External fixation of the thalamic portion of a fractured calcaneus: A new surgical technique

AbstractThe optimal treatment for intra-articular calcaneus fractures remains controversial, despite internal fixation techniques providing good results. The major point of contention is the need to reconstruct the overall morphology versus to restore the anatomy of the subtalar joint perfectly. We will describe a two-stage technique for treating intra-articular calcaneus fractures in which the primary fracture line goes through the thalamic fragment. The first procedure focuses on the overall morphology by restoring the height and length with osteotaxis being accomplished with a medial external fixator. The second procedure consists of internal fixation through a minimally invasive lateral approach to restore the anatomy of the articular facets. Any defects are filled with injectable bone substitute. This novel technique is compared to the complication rates and radiology and anatomy outcomes in published studies. This two-stage surgical technique reduces the length of hospital stays and the number of complications

Carbenic nitrile imines: Properties and reactivity

Structures and properties of nitrile imines were investigated computationally at B3LYP and CCSD(T) levels. Whereas NBO analysis at the B3LYP DFT level invariably predicts a propargylic electronic structure, CCSD(T) calculations permit a clear distinction between propargylic, allenic, and carbenic structures. Nitrile imines with strong IR absorptions above ca. 2150 cm-1 have propargylic structures with a CN triple bond (RCNNSiMe 3 and R2BCNNBR2), and those with IR absorptions below ca. 2150 cm-1 are allenic (HCNNH, PhCNNH, and HCNNPh). Nitrile imines lacking significant cumulenic IR absorptions at 1900-2200 cm -1 are carbenic (R-(C:)-N=N-R′). Electronegative but lone pair-donating groups NR2, OR, and F stabilize the carbenic form of nitrile imines in the same way they stabilize "normal" singlet carbenes, including N-heterocyclic carbenes. NBO analyses at the CCSD(T) level confirm the classification into propargylic, allenic, and carbenic reactivity types. Carbenic nitrile imines are predicted to form azoketenes 21 with CO, to form [2+2] and [2+4] cycloadducts and borane adducts, and to cyclize to 1H-diazirenes of the type 24 in mildly exothermic reactions with activation energies in the range 29-38 kcal/mol. Such reactions will be readily accessible photochemically and thermally, e.g., under the conditions of matrix photolysis and flash vacuum thermolysis

Copper-Catalyzed Synthesis of Trifluoroethylarenes from Benzylic Bromodifluoroacetates

Trifluoroethylarenes are found in a variety of biologically active molecules, and strategies for accessing this substructure are important for developing therapeutic candidates and biological probes. Trifluoroethylarenes can be directly accessed via nucleophilic trifluoromethylation of benzylic electrophiles; however, current catalytic methods do not effectively transform electron-deficient substrates and heterocycles. To address this gap, we report a Cu-catalyzed decarboxylative trifluoromethylation of benzylic bromodifluoroacetates. To account for the tolerance of sensitive functional groups, we propose an inner-sphere mechanism of decarboxylation

Liquid mixtures involving hydrogenated and fluorinated alcohols: thermodynamics, spectroscopy, and simulation

This article reports a combined thermodynamic, spectroscopic, and Computational study on the interactions and structure of binary mixtures of hydrogenated and fluorinated substances that simultaneously interact through strong hydrogen bonding. Four binary mixtures of hydrogenated and fluorinated alcohols have been studied, namely, (ethanol + 2,2,2-trifluoroethanol (TFE)), (ethanol + 2,2,3,3,4,4,4-heptafluoro-1-butanol), (1-butanol (BuOH) + TFE), and (BuOH + 2,23,4,4,4-heptafluoto-1-butanol). Excess molar volumes and vibrational spectra of all four binary mixtures have been measured as a function of composition at 298 K, and molecular dynamics simulations have been performed. The systems display a complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The combined analysis of the results from different approaches indicates that this results from a balance between preferential hydrogen bonding between the hydrogenated and fluorinated alcohols and the unfavorable dispersion forces between the hydrogenated and fluorinated chains. As the chain length increases, the contribution of dispersion increases and overcomes the contribution of H-bonds. In terms of the liquid structure, the simulations suggest the possibility of segregation between the hydrogenated and fluorinated segments, a hypothesis corroborated by the spectroscopic results. Furthermore, a quantitative analysis of the infrared spectra reveals that the presence of fluorinated groups induces conformational changes in the hydrogenated chains from the usually preferred all-trans to more globular arrangements involving gauche conformations. Conformational rearrangements at the CCOH dihedral angle upon mixing are also disclosed by the spectra

Modeling the high-energy emission in GRB 110721A and implications on the early multiwavelength and polarimetric observations

GRB 110721A was detected by the Gamma-ray Burst Monitor and the Large Area Telescope (LAT) onboard the Fermi satellite and the Gamma-ray Burst Polarimeter onboard the IKAROS solar mission. Previous analysis done of this burst showed: i) a linear polarization signal with position angle stable ($\phi_p= 160^\circ\pm11$) and high degree of $\Pi=84^{+16}_{-28}$, ii) an extreme peak energy of a record-breaking at 15$\pm$2 MeV, and iii) a subdominant prompt thermal component observed right after the onset of this burst. In this paper, the LAT data around the reported position of GRB 110721A are analysed with the most recent software and then, the LAT light curve above 100 MeV was obtained. The LAT light curve is modelled in terms of adiabatic early-afterglow external shocks when the outflow propagates into a stellar wind. Additionally, we discuss the possible origins and also study the implications of the early-afterglow external shocks on the extreme peak energy observed at 15$\pm$2 MeV, the polarization observations and the subdominant prompt thermal component.Comment: 9 pages and one figure. Accepted for publication in Ap

Multi-messenger astrophysics with THESEUS in the 2030s

Multi-messenger astrophysics is becoming a major avenue to explore the Universe, with the potential to span a vast range of redshifts. The growing synergies between different probes is opening new frontiers, which promise profound insights into several aspects of fundamental physics and cosmology. In this context, THESEUS will play a central role during the 2030s in detecting and localizing the electromagnetic counterparts of gravitational wave and neutrino sources that the unprecedented sensitivity of next generation detectors will discover at much higher rates than the present. Here, we review the most important target signals from multi-messenger sources that THESEUS will be able to detect and characterize, discussing detection rate expectations and scientific impact

Cobalt‐Catalyzed Hydrogen‐Atom Transfer Induces Bicyclizations that Tolerate Electron‐Rich and Electron‐Deficient Intermediate Alkenes

A novel CoII -catalyzed polyene cyclization was developed that is uniquely effective when performed in hexafluoroisopropanol as the solvent. The process is presumably initiated by metal-catalyzed hydrogen-atom transfer (MHAT) to 1,1-disubstituted or monosubstituted alkenes, and the reaction is remarkable for its tolerance of internal alkenes bearing either electron-rich methyl or electron-deficient nitrile substituents. Electron-rich aromatic terminators are required in both cases. Terpenoid scaffolds with different substitution patterns are obtained with excellent diastereoselectivities, and the bioactive C20-oxidized abietane diterpenoid carnosaldehyde was made to showcase the utility of the nitrile-bearing products. Also provided are the results of several mechanistic experiments that suggest the process features an MHAT-induced radical bicyclization with late-stage oxidation to regenerate the aromatic terminator