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.     

Preparative Separation of Glabridin from Glycyrrhiza glabra L. Extracts with Macroporous Resins

Abstract

In the present study, the performance and adsorption characteristics of five macroporous resins for the separation of glabridin from Glycyrrhiza glabra L. have been evaluated. The adsorption and desorption properties of glabridin on macroporous resins including HPD100, HPD300, HPD800, NKA and H103 were compared. HPD100 resin offered the best adsorption and desorption capacities based on the research results. Both Langmuir and Freundlich isotherms were used to describe the interactions between the solutes and resins at different initial concentrations. Dynamic adsorption and desorption experiments on HPD100 resin packed column were conducted to optimize the separation process of glabridin from licorice extracts. After the treatment with stepwise elution on HPD100 resin, the content of glabridin in the product increased from 0.21% to 32.2% which is 153-fold higher than it in G. glabra L. roots and the recovery yield was 79.7%. The results indicated the good ability of HPD100 resin for separation glabridin and the study may provide scientific references for the large-scale glabridin production from G. glabra L. or other plants extracts.     

Preparation of high purity squalene from soybean oil deodorizer distillate with the combination of macroporous resin and thin-film evaporation coupling distillation

ABSTRACT

In this study, the combination of macroporous adsorbent resins (MARs) and thin-film evaporation coupling distillation (TFECD) was studied systematically, with aim to obtain high value-added squalene from soybean oil deodorizer distillate (SODD). Five types of resins (X-5, D-101, D4020, DM301, and AB-8) were first used to evaluate the adsorption/desorption properties of squalene. D101 resin exhibited higher adsorption/desorption capacities and desorption ratios for squalene based on static adsorption results among the tested resins. We further investigated the adsorption kinetics, isotherms, and thermodynamics with D101 resin as adsorbent. The adsorption of squalene on D101 was best fitted to pseudo-second-order kinetic model and the Langmuir equation. The dynamic adsorption and desorption indicated that similar results were observed in the static adsorption test. The purity of squalene was increased from 7.5 to 82.5% with the recovery up to 88.5% after separation on D101 column. The resin-refined sample was directly subjected to TFECD purification. Under optimized process parameters, the final product with purity of 98.5% and recovery yield of 76.5% was confirmed by high-performance liquid chromatography (HPLC) analysis. The present study provided an effective method for large-scale production of high purity squalene.     

Separation of salidroside from the fermentation broth of engineered Escherichia coli using macroporous adsorbent resins

Salidroside (8-O-β-D-glucoside of tyrosol), a plant-derived natural product, is used for treatment of hypoxia, fatigue and aging diseases. The availability of salidroside is restricted since it is extracted from 3-5 years old Rhodiola roots, which grow very slowly in the cold region of northern hemisphere of Earth. Our laboratory has constructed an engineered Escherichia coli and established a fermentation process to produce salidroside from glucose. In this article, nine macroporous resins from polarity to non-polarity, including NKA-9, S-8, AB-8, SP825, D101, LSA-8, LX-12, LX-18 and LX-68 resins, were tested to separate salidroside from fermentation broth. After static and dynamic experiments, the weakly polar SP825 resin had a better separation efficiency among nine resins. The adsorption kinetic and isotherm of salidroside on the SP825 resin were determined, and the pseudo-second-order kinetic model and Langmuir model could be fitted well. The effects of the pH on adsorption and ethanol concentration on desorption were investigated, and an optimal separation process was established. The adsorption for salidroside in the SP825 resin column was conducted with loading 150 ml at pH 7, and desorpted by washing 50 ml of 80% ethanol solution. Under the best process conditions, the purity and yield of salidroside in the final product were 91.6% and 74.0%, respectively. The results showed that the macroporous SP825 resin would be feasible and effective to prepare salidroside and has promising application in the downstream process of microbial fermentation.     

Separation of sinigrin from Indian mustard (<Emphasis Type="Italic">Brassica juncea</Emphasis> L.) seed using macroporous ion-exchange resin

Sinigrin is a major glucosinolate present in Indian mustard (Brassica juncea L.) seeds as the precursor of the anticancer compound allyl isothiocyanate. In the present study, the adsorption and desorption characteristics of six macroporous ion-exchange resins for the separation of sinigrin from crude aqueous extracts have been compared. The results indicated that D261 resin showed the best adsorption and desorption capacity to sinigrin, and its adsorption data fit best to the Freundlich isotherm. The dynamic adsorption/desorption experiments were carried out to optimize the separation process. After treatment with D261 resin in one run, the purity of sinigrin in the product was increased 15.57-fold from 3.75% to 58.37% with the recovery of 79.82%. Meanwhile, the separation effect of D261 resin was also supported by UV and IR. The separation process using macroporous ion-exchange resin in our paper provides a novel, rapid and economical method for separation of sinigrin.     

H103大孔吸附树脂分离纯化苦参碱与氧化苦参碱的研究

通过对比苦参总碱在九种大孔树脂上的静态吸附,筛选出对苦参总碱吸附能力较强的H103树脂;研究了H103树脂对上述两种生物碱的吸附等温曲线及吸附动力学行为;考察了苦参总碱在H103树脂上的动态吸脱附过程,用薄层色谱法(TLC)对洗脱液跟踪分析,用高效液相色谱法(HPLC)检测苦参碱、氧化苦参碱含量,确定了动态吸脱附的过程参数。结果表明,H103树脂对苦参总碱的等温吸附可采用Freundlich方程描述;由吸附动力学曲线得H103树脂在100 min内达到平衡,具有较快吸附速度,吸附动力学规律可用二级速率方程表示;动态吸脱附过程的洗脱条件为：用30%乙醇-25%氨水（115:1,v/v）,80%乙醇梯度洗脱,氧化苦参碱先被洗脱,苦参碱随后,两种生物碱可达到很好的分离,经计算苦参碱收率为90.1%,氧化苦参碱收率为85.3%。     

H103大孔吸附树脂分离纯化苦参碱与氧化苦参碱

通过对比苦参总碱在9种大孔树脂上的静态吸附,筛选出对苦参总碱吸附能力较强的H103树脂;研究了H103树脂对上述两种生物碱的吸附等温曲线及吸附动力学行为;考察了苦参总碱在H103树脂上的动态吸脱附过程,用薄层色谱法(TLC)对洗脱液跟踪分析,用高效液相色谱法(HPLC)检测苦参碱、氧化苦参碱含量,确定了动态吸脱附的过程参数。结果表明,H103树脂对苦参总碱的等温吸附可采用Freundlich方程描述;由吸附动力学曲线得H103树脂在100 min内达到平衡,具有较快吸附速度,吸附动力学规律可用二级速率方程表示;动态吸脱附过程的洗脱条件为:用体积分数30%乙醇-体积分数25%氨水(体积比115∶1),体积分数80%乙醇梯度洗脱,氧化苦参碱先被洗脱,苦参碱随后,两种生物碱可达到很好的分离,经计算苦参碱收率为90.1%,氧化苦参碱收率为85.3%。     

Preparative Enrichment and Separation of Glycyrrhetinic Acid Monoglucuronide from Fermentation Broths with Macroporous Resins

Preparative enrichment and separation of Glycyrrhetinic acid monoglucuronide (GAMG) from the pretreated fermentation broth of glycyrrhizin was studied by using six macroporous resins with different physical and chemical properties. D101 resin showed the maximum effectiveness among the tested resins. The solute affinity towards D101 resin at different temperatures was described in terms of Langmuir and Freundlich isotherms, and the equilibrium experimental data were well-fitted to the two isotherms. The dynamic adsorption and desorption tests were carried out in order to optimize the operational parameters for the efficient separation of GAMG. After one run treatment with D101 resin, the contents of GAMG in the product were increased to 8.2-fold with recovery yields of 93.3%. The process achieved easy and effective enrichment and separation of GAMG with D101 resin, and it could be applied for the large-scale preparation of GAMG from the fermentation broth of glycyrrhizin.     

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。     

H-103树脂处理含酚废水的实验研究

研究了H-103大孔吸附树脂对600~1000 mg/L苯酚水溶液中酚的吸附,考察了初始酚浓度、溶液pH值及温度对吸附性能的影响. 结果表明,在20 min内吸附达到平衡,吸附动力学可用拟二级动力学模型描述. 苯酚在大孔树脂上的吸附等温线很好地符合Langmuir吸附等温方程,在25℃下其饱和吸附量和Langmuir常数分别为86.00 mg/g和0.2719 L/mg.     

大孔树脂对金银花中绿原酸的纯化研究

考察不同型号的大孔吸附树脂对金银花中的绿原酸的提取纯化效果,为进一步开发金银花的相关产品提供参考。采用HPLC法测定绿原酸含量;选用5种不同型号的大孔树采用静态吸附法,筛选出吸附效果和解吸效果较好的大孔吸附树脂;采用动态吸附法,考察大孔树脂的吸附、解吸附性能和纯化效果。NKA-9大孔树脂综合性能最佳,提取液在酸性条件下吸附量最佳。NKA-9大孔树脂对绿原酸的提取纯化效果较好,可用于工业化生产。     

不同大孔树脂吸附-解吸附喜树黄酮性能的研究

采用静态吸附和解吸方法研究了AB-8、D-101、X-5、H-103、YWD-03五种大孔树脂对喜树叶黄酮的吸附与解吸性能,结果表明,AB-8树脂对喜树叶黄酮的吸附分离综合性能最佳,中性条件下其静态吸附率为85.54%,最大解吸率高达98.75%以上。     

大孔吸附树脂对木质素磺酸钠吸附行为研究

考察了3种不同极性的大孔树脂NKA-9、AB-8、H103对木质素磺酸钠的吸附能力,发现极性树脂NKA-9的吸附量大于弱极性和非极性树脂。进一步以NKA-9极性树脂对木质素磺酸钠进行静态吸附和脱附实验,结果表明,低温和酸性条件下有利于吸附,吸附量随着木质素磺酸钠质量浓度的增大而增大,且吸附在180min后达平衡。脱附实验结果表明,甲醇溶液更有利于木质素磺酸钠的洗脱。对脱附样品进行相对分子质量(简称分子量,下同)和官能团分析发现,高酚羟基含量,低羧酸基和低磺酸基含量的木质素磺酸钠分子更容易被极性树脂NKA-9所吸附。     

大孔吸附树脂对沙棘叶总黄酮的吸附性能考察

以吸附值(mg/g)和解吸附率(%)为评价指标,通过静态吸附/解吸附分别考察LSA-40、LSA-21、DM-130、HPD450、D101和XDA-1六种大孔吸附树脂对沙棘叶总黄酮的吸附/解吸附性能。通过动态吸附/解吸附优选沙棘叶总黄酮最佳分离工艺条件。结果表明中极性树脂LSA-21在吸附/解吸附方面显示出最佳的综合性能,对沙棘叶总黄酮的静态吸附值/解吸附率分别为131.78mg/g和55.53%,经静态和动态吸附后得到的总黄酮纯度分别为19.4%和20.3%。     

Preparative separation and purification of rosavin in Rhodiola rosea by macroporous adsorption resins

Rosavin is one of the main bioactive components in Rhodiola rosea L. with known pharmacological effects. In this study, a simple method for preparative separation and purification of rosavin from R. rosea L. was developed with macroporous adsorption resins. The adsorption isotherms and desorption performances of some resins have been determined and compared. Depending on its hydrophobic force, HPD-200 resin, a styrene-divinylbenzene (SDVB) copolymer, offers the best adsorption and desorption properties for rosavin based on the research results, its adsorption data fit best to the Langmuir adsorption model. Dynamic adsorption and desorption was performed on HPD-200 resin packed in a glass column to obtain optimal parameters for the separation of rosavin. The optimum conditions were as follow. The volume, concentration, bed height and flow rate of loading sample were 4 bed volumes (BV), 0.24 mg/mL, 30 cm and 2 BV/h, respectively, at 25 °C; desorption was performed successively with 30% ethanol of 4 bed volumes, 40% ethanol of 2.5 bed volumes and 60% ethanol of 3 bed volumes. After one run treatment with HPD-200, the rosavin content in the product was increased from 0.69% to 11.02% with a recovery of 82.46%. In this case, the process throughout is 1.34 g rosavin/L adsorbent/day, solvent usage is 7.14 L ethanol/g rosavin. The simple purification scheme avoids toxic organic solvent and thus, increases the safety of the process with a potential industrial application prospect.     

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%。     

AB-8大孔树脂对1,2-环己二醇动态吸附性能研究

针对双氧水氧化环己烯合成环氧环己烷的反应体系,采用大孔树脂动态吸附分离反应液水相中的1,2-环己二醇。结果表明,在自行设计吸附柱的基础上,AB-8大孔树脂吸附分离反应液水相中1,2-环己二醇的较佳条件为：上样流速1.0 mL/min,床层高度4.0 cm,常温;通过固定床吸附数学模型得到的速率常数、相关系数、吸附量和动力学参数, 能较好地描述AB-8大孔树脂固定床吸附1,2-环己二醇的吸附动力学。以乙酸乙酯为脱附剂进行脱附较佳条件为：洗脱流速1.0 mL/min,常温;AB-8大孔树脂经5次循环使用后其吸附率和脱附率仍在80％以上。     

大孔树脂分离纯化双脱甲氧基姜黄素的研究

探讨了大孔树脂分离纯化双脱甲氧基姜黄素的最佳工艺。通过考察5种大孔树脂对双脱甲氧基姜黄素的洗脱及纯化性能，确定HZ801树脂为最佳树脂，并优化了该树脂分离纯化双脱甲氧基姜黄素的工艺条件。结果表明，在上样量为1g·100g^-1填料。依次用50％乙醇、80％乙醇、90％乙醇梯度洗脱，异丙醇为结晶溶荆时．可得到纯度大于90％、总收率大于60％的双脱甲氧基姜黄素。