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. 2020 Aug 3;10(48):28755-28765.
doi: 10.1039/d0ra05135g.

Synthesis of alginate-polycation capsules of different composition: characterization and their adsorption for [As(iii)] and [As(v)] from aqueous solutions

Cristopeer Thomas-Busani  1 , José Andrei Sarabia-Sainz  2 , Jaqueline García-Hernández  3 , Tomás J Madera-Santana  4 , Luz Vázquez-Moreno  1 , Gabriela Ramos-Clamont Montfort  1
Affiliations

Synthesis of alginate-polycation capsules of different composition: characterization and their adsorption for [As(iii)] and [As(v)] from aqueous solutions

Cristopeer Thomas-Busani et al. RSC Adv. .

Abstract

The uptake of arsenite [As(iii)] and arsenate [As(v)] by functionalized calcium alginate (Ca-Alg) beads from aqueous solutions was investigated. Ca-Alg beads were protonated with poly-l-lysine (PLL) or polyethyleneimine (PEI) using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide (EDC/NHS) or glutaraldehyde (GA) as crosslinking agents. Four types of protonated beads were prepared: Ca-Alg-EDC/NHS (PLL or PEI) and Ca-Alg-GA (PLL or PEI). Fourier transform infrared spectroscopy in total attenuated reflection mode (FTIR-ATR), analysis showed presence and increased intensity of bands corresponding to OH, NH, CH2 and CH3 groups in modifications with both polycations. In addition, thermogravimetric analysis and atomic force microscopy of all modified capsules showed an increase in thermal stability and uniformity of the capsules, respectively. Ca-Alg-EDC/NHS-PLL beads had the maximum adsorption capacity of [As(v)] (312.9 ± 4.7 μg g-1 of the alginate) at pH 7.0 and 15 minute exposure, while Ca-Alg-EDC/NHS-PEI beads had the maximum adsorption capacity of [As(iii)] (1052.1 ± 4.6 μg g-1 of alginate). However, all these EDC containing beads were degraded in the presence of citrate. Ca-Alg-GA-PEI beads removed 252.8 ± 9.7 μg of [As(v)] μg g-1 of alginate and 524.7 ± 5.3 de [As(iii)] μg g-1 of alginate, resulting the most stable capsules and suitable for As removal.

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Conflict of interest statement

There are no conflict of interest to declare.

Figures

Fig. 1
Fig. 1. Model of crosslinking reaction for modification of calcium alginate beads with poly-l-lysine (PLL) or polyethyleneimine (PEI). (A) Crosslinking reaction with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide (EDC/NHS). (B) Crosslinking with glutaraldehyde (GA).
Fig. 2
Fig. 2. Morphology of calcium alginate beads (Ca-Alg) protonated with poly-l-lysine (PLL) or polyethyleneimine (PEI). (A) Ca-Alg beads; (B) Ca-Alg-EDC/NHS-PLL; (C) Ca-Alg-EDC/NHS-PEI; (D) Ca-Alg-GA-PLL and (E) Ca-Alg-GA-PEI.
Fig. 3
Fig. 3. Attenuated total reflectance Fourier transform infrared spectroscopy for calcium alginate beads functionalized with (A) poly-l-lysine and (B) polyethylenimine.
Fig. 4
Fig. 4. Thermogravimetric/derivative thermogravimetry analysis for calcium alginate beads functionalized with poly-l-lysine (PLL). Crosslinking agents EDC/NHS: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide; GA: glutaraldehyde.
Fig. 5
Fig. 5. Thermogravimetric/derivative thermogravimetry analysis for calcium alginate beads functionalized with polyethyleneimine (PEI). Crosslinking agents EDC/NHS: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/N-hydroxysuccinimide; GA: glutaraldehyde.
Fig. 6
Fig. 6. Atomic force microscopy images topography of calcium alginate beads before (A and D) and after modification with poly-l-lysine: (B) Ca-Alg-EDC/NHS-PLL and (C) Ca-Alg-GA-PLL B or polyethyleneimine (E) Ca-Alg-EDC/NHS-PEI and (F) Ca-Alg-GA-PEI.
Fig. 7
Fig. 7. EDX in SEM images of (A) calcium alginate beads; (B) Ca-Alg-GA-PEI beads; (C) Ca-Alg-GA-PEI beads after biosorption of [As(iii)]; (D) Ca-Alg-GA-PEI beads after biosorption of [As(v)].
Fig. 8
Fig. 8. Attenuated total reflectance Fourier transform infrared spectroscopy for Ca-Alg-GA-PEI beads before and after [As(iii)] or [As(v)] adsorption.
Fig. 9
Fig. 9. Schematic representation of the complex interactions of [As(iii)] and electrostatic interaction of [As(v)] with Ca-Alg-GA-PEI amine groups.
Fig. 10
Fig. 10. Removal efficiency of Ca-Alg-GA-PEI after five desorption/adsorption cycles. Asterisk denotes significant difference (p < 0.05) between the cycles of the same oxyanion.
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