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

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

Metasomatic Vein Formation By Stationary Fluids In Carbonate Xenoliths At The Eastern Margin Of The Bergell Intrusion, Val Sissone, Italy

Fluid flow is an important mechanism associated with heat and mass transport within the Earth’s crust. The study of veins, which represent channelling of fluids, can thus be key in understanding these fluid movements, unravelling fluid composition and origin, paleo stress regimes, and the history of the host-rock. New stable isotope data on carbonates and silicates have been combined with phase petrology, mass balance, and field observations to evaluate the formation mechanism of metasomatic reaction veins in dolomitic xenoliths in the Bergell tonalites (Val Sissone, Italy). Multiple generations of extensional veins can be followed from the contact zone between the dolomites and the intrusion to a few meters within either the tonalites (with the epidote-quartz veins), or within the dolomites, where they terminate. Each type of vein contains a central zone, which is formed by open fracture crystallization. This central fracture is framed by relatively symmetric replacement zones, where the original dolomite reacted to form either forsterite, diopside, tremolite or talc, all accompanied by calcite in either a succession of reaction zones or in simpler bi-mineral (silicate + calcite) veins. The δ18O and δ13C values across the veins allow temperatures to be estimated from different mineral pairs (silicate + calcite), and which confirm vein formation along a retrograde cooling path of the intrusion. At least four different fluid infiltration events are required, the first one around 555 °C to form the forsterite-calcite veins, followed by the epidote-quartz veins at temperatures around 430 °C, then the tremolite-calcite veins at around 390 °C, and finally the talc-calcite veins at around 140 °C. The shape of the δ18O and δ13C profiles, which are flat across the central part and the replacement zones of the veins (buffered by the intrusion), change substantially over short distances. Both of these isotope profiles overlap with the equally sharp mineralogical front between the veins and the unreacted dolomites. These profiles are interpreted to be the result of an isotopic exchange mechanism driven by dissolution and re-precipitation reactions. All veins are oriented perpendicular to the contact with the intrusive body, except for the late talc veins. Elevated fluid pressures, above the confining pressures caused by the regional and intrusion emplacement stress field, are suggested to be responsible for the initial fracturing of the carbonates and intrusive rocks. The contact zones between the tonalites and carbonates likely served as fluid conduits, where fluids accumulated and the pressure built up until hydrofracturing occurred. We propose that the veins formed through episodic pulses of highly reactive fluids that remained stationary during reaction, rather than a system where fluids flushed through the veins. Based on the XCO2-constrained mass balance, the formation of the veins would only require a relatively small amount of fluid, which could potentially originate from the intrusive rocks in vicinity of the xenoliths. Veining is not ubiquitous around the Bergell intrusion, suggesting that it only may have been a localized event and thus there is no need to involve a larger convective hydrothermal system for their formation

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

Standardization of Marine Meteorological Data from FINO Offshore Platforms

KlimawandelDer Ausbau der Offshore-Windenergie gehört zu den erklärten Zielen der Bundesregierung. Um bessere Ken ntnisse der Bedingungen auf See zu erlangen, wurden drei Forschungsplattformen in der Nordsee (FINO 1 und 3) und Ostsee (FINO 2) errichtet. An diesen werden meteorologische und ozeanographische Größen in unterschiedlichen Höhen gemessen, um unter anderem Aussagen zu Vertikalprofilen der Windgeschwindigkeit treffen zu können. Da sich die Plattformen und Masten im Design unterscheiden und sich insbesondere bei den Windmessungen deutlich ein richtungsabhängiger Einfluss auf die Messungen zeigt, ist für die Vergleichbarkeit der Standorte eine standardisierte Auswertung der Messergebnisse erforderlich. Ziel des Projektes FINO-Wind ist es, die Vergleichbarkeit der Daten der drei Standorte zu verbessern und den Datennutzern nach standardisierten Methoden qualitätsgeprüfte Daten zur Verfügung zu stellen. Es sollen deshalb Standardisierungsverfahren zur Auswertung der Winddaten entwickelt werden. Insbesondere die verschiedenen Masteffekte werden eingehend untersucht und durch Windkanalmessungen, Vergleich mit LiDAR-Daten, CFD (Computational Fluid Dynamics)-Modellierungen und Anwendung der UAM (Uniform ambient flow mast correction)-Methode abgeschätzt. Daraus werden Korrekturfaktoren für Windmessungen abgeleitet, die später angewendet werden sollen. Die Messdaten, die als 10-Minuten-Werte vorliegen, werden des Weiteren einer umfassenden und automatisierten Qualitätsprüfung unterzogen. Dabei durchlaufen die Daten in aufeinanderfolgenden Schritten formale, klimatologische, zeitliche, Wiederholungs- und Konsistenzprüfungen und werden nach erfolgreichem Abschluss jeder Sequenz mit spezifischen Qualitätsflags gekennzeichnet. Aus der Analyse und dem Vergleich der Instrumentierung in unterschiedlichen Höhen, der Installation und Ausrichtung sowie die Mastkonstruktionen sollen Empfehlungen herausgearbeitet werden, wie zukünftige Anwendungen im Bereich der Offshore-Windmessungen verbessert werden können

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

On the cluster composition of supercritical water combining molecular modeling and vibrational spectroscopic data.

International audienceThe present study is aimed at a detailed anal. of supercrit. H2O structure based on the combination of exptl. vibrational spectra as well as mol. modeling calcns. of isolated H2O clusters. The authors propose an equil. cluster compn. model where supercrit. H2O is considered as an ideal mixt. of small H2O clusters (n = 1-3) at the chem. equil. and the vibrational spectra are expected to result from the superposition of the spectra of the individual clusters, Thus, it was possible to ext. from the decompn. of the midinfrared spectra the evolution of the partition of clusters in supercrit. H2O as a function of d. The cluster compn. predicted by this model is quant. consistent with the near IR and Raman spectra of supercrit. H2O analyzed using the same procedure. The authors emphasize that such methodol. could be applied to det. the portion of cluster in H2O in a wider thermodn. range as well as in more complex aq. supercrit. solns. (c) 2010 American Institute of Physics. [on SciFinder(R)