, Volume 25, Issue 12, pp 6947–6961 | Cite as

Rapid capture and visual detection of copper ions in aqueous solutions and biofluids using a novel cellulose-Schiff base

  • Lianwei Zhang
  • Ruijia Wang
  • Rui Liu
  • Xiaolin Du
  • Ranju Meng
  • Lin LiuEmail author
  • Juming Yao
Original Paper


In this work, a novel colorimetric sensor was prepared via a cellulose-polyethylenimine-based Schiff base (cellulose-Schiff base) for capturing and detecting copper ions (Cu2+) in aquatic environments and life systems. The cellulose-Schiff base displayed continuous color changes from inherent pale yellow to deep green due to the formation of a cellulose-Schiff base-Cu2+ charge transfer complex within 30 s, indicating excellent “naked-eye” detection capability for Cu2+ ions in aqueous solution. The limit of detection (LOD) was 1.054 ppm, lower than the U.S. EPA guidelines for drinking water of 1.3 ppm. Moreover, the cellulose-Schiff base colorimetric sensor was successfully used to capture and detect exogenous Cu2+ ions in biofluids (simulated urine and bovine serum). The proposed sensing mechanism of the cellulose-Schiff base for Cu2+ ions is that N atoms (C=N and N–H) in the sensor capture and concentrate Cu2+ ions to form sensor-Cu2+ complexes, then intramolecular charge transfer occurs as a consequence. In addition, test strips based on cellulose-Schiff base were developed, and provide a convenient, cheap, sensitive, and reliable monitoring platform for on-site semi-quantitative analysis of Cu2+ ions in real samples.

Graphical abstract


Schiff base Capture Visual detection Biofluids Chelation Copper ions 



The work was financially supported by the Public Technology Research Plan of Zhejiang Province (LGF18E030003, LY15E030003), National Natural Science Foundation of China (51672251), and 521 Talent Project of Zhejiang Sci-Tech University.

Supplementary material

10570_2018_2083_MOESM1_ESM.docx (590 kb)
Supplementary material 1 (DOCX 589 kb)


  1. Awual MR, Rahman IMM, Yaita T, Khaleque MA, Ferdows M (2014) pH dependent Cu(II) and Pd(II) ions detection and removal from aqueous media by an efficient mesoporous adsorbent. Chem Eng J 236:100–109CrossRefGoogle Scholar
  2. Awual MR, Eldesoky GE, Yaita T, Naushad M, Shiwaku H, AlOthman ZA, Suzuki SA (2015) Schiff based ligand containing nano-composite adsorbent for optical copper(II) ions removal from aqueous solutions. Chem Eng J 279:639–647CrossRefGoogle Scholar
  3. Bandmann O, Weiss KH, Kaler SG (2015a) Non-ceruloplasmin copper distincts subtypes in Alzheimer’s disease: a genetic study of ATP7B frequency. Lancet Neurol 14:103–113CrossRefGoogle Scholar
  4. Bandmann O, Weiss KH, Kaler SG (2015b) Wilson’s disease and other neurological copper disorders. Lancet Neurol 14:103–113CrossRefGoogle Scholar
  5. Barnham KJ, Bush AI (2014) Biological metals and metal-targeting compounds in major neurodegenerative diseases. Chem Soc Rev 43:6727–6749CrossRefGoogle Scholar
  6. Bian K, Chen FY, Humulock ZT, Tang Q, Li DY (2017) Copper inhibits the AlkB family DNA repair enzymes under Wilson’s disease condition. Chem Res Toxicol 30:1794–1796CrossRefGoogle Scholar
  7. Cheng JH, Wei KY, Ma XF, Zhou XG, Xiang HF (2013) Synthesis and photophysical properties of colorful salen-type Schiff bases. J Phys Chem C 117:16552–16563CrossRefGoogle Scholar
  8. Deng S, Zhang GS, Chen SW, Xue YN, Du ZL, Wang P (2016) Rapid and effective preparation of a HPEI modified biosorbent based on cellulose fiber with a microwave irradiation method for enhanced arsenic removal in water. J Mater Chem A 4:15851–15860CrossRefGoogle Scholar
  9. Fang XN, Liu Y, Jimenez L, Duan YK, Adkins GB, Qian L (2017) Rapid enrichment and sensitive detection of multiple metal ions enabled by macroporous graphene foam. Anal Chem 89:11758–11764CrossRefGoogle Scholar
  10. Gholam BC, Mahmood T, Ahmadreza B, Rahman H (2017) A highly sensitive and selective novel fluorescent chemosensor for detection of Cr3+ based on a Schiff base. Inorg Chim Acta 462:241–248CrossRefGoogle Scholar
  11. Giampietro R, Spinelli F, Contino M, Colabufo NA (2018) The pivotal role of copper in neurodegeneration: a new strategy for the therapy of neurodegenerative disorders. Mol Pharm 15:808–820CrossRefGoogle Scholar
  12. Gonzalez MA, Pavlovic I, Rojas-Delgado R, Barriga C (2014) Removal of Cu2+, Pb2+ and Cd2+ by layered double hydroxide–humate hybrid: sorbate and sorbent comparative studies. Chem Eng J 254:605–611CrossRefGoogle Scholar
  13. Harpe AV, Petersen H, Li YX, Kissel T (2000) Characterization of commercially available and synthesized polyethylenimines for gene delivery. J Control Release 69:309–322CrossRefGoogle Scholar
  14. Horak E, Kassa P, Hranjec M, Steinberg IM (2018) Benzimidazole functionalised Schiff bases: novel pH sensitive fluorescence turn-on chromoionophores for ion-selective optodes. Sens Actuators B 258:415–423CrossRefGoogle Scholar
  15. Hu HZ, Wang FY, Yu LS, Sugimura KK, Zhou JP, Nishio Y (2018) Synthesis of novel fluorescent cellulose derivatives and their applications in detection of nitroaromatic compounds. ACS Sustain Chem Eng 6:1436–1445CrossRefGoogle Scholar
  16. Jin LH, Han CS (2014) Ultrasensitive and selective fluorimetric detection of copper ions using thiosulfate-involved quantum dots. Anal Chem 86:7209–7213CrossRefGoogle Scholar
  17. Joo DH, Mok JS, Bae GH, Oh SE, Kang JH, Kim C (2017) Colorimetric detection of Cu2+ and fluorescent detection of PO4 3− and S2− by a multifunctional chemosensor. Ind Eng Chem Res 56:8399–8407CrossRefGoogle Scholar
  18. Jung HS, Kwon PS, Lee JW, Kim JI, Hong CS, Kim JW (2009) Coumarin-derived Cu2+-selective fluorescence sensor: synthesis, mechanisms, and applications in living cells. J Am Chem Soc 131:2008–2012CrossRefGoogle Scholar
  19. Kaler SG (2011) ATP7A-related copper transport diseases-emerging concepts and future trends. Nat Rev Neurol 7:15–29CrossRefGoogle Scholar
  20. Kim YH, Park JH, Lee M, Kim Y, Park TG, Kim SW (2005) Polyethylenimine with acid-labile linkages as a biodegradable gene carrier. J Control Release 103:209–219CrossRefGoogle Scholar
  21. Kumari S, Chauhan GS (2014) New cellulose-lysine Schiff-base-based sensor-adsorbent for mercury ions. ACS Appl Mater Interfaces 6:5908–5917CrossRefGoogle Scholar
  22. Lee M, Barin G, Ackerman CM, Muchenditsi A, Xu J, Reimer JA, Lutsenko S, Long JR, Chang CJ (2016) Copper capture in a thioether-functionalized porous polymer applied to the detection of Wilson’s disease. J Am Chem Soc 138:7603–7609CrossRefGoogle Scholar
  23. Lin TW, Huang SD (2001) Direct and simultaneous determination of copper, chromium, aluminum, and manganese in urine with a multielement graphite furnace atomic absorption spectrometer. Anal Chem 73:4319–4325CrossRefGoogle Scholar
  24. Lindh J, Ruan CQ, Stromme M, Mihranyan A (2016) Preparation of porous cellulose beads via introduction of diamine spacers. Langmuir 32:5600–5607CrossRefGoogle Scholar
  25. Liu C, Ning DH, Zhang C, Liu ZJ, Zhang RL, Zhao J, Zhao TT, Liu BH, Zhang ZP (2017) Dual-colored carbon dot rratiometric fluorescent test paper based on a specific spectral energy transfer for semiquantitative assay of copper ions. ACS Appl Mater Interfaces 9:18897–18903CrossRefGoogle Scholar
  26. Lock JY, Wyatt E, Upadhyayula S, Whall A, Nunez V, Vullev VI, Liu HN (2013) Degradation and antibacterial properties of magnesium alloys inartificial urine for potential resorbable ureteral stent applications. J Biomed Mater Res A 102:781–792CrossRefGoogle Scholar
  27. Loegel TN, Morris RN, Leska I (2017) Detection and quantification of metal deactivator additive in jet and diesel fuel by liquid chromatography. Energy Fuels 31:3629–3634CrossRefGoogle Scholar
  28. Luis A, Bruno M, Filipe EA, Daniel T, Björn L (2016) Dissolution state of cellulose in aqueous systems. 1. Alkaline solvents. Carbohydr Polym 135:1–9CrossRefGoogle Scholar
  29. Miao P, Tang YG, Wang L (2017) DNA modified Fe3O4@Au magnetic nanoparticles as selective probes for simultaneous detection of heavy metal ions. ACS Appl Mater Interfaces 9:3940–3947CrossRefGoogle Scholar
  30. Nawaz H, Tian WG, Zhang JM, Jia RN, Chen ZY, Zhang J (2018) Cellulose-based sensor containing phenanthroline for the highly selective and rapid detection of Fe2+ ions with naked eye and fluorescent dual modes. ACS Appl Mater Interfaces 10:2114–2121CrossRefGoogle Scholar
  31. Ndokoye P, Ke J, Liu J, Zhao QD, Li XY (2014) L-cysteine-modified gold nanostars for SERS-based copper ions detection in aqueous media. Langmuir 30:13491–13497CrossRefGoogle Scholar
  32. Pall HS, Blake DR, Gutteridge JM, Williams AC, Lunec J, Hall M, Taylor A (1987) Raised cerebrospinal-fluid copper concentration in Parkinson’s disease. Lancet 330:238–241CrossRefGoogle Scholar
  33. Park JH, Choi HM, Oh KW (2014) Simultaneous crosslinking and cationization of cotton cellulose by using dialdehyde and choline chloride: comparison between the pad-dry-cure and microwave irradiation process. Cellulose 21:3107–3119CrossRefGoogle Scholar
  34. Pereira CC, de Souza AO, Oreste EQ, Vieira MA, Ribeiro AS (2018) Evaluation of the use of a reflux system for sample preparation of processed fruit juices and subsequent determination of Cr, Cu, K, Mg, Na, Pb and Zn by atomic spectrometry techniques. Food Chem 240:959–964CrossRefGoogle Scholar
  35. Qiu B, Guo J, Zhang X, Sun DJ, Gu HB, Wang Q, Wang XF, Zhang X, Weeks BL, Guo ZH, Wei SY (2014) Polyethylenimine facilitated ethyl cellulose for hexavalent chromium removal with a wide pH range. ACS Appl Mater Interfaces 6:19816–19824CrossRefGoogle Scholar
  36. Quintanar K, Domínguez-Calva JA, Serebryany E, Rivillas-Acevedo L, Haase-Pettingel C, Amero C, King JA (2016) Copper and zinc ions specifically promote nonamyloid aggregation of the highly stable human γ-D crystallin. ACS Chem Biol 11:263–272CrossRefGoogle Scholar
  37. Richardson SD, Ternes TA (2011) Water analysis: emerging contaminants and current issues. Anal Chem 83:4614–4648CrossRefGoogle Scholar
  38. Ruan CQ, Strømme M, Lindh J (2016) A green and simple method for preparation of an efficient palladium adsorbent based on cysteine functionalized 2,3-dialdehyde cellulose. Cellulose 23:2627–2638CrossRefGoogle Scholar
  39. Sayed MS, Reham A, Ibrahim AIA (2017) A novel, highly sensitive, selective, reversible and turn-on chemi-sensor based on Schiff base for rapid detection of Cu(II). Spectrochim Acta A Mol Biomol Spectrosc 183:225–231CrossRefGoogle Scholar
  40. Schyrr B, Pasche S, Voirin G, Weder C, Simon YC, Foster EJ (2014) Biosensors based on porous cellulose nanocrystal-poly(vinyl alcohol) scaffolds. ACS Appl Mater Interfaces 6:12674–12683CrossRefGoogle Scholar
  41. Singh I, Sagare AP, Coma M, Perlmutter D, Gelein R, Bell RD, Deane RJ, Zhong E (2013) Low levels of copper disrupt brain amyloid-beta homeostasis by altering its production and clearance. Proc Natl Acad Sci USA 110(36):14771–14776CrossRefGoogle Scholar
  42. Sui ZY, Cui Y, Zhu JH, Han BH (2013) Preparation of three-dimensional graphene oxide-polyethylenimine porous materials as dye and gas adsorbents. ACS Appl Mater Interfaces 5:9172–9179CrossRefGoogle Scholar
  43. Udousoro I, Ikem A, Akinbo OT (2017) Content and daily intake of essential and potentially toxic elements from dietary supplements marketed in Nigeria. J Food Compos Anal 62:23–34CrossRefGoogle Scholar
  44. Xiong SQ, Ye SD, Hu XH, Xie FZ (2016) Electrochemical detection of ultra-trace Cu(II) and interaction mechanism snalysis between amine-groups functionalized CoFe2O4/reduced graphene oxide composites and metal ion. Electrochim Acta 217:24–33CrossRefGoogle Scholar
  45. Yang RT, Yu HY, Song ML, Zhou YM, Yao JM (2016) Flower-like zinc oxide nanorod clusters grown on spherical cellulose nanocrystals via simple chemical precipitation method. Cellulose 23:1871–1884CrossRefGoogle Scholar
  46. Yu B, Xu J, Liu JH, Yang ST, Luo J, Zhou Q, Wan J, Liao R, Wang H, Liu Y (2013) Adsorption behavior of copper ions on graphene oxide-chitosan aerogel. J Environ Chem Eng 1:1044–1050CrossRefGoogle Scholar
  47. Zhang H, Xu M, Wang HJ, Lei D, Qu D, Zhai YJ (2013) Adsorption of copper by aminopropyl functionalized mesoporous delta manganese dioxide from aqueous solution. Colloids Surf A 435:78–84CrossRefGoogle Scholar
  48. Zhang ZY, Chen ZP, Qu CL, Chen LX (2014a) Highly sensitive visual detection of copper ions based on the shape-dependent LSPR spectroscopy of gold nanorods. Langmuir 30:3625–3630CrossRefGoogle Scholar
  49. Zhang N, Si YM, Sun ZZ, Chen LJ, Li R, Qiao YC, Wang H (2014b) Rapid, selective, and ultrasensitive fluorimetric analysis of mercury and copper levels in blood using bimetallic gold-silver nanoclusters with “silver effect”-enhanced red fluorescence. Anal Chem 86:11714–11721CrossRefGoogle Scholar
  50. Zhao LL, Zhong SX, Fang KM, Qian ZS, Chen JR (2012) Determination of cadmium(II), cobalt(II), nickel(II), lead(II), zinc(II), and copper(II) in water samples using dual-cloud point extraction and inductively coupled plasma emission spectrometry. J Hazard Mater 239–240:206–212CrossRefGoogle Scholar
  51. Zhao Z, Chen HD, Zhang H, Ma LN, Wang ZX (2017) Polyacrylamide-phytic acid-polydopamine conducting porous hydrogel for rapid detection and removal of copper (II) ions. Biosens Bioelectron 91:306–312CrossRefGoogle Scholar
  52. Zhu WJ, Liu L, Liao Q, Chen X, Qian ZQ, Shen JY, Liang JL, Yao JM (2016) Functionalization of cellulose with hyperbranched polyethylenimine for selective dye adsorption and separation. Cellulose 23:3785–3797CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.The Key Laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, College of Materials and TextilesZhejiang Sci-Tech UniversityHangzhouChina
  2. 2.National Engineering Lab of Textile Fiber Materials and Processing TechnologyHangzhouChina

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