Structural Characterization, Adsorption and Dispersion Properties of Sodium Lignosulfonate by Horseradish Peroxidase Incubation†

doi:10.7503/cjcu20130766

Abstract

Abstract:

A novel and efficient polymerization of lignosulofonate(by-products from sulfite pulping process) was investigated in the present study. The ability of commercial horseradish peroxidase(HRP) for polymerizing sodium lignosulfonate(SL) was investigated in aqueous solution at room temperature. The gel permeation chromatography(GPC), potentiometric titration, infrared spectroscopy(IR), and ¹H nuclear magnetic resonance(¹H NMR) were used the structural characterization of SL. GPC results showed a significant increase in molecular weight(M_w) of SL. With different dosages of HRP added, SLs with different M_w could be obtained. When 6 g/L HRP was added, the M_w of SL could increase by 155%. During the HRP incubation, phenolic groups were oxidized to phenoxyl radicals. These radicals could undergo radical-couplings directly. On the other hand, unbound electron could transfer to the para- and ortho-carbon of the phenols and β-carbon of the branch, undergoing radical-couplings. Among the radical-couplings, β-O-4' and β-β' were the predominant. Moreover, the sulfonic group increased by 27% after HRP incubation. The adsorption of SL by HRP incubation was studied by electrostatic self-assembly technology. After HRP incubation, the adsorption amount of SL increased significantly. Further, because of the increase of M_w and sulfonic group content, resulting in the stronger steric hindrance and electronic repulsion, the dispersion ability of SL on TiO₂ slurry was improved.

Key words: Horseradish peroxidase, Sodium lignosulfonate, Molecular weight distribution, Structural characterization, Adsorption and dispersion property

CLC Number:

TrendMD:

ZHOU Haifeng, YANG Dongjie, QIU Xueqing, WU Xiaolei. Structural Characterization, Adsorption and Dispersion Properties of Sodium Lignosulfonate by Horseradish Peroxidase Incubation^†[J]. Chem. J. Chinese Universities, 2014, 35(4): 895.

Figures/Tables 10

Table 1 Reaction conditions and molecular weight distribution of SL by HRP incubation

Sample	Concentration of HRP/(g·L^-1)	Incubation time/h	10^-3 M_n	10^-4 M_w	M_w/M_n
D748	0	0	4.8	1.40	2.92
SL	0	0	2.7	0.99	3.69
HRP-SL 1	0.2	12	2.9	1.13	3.96
HRP-SL 2	0.5	12	3.3	1.42	4.25
HRP-SL 3	1	12	3.5	1.63	4.62
HRP-SL 4	3	12	3.8	1.90	5.03
HRP-SL 5	6	12	4.6	2.50	5.47
HRP-SL 6	1	0.33	3.5	1.61	4.58
HRP-SL 7	1	0.67	3.5	1.63	4.60
HRP-SL 8	1	1.0	3.6	1.65	4.63
HRP-SL 9	1	36	3.6	1.66	4.63
HRP-SL 10	6	0.33	4.6	2.48	5.45
HRP-SL 11	6	0.67	4.5	2.49	5.48
HRP-SL 12	6	1.0	4.6	2.51	5.47
HRP-SL 13	6	36	4.6	2.52	5.49

Fig.1 Effect of concentration of HRP on molecular weight distribution of SL by HRP incubation (A) Molecular weight distribution; (B) relationship of molecular weight and concentration of HRP.

Table 2 Phenolic and sulfonic group content of SL by HRP incubation

Sample	Concentration of phenolic group/(mmol·g^-1)	Concentration of sulfonic group/(mmol·g^-1)
SL	2.35	1.30
HRP-SL 6	1.72	1.42
HRP-SL 7	1.70	1.43
HRP-SL 8	1.74	1.42
HRP-SL 3	1.70	1.44
HRP-SL 9	1.71	1.41
HRP-SL 10	1.33	1.64
HRP-SL 11	1.32	1.63
HRP-SL 12	1.32	1.61
HRP-SL 5	1.34	1.64
HRP-SL 13	1.32	1.65

Fig.2 IR spectra of SL by HRP incubation a. SL; b. HRP-SL 3; c. HRP-SL 5.

Table 3 IR bands assignment of SL and the ratio of characteristic peak at 1512 cm-1

Peak intensity ratio	Assignment	SL	HRP-SL 3	HRP-SL 5
A₃₄₃₆/A₁₅₁₂	OH stretching in phenolic and aliphatic structures	1.588	1.430	1.347
A₂₉₃₇/A₁₅₁₂	C—H vibration in —CH₃ and —CH₂	1.002	0.987	0.969
A₂₈₅₀/A₁₅₁₂	C—H vibration in CH₃O—	0.962	0.947	0.770
A₁₇₀₃/A₁₅₁₂	C=O vibration in unconjugated ketone, carbonyl and ester groups	0.812	0.846	0.861
A₁₆₀₄/A₁₅₁₂	Aromatic skeleton vibrations	1.242	1.181	1.174
A₁₄₆₂/A₁₅₁₂	C—H deformations band of asymmetric methyl and methylene	0.948	0.921	0.872
A₁₄₂₁/A₁₅₁₂	Aromatic skeleton vibrations combined with C—H in plane deformations	0.995	0.996	0.989
A₁₃₆₆/A₁₅₁₂	Aliphatic C—H stretching in methyl groups and phenolic hydroxyl	0.961	0.906	0.842
A₁₁₆₄/A₁₅₁₂	G ring plus C—O stretching	1.686	1.437	1.318
A₁₀₇₆/A₁₅₁₂	S ring and C—O stretching	1.409	1.302	1.264
A₁₀₄₄/A₁₅₁₂	S=O stretching	1.576	1.703	1.824

Fig.3 1H NMR spectra of SL by HRP incubation a. SL; b. HRP-SL 5.

Table 4 Signal assignment in 1H NMR spectra of SL and results for quantification of functional groups(DMSO signal intensity as reference)

δ	Assignment	Amount(DMSO^-1)
δ	Assignment	SL	HRP-SL 5
7.75—7.20	Aromatic protons in positions C-2 and C-6 with C=O group	1.05	1.16
7.20—6.80	H₂, H₅, H₆ in guaiacyl units(G)	1.00	0.83
6.80—6.20	H₂, H₆ in syringyl units(S)	0.56	0.51
5.75—5.25	H_α, H_β in β-β' structures	0.89	1.06
5.00—4.75	H_α in β-O-4' structures	0.73	0.95
4.75—4.07	H_β, H_γ in β-O-4' structures	2.74	4.69
4.00—3.50	H in methoxyls	5.66	3.57
3.20—2.90	$H β$ in β-β' structures	0.61	0.76
2.56—2.44	DMSO	1.00	1.00
2.40—2.10	H in aromatic acetates	0.50	0.58
1.95—1.85	H in aliphatic acetates	0.19	0.27
1.60—0.70	Aliphatic H	1.29	2.27

Table 4 Signal assignment in 1H NMR spectra of SL and results for quantification of functional groups(DMSO signal intensity as reference)

δ	Assignment	Amount(DMSO^-1)
δ	Assignment	SL	HRP-SL 5
7.75—7.20	Aromatic protons in positions C-2 and C-6 with C=O group	1.05	1.16
7.20—6.80	H₂, H₅, H₆ in guaiacyl units(G)	1.00	0.83
6.80—6.20	H₂, H₆ in syringyl units(S)	0.56	0.51
5.75—5.25	H_α, H_β in β-β' structures	0.89	1.06
5.00—4.75	H_α in β-O-4' structures	0.73	0.95
4.75—4.07	H_β, H_γ in β-O-4' structures	2.74	4.69
4.00—3.50	H in methoxyls	5.66	3.57
3.20—2.90	$H β$ in β-β' structures	0.61	0.76
2.56—2.44	DMSO	1.00	1.00
2.40—2.10	H in aromatic acetates	0.50	0.58
1.95—1.85	H in aliphatic acetates	0.19	0.27
1.60—0.70	Aliphatic H	1.29	2.27

Fig.4 UV-Vis spectra of SL/PDAC multilayers of SL-Control

Fig.5 Absorbance of SL/PDAC multilayers at 280 nm varying with bilayer numbers by HRP incubation

Fig.6 Effect of SL by HRP incubation on particle size of TiO2 slurry a. No dispersant; b. SL; c. HRP-SL 3; d. HRP-SL 5.

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