Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd3+ extraction from aqueous solutions

Nadia H. Elsayed; Shareefa Ahmed Alshareef; Kholoud M. Alnahdi; Maha Ali Aljowni; Sana A. Khalil; Raedah A.S. Alatawi; Aliyah S. Alhawiti; Abeer Abdulaziz H. Bukhari; Hatem A. Al-Aoh; Mohammed A. Al-Duais; Kamal Shalabi; M. Monier

doi:10.1016/j.reactfunctpolym.2025.106307

Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd³⁺ extraction from aqueous solutions

Nadia H. Elsayed
, Shareefa Ahmed Alshareef
, Kholoud M. Alnahdi
, Maha Ali Aljowni
, Sana A. Khalil
, Raedah A.S. Alatawi
, Aliyah S. Alhawiti
, Abeer Abdulaziz H. Bukhari
, Hatem A. Al-Aoh
, Mohammed A. Al-Duais
, Kamal Shalabi
, M. Monier

Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The selective removal and recovery of gadolinium (Gd³⁺) ions from aqueous solutions are vital owing to their growing industrial utilization and environmental risks. In the present work, a polyacrylonitrile (PAN)-derived ion-imprinted polymer (Gd-IIP) was developed by using 2-Hydroxy-5-[(furan-2-ylmethyl)amino]benzohydrazide (FBH) as a chelating function. FBH was immobilized in DVB-crosslinked PAN microspheres by nucleophilic addition followed by subsequent Diels-Alder (DA) cross-linking with bis(maleimido)ethane (BM) for the synthesis of stable and selective Gd³⁺ binding sites. Functionalization was confirmed by characterization by FTIR, XPS, SEM, XRD, BET, and solid-state ¹³C NMR. Adsorption studies showed that Gd-IIP demonstrated high selectivity and adsorption capacity (448 mg/g) at pH 6.0, which exceeded the non-imprinted polymer (NIP). Selectivity studies against competing ions (Ni²⁺, Cu²⁺, Co²⁺, Y³⁺, Dy³⁺, and Ce³⁺) demonstrated Gd-IIP's superior affinity for Gd³⁺, with selectivity factor (β_Gd3+/Mn+) and relative selectivity (β_r) values exceeding 30, confirming precise ion recognition. Kinetic and isothermal modeling indicated pseudo-second-order adsorption, with the Sips model as the best fit. Regeneration studies showed over 97 % adsorption retention after five cycles, confirming its reusability and efficiency for wastewater treatment.

Original language	English
Article number	106307
Journal	Reactive and Functional Polymers
Volume	214
DOIs	https://doi.org/10.1016/j.reactfunctpolym.2025.106307
State	Published - Sep 2025

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 6 Clean Water and Sanitation
SDG 9 Industry, Innovation, and Infrastructure

Keywords

Diels-Alder
Gadolinium ions
Ion-imprinting
Polyacrylonitrile

Access to Document

10.1016/j.reactfunctpolym.2025.106307

Cite this

Elsayed, N. H., Alshareef, S. A., Alnahdi, K. M., Aljowni, M. A., Khalil, S. A., Alatawi, R. A. S., Alhawiti, A. S., Bukhari, A. A. H., Al-Aoh, H. A., Al-Duais, M. A., Shalabi, K., & Monier, M. (2025). Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd³⁺ extraction from aqueous solutions. Reactive and Functional Polymers, 214, Article 106307. https://doi.org/10.1016/j.reactfunctpolym.2025.106307

@article{ca7b1948476b425789e9be1ecc572865,

title = "Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd3+ extraction from aqueous solutions",

abstract = "The selective removal and recovery of gadolinium (Gd3+) ions from aqueous solutions are vital owing to their growing industrial utilization and environmental risks. In the present work, a polyacrylonitrile (PAN)-derived ion-imprinted polymer (Gd-IIP) was developed by using 2-Hydroxy-5-[(furan-2-ylmethyl)amino]benzohydrazide (FBH) as a chelating function. FBH was immobilized in DVB-crosslinked PAN microspheres by nucleophilic addition followed by subsequent Diels-Alder (DA) cross-linking with bis(maleimido)ethane (BM) for the synthesis of stable and selective Gd3+ binding sites. Functionalization was confirmed by characterization by FTIR, XPS, SEM, XRD, BET, and solid-state 13C NMR. Adsorption studies showed that Gd-IIP demonstrated high selectivity and adsorption capacity (448 mg/g) at pH 6.0, which exceeded the non-imprinted polymer (NIP). Selectivity studies against competing ions (Ni2+, Cu2+, Co2+, Y3+, Dy3+, and Ce3+) demonstrated Gd-IIP's superior affinity for Gd3+, with selectivity factor (βGd3+/Mn+) and relative selectivity (βr) values exceeding 30, confirming precise ion recognition. Kinetic and isothermal modeling indicated pseudo-second-order adsorption, with the Sips model as the best fit. Regeneration studies showed over 97 \% adsorption retention after five cycles, confirming its reusability and efficiency for wastewater treatment.",

keywords = "Diels-Alder, Gadolinium ions, Ion-imprinting, Polyacrylonitrile",

author = "Elsayed, \{Nadia H.\} and Alshareef, \{Shareefa Ahmed\} and Alnahdi, \{Kholoud M.\} and Aljowni, \{Maha Ali\} and Khalil, \{Sana A.\} and Alatawi, \{Raedah A.S.\} and Alhawiti, \{Aliyah S.\} and Bukhari, \{Abeer Abdulaziz H.\} and Al-Aoh, \{Hatem A.\} and Al-Duais, \{Mohammed A.\} and Kamal Shalabi and M. Monier",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier B.V.",

year = "2025",

month = sep,

doi = "10.1016/j.reactfunctpolym.2025.106307",

language = "English",

volume = "214",

journal = "Reactive and Functional Polymers",

issn = "1381-5148",

publisher = "Elsevier B.V.",

}

Elsayed, NH, Alshareef, SA, Alnahdi, KM, Aljowni, MA, Khalil, SA, Alatawi, RAS, Alhawiti, AS, Bukhari, AAH, Al-Aoh, HA, Al-Duais, MA, Shalabi, K & Monier, M 2025, 'Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd³⁺ extraction from aqueous solutions', Reactive and Functional Polymers, vol. 214, 106307. https://doi.org/10.1016/j.reactfunctpolym.2025.106307

TY - JOUR

T1 - Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd3+ extraction from aqueous solutions

AU - Elsayed, Nadia H.

AU - Alshareef, Shareefa Ahmed

AU - Alnahdi, Kholoud M.

AU - Aljowni, Maha Ali

AU - Khalil, Sana A.

AU - Alatawi, Raedah A.S.

AU - Alhawiti, Aliyah S.

AU - Bukhari, Abeer Abdulaziz H.

AU - Al-Aoh, Hatem A.

AU - Al-Duais, Mohammed A.

AU - Shalabi, Kamal

AU - Monier, M.

PY - 2025/9

Y1 - 2025/9

N2 - The selective removal and recovery of gadolinium (Gd3+) ions from aqueous solutions are vital owing to their growing industrial utilization and environmental risks. In the present work, a polyacrylonitrile (PAN)-derived ion-imprinted polymer (Gd-IIP) was developed by using 2-Hydroxy-5-[(furan-2-ylmethyl)amino]benzohydrazide (FBH) as a chelating function. FBH was immobilized in DVB-crosslinked PAN microspheres by nucleophilic addition followed by subsequent Diels-Alder (DA) cross-linking with bis(maleimido)ethane (BM) for the synthesis of stable and selective Gd3+ binding sites. Functionalization was confirmed by characterization by FTIR, XPS, SEM, XRD, BET, and solid-state 13C NMR. Adsorption studies showed that Gd-IIP demonstrated high selectivity and adsorption capacity (448 mg/g) at pH 6.0, which exceeded the non-imprinted polymer (NIP). Selectivity studies against competing ions (Ni2+, Cu2+, Co2+, Y3+, Dy3+, and Ce3+) demonstrated Gd-IIP's superior affinity for Gd3+, with selectivity factor (βGd3+/Mn+) and relative selectivity (βr) values exceeding 30, confirming precise ion recognition. Kinetic and isothermal modeling indicated pseudo-second-order adsorption, with the Sips model as the best fit. Regeneration studies showed over 97 % adsorption retention after five cycles, confirming its reusability and efficiency for wastewater treatment.

AB - The selective removal and recovery of gadolinium (Gd3+) ions from aqueous solutions are vital owing to their growing industrial utilization and environmental risks. In the present work, a polyacrylonitrile (PAN)-derived ion-imprinted polymer (Gd-IIP) was developed by using 2-Hydroxy-5-[(furan-2-ylmethyl)amino]benzohydrazide (FBH) as a chelating function. FBH was immobilized in DVB-crosslinked PAN microspheres by nucleophilic addition followed by subsequent Diels-Alder (DA) cross-linking with bis(maleimido)ethane (BM) for the synthesis of stable and selective Gd3+ binding sites. Functionalization was confirmed by characterization by FTIR, XPS, SEM, XRD, BET, and solid-state 13C NMR. Adsorption studies showed that Gd-IIP demonstrated high selectivity and adsorption capacity (448 mg/g) at pH 6.0, which exceeded the non-imprinted polymer (NIP). Selectivity studies against competing ions (Ni2+, Cu2+, Co2+, Y3+, Dy3+, and Ce3+) demonstrated Gd-IIP's superior affinity for Gd3+, with selectivity factor (βGd3+/Mn+) and relative selectivity (βr) values exceeding 30, confirming precise ion recognition. Kinetic and isothermal modeling indicated pseudo-second-order adsorption, with the Sips model as the best fit. Regeneration studies showed over 97 % adsorption retention after five cycles, confirming its reusability and efficiency for wastewater treatment.

KW - Diels-Alder

KW - Gadolinium ions

KW - Ion-imprinting

KW - Polyacrylonitrile

UR - https://www.scopus.com/pages/publications/105004558265

U2 - 10.1016/j.reactfunctpolym.2025.106307

DO - 10.1016/j.reactfunctpolym.2025.106307

M3 - Article

AN - SCOPUS:105004558265

SN - 1381-5148

VL - 214

JO - Reactive and Functional Polymers

JF - Reactive and Functional Polymers

M1 - 106307

ER -