Malaysian
Journal of Analytical Sciences Vol 24 No 3
(2020): 330 - 338
SYNTHESIS
AND CHARACTERIZATION OF CATALYTIC POLYMER- CLAY FILM FOR TREATMENT OF
17α-ETHINYLESTRADIOL
(Sintesis dan Pencirian
Filem Polimer-Tanah Liat dengan Pemangkin untuk Rawatan 17α-Etinilestradiol)
Nur Khairunnisa Nazri, Nabilah Ismail1*, Mohd Aidil Adhha
Abdullah1, Fatimah Hashim1, Leonard James Wright2
1Faculty
of Science and Marine Environment,
Universiti
Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia
2Centre of Green Chemical Sciences,
University of Auckland, 23 Symonds St, Private Bag 92019, Auckland, New Zealand
*Corresponding
author: nabilah.i@umt.edu.my
Received: 20 November 2019;
Accepted: 5 April 2020; Published: 9 June
2020
Abstract
Synthetic estrogen such as
17α-ethinylestradiol (EE2) is considered as one of the
pharmaceuticals found in waterways worldwide usually due to human utilization
and excretion into wastewater treatment system. In this study, catalytic
polymer-clay film was used to treat EE2 in the contaminated water by
oxidizing the pollutant. Polychloromethylstyrene was
synthesized along with the clay cloisite to form films that can anchor catalyst
Iron-tetra amido microcylic ligand (Fe-TAML). Fe-TAML works efficiently with
hydrogen peroxide to activate the iron to higher oxidation state for a film
performance. Polymer-clay was then casted, cured, cross-linked and
functionalized to form a film that can bind the catalyst into it.
Characterization of the films was done using Fourier Transform Infrared (FTIR)
to determine the presence of the functional group;
preliminary analysis of oxidation study was carried out using UV-Vis
Spectroscopy. Furthermore, the toxicity of the oxidized solution of EE2
after undergoing oxidation with catalytic polymer-clay film was investigated
using Acanthamoeba sp. to determine its toxicity towards the environment. The results of
preliminary oxidation study showed the performance of film in oxidizing the
contaminant and the result of toxicity study using MTT assay shows more than
70% of viability of Acanthamoeba sp. which indicated that the film was less toxic towards the
environment. Hence, this film has high potential for solving the problems of
contaminated water.
Keywords: ethinylestradiol, polychloromethylstyrene,
Fe-TAML, cloisite, catalytic polymer-clay
Abstrak
Estrogen
sintetik yang dikenali sebagai 17α-etinilestradiol (EE2) adalah
salah satu farmaseutikal yang terdapat dalam saluran air di seluruh dunia
kebiasaannya disebabkan penggunaan oleh manusia dan perkumuhan ke dalam sistem
rawatan air sisa. Dalam kajian ini, filem polimer-tanah liat pemangkin
digunakan untuk merawat EE2 dalam air yang tercemar dengan
menumpukan bahan pencemar dan mengoksida bahan tersebut. Poliklorometilsterina
di sintesis bersama dengan tanah liat cloisite untuk membentuk filem-filem yang
boleh melekatkan pemangkin ferum
ligan tetra amido mikrosiklik (Fe-TAML). Fe-TAML berfungsi cekap dengan
hidrogen peroksida untuk mengaktifkan ferum kepada keadaan pengoksidaan yang
lebih tinggi untuk prestasi filem. Polimer-tanah liat kemudian diacuankan,
dirawat, disilangkan dan difungsikan untuk membentuk sebuah filem yang boleh
mengikat pemangkin kepadanya. Pencirian filem dilakukan dengan menggunakan
spektroskopi inframerah transformasi Fourier (FTIR) untuk menentukan kehadiran kumpulan berfungsi. Tambahan lagi, kajian
ketoksikan EE2 yang teroksida setelah menjalani pengoksidaan dengan
filem polimer-tanah liat pemangkin telah disiasat menggunakan Acanthamoeba sp. untuk menentukan
ketoksikannya terhadap alam sekitar. Hasil kajian ketoksikan menggunakan
pengujian MTT menunjukkan lebih dari 70% ia bertahan dan menujukkan filem
tersebut kurang toksik terhadap alam sekitar. Oleh itu, filem ini mempunyai
potensi yang tinggi untuk menyelesaikan masalah berkaitan air tercemar.
Kata
kunci: ethinillestradiol, poliklorometilsterina, Fe-TAML,
cloisite, pemangkin polimer-tanah liat
References
1.
Johnson, A. C., Dumont, E., Williams, R. J.,
Oldenkamp, R., Cisowska, I. and Sumpter, J. P. (2013). Do concentrations of
ethinylestradiol, estradiol, and diclofenac in European rivers exceed proposed
EU environmental quality standards? Environmental Science &
Technology, 47(21): 12297-12304.
2.
Mills, M. R., Arias-Salazar, K., Baynes, A.,
Shen, L. Q., Churchley, J., Beresford, N., Gayathri, C., Gil, R. R., Kanda, R.,
Jobling, S. and Collins, T. J. (2015). Removal of ecotoxicity of
17α-ethinylestradiol using TAML/peroxide water treatment. Scientific
Reports, 5: 10511.
3.
Liu, Z. H., Lu, G. N., Yin, H., Dang, Z. and Rittmann, B.
(2015). Removal of natural estrogens and their conjugates in municipal
wastewater treatment plants: A critical review. Environmental Science &
Technology, 49(9): 5288-5300.
4.
Kostich, M., Flick, R. and Martinson, J. (2013). Comparing
predicted estrogen concentrations with measurements in US waters. Environmental
Pollution, 178: 271-277.
5.
De Mes, T., Zeeman, G. and Lettinga, G. (2005). Occurrence
and fate of estrone, 17β-estradiol and 17α-ethynylestradiol in STPs
for domestic wastewater. Reviews in Environmental Science and Biotechnology,
4(4): 275.
6.
Lim, Y. L., Morad, N., Lalung, J., Chan, S. Y. and Bakar, S.
A. A. (2016). Isolation and identification of
17α-ethinylestradiol-degrading bacterial strains from POME and cow dung. International
Journal of Environmental Science and Development, 7(12): 881.
7.
Desbrow, C. E. J. R., Routledge, E. J.,
Brighty, G. C., Sumpter, J. P. and Waldock, M. (1998). Identification of
estrogenic chemicals in STW effluent. 1. Chemical fractionation and in vitro
biological screening. Environmental Science & Technology, 32(11):
1549-1558.
8.
Körner, W., Spengler, P., Bolz, U.,
Schuller, W., Hanf, V. and Metzger, J. W. (2001). Substances with estrogenic
activity in effluents of sewage treatment plants in southwestern Germany. 2.
biological analysis. Environmental Toxicology and Chemistry: An
International Journal, 20(10): 2142-2151.
9.
Snyder, S. A., Villeneuve, D. L., Snyder, E.
M. and Giesy, J. P. (2001). Identification and quantification of estrogen
receptor agonists in wastewater effluents. Environmental Science &
Technology, 35(18): 3620-3625.
10. Hultman, M. T., Song, Y. and
Tollefsen, K. E. (2015). 17α-ethinylestradiol (EE2) effect on global gene
expression in primary rainbow trout (Oncorhynchus mykiss)
hepatocytes. Aquatic Toxicology, 169: 90-104.
11. Snyder, S. A., Westerhoff, P.,
Yoon, Y. and Sedlak, D. L. (2003). Pharmaceuticals, personal care products, and
endocrine disruptors in water: Implications for the water industry. Environmental
Engineering Science, 20(5): 449-469.
12. Scala-Benuzzi, M. L., Takara,
E. A., Alderete, M., Soler-Illia, G. J., Schneider, R. J., Raba, J. and
Messina, G. A. (2018). Ethinylestradiol quantification in drinking water
sources using a fluorescent paper based immunosensor. Microchemical
Journal, 141: 287-293.
13. De Wit, M., Keil, D., van der
Ven, K., Vandamme, S., Witters, E. and De Coen, W. (2010). An integrated
transcriptomic and proteomic approach characterizing estrogenic and metabolic
effects of 17α-ethinylestradiol in zebrafish (Danio rerio). General
and Comparative Endocrinology, 167(2): 190-201.
14. Bhandari, R. K., Deem, S. L.,
Holliday, D. K., Jandegian, C. M., Kassotis, C. D., Nagel, S. C., Tillitt, D.
E., vom Saal, F. S. and Rosenfeld, C. S. (2015). Effects of the environmental
estrogenic contaminants bisphenol a and 17α-ethinylestradiol on sexual
development and adult behaviors in aquatic wildlife species. General
and Comparative Endocrinology, 214: 195-219.
15. Caldwell, D. J., Mastrocco,
F., Anderson, P. D., Länge, R. and Sumpter, J. P. (2012).
Predicted‐no‐effect concentrations for the steroid estrogens
estrone, 17β‐estradiol, estriol, and
17α‐ethinylestradiol. Environmental Toxicology and Chemistry, 31(6):
1396-1406.
16. Jobling, S., Coey, S.,
Whitmore, J. G., Kime, D. E., Van Look, K. J. W., McAllister, B.
G., Beresford, N., Henshaw, A. C., Brighty, G., Tyler, C. R. and Sumpter,
J. P. (2002). Wild intersex roach (Rutilus rutilus) have reduced
fertility. Biology of Reproduction, 67(2): 515-524.
17. Harris, C. A., Hamilton, P.
B., Runnalls, T. J., Vinciotti, V., Henshaw, A., Hodgson, D., Coe, T. S.,
Jobling, S., Tyler, C. R. and Sumpter, J. P. (2010). The consequences of
feminization in breeding groups of wild fish. Environmental Health
Perspectives, 119(3): 306-311.
18. Jobling, S., Williams, R.,
Johnson, A., Taylor, A., Gross-Sorokin, M., Nolan, M., Tyler, C.R., van Aerle,
R., Santos, E. and Brighty, G. (2005). Predicted exposures to steroid estrogens
in UK rivers correlate with widespread sexual disruption in wild fish
populations. Environmental Health Perspectives, 114 (Suppl 1):
32-39.
19. Shen, L. Q., Beach, E. S.,
Xiang, Y., Tshudy, D. J., Khanina, N., Horwitz, C. P., Bier, M.E. and Collins,
T. J. (2011). Rapid, biomimetic degradation in water of the persistent drug
sertraline by TAML catalysts and hydrogen peroxide. Environmental Science
& Technology, 45(18): 7882-7887.
20. Gupta, S. S., Stadler, M.,
Noser, C. A., Ghosh, A., Steinhoff, B., Lenoir, D., Horwitz, C. P., Schramm,
K.W. and Collins, T. J. (2002). Rapid total destruction of chlorophenols by
activated hydrogen peroxide. Science, 296(5566): 326-328.
21. Kundu, S., Chanda, A., Khetan,
S. K., Ryabov, A. D. and Collins, T. J. (2013). TAML
activator/peroxide-catalyzed facile oxidative degradation of the persistent
explosives trinitrotoluene and trinitrobenzene in micellar solutions. Environmental
Science & Technology, 47(10): 5319-5326.
22. Länge, R.,
Hutchinson, T. H., Croudace, C. P., Siegmund, F., Schweinfurth, H., Hampe, P.,
Panter, G.H. and Sumpter, J. P. (2001). Effects of the synthetic estrogen
17α‐ethinylestradiol on the life‐cycle of the fathead minnow (Pimephales
promelas). Environmental Toxicology and Chemistry: An International
Journal, 20(6): 1216-1227.
23. Shappell,
N. W., Vrabel, M. A., Madsen, P. J., Harrington, G., Billey, L. O., Hakk,
H., Larsen, G. L., Beach, E. S., Horwitz, C. P., Ro, K. and Hunt, P.
G. (2008). Destruction of estrogens using Fe-TAML/peroxide catalysis. Environmental
Science & Technology, 42(4): 1296-1300.
24. George, P.
(1953). The chemical nature of the second hydrogen peroxide compound formed by
cytochrome C peroxidase and horseradish peroxidase. Titration with reducing
agents. Biochemical Journal, 54(2): 267.
25. Ellis, W.
C., Tran, C. T., Roy, R., Rusten, M., Fischer, A., Ryabov, A. D., Blumberg,
B. and Collins, T. J. (2010). Designing green oxidation catalysts for
purifying environmental waters. Journal of the American Chemical
Society, 132(28): 9774-9781.
26. Alum, A., Yoon, Y.,
Westerhoff, P. and Abbaszadegan, M. (2004). Oxidation of bisphenol A,
17β‐estradiol, and 17α‐ethynyl estradiol and byproduct estrogenicity. Environmental
Toxicology: An International Journal, 19(3): 257-264.
27. Balsiger, H. A., de la Torre, R., Lee, W.-Y. and Cox, M. B. (2010). A
four-hour yeast bioassay for the direct measure of estrogenic activity in
wastewater without sample extraction, concentration, or sterilization. Science of The Total Environment. 408(6): 1422-1429.
28. Barr, W. J., Yi, T., Aga, D., Acevedo, O. and Harper, W. F. (2011). Using
electronic theory to identify metabolites present in 17α-ethinylestradiol
biotransformation pathways. Environmental
Science & Technology, 46(2): 760-768.
29. Boone, A. J., Chang, C. H., Greene, S. N., Herz, T. and Richards, N. G. J.
(2003). Modeling the spin-dependent properties of open-shell Fe(III) -
containing systems: towards a computational description of nitrile hydratase. Coordination Chemistry Reviews 238,
291-314.
30.
Alexandre, M. and Dubois, P. (2000).
Polymer-layered silicate nanocomposites: preparation, properties and uses of a
new class of materials. Materials Science and Engineering: Reports, 28(1-2):
1-63.
31.
Strawhecker, K. E. and Manias, E. (2000). Structure
and properties of poly(vinyl alcohol)/Na+ montmorillonite
nanocomposites. Chemistry of Materials, 12(10): 2943-2949.
32.
Koo, C. M., Ham, H. T., Choi, M. H., Kim, S.
O. and Chung, I. J. (2003). Characteristics of polyvinylpyrrolidone-layered
silicate nanocomposites prepared by attrition ball milling. Polymer, 44(3):
681-689.
33.
Giannelis, E. P. (1996). Polymer layered
silicate nanocomposites. Advanced Materials, 8(1): 29-35.
34.
LeBaron, P. C., Wang, Z. and Pinnavaia, T.
J. (1999). Polymer-layered silicate nanocomposites: An overview. Applied
Clay Science, 15(1-2): 11-29.
35.
Messersmith, P. B. and Giannelis, E. P.
(1995). Synthesis and barrier properties of poly (ε‐caprolactone)
‐layered silicate nanocomposites. Journal of Polymer Science Part
A: Polymer Chemistry, 33(7): 1047-1057.
36. Yano, K., Usuki, A. and Okada,
A. (1997). Synthesis and properties of polyimide‐clay hybrid films. Journal
of Polymer Science Part A: Polymer Chemistry, 35(11): 2289-2294.
37.
Ke, Z. and Yongping, B. (2005). Improve the
gas barrier property of PET film with montmorillonite by in situ
interlayer polymerization. Materials Letters, 59(27):
3348-3351.
38.
Mosmann, T. (1983). Rapid colorimetric assay
for cellular growth and survival: application to proliferation and cytotoxicity
assays. Journal of Immunological Methods, 65(1-2): 55-63.