Optimization of Preparative Separation and Purification of Total Flavonoids from Radix Puerariae by Macroporous Resin Method

Aim To screen the optimum macroporous resin and conditions for the isolation and purification of flavonoids from Radix Puerariae. Methods The static and dynamic adsorption/desorption methods were used, and the separation and purification process was evaluated by measuring the concentration of total flavonoid in the fractions with UV spectrophotometer. Results The SP70 macroporous resin was the most effective compared with other macroporous resins. The optimum conditions were screened, which were 0.5 g· mL^- 1 corresponding to crude drug for concentration of extract, pH 5 - 6, and appended 60 times the volume of the resin bed （BV） with the adsorption speed 2 BV·h^-1, and the volume of aq. 70% （V/V） ethanol as eluant was 5 BV with desorption speed 2 BV·h^-1. By this method, the final contents of total flavonoids exceeded 80%. Conclusion The SP70 macroporous resin is the most effective one for large-scale isolation and purification of flavonoids from Radix Pueraria, which meets industrial needs.

Separation and Purification of Macranthoidin B and Dipsacoside B from Flos Lonicerae by HP-20 and HP-SS Macroporous Resin

[Objective] This study was conducted to develop a method for rapidly separating macranthoidin B and dipsacoside B from Flos Lonicerae. [Method] HP-20 and HP-SS macroporous resin were applied to separate and purify macranthoidin B and dipsacoside B from Flos Lonicerae. The extract of Flos Lonicerae was first loaded onto an HP-20 column to enrich saponins, which were then separated by an HP-SS macroporous resin column to get pure macranthoidin B and dipsacoside B.[Result] The optimal HP-20 purification conditions included： a concentration of sample liquid at 4.8 mg/ml, a sample volume of 2 BV, an adsorption flow rate at 1.5BV/h, an ethanol concentration for desorption at 60%, a desorption volume of 3 BV,and a desorption flow rate at 1.5 BV/h. Total saponins were then separated by an HP-SS macroporous resin column which was eluted sequentially by water, 20%ethanol, 30% ethanol, 40% ethanol and 50% ethanol. Two purified compounds were obtained in fractions eluted by 40% ethanol and 50% ethanol, respectively. The two compounds were identified as macranthoidin B and dipsacoside B by13 C and1H nuclear magnetic resonance spectroscopy. [Conclusion] The combination of HP-20 and HP-SS macroporous resin could efficiently separate macranthoidin B and dipsacoside B from Flos Lonicerae.

Macroporous Resin Adsorption for Purification of Flavonoids in Houttuynia cordata Thunb

Flavonoids are one main kind of effective components in Houttuynia cordata Thunb., which display a wide range of pharmacological activity. In this study supercritical fluid extraction （SFE） with carbon dioxide was first used as preparat ion step to remove the volatile components, which are also active components, from Hout-tuynia cordata Thunb. Then ultrasound-assisted extraction was used to obtain the crude flavonoids and the macro-porous resin adsorption technology was further employed to purify the flavonoids. Nine kinds of macroporous resins with different properties were tested through static adsorption, and one macroporous resin labeled as D101 was selected. The effect of several factors, such as the ratio of column height to diameter, initial concentration and pH, on both flavonoids yield and content were explored by dynamic adsorption to obtain reasonable conditions of adsorption and desorption. The experimental results show that the content of fiavonoids can be above 60% with fia- vonoids recovery of 93.3 % under the optimum conditions of purification. HPLC analysis of the final flavonoids product shows it contains quercitrin, hypefin, rutin and quercetin.

Static and dynamic studies of adsorption by four macroporous resins to enrich oridonin from Rabdosia rubescens

Oridonin,one of the active ingredients in Rabdosia rubescens(R.rubescens),has been reported to induce cell apoptosis and cell cycle arrest in many cancers.Conventional extraction methods tend to result in unsatisfied enrichment and poor quality of oridonin present in a given biomass.This paper aims to evaluate the performance and separation characteristics of four different macroporous resins to arrive at the most suitable methodology for the isolation and purification of highquality oridonin.Static absorption kinetics,thermodynamic and dynamic adsorption were evaluated.HP20 was selected for further study due to its high adsorption capacity of 32 mgg 1 and desorption ratio with 98.5%.The pseudosecondorder model was considered to be the most suitable for kinetic results,and Langmuir model was chosen to better describe the absorption thermodynamics.Under optimum conditions(flow rate of 4 ml min 1,bed depth with 6 cm and initial concentration of 2.15 mg·ml^1),the effective content of oridonin increased from 33.9%to 79.1%in the dry extract with a recovery of 81%and the purity of oridonin improved from 76%to 93%.The results confirm that HP20 provides an efficient method to purify most oridonin from R.rubescens.

Separation and purification of Arabinogalactan obtained from Larix gmelinii by macroporous resin adsorption

Arabinogalactan （AG） obtained from Larix gmelinii R. waS purified with the method of macroporous resin adsorption. Effects of various parameters on the adsorption, including adsorption time and temperature, the concentration and the dosage of raw AG the reused numbers of resin, were investigated. The effect of purification was tested through the removal rate of impurity and the contents of AG and impurity. The optimal condition was determined as follows： adsorbed at 30℃ for 2 h with the concentration of raw AG 〈0.1 g·mL^-1 and its dosage 〈 7 mL, the dose of resin was 3 g and reused for 4 times. On the basis of these, macroporous resin column was used for AG purification. The result showed that the AG yield could reach 68.28% with sugar content of 95.02%. The analysis of IR and UV showed that the effect of macroporous resin characteristics on the purification of AG was significant. The obtained product had the same functional groups with standard sample.

Comparison between Decolorization Effects of Activated Carbon and Macroporous Resin on Periplaneta americana L. Skimmed Cream

[Objective] The aim of this study was to investigate the decolorization ef- fects of activated carbon and macroporous resin on Periplaneta americana L. skimmed cream and compare the advantages and disadvantages of the two decolorization technologies. [Method] Periplaneta americana L. skimmed cream was decolored with activated carbon and macroporous resin, and freeze-dried to collect solid decolorization products. By investigating the yield, decolorization rate, protein retention rate and decolorization operation process, the advantages and disadvantages of the two decolorization technologies were compared. [Result] Both activated carbon and macroporous resin can be used for decolorization. To be specific, macroporous resin-decolorization is superior in the yield and protein retention rate, while activated carbon-decolorization is superior in decolorization rate and decolorization operation process. [Conclusion] Macroporous resin-decolorization can be used if protein is the main ingredient required in the experiment, while activated carbon-decolorization can be used if protein is not the main ingredient required.

ADSORPTION OF TANNIN ACID ONTO AN AMINATED MACROPOROUS RESIN FROM AQUEOUS SOLUTIONS

A macroporous polymeric adsorbent NG-8 was synthesized with divinylbenzene using conventional suspension polymerization technique. Its aminated product NG-9 was prepared by introducing tertiary amino groups into NG-8 for removal of tannin acid from aqueous solutions. NG-9 could be used directly without a wetting process and had higher adsorption capacity than NG-8, which might be attributed to the enhanced adsorbent-adsorbate interaction due to the tertiary amino groups on the polymeric matrix. The Langmuir equation was successfully employed to describe the adsorption process. The adsorption enthalpy change further validated the uptake of tannin acid on NG-9 to be an enhanced physical adsorption because of the Lewis acid-base interaction. In addition, adsorption kinetic studies testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate maybe for the hindrance of the tertiary amino groups and water clusters built up.

Simulation of Cefoselis hydrochloride adsorption on macroporous resin in a fixed-bed column using orthogonal collocation

Adsorption operation is of great importance for separation and purification of semi-synthetic cephalosporin compounds in pharmaceutical industry. The adsorption dynamics of Cefoselis hydrochloride(CFH) on XR 920 C adsorbent in fixed bed was predicted by the model of modified film-pore diffusion(MFPD). The intraparticle diffusion equation and mass balance equation in fixed bed are discretized into two ordinary differential equations(ODEs) using the method of orthogonal collocation which largely improves the calculation accuracy. The MFPD model parameters including the pore diffusion coefficient(Dp), external mass-transfer coefficient(kf), and the axial dispersion(DL) were estimated. The kfvalue was calculated by the Carberry equation, in which the effective diffusion coefficient Dewas fitted based on Crank Model through experimental data. Moreover, three key operating parameters(i.e., initial adsorbate concentration; flow rate of import feed, and bed height of adsorbent) and the corresponded breakthrough curves were systematically studied and optimized. Therefore,this research not only provides valuable experimental data, but also a successfully mathematical model for designing the continuous chromatographic adsorption process of CFH.

ADSORPTION AND DESORPTION OF DSD ACID MANUFACTURING WASTEWATER ON MACROPOROUS RESIN

4,4’-diaminostilbene-2, 2’-disulfonic acid (DSD acid) manufacturing wastewater was treated by a macroporous resin in a fixed-bed column. The results showed that this method was suitable for removal of chemical oxygen demands (COD) and color. About 91% COD and 99.5% color removal were obtained under the optimum adsorption conditions, i.e. temperature 20℃, flow rate 1bed volume/hour (BV/hr) and pH1-2. The resin was efficiently regenerated with aqueous sodium hydroxide and water. Furthermore, 65.5% of 4,4’-dinitrostilbene-2, 2’-disulfonic acid (DNS) could be recovered from wastewater for possible recycling to the manufacturing process. The adsorption capacity of resin remained constant during the repetition process of adsorption and desorption.

Preparation and adsorption properties of macroporous tannin resins

In this paper, a new kind of adsorption resin with multi-phenolic hydroxyl was created by immobilizing black wattle bark tannins to chloromethyl polystyrene resin. Its adsorption capacity to cation dye was tested. With an orthogonal test the optimal conditions of synthesis were determined： the concentration of sodium hydroxide solution 1.0 mol.L^-1; the reaction time is one hour and the mass concentration of tannins 5%. With single factorial experiment the optimal conditions of adsorption were confirmed： a solidified pH of 5.0; an adsorption temperature of 25℃ and a cation dye concentration of 100 mg.L^-1. The adsorption for cation dye can be similar to Langmuir isotherms.

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 from3-5 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 of80%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.

Extraction and purification of ustiloxin A from rice false smut balls by a combination of macroporous resin and high-speed countercurrent chromatography

Rice false smut is an emerging plant disease worldwide.Ustiloxin A(UstA)is the major mycotoxin found in rice false smut balls,which are fungal colonies in rice florets.In this study,a new method consisting of macroporous resin column chromatography and high-speed countercurrent chromatography(HSCCC)was developed for UstA separation.UstA was extracted by a 3.81%HCOOH solution and adsorbed by XAD-4 resin.UstA was then eluted by a 40%methanol solution supplemented with 0.1%trifluoroacetic acid(TFA).Further purification was achieved by HSCCC using a two-phase solvent system consisting of n-butanol/TFA/H_(2)O(1/0.05/1,v/v/v).Under the optimized conditions,225 mg of UstA was obtained with a purity of 97.39%in a single run,with a final recovery of 65.2%.An inhibitory effect on seed germination of wheat and maize caused by UstA was observed in a preliminary phytotoxicity assay.

STUDY ON SYNTHESIS OF PVC SERIES OFMACROPOROUS SULFORIC RESINS AND THEIR APPLICATIONS IN CATALYTIC ESTERIFICATIONAND WATER TREATMENT

The PVC series of macroporous sulfonic cation-exchange resins were prepared by thesulfonation of a macroporous PVC bead with concentrated sulfonic acid or chlorosulfonicacid, the resulting sulfonic resin was employed in the investigation of catalyticesterification and softening of water The results show that the yields of esters reach60.0-84.4% according as different fatty acids and alcohols, the refractive indexes of estersobtained resemble those reported in the references basically, meanwhile, 345L softenedwaler which holds 0.06mmol/L hardness would be prepared by 1 L wet sulfonic resinreusing for 4 times. The resulting sulfonic resins would have 1.6-2.0 or 2.5-3.0mmol/gexchange capacity by using concentrated sulfonic acid or chlorosulfonic acid assulfonating agent, respectively The sulfonic resin has a macroporous structure taking themorphology with agglomerates of minutely spherical gel particles as characteristic.

STUDIES ON THE SORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR LANTHANUM

The influences of medium pH sorption temperature, sorption time, etc. on thesorption capacity of macroporous Phosphonic acid resin for La3+ were determined Thesorption rate constant was k298 = 7.64×10-5 s-1. The complex ratio of phosphonicgroups of the resin to La3+ was 3:1. The basic sorption parameters were determinedThe sorption mechanism of macroporous phosphonic acid resin for La3+ was examinedby chemical analysis and IR- spectrometry.

Adsorption of Macroporous Phosphonic Acid Resin for Nickel

Tje adsorption bchavior and mechanism of a novel chelate resin,macroporous phosphonic acid resin（PAR）for Ni（Ⅱ）were imestigated.The stotically saturated adsorption capacity is 64.3mg·g^-1 resin at 298K in HAc-NaAc medium.The Ni（Ⅱ）adsorbed on PAR can be eluted by 0.5mal·L^-1 HCl and the elution percentage reaches 96.6%.The resin can be regenerated and reused without abvious decrease in adsorption capacity.The apparent adsorption rate constant is k298=2.6×10^-5s^-1.The adsorption behavior of PAR for Ni（Ⅱ）obeys the Freundllich isotherm.The thermodynamie adsorption parameters.enthalpy change △H,free energy change △G and entropy change △S of PAR for Ni（Ⅱ）are 3.36kJ·mol^-1,-5.47kJ·mol^-1 and 29.6J·mol^-1·K^-1,respectively.The apparent activation energy is Ea=12.2kJ·mol^-1,The molar coordination ratio of the functional group of PAR to Ni（Ⅱ）is about 4：1.The adsorption mechanism of PAR for Ni（Ⅱ）was examined by a chemical method and IR spectrometry.

Adsorption of Pb^(2+) on macroporous weak acid adsorbent resin from aqueous solutions: Batch and column studies

The adsorption properties of a novel macroporous weak acid resin （D152） for Pb^2＋ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb^2＋ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb^2＋ adsorbed on D152 resin can be eluted with 0.05 mol/L HCI quantitatively. The adsorption rate constants determined under various temperatures are k288 n=2.22×10-5 s^-1, k298 K=2.51 × 10^-5 s^-1, and k308 K= 2.95 × 10^-5 s^-1, respectively. The apparent activation energy, Ea is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH^Θ=13.3 kJ/mol, ΔS^Θ=119 J/（mol·K）, and ΔG^Θ298 K =-22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb^2＋ follows Langmuir model.

Adsorption Behaviors and Mechanism of Macroporous PhosphonicAcid Resin for Gadolinium

The adsorption behaviors and mechanism of a novel chelate resin, macroporous phosphonic acid resin(PAR)for Gd(Ⅲ)were investigated. The statically and dynamically saturated adsorption capacity is respectively 308 mg·g^(-1)resin and 296 mg·g^(-1)resin at 298 K in HAc-NaAc medium at pH 5.6. Gd(Ⅲ)adsorbed on PAR can be reductively eluted by 0.5～5.0 mol·L^(-1) HCl used as eluant and the elution percentage is up to 94.7% in 1.0 mol·L^(-1) HCl. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=3.96×10^(-5) s^(-1). The adsorption behavior of PAR for Gd(Ⅲ) conforms to the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change △H of PAR for Gd(Ⅲ)is 22.6kJ·mol^(-1). The apparent adsorption activation energy(Ea)of PAR for Gd(Ⅲ)is 5.0 kJ·mol^(-1). The molar coordination ratio of the functional group of PAR to Gd(Ⅲ)is about 3∶1. The adsorption mechanism of PAR for Gd(Ⅲ)was examined by using chemical method and IR spectrometry.

ADSORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR INDIUM

The adsorption kinetics and mechanism of a novel chelate resin, macroporous phosphonic acid resin (PAR) for In(III) were investigated. The statically saturated adsorption capacity is 216mg穏-1resin at 298K in HAc-NaAc medium. The apparent adsorption rate constant is k298=4.84?0-5 s-1. The adsorption behavior of PAR for In(III) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △H, free energy change △G and entropy change △S of PAR for In(III) are 11.5kJ/mol, -12.6kJ/mol and 80.8J/mol稫, respectively. The apparent activation energy is Ea=3.5kJ/mol. The molar coordination ratio of the functional group of PAR to In(III) is about 3∶1.

Preparation of Aminated Macroporous Polyvinyl Alcohol Resins and Evaluation for Bilirubin Adsorption

In the present study we prepared macroporous polyvinyl alcohol beads. A series of bilirubin adsorbents were generated by immobilization of eight amine agents to the beads as ligands. The adsorption of bilirubin was evaluated by in vitro static and dynamic adsorption tests. The results show that these adsorbents have excellent adsorption efficiency and capacity. Among the eight ligands, trimethylamine （TMA）, triethylamine （TEA） and 1,6- hexanediamine （HDA） showed the highest adsorption capacity. The adsorption equilibrium can be achieved in half an hour, and the adsorption percentage of bilirubin was up to 80%. Static electricity and hydrophobie interaction played the main role in bilirubin adsorption, and the adsorption was found to match the monolayer model. The excellent adsorption of these adsorbents indicates their potential in clinical treatment.

Synthesis and Efficiency of a SphericalMacroporous Epoxy-dicyandiamide ChelateResin for Preconcentrating and SeparatingTrace Au, Hg, Pd and Ru from Samples

A novel spherical macroporous epoxy-dicyandiamide chelate resin was synthesized simply and rapidly from epoxy resin and used for the preconcentration and separation of trace amounts of Au (Ⅲ ), Hg (Ⅱ ), Pd (Ⅳ) and Ru (Ⅲ) ions from solution samples. The analyzed ions can be quantitatively concentrated by the resin at a flow rate of 2. 0 mL/min at pH 4, and can also be desorbed with 15 mL of 4 mol/L HCl + 0. 3 g thiourea from the resin column with recoveries of 96. 5%-99. 0%. After the chelate resin was reused for 7 times, the recoveries of these ions were still over 92%, and 400-1 000 times of excess of Fe(Ⅲ ), Al(Ⅲ ), Ni( II), Mn( Ⅱ ), Cr (Ⅲ ), Cu ( Ⅱ ), Cd (Ⅱ ) and Pb (Ⅱ ) caused little interference with the determination of these ions by an inductively coupled plasma optical emission spectrometer (ICP-OES ). The capacities of the resin for the analytes are in the range of 0. 35~0. 92 mmol/g. The RSDs of the proposed method are in the range of 1. 1 % ~4. 0% for each kind of the analyzed ions. The recoveries of a standard added in real solution samples are between 96. 5% and 98. 5%, and the results for the analyzed ions in a powder sample are in good agreement with their reported values.