不同提取方法对烟草纤维素微观结构的影响
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摘要
为探究不同提取方法对烟草纤维素微观结构的影响,采用中性洗涤剂法、酸性洗涤剂法、酸性水解法、碱液分离法分别对烤烟和香料烟烟叶样品中的纤维素进行提取;利用交叉极化结合魔角旋转13C核磁共振(CP/MAS13C NMR)技术对不同方法获得的烟草纤维素进行微观结构表征;对比分析4种方法的得率及提取所得烟草纤维素的纯度,并通过对NMR光谱吸收峰拟合,得到烟草纤维素晶型及分布、结晶度和原纤尺寸等结构信息。结果表明:①中性洗涤剂法提取所得烟草纤维素纯度高于其他3种方法。②4种提取方法所获烟草纤维素晶型相同,均以纤维素Iβ晶型为主,但晶型分布存在明显差异。③4种提取方法中,中性洗涤剂法所获烟草纤维素结晶度最大,且基原纤尺寸和基原纤聚集束尺寸最大。对比其他3种方法,中性洗涤剂法对烟草纤维素微观结构影响最小。因此,中性洗涤剂法适合作为烟草纤维素微观结构研究中纤维素的提取方法。
In order to investigate the effects of different extraction methods on the microstructure of tobacco cellulose, the cellulose of flue-cured and oriental tobacco leaves was extracted by neutral detergent method, acid detergent method, acid hydrolysis method and alkali treatment method. The microstructure of tobacco cellulose extracted by different methods was characterized by solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance(CP/MAS13 C NMR). The yields and purity of tobacco cellulose extracted by the four methods were comparatively analyzed. The structural information such as crystal form and distribution,crystallinity and fibril size of tobacco cellulose were obtained by fitting the absorption peaks of NMR spectra.The results showed that: 1) The purity of tobacco cellulose extracted by neutral detergent method was higher than the other three methods. 2) The tobacco cellulose extracted by the four methods had the same crystal form with the dominant cellulose form of Iβcrystal, however the crystal form distribution was significantly different.3) Among the four extraction methods, the cellulose extracted by neutral detergent method had the highest crystallinity, and the sizes of elementary fibrils and elementary fibril aggregates were the largest. Compared with the other three methods, the influence of neutral detergent method on the microstructure of tobacco cellulose was the slightest. Thus, for the study of tobacco cellulose microstructure, neutral detergent method is a suitable cellulose extraction method.
In order to investigate the effects of different extraction methods on the microstructure of tobacco cellulose, the cellulose of flue-cured and oriental tobacco leaves was extracted by neutral detergent method, acid detergent method, acid hydrolysis method and alkali treatment method. The microstructure of tobacco cellulose extracted by different methods was characterized by solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance(CP/MAS13 C NMR). The yields and purity of tobacco cellulose extracted by the four methods were comparatively analyzed. The structural information such as crystal form and distribution,crystallinity and fibril size of tobacco cellulose were obtained by fitting the absorption peaks of NMR spectra.The results showed that: 1) The purity of tobacco cellulose extracted by neutral detergent method was higher than the other three methods. 2) The tobacco cellulose extracted by the four methods had the same crystal form with the dominant cellulose form of Iβcrystal, however the crystal form distribution was significantly different.3) Among the four extraction methods, the cellulose extracted by neutral detergent method had the highest crystallinity, and the sizes of elementary fibrils and elementary fibril aggregates were the largest. Compared with the other three methods, the influence of neutral detergent method on the microstructure of tobacco cellulose was the slightest. Thus, for the study of tobacco cellulose microstructure, neutral detergent method is a suitable cellulose extraction method.
引文
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[29]谭兰兰,戴亚,冯广林,等.烟草纤维素的结晶度及晶态结构的测定方法:CN104458784B[P].2016-08-17.TAN Lanlan,DAI Ya,FENG Guanglin,et al.Measuring method for crystallinity and crystalline state structure of tobacco cellulose:CN104458784B[P].2016-08-17.
[30]万金泉,肖青,王艳.固体核磁共振和原子力显微镜分析不同半纤维素含量植物纤维的微观结构[J].分析化学,2010,38(3):347-351.WAN Jinquan,XIAO Qing,WANG Yan.Analysis of microstructure of plant fibers with different hemicellulose content by solid state nuclear magnetic resonance and atomic force microscope[J].Chinese Journal of Analytical Chemistry,2010,38(3):347-351.
[31]张毅民,杨静,吕学斌,等.木质纤维素类生物质酸水解研究进展[J].世界科技研究与发展,2007,29(1):48-54.ZHANG Yimin,YANG Jing,LüXuebin,et al.Research processes in acid hydrolysis of lignocellulosic biomass[J].World Sci-Tech R&D,2007,29(1):48-54.
[32]王霞,汪春.稻草纤维素的提取及其结构表征[J].黑龙江八一农垦大学学报,2010,22(1):68-73.WANG Xia,WANG Chun.Extraction and structure characterization of straw fiber[J].Journal of Heilongjiang Bayi Agricultural University,2010,22(1):68-73.
[33]Atalla R H,Vanderhart D L.Native cellulose:a composite of two distinct crystalline forms[J].Science,1984,223(4633):283-285.
[2]Oja V,Hajaligol M R,Waymack B E.The vaporization of semi-volatile compounds during tobacco pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2006,76(1/2):117-123.
[3]Baker R R,Coburn S,Liu C,et al.Pyrolysis of saccharide tobacco ingredients:a TGA-FTIRinvestigation[J].Journal of Analytical and Applied Pyrolysis,2005,74(1/2):171-180.
[4]朱晓兰,马扩彦,高芸,等.糖或酸介质处理对烟草纤维素结构的影响[J].中国烟草学报,2016,22(2):8-13.ZHU Xiaolan,MA Kuoyan,GAO Yun,et al.Effect of sugar or acid medium treatment on cellulose structure in tobacco[J].Acta Tabacaria Sinica,2016,22(2):8-13.
[5]杨滢,周顺,王孝峰,等.不同结构烟草纤维素的燃烧热解特性[J].烟草科技,2017,50(5):38-44.YANG Ying,ZHOU Shun,WANG Xiaofeng,et al.Combustion and pyrolysis characteristics of tobacco celluloses with different structures[J].Tobacco Science&Technology,2017,50(5):38-44.
[6]杨淑蕙.植物纤维化学[M].3版.北京:中国轻工业出版社,2001:176-182.YANG Shuhui.Plant fiber chemistry[M].3rd ed.Beijing:China Light Industry Press,2001:176-182.
[7]Wang Z H,McDonald A G,Westerhof R J M,et al.Effect of cellulose crystallinity on the formation of a liquid intermediate and on product distribution during pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2013,100:56-66.
[8]Zhang J X,Luo J,Tong D M,et al.The dependence of pyrolysis behavior on the crystal state of cellulose[J].Carbohydrate Polymers,2010,79(1):164-169.
[9]Henniges U,Kostic M,Borgards A,et al.Dissolution behavior of different celluloses[J].Biomacromolecules,2011,12(4):871-879.
[10]Kim S H,Lee C M,Kafle K.Characterization of crystalline cellulose in biomass:basic principles,applications,and limitations of XRD,NMR,IR,Raman,and SFG[J].Korean Journal of Chemical Engineering,2013,30(12):2127-2141.
[11]YC/T 347-2010烟草及烟草制品中性洗涤纤维、酸性洗涤纤维、酸洗木质素的测定洗涤剂法[S].YC/T 347-2010 Tobacco and tobacco productsDetermination of neutral detergent fiber,acid detergent fiber and acid detergent lignin-Van Soest method[S].
[12]胡蝶,杨青丹,刘洪,等.木质纤维素预处理技术研究进展[J].湖南农业科学,2010(19):105-108.HU Die,YANG Qingdan,LIU Hong,et al.Research progresses of the pretreatment technology of lignocellulose[J].Hunan Agricultural Sciences,2010(19):105-108.
[13]Battegazzore D,Bocchini S,Alongi J,et al.Cellulose extracted from rice husk as filler for poly(lactic acid):preparation and characterization[J].Cellulose,2014,21(3):1813-1821.
[14]卫民,陈玉平,杨德琴,等.玉米秸秆稀硫酸水解研究[J].生物质化学工程,2007,41(5):36-38.WEI Min,CHEN Yuping,YANG Deqin,et al.Study on hydrolysis of corn stalks using dilute sulfuric acid[J].Biomass Chemical Engineering,2007,41(5):36-38.
[15]Sheltami R M,Abdullah I,Ahmad I,et al.Extraction of cellulose nanocrystals from mengkuang leaves(Pandanus tectorius)[J].Carbohydrate Polymers,2012,88(2):772-779.
[16]Kargarzadeh H,Ahmad I,Abdullah I,et al.Effects of hydrolysis conditions on the morphology,crystallinity,and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers[J].Cellulose,2012,19(3):855-866.
[17]Brendel O,Iannetta P P M,Stewart D.A rapid and simple method to isolate pure alpha-cellulose[J].Phytochemical Analysis,2000,11(1):7-10.
[18]Sun J X,Sun X F,Zhao H,et al.Isolation and characterization of cellulose from sugarcane bagasse[J].Polymer Degradation and Stability,2004,84(2):331-339.
[19]文旭,彭思瑶,蒋文伟,等.关于蔗渣纤维素提取方法的比较研究[J].化工新型材料,2017,45(9):250-252.WEN Xu,PENG Siyao,JIANG Wenwei,et al.Comparative study on the method of extracting bagasse cellulose[J].New Chemical Materials,2017,45(9):250-252.
[20]冯广林,谭兰兰,朱晓兰,等.CP/MAS13C NMR光谱法分析烟草纤维素的结构[J].中国烟草学报,2015,21(5):1-8.FENG Guanglin,TAN Lanlan,ZHU Xiaolan,et al.Analysis of tobacco cellulose structure by CP/MAS13CNMR spectroscopy[J].Acta Tabacaria Sinica,2015,21(5):1-8.
[21]朱金峰,高旭,鲜兴明,等.烤烟纤维素含量的变异及其与化学成分的关系[J].江西农业学报,2012,24(2):120-122,127.ZHU Jinfeng,GAO Xu,XIAN Xingming,et al.Variation of cellulose content and its relationship with chemical components in flue-cured tobacco leaves[J].Acta Agriculturae Jiangxi,2012,24(2):120-122,127.
[22]安宁,毛宁,陈靓,等.木质纤维素中纤维素的主要化学提取工艺[J].浙江化工,2015,46(7):29-34.AN Ning,MAO Ning,CHEN Liang,et al.Extraction of cellulose from lignocellulose by chemical methods[J].Zhejiang Chemical Industry,2015,46(7):29-34.
[23]冯利,周宁川,张方萍.酸碱蒸煮法提取小麦秸杆纤维素的研究[J].纤维素科学与技术,2015,23(2):62-67.FENG Li,ZHOU Ningchuan,ZHANG Fangping.Study on extraction of wheat straw cellulose with acid-base cooking method[J].Journal of Cellulose Science and Technology,2015,23(2):62-67.
[24]张丽,蔡玉兰,王善元,等.微波处理对棉纤维结晶结构的影响[J].纤维素科学与技术,2009,17(1):52-56.ZHANG Li,CAI Yulan,WANG Shanyuan,et al.Effects of microwave radiation treatment on the crystalline structure of cotton fibers[J].Journal of Cellulose Science and Technology,2009,17(1):52-56.
[25]Maier G,Zipper P,Stubi?ar M,et al.Amorphization of different cellulose samples by ball milling[J].Cellulose Chemistry and Technology,2005,39(3/4):167-177.
[26]Larsson P T,Westermark U,Iversen T.Determination of the cellulose Iαallomorph content in a tunicate cellulose by CP/MAS13C-NMR spectroscopy[J].Carbohydrate Research,1995,278(2):339-343.
[27]Larsson P T,Wickholm K,Iversen T.A CP/MAS13CNMR investigation of molecular ordering in celluloses[J].Carbohydrate Research,1997,302(1/2):19-25.
[28]郑明霞,李来庆,郑明月,等.碱处理对玉米秸秆纤维素结构的影响[J].环境科学与技术,2012,35(6):27-31.ZHENG Mingxia,LI Laiqing,ZHENG Mingyue,et al.Effect of alkali pretreatment on cellulosic structural changes of corn stover[J].Environmental Science&Technology,2012,35(6):27-31.
[29]谭兰兰,戴亚,冯广林,等.烟草纤维素的结晶度及晶态结构的测定方法:CN104458784B[P].2016-08-17.TAN Lanlan,DAI Ya,FENG Guanglin,et al.Measuring method for crystallinity and crystalline state structure of tobacco cellulose:CN104458784B[P].2016-08-17.
[30]万金泉,肖青,王艳.固体核磁共振和原子力显微镜分析不同半纤维素含量植物纤维的微观结构[J].分析化学,2010,38(3):347-351.WAN Jinquan,XIAO Qing,WANG Yan.Analysis of microstructure of plant fibers with different hemicellulose content by solid state nuclear magnetic resonance and atomic force microscope[J].Chinese Journal of Analytical Chemistry,2010,38(3):347-351.
[31]张毅民,杨静,吕学斌,等.木质纤维素类生物质酸水解研究进展[J].世界科技研究与发展,2007,29(1):48-54.ZHANG Yimin,YANG Jing,LüXuebin,et al.Research processes in acid hydrolysis of lignocellulosic biomass[J].World Sci-Tech R&D,2007,29(1):48-54.
[32]王霞,汪春.稻草纤维素的提取及其结构表征[J].黑龙江八一农垦大学学报,2010,22(1):68-73.WANG Xia,WANG Chun.Extraction and structure characterization of straw fiber[J].Journal of Heilongjiang Bayi Agricultural University,2010,22(1):68-73.
[33]Atalla R H,Vanderhart D L.Native cellulose:a composite of two distinct crystalline forms[J].Science,1984,223(4633):283-285.