乙酰化处理对碱木质素在四氢呋喃中微结构的影响

doi:10.3866/PKU.WHXB201411062

物理化学学报 >> 2015, Vol. 31 >> Issue (1): 128-136.doi: 10.3866/PKU.WHXB201411062

乙酰化处理对碱木质素在四氢呋喃中微结构的影响

李浩, 邓永红, 邱学青

华南理工大学化学与化工学院, 制浆造纸工程国家重点实验室, 广州 510640

收稿日期:2014-08-29 修回日期:2014-11-05 发布日期:2014-12-25
通讯作者: 邓永红, 邱学青 E-mail:yhdeng@scut.edu.cn;xueqingqiu66@163.com
基金资助:
国家重点基础研究发展规划项目(973) (2012CB215302)和国家自然科学基金(21436004, 21374032)资助

Influence of Acetylation on the Microstructure of Alkali Lignin in Tetrahydrofuran

LI Hao, DENG Yong-Hong, QIU Xue-Qing

State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China

Received:2014-08-29 Revised:2014-11-05 Published:2014-12-25
Contact: DENG Yong-Hong, QIU Xue-Qing E-mail:yhdeng@scut.edu.cn;xueqingqiu66@163.com
Supported by:
The project was supported by the National Key Basic Research Program of China (973) (2012CB215302) and National Natural Science Foundation of China (21436004, 21374032).

摘要/Abstract

摘要：

通过对比碱木质素(AL)和乙酰化碱木质素(ACAL)在四氢呋喃(THF)中溶液行为和物理化学性质的差异, 揭示了乙酰化处理对碱木质素在THF中微结构的影响. 分别采用动态光散射、凝胶渗透色谱(GPC)、透射电子显微镜(TEM)、特性粘度、荧光光谱仪、耗散型石英晶体微天平(QCM-D)和自组装技术等研究了AL和ACAL在聚集形态、聚集机理以及吸附特性等方面的特征. 研究发现, 乙酰化处理会降低碱木质素在THF中的分子间和分子内聚集程度. AL在THF中以单分子和聚集体的形式共同存在, 分子较为蜷曲; ACAL在THF中则更多地是以单分子形式存在而几乎不存在大聚集体, 分子较为伸展, 其流体力学半径要比相同绝对分子量的AL更大.THF中的AL聚集体会在液固界面上发生强烈的吸附, 但ACAL由于与溶剂间的相互作用较强而几乎不会吸附在液固界面上. 由于AL分子在THF中较为蜷曲且吸附能力较强, 因此利用以THF为流动相的GPC直接测量AL的分子量时所得结果并不准确, 为保证GPC的测量结果更加全面可靠, 需要在测量前对碱木质素进行乙酰化处理.

关键词: 碱木质素, 乙酰化, 微结构, 聚集, 分子量

Abstract:

The effect of acetylation on the microstructure of alkali lignin (AL) in tetrahydrofuran (THF) was studied. The physicochemical properties of AL and acetylated alkali lignin (ACAL) were compared. Dynamic light scattering, gel penetration chromatography (GPC), transmission electron microscopy (TEM), intrinsic viscosity, fluorescence spectrophotometry, quartz crystal microbalance with dissipation (QCM-D) measurements, and layer-by-layer (LbL) self-assembly were used to investigate the aggregation and adsorption of AL and ACAL. Intermolecular and intramolecular associations in AL decreased following acetylation. AL in THF existed mainly as mono-molecules and intermolecular associations and had a more compact conformation. ACAL existed mainly as mono-molecules with a more stretched conformation. ACAL had a larger hydrodynamic radius than AL(of the same absolute molecular mass), because of its stretched conformation. QCM-D and LbLself-assembly measurements suggested that AL aggregates have a strong tendency to adsorb at the liquid-solid interface, but ACAL hardly adsorb at this interface because of its stronger interaction with THF. The compact conformation and strong adsorption property of AL resulted in inaccurate molecular weights of non-acetylated AL, as measured by GPC with a THF mobile phase. In order to get more reliable molecular weights from GPC measurements, acetylation for AL should be used in the sample pretreatment.

Key words: Alkali lignin, Acetylation, Microstructure, Aggregate, Molecular weight

李浩, 邓永红, 邱学青. 乙酰化处理对碱木质素在四氢呋喃中微结构的影响[J]. 物理化学学报, 2015, 31(1), 128-136. doi: 10.3866/PKU.WHXB201411062

LI Hao, DENG Yong-Hong, QIU Xue-Qing. Influence of Acetylation on the Microstructure of Alkali Lignin in Tetrahydrofuran[J]. Acta Phys. -Chim. Sin. 2015, 31(1), 128-136. doi: 10.3866/PKU.WHXB201411062

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201411062

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I1/128

参考文献

(1) Bernier, E.; Lavigne, C.; Robidoux, P. Y. Int. J. Life Cycle Ass. 2013, 18, 520. doi: 10.1007/s11367-012-0503-y
(2) Azadi, P.; Inderwildi, O. R.; Farnood, R.; King, D. A. Renew. Sust. Energ. Rev. 2013, 21, 506. doi: 10.1016/j.rser.2012.12.022
(3) Yu, W. F.; Meng, X. G.; Liu, Y.; Li, X. H. Acta Phys. -Chim. Sin. 2013, 29, 2041. [于卫峰, 孟祥光,刘莹,李小红.物理化学学报, 2013, 29, 2041.] doi: 10.3866/PKU.WHXB201306282
(4) Ouyang, X. P.; Chen, Z. L.; Qiu, X. Q. Chin. J. Anal. Chem. 2014, 42, 723. [欧阳新平,陈子龙, 邱学青.分析化学, 2014, 42, 723.]
(5) Stewart, D. Ind. Crop. Prod. 2008, 27, 202. doi: 10.1016/j.indcrop.2007.07.008
(6) Sciban, M. B.; Klasnja, M. T.; Antov, M. G. Ecol. Eng. 2011, 37, 2092. doi: 10.1016/j.ecoleng.2011.08.006
(7) Braun, J. L.; Holtman, K. M.; Kadla, J. F. Carbon 2005, 43, 385. doi: 10.1016/j.carbon.2004.09.027
(8) Qian, Y.; Deng, Y. H.; Qiu, X. Q.; Li, H.; Yang, D. J. Green Chem. 2014, 16, 2156. doi: 10.1039/c3gc42131g
(9) Qiu, X. Q.; Li, H.; Deng, Y. H.; Qian, Y.; Yi, C, H. Acta Polym. Sin. 2014, No. 11, 1458. [邱学青,李浩,邓永红,钱勇,易聪华. 高分子学报, 2014, No. 11, 1458.]
(10) Lou, H. M.; Lai, H. R.; Wang, M. X.; Pang, Y. X.; Yang, D. J.; Qiu, X. Q.; Wang, B.; Zhang, H. B. Ind. Eng. Chem. Res. 2013, 52, 16101. doi: 10.1021/ie402169g
(11) Ouyang, X. P.; Ke, L. X.; Qiu, X. Q.; Guo, Y. X.; Pang, Y. X. J. Disper. Sci. Technol. 2009, 30, 1. doi: 10.1080/01932690802473560
(12) Zhou, M. S.; Kong, Q.; Pan, B.; Qiu, X. Q.; Yang, D. J.; Lou, H. M. Fuel 2010, 89, 716. doi: 10.1016/j.fuel.2009.09.015
(13) Li, Z. L.; Pang, Y. X.; Ge, Y. Y.; Qiu, X. Q. J. Phys. Chem. C 2011, 115, 24865. doi: 10.1021/jp2083117
(14) Harton, S. E.; Pingali, S. V.; Nunnery, G. A.; Baker, D. A.; Walker, S. H.; Muddiman, D. C.; Koga, T.; Rials, T. G.; Urban, V. S.; Langan, P. ACS Macro. Lett. 2012, 1, 568.
(15) Guerra, A.; Filpponen, I.; Lucia, L. A.; Saquing, C.; Baumberger, S.; Argyropoulos, D. S. J. Agric. Food Chem. 2006, 54, 5939.
(16) Glasser, W. G.; Davé, V.; Frazier, C. E. J. Wood Chem. Technol. 1993, 13, 545. doi: 10.1080/02773819308020533
(17) Guerra, A.; Gaspar, A. R.; Contreras, S.; Lucia, L. A.; Crestini, C.; Argyropoulos, D. S. Phytochemistry 2007, 68, 2570. doi: 10.1016/j.phytochem.2007.05.026
(18) Himmel, M. E.; Tatsumoto, K.; Grohmann, K.; Johnson, D. K.; Chum, H. L. J. Chromatogr. A 1990, 498, 93. doi: 10.1016/ S0021-9673(01)84238-2
(19) Merkle, G.; Auerbach, S.; Burchard, W.; Lindner, A.; Wegener, G. J. Appl. Polym. Sci. 1992, 45, 407. doi: 10.1002/app.1992.070450305
(20) Contreras, S.; Gaspar, A. R.; Guerra, A.; Lucia, L. A.; Argyropoulos, D. S. Biomacromolecules 2008, 9, 3362. doi: 10.1021/bm800673a
(21) Deng, Y. H.; Feng, X. J.; Zhou, M. S.; Qian, Y.; Yu, H. F.; Qiu, X. Q. Biomacromolecules 2011, 12, 1116. doi: 10.1021/bm101449b
(22) Saisu, M.; Sato, T.; Watanabe, M.; Adschiri, T.; Arai, K. Energ. Fuel 2003, 17, 922. doi: 10.1021/ef0202844
(23) Gosselink, R.; Abächerli, A.; Semke, H.; Malherbe, R.; Käuper, P.; Nadif, A.; Van Dam, J. Ind. Crop. Prod. 2004, 19, 271. doi: 10.1016/j.indcrop.2003.10.008
(24) Osada, M.; Sato, O.; Arai, K.; Shirai, M. Energ. Fuel 2006, 20, 2337. doi: 10.1021/ef060356h
(25) Wang, K.; Xu, F.; Sun, R. Int. J. Mol. Sci. 2010, 11, 2988. doi: 10.3390/ijms11082988
(26) Liu, L. T.; Zhang, B.; Li, J.; Ma, D.; Kou, Y. Acta Phys. -Chim. Sin. 2012, 28, 2343. [刘凌涛,张斌,李晶,马丁,寇元.物理化学学报, 2012, 28, 2343.] doi: 10.3866/PKU.WHXB201206152
(27) Cathala, B.; Saake, B.; Faix, O.; Monties, B. J. Chromatogr. A 2003, 1020, 229. doi: 10.1016/j.chroma.2003.08.046
(28) Nevárez, L. A. M.; Casarrubias, L. B.; Celzard, A.; Fierro, V.; Muñoz, V. T.; Davila, A. C.; Lubian, J. R. T.; Sánchez, G. G. Sci. Technol. Adv. Mat. 2011, 12, 045006.
(29) Qian, Y.; Deng, Y. H.; Li, H.; Qiu, X. Q. Ind. Eng. Chem. Res. 2014, 53, 10024. doi: 10.1021/ie5010338
(30) Deng, Y. H.; Zhang, W. J.; Wu, Y.; Yu, H. F.; Qiu, X. Q. J. Phys. Chem. B 2011, 115, 14866. doi: 10.1021/jp208312a
(31) Qian, Y.; Deng, Y. H.; Guo, Y. Q.; Yi, C. H.; Qiu, X. Q. Holzforschung 2013, 67, 265.
(32) Lindström, T. Colloid Polym. Sci. 1979, 257, 277. doi: 10.1007/BF01382370
(33) Du, B. Y.; Fan, X.; Cao, Z.; Guo, X. L. Chin. J. Anal. Chem. 2010, 38, 752. [杜滨阳,范潇,曹峥,郭小磊.分析化学, 2010, 38, 752.]

[1]	刘苗苗, 王文娟, 郝秀萍, 董晓燕. Aβ40和hIAPP在溶液和表面的成核与交叉成核聚集行为[J]. 物理化学学报, 2022, 38(3): 2002024 - .
[2]	曹美芳, 陈博, 阮涛, 欧阳新平, 邱学青. Pt/NbPWO双功能催化剂的制备及氢解碱木质素制备芳香单体[J]. 物理化学学报, 2022, 38(10): 2204037 - .
[3]	张自博, 邓伟, 周旭峰, 刘兆平. 稳定锂电化学沉积和溶解行为的LiC₆异质微结构界面层[J]. 物理化学学报, 2021, 37(2): 2008092 - .
[4]	熊辉, 谢歆雯, 王苗, 侯雅琦, 侯旭. 网状骨架CVD生长碳纳米管用于重盐水脱盐[J]. 物理化学学报, 2020, 36(9): 1912008 - .
[5]	葛杨, 牟许霖, 卢岳, 隋曼龄. 空气下光诱导有机金属卤化钙钛矿薄膜的降解机理[J]. 物理化学学报, 2020, 36(8): 1905039 - .
[6]	王英雄, 邓曼丽, 唐永强, 韩玉淳, 黄旭, 侯研博, 王毅琳. 含有酰胺基或酯基的可降解阳离子Gemini表面活性剂在水溶液中的聚集行为[J]. 物理化学学报, 2020, 36(10): 1909046 - .
[7]	张长胜,来鲁华. 生物分子液-液相分离的物理化学机制[J]. 物理化学学报, 2020, 36(1): 1907053 - .
[8]	焦建梅,徐桂英,辛霞. 胆酸盐参与的自组装及微纳米材料制备[J]. 物理化学学报, 2019, 35(7): 684 -696 .
[9]	王士昭, 李维军, 俞越, 刘进, 张诚. 具有聚集诱导发光特性的新型铂(Ⅱ)金属配合物及其光激发的自敏化氧化反应[J]. 物理化学学报, 2019, 35(11): 1276 -1281 .
[10]	程晓蒙,焦东霞,梁志豪,魏金金,李宏平,杨俊佼. 聚苯乙烯-聚4-乙烯基吡啶两亲嵌段共聚物在CO₂膨胀液体中的组装行为[J]. 物理化学学报, 2018, 34(8): 945 -951 .
[11]	郭肖红,周影,石利红,张彦,张彩红,董川,张国梅,双少敏. 基于乙醇和铝离子聚集诱导的铜纳米团簇[J]. 物理化学学报, 2018, 34(7): 818 -824 .
[12]	陈贻建,周洪涛,葛际江,徐桂英. 双链阴离子表面活性剂1-烷基-癸基磺酸钠在气/液界面聚集行为:分子动力学模拟研究[J]. 物理化学学报, 2017, 33(6): 1214 -1222 .
[13]	王辉,邹德春. 硫粉为硫源,多元醇辅助合成硫化钼纳米片[J]. 物理化学学报, 2017, 33(5): 1027 -1032 .
[14]	王榕,段明,熊艳,宋先雨,方申文. 反相破乳剂SP169及DMEA169在溶液中的聚集行为[J]. 物理化学学报, 2016, 32(6): 1482 -1488 .
[15]	唐伟,王兢. 金属氧化物异质结气体传感器气敏增强机理[J]. 物理化学学报, 2016, 32(5): 1087 -1104 .

乙酰化处理对碱木质素在四氢呋喃中微结构的影响

Influence of Acetylation on the Microstructure of Alkali Lignin in Tetrahydrofuran

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0