异丁香酚脱氢聚合产物的合成及其抗氧化性能研究

doi:10.3969/j.issn.0253-2417.2018.01.013

摘要/Abstract

摘要： 以木质素前驱物异丁香酚为原料，漆酶催化合成得到木质素脱氢聚合物（DHP），利用凝胶渗透色谱（GPC）、红外光谱（FT-IR）和核磁共振（¹³C NMR）对DHP的结构进行表征，并通过考察产物对二苯基苦基苯肼自由基（DPPH·）的半数抑制质量浓度（IC₅₀），以及对延缓β-胡萝卜素氧化的效果来探讨DHP的抗氧化性能。研究表明：在漆酶的催化作用下异丁香酚脱氢聚合形成的DHP在主要化学结构上与银杏磨木木质素（MWL）非常相似，¹³C NMR谱表明DHP中存在β-5、β-O-4、β-1、β-β等典型木质素结构。DHP中游离酚羟基含量随相对分子质量增加而降低，分级后发现溶于乙醚的DHP组分（DHP①）的抗氧化性能最好，其半数抑制质量浓度（IC₅₀）仅为0.12 g/L，增加DHP溶液的体积或浓度都能提高其对β-胡萝卜素氧化的抑制效果。

关键词: 木质素, 脱氢聚合, DPPH法, 抗氧化性能, β-胡萝卜素

Abstract: The lignin dehydrogenation polymers (DHP) were prepared using lignin precursor isoeugenol as raw material and laccase as catalyst.The structure of DHP was characterized by FT-IR,¹³C NMR spectroscopy and GPC.The antioxidant activity of DHP was also studied by investigating the effect of the product on the half inhibitory concentration (IC₅₀) of diphenyl picrylhydrazyl radical (DPPH·) and on retarding the oxidation of β-carotene.The results showed that the structure of DHP was similar to the Ginkgo milled wood lignin (MWL).The ¹³C NMR spectrum showed that the typical lignin substructures such as β-5,β-O-4,β-1,β-β exist in the DHP.The content of free phenolic hydroxyl in DHP decreased with the increase of molecular weight.After classification,it was found that the ether-soluble fraction (DHP①) had the best antioxidant properties.The IC₅₀ value of this fraction was only 0.12 g/L.The increase of the volume or concentration of DHP could improve the ability of inhibition of oxidation of β-carotene.

Key words: lignin, dehyrogenation polymer, DPPH method, antioxidant property, β-carotene

中图分类号:

TQ35

陈学宽, 赵厚宽, 吴宏飞, 叶哲孜, 谢益民. 异丁香酚脱氢聚合产物的合成及其抗氧化性能研究[J]. 林产化学与工业, 2018, 38(1): 87-92.

CHEN Xuekuan, ZHAO Houkuan, WU Hongfei, YE Zhezi, XIE Yimin. Preparation and Antioxidant Properties of Dehydrogenation Polymer of Isoeugenol[J]. Chemistry and Industry of Forest Products, 2018, 38(1): 87-92.

参考文献

[1] TIMELL T E. Recent progress in the chemistry of wood hemicelluloses[J]. Wood Science and Technology,1967,1(1):45-70.
[2] 王治民,杨晓慧,周永红. 木质素基聚氨酯薄膜的研究进展[J]. 化工新型材料,2013,41(7):13-15. WANG Z M,YANG X H,ZHOU Y H. The preparation of lignin polyurethane films and its modification research[J]. New Chemical Materials,2013,41(7):13-15.
[3] HERNES P J,BENNER R. Photochemical and microbial degradation of dissolved lignin phenols:Implications for the fate of terrigenous dissolved organic matter in marine environments[J]. Journal of Geophysical Research Oceans,2003,108(C9):351-378.
[4] 杨淑蕙. 植物纤维化学[M]. 3版. 北京:中国轻工业出版社,2001:69. YANG S H. Lignocellulosic Chemistry[M]. 3rd ed. Beijing:China Light Industry Press,2001:69.
[5] YANG H P,YAN R,CHEN H P,et al. Characteristics of hemicellulose,cellulose and lignin pyrolysis[J]. Fuel,2007,86(12/13):1781-1788.
[6] BOERJAN W,RALPH J,BAUCHER M. Lignin biosynthesis[J]. Annual Review of Plant Biology,2003,54:519-546.
[7] BRUNOW G,LUNDQUIST K,CARLSTRÖM K,et al. A new synthesis of model compounds for the beta-5 structural unit in lignins[J]. Acta Chemica Scandinavica,1984,B38(4):335-336.
[8] FAUSTINO H,GIL N,BAPTISTA C,et al. Antioxidant activity of lignin phenolic compounds extracted from Kraft and sulphite black liquors[J]. Molecules,2010,15:9308-9322.
[9] 张莹,雷中方. 造纸黑液提取木质素的抗氧化性研究[J]. 复旦学报:自然科学版,2010,49(1):60-64. ZHANG Y,LEI Z F. Study on antioxidant activity of lignin from pulping black liquor[J]. Fudan University Journal:Natural Science,2010,49(1):60-64.
[10] VINARDELL M P,UGARTONDO V,MITJANS M. Potential applications of antioxidant lignins from different sources[J]. Industrial Crops & Products,2008,27(2):220-223.
[11] 聂明才,霍淑平,孔振武. 木质素模型化合物的研究进展[J]. 林产化学与工业,2010,30(5):115-121. NIE M C,HUO S P,KONG Z W. Research progress of lignin model compounds[J]. Chemistry and Industry of Forest Products,2010,30(5):115-121.
[12] CATHALA B,AGUIÉ-BÉGHIN V,DOUILLARD R,et al. Properties of model compounds of lignin (dehydrogenation polymers=DHPs) at the air/water interface[J]. Polymer Degradation &Stability,1998,59(1):77-80.
[13] 叶哲孜,谢益民,吴晨曦,等. 多糖存在下异丁香酚的脱氢聚合及LCC的形成[J]. 林产化学与工业,2016,36(2):45-50. YE Z Z,XIE Y M,WU C X,et al. Dehydrogenation polymerization of isoeugenol and formation of lignin-carbohydrate complexes with presence of polysaccharide[J]. Chemistry and Industry of Forest Products,2016,36(2):45-50.
[14] CATHALA B,SAAKE B,FAIX O,et al. Evaluation of the reproducibility of the synthesis of dehydrogenation polymer models of lignin[J]. Polymer Degradation & Stability,1998,59(1):65-69.
[15] HOBALLAH M E,STUURMAN J,TURLINGS T C J,et al. The composition and timing of flower odour emission by wild Petunia axillaris coincide with the antennal perception and nocturnal activity of the pollinator Manduca sexta[J]. Planta,2005,222(1):141-150.
[16] KOEDUKA T,FRIDMAN E,GANG D R,et al. Eugenol and isoeugenol,characteristic aromatic constituents of spices,are biosynthesized via reduction of a coniferyl alcohol ester[J]. Proceedings of the National Academy of Sciences,2006,103(26):10128-10133.
[17] MUHLEMANN J K,WOODWORTH B D,MORGAN J A,et al. The monolignol pathway contributes to the biosynthesis of volatile phenylpropenes in flowers[J]. The New phytologist,2014,204(3):661-670.
[18] FREUDENBERG K,JONES K,RENNER H. Radioaktive isotope und lignin. IX:Künstliches lignin ausmarkiertem coniferylalkohol[J]. Berichte Der Deutschen Chemischen Gesellschaft,1963,96(7):1844-1849.
[19] TERASHIMA N,ATALLAL R H,RALPH S A,et al. New preparations of lignin polymer models under conditions that approximate cell wall lignification. Ⅱ:Structural characterization of the models by thioacidolysis[J]. Holzforschung,1995,50(1):9-14.
[20] 中野准三,高洁. 木质素的化学:基础与应用[M]. 北京:轻工业出版社,1988:545. NAKANO J,GAO J. Chemistry of Lignin Basic and Application[M]. Beijing:Light Industry Press,1988:545.
[21] 吴保国,赵菊兰. 差示紫外光谱法测定木素酚羟基含量[J]. 东北林业大学学报,1993,21(2):56-65. WU B G,ZHAO J L. Determination of phenolic hydroxyl groups by differential UV spectrophotometry[J]. Journal of Northeast Forestry University,1993,21(2):56-65.
[22] SHARMA O P,BHAT T K. DPPH antioxidant assay revisited[J]. Food Chemistry,2009,113(4):1202-1205.
[23] 韦献雅,殷丽琴,钟成,等. DPPH法评价抗氧化活性研究进展[J]. 食品科学,2014,35(9):317-322. WEI X Y,YIN L Q,ZHONG C,et al. Advances in the DPPH radical scavenging assay for antioxidant activity evalua[J]. Food Science,2014,35(9):317-322.
[24] 高云涛,魏薇,叶丽清,等. DPPH自由基清除活性的光度微量滴定模型及应用[J]. 光谱学与光谱分析,2015,35(2):492-496. GAO Y T,WEI W,YE L Q,et al. Photometric micro-titration model of DPPH radicals scavenging activity and its application[J]. Spectroscopy and Spectral Analysis,2015,35(2):492-496.
[25] NIHORIMBERE V,钱和,汪何雅,等. DPPH自由基比色法测定番石榴叶提取物抗氧化活性的研究[J]. 食品科学,2004,25(7):36-42. NIHORIMBERE V,QIAN H,WANG H Y,et al. Evaluation of antioxidant activity of Psidium guajava Linn (Guava) leaf extracts by means of DPPH free radical[J]. Food Science,2004,25(7):36-42.
[26] 莫文杰,余丽璇,周明松,等. 酚羟基对木质素磺酸钠染料分散剂性能的影响[J]. 高校化学工程学报,2016,30(2):423-430. MO W J,YU L X,ZHOU M S,et al. Influence of phenolic hydroxyl groups on the performance of lignosulfonate as a dye dispersant[J]. Journal of Chemical Engineering of Chinese Universities,2016,30(2):423-430.
[27] LIN S Y,DENCE C W. Methods in Lignin Chemistry[M]. Heidelberg:Springe,1992:429.
[28] EVLIYA H,OLCAY A. Oxidative polymerisation of isoeugenol and mild oxidation of synthetic polymers with alkaline cupric hydroxide[J]. Holzforschung,1974,28(4):130-135.
[29] 顾瑞军. 木素和木素-碳水化合物复合体的化学结构及形成机理[D]. 广州:华南理工大学硕士学位论文,2002. GU R J. Study on lignin and lignin-carbohydrate complexes from monolignol[D]. Guangzhou:Mastre Degree Thesis of South China University of Technology,2002.
[30] HUNNAY E. ¹³C NMR Studies of a dehydropolymer (DHP) from isoeugenol; comparison with spruce lignin[J]. Holzforschung,1989,43(1):61-64.