Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

Diffusion from sessile droplets through membranes

We analyze diffusion from a periodic array of hemispherical droplets through a membrane. We find that the multiple sources do not interact strongly, even when the droplets are closely spaced, so that the flux through the membrane appears nearly additive.     

Synthesis of cyclic mono- and bis-disulfides and their selective conversion to mono- and bis-thiosulfinates

Twelve-membered ring pseudopeptidic cyclic disulfides have been prepared by iodine oxidation of the parent dithiols. However, oxidation of N,N′-(1,2-phenylene)bis(2-mercapto-2-methylpropanamide) afforded a 25/75 mixture of cyclic mono- and bis-disulfides that were separated by selective precipitation in CHCl₃. The cyclic bis-disulfide was selectively prepared by iodine oxidation of the Ni complex of this dithiol and crystallized. Its crystal structure was solved by X-ray diffraction. All these cyclic mono- or bis-disulfides were selectively converted to cyclic mono- and bis-thiosulfinates upon stoichiometric oxidation with dimethyldioxirane at low temperature. ¹H NMR of the cyclic bis-thiosulfinate revealed the presence of four isomers, two couples of stereoisomers, as expected from the insertion of two oxygen atoms in this compound, one on each disulfide bond. The two couples of cis/trans isomers were separated by preparative TLC and identified after alkaline cleavage of the two S(O)-S bonds and metalation with Ni(II). As HO⁻ attack is selective for the sulfinyl sulfur, the nature of the Ni complexes obtained is a signature of each couple of stereoisomers.     

Anionic polymerization of star-shaped nylon 6 with a trifunctional initiator

The anionic polymerization of ?-caprolactam (CLM) has been shown to proceed at high reaction rate when catalyzed by metallic lactamates and initiated by acyllactams. The role of initiator and catalyst concentration on the process of ?-caprolactam anionic polymerization has been explored, with the aim of selecting the most suitable experimental conditions for reaction injection molding (RIM). The overall polymerization rates and physical properties for reaction injection molding of star-shaped nylon 6 homopolymer have been studied by the quasi-adiabatic process. In order to model the actual rapid molding conditions, time vs. temperature reaction profiles were measured, and the relative rates of polymerization subsequently determined from these data.     

A six-step synthesis of (S)-5-ethenyl-3-(1-methyl-2-pyrrolidinyl)pyridine (SIB-1508Y) from (S)-nicotine

The anti-Parkinson’s agent SIB-1508Y was prepared in six steps from (S)-nicotine in 20% overall yield. The strategy involves a regioselective formylation at C-5 of a 1,4-dihydronicotine intermediate.     

Variational extension of the mean spherical approximation to arbitrary dimensions

We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limitT ΔS ^MSA /ΔE ^MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while ford=2 this limit is 1. On leave from Department of Physics, University of Puerto Rico, Mayagüez Campus, Mayagüez, Puerto Rico, 00681.     

Thermodynamic characterization of interpenetrating polymer networks of poly (carbonate-urethane) and poly (methyl methacrylate)

Crosslinked poly (methyl methacrylate) and poly (carbonate-urethane) as well as full interpenetrating network on their base (IPN) were characterized by precise heat capacity measurements in the temperature interval 1.2–150 K. As judged by the positive sign of the excess Gibbs free energy in the whole temperature interval above 30 K, the apparently single-phase state of IPN is thermodynamically unstable; however, its kinetic stability is ensured by permanent chamical crosslinks prohibiting the incipient phase separation. © 1994 John Wiley & Sons, Inc.