microfluidics, MEMS, composites and membranes. Report on Progress in Physics, 75 (1): 016501
5.
Fan,
L-J., Zhang, Y. and Jones, W. E. (2005). Design and synthesis of fluorescence
“Turn-on” chemosensors based on photoinduced electron transfer in conjugated
polymers. Macromolecules, 38 (7):
2844-2849.
6.
Gangopadhyay,
R. and De, A. (2000). Conducting polymer nanocomposites: a brief overview. Chemistry of Materials, 12 (3): 608-622.
7.
Heeger,
A. J. (2001). Semiconducting and
metallic polymers: The fourth generation of polymeric materials. Journal of Physical Chemistry
B, 105 (36): 8475-8491.
8.
Vijayakumar,
N., Subramanian, E. and Padiyan, D. P.
(2012). Conducting polyaniline blends with the soft template poly(vinyl
pyrrolidone) and their chemosensor application. International Journal of Polymer Materials, 61 (11):
847-863.
9.
Akinyeye
R. O., Michira, I., Sekota, M., Ahmed, A. A., Tito, D., Baker, P. G. L., Brett,
C. M. A., Kalaji, M. and Iwuoha, E. (2007). Electrochemical synthesis and
characterization of 1,2-naphthaquinone-4-sulfonic acid doped polypyrrole. Electroanalysis, 19 (2-3): 303-309.
10.
Liu,
S., Wang, L., Luo, Y., Tian, J., Li, H. and Sun, X.
(2011). Polyaniline nanofibres for fluorescent nucleic acid detection. Nanoscale,
3 (3): 967-969.
11.
Sam,
M. S., Lintang, H. O., Sanagi, M. M., Lee, S. L. and Yuliati, L. (2014). Mesoporous carbon nitride for
adsorption and fluorescence sensor of n-nitrosopyrrolidone.
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, 124: 357-364.
12.
Minh,
T. T., Van, B. P., Van, T. D. and
Thi, H. N. (2013). The optical properties and energy
transition process in nanocomposite of polyvinyl-pyrrolidone polymer and
Mn-doped ZnS. Optical and Quantum
Electronics, 45 (2): 147-159.
13.
Nishizawa,
S., Kato, Y. and Teramae, N. (1999). Fluorescence sensing of anions via
intramolecular excimer formation in a pyrophosphate-induced self-assembly of a
pyrene-functionalized guanidium receptor. Journal
of American Chemical Society, 121 (40): 9463-9464.
14.
Wang,
P., Gan, T., Zhang, J., Luo, J. and Zhang, S. (2013).
Polyvinylpyrrolidone-enhanced electrochemical oxidation and detection of
acyclovir. Journal of Molecular Liquids,
177:129-132.
15.
Thi,
T. M., Tinh, L. V., Van, B. H., Ben, P. V. and Trung, V. Q. (2012). The effect of polyvinylpyrrolidone on the optical properties of the Ni-doped
ZnS nanocrystalline thin films synthesized by chemical method. Journal of Nanomaterials, 2012:1-8.
16.
Zhang,
J., Shen, G., Wang, W., Zhou, X. and Guo, S. (2010). Individual nanocomposite
sheets of chemically reduced graphene oxide and poly(n-vinyl pyrrolidone):
Preparation and humidity sensing characteristics. Journal of Materials Chemistry,
20 (48): 10824-10828.
17.
Taylor,
C. J., Bain, L. A., Richardson, D. J., Spiro, S. and Russell, D. A. (2004).
Construction of a whole-cell gene reporter for the fluorescent bioassay of
nitrate. Analytical Biochemistry, 328
(1): 60-66.
18.
Ito,
K., Takayama, Y., Makabe, N., Mitsui, R. and Hirokawa, T. (2005). Ion
chromatography for determination of nitrite and nitrate in seawater using Monolithic
ODS columns, Journal of Chromatography A,
1083(1-2): 63-67.
19.
Smil,
V. (1997). Global
population and the nitrogen cycle. Scientific
American, 277: 76-81.
20.
Moorcroft,
M. J., Davis, J. and Compton, R. G.
(2001). Detection and determination of nitrate and nitrite: A review. Talanta, 54 (5):
785-803.
21.
Tu,
X., Gao, Y., Yue, R., Lu, Q., Zhou, Y. and Lu, Z. (2012). An amperometric
nitrate sensor based on well-aligned cone-shaped polypyrrole-nanorods. Analytical Methods, 4 (12):
4182-4186.
22.
Bendikov,
T. A. and Harmon, T. C. (2005). A sensitive nitrate ion-selective electrode
from a pencil lead. An analytical laboratory experiment. Journal of Chemical Education, 82 (3):
439-441.
23.
Jang,
A., Zou, Z., Lee, K. K., Ahn, C. H. and Bishop, P. L. (2010). Potentiometric
and voltammetric polymer lab chip sensors for determination of nitrate, pH, and
Cd(II) in Water. Talanta, 83 (1):
1-8.
24.
Adeloju,
S. B. and Sohail, M. (2011). Polypyrrole-based bilayer nitrate amperometric
biosensor with an integrated permselective poly-ortho-phenylenediamine layer
for exclusion of inorganic interferences. Biosensors
and Bioelectronics, 26 (11): 4270-4275.
25.
Lakowicz,
J. R. (2006). Principles of Fluorescence
Spectroscopy. Springer: New York. 3rd
edition.
26.
Long,
Y., Chen, H., Yang, Y., Wang, H., Yang, Y., Li, N., Li, K., Pei, J. and Liu, F.
(2009). Electrospun nanofibrous film doped with a conjugated polymer for DNT
fluorescence sensor. Macromolecules,
42 (17): 6501-6509.
27.
Yang,
J.-S., and Swager, T. M. (1998). Fluorescent porous
polymer films as TNT chemosensors: Electronic and structural effects. Journal of American Chemical Society,
120 (46): 11864-11873.
28.
Shen,
G., Wang, W., Zhou, X. and Guo, S. (2010). Individual nanocomposite sheets of
chemically reduced graphene oxide and poly(n-vinyl pyrrolidone): Preparation
and humidity sensing characteristics. Journal
of Materials Chemistry, 20 (48):
10824-10828.
29.
Taylor,
C. J., Bain, L. A., Richardson, D. J., Spiro, S. and Russell, D. A. (2004).
Construction of a whole-cell gene reporter for the fluorescent bioassay of
nitrate. Analytical Biochemistry, 328
(1): 60-66.
30.
Ito,
K., Takayama, Y., Makabe, N., Mitsui, R. and Hirokawa, T. (2005). Ion
chromatography for determination of nitrite and nitrate in seawater using
Monolithic ODS columns, Journal of
Chromatography A, 1083(1-2): 63-67.
31.
Smil,
V. (1997). Global
population and the nitrogen cycle. Scientific
American, 277: 76-81.
32.
Moorcroft,
M. J., Davis, J. and Compton, R. G.
(2001). Detection and determination of nitrate and nitrite: A review. Talanta, 54 (5):
785-803.
33.
Tu,
X., Gao, Y., Yue, R., Lu, Q., Zhou, Y. and Lu, Z. (2012). An amperometric
nitrate sensor based on well-aligned cone-shaped polypyrrole-nanorods. Analytical Methods, 4 (12):
4182-4186.
34.
Bendikov,
T. A. and Harmon, T. C. (2005). A sensitive nitrate ion-selective electrode
from a pencil lead. An analytical laboratory experiment. Journal of Chemical Education, 82 (3):
439-441.
35.
Jang,
A., Zou, Z., Lee, K. K., Ahn, C. H. and Bishop, P. L. (2010). Potentiometric
and voltammetric polymer lab chip sensors for determination of nitrate, pH, and
Cd(II) in Water. Talanta, 83 (1):
1-8.
36.
Adeloju,
S. B. and Sohail, M. (2011). Polypyrrole-based bilayer nitrate amperometric
biosensor with an integrated permselective poly-ortho-phenylenediamine layer
for exclusion of inorganic interferences. Biosensors
and Bioelectronics, 26 (11): 4270-4275.
37.
Lakowicz,
J. R. (2006). Principles of Fluorescence
Spectroscopy. Springer: New York. 3rd
edition.
38.
Long,
Y., Chen, H., Yang, Y., Wang, H., Yang, Y., Li, N., Li, K., Pei, J. and Liu, F.
(2009). Electrospun nanofibrous film doped with a conjugated polymer for DNT
fluorescence sensor. Macromolecules,
42 (17): 6501-6509.
39.
Yang,
J.-S. and Swager, T. M. (1998). Fluorescent porous
polymer films as TNT chemosensors: Electronic and structural effects. Journal of American Chemical Society,
120 (46): 11864-11873.