Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

An SIS waveguide heterodyne receiver for 600 HGz-635 GHz

A waveguide SIS heterodyne receiver using a Nb/AlO_X/Nb junction has been built for astronomical observations of molecular transitions in the frequency range 600 GHz - 635 GHz, and has been successfully used at the Caltech Submillimeter Observatory (CSO). We report double sideband (DSB) receiver noise temperatures as low as 245 K at 600 GHz -610 GHz, and near 300 K over the rest of the bandwidth. These results confirm that SIS quasiparticle mixers work well at submillimeter-wave frequencies corresponding to photon energies of at least 90% of the superconductor energy gap. In addition, we have systematically investigated the effect on the receiver performance of the overlap between first-order and second-order photon steps of opposite sign at these frequencies. The receiver noise increases by as much as 40% in the region of overlap. We infer potential limitations for operating submillimeter-wave Nb/AlO_x/Nb mixers.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Enthalpies of dilution of electrolyte solutions by flow microcalorimetry

The enthalpies of dilution of NaCl, Me₄NBr, andn-Bu₄NBr were measured in water at 25°C with a new flow microcalorimeter. The data were analyzed with a polynomial equation, and the derived relative apparent molal enthalpies _L are in good agreement with literature values. Provided care is taken that mixing is complete, flow calorimeters are as reliable and much less time-consuming than cell-type instruments for enthalpies of dilution measurements.     

Production of a bose einstein condensate of metastable helium atoms

We recently observed a Bose-Einstein condensate in a dilute gas of ⁴He in the 2³S₁ metastable state. In this article, we describe the successive experimental steps which led to the Bose-Einstein transition at 4.7 μK: loading of a large number of atoms in a MOT, efficient transfer into a magnetic Ioffé-Pritchard trap, and optimization of the evaporative cooling ramp. Quantitative measurements are also given for the rates of elastic and inelastic collisions, both above and below the transition. Received 15 October 2001     

Beta-H transfer from the metallacyclobutane: a key step in the deactivation and byproduct formation for the well-defined silica-supported rhenium alkylidene alkene metathesis catalyst

The surface complex [([triple bond]SiO)Re([triple bond]CtBu)(=CHtBu)(CH2tBu)] (1) is a highly efficient propene metathesis catalyst with high initial activities and a good productivity. However, it undergoes a fast deactivation process with time on stream, which is first order in active sites and ethene. Noteworthy, 1-butene and pentenes, unexpected products in the metathesis of propene, are formed as primary products, in large amount relative to Re (>1 equiv/Re), showing that their formation is not associated with the formation of inactive species. DFT calculations on molecular model systems show that byproduct formation and deactivation start by a beta-H transfer trans to the weak sigma-donor ligand (siloxy) at the metallacyclobutane intermediate having a square-based pyramid geometry. This key step has an energy barrier slightly higher than that calculated for olefin metathesis. After beta-H transfer, the most accessible pathway is the insertion of ethene in the Re-H bond. The resulting pentacoordinated trisperhydrocarbyl complex rearranges via either (1) alpha-H abstraction yielding the unexpected 1-butene byproduct and the regeneration of the catalyst or (2) beta-H abstraction leading to degrafting. These deactivation and byproduct formation pathways are in full agreement with the experimental data.