Adsorption of alkaloids on ordered mesoporous carbon.

An ordered mesoporous carbon (OMC) adsorbent was synthesized, characterized, and evaluated for effective separation and purification of alkaloid compounds from aqueous solutions. The OMC adsorbent has a large BET specific surface area (1532.2m(2)/g), large pore volume (2.13cm(3)/g), and narrow pore diameter distribution with a median pore diameter of 4.21nm. Berberine hydrochloride, colchicine, and matrine were selected as the model compounds for evaluating the adsorption properties of the OMC adsorbent for alkaloid purification. Batch adsorption experiments of pure components in water were carried out to measure both adsorption equilibria and kinetics, and column breakthrough and desorption experiments were performed to validate the separation and regeneration efficacy of the OMC adsorbent. The adsorption equilibrium capacities of berberine hydrochloride, colchicine, and matrine on the OMC adsorbent at 0.100mg/L and 298K are 450, 600, and 480mg/g, respectively, which are more than double the adsorption capacities of these compounds on two commonly used commercial resins (HPD300 and HPD100B) at similar conditions. Adsorption equilibrium of all three alkaloids could be obtained within 120min at 298K. The dynamic adsorption capacities determined from the breakthrough experiments are within 12% of the estimated equilibrium capacities from the Langmuir isotherms; and 74.3-92.8% of the adsorbed amounts could be recovered by desorbing with a 70% alcohol solution. The adsorption isotherms are analyzed with both Langmuir and Freundlich models, the adsorption kinetic data with the pseudo-first-order and pseudo-second-order models, and the breakthrough curves with four breakthrough models. The large adsorption capacity, fast adsorption rate, and easy regeneration make the ordered mesoporous carbon a promising adsorbent for adsorption and purification of alkaloid compounds from the extracts of herbal plants.

[1]  Xijun Hu,et al.  Functionalized ordered mesoporous carbon for the adsorption of reactive dyes , 2012, Adsorption.

[2]  E. Kuepeli,et al.  A comparative study on the anti-inflammatory, antinociceptive and antipyretic effects of isoquinoline alkaloids from the roots of Turkish Berberis species. , 2002, Life sciences.

[3]  Y. Zu,et al.  Preparative separation of dryofragin and aspidin BB from Dryopteris fragrans extracts by macroporous resin column chromatography. , 2012, Journal of pharmaceutical and biomedical analysis.

[4]  S. Moon,et al.  Competitive adsorption characteristics of Co2+, Ni2+, and Cr3+ by IRN-77 cation exchange resin in synthesized wastewater. , 2004, Chemosphere.

[5]  G. Bennett,et al.  Adsorbents: Fundamentals and Applications , 2004 .

[6]  T. Ishikawa,et al.  Studies on the Chemical Constituents of Xanthoxylum nitidum (ROXB). D. C. (Fagara nitida ROXB.). II. Examination of the Chemical Constituents by Membrane Filtration : Identification of Magnoflorine, a Water-Soluble Quaternacy Aporphine Alkaloid , 1994 .

[7]  Sheng Dai,et al.  Hierarchical ordered mesoporous carbon from phloroglucinol-glyoxal and its application in capacitive deionization of brackish water , 2010 .

[8]  Mingzhi Dai,et al.  High capacity magnetic mesoporous carbon-cobalt composite adsorbents for removal of methylene green from aqueous solutions. , 2012, Journal of colloid and interface science.

[9]  Dan Feng,et al.  A Family of Highly Ordered Mesoporous Polymer Resin and Carbon Structures from Organic−Organic Self-Assembly , 2006 .

[10]  Lu Lv,et al.  Critical review in adsorption kinetic models , 2009 .

[11]  Paul K. Chu,et al.  Characterization of amorphous and nanocrystalline carbon films , 2006 .

[12]  Y. Wan,et al.  Ordered mesoporous carbon coating on cordierite: synthesis and application as an efficient adsorbent. , 2011, Journal of hazardous materials.

[13]  H. Fales,et al.  SEPARATION OF ALKALOIDS BY GAS CHROMATOGRAPHY , 1960 .

[14]  Yu Liu Some consideration on the Langmuir isotherm equation , 2006 .

[15]  K. Ahn,et al.  Evaluation on the adsorption capabilities of new chemically modified polymeric adsorbents with protoporphyrin IX. , 2001, Journal of chromatography. A.

[16]  E. Q. Adams,et al.  SOME ASPECTS OF THE BEHAVIOR OF CHARCOAL WITH RESPECT TO CHLORINE.1 , 1920 .

[17]  Z. Aksu,et al.  Biosorption of phenol by immobilized activated sludge in a continuous packed bed: prediction of breakthrough curves , 2004 .

[18]  Xuefeng Guo,et al.  Characterization of the pore structure of three-dimensionally ordered mesoporous carbons using high resolution gas sorption. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[19]  C. Codina,et al.  Bioactive alkaloid extracts from Narcissus broussonetii: mass spectral studies. , 2012, Journal of pharmaceutical and biomedical analysis.

[20]  C. Liang,et al.  Mesoporous carbon materials: synthesis and modification. , 2008, Angewandte Chemie.

[21]  M. Anbia,et al.  Synthesis of polyelectrolyte-modified ordered nanoporous carbon for removal of aromatic organic acids from purified terephthalic acid wastewater , 2012 .

[22]  D. Zhao,et al.  An Aqueous Cooperative Assembly Route To Synthesize Ordered Mesoporous Carbons with Controlled Structures and Morphology , 2006 .

[23]  S. Deng,et al.  Adsorptive separation studies of ethane-methane and methane-nitrogen systems using mesoporous carbon. , 2013, Journal of colloid and interface science.

[24]  Jongki Hong,et al.  HPLC Separation of Isoquinoline Alkaloids for Quality Control of Corydalis species , 2011 .

[25]  Jiamei Yu,et al.  Separation of sanguinarine and chelerythrine in Macleaya cordata (Willd) R. Br. based on methyl acrylate-co-divinylbenzene macroporous adsorbents. , 2008, Journal of chromatography. A.

[26]  J. Nelson,et al.  Application of gas adsorption kinetics. I. A theoretical model for respirator cartridge service life. , 1984, American Industrial Hygiene Association journal.

[27]  T. Swain Chemical Plant Taxonomy , 1963 .

[28]  Y. Ho,et al.  A COMPARISON OF CHEMISORPTION KINETIC MODELS APPLIED TO POLLUTANT REMOVAL ON VARIOUS SORBENTS , 1998 .

[29]  L. Nazar,et al.  Carbon/MoO2 composite based on porous semi-graphitized nanorod assemblies from in situ reaction of tri-block polymers , 2007 .

[30]  Sang Hoon Joo,et al.  Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation , 1999 .

[31]  A. Shirwaikar,et al.  In vitro antioxidant studies on the benzyl tetra isoquinoline alkaloid berberine. , 2006, Biological & pharmaceutical bulletin.

[32]  D. Zhao,et al.  Highly Efficient Adsorption of Bulky Dye Molecules in Wastewater on Ordered Mesoporous Carbons , 2009 .

[33]  Ming-hai Tang,et al.  Predictable and linear scale-up of four phenolic alkaloids separation from the roots of Menispermum dauricum using high-performance counter-current chromatography. , 2010, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[34]  Mietek Jaroniec,et al.  Synthesis of New, Nanoporous Carbon with Hexagonally Ordered Mesostructure , 2000 .

[35]  Zhonghua Liu,et al.  Completed preparative separation of alkaloids from Cephaltaxus fortunine by step-pH-gradient high-speed counter-current chromatography. , 2009, Journal of chromatography. A.

[36]  H. Chokshi,et al.  Separation of Diterpenoid Alkaloid Mixtures Using Vacuum Liquid Chromatography , 1986 .

[37]  H. R. Ing Chemistry of Alkaloids , 1949 .

[38]  D. Grout Chemistry of Alkaloids , 1967, Nature.

[39]  Shuguang Deng,et al.  Adsorption of CO(2), CH(4), N(2)O, and N(2) on MOF-5, MOF-177, and zeolite 5A. , 2010, Environmental science & technology.

[40]  K. Yasuda,et al.  Polyhydroxylated alkaloids isolated from mulberry trees (Morusalba L.) and silkworms (Bombyx mori L.). , 2001, Journal of agricultural and food chemistry.

[41]  Xiao Wang,et al.  Separation of alkaloids from herbs using high-speed counter-current chromatography. , 2011, Journal of separation science.

[42]  Y. Ito,et al.  Application of analytical and preparative high-speed counter-current chromatography for separation of alkaloids from Coptis chinensis Franch. , 1998, Journal of chromatography. A.

[43]  M. Nair,et al.  Biologically active carbazole alkaloids from Murraya koenigii. , 1999, Journal of agricultural and food chemistry.

[44]  S. Deng,et al.  Adsorption of Berberine Hydrochloride, Ligustrazine Hydrochloride, Colchicine, and Matrine Alkaloids on Macroporous Resins , 2013 .

[45]  C. Wu,et al.  Separation of five major alkaloids in gum opium and quantitation of morphine, codeine, and thebaine by isocratic reverse phase high performance liquid chromatography. , 1977, Analytical chemistry.

[46]  S. Deng,et al.  Adsorption of CO₂, CH₄, and N₂ on ordered mesoporous carbon: approach for greenhouse gases capture and biogas upgrading. , 2013, Environmental science & technology.

[47]  Henry C. Thomas,et al.  Heterogeneous Ion Exchange in a Flowing System , 1944 .

[48]  Shiguo Jia,et al.  Adsorption Characteristics of Phenol and Reactive Dyes from Aqueous Solution onto Ordered Mesoporous Carbons Prepared via a Template Synthesis Route , 2009 .

[49]  M. Wink,et al.  Alkaloids: biochemistry, ecology, and medicinal applications. , 1998 .

[50]  Shaobin Wang,et al.  Removal of dyes from aqueous solution using fly ash and red mud. , 2005, Water research.

[51]  Yu Wang,et al.  Berberine, a genotoxic alkaloid, induces ATM-Chk1 mediated G2 arrest in prostate cancer cells. , 2012, Mutation research.

[52]  C. Liang,et al.  Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction. , 2006, Journal of the American Chemical Society.

[53]  N. N. Dutta,et al.  Adsorption affinity of certain biomolecules onto polymeric resins: Interpretation from molecular orbital theory , 2006 .

[54]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[55]  S. Srivastava,et al.  Large-scale separation of clavine alkaloids from Ipomoea muricata by pH-zone-refining centrifugal partition chromatography. , 2009, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[56]  X. Pu,et al.  Thermodynamic Properties of Matrine in Ethanol , 2011 .

[57]  Aimin Li,et al.  Displacement mechanism of binary competitive adsorption for aqueous divalent metal ions onto a novel IDA-chelating resin: isotherm and kinetic modeling. , 2011, Water research.

[58]  Lily P. H. Yang Oral Colchicine (Colcrys®) , 2010, Drugs.

[59]  J. Votruba,et al.  Separation of ergot alkaloids by adsorption on silicates , 2000, Biotechnology Letters.

[60]  Effects of Surface Oxygen of Activated Carbon on Alkaloid Adsorption: A Molecular Dynamics Simulation Study , 1999 .

[61]  R. Clark Evaluating the cost and performance of field-scale granular activated carbon systems. , 1987, Environmental science & technology.

[62]  S. Towprayoon,et al.  Adsorption of three azo reactive dyes by metal hydroxide sludge: effect of temperature, pH, and electrolytes. , 2004, Journal of colloid and interface science.

[63]  J. Menéndez,et al.  Fluorescence properties of the anti-tumour alkaloid luotonin A and new synthetic analogues: pH modulation as an approach to their fluorimetric quantitation in biological samples , 2012 .

[64]  Y. Zu,et al.  Preparative separation of vitexin and isovitexin from pigeonpea extracts with macroporous resins. , 2007, Journal of chromatography. A.

[65]  F. Young Biochemistry , 1955, The Indian Medical Gazette.

[66]  Bichun Huang,et al.  Ordered mesoporous carbons with various pore sizes: Preparation and naphthalene adsorption performance , 2012 .

[67]  J. Dostál,et al.  Two Faces of Alkaloids , 2000 .