Amine-terminated dendritic polymers as a multifunctional chelating agent for heavy metal ion removals

  • Mahsa Mohseni
  • Somaye AkbariEmail author
  • Elmira Pajootan
  • Firuzmehr Mazaheri
Research Article


In this study, amine-terminated hyperbranched PAMAM (polyamidoamine) polymer (AT-HBP) was synthesized as a multifunctional chelating agent to remove two heavy metal ions (Cr(III) and Cu(II)) from the simulated wastewater solutions. The AT-HBP was characterized by Fourier transformed infrared (FTIR), dynamic light scattering (DLS), and proton nuclear magnetic resonance (1H NMR) analysis. The removal process was carried out in two different methods, centrifuged process and ultrafiltration. The concentration of heavy metal ions before and after removal was measured by inductively coupled plasma (ICP) instrument. The removal processes were evaluated by changing different parameters such as solution pH, AT-HBP dosage, and metal ion concentration. To evaluate the extend of binding of heavy metal ions in the presence of AT-HBP the presence of salt in the solution was also examined on the performance of the removal system. The overall results indicated that removal percentages higher than 98% for Cr(III) and 86% for Cu(II) were achieved for heavy metal concentrations of 100 mg/L for both removal process methods. Furthermore, the function of second generation of polypropylenimine (PPI) was compared to AT-HBP. The results reveal that the removal of Cr(III) and Cu(II) ions by AT-HBP were approximately 20% and 10% higher compared to PPI, respectively. Finally, hyperbranched dendritic polymer with lower expenses to synthesize compared to dendrimer underlined favorable properties as a multifunctional chelating agent and enhancement of ultrafiltration process for wastewater treatment.

Graphical abstract


Amine-terminated hyperbranched polymer Heavy metal ions Adsorption Chelating agent Host–guest chemistry 



This study is partially financially supported by the Centre of Excellence, Modern Methods of Identification of Textiles, Amirkabir University of Technology, Textile Engineering Department.

Supplementary material

11356_2019_4765_MOESM1_ESM.docx (71 kb)
Fig. S.1 (DOCX 70 kb)


  1. Agarwal G, Bhuptawat HK, Chaudhari S (2006) Biosorption of aqueous chromium (VI) by Tamarindus indica seeds. Bioresour Technol 97(7):949–956CrossRefGoogle Scholar
  2. Akbari S, Vasigh M, Mohseni M, Pajootan E (2015) Characterization and application of amine terminated dendritic polymer in waste-water treatment. Paper presented at the The 3rd Mełpin Conference on Technology Transfer for the, Development of New Products in Chemical SMEs, Melpin, PolandGoogle Scholar
  3. Aksu Z, Balibek E (2007) Chromium (VI) biosorption by dried Rhizopus arrhizus: effect of salt (NaCl) concentration on equilibrium and kinetic parameters. J Hazard Mater 145(1):210–220CrossRefGoogle Scholar
  4. Albrecht TWJ, Addai-Mensah J, Fornasiero D (2011) Effect of pH, concentration and temperature on copper and zinc hydroxide formation/precipitation in solution. Chemeca 2011: Engineering a Better World: Sydney Hilton Hotel, NSW, Australia, 18-21 September 2011, 2100Google Scholar
  5. Alpatova A, Verbych S, Bryk M, Nigmatullin R, Hilal N (2004) Ultrafiltration of water containing natural organic matter: heavy metal removing in the hybrid complexation–ultrafiltration process. Sep Purif Technol 40(2):155–162CrossRefGoogle Scholar
  6. Arica TA, Ayas E, Arica MY (2017) Magnetic MCM-41 silica particles grafted with poly (glycidylmethacrylate) brush: modification and application for removal of direct dyes. Microporous Mesoporous Mater 243:164–175CrossRefGoogle Scholar
  7. Arica TA, Kuman M, Gercel O, Ayas E (2019) Poly (dopamine) grafted bio-silica composite with tetraethylenepentamine ligands for enhanced adsorption of pollutants. Chem Eng Res Des 141:317–327CrossRefGoogle Scholar
  8. Aroua MK, Zuki FM, Sulaiman NM (2007) Removal of chromium ions from aqueous solutions by polymer-enhanced ultrafiltration. J Hazard Mater 147(3):752–758CrossRefGoogle Scholar
  9. Arthanareeswaran G, Thanikaivelan P, Jaya N, Mohan D, Raajenthiren M (2007) Removal of chromium from aqueous solution using cellulose acetate and sulfonated poly (ether ether ketone) blend ultrafiltration membranes. J Hazard Mater 139(1):44–49CrossRefGoogle Scholar
  10. Baharuddin NH, Sulaiman NMN, Aroua MK (2015) Removal of heavy metal ions from mixed solutions via polymer-enhanced ultrafiltration using starch as a water-soluble biopolymer. Environ Prog Sustain Energy 34(2):359–367CrossRefGoogle Scholar
  11. Barakat M (2011) New trends in removing heavy metals from industrial wastewater. Arab J Chem 4(4):361–377CrossRefGoogle Scholar
  12. Barakat M, Schmidt E (2010) Polymer-enhanced ultrafiltration process for heavy metals removal from industrial wastewater. Desalination 256(1):90–93CrossRefGoogle Scholar
  13. Barakat M, Ramadan M, Alghamdi M, Algarny S, Woodcock H, Kuhn J (2013) Remediation of cu (II), Ni (II), and Cr (III) ions from simulated wastewater by dendrimer/titania composites. J Environ Manag 117:50–57CrossRefGoogle Scholar
  14. Bayramoglu G, Arica MY (2017) Polyethylenimine and tris (2-aminoethyl) amine modified p (GA–EGMA) microbeads for sorption of uranium ions: equilibrium, kinetic and thermodynamic studies. J Radioanal Nucl Chem 312(2):293–303CrossRefGoogle Scholar
  15. Bayramoglu G, Akbulut A, Acıkgoz-Erkaya I, Arica MY (2018) Uranium sorption by native and nitrilotriacetate-modified Bangia atropurpurea biomass: kinetics and thermodynamics. J Appl Phycol 30(1):649–661CrossRefGoogle Scholar
  16. Borbély G, Nagy E (2009) Removal of zinc and nickel ions by complexation–membrane filtration process from industrial wastewater. Desalination 240(1–3):218–226CrossRefGoogle Scholar
  17. Bosman A, Janssen H, Meijer E (1999) About dendrimers: structure, physical properties, and applications. Chem Rev 99(7):1665–1688CrossRefGoogle Scholar
  18. Carvalho JWP, Carvalho FAO, Batista T, Santiago PS, Tabak M (2014) Cetyltrimethylammonium chloride (CTAC) effect on the thermal stability of oxy-HbGp: dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) studies. Colloids Surf B: Biointerfaces 118:14–24CrossRefGoogle Scholar
  19. de la Calle I, Menta M, Klein M, Séby F (2017) Screening of TiO2 and Au nanoparticles in cosmetics and determination of elemental impurities by multiple techniques (DLS, SP-ICP-MS, ICP-MS and ICP-OES). Talanta 171:291–306CrossRefGoogle Scholar
  20. Diallo MS, Christie S, Swaminathan P, Balogh L, Shi X, Um W, Papelis C, Goddard WA, Johnson JH (2004) Dendritic chelating agents. 1. Cu (II) binding to ethylene diamine core poly (amidoamine) dendrimers in aqueous solutions. Langmuir 20(7):2640–2651CrossRefGoogle Scholar
  21. Diallo MS, Christie S, Swaminathan P, Johnson JH, Goddard WA (2005) Dendrimer enhanced ultrafiltration. 1. Recovery of Cu (II) from aqueous solutions using PAMAM dendrimers with ethylene diamine core and terminal NH2 groups. Environ Sci Technol 39(5):1366–1377CrossRefGoogle Scholar
  22. Diallo MS, Arasho W, Johnson JH Jr, Goddard Iii WA (2008) Dendritic chelating agents. 2. U (VI) binding to poly (amidoamine) and poly (propyleneimine) dendrimers in aqueous solutions. Environ Sci Technol 42(5):1572–1579CrossRefGoogle Scholar
  23. El Nemr A (2009) Potential of pomegranate husk carbon for Cr (VI) removal from wastewater: kinetic and isotherm studies. J Hazard Mater 161(1):132–141CrossRefGoogle Scholar
  24. Ennigrou DJ, Gzara L, Romdhane MRB, Dhahbi M (2009) Cadmium removal from aqueous solutions by polyelectrolyte enhanced ultrafiltration. Desalination 246(1–3):363–369CrossRefGoogle Scholar
  25. Fischer M, Vögtle F (1999) Dendrimers: from design to application—a progress report. Angew Chem Int Ed 38(7):884–905CrossRefGoogle Scholar
  26. Gao C, Yan D (2004) Hyperbranched polymers: from synthesis to applications. Prog Polym Sci 29(3):183–275CrossRefGoogle Scholar
  27. Gupta U, Agashe HB, Jain NK (2007) Polypropylene imine dendrimer mediated solubility enhancement: effect of pH and functional groups of hydrophobes. J Pharm Pharm Sci 10(3):358–367Google Scholar
  28. Hasan Z, Jhung SH (2015) Removal of hazardous organics from water using metal-organic frameworks (MOFs): plausible mechanisms for selective adsorptions. J Hazard Mater 283:329–339CrossRefGoogle Scholar
  29. Hoo CM, Starostin N, West P, Mecartney ML (2008) A comparison of atomic force microscopy (AFM) and dynamic light scattering (DLS) methods to characterize nanoparticle size distributions. J Nanopart Res 10(1):89–96CrossRefGoogle Scholar
  30. Iannazzo D, Pistone A, Ziccarelli I, Espro C, Galvagno S, Giofré SV et al (2017) Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes. Environ Sci Pollut Res 24(17):14735–14747CrossRefGoogle Scholar
  31. Ilaiyaraja P, Deb AKS, Ponraju D (2015) Removal of uranium and thorium from aqueous solution by ultrafiltration (UF) and PAMAM dendrimer assisted ultrafiltration (DAUF). J Radioanal Nucl Chem 303(1):441–450CrossRefGoogle Scholar
  32. Juang R-S, Chen M-N (1996) Retention of copper (II)—EDTA chelates from dilute aqueous solutions by a polyelectrolyte-enhanced ultrafiltration process. J Membr Sci 119(1):25–37CrossRefGoogle Scholar
  33. Kotaś J, Stasicka Z (2000) Chromium occurrence in the environment and methods of its speciation. Environ Pollut 107(3):263–283CrossRefGoogle Scholar
  34. Kotte MR, Kuvarega AT, Cho M, Mamba BB, Diallo MS (2015) Mixed matrix pvdf membranes with in situ synthesized pamam dendrimer-like particles: A new class of sorbents for Cu (ii) recovery from aqueous solutions by ultrafiltration. Environ Sci Technol 49(16):9431–9442CrossRefGoogle Scholar
  35. Krawczyk M, Akbari S, Jeszka-Skowron M, Pajootan E, Fard FS (2016) Application of dendrimer modified halloysite nanotubes as a new sorbent for ultrasound-assisted dispersive micro-solid phase extraction and sequential determination of cadmium and lead in water samples. J Anal At Spectrom 31(7):1505–1514CrossRefGoogle Scholar
  36. Krot KA, de Namor AFD, Aguilar-Cornejo A, Nolan KB (2005) Speciation, stability constants and structures of complexes of copper (II), nickel (II), silver (I) and mercury (II) with PAMAM dendrimer and related tetraamide ligands. Inorg Chim Acta 358(12):3497–3505CrossRefGoogle Scholar
  37. Li Z, Wang Y, Wu N, Chen Q, Wu K (2013) Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism. Environ Sci Pollut Res 20(3):1511–1525CrossRefGoogle Scholar
  38. Martín DM, Faccini M, García M, Amantia D (2018) Highly efficient removal of heavy metal ions from polluted water using ion-selective polyacrylonitrile nanofibers. J Environ Chem Eng 6(1):236–245CrossRefGoogle Scholar
  39. Mittal T (2012) Significant manipulations of nanotechnology in water purification. Int J Enhanc Res Sci Technol Eng 2(2)Google Scholar
  40. Mohmood I, Lopes CB, Lopes I, Ahmad I, Duarte AC, Pereira E (2013) Nanoscale materials and their use in water contaminants removal—a review. Environ Sci Pollut Res 20(3):1239–1260CrossRefGoogle Scholar
  41. Nam A, Su Choi U, Yun S-T, Choi J-W, Park J-A, Lee S-H (2018) Evaluation of amine-functionalized acrylic ion exchange fiber for chromium (VI) removal using flow-through experiments modeling and real wastewater. J Ind Eng Chem 66:187–195CrossRefGoogle Scholar
  42. Niu Y, Sun L, Crooks RM (2003) Determination of the intrinsic proton binding constants for poly (amidoamine) dendrimers via potentiometric pH titration. Macromolecules 36(15):5725–5731CrossRefGoogle Scholar
  43. Rivas BL, Moreno-Villoslada I (2000) Effect of the polymer concentration on the interactions of water-soluble polymers with metal ions. Chem Lett 29(2):166–167CrossRefGoogle Scholar
  44. Rivas B, Seguel G (1998) Polychelates of poly (acrylic acid-co-acrylamide) with Cu (II), Co (II), and Ni (II) synthesis and properties. Polym Bull 40(4):431–437CrossRefGoogle Scholar
  45. Rivas BL, Pereira ED, Moreno-Villoslada I (2003) Water-soluble polymer–metal ion interactions. Prog Polym Sci 28(2):173–208CrossRefGoogle Scholar
  46. Shahamati Fard F, Akbari S, Pajootan E, Arami M (2016) Enhanced acidic dye adsorption onto the dendrimer-based modified halloysite nanotubes. Desalin Water Treat 57(54):26222–26239CrossRefGoogle Scholar
  47. Tchobanoglous G, Darby J, Bourgeous K, McArdle J, Genest P, Tylla M (1998) Ultrafiltration as an advanced tertiary treatment process for municipal wastewater. Desalination 119(1):315–321CrossRefGoogle Scholar
  48. Tomalia DA, Fréchet JM (2002) Discovery of dendrimers and dendritic polymers: a brief historical perspective. J Polym Sci A Polym Chem 40(16):2719–2728CrossRefGoogle Scholar
  49. Uludağ N, Serdaroğlu G (2018) An improved synthesis, spectroscopic (FT-IR, NMR) study and DFT computational analysis (IR, NMR, UV–Vis, MEP diagrams, NBO, NLO, FMO) of the 1, 5-methanoazocino [4, 3-b] indole core structure. J Mol Struct 1155:548–560CrossRefGoogle Scholar
  50. Wang D, Imae T (2004) Fluorescence emission from dendrimers and its pH dependence. J Am Chem Soc 126(41):13204–13205CrossRefGoogle Scholar
  51. Wang J, Ban H, Teng X, Wang H, Ladwig K (2006) Impacts of pH and ammonia on the leaching of Cu (II) and Cd (II) from coal fly ash.
  52. Xu Y, Zhao D (2005) Removal of copper from contaminated soil by use of poly (amidoamine) dendrimers. Environ Sci Technol 39(7):2369–2375CrossRefGoogle Scholar
  53. Xu Z, Xu T, Cheng Y, Ma M, Xu P, Qu H, Wen L (2008) Colorimetric determination of polyamidoamine dendrimers and their derivates using a simple and rapid ninhydrin assay. Anal Lett 41(3):444–455CrossRefGoogle Scholar
  54. Yates C, Hayes W (2004) Synthesis and applications of hyperbranched polymers. Eur Polym J 40(7):1257–1281CrossRefGoogle Scholar
  55. Yoshimura T, Ebihara A, Iwase H (2017) Tadpole-type amphiphilic dendrimers with bulky dendrons: adsorption and aggregation properties. Colloids Surf A Physicochem Eng Asp 533:197–203CrossRefGoogle Scholar
  56. Zare EN, Motahari A, Sillanpää M (2018) Nanoadsorbents based on conducting polymer nanocomposites with main focus on polyaniline and its derivatives for removal of heavy metal ions/dyes: A review. Environ Res 162:173–195CrossRefGoogle Scholar
  57. Zhang F, Wang B, He S, Man R (2014) Preparation of graphene-oxide/polyamidoamine dendrimers and their adsorption properties toward some heavy metal ions. J Chem Eng Data 59(5):1719–1726CrossRefGoogle Scholar
  58. Zhang Z, Hou X, Zhang X, Li H (2017) The synergistic adsorption of pyrene and copper onto Fe (III) functionalized mesoporous silica from aqueous solution. Colloids Surf A Physicochem Eng Asp 520:39–45CrossRefGoogle Scholar
  59. Zhu X, Zhou Y, Yan D (2011) Influence of branching architecture on polymer properties. J Polym Sci B Polym Phys 49(18):1277–1286CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Textile Engineering DepartmentAmirkabir University of Technology (Polytechnic Tehran)TehranIran
  2. 2.Department of Chemical EngineeringMcGill UniversityQCCanada

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