Nonlinear structures and thermodynamic instabilities in a one-dimensional lattice system

The equilibrium states of the discrete Peyrard-Bishop Hamiltonian with one end fixed are computed exactly from the two-dimensional nonlinear Morse map. These exact nonlinear structures are interpreted as domain walls, interpolating between bound and unbound segments of the chain. Their free energy is calculated to leading order beyond the Gaussian approximation. Thermodynamic instabilities (e.g., DNA unzipping and/or thermal denaturation) can be understood in terms of domain wall formation.     

Inverse vulcanization of elemental sulfur and styrene for polymeric cathodes in Li‐S batteries

High sulfur content copolymers were prepared via the inverse vulcanization of elemental sulfur with styrene. This reaction was carried out at a relatively low temperature and invokes a new chain transfer mechanism of abstraction of benzylic protons to form stable copolymers. The use of styrene as a comonomer for inverse vulcanization was attractive due to the low cost and wide spread industrial use of styrenics in free radical processes. The copolymers were used as the active cathode material in Li‐S batteries that exhibited outstanding device performance, maintaining 489 mAh/g capacity after 1000 cycles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 107–116     

On chemiluminescent emission from an infiltrated chiral sculptured thin film

The theory describing the far-field emission from a dipole source embedded inside a chiral sculptured thin film (CSTF), based on a spectral Green function formalism, was further developed to allow for infiltration of the void regions of the CSTF by a fluid. In doing so, the extended Bruggeman homogenization formalism — which accommodates constituent particles that are small compared to wavelength but not vanishingly small — was used to estimate the relative permittivity parameters of the infiltrated CSTF. For a numerical example, we found that left circularly polarized (LCP) light was preferentially emitted through one face of the CSTF while right circularly polarized (RCP) light was preferentially emitted through the opposite face, at wavelengths within the Bragg regime. The centre wavelength for the preferential emission of LCP/RCP light was red shifted as the refractive index of the infiltrating fluid increased from unity, and this red shift was accentuated when the size of the constituent particles in our homogenization model was increased. Also, the bandwidth of the preferential LCP/RCP emission regime decreased as the refractive index of the infiltrating fluid increased from unity.     

Dithiophosphoric Acids for Polymer Functionalization

Dithiophosphoric acids (DTPAs) are an intriguing class of compounds that are sourced from elemental sulfur and white phosphorus and are prepared from the reaction of phosphorus pentasulfide with alcohols. The electrophilic addition of DTPAs to alkenes and unsaturated olefinic substrates is a known reaction, but has not been applied to polymer synthesis and polymer functionalization. We report on the synthesis and application of DTPAs for the functionalization of challenging poly-enes, namely polyisoprene (PI) and polynorbornene (pNB) prepared by ring-opening metathesis polymerization (ROMP). The high heteroatom content within DTPA moieties impart intriguing bulk properties to poly-ene materials after direct electrophilic addition reactions to the polymer backbone introducing DTPAs as side chain groups. The resulting materials possess both enhanced optical and flame retardant properties vs the poly-ene starting materials. Finally, we demonstrate the ability to prepare crosslinked polydiene films with di-functional DTPAs, where the crosslinking density and thermomechanical properties can be directly tuned by DTPA feed ratios.     

Preparation and stereochemistry of methyl 3-(and 4)-p-chlorothiophenoxy-1-methylpiperidine-4-(and 3)-carboxylates,and cyclization to benzothiopyranopyridinones

The title piperidines were prepared by (a) methanolysis of the corresponding nitriles and (b) addition of p-chlorothiophenol to the appropriate tetrahydropyridines. Three esters were obtained with stereochemistry assigned by nmr analysis: 2 [3(a) SAr, 4(e) CO₂Me], 5 [4(e) SAr, 3(e) CO₂Me], 6 [4(a) SAr, 3(e) CO₂Me]. Compounds 2 and 6 cyclized in 70% sulfuric acid. The product structures were established by X-ray crystallography and, surprisingly, both had trans-fused rings. Compound 5 , however, did not cyclize but gave 4-(methylthio)chlorobenzene as the sole isolated product.