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.     

新型潜香化合物3,6-二甲基-2,5-吡嗪二甲酸二薄荷醇酯的热裂解产物

为开发新型高温释放型烟用香料,以2,3,5,6-四甲基吡嗪和薄荷醇为原料,经过酯化反应制备了3,6-二甲基-2,5-吡嗪二甲酸二薄荷醇酯(DPAME)。采用在线热裂解-气相色谱-质谱联用技术(Py-GC-MS)在空气氛围和不同的温度(300、600和900℃)下,对DPAME进行热裂解研究,裂解产物经GC-MS进行了定性和半定量分析。结果表明,DPAME在300℃下裂解产生了多种有致香效果的醛类、薄荷烯和薄荷醇等;在600℃和900℃下裂解产生了烯烃类、烷基吡嗪、薄荷醇和薄荷烯等香味物质,并且吡嗪类的种类和相对含量在这两个温度下明显增加。结合DPAME的热裂解产物分析和卷烟感官评吸结果,初步推测了其可能的裂解机理。采用该方法可以方便、快速地分离鉴定物质的热裂解产物,为该物质在烟草中的加香应用提供理论依据。     

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。     

Viscous waves and wave-structure interaction in a tank using adapting quadtree grids

Viscous waves and waves over a submerged cylinder in a stationary tank are simulated using a volume-of-fluid numerical scheme on adaptive hierarchical grids. A high resolution interface-capturing method is used to advect the free surface interface and the Navier–Stokes equations are discretised using finite volumes with collocated primitive variables and solved using a Pressure Implicit with Splitting of Operators (PISO) algorithm. The cylinder is modelled by using the technique of Cartesian cut cells. Results of flow of a single fluid past a cylinder at Reynolds number Re=100 are presented and found to agree well with experimental and other numerical data. Viscous free surface waves in a tank are simulated using uniform and quadtree grids for Reynolds numbers in the range from 2 to 2000, and the results compared against analytical solutions where available. The quadtree-based results are of the same accuracy as those on the equivalent uniform grids, and retain a sharp interface at the free surface while leading to considerable savings in both storage and CPU requirements. The nonlinearity in the wave is investigated for a selection of initial wave amplitudes. A submerged cylinder is positioned in the tank and its influence on the waves as well as the hydrodynamic loading on the cylinder is investigated.     

关于具有二次相关性收获率的捕食与被捕食系统极限环的存在性分析

讨论了一类两种群具有二次相关性收获率的捕食与被捕食系统,利用常微分定性方法和分支理论,得到了系统平衡点处的性态和极限环的存在性条件,并用Matlab软件对其进行数值模拟,推广了相关文献中两种群捕食模型定性分析的相应结论.     

掏槽参数对煤矿岩巷爆破效果的影响

为了提高掘进进尺，以川煤集团绿水洞矿掘进工程为背景，利用动力有限元程序LS-DYNA3D进行掏槽参数优化研究。结合井下现场实验，分析岩巷掏槽爆破不同参数动态应力、破碎范围的变化以及井下实际爆破效果。掏槽中心孔底向孔口平均有效应力峰值在有中心眼爆破较无中心眼爆破时增加了40%以上，中心眼爆破对槽腔底部的形成起主要作用。在其他条件相同的情况下单孔载荷从1.2 kg提高到1.8 kg，掏槽区中心眼底到孔口平均应力只增加20%，并且破碎范围的增加较少，实际进尺增加小于10%。现场掘进实验表明:在常规爆破载荷下，有中心眼比无中心眼爆破深度提高31%~65%，掏槽角小于78°时，随掏槽角度增加爆破进尺下降较平缓; 但掏槽角增至82°左右, 随掏槽角度增加爆破进尺下降明显。     

SiC单晶刻划过程的脆塑性转变特征研究

SiC单晶化学性能稳定、导热系数高、热膨胀系数小、耐磨性能好,广泛用于大功率器件产业。但由于其材料的硬度很大,加工非常困难。脆性材料塑性域加工为提高该类材料的表面质量,降低加工时间和成本提供了有效的途径。本文采用不同刀具角度和刀尖圆弧半径的单点金刚石刀具对4H-SiC单晶进行刻划实验,利用声发射、摩擦力传感器来监测刻划过程中声发射信号强度以及摩擦力的变化,并通过LeicaDCM3D以及SEM观察划痕沟槽表面形貌、切屑状态,综合分析以获得4H-SiC单晶在不同角度、刀尖圆弧半径下塑脆转变的临界切削深度。结果表明,增大刀具角度有利于塑性域加工;在相同条件下,刀尖圆弧半径越大,临界切削深度越大。