高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (4): 895.doi: 10.7503/cjcu20130766
• 高分子化学 • 上一篇
收稿日期:
2013-08-06
出版日期:
2014-04-10
发布日期:
2014-02-27
作者简介:
联系人简介: 邱学青, 男, 博士, 教授, 博士生导师, 主要从事木质素资源化利用的应用基础研究. E-mail: 基金资助:
ZHOU Haifeng, YANG Dongjie, QIU Xueqing*(), WU Xiaolei
Received:
2013-08-06
Online:
2014-04-10
Published:
2014-02-27
Contact:
QIU Xueqing
E-mail:cexqqiu@scut.edu.cn
Supported by:
摘要:
在室温及水溶液体系中, 采用辣根过氧化物酶(HRP)对亚硫酸法制浆造纸废液的副产物木质素磺酸钠(木钠)进行改性, 通过凝胶渗透色谱、 电位滴定、 红外光谱和核磁共振波谱等表征了HRP改性木钠的结构. 结果表明, HRP可以有效聚合木钠大分子, 调节HRP的用量, 得到不同分子量的木钠产品, 当HRP浓度为6 g/L时, 可使木钠分子量增大155%. HRP可氧化木钠分子上的酚羟基变成苯氧自由基, 该自由基可直接交联, 也可转移到酚羟基的邻位或对位再发生聚合作用, 其聚合方式主要为β-O-4'及β-β'连接. HRP改性还可使木钠磺化度增加27%. 采用静电逐层自组装技术研究了HRP改性对木钠吸附特征的影响, 结果表明, 经HRP改性后, 木钠在平板上的吸附量增大; 对TiO2浆体的分散稳定性能也得到改善, 这主要是因为分子量增大, 空间位阻作用增强; 磺化度增大, 静电排斥作用增强, 从而使TiO2颗粒更好地分散在水中.
中图分类号:
TrendMD:
周海峰, 杨东杰, 邱学青, 伍晓蕾. 辣根过氧化物酶改性木质素磺酸钠的结构特征及吸附分散性能. 高等学校化学学报, 2014, 35(4): 895.
ZHOU Haifeng, YANG Dongjie, QIU Xueqing, WU Xiaolei. Structural Characterization, Adsorption and Dispersion Properties of Sodium Lignosulfonate by Horseradish Peroxidase Incubation†. Chem. J. Chinese Universities, 2014, 35(4): 895.
Sample | Concentration of HRP/(g·L-1) | Incubation time/h | 10-3 Mn | 10-4 Mw | Mw/Mn |
---|---|---|---|---|---|
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 |
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 Mn | 10-4 Mw | Mw/Mn |
---|---|---|---|---|---|
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.
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 |
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 |
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 |
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 |
δ | Assignment | Amount(DMSO-1) | |
---|---|---|---|
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 | Hα, Hβ in β-β' structures | 0.89 | 1.06 |
5.00—4.75 | Hα in β-O-4' structures | 0.73 | 0.95 |
4.75—4.07 | Hβ, Hγ in β-O-4' structures | 2.74 | 4.69 |
4.00—3.50 | H in methoxyls | 5.66 | 3.57 |
3.20—2.90 | 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) | |
---|---|---|---|
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 | Hα, Hβ in β-β' structures | 0.89 | 1.06 |
5.00—4.75 | Hα in β-O-4' structures | 0.73 | 0.95 |
4.75—4.07 | Hβ, Hγ in β-O-4' structures | 2.74 | 4.69 |
4.00—3.50 | H in methoxyls | 5.66 | 3.57 |
3.20—2.90 | 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 |
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