Diborane (4) derivatives via coupling of amine monobromocyanoboranes: Study of the bromination of amine cyanoborane and molecular structures of the amine dibromocyanoboranes

The first examples of diborane (4) compounds derived from amine cyanoboranes are described. A series of monobromo derivatives of amine cyanoboranes (A:BHBrCN), and dibromo derivatives (A:BBr₂CN), 1-7, were prepared. Lithiation of the monobromo derivative of trimethylamine cyanoborane, using n-BuLi, did not produce the C-lithiated intermediate Li⁺ [CH₂NMe₂BHBrCN]⁻, but instead the B-lithiated intermediate Li⁺ [Me₃NBHCN]⁻, was obtained. This intermediate, when allowed to react for 16 h, coupled with the un-lithiated trimethylamine monobromocyanoborane (Me₃NBHBrCN) and resulted in diborane (4) derivative formation as the 2LiBr complex. The same result was obtained when one equiv of the trimethylamine monobromocyanoborane was added to the reaction mixture 1 h after lithiation. Following the same procedure, novel diborane (4) derivatives of amine cyanoboranes were successfully obtained, 8-11, as their 2LiBr complexes from the monobromo derivatives of the corresponding amine cyanoboranes. Molecular structures of the trimethylamine dibromocyanoborane, 6, and the triethylamine dibromocyanoborane, 7, were determined using X-ray crystallography.     

Banach algebras of singular integral operators with piecewise continuous coefficients. General contour and weight

The Banach algebra generated by one-dimensional linear singular integral operators with matrix valued piecewise continuous coefficients in the spaceL _p (,) with an arbitrary weight is studied. The contour consists of a finite number of closed curves and open arcs with satisfy the Carleson condition. The contour may have a finite number of points of selfintersection. The symbol calculus in this algebra is the main result of the paper.     

Determination of higher molecular weight aliphatic aldehydes and ketones

The visible absorption spectra have been measured for the reaction products formed by aldehydes and ketones with p-nitrobenzenediazonium fluoborate in a phosphoric acid-2-methoxyethanol solvent medium. The absorption maxima for the reaction products of higher molecular weight aldehydes and ketones are much more intense than those formed by formaldehyde, acetaldehyde and acetone. This intensity effect has been used to analyze for propionaldehyde in mixtures also containing formaldehyde, acetaldehyde or acetone. The nature of the reaction products are considered.     

Isolable acetylene complexes of copper and silver

Copper and silver play important roles in acetylene transformations but isolable molecules with acetylene bonded to Cu(i) and Ag(i) ions are scarce. This report describes the stabilization of π-acetylene complexes of such metal ions supported by fluorinated and non-fluorinated, pyrazole-based chelators. These Cu(i) and Ag(i) complexes were formed readily in solutions under an atmosphere of excess acetylene and the appropriate ligand supported metal precursor, and could be isolated as crystalline solids, enabling complete characterization using multiple tools including X-ray crystallography. Molecules that display κ²-or κ³-ligand coordination modes and trigonal planar or tetrahedral metal centers have been observed. Different trends in coordination shifts of the acetylenic carbon resonance were revealed by ¹³C NMR spectroscopy for the Cu(i) and Ag(i) complexes. The reduction in acetylene _{C C} due to metal ion coordination is relatively large for copper adducts. Computational tools were also used to quantitatively understand in detail the bonding situation in these species. It is found that the interaction between the transition metal fragment and the acetylene ligand is significantly stronger in the copper complexes, which is consistent with the experimental findings. The C C distance of these copper and silver acetylene complexes resulting from routine X-ray models suffers due to incomplete deconvolution of thermal smearing and anisotropy of the electron density in acetylene, and is shorter than expected. A method to estimate the C C distance of these metal complexes based on their experimental _{C C} is also presented.

Gaseous acetylene can be trapped on copper(i) and silver(i) sites supported by pyrazole-based scorpionates to produce isolable molecules for detailed investigations and the study of metal-acetylene bonding.     

An Alternative Approach to Understanding the Observed Positron Fraction

Space-based observations by PAMELA (Adriani et al., Nature 458, 607, 2009), Fermi-LAT (Ackerman et al., Phys. Rev. Lett. 105, 01103, 2012), and AMS (Aguilar et al., Phys. Rev. Lett. 110, 141102, 2013) have demonstrated that the positron fraction (e+/total-e) increases with increasing energy above about 10 GeV. According to the propagation model for Galactic cosmic rays in widespread use (Moskalenko & Strong, Astrophys. J. 493, 693, 1998), the production of secondary positrons from interaction of cosmic-ray protons and heavier nuclei with the interstellar medium gives a generally falling positron fraction between 10 and 100 GeV, with secondary positrons accounting for only ～20 % of the observed positron fraction at 100 GeV; so some other physical phenomena have been proposed to explain the data. An alternative approach to interpreting the positron observations is to consider these data as presenting an opportunity for re-examining models of Galactic cosmic-ray propagation. Following release of the PAMELA data, three groups published propagation models (Shaviv, et al., Phys. Rev. Lett. 103, 111302, 2009, Cowsik and Burch, Phys. Rev. D. 82, 023009, 2010, Katz et al., Mon. Not. R. Aston. Soc. 405, 1458 2010) in which the observed positron fraction is explained entirely by secondary positrons produced in the interstellar medium. In May of this year, stimulated by the AMS extension of the positron data to higher energy with excellent statistics, two of those groups presented further development of their calculations (Cowsik et al. 2013, Blum et al. 2013), again concluding that the observed positrons can be understood as secondaries. None of the authors of these five papers was registered for the 33rd International Cosmic Ray Conference (ICRC). Although I am not an author of any of these papers, I have some close familiarity with one of these recent papers, so the conference organizers invited me to bring this alternative approach to the attention of the conference. The present paper is a summary of the material I presented, along with a brief comment about reaction at the conference to this approach.     

On queueing delays of dispersed messages

We study the message queueing delays in a node of a communication system, where a message consists of a block of consecutive packets. The message delay is defined as the time elapsing between the arrival epoch of the first packet of the message to the system until after the transmission of the last packet of that message is completed. We distinguish between two types of message generation processes. The message can be generated as abatch or it can bedispersed over time. In this paper we focus on the dispersed generation model. The main difficulty in the analysis is due to the correlation between the system states observed by different packets of the same message. This paper introduces a new technique to analyze the message delay in such systems for different arrival models and different number of sessions. For anM/M/1 system with variable size messages and for the bursty traffic model, we obtain an explicit expression for the Laplace-Stieltjes transform (LST) of the message delay. Derivations are also provided for anM/G/1 system, for multiple session systems and for fixed message sizes. We show that the correlation has a strong effect on the performance of the system, and that the commonly usedindependence assumption, i.e., the assumption that the delays of packets are independent from packet to packet, can lead to wrong conclusions.     

Approximate neutrality of large-Z ions

LetN(Z) denote the number of electrons which a nucleus of chargeZ can bind in non-relativistic quantum mechanics (assuming that electrons are fermions). We prove thatN(Z)/Z1 asZ.Research partially supported by the NSERC under Grant NA7901 and by the USNSF under Grants DMS-8416049 and PHY 85-15288-A01     

Quadruplex CARS micro‐spectroscopy

We demonstrate a technique for simultaneous detection of coherent anti‐Stokes Raman scattering (CARS) at four vibrational frequencies, using simple passive optical elements and without spectrally resolved detection. The technique is based on pump and Stokes femtosecond pulses selectively exciting vibrational resonances through spectral focusing. By replicating the pump and Stokes pair into four pairs, each traveling through appropriate glass elements, we simultaneously excite four different vibrational frequencies. The resulting CARS is a periodic train of intensities detected by a single photomultiplier and frequency analyzed to retrieve its Fourier coefficients. We demonstrate detection of methanol and ethanol mixtures in water and quantitative determination of their concentration owing to the improved chemical selectivity of this quadruplex CARS scheme. Copyright © 2012 John Wiley & Sons, Ltd.