树脂法分离纯化倒提壶生物碱的研究

采用阳离子交换树脂和大孔吸附树脂联用的方法,将倒提壶生物碱提取液依次经过阳离子交换树脂和两次大孔吸附树脂,对其中的天芥菜碱和毛果天芥菜碱进行分离纯化。结果表明,倒提壶生物碱溶液采用阳离子交换树脂经过水洗和NaCl洗脱与大孔吸附树脂两次经乙醚和50%乙醇洗脱后,毛果天芥菜碱与天芥菜碱的纯度分别从0.73%和2.2%提高至81.6%和79.2%,提取量分别由4.6 mg/g和10.7 mg/g提高至50.6mg/g和92.7 mg/g。该文所建立的分离纯化方法具有成本低、污染小、周期短、操作简便和分离纯化效率高等特点,适合工业化生产。     

大孔树脂对麻黄细辛附子汤生物碱成分静态吸附及解吸附性能研究

采用高效液相色谱法(HPLC)测定麻黄细辛附子(MXF)汤复方水提液中盐酸麻黄碱、盐酸伪麻黄碱、苯甲酰新乌头原碱、苯甲酰乌头原碱、苯甲酰次乌头原碱含量,考察了4种大孔树脂(HPD–100,HPD–722,HPD–400,HPD–600型)对5种生物碱的静态吸附、解吸附性能,筛选出分离纯化麻黄细辛附子汤中生物碱的最佳树脂。结果显示,HPD–722型树脂对5种生物碱的吸附过程稳定且吸附量大,具有较高的解吸附率(87.26%),优于其它3种树脂。HPD–722型大孔树脂适用于富集麻黄细辛附子汤中的生物碱类化合物。     

SP700大孔树脂纯化酸枣仁中三萜总皂苷的研究

从7种极性不同的大孔树脂中筛选出一种对酸枣仁三萜总皂苷具有良好吸附和解吸性能的树脂—三菱SP700树脂。静态实验中,该树脂的最高吸附容量可达131.0mg皂苷/g树脂,皂苷在树脂表面的吸附符合Langmuir模型,用体积分数为90%的乙醇解吸得率最高可达97.8%;动态实验中,样液在膨胀床模式下上样,树脂的平均动态吸附容量为15mg皂苷/g树脂,上样后,用体积分数分别为50%和90%的乙醇溶液进行分段洗脱,洗脱得率最高可达到95.1%,经过纯化的皂苷提取物的含量提高了4倍。SP700大孔吸附树脂作为一种对酸枣仁中三萜总皂苷进行纯化的介质具有良好的性能和应用价值。     

强酸型离子交换树脂催化吸附制备Valienamine

以阿卡波糖为原料制备α-糖苷酶抑制剂Valienamine,通过对比硫酸、三氟乙酸和强酸型阳离子交换树脂催化水解阿卡波糖的效果,证实强酸型阳离子交换树脂效果最好,并且在催化水解的同时,产物Valienamine生成后即被吸附在树脂上,糖类副产物水洗即可除去;在实验选择的树脂中,以Amberlyst A-15催化活性最强,阿卡波糖水解率可达95.6%,国产001×7树脂水解率虽稍有逊色,但洗脱容易;选择9种大孔吸附树脂分别对Valienamine进行吸附和解析纯化试验,其中H1020型号树脂效果最好,80%甲醇解析效果最好;采用活性炭纯化Valienamine,用量为25mg/g阿卡波穰时,纯化效果最好,本实验条件下得到的Valienamine纯度为98.26%,得率为74.3%.     

大孔吸附树脂分离纯化异甘草素的研究

研究大孔吸附树脂分离纯化异甘草素的工艺条件及参数。通过研究HPD-600、D4020、D101、AB-8、NKA-II、AL-2和NKA-9树脂对异甘草素的吸附和解吸附能力,筛选最佳树脂为AB-8,并研究了其对异甘草素的吸附和解吸附性能,确定了最佳的吸附与解吸附工艺参数,吸附:pH=5,室温,流速1.5BV/h,溶液处理量为5BV;脱附:洗脱剂为70%的乙醇溶液,流速1BV/h,洗脱剂用量4.5BV。异甘草素样品溶液经AB-8树脂吸附与脱附后回收率为76.7%,纯度由2.02%提高到29.1%,提高了14.4倍。实验结果表明,AB-8树脂对异甘草素的吸附量大,脱附容易,可以应用于异甘草素的分离纯化。     

离子交换树脂对长春花中文多灵、长春质碱和长春碱的富集研究

通过D-113、110、D-151、NKC-9、001x7、D-072、D-062离子交换树脂对长春花中文多灵、长春质碱和长春碱的静态吸附容量、吸附率和解吸率等指标的考察,筛选出最佳树脂为D-151.对文多灵、长春质碱和长春碱的吸附容量分别为118.2mg/mL、102.2mg/mL和2.6mg/mL,并进一步考察其富集长春花3种生物碱的吸附和解吸附性能,确定了最佳的工艺条件和参数.吸附:上样溶液浓度为0.41mg生药/mL, pH为6.0,流速为3mL/min;解吸附:洗脱剂为20%乙醇除杂,90%乙醇(含2%氨水)洗脱.结果表明,经D-151离子交换树脂富集的长春花总生物碱中文多灵、长春质碱和长春碱的含量分别提高到34.53%、22.31%和5.86%,比传统溶剂萃取方法分别提高了2.34、3.49和2.07倍,回收率均在90%以上,D-151离子交换树脂可以用来富集长春花中的生物碱成分.     

加速溶剂萃取-高效液相色谱-电喷雾飞行时间质谱联用分析莲子心中生物碱

建立了加速溶剂萃取-高效液相色谱-电喷雾飞行时间质谱(ASE-HPLC-DAD-ESI-TOF/MS)联用技术分析莲子心中生物碱类化合物的方法。采用ASE法对药材进行提取,萃取温度为100℃,压力为9646kPa,时间为10min。采用HPLC-DAD-ESI-TOF/MS联用技术对其中的化学成分进行了分离鉴定,HPLC采用AgilentEclipseXDB-C18色谱柱;流动相为0.1%三乙胺溶液,用氨水调pH=8.0(A),色谱纯乙腈(B),梯度洗脱;进样量为20μL,流速:1.0mL/min;检测波长:282nm。ESI-TOF/MS采用正离子电离模式,毛细管电压:4500V;喷雾气压:310.05kPa;干燥气(N2)流速:10.0L/min;干燥气温度:350℃,破碎电压:150V。鉴定了其中的6种生物碱分别为:前荷叶碱、莲心季铵碱、莲心碱、异莲心碱、荷叶碱和甲基莲心碱。     

胺基修饰的高度交联聚苯乙烯树脂对间苯二酚吸附行为研究

研究了AH系列胺基修饰的超高交联树脂对水溶液中间苯二酚的静态吸附行为特征,结果表明,它们对间苯二酚的吸附容量明显高于母体交联树脂NDA-100和大孔弱碱性阴离子交换树脂D301.AH系列树脂与吸附质分子之间不仅有范德华作用力,还存在着氢键等作用力.该类树脂对间苯二酚的吸附为自发的放热过程,属于以物理作用为主兼有弱化学作用的吸附过程.吸附速率符合准一级动力学方程,表观吸附速率常数随树脂胺基含量的升高而降低.     

基于Donnan膜效应的树脂基水合氧化铁的制备及对砷的吸附性能研究

以大孔强碱性离子交换树脂D201为载体, 利用FeCl₃-HCl-NaCl溶液特有的性质制备出一种基于Donnan膜效应的新型树脂基水合氧化铁D201-HFO. 研究结果表明, D201-HFO对砷的吸附容量较美国同类专利产品ArsenX有较大提高, 同时该材料表现出对砷良好的吸附选择性和吸附动力学性能. 固定床吸附结果表明, 通过D201-HFO的吸附处理, 受污染水体中砷的含量可降至10 μg/L(我国生活饮用水新标准GB5749-2006)以下, 吸附后的D201- HFO可被NaOH-NaCl溶液彻底再生. 稳定性实验表明, HFO在D201树脂孔道内较为稳定, D201-HFO是一种性能优良、具有广泛应用前景的除砷吸附剂.     

大孔阳离子交换树脂对井冈霉素的吸附研究

比较了5种大孔树脂与常用的001×4凝胶树脂对井冈霉素的静态和动态吸附的性能实验,并选择了其中几种有代表性的树脂,研究其对井冈霉素的吸附特性及其机理.采用正交试验筛选出具有较大吸附量的大孔强酸性阳离子树脂HD-8,并对其工艺条件进行了优化,其较优吸附能力为15.34mg/ml树脂h;同时考察了HD-8树脂的解吸行为,发现用1mol/L的氨水:80%乙醇=1:1洗脱率为98.8%,洗脱效果明显.     

ISOLATION AND PURIFICATION OF ALKALOIDS FROM PLUMULA NELUMBINIS BY DOUBLE-COLUMN ADSORPTION CHROMOTOGRAPHY

The performance of adsorption and separation for liensinine, isoliensinine and neferine was studied by double-column adsorption chromatography using macroporous adsorption and cation exchange resins. The alkaloid extract with 49.2% total contents by mass representing 10.6% liensinine, 10.6% isoliensinine and 28.0% neferine respectively was prepared by D72 cation exchange resins, in which most of the impurities were water-soluble alkaloids. Furthermore, the alkaloid extract with 82.6% total contents by mass containing 33.1%, 15.0% and 34.5% of the three adsorbates respectively was prepared by double-column adsorption chromatography using AKS-W macroporous adsorption and D72 cation exchange resins. As a result, the content of single and total alkaloids has been greatly increased by the double-column adsorption chromatography.     

Fragmentation study on the phenolic alkaloid neferine and its analogues with anti-HIV activities by electrospray ionization tandem mass spectrometry with hydrogen/deuterium exchange and its application for rapid identification of in vitro microsomal metabolites of neferine

The application of mass spectrometry in drug discovery, especially in drug metabolites, is very important. This present paper is at first focused on the elucidation of fragmentation patterns of the phenolic bisbenzyltetrahydroisoquinoline alkaloid, neferine, together with its analogues isoliensinine and liensinine with anti-HIV activities using electrospray ionization tandem mass spectrometry (ESI-MS/MS) and hydrogen/deuterium (H/D) exchange. All title compounds displayed major diagnostic fragments that formed by the cleavage of the C1'--C9' bond resulting in positive group CD, and the loss of 4-ethyl-1-phenol or 4-ethyl-1-methoxybenzene following rearrangements. Their ESI-MS/MS spectra also showed the relatively stable fragment ions formed by the elimination of H2O, CH3NH2, CH3OH, and CH3-N==CH2. Secondly, the metabolites of neferine from dog hepatic microsomal incubations were analyzed and characterized by high-performance liquid chromatography (HPLC) and data-dependent ESI-MS/MS. Based on fragmentation patterns and compared with their retention times in LC, molecular weights and ultraviolet (UV) absorbances with standard compounds, six metabolites were identified as isoliensinine, liensinine and four novel bisbenzyltetrahydroisoquinoline alkaloids named as 6-O-desmethylneferine, 2'-N-desmethylneferine, 2'-N-6-O-didesmethylneferine, and 6,13-O-didesmethylneferine. All metabolites were desmethyl or didesmethyl products of neferine. The possible metabolic pathways for neferine have been proposed. The results suggest that N-demethylation and O-demethylation are two important metabolic pathways of neferine in dog hepatic microsomal incubations. This is critical for screening and development of phenolic bisbenzyltetrahydroisoquinoline alkaloids with anti-HIV activities such as neferine and its analogues isoliensinine and liensinine.     

Preparative counter-current chromatography isolation of liensinine and its analogues from embryo of the seed of Nelumbo nucifera GAERTN. using upright coil planet centrifuge with four multilayer coils connected in series

Preparative counter-current chromatography (CCC) isolation of liensinine and its analogues, isoliensinine and neferine from embryo of the seed of Nelumbo nucifera GAERTN. has been successfully performed for the first time using upright coil planet centrifuge with four multilayer coils connected in series with 1600 mL capacity. Two kinds of two-phase solvent systems were applied to preparative CCC isolation. The first was the system composed of light petroleum (b.p. 60-90 degrees C)-ethyl acetate-tetrachloromethane-chloroform-methanol-water (1:1:4:4:6:2, v/v) which was very suitable for fast and small-scale CCC isolation. The second was the system composed of ethyl acetate-tetrachloromethane-methanol-water (1:6:4:1, v/v), which was the optimum for large-scale CCC isolation. Using the first system, 1102 mg of the crude alkaloid was purified in one-step separation of 150 min, yielding 350 mg neferine, 100 mg isoliensinine and 95 mg liensinine with over 95% purity. While using the second solvent system, 5850 mg of the crude alkaloid was purified in one-step separation of 9 h, yielding 2545 mg neferine, 698 mg isoliensinine and 650 mg liensinine with over 97% purity. Structures of the compounds were identified by electrospray ionization multiple mass spectrometry, one- and two-dimensional NMR.     

Preparative separation and purification of liensinine,isoliensinine and neferine from seed embryo of Nelumbo nucifera GAERTN using high‐speed counter‐current chromatography

A preparative high‐speed counter‐current chromatography method for separation and purification of liensinine, isoliensinine and neferine from seed embryo of Nelumbo nucifera GAERTN was successfully established by using n‐hexane‐ethyl acetate‐methanol‐water (5:8:4:5, v/v, containing 0.5% NH₄OH) as the two‐phase solvent system. From 200 mg of crude extract, 18.4 mg of liensinine, 19.6 mg of isoliensinine and 58.4 mg of neferine were obtained with the purity of 96.8, 95.9, and 98.6%, respectively. The identification of the three alkaloids was performed with ¹H NMR and ¹³C NMR.     

Bisbenzylisoquinoline Alkaloids from Nelumbo nucifera

From the embryos of the seeds of Nelumbo nucifera, three bisbenzylisoquinoline alkaloids, nelumboferine and nelumborines A and B, were isolated along with four known compounds, neferine, liensinine, isoliensinine and anisic acid. The structures of the new alkaloids were determined mainly by spectroscopic methods.     

Zn2＋型磺酸树脂对维生素B12的配位吸附及洗脱性能

原位吸附;分离;Zn2＋型磺酸树脂对维生素B12的配位吸附及洗脱性能     

A new bisbenzylisoquinoline alkaloid from Plumulanelumbinis

One new bisbenzylisoquinoline alkaloid, neferine N-oxide(1), along with three known compounds,neferine(2), liensinine(3), and isoliensinine(4), were isolated from Plumulanelumbinis – the embryo of the seed of Nelumbonucifera. Their structures were elucidated by extensive spectroscopic analysis(MS,UV, IR, NMR), and the absolute configurations were determined by experimental circulardichroism(CD)spectra. Compound 1 is a new naturally occurring bisbenzylisoquinoline alkaloid with an N-oxide functionality, and the CD spectrum of(1R, 1'R) neferine is first reported. The antioxidant activities of compounds 1–4 were evaluated using the ORAC assay, which illustrated that all these compounds showed the different levels of oxygen radical absorbance capacity.     

大孔树脂分离纯化丹酚酸的研究

比较了D301R、D392、D380大孔阴离子交换树脂和X-5.AB-8、NKA-9、SP825大孔吸附树脂对丹参水溶性成分的吸附和解吸能力,筛选出效果较好的SP825进行分离纯化丹酚酸的研究.实验表明,大孔吸附树脂SP825能分离出纯度为95.32%的丹参素,在梯度洗脱条件下可得到以丹参素(水洗脱)和丹酚酸B(乙醇洗脱)为主的产品.在最佳吸附与解吸工艺参数下,丹参素、紫草酸、迷迭香酸、丹酚酸A和丹酚酸B的收率分别为:36.92%、80.39%、82.45%、43.07%和41.03%.     

大孔吸附树脂对辣椒素类物质的富集

辣椒;辣椒素;辣椒素类物质;吸附树脂;分离     

SYNTESIS OF THE COMPLEXES OF MACROPOROUS SULFONATED RESINS WITH FERRIC CHLORIDE AND THEIR CATALYTIC BEHAVIOR FOR SETERIFICATION OF ACETIC ACID WITH BUTANOL

The complex resins prepared from macroporous sulfonated resin D72(H^+ form) with ferric chloride or ferric chloride hexahydrate have both sites of Bronsted acid and Lewis acid.In the catalysis of exterification of acetic acid with butanol the complex resins show to have much higher catalytic activity than that of its matrix.a conventional sulfonated cation exchange resin D72.