CN108760791A - 一种茶油脂肪酸指标的预测方法 - Google Patents
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Abstract
本发明公开了一种茶油脂肪酸含量的预测方法,采用本发明的测定方法:1HNMR结合PLS可用来快速预测茶油脂肪酸含量,包括C16:0、C18:0、C18:1、C18:2、C18:3、TFA、SFA、USFA、MUFA、以及PUFA。
Description
技术领域
本发明属于化学分析领域,具体涉及一种茶油脂肪酸指标的预测方法。
背景技术
茶油被称为世界四大木本油料植物之一,其脂肪酸组成和橄榄油的脂肪酸组成非常相似,被誉为“东方橄榄油”。研究表明茶油除含有较高含量的油酸,少量亚油酸、亚麻酸等外,还含有多种生理活性物质如角鲨烯、甾醇、生育酚、茶多酚等其它微量非皂化物。其中甘油三酯约为95–98%,不皂化物含量约为2–5%,而甾醇占据不皂化物含量的比例最大(0.6%)。作为一种保健型的营养油脂,茶油有着与橄榄油一样的营养价值。作为含量最高的单不饱和脂肪酸,油酸可以明显降低血液中有害的“低密度脂蛋白胆固醇”而保留有益的“高密度脂蛋白胆固醇”,最终达到降低血清胆固醇的作用。由于茶油的营养保健价值很高,使其在市场上的价格远远高于日常食用油,部分商家为了眼前利益导致市场上出现了严重的茶油掺假现象,从而影响茶油的特有品质和营养特征,不仅对人类健康构成了间接威胁,也严重影响了茶油市场的健康发展。另外茶油的成分和营养风味受产地、生产工艺等因素影响也有一定变化,因此,建立茶油营养品质检测技术对于茶油质量监督以及品质控制十分重要。
目前,常用于茶油品质检测的主要有传统检测方法(如感官评价、物理化学指标的评价等)和仪器检测方法(如色谱、质谱、差式扫描量热法等),但传统检测方法时间长、化学试剂耗费大,而以上这些仪器检测方法大多需要进行繁琐的样品前处理,对样品破坏性较大。与上述方法相比,核磁共振具有具有快速、高效、无污染、无需繁琐的前处理、重现性高等优点。在预测植物油营养品质指标如角鲨烯、甾醇、三萜酸/酯、脂肪醇、蜡酯和酚类化合物中得到广泛应用。
通过核磁共振波谱可以获得样品中多种化学成分的信息,但是各种成分信号的重叠也使得图谱变得十分复杂,尤其当谱峰严重重叠,信号所包含的化学成分未知时,数据分析的难度大大增加。面对信息量大、复杂的核磁数据,如何提高其处理效率变得至关重要。所研究样品的信息,有些可以通过数据直观地反映出来,但很多重要的信息却并不能直接从数据中得到,往往需要结合正确的数学模型和有效的计算方法对数据进行分析。化学计量学是将化学体系的测量值与体系的状态建立联系的学科,本质是化学量测的基础理论与方法学。结合化学计量学方法可以全面地分析谱图数据,从复杂的核磁数据中最大限度地提取有关研究对象成分、结构等重要信息,获得有效的特征数据,建立数学模型,有助于对测量数据的解释、判别和预测,具有计算速度快和识别功能佳等优点。
偏最小二乘法(PLS)是一种描述矩阵X和响应矩阵Y相关性的多元校正分析方法,多用于定量分析,在快速预测植物油氧化稳定性,掺假比例、脂肪酸组成、十六烷值、碘值和运动粘度等质量指标中得到广泛的应用。
但是,据我们所知,没有任何关于通过1H NMR结合PLS同时预测茶油中脂肪酸含量的研究报道,因此,本发明研究的目的在于通过1H NMR结合PLS快速检测茶油营养品质,包括脂肪酸(C16:0、C18:0、C18:1、C18:2、C18:3、TFA、SFA、USFA、MUFA、PUFA)为核磁共振结合化学计量学方法在茶油品质评价和控制中的应用提供实验依据。
发明内容
本发明旨在针对现有技术的不足,提供一种茶油脂肪酸含量的预测方法,本发明是通过以下技术方案实现的:
一种茶油脂肪酸含量的预测方法:采用的是核磁共振技术,结合动力学分析建立茶油脂肪酸含量的预测模型,具体包括以下步骤:
一种茶油脂肪酸含量的预测方法,包括以下步骤:
(1)脂肪酸含量的测定:脂肪酸甲酯化:准确称取10mg样品于离心管中,分别加入10μL C21:0内标液,2mL正庚烷和0.1mL 2mol/L氢氧化钾-甲醇溶液,震摇30s,离心,取1mL上清液置于气相瓶待测;色谱条件:采用CP-Sil 88型毛细管色谱柱:100m×0.25mm×0.39mm,0.20μm,Varian Inc,USA,FID检测器,进样量为1μL,高纯氢气为载气,进样口温度250℃,检测器温度250℃,恒流模式,分流比为10:1,氢气流量为30mL/min,空气流量为300mL/min,尾吹气流量为20mL/min,载气线速为26cm/s;升温程序为:初温60℃,保持5min,以11.5℃/min升至170℃,保持25min;再以5℃/min的速率升至200℃,保持5min;最后以2℃/min升温至215℃,保持20min;
1HNMR测定:A:取200μL混合油样与800μL CDCl3混合,涡旋半分钟,室温下静至5min,取600μL转移至5mm核磁管中进行核磁实验,总计119个样品;
B:测定条件控制在:温度298K;600MHz核磁共振仪的频率600.38MHz;谱宽13ppm;每个图谱扫描32次;空扫4次;脉冲序列zg30;以四甲基硅烷(TMS,δ=0)为内标;
C:数据处理:将测得的样品自由衰减信号导入MestReNova软件中进行傅里叶变换,并进行相位校正和基线校正,1H NMR谱图手动积分,将酰基链上α-亚甲基氢,-OCO-CH2-,信号9,2.40-2.20ppm的积分面积标准化为1000,其它信号峰面积以此为参考标准,最终得到16个积分片段,获得的数据矩阵导入SIMCA 13软件,建立PLS模型,将所采集的样本分为两大类,随机取2/3的样品划分为训练集,用于建立PLS模型;剩余1/3的样品作为预测集,用于检验PLS模型;采用NO、UV、Par和Ctr等方法对原始数据进行预处理,基于最低RMSECV值选取主因子数,建立PLS模型,通过R2、RMSEE以及RMSEP来评价模型的预测能力。
本发明的有益效果
(1)1HNMR结合PLS可用来快速预测茶油脂肪酸指标,包括脂肪酸(C16:0、C18:0、C18:1、C18:2、C18:3、TFA、SFA、USFA、MUFA、PUFA)的含量;
附图说明
图1茶油和调和茶油油的1H NMR谱;
图2 PLS模型散点图。
具体实施方式
实施例1
原料与试剂:
66种植物油,包括纯茶油(n=49,来自江西省不同产地)、调和茶油(n=17);所有油样的生产日期均在2016年1月-2016年5月,储存于4℃冰箱。α-生育酚(纯度为98%):百灵威科技有限公司;二十一烷酸甲酯(C21:0,FAME)以及GLC 463脂肪酸甲酯混标:美国Nu-Chek公司;亚油酸顺反异构体甲酯混标(9c 12c C18:2,9c 12t C18:2,9t 12c C18:2,9t12t C18:2)以及亚麻酸顺反异构体甲酯混标(9c 12c 15c C18:3,9t 12t 15c C18:3,9t12c 15t C18:3,9c 12t 15t C18:3,9c 12c 15t C18:3,9c 12t 15c C18:3,9t 12c 15cC18:3,9t 12t 15t C18:3);优级纯氢氧化钾:上海阿拉丁生化科技股份有限公司;甲醇(≥99.9%):德国Merk公司;正己烷(99%):美国Honeywell公司。
仪器与设备:
BrukerAV 600MHz核磁共振波谱仪:瑞士布鲁克公司;5mm核磁共振样品管:美国Wilmad公司;
Agilent1290高效液相色谱仪:美国安捷伦公司;色谱柱:ZORBAX Eclipse plusC18:美国安捷伦公司;
6890N气相色谱仪(配有FID检测器和Rev.A.10.02色谱工作站):美国Agilent公司;
7890A-5975气相色谱-质谱联用仪:美国Agilent公司;色谱柱:HP-5MS:美国Agilent公司;
AL-104型电子天平:梅特勒-托利多仪器(上海)有限公司;QL-861型涡旋仪:海门市其林贝尔仪器制造有限公司;电子恒温不锈钢水浴锅:上海宏兴机械仪器实业制造公司;Anke TGL-16G-A型离心机:上海安亭科学仪器厂;Milli- QAcademic超纯水***:美国Millipore公司;DragonLab移液器:北京大龙实验室仪器有限公司。
实验步骤与过程:
脂肪酸含量的测定:脂肪酸甲酯化:准确称取10mg样品于离心管中,分别加入10μLC21:0内标液,2mL正庚烷和0.1mL 2mol/L氢氧化钾-甲醇溶液,震摇30s,离心,取1mL上清液置于气相瓶待测;色谱条件:采用CP-Sil 88型毛细管色谱柱:100m×0.25mm×0.39mm,0.20μm,Varian Inc,USA,FID检测器,进样量为1μL,高纯氢气为载气,进样口温度250℃,检测器温度250℃,恒流模式,分流比为10:1,氢气流量为30mL/min,空气流量为300mL/min,尾吹气流量为20mL/min,载气线速为26cm/s;升温程序为:初温60℃,保持5min,以11.5℃/min升至170℃,保持25min;再以5℃/min的速率升至200℃,保持5min;最后以2℃/min升温至215℃,保持20min;
1H NMR测定:A:取200μL混合油样与800μL CDCl3混合,涡旋半分钟,室温下静至5min,取600μL转移至5mm核磁管中进行核磁实验,总计66个样品;
B:测定条件控制在:温度298K;600MHz核磁共振仪的频率600.38MHz;谱宽13ppm;每个图谱扫描32次;空扫4次;脉冲序列zg30;以四甲基硅烷(TMS,δ=0)为内标。
测定结果:
脂肪酸组成:脂肪酸组成与茶油的营养功能密切相关,根据GB11765-2003可知茶油富含油酸(74-87%)和亚油酸(7-14%)等多不饱和脂肪酸,而饱和脂肪酸含量较低(7-11%)。由表1可知,C18:1、C18:2和SFA分别为79.59%、7.99%和10.88%,均在国标范围内。根据进一步的研究可知C18:1在茶油中含量最高,其次为C16:0、C18:2、C18:0和C18:3,其含量分别为8.54%、7.99%、2.18%和0.68%。除了上述主要脂肪酸,茶油中还存在一些微量脂肪酸,如C14:0、C16:1、C17:0、C20:0、C20:3、C22:1以及C22:3。此外,基于该方法,还检测到了少量反式脂肪酸(0.55%)。上述结果与之前文献中的结果相近。与纯茶油相比,调和茶油以C16:0(7.23%)、C18:0(3.03%)、C18:1(44.94%)、C18:2(34.37%)以及C18:3(7.3%)为主,此外,调和茶油中还含有少量的C20:2。
表1茶油及调和茶油脂肪酸测定结果
TFA:反式脂肪酸;SFA:饱和脂肪酸;USFA:不饱和脂肪酸;MUFA:单不饱和脂肪酸;PUFA:多不饱和脂肪酸
1H NMR:说明书附图一为纯茶油和调和茶油的1HNMR谱图,相应化学位移对应的官能团见表2,。两类植物油主要成分为甘油三酯,含有少量的甘油二酯、角鲨烯、甾醇、环阿屯醇等。对比茶油和调和茶油的特征指纹图谱,可以看出二者在甘油二酯、亚麻酸、亚油酸以及甾醇等物质含量上差异较明显。且调和茶油中甘油二酯、亚麻酸、亚油酸以及甾醇含量均高于纯茶油,但茶油中的环阿屯醇信号强度比调和茶油高。上述差异表明不同植物油之间的脂肪酸组成以及微量成分可以通过1H NMR谱图快速反映出来。
表2茶油中主要化合物的1H NMR信号归属
s:single;d:doublet;t:triplet;m:multiplet;dt:double of triplet;dd:doublet of doblet.
1H NMR结合PLS对茶油脂肪酸含量的预测:借助PLS,建立C16:0、C18:0、C18:1、C18:2、C18:3、TFA、SFA、USFA、MUFA和PUFA等脂肪酸的含量预测模型结果如表3。
表3不同预处理方法对脂肪酸PLS模型的影响
由表3中可知,与NO法相比,原始数据经UV、Par和Ctr等标度化方法预处理后,其对应的大多数PLS模型最佳主因子数均有所下降,除了UV法下的C18:0模型,主因子数最高,为7,进一步结合R2、RMSEE和RMSEP值分析可知:C18:2、TFA、MUFA和PUFA经UV、Par和Ctr等标度化方法预处理后,R2与RMSEE值相差不大,但RMSEP值均高于未经预处理的PLS模型,可能原因是应用标度化方法对原始数据进行预处理时,在去除噪声的同时也去除了许多与性质矩阵相关的信息,UV作为预处理方法可以使C16:0和SFA预测模型中RMSEP值最小,分别为0.290912%和0.227106%,而Par作为一种介于自标度化和中值标度化的前处理方法,可以使C18:0和C18:3的RMSEE和RMSEP值最小,C18:1和USFA在Ctr标度化方法下模型较好,此时R2分别为0.999和0.9673,RMSEE和RMSEP值最小。最终建立的脂肪酸含量预测模型见说明书附图二,10种脂肪酸预测模型中,RMSEE和RMSEP值接近于0。除了TFA模型中R2(0.8765)较低,其它脂肪酸模型的R2≥0.9512,其中C18:1、C18:2、MUFA和PUFA模型中R2≥0.99,预测能力较好。
Claims (1)
1.一种茶油脂肪酸指标的预测方法,其特征在于,包括以下步骤:
(1)脂肪酸含量的测定:脂肪酸甲酯化:准确称取10mg样品于离心管中,分别加入10μLC21:0内标液,2mL正庚烷和0.1mL 2mol/L氢氧化钾-甲醇溶液,震摇30s,离心,取1mL上清液置于气相瓶待测;色谱条件:采用CP-Sil 88型毛细管色谱柱:100m×0.25mm×0.39mm,0.20μm,Varian Inc,USA,FID检测器,进样量为1μL,高纯氢气为载气,进样口温度250℃,检测器温度250℃,恒流模式,分流比为10:1,氢气流量为30mL/min,空气流量为300mL/min,尾吹气流量为20mL/min,载气线速为26cm/s;升温程序为:初温60℃,保持5min,以11.5℃/min升至170℃,保持25min;再以5℃/min的速率升至200℃,保持5min;最后以2℃/min升温至215℃,保持20min;
(2)1H NMR测定:A:取200μL混合油样与800μL CDCl3混合,涡旋半分钟,室温下静至5min,取600μL转移至5mm核磁管中进行核磁实验,总计66个样品;
B:测定条件控制在:温度298K;600MHz核磁共振仪的频率600.38MHz;谱宽13ppm;每个图谱扫描32次;空扫4次;脉冲序列zg30;以四甲基硅烷(TMS,δ=0)为内标;
C:数据处理:将测得的样品自由衰减信号导入MestReNova软件中进行傅里叶变换,并进行相位校正和基线校正,1H NMR谱图手动积分,将酰基链上α-亚甲基氢,-OCO-CH2-,信号9,2.40-2.20ppm的积分面积标准化为1000,其它信号峰面积以此为参考标准,最终得到16个积分片段,获得的数据矩阵导入SIMCA13软件,建立PLS模型,将所采集的样本分为两大类,随机取2/3的样品划分为训练集,用于建立PLS模型;剩余1/3的样品作为预测集,用于检验PLS模型;采用NO、UV、Par和Ctr等方法对原始数据进行预处理,基于最低RMSECV值选取主因子数,建立PLS模型,通过R2、RMSEE以及RMSEP来评价模型的预测能力。
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