Synthesis and cationic polymerization of halogen bonding vinyl ether monomers.

Halogen bonding is rapidly becoming recognized as a viable and useful intermolecular interaction in supramolecular chemistry. While various monomers amenable to radical polymerization methods containing halogen bonding donors have been developed, this study aims to expand the type of monomers that incorporate this intermolecular interaction to facilitate use of cationic polymerization by developing three novel vinyl ether monomers containing halogen bonding donor moieties: 2,3,5,6-tetrafluoro-4-iodophenoxyethyl vinyl ether (C2I), 2,3,5,6-tetrafluoro-4-iodophenoxybutyl vinyl ether (C4I), and 2-(2,3,5,6-tetrafluoro-4-iodophenoxyethoxy)ethyl vinyl ether (O3I). Well controlled cationic polymerization is achievable through the use of a proton trap, 2,6-di--butylpyridine.

Bioinspired Approach to Silica Nanoparticle Synthesis Using Amine-Containing Block Copoly(vinyl ethers): Realizing Controlled Anisotropy.

Core-shell polymer-silica hybrid nanoparticles smaller than 50 nm in diameter were formed in the presence of micelles of poly(2-aminoethyl vinyl ether--isobutyl vinyl ether) (poly(AEVE--IBVE)) through the hydrolysis and polycondensation of alkoxysilane in aqueous solution at a mild pH and temperature. The size of the nanoparticles as well as the number and size of the core parts were effectively controlled by varying the molecular weight of the copolymers. The polymers could be removed by calcination to give hollow silica nanoparticles with Brunauer-Emmett-Teller surface areas of more than 500 m g.

Ring-Like Assembly of Silica Nanospheres in the Presence of Amphiphilic Block Copolymer: Effects of Particle Size.

Block copolymer-mediated self-assembly of colloidal nanoparticles has attracted great attention for the fabrication of a wide variety of nanoparticle arrays. We have previously shown that silica nanospheres (SNSs) 15 nm in diameter assemble into ring-like nanostructures in the presence of amphiphilic block copolymers poly[(2-ethoxyethyl vinyl ether)- block-(2-methoxyethyl vinyl ether)] (EOVE-MOVE) in an aqueous phase. Here, the effects of particle size of SNSs on this polymer-mediated self-assembly are studied systematically using scanning electron microscopy to observe SNSs of seven different sizes between 13 to 42 nm.

Energetic-Energetic Cocrystals of Diacetone Diperoxide (DADP): Dramatic and Divergent Sensitivity Modifications via Cocrystallization.

Here we report a series of energetic-energetic cocrystals that incorporate the primary explosive diacetone diperoxide (DADP) with a series of trihalotrinitrobenzene explosives: 1:1 DADP/1,3,5-trichloro-2,4,6-trinitrobenzene (TCTNB), 1:1 DADP/1,3,5-tribromo-2,4,6-trinitrobenzene (TBTNB), and 1:1 DADP/1,3,5-triiodo-2,4,6-trinitrobenzene (TITNB). Acetone peroxides are attractive for their inexpensive and facile synthesis, but undesirable properties such as poor stability, intractably high sensitivity and low density, an indicator for low explosive power, have limited their application. Here through cocrystallization the density, oxygen balance, and stability of DADP are dramatically improved.

Structural and electronic characterization of non-heme Fe(II)-nitrosyls as biomimetic models of the Fe(B) center of bacterial nitric oxide reductase.

The detoxification of nitric oxide (NO) by bacterial NO reductase (NorBC) has gained much attention as this reaction provides a paradigm as to how NO can be detoxified anaerobically in cells. However, a clear mechanistic picture of how the heme/non-heme active site of NorBC activates NO is lacking, mostly as a result of insufficient knowledge about the properties of the non-heme iron(II)-NO adduct. Here we report the first biomimetic model complexes for this species that closely resemble the coordination environment found in the protein, using the ligands BMPA-Pr and TPA.