叶黄素的热解产物分析

叶黄素的热解产物分析侯英,徐济仓,王保兴,杨燕,杨勇,王玉,刘静烟草科技云南瑞升烟草技术(集团)有限公司,昆明市高新技术产业开发区科医路41号650106关键词:叶黄素;烟草;热解;气相色谱-质谱分析;固相微革取摘要:为研究叶黄素对卷烟燃吸品质的影响,分别在300、600、900℃和气、10%氧气+90%氮气、大气环境中进行了叶黄素热解试验,热解产物经固相微萃取后进行GC/MS分析,并用叶黄素进行了卷烟加香试验。结果表明:①在所试验的温度和氛围中,叶黄素的裂解产物主要是甲苯、对-二甲苯、1,2-二氢-1,1,6-三甲基一幕和2,7-二甲基慕等,另外还有少量的氧化异佛尔酮、巨豆三烯酮、醛和烯烃类物质等;②叶黄素裂解产物的种类和相对含量都随着裂解温度的变化而变化,而裂解氛围则影响不大;③添加叶黄素的卷烟烟气香气略增加,但其杂气、刺激性都明显增大,余味变差。因此,添加叶黄素不利于卷烟抽吸品质的提高。中图分类号:TS264.3文献标识码:B文章编号:1002-0861(2007)12-0027-06Analysis of Pyrolytic Products of LuteinHOU YING. XU JI-CANG, WANG BAO-XING, YANG YAN, YANG YONG, WANG YU, andLIU JINGYunnan Reascend Tobacco Technology Group )Co, Ltd, Kunming 650106, ChinaKeywords: Lutein; Tobacco; Pyrolysis; Gas chromatography/mass spectrometry: Solid phaiAbstract: To investigate the effect of lutein on the smoking quality of cigarettes, the lutein wapyrolysed in various surroundings(N2, 10%02 +90% N2, and air )at 300C, 600 and900 C, respectively. The pyrolytic products adsorbed by solid phase microextraction were analyzedwith gas chromatography/mass spectrometry, and lutein was applied to cigarettes as a favor. Theresults showed that: 1)in all pyrolytic environments and temperatures, the major components ofpyrolytic products were tolune, p-xylene, 1, 2-dihydro-1, 1, 6-trimethylnaphthalene, 2, 7dimethylnaphthalene, etc, and the minor components were isophorone, megastigmatrienone,aldehydes, alkenes, etc; 2)the kind and relative content of pyrolytic products changed with thechange of temperatures, while the influence of environment was negligible; 3 )lutein adding wouldenhance the aroma of cigarette smoke, but increase the offensive odor and imitantcy, and deterioratethe aftertaste. Therefore, the addition of lutein was not beneficial to improve the smoking quality of期基金项目:国家烟草专卖局基金资助项目“烟草中主要致香成分及重要烟用单体香料热裂解行为研究”(110200101044)。作者简介:侯英(1973-),女,硕士,云南瑞升烟草技术(集团)有限公司中国煤化工分析研究收稿日期:2007-06-29CNMHG责任编辑:刘立全E-mail:lq@tobaccoinfo.com,cn电话:037167672637烟叶中各种色素的含量和性质不仅直接影响He,流速1mL/min;升温程序:50℃(1min)其外观质量,而且还间接地影响其内在品质{。3℃/mim100℃(1min)260℃(10烟叶中的黄色素主要是类胡萝卜素,是以异戊二min);接口温度:280℃;离子(EI)源温度:250烯为单元组成的一类色素属萜类化合物。新鲜℃;电离能量:70eV;质量扫描范围:35烟叶中已有18种类胡萝卜素被分离和表征,其中455B-胡萝卜素和叶黄素是主要成分。目前,人们通过NST98标准谱库检索定性,峰面积归★烟草科技93大多关注陈化烟叶中类胡萝卜素和其降解产物的化法定量。含量变化及其与烟叶品质的关系4,而有关类1.22加香与评吸胡萝卜素的热解产物对卷烟抽吸品质的影响则少用微量喷雾器分别向25g/份烟丝中均匀地见报道。因此,考察了热解温度和氛围对叶黄素喷加1mL乙醇(对照)、1mL2.5mg/m和1mL热解产物以及叶黄素对卷烟抽吸品质的影响,旨5.0mg/mL叶黄素的乙醇溶液,喷后将烟丝卷制在为卷烟加香提供参考。成烟支,放人恒温(22℃±1℃)恒湿(RH60%±1材料与方法2%)箱内调节48h,请本公司评委按GB560641996《卷烟感官技术要求》进行评吸。11材料和仪器叶黄素(96.6%,德国 Augsburg公司);高纯2结果与讨论氮气、10%(体积分数,下同)氧气+90%氮气混2.1裂解温度和氛围对叶黄素热解产物的彩响合气(昆明市氧气厂)。由图2和表1看出:叶黄素在不同温度和不同6890N/5973N气相色谱/质谱联用仪(美国氛围中裂解,主要生成烯烃、酮类醛类、醇类、苯和agilent公司); PYROPROBE2000热裂解仪(美国萘及其同系物等,且其种类和相对含量(归一化峰CDs公司),配备热裂解专用石英管;AB204S分面积)都随着裂解温度和氛围的不同而异。析天平(感量0.0001g,瑞士 Mettler Toledo公在相同的氛围中,随着裂解温度的升高司);固相微萃取(sPME)装置(配搅拌/加热台、类、醇类、烯烃类、芳烃类明显增加,尤其是烯烃类SPME手柄及75 m Carboxen-PDMS固相微萃取和芳烃类,600℃和900℃下比300℃下增加了头)(美国 SUPELCO公司)。10多种,如在10%02中裂解,300℃下生成481.2实验方法种裂解产物,烯烃类和芳烃类分别为17种和141.2.1叶黄素的热解及其裂解产物的CC/MS种,其相对含量各为4.14%和83.85%,600℃和分析900℃下各生成80种,600℃下烯烃类和芳烃类准确称取2mg叶黄素,放入裂解专用石英管分别为27种和32种,其相对含量各为779%和中,两端塞人石英棉然后置于热裂解仪的裂解头4.24%,900℃下烯烃类和芳烃类分别为27种加热丝中,再将裂解手柄插入20mL热裂解瓶和35种其相对含量为556%和38.19%,特别(图1)中然后分别向热裂解瓶中通入氮气、10%是在900℃下生成了1-甲基-9H-芴、9-甲基氧气+90%氮气混合气和大气,并分别在不同温9H-芴和4-甲基-菲等稠环芳烃类而醛类、20℃/t度下热解。热解温度为:30℃300、600年第期总第和900℃(10s)。热解完毕后,将SPME手柄插sPME手柄人该热裂解瓶中,伸出萃取头,于70℃下萃取15萃取完成后,将萃取头抽回到萃取手柄中取出SPME手柄,并立即将萃取头插人GC的汽化室(温度240℃)中进行脱附,脱附时间1min,脱附的热解产物随载气进入GC毛细管柱中分离样品热裂解头后进行MS鉴定。GC/MS条件为中国煤化色谱柱: HP-5MS毛细管柱(30mx0.25mmCNMHGi.d.x0.25md.f.);进样口温度:240℃;载气物的SPME苯取气3℃4008001200160020002400280040080012001600200024002800400800120016002000240028010%氧气+0%氯气300℃10%氧作+0%氯气90c烟草科技84008001200160020024002800408001200160020002402840080012001600200024002800大气环境300C大气环境60℃大气环境900℃4008001001600200024002840080012001600200240028004008001200160020002402800保留时间(min)保留时间(min)保留时间(min)图2叶黄囊在300、600、900℃和氮气、10%氧气+90%氨气和大气中泰解产物的TIC图比较表1叶黄素在300600900℃和氯气、10%氯气+90%氯气、大气中热解产物及其相对含量①(%)匹配空气10%O2时间热解产物度300℃600℃900℃300℃600℃900℃300℃600℃900℃267(E)-3-甲基-1,3,5-已三烯900.160.120.080.110.170.150.120.080.06812-甲基呋哺800.120.020.040.110.040.110.150.150.029417.304.072.2518.305.992.7823.505.721.44草化学:855-(1,1一二甲基乙基)-1,3环戊二烯910.030.090.180.020.270.040.080.070.051,2,5,5-四甲基-1环已二烯800.170.130.120.060.120.140.080.130.044.385,5-二甲基一2一乙基-1,3环戊二烯00.120.070.010.070.070.043-甲基-2-己酮0.010.010.010.020.120.02②0.060.080.040.090.100.071-亚甲基-3-(1-甲基亚乙基)环戊烷820.120.070.050.070.060.030.080.060.01P-二甲苯9730.405.232.8954.809473.6227.905.941.42年第期总第期5.130.110.110.350.240.340.180.336.01B-萜品烯冰片0.020中国煤化工1-乙基-2-甲苯0.CNMHG.48 0.67(续表1)匹配空气10%0时间热解产物度300℃600℃900℃300℃600℃900℃300℃600℃900℃1-乙基-3-甲苯0.070.100.320.150.030.300.147.112,6-二甲基-1,3,5,7-辛四烯90.030.040.030.017.34甲基苯乙烯乙烯基甲苯0.040.780.990.041.471.330.061.320.958141-甲基-4-(1-甲基乙烯基)苯950.290.350.040.251.300.490.350.200.288471-甲基-4-(1-甲基乙基)苯0.150.120.014-乙基-2,6-二甲基吡啶0.030.030.050.032-乙酰基-5-甲基呋哺800.010.010.010.190.060.020.220.090.048.913,5,5-三甲基-3-环940.050.040.170.100.370.190.380.460.07己烯-1-酮9.020.060.190.150.340.150.201-甲基-4-(2-丙烯基)苯800.070.030.050.020.300.140.040.029.21乙烯基苯甲醇0.030.070.060.050.050.1l1-乙基-2,3-二甲苯0.050.090.030.040.040.03一甲基苯甲醛950.400.200.560.060.150.111.060.600.592-乙烯基-1,4-二甲苯860.090.600.040.101.070.760.190.710.411,2,45-四甲苯0.050.314-甲基苯甲醛960.280.230.510.070.050.230.500.610.592-乙烯基-1,3-二甲苯0.100.050.110.140.04甲基苯并呋喃0.110.080.170.19壬醛860.160.050.160.1210.962-乙烯基-1,3,5-三甲苯0.090.990.540.120.093-甲基-2-丁烯基苯940.400.770.370.240.150.530.210.970.4911.16氧化异佛尔酮800.110.150.130.020.110.110.210.150.1411.23(1-甲基-1-丁烯基)苯920.310.270.060.050.130.13一11.292-乙烯基-1,3,5-三甲苯820.030.090.130.030.130.040.040.110.2811.521-丁烯基苯970.070.190.230.010.570.310.120.420.1811.672-甲基-1-丁烯基苯910.120.200.200.100.260.160.160.540.09期11.822,3-二氢-4-甲基-1H-茚810.110.040.060.090.090.040.150.120.033苯基-1,2-丁二烯0.250.480.680.6912.561,55-三甲基-6-亚0.050.100.100.08甲基环己烯0.120.113,5-二甲基苯酚0.340.284-乙基苯甲醛中国煤化工50.450.240.1313.08CNMHG0.391.73(综表1)保留匹配空气10%02时间热解产物(min)度300℃600℃900℃300℃600℃900℃300℃600℃900℃13.251,2,3,4-四氢-6-甲基蔡0.430.2100.280.17(2-丁烯基)-2,3-二甲苯800.480.150.140.380.140.090.640.170.0913.41,3-二甲基-1H-茚0.110.180.170.660.200.1013.582,6,6-三甲基-1,3环已二烯-1-甲醛800.120.200.310.100.350.300.210.420.152-(2-羟基苯基)一830.160.150.110.110.170.190.320.170.0813.9858-二氢-1-酚820.080.150.310.020.400.220.220.380.2014.93(1-甲基戊-1,3-二烯基)851.521.040.681.181.420.890.851.210.7315.092,3-二甲基-1H-茚901.702.332.280.505.242.352.974.412.0015.211,2-二氢-6-甲基萘870.170.890.860.040.990.910.031.040.87对-二丙烯基苯900.040.680.350.020.240.170.060.280.2216.212-甲基萘955.891.991.021.274.821.0311.103.960.9116.41巨豆三烯酮A800.280.310.360.060.060.290.060.210.3917.181,2-二氢-1,1,6-三甲基萘9614.07.414.558.624.342.632.193.592.671,1,3-三甲基-1H-茚931.320.530.290.320.340.200.080.270.18巨豆三烯酮B800.750.780.690.230.590.470.170.700.782,7-二甲基9711.3010.909.93.3813.6010.2013.2014.0012.00★烟草化学l8.432,6-二甲基萘960.150.910.970.080.720.810.230.981.581,6-二甲基萘970.883.873.510.212.532.890.563.344,48巨豆三烯酮C960.440.490.260.140.300.260.340.610.4518.9联苯0.370.520.040.250.440.161.081945-脱氢一异长叶烯0.190.180.020.330.142-异丙基蓁0.150.150.540.630.581.0919.59巨豆三烯酮D830.320.650.660.070.390.630.140.630.911,6,7-三甲基蔡840.261.122.310.171.691.770.350.282.371,4,6-三甲基萘0.930.391.371.251.310.8521.30,4’-二甲基联苯1.240950.531.480.911.982,2’一二甲基联苯0.300.290.090.200.160.331,1-二苯基乙烯1.290.400.120.690.290.8923.201-甲基-9H-芴0.320.660.310.990.330.250.280.470.150.540.270.5624.612,3-二甲基-9H-芴0.170.200.060.180.060.20期总第25.614一甲基菲0.142,5-二甲基菲2,3,5-三甲基菲0.0注:①归一化峰面积;②“一”表示未检出YHa中国煤化工0.07CNMHG酚类、烷烃类和杂环类裂解产物则变化不大。001%叶黄素后,卷烟烟气的香气、谐调性和说明在这3种温度下,叶黄素的裂解产物主要是余味变化不明显,其杂气、刺激性有所增加;加入芳烃类,而且随着热解温度的升高生成了稠环0.02%叶黄素后,烟气的谐调性变化不明显,其香芳烃。气、杂气、刺激性都有所增加,余味变差。烟气香在相同温度下,叶黄素在不同氧气含量的氛气的增加可能是由于叶黄素热裂解产生了氧化异围中裂解除了在600℃和900℃下氮气(无氧)佛尔酮、巨豆三烯酮等物质,而杂气、刺激性的明烟草科技氛围中烯烃类裂解产物的种类明显低于相同温度显增加可能与叶黄素热解时产生的大量的苯及其下在空气和10%O2氛围中的外,其余各裂解产物同系物有关。说明在烟丝中加人叶黄素,虽然略的种类和相对含量相同温度下不同氛围无明显区微提高了卷烟烟气的香气,但却明显增加了杂气别,说明裂解氛围对叶黄素的裂解产物种类及其和刺激性,利大于弊。3≌-3即相对含量的影响不大另外,叶黄素在不同温度和不同氛围中还裂变2加叶黄素卷烟的感官评吸结果解产生几种香气成分,主要有氧化异佛尔酮和巨卷烟叶黄累香气谐调性杂气刺激性余味豆三烯酮等但其种类和数量都比较小。其形成样品用量(%)对照32.05.014.014.016机理可能符合文献[1]的介绍(图3),即在含氧0.0132.05.013.013.016氛围中,若叶黄素在9-10位发生双键断裂,可以0.0233.04.513.013.015生成3-羟基-a-紫罗兰酮,经过氧化还原,生成3-氧代-α-紫罗兰醇,再脱水就形成了烟草中特别重要的香味成分巨豆三烯酮。若在6-73结论位置上发生碳链断裂,可以生成非常重要的香味热裂解和卷烟加香试验结果表明,在卷烟烟成分氧化异佛尔酮。但本实验叶黄素在氮气氛围丝中加入一定量的叶黄素,不利于卷烟的抽吸品中裂解也生成了这些香气成分,是其形成机理有质的提高因为在卷烟燃烧时,叶黄素的热解虽然别,还是热解过程中可能混入了少量氧气有待进能生成一定量的香气成分,但是同时也产生大量步研究。的有害成分,使卷烟烟气的杂气、刺激性增加,因22叶黄素对卷烟吸味品质的影响此,若能在加工期间或通过某种技术降低烟叶中从表2可以看出,与对照相比,在烟丝中加人的叶黄素,可能有利于卷烟减害及其抽吸品质的提高。人参考文献[1]王瑞新.烟草化学[M].北京:中国农业出版[2]杨立均,宫长荣,马京民烘烤过程中烟叶色素的降氧化异佛尔解及与化学成分的相关分析[J]中国烟草科学3-羚基-紫罗兰酮2002(2):57[3]史宏志韩锦峰,官春云.烟叶香气前体物在成熟和年第期总第期氧化还原调制过程中的变化[].作物研究,1996,10(2):巨豆三烯酮[4]杨虹琦,周冀衡罗泽民,等不同产区烤烟中质体3氧代一紫罗兰醇色素及降解产物的研究[].西南农业大学学报图3叶黄囊裂解产生香气成分的机理1(自然科学版),2004,26(5):6404644中国煤化工CNMHG