Abstract
We describe core-shell structured magnetic chitosan microspheres (Rho-MCS) that were modified with a rhodamine spirolactam fluorescent probe. They are shown to be a viable fluorescent probe for the determination of mercury ion, and for its removal and preconcentration. The microspheres were characterized by FTIR, thermogravimetric analysis and high-resolution digital images, and these confirmed the successful loading with rhodamine probe. The microspheres represent excellent bare-eye colorimetric and fluorescent turn on probes for Hg(II) via a mechanism based on chelation-enhanced fluorescence. Hg(II) can be quantified with a limit of detection of 15 nM. The effects of pH, temperature, contact time and initial concentration on adsorption were also investigated. The results indicate that Rho-MCS possess high adsorption capacity (337 mg g−1) and superb removal capability (up to 97 %). A kinetic study shows that the adsorption mechanism can be described by a pseudo second-order equation, while the adsorption isotherm can be fit to a Langmuir model. Hg(II)-loaded Rho-MCS can be recycled by addition of ethylenediaminetetraacetic acid (EDTA). The capability for removal of Hg(II) was maintained above 86 % after five consecutive adsorption-desorption cycles.
Similar content being viewed by others
References
Sivaraman G, Anand T, Chellappa D (2012) Turn-on fluorescent chemosensor for Zn(II) via ring opening of rhodamine spirolactam and their live cell imaging. Analyst 137(24):5881–5884. doi:10.1039/c2an36209k
Sivaraman G, Sathiyaraja V, Chellappa D (2014) Turn-on fluorogenic and chromogenic detection of Fe(III) and its application in living cell imaging. J Lumin 145:480–485. doi:10.1016/j.jlumin.2013.08.018
Zhang T, Kim B, Levard C, Reinsch BC, Lowry GV, Deshusses MA, Kim H (2012) Methylation of mercury by bacteria exposed to dissolved, nanoparticulate, and microparticulate mercuric sulfides. Environ Sci Technol 46(13):6950–6958. doi:10.1021/es203181m
Ishihara N (1982) Minamata disease. Trace Elem Electrolytes 31(2):86–88. doi:10.5414/TEX01331
Laffont L, Sonke JE, Maurice L, Monrroy SL, Chincheros J, Amouroux D, Behra P (2011) Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury. Environ Sci Technol 45(23):9910–9916. doi:10.1021/es202353m
Hoyle I, Handy RD (2005) Dose-dependent inorganic mercury absorption by isolated perfused intestine of rainbow trout, Oncorhynchus mykiss, involves both amiloride-sensitive and energy-dependent pathways. Aquat Toxicol 72(1–2):147–159. doi:10.1016/j.aquatox.2004.11.015
Fu FL, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manage 92(3):407–418. doi:10.1016/j.jenvman.2010.11.011
Chiarle S, Ratto M, Rovatti M (2000) Mercury removal from water by ion exchange resins adsorption. Water Res 34(11):2971–2978. doi:10.1016/S0043-1354(00)00044-0
Shen ZM, Ma J, Mei ZJ, Zhang JD (2010) Metal chlorides loaded on activated carbon to capture elemental mercury. J Environ Sci 22(11):1814–1819. doi:10.1016/S1001-0742(09)60324-7
Johari K, Saman N, Mat H (2014) A comparative evaluation of mercury(II) adsorption equilibrium and kinetics onto silica gel and sulfur-functionalised silica gels adsorbents. Can J Chem Eng 92(6):1048–1058. doi:10.1002/cjce.21949
Xiong CH, Yao CP (2009) Synthesis, characterization and application of triethylenetetramine modified polystyrene resin in removal of mercury, cadmium and lead from aqueous solutions. Chem Eng J 155(3):844–850. doi:10.1016/j.cej.2009.09.009
Jainae K, Sanuwong K, Nuangjamnong J, Sukpirom N, Unob F (2010) Extraction and recovery of precious metal ions in wastewater by polystyrene-coated magnetic particles functionalized with 2-(3-(2-aminoethylthio)propylthio)ethanamine. Chem Eng J 160(2):586–593. doi:10.1016/j.cej.2010.03.080
Wang XH, Deng WY, Xie YY, Wang CY (2013) Selective removal of mercury ions using a chitosan–poly(vinyl alcohol) hydrogel adsorbent with three-dimensional network structure. Chem Eng J 228:232–242. doi:10.1016/j.cej.2013.04.104
Mladenova EK, Dakova IG, Karadjova IB (2011) Chitosan membranes as sorbents for trace elements determination in surface waters. Environ Sci Pollut Res 18(9):1633–1643. doi:10.1007/s11356-011-0529-x
Kushwaha S, Sreedhar B, Padmaja P (2010) Sorption of phenyl mercury, methyl mercury, and inorganic mercury onto chitosan and barbital immobilized chitosan: spectroscopic, potentiometric, kinetic, equilibrium, and selective desorption studies. J Chem Eng Data 55(11):4691–4698. doi:10.1021/je100317t
Guibal E (2004) Interactions of metal ions with chitosan-based sorbents: a review. Sep Purif Technol 38(1):43–74. doi:10.1016/j.seppur.2003.10.004
Meng QT, He C, Su WP, Zhang XL, Duan CY (2012) A new rhodamine-chitosan fluorescent material for the selective detection of Hg2+ in living cells and efficient adsorption of Hg2+ in natural water. Sens Actuators B 174:312–317. doi:10.1016/j.snb.2012.03.072
Tan LJ, Wan AJ, Li HL (2013) Fluorescent chitosan complex nanosphere diazeniumdiolates as donors and sensitive real-time probes of nitric oxide. Analyst 138(3):879–886. doi:10.1039/c2an36548k
Jiang DS, Long SY, Huang J (2005) Immobilization of Pycnoporus sanguineus laccase on magnetic chitosan microspheres. Biochem Eng J 25(1):15–23. doi:10.1016/j.bej.2005.03.007
Nie R, Chang XJ, He Q, Hu Z, Li ZH (2009) Preparation of p-tert[(dimethylamino)methyl]-calix[4]arene functionalized aminopropylpolysiloxane resin for selective solid-phase extraction and preconcentration of metal ions. J Hazard Mater 169(1–3):203–209. doi:10.1016/j.jhazmat.2009.03.084
Zheng H, Qian ZH, Xu L, Yuan FF, Lan LD, Xu JG (2006) Switching the recognition preference of rhodamine b spirolactam by replacing one atom: design of rhodamine b thiohydrazide for recognition of Hg(II) in aqueous solution. Org Lett 8(5):859–861. doi:10.1021/ol0529086
Wang Y, Li B, Zhang L, Li P, Wang L, Zhang J (2012) Multifunctional magnetic mesoporous silica nanocomposites with improved sensing performance and effective removal ability toward Hg(II). Langmuir 28(2):1657–1662. doi:10.1021/la204494v
Samuels RJ (1981) Solid state characterization of the structure of chitosan films. J Polym Sci Polym Phys Ed 19(7):1081–1105. doi:10.1002/pol.1981.180190706
Yan FY, Wang M, Cao DL, Yang N, Fu Y, Chen L, Chen LG (2013) New fluorescent and colorimetric chemosensors based on the rhodamine detection of Hg2+ and Al3+ and application of imaging in living cells. Dyes Pigments 98(1):42–50. doi:10.1016/j.dyepig.2013.02.002
Liu B (2014) Preparation and characterization of an optical sensor based on magnetic core and fluorescence “Off-On” probe for Hg(II) sensing and removal. Sensors Actuators B Chem 198:342–349
Liu BY, Zeng F, Wu SZ, Wang JS, Tang FC (2013) Ratiometric sensing of mercury(II) based on a FRET process on silica core-shell nanoparticles acting as vehicles. Microchim Acta 180(9):845–853
Li HT, He XD, Huang H, Lian SY, Liu Y, Kang ZH, Lee ST (2011) One-step ultrasonic synthesis of water-soluble carbon nanoparticles with excellent photoluminescent properties. Carbon 49:605–609
Kuang SP, Wang ZZ, Liu J, Wu ZC (2013) Preparation of triethylene-tetramine grafted magnetic chitosan for adsorption of Pb(II) ion from aqueous solutions. J Hazard Mater 260:210–219. doi:10.1016/j.jhazmat.2013.05.019
Liu JP, Yang J, Li H, Lu F (2014) Fast response Hg(II) sensing and removal core-shell nanocomposite: construction, characterization and performance. Dyes Pigments 106:168–175. doi:10.1016/j.dyepig.2014.03.015
Liu B (2014) Preparation and characterization of an optical sensor based on magnetic core and fluorescence “Off-On” probe for Hg(II) sensing and removal. Sens Actuators B 198:342–349. doi:10.1016/j.snb.2014.03.072
Chen YT, Mu SY (2014) Core-shell structured Fe3O4 nanoparticles functionalized with rhodamine derived probe for the detection, adsorption and removal of Hg(II): a sensing system with ‘warning’ signal. Sens Actuators B 192:275–282. doi:10.1016/j.snb.2013.10.135
Wang Y, Qi YX, Li YF, Wu JJ, Ma XJ, Yu C, Ji L (2013) Preparation and characterization of a novel nano-absorbent based on multi-cyanoguanidine modified magnetic chitosan and its highly effective recovery for Hg(II) in aqueous phase. J Hazard Mater 260:9–15. doi:10.1016/j.jhazmat.2013.05.001
Acknowledgments
The work described in this manuscript was supported by the National Natural Science Foundation of China (Nos. 21174103, 21374078) and Tianjin Research Program of Application Foundation and Advanced Technology (No. 15JCYBJC18100).
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(DOC 320 kb)
Rights and permissions
About this article
Cite this article
Shi, D., Yan, F., Zhou, X. et al. Preconcentration and fluorometric detection of mercury ions using magnetic core-shell chitosan microspheres modified with a rhodamine spirolactam. Microchim Acta 183, 319–327 (2016). https://doi.org/10.1007/s00604-015-1644-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00604-015-1644-z