A Review on Pretreatment Method for the Analysis of Complex Chemical Composition of Resinite
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摘要: 树脂化石复杂有机组分的分离检测及解析一直是树脂化石研究中的热点和难点，早期前处理方法和一维气相色谱-质谱的分离分析效率有限，挥发性组分数据易丢失，峰重叠现象严重，很难对其化学组成进行准确鉴定。本文对比分析了4种前处理方法(溶剂萃取、化学衍生化、热裂解和固相微萃取)在树脂化石前处理中的适用范围和优缺点。(1)溶剂萃取法适用于分析树脂化石中倍半萜类、三萜类、酚类、饱和烃、芳烃等物质，但石化程度高的琥珀所需溶解时间长且不能完全溶解，不适用此方法，石化程度低的柯巴树脂更适用于此方法。(2)化学衍生化法适用于定性分析基团中有活泼氢的分子，衍生化后可有效改善相关分子的挥发性、稳定性和增强响应信号强度。(3)热裂解法主要针对树脂化石有机聚合物的主要骨架，但是以裂解碎片还原初始结构会存在一定偏差。(4)固相微萃取法适用于树脂化石中的挥发份/半挥发份的分析，但易出现检出物不完全的情况。结合顶空高容量固相萃取法和直接热脱附法样品前处理技术和全二维气相色谱-质谱技术，可检测到传统分析方法3~4倍的化合物种类数量, 并通过非靶向代谢组学策略分析不同产地树脂化石色谱质谱结果，可筛查出更具代表性的特征化学信息，研究复杂有机组分的分离、同分异构物的准确判别，解决固相复杂有机组分检测解析的突出难题，在挥发性-半挥发性有机组分分离及二次富集、高特异性生物标志物筛选方面高效解析，为树脂化石在其古生态环境复原及成熟演化过程探究奠定理论和技术基础。Abstract: The separation, detection, and analysis of complex organic compositions in fossil resin have always been a hot and difficult point in the research. The early sample pretreatment methods and the separation and analysis efficiency of one-dimensional gas chromatography-mass spectrometry (1D GC-MS) were limited, overlapping spectral peaks and missing mass spectra peaks of trace substances easily occurred in the chromatography-mass spectrometry analysis, .Hence, it was difficult to accurately identify its chemical compositions. In this review, it systematically summarizes the application, advantages, and disadvantages of four pretreatment methods (solvent extraction, chemical derivatization, pyrolysis, and solid phase microextraction) used in the compositions analysis of resinites. (1)Solvent extraction is suitable for the analysis of sesquiterpenes, triterpenes, phenols, saturated hydrocarbons, aromatic hydrocarbons, and other substances in the resin fossils. However, amber with high degree of petrifaction requires a long time to dissolve and cannot be completely dissolved, hence, solvent extraction is much more applicable to copal with lower degree rather than highly fossilized amber. (2)Chemical derivatization is applicable to qualitative analysis of molecules with active hydrogen in the group, which can effectively improve the volatility and stability of related molecules and enhance the response signal intensity after derivatization. (3)Thermal pyrolysis mainly aims at the analysis of the main macromolecular skeleton of the resinite, but there will be some deviation in the reduction of the initial structure by the pyrolysates. (4)Solid phase microextraction is suitable for the analysis of volatile/semi-volatile components in amber, but it is prone to incomplete detection. The sample pretreatment technologies of headspace high-capacity solid phase microextraction and direct thermal desorption combining with comprehensive two-dimensional gas chromatography and mass spectrometry (GC-MS) were creatively proposed, which could detect 3-4 times as many compounds number as the traditional analysis method. More representative biomarkers can be screened by untargeted metabolomics strategies to analyze the GC-MS results of resinites from different habitats. Our team will focus on the isolation of complex organic components and the accurate identification of isomers, and reveal the origin of ancient plants and genesis of resin fossils of different origins and ages. It is expected to solve the outstanding problems in the detection and analysis of complex organic components in the solid phase, and efficiently analyze volatile and semi volatile organic compounds in terms of separation, secondary enrichment, and screening of highly specific biomarkers, which provides a theoretical and technical foundation for the exploration of reconstruction of their palaeoecological environment and maturation evolution.
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Keywords:
- resinite /
- amber /
- solvent extraction /
- chemical derivatization /
- pyrolysis /
- solid phase microextraction
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图 1 Ⅰ型树脂化石的基本结构及其单体结构示意图[9]
Figure 1. The basic structure of ClassⅠ resinites and its monomeric structure
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图 2 树脂化石化学分析流程和常见的前处理方法
Figure 2. The chemical analytical workflow and common pretreatment methods for resinites
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图 3 样品制备与组分分离的基础步骤
Figure 3. Basic steps in sample preparation and component separation
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图 4 缅甸琥珀(a)和多米尼加琥珀(b)的高效液相色谱-紫外检测结果
Figure 4. HPLC chromatograms of amber from Myanmar (a) and amber from Dominican Republic (b)
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图 5 化学衍生化法分离组分的步骤
Figure 5. Steps for the separation of components by chemical derivatization
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图 6 相对于TMAH甲基化反应，HMDS硅烷化反应具有更高的灵敏度和最佳峰值分辨率[21]
Figure 6. The higher sensitivity and a best resolution of peaks achieved from the derivatization with HMDS, compared to the TMAH methylation reaction
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图 8 缅甸金珀在420 ℃和520 ℃裂解温度时的热裂解-气相色谱-质谱图
Figure 8. Py-GC-MS of golden amber from Myanmar at pyrolysis temperatures of 420 ℃ and 520 ℃
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图 10 基于固相微萃取技术的琥珀挥发性有机物/半挥发性有机物成分检测
Figure 10. Detection of amber volatile organic compounds/semi volatile organic compounds based on solid phase microextraction technology
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图 11 顶空高容量固相萃取对于高沸点，半挥发性化合物的灵敏度更好
Figure 11. Headspace high volume solid phase extraction is more sensitive to high boiling point and semi volatile compounds
表 2 琥珀与不同溶剂(含化学式)的反应时间和效果[41]
Table 2 Chemical reaction of the amber to different solvents, their chemical formula, and the duration of the reaction[9]
溶剂 化学式 时间 效果 Acetone C3H6O ∞ 在丙酮中浸泡了几天后，琥珀仅有表面受到了影响，琥珀样品变得很脆且碎 Dichlormethane CH2Cl2 ~1 h 琥珀在二氯甲烷中快速溶解了，但溶剂对包裹体是否有影响还未进行检测 Trichlormethane CHCl3 ~0.5 h 琥珀快速地褪色并且溶解，并且琥珀内部的包裹体脱水 Dimethylformamide HCO-N(CH3)2 ∞ 琥珀样品仅漂浮在溶剂表面，几周后都没有变化 Formaldehyde CH2O ∞ 琥珀样品仅漂浮在溶剂表面，几周后都没有变化 Petroleum ether CnH2n+2(n=5~8) ∞ 石油醚具有多个闪点，使琥珀具有弹性且变得不透明; 此外，石油醚还浸渍了样品, 琥珀开始产生线状条纹; 几个小时后，浸泡在石油醚中的琥珀变成了泥土状、粘稠的混合物 Turpentine oil predominantly C10H16 (α-Pinen) ~2 d 溶解琥珀的时间最长，但溶解的效果很好; 溶剂对包裹体是否有影响还未进行检测 Orange oil predominantly C10H16 (d-limonene) 3~4 h 溶解琥珀的能力很强，至今为止没有发现橙油会损坏包裹体 Toluene C6H5CH3 ~1 h 溶解琥珀的能力很强，与少量的乙醇混合时效果最好；包裹体残留在溶剂中时会脱水 Xylene C6H4(CH3)2 ~1 h 比甲苯溶解琥珀的效果更强; 溶剂对包裹体是否有影响还未进行检测 
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