A flexible Schiff base probe for spectrophotometric detection of chromium (III)

  • A. Minhaz
  • A. AnwarEmail author
  • I. Ahmad
  • R. Khattak
  • M. Yaseen
  • F. Ahmed
  • M. R. Shah
  • N. A. Khan
  • M. Ishaq
Original Paper


A new Schiff base chemosensor (2,2′-(1E,1′E)-(hexane-1,6-diylbis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)diphenol) was synthesized (denoted as C6) and characterized by NMR, ESI–MS and FTIR analysis. C6 was screened against several toxic and hazardous materials including heavy metals via spectrophotometry, and Cr+3 was found to produce a distinctive hyperchromic shift in the absorbance of C6. Further analytical evaluation to decipher the supramolecular interaction between C6 and Cr+3 showed that C6 acted as selective chemosensor and exhibited high sensitivity toward Cr+3 in the presence of a wide range of other metal ions. The limit of detection for Cr+3 by using C6 via spectrophotometric detection was found to be around 10 µM. Furthermore, a chemosensing protocol was successfully utilized to recognize Cr+3 in real samples of tap water. Hence, C6 provides a rapid, sensitive and robust method for the detection and possible removal of Cr+3 from aqueous solution and holds potential for its monitoring in the environment.


Chemosensor Cr+3 Schiff base Spectrophotometry Supramolecular Metal recognition 



The authors gratefully acknowledge the financial support from Higher Education Commission, Pakistan (Case No. 106-2077-PS6-065) and H.E.J. Research Institute of Chemistry, International Centre for Chemical and Biological Sciences, University of Karachi, Pakistan.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

13762_2018_2103_MOESM1_ESM.docx (1 mb)
Supplementary material 1 (DOCX 1037 kb)


  1. Abdou AA (2013) Spectrophotometric determination of chromium (III) in Egyptian ilmenite from phosphate solution using Egyptian white sand (EWS) as a selective adsorbent. Afr J Pure Appl Chem 7:1–11Google Scholar
  2. Anwar A, Shah MR, Muhammad SP, Ali K, Khan NA (2018) Synthesis of 4-formyl pyridinium propylthioacetate stabilized silver nanoparticles and their application in chemosensing of 6-aminopenicillanic acid (APA). Int J Environ Sci Technol 2018:1–8Google Scholar
  3. Behbahani M, Taghizadeh M, Bagheri A, Hosseini H, Salarian M, Tootoonchi A (2012) A nanostructured ion-imprinted polymer for the selective extraction and preconcentration of ultra-trace quantities of nickel ions. Microchim Acta 178:429–437CrossRefGoogle Scholar
  4. Bhalla V, Tejpal R, Kumar M, Sethi A (2009) Terphenyl derivatives as “turn on” fluorescent sensors for mercury. Inorg Chem 48:11677–11684CrossRefGoogle Scholar
  5. Collins EM, McKervey MA, Madigan E, Moran MB, Owens M, Ferguson G, Harris SJ (1991) Chemically modified calix [4] arenes. Regioselective synthesis of 1, 3-(distal) derivatives and related compounds. X-Ray crystal structure of a diphenol-dinitrile. J Chem Soc Perkin Trans 1:3137–3142CrossRefGoogle Scholar
  6. Cozzi PG (2004) Metal-Salen Schiff base complexes in catalysis: practical aspects. Chem Soc Rev 33:410–421CrossRefGoogle Scholar
  7. Dai J, Ren F, Tao C (2012) Adsorption of Cr(VI) and speciation of Cr(VI) and Cr(III) in aqueous solutions using chemically modified chitosan. Int J Environ Res Public Health 9:1757–1770CrossRefGoogle Scholar
  8. Dhal B, Thatoi H, Das N, Pandey B (2013) Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: a review. J Hazard Mater 250:272–291CrossRefGoogle Scholar
  9. Dong C, Wu G, Wang Z, Ren W, Zhang Y, Shen Z, Li T, Wu A (2016) Selective colorimetric detection of Cr(III) and Cr(VI) using gallic acid capped gold nanoparticles. Dalton Trans 45:8347–8354CrossRefGoogle Scholar
  10. Ganjali MR, Norouzi P, Faridbod F, Ghorbani M, Adib M (2006) Highly selective and sensitive chromium (III) membrane sensors based on a new tridentate Schiff’s base. Anal Chim Acta 569:35–41CrossRefGoogle Scholar
  11. Gupta VK, Singh A, Gupta B (2006) A cerium (III) selective polyvinyl chloride membrane sensor based on a Schiff base complex of N, N′-bis [2-(salicylideneamino) ethyl] ethane-1, 2-diamine. Anal Chim Acta 575:198–204CrossRefGoogle Scholar
  12. Gupta VK, Singh AK, Gupta B (2007) Schiff bases as cadmium (II) selective ionophores in polymeric membrane electrodes. Anal Chim Acta 583:340–348CrossRefGoogle Scholar
  13. Habila M, Unsal YE, Alothman ZA, Shabaka A, Tuzen M, Soylak M (2015) Speciation of chromium in natural waters, tea, and soil with membrane filtration flame atomic absorption spectrometry. Anal Lett 48:2258–2271CrossRefGoogle Scholar
  14. Hashemi M, Daryanavard SM (2012) Ultrasound-assisted cloud point extraction for speciation and indirect spectrophotometric determination of chromium (III) and (VI) in water samples. Spectrochim Acta Part A Mol Biomol Spectrosc 92:189–193CrossRefGoogle Scholar
  15. H-M Jiang, Yang T, Y-h Wang, Lian H-Z HuX (2013) Magnetic solid-phase extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) and Cr(VI) in environmental waters. Talanta 116:361–367CrossRefGoogle Scholar
  16. Huang Y-F, Li Y, Jiang Y, Yan X-P (2010) Magnetic immobilization of amine-functionalized magnetite microspheres in a knotted reactor for on-line solid-phase extraction coupled with ICP-MS for speciation analysis of trace chromium. J Anal Atom Spectrom 25:1467–1474CrossRefGoogle Scholar
  17. Jamaluddin AM, Reazul H (2011) A rapid spectrophotometric method for the determination of chromium in environmental samples using Bis (salicylaldehyde) orthophenylenediamine. Res J Chem Sci 1:46–59Google Scholar
  18. Johnson CP, Atwood JL, Steed JW, Bauer CB, Rogers RD (1996) Transition metal complexes of p-sulfonatocalix [5] arene. Inorg Chem 35:2602–2610CrossRefGoogle Scholar
  19. Jugade R, Joshi AP (2006) Highly sensitive adsorptive stripping voltammetric method for the ultra-trace determination of chromium (VI). Anal Sci 22:571–574CrossRefGoogle Scholar
  20. Katz SA, Salem H (1993) The toxicology of chromium with respect to its chemical speciation: a review. J Appl Toxicol 13:217–224CrossRefGoogle Scholar
  21. Keith C, Borazjani H, Diehl SV, Su Y, Baldwin B (2006) Removal of copper, chromium, and arsenic by water hyacinths. In: 36th Annual Mississippi water resources conference, pp 13–18Google Scholar
  22. Kimbrough DE, Cohen Y, Winer AM, Creelman L, Mabuni C (1999) A critical assessment of chromium in the environment. Crit Rev Environ Sci Technol 29:1–46CrossRefGoogle Scholar
  23. Leśniewska B, Godlewska-Żyłkiewicz B, Wilczewska AZ (2012) Separation and preconcentration of trace amounts of Cr(III) ions on ion imprinted polymer for atomic absorption determinations in surface water and sewage samples. Microchem J 105:88–93CrossRefGoogle Scholar
  24. Liu Y et al (2013) Speciation, adsorption and determination of chromium (III) and chromium (VI) on a mesoporous surface imprinted polymer adsorbent by combining inductively coupled plasma atomic emission spectrometry and UV spectrophotometry. J Sep Sci 36:3949–3957CrossRefGoogle Scholar
  25. López-García I, Briceño M, Vicente-Martínez Y, Hernández-Córdoba M (2013) Ultrasound-assisted dispersive liquid–liquid microextraction for the speciation of traces of chromium using electrothermal atomic absorption spectrometry. Talanta 115:166–171CrossRefGoogle Scholar
  26. Martin MT, Judson RS, Reif DM, Kavlock RJ, Dix DJ (2009) Profiling chemicals based on chronic toxicity results from the US EPA ToxRef Database. Environ Health Perspect 117:392–399CrossRefGoogle Scholar
  27. Meouche W, Branger C, Beurroies I, Denoyel R, Margaillan A (2012) Inverse suspension polymerization as a new tool for the synthesis of ion-imprinted polymers. Macromol Rapid Commun 33:928–932CrossRefGoogle Scholar
  28. Minhaz A, Ishaq M, Ahmad I, Ahmed F, Shah MR (2016) Highly selective supramolecular detection of pefloxacin with gold nanoparticles. Sensor Lett 14:310–318CrossRefGoogle Scholar
  29. Narin I, Soylak M, Kayakirilmaz K, Elci L, Dogan M (2002) Speciation of Cr(III) and Cr(VI) in tannery wastewater and sediment samples on Ambersorb 563 resin. Anal Lett 35:1437–1452CrossRefGoogle Scholar
  30. Safavi A, Maleki N, Shahbaazi H (2006) Indirect determination of hexavalent chromium ion in complex matrices by adsorptive stripping voltammetry at a mercury electrode. Talanta 68:1113–1119CrossRefGoogle Scholar
  31. Sari A, Mendil D, Tuzen M, Soylak M (2008) Biosorption of Cd (II) and Cr(III) from aqueous solution by moss (Hylocomium splendens) biomass: equilibrium, kinetic and thermodynamic studies. Chem Eng J 144:1–9CrossRefGoogle Scholar
  32. Singh AK, Gupta VK, Gupta B (2007) Chromium (III) selective membrane sensors based on Schiff bases as chelating ionophores. Anal Chim Acta 585:171–178CrossRefGoogle Scholar
  33. Soares R et al (2009) Simultaneous speciation of chromium by spectrophotometry and multicomponent analysis. Chem Spec Bioavailab 21:153–160CrossRefGoogle Scholar
  34. Verboom W, Durie A, Egberink RJ, Asfari Z, Reinhoudt DN (1992) Ipso nitration of p-tert-butylcalix [4] arenes. J Organ Chem 57:1313–1316CrossRefGoogle Scholar
  35. Vincent JB (2010) Chromium: celebrating 50 years as an essential element? Dalton Trans 39:3787–3794CrossRefGoogle Scholar
  36. Wilbur SB (2000) Toxicological profile for chromium. US Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease RegistryGoogle Scholar
  37. Zeng HH, Wu H, Peng D, Liu F, Shi WG, Qiu JD (2018) Fast and selective detection of Cr(III) in environmental water samples using phosphovanadate Y (V0. 2P0. 8O4): eu3 + fluorescence nanorods. ACS Sensors 3:1569–1575CrossRefGoogle Scholar
  38. Zhang H, Liu Q, Wang T, Yun Z, Li G, Liu J, Jiang G (2013) Facile preparation of glutathione-stabilized gold nanoclusters for selective determination of chromium (III) and chromium (VI) in environmental water samples. Anal Chim Acta 770:140–146CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2018

Authors and Affiliations

  • A. Minhaz
    • 1
  • A. Anwar
    • 2
    Email author
  • I. Ahmad
    • 3
  • R. Khattak
    • 1
  • M. Yaseen
    • 3
  • F. Ahmed
    • 4
  • M. R. Shah
    • 4
  • N. A. Khan
    • 2
  • M. Ishaq
    • 3
  1. 1.Department of Chemistry, Shaheed Benazir Bhutto Women UniversityPeshawarPakistan
  2. 2.Department of Biological Sciences, School of Science and TechnologySunway UniversitySubang JayaMalaysia
  3. 3.Institute of Chemical SciencesUniversity of PeshawarPeshawarPakistan
  4. 4.International Center for Chemical and Biological Sciences, H.E.J. Research Institute of ChemistryUniversity of KarachiKarachiPakistan

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