An ab initio molecular orbital study of intramolecular H-bonding: 1,3 propanediol

An ab initio molecular orbital calculation has been carried out for three different conformations of 1,3 propanediol, one of which permits intramolecular H-bond studied by ab initio quantum mechanical methods. The ΔE for H-bonding formation is compated to be 0.9 kcal/mole and the charge redistributions and molecular orbital energy changes are compared to those found in intermolecular H-bonds.     

Efficient alkyne homocoupling catalysed by copper immobilized on functionalized silica

Copper immobilized on a functionalized silica support is a good catalyst for the homocoupling of terminal alkynes. The so‐called Glaser–Hay coupling reaction can be run in air with catalytic amounts of base. The copper catalyst is active for multiple substituted alkynes, in both polar and non‐polar solvents, with good to excellent yields (75–95%). Depending on the alkyne, full conversion can be achieved within 3–24 h. The catalyst was characterized by TGA, inductively coupled plasma and X‐ray photoelectron spectroscopy. Leaching tests confirm that the catalyst is and remains heterogeneous. Importantly, the overall reaction requires only alkyne and oxygen (in this case, air) as reagents, making this a clean catalytic oxidative coupling reaction. Copyright © 2012 John Wiley & Sons, Ltd.     

Machine-Driven Chemoenzymatic Synthesis of Glycopeptide

Historically, researchers have put considerable effort into developing automation systems to prepare natural biopolymers such as peptides and oligonucleotides. The availability of such mature systems has significantly advanced the development of natural science. Over the past twenty years, breakthroughs in automated synthesis of oligosaccharides have also been achieved. A machine-driven platform for glycopeptide synthesis by a reconstructed peptide synthesizer is described. The designed platform is based on the use of an amine-functionalized silica resin to facilitate the chemical synthesis of peptides in organic solvent as well as the enzymatic synthesis of glycan epitopes in the aqueous phase in a single reaction vessel. Both syntheses were performed by a peptide synthesizer in a semiautomated manner.     

A Simple and Efficient Device and Method for Measuring the Kinetics of Gas‐Producing Reactions

We present a new device for quantifying gases or gas mixtures based on the simple principle of bubble counting. With this device, we can follow reaction kinetics down to volume step sizes of 8–12 μL. This enables the accurate determination of both time and size of these gas quanta, giving a very detailed kinetic analysis. We demonstrate this method and device using ammonia borane hydrolysis as a model reaction, obtaining Arrhenius plots with over 300 data points from a single experiment. Our device not only saves time and avoids frustration, but also offers more insight into reaction kinetics and mechanistic studies. Moreover, its simplicity and low cost open opportunities for many lab applications.     

A Communication Multiplexer Problem: Two Alternating Queues with Dependent Randomly-Timed Gated Regime

Two random traffic streams are competing for the service time of a single server (multiplexer). The streams form two queues, primary (queue 1) and secondary (queue 0). The primary queue is served exhaustively, after which the server switches over to queue 0. The duration of time the server resides in the secondary queue is determined by the dynamic evolution in queue 1. If there is an arrival to queue 1 while the server is still working in queue 0, the latter is immediately gated, and the server completes service there only to the gated jobs, upon which it switches back to the primary queue. We formulate this system as a two-queue polling model with a single alternating server and with randomly-timed gated (RTG) service discipline in queue 0, where the timer there depends on the arrival stream to the primary queue. We derive Laplace–Stieltjes transforms and generating functions for various key variables and calculate numerous performance measures such as mean queue sizes at polling instants and at an arbitrary moment, mean busy period duration and mean cycle time length, expected number of messages transmitted during a busy period and mean waiting times. Finally, we present graphs of numerical results comparing the mean waiting times in the two queues as functions of the relative loads, showing the effect of the RTG regime.     

Size-dependent tunneling and optical spectroscopy of CdSe quantum rods

Photoluminescence excitation spectroscopy and scanning-tunneling spectroscopy are used to study the electronic states in CdSe quantum rods that manifest a transition from a zero-dimensional to a one-dimensional quantum-confined structure. Both optical and tunneling spectra show that the level structure depends primarily on the diameter of the rod and not its length. With increasing diameter, the band gap and the excited state level spacings shift to the red. The level structure was assigned using a multiband effective-mass model, showing a similar dependence on rod dimensions.     

X-ray laser research at the LULI (Palaiseau)

The X-ray laser program at Palaiseau is based on the recombination scheme in lithiumlike ions, which requires a moderate pump power and seems to be promising for the purpose of scaling to shorter wavelengths. In aluminum plasmas, peak gain values of 2-2.5 cm^-1 have been obtained at a wavelength of 105.7 Å corresponding to the 3d -5f transition, 6 ns after the top of a 2 ns laser pulse. The same transition in sulfur is emitted at 65.2 Å and has shown a gain of 1 cm^-1 in a preliminary time-integrated experiment. Simulations using a collisional-radiative model as the postprocessor of a hydrodynamic numerical code predict amplifications for the 3d-4f, 3d-5f, and 4d-5f transitions. A new experiment, in progress at the present time, has been designed to enhance the gain-length product up to 10-15 at 105.7 Å. The recently extended facilities of the LULI make it possible to produce a 6-cm-long plasma column, keeping the flux density at the same level as in the previous experiments     

d-critical modules of length 2 over weyl algebras

We construct a family of modules over Weyl algebras with the property of being non-simple of finite length and alsod-critical (i.e.d(M)>d(M/N) for every non-trivial submoduleN, ofM). Hered stands for the Gelfand-Kirillov dimension. We further study some properties of these modules.