Synergistic Computational‐Experimental Approach to Improve Ionene Polymer‐Based Functional Hydrogels

Abstract

The manifold applications of ionene‐based materials such as hydrogels in daily life, biomedical sciences, and industrial processes are a consequence of their unique physical and chemical properties, which are governed by a judicious balance between multiple non‐covalent interactions. However, one of the most critical aspects identified for a broader use of different polyelectrolytes is the need of raising their gelation efficiency. This work focuses on surfactant‐free ionene polymers 1−3 containing DABCO and N,N′‐(x‐phenylene)dibenzamide (x = ortho‐/meta‐/para‐) linkages as model systems to develop a combined computational‐experimental approach to improve the hydrogelation through a better understanding of the gelation mechanism. Molecular dynamics simulations of isomeric ionenes 1–3 with explicit water molecules point out remarkable differences in the assembly of the polymeric chains in each case. Interchain regions with high degree of hydration (i.e., polymer···water interactions) and zones dominated by polymer···polymer interactions are evident in the case of ortho‐ (1) and meta‐ (2) isomeric ionenes, whereas domains controlled by polymer···polymer interactions are practically inexistent in 3. In excellent agreement, ortho‐ionene 1 provides experimentally the best hydrogels with unique features such as thixotropic behavior and dispersion ability for single‐walles carbon nanotubes.

Antimicrobial and Hemolytic Studies of a Series of Polycations Bearing Quaternary Ammonium Moieties: Structural and Topological Effects

“…In our previous work, we demonstrated a remarkable influence of the substitution pattern on the central benzene ring (i.e., para -, meta -, ortho -) on the hydrogelation [32] and dye uptake properties [34] of some of these polymers. In this study, the antimicrobial activity against the Gram-negative bacterium Escherichia coli has been determined for a library of 13 ionenes with different topologies and diamine linkers (Figure 1).…”

Cationic Polymers Bearing Quaternary Ammonium Groups-Catalyzed CO2 Fixation with Epoxides

“…In both cases catalyst quantities of 0.5-1 mol% allowed us to reach conversions of more than 50% after 4 h reaction time (120 °C), and almost complete conversion when doubling the reaction time in the presence of 0.5 mol% D 1,4 (entry 14). In addition, also the cyclohexyl-based polymer E and the pyridiniumbased F showed some promising initial catalytic potential (entries 15,16).…”

“…ortho-, meta-, para-) in some of these polymers was found to play a key role on the hydrogelation [15], dye uptake [16] and antimicrobial properties [17]. In addition, our groups and others have shown that these versatile polymers can also serve as easily recoverable and reusable phase-transfer catalysts for a variety of different transformations [18][19][20].…”

“…MALDI-TOF measurements were collected with a Bruker Autoflex III Smartbeam spectrometer and on an Agilent atmospheric pressure photoionization (APPI) source on an Agilent 6520 quadrupole time-of-flight (QTOF) in the positive mode. The ionenes were synthesized as described recently [15,17]. The used epoxides were purchased from commercial suppliers and used without further purification.…”

Examining the compatibility of collagen and a polythiophene derivative for the preparation of bioactive platforms

“…Thinking in a new family of bioactive platforms based on PEDOT-collagen biocomposites (hereafter denoted P(EDOT:CLG), in this work we used an experimental-computational approach that was proven to be successful for the development of advanced functional materials. 34,35 First, the P(EDOT:CLG) has been prepared and characterized as bioactive matrix for cell adhesion and proliferation. After such experimental characterization, specific interactions between the building blocks of the two components of this biocomposite have been investigated using ab initio quantum mechanical (QM) calculations and hybrid quantum mechanical/molecular mechanicalmolecular dynamics (QM/MM-MD) simulations.…”