Hydroxy- and silyloxy-substituted TEMPO derivatives for the living free-radical polymerization of styrene and n-butyl acrylate: synthesis, kinetics, and mechanistic studies

The synthesis of new 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) styryl derivatives as mediators for the living free-radical polymerization is described. Two of the alpha-methyl groups at the 2- and 6-position of the parent TEMPO styryl alkoxyamine have been replaced by hydroxymethyl and silyloxymethyl groups. To further increase the steric hindrance around the alkoxyamine oxygen atom, the remaining two methyl groups have been substituted with larger ethyl groups. Styrene polymerizations using hydroxy-substituted TEMPO derivatives are fast, but are not well-controlled. As previously shown for other OH-substituted alkoxyamines, intramolecular H-bonding leads to an acceleration of the C-O bond homolysis and, hence, to an acceleration of the polymerization process. However, the OH groups also increase the alkoxyamine decomposition rate constant. The kinetics of the C-O bond homolysis have been determined using EPR spectroscopy. Decomposition studies have been conducted with the aid of 1H NMR spectroscopy. In contrast to the OH-substituted alkoxyamines, highly hindered silyloxy-substituted TEMPO alkoxyamines turned out to be excellent mediator/initiators for the controlled styrene polymerization. Polystyrene with M(n) of up to 80 000 g/mol and narrow polydispersities (PDI) has been prepared using the new alkoxyamines. Reactions have been conducted at 105 degrees C; however, even at 90 degrees C controlled but slow polymerizations can be achieved. Furthermore, and more importantly, poly(n-butyl acrylates) with narrow PDIs (<1.15) have been prepared at 105 degrees C with the new alkoxyamines. Controlled acrylate polymerization can be conducted at temperatures as low as 90 degrees C. The silylated alkoxyamines presented belong to the most efficient initiator/mediators for the controlled acrylate polymerization known to date. The effect of the addition of free nitroxide on the acrylate polymerization is discussed. Moreover, the synthesis of diblock copolymers with narrow PDIs is described.     

Terahertz frequency standard based on three-photon coherent population trapping

A scheme for a terahertz frequency standard based on three-photon coherent population trapping in stored ions is proposed. Assuming the propagation directions of the three lasers obey the phase matching condition, we show that stability of few 10(-14) at 1 s can be reached with a precision limited by power broadening to 10(-11) in the less favorable case. The referenced terahertz signal can be propagated over long distances, the useful information being carried by the relative frequency of the three optical photons.     

Collisions of ultracold trapped cesium Feshbach molecules

We study collisions in an optically trapped, pure sample of ultracold Cs₂ molecules in various internal states. The molecular gas is created by Feshbach association from a near-degenerate atomic gas, with adjustable temperatures in the nanokelvin range. We identify several narrow loss resonances, which point to the coupling to more complex molecular states and may be interpreted as Feshbach resonances in dimerdimer interactions. Moreover, in some molecular states we observe a surprising temperature dependence in collisional loss. This shows that the situation cannot be understood in terms of the usual simple threshold behavior for inelastic two-body collisions. We interpret this observation as further evidence for a more complex molecular structure beyond the well-understood dimer physics.     

Copper-Catalyzed Carbonylative Hydroamidation of Styrenes to Branched Amides

Amides are one of the most ubiquitous functional groups in synthetic and medicinal chemistry. Novel and rapid synthesis of amides remains in high demand. In this communication, a general and efficient procedure for branch-selective hydroamidation of vinylarenes with hydroxyamine derivatives enabled by copper catalysis has been developed for the first time. The reaction proceeds under mild conditions and tolerates a broad range of functional groups. Applying a chiral phosphine ligand, an enantioselective variant of this transformation was achieved, affording a variety of chiral α-amides with excellent enantioselectivities (up to 99 % ee) and high yields.     

The Lower Estimate for Linear Positive Operators (II)

We will use the method introduced in the first part of our paper (see [5]) to give the best lower estimate of ∥f - B _n f ∥ for the Bernstein polynomial operators by means of a modified modulus of smoothness. The key role in our approach is the estimate of the derivative of the iterated Bernstein polynomial operators.     

Exploiting Large‐Pore Metal–Organic Frameworks for Separations through Entropic Molecular Mechanisms

We review the molecular mechanisms behind adsorption and the separations of mixtures in metal–organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next‐generation adsorbents, the separation efficiency of the materials needs to be improved. The performance under industrially relevant conditions largely depends on two factors: 1) the separation selectivity and 2) the pore volume capacity of the material. Enthalpic mechanisms can lead to increased selectivities, but these are mostly restricted to the low loading regime, and hence these mechanisms are unable to make use of all of the large‐pore volume that a metal–organic framework can provide. Industrial processes routinely operate in the pore saturation regime. In this Review, we focus on entropic molecular separation mechanisms that are effective under these conditions and, in particular, on a recent methodology to obtain high selectivities at high pore loading.     

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Quantum interference spectroscopy of rubidium-helium exciplexes formed on helium nanodroplets

Femtosecond multiphoton pump-probe photoionization is applied to helium nanodroplets doped with rubidium (Rb). The yield of Rb+ ions features pronounced quantum interference (QI) fringes demonstrating the coherence of a superposition of electronic states on a time scale of tens of picoseconds. Furthermore, we observe QI in the yield of formed RbHe exciplex molecules. The quantum interferogram allows us to determine the vibrational structure of these unstable molecules. From a sliced Fourier analysis one cannot only extract the population dynamics of vibrational states but also follow their energetic evolution during the RbHe formation.     

Metastable level lifetimes from electron-shelving measurements with ion clouds and single ions

The lifetime of the -level in singly-ionized calcium has been measured by the electron-shelving technique on different samples of rf trapped ions. The metastable state has been directly populated by exciting the dipole-forbidden transition. In ion clouds, the natural lifetime of this metastable level has been measured to be ( ) ms. For the single-ion case, we determined a lifetime of ( ) ms. The -error bars at the 2%-level have different origins for the two kinds of experiments: data fitting methods for lifetime measurements in an ion cloud and control of experimental parameters for a single ion. De-shelving effects are extensively discussed. The influence of differing approaches for the processing of the single-ion quantum jump data on the lifetime values is shown. Comparison with recent measurements shows excellent agreement when evaluated from a given method.Received: 14 November 2003, Published online: 24 February 2004PACS: 32.70.Cs Oscillator strengths, lifetimes, transition moments - 32.80.Pj Optical cooling of atoms, trapping