The Tetracyanopyridinide Dimer Dianion, σ‐[TCNPy]22−

The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) and Cr(C₆H₆)₂ forms diamagnetic σ‐[TCNPy]₂^2? possessing a 1.572(3) Å intrafragment sp³–sp³ bond. This is in contrast to the structurally related 1,2,4,5‐tetracyanobenzene and 1,2,4,5‐tetracyanopyrazine that form π‐dimer dianions possessing long, multicenter bonds.     

Interplay of thermochemistry and Structural Chemistry, the journal (volume 23, 2012, issues 1–3) and the discipline

In the current review of the journal Structural Chemistry, the contents of the issues 1–3 for the calendar year 2012 are related to thermochemistry. A brief thermochemical commentary is added to the summary of each article.     

Iron pentacarbonyl as a precursor for molecule-based magnets: formation of Fe[TCNE](2) (T(c) = 100 K) and Fe[TCNQ](2) (T(c) = 35 K) magnets

The reaction of tetracyanoethylene (TCNE) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) with Fe(CO)(5) leads to formation of magnetically ordered materials of Fe[TCNE](2) (T(c) = 100 K) and Fe[TCNQ](2) (T(c) = 35 K) composition, respectively. In contrast, the reaction with 1,2-dichloro-5,6-dicyanobenzoquinone (DDQ) leads to a paramagnetic material.     

Conformationally constrained alpha-boc-aminophosphonates via transition metal-catalyzed/curtius rearrangement strategies

A transition metal-catalyzed/Curtius rearrangement sequence toward the development of conformationally constrained alpha-Boc-aminophosphonates 2-6 is described. An approach using the versatile tert-butylphosphonoacetate moieties 1a and 1b to derive an array of mono- and bicyclic alpha-Boc-aminophosphonate systems is presented. Conformational constraint is incorporated using either the ring-closing metathesis reaction catalyzed by the first generation Grubbs catalyst or intramolecular cyclopropanation mediated by Rh2(OAc)4. Using the tert-butyl ester functionality in 1a or 1b as a potential amino group, the Curtius rearrangement provides an efficient route toward the target alpha-Boc-aminophosphonates.     

Hydrodynamics of binary fluid phase segregation

Starting with the Vlasov-Boltzmann equation for a binary fluid mixture, we derive an equation for the velocity field u when the system is segregated into two phases (at low temperatures) with a sharp interface between them. u satisfies the incompressible Navier-Stokes equations together with a jump boundary condition for the pressure across the interface which, in turn, moves with a velocity given by the normal component of u. Numerical simulations of the Vlasov-Boltzmann equations for shear flows parallel and perpendicular to the interface in a phase segregated mixture support this analysis. We expect similar behavior in real fluid mixtures.     

Measuring the speed of sound of quintessence

Quintessence, a time-varying energy component that may account for the accelerated expansion of the universe, can be characterized by its equation of state and sound speed. In this paper, we show that if the quintessence density is at least 1% of the critical density at the surface of last scattering the cosmic microwave background anisotropy can distinguish between models whose sound speed is near the speed of light versus near zero, which could be useful in distinguishing competing candidates for dark energy.     

Paradigms and Paradoxes: Electronegativity and Bond Energies—Living Legacies of Linus and Lee

In this paper we will discuss Pauling's classic Eq. (1) that relates bond energies, "D," and electronegativities, "x." Recast to be applicable to enthalpies of formation and reaction, we apply it to the study of hydrogenolysis reactions of dienes, diynes, and alkanes, halogenolysis reactions (with chlorine, bromine, and iodine) and metathetical reactions of organosulfur species (sulfides, sulfoxides, and sulfones). It is with great regret that this equation is found wanting.     

<Emphasis Type="Italic">Rgcs1</Emphasis>, a dominant QTL that affects retinal ganglion cell death after optic nerve crush in mice

Background  

Intrinsic apoptosis of neuronal somas is one aspect of neurodegenerative diseases that can be influenced by genetic background. Genes that affect this process may act as susceptibility alleles that contribute to the complex genetic nature of these diseases. Retinal ganglion cell death is a defining feature of the chronic and genetically complex neurodegenerative disease glaucoma. Previous studies using an optic nerve crush procedure in inbred mice, showed that ganglion cell resistance to crush was affected by the Mendelian-dominant inheritance of 1–2 predicted loci. To assess this further, we bred and phenotyped a large population of F2 mice derived from a resistant inbred strain (DBA/2J) and a susceptible strain (BALB/cByJ).