Process research of macroporous resin chromotography for separation of N-(p-coumaroyl)serotonin and N-feruloylserotonin from Chinese safflower seed extracts

N-(p-Coumaroyl)serotonin (CS) and N-feruloylserotonin (FS) are two bioactive serotonin derivatives in safflower (Carthamus tinctorius L.) seeds with many biological effects. In the present study, the sorption and desorption characteristics of six widely used macroporous resins, coded D312, 860021, DM131, HZ801, AB-8 and XDA-1, respectively, is critically evaluated and compared for enrichment and preparative separation of CS and FS. Static adsorption and desorption experiments on these resins showed that XDA-1 had the best adsorption and desorption equilibrium for CS and FS, and its adsorption equilibrium fits the best to the Langmuir isotherm. Dynamic adsorption and desorption experiments on XDA-1 resin packed column were conducted to establish the optimum parameters as: CS and FS concentration in sample solution 0.346 and 0.276 mg/mL, respectively, sample size 5-bed volumes (BV), sample flow rate 2 mL/min, temperature 25 °C (for adsorption); eluent 80% ethanol, 11 BV, flow rate 1 mL/min (for desorption). After one run of adsorption and desorption, the contents of CS and FS were increased from 2.01%, 1.67% to 24.1% and 22.4%, and the recoveries were 77.2% and 68.5%, respectively. The chromatographic process optimized in the present work is a promising basis for large scale preparation of CS and FS upon further scaling up tests.     

大孔吸附树脂纯化芹菜黄酮的研究

研究6种大孔吸附树脂对芹菜黄酮类物质的吸附和解吸性能,筛选出吸附率较高的XAD-16树脂,并对XAD-16树脂静态吸附和动态吸附解吸工艺做了研究。优化出XAD-16树脂纯化芹菜黄酮的最佳工艺参数为：室温下吸附;上样流速4 BV/h,在上样浓度0.55 mg/mL下,上样体积为15倍柱床体积;洗脱溶剂采用体积分数50%的乙醇,洗脱流速为6 BV/h,洗脱液量为4倍柱床体积。     

Large-Scale Preparative Isolation of Rosavin from Rhodiola rosea via Ion Liquids MAE and Subsequent Flash Adsorption Chromatography

Rosavin was a major active compound from Rhodiola rosea. It is known that it possesses stimulant, antidepressant, and anticancer properties. In the present study, a two-step flash column chromatography has been developed for the large-scale preparative separation and purification of rosavin from the extracts of Rhodiola rosea, which were obtained by microwave assisted extraction (MAE) using ion liquids (ILs) as extraction solvent under the optimized conditions (microwave power 1200 W, extraction time 6 min, solid-liquid ratio 1:20, microwave temperature 120°C) resulting from the analysis of the D-optimal design. In the first separation, the Rhodiola rosea extract was loaded into polyamide and HPD-200 macroporous resin flash columns in series for efficient enrichment of rosavin. In the second one, the rosavin-rich crude sample after the serial column chromatography was subjected to final purification by silica gel flash chromatography. After the two-step separation, 529.1 mg of rosavin was obtained at a purity of 98.2% and a recovery of 60.6%. The separation process can provide a new method for large-scale separation and purification of rosavin for its pharmaceutical and practical use.     

藤茶多酚分离纯化及其对口腔变形链球菌抑制作用研究

采用Folin-Ciocaileu比色法测定藤茶多酚质量浓度,计算吸附率和洗脱率,比较5种不同性质大孔树脂对藤茶多酚静态吸附和解吸的影响,优选出HPD-100型树脂。进一步通过单因素试验得到藤茶多酚分离纯化的优选工艺条件为:上样液藤茶多酚粗提物质量浓度2.4 g/L、流速2.0 BV/h、体积6.5 BV;洗脱剂乙醇体积分数60%、流速3 BV/h、体积7.5 BV。在此条件下,经大孔树脂处理后藤茶多酚质量分数由29.9%提高到69.8%。抑菌试验表明,经大孔树脂处理后的藤茶提取物具有显著抑制口腔变形链球菌生长的作用,其最低抑菌浓度为3.13 g/L。     

Preparative enrichment and purification of nevadensin from Lysionotus pauciflorus using macroporous resins

An efficient method using macroporous adsorption resins for preparative enrichment and purification of nevadensin from Lysionotus pauciflorus Maxim was developed. The results indicated that non-polar HPD-100 resin offered the best adsorption and desorption performance, its adsorption data were well-fitted to the Freundlich isotherm and the pseudo-second-order kinetics model. Dynamic adsorption and desorption experiments have been investigated for optimization of chromatographic parameters. Through one cycle of dynamic adsorption/desorption, the purity of nevadensin in the extract, increased about 8.82-fold from 8.58% to 75.70%, with a recovery yield of 69.90%. The results suggested that HPD-100 resin can separate nevadensin effectively from plant material.     

Enrichment and Purification of Total Chlorogenic Acids from Tobacco Waste Extract with Macroporous Resins

In the present study, an evaluation was conducted on the performance and separation characteristics of nine macroporous resins for the enrichment and purification of total chlorogenic acids from tobacco (Nicotiana tobaccum L.) waste extracts. Based on the results, XAD-4 offered higher adsorption and desorption capacities for total chlorogenic acids than other resins. To optimize the separation process of total chlorogenic acids, a column packed with XAD-4 resin was used to perform dynamic adsorption and desorption tests. The results show that the highest purity of the total chlorogenic acids product was 89.27% when optimum parameters for the adsorption process packed with the XAD-4 resin were as follows: flow rate 3.6 BV/h, pH 3.0; for desorption: ethanol–water (40:60, v/v) used as eluent, flow rate 3.6 BV/h, respectively. Therefore, the XAD-4 resin revealed a good ability to enrich and purify total chlorogenic acids. The method developed will provide a potential approach for the large-scale separation and purification of chlorogenic acid in pharmaceutical applications as a medical intermediate or a material for traditional Chinese medicine.     

大孔树脂富集多舌飞蓬总咖啡酸酯的工艺研究

摘要：考察了13种不同极性的大孔树脂对多舌飞蓬中总咖啡酸酯的富集纯化能力,发现极性树脂NKA-2的静态吸附率为92.51%、解吸率为98.51%,明显优于其他树脂。进一步以NKA-2极性树脂对多舌飞蓬总咖啡酸酯进行静态吸附与动态吸附实验,结果表明,最佳上样质量浓度为300 g/L,最佳上样流速为2 BV/h,树脂吸附容量为6 mL/g,即单位NKA-2树脂可以处理1.8 g生药。解吸实验结果表明,体积分数为60 %的乙醇溶液更有利于多舌飞蓬总咖啡酸酯的洗脱,用量为8 BV。用上述条件对多舌飞蓬总咖啡酸酯富集纯化,使总咖啡酸酯的纯度由18.09 %提高到58.06 %,回收率高达94.78 %。说明NKA-2型大孔吸附树脂综合性能良好,可用于多舌飞蓬中总咖啡酸酯成分的富集和纯化。     

大孔树脂纯化萼翅藤总黄酮工艺

筛选纯化萼翅藤总黄酮的最佳树脂,并对影响这种树脂分离的主要因素进行研究,确定大孔树脂纯化总黄酮的最佳工艺参数。选择4种大孔树脂分别对萼翅藤总黄酮进行静态与动态吸附性能研究,考察影响分离的各种因素如上样液pH值、上样液质量浓度、上样量和洗脱剂体积分数等。HPD-450树脂分离效果最好,Langmuir等温吸附模型较Freundlich模型更适宜描述树脂对萼翅藤总黄酮的吸附,其吸附分离萼翅藤总黄酮的最佳工艺为:上样液pH值为5,质量浓度为0.6—0.8 mg/mL,上样量为3 BV(树脂床体积),洗脱液为体积分数70%的乙醇,洗脱剂用量为3 BV。经HPD-450树脂吸附分离后,总固物中总黄酮质量分数从20.23%提高到75.86%,纯度提高了3倍多,回收率为62.65%。     

大孔树脂法分离纯化申嗪霉素的工艺研究

通过大孔吸附树脂对申嗪霉素发酵滤液静态吸附和解吸试验,从6种大孔吸附树脂中筛选出分离纯化申嗪霉素最优的树脂,考察了该树脂对申嗪霉素的静态、动态吸附与解吸性能并对吸附与洗脱的最佳条件进行了研究。结果表明:AB-8树脂对申嗪霉素有很好的吸附和解吸性能,其最优的动态吸附工艺条件为:上样液浓度3 000μg/mL,上样量4 BV,上样流速2 BV/h;最优的解吸条件为:洗脱剂为80%乙醇溶液,洗脱液用量3 BV,洗脱流速1 BV/h。在此优化条件下,申嗪霉素的吸附率、解吸率、收率、纯度的平均值分别达到(90.33±0.14)%、(90.87±0.12)%、(82.1±0.1)%和(90.74±0.14)%(n=5)。     

大孔吸附树脂分离纯化马缨丹总黄酮的工艺研究

探讨大孔吸附树脂纯化马缨丹总黄酮的最佳工艺,通过对4种型号大孔树脂的静态实验,筛选出最佳树脂;考察最佳树脂对马缨丹总黄酮的吸附及洗脱性能,优化工艺参数。结果表明:AB-8为最佳树脂,其最佳工艺条件为:上样液质量浓度0.198 mg/mL,吸附流速为2.0 mL/min,吸附pH为4.0;洗脱剂为70%乙醇,洗脱用量5 BV,减压浓缩得马缨丹总黄酮浸膏,纯度为32.45%。     

大孔树脂对茶皂素的动态吸附工艺优化

以60％的粗茶皂素为原料,考察了不同大孔树脂对茶皂素的纯化效果,确定用A型树脂进行纯化。研究得出较佳动态吸附一脱附优化工艺为：乙醇浓度50％、上样液浓度30mg／mL、上样液流速1BV／h：洗脱液浓度80％、洗脱剂用量1．75BV、洗脱液流速为1BV／h。在此条件下树脂对茶皂紊的吸附率为96．07％,洗脱率达90．23％,所得茶皂素的纯度达88.90％。     

Purification of Soybean Phosphatidylcholine Using D113-III Ion Exchange Macroporous Resin Packed Column Chromatography

Ten ion-exchange resins were compared for their abilities to separate soybean phosphatidylcholine (PC). D113-III resin was selected for PC purification among ten resins tested. The optimum PC adsorption conditions were: concentration of PC solution, 3 mg/mL; pH of PC solution, 7.5; and adsorption flow rate, 1 mL/min. The optimum PC desorption conditions were: eluent, 95% ethanol aqueous solution; and elution flow rate, 1 mL/min. Under these conditions, the PC content in the product and the amount of product were 94 and 80% (wt.%), respectively, and the D113-III resin was able to be used at least six times for purifying PC. The adsorption and desorption characteristics were also studied.     

Enrichment and Purification of Syringin, Eleutheroside E and Isofraxidin from Acanthopanax senticosus by Macroporous Resin

In order to screen a suitable resin for the preparative simultaneous separation and purification of syringin, eleutheroside E and isofraxidin from Acanthopanax senticosus, the adsorption and desorption properties of 17 widely used commercial macroporous resins were evaluated. According to our results, HPD100C, which adsorbs by the molecular tiers model, was the best macroporous resin, offering higher adsorption and desorption capacities and higher adsorption speed for syringin, eleutheroside E and isofraxidin than other resins. Dynamic adsorption and desorption tests were carried out to optimize the process parameters. The optimal conditions were as follows: for adsorption, processing volume: 24 BV, flow rate: 2 BV/h; for desorption, ethanol-water solution: 60:40 (v/v), eluent volume: 4 BV, flow rate: 3 BV/h. Under the above conditions, the contents of syringin, eleutheroside E and isofraxidin increased 174-fold, 20-fold and 5-fold and their recoveries were 80.93%, 93.97% and 93.79%, respectively.     

大孔吸附树脂分离纯化猪毛菜总黄酮及其抗氧化活性

采用不同大孔吸附树脂分离纯化猪毛菜总黄酮,并对纯化后的总黄酮进行体外抗氧化活性测试。通过考察影响树脂静态和动态吸附与洗脱的主要因素,确定猪毛菜总黄酮分离纯化优化工艺条件。静态吸附实验表明,AB-8树脂分离纯化效果较好,并且吸附符合Langmuir和Freundlich方程。动态吸附和解吸的最佳工艺条件为:上样液质量浓度1.25 g/L、p H=4.5、上样流速2 m L/min、上样量2.5 BV(BV指树脂柱内装载树脂的体积)、洗脱剂为体积分数80%的乙醇溶液、洗脱流速1.0 m L/min,洗脱剂用量4 BV。所得洗脱液中黄酮质量分数从纯化前10.20%增加到纯化后51.89%,回收率为84.43%。体外实验表明,纯化后的黄酮可以清除羟自由基和超氧阴离子自由基,并有较好的还原力。纯化后的黄酮可以作为一种潜在的天然抗氧化剂。     

大孔吸附树脂纯化化香树果序总黄酮工艺研究

以吸附量和解吸率为指标对9种大孔吸附树脂进行对比,H-327B是分离纯化化香树总黄酮的理想树脂;热力学、动力学研究表明,Langmuir模型描述化香树果序黄酮在大孔树脂上的吸附规律更为适宜,该吸附属单分子层吸附,提高温度有利于吸附的进行,吸附过程可自发进行;对吸附?解吸工艺条件优化研究表明:当上样质量浓度为8.9 mg/mL、流速为3 BV/h时,H-327B型树脂对化香树果序总黄酮的吸附量较大。采用体积分数90%乙醇水溶液进行洗脱时,用5 BV乙醇洗脱,解吸率达到65%。     

大孔树脂纯化栾树叶多酚工艺研究

以栾树叶多酚提取物为原料,比较了7种大孔树脂对栾树叶多酚的静态吸附与解吸效果,结果表明AB-8树脂性能最佳,其24h静态吸附量为13.74mg/g,解吸率为98.35%,3h内达到吸附平衡与解吸平衡。AB-8树脂动态吸附较佳条件为上样液质量浓度为4g/L,上样液pH值为6,在此条件下吸附率为88.21%,动态洗脱较佳条件为洗脱剂乙醇体积分数为60%,洗脱速度为1mL/min,解吸率达到89.91%,在该条件下栾树叶总多酚经AB-8树脂纯化后,质量分数由50.36%增加到72.37%,回收率为86.83%。     

大孔树脂法分离纯化阿维菌素工艺研究

研究了大孔树脂分离纯化阿维菌素的工艺。采用HPLC检测方法,从7种大孔树脂中筛选出吸附阿维菌素性能最好的树脂并优化其吸附和洗脱参数。结果表明,采用大孔树脂HZ816吸附阿维菌素的效果最佳,其动态吸附量为62mg·mL^-1,在吸附流速为1．5～2BV·h^-1、90％乙醇作为洗脱剂的优化条件下,解吸收率大于90％、阿维菌素中B1a含量大于91％、总收率大于65％。该阿维菌素分离纯化方法工艺简单。分离效果好,适于工业化生产。     

树脂吸附法处理高浓度邻甲酚工业废水研究

对邻甲酚含量1.992 g/L,COD值高达15 568.4 mg/L,pH约为2的含酚废水进行处理,确定N3520树脂为最佳吸附剂,最佳处理条件为:温度为室温;流速4 BV/h,最大处理量为26 BV,经吸附法处理后,吸附流出液中邻甲酚含量<0.5 mg/L,邻甲酚去除率>99%,COD去除率为97.6%。树脂采用5%NaOH-60%乙醇作脱附剂,最佳脱附条件为:温度40℃,流速1.0 BV/h,用量2 BV。经脱附处理可回收邻甲酚。     

树脂法精制蜂胶高生物活性黄酮醇

考察了5种树脂对蜂胶中的水溶性黄酮醇的吸附和洗脱性能。以质量分数为65%的乙醇为提取剂,提取温度为38℃,以质量分数为60%的乙醇洗脱,通过比较吸附量、洗脱率以及所得水溶性黄酮醇的含量,最后得出以V(D4020)∶V(聚酰胺)=2∶1的混合型树脂为最佳选择。采用该种树脂,水溶性黄酮醇的最大吸附量为32.76mg/mL,洗脱率为94.68%,提取率为8.27%。     

Optimization of Sulforaphane Separation from Broccoli Seeds by Macroporous Resins

Abstract

In this study, the adsorption and desorption properties of sulforaphane on macroporous resins (HP20, SP207, SP850, and HP2MGL) were investigated. Analysis revealed that SP850 resin was most effective in the separation of sulforaphane. The equilibrium experimental data obtained at different temperatures were well fitted to the Langmuir and Freundlich isotherms. To optimize the separation process, dynamic adsorption and desorption tests were performed with a column packed with SP850 resin. The results showed that the optimum parameters for adsorption were as follows: flow rate: 5 BV/h, pH 2, temperature: 25°C; for desorption: ethanol–water (40:60, v/v), 6 BV as an eluent, flow rate: 6 BV/h. The highest purity of sulforaphane product was 85.9%, i.e., 107‐fold higher than those in broccoli seeds through one run treatment on the column packed with SP850 resin under normal conditions. This indicated the high efficiency of SP850 resin in separating sulforaphane.