Regularities of the radical copolymerization of dodecyl (meth) acrylate and a new cationic monomer N-(dibutylaminomethyl) methacrylamide

The regularities of radical copolymerization of dodecyl methacrylate (DMA) or dodecyl acrylate (DA) with a new cationic monomer - N-(dibutylaminomethyl) methacrylamide (DBAMMA) in toluene solutions were determined. The copolymers formed at low conversions in the DMA-DBAMMA system are enriched in ether units, and in the DA-DBAMMA system - in aminoamide units. The relative activities of comonomers determined by the Feineman-Ross and Kehlen-Tudosh methods in the first case were 1.56-1.60 (DMA) and 0.87-0.89 (DBAMMA), in the second case - 0.53-0.64 (DA) and 0.80-0.90 (DBAMMA).

Systematic Modification of the Glass Transition Temperature of Ion-Pair Comonomer Based Polyelectrolytes and Ionomers by Copolymerization with a Chemically Similar Cationic Monomer

Ion-pair comonomers (IPCs) where both the anion and cation contain polymerizable functional groups offer a route to prepare polyampholyte, ion-containing polymers. Polymerizing vinyl functional groups by free-radical polymerization produces bridging ion-pairs that act as non-covalent crosslinks between backbone segments. In particular the homopolymerization of the IPC vinyl benzyl tri-n-octylphosphonium styrene sulfonate produces a stiff, glassy polymer with a glass transition temperature (Tg) of 191 °C, while copolymerization with a non-ionic acrylate produces microphase separates ionomers with ion-rich and ion-poor domains. This work investigates the tuning of the Tg of the polyelectrolyte or ion-rich domains of the ionomers by copolymerizing with vinyl benzyl tri-n-octylphosphonium p-toluene sulfonic acid. This chemically similar repeat unit with pendant rather than bridging ion-pairs lowers the Tg compared to the polyelectrolyte or ionomer containing only the IPC segments. Rheological measurements were used to characterize the thermomechanical behavior and Tg of different copolymers. The Tg variation in the polyelectrolyte vs. weight fraction IPC could be fit with either the Gordon–Taylor or Couchman–Karasz equation. Copolymerization of IPC with a chemically similar cationic monomer offers a viable route to systematically vary the Tg of the resulting polymers useful for tailoring the material properties in applications such as elastomers or shape memory polymers.

Molecular imprinting of bovine serum albumin and lysozyme within the matrix of polyampholyte hydrogels based on acrylamide, sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid and (3-acrylamidopropyl)trimethyl ammonium chloride

Molecularly-imprinted polyampholyte (MIP) hydrogels based on nonionic monomer – acrylamide (AAm), anionic monomer – sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and cationic monomer – (3-acrylamidopropyl)trimethyl ammonium chloride (APTAC) were obtained by immobilization of bovine serum albumin (BSA) and lysozyme in situ polymerization conditions. It was found that the best amphoteric hydrogel for sorption of BSA is APTAC-75H while for sorption of lysozyme is AMPS-75H. The sorption capacity of APTAC-75H and AMPS-75H with respect to BSA and lysozyme is 305.7 and 64.1-74.8 mg per 1 g of hydrogel respectively. Desorption of BSA and lysozyme from MIP template performed by aqueous solution of 1M NaCl is equal to 82-88%. Separation of BSA and lysozyme from their mixture was performed on MIP templates. The results of adsorption-desorption cycles of BSA on adjusted to BSA polyampholyte hydrogel APTAC-75H and of lysozyme on adjusted to lysozyme polyampholyte hydrogel AMPS-75H show that the mixture of BSA and lysozyme can be selectively separated with the help of MIP hydrogels.

Salt tolerant acrylamide-based quenched polyampholytes for polymer flooding

In our previous papers [1, 2] we considered the behavior of linear and crosslinked polyampholytes based on fully charged anionic monomer — 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) and cationic monomer — (3-acrylamidopropyl)trimethylammonium chloride (APTAC) in aqueous-salt solutions, swelling and mechanical properties. In the present paper we report the applicability of salt tolerant amphoter-ic terpolymers composed of AMPS, APTAC and acrylamide (AAm) in enhanced oil recovery (EOR). The amphoteric terpolymers of different compositions, particularly [AAm]:[AMPS]:[APTAC] = 50:25:25; 60:20:20; 70:15:15; 80:10:10 and 90:5:5 mol.% were prepared by free-radical polymerization, identified and their viscosifying ability with respect to reservoir saline water (salinity is 163 g⋅L-1) at 60 °C was tested. It was found that due to polyampholytic nature, the AAm-AMPS-APTAC terpolymers exhibited improved viscosifying behavior at high salinity water. As a result, the appropriate salt tolerant sample [AAm]:[AMPS]:[APTAC] = 80:10:10 mol.% was selected for polymer flooding experiments. Polymer flood-ing experiments on high permeable sand pack model demonstrated that only 0.5 % oil was recovered by am-photeric terpolymer. While injection of polyampholyte solution into preliminarily water flooded core sample resulted in the increase of oil recovery up to 4.8–5 %. These results show that under certain conditions the amphoteric terpolymers have a decent oil displacement ability.

Synthesis of Polymer Grafted Starches and Their Flocculation Properties in Clay Suspension

Starch-based flocculants have been emerged as a promising alternative to conventional synthetic flocculants in wastewater treatment, especially for the treatment of oil sand tailings, as they are low cost, safe, biodegradable, fairly shear-stable, readily available from reproducible agricultural resources, and do not result in secondary pollution. In this paper, three types of polymer-grafted starches (St-g-Polymer) with different charge properties were synthesized and their molecular structures were controlled by atom transfer radical polymerization (ATRP). The correlations between the charge properties of starch-based flocculants, external environmental parameters, and flocculation performance were systematically investigated by conducting jar tests under various environmental conditions. It was found that the charge properties of the branch chain had a significant impact on flocculation performance. The cationic St-g-Polymer demonstrated the best performance due to the grafting of the cationic monomer to the starch backbone which improved the solubility of the copolymer and aided in the removal of small/water-soluble particles. The results obtained could assist in guiding the selection and design of suitable biodegradable flocculants when treating targeted wastewater.

Water-Soluble and Cytocompatible Phospholipid Polymers for Molecular Complexation to Enhance Biomolecule Transportation to Cells In Vitro

Water-soluble and cytocompatible polymers were investigated to enhance a transporting efficiency of biomolecules into cells in vitro. The polymers composed of a 2-methacryloyloxyethyl phosphorylcholine (MPC) unit, a hydrophobic monomer unit, and a cationic monomer unit bearing an amino group were synthesized for complexation with model biomolecules, siRNA. The cationic MPC polymer was shown to interact with both siRNA and the cell membrane and was successively transported siRNA into cells. When introducing 20–50 mol% hydrophobic units into the cationic MPC polymer, transport of siRNA into cells. The MPC units (10–20 mol%) in the cationic MPC polymer were able to impart cytocompatibility, while maintaining interaction with siRNA and the cell membrane. The level of gene suppression of the siRNA/MPC polymer complex was evaluated in vitro and it was as the same level as that of a conventional siRNA transfection reagent, whereas its cytotoxicity was significantly lower. We concluded that these cytocompatible MPC polymers may be promising complexation reagent for introducing biomolecules into cells, with the potential to contribute to future fields of biotechnology, such as in vitro evaluation of gene functionality, and the production of engineered cells with biological functions.

Water-soluble and Cytocompatible Phospholipid Polymers for Molecular Complexation to Enhance Biomolecule Transportation to Cell in vitro

Water-soluble and cytocompatible polymers were investigated to enhance a transporting efficiency of biomolecules into cells in vitro. The polymers composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) unit, a hydrophobic monomer unit, and a cationic monomer unit bearing an amino group were synthesized for complexation with model biomolecules, siRNA. The cationic MPC polymer was shown to interact with both siRNA and the cell membrane and was successively transported siRNA into cells. When introducing 20 − 50 mol% hydrophobic units into the cationic MPC polymer, transport of siRNA into cells. The MPC units (10 − 20 mol%) in the cationic MPC polymer were able to impart cytocompatibility, while maintaining interaction with siRNA and the cell membrane. The level of gene suppression of the siRNA/MPC polymer complex was evaluated in vitro and it was as the same level as that of a conventional siRNA transfection reagent, whereas its cytotoxicity was significantly lower. We concluded that these cytocompatible MPC polymers may be promising complexation reagent for introducing biomolecules into cells, with the potential to contribute to future fields of biotechnology, such as in vitro evaluation of gene functionality, and the production of engineered cells with biological functions.

Noncovalent structural locking of thermoresponsive polyion complex micelles, nanowires, and vesicles via polymerization-induced electrostatic self-assembly using an arginine-like monomer

The noncovalent locking of nanostructured thermoresponsive polyion complexes can be achieved via polymerization-induced electrostatic self-assembly (PIESA) using an arginine-like cationic monomer.