毛竹竹青和竹黄半纤维素的提取与结构表征

doi:10.3969/j.issn.0253-2417.2015.05.006

摘要/Abstract

摘要： 以毛竹加工剩余物为原料,分离出竹青和竹黄。经粉碎过筛、苯/乙醇脱蜡和次氯酸钠脱木质素3个过程得到相应的综纤维素,然后用1%、5%和10%的KOH依次提取综纤维素得到半纤维素,竹青、竹黄半纤维素的总提取率分别为81.74%和85.36%。对所提取的半纤维素进行成分分析、分子量测定、红外光谱和核磁共振分析,结果表明,竹青、竹黄半纤维素成分主要为木糖,分别占61.02%~73.76%和65.22%~80.00%。竹黄半纤维素的重均分子质量为44 870~48 560 g/mol,高于竹青半纤维素的重均分子质量(43 970~46 245 g/mol)。竹青、竹黄碱溶半纤维素都是典型的阿拉伯糖基木聚糖结构,主链为β-D-吡喃木糖形成的木聚糖,在木糖基的C-2位连接着4-O-甲基-α-D-葡萄糖醛酸,C-3位连有α-L-呋喃阿拉伯糖,同时部分木质素通过苯苷键与半纤维素中的糖基相连。

关键词: 竹青, 竹黄, 半纤维素, 结构表征, 核磁共振

Abstract: Bamboo green and bamboo yellow separated from Moso bamboo residues were delignified by NaClO₂ after grinded, sifted and dewaxed by toluene-ethanol to achieve holocellulose. The resulted holocellulose was constantly extracted with 1%, 5% and 10% KOH to obtain hemicellulose. The yields of hemicellulose acquired from bamboo green and bamboo yellow were calculated as 81.74% and 85.36%, respectively. Then, the chemical compositions and structures of these hemicelluloses were characterized by HPAEC, GPC, FT-IR, ¹H NMR and 2D HSQC techniques. The results indicated that the proportions of xylose in the bamboo green and bamboo yellow hemicellulose preparations were 61.02%-73.76% and 65.22%-80.00%, respectively. The weight average molecular weight of hemicellulose preparations of bamboo yellow were 44 870-48 560 g/mol, which were higher than that of bamboo green hemicellulose preparations (43 970-46 245 g/mol). It was demonstrated that the back chain of hemicelluloses were composed of β-D-xylan. Meanwhile, α-L-arabinofuranose and 4-O-methyl-α-D-glucuronic acid were linked to back chain of hemicellulose at C-3 and C-2 of xylan, respectively, and part of lignins were linked to hemicelluloses by phenyl glucoside bond.

Key words: bamboo green, bamboo yellow, hemicellulose, characterization, NMR

中图分类号:

TQ35

黄曹兴, 何娟, 闵斗勇, 李鑫, 勇强. 毛竹竹青和竹黄半纤维素的提取与结构表征[J]. 林产化学与工业, 2015, 35(5): 29-36.

HUANG Cao-xing, HE Juan, MIN Dou-yong, LI Xin, YONG Qiang. Isolation and Characterization of Hemicellulose from Moso Bamboo Green and Bamboo Yellow[J]. Chemistry and Industry of Forest Products, 2015, 35(5): 29-36.

参考文献

[1] HUANG Cao-xing,CHU Qiu-lu,XIE Yi-hui,et al.Effect of kraft pulping pretreatment on the chemical composition,enzymatic digestibility,and sugar release of Moso bamboo residues[J].BioResources,2014,10(1):240-255.
[2] 周建钟,冯炎龙,刘力.竹青竹黄的化学成分及综合利用[J].林产化工通讯,2003,37(2):8-10. ZHOU Jian-zhou,FENG Yan-long,LIU Li.Chemical constituents of the outer and the inner of bamboo,and its comprehensive utilization[J].Journal of Chemical Industry of Forest Products,2003,37(2):8-10.
[3] SUN Run-cang,LAWTHER J M,BANKS W B.Fractional and structural characterization of wheat straw hemicelluloses[J].Carbohydrate Polymers,1996,29(4):325-331.
[4] 刘力,俞友明,郭建忠.竹材化学与利用[M].杭州:浙江大学出版社,2006. LIU Li,YU You-ming,GUO Jian-zhong.Bamboo Chemical and Utilization[M].Hangzhou:Zhejiang University Press,2006.
[5] BALAKSHIN B,CAPANEMA E,GRACZ H,et al.Quantification of lignin-carbohydrate linkages with high-resolution NMR spectroscopy[J].Planta,2011,233(6):1097-1110.
[6] HUANG Cao-xing,HE Juan,LI Xin,et al.Facilitating the enzymatic saccharification of pulped bamboo residues by degrading the remained xylan and lignin-carbohydrates complexes[J].Bioresource Technology,2015,192:471-477.
[7] TIMELL T E.Isolation of galactoglucomannans from wood of gymnosperms[J].Tappi Journal,1961,44(2):88-96.
[8] SUN Run-cang,SUN Xiao-feng.Fractional and structure characterization of hemicelluloses isolated by alkali and alkaline peroxide from barley straw[J].Carbohydrate Polymers,2002,49(4):415-423.
[9] VILA C,SANTOS V,PARAJO J C.Simulation of an organosolv pulping process:Generalized material balances and design calculations[J].Industrial and Engineering Chemistry Research,2003,42(2):349-359.
[10] IBRAHIM M,GLASSER W G.Steam-assisted biomass fractionation Ⅲ.A quantitative evaluation of the “clean fractionation” concept[J].Bioresource Technology,1999,70(2):181-192.
[11] WEN Jia-long,YUAN Tong-qi,XU Feng,et al.Fractionation of bamboo culms by autohydrolysis,organosolv delignification and extended delignification:Understanding the fundamental chemistry of the lignin during the integrated process[J].Bioresource Technology,2013,150:278-286.
[12] SLUITER A,RUIZ R,SCARLATA C,et al.Determination of extractives in biomass[R].Laboratory Analytical Procedure(LAP),2005-07-17.
[13] WEN Jia-long,SUN Shao-long,XUE Bai-liang,et al.Recent advances in characterization of lignin polymer by solution-State Nuclear Magnetic Resonance (NMR) methodology[J].Materials,2013,6(1):359-391.
[14] 任俊莉,彭锋,彭新文,等.农业秸秆半纤维素分离及纯化技术研究进展[J].纤维素科学与技术 2010,18(3):56-67. REN Jun-li,PENG Feng,PENG Xin-wen,et al.Progress in isolation and purification of hemicellulose from agriculture straw[J].Journal of Cellulose Science and Technology,2010,18(3):56-67.
[15] SUN Jing-xia,SUN Xiao-feng,SUN Run-cang,et al.Inhomogeneities in the chemical structure of sugarcane bagasse lignin[J].Journal of Agricultural and Food Chemistry,2003,51(23):6719-6725.
[16] LAWTHER J M,SUN Run-cang,BANKS W B.Effects of extraction conditions and alkali type on yield and composition of wheat straw hemicellulose[J].Journal of Applied Polymers Science,1996,60(11):1827-1837.
[17] CHAIKUMPOLLERT O,METHACANON P,SUCHIVA K.Structural elucidation of hemicelluloses from Vetiver grass[J].Carbohydrate Polymers,2004,57(2):191-196.
[18] PENG Pai,PENG Feng,BIAN Jing,et al.Isolation and structural characterization of hemicelluloses from the bamboo species Phyllostachys incarnata Wen[J].Carbohydrate Polymers,2011,86(2):883-890.
[19] YUAN Tong-qi,XU Feng,SUN Run-cang,et al.Structural and physico-chemical characterization of hemicelluloses from ultrasound-assisted extractions of partially delignified fast-growing poplar wood through organic solvent and alkaline solutions[J].Biotechnology Advances,2010,28(5):583-593.
[20] WEDIG C L,JASTCR E H,MOORE K J.Hemicellulose monosaccharide composition and in vitro disappearance of orchard grass and alfalfa hay[J].Journal of Agriculture and Food Chemistry,1987,35(2):214-218.
[21] 周燕,谢益民,甘定能,等.蓝花楹木质素-碳水化合物复合体在硫酸盐法蒸煮过程中的变化[J].林产化学与工业,2007,27(2):49-52. ZHOU Yan,XIE Yi-min,GAN Ding-neng,et al.Change of lignin- carbohydrate comp lexes in Jacaranda copaia Aub.l D.Don.during Kraft cooking[J].Chemistry and Industry of Forest Products,2007,27(2):49-52.
[22] SUN Run-cang,GOODWIN A,LAWTHER J M,et al.Fractionation and characterization of polysaccharides from abaca fibre[J].Carbohydrate Polymers,1998,37(4):351-359.
[23] HOFFMANN R A,ROZA M,MAAT J,et al.Structural characteristics of the cold-water-soluble arabinoxylans from the white flour of the soft wheat variety Kadet[J].Carbohydrate Polymers,1991,15(4):415-430
[24] IZYDORCZYK M S,BILIADERIS C G.Cereal arabinoxylans:Advances in structure and physicochemical properties[J].Carbohydrate Polymers,1995,28(1):33-48.
[25] KACURAKOVA M,MATHLOUTHI M.FT-IR and laser-Raman spectra of oligosaccharides in water:Characterisation of the glycosidic bond[J].Carbohydrate Research,1996,284(2):145-157.
[26] ROY A K,SEN S K,BAG S C,et al.Infrared spectra of jute stick and alkali-treated jute stick[J].Journal of Applied Polymer Science,1991,42(11):2943-2950.
[27] SUN Run-cang,LAWTHER J M,BANKS W B.Isolation and physicochemical characterization of xylose-rich pectic polysaccharides from wheat straw[J].International Journal of Polymer Analysis and Characterization,1998,4(4):345-356.
[28] WEN Jia-long,SUN Yong-chang,XU Feng,et al.Fractional isolation and chemical structure of hemicellulosic polymers obtained from Bambusa rigida species[J].Journal of Agriculture and Food Chemistry,2010,58(21):11372-11383.
[29] BENDAHOU A,DURFRESNE A,KADDAMI H,et al.Isolation and structural characterization of hemicelluloses from palm of Phoenix dactylifera[J].Carbohydrate Polymers,2007,68(3):601-608.
[30] HABIBI Y,MAHROUZ M,VIGNON M R.Isolation and structure of D-xylans from pericarp seeds of Opuntia ficus-indica prickly pear fruits[J].Carbohydrate Research,2002,337(17):1593-1598.
[31] HOFFMANN R A,GEIJTENBEEK T,KAMERLINT J P,et al. ¹H NMR study of enzymically generated wheat-endosperm arabinoxylan oligosaccharides:Structures of hepta to tetradeca-saccharides containing two or three branched xylose residues[J].Carbohydrate Research,1992,223:19-44.
[32] EBRINGEROVA A,ALFOLDI J,HROMADKOVA Z,et al.Water-soluble p-carboxybenzylated beechwood 4-O-methylglucuronoxylan:Structural features and properties[J].Carbohydrate Polymers,2000,42(2):123-131.
[33] HABIBI Y,MAHROUZ M,VIGNON M R.Arabinan-rich polysaccharides isolated and characterized from the endosperm of the seed of Opuntia ficusindica prickly pear fruits[J].Carbohydrate Polymers,2005,60(3):319-329.