SUMMARY Hedgehog (Hh) proteins regulate important developmental processes including cell proliferation and differentiation. While Patched acts as the main Hh receptor, in Drosophila, Hh signaling absolutely requires the additional Hh-binding proteins Ihog and Boi. Here we show that, unexpectedly, cerebellar granule neuron progenitors (CGNPs) lacking Boc and Cdon, the vertebrate orthologs of Ihog and Boi, still proliferate in response to Hh. This is because in their absence, Gas1, a Hh-binding protein not present in Drosophila, mediates Hh signaling. Consistently, only CGNPs lacking all three molecules Boc, Cdon, and Gas1 have a complete loss of Hh-dependent proliferation. In a complementary manner, we find that a mutated Hh ligand which binds Patched1 but neither Boc, Cdon, nor Gas1 cannot activate Hh signaling. Together, this demonstrates an absolute requirement for Boc, Cdon, and Gas1 in Hh signaling and reveals a distinct requirement for ligand-binding components that distinguishes the vertebrate and invertebrate Hh receptor systems.

Polynitrogen compounds have been actively pursued driven by their potential as ultra-high-performing propellants or explosives. Despite remarkable breakthroughs over the past two decades, the two figures of merit for a compelling material, namely a large fraction of nitrogen by weight and a bulk stability under ambient conditions, have not yet been achieved. We report the synthesis of a lithium pentazolate solid by compressing and laser-heating lithium embedded in molecular N around 45 GPa along with its recovery under ambient conditions. The observation by Raman spectroscopy of vibrational modes unique to the cyclo-N anion is the signature of the formation of LiN. Mass spectroscopy experiments confirm the presence of the pentazolate anion in the recovered compound. A monoclinic lattice is obtained from X-ray diffraction measurements and the volume of the LiN compound under pressure is in good agreement with the theoretical calculations.

Studies of polynitrogen phases are of great interest for fundamental science and for the design of novel high energy density materials. Laser heating of pure nitrogen at 140 GPa in a diamond anvil cell led to the synthesis of a polymeric nitrogen allotrope with the black phosphorus structure, bp-N. The structure was identified in situ using synchrotron single-crystal x-ray diffraction and further studied by Raman spectroscopy and density functional theory calculations. The discovery of bp-N brings nitrogen in line with heavier pnictogen elements, resolves incongruities regarding polymeric nitrogen phases and provides insights into polynitrogen arrangements at extreme densities.

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The synthesis of polynitrogen compounds is of fundamental importance due to their potential as environmentally-friendly high energy density materials. Attesting to the intrinsic difficulties related to their formation, only three polynitrogen ions, bulk stabilized as salts, are known. Here, magnesium and molecular nitrogen are compressed to about 50 GPa and laser-heated, producing two chemically simple salts of polynitrogen anions, MgN4 and Mg2N4. Single-crystal X-ray diffraction reveals infinite anionic polythiazyl-like 1D N-N chains in the crystal structure of MgN4 and cis-tetranitrogen N44− units in the two isosymmetric polymorphs of Mg2N4. The cis-tetranitrogen units are found to be recoverable at atmospheric pressure. Our results respond to the quest for polynitrogen entities stable at ambient conditions, reveal the potential of employing high pressures in their synthesis and enrich the nitrogen chemistry through the discovery of other nitrogen species, which provides further possibilities to design improved polynitrogen arrangements.

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The high pressure chemistry of transition metals and nitrogen was recently discovered to be richer than previously thought, due to the synthesis of several transition metal pernitrides. Here, we explore the pressure-temperature domain of iron with an excess of nitrogen up to 91 GPa and 2200 K. Above 72 GPa and 2200 K, the iron pernitride FeN is produced in a laser-heated diamond anvil cell. This iron-nitrogen compound is the first with a N/Fe ratio greater than 1. The FeN samples were characterized from the maximum observed pressure down to ambient conditions by powder X-ray diffraction and Raman spectroscopy measurements. The crystal structure of FeN is resolved to be a Pnnm marcasite structure, analogously to other transition metal pernitrides. On the basis of the lattice's axial ratios and the recorded N-N vibrational modes of FeN, a bond order of 1.5 for the nitrogen dimer is suggested. The bulk modulus of the iron pernitride is determined to be of K = 344(13) GPa, corresponding to an astounding increase of about 208% from pure iron. Upon decompression to ambient conditions, a partial structural phase transition to the theoretically predicted R3̅ m FeN is detected.

The heterocyclic bisdithiazolyl radical 1b (R1 = Me, R2 = F) crystallizes in two phases. The α-phase, space group P2₁/n, contains two radicals in the asymmetric unit, both of which adopt slipped π-stack structures. The β-phase, space group P2₁/c, consists of cross-braced π-stacked arrays of dimers in which the radicals are linked laterally by hypervalent 4-center 6-electron S···S-S···S σ-bonds. Variable-temperature magnetic susceptibility measurements on α-1b indicate Curie-Weiss behavior (with Θ = -14.9 K), while the dimer phase β-1b is diamagnetic, showing no indication of thermal dissociation below 400 K. High-pressure crystallographic measurements indicate that the cross-braced π-stacked arrays of dimers undergo a wine-rack compression, but the dimer remains intact up to 8 GPa (at ambient temperature). The resistance of β-1b to dissociate under pressure, also observed in its conductivity versus pressure profile, is in marked contrast to the behavior of the related dimer β-1a (R1 = Et, R2 = F), which readily dissociates into a pair of radicals at 0.8 GPa. The different response of the two dimers to pressure has been rationalized in terms of differences in their linear compressibilities occasioned by changes in the degree of cross-bracing of the π-stacks. Dissociation of both dimers can be effected by irradiation with visible (λ = 650 nm) light; the transformation has been monitored by optical spectroscopy, magnetic susceptibility measurements, and single crystal X-ray diffraction. The photoinduced radical pairs persist up to temperatures of 150 K (β-1b) and 242 K (β-1a) before reverting to the dimer state. Variable-temperature optical measurements on β-1b and β-1a have afforded Arrhenius activation energies of 8.3 and 19.6 kcal mol(-1), respectively, for the radical-to-dimer reconversion. DFT and CAS-SCF calculations have been used to probe the ground and excited electronic state structures of the dimer and radical pair. The results support the interpretation that the ground-state interconversion of the dimer and radical forms of β-1a and β-1b is symmetry forbidden, while the photochemical transformation is symmetry allowed.