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A complex crystallization behavior was observed for the alternating copolymer DMDS- alt -DVE synthesized via thiol-ene step-growth polymerization. Understanding the underlying complex crystallization processes of such innovative polythioethers is critical for their application, for example, in polymer coating technologies. These alternating copolymers have polymorphic traits, resulting in different phases that may display distinct crystalline structures. The copolymer DMDS- alt -DVE was studied in an earlier work, where only two crystalline phases were reported: a low melting, L - T m , and high melting, H - T m phase. Remarkably, the H - T m form was only achieved by the previous formation and melting of the L - T m form. We applied calorimetric techniques encompassing seven orders of magnitude in scanning rates to further explore this complex polymorphic behavior. Most importantly, by rapidly quenching the sample to temperatures well below room temperature, we detected an additional polymorphic form (characterized by a very low melting phase, denoted VL - T m ). Moreover, through tailored thermal protocols, we successfully produced samples containing only one, two, or all three polymorphs, providing insights into their interrelationships. Understanding polymorphism, crystallization, and the resulting morphological differences can have significant implications and potential impact on mechanical resistance and barrier properties., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

We synthesized a directed library of compounds to explore the structure-activity relationships of peroxisome proliferator-activated receptor δ (PPARδ) activation relative to mesenchymal stem cell (MSC) osteogenesis. Our scaffold used para-substituted cinnamic acids as a polar headgroup, a heteroatom and heterocycle core connecting units, and substituted phenyl groups for the lipophilic tail. Compounds were screened for their ability to increase osteogenesis in MSCs, and the most promising were examined for subunit specificity using a quantitative PPAR transactivation assay. Six compounds were selected for in vivo studies in an ovariectomized mouse model of human postmenopausal osteoporosis. Four compounds improved bone density in vivo, with two ( 12d and 31a ) having activity comparable to that of GW0742, a well-studied PPARδ-selective agonist. 31a (2-methyl-4-[ N -methyl- N -[5-methylene-4-methyl-2-[4-(trifluoromethyl)phenyl]thiazole]]aminocinnamic acid) had the highest selectivity for PPARδ compared to other subtypes, its selectivity far exceeding that of GW0742. Our results confirm that PPARδ is a new drug target for possible treatment of osteoporosis via in situ manipulation of MSCs.

Changes in surface energy and electrical conductivity of polyimide (PI)-based nanocomposite films filled with carbon nanotubes (CNTs) induced by UV exposure are gaining considerable interest in microelectronic, aeronautical, and aerospace applications. However, the underlying mechanism of PI photochemistry and oxidation reactions induced by UV irradiation upon the surface in the presence of CNTs is still not clear. Here, we probed the interplay between CNTs and PIs under UV exposure in the surface properties of CNT/PI nanocomposite films. Changes in contact angles and surface electrical conductivity at the surface of CNT/PI nanocomposite films after UV exposure were measured. The unpaired electron intensity of free radicals generated by UV exposure was monitored by electron paramagnetic resonance. Our study indicates that the covalent interactions between CNTs and radicals generated by UV irradiation on the PI surfaces tailor the surface energy and surface conductivity through anchoring radicals on CNTs. Surprisingly, adding CNTs into PI films exposed to UV leads to antagonistic contributions of dispersion and polar components to the surface energy. The surface electrical conductivity of the CNT/PI nanocomposite films has been improved due to an enhanced hopping behavior with dense π-conjugated CNT sites. To explain the observed changes in surface energy and surface conductivity of CNT/PI nanocomposite films induced by UV exposure, a qualitative model was put forward describing the covalent interactions between UV-induced PI free radicals and CNTs, which govern the chemical nature of surface components. This study is helpful for characterizing and optimizing nanocomposite surface properties by tuning the covalent interactions between components at the nanoscale.

The photophysical properties of a phenyl-substituted poly(thiophene), poly(3-(2,5-dioctylphenyl)thiophene) (PDOPT), were studied as a function of polarization and degree of orientation of the crystalline structure. Under well-chosen controlled conditions, large-sized spherulitic crystals of PDOPT were successfully prepared from the melt. From polarized optical microscopy and X-ray diffraction, the molecular orientation of PDOPT within the spherulite was determined, indicating that the fastest growth direction of the spherulite was the a -axis. This implied that crystallization of PDOPT was directed by the packing of the side chains rather than the backbones, which are significantly separated. As the crystalline lamellae were all radially oriented, the local absorbance strongly depended on the polarization of the incoming light. Compared to randomly oriented crystals in a quenched and thus rapidly crystallized sample, PDOPT spherulites displayed red-shifted absorption and emission spectra, combined with a reduced photoluminescence quantum yield. Even for these markedly separated polymer backbones (1.47 nm), the reduced photoluminescence suggests an enhancement of interchain interactions of highly ordered bulky substituted polythiophene induced by crystallization.