Imidazolium Quaternized Polymers Based On Poly(Chloromethyl Styrene) and their Complexes with FBS Proteins and DNA

Abstract

A novel series of imidazolium quaternized polymers based on poly(chloromethyl styrene) has been designed and synthesized, using nitroxide mediated polymerization and post‐polymerization functionalization. They are characterized by ATR‐FTIR (attenuated total reflectance‐Fourier transform infrared spectra) and 1H NMR in terms of functional groups and composition, which indicate the success of the synthetic scheme utilized. The solution behavior of the quaternized polymers has been investigated in water, phosphate buffer saline (PBS), and PBS(90%)‐FBS(10%) (fetal bovine serum) by static, dynamic, and electrophoretic light scattering. The functionalized polymers have been studied in terms of structure and stability during changes in temperature and ionic strength of their aqueous solutions. The copolymers form stable aggregates with positive surface charge. All cationic polymers are found to interact extensively with DNA via electrostatic interactions, forming stable complexes at certain ratios of the components.

Three-Dimensional Nucleic Acid Nanostructures Based on Self-Assembled Polymer-Oligonucleotide Conjugates of Comblike and Coil-Comb Chain Architectures

“…First, the polychloromethylstyrene (PCMS) homopolymer and also block (PCMS-b-PS) and random P(CMS-ran-S) copolymers of styrene and chloromethylstyrene were prepared by nitroxide-mediated controlled radical polymerization (Figure 1, Figure S2 in the SI) as described elsewhere. 33 The molar mass characteristics and composition of the starting (co)polymers are presented in Table 1. Next, by treatment of the (co)polymers with sodium azide in DMF at 60 °C overnight, the pendant chlorides were converted into azides (Figure 1, Figure S2 in the SI) to prepare polyazidomethylstyrene (co)polymers − PN 3 MS homopolymer and block, PN 3 MS-b-PS, and random, P(N 3 MS-ran-S) copolymers.…”

“…Polychloromethylstyrene homopolymer (PCMS), polychloromethylstyrene-b-polystyrene block copolymer (PCMS-b-PS), and poly-(chloromethylstyrene-ran-styrene) random copolymer (P(CMS-ran-S)) were synthesized by nitroxide-mediated controlled radical polymerization. 33 In brief, the reactions took place in vacuum-sealed glass ampules, while the resulting polymers were recovered after three freeze−thaw cycles and heating in an oil bath for 4 h at 125 °C. For the synthesis of PCMS, 1-phenyl-1-(2,2,6,6-tetramethyl-1piperidinyloxy)ethane (unimolecular initiator) and p-chloromethylstyrene (CMS) were used, with acetic anhydride as an accelerator.…”

Cross-Linking and Evaluation of the Thermo-Mechanical Behavior of Epoxy Based Poly(ionic Liquid) Thermosets

“…Similar structures can be produced by grafting an ionic group to the backbone as a side chain [57,[60][61][62] or via polymerization of a dihalide with bisimidazole molecules [63][64][65][66]. The latter results in ionenes, which are polymers with ionic moieties in their backbone [67].…”

Pressure-Dependent Stability of Imidazolium-Based Ionic Liquid/DNA Materials Investigated by High-Pressure Infrared Spectroscopy

“…The alkyl side chain of an imidazolium cation may participate in aggregation and association with anions in bulk ILs, although the hydrophilic and Coulomb forces remain the dominant interactions [11][12][13][14][15]. On top of that, several reports [17][18][19][20][21][22][23][24] show that the hydrophobic alkyl chains can stabilize biopolymers like nucleic acids via forming the association through electrostatic interactions between the DNA molecule and cations of IL.DNA molecules can associate with cations of IL via the negatively charged backbone and hydrophobic groove interaction of DNA [19][20][21][22][23][24]. The cluster structure of ILs can be disturbed by mixing with an additive-like DNA via electrostatic interaction between the cation head group of ILs and phosphate anion of DNA and hydrophobic association between the alkyl part of IL cation and the groove region or nitrogenous base of DNA [19][20][21][22][23][24].…”

“…The alkyl side chain of an imidazolium cation may participate in aggregation and association with anions in bulk ILs, although the hydrophilic and Coulomb forces remain the dominant interactions [11][12][13][14][15]. On top of that, several reports [17][18][19][20][21][22][23][24] show that the hydrophobic alkyl chains can stabilize biopolymers like nucleic acids via forming the association through electrostatic interactions between the DNA molecule and cations of IL.…”