Metathesis-Based Monoliths:  Influence of Polymerization Conditions on the Separation of Biomolecules

Mayr, Betina; Tessadri, T R; Post, E.; Buchmeiser, Michael R.

doi:10.1021/ac010452+

Cited by 82 publications

(51 citation statements)

References 36 publications

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“…Other very important materials accessible by ROMP are monolithic supports, reported by Buchmeiser and co-workers, which were used for the chromatography of biological samples, polymers and DNA fragments 37,38 . ROMP copolymers have also been used to synthesize stable emulsions of polymeric particles 39,40 .…”

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confidence: 99%

Catalytic living ring-opening metathesis polymerization

Nagarkar

Kilbinger

2015

Nature Chem

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In living ring-opening metathesis polymerization (ROMP), a transition-metal-carbene complex polymerizes ring-strained olefins with very good control of the molecular weight of the resulting polymers. Because one molecule of the initiator is required for each polymer chain, however, this type of polymerization is expensive for widespread use. We have now designed a chain-transfer agent (CTA) capable of reducing the required amount of metal complex while still maintaining full control over the living polymerization process. This new method introduces a degenerative transfer process to ROMP. We demonstrate that substituted cyclohexene rings are good CTAs, and thereby preserve the 'living' character of the polymerization using catalytic quantities of the metal complex. The resulting polymers show characteristics of a living polymerization, namely narrow molecular-weight distribution, controlled molecular weights and block copolymer formation. This new technique provides access to well-defined polymers for industrial, biomedical and academic use at a fraction of the current costs and significantly reduced levels of residual ruthenium catalyst. In olefin metathesis reactions, olefinic bonds are rearranged with the help of a transition-metal catalyst 1,2 . In the early days following the discovery of this reaction, ill-defined catalysts 3 were used to carry out this transformation. After Herisson and Chauvin 4 had proposed a reaction mechanism, the olefin metathesis reaction was better understood and soon gained much popularity. Typical catalysts used for olefin metathesis reactions include those based on ruthenium (developed mainly by the Grubbs group 5 ), tungsten and molybdenum (developed mainly by the Schrock group 6 ). Owing to the low oxophilicity of ruthenium compared to those of molybdenum and tungsten, the ruthenium metathesis catalysts (commonly known as Grubbs' catalysts) are more tolerant towards many polar functional groups and residual impurities, as well as to water 7 . Therefore, these catalysts are the catalysts of choice in highly functional organic chemistry transformations as well as for the majority of metathesis polymerizations carried out today. Catalysts G1 (first generation) and G3 (third generation) are the most widely used ruthenium initiators for ring-opening metathesis polymerization (ROMP). In comparison to the G1 initiator, the third-generation catalyst G3 exhibits very fast initiation and propagation rates, and thereby gives polymers with very narrow dispersities and an excellent control over their molecular weights. Owing to its superior stability as well as the favourable polymerization kinetics, the third-generation Grubbs' catalyst G3 was used for this work. ROMP is a polymerization technique that uses the metathesis of cyclic olefins to synthesize linear polymers. Depending on the structure of the monomer, such polymerizations can be controlled perfectly to give polymers with a narrow molecular weight distribution and a controlled average molecular weight. Ring-strained monomers, li...

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confidence: 99%

Catalytic living ring-opening metathesis polymerization

Nagarkar

Kilbinger

2015

Nature Chem

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“…Furthermore, Buchmeiser and co-workers have demonstrated a similar ability to separate biomolecules using reverse-phase chromatography with copolymers of NBE and 1,4,4a,5,8,8a-hexaydro-1,4,5,8-exo,endo-dimethanonaphthalene (DMN-H6) grafted onto borosilicate monoliths. [93] Separation of the various proteins was found to be dependent on physicochemical properties and microstructure of the grafted monoliths. These two examples show the usefulness of surface-initiated techniques for chromatographic separations.…”

Section: Chromatographic Supportsmentioning

confidence: 99%

“…Of particular interest in this area is work by Buchmeiser and co-workers centered on the use of ROMP to grow functionalized norbornenes from silica surfaces. [20,93,94] For the chromatographic separation of phenols, anilines, lutidines, and hydroxyquinolines, they have demonstrated the ability to grow poly(norborn-2-ene) (PNBE), poly(7-oxanorborn-2-ene-5,6 dicarboxylic acid) (PONDCA), or copolymers of these two compounds on silica supports. [20] As compared to supports created by coating solution polymers onto silica, which tends to clog pores and reduce surface area, the surface-initiated supports provided much improved separations.…”

Section: Chromatographic Supportsmentioning

confidence: 99%

Physicochemical Properties of Surface‐Initiated Polymer Films in the Modification and Processing of Materials

Jennings¹,

Brantley

2004

Advanced Materials

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This article reviews the physicochemical aspects of surface‐initiated polymer films used to modify planar and non‐planar surfaces and to produce micro‐ and nanoscale patterned features. Particular emphasis is placed on the molecular composition of the polymer and its effect on surface and bulk properties of ultrathin films. Recent advances in the use of responsive polymer films that exhibit dramatically altered properties upon changes in solvent, temperature, or ionic strength are reviewed. The uses of surface‐initiated polymer films to modify materials' properties and impact applications in chromatography, nanoparticle‐templated synthesis, and carbon nanotube dispersion are highlighted.

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“…Glass cartridges (20 x 10 mm i.d.) were cleaned as described earlier 78 . The columns were then dried for 2 h under vacuum, then closed at one end with frits and end fittings, respectively, and cooled to 0 °C.…”

Section: General Procedures For the Preparation Of Monolithsmentioning

confidence: 99%

“…11 Within that context, the use of ring-opening metathesis polymerization (ROMP) has widened the scope and range of applications of polymeric monoliths including polymeric monoliths as catalytic supports for both batch and continuous processes. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] This is related to the unprecedented tolerance versus functional groups that can be introduced onto the inner surface of the porous, cross-linked matrix. Very recently, electron beam-(EB) based synthetic protocols, allowing for the large volume synthesis of such supports, have been added to the synthetic armor.…”

Section: Introductionmentioning

confidence: 99%

Creation of Pd-nanoparticles within the pores of ring opening metathesis polymerization-derived polymeric monoliths for use in organometallic catalysis

Buchmeiser¹,

Bandari²,

Prager³

et al. 2011

Arkivoc

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Polymeric monolithic supports displaying micro-, meso-and macroporosity have been prepared via ring opening metathesis polymerization (ROMP) from (Z)-9-oxabicyclo[6.1.0]non-4-ene (OBN) and tris(cyclooct-4-en-1-yloxy)methylsilane (CL) by the use of the 2 nd -generation Grubbs-initiator RuCl 2 (Py) 2 (IMesH 2 )(CHPh) 1 in the presence of a phase separation-enforcing macroporogen, i.e. 2-propanol, and a microporogen, i.e. toluene. The porous supports were then subject to pore sizeselective functionalization by hydrolyzing the epoxy-groups within pores >6 nm to the corresponding vic-diol with the aid of poly(styrenesulfonic acid) (PS-SO 3 H). The remaining epoxide moieties located within the small pores (diameter <6 nm) were then reacted with N,Ndipyrid-2-ylamine to yield the corresponding dipyrid-2-ylamin-functionalized monolithic supports. Typical loadings with functional monomer were in the range of 6-7 µmol/g. These chelating ligands located within the small pores were then used for the immobilization of Pd II . Quantitative metal loadings (approx. 1 mg/g) could be accomplished. Reduction of the Pd II with NaBH 4 resulted in the formation of Pd nanoparticles <4 nm in diameter that were still exclusively located within the small pores. These Pd-loaded monoliths were used in a series of Sonogashira-Hagihara and Suzuki-type couplings. Scanning electron microscopy measurements on the metal loaded monoliths prior to the catalytic reactions revealed that the metal nanoparticles that formed were immobilized within the small pores. These findings are supported by the comparably low metal content in the coupling products. Thus, metal leaching was <0.13 %.

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Metathesis-Based Monoliths: Influence of Polymerization Conditions on the Separation of Biomolecules

Cited by 82 publications

References 36 publications

Catalytic living ring-opening metathesis polymerization

Catalytic living ring-opening metathesis polymerization

Physicochemical Properties of Surface‐Initiated Polymer Films in the Modification and Processing of Materials

Creation of Pd-nanoparticles within the pores of ring opening metathesis polymerization-derived polymeric monoliths for use in organometallic catalysis

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