Surface Template Polymerization Research Articles

Note: Zr(IV)-Immobilized Resin Prepared by Surface Template Polymerization for Fluoride Ion Removal

A novel adsorbent Zr(IV)-immobilized resin was prepared to remove fluoride ions from tap water and industrial wastewater. In order to enhance both the kinetics and efficiency, large pathways were formed in the resin for fluoride ion adsorption and the Zr(IV)-phosphate complexes were immobilized on the polymer surface by surface-template polymerization. The Zr(IV)-immobilized resin had a fluoride adsorption capacity of 0.30 mmol/g. The morphology of the Zr(IV)-immobilized resin was evaluated by measuring the specific surface area, pore volume, and pore size distribution. The resin possessed large amounts of large macropores with diameters around 300 nm. The molecular structure at the fluoride adsorption sites was investigated by measuring the amounts of phosphorus, zirconium, and fluoride ion in the resin, and developing a model complex using computational chemistry. On the polymer surface, a fluoride ion/Zr(IV)/dioleyl phosphoric acid complex with an ideal F:Zr:P mole ratio of 3:1:3 could be formed.

The effect of polystyrene as a porogen on the fluoride ion adsorption of Zr(IV) surface-immobilized resin

A novel adsorbent, Zr(IV)-immobilized resin, was prepared by surface template polymerization. This adsorbent, prepared by adding polystyrene (PS) to resin, has a high adsorption capacity for the removal of fluoride ion from aqueous solutions. The adsorption capacity increased with rising PS concentration, since the specific surface area can be effectively increased by adding polystyrene as a porogen. The adsorption isotherm has been modeled by the Langmuir and Freundlich equations. The adsorption isotherms were well described by the Langmuir equation. The removal of fluoride was also carried out using a column method. The presence of PS in the resin exerted a remarkable influence on the uptake of fluoride ion. The fluoride adsorbed on the resin was quantitatively eluted with 0.1 M NaOH.

Zr(IV)-immobilized Affinity Beads Prepared by Surface Template Polymerization for Capturing Phosphorylated Proteins

AbstractA novel immobilized metal affinity chromatography (IMAC) bead, Zr(IV)-immobilized resin, was prepared by surface template polymerization to enrich phosphorylated proteins and peptides from complex peptides mixtures. In order to enhance both the kinetics and the efficiency, large pathways for the proteins and peptides in the resin were formed, and the Zr(IV)-phosphate complexes were immobilized on the polymer surface. The morphology of the Zr(IV)-immobilized resin was evaluated the by measuring the specific surface area, pore volume, and pore distribution. The resin possessed large amount of the large-macro pores around 300 nm. The separation performance of β-casein from bovine serum albumin (BSA) solution was evaluated by phosphopeptide enrichment and MALDI-TOF MS analysis. The Zr(IV)-immobilized resin showed the high selectivity of the phosphopeptide.

Lanthanoid Element Recognition on Surface-Imprinted Polymers Containing Dioleylphosphoric Acid as a Functional Host

Surface-imprinted polymers have been newly developed for the separation of lanthanoid elements: i.e. La(III), Ce(III), and Dy(III). The imprinted polymers were prepared by surface template polymerization with dioleylphosphoric acid, which exhibits a high affinity to lanthanoids, as a functional host molecule. Separation behavior of La(III), Ce(III) and Dy(III) was investigated with the imprinted polymers, and the imprinting effect of the polymers was evaluated in comparison with that of the unimprinted polymers and also with a conventional solvent extraction method for the same lanthanoid ions. The results indicate that the increase of selectivity for Dy(III) compared to the rest of the ions by the surface-imprinted polymers originated from a synergistic effect of both the affinity with the functional host molecule in nature and the size exclusion by the cavity formed on the polymer surface.

Condensed-Phosphate Imprinted Resins Prepared by a Surface Template Polymerization Method

Condensed-phosphate templated resins were prepared by a surface template polymerization method using oleylamine as a functional surfactant, oleyl alcohol as a co-surfactant, divinylbenzene as a matrix-forming monomer, and tripolyphosphate, pyrophosphate, and phosphate as templates. When tripolyphosphate-templated resins were prepared by using oleylamine alone as surfactant, a template effect was not observed. However, we successfully templated tripolyphosphate by using, along with oleylamine and oleyl alcohol or polyethylene glycol monooleyl ether (PGME) as a co-surfactant. The thus-prepared templated resin adsorbed the template molecule more effectively than did a non-templated resin. A resin prepared using oleyl alcohol as a co-surfactant showed a higher adsorptivity than that prepared by using PGME (n = 2, 10). The amount of oleyl alcohol to be used in resin preparation was studied, and a double molar amount of oleylamine was found optimal. We also investigated the adsorption of other anions, such as phosphate, pyrophosphate, and ferrocyanide, on the tripolyphosphate-templated resin. Pyrophosphate and ferrocyanide ions were adsorbed more effectively on the templated resin than on the non-templated. Conversely, tripolyphosphate showed less adsorptivity on the phosphate- and pyrophosphate-templated resins than on the non-templated resin.

Metal-imprinted microsphere prepared by surface template polymerization and its application to chromatography

A metal ion-imprinted microsphere was prepared by surface molecular template polymerization. Trimethylolpropane trimethacrylate (TRIM), zinc ions, 1,12-dodecanediol-O, O′-diphenyl phosphonic acid (DDDPA) were used as a crosslinking agent, an imprint molecule, and a functional host molecule. The Zn(II)-imprinted microspheres, which are spherically well-defined particles, were prepared by using water-in-oil-in-water (W/O/W) multiple emulsions. The combination of TRIM and DDDPA serves to align the recognition sites resulting in better template sites produced on the polymer surface. We firstly conducted diagnostic zinc- and copper-ion adsorption tests with the Zn(II)-imprinted and unimprinted microspheres in order to make an assessment on the effectiveness of the molecular imprinting technique. Further, the metal-imprinted microspheres were applied to the column operation. The separation and recovery of metals were carried out by an adsorption column packed with the Zn(II)-imprinted microspheres. This performance was compared to that of commercial chelating resins that possess similar phosphoric functional groups. The Zn(II)-imprinted polymer shows an extremely high selectivity to the imprinted zinc ions compared to that of the commercial chelating resin. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 689–696, 2000

Lanthanide-Imprinted Resins Prepared by Surface Template Polymerization.

Neodymium (Nd3+)-imprinted polymers were prepared by the surface template polymerization technique. Two types of phosphonates were utilized as functional molecules. These Nd(III)-imprinted polymers were applied to the mutual separation of lanthanides; La(III) and Nd(III). The relationship between the imprint effect and the chemical properties of the functional molecules was investigated concerning the performance of the Nd(III)-imprinted polymers. A high interfacial property derived from the structure of the functional molecule, was found to be essential for creating high selectivity and high adsorption ability on the Nd(III)-imprinted polymers.

Metal-Imprinted Microsphere Prepared by suriace Template Polymerization with W/O/W Emulsions.

A Zn(II)-imprinted microsphere is prepared by surface template polymerization with W/O/W emulsions. Dioleyl phosphoric acid, which has two long alkyl chains in the hydrophobic moiety, and divinylbenzene were employed as a functional host and a cross-linking agent, respectively. In order to create a spherical imprinted polymer, composition of the external aqueous phase in the W/O/W emulsion is a key factor: the value of the ionic strength to prevent shrinking of emulsions during polymerization and the choice of the water-soluble surfactant for stabilizing the spherical W/O emulsion are important. The metal-imprinted beads exhibit a high selectivity towards target zinc ions over copper ions. The novel preparation technique is very useful for an industrial application because it can easily control the particle size between 10 and 100 μm.

Spacer effect of novel bifunctional organophosphorus monomers in metal-imprinted polymers prepared by surface template polymerization

The interfacial activity and the molecular structure of functional monomers are critical factors that determine the success of synthesizing metal-imprinted polymers by surface template polymerization. From this point of view, first we prepared three distinct novel bifunctional organophosphorus monomers that are interspaced, in each case, by an alkyl spacer having a specific length. Each monomer carries two phosphonic acid groups and two aromatic groups in its molecular structures. Further, by using the synthesized bifunctional monomers, we prepared highly selective Zn(II)-imprinted polymers by the surface template polymerization initiated from a water-in-oil emulsion. To evaluate the template effect, we conducted diagnostic adsorption studies on Zn(II)-imprinted and unimprinted polymers with zinc ions. A high interfacial activity was found to be required for the functional monomers to create the predominant template effect. It became clear that Zn(II)-imprinted polymers having bifuctional monomers with 12-length alkyl chains (1,12-dodecanediol-O, O'-diphenyl phosphonic acid: DDDPA) yielded the best results. Moreover, analysis results of adsorption behavior supported a high-performance of the Zn(II)-imprinted polymers with DDDPA.

Spacer effect of novel bifunctional organophosphorus monomers in metal‐imprinted polymers prepared by surface template polymerization

Spacer effect of novel bifunctional organophosphorus monomers in metal‐imprinted polymers prepared by surface template polymerization

An Enantioselective Polymer Prepared by the Surface Molecular-Imprinting Technique

Abstract An enantioselective imprinted polymer was prepared by the surface template polymerization technique. An organophosphorus extractant was effective as a functional host molecule for recognizing a certain amino acid. The imprinted polymer exhibited a high template effect toward L-tryptophan methylester compared to its D-isomer, while a reference polymer prepared without an imprinting molecule did not show any selectivity among the enantiomers.

Metal Ion-Imprinted Polymer Prepared by the Combination of Surface Template Polymerization with Postirradiation by γ-rays

Zinc ion-imprinted polymers were prepared by the combination of surface template polymerization and irradiation by γ-rays. Dioleyl phosphate, which has two C−C double bonds in the oleyl chains, and divinylbenzene were employed as a functional monomer and a cross-linking agent, respectively. After the surface template polymerization with water-in-oil emulsions, the imprinted resins were irradiated with γ-rays to make the polymer matrices more rigid and also to allow the functional monomer to attach firmly to the matrices. The irradiated imprinted resin exhibits a tremendously high selectivity toward zinc ions over copper ions. Thus it is understood that the postirradiated imprinted polymers are characterized by stable and highly specific recognition sites. The combination of surface template polymerization with irradiation with γ-rays offers a potential technique to construct highly selective molecular-recognizing polymers applicable to the adsorption of various water-soluble substances.

Template-Dependent Selectivity in Metal Adsorption on Phosphoric Diester-Carrying Resins Prepared by Surface Template Polymerization Technique

Abstract The surface templated resins for three different metal ions such as Cu2+, Zn2+ or Cd2+ as the template guest were prepared by emulsion polymerization using oleyl phenyl hydrogenphosphate as a host surfactant, sodium dodecyl sulfate (SDS) as a co-surfactant and divinylbenzene as a resin matrix-forming monomer. The Cu2+-imprinted resin adsorbed Cu2+ much more effectively than did the nonimprinted, the Zn2+- and Cd2+-imprinted ones. On the other hand, the Cd2+-imprinted resin showed a more highly effective binding to Cd2+ than those of the Cu2+-imprinted, Zn2+-imprinted, and nonimprinted resins. In fact, the Cu2+-imprinted resin did not adsorb any significant amount of Cd2+. The selective feature of the surface templated resins to the target ion was thus successfully demonstrated. The template-dependent selectivity should be ascribed to a favorable placement of the surface-anchored metallophilic groups for multidentate coordination to the specific metal ion.

Metal Ion-Imprinted Resins with a Novel Bifunctional Monomer by Surface Template Polymerization.

Metal Ion-Imprinted Resins with a Novel Bifunctional Monomer by Surface Template Polymerization.

Ferrocyanide-Templated Resins Prepared by Surface Template Polymerization.

The ferrocyanide-templated resin was prepared by the “surface template polymerization method”, using ferrocyanide ion as a template, oleylamine as a functional surfactant monomer and divinylbenzene as a matrix-forming monomer. Decyltrimethylammonium chloride (DTAC; quarternary ammonium salt) was found to be suitable as an auxiliary surfactant, when preparing the templated resin: DTAC stabilized the emulsion and was easily removed from the resin by washing with alkaline solution after the polymerization. The templated resin adsorbed ferrocyanide ions about 2 times as much as the non-templated resin. Although the structure of the complex between ferrocyanide and amino groups on the resin surface remains for further study, we found preparation conditions of the anion-templated resin using oleylamine and DTAC.

Template-Dependent Metal Adsorptivity of Dialkyl Phosphate-Type Resins Prepared by Surface Template Polymerization Technique

The imprinting method was applied to the preparation of organophosphate-carrying resins by using dioleyl phosphoric acid as an amphiphilic host monomer, in the presence or in the absence of Cu 2+ or Zn 2+ ion. As a result, the Cu 2+ -imprinted resin adsorbed Cu 2+ much more effectively than did the unimprinted one, while the Zn 2+ -imprinted one showed an absorption ability to Cu 2+ as small as the unimprinted.

Novel metal ion-imprinted resins prepared by surface template polymerization with W/O emuslion.

Novel metal ion-imprinted resins prepared by surface template polymerization with W/O emuslion.