Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Recent developments regarding charged multiblock copolymers that can form physical networks and exhibit robust mechanical properties herald new and exciting opportunities for contemporary technologies requiring amphiphilic attributes. Due to the presence of strong interactions, however, control over the phase behavior of such materials remains challenging, especially since their morphologies can be solvent‐templated. In this study, transmission electron microscopy and microtomography are employed to examine the morphological characteristics of midblock‐sulfonated pentablock ionomers prepared from solvents differing in polarity. Resultant images confirm that discrete, spherical ion‐rich microdomains form in films cast from a relatively nonpolar solvent, whereas an apparently mixed morphology with a continuous ion‐rich pathway is generated when the casting solvent is more highly polar. Detailed 3D analysis of the morphological characteristics confirms the coexistence of hexagonally‐packed nonpolar cylinders and lamellae, which facilitates the diffusion of ions and/or other polar species through the nanostructured medium.

     

Formation of Hierarchical Lamellae‐in‐Lamella Nanostructures from Polymer Blends Via Controlled Nonequilibrium Freezing

The creation of hierarchical nanostructures in polymeric materials has been intensively studied due to the great potential to tailor their physicochemical properties. Although much success has been achieved over the past decades in block copolymers, hierarchical structure engineering in polymer blends remains a great challenge. Here, the formation of hierarchical lamellae‐in‐lamella nanostructures from polymer blends via controlled nonequilibrium freezing is reported. Polymer blends are first dissolved in molten hexamethylbenzene (HMB) to form a homogeneous melt. When cooled to below its melting temperature, the HMB is crystallized and depleted, and the polymers are directionally solidified. This process is rapid enough that phase separation of the polymer blends is kinetically trapped at the nanoscale level. Then, the polymer blend epitaxially crystallizes onto the HMB inside the nanophase, resulting in the hierarchical lamellae‐in‐lamella structure. This structure is stable under ambient conditions and tunable depending on the annealing temperature and blending ratio.

     

Controlled electropolymerization based on self-dimerizations of monomers

Electropolymerization is one of the most important methodologies to synthesize and develop conducting polymers. The complexity of the polymerization mechanism, ion doping processes and structural defects are considered to be symbiotic and unavoidable, making the stagnant state and huge band gap with advanced interdisciplinary research fields and important applications in the last three decades. Herein, we provide a point of view into controlled electropolymerization by regioselective activation reactions of monomers, where self-dimerizations instead of self-electropolymerizations were utilized. The resulting dimers play a role in the connections between functional building blocks to form functional polymers on demand. This account highlights the typical findings in controlled electropolymerizations as a forum for discussing new opportunities in exploiting novel designs and applications.     

Nanocomposite Polymer Electrolytes of Sodium Alginate and Montmorillonite Clay

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na⁺)- or lithium (SCa-3-Li⁺)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na⁺ and SCa-3-Li⁺ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na⁺ clay presented the highest conductivity of 1.96 × 10⁻² S/cm², and Alg with 10 wt% of SCa-3-Li⁺ showed conductivity of 1.30 × 10⁻² S/cm², both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.     

A multifrequency EPR study of poly(PADPA) synthesized with Trametes versicolor laccase from the aniline dimer p-aminodiphenylamine (PADPA) in the presence of anionic vesicles

Poly(PADPA) synthesized with the enzyme Trametes versicolor laccase (TvL) at pH = 3.5 in aqueous solution from the aniline dimer p-aminodiphenylamine (PADPA) was studied by EPR spectrometry at X-band and W-band frequencies. For the synthesis of poly(PADPA), vesicles formed from AOT (sodium bis-(2-ethylhexyl)sulfosuccinate) were used as structure-directing templates, and TvL/O₂ as catalyst and oxidant. The isolated product is abbreviated as “poly(PADPA)-TvL-AOT” to distinguish it from poly(PADPA) obtained by other means. The EPR spectrum of poly(PADPA)-TvL-AOT recorded at room temperature is complex. It can be decomposed into two separate Dyson–type spectral components. Furthermore, the spectra measured at high frequency exhibit a line broadening behavior in comparison to the spectra recorded at low frequency where there is no line broadening. This behavior was used to estimate the effective inter-chain spin exchange interaction for each monitored spectral component. The obtained effective distances between the polymer (or oligomer) chains in both identified components of poly(PADPA)-TvL-AOT can be explained by considering slightly different interactions between the chains and the AOT molecules present in the sample. Additionally, due to different average g tensor values, g_av, of these components, it seems that each spectral component originates from one of two different molecular subunits (or local structural motifs) within the polymer (or oligomer) chains.     

Design of Optical Directional Couplers Made of Polydimethysiloxane Liquid Crystal Channel Waveguides

We present numerical simulations of a directional coupler based on three-dimensional waveguides made of a nematic liquid crystal, acting as the waveguide core, infiltrated in polydimethysiloxane channels. Modeling is based on the combination of minimization of Oseen-Frank energy of the liquid crystal molecules with a beam propagation algorithm. Design of the coupler waveguides is optimized to minimize coupling lengths and maximise efficiencies. Such components can be made at low cost on flexible plastic substrates and can be also integrated with optofluidic devices for biomedical applications.     

Preparation of Stereoregular Isotactic Poly(mandelic acid) through Organocatalytic Ring‐Opening Polymerization of a Cyclic O‐Carboxyanhydride

Poly(mandelic acid) (PMA) is an aryl analogue of poly(lactic acid) (PLA) and a biodegradable analogue of polystyrene. The preparation of stereoregular PMA was realized using a pyridine/mandelic acid adduct (Py?MA) as an organocatalyst for the ring‐opening polymerization (ROP) of the cyclic O‐carboxyanhydride (manOCA). Polymers with a narrow polydispersity index and excellent molecular‐weight control were prepared at ambient temperature. These highly isotactic chiral polymers exhibit an enhancement of the glass‐transition temperature (T_g) of 15 °C compared to the racemic polymer, suggesting potential future application as high‐performance commodity and biomedical materials.