原子吸收法在有机分析中的应用（Ⅲ）：茶叶中茶多酚的测定

研究了间接测定茶叶中茶多酚的原子吸收，用甲基异丁酮和丁醇的混合溶剂萃取茶汤中的茶多酚，与氨基酸分离后，加入碱性Ｃｕ３（ＰＯ４）２悬浮液反萃取并同茶多酚作用，离心沉降未作用的Ｃｕ３（ＰＯ４）２后，用原子吸收法测定Ｃｕ，可求得茶多酚的含量，本法可消除茶叶共存氨基酸的干扰，测定结果同标准方法一致，回收率范围为９４％－１０４％，平均标准偏差为３．１％。     

超声法提取余甘树皮中单宁的研究

本文研究了以水替代有机溶剂作为提取剂，利用超声技术提取余甘树皮中单宁的最佳条件。研究结果表明：当超声频率为40kHz，功率为100W，作用时间为15-20min，固液比为1：24时，可一次性提取得到含量较高的缩合型单宁，同时达到节约有机提取剂和减少污染的双重效果。     

响应面试验优化超声波辅助提取龙眼愈伤组织中单宁的工艺

为提高龙眼愈伤组织中单宁的提取率,采用超声波辅助浸提法,基于乙醇浓度（A）、超声波功率（B）与提取时间（C） 3个单因素试验,通过响应面试验优化设计,建立了龙眼愈伤组织单宁提取工艺。 研究结果表明,龙眼愈伤组织中单宁的最佳提取条件为乙醇浓度61%、超声波功率140 W,提取时间54 min,提取温度60 ℃,在此工艺条件下,提取量为7.53 mg·g^-1。     

Effect of irradiation on anti-nutrients (total phenolics, tannins and phytate) in Brazilian beans

The Brazilian bean varieties Phaseolus vulgaris L. var. Carioca and Vigna unguiculata (L.) Walp var. Macaçar were irradiated with doses of 0.5, 1.0, 2.5, 5.0 and 10 kGy and subsequently stored at ambient temperature for 6 months. The anti-nutrients phenolic compounds, tannins and phytate were determined to be 0.48 mg g⁻¹ dry basis, 1.8 mg g⁻¹ dry basis and 13.5 μmol g⁻¹ dry basis in the raw non-irradiated Carioca beans and 0.30 mg g⁻¹ dry basis, 0.42 mg g⁻¹ dry basis and 7.5 μmol g⁻¹ dry basis in the raw non-irradiated Macaçar beans. After soaking and cooking a higher content of phenolic compounds and a lower phytate content was observed in both bean varieties. Tannin content was not affected by soaking and cooking of Carioca beans, but higher after soaking and cooking of Macaçar beans. Using radiation doses relevant for food did not effect the content of the anti-nutrients under investigation in both bean varieties.     

Preliminary extraction of tannins by 1‐butyl‐3‐methylimidazole bromide and its subsequent removal from Galla chinensis extract using macroporous resins

In recent years, ionic liquids have become increasingly attractive as ‘green solvents’ used in the extraction of bioactive compounds from natural plant. However, the separation of ionic liquid from the target compounds was difficult, due to their low vapour pressure and high stabilities. In our study, ionic liquid‐based ultrasonic and microwave‐assisted extraction was used to obtain the crude tannins, then the macroporous resin adsorption technology was further employed to purify the tannins and remove the ionic liquid from crude extract. The results showed that XDA‐6 had higher separation efficiency than other tested resins, and the equilibrium experimental data were well fitted to Langmuir isotherms. Dynamic adsorption and desorption were performed on XDA‐6 packed in glass columns to optimise the separation process. The optimum conditions as follows: the ratio of column height to diameter bed was 1:8, flow rate 1 BV/h (bed volume per hour), 85% ethanol was used as eluant while the elution volume was 2 BV. Under the optimised conditions, the adsorption and desoption rate of tannins in XDA‐6 were 94.81 and 91.63%, respectively. The content of tannins was increased from 70.24% in Galla chinensis extract to 85.12% with a recovery of 99.06%. The result of ultra‐performance liquid chromatography (UPLC)‐MS/MS analysis showed that [bmim]Br could be removed from extract.     

Structure degradation, conservation and rearrangement in the carbonisation of polyflavonoid tannin/furanic rigid foams – A MALDI-TOF investigation

Carbonisation of polyflavonoid tannin–formaldehyde–furfuryl alcohol rigid foams yields a three-dimensional network in which polynuclear aromatic hydrocarbon chains of high molecular weight are also covalently linked to some furan resin structures surviving carbonisation. Structure conservation on carbonising extends to furanic structures derived by the self-condensation of furfuryl alcohol which are integral part of the total network. Some complex, three-dimensional structures derived by the rearrangement to polyaromatic hydrocarbons of polyflavonoid tannins, constituted of aromatic benzene and furan rings, and some formaldehyde-derived methylene bridges appear to be formed. The fragments observed are fragments of the continuous network formed and converted by carbonisation. MALDI-TOF appears to be a suitable method for examining oligomer residues present in carbonised complex polycondensation polymer networks and it appears to be capable of determining aspects of the structure and characteristics of complex solids which are too difficult to determine by other techniques.     

Online solid‐phase extraction with high‐performance liquid chromatography and mass spectrometry for the determination of five tannins in traditional Chinese medicine injections

A rapid analytical method based on online solid‐phase extraction with high‐performance liquid chromatography and mass spectrometry has been established and applied to the determination of tannin compounds that may cause adverse effects in traditional Chinese medicine injections. Different solid‐phase extraction sorbents have been compared and the elution buffer was optimized. The performance of the method was verified by evaluation of recovery (≥40%), repeatability (RSD ≤ 6%), linearity (r² ≥ 0.993), and limit of quantification (≤0.35 μg/mL). Five tannin compounds, gallic acid, cianidanol, gallocatechin gallate, ellagic acid, and penta‐O‐galloylglucose, were identified with concentrations ranging from 3.1–37.4 μg/mL in the analyzed traditional Chinese medicine injections.     

Characterization of thermally assisted hydrolysis and methylation products of polyphenols from modern and archaeological vine derivatives using gas chromatography-mass spectrometry

If some ceramics, such as vinary amphorae attest the consumption and trade of wine in the Roman world, the first wine productions in Occident often stay undocumented. Chemical analysis of organic materials preserved in archaeological vessels is the only way to bring new lights about the elaboration and the consumption of this fermented beverage. To determine the preservation state of wine and other grape derivatives residues, we proceeded to in situ tetramethylammonium hydroxide (TMAH) treatment followed by thermally assisted hydrolysis and methylation—gas chromatography—mass spectrometry (THM-GC-MS). The objectives of the study were (i) the understanding of the pyrolytic mechanisms of proanthocyanidins and (ii) the assessment of the usefulness of thermochemolysis for the identification of phenolic markers from polymeric solid deposit in modern wine bottle and Roman amphorae. THM-GC-MS was revealed to be an efficient method for the characterization of fruit derivatives even if mixed with another organic material, such as pitch used to ensure the watertightness of the ceramic container. The preservation of tannins during millennia in archaeological context is here enlightened for the first time by using analytical pyrolysis. The proposed identification of vinary residues is now based on the detection of the association of more than 30 pyrolytic markers derived from di- and trimethoxylated benzenoid compounds. THM-GC-MS represents a new method for the rapid detection of wine traces in ancient ceramics, adapted to tiny samples (<0.1 mg), allowing to precise the role and function of pottery during antiquity.     

Flow nephelometric analysis of protein-tannin interactions

The interaction of tannins from different sources (grape skin, grape seed and wine) with bovine serum albumin (BSA) was studied using a continuous flow method with nephelometric detection. The tannin samples were mixed in a reaction chamber with increasing BSA concentration and the resulting tannin-BSA insoluble aggregates passed through a flow cell where the turbidity was monitored. Based on this technique, the tannin specific activity (TSA) of wine can be directly determined from different wine flows without previous dilutions or any other treatment. The maximum amount of insoluble aggregates formed with BSA and wine or grape skin tannins seemed to remain constant even with the addition of an excess of protein, whereas a decrease in the amount of insoluble aggregates with an excess of BSA was observed in the case of grape seed tannins. It should be noted that BSA was used in these experiments as a model protein and only as an analytical reagent since bovine additives are not allowed in wine.