An Unusually Small Singlet-Triplet Gap in a Quinoidal 1,6-Methano[10]annulene Resulting from Baird's 4n π-Electron Triplet Stabilization.

Within the continuum of π-extended quinoidal electronic structures exist molecules that by design can support open-shell diradical structures. The prevailing molecular design criteria for such structures involve proaromatic nature that evolves aromaticity in open-shell diradical resonance structures. A new diradical species built upon a quinoidal methano[10]annulene unit is synthesized and spectroscopically evaluated. The requisite intersystem crossing in the open-shell structure is accompanied by structural reorganization from a contorted Möbius aromatic-like shape in S0 to a more planar shape in the Hückel aromatic-like T1. This stability was attributed to Baird's Rule which dictates the aromaticity of 4n π-electron triplet excited states.

Hemostatic and Absorbent PolyHIPE-Kaolin Composites for 3D Printable Wound Dressing Materials.

A novel hemostatic and absorbent wound dressing material compatible with 3D printing is developed to address deficiencies in current wound dressing protocol. The design involves an open celled, microporous hydrogel foam via a high internal phase emulsion (HIPE) template with biocompatible components and tunable hemostatic character by kaolin loading, the viscosity and cure kinetics of which are tailored for 3D printing applications. The use of nontoxic mineral oil organic phase results in cytocompatability with human dermal fibroblasts. Kaolin distribution is shown by X-ray diffraction and elemental dispersive spectroscopy to be exfoliated and dispersed in the hydrogel dressing. In addition to demonstrating high fluid absorption and noncytotoxicity of relevant cell lines, the high internal phase emulsion polymers (polyHIPEs) also match the hemostatic performance of commercial wound dressing materials. Furthermore, the polyHIPEs display the requisite rheological properties for 3D printing that result in the fabrication of a prototype dressing with hierarchical porosity and a large number of controllable form factors.

Hemostatic kaolin-polyurethane foam composites for multifunctional wound dressing applications.

There are numerous challenges associated with the acute care of traumatic limb injuries in forward military settings. A lack of immediate medical facilities necessitates that the wound dressing perform multiple tasks including exudate control, infection prevention, and physical protection of the wound for extended periods of time. Here, kaolin was incorporated into recently developed robust polyurethane (PU) hydrogel foams at 1-10wt% in an effort to impart hemostatic character. ATR-IR and gel fraction analysis demonstrated that the facile, one-pot synthesis of the PU hydrogel was unaffected by kaolin loading, as well as the use of a non-toxic catalyst, which significantly improved cytocompatibility of the materials. Kaolin was generally well dispersed throughout the PU matrix, though higher loadings exhibited minor evidence of aggregation. Kaolin-PU composites exhibited burst release of ciprofloxacin over 2h, the initial release rates of which increased with kaolin loading. Kaolin loading imparted excellent hemostatic character to the PU foams at relatively low loading levels (5wt%). This work demonstrates the simple and inexpensive synthesis of robust, hemostatic, and absorptive kaolin-PU foams that have promising potential as multifunctional wound dressing materials.

Ultrafast Excited-State Dynamics of ortho-Terphenyl and 1,2-Diphenylcyclohexene: The Role of "Ethylenic Twisting" in the Nonadiabatic Photocyclization of Stilbene Analogs.

Nonadiabatic photocyclization is the fundamental step underlying photoswitching and light-assisted bond formation within diarylethylenes, yet the details of the nuclear dynamics leading to cyclization remain unclear. We have examined the ultrafast excited-state dynamics of o-terphenyl (OTP) and 1,2-diphenylcyclohexene (DPCH) in solution to determine how variation in structural constraints impacts the course of nonadiabatic photocyclization specifically in stilbenoids. Measured spectral dynamics reflect cyclization through a S1-to-S0 transition for both systems on picosecond time scales, with excited-state decay appreciably faster for DPCH versus OTP. Supportive ab initio calculations reveal a higher energetic penalty in OTP versus DPCH for reaching the lowest-energy conical intersection from the S1 minimum; this penalty is associated primarily with twisting about the carbon-carbon bond that bridges terminal phenyl groups, a structural change that has a critical role in nonadiabatic cis-trans isomerization of diarylethylenes. Findings provide a new experimental perspective on the elusive nuclear dynamics underlying cis-stilbene photocyclization.