Cu-NIC-TMED富集黄芩中黄芩苷的规律及机理

以烟酸(NIC)为配体制备了金属-有机骨架材料(MOFs)铜-烟酸-四甲基乙二胺配位聚合物(Cu-NICTMED),并将其用于黄芩中黄芩苷的吸附、分离和纯化,建立了一种无毒无害、环境友好、流程简化且效率较高的提取方法.采用溶剂热法合成Cu-NIC-TMED,然后对其进行结构表征,以实现适当的配位及准确合成.研究了Cu-NIC-TMED吸附黄芩苷的规律和机理:该吸附符合准二级动力学方程,平衡吸附数据符合Langmuir吸附等温模型.同时,通过对响应面(RSM)进行优化得到最佳吸附参数.在最佳吸附参数条件下, Cu-NIC-TMED对黄芩中黄芩苷的吸附率高达84.08%,且对黄芩中其它成分的吸附效果微乎其微.使用pH=6.8的磷酸盐缓冲溶液（PBS）作为解吸溶液, Cu-NIC-TMED解吸黄芩苷的解吸率为41.24%,黄芩苷的纯度由吸附前的21.55%提高到解吸后的75.77%, Cu-NIC-TMED在吸附前后具有良好的稳定性,回收率达到78.64%.因此, Cu-NIC-TMED在黄芩苷的吸附纯化中具有应用价值.     

大孔吸附树脂的合成及其对黄芩甙的吸附性能

用吸附树脂纯化分离中药黄芩中的黄苓甙是天然药物研究新技术。但吸附树脂交联聚苯乙烯疏水性强,水相与树脂之间的界面能较大,通过氯甲基化引入极性基团可以改善树脂的吸附性能。本文通过对氯甲基化后的交联聚苯乙烯(氯球)进行后交联以改善树脂孔结构,并通过胺化反应增加树脂的极性和亲水性,研究所合成一系列大孔吸附树脂的碱基含量对黄苓甙的静态吸附性能的影响。     

黄芩素和黄芩苷与人血清白蛋白相互作用的光谱研究

采用荧光光谱、紫外-可见光谱和表面增强拉曼光谱研究了黄芩素和黄芩苷与人血清白蛋白的相互作用, 得到了分子间的结合状态和吸附形态方面的信息. 通过比较黄芩素和黄芩苷的普通拉曼和表面增强拉曼光谱, 确立了黄芩素和黄芩苷的正常构象, 同时考察了结合上人血清白蛋白后不同浓度黄芩素和黄芩苷的吸附方式差别.     

D241树脂分离纯化黄芩总黄酮的研究

本文研究了用241树脂分离纯化黄芩总黄酮的方法和工艺。实验结果表明：D241树脂对黄芩总黄酮的静态交换容量是77mg/ml树脂。在pH11.0、流速2.0BV/h、提取液中总黄酮浓度17.5mg/ml条件下，D241树脂对黄芩总黄酮的动态交换容量为43.8mg/ml。用60％甲醇作为黄芩总黄酮洗脱剂，在PH4.0、洗脱流速1.5BV/h条件下，4．5BV洗脱剂即可完全洗脱被D241树脂交换的黄芩总黄酮。与酸沉淀法相比较，经过除去果胶，总黄酮纯度由33．34％提高到74．9％，粗品收得率由11.52%降低至4.83%；经过D241树脂分离纯化，其纯度达到91.5%，产品收得率3.54%。     

黄芩及其制剂中黄芩素和黄芩甙的

用毛细管区带电泳 -电化学检测法测定了黄芩及其制剂中黄芩素和黄芩甙的含量。研究了电极电位、电解液酸度和浓度、电泳电压及进样时间等对电泳的影响 ,得到了较为优化的测定条件。以直径为300μm的碳圆盘电极为检测电极 ,电极电位为0.90V(vsSCE) ,在100mmol/L硼酸盐缓冲液(pH9.0)中 ,上述两组分在8min内完全分离。黄芩素和黄芩甙浓度与电泳峰电流分别在5.0×10 -7～1.0×10 -3mol/L和1.0×10 -6～1.0×10 -3mol/L范围内呈良好线性 ,检出限分别为2.24×10 -7mol/L和5.48×10 -7mol/L。7次测定分别含5.0×10 -4mol/L黄芩素和黄芩甙试样溶液 ,峰高的相对标准偏差分别为3.53%和4.03%。     

黄芩及其制剂中黄芩素和黄芩甙的毛细管区带电泳—电化学检测

用毛细管区带电泳－电化学检测法测定了黄芩及其制剂中黄芩素和黄芩甙的含量。研究了电极电位、电解液酸度和浓度、电泳电压及进样时间等对电泳的影响,得到了较为优化的测定条件。以直径为300μm的碳圆盘电极为检测电极,电极电位为0.90V(vsSCE),在100mmol/L硼酸盐缓冲液(pH9.0)中,上述两组分在8min内完全分离。黄芩素和黄芩甙浓度与电泳峰电流分别在5.0×10     

黄芩中黄芩苷的亚临界水提取及高效液相色谱分析

建立了黄芩药材中黄芩苷的亚临界水提取 高效液相色谱测定方法。分别考察了温度、压力、提取时间、提取物颗粒度、溶剂比等因素对提取量的影响,并与有机溶剂提取法比较。结果表明,当两者具有相同的提取效果时,亚临界水提取法的提取时间及提取溶剂的消耗量大大减少,避免了使用有机溶剂造成的污染。黄芩苷提取最佳条件为:样品颗粒度80～100目,溶剂比0.2 mL/mg ,5 MPa,130 ℃保持10 min。并通过提取 高效液相色谱联机分析实现了对提取物的实时监测。该技术有望成为从中药材中提取脂溶性成分的有效方法。     

新型胺基修饰的超高交联聚合吸附剂吸附水中酚类化合物的研究

合成了新的胺基修饰的超高交联AH系列吸附树脂．以弱碱树脂D301和超高交联吸附树脂ND100为参照，测定了AH系列吸附树脂吸附水中苯酚、对氯苯酚、对甲苯酚、对硝基苯酚的吸附性能。结果表明：修饰的超高交联吸附树脂对苯酚．对甲苯酚、对氟苯酚的吸附量比ND100和D301更大，而D301树脂对对硝基苯酚有最大的吸附量．提出了AH系列树脂对4种酚类化合物吸附行为的作用机理．     

弱碱HYY树脂对链霉素分离纯化的研究

作者用ＨＹＹ弱碱树脂对链霉素的分离纯化进行了实验，详细地研究了树脂的吸附和脱附性能，吸附量达２８万／ｍｌ树脂，脱附率达９６％，获得了较满意的结果。     

黄芩甙的线性扫描伏安法测定研究

研究了黄芩甙在多壁碳纳米管修饰电极上的伏安行为。结果表明 ,该修饰电极对黄芩甙产生较强的吸附催化作用 ,催化电流与黄芩甙浓度在 1 .0× 1 0 - 7～ 6.0×1 0 - 5mol·L- 1范围内呈线性关系。利用本法测定了中药黄芩中的黄芩甙的含量 ,效果良好     

EFFECT OF pH ON THE ADSORPTION OF p-AMINOBENZOIC ACID ON POLYSTYRENE-BASED ADSORBENTS

In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.     

Polanyi-based models for the adsorption of naphthalene from aqueous solutions onto nonpolar polymeric adsorbents

In this research, naphthalene was adopted as the representative model compound of PAHs, and static adsorption of naphthalene from aqueous solution onto three commercial polymeric adsorbents with different pore structure was investigated. Nonlinear isotherms models, i.e., Freundlich, Langmuir, and Polanyi-Dubinin-Manes (PDM) models were tested to fit experimental data, and the experimental data were found to fit well by the PDM model. Through both isotherm modeling and constructing "characteristic curve," Polanyi theory was useful to describe the adsorption process of naphthalene by polymeric adsorbents, providing evidence that a micropore filling phenomenon was involved during the adsorption process. In addition, a good linear correlation was obtained between the naphthalene adsorption capacities and the micropore volume of adsorbents (Vmicro), whereas no linear relationship was found between the naphthalene adsorption capacities and the specific surface area of adsorbents. Based on the PDM model, the micropore volumes of adsorbents was introduced to normalize the equilibrium adsorbed volume (qv), plots of qv/V(micro) vs adsorption potential density for naphthalene on three different polymeric adsorbents were collapsed to a single correlation curve, which would be of great benefit to predict the adsorption capacity of adsorbent for the purpose of adsorption engineering design.     

A comparative adsorption study of β-naphthol on four polymeric adsorbents from aqueous solutions

Adsorptive removal of aromatic compounds from aqueous solutions by polymeric adsorbents has attracted many concerns in recent years. A comparative adsorption study including equilibria, kinetics and column dynamics of β-naphthol from aqueous solutions was carried out using two hypercrosslinked polymeric adsorbents (HJ-1 and TEPA) we developed and two commercial polymeric adsorbents (XAD-4 and XAD-7). The adsorption isotherms could be well described by the Freundlich equation, and the adsorption equilibrium capacities of β-naphthol followed an order of q(e)((TEPA))>q(e)((HJ-1))>q(e)((XAD-4))>q(e)((XAD-7)). The isosteric adsorption enthalpies on HJ-1 and TEPA decreased with increasing adsorption fractional loading, while a constant enthalpy was observed for XAD-4 and XAD-7, implying that HJ-1 and TEPA had a heterogeneous surface while XAD-4 and XAD-7 possessed a homogenous surface. The surface energetic heterogeneity of HJ-1 and TEPA could be well characterized by the Do's model. The adsorption kinetics were fitted by both pseudo-first-order and pseudo-second-order rate equations, and the intra-particle diffusion was found to be the rate-limiting step. The adsorption breakthrough data were well correlated by the Thomas and Clark models, and the dynamic capacities for TEPA, HJ-1, XAD-4 and XAD-7 adsorbents were calculated to be 341.7, 321.6, 268.0 and 173.8 mg/g dry resin, which were within 90% of the corresponding equilibrium capacities obtained in the batch experiments.     

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.     

A comparison study between polymeric ligand and monomeric ligand for oligopeptide adsorption

This work aimed to compare two types of affinity ligands, i.e. polymeric and monomeric ligands, by investigating their adsorption affinity, capacity and selectivity to oligopeptide. The peptide NH(2)-VVRGCTWW-COOH (VW-8) was chosen as the target adsorbate, while histidine (His), aspartic acid (Asp), and leucine (Leu) were selected as the ligands, respectively. For each kind of ligand, both monomeric (M) and polymeric (P) forms were introduced onto the Sepharose matrix respectively to obtain the corresponding adsorbents. Both affinity tests using isothermal titration calorimetry (ITC) and adsorption capacities using static adsorption experiments indicated that the adsorbents with polymeric ligands (MX-P) exhibited better adsorption ability for VW-8 than the adsorbents with monomeric ligands (MX-M). In particular, the MX-PHis exhibited its affinity constant of 2.39 × 10(6) M(-1) and its adsorption capacity of 77.4 mg/g for VW-8, which was approximately 8-10 times higher than that of MX-MHis. Such distinct adsorption abilities between polymeric and monomeric ligands were interpreted based on nuclear magnetic resonance (NMR) and ITC data, and the results indicated that such better characters of polymeric ligands were ascribed to their good flexibility which facilitated the cooperative effects as well as the accessibility of ligands to the peptide. Additionally, the selective adsorption experiments indicated that all the adsorbents with polymeric ligands exhibited good selectivity to the peptide VW-8.     

不同基团修饰的吸附树脂对芳香两性化合物的吸附等温线研究

研究了带有不同功能基团的超高交联吸附树脂NG-10和NJ-99对水溶液中芳香两性化合物氨基苯甲酸的静态吸附性能,并与不带功能基团的吸附树脂CHA-111和XAD-4进行了比较.研究结果表明,树脂NJ-99对水溶液中氨基苯甲酸的吸附能力高于其他树脂.邻氨基苯甲酸在4种树脂上的吸附量均大于对氨基苯甲酸,主要原因是其溶解度小.吸附等温线采用经验的Freundlich方程和理论的Langmuir吸附方程来拟合,在实验所研究的浓度范围内,方程的拟合相关性均很好.     

大孔交联聚苯乙烯吸附树脂的合成及其对叶绿素铜的吸附性能

通过改变苯乙烯-二乙烯苯共聚物的交联度和使用不同结构的二乙烯苯,合成了树脂Ⅰ-Ⅵ,在工业二乙烯苯共聚体系中加入少量丙烯酸甲酯合成了树脂Ⅶ;交联聚苯乙烯经Friedel-Grafts酰化反应在其苯环上引入乙酰基制备了树脂Ⅷ。用物理技术和化学方法表征了树脂的结构。树脂对叶绿素铜的吸附量不仅与其二乙烯苯含量有关,还与二乙烯基的位置(间-,对-)异构有关,树脂骨架极性的增加,不利于树脂对叶绿素铜的吸附。     

Adsorption behavior, thermodynamics, and mechanism of phenol on polymeric adsorbents with amide group in cyclohexane

Macroporous cross-linked poly(N-methyl-N-p-vinylbenzylacetamide) (PMVBA), poly(N-methyl-N-p-vinylbenzylcaprolactam) (PMVBC), and poly(N-methyl-N-p-vinylbenzylurea) (PMVBU) were synthesized and their adsorption behavior for phenol in cyclohexane was investigated. The results indicated that the adsorption capacities of phenol on the three adsorbents followed the order PMVBU > PMVBA > PMVBC. Adsorption isotherms of phenol on the three polymeric adsorbents were measured and correlated to a Freundlich isotherm. Adsorption enthalpy, adsorption Gibbs free energy, and adsorption entropy were calculated using thermodynamic function relationships. It was found that the adsorption enthalpy of phenol on PMVBU was almost twice that on PMVBA and PMVBC. Analysis of the adsorption mechanism suggested that hydrogen bonding was the primary driving force for phenol adsorbed on the adsorbents in cyclohexane, and multiple hydrogen bonding was involved for PMVBU with phenol.     

苯甲酰基修饰的吸附树脂对对甲苯胺的吸附机理研究

合成了用苯甲酰基修饰的新型吸附树脂ZH-03和ZH-04,同时研究了它们和AmberliteXAD-4对不同温度下水溶液中对甲苯胺的静态吸附和脱附性能,并对吸附机理进行了探讨。结果表明,经化学修饰后的树脂ZH-03和ZH-04对水溶液中对甲苯胺的吸附过程在合适温度时存在化学络合吸附作用,对吸附剂进行苯甲酰基修饰可以提高吸附剂对水溶液中对甲苯胺的吸附容量。     

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

1.INTRODUCTIONThepolymericadsorbentAmberliteXAD-4isconsideredoneofthemostsuitablepolymericadsorbentsforremovingphenoliccompoundsfromwaterstreams[1,2]becauseitischemicallystable,notsolubleinsolventsandmoreselectiveforaromaticringsduetoitshydrophobicproperties.However,methanol,acetoneoracetonitrile,hastobeusedtoenhancethesurfacecontactbetweenadsorbentandthesolute.DavankovandTsyurupadescribedanewseriesofadsorbents[3,4].Thistechniqueyieldedpolystyrenesorbentsofunusualhypercrosslinkedstructu…