Polyethylene Incorporating Diels-Alder Comonomers: A "Trojan Horse" Strategy for Chemically Recyclable Polyolefins.

Polyolefins with periodic unsaturation in the backbone chain are sought after for synthesizing chemically recyclable polymers or telechelic polyolefin macromonomers. Here we introduce a bottom-up synthesis of unsaturated high-density polyethylene (HDPE) via copolymerization of ethylene with dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-3,5-dicarboxylate followed by post-polymerization retro-Diels-Alder to unveil hidden double bonds in the polymer backbone. The incorporation of this "Trojan Horse" comonomer was varied and a series of unsaturated HDPE polymers with block lengths of 1.2, 1.9, and 3.5 kDa between double bonds was synthesized. Cross metathesis of unsaturated HDPE samples with 2-hydroxyethyl acrylate yielded telechelic ester terminated PE macromonomers suitable for the preparation of ester-linked PE. These materials were depolymerized and repolymerized, making them suitable candidates for chemical recycling. The ester-linked PE displayed thermal and mechanical properties comparable to commercial HDPE.

Aerobic Solid State Red Phosphorescence from Benzobismole Monomers and Patternable Self-Assembled Block Copolymers.

The synthesis of the first bismuth-containing macromolecules that exhibit phosphorescence in the solid state and in the presence of oxygen is reported. These red emissive high molecular weight polymers (>300 kDa) feature benzobismoles appended to a hydrocarbon scaffold, and were built via an efficient ring-opening metathesis (ROMP) protocol. Moreover, our general procedure readily allows for the formation of cross-linked networks and block copolymers. Attaining stable red phosphorescence with non-toxic elements remains a challenge and, thus, our new class of soluble (processable) polymeric phosphor is of great interest. Furthermore, the formation of bismuth-rich cores within organic-inorganic block copolymer spherical micelles is possible, leading to patterned arrays of bismuth in the film state.

Understanding the Origin of Phosphorescence in Bismoles: A Synthetic and Computational Study.

A series of bismuth heterocycles, termed bismoles, were synthesized via the efficient metallacycle transfer (Bi/Zr exchange) involving readily accessible zirconacycles. The luminescence properties of three structurally distinct bismoles were explored in detail via time-integrated and time-resolved photoluminescence spectroscopy using ultrafast laser excitation. Moreover, time-dependent density functional theory computations were used to interpret the nature of fluorescence versus phosphorescence in these bismuth-containing heterocycles and to guide the future preparation of luminescent materials containing heavy inorganic elements. Specifically, orbital character at bismuth within excited states is an important factor for achieving enhanced spin-orbit coupling and to promote phosphorescence. The low aromaticity of the bismole rings was demonstrated by formation of a CuCl π-complex, and the nature of the alkene-CuCl interaction was probed by real-space bonding indicators derived from Atoms-In-Molecules, the Electron Localizability Indicator, and the Non-Covalent Interaction index; such tools are of great value in interpreting nonstandard bonding environments within inorganic compounds.

Marriage of heavy main group elements with π-conjugated materials for optoelectronic applications.

This review article summarizes recent progress in the synthesis and optoelectronic properties of conjugated materials containing heavy main group elements from Group 13-16 as integral components. As will be discussed, the introduction of these elements can promote novel phosphorescent behavior and support desirable molecular and polymeric properties such as low optical band gaps and high charge mobilities for photovoltaic and thin film transistor applications.

Proximal FAD histidine residue influences interflavin electron transfer in cytochrome P450 reductase and methionine synthase reductase.

Cytochrome P450 reductase (CPR) and methionine synthase reductase (MSR) transfer reducing equivalents from NADPH to FAD to FMN. In CPR, hydride transfer and interflavin electron transfer are kinetically coupled steps, but in MSR the two catalytic steps are represented by two distinct kinetic phases leading to transient formation of the FAD hydroquinone. In human CPR, His(322) forms a hydrogen-bond with the highly conserved Asp(677), a member of the catalytic triad. The catalytic triad is present in MSR, but Ala(312) replaces the histidine residue. To examine if this structural variation accounts for differences in their kinetic behavior, reciprocal substitutions were created. Substitution of His(322) for Ala in CPR does not affect the rate of NADPH hydride transfer or the FAD redox potentials, but does impede interflavin electron transfer. For MSR, swapping Ala(312) for a histidine residue resulted in the kinetic coupling of hydride and interflavin electron transfer, and eliminated the formation of the FAD hydroquinone intermediate. For both enzymes, placement of the His residue in the active site weakens coenzyme binding affinity. The data suggest that the proximal FAD histidine residue accelerates proton-coupled electron transfer from FADH2 to the higher potential FMN; a mechanism for this catalytic role is discussed.