Flow injection photoinduced chemiluminescence determination of imazalil in water samples

The final publication is available at link.springer.com[EN] In this work, a fast, simple and economic method is proposed for the determination of imazalil in water samples by flow injection photoinduced chemiluminescence. In this method, imazalil degrades in basic media through the use of a photoreactor, and the resulting photofragments react with ferricyanide and generate the direct chemiluminescence signal. To the authors' knowledge, this is the first time that a chemiluminescence method has been proposed for the determination of this fungicide. All physical and chemical parameters in the flow injection chemiluminescence system were optimized in the experimental setting. In the absence of preconcentration, the linear dynamic range for imazalil was 0.75-5 mg L(-1) and the detection limit was 0.171 mg L(-1). The application of solid-phase extraction with C18 cartridges allowed the elimination of interference ions, the reduction of the linear dynamic range to 15-100 mu g L(-1), and a detection limit of 3.4 mu g L(-1). This detection limit is below the maximum concentration level established by the Regulations of the Hydraulic Public Domain for pesticide dumping. The sample throughput after solid-phase extraction of the analyte was 12 samples h(-1). The intraday and interday coefficients of variation were below 9.9% in all cases. This method was applied to the analysis of environmental water samples, and recoveries of between 95.7 and 110% were obtained.The authors are grateful to The Spanish Ministry of Education and Science and FEDER funds for financial support (project CTM2006-11991). The translation of this paper was funded by the Universidad Politécnica de Valencia, Spain.Meseguer-Lloret, S.; Torres-Cartas, S.; Gómez Benito, C. (2010). Flow injection photoinduced chemiluminescence determination of imazalil in water samples. Analytical and Bioanalytical Chemistry. 398(7-8):3175-3182. https://doi.org/10.1007/s00216-010-4227-1S317531823987-8EC (1998) Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. European Council, BrusselsSpanish Ministry of Public Works and Transportation (1986) Royal Decree 849/1986 of 11 April of the Regulations of the Hydraulic Public Domain. Spanish Ministry of Public Works and Transportation, MadridPicó Y, la Farré M, Soler C, Barceló D (2007) J Chromatogr A 1176(1-2):123–134Ibáñez M, Sancho JV, Hernández F, McMillan D, Rao R (2008) Trends Anal Chem 27(5):481–489Yoshioka N, Akiyama Y, Teranishi K (2004) J Chromatogr A 1022(1–2):145–150Watanabe E, Yoshimura Y, Yuasa Y, Nakazawa H (2001) Anal Chim Acta 433(2):199–206Ito Y, Ikai Y, Oka H, Hayakawa J, Kagami T (1998) J Chromatogr A 810(1-2):81–87Garrido J, de Alba M, Jimenez I, Casado E, Folgueiras ML (1997) J Chromatogr A 765(1):91–97Charlton AJA, Jones A (2007) J Chromatogr A 1141(1):117–122Rodríguez R, Picó Y, Font G, Mañes J (2001) J Chromatogr A 924(1-2):387–396Balinova A (1995) Anal Chim Acta 311(3):423–427Menezes Filho A, Neves dos Santos F, Afonso de Pereira P (2010) Mikrochemical J 96:139–145Beale DJ, Porter NA, Roddick FA (2009) Talanta 78(2):342–347Albert-García JR, Martínez-Calatayud J (2008) Talanta 75(3):717–724Meseguer-Lloret S, Campíns-Falcó P, Tortajada-Genaro LA, Blasco-Gómez F (2003) Int J Environ Anal Chem 83(5):405–416Moliner-Martínez Y, Meseguer-Lloret S, Tortajada-Genaro LA, Campíns-Falcó P (2003) Talanta 60(2-3):257–268Lin Q, Guiraúm A, Escobar R, de la Rosa F (1993) Anal Chim Acta 283(1):379–385Townshend A, Ruengsitagoon W, Thongpoon C, Liawruangrath S (2005) Anal Chim Acta 541:105–111Lattanzio G, García-Campaña AM, Soto-Chinchilla JJ, Gámiz-Gracia L, Girotti S (2008) J Pharm Biomed Anal 46(2):381–385Catalá Icardo M, García Mateo JV, Fernández Lozano M, Martínez Calatayud J (2003) Anal Chim Acta 499(1-2):57–69Ciborowski M, Catalá Icardo M, García Mateo JV, Martínez Calatayud J (2004) J Pharm Biomed Anal 36(4):693–700Yang XF, Li H (2004) Talanta 64(2):478–483Gómez-Taylor B, Palomeque M, García Mateo JV, Martínez Calatayud J (2006) J Pharm Biomed Anal 41(2):347–357López Paz JL, Catalá-Icardo M (2008) Anal Chim Acta 625(2):173–179López Malo D, Martínez Calatayud J (2008) Talanta 77(2):561–56

Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV)

A new, fast, selective and sensitive method has been developed for the simultaneous determination of nine organothiophosphorus (OTP) pesticides, namely omethoate, dimethoate, disulfoton-sulfoxide, methidathion, phosmet, malathion, diazinon, pirimiphos-methyl and chlorpyrifos. The pesticides were separated on a Kinetex C18 column by gradient elution with acetonitrile:water. A post-column basic hydrolysis of the pesticides and later a chemiluminescence (CL) reaction with cerium (IV) in acid medium was carried out. Hexadecylpyridinium chloride highly enhanced the CL emission. Under optimized conditions, linearity, precision, limits of detection and quantification, and accuracy were determined. Both selectivity and sensitivity were compared with those obtained with UV detection. In combination with SPE, limits of detection in the range 15-80 ng/L and 5-30 ng/L were obtained when 250 mL and 1000 mL of solution were treated, respectively. When applied to 250 mL of sample the inter-day precision of the method was between 3.5% and 7.3% and the intra-day precision between 2.9% and 6.0%. The method was applied to determine OTP pesticides in spiked water samples from different origins: irrigation, river, sea, ground, spring, mineral and tap waters, being the percentage of recovery of added amounts near 100% form most of the pesticides.Catalá Icardo, M.; Lahuerta Zamora, L.; Torres-Cartas, S.; Meseguer-Lloret, S. (2014). Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV). Journal of Chromatography A. 1341:31-40. doi:10.1016/j.chroma.2014.03.0243140134

Selective and sensitive chemiluminescence determination of MCPB: flow injection and liquid chromatography

This paper was published in Applied Spectroscopy and is made available as an electronic reprint with the permission of OSA. The paper can be found at the following URL on the OSA website: http://dx.doi.org/10.1177/0003702815620133 . Systematic or multiple reproduction or distribution to multiple locations via electronic or other means is prohibited and is subject to penalties under law.Two new chemiluminescence (CL) methods are described for the determination of the herbicide 4-(4-chloro-o-tolyloxy) butyric acid (MCPB). First, a flow injection chemiluminescence (FI-CL) method is proposed. In this method, MCPB is photodegraded with an ultraviolet (UV) lamp and the photoproducts formed provide a great CL signal when they react with ferricyanide in basic medium. Second, a high-performance liquid chromatography chemiluminescence (HPLC-CL) method is proposed. In this method, before the photodegradation and CL reaction, the MCPB and other phenoxyacid herbicides are separated in a C18 column. The experimental conditions for the FI-CL and HPLC-CL methods are optimized. Both methods present good sensitivity, the detection limits being 0.12 mg L 1 and 0.1 mg L 1 (for FI-CL and HPLC-CL, respectively) when solid phase extraction (SPE) is applied. Intra- and interday relative standard deviations are below 9.9%. The methods have been satisfactorily applied to the analysis of natural water samples. FI-CL method can be employed for the determination of MCPB in simple water samples and for the screening of complex water samples in a fast, economic, and simple way. The HPLC-CL method is more selective, and allows samples that have not been resolved with the FI-CL method to be solved.Meseguer-Lloret, S.; Torres-Cartas, S.; Catalá-Icardo, M.; Gómez Benito, C. (2016). Selective and sensitive chemiluminescence determination of MCPB: flow injection and liquid chromatography. Applied Spectroscopy. 70(2):312-321. doi:10.1177/0003702815620133S312321702Moral, A., Caballo, C., Sicilia, M. D., & Rubio, S. (2012). Highly efficient microextraction of chlorophenoxy acid herbicides in natural waters using a decanoic acid-based nanostructured solvent prior to their quantitation by liquid chromatography–mass spectrometry. Analytica Chimica Acta, 709, 59-65. doi:10.1016/j.aca.2011.10.016Herrero-Hernández, E., Rodríguez-Gonzalo, E., Andrades, M. S., Sánchez-González, S., & Carabias-Martínez, R. (2013). Occurrence of phenols and phenoxyacid herbicides in environmental waters using an imprinted polymer as a selective sorbent. Science of The Total Environment, 454-455, 299-306. doi:10.1016/j.scitotenv.2013.03.029Baggiani, C., Giovannoli, C., Anfossi, L., & Tozzi, C. (2001). Molecularly imprinted solid-phase extraction sorbent for the clean-up of chlorinated phenoxyacids from aqueous samples. Journal of Chromatography A, 938(1-2), 35-44. doi:10.1016/s0021-9673(01)01126-8Wintersteiger, R., Goger, B., & Krautgartner, H. (1999). Quantitation of chlorophenoxy acid herbicides by high-performance liquid chromatography with coulometric detection. Journal of Chromatography A, 846(1-2), 349-357. doi:10.1016/s0021-9673(99)00429-xPeruzzi, M., Bartolucci, G., & Cioni, F. (2000). Determination of phenoxyalkanoic acids and other herbicides at the ng/ml level in water by solid-phase extraction with poly(divinylbenzene-co-N-vinylpyrrolidone) sorbent and high-performance liquid chromatography–diode-array detection. Journal of Chromatography A, 867(1-2), 169-175. doi:10.1016/s0021-9673(99)01141-3Ranz, A., & Lankmayr, E. (2006). Screening and optimization of the derivatization of polar herbicides with trimethylanilinium hydroxide for GC-MS analysis. Journal of Biochemical and Biophysical Methods, 69(1-2), 3-14. doi:10.1016/j.jbbm.2006.02.007Nuhu, A. A., Basheer, C., Alhooshani, K., & Al-Arfaj, A. R. (2012). Determination of phenoxy herbicides in water samples using phase transfer microextraction with simultaneous derivatization followed by GC-MS analysis. Journal of Separation Science, 35(23), 3381-3388. doi:10.1002/jssc.201200218Jiménez, J. J. (2013). Simultaneous liquid–liquid extraction and dispersive solid-phase extraction as a sample preparation method to determine acidic contaminants in river water by gas chromatography/mass spectrometry. Talanta, 116, 678-687. doi:10.1016/j.talanta.2013.07.052EREMIN, S., LAASSIS, B., & AARON, J. (1996). Photochemical-fluorimetric method for the determination of total chlorophenoxyacid herbicides. Talanta, 43(3), 295-301. doi:10.1016/0039-9140(95)01751-8Jafari, M. T., Saraji, M., & Yousefi, S. (2012). Negative electrospray ionization ion mobility spectrometry combined with microextraction in packed syringe for direct analysis of phenoxyacid herbicides in environmental waters. Journal of Chromatography A, 1249, 41-47. doi:10.1016/j.chroma.2012.06.024Tsogas, G. Z., Giokas, D. L., Nikolakopoulos, P. G., Vlessidis, A. G., & Evmiridis, N. P. (2006). Determination of the pesticide carbaryl and its photodegradation kinetics in natural waters by flow injection–direct chemiluminescence detection. Analytica Chimica Acta, 573-574, 354-359. doi:10.1016/j.aca.2005.11.058Albert-García, J. R., & Calatayud, J. M. (2008). Determination of the herbicide benfuresate by its photo-induced chemiluminescence using flow multicommutation methodology. Talanta, 75(3), 717-724. doi:10.1016/j.talanta.2007.12.003Catalá-Icardo, M., López-Paz, J. L., Choves-Barón, C., & Peña-Bádena, A. (2012). Native vs photoinduced chemiluminescence in dimethoate determination. Analytica Chimica Acta, 710, 81-87. doi:10.1016/j.aca.2011.10.043Gómez-Benito, C., Meseguer-Lloret, S., & Torres-Cartas, S. (2013). Sensitive determination of Fenamiphos in water samples by flow injection photoinduced chemiluminescence. International Journal of Environmental Analytical Chemistry, 93(2), 152-165. doi:10.1080/03067319.2012.663755Beale, D. J., Porter, N. A., & Roddick, F. A. (2009). A fast screening method for the presence of atrazine and other triazines in water using flow injection with chemiluminescent detection. Talanta, 78(2), 342-347. doi:10.1016/j.talanta.2008.11.033Catalá-Icardo, M., López-Paz, J. L., & Pérez-Plancha, L. M. (2014). Fast Determination of Thiacloprid by Photoinduced Chemiluminescence. Applied Spectroscopy, 68(6), 642-648. doi:10.1366/13-07330Torres-Cartas, S., Gómez-Benito, C., & Meseguer-Lloret, S. (2011). FI on-line chemiluminescence reaction for determination of MCPA in water samples. Analytical and Bioanalytical Chemistry, 402(3), 1289-1296. doi:10.1007/s00216-011-5567-1Catalá-Icardo, M., Lahuerta-Zamora, L., Torres-Cartas, S., & Meseguer-Lloret, S. (2014). Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV). Journal of Chromatography A, 1341, 31-40. doi:10.1016/j.chroma.2014.03.024Huertas-Pérez, J. F., & García-Campaña, A. M. (2008). Determination of N-methylcarbamate pesticides in water and vegetable samples by HPLC with post-column chemiluminescence detection using the luminol reaction. Analytica Chimica Acta, 630(2), 194-204. doi:10.1016/j.aca.2008.09.047Orejuela, E., & Silva, M. (2003). Monitoring some phenoxyl-type N-methylcarbamate pesticide residues in fruit juices using high-performance liquid chromatography with peroxyoxalate-chemiluminescence detection. Journal of Chromatography A, 1007(1-2), 197-201. doi:10.1016/s0021-9673(03)00934-8GALERA, M., GARCIA, M., & VALVERDE, R. (2008). Determination of photoirradiated high polar benzoylureas in tomato by HPLC with luminol chemiluminescence detection. Talanta, 76(4), 815-823. doi:10.1016/j.talanta.2008.04.052Rosales-Conrado, N., León-González, M. E., Pérez-Arribas, L. V., & Polo-Díez, L. M. (2005). Effect of temperature on the separation of chlorophenoxy acids and carbamates by capillary high-performance liquid chromatography and UV (or diode array) detection. Journal of Chromatography A, 1081(1), 114-121. doi:10.1016/j.chroma.2004.12.083Geerdink, R. B., van Tol-Wildenburg, S., Niessen, W. M. A., & Brinkman, U. A. T. (1997). Determination of Phenoxy Acid Herbicides From Aqueous Samples by Improved Clean-up on Polymeric Pre-columns at High pH. The Analyst, 122(9), 889-894. doi:10.1039/a702338

Photografted fluoropolymers as novel chromatographic supports for polymeric monolithic stationary phases

[EN] In this study, porous polymer monoliths were in situ synthesized in fluoropolymers tubing to prepare microbore HPLC columns. To ensure the formation of robust homogeneous polymer monoliths in these housing supports, the inner surface of fluoropolymer tubing was modified in a two-step photografting process. Raman spectroscopy and scanning electron microscopy (SEM) confirmed the successful modification of the inner poly(ethylene-co-tetrafluoroethylene) (ETFE) wall and the subsequent attachment of a monolith onto the wall. Poly(glycidyl methacrylate-co-divinylbenzene), poly(butyl methacrylate-co-ethyleneglycol dimethacrylate) and poly(styrene-co-divinylbenzene) monoliths were in situ synthesized by thermal polymerization within the confines of surface vinylized ETFE tubes. The resulting monoliths exhibited good permeability and mechanical stability (pressure resistance up to 9¿MPa). The chromatographic performance of these different monolithic columns was evaluated via the separation of alkyl benzenes and proteins in a conventional HPLC system.This work was supported by project PROMETEO/2016/145 (Conselleria d'Educacio, Investigacio, Cultura i Esport,Esport, Generalitat Valenciana, Spain). The authors also thank Dr. S. Laredo-Ortiz from the Atomic Spectroscopy section of the SCSIE (University of Valencia), for her help in Raman measurements.Catalá-Icardo, M.; Torres-Cartas, S.; Meseguer-Lloret, S.; Simó-Alfonso, E.; Herrero Martínez, J. (2018). Photografted fluoropolymers as novel chromatographic supports for polymeric monolithic stationary phases. Talanta. 187:216-222. doi:10.1016/j.talanta.2018.05.026S21622218

Recent Advances in Molecularly Imprinted Membranes for Sample Treatment and Separation

[EN] This review describes the recent advances from the past five years concerning the development and applications of molecularly imprinted membranes (MIMs) in the field of sample treatment and separation processes. After a short introduction, where the importance of these materials is highlighted, a description of key aspects of membrane separation followed by the strategies of preparation of these materials is described. The review continues with several analytical applications of these MIMs for sample preparation as well as for separation purposes covering pharmaceutical, food, and environmental areas. Finally, a discussion focused on possible future directions of these materials in extraction and separation field is also given.This work was supported by project RTI2018-095536-B-I00 (Ministry of Science, Innovation and Universities, Spain).Torres-Cartas, S.; Catalá-Icardo, M.; Meseguer-Lloret, S.; Simó-Alfonso, EF.; Herrero-Martínez, JM. (2020). Recent Advances in Molecularly Imprinted Membranes for Sample Treatment and Separation. Separations. 7(4):1-28. https://doi.org/10.3390/separations7040069S1287

Extraction and preconcentration of organophosphorus pesticides in water by using a polymethacrylate-based sorbent modified with magnetic nanoparticles

[EN] A polymethacrylate-based sorbent modified with magnetic nanoparticles (MNPs) has been synthesized and used as sorbent for solid-phase extraction (SPE) and magnetic solid-phase extraction (MSPE) of three organophosphorus pesticides (phosmet, pirimiphos-methyl, and chlorpyrifos) in water samples followed by high-performance liquid chromatography diode array detection. The sorbent was prepared from a glycidyl methacrylate-based polymer, modified with a silanizing agent, followed by immobilization of MNPs on the surface of the material. The sorbent was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Comparative studies of this support were done both in conventional SPE cartridge and MSPE approach. Several extraction parameters (loading pH, elution solvent, eluting volume, and loading flow rate) were investigated in detail. Under optimal conditions, the proposed sorbent gave an excellent enrichment efficiency of analytes and detection limits between 0.01 and 0.25 μg L−1. The recoveries of organophosphorus pesticides in spiked water samples were in the range of 71 98%, and the developed sorbent showed a high reusability (up to 50 uses without losses in recovery). The proposed method was satisfactorily applied to the analysis of these pesticides in water samples from different sources.This work was supported by projects CTQ2014-52765-R (MINECO of Spain and FEDER) and PROMETEO/2016/145 (Conselleria de Educacion, Investigacion, Cultura y Deporte of Generalitat Valenciana, Spain).Meseguer-Lloret, S.; Torres-Cartas, S.; Catalá-Icardo, M.; Simó-Alfonso, EF.; Herrero-Martínez, JM. (2017). Extraction and preconcentration of organophosphorus pesticides in water by using a polymethacrylate-based sorbent modified with magnetic nanoparticles. Analytical and Bioanalytical Chemistry. 409(14):3561-3571. https://doi.org/10.1007/s00216-017-0294-xS3561357140914Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumptionBotitsi HV, Garbis SD, Economou A, Tsipi DF. Current mass spectrometry strategies for the analysis of pesticides and their metabolites in food and water matrices. Mass Spectrom Rev. 2011;30:907–39.Kuster M, López de Alda M, Barceló D. Liquid chromatography tandem mass spectrometry analysis and regulatory issues for polar pesticides in natural and treated waters. J Chromatogr A. 2009;1216:520–9.Catalá-Icardo M, Meseguer-Lloret S, Torres-Cartas S. Photoinduced chemiluminescence determination of carbamate pesticides. Photochem Photobiol Sci. 2016;15:626–34.Huertas-Pérez JF, García-Campaña AM. Determination of N-methylcarbamate pesticides in water and vegetable samples by HPLC with post-column chemiluminescence detection using the luminol reaction. Anal Chim Acta. 2008;630(2):194–204.Samadi S, Sereshti H, Assadi Y. Ultra-preconcentration and determination of thirteen organophosphorus pesticides in water sample using solid-phase extraction followed by dispersive liquid-liquid microextraction and gas chromatography with flame photometric detection. J Chromatogr A. 2012;1219:61–5.He L, Luo X, Xie H, Wang C, Jiang X, Lu K. Ionic liquid-based dispersive liquid–liquid microextraction followed high-performance liquid chromatography for the determination of organophosphorus pesticides in water sample. Anal Chim Acta. 2009;655:52–9.Wu C, Liu N, Wu Q, Wang C, Wang Z. Application of ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of some organophosphorus pesticides in water samples. Anal Chim Acta. 2010;679:56–62.Peng G, Lu Y, He Q, Mmereki D, Zhou G, Chen J, et al. Determination of 3,5,6-trichloro-2-pyridinol, phoxim and chlorpyrifos-methyl in water samples using a new pretreatment method coupled with high-performance liquid chromatography. J Sep Sci. 2016;38:4204–10.Báez ME, Rodríguez M, Lastra O, Contreras P. Solid phase extraction of organophosphorus, triazine, and triazole-derived pesticides from water samples. A critical study. J High Resolut Chrom. 1997;20:591–6.Rocha AA, Monteiro SH, Andrade GCRM, Vilca FZ, Tornisielo CL. Monitoring of pesticides residues in surface and subsurface waters, sediments and fish in center-pivot irrigation areas. J Braz Chem Soc. 2015;25(11):2269–78.Hadjmohammadi MR, Peyrovi M, Biparva P. Comparison of C18 silica and multi-walled carbon nanotubes as the adsorbents for the solid-phase extraction of Chlorpyrifos and Phosalone in water samples using HPLC. J Sep Sci. 2010;33:1044–51.Pelit L, Dizdas TN. Preparation and application of a polythiophene solid-phase microextraction fiber for the determination of endocrine-disruptor pesticides in well waters. J Sep Sci. 2013;36:3234–41.Ibrahim WAW, Nodeh HR, Aboul-Enein HY, Sanagi MM. Magnetic solid phase extraction based on modified ferum oxides for enrichment, preconcentration and isolation of pesticides and selected pollutants. Crit Rev Anal Chem. 2015;45:270–87.Li XS, Zhu GT, Luo YB, Yuan BF, Feng YQ. Synthesis and applications of functionalized magnetic materials in sample preparation. Trends Anal Chem. 2013;45:233–47.Maddah B, Shamsi J. Extraction and preconcentration of trace amounts of diazinon and fenitrothion from environmental water by magnetite octadecylsilane nanoparticles. J Chromatogr A. 2012;1256:40–5.Xie J, Liu T, Song G, Hu Y, Deng C. Simultaneous analysis of organophosphorus pesticides in water by magnetic solid phase extraction coupled with GC-MS. Chromatographia. 2013;76:535–40.Heidari H, Razmi H. Multiresponse optimization of magnetic solid phase extraction based on carbon coated Fe3O4 nanoparticles using desirability function approach for the determination of the organophosphorus pesticides in aquatic samples by HPLC-UV. Talanta. 2012;99:13–21.Yan S, Qi TT, Chen DW, Li Z, Li XJ, Pan SY. Magnetic solid-phase extraction based on magnetite/reduced graphene oxide nanoparticles for determination of trace isocarbophos residues in different matrices. J Chromatogr A. 2014;1347:30–8.Tavakoli M, Hajimahmoodi M, Shemirani F. Trace level monitoring of pesticides in water samples using fatty acid coated magnetic nanoparticles prior to GC-MS. Anal Methods. 2014;6:2988–97.Tang Q, Wang X, Yu F, Qiao X, Xu Z. Simultaneous determination of ten organophosphorus pesticide residues in fruits by gas chromatography coupled with magnetic separation. J Sep Sci. 2014;27:820–7.Shen H, Zhu Y, Wen X, Zhuang Y. Preparation of Fe3O4-C18 nano-magnetic composite materials and their cleanup properties for organophosphorous pesticides. Anal Bioanal Chem. 2007;387:2227–37.Bagheri H, Zandi O, Aghakhani A. Magnetic nanoparticle-based micro-solid phase extraction and GC–MS determination of oxadiargyl in aqueous samples. Chromatographia. 2011;74:483–8.Moravcova D, Rantamaki AH, Dusa F, Wiedmer SK. Monoliths in capillary electrochromatography and capillary liquid chromatography in conjunction with mass spectrometry. Electrophoresis. 2016;37(7–8):880–912.Nema T, Chan ECY, Ho PC. Applications of monolithic materials for sample preparation. J Pharm Biomed Anal. 2014;87:130–41.Vergara-Barberán M, Lerma-García MJ, Simó-Alfonso EF, Herrero-Martínez JM. Solid-phase extraction based on ground methacrylate monolith modified with gold nanoparticles for isolation of proteins. Anal Chim Acta. 2016;917:37–43.Vukoje ID, Dzunuzovic ES, Vodnik VV, Dimitrijevic S, Ahrenkiel SP, Nedeljkovic JM. Synthesis, characterization, and antimicrobial activity of poly(GMA-co-EGDMA) polymer decorated with silver nanoparticles. J Mater Sci. 2014;49:6838–44.Krenkova J, Foret F. Iron oxide nanoparticle coating of organic polymer-based monolithic columns for phosphopeptide enrichment. J Sep Sci. 2011;34(16–17):2106–12.Daou TJ, Begin-Colin S, Grenèche JM, Thomas F, Derory A, Bernhardt P, et al. Phosphate adsorption properties of magnetite-based nanoparticles. Chem Mater. 2007;19:4494–505.Mezenner NY, Bensmaili A. Kinetics and thermodynamic study of phosphate adsorption on iron hydroxide-eggshell waste. Chem Eng J. 2009;147:87–96.Yang C, Wang G, Lu Z, Sun J, Zhuang J, Yang W. Effect of ultrasonic treatment on dispersibility of Fe3O4 nanoparticles and synthesis of multi-core Fe3O4/SiO2 core/shell nanoparticles. J Mater Chem. 2005;15:4252–7.Carrasco-Correa EJ, Ramis-Ramos G, Herrero-Martínez JM. Methacrylate monolithic columns functionalized with epinephrine for capillary electrochromatography applications. J Chromatogr A. 2013;1298:61–7.Waldron RD. Infrared spectra of ferrites. Phys Rev. 1955;99:1727–35.Yamaura M, Camilo RL, Sampaio LC, Macedo MA, Nakamura M, Toma HE. Preparation and characterization of (3-aminopropyl)triethoxysilane-coated magnetite nanoparticles. J Magn Magn Mat. 2004;279:210–7.Jiang L, Sun W, Kim J. Preparation and characterization of ω-functionalized polystyrene–magnetite nanocomposites. Mater Chem Phys. 2007;101:291–6.Dallas P, Georgakilas V, Niarchos D, Komninou P, Kehagias T, Petridis D. Synthesis, characterization and thermal properties of polymer/magnetite nanocomposites. Nanotechnology. 2006;17:2046–53.Zhao XL, Shi YL, Wang T, Cai YQ, Jiang GB. Preparation of silica-magnetite nanoparticle mixed hemimicelle sorbents for extraction of several typical phenolic compounds from environmental water samples. J Chromatogr A. 2008;1188:140–7.Sitko R, Gliwinska B, Zawisza B, Feist B. Ultrasound-assisted solid-phase extraction using multiwalled carbon nanotubes for determination of cadmium by flame atomic absorption spectrometry. J Anal At Spectrom. 2013;28:405–10.Suslick KS, Price GJ. Application of ultrasound to materials chemistry. Annu Rev Mater Sci. 1999;29:295–326.Boqué R, Heyden YV. The limit of detection. LCGC Eur. 2009;22(2):1–4.Catalá-Icardo M, Lahuerta-Zamora L, Torres-Cartas S, Meseguer-Lloret S. Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV). J Chromatogr A. 2014;1341:31–40

Polymer-based materials modified with magnetite nanoparticles for enrichment of phospholipids

[EN] A polymeric material modified with magnetic nanoparticles (MNPs) has been synthesized and evaluated as sorbent both for solid-phase extraction (SPE) and dispersive magnetic solid-phase extraction (MSPE) of phospholipids (PLs) in human milk samples. The synthesized sorbent was characterized by scanning electron microscopy and its iron content was also determined. Several experimental variables that affect the extraction performance (e.g. loading solvent, breakthrough volume and loading capacity) were investigated and a comparison between conventional SPE and MSPE modalities was done. The proposed method was satisfactorily applied to the analysis of PLs in human milk fat extracts in different lactation stages and the extracted PLs were determined by means of hydrophilic interaction liquid chromatography using evaporative light scattering detection.Project CTQ2017-84995-R (MINECO of Spain and FEDER) and PROMETEO/2016/145 (Generalitat Valenciana). I. T-D thanks the MINECO for an FPU grant for Ph,D. studies.Ten-Domenech. I.; Martínez-Pérez-Cejuela, H.; Simó-Alfonso, E.; Torres-Cartas, S.; Meseguer-Lloret, S.; Herrero Martínez, J. (2018). Polymer-based materials modified with magnetite nanoparticles for enrichment of phospholipids. Talanta. 180:162-167. https://doi.org/10.1016/j.talanta.2017.12.042S16216718

Preparation of organic monolithic columns in polytetrafluoroethylene tubes for reversed-phase liquid chromatography

[EN] In this work, a method for the preparation and anchoring of polymeric monoliths in a polytetrafluoroethylene (PTFE) tubing as a column housing for microbore HPLC is described. In order to assure a covalent attachment of the monolith to the inner wall of the PTFE tube, a two-step procedure was developed. Two surface etching reagents, a commercial sodium naphthalene solution (Fluoroetch®), or mixtures of H2O2 and H2SO4, were tried and compared. Then, the obtained hydroxyl groups on the PTFE surface were modified by methacryloylation. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and scanning electron microscopy (SEM) confirmed the successful modification of the tubing wall and the stable anchorage of monolith to the wall, respectively. Special emphasis was also put on the reduction of the unwanted effects of shrinking of monolith during polymerization, by using an external proper mold and by selecting the adequate monomers in order to increase the flexibility of the polymer. Poly(glycidyl methacrylate-co-divinylbenzene) monoliths were in situ synthesized by thermal polymerization within the confines of surface-vinylized PTFE tubes. The modified PTFE tubing tightly held the monolith, and the monolithic column exhibited good pressure resistance up to 20 MPa. The column performance was also evaluated via the isocratic separation of a series of alkylbenzenes in the reversed-phase mode. The optimized monolithic columns gave plate heights ranged between 70 and 80 um. The resulting monoliths were also satisfactorily applied to the separation of proteins.This work was supported by projects CTQ2014-52765-R (MINECO of Spain and Fondo Europeo de Desarrollo Regional, FEDER) and PROMETEO/2016/145 (Conselleria d'Educacio, Investigacio, Cultura i Esport, Generalitat Valenciana, Spain). The authors also thank Dr. P. Amoros del Toro from Institute of Materials Science (University of Valencia) and Dr. S. Armenta from Department of Analytical Chemistry for their help in surface area and FT-IR measurements, respectively.Catalá-Icardo, M.; Torres-Cartas, S.; Meseguer-Lloret, S.; Gómez Benito, C.; Carrasco-Correa, E.; Simó-Alfonso, EF.; Ramis-Ramos, G.... (2017). Preparation of organic monolithic columns in polytetrafluoroethylene tubes for reversed-phase liquid chromatography. Analytica Chimica Acta. 960:160-167. https://doi.org/10.1016/j.aca.2017.01.01216016796

Photoinduced chemiluminescence determination of carbamate pesticides

A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate pesticides, namely aldicarb, butocarboxim, ethiofencarb, methomyl, methiocarb, thiodicarb, thiofanox and thiophanate-methyl. After chromatographic separation, quinine (sensitizer) was incorporated and the flow passed through an UV lamp (67 s of irradiation time) to obtain the photoproducts, which reacted with acidic Ce(IV) and provided a CL emission. The PICL method showed great selectivity for carbamate pesticides containing sulphur in their chemical structure. A solid-phase extraction process increased sensitivity (LODs ranging from 0.06 to 0.27 ng mL−1) and allowed the carbamate pesticides in surface and ground water samples to be determined, with recoveries in the range 87 110% (except for thiophanate-methyl, whose recoveries were between 60 and 75%). The intra- and inter-day precision was evaluated, with RSD ranging from 1.1 to 7.5% and from 2.6 to 12.3%, respectively. A discussion about the PICL mechanism is also included.Catalá-Icardo, M.; Meseguer-Lloret, S.; Torres-Cartas, S. (2016). Photoinduced chemiluminescence determination of carbamate pesticides. Photochemical and Photobiological Sciences. 15:626-634. doi:10.1039/c6pp00056hS62663415Santaladchaiyakit, Y., Srijaranai, S., & Burakham, R. (2012). Methodological aspects of sample preparation for the determination of carbamate residues: A review. Journal of Separation Science, 35(18), 2373-2389. doi:10.1002/jssc.201200431Pesticides in Ground and Drinking water, ed. M. Fielding, Water Pollution Research Report 27, Commission of the European Communities, Brussels, 1991Melchert, W. R., & Rocha, F. R. P. (2010). A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation. Talanta, 81(1-2), 327-333. doi:10.1016/j.talanta.2009.12.005Chu, N., & Fan, S. (2009). Sequential injection kinetic spectrophotometric determination of quaternary mixtures of carbamate pesticides in water and fruit samples using artificial neural networks for multivariate calibration. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 74(5), 1173-1181. doi:10.1016/j.saa.2009.09.030Pacioni, N. L., & Veglia, A. V. (2007). Determination of poorly fluorescent carbamate pesticides in water, bendiocarb and promecarb, using cyclodextrin nanocavities and related media. Analytica Chimica Acta, 583(1), 63-71. doi:10.1016/j.aca.2006.10.010Yang, E.-Y., & Shin, H.-S. (2013). Trace level determinations of carbamate pesticides in surface water by gas chromatography–mass spectrometry after derivatization with 9-xanthydrol. Journal of Chromatography A, 1305, 328-332. doi:10.1016/j.chroma.2013.07.055Fernández-Ramos, C., Šatínský, D., & Solich, P. (2014). New method for the determination of carbamate and pyrethroid insecticides in water samples using on-line SPE fused core column chromatography. Talanta, 129, 579-585. doi:10.1016/j.talanta.2014.06.037Wang, X., Cheng, J., Wang, X., Wu, M., & Cheng, M. (2012). Development of an improved single-drop microextraction method and its application for the analysis of carbamate and organophosphorus pesticides in water samples. The Analyst, 137(22), 5339. doi:10.1039/c2an35623fFytianos, K., Pitarakis, K., & Bobola, E. (2006). Monitoring ofN-methylcarbamate pesticides in the Pinios River (central Greece) by HPLC. International Journal of Environmental Analytical Chemistry, 86(1-2), 131-145. doi:10.1080/03067310500248171Fu, L., Liu, X., Hu, J., Zhao, X., Wang, H., & Wang, X. (2009). Application of dispersive liquid–liquid microextraction for the analysis of triazophos and carbaryl pesticides in water and fruit juice samples. Analytica Chimica Acta, 632(2), 289-295. doi:10.1016/j.aca.2008.11.020Shi, Z., Hu, J., Li, Q., Zhang, S., Liang, Y., & Zhang, H. (2014). Graphene based solid phase extraction combined with ultra high performance liquid chromatography–tandem mass spectrometry for carbamate pesticides analysis in environmental water samples. Journal of Chromatography A, 1355, 219-227. doi:10.1016/j.chroma.2014.05.085Latrous El Atrache, L., Ben Sghaier, R., Bejaoui Kefi, B., Haldys, V., Dachraoui, M., & Tortajada, J. (2013). Factorial design optimization of experimental variables in preconcentration of carbamates pesticides in water samples using solid phase extraction and liquid chromatography–electrospray-mass spectrometry determination. Talanta, 117, 392-398. doi:10.1016/j.talanta.2013.09.032Cahill, M. G., Caprioli, G., Stack, M., Vittori, S., & James, K. J. (2011). Semi-automated liquid chromatography–mass spectrometry (LC–MS/MS) method for basic pesticides in wastewater effluents. Analytical and Bioanalytical Chemistry, 400(2), 587-594. doi:10.1007/s00216-011-4781-1López-Paz, J. L., Catalá-Icardo, M., & Langa-Sánchez, A. (2014). Determination ofN-methylcarbamate pesticides using flow injection with photoinduced chemiluminescence detection. International Journal of Environmental Analytical Chemistry, 94(6), 606-617. doi:10.1080/03067319.2013.879295López-Paz, J. L., & Catalá-Icardo, M. (2011). Analysis of Pesticides by Flow Injection Coupled with Chemiluminescent Detection: A Review. Analytical Letters, 44(1-3), 146-175. doi:10.1080/00032719.2010.500788Huertas-Pérez, J. F., & García-Campaña, A. M. (2008). Determination of N-methylcarbamate pesticides in water and vegetable samples by HPLC with post-column chemiluminescence detection using the luminol reaction. Analytica Chimica Acta, 630(2), 194-204. doi:10.1016/j.aca.2008.09.047Pérez-Ruiz, T., Martínez-Lozano, C., & García, M. D. (2007). Determination of N-methylcarbamate pesticides in environmental samples by an automated solid-phase extraction and liquid chromatographic method based on post-column photolysis and chemiluminescence detection. Journal of Chromatography A, 1164(1-2), 174-180. doi:10.1016/j.chroma.2007.07.006Orejuela, E., & Silva, M. (2003). Monitoring some phenoxyl-type N-methylcarbamate pesticide residues in fruit juices using high-performance liquid chromatography with peroxyoxalate-chemiluminescence detection. Journal of Chromatography A, 1007(1-2), 197-201. doi:10.1016/s0021-9673(03)00934-8Catalá-Icardo, M., Lahuerta-Zamora, L., Torres-Cartas, S., & Meseguer-Lloret, S. (2014). Determination of organothiophosphorus pesticides in water by liquid chromatography and post-column chemiluminescence with cerium(IV). Journal of Chromatography A, 1341, 31-40. doi:10.1016/j.chroma.2014.03.024Galera, M. M., García, M. D. G., & Valverde, R. S. (2006). Determination of nine pyrethroid insecticides by high-performance liquid chromatography with post-column photoderivatization and detection based on acetonitrile chemiluminescence. Journal of Chromatography A, 1113(1-2), 191-197. doi:10.1016/j.chroma.2006.02.013Meseguer-Lloret, S., Torres-Cartas, S., Catalá-Icardo, M., & Gómez-Benito, C. (2015). Selective and Sensitive Chemiluminescence Determination of MCPB: Flow Injection and Liquid Chromatography. Applied Spectroscopy, 70(2), 312-321. doi:10.1177/0003702815620133Pesticide properties database (PPDB). University of Hertfordshire, http://sitem.herts.ac.uk/aeru/ppdb/en/index.htmPulgarín, J. A. M., Molina, A. A., & López, P. F. (2006). Automatic chemiluminescence-based determination of carbaryl in various types of matrices. Talanta, 68(3), 586-593. doi:10.1016/j.talanta.2005.04.051Waseem, A., Yaqoob, M., & Nabi, A. (2007). Flow-injection determination of carbaryl and carbofuran based on KMnO4–Na2SO3 chemiluminescence detection. Luminescence, 22(4), 349-354. doi:10.1002/bio.970Tsogas, G. Z., Giokas, D. L., Nikolakopoulos, P. G., Vlessidis, A. G., & Evmiridis, N. P. (2006). Determination of the pesticide carbaryl and its photodegradation kinetics in natural waters by flow injection–direct chemiluminescence detection. Analytica Chimica Acta, 573-574, 354-359. doi:10.1016/j.aca.2005.11.058Xie, Z., Ouyang, X., Guo, L., Lin, X., & Chen, G. (2005). Determination of carbofuran by flow-injection with chemiluminescent detection. Luminescence, 20(3), 226-230. doi:10.1002/bio.825Liu, H., Hao, Y., Ren, J., He, P., & Fang, Y. (2007). Determination of tsumacide residues in vegetable samples using a flow-injection chemiluminescence method. Luminescence, 22(4), 302-308. doi:10.1002/bio.963Amorim, C. M. P. G., Albert-García, J. R., Montenegro, M. C. B. S., Araújo, A. N., & Calatayud, J. M. (2007). Photo-induced chemiluminometric determination of Karbutilate in a continuous-flow Multicommutation assembly. Journal of Pharmaceutical and Biomedical Analysis, 43(2), 421-427. doi:10.1016/j.jpba.2006.07.006DeMarco, A. C., & Hayes, E. R. (1979). Photodegradation of thiolcarbamate herbicides. Chemosphere, 8(5), 321-326. doi:10.1016/0045-6535(79)90117-6Prevention, Pesticides and Toxic Substances (7508C) Reregistration eligibility decision. Thiophanate-methyl, Environmental Protection Agency (EPA), 2005Sanz-Asensio, J., Plaza-Medina, M., Martı́nez-Soria, M. ., & Pérez-Clavijo, M. (1999). Study of photodegradation of the pesticide ethiofencarb in aqueous and non-aqueous media, by gas chromatography–mass spectrometry. Journal of Chromatography A, 840(2), 235-247. doi:10.1016/s0021-9673(99)00219-8D. Barceló and M. C.Hennion, Techniques and instrumentation in analytical chemistry, Elsevier, Amsterdam, The Netherlands, 1997, vol. 19Capitán-Vallvey, L. (2000). Chemiluminescence determination of sodium 2-mercaptoethane sulfonate by flow injection analysis using cerium(IV) sensitized by quinine. Talanta, 51(6), 1155-1161. doi:10.1016/s0039-9140(00)00291-5NIE, L., MA, H., SUN, M., LI, X., SU, M., & LIANG, S. (2003). Direct chemiluminescence determination of cysteine in human serum using quinine–Ce(IV) system. Talanta, 59(5), 959-964. doi:10.1016/s0039-9140(02)00649-5J. R. Lakowicz , Principles of Fluorescence Spectroscopy, 3rd edn, Springer, New York, 2006Hamilton, D. J., Ambrus, Á., Dieterle, R. M., Felsot, A. S., Harris, C. A., Holland, P. T., … Wong, S.-S. (2003). Regulatory limits for pesticide residues in water (IUPAC Technical Report). Pure and Applied Chemistry, 75(8), 1123-1155. doi:10.1351/pac20037508112