基于捕集柱阵列的制备型二维液相色谱纯化烟草中的4个组分

二维液相色谱(2D-LC)因具有较高的峰容量,在复杂样品的分离分析中获得了广泛的关注。然而,制备型2D-LC以纯化高纯单体为目标,在方法开发和设备构成等方面与分析型2D-LC有较大的不同,目前尚未得到充分的开发,在大规模的制备纯化中应用较少。本文以一套制备液相色谱模块为分离系统,以稀释泵、切换阀和捕集柱阵列为接口,构建了新型的制备型2D-LC系统,旨在规模化纯化多个活性成分。以烟叶中可以用作医药原料的烟碱、绿原酸、芦丁和茄尼醇等组分为目标物,考察了不同类型填料对样品的捕集效率、过载条件下的色谱保留行为等,优化了制备色谱条件。进而利用在线2D-LC系统实现了烟叶提取物的纯化,通过一次运行获得了4个高纯化合物。该系统具有中压色谱纯化成本低、系统在线运行自动化程度高、稳定性好及容易放大等优点。烟叶中活性化学成分的回收利用对促进烟草行业的发展及带动地方农业经济开发具有重大的意义。     

Separation,identification, and structural characterization of sucrose ester isomers from tobacco

Sucrose esters (SEs) are crucial tobacco smoke flavor precursors and play a significant role in tobacco's functionality. Due to their structural complexity, the separation and analysis of SEs in tobacco remain a major challenge, and massive structures of SEs have not yet been fully identified. In this study, the fractions enriched in SEs were obtained from oriental and flue-cured tobacco through a series of pretreatments, and two types of SEs (Types I and II) were distinguished by liquid chromatography-tandem mass spectrometry (LC-MSⁿ) analysis, with Type II SEs newly characterized in tobacco. Five groups of main SEs were further purified using preparative high-performance LC (HPLC) coupled to an evaporative light scattering detector, and their structures were characterized by nuclear magnetic resonance spectrometry techniques including ¹H, ¹³C, correlation spectroscopy, heteronuclear single quantum correlation, and heteronuclear multiple bond correlation. By combining LC-MSⁿ and nuclear magnetic resonance spectrometry, the structures of eight SE isomers were finally proposed, of which four were newly identified. These findings further enhance the understanding of the structural diversity of SEs in tobacco, serving as a valuable reference for future research on the elucidation, synthesis, and metabolism of SEs.     

离子色谱法测定电子烟烟液中氨的含量

建立了测定电子烟烟液中的氨含量离子色谱法。样品经10 mol·L-1盐酸溶液萃取10 min后,采用Dionex Ion Pac CS16A阳离子交换柱分离,以MSA为淋洗液进梯度洗脱,用电化学检测器检测。氨的质量浓度在0.05~1.0 mg·L-1范围内与峰面积呈线性关系,检出限(3S/N)为0.035μg·g-1,测定下限(10S/N)为0.12μg·g-1。方法用于12种市售品牌电子烟烟液中氨的测定,加标回收率在93.2%~106%之间,测定值的相对标准偏差(n=5)小于4%。     

原子吸收光谱法测定烟叶中的重金属总量及形态分析

采用火焰原子吸收光谱法测定烟叶中Mn,Cu,Zn元素,石墨炉原子吸收光谱法测定Cd,Cr,Pb元素,以HNO3-H2O2微波消解法获取烟叶中的重金属总量,以超声水提取法获取水溶态重金属进行初级形态分析,以Tessier逐级提取法获取5种形态的重金属进行次级形态分析。实验结果表明,原子吸收光谱法检测6种重金属线性良好,相关系数(r2)不低于0.998 8,检出限为0.16~3.1μg·L-1。烟叶样品中Mn,Cu,Zn,Cd元素主要以可交换态和碳酸盐结合态的形式存在;Cr主要以残渣态的形式存在;而Pb主要以碳酸盐结合态和残渣态的形式存在。     

不同微波膨胀烟梗的化学感官特性研究

研究不同来源包括产地、部位、年份、品种的烟梗原料经相同的微波膨胀工艺处理后的常规化学成分、致香成分、主流烟气(主要包括抽吸口数、焦油、烟碱及一氧化碳释放量)及感官特性差异,指导微波膨胀梗丝在产品中的配伍应用,为建立不同来源微波膨胀梗原料的品质特征评价体系及微波膨胀梗丝的工业应用提供依据。结果表明:不同产地来源的微波膨胀梗丝常规化学成分、致香成分、主流烟气存在差异。不同年份的微波膨胀梗丝间感官质量无明显差异,不同产地、品种、部位来源的微波膨胀梗丝总体感官质量存在差异。     

Simultaneous quantification of ten Amadori compounds in tobacco using liquid chromatography with tandem mass spectrometry

Amadori compounds are aroma precursors formed in the initial phase of the Maillard reaction. Based on their similar structures, simultaneous quantification of more than six Amadori compounds in tobacco has not been reported yet. In this study, a simple and rapid method was developed to simultaneously quantify ten Amadori compounds including the isomers of Fructose‐isoleucine and Fructose‐leucine in tobacco. The separation was performed on an Atlantis T₃ column (2.1 × 250 mm, 5 μm) by gradient elution using acetonitrile and water as the mobile phases. The quantification method was systematically evaluated and proven to be sensitive and accurate. The linearity was good, with correlation coefficients of 0.9977–0.9999. The limits of detection and quantitation were 1.354–2.532 and 4.516–8.444 ng/mL, respectively. The recoveries were 84.0–119.6%, and the relative standard deviations were 1.33–5.40%. The method was used to analyze the changes in the amounts of ten Amadori compounds in tobacco before and after tobacco primary processing. The analysis shows that the Maillard reaction occurs during the short processing period.     

Simultaneous determination of residues of metalaxyl,cyazofamid and a cyazofamid metabolite in tobacco leaves and soil by liquid chromatography with tandem mass spectrometry

A simple method was developed and validated for the simultaneous determination of metalaxyl, cyazofamid and the cyazofamid metabolite 4‐chloro‐5‐p‐tolylimidazole‐2‐carbonitrile (CCIM) by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile containing 0.1% acetic acid, and the extracts were purified using octadecylsilane. The proposed method showed satisfactory linearity (R² ≥ 0.9985) for the target compounds. The limits of detection for metalaxyl, cyazofamid and CCIM were 0.006, 0.06 and 0.06 mg/kg in soil and green tobacco leaves and 0.03, 0.3 and 0.3 mg/kg in cured tobacco leaves, respectively. The limits of quantification for metalaxyl, cyazofamid and CCIM were 0.02, 0.2 and 0.2 mg/kg in soil and green tobacco leaves and 0.1, 1 and 1 mg/kg in cured tobacco leaves, respectively. The average recoveries from soil and tobacco were 72.91–98.40% for metalaxyl, 76.73–105.80% for cyazofamid and 74.48–106.45% for CCIM. The relative standard deviation range was 1.23–6.99%. The developed method was successfully applied to analysis of residues of metalaxyl, cyazofamid and CCIM in real soil and tobacco samples. The results indicated that the established method could meet the requirement for the analysis of trace amounts of all three analytes in soil and tobacco.     

Two New 4‐Hydroxyisoflavanes from the Root of Codonopsis cordifolioidea and Their Anti‐virus Activities

Two new 4‐hydroxyisoflavanes, cordifoliflavanes A and B (1 and 2), were isolated from the roots of Codonopsis cordifolioidea. Their structures were elucidated by spectroscopic methods, including extensive 1D‐ and 2D‐NMR techniques. Compounds 1 and 2 were tested for their anti‐HIV‐1 activities and anti‐tobacco mosaic virus activities. The results showed that compounds 1 and 2 have modest anti‐HIV‐1 activities and anti‐tobacco mosaic virus activities, respectively.     

对直接标准化算法的改进及其应用

由于各种仪器之间存在差异,主机上建立的定量模型用于从机会导致预测结果出现较大偏差。目前主要通过有标样方法和无标样方法来减小预测偏差。该文对现有标样方法中的直接标准化算法进行改进,在转移矩阵的建立过程中,对从仪器数据矩阵进行主成分分解,以预测均方差为判定标准,确定最终的转移矩阵。并以玉米和烟草数据为对象,测试了该法的有效性。玉米样品含有2种成分:水分和蛋白质;烟草样品含有4种成分:还原糖、总糖、总氮和总碱。结果表明,对于玉米样品中的2种成分,采用改进的方法可显著提高预测的准确度;对于烟草中的4种成分而言,采用改进的方法可获得稳健的预测结果。     

Teflon AF 2400管冷蒸气发生-原子荧光法分析烟草中的痕量汞

采用具有高气体渗透性和紫外光透过性的无定形聚四氟乙烯管(Teflon AF-2400)作为蒸气发生原子荧光系统的气液分离器和检测池,建立了微型化汞蒸气发生原子荧光检测系统。考察了Teflon AF-2400管长度、还原剂种类和浓度、酸介质种类和浓度、进样流速以及氩气流速对测量体系的影响。在优化实验条件下,该方法的线性范围为0.07~10μg/L(r=0.998 0),检出限为0.02μg/L,相对标准偏差(n=11)为3.3%。该系统体积小、样品消耗少、灵敏度高。方法已成功应用于卷烟样品中汞含量的检测,回收率为97%~102%。