Preparation of partly hydrophobized, crosslinked polyacrylamide particles by terpolymerization of acrylamide/N,N-methylenebisacrylamide/styrene in inverse microemulsion

Bartoň, Jaroslav; Kawamoto, Sakurako; Fujimoto, Keiji; Kawaguchi, Haruma; Capek, Ignác

doi:10.1002/(sici)1097-0126(200004)49:4<358::aid-pi376>3.0.co;2-1

Cited by 17 publications

(14 citation statements)

References 13 publications

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“…The triethylene glycol pendant group incorporated in 6 increases its water solubility, making it much more hydrophilic and therefore more suitable for use in inverse emulsion polymerization than its para-methoxysubstituted analog, 1. Even monomers such as acrylic acid are difficult to polymerize in inverse emulsion because they partition into the organic phase of the polymerization, causing termination (15). The triethylene glycol chain of 6 is also expected to contribute to the stabilization of the final particles while also enhancing their dispersability.…”

Section: Resultsmentioning

confidence: 99%

“…However, neutral, biocompatible surfactants are preferred for the synthesis of proteinloaded microgels because of their reduced interactions with proteins and lower toxicity. Because crosslinking monomer 1 is relatively hydrophobic, we hypothesized that decreasing its hydrophobicity would improve its performance because inverse emulsion polymerizations are very sensitive to the hydrophobic͞ hydrophilic balance of the reactants (15).…”

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confidence: 99%

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A macromolecular delivery vehicle for protein-based vaccines: Acid-degradable protein-loaded microgels

Murthy

Schuck

et al. 2003

Proc. Natl. Acad. Sci. U.S.A.

389

361

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The development of protein-based vaccines remains a major challenge in the fields of immunology and drug delivery. Although numerous protein antigens have been identified that can generate immunity to infectious pathogens, the development of vaccines based on protein antigens has had limited success because of delivery issues. In this article, an acid-sensitive microgel material is synthesized for the development of protein-based vaccines. The chemical design of these microgels is such that they degrade under the mildly acidic conditions found in the phagosomes of antigenpresenting cells (APCs). The rapid cleavage of the microgels leads to phagosomal disruption through a colloid osmotic mechanism, releasing protein antigens into the APC cytoplasm for class I antigen presentation. Ovalbumin was encapsulated in microgel particles, 200 -500 nm in diameter, prepared by inverse emulsion polymerization with a synthesized acid-degradable crosslinker. Ovalbumin is released from the acid-degradable microgels in a pH-dependent manner; for example, microgels containing ovalbumin release 80% of their encapsulated proteins after 5 h at pH 5.0, but release only 10% at pH 7.4. APCs that phagocytosed the acid-degradable microgels containing ovalbumin were capable of activating ovalbumin-specific cytoxic T lymphocytes. The aciddegradable microgels developed in this article should therefore find applications as delivery vehicles for vaccines targeted against viruses and tumors, where the activation of cytoxic T lymphocytes is required for the development of immunity.polymer ͉ crosslinker ͉ encapsulation ͉ vaccination ͉ cytotoxic T lymphocyte

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

A macromolecular delivery vehicle for protein-based vaccines: Acid-degradable protein-loaded microgels

Murthy

Schuck

et al. 2003

Proc. Natl. Acad. Sci. U.S.A.

389

361

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confidence: 99%

“…Several examples of the copolymerization of the partially water-soluble monomer acrylamide (AAm) and oil-soluble monomers such as methacrylic acid 26 and styrene 27,28 have been recently reported with precipitation polymerization, 26 inverse microemulsion polymerization, 27 and water/oil/water emulsion by SPG membrane emulsification and subsequent suspension polymerization. 28 In our previous studies, poly(St-co-DVB) and poly (MMA-co-DVB) microspheres containing various concentrations of divinylbenzene (DVB), from 5 to 75 mol %, were synthesized by precipitation polymerization, and their unexpected thermal properties, superior to those of crosslinked polymers prepared by emulsion and suspension polymerization, were found to be due to a fully crosslinked microstructure.…”

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confidence: 99%

Synthesis of poly(acrylamide‐co‐divinylbenzene) microspheres by precipitation polymerization

Jin

Yang

Shim

et al. 2005

J. Polym. Sci. A Polym. Chem.

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The synthesis and application of polymeric microspheres are of great importance from both academic and industrial points of view. As polymeric microspheres have been used in wider fields of conventional 1 and more sophisticated 2-6 areas, the development of a new process to prepare such materials has received much attention. Polymer microspheres of a particular size and uniformity are generally obtained with one of the heterogeneous polymerizations, including suspension, emulsion, dispersion, seeded, and precipitation polymerizations. Moreover, each polymerization is branched to several subsidiary methods, such as macroemulsion, miniemulsion, microemulsion, and soap-free emulsion polymerizations.Fully crosslinked monodisperse polymer microspheres have unique applications because of their superior strength, thermal and solvent resistance, and antislip properties.7 However, the synthesis of such microspheres is limited to a few techniques, such as seeded polymerization, [8][9][10][11] Shirasu porous glass (SPG) membrane emulsification followed by postpolymerization, 12,13 and precipitation polymerization.14 Precipitation polymerization, in particular, has advantages over the other techniques because crosslinked microspheres can be readily prepared in a single process without any auxiliary apparatus to make the size distribution of the particles narrow. Therefore, homoand copolymerization systems have been thoroughly investigated, including poly(divinylbenzene), 15 poly (methacrylic acid-co-polyethylene oxide methyl ether methacrylate), 16 poly(methacrylate-co-divinylbenzene), 17 poly(chloromethylstyrene-co-divinylbenzene), 18 poly(divinylbenzene-co-maleic anhydride) 19 , poly(methyl methacrylate-co-divinylbenzene)[poly(MMA-co-DVB)], [20][21][22] and poly(styrene-co-divinylbenzene) [poly(St-co-DVB)]. 23In addition, mechanistic studies to elucidate the formation of stable microspheres in the absence of any stabilizer have been reported 24,25 in which the absorption of oligomeric species onto the nuclei and the high degree of crosslinking are the primary reasons for the formation and stable growth of the microspheres.Several examples of the copolymerization of the partially water-soluble monomer acrylamide (AAm) and oil-soluble monomers such as methacrylic acid 26 and styrene 27,28 have been recently reported with precipitation polymerization, 26 inverse microemulsion polymerization, 27 and water/oil/water emulsion by SPG membrane emulsification and subsequent suspension polymerization. 28In our previous studies, poly(St-co-DVB) and poly (MMA-co-DVB) microspheres containing various concentrations of divinylbenzene (DVB), from 5 to 75 mol %, were synthesized by precipitation polymerization, and their unexpected thermal properties, superior to those of crosslinked polymers prepared by emulsion and

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“…3, curve (1 [14]. The addition of MBA to the AAm microemulsion strongly decreased the overall rate of AAm polymerization [15]. The decrease in the rate is attributed to the shift of the reaction loci from the core to the surface of the polymer particle [16,17].…”

Section: Polymerization Ratementioning

confidence: 99%

On the inverse miniemulsion copolymerization and terpolymerization of acrylamide, N, N′-methylenebis(acrylamide) and methacrylic acid

Capek

2003

Open Chemistry

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The kinetics of free-radical copolymerization and terpolymerization of acrylamide (AAm), N; N 0 -methylenebis(acrylamide) (MBA) and methacrylic acid (MA) in the inverse water/monomer/cyclohexane/Tween 85 miniemulsion was investigated. Polymerizable sterically-stable miniemulsions were formulated in cyclohexane as a continuous medium. Polymerizations are very fast and reach the nal conversion within several minutes. The dependence of the polymerization rate vs. conversion is described by a curve with two nonstationary rate intervals. The maximum rate of polymerization slightly increases with increasing concentration of crosslinking monomer (MBA) and strongly decreases by the addition of MA. The rate of polymerization is inversely proportional to the 0.9 th and 1.8 th power of the particle concentration without and with MA, respectively. The number of polymer particles is inversely proportional to the 0.18 th and 0.13 th power of MBA concentration. The kinetic and colloidal parameters of the miniemulsion polymerization are discussed in terms of microemulsion polymerization model.

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Preparation of partly hydrophobized, crosslinked polyacrylamide particles by terpolymerization of acrylamide/N,N-methylenebisacrylamide/styrene in inverse microemulsion

Cited by 17 publications

References 13 publications

A macromolecular delivery vehicle for protein-based vaccines: Acid-degradable protein-loaded microgels

A macromolecular delivery vehicle for protein-based vaccines: Acid-degradable protein-loaded microgels

Synthesis of poly(acrylamide‐co‐divinylbenzene) microspheres by precipitation polymerization

On the inverse miniemulsion copolymerization and terpolymerization of acrylamide, N, N′-methylenebis(acrylamide) and methacrylic acid

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