The visual prosthesis (or "bionic eye") has become a reality but provides a low resolution view of the world. Simulating prosthetic vision in normal-vision observers, previous studies report good face recognition ability using tasks that allow recognition to be achieved on the basis of information that survives low resolution well, including basic category (sex, age) and extra-face information (hairstyle, glasses). Here, we test within-category individuation for face-only information (e.g., distinguishing between multiple Caucasian young men with hair covered). Under these conditions, recognition was poor (although above chance) even for a simulated 40×40 array with all phosphene elements assumed functional, a resolution above the upper end of current-generation prosthetic implants. This indicates that a significant challenge is to develop methods to improve face identity recognition. Inspired by "bionic ear" improvements achieved by altering signal input to match high-level perceptual (speech) requirements, we test a high-level perceptual enhancement of face images, namely face caricaturing (exaggerating identity information away from an average face). Results show caricaturing improved identity recognition in memory and/or perception (degree by which two faces look dissimilar) down to a resolution of 32×32 with 30% phosphene dropout. Findings imply caricaturing may offer benefits for patients at resolutions realistic for some current-generation or in-development implants.

A new class of coinage-metal chalcogenide compounds [AuM(μ-E)(IPr)] (M = Ag, Au; E = S, Se, Te) has been synthesized from the combination of N-heterocyclic carbene-ligated gold(I) trimethylsilylchalcogenolates [(IPr)AuESiMe] and ligand-supported metal acetates. Phosphorescence is observed from these clusters in glassy 2-methyltetrahydrofuran and in the solid state at 77 K, with emission energies that depend on the selection of metal/chalcogen ion composition. The ability to tune the emission is attributed to electronic transitions of mixed ligand-to-metal-metal-charge-transfer (IPr → AuM) and interligand (IPr → E) phosphorescence character, as revealed by time-dependent density functional theory computations.N-heterocyclic carbenes (NHCs) have been applied as ancillary ligands in the synthesis of luminescent gold(I) chalcogenide clusters and this approach allows for unprecedented selectivity over the metal and chalcogen ions present within a stable octanuclear framework.

Tetrapyrroles are of great interest for solar cell and photodynamic therapy applications due to their structural analogy with chlorophyll, a natural photosensitizer. Unsubstituted symmetric porphyrins exhibit weak absorption in the red region which makes them unsuitable for these applications. The push-pull peripheral decoration modifies the energies of the frontier molecular orbitals, which in turn influences the tetrapyrrole's spectroscopic properties. The absorption, magnetic circular dichroism, and emission spectra were measured for four zinc tetratolylporphyrin compounds substituted peripherally with a fused dimethoxybenzo group as an electron withdrawing group (EWG) on one pyrrole and on the opposite pyrrole, a single acetamido (1), a nitro (2), a proton (3), or a benzoylamino (4) substituent. Unusually, the magnetic circular dichroism spectrum of 2 exhibited a negative A term for the lowest energy absorption band (the Q band) and its emission spectrum was also unlike those of 1, 3, and 4. A complete computational analysis was carried out to obtain the energies and electron distribution, shown by electron density surfaces, of the four Gouterman MOs. TD-DFT calculations showed that for 2, ΔLUMO was greater than ΔHOMO, which accounted for the observed negative A term. The trend in the estimated MCD A term magnitudes, normalized to the absorbance as [A/(dipole strength) BM], provides experimental confirmation of the computationally determined ratio of ΔLUMO/ΔHOMO data. The value of ΔHOMO was confirmed by the trend in oscillator strengths. A series of fictive porphyrins (F1-F5) incorporating simple push-pull substituents were designed and their electronic structures were investigated using TD-DFT calculations. The substituents in the five fictive molecules illustrate the differential effect of the donor and acceptor groups in the β-position of the pyrroles on the relative stabilities of the four Gouterman orbitals. NO groups result in the greatest splitting of the LUMO pair. We show that on using strong EWGs, opposite electron donating groups result in a ΔLUMO > 0, which red-shifts the Q band and introduces a strong dipole. With the nitro and formyl EWGs, ΔLUMO becomes greater than ΔHOMO, resulting in a complex electronic structure of the Q band, recognizable by a negative A term suggesting a design objective for future photosensitizers.

Differences in the pathogenesis of radiation-induced lung injury among murine strains offer a unique opportunity to elucidate the molecular mechanisms driving the divergence in tissue response from repair and recovery to organ failure. Here, we utilized two well-characterized murine models of radiation pneumonitis/fibrosis to compare and contrast differential gene expression in lungs 24 hours after exposure to a single dose of whole thorax lung irradiation sufficient to cause minor to major morbidity/mortality. Expression of 805 genes was altered as a general response to radiation; 42 genes were identified whose expression corresponded to the threshold for lethality. Three genes were discovered whose expression was altered within the lethal, but not the sublethal, dose range. Time-course analysis of the protein product of the most promising gene, resistin-like molecule alpha, demonstrated a significant difference in expression between radiosensitive versus radiotolerant strains, suggesting a unique role for this protein in acute lung injury.

A series of phosphorescent homo-and heterometallic copper(I)−chalcogenide clusters stabilized by cyclic (alkyl)(amino)carbene ligands [Cu 4 M 4 (μ 3 -E) 4 (CAAC Cy ) 4 ] (M = Cu, Ag, Au; E = S, Se) has been synthesized by the reaction of the new copper(I) trimethylsilylchalcogenolate compounds [(CAAC Cy )CuESiMe 3 ] with ligand-supported group 11 acetates. The clusters are emissive at 77 K in solution and the solid state, with emission colors that depend on the metal/chalcogen composition. Electronic structure calculations point to a common 3 [(M + +E 2− )LCT] emissive state for the series.